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Product and Process Design Pri

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CD-8-1

Chapter 8

Reactor-Separator-Recycle Networks



8.0 OBJECTIVES

The presence of at least one chemical reactor and one or more separation sections for the
separation of the effluent mixture leaving the reactor(s) characterizes many chemical processes.
In almost all cases, one or more of the streams leaving the separation section(s) is (are) recycled
to the reactor. In Chapter 6, the design of reactors and reactor networks was considered without
regard for the separation section(s) and possible recycle there from. Chapter 7 was concerned
with the design of separation sections in the absence of any consideration of the reactor section.
Chapter 5, which dealt with the synthesis of the entire process, included a few examples of the
interaction between the reactor and separation sections. This chapter extends that introduction to
give a more detailed treatment of reactor-separator-recycle networks.

After studying this chapter, the reader should

1. Be able to determine the best location for the separation section, either before or after the
reactor.

2. Understand the tradeoffs between purge-to-recycle ratio, recycle ratio, and raw material loss,
when dealing with inert or byproduct chemicals that are difficult to separate from the
reactants.

3. Understand the need to determine the optimal reactor conversion, involving the tradeoff
between the cost of the reactor section and the cost of the separation section(s) in the
presence of recycle, even when chemical equilibrium greatly favors the products of the
reaction.

CD-8-2
4. Understand the conditions under which the recycle of byproducts to extinction can be
employed to reduce waste and increase yield.

5. Be aware of the snowball effect in a reactor-separator-recycle network and the importance of
designing an adequate control system, which is presented in Sections 20.3 (Example 20.11)
and 21.5 (Case Study 21.3).


8.1 INTRODUCTION

The feed to a reactor section of a chemical process almost always is a combined feed consisting
of a fresh feed mixed with one or more recycle streams, as shown in Figure 7.1. Fresh reactor
feeds rarely contain only the reactants for the desired reaction. Besides the reactants, they may
contain inert chemicals, potential reactants for side reactions, catalyst poisons, and products of
the desired reaction(s). Recycle streams are intended to contain only unconverted reactants of the
desired reaction(s). However, more commonly, recycle streams also contain products of the
desired reaction(s), products of undesired side reactions, and inert chemicals.

Reactor effluents are almost never products that meet purity specifications. Besides the
products, effluents may contain reactants, inerts, products of undesired side reactions, and feed
impurities. Thus, almost every chemical process that involves a chemical reaction section also
involves one or more separation sections in addition to one or more recycle streams. A major
challenge of process design is to devise an optimal scheme for uniting the reaction and separation
functions of a process. This chapter presents many of the considerations involved in that
optimization. Although Figure 7.1 shows only one reactor section, multiple reactor sections are
sometimes required, with separation sections located between each pair of reactor sections


CD-8-3
8.2 LOCATING THE SEPARATION SECTION WITH RESPECT TO THE
REACTOR SECTION

In many, perhaps most, chemical processes, a separation section is located after the reaction
section, as shown in Figure 7.1. In this separation section, products are purified and unconverted
reactants are recovered for recycle back to the reactor. In this manner, a process involving
reactions with unfavorable chemical equilibrium constants, K
c
, at reactor conditions can achieve
high overall process conversions to desired products. Important industrial examples are the
hydrogenation of nitrogen to ammonia,

2 2 3
N + 3H 2NH ↔

and the hydrogenation of carbon monoxide to methanol,

2 3
CO + 2H CH OH ↔

both of which are exothermic reactions, whose chemical equilibrium constants, therefore,
decrease with increasing temperature according to the van’t Hoff equation:


o
2
ln
c rx
P
K H
T RT
∂ ∆  
=
 

 
(8.1)

In these two examples, the chemical equilibrium constants are both less than unity and
reactor conversions are less than 50% at temperatures high enough to achieve reasonable reaction
rates. Because both reactions involve shrinkage in the number of moles (4 to 2 for the ammonia
reaction and 3 to 1 for the methanol reaction), the reactor conversion can also be increased by
increasing the pressure, but practical considerations limit the operating pressure. However, with
the recovery and recycle of unconverted reactants, overall process conversions of 100% are
approached.

CD-8-4
Although product purification may require extreme measures to achieve product
specifications, recycle streams rarely require a significant degree of purification with respect to
recycled reactants. When two or more reactants are involved, they do not have to be recovered
separately for recycle unless their separation indexes (e.g., relative volatility) are separated by the
product(s), as shown in the next two examples.

Example 8.1 Styrene Manufacture.
In the styrene manufacture process of Figure 10.61, the main reaction is

Methanol + Toluene → Styrene + Hydrogen + Water

The following side reaction also occurs:

Methanol + Toluene → Ethylbenzene + Water

The reactor effluent contains appreciable percentages of unreacted methanol and toluene.
In this process, both styrene and ethylbenzene are products and must be purified to meet
strict specifications. Water from the main reaction must be treated to the extent required
for disposal to a sewer or for another use. Methanol and toluene are recovered and
recycled. They are adjacent in relative volatility and, therefore, when distillation is used,
they need not be separated; and because they are recycled they need not be purified to a
high degree. Typically, the recycle stream might contain 5% ethylbenzene plus styrene.

Example 8.2. Cumene Manufacture.
A more complex example is the manufacture of cumene (isopropyl benzene) by the
alkylation of benzene with propylene, taken from the 1997 National Student Design
Competition of the AIChE. Cumene is widely used to make acetone and phenol. The fresh
feeds are as follows, where the benzene feed is nearly pure, but a refinery cut of a
propylene-propane mixture is used rather than a more expensive feed of nearly pure
propylene.

CD-8-5
Component
Propylene feed,
lbmol/hr
Benzene feed,
lbmol/hr
Water 0.1800
Ethane 4.6440
Propylene 1,029.2075
Propane 465.6127
1-Butene 0.0300
Isobutane 0.3135
Methylcyclopentane, MCP 1.1570
Benzene 997.5130
Methylcyclohexane, MCH 0.2030
Toluene 0.1270

The main reaction, conducted with a catalyst, is:

Propylene + Benzene → Isopropylbenzene (Cumene)

A number of undesirable side reactions involving the main reactants also occur, including:

Propylene + Benzene → n-Propylbenzene
Cumene + Propylene → m-Diisopropylbenzene (m-DIPB)
Cumene + Propylene → p-Diisopropylbenzene (m-DIPB)
Other reactions that produce alkylation heavies

All of the impurities in the propylene and benzene fresh feed streams, including the large
amount of propane in the propylene feed, are essentially inert, with the exception of 1-
Butene, which enters into the following undesirable side reactions:

1-Butene + Benzene → t-Butylbenzene (t-BB)
1-Butene + Benzene → 1-isopropyl,4-methyl Benzene (p-Cymene)

CD-8-6
Potential products and byproducts include cumene, propane, DIPBs, t-BB, p-cymene, inert
light hydrocarbons, inert aromatic compounds, and water. A main objective of the process
is to maximize the production of cumene and minimize the amounts of byproduct and
waste streams. The cumene product must meet the following specifications:

Cumene purity, wt% 99.97 minimum
Butylbenzenes, ppm (by wt) 40 maximum
Toluene, ppm (by wt) 15 maximum
Cymene, ppm (by wt) 10 maximum
Benzene and paraffins, ppm (by wt) 10 maximum
Others, ppm (by wt) 225 maximum

The propane byproduct is used as either fuel gas or LPG. Thus, it can contain water and
light hydrocarbons. However, the aromatic content cannot exceed 0.01 wt%.

Experimental alkylation data show that the two reactions above that produce DIPBs can
result in a serious loss (> 10%) of potential cumene product. To reduce this loss, two
remedies are applied, the first of which is related to Heuristic 2 in Table 5.2: (1) the use of a
large excess of benzene in the combined feed to the alkylation reactor, for example, a 4.0
molar ratio of benzene to propylene to reduce the DIPB formation reactions, and (2) the
addition of a trans-alkylation reactor where the DIPBs are reacted with benzene to produce
cumene according to the reaction:

DIPB + Benzene → 2 Cumene
Other reactions that produce trans-alkylation heavies

Solution
A preliminary block flow diagram, suggested for the cumene process, is shown in
Figure 8.1. The process consists of one separation section, consisting of three columns,
situated between two reactor sections, one for alkylation and one for trans-alkylation. The
separations are all distillations, where approximate measures for the ease of distillation,
CD-8-7
assuming ideal liquid solutions, are the differences between the normal boiling points of the
components in the alkylation reactor effluent:

Component Formula
Molecular
weight
Normal boiling
point,
o
C
Water H
2
O 18.02 100
Ethane C
2
H
6
30.07 -88.6
Propylene C
3
H
6
42.08 -47.4
Propane C
3
H
8
44.11 -42.1
Isobutane C
4
H
10
58.13 -11.7
1-Butene C
4
H
8
56.12 -6.3
Methylcyclopentane C
6
H
12
84.16 71.8
Benzene C
6
H
6
78.12 80.1
Methylcyclohexane C
7
H
14
98.19 100.9
Toluene C
7
H
8
92.16 110.6
Cumene C
9
H
12
120.2 152.4
n-Propylbenzene C
9
H
12
120.2 159.2
t-Butylbenzene C
10
H
14
134.2 169.0
p-Cymene C
10
H
14
134.2 177.1
m-DIPB C
12
H
18
162.3 203.2
p-DIPB C
12
H
18
162.3 210.3
Trans-alkylation heavies 201.7 261.3
Alkylation heavies 206.4 278.8


CD-8-8

Figure 8.1 Cumene process.
Benzene
feed
Propylene
feed
Propane Cumene
Alkylation
Reactor
Trans-alkylation
Reactor
Benzene
Benzene Recycle
Benzene
Recycle
C1 C2 C3

CD-8-9
Note that the fresh propylene feed contains approximately 31 mol%
propane. Because propane is inert, Heuristic 3 of Table 5.2 should be considered.
Propane can be removed in a separation section before or after the alkylation
reactor. However, if removed before the reactor, a difficult separation between
propane and propylene is required, as discussed in Section 7.2, because the boiling-
point difference is only 5.3
o
C (relative volatility < 1.3). In the alkylation reactor,
essentially all of the propylene, as well as all of the 1-butene, are reacted.
Therefore, after the reactor, propylene is not present to be separated from propane.
Instead, the propane, together with water and small amounts of inert light
hydrocarbons in the propylene feed, are easily removed from the excess benzene in
the reactor effluent in the depropanizer, C1. Here, the difference in boiling points
between the key components is 112.2
o
C (relative volatility > 10). Following the
depropanizer is a benzene-recovery distillation column, C2, where benzene is
removed, with a portion recycled to the alkylation reactor and the remainder sent to
the trans-alkylation reactor. The main separation is between benzene and cumene
with a boiling-point difference of 72.3
o
C (relative volatility > 5). Finally, cumene
product is recovered as the distillate in distillation column, C3, where the bottoms
product, comprised of DIPBs, is sent to the trans-alkylation reactor to be converted
to cumene. In the trans-alkylation reactor, a 4.0 molar ratio of benzene to total
DIPBs is used, but the conversion of DIPBs is only 50%. By recycling the effluent
from the trans-alkylation reactor, no net production of DIPBs is incurred. Based on
laboratory experiments and other considerations, the benzene recycle to the
alkylation reactor can contain up to 10 mol% impurities. However, the combined
feed to the alkylation reactor must not contain more than 1.3 mol% cumene.

A cardinal rule, implied in Heuristic 4 of Table 5.2, that must be adhered to
when developing a process flowsheet, is to provide exits from the process for all
inert species that enter the process as impurities in the fresh feed(s) or are formed in
irreversible side reactions. In the cumene process, these species include water and
ethane, which are more volatile than propane; isobutane, MCP, MCH, and toluene,
which are more volatile than cumene; and n-propylbenzene, tBB, and p-cymene,

CD-8-10
which are more volatile than the DIPBs. Based on the product specifications for
the propane and cumene products, calculations show that the total amounts of these
species produced do not leave with one or both products. Consequently, two
alternatives, suggested in Heuristic 4 of Table 5.2, must be evaluated. The first is
to add separators to the process flowsheet. When too expensive, the second
includes one or more purge or drag streams, resulting in the loss of reactant(s),
product(s), or both. Two drag streams, one from the distillate of the benzene
recovery column and one from the bottoms of the cumene recovery column, are
used, leading to a benzene loss of about 2% and a cumene loss of less than 1%.
Inclusion of drag streams and the resulting material balance calculations are the
subjects of Exercise 8.1 at the end of this chapter.

Chemical processes, especially those utilizing a catalyst in the chemical reactor,
may require a feed separation section, as shown in Figure 7.1, to purify the fresh feed
before it enters the reactor. In this separation section, catalyst poisons are removed as
well as components, other than reactants for the main reaction(s), that may enter into
undesirable side reactions in the reactor section. In general, inert chemicals can be
removed in separation sections either before or after the reactor, wherever the separation
index is more favorable, as discussed above for the cumene process. However, when
removed after the reactor, a larger reactor is required because of the higher flow rate and
lower reactant concentrations. As an example, consider the manufacture of sulfuric acid.
The feed stocks are air and either sulfur or sulfide ores, where the first reaction is the
oxidation of sulfur or sulfide to sulfur dioxide, the second reaction is the catalytic
oxidation of SO
2
to SO
3
, and the third reaction is the absorption of SO
3
in water to form
sulfuric acid. Before the first reactor, moisture must be removed from the entering air to
avoid corrosion and allow the use of carbon steel. Before entering the second reactor,
dust, fluorides, and arsenic and vanadium compounds must be removed from the feed gas
to prevent catalyst poisoning.

What should be done when the fresh feed contains an appreciable percentage of
product chemicals? This occurs most frequently in isomerization reactions involving

CD-8-11
light paraffin hydrocarbons, as illustrated in Example 5.2. Suppose the reaction is
A↔B. In this case, it is important to remove the product B from the fresh feed before it
enters the reactor so as to increase the rate of reaction and achieve the highest equilibrium
conversion possible. However, because reactor conversion is usually incomplete for
isomerization reactions, A is commonly separated from B, with A recovered and
recycled. Unless other chemicals formed in the reactor interfere with the A-B separation,
the two A-B separators are combined, with the resulting separator placed before the
reactor. Exercise 8.2 considers separator placement for a pentane isomerization process.



8.3 TRADEOFFS IN PROCESSES INVOLVING RECYCLE


Reactions with very large chemical equilibrium constants (e.g., > 10,000) at reactor
conditions of temperature and pressure provide an opportunity for approaching 100%
conversion during a single pass through the reactor. In addition, when the feed contains
stoichiometric proportions of the reactants with no impurities and the reaction leads to
only one product, then in principle no separation section is needed. One such situation
exists. It is the manufacture of anhydrous hydrogen chloride gas from pure, evaporated
chlorine and a stoichiometric amount of pure, electrolytic hydrogen by the reaction:

H
2
+ Cl
2
→ 2 HCl

The only pieces of equipment required are a reactor, compressors, and heat exchangers.
Such a process is rare. Even when 100% reactor conversion is theoretically possible, the
optimal reactor conversion is less than 100% and a separation section is necessary. The
main reason for this is the rapid decline in reaction rate as the reacting mixture is depleted
of reactants. Thus, in most processes where a chemical reactor is required, consideration
must be given to the tradeoffs between the cost of the reactor section and the cost of the
separation section that follows it.


CD-8-12
A number of factors affect the tradeoff between the reactor and separation
sections, many of which were introduced in Chapters 3-7. These include

1. The fractional conversion in the reactor of the limiting reactant. This directly affects
the need for and cost of the separation section.

2. The entering temperature to and mode of operation (adiabatic, isothermal,
programmed temperature profile, etc.) for the reactor. This affects heating and/or
cooling costs and reactor effluent composition when side reactions are possible.

3. Reactor pressure, particularly for gas-phase reactions where the number of reactant
molecules is greater than the number of product molecules. In this case, reaction
kinetics may favor a higher pressure, but at the higher cost of gas compression.

4. Use of an excess of one reactant to minimize side reactions and/or increase the rate of
reaction. This increases the cost of the separation system.

5. Use of an inert diluent in an adiabatic reactor to reduce the change in temperature.
This increases the cost of the separation system.

6. Use of a gas or liquid purge stream to avoid difficult separations. This reduces the
cost of the separation system, but results in the loss of reactants and may increase the
cost of the reactor section, depending on the purge-to-recycle ratio (ratio of purge
flow rate to recycle flow rate).

The use of process simulation, in conjunction with optimization, as discussed in
Chapter 18, allows one to determine optimal values of reactor conversion, entering
temperature, mode of operation, pressure, molar ratio of reactants in a combined reactor
feed, diluent ratio, and purge-to-recycle ratio.



CD-8-13
8.4 OPTIMAL REACTOR CONVERSION

Return to the toluene hydrodealkylation process in Section 4.3, with the reaction
kinetics in Example 6.2. To illustrate the effect of achieving a high conversion on reactor
size, simplify the combined reactor feed by eliminating methane and neglect biphenyl
formation. Also, to avoid carbon formation, assume a molar ratio of hydrogen to toluene
of 5 for the combined feed to the reactor. At typical reactor conditions, the reverse
reaction is considered to be negligible and Eq. (6.31) gives the forward reaction rate, r
f
,
where the Arrhenius equation for the rate constant, k
f
, as a function of temperature is
taken from the paragraph below Eq. (6.31). Thus,

r
f
=
2 2
1/2 10 1/2 toluene
H toluene H toluene
52, 000
6.3 10 exp
f
dC
k C C C C
dt RT
−  
− = = ×
 
 
(8.2)

where R = 1.987 cal/mol-K; concentrations, C
i
, are in kmol/m
3
; time, t, is in sec; and
temperature, T, is in K. Next, the volume of both isothermal and adiabatic PFRs is
computed for a series of conversions from 1% to 99%, for the following feed conditions:


Temperature,
o
F 1,200
Pressure, psia (0 pressure drop) 500

Component flow rates, lbmol/hr:
Hydrogen 2,500
Toluene 500


The calculations can be performed with any process simulator. Using the
CHEMCAD program, the results for the isothermal case, plotted as reactor volume
against fractional conversion of toluene, are shown in Figure 8.2, with the adiabatic case
in Figure 8.3. For the isothermal case, the reactor volume increases almost linearly as

CD-8-14
conversion increases to 0.4. The volume then increases more rapidly until at conversions
near 0.8, the volume turns up sharply. The reactor volume is 4,080 ft
3
at a conversion of
0.9, but twice that at a conversion of 0.99.

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
2
4
6
8
R
e
a
c
t
o
r

V
o
l
u
m
e

[
1
,
0
0
0

f
t
3
]
Fractional Conversion of Toluene
Figure 8.2 Required reactor volume for toluene hydrodealkylation in an isothermal PFR.

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
0.2
0.4
0.6
0.8
1
1.2
R
e
a
c
t
o
r

V
o
l
u
m
e

[
1
,
0
0
0

f
t
3
]
Fractional Conversion of Toluene
Figure 8.3 Required reactor volume for toluene hydrodealkylation in an adiabatic PFR.

As seen in Figure 8.3, the effect of conversion on reactor volume for the adiabatic
case is very different from the isothermal case in Figure 8.2. At all conversions, the
reactor volume is less for the adiabatic case. Furthermore, the difference in reactor
volumes widens as the conversion is increased. For example, at a 50% conversion, the
isothermal reactor volume is 2.25 times that of the adiabatic reactor. At a 99%
conversion, the ratio becomes 8. The adiabatic case benefits by the increase in

CD-8-15
temperature with increasing conversion. The exothermic heat of reaction is considerable
at between 21,000 and 22,000 Btu/lbmol of toluene reacted. However, the large excess
of hydrogen acts as a heat carrier, curtailing the adiabatic rise in temperature.
Nevertheless, the temperature increases by approximately 2.2
o
F per 1% increase in
conversion. Thus, at 99% conversion, the reactor outlet temperature is 1,423
o
F. As the
conversion increases, the concentration of toluene in Eq. (8.2) decreases, causing the rate
of reaction to decrease. The decrease of the hydrogen concentration is not nearly as
pronounced because of its large excess in the reactor feed. In the adiabatic case, the
decrease in toluene concentration with conversion is offset by the increase in the rate
constant with temperature because the activation energy is moderately high at 52,000
cal/mol. This results in an approximate doubling of the rate constant with every 50
o
F
increase in temperature. Thus, in Figure 8.3 for the adiabatic case, unlike the isothermal
case, the increase in reactor volume is less than linear up to an inflection point at a
conversion of approximately 50%. Only beyond a conversion of 90% does the reactor
volume turn up sharply.

When striving for high reactor conversions, it may be necessary to consider the
reverse reaction even when the reaction is considered to be irreversible. This is the case
for the hydrodealkylation of toluene. A rate equation for the reverse reaction can be
derived from the rate equation for the forward reaction, given by Eq. (8.2), by assuming
that the two rate equations are consistent with the chemical-reaction equilibrium constant.
Assume that the gas reacting mixture is ideal at the high temperature of the reaction.
Then, the chemical equilibrium constant can be expressed in terms of concentrations and
equated to the ratio of the rate constants by:

4
2
CH benzene
H toluene
f
c
b
C C k
K
C C k
= = (8.3)

But in chemical equilibrium, the rate of the forward reaction is equal to the rate of the
backward reaction. Therefore, from Eq. (8.2), with an as yet undetermined dependence
of component concentrations on the backward rate,

CD-8-16

2
1/2
H toluene f
k C C =
2 4
H toluene CH benzene b
k C C C C
α β γ δ
(8.4)

To determine the exponents, α, β, γ, and δ, combine Eqs. (8.3) and (8.4),

2 4 4
2 2
H toluene CH benzene CH benzene
1/ 2
H toluene H toluene
f
b
C C C C C C k
k C C C C
α β γ δ
= = (8.5)

By equating exponents in Eq. (8.5), α = -1/2, β = 0, γ = 1, and δ = 1. Therefore, the form
of the rate equation for the backward reaction is

2 4
-1/2
H CH benzene b b
r k C C C = (8.6)

To determine the Arrhenius expression for k
b
from Eq. (8.3), an expression for K
c
as a
function of temperature is needed. Based on the correlations of Yaws (1977), the
standard Gibbs free energy of reaction,
o
rx
G ∆ , in cal/mol, as a function of the absolute
temperature, T, in K, for the hydrodealkylation of toluene,

H
2
+ C
7
H
8
→ CH
4
+ C
6
H
6

is given by:

o
rx
11, 200 2.1 G T ∆ = − − (8.7)

From thermodynamics,
o
rx
G ∆ is related to the chemical-reaction equilibrium constant by
the equation:

o
rx
exp
c
G
K
RT
  −∆
=
 
 
(8.8)

CD-8-17

Combining Eqs. (8.7) and (8.8) and substituting 1.987 for R, gives:


5, 636 5, 636
exp 1.057 2.878exp
c
K
T T
   
= + =
   
   
(8.9)


From Eq. (8.3), using the temperature-dependent expressions for k
f
in Eq. (8.2) and K
c
in
Eq. (8.9),
10
10
52, 000
6.3 10 exp
63, 200
2.19 10 exp
5, 636
2.878exp
f
b
c
k
RT
k
K RT
T
−  
×
 
−  
 
= = = ×
 
 
 
 
 
(8.10)


Combining Eqs. (8.6) and (8.10), the rate law for the backward reaction becomes


2 4
10 -1/2
H CH benzene
63, 200
2.19 10 exp
b
r C C C
RT
−  
= ×
 
 
(8.11)


When the reactor calculations are repeated for up to 99% conversion of toluene, taking
into account the reverse reaction, reactor volumes for both isothermal and adiabatic cases
increase only slightly (< 1%). This is largely due to the large concentration of hydrogen,
which according to Eq. (8.11) decreases the rate of the reverse reaction. Reaction
equilibrium calculations for this example give a 99.98% conversion for the isothermal
case and a 99.96% conversion for the adiabatic case. However, when only the
stoichiometric quantity of hydrogen is used in the feed, the equilibrium isothermal
conversion decreases to 97.3%.


8.5 RECYCLE TO EXTINCTION

In many chemical processes, the main reaction is accompanied by one or more side
reactions that produce byproducts. When the main reaction is irreversible or has a large

CD-8-18
chemical-reaction equilibrium constant, but one or more of the side reactions are so-
called reversible reactions with chemical-reaction equilibrium constants on the order of
one or less, the possibility of increasing the overall yield of the desired product(s) from
the main reaction by eliminating the net production of byproduct(s) exists. This is
accomplished by applying a concept sometimes referred to as recycle to extinction. The
concept must be applied with care and must be supported by reaction rates that are
sufficiently high. This is particularly true when the main reaction is catalyzed because
the catalyst may not support the side reaction(s). Experimental verification is essential.

The recycle to extinction concept is introduced briefly in Example 5.4 and in
Section 7.1, illustrated for the toluene-hydroalkylation process in Figure 7.4. Two
alternatives are considered: (1) production of the byproduct, and (2) recovery and recycle
to extinction of the byproduct. In this process, the main reaction is the hydrogenation of
toluene to the main product, benzene, and methane:

H
2
+ C
7
H
8
→ CH
4
+ C
6
H
6

As shown in Section 8.3, this reaction, while not completely irreversible at typical reactor
operating conditions, has a chemical-reaction equilibrium constant high enough to give
conversions greater than 99%. When the main reaction is carried out thermally, in the
absence of a catalyst, it is accompanied by the following side reaction that produces the
byproduct, biphenyl:

2 C
6
H
6


H
2
+ C
12
H
10


The chemical-reaction equilibrium constant for this reaction is written as:

2
benzene
biphenyl H
2
C
C C
K
c
= (8.12)

Although not always considered, a further reaction to triphenyl also occurs,

CD-8-19

C
6
H
6
+ C
12
H
10


H
2
+ C
18
H
14
,

with a chemical-reaction equilibrium constant written as:


biphenyl benzene
triphenyl H
2
C C
C C
K
c
= (8.13)

From Hougen and Watson (1947), the chemical-reaction equilibrium constant for
Eq. (8.12) ranges from 0.045 to 0.32 over a temperature range of 700 to 1,400
o
F, while
for Eq. (8.13), the constant increases from 0.23 to 0.46 over the same temperature range.
When the biphenyl and triphenyl byproducts are recovered and recycled to the reactor,
they build to their equilibrium concentrations at the reactor outlet, as determined from
Eqs. (8.12) and (8.13), such that no net production of either biphenyl or triphenyl occurs.
In effect, the byproducts are recycled to extinction. In this manner, the production of
undesirable byproducts is eliminated and the overall yield of the main product(s) is
increased. A disadvantage of recycling the byproducts to extinction is that the
byproducts and unconverted reactants increase the cost of recycling. However, the cost
of the separation system downstream of the reactor may be reduced when the byproducts
are recovered together with one or more of the reactants in a single recycle stream. This
occurs in the toluene hydrodealkylation process in which the biphenyl and triphenyl are
recovered with toluene.

A second example in which recycle to extinction should be considered is the
hydrolysis of ethylene to ethyl alcohol:

2 4 2 2 5
C H + H O C H OH →

which is accompanied by a reversible side reaction that produces diethylether and water,

2 C
2
H
5
OH ↔ (C
2
H
5
)
2
O + H
2
O

CD-8-20

for which the chemical-reaction equilibrium constant at typical reactor conditions is 0.2.
By recovering and recycling diethylether and water, the overall yield of alcohol is
increased.

A third example is the steam reforming of methane (or natural gas) in the
presence of a nickel-supported catalyst to produce synthesis gas (CO + H
2
), an
intermediate that can be used to produce acetic acid, ammonia, gasoline, or methanol.
The main reaction is:

CH
4
+ H
2
O ↔ CO + 3 H
2

Typically, the reactor operation at adiabatic conditions gives an outlet temperature of
approximately 800
o
C, which limits the extent of the reaction to that of chemical
equilibrium, with an equilibrium constant of 126.8, with compositions in partial pressures
in atm. Reactor pressure is generally set by the available pressure of the methane and
may be as high as 30 atm.

In the presence of the catalyst, a number of side reactions occur as discussed by
Rase (1977). However, the only one of significance is the water-gas shift reaction:

CO + H
2
O ↔ CO
2
+ H
2


At 800
o
C, the chemical-reaction equilibrium constant for this reaction is 0.929, with
compositions in partial pressures in atm. When CO
2
is recovered and recycled to
extinction, is the overall yield of synthesis gas increased? This is the subject of Example
8.3.

Example 8.3. Steam Reforming of Naphtha.
The fresh feed to a steam reformer is 13.5 kmol/hr of methane and 86.5
kmol/hr of steam. If the outlet conditions of the reactor are 800
o
C and 12.2 atm and

CD-8-21
chemical equilibrium is achieved for both the steam reforming and water-gas shift
reactions, determine the kmol/hr of synthesis gas produced when:
(a) the CO
2
produced is not recovered and recycled.
(b) the CO
2
is recovered from the reactor effluent and recycled to extinction.

Solution
(a) At 800
o
C, the two chemical equilibrium equations are:

2
4 2
2
3
CO H
CH H O total
126.8
n n
P
n n n
 
=
 
 


2 2
2
CO H
CO H O
0.929
n n
n n
=
where P

= 12.2 atm and n
i
are in kmol/hr. Since these two equations contain
five unknowns, three atom-balance equations are needed. They are:

4 2
2 4 2
2 2
CH CO CO
H CH H O
H O CO CO
Carbon balance: 13.5
Hydrogen balance: 2(86.5) 4(13.5) 227.0 2 4 2
Oxygen balance: 86.5 2
n n n
n n n
n n n
= + +
+ = = + +
= + +


where the left-hand sides are in kg⋅atom/hr of the elements, C, H, and O in the
fresh feed. Solving these five equations gives:

Component Fresh Feed, kmol/hr Reactor Effluent, kmol/hr
Methane 13.5 0.605
Water 86.5 66.229
Hydrogen 0 46.061
Carbon monoxide 0 5.521
Carbon dioxide 0 7.375
Total 100.0 125.791

CD-8-22

From these results, 95.5% of the methane is reacted. The production of
synthesis gas is 5.521 + 46.061 = 51.582 kmol/hr.

(b) For recycle of CO
2
to extinction, the CO
2
in the reactor effluent is recycled and
added to the fresh feed to give a combined feed. At chemical equilibrium, the
flow rate of CO
2
in the reactor effluent is the same as that in the combined feed.
The two chemical equilibrium equations remain the same, but the three atom
balance equations become:

2 4 2
2 4 2
2 2 2
CO CH CO CO
H CH H O
CO H O CO CO
Carbon balance: 13.5
Hydrogen balance: 2(86.5) 4(13.5) 227.0 2 4 2
Oxygen balance: 86.5 2 2
n n n n
n n n
n n n n
+ = + +
+ = = + +
+ = + +


Solving the revised equations gives:

Component Combined Feed, kmol/hr Reactor Effluent, kmol/hr
Methane 13.5 0.549
Water 86.5 73.544
Hydrogen 0 38.859
Carbon monoxide 0 12.946
Carbon dioxide 22.763 22.763
Total 122.763 148.661

Observe that there is no net production of CO
2
. The percent conversion of
methane is slightly greater at 95.9%, with the production of synthesis gas
slightly increased to 12.946 + 38.859 = 51.805 kmol/hr. Note that in case (a),
the production of CO
2
from CO by the water-gas shift reaction gives an
additional mole of H
2
for every mole of CO
2
produced. Thus, by eliminating
the net production of CO
2
, less H
2
is produced. The usual benefit of the
increased yield of the main product(s) by recycle to extinction is not achieved

CD-8-23
in this case. However, in case (b), CO
2
is not emitted to the atmosphere where
it contributes to global warming. This is considered in more detail by
Mulholland and Dyer (1999).


8.6 SNOWBALL EFFECTS IN THE CONTROL OF PROCESSES INVOLVING
RECYCLE

In recent years, chemical engineers engaged in process design in industry have become
increasingly aware of the need to understand the interaction of process design and
process control when developing a control system for an entire chemical plant. When the
process does not involve recycle, the development of the control system is relatively
straightforward because the process can be treated in a sequential manner. However, the
majority of chemical processes involve recycle, for which the development of a feasible
and efficient control system, particularly for a reactor-separator-recycle network, is not at
all straightforward. This is due to the possibility of the so-called snowball effect, which
refers to a situation where a small disturbance, for example, in the fresh feed rate to a
reactor, causes a very large change in the flow rate of the recycle stream. When this
occurs, either the reactor or the separation system, or both, may not be able to handle the
increased load. Whether or not the snowball effect occurs depends on the design of the
control system, which is the subject of Sections 20.3 (Example 20.11) and 21.5 (Case
Study 21.3).


8.7 SUMMARY

Having studied this chapter, when designing reactor-separator-recycle networks, the
reader should

1. Understand the considerations in determining the best locations, with respect to the
reactor section, of the separation sections.

CD-8-24
2. Be aware of the many tradeoffs between the reactor section and the separation
section(s) when recycle is used.
3. Know that the optimal fractional conversion of the limiting reactant in the reactor
section is usually less than 100% of the equilibrium conversion.
4. Be able to apply the concept of recycle to extinction to reduce waste and increase the
yield of the main product.
5. Be aware that the snowball effect can occur in a reactor-separator-recycle network.


REFERENCES

Hougen, O. A. and K. M. Watson, Chemical Process Principles, Part Three, Kinetics and
Catalysts, John Wiley & Sons, New York (1947).

Mulholland, K. L. and J. A. Dyer, Pollution Prevention: Methodology, Technologies and
Practices, AIChE, New York (1999).

Rase, H. F., Chemical Reactor Design for Process Plants, Vol. 2, Case Studies and
Design Data, Wiley-Interscience, New York (1977).

Yaws, C. L., Physical Properties, McGraw-Hill, New York (1977).


EXERCISES

8.1 Cumene process with drag (purge) streams. In Section 8.2, a process for producing
cumene by the alkylation of benzene with propylene is described. The flowsheet
for the process is given in Figure 8.1. However, that flowsheet does not provide for
the removal of water, ethane, isobutane, MCP, MCH, toluene, n-propylbenzene,
tBB, and p-cymene. For their removal, it is proposed to add two drag (purge)
streams to the flowsheet: one from the distillate of the benzene recovery column,

CD-8-25
C2; the other from the bottoms of the cumene recovery column, C3. Also, the
flowsheet in Figure 8.1 does not provide for an exit for the heavies produced in the
alkylation and trans-alkylation reactors in the event that their amounts are too large
to be included in the allowable impurity in the cumene product. Thus, it may be
necessary to add a fourth distillation column, C4, following C3, with the distillate
from C4 fed to the trans-alkylation reactor and the bottoms from C4 being a heavies
product. If so, the heavies must not contain more than 5% of the DIPBs and lighter
entering C4.

Most of the data for the cumene process is given in Section 8.1. However, missing
are the product distributions for the two reactors. These are as follows from
laboratory studies:

Component
Alkylation Reactor
Change in pounds per 100
pounds of propylene in the
combined feed
Trans-alkylation Reactor
Change in pounds per 100
pounds of propylene in the
combined feed to the
Alkylation Reactor

Propylene -100.0000 0.0000
1-Butene -0.0039
Benzene -168.1835 -16.3570
Toluene -0.0214
Cumene 232.7018 50.7652
n-Propylbenzene 0.0346 0.0087
p-Cymene 0.0306 -0.0025
t-BB 0.0080 -0.0007
m-DIPB 20.3314 -20.2323
p-DIPB 14.7797 -14.4953
Alkylation Heavies 0.3227
Trans-alkylation Heavies 0.0000 0.3121
Total change 0 0

CD-8-26

Note, again, that the conversion of DIPBs in the trans-alkylation reactor is only
50%.

Using the above data and that in Section 8.1, revise the flowsheet in Figure 8.1 and
produce a complete material balance with the component flow rates in lbmol/hr for
each stream in your flowsheet. Try to maximize the production of cumene. Be
sure to add two drag streams for removal of byproducts, and a fourth distillation
column, if necessary. Compute the overall percent conversion of benzene to
cumene and the annual production of cumene in lb/yr if the operating factor is 0.95.
If a heavies product is produced, what could it be used for?

8.2 The feed to a pentane isomerization process consists of 650 kmol/hr of n-pentane
and 300 kmol/hr of isopentane. The effluent from the catalytic isomerization
reactor will contain 6.5 moles of isopentane for every mole of n-pentane. The
catalyst prevents the formation of neopentane. If the isopentane product, produced
by separating isopentane from n-pentane by distillation, is to contain only 2 wt% n-
pentane and the separation system is to be placed before the reactor, calculate the
total flow rate and composition of the reactor effluent, the combined feed to the
reactor, and the bottoms product from the distillation column. Design the
distillation column. Repeat the material balance calculations and the design of the
distillation column if the separation system is placed after the reactor. Based on
your results and without determining any capital or operating costs, which
separation system placement is preferred?


CD-9-1

Chapter 9

Second-Law Analysis

9.0 OBJECTIVES

The first law of thermodynamics is widely used in design to make energy balances around
equipment. Much less used are the entropy balances based on the second law of thermodynamics.
Although the first law can determine energy transfer requirements in the form of heat and shaft
work for specified changes to streams or batches of materials, it cannot even give a clue as to
whether energy is being used efficiently. As shown in this chapter, calculations with the second
law or a combined first and second law can determine energy efficiency. The calculations are
difficult to do by hand, but are readily carried out with a process simulation program. When the
second-law efficiency of a process is found to be low, a better process should be sought. The
average second-law efficiency for chemical plants is in the range of only 20-25%. Therefore,
chemical engineers need to spend more effort in improving energy efficiency.

After studying this chapter, the reader should

1. Understand the limitations of the first law of thermodynamics.
2. Understand the usefulness of the second law and a combined statement of the first and
second laws.
3. Be able to specify a system and surroundings for conducting a second-law analysis.
4. Be able to derive and apply a combined statement of the first and second laws for the
determination of lost work or exergy.
5. Be able to determine the second-law efficiency of a process and pinpoint the major areas of
inefficiency (lost work).
6. Understand the causes of lost work and how to remedy them.
7. Be able to use a process simulation program to perform a second-law analysis.
CD-9-2

9.1 INTRODUCTION

A chemical process uses physical and/or chemical operations to transform feed materials
into products of different composition. Table 9.1 lists the types of operations that are most widely
used. Depending on the production rate and the operations used, the process is conducted
batchwise, continuously, or cyclically. A continuous, heat-integrated process that illustrates
several of the operations in Table 9.1 is shown in Figure 9.1, where benzene and a mixture of
xylene isomers are produced by the disproportionation of toluene. The heart of the process is a
fixed-bed catalytic reactor, R-1, where the main chemical change is the reaction
2C
7
H
8
→ C
6
H
6
+ C
8
H
10
isomers

Table 9.1 Common Operations in Chemical Processing
Operation Examples of Equipment Used
Change in chemical species Reactor
Separation of chemicals Distillation, absorption, liquid-liquid extraction
Separation of phases Settler
Pressure change Pump, compressor, valve, turbine, expander
Temperature or phase change Heat exchanger, condenser
Mixing Agitated vessel, in-line mixer
Dividing Pipe tee
Size enlargement of solids Pellet mill
Size reduction of solids Jaw crusher
Separation of solids by size Screen


This reaction is conducted in the presence of hydrogen to minimize the undesirable formation of
coke by condensation reactions. However, other undesirable side reactions such as
C
7
H
8
+ H
2
→ C
6
H
6
+ CH
4

occur and produce light paraffins. Chemicals in the reactor effluent are separated from each other
as follows. Hydrogen is recovered for recycle by partial condensation in exchanger E-2 with phase
separation in flash drum D-1; light paraffin gases are removed in fractionator C-1; benzene is
recovered and purified in fractionator C-2; and mixed xylenes are recovered and purified, and
unreacted toluene is recovered for recycle in fractionator C-3. Compressors K-1 and K-2 bring
CD-9-3


Figure 9.1 Process for disproportionation of toluene to benzene and xylenes.
CD-9-4
fresh hydrogen and recycled hydrogen, respectively, to reactor pressure. Pump P-1 brings fresh
toluene to reactor pressure. Pumps P-2, P-3, and P-4 deliver reflux to fractionators C-1, C-2, and
C-3, respectively. Pumps P-3 and P-6 deliver benzene and xylene products, respectively, to
storage, and pump P-5 recycles toluene. Furnace F-1 uses the combustion of fuel oil with air to
bring reactants to reactor temperature, after preheater E-1 has recovered a portion of the thermal
energy in the reactor effluent. Cooling water is used in overhead condensers E-4, E-6, and E-9, and
steam is used in reboilers E-5, E-7, and E-10 of fractionators C-1, C-2, and C-3, respectively.
Benzene and xylene products are cooled by water in coolers E-8 and E-11 (not shown in Figure
9.1) before being sent to storage. Exchanger E-3 preheats feed to fractionator C-1 with bottoms
from the same fractionator. Cooling water is supplied mainly by recycle from cooling tower T-1
by pump P-7. Electricity for all pumps and compressors, and steam for reboilers is produced from
coal-fired power plant B-1. The overall input to and output from the process is represented
schematically in Figure 9.2.

Ideally, each operation in a process would be conducted in a reversible manner to achieve
the minimum energy input or the maximum energy output, corresponding to a second-law
thermodynamic efficiency of 100%. Even if this were technically feasible, such a process would be
uneconomical because of excessive capital investment in equipment, which would have to be
essentially infinite in size to minimize transport gradients. Nevertheless, it is economical to modify
existing processes to reduce energy consumption, and to design new processes to operate at higher

Figure 9.2 Overall process streams for toluene disproportionation.
CD-9-5
thermodynamic efficiencies. A second-law thermodynamic analysis identifies inefficient processes
and the operations within these processes that are the most wasteful of energy, so that the process
engineer can direct his or her efforts to conserving energy.


9.2 THE SYSTEM AND THE SURROUNDINGS

To conduct a second-law analysis, a process is divided into a system and surroundings. The system
is the matter contained in the operating unit(s) on which the engineer wishes to focus. Everything
not in the system is in the surroundings. The boundaries of the system may be real or imaginary,
rigid or movable, and open or closed to the transfer of matter between the system and the
surroundings. Some references call a closed system simply a system, and an open system, into
and/or out of which matter can flow, a control volume. They refer to the boundary of the control
volume as the control surface across which matter can flow.

Batch, cyclic, and continuous processes are shown schematically in Figure 9.3. Batch and
cyclic processes are usually divided into a closed system (or simply a system) and surroundings;
continuous processes are divided into an open system (or control volume) and surroundings.



Figure 9.3 Common methods of processing.
CD-9-6

The division of a process into system and surroundings is the choice of the one performing
the thermodynamic analysis. Many choices are possible for a chemical process. For example, in
Figure 9.1, the system can be the complete process, with the surroundings being the ambient air,
water, and so forth, surrounding the equipment (commonly referred to as the infinite surroundings,
dead state, or infinite heat reservoir) and the storage tanks for the raw materials and products.

More commonly, utility plants (e.g., the steam power plant and cooling-water system) are
considered separately from the rest of the process. This is shown schematically in Figure 9.4,
where the process is divided into three systems. The benzene-mixed xylenes plant is sufficiently
complex that it is advisable to divide it into a reaction section and a separation section, as shown in
Figure 9.5. Any individual operation in the process - for example, fractionator C-2 - can be the
system and everything else the surroundings. Finally, a portion of a single operation can be the
system - for example, one tray in fractionator C-2.


Figure 9.4 Partitioning of the toluene disproportionation plant.
CD-9-7


9.3 ENERGY TRANSFER

Heat or work, or both, can be transferred across the boundaries of closed or open systems. If no
heat is transferred across its boundaries, the system is said to be adiabatic or thermally isolated; and
if neither work nor heat is transferred, the system is said to be totally isolated.

The most useful kind of energy transfer is work. For example, a rotating or reciprocating
shaft at the boundary of a system causes shaft work. Less useful, but more common, is heat
transfer, which occurs when the temperatures of the system and the surroundings differ. If the
system is at the higher temperature, it loses energy and the surroundings gain energy; and if the
system is at the lower temperature, it gains energy and the surroundings lose energy.

A number of devices are used in processes to transfer work between a system and its
surroundings. Pumps, compressors, blowers, and fans convert shaft work into fluid energy for the
main purpose of increasing fluid pressure. Turbines and expanders take energy from a fluid,
causing fluid pressure to decrease, and convert the energy to shaft work for use elsewhere. A
motor converts electrical work to shaft work. A generator converts shaft work to electrical work.


As an example of energy transfer by work, consider Figure 9.6(a), where an incompressible
liquid at 25
o
C having a specific volume, V, of 0.001 m
3
/kg is pumped continuously at a rate m of

Figure 9.5 Partitioning of the toluene disproportionation process.
CD-9-8
10 kg/s from a pressure P
1
of 0.1 MPa to a pressure P
2
of 2.0 MPa, with no change in kinetic or
potential energy, by a rotating shaft driven by an electrical motor. In the absence of electrical
resistance, shaft friction, and fluid friction,
Electrical work input to the electric motor
= shaft work delivered to the pump by the motor
= shaft work delivered to the liquid by the pump
= isothermal, isokinetic, isopotential energy increase of liquid
= W

= ( )
2 1
mV P P − = 10(0.001)(2,000,000 - 100,000)
= 19 kN-m/s (kJ/s or kW)


In actual equipment (as shown in Figure 9.6(b)), electrical resistance may permit only a
95% transfer of electrical work to the motor shaft, shaft friction may permit only a 90% transfer of
shaft work to the fluid, and fluid friction may cause a rise in fluid temperature equivalent to a 5%
loss of the shaft work. For the same increase in fluid pressure, the electrical work input to the
electric motor is then

input
19
23.39 kW
(0.95)(0.90)(0.95)
W = =

Figure 9.6 Comparison of reversible and irreversible pumping operations.
CD-9-9

The difference, 23.39 - 19.00 = 4.39 kW, between the rate of electrical work input to the
motor and the rate of energy required to increase the fluid pressure is the power not used in
accomplishing the desired goal. This excess power causes temperatures in the system and/or the
surroundings to rise.

If the temperature of a system or a part of the surroundings remains reasonably constant
when heat transfer between these two regions occurs, then the system or the part of the
surroundings is called a heat reservoir. Heat reservoirs include heating media, such as steam, hot
water, Dowtherm, oil, molten salts, mercury, and flue gases produced by combustion; and cooling
media such as air, water, chilled water, ammonia, propane, and other refrigerants. For each of
these reservoirs, it is convenient to assign a temperature. It is also convenient to distinguish
between finite-sized heat reservoirs, which are designed to operate at certain desired temperatures,
T
i
, and the essentially infinite heat reservoirs that exist in the natural environment, such as
atmospheric air, oceans, and large lakes or rivers at temperatures designated as T
0
.


9.4 THERMODYNAMIC PROPERTIES

When work and/or heat is transferred to or from a system, energy changes occur. The most
common forms of energy are those associated with (1) macroscopic motion (kinetic energy), (2)
location in a gravitational field (potential energy), and (3) internal energy due to translational,
rotational, and vibrational motions of molecules, atoms, and electrons; together with the potential
energy due to forces acting between molecules, atoms, electrons, and nuclei. The first two forms of
energy are taken relative to some arbitrary reference, such as a point on the surface of the earth. In
most chemical processes, changes to these two forms of energy are relatively small and are often
ignored. An exception is the combustion chamber and nozzle of a rocket engine, where the heat of
reaction (internal energy) is converted to kinetic energy. Internal energy is most important in
chemical processing and is taken relative to some arbitrary reference condition.

CD-9-10
The internal energy of a substance is a state property, because its value depends on the state
or condition of the substance, which is determined by temperature, pressure, composition, phase (if
more than one phase is possible), and the reference condition. Changes in internal energy are
independent of the path employed in moving from one state to another.

Another state property, closely related to internal energy, is enthalpy, defined by the
relation
H U PV = + (9.1)
This property is particularly convenient for continuous processes because the two terms on the
right-hand side frequently appear together in energy balance equations.

The most desirable reference conditions for internal energy and enthalpy in processes where
chemical reactions take place are 0 K or 25
o
C, zero pressure, and standard chemical elements, such
as C (graphite), H
2
(gas), O
2
(gas), N
2
(gas), Cl
2
(gas), and S (rhombic sulfur), rather than the
chemical species themselves that are in the mixture. With this reference condition, internal energy
and enthalpy changes automatically take into account heat of reaction. Felder and Rousseau (2000)
discuss this reference condition. As an example, the enthalpy of 1 kg of superheated steam at
300
o
C and 1 MPa relative to the elements H
2
(gas) and O
2
(gas) at 0 K and 0 Pa is determined to be
-12,209.3 kJ. Alternatively, from the steam tables in van Wylen et al. (1994), for a reference
condition of saturated liquid water at 0
o
C, the enthalpy is 3,051.2 kJ/kg.

It is well known from thermodynamic principles that energy transferred as work is more
useful than energy transferred as heat. Work can be completely converted to heat, but only a
fraction of heat can be converted to work. Furthermore, as the temperature of a system is
decreased, heat transferred from the system becomes less useful and less of the heat can be
converted to work. A state property that accounts for the differences between heat and work is
entropy, S. When heat is transferred into a closed system at temperature T, the entropy of the
system increases because entropy transfer accompanies heat transfer. By contrast, work transfer
(shaft work) is not accompanied by entropy transfer. When heat is transferred at a rate Q

from a
surrounding heat reservoir at a constant temperature, T
reservoir
, into a system, the heat reservoir
experiences a decrease in entropy given by
CD-9-11
reservoir
reservoir
Q
S
T

∆ =

(9.2)
where S ∆

is the entropy change in Btu/hr-
o
R. The lower the value of T, the greater the decrease in
entropy.

For a pure, ideal gas, only temperature affects U and H. However, the entropy, S, of an
ideal gas is affected by both temperature and pressure. Accordingly, the reference pressure for U
and H is usually taken as zero. For S, the reference pressure is usually taken as 1 atm to avoid a
value of S equal to minus infinity. At a reference temperature of 0 K, the entropy of a crystalline
substance is zero, by the third law of thermodynamics.

Typical Entropy Changes

In general, when heat is transferred to a nonisothermal system, its entropy change, S

∆ , is:

= ∆
2
1
T
Q d
S

(9.3)
Using Eq. (9.3), entropy changes can be computed for several common systems, as illustrated next.

Isobaric Heat Transfer. Consider the stream at constant P in Figure 9.7. According to the
first law of thermodynamics, the rate of heat transfer to the differential section, Q d

, is:
dT c m dH m Q d
p

= = (9.4)
where m is the mass flow rate and c
p
is the heat capacity. Substituting in Eq. (9.3):
2
1

1 2

T
p
T
c dT
S
T

∆ =

(9.5)
Here, S is the specific entropy; that is, m S

/ . For constant c
p
:
1
2
2 1
ln
T
T
c S
p
= ∆


(9.6)

T
1 T
2
Q d


Figure 9.7 Isobaric flow through a pipe.

CD-9-12
Ideal Gas at Constant Temperature. Figure 9.8 shows the isothermal flow of an ideal gas,
with a decrease of pressure from P
1
to P
2
. For this system, the differential change in the specific
enthalpy is:
dH = TdS + VdP = c
p
dT = 0 (9.7)
where V is the specific volume. Rearranging:
dP
T
V
dS − = (9.8)
Substituting for an ideal gas, V = RT/P:
P
dP
R dS − = (9.9)
and integrating:
2
1
2 1
ln
P
P
R S = ∆


(9.10)


P
1 P
2


Figure 9.8 Isothermal flow through a pipe

Ideal Gas Mixing. When C species are mixed at constant pressure and temperature, as
illustrated in Figure 9.9, the change in the entropy flow rate is given by Eq. (9.10), applied
separately for each species j:
j
j j
P
P
R m S m
j
ln
2 1
= ∆


(9.11)
where P
j
= x
j
P is the partial pressure of species j, and x
j
is its mole fraction, and
j
m is its molar
flow rate. Summing over all of the species, the change in the enthalpy flow rate for the mixing
process is:
j
C
j
j
P
P
R m S m ln
1
2 1 ∑
=

= ∆
(9.12)
or
j
C
j
j
x R x S ln
1
2 1 ∑
=

− = ∆
(9.13)
CD-9-13
where x
j
= P
j
/P = / .
j
m m


P m
2

1
m
C
m
P
P
.
.
.
1

2
P
1
C
j
j
j
j
m m
m
x
m
=
=
=

Figure 9.9 Isothermal mixing of C ideal gas species.

Thermodynamic Availability

When matter is taken from state 1, at a given velocity, elevation, composition, temperature T, and
pressure P, to state 2, at a different velocity, elevation, composition, T, and P, it is of interest to
determine the maximum amount of useful work that can be extracted or the minimum amount of
work that is needed. Ignoring kinetic energy and potential energy differences and referring
enthalpies to the elements, the first law of thermodynamics can be used to determine the net
amount of energy transferred by heat and/or work in moving from state 1 to state 2, which is
simply the change in enthalpy. The first law cannot be used to determine the maximum or
minimum amount of useful work, which depends on the details of the process used to effect the
change in state. The maximum or minimum is achieved only if the process is reversible.

To determine the maximum rate at which work is performed,
max
W

, in bringing a stream to
equilibrium with its surroundings, a reversible path can be selected, as illustrated in Figure 9.10. A
stream at molar flow rate, m , in state 1, at T
1
and elevated pressure, P
1
, is fed to turbine I, which
operates adiabatically and reversibly. It is expanded to P
2
and the environmental temperature, T
0
,
while producing shaft work at the rate,
I
s
W

. The effluent stream from turbine I is expanded
isothermally (non-adiabatically) and reversibly in turbine II to the environmental pressure, P
0
. The
path is shown in the P-V and T-S diagrams, the second of which shows the isentropic behavior of
turbine I.
CD-9-14


1 1
, , P T m
I
s
W
2 0
, P T
0
I
= Q

II
s
W

0 0
, P T
I
II
P
P
1

P
2

P
0

V
T
1
S
1
S
2

T
0
II
Q

Figure 9.10 Reversible path.

Ignoring kinetic and potential energy changes, the first law of thermodynamics, applied to
the overall process is:
s
W Q H m

− = ∆
→0 1
(9.14)
where Q

is the rate of heat transfer to turbine 2, and
s
W

is the sum of the shaft work rates
delivered by the two turbines.

For turbine 2, applying the differential form of Eq. (9.3):
0
T
Q d
dS m

= (9.15)
and integrating:
0 1 0 0 →
∆ = =

S m T dS T m Q

(9.16)

Substituting in the first law, Eq. (9.14):
CD-9-15
s
W S m T H m

− ∆ = ∆
→ → 0 1 0 0 1
(9.17)
and rearranging:
) (
0 1 0 0 1
2 1
→ →
∆ − ∆ − = + = S T H m W W W
s s s


(9.18)

This reversible work is the maximum work “available” in bringing the feed stream to the
environmental conditions; that is,
s
W

is the maximum rate of obtaining work, which can be written
0 1→
A m . The intensive property,
0 1→
A , was initially referred to as the thermodynamic availability
and is commonly referred to as the exergy. The concept of availability was first developed in detail
by Keenan (1951).

It follows that the change in availability of a stream, when it is converted from state 1 to
state 2 in a chemical process, as shown in Figure 9.11, is:
1 2 2 1 1 2 0 1 2
A A A H T S
→ → →
∆ = − = ∆ − ∆ (9.19)
That is, the change in the maximum work available from the stream is a function solely of its
changes in enthalpy and entropy, and the environmental temperature. Like H and S, A is a state
function, independent of path, but dependent on the temperature, T
0
, and pressure, P
0,
of the dead
state. If chemical reactions occur, the availability also depends on the composition of the dead
state.
T
1
, P
1

A
1
T
2
, P
2
A
2

Figure 9.11 Availability change upon processing.

Typical Availability Changes

In this subsection, availability changes are computed for several simple processes to show the
significant impact of the change in entropy. These are taken from the monograph by Sussman
(1980), who presents many other excellent examples, including three that take into account
chemical reaction, one of which deals with a complete methane reforming process. In all cases, the
environmental (dead-state) temperature in the following examples is taken as 298 K = 537
o
R.
CD-9-16

Superheating Steam. As shown in Figure 9.12, saturated steam at 250 psia and 401°F is
superheated isobarically to 600°F, with the enthalpy and entropy values taken from the steam
tables. Substituting in Eq. (9.19):

1 2 1 2 0 1 2
(1, 319 1, 201.1) 537(1.6502 1.5264)
117.9 66.5
Btu
51.4
lb
A H T S
→ → →
∆ = ∆ − ∆
= − − −
= −
=


Superheater
1
2
Sat’d. Steam
250 psia
401°F

H
1
= 1,201.1 Btu/lb
S
1
=1.5264 Btu/lb°R

250 psia
600°F

H
2
= 1,319 Btu/lb
S
2
= 1.6502 Btu/lb°R

Figure 9.12 Steam superheater.

Although the enthalpy of the stream is increased by 117.9 Btu/lb, which equals the heat
transferred to the stream, the maximum work that can be obtained from stream 2, if it is taken to
the environmental conditions, is increased by only 51.4 Btu/lb, which is less than 50 % of the heat
transferred, because the entropy term increases so significantly.

Liquefying Air. As shown in Figure 9.13, air at 25°C and 1 atm is condensed isobarically
to a saturated liquid at -194.5°C. Substituting in Eq. (9.19):

1 2 1 2 0 1 2
(25.74 127.11) 298(0 0.9260)
101.37 275.95
kcal
174.6
kg
A H T S
→ → →
∆ = ∆ − ∆
= − − −
= − +
=

CD-9-17

Note that the enthalpy and entropy data are obtained from the air tables, where the reference state is
saturated liquid air at 25°C. The change in enthalpy, -101.37 kcal/kg, is the heat removed from the
condenser, using a refrigerator that requires considerable compression work. In this case, the
entropy change is sufficiently negative to cause the entropy to be about three times more positive
than the negative enthalpy change. This causes a large increase in the availability of the liquid air.
Stated differently, 174.6 kcal/kg is the maximum work obtained from the liquid air in returning it to
the environmental state, and is the minimum work of refrigeration in liquefying air.

Condenser
1
2
Air
25°C
1 atm

H
1
=127.11 kcal/kg
S
1
= 0.9260 kcal/kg-K

Sat’d. Liquid
-194.5°C
1 atm

H
2
= 25.74 kcal/kg
S
2
= 0

Figure 9.13 Condensation of air.

Throttling. As shown in Figure 9.14, superheated steam is throttled adiabatically across a
valve from 600°F and 250 psia to 100 psia. Using the steam tables, for this isenthalpic process, its
temperature is reduced to 578°F and its entropy is increased from 1.6502 Btu/lb-°R to 1.7483
Btu/lb-°R. Substituting in Eq. (9.19):
1 2 1 2 0 1 2
0 537(1.7483 1.6502)
0 52.68
Btu
52.68
lb
A H T S
→ → →
∆ = ∆ − ∆
= − −
= −
= −


When throttling, the entire change in availability is due to the negative change in entropy. Stated
differently, the entropy term is the maximum loss of the ability of the stream to do work in
transferring to its environmental (dead) state. Using Eq. (9.19), A
1
is computed to be 434.9 Btu/lb,
and consequently, 12% of its “available” work is lost in throttling. As considered subsequently in
CD-9-18
this chapter, the possibility of replacing the valve with a turbine to recover power should be
considered when the pressure of a stream must be reduced.

1
2
Steam
600°F
250 psia

H
1
= H
2
= 1,319 Btu/lb
S
1
= 1.6502 Btu/lb-°R

578°F
100 psia

S
2
= 1.7483 Btu/lb-°R

Figure 9.14 Throttling steam.

Isothermal Mixing. In Figure 9.15, nitrogen and oxygen gases are mixed isobarically and
adiabatically to give concentrations proportional to those in air. To obtain the change in
availability, Eq. (9.19) applies, with Eq. (9.13) substituted to give
1 2 1 2 0 1 2
2
0
1
0 ln
0 298(0.79 ln0.79 0.21 ln0.21) 1.987
cal
304.3
mol air
j j
j
A H T S
T x R x
→ → →
=
∆ = ∆ − ∆
= +
= + +
= −


The positive entropy change upon mixing results in the negative change in availability. Stated
differently, 304.3 cal of work are the minimum required to separate air into nitrogen and oxygen
gases.

N2

Ideal 25
°
C
gases 1 atm

O2

0.79 mol N2
0.21 mol O2



Figure 9.15 Isothermal mixing to air.


CD-9-19
Thermal Mixing. In Figure 9.16, 0.5 kg/s of water at 100° and 1 atm is mixed adiabatically
and isobarically with 0.5 kg/s of water at 0°C and 1 atm. The resulting temperature is 50°C. Using
Eq. (9.19), with Eq. (9.6) substituted, the availability of the mixed stream is computed:
( )
0
2 2 0 0 2 0 0 2 0
2
( ) ln
298
(1)(298 323) 298(1) ln
323
[ 25 24.01]
kcal
0.99
kg
p p
T
A H T S c T T T c
T
→ →
( | |
= − ∆ − ∆ = − − −
( |
\ . ¸ ¸
(
= − − −
(
¸ ¸
= − − +
=

Similarly, the availabilities of the hot and cold feed streams are computed: A
1,hot
= 8.1 kcal/kg and
A
2,cold
= 1.11 kcal/kg. Consequently, the availability change upon thermal mixing is:
s
kcal
62 . 3 ) 11 . 1 )( 5 . 0 ( ) 1 . 8 )( 5 . 0 ( ) 99 . 0 )( 1 ( ) (
2 1
− = − − = ∆

A m

100°C

0.5 kg/s

H
2
O

0°C
0.5 kg/s

State 2

50°C

Figure 9.16 Thermal mixing of water.

The availability change upon thermal mixing is illustrated conveniently in an availability
flow diagram, as shown in Figure 9.17, where the widths of the arrows are approximately
proportional to the availability flow rates. Combining the availability flow rates for the hot and
cold streams, the availability flow rate entering the mixer is 4.05 + 0.555 = 4.61 kcal/s. In the
mixer, this is divided into 0.99 kcal/s, which leaves in the mixed effluent stream, and 3.62 kcal/s,
which is lost to the environment; that is, approximately 78% of the availability to do work is lost
upon thermal mixing. Clearly, this loss decreases as the temperatures of the hot and cold streams
approach each other. Sussman (1980) makes extensive use of availability flow diagrams like that
in Figure 9.17.
CD-9-20

Hot 4.05 kcal/s
Mixer
Cold
0.555 kcal/s
3.62 kcal/s
0.99 kcal/s

Figure 9.17 Availability flow diagram for thermal mixing of water.


9.5 EQUATIONS FOR SECOND-LAW ANALYSIS

In this section, the first and second laws of thermodynamics are used to derive useful equations for
computing the lost work of any process. A general energy balance (first law of thermodynamics)
can be written for a system bounded by the control volume shown in Figure 9.18. Streams at
certain fixed states flow at fixed rates into or out of the control volume, heat and work are
transferred at fixed rates across the boundaries of the control volume, matter within the control
volume undergoes changes in amount and state, and the boundaries of the control volume expand
or contract. The energy balance for such a control volume over a period of time, ∆t, is
( )
( )
sys
0
flowing streams
i i
i i
mU
mH Q Q W
t

+ ∆ = − −

∑ ∑

(9.20)
where ( )
sys
mU ∆ is the change in internal energy of the system, ( )
flowing streams
mH ∆ is the sum of
enthalpy flows leaving the system minus the sum of those entering the system,
0
Q

is positive for
heat transfer from the infinite surroundings at T
0
to the control volume, and
i
Q

is positive for heat
transfer to the control volume from a heat reservoir at temperature T
i
different from T
0
. Eq. (9.20)
ignores changes in kinetic energy and potential energy for both the system and the flowing streams.
The term

i
i
W

is positive for work done by the system on the surroundings and includes
mechanical shaft work, electrical work, and work resulting from the expansion (or contraction) of
the control volume itself against the surroundings
( )
surr sys
P V ∆ .
CD-9-21


Figure 9.18 Control volume for open system.

An entropy balance for the system in Figure 9.18 can be written in a manner analogous to
that used for the energy balance, Eq. (9.20), except that here we prefer to write an entropy balance
for both the control volume and the surroundings. The result is
( )
( )
sys
0
flowing streams
0
i
irr
i i
mS
Q Q
mS S
t T T

+ ∆ − − = ∆


(9.21)
where ( )
sys
mS ∆ is the change of entropy of the system, ( )
flowing streams
mS ∆ is the sum of entropy
flows leaving the system minus the sum of those entering the system,
0 0
Q T −

is the rate of
decrease in entropy of the infinite surroundings when heat is transferred from the infinite
surroundings at T
0
to the system in the control volume, and
( )
i i
Q T −


is the sum of the rates of
entropy decrease in the various heat reservoirs at various temperatures, T
i
, that are used to transfer
heat into the system. Unlike energy, entropy is not conserved. The term
irr
S ∆

is the increase in
entropy of the universe due to the process. It is zero only for a reversible process. Otherwise, it is
positive and is a measure of the irreversibility of the process.

Although
irr
S ∆

is a fundamental quantity, it is of limited practical use because of the
difficulty in interpreting the significance of its magnitude. As with another fundamental
thermodynamic quantity, chemical potential, it is preferred by chemical engineers to use a
CD-9-22
surrogate property. For chemical potential, that quantity is fugacity; for
irr
S ∆

, it is availability
(exergy), which was defined earlier and arises naturally, as will be shown next, when the first and
second laws of thermodynamics are combined.

To derive availability, combine Eqs. (9.20) and (9.21) by eliminating
0
Q

. The result is
( )
( )
0
sys
0
0 0
flowing streams
1 0
i i irr
i i
i
m U T S
T
m H T S Q W T S
t T
∆ − (
| | ¸ ¸
+ ∆ − − − + + ∆ = (
|
¸ ¸

\ .
∑ ∑

(9.22)
In this equation, in the second term on the left-hand side, we see that the enthalpy and entropy
appear together to form a combined factor that is similar to the Gibbs free energy. However, the
entropy is multiplied by the dead-state temperature, T
0
, instead of the stream temperature, T. In
addition, the first term on the left side can be rewritten to give the same combination,
0
H T S − , by
substituting Eq. (9.1), the definition of enthalpy, for the internal energy. The result is
( )
( )
0
sys
0
0 0
flowing streams
1 0
i i irr
i i
i
m H T S PV
T
m H T S Q W T S
t T
∆ − − (
| | ¸ ¸
+ ∆ − − − + + ∆ = (
|
¸ ¸

\ .
∑ ∑

(9.23)
We now define an availability function, B, for the combination of enthalpy and entropy in
Eq. (9.23):
B = H – T
0
S (9.24)
The availability function in Eq. (9.24) and availability in Eq. (9.19) differ from each other in that
the availability is referenced to a dead state at T
0
, P
0
, and a composition for every element in the
periodic table) and is, therefore, an absolute quantity. The availability function, by contrast, can be
referenced to any state and is not an absolute quantity. In Eq. (9.23), however, only the change in
availability function appears. By their definitions, the change in availability function is exactly
equal to the change in availability. When evaluating a process, only the change in availability or
availability function, ∆A or ∆B, respectively, is important. If one is interested in the maximum
useful work that can be extracted from a material that is brought to equilibrium with the dead state,
then the availability, A, is of importance. In the second-law analysis of a process, we will use ∆B.

CD-9-23
In addition, we also note in Eq. (9.22) that
irr
S ∆

is multiplied by T
0
and that their product
has the units of energy flow. Accordingly, it is given the name lost work, LW

, or loss of
availability or exergy:
0 irr
LW T S = ∆

(9.25)
Substitution of Eqs. (9.24) and (9.25) into Eq. (9.23) gives
( )
( )
sys
0
flowing streams
1 0
i i
i i
i
m B PV
T
m B Q W LW
t T
∆ − (
| | ¸ ¸
+ ∆ − − + + = (
|
¸ ¸

\ .
∑ ∑

(9.26)
Alternatively, Eq. (9.26) may be rearranged to the following form:
( )
( )
sys
0
flowing streams
1
i i
i i
i
m B PV
T
W LW m B Q
t T
∆ − (
| | ¸ ¸
+ = − − ∆ + − (
|
¸ ¸

\ .
∑ ∑

(9.27)
For a reversible process,
irr
S ∆

and, therefore, T
0
irr
S ∆

and LW

, are zero. For an irreversible
process,
irr
S ∆

and LW

are positive. The lost work represents the energy flow (power) lost because
of irreversibilities in the process. The lost work is much easier to relate to than .
irr
S ∆



The significance of Eq. (9.27) is best illustrated by a simple case. Consider a continuous,
steady-state, adiabatic process, where Eq. (9.27) simplifies to
( )
flowing streams
i
i
W LW m B + = −∆ (
¸ ¸



(9.28)
If the process decreases the availability function for the flowing streams, then the right-hand
side of Eq. (9.28) will be a positive quantity. That decrease will be converted to useful work done
on the surroundings and/or lost work. However, if the lost work is greater than the decrease in
availability, work will have to be transferred from the surroundings to the processing system. If the
process is also reversible, then

i
i
W

is the maximum work that can be extracted from the decrease
in availability. Thus, for such a reversible process,
( )
flowing streams
max
, for ( )
i
i
W m B B
| |
= −∆ ∆ = − (
| ¸ ¸
\ .



(9.29)
If the process increases the availability function for the flowing streams, then the right-hand
side of Eq. (9.28) will be a negative quantity. That increase will require work to be done by the
CD-9-24
surroundings on the process (i.e., a negative value for

i
i
W

). If lost work (a positive quantity)
occurs in the process because of irreversibilities, then, according to Eq. (9.28), an equivalent
amount of additional work must be done on the process by the surroundings to satisfy the change in
availability function. If the process is reversible, then

i
i
W

is the minimum work required for the
increase in availability. Thus, for such a reversible process,
( )
flowing streams
min
, for ( )
i
i
W m B B
| |
= −∆ ∆ = + (
| ¸ ¸
\ .


(9.30)
Eqs. (9.26) and (9.27) are availability balances. The heat and the work terms are transfers of
availability to or from the process. For a continuous, steady-state process, let us compare an
energy balance to an availability balance. The comparison is facilitated by rewriting Eq. (9.20) for
the energy balance and Eq. (9.26) for the availability balance, respectively, in the following forms,
where work and heat terms are all positive because they are labeled into or out of the system:

Energy balance:
( ) ( )
in out
in
out
in
out
0
+
+
mH mH
W W
Q Q
= −


∑ ∑
∑ ∑
∑ ∑




(9.31)
Availability balance:
( ) ( )
in out
in
out
0 0
in out

+
+ 1 1
LW mB mB
W W
T T
Q Q
T T
= −

( ( | | | |
− − −
| | ( (
\ . \ . ¸ ¸ ¸ ¸
∑ ∑
∑ ∑
∑ ∑

(9.32)
By comparing these two equations, we note the following:
1. The left-hand side of Eq. (9.31) is zero. That is, energy is conserved. The left-hand
side of Eq. (9.32) is zero only for a reversible process. Otherwise, the left-hand side is
positive and availability is not conserved. In an irreversible process, some availability
is lost.
CD-9-25
2. In the energy balance, work and heat are counted the same. In the availability
balance, work and heat are not counted the same. All work input increases the
availability of material flowing through the process. Only a portion of heat transferred
into a system is available to increase the availability of flowing streams. The heat is
degraded by a coefficient equal to ( )
0
1 / T T − . This coefficient is precisely the Carnot
cycle efficiency for a heat engine that takes heat from a source at temperature, T, and
converts a portion of it to useful work, discharging the balance to a sink at a lower
temperature, T
0
. Note that in the availability balance, T is not the temperature of the
process stream within the system, but is the temperature of the heat source or sink
outside the system.
3. The energy balance, which is valid whether the process is reversible or not, has no
terms that take into account irreversibility. Thus, the energy balance cannot be used
to compute the minimum or maximum energy requirements when taking material
from inlet to outlet states. The availability balance does have a term, LW

, that is a
measure of irreversibility. When the lost work is zero, the process is reversible and
Eq. (9.32) can be used to determine the maximum or minimum energy requirements to
cause a change in availability.

Regardless of whether a net availability of heat or work is transferred to or from a process,
the energy balance must be satisfied. Thus, the energy and availability balances are used together to
determine energy requirements and irreversibilities that lead to lost work. The more efficient a
process, the smaller the lost work.


9.6 EXAMPLES OF LOST-WORK CALCULATIONS

Before proceeding with a discussion of the second-law thermodynamic efficiency in the next
section, two examples are provided to illustrate the calculation of lost work for chemical processes.


CD-9-26
EXAMPLE 9.1
For the first example, consider the continuous two-stage compression of nitrogen gas shown in
Figure 9.19, which is based on actual plant operating conditions. The system or control volume is
selected to exclude the electric power generation plant and cooling-water heat sink. Assume that
the temperature, T, of the cooling water is essentially equal to the dead-state temperature, T
0
.
Calculate the lost work.

Figure 9.19 Continuous process for compression of nitrogen.

SOLUTION
For this process, Eq. (9.32) reduces to
( ) ( )
electrical in
1 2
LW mB mB W = − +

(9.33)
where B = H – T
0
S.
The enthalpies and entropies of the entering and exiting nitrogen gas, computed from a
modified Benedict-Webb-Rubin (BWR) equation of state, are

1 2
o o
1 2
132.46 Btu/lb 182.49 Btu/lb
1.6335 Btu/lb- R 1.5758 Btu/lb- R
H H
S S
= =
= =


The electrical work input is given as 107.3 kW and T
0
is given as 536.7
o
R. The entering and
exiting availability functions are
CD-9-27

1
2
132.46 (536.7)(1.6335) 744.24 Btu/lb
182.49 (536.7)(1.5758) 663.24 Btu/lb
B
B
= − = −
= − = −


The flow rate of nitrogen through the process is 3,600 lb/hr. Therefore, the change in
availability of nitrogen is
3,600[-663.24 - (-744.24)] = 291,600 Btu/hr

Because the availability increases, energy must be transferred into the system. The electrical power
input of 107.3 kW is equivalent to 366,400 Btu/hr. This is greater than the availability increase,
which represents the minimum energy input corresponding to a reversible process. Thus, the
compression process has irreversibility. To determine the extent of the irreversibility, substitute the
change in availability of the nitrogen, and the work input into the availability balance, Eq. (9.33),
for the lost work:

( ) ( )
electrical in
1 2
291, 600 366, 400 74, 800 Btu/lb LW mB mB W = − + = − + =



This is equivalent to 21.9 kW or 29.4 hp.

Where does the irreversibility occur? To answer this, separate second-law analyses are
needed for each of the two compressors and the intercooler. Unfortunately, data on the nitrogen
leaving the first compressor and leaving the intercooler are not provided. Therefore, these separate
analyses cannot be made.

How can we apply the first law of thermodynamics to the nitrogen compression problem?
We can apply an energy balance to calculate how much heat must be transferred from the nitrogen
to cooling water in the intercooler:
( )
electrical in out 2 1
W Q m H H = + −

(9.34)
Therefore,

out
Q

= 366,400 - (3,600)(182.49 - 132.46) = 366,400 - 180,100 = 186,300 Btu/hr
CD-9-28

Note that the enthalpy increase of 180,100 Btu/hr is far less than the minimum amount of energy of
291,600 Btu/hr that must be added. Even if the compressors and the intercooler were reversible,
291,600 - 180,100 = 111,500 Btu/hr of energy would have to be transferred out of the system.
Although this is considerably less than the 186,300 Btu/hr for the actual process, it is still a large
amount.

EXAMPLE 9.2
As a second example, consider the plant operating data shown in Figure 9.20 for a propane
refrigeration cycle. Saturated propane vapor (state 1) at 0
o
F and 38.37 psia for a flow rate of 5,400
lb/hr is compressed to superheated vapor (state 2) at 187 psia and 113
o
F. The propane is then
condensed with cooling water at 77
o
F in the refrigerant condenser to state 3 at 98.7
o
F and 185 psia.
Reducing the pressure across the valve to 40 psia causes the propane to become partially vaporized
(state 4) at the corresponding saturation temperature of 2
o
F. The cycle is completed by passing the
propane through the refrigerant evaporator, where the propane absorbs heat from the matter being
refrigerated and from which it emerges as a saturated vapor (state 1), thus completing the cycle.
Calculate the lost work.

Figure 9.20 Operating conditions for propane refrigeration cycle.

CD-9-29
SOLUTION
Let the system be circulating propane and the electric motor drive of the compressor, but not the
cooling water used in the condenser or the matter being refrigerated in the evaporator.

For each pass through the cycle, there is no net enthalpy change for the propane. The
energy balance, if applied incorrectly, would therefore indicate that no energy is required to run the
cycle. But, of course, energy input is required at the compressor, and heat is transferred to the
system from the matter being refrigerated at the evaporator. By an energy balance, the sum of
these two energy inputs is transferred out of the system to cooling water at the condenser.

Again, it is emphasized that the first law of thermodynamics cannot be used to determine
minimum or maximum energy transfer to or from a system. Instead, we must use the second law or
the availability balance (combined first and second laws). For the propane refrigeration cycle, the
availability balance of Eq. (9.32) simplifies to
0 0
in in out
Evaporator Condenser
1 1
T T
LW W Q Q
T T
| |
| |
= + − − −
|
|
|
\ .
\ .


(9.35)
For a reversible cycle, the lost work would be zero, and this form of the availability balance
is the classical result for the refrigeration (reverse Carnot) cycle. To prove this, the first law gives
in in out
W Q Q + =

(9.36)
Substitution of this equation into the lost-work equation, Eq. (9.35), with 0 LW =

, so as to
eliminate
out
Q

, gives the following widely used equation for the coefficient of performance (COP)
of a refrigeration cycle:
Evaporator
in
in Condenser Evaporator
COP
T
Q
W T T
= =

(9.37)
The lost work for the cycle is computed in the following manner. First, we take the dead-
state temperature, T
0
, to be the cooling-water temperature, T
Condenser
. The lost work then reduces to
0
in in
Evaporator
1
T
LW W Q
T
| |
= + −
|
|
\ .


(9.38)
The electrical work input is given in Figure 9.20 as 70 kW. The heat transferred in the
evaporator is obtained most readily from an energy balance on the propane as it flows from state 3
CD-9-30
(saturated liquid at 185 psia) to state 1 (saturated vapor at 38.37 psia), noting that no enthalpy
change occurs across the valve:
( ) ( )
in propane 1 4 propane 1 3
Q m H H m H H = − = −

(9.39)
From above, the propane circulation rate is 5,400 lb/hr. Again, we estimate enthalpies and entropies
from a modified Benedict-Webb-Rubin (BWR) equation of state, which gives

H
1
= -686.6 Btu/lb and H
3
= H
4
= -797.2 Btu/lb
Thus,
in
Q

= 5,400[(-686.6) - (-797.2)] = 597,200 Btu/hr = 174.9 kW

The temperatures are

T
0
= 77 + 459.7 = 536.7
o
R and T
Evaporator
= 10 + 459.7 = 469.7
o
R

The second term on the right-hand side of the lost-work equation, Eq. (9.38), for the propane
refrigeration cycle is the reversible work input that corresponds to the heat input. It is

536.7
1 174.9 24.95 kW
469.7
| |
− = −
|
\ .

The lost work is
( ) 70 24.95 45.05 kW LW = + − =

In a reversible cycle, with LW

= 0, only 70 - 45.05 or 24.95 kW of electrical work input would be
required.


9.7 THERMODYNAMIC EFFICIENCY

The thermodynamic efficiency of an operation or an entire process depends on its main goal and
the work lost in accomplishing that goal. Goals differ from application to application. For
CD-9-31
example, the main goal of an adiabatic turbine operating continuously might be to produce work.
The main goal of a refrigeration cycle might be the transfer of heat from the stream being
refrigerated to the refrigerant. In continuous chemical processes that involve reactors, separators,
heat exchangers, and shaft-work devices, the main goal is the increase or decrease of the
availability function of the streams flowing across the boundaries of the system. For a complex
batch chemical process, the main goal is the increase or decrease of the batch availability function
m(B - PV) of the system.

To derive general expressions for thermodynamic efficiency, we write Eq. (9.26), the
combined energy and entropy balance, in the form

( )
( )
sys
0
flowing streams
1
i i
i i
i
m B PV
T
LW W mB Q
T t
∆ − (
| | ¸ ¸
= − − ∆ + − −
|

\ .
∑ ∑

(9.40)

Table 9.2 Possible Main Goals of an Operation or Process
Main Goal Explanation
W −

Work transfer
( ) mB −∆ Change in availability function of flowing streams
0
1
1
i
T
Q
T
| |

|
\ .

Work equivalent of heat transfer
( )
sys
m B PV
t
∆ − (
¸ ¸



Change in batch availability function of system

Each of the terms on the right-hand side of Eq. (9.40) represents a possible main goal. The
availabilities of some main goals are listed in Table 9.2. The thermodynamic efficiency is
computed from one of two equations, depending on the sign of the term that represents the main
goal on the right-hand side of Eq. (9.40). If the sign is positive, the thermodynamic efficiency is
given by
( )goal
main goal
main goal
LW
+

η =

(9.41)
CD-9-32
If the numerical value of the main goal selected is negative, the thermodynamic efficiency is given
by
( )goal
main goal
main goal LW

η =



(9.42)
The application of Eq. (9.42) always results in a positive efficiency that is equal to or less
than unity (i.e., 100%), because the main goal has a negative sign and the lost work is greater than
or equal to zero. On the other hand, Eq. (9.41) can give values ranging from less than zero up to
unity. A negative efficiency results when the lost work is greater than the absolute value of the
main goal. For example, consider a continuous process in which the main goal is to decrease the
availability function of the flowing streams. If the process is reversible and exchanges heat only
with the infinite surroundings, then LW

= 0 and work could be done on the surroundings. If,
however, the process is so irreversible that, instead, work must be done on the system by the
surroundings, then LW

will be greater than the main goal, ( )
flowing streams
mB −∆ , and Eq. (9.41) will
yield a negative efficiency. Thermodynamic efficiencies greater than unity are impossible.

The application of Eqs. (9.41) and (9.42) for the calculation of thermodynamic efficiency
may be illustrated by considering the two examples in the preceding section. For the continuous,
steady-state, steady-flow, two-stage compression process shown in Figure 9.19, the main goal is to
change the availability function of the nitrogen gas. The calculations previously presented give

Main goal = 600 , 291 ) (
1 2
− = − − B B m Btu/hr

LW =

74,800 Btu/hr

Because the main goal has a negative value, we apply Eq. (9.42) to obtain

291, 600
0.796 or 79.6%
291, 600 74, 800

η = =
− −


This is consistent with the previous calculation of 20.4% for the loss of input electrical energy.

CD-9-33
In the refrigeration cycle of Figure 9.20, the main goal - the transfer of heat from the matter
being refrigerated at 10
o
F to the propane refrigerant - requires the work of a reversible Carnot
cycle, which was calculated to be -25 kW. This work was accompanied by 45 kW of lost work.
Thus, Eq. (9.42) gives
25
0.357 or 35.7%
25 45

η = =
− −


9.8 CAUSES OF LOST WORK

Lost work is caused by irreversibilities; their major causes are:

1. Mixing of two or more streams or batches of material that differ in temperature,
pressure, and/or composition. Such mixing leads to significant increases in entropy, but
may be unavoidable when preparing a composite feed for chemical reaction. Often,
however, such mixing can be avoided when recycling material. Quenching a hot stream
with a cold stream increases entropy.

2. Finite driving forces for transport processes. For reasonable-size processing equipment,
finite driving forces are needed for heat transfer and mass transfer. However, the
smaller the driving forces, the smaller is the lost work. In distillation, small driving
forces are best achieved with countercurrent flow of vapor and liquid at reflux ratios
close to minimum. For heat exchangers, small temperature-driving forces are achieved
with countercurrent flow and small temperature approaches at either end of the
exchanger.

3. Fluid friction and drag. Significant decreases in skin friction for flow of fluids in pipes
can be achieved by increasing pipe diameter, thereby reducing fluid velocity. Reducing
the velocity or streamlining the shape of the object can reduce form drag for flow of
fluid past submerged objects.

CD-9-34
4. Chemical reactions occurring far from equilibrium. To minimize lost work, reactions
should be carried out with little or no dilution, with minimal side reactions, and at
maximum yields to avoid separations and byproduct formation. This is best achieved
by using selective catalysts. If the reaction is exothermic, it is best carried out at high
temperature to maximize the usefulness of the energy produced. If the reaction is
endothermic, it is best carried out at below ambient temperature to utilize heat from the
dead state.

5. Transferring heat to cooling water, especially when that heat is available at an elevated
temperature. Good uses should be found for waste heat.

6. Mechanical friction in machinery such as pumps, compressors, and turbines.

Second-law thermodynamic efficiency of the majority of chemical processes is in the range
of 25 - 30%. Economic analyses have shown that it is worthwhile to seek ways to improve this
efficiency to at least 60%. Machinery is available with efficiencies of 80% and higher.


9.9 THREE EXAMPLES OF SECOND-LAW ANALYSIS

In this section, three detailed examples of second-law analysis are presented for chemical
processes. Each example includes the calculation of lost work, the determination of where the lost
work occurs, and consideration of how the lost work can be reduced. The examples involve (1) the
propane refrigeration cycle introduced in Section 9.6, (2) the separation of a mixture of propylene
and propane by distillation, and (3) a process for the hydrogenation of benzene to cyclohexane.
The third example is computed with ASPEN PLUS.

EXAMPLE 9.3 A Refrigeration Cycle

In Sections 9.6 and 9.7, the total rate of lost work and overall thermodynamic efficiency of a
propane refrigeration cycle, shown in Figure 9.20, is calculated. Now, consider this cycle in detail
CD-9-35
to determine where the lost work occurs with respect to each of the four steps in the cycle. Then,
attempt to improve the efficiency of the cycle by concentrating on those steps where most of the
lost work occurs. Although the overall process is a cycle, each separate step in the cycle can be
treated as a continuous process so that Eq. (9.27) applies.

SOLUTION

Compressor: State 1 to State 2
For this step,
( ) ( )
1 2 1 0 1 2 0 2 elec
LW m H T S H T S W

= − − − − (
¸ ¸


The thermodynamic properties of propane are obtained from a modified BWR equation as
above. Note that states 1 and 2 are both vapor. The rate of lost work in kilowatts is
( ) ( ) ( ) ( ) ( ) { } ( )
4
1 2
2.929 10 (5, 400) 686.60 536.67 1.3507 655.41 536.67 1.3501 70
49.83 70 20.17 kW
LW


= × − − − − − − − ( (
¸ ¸ ¸ ¸
= − + =

This represents 20.17/45.05 = 0.448, or 44.8% of the total lost work for the cycle. This lost work
results because of motor and compressor irreversibilities.

Refrigerant Condenser: State 2 to State 3
For heat rejection from the propane refrigerant to cooling water at the temperature of the infinite
surroundings, T
0
,
( ) ( )
2 3 2 0 2 3 0 3
LW m H T S H T S

= − − − (
¸ ¸

State 3 is a saturated liquid, so
( ) ( )( ) ( )( ) { }
4
2 3
2.929 10 (5, 400) 655.41 536.67 1.3501 797.2 536.67 1.0963
8.83 kW
LW


= × − − − − − ( (
¸ ¸ ¸ ¸
=

This represents 8.83/45.05 = 0.196, or 19.6% of the total lost work for the cycle. This lost work
results because of a frictional pressure drop of 2 psi through the heat exchanger and the rather large
temperature driving force for heat transfer.

CD-9-36
Valve: State 3 to State 4
Assume that this step is adiabatic with H
3
= H
4
. Then
( ) ( )
3 4 0 3 0 4
LW m T S T S

= − − − (
¸ ¸

Because state 4 is a partially vaporized condition, the fractions of vapor and liquid must be
determined to obtain S
4
. That is, if ψ is the weight fraction vaporized, then
( ) ( )( )
4 4 4
1
V L
S S S = ψ + −ψ
where V and L represent vapor and liquid, respectively. The weight fraction vaporized can be
determined by noting that
( ) ( )( )
3 4 4 4
1
V L
H H H H = = ψ + −ψ
and by solving for ψ to obtain
( )
( ) ( )
3 4
4 4
797.2 ( 855.7)
0.345
686.1 ( 855.7)
L
V L
H H
H H

− − −
ψ = = =
− − − −

Therefore,
S
4
= (0.345)(1.3501) + (1 - 0.345)(0.9831) = 1.1097 Btu/lb-
o
R
and thus
( ) ( )( ) ( )( ) { }
4
3 4
2.929 10 (5, 400) 536.67 1.0963 536.67 1.1097
11.37 kW
LW


= × − − − ( (
¸ ¸ ¸ ¸
=

This represents 11.37/45.05 = 0.252, or 25.2% of the total lost work for the cycle. This lost work
occurs because of the frictional pressure drop across the valve.

Refrigerant Evaporator: State 4 to State 1
For this step,
( ) ( )
0
4 1 4 0 4 1 0 1
1
i
i
T
LW m H T S H T S Q
T

| |
= − − − + − (
|
¸ ¸
\ .


where T
i
, the temperature of the matter being refrigerated, is 10
o
F (469.7
o
R). From the energy
balance, the heat transfer rate in the refrigerant evaporator is
( )
1 4 i
Q m H H = −

Therefore,
CD-9-37
( ) ( ) ( )
0
4 1 4 0 4 1 0 1 1 4
1
i
T
LW m H T S H T S m H H
T

| |
= − − − + − − (
|
¸ ¸
\ .

Simplifying,
( )
( )( )( ) ( )
( ) ( )
1 4
4 1 0 1 4
4
686.60 797.20
2.929 10 5, 400 536.67 1.3507 1.1097
469.67
4.68 kW
i
H H
LW mT S S
T


( −
= − −
(
¸ ¸
− − − (
= × − −
(
¸ ¸
=

This represents 4.68/45.05 = 0.104, or 10.4% of the total lost work for the cycle. This lost work
occurs because of frictional pressure drop through the heat exchanger and the small but finite
temperature driving force for heat transfer. Table 9.3 summarizes the preceding analysis.

Table 9.3 Lost Work for Propane Refrigeration Cycle
Step in Cycle State to State ( ) kW LW

Percentage of Total
LW

Compressor 1 - 2 20.17 44.8
Refrigerant condenser 2 - 3 8.83 19.6
Valve 3 - 4 11.37 25.2
Refrigerant evaporator 4 - 1 4.68 10.4
45.05 100.0

How can the thermodynamic efficiency of this refrigeration cycle by improved? Table 9.3
shows that the major loss is due to the compressor, with moderate losses in the refrigerant
condenser and the valve, but only a small loss in the refrigerant evaporator. Some improvements
can be made by maintaining the same basic cycle, but adjusting the operating conditions and
changing the equipment to accomplish the following:

1. Increase the efficiency of the compressor.

2. Reduce the frictional pressure drop in the refrigerant condenser. Use a higher-temperature
coolant for the refrigerant condenser or reduce the compressor discharge pressure to lower
the temperature of the refrigerant at states 2 and 3.

CD-9-38
3. Replace the valve with a power-recovery turbine.

4. Reduce the frictional pressure drop in the refrigerant evaporator. Increase the pressure at
state 4 to reduce the temperature-driving force in the refrigerant evaporator.


Figure 9.21 Revised propane refrigeration cycle.

A revised cycle that incorporates these improvements is shown in Figure 9.21. Comparison
of the cycle with the original one in Figure 9.20 shows the following:

1. The valve is replaced by a power-recovery turbine that supplies a portion of the power
required by the compressor.

2. The frictional pressure drop in the refrigerant evaporator is reduced from 1.63 psi (40.0 -
38.37) to 0.5 psi (44.85 - 44.35).

3. The frictional pressure drop in the refrigerant condenser is reduced from 2 psi (187 - 185) to
0.5 psi (154.9 - 154.4).

CD-9-39
4. The compressor inlet and discharge pressures are changed from 38.37 psia to 44.35 psia and
from 187 psia to 154.9 psia, respectively, thus reducing the compression ratio from 4.874 to
3.493. The corresponding changes in refrigerant temperature cause reductions in the
minimum temperature-driving forces in the condenser and evaporator from 21.7
o
F (98.7 -
77) to 8
o
F (85 - 77) and from 8
o
F (10 - 2) to 2
o
F (10 - 8), respectively.

Next, the lost work is calculated assuming that the power-recovery turbine and the
compressor operate isentropically. Also, the rate of heat transfer in the refrigerant evaporator is
assumed to be the same as for the original cycle (597,200 Btu/hr, as calculated above). Required
thermodynamic properties of propane for the revised cycle are

Temperature
(
o
F)
Pressure
(psia)
Phase
Enthalpy
(Btu/lb)
Entropy
(Btu/lb-
o
R)
85.0 154.40 Sat’d. liquid -806.1 1.0805
8.0 44.85 Sat’d. vapor -684.4 1.3485
8.0 44.85 Sat’d liquid -852.3 0.9899
7.4 44.35 Sat’d vapor -684.6 1.3486
100.0 154.90 Vapor -658.1 1.3518
90.0 154.90 Vapor -663.0 1.3431

It is worthwhile to begin calculations with the refrigerant condenser, where the known heat
duty permits us to determine the propane flow rate.

From State 4 to State 1
( )
1 4 i
Q m H H = −

Therefore,
1 4 4
597, 200
684.6
i
Q
m
H H H
= =
− − −

To obtain H
4
, note that since the power-recovery turbine is assumed to operate isentropically, S
4
=
S
3
= 1.0805 Btu/lb-
o
R. Also note that (S
4
)
V
> 1.0805 > (S
4
)
L
. Therefore, state 4 is partially
vaporized propane. If ψ is the weight fraction vaporized,
CD-9-40
( ) ( )( )
4 3 4 4
1
V L
S S S S = = ψ + −ψ
and therefore,
( )
( ) ( )
( ) ( )( )
( ) ( ) ( )
3 4
4 4
4 4 4
1.0805 0.9899
0.2526
1.3485 0.9899
1
0.2526 684.4 1 0.2526 852.3 809.9 Btu/lb
L
V L
V L
S S
S S
H H H


ψ = = =
− −
= ψ + − ψ
= − + − − = −

Thus,
( )
597, 200
4, 766 lb/hr
684.6 809.9
m = =
− − −

From State 3 to State 4
Letting
T
W

= rate of work transferred from the propane by the turbine,
( )
( )
4 3
4, 766 809.9 806.1 18,110 Btu/hr
T
W m H H − = −
= − − − = − (
¸ ¸

or
T
W

= 18,110 Btu/hr

From State 1 to State 2
Letting
C
W −

= rate of work transferred by the compressor to the propane,
( )
2 1 C
W m H H − = −

The enthalpy, H
2
, depends on the temperature of the propane leaving the compressor. It can be
obtained by noting that
S
2
= S
1
= 1.3486 Btu/lb-
o
R
because of the isentropic compression assumption. From the thermodynamic data given,

( ) ( ) ( ) o o
2
100 F 90 F V
V V
S S S > >
By interpolation, T
2
= 96.32 °F and H
2
= -659.9 Btu/lb. Therefore,
( ) 4, 766 659.9 684.6 117, 720 Btu/hr
C
W = − − − − = − (
¸ ¸

CD-9-41
Of this amount, 18,110 Btu/hr is supplied from the power-recovery turbine. Therefore, the
theoretical electrical power input,
E
W

, is
117, 720 18,110 99, 610 Btu/hr
E
W = − + = −

For the cycle,
0
1
536.67
99, 610 597, 200 1 14, 420 Btu/hr
469.67
E i
i
T
LW W Q
T
| |
= − + −
|
\ .
| |
= + − =
|
\ .


or
(14, 420)(1.0544)
4.22 kW
3, 600
=
This rate of lost work represents a large reduction from the value of 45.05 kW computed for the
original cycle. The reduction is so large because isentropic compression and expansion has been
assumed unrealistically for the revised cycle. To account for irreversibilities in compression and
expansion, refer to Exercise 9.22.

EXAMPLE 9.4 Separation of a Propylene-Propane Mixture by Distillation

The initial design of a distillation operation for the continuous, steady-state, steady-flow
separation of a propylene-propane mixture is shown in Figure 9.22. Conventional distillation is
used with a bottoms pressure of 300 psia so that cooling water can be used in the partial condenser
to provide reflux. The relative volatility of propylene to propane is quite low, varying from 1.08 to
1.14 for conditions at the top of the fractionator to conditions at the bottom of the fractionator,
respectively; thus, a large external reflux ratio of 15.9 is required at operation near the minimum
reflux. Because of high product purities, as well as the low average relative volatility, 200 stages
are required at 100% tray efficiency. With 24-in. tray spacing, two columns in series are needed
because a single column would be too tall. Therefore, an intercolumn pump is shown in addition to
the reflux pump. Total pressure drop for the two columns is 20 psi.

As shown in Figure 9.22, the system is chosen so that it does not include the 77
o
F cooling
water used as the coolant in the partial condenser or the 220
o
F saturated steam used as the heating
CD-9-42
medium in the partial reboiler. Enthalpies of the feed stream and the two product streams are given
in Table 9.4, with reference to the elements H
2
(gas) and C (graphite) at 0
o
R and 0 psia using the
Soave-Redlich-Kwong (SRK) equation of state with standard heats of formation. Entropies given
are referred to 0
o
R and 1 atm.

Figure 9.22 Distillation system for propylene-propane separation.

Table 9.4 Properties for Propylene-Propane Separation
State Stream
Phase
Condition
T(
o
F) P(psia)
m
(lbmol/hr)
H
(Btu/lbmol)
S
(Btu/lbmol-
o
R)
1 Feed Saturated liquid 125.7 294 600 -4,133.4 50.92
2 Distillate Saturated vapor 116.0 380 351 20,239.7 57.81
3 Bottoms Saturated liquid 135.8 300 249 -31,218.8 51.16

The rate of lost work is
( ) ( ) ( )
0
1 1 0 1 2 2 0 2 3 3 0 3 reboiler
stm
1
i
elec
i
T
LW W m H T S m H T S m H T S Q
T
| |
= − + − − − − − + − (
|
¸ ¸
\ .



where the work equivalent of the heat transferred to the condenser is zero because the temperature
of the cooling water is assumed to be T
0
. Thus, LW

(in kilowatts) is given by
CD-9-43
( )
| |
| |
| |
( )
4
4
( 1.96 23.55 23.55)
600 4,133.4 (536.67)(50.92)
2.929 10 351 20, 239.7 (536.67)(57.81)
249 31, 218.8 (536.67)(51.16)
536.67
2.929 10 1 (32, 362, 300)
679.67
4
LW


= − − − −
¦ ¹ − −
¦ ¦
+ × − −
´ `
¦ ¦
− − −
¹ )
| |
+ × −
|
\ .
=

9.06 140.81 1, 994.33 1, 902.58 kW − + =


The thermodynamic efficiency is computed from Eq. (9.41) because the main goal is to
change the availability function of the streams, which is
( )
flowing streams
140.81 kW mB −∆ = −
Thus, as in most continuous separation operations, the availability function of the flowing streams
has been increased. In this example, the increase is brought about mainly by the transfer of heat in
the reboiler, giving
( )
( )
140.81
0.0689 or 6.89%
140.81 1, 902.58
mB
mB LW
−∆

η = = =
−∆ − − −

This is a very low efficiency, but typical of conventional distillation of mixtures with a low relative
volatility because of the large energy expenditures required in the reboiler. Therefore, other
separation methods, such as adsorption, have been explored for this application. Also, elaborate
schemes for reducing the reboiler heat duty in distillation have been devised, including multieffect
distillation and operation at lower pressures using heat pumps, as discussed in Section 10.9. One
such alternative scheme, using reboiler-liquid flashing, for the separation of propylene from
propane is shown in Figure 9.23. The feed is reduced in pressure to 108 psia by a power-recovery
turbine and then distilled in a single column operating at a bottoms pressure of 112 psia. Liquid
leaving the bottom tray is flashed across an expansion valve to a pressure corresponding to a
saturation temperature lower than the saturation temperature of the overhead vapor so that the
partial condenser can be used as a reboiler. A compressor is needed to return the reboiled vapor to
the bottom of the column. Because the required reboiler duty is somewhat larger than the required
condenser duty, an auxiliary steam-heated reboiler is needed. The large reduction in reboiler steam
is somewhat offset by the power requirement of the compressor.
CD-9-44

Figure 9.23 Low-temperature distillation with reboiler-liquid flashing for propylene-propane
separation.

The following enthalpy and entropy data apply to Figure 9.23.
Stream Phase Enthalpy (Btu/lbmol) Entropy (Btu/lbmol-
o
R)
Feed Saturated liquid -4,133.4 50.92
Distillate Saturated vapor 19,672.6 58.40
Bottoms Saturated liquid -33,682.1 46.87

The rate of lost work for the system is given by
( ) ( ) ( )
( )
| |
| |
| |
0
1 1 0 1 2 2 0 2 3 3 0 3 reboiler
stm
4
1
(29 14 381)
600 4,133.4 (536.67)(50.92)
2.929 10 351 19, 672.6 (536.67)(58.40)
249 33, 682.1 (536.67)(46.87)
i
elec
i
T
LW W m H T S m H T S m H T S Q
T

| |
= − + − − − − − + − (
|
¸ ¸
\ .
= − − −
− −
+ × − −
− − −



( )
4
536.67
2.929 10 1 (2, 820, 000)
679.67
366.0 38.2 173.8 501.6 kW

¦ ¹
¦ ¦
´ `
¦ ¦
¹ )
| |
+ × −
|
\ .
= − + =

CD-9-45
Since ( )
flowing streams
38.2 kW mB −∆ = − ,
( )
( )
38.2
0.07 or 7.0%
38.2 501.6
mB
mB LW
−∆

η = = =
−∆ − − −

Although the lost work is much lower than the value of 1,902.58 kW computed for the system in
Figure 9.22, the thermodynamic efficiency is still low. The two cases are not really comparable
because the product conditions are not the same.

EXAMPLE 9.5 A Process for Converting Benzene to Cyclohexane
Here, a process is considered that involves a chemical reactor as well as separators, heat
exchangers, and pumps. A continuous, steady-state, steady-flow process for manufacturing
approximately 10 million gallons per year of high-purity cyclohexane by the catalytic
hydrogenation of high-purity benzene, at elevated temperature and pressure, is shown in Figure
9.24. The heart of the process is a reactor in which liquid benzene from storage, together with
makeup hydrogen and recycle hydrogen in stoichiometric excess, take part in the reaction
C
6
H
6
+ 3H
2
→ C
6
H
12


Figure 9.24 Process flow diagram and design basis for hydrogenation of benzene to cyclohexane.

CD-9-46
Figure 9.24 includes all major equipment and streams together with a set of operating
conditions for making a preliminary design and second-law analysis. As shown, 92.14 lbmol/hr of
pure liquid benzene feed (S1) at 100
o
F and 15 psia is pumped by P1 to 335 psia and mixed in-line
and adiabatically at M1 with impure hydrogen makeup gas (S3) containing 0.296 mol% nitrogen at
120
o
F and 335 psia, gas recycle (S4), and a cyclohexane recycle (S5) to produce the combined
reactor feed (S6). In the cooled reactor, R1, 99.86% of the benzene in stream S6 is hydrogenated to
produce the saturated-vapor reactor effluent (S7) at 392
o
F and 315 psia. This effluent is reduced in
temperature to 120
o
F at 300 psia by the cooler, H1, and then separated at these conditions in the
high-pressure flash drum, F1, into a hydrogen-rich vapor and a cyclohexane-rich liquid. A total of
8.166% of the vapor from this flash drum is purged to stream S11 at line tee D1, with the
remaining vapor (S12) recycled to the reactor, R1, to provide an excess of hydrogen. At the line
tee, D2, 62% of the liquid (S10) from flash drum F1 is sent in stream S14 to a low-pressure
adiabatic flash drum, F2, at 15 psia. Gas from F2 is vented to stream S15, while liquid is taken as
cyclohexane product S16. The remaining liquid S13 from F1 is recycled by pump P2 to reactor R1
to control the pressure of the saturated-vapor reactor effluent.

It is convenient to use computer simulation to perform mass and energy balance
calculations automatically for continuous-flow, steady-state processes like the one in Figure 9.24.
For this example, ASPEN PLUS is used. This requires that the process flow diagram be converted
to a simulation flowsheet as discussed in Section 4.3. That flowsheet is shown in Figure 9.25, in
which each stream has a unique name, the same as or similar to that shown in Figure 9.24. Each
operation is a simulation unit within which two names appear. The top name, e.g., R1 for the
reactor, is a unique user-specified unit name or so-called block i.d. The bottom name, e.g.,
RSTOIC for the reactor, refers to the selected ASPEN PLUS model, or subroutine, for the
operation. As discussed earlier, in many cases, a particular operation can be simulated with two or
more models. The information given in Figures 9.24 and 9.25 is sufficient to prepare the input for
a simulation. As discussed earlier, specifications can be entered interactively in the ASPEN PLUS
program. Specifications entered on input forms are converted by ASPEN PLUS to a compact
listing that can be displayed if desired. The listing is given in Figure 9.26, where the flowsheet
topology is followed by the list of components with user-selected names followed by data bank
names. Thermodynamic properties are computed by option SYSOP1, which is the Chao-Seader
CD-9-47
method with the Grayson-Streed constants for estimating K values and the Redlich-Kwong
equation of state for obtaining the departure functions for the effect of pressure on enthalpy and
entropy. All mixture enthalpies and entropies are referenced to the elements at 25
o
C. Therefore,
energy and entropy balances automatically account for enthalpy and entropy changes due to
chemical reaction. This greatly simplifies the calculations when chemical reactions occur as in this
cyclohexane process. The availability function, B, is readily computed from its definition, Eq.
(9.24), for a selected value of T
0
. Specifications for the two inlet streams, S1 and S3, follow. The
ASPEN PLUS program concludes with the operating conditions for each simulation unit.


Figure 9.25 ASPEN PLUS flowsheet for the cyclohexane process.

In Figure 9.25, two recycle loops are clearly seen. However, no recycle convergence
method is specified in the ASPEN PLUS program, and the flowsheet does not show the
convergence units. Accordingly, ASPEN PLUS selects, by default, the tear streams, initial
component flow rates of zero for the tear streams, and a convergence method. The converged
results of the simulation for the ASPEN PLUS program in Figure 9.26 are given in Figure 9.27,
where component and total molar flow rates, temperature, pressure, molar enthalpy, molar vapor
and liquid fractions, molar entropy, density, and average molecular weight are listed. By
comparing streams S1 and S16, it is seen that the overall yield of cyclohexane from the process is
91.2899/92.1400 or 99.08%. By comparing streams S3 and S16, it is seen that an overall excess of
CD-9-48
[(282.9599/3)/91.2899] - 1.0 or only 3.32% H
2
is used. Examination of stream S4 or S12 shows
that relatively little N
2
is recycled, although the amount is large relative to the N
2
in the makeup
hydrogen. The amount of cyclohexane recycle in stream S5 or S13 is considerable compared to the
benzene feed S1. The energy balance results are summarized in Table 9.5, where the net energy
transfer rates are listed for each operation, and are considerable for the reactor, R1, and the partial
condenser, H1.


Figure 9.26 ASPEN PLUS input in paragraph form for the cyclohexane process.

Table 9.5 Net Energy Transfer Rate for the Simulation Units in the Cyclohexane Process
Operation Net Energy Transfer Rate
R1 4,704,200 Btu/hr out
H1 3,457,300 Btu/hr out
K1 5,230 Bhp in
P1 3,455 Bhp in
P2 0.288 Bhp in
CD-9-49


Figure 9.27 Converged results for process streams of the cyclohexane process.

CD-9-50


Figure 9.28 Second-law analysis of the cyclohexane process.
CD-9-51
The results in Figure 9.27 and Table 9.5 are used to perform a second-law analysis. The
dead-state temperature is taken as 100
o
F. The calculation of lost work for the entire process and
the corresponding second-law efficiency is carried out conveniently on a spreadsheet by
transferring results from ASPEN PLUS, as shown in Figure 9.28. Note that the availability
function for each stream can be computed and printed by ASPEN PLUS. The overall efficiency is
only 25.7%. Similar analyses are carried out readily for the separate operations in the process. The
fraction of the total lost work for each operation is as follows:

Operation % of Total Lost Work
Feed pump P1 0.23
Recycle pump P2 0.02
Recycle compressor K1 0.12
Mixer M1 – Reactor R1 74.52
Cooler H1 – Flash F1 24.55
Flash F2 with valve 0.56
Total 100.00

This table shows clearly that the reactor and cooler are, by far, the largest contributors to the
inefficiency of the process. Some reduction in lost work can be achieved by replacing the partial
condenser with two or three heat exchangers operating with coolants at different temperature
levels. But what can be done with the reactor? Would it be better to operate it at a lower or higher
temperature? Should a larger excess of hydrogen be used? Clearly, there is room for considerable
improvement in the reactor operation. See Exercise 9.23.


CD-9-52
9.10 SUMMARY

Having studied this chapter, the reader should

1. Know the differences between and the limitations of the first and second laws of
thermodynamics.

2. Understand the concepts of the irreversible change in entropy and lost work or exergy.

3. Be able to use a process simulator to compute lost work and second-law efficiency.

4. Be able to pinpoint major causes of lost work in a process and determine ways to improve
the efficient use of energy.

REFERENCES

Felder, R.M., and R.W. Rousseau, Elementary Principles of Chemical Processes, 3rd edition,
Wiley, New York (2000).
Keenan , J. H., “Availability and Irreversibility in Thermodynamics”, British Journal of Applied
Physics, 2, 183-192 (1951).
Rant, Z., Exergie, ‘Ein Neues Wort Fur Technische Arbeitfahrigkeit”, Forschung Ing-Wes, 22, 1,
36-37 (1956).
Sommerfeld, J. T., “Analysis and Simulation of a Solar-powered Refrigeration Cycle,” Chem. Eng.
Educ., Winter (2001).
Sussman, M. V., Availability (Exergy) Analysis – A Self Instruction Manual, Tufts University
(1980).
van Wylen, G.J., R.E. Sonntag, and C. Borgnakke, Fundamentals of Classical Thermodynamics,
4th edition, Wiley, New York (1994).
CD-9-53
EXERCISES

9.1 A stream of hot gases at 1,000
o
C, having a specific heat of 6.9 cal/mol-
o
C, is used to
preheat air fed to a furnace. Because of insufficient insulation, the hot gas cools to 700
o
C
before it enters the air preheater. How much availability per mole does it lose?

9.2 An ideal gas, with C
p
= 7 cal/mol-
o
C, is compressed from 1 to 50 atm while its temperature
rises from 25 to 150
o
C. How much does its availability change per mole?

9.3 Superheated steam at 250 psia and 500
o
F is compressed to 350 psia. The isentropic
efficiency of the compressor is 70%. For the compressor, compute its
a. Lost work
b. Thermodynamic efficiency

9.4 Steam at 400
o
F, 70 psia, and 100 lb/hr is compressed to 200 psia. The electrical work is 4.1
kW. Determine the
a. Lost work
b. Thermodynamic efficiency
c. Isentropic efficiency

9.5 The rate of heat transfer between Reservoir A at 200
o
F and Reservoir B at 180
o
F is 1,000
Btu/hr.
a. Compute the lost work.
b. Adjust the temperature of Reservoir A to 10
o
F. For the same heat duty and lost work,
compute the temperature of Reservoir B. How do the approach temperatures, ∆T
AB
,
compare?

9.6 Nitrogen gas at 25
o
C and 1 atm, with C
p
= 7 cal/mol-K, is cooled to -100
o
C at 1 atm.
Assuming an ideal gas, calculate the minimum work per mole required for cooling. What is
the maximum work per mole that can be obtained when the gas is returned to 25
o
C and 1
atm?
CD-9-54

9.7 An equimolar stream of benzene and toluene at 1,000 lbmol/hr and 100
o
F is mixed with a
toluene stream at 402.3 lbmol/hr and 50
o
F, as discussed in connection with Figures 4.8 and
4.9. Assuming ideal vapor and liquid mixtures, use a process simulator to compute the
a. Change of availability upon mixing
b. Lost work
c. Thermodynamic efficiency

9.8 Consider the cooler, H2, in the monochlorobenzene separation process in Figure 4.23 and
4.24. Assume that the heat is transferred to an infinite reservoir of cooling water at 77
o
F.
a. Using the enthalpy and entropy values in the results for the sample problem in the
ASPEN PLUS section of the CD-ROM that accompanies this textbook, determine the lost
work associated with the cooler.
b. Let the reservoir be at 100
o
F and repeat (a).

9.9 Two streams, each containing 0.5 lb/hr steam at 550 psia, are mixed as shown:

a. Compute the heat loss to an environmental reservoir at 77
o
F.
b. Compute the lost work and thermodynamic efficiency.

9.10 1,000 lb/hr of saturated water at 600 psia is superheated to 650
o
F and expanded across a
turbine to 200 psia, as illustrated.

CD-9-55
Calculate the
a. Isentropic efficiency of the turbine
b. Lost work for the process
c. Thermodynamic efficiency of the process

9.11 Superheated steam at 580
o
F and 500 psia is expanded across a turbine, as shown below, to
540
o
F and 400 psia. 0.9 kW of shaft work are produced. The turbine exhaust is cooled by
a 77
o
F reservoir to its dew point at 400 psia.

Determine the
a. Flow rate of steam in lb/hr
b. Isentropic efficiency of the turbine
c. Lost work
d. Thermodynamic efficiency

9.12 Calculate the minimum rate of work in watts for the gaseous separation at ambient
conditions indicated in the following diagram.


CD-9-56
9.13 Calculate the minimum rate of work in watts for the gaseous separation at ambient
conditions of the feed indicated below into the three products shown.


9.14 For the adiabatic flash operation shown below, calculate the
a. Change in availability function (T
0
= 100
o
F)
b. Lost work
c. Thermodynamic efficiency


Flow rate, lbmol/hr
Stream 1 Stream 2 Stream 3
H
2
0.98 0.95 0.03
N
2
0.22 0.21 0.01
Benzene 0.08 0.00 0.08
Cyclohexane 91.92 0.69 91.23
Stream 1 Stream 2 Stream 3
Temperature,
o
F 120 119.9 119.9
Pressure, psia 300 15 15
Enthalpy, 1,000 Btu/hr -3,642.05 -14.27 -3,627.78
Entropy, 1,000 Btu/hr-
o
R 4.920 0.094 4.860

CD-9-57
9.15 Consider the results of an ASPEN PLUS simulation of the following flash vessel:


Heat is obtained from a large reservoir at 150
o
F. Calculate the
a. Rate of heat addition
b. Lost work
c. Thermodynamic efficiency

CD-9-58
9.16 A partial condenser operates as shown below. Assuming that T
0
= 70
o
F, calculate the
a. Condenser duty
b. Change in availability function
c. Lost work
d. Thermodynamic efficiency


Flow Rate, lbmol/hr
Stream 1 Stream 2 Stream 3 Stream 4 Stream 5
H
2
72.53 65.15 5.80 0.60 0.98
N
2
7.98 7.01 0.62 0.13 0.22
Benzene 0.13 0.00 0.00 0.05 0.08
Cyclohexane 150.00 1.61 0.14 56.33 91.92
Stream 1 Stream 2 Stream 3 Stream 4 Stream 5
Temperature,
o
F 392 120 120 120 120
Pressure, psia 315 300 300 300 300
Enthalpy, 1,000 Btu/hr -2,303.29 241.76 21.61 -2,231.84 -3,642.05
Entropy, 1,000 Btu/hr-
o
R 14.68 2.13 0.19 3.02 4.92

CD-9-59
9.17 A light-hydrocarbon mixture is to be separated by distillation, as shown in Figure 9.29, into
ethane-rich and propane-rich fractions. Based on the specifications given and use of the
Soave-Redlich-Kwong equation for thermodynamic properties, use ASPEN PLUS with the
RADFRAC distillation model to simulate the column operation. Using the results of the
simulation, with T
0
= 80
o
F, a condenser refrigerant temperature of 0
o
F, and a reboiler steam
temperature of 250
o
F, calculate the
a. Irreversible production of entropy, Btu/hr-
o
R
b. Change in availability function in Btu/hr
c. Lost work in Btu/hr, kW, and Hp
d. Thermodynamic efficiency


Figure 9.29 Distillation process for Exercise 9.17.

CD-9-60
9.18 A mixture of three hydrocarbons is to be separated into three nearly pure products by
thermally coupled distillation at 1 atm, as shown in Figure 9.30.

Figure 9.30 Thermally coupled distillation process for Exercise 9.18.

Based on the specifications given and other specifications of your choice to achieve
reasonably good separations, together with use of the Peng-Robinson equation for
thermodynamic properties, use ASPEN PLUS with the MULTIFRAC distillation model to
simulate the column. Using the results of the simulation, with T
0
= 100
o
F, calculate the
a. Irreversible production of entropy, Btu/hr-
o
R
b. Change in availability function in Btu/hr
c. Lost work in Btu/hr, kW, and Hp
d. Thermodynamic efficiency
CD-9-61
9.19 Consider the hypothetical perfect separation of a mixture of ethylene and ethane into pure
products by distillation as shown in Figure 9.31.

Figure 9.31 Distillation process and data for Exercise 9.19: (a) distillation; (b) reboiler.
Two schemes are to be considered: conventional distillation and distillation using a heat
pump with reboiler liquid flashing. In both cases the column will operate at a pressure of
200 psia, at which the average relative volatility is 1.55. A reflux ratio of 1.10 times
minimum, as computed from the Underwood equation, is to be used. Other conditions for
the scheme using reboiler liquid flashing are shown below. Calculate for each scheme:
a. Change in availability function (T
0
= 100
o
F)
b. Lost work
c. Thermodynamic efficiency
Other thermodynamic data are
Latent Heat of
Vaporization (Btu/lbmol)
Ethylene at 200 psia 4,348
Ethane at 200 psia 4,751
Ethane at 90 psia 5.473
CD-9-62
9.20 Consider a steam engine that operates in a Rankine cycle, as illustrated below:

The turbine exhaust is a saturated vapor.
a. Find the saturation temperature of the turbine exhaust.
b. For an isentropic efficiency of 90 percent, determine the shaft work delivered by the
turbine. What is the temperature of the feed to the turbine?
c. Compute the lost work for the turbine.
d. Compute the thermodynamic efficiency for the turbine.

9.21 A reactor is to be designed for the oxidation of sulfur dioxide, with excess oxygen from air,
to sulfur trioxide. The entering feed, at 550 K and 1.1 bar, consists of 0.219 kmol/s of
nitrogen, 0.058 kmol/s of oxygen, and 0.028 kmol/s of sulfur dioxide. The fractional
conversion of sulfur dioxide is 50%. The reaction is very exothermic. Three cases are to be
considered:
1. Adiabatic reaction.
2. Isothermal reaction with the heat of reaction transferred to boiler feed water at 100
o
C.
3. Isothermal reaction with the heat of reaction transferred to boiler feed water at 200
o
C.

For each case, compute the lost work in kW.

9.22 For the revised propane refrigeration cycle in Figure 9.21 (Example 9.3), let the isentropic
efficiencies of the turbine and compressor be 0.9 and 0.7, respectively. Compute the
a. Lost work for the four process units and the entire cycle.
b. Thermodynamic efficiency of the cycle.

CD-9-63
9.23 Alter the design of the cyclohexane process in Example 9.5 to reduce the lost work and
increase the thermodynamic efficiency. Use a simulation program to complete the material
and energy balances, and compute the entropies and availability functions for all of the
streams, as well as the lost work for each piece of equipment.

9.24 The chilled-water plant at the University of Pennsylvania sends chilled water to the
buildings at 42°F and receives warmed water at 55°F. A refrigerant is vaporized in the
refrigerant condenser at 38°F, as it removes heat from warmed water. The refrigerant is
condensed to a saturated liquid at 98°F. The condensing medium is water at 85°F, which is
heated to 95°F as it absorbs heat rejected from the refrigerant. The warmed condenser
water is cooled in a cooling tower, in which it is sprayed over a stream containing ambient
air. Assume that the ambient air is at 100°F and 95% humidity on a hot summer day and is
rejected at 100% humidity. For Phase I of the plant, the cooling capacity is 20,000 tons.
a. Calculate the flow rates of the chilled water and condenser water in gal/min.
b. Select a refrigerant and its operating pressures. Assuming an isentropic efficiency
of 70% for the compressor, determine the refrigerant flow rate and the brake
horsepower for the compressor.
c. Calculate the lost work and thermodynamic efficiency.

9.25 Consider the solar or waste-heat refrigeration cycle in Figure 9.32, which was proposed by
Sommerfeld (2001). In addition to the conventional refrigeration loop, a portion of the
condensate is pumped to an elevated pressure, where it is vaporized using solar energy or
low-temperature waste energy in a chemical complex. Its saturated vapor effluent is
expanded to recover power in a turbine and mixed with the gases from the compressor.

CD-9-64

Figure 9.32 Solar or waste-heat refrigeration cycle.

Use a process simulator to solve the material and energy balances for the following
specifications:
R-134a refrigerant
4-ton refrigeration load at 20°F
Refrigerant evaporator effluent - saturated vapor at 40°F
Condenser heat rejected to environment at 77°F
Condenser effluent - saturated liquid at 125°F
Solar or waste-heat available at 220°F
Solar or waste-heat collector effluent - saturated vapor at 200°F
Isentropic efficiency of the compressor = 70%
Isentropic efficiency of the turbine = 90%
Isentropic efficiency of the pump = 100%
a. Determine the flow rates of refrigerant in both loops; the three operating pressures; the
condenser and collector heat duties; the power consumed or generated by the
compressor, pump, and turbine; the coefficient of performance, lost work, and
thermodynamic efficiency for the refrigerator.
b. Vary the condenser effluent temperature to determine its effect on the solution in part a.








ASPEN ICARUS PROCESS EVALUATOR (IPE)

Equipment Sizing and Costing Using
ASPEN PLUS to Initiate Evaluation


Notes prepared by:


Robyn B. Nathanson
Warren D. Seider
University of Pennsylvania

May 2003



Previous versions were coauthored with:


Holger Nickisch
Maizatul Zain
University of Pennsylvania

Robert Nedwick
Pennsylvania State University



CD-IPE-i

CONTENTS

INTRODUCTION 1

PREPARING AN ASPEN PLUS SIMULATION FOR ASPEN IPE 2

Additional Mixture Properties 3

INVESTMENT ANALYSIS USING ASPEN IPE 3

DEPROPANIZER 3

Initial Setup 3
Mapping Process Simulation Units into Aspen IPE 8
Standard Basis 17
Equipment Costing 19
Total Permanent Investment 25
Adding Equipment 25
Applying Alternative Utilities 34

MONOCHLOROBENZENE SEPARATION PROCESS 37

Initial Setup 37
Mapping Process Simulation Units to Aspen IPE 39
Standard Basis 45
Equipment Costing 45
Total Permanent Investment 50

ASPEN IPE FOLDERS AND FILES 51

REFERENCES 51

APPENDIX I - DEPROPANIZER – ASPEN PLUS REPORT 52

APPENDIX II - DESIGN CRITERIA SPECIFICATIONS 58

APPENDIX III - ASPEN IPE CAPITAL ESTIMATE REPORT FOR THE 61
DEPROPANIZER

APPENDIX IV - ASPEN IPE CAPITAL ESTIMATE REPORT FOR THE 70
MONOCHLOROBENZENE SEPARATION PROCESS



CD-IPE-1
INTRODUCTION


These notes are prepared to provide a step-by-step procedure for estimation of the
total capital investment using the Aspen Icarus Process Evaluator (Aspen IPE). Aspen
IPE is a software system provided by Aspen Technology, Inc., for economic evaluation
of process designs. It determines the capital expenditure, operating costs, and the
profitability of proposed designs. Aspen IPE has an automatic, electronic expert system
which links to process simulation programs. It is used to (1) extend the results of process
simulation, (2) generate rigorous size and cost estimates for processing equipment, (3)
perform preliminary mechanical designs, and (4) estimate purchase and installation costs,
indirect costs, the total capital investment, the engineering-procurement-construction
planning schedule, and profitability analyses.

Aspen IPE usually begins with the results of a simulation from one of the major
process simulators (e.g., ASPEN PLUS, HYSYS, CHEMCAD, and PRO/II), it being
noted that users can, alternatively, provide equipment specifications and request
investment analysis without using the process simulators. In these notes, only results
from ASPEN PLUS are used to initiate Aspen IPE evaluations and only capital cost
estimation is emphasized. Readers should refer to the Aspen IPE User’s Guide (press the
Help button in Aspen IPE) for detailed instructions, explanations, and for improvements
in new versions of the software system.

These notes are organized as follows:

1. Instructions are provided to prepare an ASPEN PLUS simulation for use with
Aspen IPE.

2. A depropanizer example is provided to illustrate the use of Aspen IPE. The
depropanizer is a distillation tower to recover propane and lighter species
from a normal-paraffins stream, as shown in Figure 1. The simulation
flowsheet and selected results are shown in Appendix I and in the multimedia
tutorial on the CD-ROM that contains these course notes (ASPEN → Tutorials
→ Separation Principles → Flash and Distillation). Also, a copy of the file,
RADFRAC.bkp, is provided on the CD-ROM.

3. Additional features of Aspen IPE are introduced for a more complete process,
the monochlorobenzene (MCB) separation process, which is discussed in
Sections 4.4 of the textbook (Seider et al., 2004). A copy of the simulation
file, MCB.bkp, is provided on the CD-ROM that contains these notes.

After completing these notes, to practice estimating capital costs using Aspen
IPE, you may wish to solve Exercises 16.4 and 17.21 in the textbook.

In these notes, all of the calculations were carried out using Aspen IPE, Version
11.1, with the design and cost basis date being the First Quarter 2000.

CD-IPE-2






Figure 1 Depropanizer



PREPARING AN ASPEN PLUS SIMULATION FOR ASPEN IPE

To estimate equipment sizes and costs using Aspen IPE for a process simulated
with ASPEN PLUS, it is necessary to prepare the simulation results for use with Aspen
IPE. While this is accomplished in a similar manner for most of the major process
simulators, these notes focus on the steps to prepare ASPEN PLUS simulations. For the
steps when using the other process simulators, the reader should refer to the Aspen IPE
User’s Guide (press the Help button in Aspen IPE).

It is normally necessary to adapt the simulation file in two ways. First, to
estimate equipment sizes, Aspen IPE usually requires estimates of mixture properties not
needed for the material and energy balance, and phase equilibria calculations performed
by the process simulators. For this reason, it is necessary to augment the simulation
report files with estimates of mixture properties, such as viscosity, thermal conductivity,
CD-IPE-3
and surface tension, for the streams in the simulation flowsheet. Second, Aspen IPE
requires specifications to estimate equipment sizes that are not computed by some of the
approximate simulation models. This is the case, for example, when the DISTL and
RSTOIC models are used in ASPEN PLUS. These must be replaced by more rigorous
models, such as the RADFRAC and RPLUG models. This replacement can be viewed as
the first step in computing equipment sizes and costs. Note that it is also possible to
provide specifications for computing equipment sizes without using ASPEN PLUS.

Additional Mixture Properties

Estimates for the additional stream properties are added using the PROPSETS.apt
file on the CD-ROM that contains these course notes. To accomplish this, the ASPEN
PLUS simulation file is opened first; e.g., RADFRAC.bkp (which is available on the CD-
ROM that contains these course notes). Under the File pull-down menu, the Import entry
and the PROPSETS.apt file are selected. Aspen IPE automatically adds three new
property sets, after which the file can be saved as RADFRAC-IPE.bkp, a copy of which
is on the CD-ROM that contains these notes. To check that this has been accomplished,
using the Data pull-down menu, select Setup and then Report Options. Then, display the
Streams page by selecting the appropriate tab and click the Property Sets button.
Observe that all three Aspen IPE property sets have been entered into the Selected
Property Sets box. Now that the Aspen IPE property sets have been added, it is
necessary to re-run the simulation.

It remains to transfer the ASPEN PLUS simulation results into Aspen IPE. This
is accomplished by selecting Send To Æ Aspen Icarus from the File pull-down menu in
ASPEN PLUS. The simulation results are loaded automatically into Aspen IPE.



INVESTMENT ANALYSIS USING ASPEN IPE

In this section, the use of Aspen IPE for equipment sizing and costing is
illustrated for a depropanizer and for the monochlorobenzene separation process.


DEPROPANIZER

This example involves the single distillation column shown in Figure 1, with its
simulation flowsheet and selected results shown in Appendix I and on the multimedia
tutorial on the CD-ROM that contains these course notes (ASPEN → Tutorials →
Separation Principles → Flash and Distillation).

Initial Setup

Having sent the ASPEN PLUS simulation file to Aspen IPE, it is opened
automatically and the Create New Project dialog box appears:

CD-IPE-4


The user can either select an existing project in which to start a new scenario, or enter a
new Project Name. The Project Name RADFRAC-IPE is assigned automatically from
the ASPEN PLUS file name, however punctuation marks are not allowed, so enter the
Project Name DEC3 instead. Note that the underscore and space characters are
permitted. After pressing the OK button, the first of four dialog boxes, not shown here,
appear. The first is the Project Properties dialog box, in which a Project Description and
further remarks may be entered. A units of measure set is also chosen, which for this
example is the Inch-Pound (IP) units set.

Second, the Input Units of Measure Specifications dialog box is displayed. This
form allows the user to customize the units of measure that will appear on input
specification forms. Click the Close button to accept the default settings.

Third, the General Project Data dialog box appears. Since no adjustments are
needed in this example, press the OK button. Fourth, the Load Simulator Data? dialog
box is displayed. Enter Yes to do so.

Aspen IPE now opens two windows shown below. The narror Project Explorer,
on the left, is in Project View mode, and a wider Main window, initially blank, is on the
right. Note that two additional windows, Palette and Property, can be opened using the
View pulldown menu. Aspen IPE allows the user to specify many parameters for
equipment sizing or to accept default values. These are the basis for sizing the equipment
and for specifying its utilities. The first step in completing this simulation is to examine
the project Design Criteria. This can be done by selecting the Project Basis View tab in
the Project Explorer. Note that the Design Criteria and Utility Specifications entries
under the Process Design heading are the most relevant when estimating equipment sizes
and costs. Double-click on Design Criteria to cause the Design Criteria-IP form to
appear in the Main window:
CD-IPE-5



Default values are provided for many of the entries, but they can be modified as
necessary, and missing entries can be entered. Particular attention should be paid to the
design pressure and temperature, to the overdesign factors, to the residence times in the
process vessels, as well as to other tower information. The user must be careful to check
all of the relevant specifications that apply to the equipment under study. Note that the
design criteria are defined in the Aspen IPE User’s Guide, which can be accessed using
the Help button in Aspen IPE, with the values specified for the depropanizer process
shown in Appendix II (Defining the Project Basis → Process Design → Design
Criteria). Note also that design criteria files can be created for use with other design
projects. For implementation details, see the Aspen IPE User’s Guide.

Also, it is usually important to examine the default values associated with the
utilities. For this purpose, the Utility Specifications entry under the Process Design
heading is selected to produce the Develop Utility Specifications dialog box:



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Note that all existing utilities to be used by Aspen IPE are listed. Default values should
be examined and modified, and missing utilities should be added. For example, because
the textbook recommends that process designs accept cooling water at 90°F and heat it to
120°F, it is necessary to replace the temperatures associated with the cooling water
utility. To modify these temperatures, double-click on the Cooling Water entry, which
produces the Utility Specifications dialog box:



Then, the inlet and exit temperatures are changed to 90 and 120°F. Other default values
can be changed similarly. Click OK when finished.
CD-IPE-7
To add a utility not in the existing utility list, click on the Create option on the
Develop Utility Specifications dialog box. As shown below, low-pressure steam is added
as a utility, which is named Steam @50PSI and has the Steam Fluid Class.



After the Create button is pressed, the new utility is displayed as shown below, where the
entries have already been made from the steam tables of Smith et al. (2001).




When complete, the OK button is pressed to return to the Develop Utility Specification
dialog box. Then, the Close button is pressed to return to the IPE Main window. Note
that utility files can be created for use on other design projects. For implementation
details, see the Aspen IPE User’s Guide.


CD-IPE-8
Other specifications can be changed in a manner similar to those described for the
utilities and design criteria. More information and definitions are provided in
the Aspen IPE User’s Guide (Defining the Project Basis → Process Design).

Mapping Process Simulation Units into Aspen IPE

Having completed the initial setup, the next step is to map the process simulation units
(that is, blocks, modules, or subroutines) into more descriptive models of process equipment
(e.g., mapping a HEATX simulation unit into a floating-head, shell-and-tube heat exchanger;
mapping a RADFRAC simulation unit into a tray tower, condenser, reflux accumulator, etc.) and
associated plant bulks, which include installation items, such as piping, instrumentation,
insulation, paint, etc. After Aspen IPE completes the mapping and reserves storage for the
installation items, equipment sizes are computed. Note that the mapping and equipment sizing
steps are accomplished in sequence, with sizes and costs of the installation items estimated
during the Equipment Costing step. To begin the mapping step in the IPE Main window, the
Map Simulator Items button on the toolbar is pressed to produce the Map dialog box:



For the depropanizer, all items are mapped and sized in sequence, since the Size
ICARUS Project Components button is checked. When this button is not checked, only
the mapping step is completed. Also, when there are multiple process units of a certain
type, it may be preferable to map each process unit independently. For example, if two
distillation towers differ in tray efficiency, it is necessary to map them separately and
change the tray efficiency under Design Criteria before each tower is mapped. In this
case, with just one tower, it is simplest to press the Map all Items button under Source.
Under Basis, the Default and Simulator Data button should be selected, as shown. After
pressing OK, the Project Component Map Preview dialog box is produced:

CD-IPE-9


For each Simulator Item (unit or block), the Current Map List shows all
corresponding equipment items in Aspen IPE. Observe that for the default configuration,
Standard-Total, five equipment items are included: TW-TRAYED (tower), HE FIXED T-S
(condenser), HT HORIZ-DRUM (reflux accumulator), CP CENTRIF (reflux pump), and
RB U-TUBE (reboiler). Note that the two C entries denote stream splitters. Note also that
to include a reboiler (bottoms) pump, a distillate pump, and two product heat exchangers,
the configuration is switched from Standard-Total to Full-Single. For this example, a
reboiler pump will be added, as discussed in the section on Adding Equipment.
Furthermore, each equipment item has a specific type assigned by Aspen IPE that can be
modified. To modify the equipment type, highlight the item to be modified. In this
example, the kettle reboiler with U-tubes is replaced by a kettle reboiler with a floating
head. To begin, the RB U-TUBE reboiler is deleted by highlighting it and pressing Delete
One Mapping:


CD-IPE-10


New Mapping is pressed and reb is highlighted on the screen that appears. Then, OK is
pressed.



Next, Heat Exchangers, heaters is highlighted on the ICARUS Project Component
Selection dialog box that appears, and OK is pressed.



Reboiler is chosen from the dialog box that appears, and finally a Kettle type reboiler
with floating head is selected as the last step of the replacement procedure.
CD-IPE-11

















After these steps are completed, the modified mapping should appear on the Project
Component Map Preview dialog box:




Other mappings can be altered in a similar fashion. For example, for the condenser, the
mapping is altered from a shell-and-tube heat exchanger with a fixed tube sheet to one
with a floating head. When the desired changes are completed, press OK to continue and
wait for the equipment mapping and sizing to be completed.

CD-IPE-12
At this point, the equipment items have been sized by Aspen IPE (because the
Size ICARUS Project Components button was checked in the Map dialog box), whose
calculations are based upon the simulator data, as well as the default values specified
earlier. As each equipment item is sized, it appears in the Aspen IPE Main window as a
list; that is, the List window. Note that the Project Explorer window displays the Process
View:



The blue boxes to the left of each item in the list indicate the Project Components.
The yellow arrows inside the boxes indicate that the equipment item was obtained from
the mapping of a process simulation unit, whose name appears after its box. Note that by
default Aspen IPE lists all of the equipment items in the Workbook Mode, as shown
above. The List tab at the bottom of the Main window denotes that the equipment items
are listed in the Workbook Mode. Also note that user-inputted equipment items, such as a
reboiler pump (not included in the above frame), are represented in the Workbook by blue
boxes without the yellow arrow. To add these equipment items, see the section Adding
Equipment. The OK in the Status column of the Workbook indicates that the minimum
required information for costing the equipment is available. When one or more items are
missing, a question mark appears instead, alerting the user to provide a specification(s) so
that the equipment-sizing step can proceed.

In addition, it is possible to view the IPE Process Flow Diagram. This is
accomplished using the View pulldown menu and clicking on Process Flow Diagram to
produce:

CD-IPE-13





Note that the unit icons and streams have been repositioned using “drag and drop”
facilities. It is also possible to view a list of the process streams utilized by Aspen IPE;
that is, a list of all streams and their physical properties in the Process Flow Diagram.
Using the View pulldown menu, click on Streams List to produce:


CD-IPE-14



Finally, the IPE Block Flow Diagram shows the simulation flowsheet. It is displayed
using the View pulldown menu and clicking on Block Flow Diagram to give:




Mapping Results. After Aspen IPE has mapped and sized the equipment items, it
is prudent to check the results, especially for major equipment items such as towers,
compressors, and chemical reactors. These items are usually very expensive, and
consequently, it is a good practice to estimate equipment sizes independently for
comparison with the Aspen IPE results. To view the Aspen IPE results for an equipment
item, double click on the item on the IPE Workbook window or on its icon in the Process
Flow Diagram. For example, the following component specification form, which
contains some of the sizing results, is obtained for the depropanizer tower.
CD-IPE-15


Observe that the depropanizer tower was designed by Aspen IPE to have a 5 ft
diameter and a 42 ft (tangent-to-tangent) height using sieve trays. Note that the number
of trays is the number of equilibrium stages (12 = 14 – 2, excluding the condenser and
reboiler) divided by the tray efficiency (0.8), which is 12/0.8 = 15. With a 2-ft tray
spacing, a 4-ft high disengagement region at the top and a 10-ft high sump at the bottom,
the nominal vessel tangent-to-tangent height is 2 × 14 + 4 + 10 = 42 ft, as shown by
Aspen IPE. Also, Aspen IPE calculated a design temperature and pressure in accordance
with the Design Criteria specifications, used the default shell material, A515 (which is
carbon steel for pressure vessels at intermediate and higher temperatures), and used the
default tray material, A285C (which is for carbon steel plates in pressure vessels that
have low and intermediate strength). Material codes, alloy types, and maximum service
temperatures are tabulated in the chapter on Materials Selection in the ICARUS Reference
Manual (press the Help button in Aspen IPE and follow the path Aspen Icarus Process
Evaluator 11.1 → Icarus Reference). Furthermore, the effect of material on size and cost
can be determined easily. In some cases, a high-strength alloy, that is more expensive per
pound, may have thinner walls and be less expensive than a low-strength material that is
less expensive per pound.

Changes can be made to any of the equipment sizes computed by Aspen IPE or to
the default values used by Aspen IPE. As changes are made, dependent results are
adjusted by Aspen IPE.

A more detailed report can be obtained in two ways. First, right click on the
equipment item in the Process Flow Diagram and select Item Report in the menu that
appears. Alternatively, right click on the equipment item in the Project View of the
CD-IPE-16
Project Explorer in the Main window (or in the List View) and select Item Report in the
menu that appears. These steps produce the Item Report, a portion of which is illustrated
here for the condenser:



Note that only a small portion of the Item Report is shown above. The raw
surface area, 9,652 ft
2
, is quite large because the log-mean temperature difference,
12.7°F, is relatively small. This is related to the condenser pressure which was set at 248
psia. At this pressure, the distillate enters the condenser at 125°F and leaves as a
saturated vapor at 115°F. Using cooling water heated from 90 to 120°F, the small log-
mean temperature difference is obtained. It might be preferable to increase the column
pressure to increase the log-mean temperature difference and reduce the condenser area.
However, at a higher pressure the separation would become somewhat more difficult,
resulting in more trays. Note that Aspen IPE can easily compare the capital costs at
various pressures. Note also that Aspen IPE used two floating-head, shell-and-tube heat
exchanger in parallel for condensing the overhead vapor. Each condenser has two tube
passes with a temperature correction factor [F
T
in Eq. (13.7)] of 0.635. The number of
tube and shell passes for each exchanger can be seen on the report produced by double
clicking on the condenser in the IPE Workbook window or on the condenser icon in the
Process Flow Diagram. It might be possible to improve the condenser design by re-
sizing the unit with different numbers of shell and tube passes to give a correction factor
close to unity.

CD-IPE-17
Standard Basis

Six standard basis profiles are available within Aspen IPE for estimating the
capital cost. These model the nature of the contractor to execute the project, depending
on the size of the project, as shown below. Three of the profiles are for projects to be
executed by an Owner company (0, 1, and 2), and the other three are for projects to be
executed by Engineering and Construction firms (3, 4, and 5). For the small
depropanizer project of this example, the LOCAL CONTRACTOR is appropriate.



To select a standard basis profile for a project, in the Project Basis view, right-click on
the Basis for Capital Costs. Click Select to choose the most appropriate profile.

The Basis for Capital Costs includes specifications for process controls, plant
location, currency, wage rates, units of measure, and contractor profiles. Default values
are provided for all entries, most of which need not be adjusted.

When modifying the Basis for Capital Costs, changes can be made to the General
Standard Basis Specifications or to the Construction Workforce and Indexing. To view
the General Standard Basis Specifications, the Project Basis tab is selected in the Project
Explorer. Double-click the General Specs entry under the Basis for Capital Costs
heading to produce the Standard Basis-IP dialog box:

CD-IPE-18


For the depropanizer column, most of the default values are acceptable. Because
a single distillation system would be installed normally on an existing plant site, using
utilities provided by the site, the Project Type would not be selected as Grass
Roots/Clear field. This Project Type would cause new items, already provided at the site,
to be included in the design and cost estimates. Typically, these include a new control
system and electrical substation components.

Under Project Type, click on the Value field to produce a pulldown menu that
displays the options:

Grass Roots/Clear field
Plant addition – adjacent to existing plant
Plant additions – inside existing plant
Plant addition – suppressed infrastructure
Plant modification/Revamp

While guidelines are not provided concerning the selection of Project Type, costs can be
computed for each option, if desired. Through examination of the results, the default
values and items included or omitted can be observed. When selecting Plant addition –
suppressed infrastructure, items involving the new control system, electrical switchgear,
and transformers, are not provided. These are not needed for the addition of the
depropanizer column to an existing process.

CD-IPE-19
Equipment Costing

Aspen IPE estimates the purchase and installed cost of each equipment item
individually or provides estimates for all of the equipment items (i.e., the entire project)
using a single command. For an individual unit, right click on the unit in the List View
and select Evaluate Item. Aspen IPE produces a detailed item report for the unit. For the
depropanizer tower, by scrolling about a third of the way down the report, the following
summary of the cost estimates appears:



Observe that the tower designed by Aspen IPE has a Purchased (Equipment and Setting)
Cost of $64,100 and an Installed Direct Cost of $192,600, which includes the cost of the
tower and setting it in place on its foundation (civil). At this point, the designer can
observe the effects of modifications in the design specifications on these costs for the
unit. Be aware that the Total Material and Manpower Cost is the cost of the equipment
item and the direct cost of installation materials and labor (directly related to the
equipment item). These include the piping and field instruments that bring the process
streams to and from the tower; the foundation to support the tower, structural steel (e.g.,
ladders and platforms attached to the tower); electrical lighting, heat tracing, cable, and
local components; insulation; piping; and fireproofing. It does not include: (1) the
fractional cost of buildings, pipe racks, the project control system or electrical
substations, fire control systems, chemical and storm sewers and drains, treatment
systems, fences, guard houses, etc.; (2) the work required to perform basic and detail
engineering, to procure all project components, and to manage the engineering process;
and (3) taxes, freight to the site, permits, royalties, etc.
CD-IPE-20

Consequently, the total material and manpower cost is not the total bare module
cost discussed in Section 16.3 of the textbook. The estimate reported by Aspen IPE does
not include contractor engineering costs, indirect costs, cost of pipe racks and intra-plant
piping, and the cost of sumps and sewers, which can be added to the project as additional
items. Furthermore, because the report focuses on an equipment item and its associated
installation items and costs, materials and manpower items not typically charged to the
tower (e.g., charges for instrument testing, pipe testing, and equipment grounding) are
excluded. These costs are accumulated for each area that contains project components
and are summed for the entire project, as discussed later in this section.

To have Aspen IPE estimate the capital costs of all the units at once (i.e., the
entire project), press the Evaluate Project button on the IPE Main window. The Evaluate
Project dialog box appears. The dialog box shows the default report file name,
CAP_REP.CCP. The contents of this report are viewed in the ICARUS Editor. If you
prefer a different name, e.g., DEC3 as shown below, enter it in the Report File field.



When finished with its evaluation, Aspen IPE displays a window that contains an
executive summary of its results. This window is not shown here. Note that when the
user presses the Tools pulldown menu, selects Options, and then View Spreadsheet in
Excel, Aspen IPE is activated to prepare several spreadsheets, including the Equipment
Summary, Utility Summary (available in Version 12.1), ProjSum, Executive Summary,
and Run Summary spreadsheets. For the details of these spreadsheets, see the Aspen
IPE User’s Guide (press the Help button and follow the path Aspen Icarus Process
Evaluator User’s Manual → Evaluating the Project → Reviewing Investment Analysis).

To view a detailed report of the capital costs, access the ICARUS Editor by
pressing the Capital Costs ($) button on the IPE Main window. On the Select Report
Type to View dialog box, mark the Evaluation Reports checkbox and press the OK button.
Note that when the Interactive Reports checkbox is pressed, the Aspen ICARUS Reporter
dialog box is produced. This permits the user to select individual items to be examined
rather than entire reports as discussed below.
CD-IPE-21



The ICARUS Editor displays the report in two adjacent windows, with the major
subject headings listed in the left-hand window. Most of this information, though
necessary for obtaining accurate cost estimates, is far too detailed for most estimates
during the conceptual design stage, and hence, is normally not printed by process
engineers, for whom these course notes are intended. Of greatest interest to process
engineers, is the information in the following two sections:

1. Equipment List
2. CONTRACTOR NO. 1 PRIME CONTRACTOR

which are accessed by double-clicking on these titles in the left-hand window. It is
recommended that just small portions of the report be printed. This is accomplished by
highlighting the desired section and pressing the Print button on the toolbar. It is often
preferable to print in landscape format.

When the appropriate specifications are made, Aspen IPE computes annual
operating costs, as well as a complete profitability analysis, the results of which appear in
this Investment Analysis spreadsheet. These notes discuss capital cost estimation only
because the spreadsheet, Profitability Analysis-1.0.xls, which is discussed in Section 17.8
of the textbook, is used to compute operating costs, working capital, and profitability
measures.

As shown below, the List of Equipment and Bulk Material by Area portion of the
report is displayed when the Equipment List is accessed. This provides the Purchased
(Equipment & Setting) and Installed Direct Costs (i.e., Total Material and Manpower
Cost or Total Direct Materials and Labor Cost) for each piece of equipment, e.g., the
reboiler as shown next. Note that the right-hand window below is displayed using a 7-
point font. This is achieved by pressing the Select Font button on the toolbar.
Furthermore, portions of the complete printed output are provided in Appendix III of
these notes.

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In summary, the equipment sizes, purchase costs, and total material and
manpower cost for the depropanizer system (without the reboiler pump) are as follows:


Simulation Unit

Equipment Item

Size

Purchase Cost
Total Material
and Manpower Cost

D1 Tower 5.0 ft diam.
42 ft height
64,100 192,600
Reflux pump 5 Hp 5,200 35,200
Reboiler 3,580 ft
2
52,600 115,000
Condenser 11,100 ft
2
5,550 ft
2
/shell
139,400 229,600
Reflux accumulator

2,350 gal 19,000 74,400
TOTAL $280,300 $646,800


The Contract Summary section of the Capital Estimate Report is displayed when
the CONTRACT NO. 1 PRIME CONTRACTOR is accessed. The entries shown below are
in a 6-point font and are totals for all of the equipment items (i.e., the entire project).
Note that selected portions of the complete printed output are provided in Appendix III of
these notes.

CD-IPE-23


Note that the entry for the purchased equipment, $289,200, from line 1, is
approximately the sum of the entries for the pieces of equipment provided above,
$280,300. The difference is due to the Misc. Item Allowance ($8,500) and the Warehouse
Spares ($370). These additional items are in Code of Accounts 105 and 107 and appear
in the Code of Accounts Summary section of the Capital Estimate Report (just below the
Contract Summary.)

The total direct material and manpower costs for construction of the plant are
$605,400 and $152,100, as shown in line 11. These sum to $757,500 and include items
that cannot be charged to the individual equipment items (e.g., charges for instrument
testing, pipe testing, and equipment grounding). Note that the installed costs of the
equipment items are displayed on the List View:

CD-IPE-24


The installed costs sum to $646,800; that is, $108,700 less than the total direct cost of
materials and manpower for installation of the plant, $757,500. This Installed Direct
Cost, C
DI
, is referred to in Chapter 16 of the textbook as the Total Direct Materials and
Labor Cost, C
DML
. Finally, the materials and manpower items that are not chargeable to
the individual equipment items are displayed in the Area Bulk Report within the Capital
Estimate Report:


A R E A B U L K R E P O R T


=================================================================================================================================
: : : : : M A N P O W E R : TOTAL :
: : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT :
:ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD:
=================================================================================================================================
AREA MISC CONCRETE ITEMS 638. 138 2341. 2979.

AREA PIPE TESTING 0. 192 4564. 4564.

GRADE UNPAVED AREA 7534. 127 2648. 10182.
Area length 50.000 FEET
Area width 50.000 FEET

AREA INSTRUMENT TESTING 0. 95 2124. 2124.

AREA INSTR. RUNS,TRAYS,JBOX. 3086. 60 1266. 4352.

AREA EQUIPMENT GROUNDING 185. 11 231. 416.

AREA PILED FOUNDATION 8807. 83 1407. 10214.
Number of piles 14

AREA ELECTRICAL TESTING 0. 16 344. 344.

AREA ROTATING EQP SPARE PARTS 370. 0 0. 370.



CD-IPE-25
These non-chargeable items add to $35,545. Together with the Other item on line 10 of
the Contract Summary, $56,300, and Code of Accounts item 105, for equipment
contingencies to allow for design changes, $8,500, these sum to approximately $100,300
(which is sufficiently close to $108,700, the difference reported above).

Returning to the Capital Estimate Report, material and manpower costs
associated with G and A (General and Administrative) Overheads, $18,200 and $4,600,
are obtained from line 13, and material and manpower charges associated with Contract
Fees, $21,900 and $16,500, from line 14. These sum to $61,200. The contractor
engineering and indirect costs are in row 15, BASE TOTAL, in the first column, under
DESIGN ENG’G AND PROCUREMENT K-USD, and in the fifth column, under
CONSTRUCTION INDIRECTS K-USD. These are:

Contractor Engineering Costs $383,700
Indirect Costs $365,700

Together with the fees for materials and manpower G and A Overheads and Contract
Fees, these are added to the total direct installed equipment costs, C
DI
, to give the IBL
Total Bare Module Cost, C
TBM
.

Finally, all of the Aspen IPE results can be reproduced using the DEC3 folder (on
the CD-ROM in the Aspen Eng. Suite folder) from within Aspen IPE.

Total Permanent Investment

The total permanent investment is computed by the spreadsheet, Profitability
Analysis-1.0.xls, discussed in Section 17.8 of the textbook. When using the Aspen IPE
option, the user enters:

Total Direct Materials and Labor Costs $757,500
Material and Labor G&A Overhead and Contractor Fees 61,200
Contractor Engineering Costs 383,700
Indirect Costs 365,700

Adding Equipment

Thus far, all of the equipment items have originated with the simulation units
from an ASPEN PLUS simulation. After the mappings have been completed, yellow
arrows are placed in the blue boxes associated with each equipment item in the Aspen
IPE Main window. Also, in the Process Flow Diagram, all of the streams are yellow,
with the exception of the IPE-generated utility streams, which are green. When it is
desirable to add a piece of equipment that is not in a simulation or has not been created
during the mapping of simulation units by Aspen IPE, the following steps are taken.
From the IPE Main window, press the Project View tab at the bottom of the left-hand
window (i.e., the Project Explorer window) to give:

CD-IPE-26


Then, highlight Main Project, right click, and press Add Area to produce the Area
Information dialog box in which an Area Name (e.g., New Item) is entered with its
dimensions. Here, a 50’x 50’ area is reserved and used to estimate piping lengths, etc.
This is adequate for most applications. Note that the original area for the plant, which
was named Miscellaneous Flowsheet Area by Aspen IPE, is also 50’ x 50’ by default.



Press OK and the new area, which is named New Item, appears on the Project View (left
window) of the IPE Main window.

CD-IPE-27


Next, highlight the New Item area, right click, and click on Add Project Component to
produce the ICARUS Project Component Selection dialog box. For the addition of a
reboiler pump, enter Reboiler Pump as the Project Component Name, highlight Process
equipment and press the OK button.



Continue through the appropriate menus until the desired equipment type is obtained,
which in this example is a centrifugal pump.

CD-IPE-28






CD-IPE-29



After the OK button is pressed, the pump specification form is displayed.



CD-IPE-30
Note that the specifications are incomplete because the Reboiler pump has not been
connected into the main process, which resides in the Miscellaneous Flowsheet Area, as
shown in the IPE Process Flow Diagram:




The Reboiler pump is positioned in the upper-left-hand corner of the Process Flow
Diagram in the New Item area, independent of the Miscellaneous Flowsheet Area.
Observe that the Reboiler pump appears in the New Item area on the Project View.

Before proceeding, after completing this example, it was brought to our attention
that reboiler pumps are used normally with vertical reboilers, not with kettle reboilers.
When appropriate to add a reboiler pump, or any other equipment item, to the mapping,
the procedures in this section should be followed.

To insert the Reboiler pump into the liquid stream from the sump, ICP-BE, press
the Edit Connectivity button and place the cursor over the Reboiler pump, after which the
cursor becomes a hand. Keeping the left-mouse button depressed, drag the Reboiler
pump over the ICP-BE stream. Release the mouse and click with the left-mouse button to
insert the Reboiler pump. After the streams are realigned, the Process Flow Diagram
appears as follows:

CD-IPE-31


Note that a new stream, which appears in white, has been created and named ICP-BE_2
by Aspen IPE.

Although the Reboiler pump has been inserted into the process, it remains in the
New Item area. To move it into the Miscellaneous Flowsheet area, in the Project View,
drag and drop the Reboiler pump from the New Item Area to the Miscellaneous Flowsheet
area. This results in:








CD-IPE-32
Next, right click on the Reboiler pump and select Size Item on the menu that
appears. After the pump is sized, double click on the pump icon to display the
component specification form:



Note that the design capacity of the Reboiler pump has been adjusted to 765.5 gpm,
which is 10 percent higher than the flow rate leaving the sump, a default specification in
the Design Criteria. At this point, a fluid head of 20 ft is entered, which should be
sufficient to convey the bottoms liquid to the reboiler. To obtain the variables for the
ICP-BE stream, double-click on it:


CD-IPE-33

Observe that 765.5 gpm is 10 percent higher than 695.9 gpm, which is equivalent to the
liquid mass flow rate, 160,645 lb/hr. When the effluent stream, ICP-BE_2, is clicked on,
the stream report does not display the stream properties because the stream has been
referenced to the ICP-BE stream.

This procedure is repeated to add other equipment items, which may be added to
the New Item area or to other new areas.

To estimate the installed cost of the Reboiler pump, either right click on Reboiler
pump in the Project View or on its icon in the Process Flow Diagram. Then, select
Evaluate Item. A brief report that contains the installed cost, $44,700, can be accessed by
highlighting Reboiler pump in the Project View and pressing the List tab to obtain the
Workbook. A complete report is obtained by re-evaluating the capital estimates for the
process. This is accomplished by pressing the Evaluate Project button and requesting
that all equipment items be re-evaluated. The detailed report appears in the Capital
Estimate Report in the List of Equipment and Bulk Material by Area section. It can be
accessed by selecting Equipment List under Miscellaneous Flowsheet in the left-hand
window:



Note that no equipment items remain in the New Item section of the report.

Having added the Reboiler pump, the total permament investment can be re-
estimated as discussed in the prior section. This discussion is not repeated here.

Finally, all of the Aspen IPE results can be reproduced using the DEC3RP folder
(on the CD-ROM in the Aspen Eng. Suite folder) from within Aspen IPE.
CD-IPE-34
Applying Alternative Utilities

When desired, the default utility applied by Aspen IPE can be altered interactively
for a particular equipment item, such as a condenser or reboiler, after it has been mapped.
For example, when the resulting surface area of a reboiler is too large due to a small log-
mean-temperature-difference, the steam utility can be replaced with steam at a higher
pressure to reduce the area, being careful to stay in the nucleate boiling region.

This is illustrated for the reboiler of the depropanizer as an example. For this
reboiler, Aspen IPE uses steam at 50 psi as the default utility. To change to higher-
pressure steam, say at 100 psi, the following steps are taken.

In the Process View or Process Flow Diagram, right click on the reboiler and
select Re-Size Item from the menu that appears. This produces the Interactive Sizing
dialog box, as shown below:




In the Item 1 column that contains the values, the items for Hot Inlet Stream and
Hot Outlet Stream are ICUST-IN and ICUST-EX, respectively, which correspond to the
default utility, in this case, steam at 50 psi. To change to steam at 100 psi, right click on
the appropriate cells and select Steam @ 100 PSI – IPE Utility from the pull-down menu
that appears. Next, delete the Final Surface Area, previously computed, since it must be
re-sized by Aspen IPE:

CD-IPE-35


When OK is pressed, the reboiler is re-sized.

After the reboiler is re-sized, right click on the reboiler again and select Item
Report from the pop-up menu. In the Sizing Data section, the new results for the reboiler
are displayed:



CD-IPE-36
Using steam at 100 psi, the surface area is 1,262 ft
2
, reduced from 3,580 ft
2
, while the
log-mean-temperature-difference is 72.7°F, increased from 25.7°F.

Finally, the capital cost of the entire process is re-evaluated since the cost of the
smaller reboiler is lower. This is accomplished by pressing the Evaluate Project button
on the toolbar and selecting Evaluate All Items. The results appear in the Capital
Estimate Report in the List of Equipment and Bulk Material by Area section. They are
accessed by selecting Equipment List under Miscellaneous Flowsheet in the left-hand
window:




These steps are repeated when it is desired to change the default utilities for other
equipment items in the process.

Furthermore, for most equipment items, other specifications can be adjusted using
interactive sizing. This can be accomplished for condensers, reboilers, flash drums,
reflux accumulators, storage vessels, pumps, and compressors. Note, however, that
interactive sizing is not possible for reactor vessels. For a complete listing of equipment
items that can be sized interactively, refer to the chapter on Sizing Project Components in
the Aspen IPE User’s Guide (Aspen Icarus Process Evaluator User’s Manual → Sizing
Project Components).


CD-IPE-37
MONOCHLOROBENZENE SEPARATION PROCESS


In this section, equipment sizes and costs are estimated for the
monochlorobenzene (MCB) separation process, which is discussed in Section 4.4 of the
textbook and in the multimedia portion of the CD-ROM (ASPEN → Principles of
Flowsheet Simulation → Interpretation of Input and Output → Sample Problem) that
contains these course notes. Beginning with the file, MCB.bkp, which is available on the
CD-ROM, additional mixture properties are added and the DISTL subroutine, used to
model the D1 distillation column, is replaced with the RADFRAC subroutine. The reflux
ratio computed using the RADFRAC subroutine is 3.35, as compared with 4.29
computed using the approximate DISTL subroutine. Also, the stream flow rates differ
slightly (< 1%). Both of the files, MCB-IPE.bkp and MCB-IPE.rep, are on the CD-
ROM.


Initial Setup

After sending the file, MCB-IPE.rep to Aspen Icarus, the user is ready to use
Aspen IPE. Aspen IPE is opened automatically and the Create New Project dialog box
appears. After the Project Name MCB is entered, the Inch-Pound (IP) unit set is selected
in the Project Properties dialog box.

After OK is pressed, Aspen IPE loads the information associated with each
process model in ASPEN PLUS. When completed, the IPE Main window appears:


CD-IPE-38
The MCB separation process has two types of columns, an absorber and a
distillation column, each having a distinct tray efficiency. Absorber efficiencies are
normally low, at roughly 20%, while efficiencies for distillation columns are
considerably higher, in this case at about 60%. This difference must be taken into
account when proceeding with Aspen IPE.

Because Aspen IPE allows only one specification for the tray efficiency, it is
necessary to map and size each of the columns separately, with the appropriate efficiency
specified in the Design Criteria prior to each mapping. Note that in the Design Criteria-
IP dialog box, the parameters for trayed towers, including the tray efficiency are near the
bottom of the list:



To size the absorber column (A1-block), a tray efficiency of 0.2 (or 20%) is entered. No
other changes to the default values are necessary.

Changes to the Utility Specifications, such as the cooling water temperatures, are
made at this point.







CD-IPE-39
Mapping Process Simulation Units to Aspen IPE

To map a single process unit, right-click on the selected item on the Aspen IPE
Main window, and choose Map. In the Map dialog box, select Map Selected Item(s), and
use Default and Simulator Data as the basis:



Press OK to produce the Project Component Map Preview dialog box (not shown here).
Since the Current Map List does not need to be altered, select OK to map the A1 unit.
When the mapping and equipment sizing has been completed, the A1 unit has been
added to the list of Project Components, as shown below:


CD-IPE-40
Before mapping the distillation unit, D1, the tray efficiency is changed to 0.6 in
the Design Criteria. Subsequently, each of the remaining equipment items is mapped
and sized, one at a time, as described above. Note that the unit H1 is too small to be
mapped as a floating-head heat exchanger. Consequently, it is necessary to change the
default equipment type to a Double-pipe heat exchanger, which is more appropriate for
this application. To change the mapping, select HE FLOAT-HEAD in the Current Map
List and press the Delete One Mapping button:



Then, select New Mapping, Heat exchangers, and then heaters to give:


CD-IPE-41
From the next dialog box, select Heat exchanger and finally choose the Double-pipe heat
exchanger:


After these steps are completed, the Current Map List is modified in the Project
Component Map Preview dialog box:



Note that when the sizing calculations are being carried out for the flash vessel,
F1, two Message dialog boxes appear. The first indicates that the diameter is calculated
to be 2.007 ft, but that the user-specified minimum value of 3 ft is used instead. The
second indicates that the L/D ratio is 1.67, rather than 3.0 from the Design Criteria.
CD-IPE-42
Also, for the heat exchanger, H1, a 1-degree difference between the inlet and outlet
temperatures of the hot stream is assumed. The unit M1 is a mixing junction between
two pipes and the unit S1 is a simple pipeline splitter. Size and cost estimates are not
needed for these units. The unit T1 represents a treater, which is not being considered at
this point in the design of the MCB separation process.

Aspen IPE maps the mixer M1 and splitter S1 as Quoted Items with zero cost.
The default mapping for the treater T1 is a VT CYLINDER, with size and cost estimates
computed. This default mapping is replaced with a Quoted Item having zero cost. To
accomplish this, delete the mapping for T1. In the Project View, right click on T1, then
on Map. On the Map dialog box, click on OK to produce the Project Component Map
Preview dialog box. Delete the VT CYLINDER mapping and click on New Mapping, to
produce the ICARUS Project Component Selection dialog box. Click on Project
Components, select Quoted equipment, and click OK. This places the unit T1 into the
List View with a C, to indicate that it is a Quoted Item having zero cost.

After all of the equipment items have been mapped and sized successfully, the
IPE Main window is displayed:



Note that the three C entries represent Quoted Items having zero cost. The associated
Process Flow Diagram is:

CD-IPE-43




When the mapping and sizing are completed it is prudent to check the equipment
sizes computed by Aspen IPE, especially for major equipment items such as towers, large
heat exchangers, compressors, and chemical reactors. For the MCB separation process,
the two towers are of particular interest. To view the Aspen IPE result for an equipment
item, double click on the item of interest in the IPE Main window. For the absorber, this
produces the following results:

CD-IPE-44


Note that the column is designed to have a 1.5 ft diameter, a 42 ft (tangent-to-tangent)
height, and 15 trays, in accordance with the specifications in Figure 4.23 of the textbook
(Seider et al., 2004). Because of the small diameter, a packed column would be
preferred, but is not considered here.


CD-IPE-45
Similarly, the distillation column is designed to have a 3 ft diameter, a 72 ft (tangent-to
tangent) height, and 30 trays, also in accordance with Figure 4.23 in the textbook (Seider
et al., 2004).

Standard Basis

As for the depropanizer discussed earlier, the MCB separation process can be
viewed as representing an addition to an existing plant. Consequently, the standard basis
profile is selected to be LOCAL CONTRACTOR and the Project Type is selected as Plant
addition – suppressed infrastructure.

Equipment Costing

Aspen IPE estimates purchase and installed costs for the equipment units
individually or for the entire project using a single command. For the MCB separation
process, it is convenient to have Aspen IPE estimate the costs for the entire project at
once. After pressing the Evaluate Project button on the IPE Main window, the Evaluate
Project dialog box appears:



As discussed for the depropanizer, Aspen IPE prepares the Capital Estimate Report,
MCB.ccp, which contains detailed listings of the items to be procured to install the
equipment (classified in the areas of piping, instrumentation, electrical, structural steel,
and insulation), estimates of the man-hours required for installation, estimates of the
costs, and an installation schedule. Estimates for contractor engineering and indirect
costs are listed as well.

The ICARUS Editor displays the report in two adjacent windows, with a listing of
the major subject headings listed in the left-hand window. Most of this information,
though necessary for obtaining accurate cost estimates, is far too detailed for most
estimates made in the conceptual design stage, and hence, is normally not printed by
process engineers, for whom these notes are intended. Of greatest interest to process
engineers, is the information in the following two sections:
CD-IPE-46
1. Equipment List
2. CONTRACTOR NO. 1 PRIME CONTRACTOR

which are accessed by double-clicking on these titles in the left-hand window. It is
recommended that just small portions of the report be printed. This is accomplished by
highlighting the desired section and pressing the Print button on the toolbar. It is often
preferable to print in landscape format.

As shown below, for the absorber, the List of Equipment and Bulk Material by
Area portion of the report is displayed when the Equipment List is accessed. This
provides the Purchased (Equipment & Setting) and Installed Direct Costs (i.e., Total
Material and Manpower Cost or Total Direct Materials and Labor Cost) for each piece
of equipment. Note that the right-hand window below is displayed using a 7-point font.
This is achieved by pressing the Select Font button on the toolbar. Furthermore, portions
of the complete printed output are provided in Appendix IV of these notes.




In summary, the equipment sizes, purchase costs, and total material and
manpower cost for the MCB separation process are tabulated below:
CD-IPE-47


Simulation Unit

Equipment Item

Size

Purchase Cost
Total Material
and Manpower Cost

P1

Pump 1.12 kW 2,800 19,800
A1 Tower 1.5 ft diam.
42 ft height

16,000 110,000
D1 Tower 3.0 ft diam.
72 ft height
53,500 179,200
Reflux pump 2.24 kW 3,300 24,000
Reboiler 921 ft
2
23,500 71,800
Condenser 155 ft
2
12,200 50,600
Reflux accumulator

238 gal 7,500 51,300
H1

Heat exchanger 161 ft
2
16,100 58,100
H2

Heat exchanger 196 ft
2
12,400 52,900
F1

Flash vessel 264 gal 7,100

54,200
TOTAL $154,400 $671,900

The Contract Summary section of the Capital Estimate Report is displayed when
the CONTRACT NO. 1 PRIME CONTRACTOR is accessed. The entries shown below are
in a 6-point font and are totals for all of the equipment items in the project. Note that
portions of the complete printed output are provided in Appendix IV of these notes.

CD-IPE-48



Note that the entry for the purchased equipment, $159,500, from line 1, is
approximately the sum of the entries for the pieces of equipment provided above,
$154,400. The difference is due to the Misc. Item Allowance ($4,700) and the Warehouse
Spares ($430). These additional items are in Code of Accounts 105 and 107 and appear
in the Code of Accounts Summary section of the Capital Estimate Report (just below the
Contract Summary.)

The total direct material and manpower costs for construction of the plant are
$536,200 and $249,500, as shown in row 11. These sum to $785,700 and include items
that cannot be charged to the individual equipment items (e.g., charges for instrument
testing, pipe testing, and equipment grounding). Note that the installed costs of the
equipment items are displayed on the List View:

CD-IPE-49


These installed costs sum to $671,900; that is, $113,800 less than the total direct cost of
materials and manpower for installation of the plant, $785,700. This Installed Direct
Cost, C
DI
, is referred to in Chapter 16 of the textbook as the Total Direct Materials and
Labor Cost, C
DML
. Finally, the materials and manpower items that cannot be charged to
the individual equipment items are displayed in the Area Bulk Report within the Capital
Estimate Report:


A R E A B U L K R E P O R T


=================================================================================================================================
: : : : : M A N P O W E R : TOTAL :
: : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT :
:ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD:
=================================================================================================================================
AREA MISC CONCRETE ITEMS 916. 198 3358. 4274.

AREA PIPE TESTING 0. 328 7771. 7771.

GRADE UNPAVED AREA 7534. 127 2648. 10182.
Area length 50.000 FEET
Area width 50.000 FEET

AREA INSTRUMENT TESTING 0. 179 4012. 4012.

AREA INSTR. RUNS,TRAYS,JBOX. 3471. 68 1450. 4921.

AREA EQUIPMENT GROUNDING 369. 23 462. 831.

AREA PILED FOUNDATION 13840. 131 2211. 16051.
Number of piles 22

AREA ELECTRICAL TESTING 0. 20 430. 430.

AREA ROTATING EQP SPARE PARTS 430. 0 0. 430.



CD-IPE-50
These additional costs sum to approximately $48,902. Together with the Other item on
line 10 of the Contract Summary, $49,900, and Code of Accounts item 105, for
equipment contingencies to allow for design changes, $4,700, these sum to approximately
$103,500 (which, for profitability analysis in the conceptual design stage, is sufficiently
close to $113,800, the difference reported above).

Returning to the Contract Summary, material and manpower costs associated with
G and A (General and Administrative) Overheads, $16,100 and $7,500, are obtained
from line 13, and material and manpower charges associated with Contract Fees, $20,400
and $25,700, from line 14. These sum to $69,700. The contractor engineering and
indirect costs are in row 15, BASE TOTAL, in the first column, under DESIGN ENG’G
AND PROCUREMENT K-USD, and in the fifth COLUMN, under CONSTRUCTION
INDIRECTS K-USD. These are:

Contractor Engineering Costs $558,300
Indirect Costs $482,600

Together with the fees for materials and manpower G and A Overheads and Contract
Fees, these are added to the total direct installed equipment costs, C
DI
, to give the IBL
Total Bare Module Cost, C
TBM
.

Finally, all of the Aspen IPE results can be reproduced using the MCB folder (on
the CD-ROM in the Aspen Eng. Suite folder) from within Aspen IPE.


Total Permanent Investment

The total permanent investment is computed by the spreadsheet, Profitability
Analysis-1.0.xls, discussed in Section 17.8 of the textbook. When using the Aspen IPE
option, the user enters:

Total Direct Materials and Labor Costs $785,700
Material and Labor G&A Overhead and Contractor Fees 69,700
Contractor Engineering Costs 558,300
Indirect Costs 482,600





CD-IPE-51
ASPEN IPE FOLDERS AND FILES


When a new project is created within Aspen IPE, a folder having the project name
(e.g., DEC3) is created in the Program Files|Aspen Tech\ Aspen Icarus 11.1\
Data\Archive_IPE folder. As work with Aspen IPE proceeds, various files are created
and stored in this project folder; for example, the DEC3.ccp file, which contains the
Capital Estimate Report for the depropanizer.

When returning to work with Aspen IPE, using the File pulldown menu, open the
folder having the appropriate project name. This produces the Open an IPE Project
dialog box. Select the Project Name and press the OK button. This produces the
Process/Project View window; that is, the IPE Main window.

When working in the Process/Project View window, to examine any portion of
the Capital Estimate Report (which is automatically stored in your Projects folder after it
has been generated), press the Capital costs button ($) on the toolbar. This produces the
Select Report Type To View dialog box. Select one of the two options to have Aspen IPE
display the capital cost report as an HTML file or in the ICARUS Editor. Then, press
OK. Note that when more than one report file exists, the Select Capital Cost Report File
dialog box is produced, from which the appropriate report file is selected. This produces
the Capital Estimate Report.

It is also possible to examine a .ccp file using the NETSCAPE or EXPLORER
browser by double-clicking on the appropriate file, which has a browser icon, in its
associated project folder. Each item in the contents that is produced provides a link to its
section of the Capital Estimate Report.


REFERENCES


Lewin, D. R., W. D. Seider, J. D. Seader, E. Dassau, J. Golbert, D. N. Goldberg, M. J. Fucci, and
R. B. Nathanson, CD-ROM, Using Process Simulators in Chemical Engineering: A Multimedia
Guide for the Core Curriculum, Version 2.0, Wiley, 2003.

Seider, W. D., J. D. Seader, and D. R. Lewin, Process Design Principles: Synthesis, Analysis,
and Evaluation, Wiley, 1999.

Seider, W. D., J. D. Seader, and D. R. Lewin, Product and Process Design Principles: Synthesis,
Analysis, and Evaluation, Second Edition, Wiley, 2004.

Smith, J. M., H. C. Van Ness, and M. M. Abbott, Introduction to Chemical Engineering
Thermodynamics, Sixth Edition, McGraw-Hill, 2001.
CD-IPE-52














APPENDIX I

DEPROPANIZER






ASPEN PLUS Report
CD-IPE-53
ASPEN PLUS Flowsheet - simulation results can be reproduced using the file
RADFRAC.bkp on the CD-ROM

FEED
BOT
DIS
D1


ASPEN PLUS Program

IN-UNITS ENG
DEF-STREAMS CONVEN ALL
DATABANKS PURE93 / AQUEOUS / SOLIDS / INORGANIC / &
NOASPENPCD
PROP-SOURCES PURE93 / AQUEOUS / SOLIDS / INORGANIC
COMPONENTS
C2H6 C2H6 /
C3H8 C3H8 /
C4H10-1 C4H10-1 /
C5H12-1 C5H12-1 /
C6H14-1 C6H14-1
FLOWSHEET
BLOCK D1 IN=FEED OUT=DIS BOT
PROPERTIES RK-SOAVE
USER-PROPS DRUSR2 1 2 3
PROP-DATA RKSKIJ-1
IN-UNITS ENG
PROP-LIST RKSKIJ
BPVAL C2H6 C3H8 -2.2000000E-3
BPVAL C2H6 C4H10-1 6.70000000E-3
BPVAL C2H6 C5H12-1 5.60000000E-3
BPVAL C2H6 C6H14-1 -.0156000000
BPVAL C3H8 C4H10-1 0.0
BPVAL C3H8 C5H12-1 .0233000000
BPVAL C3H8 C6H14-1 -2.2000000E-3
BPVAL C3H8 C2H6 -2.2000000E-3
BPVAL C4H10-1 C3H8 0.0
BPVAL C4H10-1 C5H12-1 .0204000000
BPVAL C4H10-1 C6H14-1 -.0111000000
BPVAL C4H10-1 C2H6 6.70000000E-3
BPVAL C5H12-1 C3H8 .0233000000
BPVAL C5H12-1 C4H10-1 .0204000000
BPVAL C5H12-1 C2H6 5.60000000E-3
STREAM FEED
SUBSTREAM MIXED TEMP=225 PRES=250
MOLE-FLOW C2H6 30 / C3H8 200 / C4H10-1 370 / C5H12-1 &
350 / C6H14-1 50
CD-IPE-54
BLOCK D1 RADFRAC
PARAM NSTAGE=14
COL-CONFIG CONDENSER=PARTIAL-V
FEEDS FEED 7
PRODUCTS BOT 14 L / DIS 1 V
P-SPEC 1 248
COL-SPECS D:F=.226 DP-COL=4 MOLE-RR=6.06
SPEC 1 MOLE-FLOW 191 PHASE=V STAGE=1 COMPS=C3H8
VARY 1 MOLE-RR 3 9
STREAM-REPOR MOLEFLOW

Stream Variables

BOT DIS FEED
------------

STREAM ID BOT DIS FEED
FROM : D1 D1 ----
TO : ---- ---- D1

SUBSTREAM: MIXED
PHASE: LIQUID VAPOR MIXED
COMPONENTS: LBMOL/HR
C2H6 3.5935-03 29.9964 30.0000
C3H8 9.0000 191.0000 200.0000
C4H10-1 365.0282 4.9718 370.0000
C5H12-1 349.9682 3.1817-02 350.0000
C6H14-1 50.0000 5.6799-06 50.0000
TOTAL FLOW:
LBMOL/HR 774.0000 226.0000 1000.0000
LB/HR 5.1173+04 9615.6886 6.0789+04
CUFT/HR 1757.1876 4228.0955 7798.4407
STATE VARIABLES:
TEMP F 260.8017 115.0748 225.0000
PRES PSI 252.0000 248.0000 250.0000
VFRAC 0.0 1.0000 0.2831
LFRAC 1.0000 0.0 0.7169
SFRAC 0.0 0.0 0.0
ENTHALPY:
BTU/LBMOL -6.1678+04 -4.4212+04 -5.7856+04
BTU/LB -932.8868 -1039.1178 -951.7619
BTU/HR -4.7738+07 -9.9918+06 -5.7856+07
ENTROPY:
BTU/LBMOL-R -105.9894 -66.3064 -96.4772
BTU/LB-R -1.6031 -1.5584 -1.5871
DENSITY:
LBMOL/CUFT 0.4405 5.3452-02 0.1282
LB/CUFT 29.1220 2.2742 7.7950
AVG MW 66.1148 42.5473 60.7885

Process Unit Output

BLOCK: D1 MODEL: RADFRAC
-------------------------------
INLETS - FEED STAGE 7
OUTLETS - DIS STAGE 1
BOT STAGE 14
PROPERTY OPTION SET: RK-SOAVE STANDARD RKS EQUATION OF STATE


CD-IPE-55
*** MASS AND ENERGY BALANCE ***
IN OUT RELATIVE DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR) 1000.00 1000.00 -0.113687E-15
MASS(LB/HR ) 60788.5 60788.5 -0.263325E-14
ENTHALPY(BTU/HR ) -0.578562E+08 -0.577303E+08 -0.217615E-02

**** INPUT DATA ****
NUMBER OF STAGES 14
ALGORITHM OPTION STANDARD
ABSORBER OPTION NO
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.000100000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.000100000

**** COL-SPECS ****
MOLAR VAPOR DIST / TOTAL DIST 1.00000
MOLAR REFLUX RATIO 6.06000
DISTILLATE TO FEED RATIO 0.22600

**** RESULTS ****

*** COMPONENT SPLIT FRACTIONS ***

OUTLET STREAMS
--------------
DIS BOT
COMPONENT:
C2H6 .99988 .11978E-03
C3H8 .95500 .45000E-01
C4H10-1 .13437E-01 .98656
C5H12-1 .90906E-04 .99991
C6H14-1 .11360E-06 1.0000

*** SUMMARY OF KEY RESULTS ***
TOP STAGE TEMPERATURE F 115.075
BOTTOM STAGE TEMPERATURE F 260.802
TOP STAGE LIQUID FLOW LBMOL/HR 2,006.29
BOTTOM STAGE LIQUID FLOW LBMOL/HR 774.000
TOP STAGE VAPOR FLOW LBMOL/HR 226.000
BOTTOM STAGE VAPOR FLOW LBMOL/HR 1,655.79
MOLAR REFLUX RATIO 8.87737
MOLAR BOILUP RATIO 2.13927
CONDENSER DUTY (W/O SUBCOOL) BTU/HR -0.115854+08
REBOILER DUTY BTU/HR 0.117112+08

**** PROFILES ****

**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW.


CD-IPE-56
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR

1 115.07 248.00 -50783. -44212. -.11585+08
2 125.28 248.31 -51581. -44928.
3 136.57 248.62 -52692. -45507.
5 170.39 249.23 -55843. -47215.
6 190.65 249.54 -57560. -48372.
7 209.38 249.85 -59032. -49521.
8 217.28 250.15 -59293. -50212.
11 235.62 251.08 -59970. -51780.
12 241.42 251.38 -60295. -52207.
13 248.99 251.69 -60816. -52686.
14 260.80 252.00 -61678. -53340. .11711+08

STAGE FLOW RATE FEED RATE PRODUCT RATE
LBMOL/HR LBMOL/HR LBMOL/HR
LIQUID VAPOR LIQUID VAPOR MIXED LIQUID VAPOR
1 2006. 226.0 226.0000
2 1955. 2232.
3 1864. 2181.
5 1677. 1989.
6 1600. 1903. 283.3846
7 2334. 1542. 716.6153
8 2372. 1560.
11 2453. 1661.
12 2454. 1679.
13 2430. 1680.
14 774.0 1656. 774.0000

**** MASS FLOW PROFILES ****

STAGE FLOW RATE FEED RATE PRODUCT RATE
LB/HR LB/HR LB/HR
LIQUID VAPOR LIQUID VAPOR MIXED LIQUID VAPOR
1 0.8848E+05 9616. 9615.6886
2 0.8897E+05 0.9810E+05
3 0.8829E+05 0.9859E+05
5 0.8877E+05 0.9759E+05
6 0.8996E+05 0.9838E+05 .15740+05
7 0.1382E+06 0.8384E+05 .45048+05
8 0.1425E+06 0.8706E+05
11 0.1523E+06 0.9845E+05
12 0.1544E+06 0.1012E+06
13 0.1558E+06 0.1032E+06
14 0.5117E+05 0.1047E+06 .51173+05

**** MOLE-X-PROFILE ****
STAGE C2H6 C3H8 C4H10-1 C5H12-1 C6H14-1
1 0.57253E-01 0.88576 0.56268E-01 0.71663E-03 0.36784E-06
2 0.26424E-01 0.84979 0.12085 0.29316E-02 0.41399E-05
3 0.14274E-01 0.74938 0.22597 0.10340E-01 0.39505E-04
5 0.75715E-02 0.43455 0.48005 0.75943E-01 0.18785E-02
6 0.66748E-02 0.29446 0.53451 0.15547 0.88845E-02
7 0.40998E-02 0.20293 0.52813 0.23898 0.25864E-01
8 0.16827E-02 0.15681 0.56948 0.24609 0.25942E-01
11 0.10271E-03 0.56172E-01 0.63050 0.28601 0.27216E-01
12 0.38791E-04 0.36411E-01 0.61454 0.31913 0.29880E-01
13 0.14072E-04 0.21933E-01 0.56594 0.37366 0.38453E-01
14 0.46428E-05 0.11628E-01 0.47161 0.45216 0.64599E-01


CD-IPE-57
**** MOLE-Y-PROFILE ****
STAGE C2H6 C3H8 C4H10-1 C5H12-1 C6H14-1
1 0.13273 0.84513 0.21999E-01 0.14078E-03 0.25132E-07
2 0.64894E-01 0.88165 0.52798E-01 0.65833E-03 0.33314E-06
3 0.37438E-01 0.84931 0.11061 0.26424E-02 0.37136E-05
5 0.23512E-01 0.62700 0.32189 0.27326E-01 0.27279E-03
6 0.22436E-01 0.48332 0.42565 0.66941E-01 0.16554E-02
7 0.14670E-01 0.37152 0.48748 0.12031 0.60259E-02
8 0.61322E-02 0.29788 0.55617 0.13318 0.66399E-02
11 0.38744E-03 0.11540 0.69553 0.18013 0.85532E-02
12 0.14792E-03 0.76709E-01 0.70375 0.20941 0.99812E-02
13 0.54526E-04 0.47830E-01 0.68040 0.25783 0.13882E-01
14 0.18479E-04 0.26750E-01 0.61003 0.33697 0.26231E-01






CD-IPE-58















APPENDIX II

DESIGN CRITERIA SPECIFICATIONS












CD-IPE-59

CD-IPE-60



































CD-IPE-61














APPENDIX III


ASPEN IPE CAPITAL ESTIMATE REPORT
FOR THE DEPROPANIZER


Selected portions of the

List of Equipment and Bulk Material by Area

and the

Contract Summary
CD-IPE-62
Depropanizer Without the Reboiler Pump (see DEC3 Folder)


C O N T R A C T S U M M A R Y

PRIME CONTRACTOR (CONTRACT NO. 1)


=================================================================================================================================
: : : DESIGN : C O N S T R U C T I O N : MISC. AND : : PERCENT :
:NO.: I T E M : ENG'G AND :-------------------------------------------------: ALL *: AMOUNT : OF :
: : :PROCUREMENT: MATERIAL : MANHOURS : MANPOWER : INDIRECTS :SUBCONTRACTS : : CONTRACT :
: : : K-USD : K-USD : : K-USD : K-USD : K-USD : K-USD : TOTAL :
=================================================================================================================================

1 PURCHASED EQUIPMENT - 289.2 - - - - 289.2 18.4

2 EQUIPMENT SETTING - - 265. 5.6 - - 5.6 0.4

3 PIPING - 93.2 2599. 59.7 - - 152.9 9.8

4 CIVIL - 15.4 710. 12.0 - - 27.5 1.8

5 STEEL - 7.0 218. 3.9 - - 10.9 0.7

6 INSTRUMENTATION - 89.6 1455. 33.3 - - 122.9 7.8

7 ELECTRICAL - 17.5 380. 7.9 - - 25.5 1.6

8 INSULATION - 34.7 1242. 24.3 - - 58.9 3.8

9 PAINT - 2.5 343. 5.4 - - 7.9 0.5

10 OTHER 350.7 56.3 - 0.0 321.3 - 728.3 46.5
-------------------- ------- --------- --------- -------- -------- -------- ------------ -----
11 SUBTOTAL, DIRECT 350.7 605.4 7210. 152.1 321.3 - 1429.6 91.2

12 SUBCONTRACTS - - - - 0.0 0.0 0.0

13 G AND A OVERHEADS 0.0 18.2 4.6 9.6 0.0 32.4 2.1

14 CONTRACT FEE 33.0 21.8 16.5 34.8 0.0 106.0 6.8
-------------------- ------- --------- -------- -------- -------- ------------ -----
15 BASE TOTAL 383.7 645.4 173.2 365.7 0.0 1568.0 100.0

16 ESCALATION 0.0 0.0 0.0 0.0 0.0 0.0 0.0
17 CONTINGENCIES 69.1 116.2 31.2 65.8 0.0 282.2 18.0
18 SPECIAL CHARGES - - - - 0.0 0.0 0.0
-------------------- ------- --------- -------- -------- -------- ------------ -----
19 TOTAL 452.7 761.6 204.3 431.6 0.0 1850.2 118.0

=================================================================================================================================
* NO SUBCONTRACTS



















CD-IPE-63

C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
HT - 3 HORIZ DRUM D1-cond acc Shell material A 515 19000
CODE OF ACCOUNT: 114 Liquid volume 2350.23 GALLONS
TAG NO.: D1-cond acc Vessel diameter 5.000 FEET
Vessel tangent to tangent length 16.00 FEET
Design temperature 250.00 DEG F
Design gauge pressure 258.30 PSIG
Application CONT
Base material thickness 0.625 INCHES
Total weight 9600 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 19000. 1.0000 : 593. 0.0312 29 : 0.031 :
PIPING : 14291. 0.7522 : 8952. 0.4712 391 : 0.626 :
CIVIL : 1587. 0.0835 : 2031. 0.1069 120 : 1.280 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 21954. 1.1555 : 3823. 0.2012 164 : 0.174 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
PAINT : 801. 0.0421 : 1399. 0.0736 89 : 1.748 :
-------------------------------------------------------------------------
SUBTOTAL : 57633. 3.0333 : 16799. 0.8842 793 : 0.291 :
TOTAL MATERIAL AND MANPOWER COST =USD 74400. INST'L COST/PE RATIO = 3.916

==========================================================================================================================






===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
CP - 4 CENTRIF D1-reflux pump Casing material CS 5200
CODE OF ACCOUNT: 161 Liquid flow rate 401.99 GPM
TAG NO.: D1-reflux pu Fluid head 50.00 FEET
Design temperature 250.00 DEG F
Speed 3600.00 RPM
Driver power 5.000 HP
Design gauge pressure 258.30 PSIG
Driver type MOTOR
Seal type SNGL
Total weight 530 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 5200. 1.0000 : 383. 0.0737 19 : 0.074 :
PIPING : 9746. 1.8743 : 4684. 0.9007 204 : 0.481 :
CIVIL : 170. 0.0327 : 523. 0.1005 31 : 3.077 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 6262. 1.2042 : 1747. 0.3359 76 : 0.279 :
ELECTRICAL : 596. 0.1147 : 898. 0.1727 42 : 1.506 :
INSULATION : 2557. 0.4918 : 1928. 0.3708 98 : 0.754 :
PAINT : 144. 0.0276 : 350. 0.0673 22 : 2.437 :
-------------------------------------------------------------------------
SUBTOTAL : 24675. 4.7452 : 10512. 2.0216 492 : 0.426 :
TOTAL MATERIAL AND MANPOWER COST =USD 35200. INST'L COST/PE RATIO = 6.769

==========================================================================================================================
Equipment mapped from 'D1'.
QUOTE
EQP- 5 D1-overhead split Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: D1-overhead


==========================================================================================================================













CD-IPE-64
C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
QUOTE
EQP- 6 D1-bottoms split Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: D1-bottoms s


==========================================================================================================================
Equipment mapped from 'D1'.
RB - 7 KETTLE D1-reb Tube material A 214 52600
CODE OF ACCOUNT: 262 Heat transfer area 3579.55 SF
TAG NO.: D1-reb Shell material A285C
TEMA type BKT
Shell design gauge pressure 262.00 PSIG
Shell design temperature 310.80 DEG F
Shell diameter 54.00 INCHES
Shell length 25.00 FEET
Tube port diameter 36.00 INCHES
Tube design gauge pressure 60.30 PSIG
Tube design temperature 331.00 DEG F
Tube outside diameter 1.000 INCHES
Tube length extended 20.00 FEET
Total weight 34300 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 52600. 1.0000 : 1152. 0.0219 52 : 0.022 :
PIPING : 13678. 0.2600 : 11432. 0.2173 495 : 0.836 :
CIVIL : 1436. 0.0273 : 1881. 0.0358 111 : 1.310 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 13153. 0.2501 : 4707. 0.0895 205 : 0.358 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 8253. 0.1569 : 5679. 0.1080 291 : 0.688 :
PAINT : 292. 0.0056 : 736. 0.0140 47 : 2.519 :
-------------------------------------------------------------------------
SUBTOTAL : 89412. 1.6999 : 25587. 0.4864 1201 : 0.286 :
TOTAL MATERIAL AND MANPOWER COST =USD 115000. INST'L COST/PE RATIO = 2.186

==========================================================================================================================






===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
TW - 10 TRAYED D1-tower Shell material A 515 64100
CODE OF ACCOUNT: 111 Number of trays 15
TAG NO.: D1-tower Vessel diameter 5.000 FEET
Vessel tangent to tangent height 42.00 FEET
Design temperature 310.80 DEG F
Design gauge pressure 262.30 PSIG
Application DISTIL
Tray type SIEVE
Tray spacing 24.00 INCHES
Tray material A285C
Tray thickness 0.188 INCHES
Base material thickness 0.625 INCHES
Total weight 31500 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 64100. 1.0000 : 1877. 0.0293 92 : 0.029 :
PIPING : 20847. 0.3252 : 14937. 0.2330 651 : 0.716 :
CIVIL : 1572. 0.0245 : 2153. 0.0336 127 : 1.370 :
STRUCTURAL STEEL : 7021. 0.1095 : 3924. 0.0612 218 : 0.559 :
INSTRUMENTATION : 36315. 0.5665 : 16719. 0.2608 729 : 0.460 :
ELECTRICAL : 1678. 0.0262 : 909. 0.0142 45 : 0.542 :
INSULATION : 10270. 0.1602 : 8250. 0.1287 423 : 0.803 :
PAINT : 643. 0.0100 : 1376. 0.0215 88 : 2.141 :
-------------------------------------------------------------------------
SUBTOTAL : 142445. 2.2222 : 50145. 0.7823 2373 : 0.352 :
TOTAL MATERIAL AND MANPOWER COST =USD 192600. INST'L COST/PE RATIO = 3.005

==========================================================================================================================






CD-IPE-65
C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
HE - 13 FLOAT HEAD D1-cond Tube material A 214 139400
CODE OF ACCOUNT: 261 Number of shells 2
TAG NO.: D1-cond Area per shell 5551.00 SF
Shell material A285C
TEMA type BES
Shell design gauge pressure 258.61 PSIG
Shell design temperature 250.00 DEG F
Shell diameter 46.00 INCHES
Shell length 23.00 FEET
Tube design gauge pressure 60.30 PSIG
Tube design temperature 250.00 DEG F
Tube outside diameter 1.000 INCHES
Tube length extended 20.00 FEET
Total weight 89200 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 139400. 1.0000 : 1601. 0.0115 73 : 0.011 :
PIPING : 34630. 0.2484 : 15175. 0.1089 665 : 0.438 :
CIVIL : 1237. 0.0089 : 1693. 0.0121 100 : 1.369 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 8835. 0.0634 : 2876. 0.0206 125 : 0.326 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 13585. 0.0975 : 8413. 0.0604 430 : 0.619 :
PAINT : 636. 0.0046 : 1512. 0.0108 96 : 2.377 :
-------------------------------------------------------------------------
SUBTOTAL : 198323. 1.4227 : 31270. 0.2243 1489 : 0.158 :
TOTAL MATERIAL AND MANPOWER COST =USD 229600. INST'L COST/PE RATIO = 1.647

==========================================================================================================================
























































CD-IPE-66

A R E A B U L K R E P O R T


=================================================================================================================================
: : : : : M A N P O W E R : TOTAL :
: : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT :
:ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD:
=================================================================================================================================
AREA MISC CONCRETE ITEMS 638. 138 2341. 2979.

AREA PIPE TESTING 0. 192 4564. 4564.

GRADE UNPAVED AREA 7534. 127 2648. 10182.
Area length 50.000 FEET
Area width 50.000 FEET

AREA INSTRUMENT TESTING 0. 95 2124. 2124.

AREA INSTR. RUNS,TRAYS,JBOX. 3086. 60 1266. 4352.

AREA EQUIPMENT GROUNDING 185. 11 231. 416.

AREA PILED FOUNDATION 8807. 83 1407. 10214.
Number of piles 14

AREA ELECTRICAL TESTING 0. 16 344. 344.

AREA ROTATING EQP SPARE PARTS 370. 0 0. 370.

CD-IPE-67
Depropanizer With the Reboiler Pump (see DEC3RP Folder)


C O N T R A C T S U M M A R Y

PRIME CONTRACTOR (CONTRACT NO. 1)


=================================================================================================================================
: : : DESIGN : C O N S T R U C T I O N : MISC. AND : : PERCENT :
:NO.: I T E M : ENG'G AND :-------------------------------------------------: ALL *: AMOUNT : OF :
: : :PROCUREMENT: MATERIAL : MANHOURS : MANPOWER : INDIRECTS :SUBCONTRACTS : : CONTRACT :
: : : K-USD : K-USD : : K-USD : K-USD : K-USD : K-USD : TOTAL :
=================================================================================================================================

1 PURCHASED EQUIPMENT - 296.9 - - - - 296.9 17.9

2 EQUIPMENT SETTING - - 287. 6.1 - - 6.1 0.4

3 PIPING - 107.8 2865. 65.9 - - 173.7 10.5

4 CIVIL - 15.6 744. 12.6 - - 28.2 1.7

5 STEEL - 7.0 218. 3.9 - - 10.9 0.7

6 INSTRUMENTATION - 95.9 1536. 35.1 - - 131.0 7.9

7 ELECTRICAL - 18.2 426. 8.9 - - 27.1 1.6

8 INSULATION - 38.5 1355. 26.5 - - 65.0 3.9

9 PAINT - 2.7 374. 5.9 - - 8.6 0.5

10 OTHER 371.0 59.7 - 0.0 333.4 - 764.1 46.1
-------------------- ------- --------- --------- -------- -------- -------- ------------ -----
11 SUBTOTAL, DIRECT 371.0 642.3 7805. 164.9 333.4 - 1511.6 91.3

12 SUBCONTRACTS - - - - 0.0 0.0 0.0

13 G AND A OVERHEADS 0.0 19.3 4.9 10.0 0.0 34.2 2.1

14 CONTRACT FEE 34.5 22.5 17.7 35.7 0.0 110.4 6.7
-------------------- ------- --------- -------- -------- -------- ------------ -----
15 BASE TOTAL 405.5 684.0 187.5 379.2 0.0 1656.2 100.0

16 ESCALATION 0.0 0.0 0.0 0.0 0.0 0.0 0.0
17 CONTINGENCIES 73.0 123.1 33.7 68.3 0.0 298.1 18.0
18 SPECIAL CHARGES - - - - 0.0 0.0 0.0
-------------------- ------- --------- -------- -------- -------- ------------ -----
19 TOTAL 478.5 807.2 221.2 447.4 0.0 1954.3 118.0

=================================================================================================================================
* NO SUBCONTRACTS



















CD-IPE-68


C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
CP - 8 CENTRIF reboiler pump Casing material CS 7000
CODE OF ACCOUNT: 161 Liquid flow rate 756.52 GPM
Fluid head 20.00 FEET
Design temperature 298.99 DEG F
Speed 3600.00 RPM
Driver power 3.000 HP
Design gauge pressure 262.00 PSIG
Driver type MOTOR
Seal type SNGL
Total weight 630 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 7000. 1.0000 : 463. 0.0662 23 : 0.066 :
PIPING : 14619. 2.0884 : 5699. 0.8141 248 : 0.390 :
CIVIL : 160. 0.0229 : 504. 0.0720 30 : 3.146 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 6277. 0.8967 : 1747. 0.2495 76 : 0.278 :
ELECTRICAL : 596. 0.0852 : 898. 0.1283 42 : 1.506 :
INSULATION : 3826. 0.5465 : 2219. 0.3170 113 : 0.580 :
PAINT : 201. 0.0287 : 487. 0.0695 31 : 2.420 :
-------------------------------------------------------------------------
SUBTOTAL : 32680. 4.6685 : 12016. 1.7166 563 : 0.368 :
TOTAL MATERIAL AND MANPOWER COST =USD 44700. INST'L COST/PE RATIO = 6.386

==========================================================================================================================





























CD-IPE-69


A R E A B U L K R E P O R T


=================================================================================================================================
: : : : : M A N P O W E R : TOTAL :
: : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT :
:ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD:
=================================================================================================================================
AREA MISC CONCRETE ITEMS 657. 142 2413. 3070.

AREA PIPE TESTING 0. 211 5002. 5002.

GRADE UNPAVED AREA 7534. 127 2648. 10182.
Area length 50.000 FEET
Area width 50.000 FEET

AREA INSTRUMENT TESTING 0. 100 2242. 2242.

AREA INSTR. RUNS,TRAYS,JBOX. 3086. 60 1266. 4352.

AREA EQUIPMENT GROUNDING 222. 14 277. 499.

AREA PILED FOUNDATION 8807. 83 1407. 10214.
Number of piles 14

AREA ELECTRICAL TESTING 0. 17 376. 376.

AREA ROTATING EQP SPARE PARTS 860. 0 0. 860.































CD-IPE-70















APPENDIX IV


ASPEN IPE CAPITAL ESTIMATE REPORT
FOR THE MONOCHLOROBENZENE
SEPARATION PROCESS


Selected portions of the

List of Equipment and Bulk Material by Area

and the

Contract Summary

















CD-IPE-71

C O N T R A C T S U M M A R Y

PRIME CONTRACTOR (CONTRACT NO. 1)


=================================================================================================================================
: : : DESIGN : C O N S T R U C T I O N : MISC. AND : : PERCENT :
:NO.: I T E M : ENG'G AND :-------------------------------------------------: ALL *: AMOUNT : OF :
: : :PROCUREMENT: MATERIAL : MANHOURS : MANPOWER : INDIRECTS :SUBCONTRACTS : : CONTRACT :
: : : K-USD : K-USD : : K-USD : K-USD : K-USD : K-USD : TOTAL :
=================================================================================================================================

1 PURCHASED EQUIPMENT - 159.5 - - - - 159.5 8.4

2 EQUIPMENT SETTING - - 390. 8.3 - - 8.3 0.4

3 PIPING - 76.9 4404. 101.6 - - 178.6 9.4

4 CIVIL - 23.1 1086. 18.4 - - 41.5 2.2

5 STEEL - 12.6 333. 6.0 - - 18.6 1.0

6 INSTRUMENTATION - 147.7 2704. 61.9 - - 209.6 11.1

7 ELECTRICAL - 20.0 485. 10.1 - - 30.1 1.6

8 INSULATION - 44.3 1924. 37.7 - - 82.0 4.3

9 PAINT - 2.3 346. 5.4 - - 7.7 0.4

10 OTHER 513.1 49.9 - 0.0 425.9 - 988.9 52.1
-------------------- ------- --------- --------- -------- -------- -------- ------------ -----
11 SUBTOTAL, DIRECT 513.1 536.2 11672. 249.5 425.9 - 1724.8 91.0

12 SUBCONTRACTS - - - - 0.0 0.0 0.0

13 G AND A OVERHEADS 0.0 16.1 7.5 12.8 0.0 36.4 1.9

14 CONTRACT FEE 45.2 20.4 25.7 43.9 0.0 135.2 7.1
-------------------- ------- --------- -------- -------- -------- ------------ -----
15 BASE TOTAL 558.3 572.8 282.7 482.6 0.0 1896.3 100.0

16 ESCALATION 0.0 0.0 0.0 0.0 0.0 0.0 0.0
17 CONTINGENCIES 100.5 103.1 50.9 86.9 0.0 341.3 18.0
18 SPECIAL CHARGES - - - - 0.0 0.0 0.0
-------------------- ------- --------- -------- -------- -------- ------------ -----
19 TOTAL 658.7 675.9 333.6 569.4 0.0 2237.6 118.0

=================================================================================================================================
* NO SUBCONTRACTS





















CD-IPE-72


C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'A1'.
TW - 2 TRAYED A1-tower Shell material A 515 16000
CODE OF ACCOUNT: 111 Number of trays 15
TAG NO.: A1-tower Vessel diameter 1.500 FEET
Vessel tangent to tangent height 42.00 FEET
Design temperature 320.00 DEG F
Design gauge pressure 60.30 PSIG
Application DISTIL
Tray type SIEVE
Tray spacing 24.00 INCHES
Tray material A285C
Tray thickness 0.188 INCHES
Base material thickness 0.500 INCHES
Total weight 6400 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 16000. 1.0000 : 512. 0.0320 25 : 0.032 :
PIPING : 8486. 0.5304 : 14966. 0.9354 647 : 1.764 :
CIVIL : 909. 0.0568 : 1434. 0.0896 84 : 1.578 :
STRUCTURAL STEEL : 4590. 0.2869 : 2162. 0.1351 120 : 0.471 :
INSTRUMENTATION : 31542. 1.9714 : 16719. 1.0449 729 : 0.530 :
ELECTRICAL : 1152. 0.0720 : 696. 0.0435 34 : 0.604 :
INSULATION : 4921. 0.3075 : 4701. 0.2938 240 : 0.955 :
PAINT : 380. 0.0238 : 860. 0.0538 55 : 2.264 :
-------------------------------------------------------------------------
SUBTOTAL : 67980. 4.2488 : 42051. 2.6282 1934 : 0.619 :
TOTAL MATERIAL AND MANPOWER COST =USD 110000. INST'L COST/PE RATIO = 6.875

=========================================================================================================================






===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
TW - 3 TRAYED D1-tower Shell material A 515 53500
CODE OF ACCOUNT: 111 Number of trays 30
TAG NO.: D1-tower Vessel diameter 3.000 FEET
Vessel tangent to tangent height 72.00 FEET
Design temperature 353.02 DEG F
Design gauge pressure 35.30 PSIG
Application DISTIL
Tray type SIEVE
Tray spacing 24.00 INCHES
Tray material A285C
Tray thickness 0.188 INCHES
Average wall thickness 0.417 INCHES
Total weight 21400 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 53500. 1.0000 : 1727. 0.0323 84 : 0.032 :
PIPING : 13675. 0.2556 : 17933. 0.3352 778 : 1.311 :
CIVIL : 1136. 0.0212 : 1685. 0.0315 99 : 1.484 :
STRUCTURAL STEEL : 7974. 0.1491 : 3845. 0.0719 213 : 0.482 :
INSTRUMENTATION : 35223. 0.6584 : 16909. 0.3161 737 : 0.480 :
ELECTRICAL : 2230. 0.0417 : 1193. 0.0223 59 : 0.535 :
INSULATION : 11094. 0.2074 : 9098. 0.1701 466 : 0.820 :
PAINT : 620. 0.0116 : 1350. 0.0252 86 : 2.178 :
-------------------------------------------------------------------------
SUBTOTAL : 125452. 2.3449 : 53740. 1.0045 2522 : 0.428 :
TOTAL MATERIAL AND MANPOWER COST =USD 179200. INST'L COST/PE RATIO = 3.350

==========================================================================================================================











CD-IPE-73


C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
HE - 4 FIXED T S D1-cond Tube material A 214 12200
CODE OF ACCOUNT: 261 Heat transfer area 154.71 SF
TAG NO.: D1-cond Shell material A285C
TEMA type BEM
Shell design gauge pressure 35.30 PSIG
Shell design temperature 255.39 DEG F
Shell diameter 8.000 INCHES
Shell length 20.00 FEET
Tube design gauge pressure 60.30 PSIG
Tube design temperature 255.39 DEG F
Tube outside diameter 1.000 INCHES
Tube length extended 20.00 FEET
Total weight 1800 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 12200. 1.0000 : 841. 0.0689 38 : 0.069 :
PIPING : 9609. 0.7876 : 8169. 0.6696 358 : 0.850 :
CIVIL : 669. 0.0549 : 1120. 0.0918 66 : 1.673 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 7741. 0.6345 : 2859. 0.2344 125 : 0.369 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 3692. 0.3026 : 2988. 0.2449 152 : 0.809 :
PAINT : 213. 0.0175 : 516. 0.0423 33 : 2.419 :
-------------------------------------------------------------------------
SUBTOTAL : 34124. 2.7971 : 16492. 1.3518 772 : 0.483 :
TOTAL MATERIAL AND MANPOWER COST =USD 50600. INST'L COST/PE RATIO = 4.148

=========================================================================================================================






==========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
HT - 5 HORIZ DRUM D1-cond acc Shell material A 515 7500
CODE OF ACCOUNT: 114 Liquid volume 237.96 GALLONS
TAG NO.: D1-cond acc Vessel diameter 3.000 FEET
Vessel tangent to tangent length 4.500 FEET
Design temperature 254.98 DEG F
Design gauge pressure 35.30 PSIG
Application CONT
Base material thickness 0.313 INCHES
Total weight 1500 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 7500. 1.0000 : 511. 0.0681 25 : 0.068 :
PIPING : 5991. 0.7988 : 8621. 1.1495 373 : 1.439 :
CIVIL : 995. 0.1326 : 1453. 0.1937 86 : 1.461 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 16896. 2.2527 : 3624. 0.4832 156 : 0.215 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 2474. 0.3298 : 2678. 0.3571 136 : 1.083 :
PAINT : 142. 0.0189 : 376. 0.0501 24 : 2.642 :
-------------------------------------------------------------------------
SUBTOTAL : 33997. 4.5329 : 17263. 2.3017 800 : 0.508 :
TOTAL MATERIAL AND MANPOWER COST =USD 51300. INST'L COST/PE RATIO = 6.840

==========================================================================================================================

















CD-IPE-74


C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
CP - 6 CENTRIF D1-reflux pump Casing material CS 3300
CODE OF ACCOUNT: 161 Liquid flow rate 37.44 GPM
TAG NO.: D1-reflux pu Fluid head 70.00 FEET
Design temperature 254.98 DEG F
Speed 3600.00 RPM
Driver power 1.000 HP
Design gauge pressure 35.30 PSIG
Driver type MOTOR
Seal type SNGL
Total weight 200 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 3300. 1.0000 : 205. 0.0621 10 : 0.062 :
PIPING : 3202. 0.9704 : 4783. 1.4493 206 : 1.494 :
CIVIL : 141. 0.0429 : 468. 0.1417 27 : 3.306 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 4916. 1.4896 : 1747. 0.5293 76 : 0.355 :
ELECTRICAL : 596. 0.1807 : 898. 0.2721 42 : 1.506 :
INSULATION : 1685. 0.5106 : 1734. 0.5256 88 : 1.029 :
PAINT : 79. 0.0241 : 218. 0.0661 14 : 2.746 :
-------------------------------------------------------------------------
SUBTOTAL : 13920. 4.2181 : 10052. 3.0462 463 : 0.722 :
TOTAL MATERIAL AND MANPOWER COST =USD 24000. INST'L COST/PE RATIO = 7.273

==========================================================================================================================
Equipment mapped from 'D1'.
QUOTE
EQP- 7 D1-overhead split Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: D1-overhead


==========================================================================================================================






==========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'D1'.
QUOTE
EQP- 8 D1-bottoms split Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: D1-bottoms s


==========================================================================================================================
Equipment mapped from 'D1'.
RB - 9 U TUBE D1-reb Tube material A 214 23500
CODE OF ACCOUNT: 262 Heat transfer area 921.20 SF
TAG NO.: D1-reb Shell material A285C
TEMA type BKU
Shell design gauge pressure 35.30 PSIG
Shell design temperature 353.02 DEG F
Shell diameter 39.00 INCHES
Shell length 13.00 FEET
Tube port diameter 26.00 INCHES
Tube design gauge pressure 110.30 PSIG
Tube design temperature 377.80 DEG F
Tube outside diameter 1.000 INCHES
Tube length extended 20.00 FEET
Total weight 9100 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 23500. 1.0000 : 713. 0.0303 32 : 0.030 :
PIPING : 8327. 0.3543 : 9585. 0.4079 416 : 1.151 :
CIVIL : 1067. 0.0454 : 1526. 0.0649 90 : 1.431 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 12322. 0.5243 : 4641. 0.1975 203 : 0.377 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 5213. 0.2218 : 4266. 0.1815 218 : 0.818 :
PAINT : 189. 0.0081 : 480. 0.0204 31 : 2.536 :
-------------------------------------------------------------------------
SUBTOTAL : 50618. 2.1540 : 21210. 0.9026 990 : 0.419 :
TOTAL MATERIAL AND MANPOWER COST =USD 71800. INST'L COST/PE RATIO = 3.055

CD-IPE-75
==========================================================================================================================

C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'F1'.
VT - 10 CYLINDER F1 Shell material A 515 7100
CODE OF ACCOUNT: 113 Liquid volume 264.40 GALLONS
TAG NO.: F1 Vessel diameter 3.000 FEET
Vessel tangent to tangent height 5.000 FEET
Design temperature 320.00 DEG F
Design gauge pressure 35.30 PSIG
Application CONT
Base material thickness 0.313 INCHES
Total weight 1400 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 7100. 1.0000 : 512. 0.0721 25 : 0.072 :
PIPING : 7383. 1.0398 : 8809. 1.2406 381 : 1.193 :
CIVIL : 659. 0.0929 : 1103. 0.1554 65 : 1.673 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 17931. 2.5255 : 3739. 0.5266 161 : 0.209 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 3291. 0.4635 : 3060. 0.4309 156 : 0.930 :
PAINT : 172. 0.0242 : 448. 0.0631 29 : 2.605 :
-------------------------------------------------------------------------
SUBTOTAL : 36536. 5.1459 : 17670. 2.4887 817 : 0.484 :
TOTAL MATERIAL AND MANPOWER COST =USD 54200. INST'L COST/PE RATIO = 7.634

==========================================================================================================================






===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'H1'.
HE - 11 JACKETED H1 Material CS 16100
CODE OF ACCOUNT: 263 Heat transfer area 160.11 SF
TAG NO.: H1 Tube length 20.00 FEET
Number of tubes per shell 1
Design gauge pressure 60.30 PSIG
Temperature 331.00 DEG F
Number of sections 8
Total weight 7280 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 16100. 1.0000 : 2195. 0.1363 100 : 0.136 :
PIPING : 9192. 0.5709 : 8144. 0.5059 357 : 0.886 :
CIVIL : 1937. 0.1203 : 2415. 0.1500 143 : 1.247 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 5647. 0.3507 : 1635. 0.1016 69 : 0.290 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 5778. 0.3589 : 4314. 0.2680 220 : 0.747 :
PAINT : 213. 0.0132 : 516. 0.0320 33 : 2.419 :
-------------------------------------------------------------------------
SUBTOTAL : 38867. 2.4141 : 19219. 1.1937 922 : 0.494 :
TOTAL MATERIAL AND MANPOWER COST =USD 58100. INST'L COST/PE RATIO = 3.609

==========================================================================================================================






















CD-IPE-76



C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'H2'.
HE - 12 FLOAT HEAD H2 Tube material A 214 12400
CODE OF ACCOUNT: 261 Heat transfer area 195.80 SF
TAG NO.: H2 Shell material A285C
TEMA type BES
Shell design gauge pressure 35.30 PSIG
Shell design temperature 353.02 DEG F
Shell diameter 10.00 INCHES
Shell length 22.00 FEET
Tube design gauge pressure 60.30 PSIG
Tube design temperature 353.02 DEG F
Tube outside diameter 1.000 INCHES
Tube length extended 20.00 FEET
Total weight 2500 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 12400. 1.0000 : 874. 0.0705 40 : 0.070 :
PIPING : 9626. 0.7763 : 8205. 0.6617 360 : 0.852 :
CIVIL : 679. 0.0547 : 1132. 0.0913 67 : 1.669 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 7742. 0.6243 : 2868. 0.2313 125 : 0.370 :
ELECTRICAL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSULATION : 5130. 0.4137 : 3490. 0.2814 177 : 0.680 :
PAINT : 215. 0.0173 : 519. 0.0418 33 : 2.417 :
-------------------------------------------------------------------------
SUBTOTAL : 35791. 2.8863 : 17087. 1.3780 802 : 0.477 :
TOTAL MATERIAL AND MANPOWER COST =USD 52900. INST'L COST/PE RATIO = 4.266

==========================================================================================================================






==========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'M1'.
QUOTE
EQP- 14 M1 Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: M1


==========================================================================================================================
Equipment mapped from 'S1'.
QUOTE
EQP- 15 S1 Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: S1


==========================================================================================================================
Equipment mapped from 'P1'.
CP - 18 CENTRIF P1 Casing material CS 2800
CODE OF ACCOUNT: 161 Liquid flow rate 22.73 GPM
TAG NO.: P1 Fluid head 62.10 FEET
Design temperature 250.00 DEG F
Speed 3600.00 RPM
Driver power 1.500 HP
Fluid viscosity 0.583 CPOISE
Design gauge pressure 60.30 PSIG
Driver type MOTOR
Seal type SNGL
Total weight 210 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 2800. 1.0000 : 205. 0.0732 10 : 0.073 :
PIPING : 1441. 0.5146 : 4641. 1.6576 200 : 3.221 :
CIVIL : 148. 0.0529 : 481. 0.1717 28 : 3.246 :
STRUCTURAL STEEL : 0. 0.0000 : 0. 0.0000 0 : 0.000 :
INSTRUMENTATION : 4228. 1.5102 : 1747. 0.6239 76 : 0.413 :
ELECTRICAL : 596. 0.2129 : 898. 0.3207 42 : 1.506 :
INSULATION : 999. 0.3569 : 1391. 0.4967 71 : 1.392 :
PAINT : 48. 0.0171 : 139. 0.0495 9 : 2.903 :
-------------------------------------------------------------------------
SUBTOTAL : 10261. 3.6645 : 9501. 3.3933 436 : 0.926 :
TOTAL MATERIAL AND MANPOWER COST =USD 19800. INST'L COST/PE RATIO = 7.071
CD-IPE-77

==========================================================================================================================


C O M P O N E N T L I S T

===========================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A --------------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
===========================================================================================================================
Equipment mapped from 'T1'.
QUOTE
EQP- 19 T1 Number of identical items 1 0
CODE OF ACCOUNT: 100
TAG NO.: T1


==========================================================================================================================












































































CD-IPE-78




A R E A B U L K R E P O R T


=================================================================================================================================
: : : : : M A N P O W E R : TOTAL :
: : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT :
:ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD:
=================================================================================================================================
AREA MISC CONCRETE ITEMS 916. 198 3358. 4274.

AREA PIPE TESTING 0. 328 7771. 7771.

GRADE UNPAVED AREA 7534. 127 2648. 10182.
Area length 50.000 FEET
Area width 50.000 FEET

AREA INSTRUMENT TESTING 0. 179 4012. 4012.

AREA INSTR. RUNS,TRAYS,JBOX. 3471. 68 1450. 4921.

AREA EQUIPMENT GROUNDING 369. 23 462. 831.

AREA PILED FOUNDATION 13840. 131 2211. 16051.
Number of piles 22

AREA ELECTRICAL TESTING 0. 20 430. 430.

AREA ROTATING EQP SPARE PARTS 430. 0 0. 430.


CD-A-II-1
DESIGN PROBLEM STATEMENTS

A-II.0 CONTENTS AND INTRODUCTION
Petrochemicals Problem No.
Batch Di (3-pentyl) Malate Process A-II.1.1
Acetaldehyde from Acetic Acid A-II.1.2
Ethylene by Oxidative Dehydrogenation of Ethane A-II.1.3
Butadiene to n-Butyraldehyde and n-Butanol A-II.1.4
Methacrylic Acid to Methylmethacrylate A-II.1.5
Coproduction of Ethylene and Acetic Acid from Ethane A-II.1.6
Methylmethacrylate from Propyne A-II.1.7
Mixed-C
4
Byproduct Upgrade A-II.1.8
Hydrogen Peroxide Manufacture A-II.1.9
Di-tertiary-butyl-peroxide Manufacture A-II.1.10
Vinyl Acetate Process A-II.1.11
PM Acetate Manufacture A-II.1.12
Propoxylated Ethylenediamine A-II.1.13
Petroleum Products
Fuel Additives for Cleaner Emissions A-II.2.1
CD-A-II-2

Gas Manufacture
Nitrogen Rejection Unit (from natural gas) A-II.3.1
Ultra-pure Nitrogen Generator A-II.3.2
Nitrogen Production A-II.3.3
Krypton and Xenon from Air A-II.3.4
Ultra-High-Purity Oxygen A-II.3.5
Foods
Monosodium Glutamate A-II.4.1
Polysaccharides from Microalgae A-II.4.2
Alitame Sweetener A-II.4.3
Pharamaceuticals
Generic Recombinant Human Tissue Plasminogen Activator (tPA) A-II.5.1
Penicillin Manufacture A-II.5.2
Novobiocin Manufacture A-II.5.3
Polymers
Polyvinyl Acetate Production for Polyvinyl Alcohol Plant A-II.6.1
Butadiene to Styrene A-II.6.2
Biodegradable PHBV Copolymer A-II.6.3
Xantham Biopolymer A-II.6.4
Rapamycin-Coated Stents for Johnson & Johnson A-II.6.5
Environmental – Air Quality
R134a Refrigerant A-II.7.1
Biocatalytic Desulfurization of Diesel Oil A-II.7.2
CD-A-II-3
Sulfur Recovery Using Oxygen-Enriched Air A-II.7.3
California Smog Control A-II.7.4
Zero Emissions A-II.7.5
Volatile Organic Compound Abatement A-II.7.6
Recovery and Purification of HFC by Distillation A-II.7.7
Carbon Dioxide Fixation by Microalgae for Mitigating the Greenhouse
Effect

A-II.7.8
Hydrogen Generation for Reformulated Gasoline A-II.7.9
Environmental – Water Treatment
Effluent Remediation from Wafer Fabrication A-II.8.1
Recovery of Germanium from Optical Fiber Manufacturing Effluents A-II.8.2
Solvent Waste Recovery A-II.8.3
Environmental – Soil Treatment
Phytoremediation of Lead-Contaminated Sites A-II.9.1
Soil Remediation and Reclamation A-II.9.2
Environmental – Miscellaneous
Fuel Processor for 5 KW PEM Fuel Cell Unit A-II.10.1
Combined Cycle Power Generation A-II.10.2
Production of Low-Sulfur Diesel Fuel A-II.10.3
Waste Fuel Upgrading to Acetone and Isopropanol A-II.10.4
Conversion of Cheese Whey (Solid Waste) to Lactic Acid A-II.10.5
Ethanol from Corn Syrup A-II.10.6

CD-A-II-4
This appendix contains the problem statements for 50 design projects, each prepared for design
teams of three students at the University of Pennsylvania by chemical engineers in the local
chemical industry. At Penn, each team selects its design project during the first lecture course in
the fall, and spends the spring semester completing the design. In the spring, each group meets
regularly with its faculty advisor and industrial consultants, including the individual who provided
the problem statement, to report on its progress and gain advice.

The problem statements in the file, Design Problem Statements.pdf, on the CD-ROM are in their
original forms, as they were presented to the student design teams on the date indicated. Some
provide relatively little information, whereas others are fairly detailed concerning the specific
problems that need to be solved to complete the design. The reader should recognize that, in nearly
every case, as the design team proceeded to assess the primitive problem statement and carry out a
literature search, the specific problems it formulated were somewhat different than stated herein.
Still, these problem statements should be useful to students and faculty in several respects. For
students, they should help to show the broad spectrum of design problems that chemical engineers
have been tackling in recent years. For the faculty, they should provide a basis for similar design
projects to be created for their courses.

In formulating design problem statements, the industrial consultants strive to create process
opportunities that lead to designs that are timely, challenging, and offer a reasonable likelihood that
the final design will be attractive economically. Every effort is made to formulate problems that
can be tackled by chemical engineering seniors without unduly gross assumptions and for which
good sources of data exist for the reaction kinetics and thermophysical and transport properties. In
this respect, this was accomplished in each of the problems included herein; furthermore,
successful designs were completed by a student design team for most of these problems.

As seen in the contents, the projects have been assigned to one of the following areas, in some
cases arbitrarily: Petrochemicals, Petroleum Products, Gas Manufacture, Foods, Pharmaceuticals,
Polymers, and Environmental.

CD-A-II-5
Credit is given to each formulator on his problem statement. In addition, the names of the
contributors are listed below with many thanks, as their contributions in preparing these design
problems have been crucial to the success of the design course.

Rakesh Agrawal Air Products and Chemicals
E. Robert Becker Environex, Wayne, PA
David D. Brengel Air Products and Chemicals
Robert M. Busche Bio-en-gene-er Associates, Wilmington, DE
Leonard A. Fabiano CDI Corporation (formerly ARCO Chemical and Lyondell)
Brian E. Farrell Air Products and Chemicals
Mike Herron Air Products and Chemicals
F. Miles Julian DuPont
Ralph N. Miller DuPont
Robert Nedwick Pennsylvania State University (formerly ARCO Chemical and
Lyondell)
Frank Petrocelli Air Products and Chemicals
Mark R. Pillarella Air Products and Chemicals
William B. Retallick Consultant, West Chester, PA
Matthew J. Quale Mobil Technology Company
David G.R. Short University of Delaware (formerly DuPont)
Peter Staffeld Exxon/Mobil
Albert Stella General Electric (formerly AlliedSignal)
Bjorn D. Tyreus DuPont
Kamesh G. Venugopal Air Products and Chemicals
Bruce Vrana DuPont
Andrew Wang Air Products and Chemicals
Steve Webb Air Products and Chemicals
John Wismer Atochem North America
Jianguo Xu Air Products and Chemicals

CD-A-II-6
A-II.1 PETROCHEMICALS


A-II.1.1 Batch Di (3-pentyl) Malate Process
(Frank Petrocelli and Andrew Wang, Air Products and Chemicals, January 2002)

Your company, a small specialty chemicals manufacturing operation, is considering producing
di(3-pentyl) malate for the additives market. Your marketing team has projected the following
sales estimates for this product:

Anticipated Sales (in thousands of pounds)

1 2 3 4 and beyond
Sales @ $6.50/lb 100 600 1,600 3,000
Sales @ $8.00/lb 75 450 1,200 2,250

You currently have a fully depreciated, 1,000-gallon batch reactor that is used to manufacture
another product (Product X). This reactor is made of 316SS, which is sufficiently corrosion-
resistant for producing the new product as well. Product X is made in 6,000-pound batches that
require 36 reactor hours per batch and is sold at a profit of $0.88 per pound. 100 such batches are
produced annually (not expected to change); the rest of the time the reactor is idle. This reactor is
jacketed for heating and uses 175 psig saturated steam. The jacket has a heat-transfer area of 88 ft
2

and an estimated overall heat-transfer coefficient of 100 Btu/ft
2
hr°F.


Di(3-pentyl) malate is made by batch reaction of malic acid with an excess of 3-pentanol, using 0.1
weight percent of an acid catalyst such as sulfuric acid (see reaction above). Water is produced as a
co-product and must be removed to drive the reaction to completion. Water and 3-pentanol form a
low-boiling azeotrope (see CRC Handbook for data) that forms two liquid phases upon
condensation. A typical process scheme would be to carry out the batch reaction above the
azeotrope temperature while condensing the overhead vapors into a decanter, recycling the organic
layer to the reactor and removing the aqueous layer (Figure 1, top). This approach can be used with
your existing reactor. A more sophisticated approach would involve interposing a distillation
column between the reactor and the condenser, allowing the alcohol-rich vapors off the reactor to
strip water out of the organic recycle (Figure 1, bottom). When the desired conversion is achieved,
the product must be treated with aqueous sodium hydroxide to neutralize the residual acidity (due
both to the catalyst and the unreacted malic acid). The residual 3-pentanol must be stripped off
OH
O
OH
O
OH
+ 2 ROH
OR
O
OR
O
OH
+ 2 H
2
O
Acid Catalyst
CD-A-II-7
using vacuum (50 mm Hg) with nitrogen sparge at 120°C. Your R&D group has come up with the
mass-transfer estimates given in Table 1. Finally, the product must be filtered to remove the salts
of neutralization. Your company currently has no vacuum or filtration equipment.

Table 1. Mass Transfer Data
( ) y y a k
dt
dx
L
− =
*
where x is the mole fraction of 3-pentanol in the liquid , y* is the
vapor phase mole fraction of 3-pentanol in equilibrium with x, and y is the vapor
phase mole fraction of 3-pentanol. Assume that the Henry’s law constant for 3-
pentanol in the product is 1,200 mm Hg.

Superficial Gas Velocity (scf/ft
2
,min) 2 5 10 20 50
k
L
a (1/hr) 0.076 0.12 0.17 0.24 0.37

The required product specifications are:

Residual acidity (prior to neutralization) <0.1N
Residual 3-pentanol <0.1 wt.%
Purity (moles ester / total moles) >98 wt.%

You are being asked to provide the following:

1. An equipment design for a dedicated batch-reactor system to produce dibutyl malate, including
a capital cost estimate for both process options shown in Figure 1.
2. A batch ticket for a typical production batch. This will itemize the individual steps the operator
will follow to produce the batch, including amounts of materials being added, estimated
duration of each step and the safety procedures and precautions that must be followed. It
should also specify when samples must be taken and what the criteria are for proceeding to the
next step.
3. A recommendation to management on whether/when to build the dedicated equipment or use
the existing reactor, supported by appropriate financial information.

Key process determinations:

Which process option should you use for a new design – with or without the distillation
column?
How much heat-transfer surface is required and what heating medium (assume you have
saturated steam available at 175 psig for $5 per million Btu)?
What type of agitation is needed (horsepower and impeller design)?
How long will the reaction take? What is the reaction profile (concentrations and temperature
vs. time)? How does the composition of the vapor from the reactor change with time?
What ratio of alcohol to malic acid should be charged?
What types of process control systems are required to ensure product quality?
What are you going to do with the aqueous byproduct and the recovered excess alcohol?
Is it worth buying any additional vessels for post-treatment, filtration, storage, etc.?
What kind of vacuum system should you purchase?
CD-A-II-8
What equipment will be needed for filtration?
What will your overall batch cycle time be?

Costs:

Malic Acid, 1,000 kg supersacks, $2,750 each; 50 lb bags, $78 each
3-pentanol, 55 gal drums, $2.55/lb; 5000 gal tank truck @ $1.95/lb
Sulfuric Acid, use market price
Electricity, $0.05 per KWH.
Cooling water, 90°F, $0.50/1,000 gal

Data & Additional Information:

The viscosity (cP) of the reactor contents can be estimated using the equation
0.00211*exp(2,600/T), where T is in Kelvin.
Product density is 1.03 g/cc. Assume that this is also the density of the reactor contents at every
point in the reaction.
Residual acidity can be measure by titration, requiring 15 minutes to obtain a measurement
from the time the sample is taken. Residual alcohol and product purity are measured by
chromatography, requiring 45 min from the time the sample is taken.

Use the following reaction rate expressions in your model, treating the two acid groups on each
malic acid molecule as if they are two separate molecules:

Acid + 3-Pentanol = Ester + Water
2Ester = Dimer + 3-Pentanol

Formation of ester:
Rate (mol/L-min) = 1,000,000 exp[-15,000/RT]*[Acid][BuOH]
Back-Reaction:
Rate (mol/L-min) = 1,000,000 exp[-16,000/RT]*[Ester][Water]
Byproduct (Dimer) Reaction:
Rate (mol/L-min) = 10,000,000 exp[-23,000/RT]*[Ester]
2

Make the following additional assumptions (and be sure to document additional assumption you
make):

Malic acid completely dissolves in 3-pentanol at 70°C.
The heat capacity of the reactor contents is 0.50 Btu/lb°F throughout the process.
Assume that the reaction occurs at atmospheric pressure.
Assume that all products of neutralization are insoluble.
Assume that during filtration only the resistance of the cake itself is significant.
No additional equipment must be purchased to transport or charge the solid malic acid.
CD-A-II-9


Figure 1. Reaction Schemes for Di(3-pentyl) Malate Manufacture


Org
Aqu
VENT
AQUEOUS BYPRODUCT
Org
Aqu
VENT
AQUEOUS BYPRODUCT
CD-A-II-10
A-II.1.2 Acetaldehyde from Acetic Acid
(Bruce Vrana, DuPont, January 2002)

Acetaldehyde is a versatile chemical intermediate. It is commercially made via the Wacker
process, the partial oxidation of ethylene. That process is very corrosive, requiring expensive
materials of construction. And like all oxidations, over-oxidation of the ingredient and the product
reduce the yield, and convert expensive ethylene into carbon oxides.

Acetic acid, produced from inexpensive methanol, would be a good feedstock, if a selective route
to acetaldehyde could be found. Because of the possible legislation of MTBE out of gasoline, there
may be a worldwide glut of methanol, so any chemicals that use methanol may become much more
economically attractive. But the reduction of acetic acid to acetaldehyde is notoriously difficult,
because aldehydes are easier than acids to reduce.

However, Eastman Chemical has developed a selective palladium catalyst that gives acetaldehyde
with selectivity of up to 86% at 46% conversion. Byproducts formed include ethanol, acetone and
ethyl acetate, all of which can be sold after purification.

O H CH CH CO CH H COOH CH
O H CH CH COO CH OH CH CH COOH CH
O H OH CH CH H COOH CH
reaction main O H CHO CH H COOH CH
2 4 3 3 2 3
2 3 2 3 2 3 3
2 2 3 2 3
2 3 2 3
2 2
2
) (
+ + − − → + −
+ − − − ↔ − + −
+ − → + −
+ − → + −


Distillation of the product will be complicated by the existence of azeotropes between ethanol and
ethyl acetate, water and ethanol, and water and ethyl acetate. And the acetic acid-water and
acetone-water mixtures are famous for their tangent pinches. Rigorous distillation simulations with
thermodynamics that accurately predict each of these azeotropes and pinches will be required to
have confidence in the design.

Your company has asked your group to determine whether this new technology should be used in
your Gulf Coast plant. Your job is to design a process and plant to produce 100 MM lb/yr of
acetaldehyde from acetic acid, which is available on the site. Based on past experience, you know
that you will have to defend any decisions you have made throughout the design, and the best
defense is economic justification.

Assume a U.S. Gulf Coast location on the same site as a large chemical plant. Acetaldehyde can be
sold for $0.48/lb, according to your marketing organization. Acetic acid is available on your site
for $0.16/lb. However, if MTBE is legislated out of gasoline, that price might drop to $0.12/lb.
Test your economics with both prices, and make appropriate recommendations. Hydrogen can be
purchased over the plant fence for $0.50/lb at 200 psig. Ethanol, if 99.95% pure, can be sold (on an
excise tax-free basis) for $2.50/gal; however, the ethanol-water azeotrope can also be sold into the
CD-A-II-11
fuel market for $1.60/gal. You may sell either or both grades of ethanol, depending on which is
most economical to produce. Ethyl acetate can be sold for $0.60/lb. Acetone can be sold for
$0.20/lb. You will need storage tanks, truck or railcar loading stations, etc., for each byproduct that
you sell, or you may burn them in the boiler for fuel value. Byproducts sold must also meet normal
purity specs for that chemical. All prices listed are in 2002 dollars.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be controllable and safe to operate.
Remember that you will be there for the start-up and will have to live with whatever design
decisions you have made.

References:

U. S. Patent 6,121,498 to Eastman Chemical.


A-II.1.3 Ethylene by Oxidative Dehydrogenation of Ethane
(Bruce Vrana, DuPont, January 2001)

Ethylene is the largest volume organic chemical product, with world production over 50 billion
pounds per year. It is normally produced by steam cracking of ethane or heavier hydrocarbons.
This process is quite energy and capital intensive.

Dow Chemical has recently applied for a patent on a new process, which may require significantly
less investment. In this process, ethane is passed over a catalyst at very high space velocity
(100,000/hr or higher), and reacts with oxygen (exothermically!), producing ethylene in good
selectivity (greater than 80% under some conditions) and high conversion. The selectivity is
similar to that in the conventional steam cracking process, but the conversion is higher. Hydrogen
in the feed improves the conversion while minimizing the amount of over-oxidation of the
feedstock.

Because the reaction with oxygen is exothermic, the expensive furnaces of the steam cracking
process should not be required. Much less coke is produced in this reactor system, according to
Dow, which should result in a much more operable plant.

Dow has patented both a fixed bed supported catalyst and a fluidized bed reactor. The fluidized
bed has a slightly higher selectivity, and would probably be easier to manage the heat load than the
less expensive fixed bed reactor. You should use economics and technical criteria to guide your
decision about which reactor technology to use in the plant design, and discuss this major decision
in your report.

Your company has 1 MMM pounds per year of ethane, which is currently being produced at your
Gulf Coast plant and sold for $0.07/lb in 2000. Your team has been asked to evaluate the economic
viability of the Dow process for your plant, as a way of upgrading your product and increasing your
sales revenue. Your job is to determine the economic optimum design, maximizing the net present
CD-A-II-12
value (NPV) of the project. You may consume all or part of the ethane, which is available. Based
on past experience, you know that you will have to be able to defend any decisions you have made
throughout the design, and the best defense is economic justification. Your plant design must be
backed up with a rigorous simulation of the entire process, with all recycle loops closed.

Your marketing organization believes they can sell ethylene for $0.25/lb in 2001 dollars. Pipeline
oxygen in your area costs $0.02/lb. It would be a good idea to test the sensitivity of the optimum
plant design and economics to uncertainty in the selling prices of the product and the raw material.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be controllable and safe to operate, an
important consideration with oxygen and hydrocarbons. Remember that you will be there for the
start-up and will have to live with whatever design decisions you have made.

Reference

World Patent Applications 00/14035 and 00/14180 to Dow.


A-II.1.4 Butadiene to n-Butyraldehyde and n-Butanol
(Bruce Vrana, DuPont, January 2000)

n-Butyraldehyde is conventionally produced from propylene and highly toxic synthesis gas in the
so-called oxo process. The n-butyraldehyde is used to make 2-ethyl hexanol via aldol condensation
as well as n-butanol. These oxo alcohols are frequently used, in either the alcohols or ester form, as
solvents.

Because propylene is frequently quite expensive and in short supply, BASF has applied for a patent
on a new route to n-butyraldehyde and/or n-butanol starting from butadiene. They found that a
homogeneous palladium acetonylacetonate catalyst with phosphine ligands would allow butadiene
to react with n-butanol to produce 1-n-butoxy-2-butene (nBB). nBB will then react with more n-
butanol to produce the acetal, using a homogeneous phosphine modified ruthenium catalyst. The
acetal can be hydrolyzed to n-butyraldehyde, or hydrogenated and hydrolyzed to n-butanol using
the same Ru catalyst.


CH
2
=CHCH=CH
2
+ BuOH → BuO-CH
2
CH=CHCH
3
[nBB]

nBB + BuOH → (BuO)
2
CHCH
2
CH
3
[Acetal]

Acetal + H
2
O → O=CHCH
2
CH
2
CH
3
+ 2 BuOH

Acetal + H
2
+ H
2
O → 3 BuOH


CD-A-II-13
Unfortunately, in the first reactor, a side reaction produces 2-butoxy-3-butene (iBB). The iBB can
be isomerized to nBB using an acid ion exchange resin or a Pd catalyst. Unfortunately, this
isomerization reaction is likely to be equilibrium limited.

BASF also found that while this reaction works well with pure butadiene, it will also work with
"crude" butadiene, the C4 olefin cut from an ethylene cracker. The butenes in the C4 cut are inert
under the reaction conditions.

Your company has asked your group to determine whether this new technology should be used in
your Gulf Coast plant, and if so, what the economic optimum feedstock and product would be. The
goal is to maximize the net present value (NPV) of the project. Based on past experience, you
know that you will have to be able to defend any decisions you have made throughout the design,
and the best defense is economic justification.

Your company has 200 MM lb/yr of crude butadiene, which is currently being burned for fuel
value. Thus, one possible feedstock would be the butadiene contained in the crude. You would
receive a credit for the unused C4's in the stream, so you would only have to pay fuel value for the
butadiene you actually consume in the process. Of course, the inert C4's will dilute the reactor
contents, making it larger, and complicate the separation train. As an alternative, you could
purchase pure butadiene for $0.15/lb in 2001 dollars, which would result in smaller vessels.

The composition of your plant's C4 cut, which has already passed through your MTBE plant to
react away the isobutylene, is:

43% BD
28% 1-butene
10% cis-2-butene
10% trans-2-butene
6% n-butane
3% isobutene

For a product, you could produce n-butyraldehyde or n-butanol, or some combination of the two.
Your marketing organization believes they could sell the aldehyde for $0.40/lb, and n-butanol for
$0.40/lb also, both in 2001 dollars.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be controllable and safe to operate.

Reference

World Patent Application 98/41494 to BASF


CD-A-II-14
A-II.1.5 Methacrylic Acid to Methylmethacrylate
(Bruce Vrana, DuPont, January 1999)

Methyl methacrylate (MMA) is a monomer or comonomer in many polymers, most notably
Plexiglas (R). Although it is the methyl ester of methacrylic acid, it is not often produced from
methacrylic acid.

BASF has recently patented a reactive azeotropic distillation process to produce esters from
methacrylic acid and alcohols, involving a total of 3 columns. Although the patent example is for
butyl methacrylate, they claim methyl methacrylate as well.

Design a process and plant to produce 100 MM lb/yr of MMA from methacrylic acid that your
plant already produces. Use the process concept that BASF introduces, with appropriate
modifications (improvements) for MMA.

Your process design must be supported by rigorous distillation simulations. VLE and LLE data are
available in the DECHEMA Chemistry Data Series (Gmehling et al., 1980). Do not blindly use
activity coefficients from a simulation program.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be controllable and safe to operate.
Assume a U.S. Gulf Coast location on the same site as a large oil and petrochemical plant. 99.95%
pure MMA can be sold or transferred for $0.60/lb, according to your marketing organization. The
acid feed contains 5% water (by weight). Because it is impure, the cost of the acid in the stream is
$0.40/lb. Your marketing organization projects that the long-term average price of methanol is
$0.40/gal.

References

U.S. Patent 5,734,074 to BASF

Gmehling, J., U. Onken, W. Arlt, P. Grenzheuser, U. Weidlich, and B. Kolbe, Vapor-Liquid
Equilibrium Data Collection, 13 Parts, DECHEMA, Frankfort, Germany (1980)


A-II.1.6 Coproduction of Ethylene and Acetic Acid from Ethane
(Bruce Vrana, DuPont, January 2000)

Ethylene is the largest-volume organic chemical, with world production over 50 billion pounds per
year. It is normally produced by steam cracking of ethane or heavier hydrocarbons. Acetic acid is
another large-volume chemical, with annual world production in the billions of pounds. Acetic
acid is normally produced using the Monsanto process from methanol and highly-toxic carbon
monoxide, although there are some older technology plants still running.

CD-A-II-15
Saudi Basic Industries (Sabic) has applied for a patent on a new catalyst which will coproduce
ethylene and acetic acid from ethane and air. Their catalyst is a phosphorus-modified
molybdenum-niobium vanadate. At different phosphorus levels, the catalyst will produce different
ratios of ethylene to acetic acid. Selectivity to the two products is also a function of conversion
(i.e., space velocity). As conversion increases, the selectivity to ethylene decreases and the
selectivity to acetic acid increases. However, the total selectivity to the useful products decreases
as conversion increases. The process runs at higher pressures, about 200 psig, than a conventional
ethylene furnace.

Your company manufactures 2 MMM lb/yr of ethane which is currently being produced at your
Gulf Coast plant and sold for $0.07/lb in 1999. Your team has been asked to evaluate the economic
viability of the Sabic process for your plant, as a way of upgrading your product and increasing
your sales revenue. Your job is to determine the economic optimum design, producing whatever
products will maximize the net present value (NPV) of the project. You may consume all or part of
the ethane which is available and make any ratio of ethylene to acetic acid which can be produced
by the catalyst. Based on past experience, you know that you will have to defend any decisions you
have made throughout the design, and the best defense is economic justification.

Your marketing organization believes they can sell ethylene for $0.25/lb in 2000 dollars. Although
they are less certain because it is a new product for your company, they also believe they can sell
acetic acid for $0.19/lb in 2000 dollars. It would be a good idea to test the sensitivity of the
optimum plant design and economics to uncertainty in the selling prices of both products.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be controllable and safe to operate.

Reference

World Patent Application 99/13980 to Sabic


A-II.1.7 Methylmethacrylate from Propyne
(Bruce Vrana, DuPont, January 1999)

Methyl methacrylate (MMA) is a monomer or comonomer in many polymers, most notably
Plexiglas (R). The conventional process has many drawbacks, including the use of sulfuric acid as a
catalyst. Most manufacturers neutralize the sulfuric acid with ammonia, producing byproduct
ammonium sulfate which must be sold or disposed of. HCN is also used in the process, requiring
the MMA plant to be linked to a source of hazardous HCN.

Shell has patented a new process with several advantages over conventional MMA processes. A
major advantage is that neither HCN nor sulfuric acid are used. Shell found that propyne can be
carbomethoxylated (reacted with CO and methanol) to produce MMA directly. The main
disadvantage is that propyne is not normally considered a viable feedstock due to its scarcity and
CD-A-II-16
the impurities it contains. Shell's new catalyst tolerates impurities in the propyne much better than
prior catalysts.

Your job is to develop a scenario for Shell to commercialize this process. You must first find a
suitable feedstock for this process from the normal refinery and/or petrochemical streams available.
Producing propyne to provide the feedstock is discouraged, due to high cost. Having found a
stream which contains suitable quantities of propyne in high enough purity for this process to be
feasible, design a plant to produce 100 MM lb/yr of MMA by the new Shell process. Determine the
overall economic feasibility of the plant.

The plant design should be as environmentally friendly as possible. Recover and recycle process
chemicals to the maximum economic extent. Also, energy consumption should be minimized, to
the extent economically justified. The plant design must also be controllable and safe to operate.

Assume a U.S. Gulf Coast location on the same site as a large oil and petrochemical plant. MMA
can be sold or transferred for $0.60/lb, according to your marketing organization. Value the
propyne as appropriate for alternative uses for the stream (i.e., if the stream you are using is
normally burned, value the propyne at fuel value). A major gas vendor is willing to locate across
the fence from you and supply CO at the required pressure for $0.12/lb. Your marketing
organization projects that the long-term average price of methanol is $0.40/gal.

Reference

U.S. Patent 5,719,313 to Shell Oil Company


A-II.1.8 Mixed-C
4
Byproduct Upgrade
(Leonard A. Fabiano and Robert Nedwick, Lyondell, January 1999)

Your company is a major player in commodity petrochemicals, specifically producing olefins via
the cracking of ethane, propane, butane and naphthas. At one of your Gulf Coast sites, the major
products are ethylene and propylene in addition to a number of smaller fuel streams. The crude C4
product, which because of the feed mix has been a relatively small portion of the product slate, is
currently being sold at fuel value. Now, due to a change in feed mix, the C4 yield from the
cracking furnaces has increased significantly. Management would like to upgrade this stream
above fuel value. The expected feed composition and flow rate are as follows:


Composition wt%

Methyl Acetylene 0.4
Propadiene 0.1
Propane 0.1
1,3 Butadiene 46.5
Ethyl Acetylene 0.1
Vinyl Acetylene 0.4
1-Butene 11.0
CD-A-II-17
Cis-2-Butene 4.1
Trans-2-Butene 5.4
Iso-Butene 30.1
Iso-Butane 0.6
N-Butane 0.6
Iso-Pentane 0.6
Total 100.0

Flow rate, lb/hr 100,000


The company would like to maintain its focus on commodity chemicals and is interested in high
volume products. Your project team has been assembled to determine:

1. What components are worth considering for recovery?

2. What processing options are available for the components of interest?

3. What is the most economical processing route?

and to develop a design package that will meet a 15% return on investment.


A-II.1.9 Hydrogen Peroxide Manufacture
(Bruce M. Vrana, DuPont, January 1999)

Hydrogen peroxide is an oxidant used in many markets, including the pulp and paper industry.
Almost all of the world capacity is based on alternately hydrogenating and oxidizing an expensive
alkylanthraquinone.

Enichem has applied for a patent on a process based on oxidizing carbon monoxide in a complex
aqueous solution. Rather than using expensive hydrogen, this process incorporates the hydrogen
from water. The overall chemistry is:

CO + H
2
O + O
2
→ H
2
O
2
+ CO
2


The application cites data with reactor productivities comparable to or even better than the
conventional chemistry. Design a process and plant to produce 100 MM lb/yr of 50% H
2
O
2
using
this proposed reaction path.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be controllable and safe to operate.

Assume a U.S. Gulf Coast location on a large plant complex. H2O2 can be sold or transferred for
$0.60/lb, according to your marketing organization, on a 100% basis. A major gas vendor is willing
CD-A-II-18
to locate across the fence from you and supply CO at the required pressure for $0.12/lb and oxygen
for $0.02/lb.

Reference

European Patent Application 808796 by Enichem.


A-II.1.10 Di-tertiary-butyl-peroxide Manufacture
(Leonard A. Fabiano, ARCO Chemical, January 1995)

It is desired to design a process to produce 100 million pounds per year di-tertiary-butyl-peroxide
(DTBP) based primarily on a Texaco patent. DTBP is an important chemical that has use, for
example, as a catalyst in various organic syntheses and has special utility as an additive to diesel
fuel formulations to improve its combustion characteristics. It behaves in an analogous way to
diesel fuel as octane enhancers (e.g., MTBE) behave in gasoline (see U.S. Patent 5,312,998,
column 1, lines 29-33). The product must contain less than 0.3 weight percent tertiary-butyl-
alcohol (TBA) and essentially no other peroxides. The plant will be constructed at a Gulf Coast
location adjacent to a feedstock-producing facility. Texaco and ARCO have facilities in this area.

Specific kinetic data are not available but hourly space velocities are provided in the Texaco patent
(80-100˚C, 1-2 vol. TBHP per vol. catalyst per hour – U.S. Patent 5,345,009, column 4, lines 23-
44). Phase equilibrium data are to be developed from the DIPPR databank and UNIFAC estimates
using ASPEN PLUS.

Specifics

Your group is requested to develop and analyze a process to produce DTBP based on information
provided in U.S. Patent 5,345,009 assigned to Texaco Chemical Company, and U.S. Patents
5,288,919 and 5,312,998 assigned to ARCO Chemical Company.

Assistance will be provided in making decisions, but will be very specific with references in the
open patent literature. It should be apparent in this problem statement of this most timely process
study that I must be careful not to release proprietary information which is contained in a very
recent patent application for which I am one of the inventors. The results of this comparison of the
Texaco process, as devised by your group, with the ARCO process is typical of an exercise that all
companies must undertake to analyze the economic viability of all new ventures.

We are interested in comparing the Texaco technology with the confidential process developed by
ARCO. However, you are expected to be very creative and devise a continuous process to
minimize costs. It is suggested that you focus on Texaco patent (5,345,009 - column 2, lines 65 to
the end, and column 3, lines 1-6). Paraphrasing, di-tertiary-butyl-peroxide (DTBP) is formed when
tertiary-butyl-hydroperoxide (TBHP) and an enhanced amount of tertiary-butyl-alcohol (TBA) are
brought into contact with a palladium-coated, carbon catalyst; that is,

TBA + TBHP → DTBP

CH
3
CH
3
CH
3
CH
3

| | | |
CH
3
COH CH
3
COOH CH
3
C-OO-CCH
3

| | | |
CH
3
CH
3
CH
3
CH
3

CD-A-II-19

ARCO Patent 5,288,919 (column 1, lines 5-11) suggests alternatively:

TBA + Isobutylene (
=
4
iC ) + TBHP → DTBP

The two routes above are basically the same since TBA under the proper conditions and in the
presence of a catalyst reacts to form isobutylene and water according to the reversible reaction:

TBA =
=
4
iC + H
2
O

The isobutylene is the molecule that reacts directly with the TBHP.

ARCO Patent 5,312,998 (column 3, lines 31-40) offers the same possibilities. TBHP is
catalytically reacted with TBA to form DTBP. Isobutylene can be added to the reaction mixture
and it is generally advantageous to use a substantial excess of TBA and/or iC
4
relative to the TBHP
to achieve high TBHP conversion; e.g., 90% or more. Conditions for the reaction (with different
catalysts) are proposed in U.S. Patent 5,345,009 (column 4, lines 24-33). The reaction may be
conducted at a temperature within the range of about 40˚C to about 160˚C at super-atmospheric
pressures. A contact time of about 0.5-10 hours is required. U.S. Patent 5,288,919 (column 2, lines
19-29) suggests temperatures ranging from 20-150˚C at a sufficient pressure to ensure a liquid-
phase reaction.

U.S. Patent 5,312,998 (column 2, lines 5-19) suggests that there can be a two-liquid phase reaction
carried out in the temperature range of about 70-110˚C.

Similarities - Despite the Differences in Catalysts

U.S. Patent 5,345,009 (column 3, lines 15-29) suggests a typical feed stock for the Texaco process,
but specifics of other components are not described. U.S. Patent 5,288,919 (column 3, lines 29-39)
suggests a typical debutanized feed stock composition of 58 weight % TBA and 40 weight %
TBHP, with the remainder comprised of 0.2% methanol, 1.3% acetone, and 0.5% water. For the
Texaco process, let's use a mixture of 70% TBA, 30% TBHP and assume that this mixture makes
up 98% of the mixture based upon the ARCO patent. The remaining 2% is assumed to be as above.

Note that TBA and DTBP, as well as TBA and water, form azeotropes.

Let's brainstorm and develop several likely candidate processes to evaluate and perhaps compare
before we embark on detailed evaluations.

Alternative Process

ARCO produces TBHP-70, a possible "purified" feedstock for the reaction:

TBHP +
=
4
iC → DTBP + TBA

TBHP-70 is essentially 70% TBHP and 30% water. Would this provide an economically viable
process?

References

U.S. Patent 5,345,009 (September 6, 1994).
U.S. Patent 5,288,919 (February 22, 1994).
U. S. Patent 5,312,998 (May 17, 1994).
CD-A-II-20


A-II.1.11 Vinyl Acetate Process
(Björn D. Tyreus, DuPont, January 1997)

Our company, BCI (Better Chemicals Inc.) has recently discovered a new product which we intend
to manufacture in the near future. This product uses vinyl acetate as one of the main raw materials.
We expect to use 300 MM PPY of vinyl acetate in our new process. In reviewing the economics of
our new product, we found that it was negatively impacted by the relatively high market price of
vinyl acetate ($0.44/lb). A closer investigation showed us that the most popular route to vinyl
acetate is from ethylene and acetic acid oxidized by oxygen. The site where our new process will
be constructed happens to use all three ingredients needed for vinyl acetate. Very favorable, long
term contracts for their use have been negotiated. We thus find that we can obtain large quantities
of acetic acid for $0.27/lb and ethylene for $0.20/lb. Oxygen costs us $0.02/lb. With these raw
material prices, we feel that we can manufacture vinyl acetate far below the market price of
$0.44/lb and thus make our new product that much more profitable. In assessing the project to
manufacture our own vinyl acetate, we used some approximate estimating techniques [1] to
evaluate the investors rate of return we could expect from a 300 MM PPY vinyl acetate plant as a
function of the onsite capital investment. In these calculations, the onsite cost consists of the
installed cost of all process equipment within battery limits. We estimate the offsite cost to be 45%
of the onsite cost and apply a 25% contingency such that the fixed capital is related to the onsite
cost as

Fixed Capital = 1.25 (onsite + 0.45 onsite)

The results of our venture guidance calculations are shown in the figure below





CD-A-II-21
While we do not know exactly how much we need to invest into the vinyl acetate process (this is
one of the questions we have for you), we crudely estimate it to be less than $50-60 MM onsite.
Since the cost of capital is 12%, we therefore expect this to be a profitable venture.

We now turn to the technology of the vinyl acetate process. Reference [2] gives an overview of the
process and states that the main reaction is

H
2
C = CH
2
+ CH
3
COOH + 1/2O
2
→ H
2
C = CHOOC-CH
3
+ H
2
O (R1)

Reference [2] also indicates that the most economic route to vinyl acetate, when acetic acid is
available, is to convert the raw materials to product in the vapor phase over a palladium catalyst.
We therefore asked our research chemists to develop a catalyst suitable for the operation. They
found a suitable catalyst by impregnating a silica base with 2% palladium along with some other
proprietary chemicals. The chemists performed numerous experiments with the catalyst and found
that it is quite selective towards vinyl acetate and quite active as measured in its space time yield
(STY, grams of vinyl acetate/hr per liter of catalyst). The only significant side reaction we could
notice is the combustion of ethylene to carbon dioxide and water

H
2
C = CH
2
+ 3O
2
→ 2CO
2
+ 2 H
2
O (R2)

Once the catalyst was developed our chemical engineers designed a kinetic study using a
laboratory-scale reactor to quantify the performance of the catalyst for the purpose of designing a
commercial-scale reactor. For commercial purposes the catalyst support will be pelletized such that
the bulk average density of the final catalyst is 30 lb/ft
3
. The following rate expressions were
obtained:

For R1:

( )
( ) ( )( )
(
¸
(

¸

⋅ + + +
+
=
=

catalyst lb min
VAc lbmol
8 . 6 1 7 . 1 1 583 . 0 1
7 . 1 1
1036 . 0
2 2
2
2
2 / 674 , 3
1
HAc O H O
O H HAc
C
O
T
p p p
p p p p
e r

and for R2:

( )
( )
(
¸
(

¸

⋅ + +
+
⋅ =

catalyst lb min
burned ethylene lbmol
68 . 0 1 76 . 0 1
68 . 0 1
10 9365 . 1
2 2
2 2 / 116 , 10 5
2
O H O
O H O
T
p p
p p
e r

In these expressions, T is absolute temperature in kelvins and p is the partial pressure of a
component in psia. We also calculated the heat of reaction in the ideal gas standard state (25°C, 1
atm) by using available heats of formation of the components. The standard state heat of reaction is
-42.1 kcal /mol of vinyl acetate for R1 and -316 kcal /mol of ethylene for R2. The reactions are
thus quite exothermic, which we also observed in the laboratory.

Based on this information BCI is requesting that your company design a cost effective process to
make 300 MM PPY of crude vinyl acetate. Since vinyl acetate and water form a heterogeneous
azeotrope we refer to crude vinyl acetate as the acetic acid “free”, liquid product which could be
CD-A-II-22
decanted off from the reaction water. The crude vinyl acetate will then contain water up to its
solubility limit at say 20°C which is about 5 mol% water. The acetic acid in the crude vinyl acetate
must be less than 0.1 mol%. BCI has existing columns on site capable of removing the remaining
water, acetic acid and other byproducts from the crude vinyl acetate. We also suggest that you
would use one of many standard principles (e.g. carbonate wash) for removing the byproduct
carbon dioxide from the reaction mixture. In your flowsheet you need not design or analyze the
carbon dioxide removal step in detail but simply assume that 99.5% of the carbon dioxide will be
selectively removed from any stream sent to such a facility. The size (and cost) of the carbon
dioxide removal unit will be proportional to the flow rate and composition of the stream sent to it.
You may cost estimate the carbon dioxide removal unit as two packed towers (one absorber and
one desorber) each with 30 equivalent stages. In the first tower, the absorber, CO
2
is absorbed in a
cold liquid (assume water) containing a carbonate. In the second tower, the desorber, the CO
2
is
liberated by reboiling the recirculating liquid. Based on our requirement that the desorber must
operate at atmospheric pressure and that we would like to use cooling water for the absorption
cooler, we have estimated the following heat load requirements for the CO
2
removal unit. This
should aid you in estimating the diameter of the towers and the sizes of the heat exchangers
depending on the nature of the stream you opt to purify.

Mol% Carbon Dioxide in the Vapor
Stream Sent to the Absorption
Tower
Heating Requirement in the
Desorption Tower and Cooling
Requirement of the Recirculation
Liquid [kcal/kmol Vapors Sent to
Absorption]
0.5 125
1 219
2 380
5 770
10 1,260
15 1,640


You may further assume that acetic acid is available from our tank farm as a liquid at 30°C. You
may also assume that both ethylene and oxygen are available from separate gas headers at 200 psig
and 30°C. The ethylene gas is 99.9% pure, the balance being ethane. The following utilities and
services are available as needed at the battery limits. Costs are in 1996 dollars

150 psig steam $5/1,000 lb
50 psig stream $4/1,000 lb
Cooling tower water $0.09/1,000 gal
Raw water (makeup) $0.55/1,000 gal
-25°C Refrigeration $0.12/hr ⋅ ton
Electricity $0.065/kWhr

In designing the process we would like you to propose a design which minimizes the total product
cost of crude vinyl acetate at the nominal rate of 300 MM PPY of pure vinyl acetate. Assume a
CD-A-II-23
90% operating utility (7,884 hr/yr) and assume that 99% of the vinyl acetate in the crude stream can
be recovered. The results we expect from your work include

• An optimized flowsheet
• Total installed equipment costs (onsite cost)
• A profitability analysis of the project
• A control scheme based on an in-depth operability analysis of the process

Physical properties for all components required in this study should be readily accessible from
publicly available sources (e.g. DIPPR, HYSYS.Plant, etc.). This also pertains to mixture
properties with the possible exception of the vinyl acetate (1)/water (2) binary. We therefore
provide you with our best estimate of the VLE and LLE data for this pair.

VLE INFORMATION
CONSTANTS A
12
A
21
α αα α
12

van Laar 4.1549 2.1198
Wilson 1,384.5959 2,266.3927
NRTL 1,549 2,336 0.38

LLE INFORMATION
Solubility of water in vinyl acetate at 20°C : 4.949 mol%
Solubility of vinyl acetate in water at 20°C : 0.241 mol%

References

[1] Douglas, J.M., Conceptual Design of Chemical Processes, McGraw-Hill, 1988
[2] “Make Vinyl Acetate from Ethylene”, Hydrocarbon Processing, 46, 4, 146-149 (1967)


A-II.1.12 PM Acetate Manufacture
(Leonard A. Fabiano, ARCO Chemical, January 1993)

PM Acetate (propylene glycol mono-methyl-ether acetate) is a specialty solvent used in resins,
coatings and cleaner formulations. Current sales volumes are 10 MM lb/yr and it is being produced
batchwise by outside "tollers". Due to expected increases in demand, the PENNCO (your
company's name) is interested in building its own continuous plant in the Houston area. The
economic size must be determined that will yield a 15% after tax return while the sales build to 20
MM lb/yr in three years. Consider first a 20 MMlb/yr facility which will be integrated into an
existing facility. Our R&D groups have developed a considerable amount of data on the process;
i.e., chemical kinetics and VLE data. This information will be supplied after the design group signs
a non-disclosure agreement with ARCO.

The primary chemistry is as follows:


CD-A-II-24
PM Acetate Chemistry

| | | | | | | | |
-C-C-C-O-C- + O=C-C- = -C-C-C-O-C- + H
2
O
| | | | | | H
+
| | | |
OH OH O
|
O=C-C

PM HOAc PMA




Byproducts from Ether Cleavage


H
+
+
H O
2

PG + MeOH
H
+
allyl ether + MeOH
PG Acetate and PG Diacetate + H O
MeAc + H O
PG + HOAc
MeOH + HOAc
PM
2

2



where HOAc is acetic acid, PM is propylene glycol mono-methyl-ether, PG is propylene glycol,
MeOH is methanol, and MeAc is methyl acetate.

Data have been developed on a boiling reactor concept that utilizes a liquid catalyst and a fixed-bed
reactor concept that utilizes an acid resin catalyst. The fixed-bed option offers several advantages,
in particular, in raw materials cost and handling, and in materials of construction. It is requested
that you investigate the fixed-bed concept and compare it with a reactive distillation concept that
utilizes the solid catalyst.

The expected market price, chemical kinetics and VLE data, and utility costs will be supplied at a
later date. Where VLE data are lacking you may use the UNIFAC correlation. Your company has
access to ASPEN PLUS which has a reactive distillation subroutine (RADFRAC).


CD-A-II-25
Reaction Separation
Waste Water
PMA Product
Heavies Waste
Unreacted PM, HOAc
PM
HOAc


Figure 1. Simplified Flowsheet for Fixed-bed Process


A-II.1.13 Propoxylated Ethylenediamine
(Brian E. Farrell and David D. Brengel, Air Products and Chemicals, January
1994)

Ethylenediamine (EDA) is a versatile building block in the chemical industry for amine-based
compounds.

H N
2
NH
2

EDA

A family of amine compounds can be formed from the reaction of EDA with propylene oxide (PO).

O
CH
3

PO

Between 1 and 4 moles of PO can be added per mole of EDA. The monopropoxylated EDA can be
used as an intermediate in the synthesis of a polyurethane catalyst. The di- and tri-propoxylates can
be used as cross-linkers for epoxy systems. The fully propoxylated molecule is used as a cross-
linker in polyurethane systems.

Your assignment, should you decide to accept it, is to synthesize and purify each of the EDA-PO
reaction products. The required amount of each product will be determined according to market
demand. IMF, the company that you work for, has performed extensive market research and will
provide you with an estimate of market demand and selling price for each of the four compounds.
The IMF research department has synthesized the four materials in small quantities and will make
available their findings with regard to reaction kinetics and thermodynamics. You will be
responsible for designing a reactor system and distillation process that best meets the anticipated
market demands, while simultaneously maximizing IMF's profits.

CD-A-II-26


A-II.2 PETROLEUM PRODUCTS


A-II.2.1 Fuel Additives for Cleaner Emissions
(E. Robert Becker, Environex, January 1993)

Carbon monoxide and ozone levels are in excess of the National Ambient Air Quality Standards in
the Northeastern states, which constitute a corridor from Virginia to New England. The principal
source of carbon monoxide are emissions from automobiles. The coalition of Northeastern
regulators have mandated cleaner burning fuels for the region; however, demand is uncertain since
the member states can opt into the plan until 1995. The use of methyl-tert-butyl-ether (MTBE) as
an octane enhancer provides significant reductions in carbon monoxide emissions.

Your company has technology for the production of MTBE. Your assignment is to provide
management with a cost estimate for a 100,000 gallon per day MTBE plant in the Philadelphia tri-
state area. Your report should estimate the product prices necessary for annual production rates of
100,000, 70,000, and 50,000 gallons. You have a stream of butane available from an adjoining
refinery and you have to purchase methanol from a nearby chemical plant. Steam can be purchased
from a cogenerator.

The process involves the dehydrogenation of isobutane to isobutene which is reacted with methanol
to produce MTBE. Particular attention should be given to the dehydrogenation reactor design and
operation. Technical and economic data for the design are attached.


Technical data

The rate of iso-butane dehydrogenation in kmol/kg cat-hr is:


Rate =
2
) 4 1 (
/ (
h
h e a
r
p
K p p p
k
+



where k
r
= 1.8x 10
7

) 42 / 000 , 30 ( c RT
e
− −



The rate of coke formation in kg carbon/kg catalyst-hr is:

Rate =
2 5 . 0
) 7 . 1 1 (
h
e
c
p
p
k
+


CD-A-II-27
where
c
k = 5x 10
5
e
(-21,000/RT - 45 x c)

c = kg carbon per kg catalyst
p
a
= partial pressure of isobutane [bar]
p
e
= partial pressure of olefin [bar]
p
h
= partial pressure of hydrogen [bar]
K = chemical equilibrium constant

The catalyst is 0.3 cm chromia alumina spheres with 0.48 void fraction and 1,200 kg/m
3
bulk
density. The carbon is removed from the catalyst by burning in air at a rate of 0.1 kg carbon/kg
catalyst-hr. The maximum catalyst temperature is 740˚C. The catalyst is replaced annually.

The reaction of isobutylene and methanol is assumed to go to 98% equilibrium without side
reactions. The dehydrogenation reaction produces isobutene, hydrogen, propylene, and methane.


Cost and Economic Data

95% isobutane-5% n-butane is $ 0.70/gallon
Methanol is $0.75/gallon
Steam at 700˚C and 10 bar is available at $8.00/1,000 lb
Electricity cost is $ 0.07/kWhr
Fuel gas is valued at $2.00/MMBtu
Cooling water is $0.15/1,000 gal
Catalyst is $15/kg

Annual effective interest rate = 12% per year
Project life 10 years
Minimum investor’s rate of return (IRR) is 15%


A-II.3 GAS MANUFACTURE


A-II.3.1 Nitrogen Rejection Unit (from natural gas)
(William B. Retallick, Consultant, January 2002)

This unit is part of a gas plant, which prepares raw natural gas for sale to a pipeline. The front end
of the gas plant has already removed the natural gas liquids from the gas. It remains for the
rejection unit to remove nitrogen and also recover helium, a valuable by-product. Flow diagrams
for the unit are included in a paper by Scott Troutmann, of Air Products and Chemicals, and Kim
Janzen, of Pioneer Natural Resources. The unit uses two stripping columns. You can produce a
side stream from the first stripping column that contains about 50 mol% nitrogen. This will be used
to fuel the gas turbines, which drive the compressors.

The feed consists of two streams:
CD-A-II-28
Flow rate, million SCFD 40 20
Pressure, psig 400 400
Helium, mol% 1.0 2.5
Nitrogen 16.0 28.0
Methane balance
Ethane 1.5 0.6
Propane 0.1 0.05
CO
2
0.01 0.00

1. Pipeline gas is to be delivered at 1,200 psig, containing no more than 2 mol% N
2
.

2. Crude helium product contains at least 65 mol% helium, a maximum of 1 mol% methane,
with the balance N
2
, and is delivered at 1,200 psig. Recovery of helium is at least 96 mol%.

3. The selling price of crude helium is $25 per 1,000 ft
3
of helium content.

4. When heat is transferred (irreversibly) with a temperature difference, ∆T, the lost work is
Q∆T/T, where T is the temperature of the warm fluid.

At cryogenic temperatures, where T is smaller, the losses are greater. Hence, to avoid
increases in the lost work as T decreases, the minimum internal temperature difference
(MITD) must be reduced. As you carefully select the MITD, consider the range of 1 - 6 K
for your design.

5. Simplify your calculations with the units K, kg and atm.

6. Purchased electricity costs $0.70 per kWh.

7. The plant is located in Texas.

8. The cryogenic vessels and exchangers are of 304L stainless steel.

9. The heat exchangers are plate exchangers.

10. You can display the economics of your process by graphing the investor’s rate of return
(IRR) as a function of the cost of the feed divided by the sales price of the gas.

Reference

Trautmann, S. R., and K. H. Janzen, “Innovative NRU Design at Pioneer Natural Resources’ Fain
Gas Plant.


CD-A-II-29
A-II.3.2 Ultra-pure Nitrogen Generator
(Jianguo Xu, Rakesh Agrawal, Mike Herron, Air Products and Chemicals,
January 2000)

As the semiconductor industry goes to submicron and deep submicron designs, the purity
requirement for nitrogen gas is becoming higher and higher. The current specification for nitrogen
requires the impurity levels to be below 10 parts per billion by volume.

Your company, UltraPureGas, is approached by a major semiconductor manufacturer (Advanced
SemiCon) to submit a proposal to supply 200 ton/day of nitrogen at a pressure of 10 bar absolute to
their megafab in Austin, Texas. The maximum allowable total impurities content (excluding noble
gases such as argon, neon, and helium) is 10 parts per billion by volume. The customer also
indicated that to avoid potential particulate contamination, nitrogen product compressors should be
avoided. You, the lead process engineer for this project, are asked to come up with a low-cost
design (which means you have to compare the different known processes and/or invent new
processes and find the low-cost option).

References:

Agrawal R., and R. M. Thororgood, "Production of Medium Pressure Nitrogen by Cryogenic Air
Separation", Gas Separation & Purification, 5, 203 (1991).

Agrawal, R., and D. Woodward, "Efficient Cryogenic Nitrogen Generators – An Energy Analysis",
Gas Separation & Purification, 5, 139 (1991).

Carey, G., A. Yip, and T. Young, Nitrogen Production, Design Project Report, Towne Library,
Univ. Pennsylvania, 1999.

Isalski, W. H., Separation of Gases, Oxford Science Publications, Clarendon Press, Oxford, 1989.

Latimer, R. E., "Distillation of Air", Chem. Eng. Prog., 63(2), 35 (1967).

Linde, W., and R. Reider, in "The Invisible Industry", The International Oxygen Manufacturers
Association, Cleveland, Ohio, 1997.

McGuiness, R. M., in "Oxygen-Enhanced Combustion", C. E. Baukal, Editor, CRC Press, Boca
Raton, 1998, Chapter 3.

Scott, R. B., Cryogenic Engineering, Met-Chem Research Inc., Boulder, Colorado, 1988.

Scurlock, R. G., Editor, History and Origins of Cryogenics, Clarendon Press, Oxford, 1992.

Thorogood, R. M., in Cryogenic Engineering, B. A. Hands, Editor, Academic Press, London, 1986,
Chapter 16.

Timmerhaus, K. D., and T. M. Flynn, Cryogenic Process Engineering, Plenum Press, New York,
1989.
CD-A-II-30

Venet, F. C., E. M. Dickson, and T. Nagamura, "Understand the Key Issues for High Purity
Nitrogen Production", Chem. Eng. Prog., p.78, January, 1993.

Wilson, K. B., A. R. Smith, and A. Theobald, "Air Purification for Cryogenic Air Separation
Units", IOMA Broadcaster, January, 1984.


A-II.3.3 Nitrogen Production
(Rakesh Agrawal, Air Products and Chemicals, January 1999)

Our Polymers Division needs a supply of moderately high purity nitrogen for its production
applications. We would like to study the feasibility of incorporating new nitrogen plants with a
minimum capacity of 5,000 SCFH (to handle current production) with the possibility of expansion
to 40,000 SCFH. This plant is projected for 2005 when we expect the polymer market to expand
significantly.

I am writing to you at this time to request a preliminary design for a nitrogen plant that produces
20,000 SCFH of polymerization grade nitrogen. In your design you will need to compute the price
of nitrogen that yields an investors rate of return (IRR) of 15%. You should compare this
calculated price with the price given in the Chemical Marketing Reporter.

Attached are relevant data on feedstocks, product specifications, utilities and economic data that
should be useful for this design project. Additional data are also available in several articles in the
library. For this production rate there are several competing technologies. To produce a
competitive design, we would like to consider all of these technologies. These articles form only
the start of your literature search. You will need to investigate potential ideas for this project
thoroughly.

When preparing your design, you may also make the following assumptions:

1. Nitrogen product should be delivered as dry gas at ambient conditions
2. The plant should be designed for 8000 hours of operation per year
3. The product nitrogen should be at least 99% pure

Product Specifications

20,000 SCFH nitrogen gas
Minimum Nitrogen 99 vol %

Feedstock

Air at ambient conditions

CD-A-II-31
Utilities

Cooling Water:

90°F supply temperature
115°F maximum return temperature

Steam System:

Saturated Steam from Offsite Boilers
Available at 150 and 600 psig

Process Water

Available at 90°F

Ambient Design Temperature:
100°F dry bulb, 90°F wet bulb

Economic Data

The following data are necessary for the economic evaluation. These include estimates needed for
the 2005 analysis and follow trends over recent years.

1. Wage Rate 1998 2005

Labor ($/hr) 15.00 20.00
Supervision ($/hr) 25.00 30.00

Engineering ($/hr) 45.00 56.25

2. Utilities (Unit Costs)

Unit 1998 2005

150 psig steam 1000 lb 3.31 4.00
600 psig steam 1000 lb 4.20 5.00
Fuel Oil (This is also the Fuel Value
used for the purge)
106 Btu 2.02 2.50
Cooling Water 106 gal 68.10 70.00
Process Water 1000 gal 180.00 200.00
Electricity 1000 kWh 40.00 50.00
Steam Condensate 1000 gal 5.00 6.00
Inert Gas, low press. 1000 SCF 0.38 0.50

CD-A-II-32
3. Waste Treatment

Units 1996 2005

Hydraulic $/yr/GPM 400.00 600.00
Organic $/yr per lb/day 50.00 70.00

4. General Data

Payroll Charge 20 % of wages
Offsite, Utility Investment 40% of onsite investment
Repairs, Onsite 4%/yr of onsite investment
Repairs, Offsite 2%/yr of offsite investment
Supplies and Materials 2%/yr of onsite investment
Depreciation 8%/yr of total investment
Taxes, Insurance 3%/yr of total investment
Life of project 12 years
Income tax 32%
Minimum investors rate of return (IRR) 15%
Predicted Chemical Engineering
Cost Index (2005) 400


Avoid steam systems. All compressors run on electricity rather than steam turbines.

References

Isalski, W. H., Separation of Gases, Clarendon Press, Oxford, 1989 (see Chapter 3)

Hands, B. A., Ed., Cryogenic Engineering, Academic Press, 1986 (see Chapter 16)

Baukal, C. E., Ed., Oxygen Enhanced Combustion, CRC Press, 1998 (see Chapter 3 on oxygen
production - a great reference for cryogenic plant design)


A-II.3.4 Krypton and Xenon from Air
(Rakesh Agrawal and Brian E. Farrell, Air Products and Chemicals, January
1991)

Krypton and Xenon are rare gases which are normally recovered from air. Recently, their demand
has been on the rise. They are used in various applications - in several medical devices, long-
lasting light bulbs, nuclear magnetic resonance, etc. The concentration of each of these gases in air
is extremely low (below 5ppm). This makes their recovery from air challenging and technically
exciting.

To produce reasonable quantities of krypton and xenon, both gases are recovered from large-
tonnage plants for air separation that produce oxygen in quantities greater than 500 tons/day. These
CD-A-II-33
large plants are cryogenic in nature and operate at temperatures as low as -195˚C. Air is composed
primarily of oxygen (20.95 mole %), nitrogen (78.12%) and argon (0.93%). However, besides
argon, it has several contaminants such as hydrogen, helium, neon, carbon monoxide, methane and
other hydrocarbons, water and carbon dioxide. Most of these contaminants are in much higher
concentrations than krypton and xenon. The feed to the cryogenic air separation unit (ASU) is
pressurized to about 6 atm before water, carbon dioxide and some hydrocarbons are adsorbed on
molecular sieves. The air stream is cooled to near its dew point and distilled to recover nitrogen,
argon and oxygen. Of these three constituents, nitrogen is the most volatile and oxygen the least.
Contaminants such as hydrogen, helium, neon, and carbon monoxide concentrate at the top of the
distillation column and leave with the nitrogen product. Krypton and xenon, along with methane,
ethane, propane and some ethylene and propylene, are concentrated in the liquid oxygen (LOX)
collected at the bottom of the distillation column. All of these components have boiling points
higher than oxygen and are heavier. The efficient and economical recovery of krypton and xenon
from LOX is the subject of this design project.

First, a conventional plant to recover krypton and xenon from the LOX will be designed. In this
process, a portion of the LOX stream containing krypton, xenon and other hydrocarbons is
withdrawn from the bottom of the main distillation column and passed through a bed to adsorb all
the heavier hydrocarbons, including propylene and ethylene. None of the methane is adsorbed
while some of ethane and propane are adsorbed. The LOX stream is fed to the top of the first
distillation column to concentrate krypton and xenon (since the concentration in the feed LOX is
below 50 ppm). However, the concentration of krypton and xenon in the bottom distillate from this
column cannot be increased by more than a factor of about ten. The primary reason is that, along
with krypton and xenon, hydrocarbons concentrate in the liquid phase. Concentrations of methane
in liquid oxygen exceeding 50 ppm are unacceptable because they are explosive and present a
safety hazard. The vapor from the top of this column is returned to the main distillation column
and the liquid oxygen from the bottom, containing krypton, xenon, methane, ethane and propane, is
vaporized in heat exchangers. The vaporized stream is heated to about 550˚C and sent to a catalytic
unit to burn the hydrocarbons. The effluent from the catalytic unit is cooled and is passed through
a molecular sieve adsorbent to remove the water and carbon dioxide formed during the reaction.
The resulting stream is cooled to cryogenic temperatures, liquified and distilled to recover krypton
and xenon. The oxygen stream from this distillation step is recycled to the first distillation column
to recover krypton and xenon.

After the conventional process is designed, more recent technology will be considered. It may be
possible to reject methane from the first distillation column and concentrate krypton and xenon by
several orders of magnitude (as compared to a factor of about ten). Also, these processes can be
made inherently safe by feeding nitrogen to the stripping section of a second distillation column,
thereby displacing most of the oxygen from the krypton and xenon in the stripping section. Design
of these processes should expose the opportunities for integrating the krypton/xenon distillation
columns with heat and mass from the main air distillation units.


A-II.3.5 Ultra-High-Purity Oxygen
(Mark R. Pillarella and Rakesh Agrawal, Air Products and Chemicals, January
1992)

Computers have revolutionized industry and technology over the past 15 years and can be expected
to continue to do so. Improvements in computer technology are driven by improvements in
semiconductor technology. For the production of high quality, defect-free semiconductors, ultra-
high purity (UHP) oxygen is essential in the etching process. Typical cryogenic processes can
produce oxygen with parts-per-million by volume impurities, but semiconductor manufacturing
requires oxygen with impurities less than parts-per-billion by volume.
CD-A-II-34

Your company, OxyPure, is submitting a proposal for a multi-million dollar contract to supply
ultra-high purity oxygen to a major semiconductor manufacturer (SemiCon) in Southern California.
OxyPure operates a conventional oxygen plant in Southern California which produces 400 metric
tons per day of 1.3 bara standard grade gaseous oxygen (99.5% oxygen, 0.5% argon, 10 ppm
methane, 0.5 ppm other hydrocarbons, 5 ppm krypton, 0.4 ppm xenon, 0.1 ppm nitrous oxide,
essentially no nitrogen). The process flow diagram is shown in the Figure 2. Your process
engineering team has been assigned the task of evaluating several process schemes for modifying
the existing plant to supply the semiconductor customer.

SemiCon requires 10-40 metric tons per day of 1.0 bara gaseous UHP oxygen. They have
requested that proposals be submitted for two purity specifications;

(1) Less than 25 ppb of hydrocarbons; concentration levels of the other impurities acceptable.

(2) Less than 5 ppb argon and less than 5 ppb of the remaining impurities.

The process schemes to be evaluated are:

(A) Part of the standard grade oxygen can be reacted over a palladium or another suitable noble
metal catalyst at 500°C, converting the hydrocarbons and some of the oxygen to carbon
dioxide and water:

CH
4
+ 2O
2
→ CO
2
+ 2H
2
O

The reactor effluent is passed through an adsorption bed (containing 5A or 13X molecular
sieve adsorbent) to remove the CO
2
and H
2
O (Giacobbe, 1989, 1991).

(B) Part of the standard grade oxygen can be fed to a standard three-component distillation
process (requiring two additional distillation columns) to remove both the light and heavy
impurities (King, 1980).

(C) A side stream can be withdrawn from the upper column and fed to an additional distillation
column which removes the remaining impurities to produce UHP oxygen.

Develop each process scheme and compare the product purity, efficiency, and economics.
Necessary process information will be supplied for the conventional oxygen plant.

References

Giacobbe, F.W., "Use of Physical Adsorption to Facilitate the Production of High Purity Oxygen",
Gas Separation & Purification, Vol. 3, 1989.

Giacobbe, F.W., "Adsorption of Very Low Level Carbon Dioxide Impurities in Oxygen on a 13X
Molecular Sieve", Gas Separation & Purification, Vol. 5, 1991.

King, C.J., Separation Processes, 2nd ed., McGraw-Hill, New York, 1980.







CD-A-II-35

Figure 2. A conventional process for oxygen production.


A-II.4 FOODS


A-II.4.1 Monosodium Glutamate
(Robert M. Busche, Bio-en-gene-er Associates, January 1991)

In its efforts to expand into new specialty chemical markets, your company is considering
manufacturing the flavor enhancer MSG (monosodium-L-glutamate monohydride) for the U.S.
market by way of a joint venture with the Ajinomoto Company. Ajinomoto is the Japanese
company that presently dominates the world market for MSG. The market situation in 1984 in
millions of annual pounds was:



Production Consumption

S.E. Asia 397 300
Japan 191 175
Western Europe 106 105
South America 63 22
North America 0 73
Oceania 0 18
P.R. China and Others 110 174

CD-A-II-36
With the help of Ajinomoto, the Marketing Department believes that it can capture a 50 million
pound share of the North American market by the year 2000. Sales are expected to start at 20
million annual pounds in 1992; 30 in 1994; 41 in 1996; and 48 in 1998.

Presumably, the plant design will be based on the Ajinomoto batch fermentation process converted
to a continuous mode using the aerobic bacterium Brevibacterium ammoniagenes. However, your
Research Department recently was able to isolate a gene for a hemoglobin-like molecule from the
aerobe Vitreocilla and express it in Brevibacterium. The recombinant cells contain hem and
active hemoglobin. As a result, they appear to grow faster and to considerably higher cell densities
than the conventional cells, especially when dissolved oxygen is less than 5% of air saturation.

Before committing to the joint venture, your president would like you, as Director of the Corporate
Planning Department, to assess the expected economic performance of the Japanese process, as
operated at your plant in Iowa and also to ascertain the sensitivity of the process economics to the
use of the new organism.

The Japanese process operates with two fermenter stages. In the first stage, cells are grown to a
density of 17.5 g/liter before inducing product expression. The cells are grown from glucose (corn
syrup) according to the overall reaction:

C
6
H
12
O
6
+ 3O
2
= 3CH
2
O + 3CO
2
+ 3H
2
O

Six hours are allowed for growth.

The product is produced form the resting cells in the second stage, at pH 7.0-8.0, over a 28 hour
period, at a concentration of 90 g/liter. The overall reaction to products is:

C
6
H
12
O
6
+ 2.2065O
2
+ 0.843NH
3
= 0.843 C
5
H
9
O
4
N + 1.785CO
2
+ 3.471 H
2
O

Glucose conversion is essentially 100%. There is reason to believe that, with the new aerobe,
production time might be reduced and cell density increased to, hopefully, 50 g/liter and, perhaps
100 g/liter. The allowable cell density will depend on viscosity restrictions to aeration performance
of the new bacterium.

References

Hubbard, D.W., L.R. Harris, and M.K. Wierenga, "Scale-up of Polysaccharide Fermentation",
Chem. Eng. Prog., 55-61, August, 1988.

Khosla, C., and J.E. Bailey, "The Vitreoscilla Hemoglobin Gene: Molecular Cloning, Genetic
Expression, and Its Effects on In Vivo Heme Metabolism in Escherichia coli", Mol. Gen. Genet.,
214, 158-161 (1988).

Khosla, C., and J.E. Bailey, "Heterologous Expression of a Bacterial Haemoglobin Improves the
Growth Properties of Recombinant E coli", Nature, 331, 633-635 (1988).

CD-A-II-37
Khosla, C., and J.E. Bailey, "Characteristics of the Oxygen-Dependent Promoter of the Vitreoscilla
Hemoglobin Gene in Escherichia coli," J. Bacteriol., 171, 11, 5995-6004 (1989).

Tsai, L.B., M. Mann, F. Morris, C. Rotgers, and D. Penton, “The Effect of Organic Nitrogen and
Glucose on the Production of Recombinant Human Insulin-like Growth Factor in High Density
Escherichia coli Fermentations,” J. Ind. Microbiol., 2, 181-187 (1987).

Zabriskie, D.W., and E.J. Arcuri, Enzyme Microb. Technol., 8, 706-7l7 (1986).


A-II.4.2 Polysaccharides from Microalgae
(Robert M. Busche, Bio-en-gene-er Associates, January 1986)

Research Department has discovered a way to produce polysaccharides (also known as water-
soluble gums or biopolymers) from Porphyridium cruentum, a marine microalga. Process data are
provided in the reference. The product is expected to find uses in existing food markets as a water-
binding thickening agent, competing with such products as xanthan gum, agaur, alginates and
carboxymethylcellulose. A very large potential new use is for enhanced oil recovery, where it can
be used to increase the viscosity of sweep water relative to that of crude oil so as to promote the
mobility of the residual oil in the reservoir. In this service, biopolymers are injected at a rate of 1.4
to 1.7 lb/barrel of oil recovered. Excluding the polymer, the cost of the polymer/sulfonate
surfactant flood amounts to $30 to $40 per barrel of oil (including capital charges).

Your management has asked you to determine if the new product can be produced at a low enough
cost to compete in the food and/or EOR markets.

Reference

Anderson, D.B., and D.E. Eakin, A Process for the Production of Polysaccharides from
Microalgae, Battelle Pacific Northwest Laboratories, Richland, WA (1985).



A-II.4.3 Alitame Sweetener
(Robert M. Busche, Bio-en-gene-er Associates, January 1987)

A new sweetener, named Alitame by its inventors in your Research Division, is a dipeptide amide
of L-aspartic acid and D-alanine. In contrast, aspartame, the amino acid-based sweetener currently
approved by the FDA, is a dipeptide ester and contains L-phenylalanine instead of D-alanine. The
New Products Department has tested the new material in a variety of uses and claims that it is
stable enough for use in baked goods and has a longer shelf life than aspartame. It is also 12 times
as sweet as aspartame and would not be harmful to people with the metabolic disorder,
phenylketonuria, who must limit the intake of substances containing phenylalanine. Use is
projected in foods, beverages, toiletries, and pharmaceuticals.

Alitame is made in a patented process from the corresponding acid and amine. Although alanine
can be purchased from the Japanese, your company is interested in producing both precursors if
CD-A-II-38
economically attractive. You have been asked to evaluate the possibilities and recommend a course
of action that is economically viable.

References

Brennen, T.M., and M.E. Hendrick, “Branched Amides of L ÃAspartyl-D-amino Acid Dipeptides”,
U.S. Patent 4,411,925 (October 25, 1983).

Brennen, T.M., and M.E. Hendrick, U.S. Patent 4,517,379 (May 14, 1985).


A-II.5 PHARMACEUTICALS


A-II.5.1 Generic Recombinant Human Tissue Plasminogen Activator (tPA)
(Scott L. Diamond, University of Pennsylvania, January 2000)

Setting:

Plasminogen activators are powerful enzymes that trigger the proteolytic degradation of blood clots
that cause strokes and heart attacks. Genentech owns the patent for tPA, and currently sells 100 mg
doses of recombinant tPA (activase) for about $2,000. The annual sales for tPA are about $300
MM/yr. However, the patent for tPA will be expiring soon. In response, Genentech has developed
a next generation, FDA-approved, plasminogen activator called “TNK-tPA” which is slightly easier
and safer for clinicians to use.

While a generic form of tPA may not compete well against TNK-tPA in the U.S., there may exist
the opportunity to market a low-cost generic tPA in foreign markets where urokinase and
streptokinase are low-cost (~$200/dose) alternatives that are associated with increased bleeding
risks. Additionally, reduced healthcare reimbursements to U.S. hospitals may allow a generic tPA
to compete against TNK-tPA or activase.


Process:

Produce recombinant tPA using CHO cells. Since Genentech will not license their CHO cells, your
group will be responsible for cloning the human tPA gene and creating a stably expressing cell line
for your process.

Constrants:

1) The product must be sold as a lyophilized, sterile powder (100 mg/bottle).

2) The product must be free of endotoxin contamination.

3) Affinity chromatography will be necessary.
CD-A-II-39

4) Your separation system will operate as a batch system.

5) Your annual production will need to range from 30 to 100 kg/yr.

Determine:

1) Compare the cost of batch and CSTR (4 months per run) bioreactor operations.

2) Design a reverse osmosis/deionized water purification system to supply all process water.

3) Determine the steam requirements for sterilization of the bioreactors.

4) Does an economic opportunity exist for the production of generic tPA? Assume that
Genentech is your only competitor.

5) Estimate the actual production cost per 100 mg/dose for Genentech to make tPA.


Assumptions:

1) Your reactor will use serum-free growth medium.

2) You have licensed the use of a hybridoma cell line that secretes tPA monoclonal antibody
for the development of your affinity columns (life of column is 3 years). The license costs
$120,000/yr.

Prerequisite:

The members of this design group must have completed ChE 479, Intro. to Biotech. and Biochem.
Eng., or the equivalent.


A-II.5.2 Penicillin Manufacture
(Robert M. Busche, Bio-en-gene-er Associates, January 1990)

Your large pharmaceutical company controls a major share of the worldwide penicillin market,
which in 1985 reached about $600 million. However, your plants are relatively old and completely
depreciated, with rising production costs. Management is alarmed that over recent years some
market share has been lost to companies entering the market with new plants. A decision must be
made as to whether to milk the present business as a cash cow without attempting to modernize
(and without regard for further erosion of sales) or to build new facilities to replace the older plants
while aggressively seeking to recapture the market share.

In the latter case, the Marketing Department forecasts that an additional 5 million pounds (about
3.6 billion units) of penicillin G potassium (potassium salt of benzyl penicillin acid) will be
CD-A-II-40
required by the year 2000; with 2 MM pounds by 1992; 3 MM by 1994; 4.1 MM by 1996; and 4.8
MM by 1998. Penicillin G potassium presently sells for about $18 per pound ($25 per billion units).

If a new plant is to be built, the design will be based on state-of-the-art technology using highly
mutated strains of Penicillium chrysogenum growing on glucose (corn syrup). A conventional batch
process will be used unless adaptation to a fed-batch or continuous process appears feasible. A
crystalline product will be obtained after solvent extraction of the beer with amyl acetate or butyl
acetate.

As Director of Engineering, you have been asked to design the plant, determine the investment
required and assess the expected financial performance. You have also been asked to determine the
cost-of-sales for the old plant at which it would no longer be competitive in profitability with a new
plant.

References

Atkinson, B., and F. Mavituna, Biochemical Engineering and Biotechnology Handbook, Nature
Press, New York (1983).

Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Academic Press, New York (1991).

Peppler, H.J., and D. Perlman, Microbial Technology, 2nd ed., Academic Press, New York (1979).

Windholz, M., The Merck Index, 10th ed., Merck & Co., Rahway, NJ (1983).


A-II.5.3 Novobiocin Manufacture
(Robert M. Busche, Bio-en-gene-er Associates, January 1986)

Novobiocin is a general antibiotic produced by an aerobic fermentation of glucose by the organism
Streptomyces niveus. The basic elements of the process appear to be the fermentation of S. niveus
in an appropriate medium of substrate and minerals, the adsorption of Novobiocin (as well as other
non-effective components expressed by the organism) on an ion exchange resin, and the desorption,
concentration, and crystallization of a crude Novobiocin product consisting of 45% Novobiocin,
21% Isonovobiocin, and 34% other similar molecules.

The Research Director of your large pharmaceutical company is interested in initiating research on
producing this product, but before committing funds, has asked you to evaluate the technoeconomic
position the company might develop in this new business. From very preliminary studies, it
appears that the amount of Novobiocin made per fermenter batch is small, and that much
processing will have to be devoted to increasing yield and improving recovery efficiency. Also, as
a result of low product concentration, oxygen transfer in the fermenter and power requirements
appear critical to the design and cost.

Your Information Specialist has developed the following literature references to serve as the basis
for your evaluation.
CD-A-II-41

References

Belter, P.A., F.L. Cunningham, and J.W. Chen, “Development of a Recovery Process for
Novobiocin,” Biotech. & Bioeng., 15, 533-549 (1973).

Karow, E.O., W.H. Bartholomew, and M.R. Sfat, “Oxygen Transfer and Agitation in Submerged
Fermentations,” J. Agr. Food Chem., 1(4), 302-306 (1953).

Kominek, L.A., “Biosynthesis of Novobiocin by Streptomyces niveus,” Antimicrob. Agent
Chemother, 1(2), 123-134 (1972).

Mou, D.-G., and C.L. Cooney, “Application of Dynamic Calorimetry for Monitoring Fermentation
Processes,” Biotech. & Bioeng., 18, 1371-1392 (1976).

Steele, R., and W.D. Maxon, “Some Effects of Turbine Size on Novobiocin Fermentation,”
Biotech. & Bioeng., 4, 231-240 (1962).


A-II.6 POLYMERS


A-II.6.1 Polyvinyl Acetate Production for Polyvinyl Alcohol Plant
(Frank Petrocelli and Steve Webb, Air Products and Chemicals, January
2000)

A grass roots facility to produce polyvinyl alcohol (PVOH) is being constructed in a chemical
complex on the U.S. Gulf Coast. Your design team will complete the process engineering for the
unit which produces polyvinyl acetate (PVAC). PVAC is further reacted in another part of the
facility to produce the PVOH final product. The polyvinyl acetate unit includes the polymerization
reactor system and the downstream recovery process. Your design must be capable of an annual
production rate of 100 MMlb of PVAC intermediate.

PVAC is produced by the free-radical polymerization of vinyl acetate. Your company, PolyPenn,
Inc., has experience and process knowledge using a continuous solution polymerization in which
the solvent is methanol. The process uses a thermal initiator, which costs $5.00/lb. The
decomposition kinetics for the initiator are given by the following expression:

d[I]/dt = - k
d
* [I]
k
d
= 1.4E12 * exp (-23,900/RT) s
-1

R = 1.9872 cal/(mol-K), T is in K

To a first approximation, the polymerization follows classical free-radical polymerization kinetics
(as described by Flory; see references by Billmeyer and by Finch). Reaction conditions must be
chosen to produce a medium-molecular-weight grade of PVAC, defined as a grade having a
number-average molecular weight of 130,000 (i.e., the number-average degree of polymerization,
CD-A-II-42
X
n
= 1,500 repeat units per polymer chain). Again, the references by Billmeyer and by Finch
contain mathematical expressions for determining the polymer molecular weight as a function of
reaction conditions. The reaction temperature must be maintained between 145 and 180°F, and the
reaction pressure must be < 15 psig (this combination of conditions has been shown to reduce the
possibility of a runaway reaction in the event of a process upset). Also, for safety concerns (to limit
the amount of reacting material), the maximum size of any single reactor will be 10,000 gal.

Several decisions must be made in the initial design to choose among options for the process.
Typically, the reaction does not proceed to complete conversion. The molecular weight of the final
PVAC is influenced by the level of conversion (higher conversion lowers molecular weight) and
the concentration of methanol in the reactor (increasing methanol lowers molecular weight). The
polymerization can occur in a series of polymerization reactors. Your design team must decide on
the type of reactor (i.e., CSTR, PFTR, recycle loop), the number of reactors, reactor size, and the
method of heat removal (cooling jacket, cooling coil, and/or overhead condenser). Increasing the
reactor size and the number of reactors can allow higher conversions for a given molecular weight,
which would reduce recovery cost for the monomer. Obviously, there is a trade-off between the
recovery cost and increased capital cost. Additionally, increased reactor size may reduce initiator
use and cost. Your objective should be to find a design which achieves a minimum total cost over
the entire plant life.

After the polymerization reactors, the unreacted monomer must be removed from the polymer
stream. In your company’s existing polymerization units, the monomer is removed in a
distillation/stripping column. Methanol vapor is fed to the bottom of the column and a mixture of
methanol and vinyl acetate monomer is taken as an overhead product. The PVAC exits from the
bottom of the column in a methanol solution. To minimize product color formation, column
temperatures should not exceed 240°F. The bottoms from the PVAC/methanol column must have a
solids content of 36 to 40% to be suitable for existing processing equipment downstream.

Some of the overhead product can be recycled and mixed with the reactor feed; the fraction which
can be recycled is dependent on its composition. Excess overhead product is separated into pure
vinyl acetate and methanol in a separate, existing recovery process - assume a processing cost of
$0.005/lb of recycle for this operation.

Ample cooling water is available at a supply temperature of 90°F and must be returned no higher
than 110°F. Cooling water cost is $0.50/1,000 gal. Saturated steam is available at 150 and 600
psig. The cost of steam is $5.00/MMBtu. Electricity is available at a cost of $0.05/kWh. Use the
market price for the cost of raw materials.

References (an incomplete list):

Billmeyer, Jr., F. W., Textbook of Polymer Science, 2
nd
Edition, Wiley, New York, 1971.

Finch, C. A., Polyvinyl Alcohol Developments, Wiley, New York, 1992.

Liu, D. D., and J. M. Prausnitz, J. Poly. Sci. Poly. Phys., 15, 145 (1977)

CD-A-II-43
Matsumura, K., et al., Kagaku Kogaku, 38, 388 (1974)

Merk, W., et al., J. Phys. Chem., 84, 1694 (1980)

Nakajima, A., et al., J. Poly. Sci., 35, 489 (1959)


A-II.6.2 Butadiene to Styrene
(Bruce Vrana, DuPont, January 1997)

Butadiene (BD) is produced by the expensive extraction of BD from a crude C4 stream in an
ethylene plant. The BD value is about $0.06/lb when it is contained in the crude C4 stream, but
about $0.18/lb after it is extracted. Because of this price difference, processes are always being
sought to use the BD in the crude C4 stream without extracting it, and returning the remaining C4
stream to the ethylene plant. A typical crude C4 stream has the following composition in weight
percent:

30% BD
30% isobutene
20% 1-butene
7% cis-2-butene
7% trans-2-butene
4% n-butane
2% isobutane

Dow has developed a process to dimerize the BD in a crude C4 stream to vinylcyclohexene (VCH)
using a proprietary copper-loaded zeolite catalyst. The second step converts VCH to styrene via
oxidative dehydrogenation using another proprietary tin/antimony oxide catalyst.

Develop a plant design for a world-scale 1 MMM lb/yr styrene process using the new Dow
technology, and determine the overall economics.

The plant design should be as environmentally friendly as possible. Recover and recycle process
materials to the maximum economic extent. Also, energy consumption should be minimized, to the
extent economically justified. The plant design must also be safe to operate (e.g., no flammable or
explosive mixtures).

Assume a U.S. Gulf Coast location. The BD contained in the crude C4 stream is valued at $0.06/lb
in 1997 dollars, and any remaining C4s may be returned to the ethylene plant at no cost. Styrene
sells for $0.30/lb. Oxygen may be purchased across the fence for $0.02/lb.

References

Patent Watch, Chemtech, 20 (May 1995).

U.S. Patent 5,329,057, July 12, 1994.
CD-A-II-44
A-II.6.3 Biodegradable PHBV Copolymer
(Robert M. Busche, Bio-en-gene-er Associates, January 1995)

Because of the capacity limitations of urban landfills, biodegradable plastic packaging materials are
of interest as a means to reduce the load on solid waste disposal systems.

Your research department has developed a mutant form of the bacterium Alcaligenes eutropus that
expresses biodegradable poly (hydroxybutyrate) homopolymers and poly (hydroxybutyrate-
valerate) copolymers. Although the copolymer has a lower melting point, it processes more easily
than the homopolymer. As a result, both may have value in plastic packaging. Under optimum
conditions both the homopolymer and copolymer are produced at volumetric productivities of
about 1.0 g/L-hr. Both products are best produced under phosphate limitation. The copolymer is
produced by adding n-propanol to the ethanol feed. The current research has been based on a fed-
batch fermentation system. However, it has been proposed to use two-stage continuous culture in
which the cells are first grown under conditions for optimum cell growth, followed by a second
stage under conditions optimum for product accumulation. Your research department is eager to
move ahead with the design of a commercial facility and will provide copies of appropriate
references.

In the meantime, however, Dr. Douglas Dennis, an associate professor in the Biology Department
of James Madison University, has cloned into a recombinant E. coli bacterium the genes that
catalyze PHB formation in Alcaligenes. It appears that the new system produces polymer at the
rate of 2.7 g/L-hr. He has offered to provide an exclusive license to Imperial Chemical Industries
(ICI) and will consult on a plant based on the recombinant organism.

As head of the ICI corporate plans department, you have been asked to evaluate the commercial
potential for developing a process to produce both homopolymers and copolymers at your plant at
Atlas Point, south of Wilmington, Delaware. It is of interest to evaluate the economics of both a
homopolymer and a copolymer product and to suggest an optimum split, if one exists. Your
marketing department has suggested a combined capacity of 50 million pounds per year for the first
plant. Either of the alternative processes could be considered.

References

Alderete, J.E., D.W. Karl, and C.H. Park, Production of Poly(hydroxybutyrate) Homopolymer and
Copolymer from Ethanol and Propanol in a Fed-Batch Culture, Biotechnol. Prog., 9, 520-525
(1993).

Anon., E-Coli May Produce Better Plastics, Bioprocess. Technol., 3, (September 1989).


A-II.6.4 Xantham Biopolymer
(Robert M. Busche, Bio-en-gene-er Associates, January 1986)

About 460 billion barrels of crude oil have been discovered in the United States to date, but only
120 billion barrels have been recovered by primary gas drives or secondary water floods. A large
CD-A-II-45
proportion of the remainder could be recovered, albeit at higher cost, by tertiary methods (enhanced
oil recovery).

One such method involves the use of water-soluble polymers such as polyacrylamide to increase
the relative viscosity of sweep water to that of the crude oil so as to promote the mobility of the
residual oil in the reservoir. Polyacrylamide, although relatively cheap, does not possess the useful
properties of polysaccharides such as xanthan gums, scleroglucan, dextran, etc. The biopolymers
are injected at a rate of 1.4 to 1.7 lb/barrel of oil recovered. Excluding the polymer, the cost of the
polymer/surfactant flood amounts to $30 nd $40/barrel, including capital charges.

Your company, a major oil producer, is concerned about the rapid decline in productivity of its
Canyon Reef Reservoir in Kent County, Texas. Your Oil Production Department, which holds
some patents on producing xanthan biopolymers, is considering forming a joint venture with a food
company for developing and operating a fermentation facility to produce the 20 million annual
pounds of polymer needed captively for a polymer flood of Canyon Reef. Merchant sales of
xanthan for food uses by the partner would also be considered if economically desirable.

Your Research Department has confirmed that xanthan can be produced from glucose by the
organism Xanthomonas campestris. Process and product data are summarized in the reports listed
below.

Management has asked you to determine whether xanthan might be produced at a sufficiently low
price to make the proposed EOR operation competitive with the importation of foreign crudes over
the next decade. Your Senior Vice President has also asked whether selling xanthan for current
food uses would help to launch the new business at an earlier date than that compatible with EOR
market economics.

References

Dintzis, F.R., G.E. Babcock, and R. Tobin, “Studies on Dilute Solutions and Dispersions of the
Polysaccharide from Xanthomonas campestris, NRRL B-1459, Carbohyd. Res., 13, 257-267
(1970).

Evans, C.G.T., R.G. Yeo, and D.C. Ellwood, Chap. 3, “Continuous Culture Studies on the
Production of Extracellular Polysaccharides by Xanthomonas juglandis,” in R.C.W. Berkeley,
G.W. Gooday and D.C. Ellwood, Eds., Microbial Polysaccharides &
Polysaccharosis, Academic Press, New York (1979).

Jeanes, A., P. Rogovin, M.C. Cadmus, R.W. Silman, and C.A. Knutson, Polysaccharide (Xanthan)
of Xanthomonas campestris, NRRL B-1459: Procedures for Culture Maintenance and
Polysaccharide Production, Purification and Analysis, ARS-NC-51, USDA Agricultural Research
Service (November 1976).

Kidby, D., P. Sandford, A. Herman, and M. Cadmus, “Maintenance Procedures for the Curtailment
of Genetic Instability: Xanthomonas campestris, NRRL B-1459,” Appl. Env. Microbiol., 33(4),
840-845 (April 1977).
CD-A-II-46

Maury, L.G. (Kelco Biospecialties Ltd.), “Production of Xanthan Gum by Emulsion Fermentation,”
U.S. Patent 4,352,882 (October 5, 1982).

Moraine, R.A., and P. Rogovin, “Kinetics of the Xanthan Fermentation,” Biotech. & Bioeng., 15,
225-237 (1973).

Philips, J.C., J.W. Miller, W.C. Wernau, B.E. Tate, and M.H. Auerbach, “A New High-Pyruvate
Xanthan for Enhanced Oil Recovery,” Society of Petroleum Engineers, SPE No. 10617 (1982).

Sandford, P. A., J.E. Pittsley, C.A. Knutson, P.R. Watson, M.C. Cadmus, and A. Jeanes, “Variation
in Xanthomonas campestris NRRL B-1459: Characterization of Xanthan Products of Differing
Pyrubic Acid Compound,” ACS Symposium Series No. 45, Extracellular Microbial
Polysaccharides, P.A. Sandford and A. Laskin, Eds., American Chemical Society, New York
(1977).

Silman, R.W., and P. Rogovin, “Continuous Fermentation to Produce Xanthan Biopolymer:
Laboratory Investigation,” Biotech. & Bioeng., 12, 7583 (1970).

Sloneker, J.H., D.G. Orentas, and A. Jeanes, “Exocellular Bacterial Polysaccharides from
Xanthomonas campestris, NRRL B-1459, Part III Structure,” Can. J. Chem., 42, 1261 (1964).

Weisrock, W.P. (Standard Oil Company, Indiana), “Methods for Improving Xanthan Yield,” U.S.
Patent 4,301,247 (November 17, 1981).

Weisrock, W.P. (Standard Oil Company, Indiana), “Method for Improving Specific Xanthan
Productivity During Continuous Fermentation,” U.S. Patent 4,311,796 (January 19, 1982).

Weisrock, W.P. (Standard Oil Company, Indiana), “Semicontinuous Method for Production of
Xanthan Gum Using Xanthomonas campestris ATCC 31601,” U.S. Patent 4,328,310 (May 4,
1982).

Weisrock, W.P. (Standard Oil Company, Indiana), “Semicontinuous Method for Production of
Xanthan Gum Using Xanthomonas campestris ATCC 31600 and Xanthomonas campestris ATCC
31602,” U.S. Patent 4,328,308 (May 4, 1982).

Wernau, W.C. (Pfizer, Inc.), “Crude Oil Recovery,” U.S. Patent 4,352,741 (October 5, 1982).


A-II.6.5 Rapamycin-Coated Stents for Johnson & Johnson
(Scott L. Diamond, University of Pennsylvania, January 2002)

In the treatment of heart disease, a common procedure involves balloon angioplasty to expand a
narrowed coronary artery followed by placement of a metal support called a stent to keep the vessel
open. Stenting helps reduce vessel closure, a process called restenosis. However, even stented
vessels can undergo restenosis. There were 926,000 angioplasties in the U.S. in 1998 and 800,000
CD-A-II-47
angioplasties outside the U.S. in 1999. Johnson & Johnson recently finished a clinical trial with
polymer-coated stents that slowly release the drug rapamycin. In 238 patients in Europe, not a
single patient had restenosis after 6 months with the rapamycin-coated stents. Johnson & Johnson
is positioned to obtain over 50% market share in the highly competitive stent market.

Production Criteria

1) Produce and purify medical grade Sirolimus (rapamycin) via batch bioprocessing using
streptomyces fermentation. Determine how much rapamycin you must produce annually and
how many batches will be necessary.

2) You will be provided with the metal stents from the Stent Manufacturing Group. You will
carry out the drug-polymer coating of the stents and deliver the drug-polymer coated stents to
the Catheter Manufacturing Group on a monthly basis.

3) You will buy pure medical-grade speciality chemical components for the polymer coating, but
must develop the coating technology to achieve the correct drug loading and release
characteristics needed in the clinical application. You will have to design a spray-coating
process using ultrasonic nozzles as well as a drying process to remove the solvent. Solvent
recovery is also required. Degradable polymers will include ε-caprolactone-co-glycolic acid.

4) Manufacture: 500,000 drug-polymer coated stents in year 1
1,500,000 drug-polymer coated stents in year 2 and after.

5) Estimate the capital cost and annual operating cost of the drug manufacture and coating
systems.


References

www.uspto.gov U. S. Patent 6,153,252
U. S. Patent 6,273,913

www.ncbi.nlm.nih.gov/ Search pubmed: rapamycin stent
rapamycin streptomyces

Marx, S. O., and A. R. Marks, “Bench to bedside: the development of rapamycin and its application
to stent restenosis,” Circulation. 2001, Aug 21;104(8):852-5. No abstract available.

Chan, A. W., D. P. Chew, and A. M. Lincoff, “Update on Pharmacology for Restenosis,”
Curr. Interv. Cardiol. Rep. 2001 May; 3(2):149-155.

Hofma, S. H., H. M. van Beusekom, P. W. Serruys, and W. J. van Der Giessen , “Recent
Developments in Coated Stents,” Curr. Interv. Cardiol. Rep. 2001 Feb;3(1):28-36.

Sigwart, U., S. Prasad, P. Radke, and I. Nadra, “Stent coatings,” J. Invasive Cardiol., 2001
Feb;13(2):141-2; discussion 158-70.
CD-A-II-48
A-II.7 ENVIRONMENTAL – AIR QUALITY


A-II.7.1 R134a Refrigerant
(John Wismer, Atochem North America, January 2001)

A major shift is occurring in the fluorochemicals industry, particularly in that part of the industry
which manufactures refrigerants. This involves the shift away from chlorine containing CFC’s
(chlorofluorocarbons) and HCFC’s (Hydrochlorofluorocarbons) to HFC’s (Hydrofluorocarbons).
This is because molecules containing chlorine degrade the protective ozone layer of the upper
atmosphere. In automotive refrigerants, the shift has been away from R12 (Dichloro-
difluoromethane) and towards R134a (1,1,1,2-tetrafluoroethane). This market is still growing as
older air conditioning systems are phased out around the world. Refrigerants use a nomenclature
which is universally accepted in the industry. A simplistic version involves the “rule of 90", in
which 90 is added to the refrigerant’s numeric code. In the resulting number, the last digit denotes
the number of fluorine atoms, the second to the last, the number of hydrogen atoms, and the third
from the last, the number of carbon atoms. When another digit occurs, it denotes the number of
chlorine atoms. When the compound is unsaturated, an extra digit is added to the left to indicate
the degree of saturation; “1" indicates a double bond in the molecule. The suffix letters denote the
isomers based on symmetry considerations.

A major focus of the fluorochemicals industry has been to make use of retired HCFC or CFC
manufacturing equipment in the manufacture of new refrigerants. This project involves Penn
Refrigerants, a company with a fluorochemicals complex, which has several pieces of unused
equipment, particularly for distillation. It has a significant infrastructure for handling emissions,
including an aqueous acid neutralization system, an incinerator for liquid organic wastes containing
acids, and a thermal oxidizer for combustion of gaseous wastes. In other words, small waste
streams should not be a problem. It also has significant utilities infrastructure, including low
temperature refrigeration (30 tons @ -40°C), a boiler plant capable of producing 150 psig steam
with 20K lb/hr of unused capacity, an electrical substation which can supply both 460V and 220V
3-phase power, and a large excess of cooling tower capacity.

Penn Refrigerants is aware that there are several technologies available to manufacture R134a.
They are considering licensing ICI’s patented process. You (Quaker Consultants) have been
approached to evaluate the capital required to retrofit the Penn Refrigerants plant on the Gulf Coast
to make R134a using the ICI technology.

The ICI process is documented in U.S. Patent 5,382,722. It involves two reaction steps:

TCE + 3HF → R133a + 2HCl (1)

R133a + HF → R134a + HCl (2)

Not mentioned in the patent, but implied, is that gas phase reaction (2) has a relatively severe
equilibrium limitation. Its heat of reaction is about 6.5 kcal/mol (i.e., endothermic) and the entropy
of reaction is about -2.5 cal/mol-K. Also, the patent mentions a R1122 impurity which boils in the
CD-A-II-49
same range as R134a. This is the most troublesome olefin, but there may be others. One way to
destroy these olefins is with chlorination technology. Penn Refrigerants has chlorine storage and
feed systems available in their plant. Chlorination can be accomplished photochemically or
perhaps, more simply, catalytically. The R134a molecule is resistant to chlorination at the
temperatures used to saturate the double bond. The saturated chlorine-containing compound is
much less volatile than R134a.

Penn Refrigerants has placed constraints on its plant:

Gaseous HF or HCl cannot be compressed.

HCl must be recovered by distillation and absorbed
into aqueous form at 36% concentration.

Inconel 600 or better is required for reactor and HF
reboiler service

There are useful VLE data for mixtures of HF, R133a, and R134a in the Journal of Fluorine
Chemistry, 61, 123-131 (1993). Some LLE data are in European Patent No.
0 509 449 A2. Hydrogen fluoride has some odd thermodynamic characteristics which can make
equipment design of HF systems tricky. A good guess at its enthalpy chart with a good discussion
appears in a paper by Yarboff and Lightcap (J. Chem. Eng. Data, 9, 2, 178, 1964). ASPEN PLUS
uses a special equation of state to approximate the HF association effects. Does this approximation
agree with the Yarboff and Lightcap chart? If not, how might this affect your design?

A listing of major equipment is as follows:

Off Sites
Rail Car Unloading Station with ½ mi spur
Aqueous HCl Storage
Boiler Plant (20K lb/hr excess cap)
Refrigeration at -40°C (30 ton)
Cooling Towers - much excess capacity
Waste Water Lagoon and Neutralization
Liquid Waste Incinerator
Thermal Oxidizer (Gaseous Waste)
High Pressure Refrigerant Storage (400 psig) – 4 x 20,000 gal
HF Storage - 4 x 20,000 gal
Organic Feed Storage - 200,000 gal
Chlorine Storage – 5,000 gal

Process Equipment:
3 3 ft x 80 ft Distillation Cols. with Pall ring random packing (304SS)
3 Condenser Systems – 3,000 ft
2
, 1,000 ft
2
, 600 ft
2
; CS Shell/SS Tubes
3 Reboiler Systems - all 150 ft
2
; CS Shell/SS Tubes
HF Feed Station (1 pump with in line spare; day tank)
CD-A-II-50
Organic Feed Station (1 pump with in line spare, day tank)
Chlorine Feed Station (1 pump with in line spare)
Chlorine Vaporizer (100 ft
2
)
Aqueous HCl Storage - 300K gal

References

U.S. Patent 5,382,722.

Journal of Fluorine Chemistry, 61, 123-131 (1993).

European Patent No. 0 509 449 A2.

Yarboff and Lightcap, J. Chem. Eng. Data, 9, 2, 178 (1964).


A-II.7.2 Biocatalytic Desulfurization of Diesel Oil
(Robert M. Busche, Bio-en-gene-er Associates, January 1994)

The EPA's revised pollution guidelines for on-highway diesel fuels took effect on October 1, 1993,
and additional Clean Air Act amendments are pending. As a result, the sulfur content of diesel fuel
will have to be reduced from 1 to 2% down to 0.05% as compared with 0.3% conventionally
attainable with high-pressure hydrodesulfurization.

For a number of years researchers have attempted with little success to develop a biological system
to remove organic sulfur. However, in 1989, J.J. Kilbane at the Institute of Gas Technology
succeeded in isolating a bacterium that oxidized dibenzothiophene to 2-hydroxybiphenyl and
liberated sulfur.

Based on this discovery, scientists at Energy Biosystems Corp. of Houston, TX, have been
developing a biocatalytic desulfurization process using the bacterial enzyme IGTS8 to catalyze the
reaction in a CSTR bioreactor. The extracellular enzyme is produced by the bacterium in an aerobic
fermenter. The enzyme is then transferred as a supernatant solution to the bioreactor, where it
mixes with high-sulfur diesel oil, oxygen, and other process chemicals. In the reactor, the sulfur is
enzymatically removed from the oil to levels substantially below the 0.05% new regulatory limit
without reducing fuel value. After reaction is completed, the water/oil emulsion is fed to a separator
and the desulfurized oil is transferred to storage. The aqueous phase is sent to a separations unit to
remove the sulfur, after which the enzyme/water mixture is recycled to the bioreactor after taking a
purge of spent enzyme.

Dr. Daniel J. Monticello, VP Research for EBC, has recently invited your oil company to join a
consortium to develop the process to the point of commercialization. Before deciding to accept this
invitation, the director of your Refining Division has asked you to evaluate the expected economics
of the proposed process as compared with the demonstrated costs for hydrodesulfurization in the
30,000-BPD diesel unit in your Richmond, CA, refinery. You are asked to identify the major cost
CD-A-II-51
elements and assess the sensitivity of cost to process improvements that might be effected with
further research on economically critical process parameters.

References

Cooney, C.L., D. Hopkins, D. Petrides, and D.J. Monticello, Microbial Desulfurization of Fuels: A
Process Engineering Perspective, Dept. Chem. Eng., M.I.T., Cambridge, MA (1991).

Foght, J.M., P.M. Fedorak, M.R. Gray, and D.W.S. Westlake, “Microbial Desulfurization of
Petroleum,” in Microbial Mineral Recovery, H.L. Ehrlich and C.L. Brierley, Eds., p. 379, McGraw-
Hill, New York (1990).

Kilbane, J.J., II, and K. Jackowski, “Biodesulfurization of Water-Soluble Coal-Derived Material by
Rhodococcus Rhodochrous IGTS8,” Biotech. Bioeng., 40, 1107-1114 (1992).


A-II.7.3 Sulfur Recovery Using Oxygen-Enriched Air
(Mark R. Pillarella and Rakesh Agrawal, Air Products and Chemicals, January
1993)

The Clean Air Act, passed in 1990 and scheduled to become effective in 1995, will force chemical
companies to reduce their emissions, into the atmosphere, of many environmentally detrimental
chemicals. These include sulfur which occurs as H
2
S in sour natural gas and refinery gas.
Recognizing that sulfur recovery is a fast-growing business, you have recently formed your own
engineering company, SULFREC, which specializes in sulfur recovery. A small chemical
company has requested that SULFREC submit a bid to design a process for removal of sulfur from
a 23-metric-ton-per-day gas stream (90 wt% H
2
S and 10 wt% CO
2
) using the modified Claus
process described below. The principal reactions are:

The H
2
S - CO
2
gas is at 38°C and 1.72 bara. Ninety-five percent of the H
2
S is converted to sulfur.
The sulfur recovery system is to be installed in Houston, Texas.

The modified-Claus process typically uses air as its oxygen source. However, O
2
-enriched air may
provide a more economical alternative. Your company has decided to investigate three alternative
designs, each using the modified-Claus process, but with different oxygen sources:

1. Ambient air

2. O
2
-enriched air using a membrane

3. O
2
-enriched air using vacuum swing adsorption (VSA)

CD-A-II-52
The company requesting the bid has stipulated that a comparison of the three alternatives, as well
as a full design of the most economical process, be submitted.

Information on the modified-Claus process is available in the literature. Information for the design
of the membrane and VSA processes will be supplied by Mark Pillarella at your request.

References

George, Z.M., “Regeneration Process for Poisoned Claus Alumina Catalyst,” U.S. Patent 4,183,823
(January 15, 1980).

Goar, B.G., “Tighter Control of Claus Plants Needed by TGCU System,” Oil and Gas J., 134-137
(August 22, 1977).

Goar, B.G., “Current Claus Tail Gas Clean-up Processes,” Proceedings of the 57th Annual GPA
Convention, New Orleans, LA (March 20-22, 1978).

Kerr, R.K., and E.M. Berlie, “The Claus Process md Reaction Furnace/Burner Operation,” Energy
Processing/Canada (May-June 1977).

Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd ed., Vol. 19, Wiley-Interscience, New
York (1969).

Knight, W.P., “Evaluate Waste Heat Steam Generators,” Hydrocarbon Processing, 248-252
(September 1968).

Knight, W.P., “Improve Sulphur Condensers,” Hydrocarbon Processing, 239-241 (May 1978).

Kunkel, L.V., “GPA H
2
S Removal Panel - Part 3, Claus Process Improvements in Sulphur
Recovery,” Oil and Gas J., 92-99 (August 7, 1978).

Norman, W.S., “There Are Ways to Smoother Operation of Sulphur Plants,” Proceedings of the
Gas Conditioning Conference, Norman, OK (March 1976).

Parnell, D.C., “Claus Sulphur Recovery Unit Start-ups,” Chem. Eng. Prog., 69 (8) (August 1973).

Paskall, H.G., and J.A. Sames, “Optimizing Claus Sulphur Plant Operations,” Sulphur '82:
Proceedings of the International Conference, London (November 1982).

Pearson, “Developments in Claus Catalysts,” Hydrocarbon Processing (February 1973).

Stern, A., Air Pollution Volume III, 2nd ed., p. 660, Academic Press, New York (1968).

Wright, R.D., and J.W. Strange, “Modified Sulphur-Recovery Process Meets Air-Quality
Regulations,” Oil and Gas J., 99-102 (February 22, 1978).


CD-A-II-53
A-II.7.4 California Smog Control
(E. Robert Becker, Environex, January 1995)

Background

A primary gaseous air pollutant from combustion sources such as power plants is oxides of
nitrogen (NO
x
). Since NO
x
is a known precursor to ozone formation, the Clean Air Act
Amendments of 1990 call for reduction of NO
x
from certain facilities throughout the United States.

You are a project engineer for an independent power producer in California. The state has
mandated that your company reduce NO
x
emissions from your Los Angeles facility by 200 tons per
year.

The LA facility currently operates two units, a 25-MW combustion turbine and a set of four 3-MW
(12 MW total) diesel engines. The diesel engines share a common exhaust stream. The NO
x

reduction can come from either unit or both.

You are to design the NO
x
removal system for each unit and determine which of the two systems is
the most cost effective for NO
x
removal.

The primary form of NO
x
for a combustion source is nitric oxide (NO). The NO
x
removal system
to be considered is Selective Catalytic Reduction (SCR).

SCR System Background

SCR removes NO
x
by reacting it with gaseous ammonia (NH
3
) at about 700°F in the presence of a
catalyst according to the reaction:

4 NO + 4 NH
3
+ O
2
→ 4 N
2
+ 6 H
2
O

Kinetics

The rate of reaction is first order in NO
x
and the overall apparent rate constant (combination of
mass transfer and reaction rate) is 43,000 1/hr at 700°F.

A typical SCR system has four major components:

• A liquid ammonia storage tank
• An ammonia vaporizer
• An ammonia injection grid (to evenly disperse the NH
3
across the duct)
• A catalyst

The ammonia injection grid must be designed to evenly distribute the ammonia across the duct
without restricting flow. Since NO concentrations vary across the duct, the ammonia injection grid
must also be designed such that ammonia injection can be adjusted to match the NO concentrations
across the duct of the exhaust system.
CD-A-II-54

Several types of catalysts are used for SCR. The catalyst for this design is an extruded, square
pitched homogeneous catalyst. A schematic of a catalyst brick is given in the figure.

6 in.
6 in.
a
b
pitch


Figure SCR Catalyst Brick

The catalyst bricks are 6 by 6 inches and can be cut up to 3 feet in length. Catalyst bricks are then
arranged side by side and front to back as necessary to achieve the desired dimensions.

The pressure drop over the catalyst is given by:

∆P =
f L v
2
ρ
4 R


where,
f =
57 1 + 0. 0445
2 R
L
|
\
|
.
Re
|
\
|
.
0.5
Re

Nomenclature

L total length of the catalyst in the reactor (e.g. for 2 stacks of 3-ft-long bricks L = 6 ft)
a wall thickness (see the figure)
b open channel width (see the figure)
ε voidage = b
2
/(b+a)
2
(refer to the figure)
f friction factor
ρ gas density
R hydraulic radius of catalyst channel (2 x channel cross section/wetted perimeter)
v gas velocity in the catalyst channel
Re Reynolds number


Design Specifications

Part of your assignment is to design the ammonia injection grid, catalyst and catalyst housing.
Specify the number and arrangement of catalyst bricks and total catalyst volume. The ammonia
CD-A-II-55
injection grid is composed of a series of pipes with holes or nozzles to inject the NH
3
. Keep in
mind that the grid should be designed to evenly distribute the NH
3
across the duct and be flexible
enough to adjust to match NO concentration variations.

Compare the cost of the two units to determine which is the economic choice. Compare both
capital costs and NH
3
consumption over a 10-year catalyst life and the incremental cost on the
power generated.

The turbine and engine specifications are as follows:

Combustion Turbine Diesel Generator (1 of 4)
Power Output 25 MW 3 MW
Fuel Natural Gas Diesel
Exhaust Flow 8,000,000 SCFH 600,000 SCFH
Engine Outlet Temperature 960°F 850°F
NO
x
Emissions 150 ppm 2.0 g/kWhr
Max. Pressure Drop
5 in. H
2
O 5 in. H
2
O
Pressure Drop Cost
$25,000/in. H
2
O per yr
none

Anhydrous NH
3
Cost
170 $/ton
Flue Gas Composition
N
2

73.19 vol%
O
2

13.40 vol%
CO
2

3.40 vol%
H
2
O
10 vol%
SO
2

10 ppmv
CO 25 ppmv
NO
x
as calculated


Catalyst Parameters
Pitch 5.9 mm
Wall Thickness 1.0 mm
Catalyst Cost 300 $/ft
3

Operating Temperature 700 ± 50°F



CD-A-II-56
A-II.7.5 Zero Emissions
(F. Miles Julian, DuPont, January 1991)

For many years your plant on the Texas Gulf Coast has produced tetrahydrofuran (THF) for use as
a synthetic fiber intermediate. The reaction is carried out in water solution, producing a crude THF
which also contains lower aliphatic alcohols as byproducts plus some gamma-butyrolactone (GBL),
which is an unreacted intermediate. The THF is purified in a three-column distillation train. The
impurities have been incinerated or sent with the water to the biological effluent treatment system.

Last week (without consulting the technical staff) your company's Board of Directors issued
a press release stating that the plant is to be converted to a "Zero Emissions" operation by January
1, 1994. Your boss, the Chief Engineer, practically had a coronary on the spot, but he recovered in
time to assign the job to your team. He also scheduled you to make a presentation to the Board of
Directors on April 30, to outline your recommendations and present the economics of the various
possible solutions. In practical terms your job is to reduce emissions to the lowest possible level,
but to do it in the most cost-effective manner.

Some of the ground rules are:

• The three existing columns are not to be modified.

• Fluegas is considered to be an emission (greenhouse effect), so incineration is not
acceptable.

• The cooling tower is not included in the Zero Emissions envelope.

• The biological treatment system is not an acceptable solution for the waste water.

If you can't burn it and can't discharge it, what can you do with it?

A local solvent supplier has offered to buy any of the alcohols which meet the purity
specifications shown below. He has quoted the following prices for tank truck quantities:

99.8% Methanol 11¢/lb 99.5% Propanol 29¢/lb
99.7% Ethanol 29¢/lb 99.9% Butanol 54¢/lb

As an alternative, any mixture of alcohols can be sold as a gasoline additive for 9¢/lb, as long as it
contains no more than 0.5% (wt) water.

THF can be recycled to the crude THF tank at an operating cost savings of 25¢/lb, and GBL
can be recycled to an earlier step in the process at a savings of 15¢/lb. Any water and impurities
which accompany these recycles must be reprocessed through the distillation train, but you may
assume the existing columns can handle this.

Waste water can be used as cooling tower makeup, as long as its organic content is below
50 ppmw. It will replace raw water at a price of 35¢/Mgal.
CD-A-II-57

The waste streams you must deal with are (lb/hr):

Waste 1 Waste 2

Water 20,800 0
THF 11 83
GBL 385 0
Methanol 0 13
Ethanol 0 63
Propanol 361 90
Butanol 556 3

Binary activity coefficient data for these compounds are available.

The following utilities are available for your use:

150 psig steam, dry & saturated, @ $3.25 per Mlb.
50 psig steam, dry & saturated, @ $2.95 per Mlb.
Electricity @ 5.6¢/kWhr
Cooling Tower Water (30˚C) @ 5¢/Mgal


A-II.7.6 Volatile Organic Compound Abatement
(E. Robert Becker, Environex, January 1994)

The 1990 Clean Air Act requires the reduction of volatile organic compound (VOC) emissions. All
VOC emission sources of 10 tons/year or greater are required to retrofit abatement processes using
the best available control technology (BACT).

A paint spraying plant emits VOCs from the vent of its paint spray booths. The stream contains
primarily toluene, methyl ethyl ketone (MEK), and xylene, with small impurities of silicone and
phosphorus. The concentration of VOCs in the dryer effluent varies between a minimum of 0.3
wt% VOC and a maximum of 1.2 wt% VOC with an approximate composition of 50% toluene,
25% MEK, and 25% xylene.

You are commissioned by the painting company to evaluate three alternative technologies for VOC
reduction: thermal incineration, catalytic incineration, and carbon adsorption of the VOCs followed
by destruction. A nearby bottle washing plant can use low-quality steam.

Design an emission control plant for 50,000 scfm of vent gas at 100°F and 25% relative humidity
for 99% removal. The plant is located in Dearborn, Michigan, and the paint spray booths operate
on a single 12-hour shift per day. Include the necessary start-up controls. The available fuel is
natural gas or oil. Calculate the capital and operating cost and the $/lb or ton of VOC removed.
Compare the three processes and recommend which is most suitable for this application.

CD-A-II-58

A-II.7.7 Recovery and Purification of HFC by Distillation
(Ralph N. Miller, DuPont, January 1997)

Your company, BIG-D CHEMICALS, is a major producer of pentafluoroethane (CF
3
CHF
2
), which
is also known as hydrofluorocarbon 125 or HFC-125. HFC-125 is one of the new ozone-friendly
fluorocarbons, and it is a replacement for chloropentafluoroethane (CF
3
-CClF
2
) or CFC-115 in
many refrigerant applications.

In the production of HFC-125, some CFC-115 is produced, and this material must be removed from
the HFC-125 product. In addition, hydrochloric acid (HCl) is always produced as a byproduct, and
it must be recovered as a reasonably pure stream for the process to be attractive.

Your new job with BIG-D is to find the most economical process to recover HFC-125 from a
mixture which contains HFC-125, HCl, and CFC-115. The HFC-125 product must contain no
more than 100 ppm-wt of other organic impurities (e.g., CFC-115, HCFC-124, etc.) and the acidity
level (as HCl) must not exceed 10 ppm-wt. In addition, the process will be more economically
attractive if you can recover anhydrous HCl which contains no more than 10 ppm-wt of organic
impurities. If you are unable to meet the anhydrous HCl purity specification, the HCl must be
absorbed in water (35 wt%) and subsequently air stripped to remove the organic impurities.
Aqueous HCl solutions are a drug on the market and have essentially no value; the absorption route
is used only to avoid neutralization and waste disposal costs. Organics in the air stripper offgas
must be collected and disposed of in an environmentally acceptable manner (e.g., incineration).

For the process to be economical, CFC-115 must be recovered and recycled to the reactor.
Although recycle CFC-115 may contain up to 5 wt% HFC-125, there is a cost penalty associated
with HFC-125 recycle, so you will probably want to minimize HFC-125 in the CFC-115 stream.
The recycle CFC-115 may also contain up to 1 wt% HCl; there is no cost penalty associated with
HCl recycle at this level.

The composition of the feed stream to the new recovery/purification process is: HFC-125 5,000
pph, CFC-115 500 pph, HCl 2,000 pph (available as a saturated vapor at 275 psig). The feedstock
value of this stream is $2.50/lb.

The values of the various product and byproduct streams are as follows:

HFC-125 product (100 ppm organics, 10 ppm HCl) $5.00/lb
HFC-125 in CFC-115 recycle 3.50/lb
Recycle CFC-115 2.50/lb
Anhydrous HCl (<10 ppm organics) 0.15/lb
Aqueous HCl (<100 ppm organics) 0.02/lb

The following utilities and services will be available as/when needed at the battery limits of the
new purification facility. Costs are in 1997 dollars.

Cooling tower water $0.09/1,000 gal *1
CD-A-II-59
150-psig steam $5.00/1,000 lb *1
50-psig steam $4.00/1,000 lb *1
Cooling tower water $0.09/1,000 gal *1
Raw water makeup $0.55/1,000 gal *1
-25°C Refrigeration $0.12/hr/ton *2
-45°C Refrigeration $0.20/hr/ton *2
Electricity $0.065/kWhr *1

*1 Includes allocated investment.
*2 Includes electrical costs for compressors and circulating pumps. Costs for required
cooling water or allocated investment are not included. Compression requirements: -25
°C Refrig. = 2.4 Hp/ton; -45°C Refrig. = 3.6 Hp/ton.

BIG-D's fluorochemicals facility is located on the U.S. Gulf Coast. The new plant will be situated
adjacent to an existing fluorochemicals manufacturing plant and will share some common facilities
(i.e., control room, maintenance shops, technical office building, etc.). Storage facilities exist for
both anhydrous and aqueous HCl. Except for the above, all equipment will be new (i.e., there is no
used/existing equipment available for your use). You can assume an operating utility of 85% (7,446
hours per year) for both new and existing facilities.

CFC-115 (nbp = -39.1°C) and HFC-125 (nbp = -48.1°C) can be removed from HCl (nbp = -
77.5°C) by conventional distillation; this process is energy intensive and requires low temperatures,
but it has been demonstrated in the laboratory. BIG-D's research people have been very creative
and have also developed an extractive distillation process for recovering HFC-125 and making
high-purity anhydrous HCl. The extractive distillation process requires more equipment but uses
less energy. Potential extractants are HCFC-123 (CF
3
-CHCl
2
), which is valued at $3.00/lb, and
HCFC-124 (CF
3
-CHClF), which is valued at $3.50/lb. These materials are available on site as
pressurized liquids at 10°C and 100 psig.

Your assignment is to develop both conventional and extractive distillation processes for
recovering HFC-125 and HCl from the specified feed mixture. You will need to develop optimum
flow sheets, size and cost equipment for each case, and compare the economics of the two
processes. Your flow sheets should include energy recovery (heat integration) as appropriate. You
will also need to develop a control strategy for your preferred case; the control scheme should
address start-up and shut-down conditions as well as steady-state operation.

Notes

1. CFC-115, HFC-125, and HCFCs 123 and 124 are nonflammable and noncorrosive. Carbon
steel is a satisfactory material of construction for pressure vessels; if the temperature is less than
0°C (either operating or upset conditions), a Charpy impact test is required. HCl may be
handled in either stainless steel or low-temperature carbon steel (Charpy impact tested)
equipment.

2. On the U.S. Gulf Coast, cooling towers will supply water at about 31°C in the summertime.
This should be the design basis for any water-cooled condensers or heat exchangers. The CTW
CD-A-II-60
supply temperature is about 10°C during the coldest months. CTW is high in chlorides (due to
evaporation) and is quite corrosive.

3. The largest distillation column on the plant site is 150 ft tall. It was designed by the Plant
Manager when he was a junior engineer a number of years ago. He is quite proud of this
column, and he often points it out to new visitors to the site. You probably don't want to change
this (or his feelings about you).

4. If any of the new process steps operate under vacuum, you should assume there will be air
leakage into the process. While this is not a safety hazard, you will need to include facilities to
remove inerts from the HFC-125 product.

5. Purity requirements for the new HFC products are much more stringent than for your current
CFC products. As a result, analytical techniques have not yet been fully developed to analyze
for low levels of some trace impurities. BIG-D's analytical chemists are currently working to
develop more sensitive analytical methods to identify other impurities.

6. Thermodynamics/physical property information will be provided for the chemical species
which are not available in your simulator's database.

Reference

“Process for Separating HCl and Halocarbons,” U.S. Patent 5,421,964, assigned to E.I. DuPont de
Nemours and Company, Wilmington, DE (June 6, 1995).


A-II.7.8 Carbon Dioxide Fixation by Microalgae for Mitigating the Greenhouse Effect
(Robert M. Busche, Bio-en-gene-er Associates, January 1993)

Although reducing the concentration of carbon dioxide in the atmosphere and its concomitant
greenhouse effect has become an increasingly important public issue, little progress has been made
because the demand for electric power based on fossil fuels continues to grow. Worldwide, one-
third of all carbon dioxide emissions come from electric generating plants. Emission levels can be
lowered in one of three ways: (1) converting to alternative non-fossil fuels such as nuclear or
biomass; (2) increasing the energy efficiency of the fossil fuel-based process; or (3) preventing
carbon dioxide in the flue gas from reaching the atmosphere.

In Japan, Mitsubishi Heavy Industries, Ltd., and Tohoku Electric Company, Inc., have been
experimenting with the use of microalgae to fix carbon dioxide in stack gas for subsequent recycle
as a solid fuel. In this process, the algae, Nannochloropsis salina and Phaeodactylum tricornutum,
are grown in sea water contained in shallow lagoons under an atmosphere of flue gas containing 10
to 12% carbon dioxide. The nutrients NaNO
3
for nitrogen and NaH
2
PO
4
for phosphorus are added
in small concentrations. After harvesting, the microalgae is dried and recycled to the power house
as a solid fuel. The kinetics of the process were defined in the study.

As Branch Chief for the Department of Energy's Office of Carbon Dioxide Emission Control, you
have been asked by the Deputy Secretary to evaluate the possible use of this approach in designing
CD-A-II-61
the emission control facilities for the proposed 600-megawatt generating station to be built between
Los Angeles and San Diego to service the expanding needs of these communities. Government
land can be made available for this purpose.

Specifically, you are asked to evaluate the cost and investment for an algae facility compared with
the best alternative of your choice for reducing emissions by 50%. Alternative approaches to
emission reduction are evaluated in the first four references. Your comments on the efficacy of
other alternatives will also be of interest. Results should be expressed in terms of $/kWhr of
generated electricity. Please test the sensitivity of cost to the levels of emission reduction for the
approaches you consider.

Likewise, since the most effective way to reduce emissions is to increase the energy efficiency of
the generation process, please ascertain the potential equivalent cost reduction vis-a-vis
improvements in energy efficiency, and hence, determine the limiting minimum power cost at
100% efficiency. If data are available for the generation station under evaluation, determine the
pertinent potential cost savings due to improvements in the energy efficiency.

References

Golomb, D., et al., “Feasibility, Modeling and Economics of Sequestering Power Plant CO
2

Emissions in the Deep Ocean,” MIT-EL 89-003 (December 1989).

Haggin, J., “Methods to Reduce CO
2
Emissions Appraised,” C&E News, 24 (September 21, 1992).

Herzog, H., E.M. Drake, and J.W. Tester, “Current Status and Future Directions of Sequestering
Power Plant CO
2
,” MIT, Cambridge, MA (1992).

Herzog, H., D. Golomb, and S. Zemba, “Feasibility, Modeling, and Economics of Sequestering
Power Plant CO
2
Emissions in the Deep Ocean,” Environ. Prog. (February 1991).

Negoro, M., et al., “Carbon Dioxide Fixation by Microalgae Photosynthesis Using Actual Flue Gas
Discharged from a Boiler,” 14th Symposium on Biotechnology for Fuels and Chemicals,
Gatlinburg, TN (May 1992).



A-II.7.9 Hydrogen Generation for Reformulated Gasoline
(E. Robert Becker, Environex, January 1994)

As a result of the Clean Air Act Amendments, hydrogen consumption within refineries will
increase and hydrogen byproduct production from catalytic gasoline reforming will decrease. This
increased use will be brought about by the required reduction of benzene, olefin, aromatics, and
sulfur in gasoline and the reduction of aromatics and sulfur in diesel fuel. This demand will, in
most cases, be met by on-site facilities for the production of hydrogen.

Hydrogen is currently produced by either steam reforming of methane or by partial oxidation of
methane with high-purity oxygen and steam. Your research department has developed a new
CD-A-II-62
autocatalytic reactor using air, methane, and steam that has some very definite advantages. They
are:

1. Refinery use will require high-purity hydrogen (99.9%) to minimize inert build-up in the
recycle hydrogenation processes. In the autocatalytic process, the hydrogen separation is
much easier than the nitrogen-oxygen separation and is less energy demanding than the
reforming operation with steam.

2. The catalytic process operates at a lower temperature than is required for the steam
reforming (1,000˚C as compared with 1,400˚C for the Shell/Texaco process). Moreover,
the equipment is much simpler. The process can also be operated at higher pressures, thus
saving on compression of the product hydrogen.

In the proposed process, methane, steam, and air are each preheated to 600-700˚C and fed into a
catalytic reactor containing a bed of refractory nickel catalyst. Initial combustion results in a
temperature up to 1,000˚C. The gas passes through heat exchange and a heat recovery boiler before
entering a multi-stage CO shift converter. The gas then passes through a CO
2
wash tower to a
cryogenic separation unit where the hydrogen is separated from the nitrogen, argon and methane.

You are required to prepare a preliminary cost estimate for a plant to produce 50 MM scfd 99.0%
hydrogen at 30 atm. The following design data should be used for this evaluation.

H
2
O/CH
4
feed ratio > 2.0 to prevent carbon formation

CO shift conversion is 99% of equilibrium.

Cost Data

Methane (100%) 30 atm $2.00/Mscf
Steam 30 atm satd. $6.00/1,000 lb
Power $0.07/kWhr
Cooling Water 90˚F $0.15/1,000 gal
Catalyst cost $10.00/kg

Economic Guidelines

Annual effective interest rate = 9%/yr
Project life = 10 yr
Minimum acceptable investor’s rate of return (IRR) = 15%

Catalyst

The refractory nickel catalyst is a spherical pellet of 0.005 m diameter. The catalyst bed has a void
fraction of 0.48 and a bulk density of 1200 kg/m
3
. The catalyst must be replaced annually.

Kinetic Data

Rate of methane reacting (kmol/kg cat./hr) = 1.96 x 10
7
exp(-44,200/RT) x P
M
/(1 + 4P
H
)
2


where P
M
= partial pressure of methane in bar
P
H
= partial pressure of hydrogen in bar

CD-A-II-63
The reaction on the catalyst is limited by the cracking reaction of methane, and the product gases
(CH
4
, CO, CO
2
, H
2
, H
2
O) exist in near-equilibrium conditions.


A-II.8 ENVIRONMENTAL – WATER TREATMENT

A-II.8.1 Effluent Remediation from Wafer Fabrication
(1993 Environmental Design Contest Problem)

It is required to design a plant to clean 15,000 gpd of the following waste stream from a wafer
fabrication/computer manufacturing facility:

Cu 120 mg/L as Cu
Pb 20 mg/L as Pb
Sn 20 mg/L as Sn
Oil and grease 250 mg/L
Suspended solids (suspended copper,
fiberglass, bentonite clay, etc.) 650 mg/L
Acids
Fluoroacetic Acid 100 mg/L
Fluoroboric Acid 300 mg/L
Acetone 350 mg/L
EDTA 120 mg/L
Methyl Methacrylate 200 mg/L
Ammonium Hydroxide 200 mg/L
Formaldehyde 50 mg/L
Methanol 200 mg/L
Hardness 150 mg/L as CaCO
3


The treated effluent stream must satisfy the following limits:

COD = 300 mg/L F = 5 mg/L
Cu = 2.7 mg/L TOC = 130 mg/L
Pb = 0.4 mg/L Oil and Grease = 30 mg/L
Sn = 1.0 mg/L TSS = 200 mg/L
B = 1.0 mg/L pH = 6-8
NH
4
+
= 20 mg/L as N Total metals = 4.5 mg/L

where COD is chemical oxygen demand, TOC is total oxygen content, and TSS is total suspended
solids.

There are no restrictions on the method(s) you select for remediation (e.g., physical, chemical,
biochemical, leading, etc.). However, it is desirable not to generate much additional waste in the
clean-up process. It is also desirable to find modifications that reduce the waste generation to
levels that satisfy the effluent limits. Note that your company has sufficient capacity to store the
CD-A-II-64
contaminated stream for one month. Your design report should address health and regulatory
issues.


A-II.8.2 Recovery of Germanium from Optical Fiber Manufacturing Effluents
(Based on the AIChE Student Contest Problem, January 1991)

The manufacturing process for making optical fibers involves high temperature oxidation of silicon
tetrachloride (SiCl
4
) to form glass particles (SiO
2
and GeO
2
) that are incorporated into a glass
preform rod. This rod is subsequently drawn in a furnace to produce optical fiber. Germanium
tetrachloride is added to increase the refractive index of the glass core in the optical fiber preform.
It is known from experimental studies that the oxidation of GeCl
4
to GeO
2
proceeds to only 25%
completion whereas oxidation of SiCl
4
is nearly complete. In addition, particle deposition is only
50% efficient, resulting in further losses of germanium. Due to this loss and the high cost of
germanium, a need exists for developing a process to recover germanium from optical fiber
manufacturing effluents. For environmental reasons, the process design must also provide for the
removal of chlorine and particles.

Your company currently operates with 50 preform manufacturing units. Each unit is equipped with
a small packed-column scrubber that is known to be underdesigned based on the current effluent
production rates. The scrubbing solution is not recirculated and there is no recovery of germanium.
Your engineering group has been designated to prepare a process design for a new scrubbing
system to efficiently remove GeCl
4
, Cl
2
, and particles from the effluent stream:

GeCl
4
200 g/min
SiO
2
75
GeO
2
1
Cl
2
375
O
2
7

The new scrubbing system should remove 99% of both GeCl
4
and Cl
2
. You should also design a
system to recover germanium and convert it to GeCl
4
.

In the existing process, vapors of SiCl
4
and GeCl
4
in an excess of oxygen are introduced into the
optical fiber preform production units where the following reactions occur at high temperature:

SiCl
4
+ O
2
=

SiO
2
+ 2Cl
2
(1)
GeCl
4
+ O
2
=

GeO
2
+ 2Cl
2
(2)

Both reactions reach equilibrium which corresponds to 100% completion for reaction 1 and 25%
completion for reaction 2. Incorporation of solid particles into the glass preform rod is only 50%
efficient. The effluent stream therefore contains SiO
2
and GeO
2
particles, unreacted GeCl
4
and O
2
,
and the reaction product Cl
2
.

Currently, effluents from each preform production unit are drawn into small (0.25 m diameter, 0.5
m high) packed bed scrubbers. The scrubbing liquid is an aqueous NaOH solution adjusted to pH
13. A single fan unit draws the effluents into the scrubbers. Due to operating requirements, it is
not possible to make a tight seal between the effluent stream outlet and the inlet to the scrubbing
system. Hence, the effluent stream gets diluted with a large amount of room air as it enters the
scrubber.
CD-A-II-65

Within the scrubbers, GeCl
4
and Cl
2
are removed from the gas stream by absorption and converted
to soluble species according to the following reactions:

GeCl
4
+ 5OH
-
=

HGeO
-
3
+ 4Cl
-
+ 2H
2
O (3)
Cl
2
+ 2OH
-
=

ClO
-
+ Cl
-
+ H
2
O (4)

The particles dissolve according to:

GeO
2
+ OH
-
=

HGeO
-
3
(5)
SiO
2
+ OH
-
=

HSiO
-
3
(6)

Hydrogen peroxide (H
2
O
2
) is also added to the system to reduce the hypochlorite concentration
according to:

ClO
-
+ H
2
O
2
=

Cl
-
+ H
2
O + O
2
(7)

The R&D department has found that germanate (HGeO
-
3
) can be quantitatively removed from
solution by precipitating with a divalent cation such as Mg
2+
according to:

Mg
2+
+ HGeO
-
3
=

MgGeO
-
3
(ppt) + H
+
(8)

Similarly, silicate ions are precipitated according to:

Mg
2+
+ HSiO
-
3
=

MgSiO
3
(ppt) + H
+
(9)

Experiments have shown that HGeO
-
3
and HSiO
-
3
are precipitated equally well and that a mole
ratio of 1.25 to 1 for Mg to total of Ge + Si is required to precipitate 100% of the Ge and Si. Mg
can also be precipitated as Mg(OH)
2
according to:

Mg
2+
+ 2OH
-
=

Mg(OH)
2
(ppt) (10)

The R&D department has also measured the solubility of Ge and Si in scrubbing solutions at
various pH values. The results are presented in a table (available from the AIChE) and may be
useful in the design of a germanium recovery system.

MgGeO
3
can be used as a feed to make GeCl
4
which, after purification, can be used in optical
fiber production. The tetrachloride is formed according to:

MgGeO
3
+ 6HCl =

GeCl
4
+ MgCl
2
+ 3H
2
O (11)

Additional reactions that may also take place include:

MgSiO
3
+ 6HCl =

SiCl
4
+ MgCl
2
+ 3H
2
O (12)
MgGeO
3
+ 2HCl =

GeO
2
+ MgCl
2
+ H
2
O (13)
MgSiO
3
+ 2HCl =

SiO
2
+ MgCl
2
+ H
2
O (14)
Mg(OH)
2
+ 2HCl =

MgCl
2
+ 2H
2
O (15)
NaOH + HCl =

NaCl + H
2
O (16)
CD-A-II-66

These reactions are known to occur rapidly.


A-II.8.3 Solvent Waste Recovery
(David G. R. Short, DuPont, January 1997)

Your company operates a polymer-processing facility which has three major waste streams. While
there have been no major problems with the regulatory agencies in the past, the new CEO wants all
facilities to have an environmentally friendly image. And there is a definite smell from your bio-
pond which the neighbors complain about when the wind shifts. In addition, the existing permits
are coming up for renewal. While the negotiations are seen as friendly, the expected outcome is to
renew the current permit provided that an improved waste system is in place by the year 2002. The
CEO thinks there is an economic incentive to have the facility running sooner.

Waste Streams

1. Air Stream: 40,000 scfm (60°F, 1 atm) air at 120°F, 2 psig. Contains 7 lb/hr acetaldehyde
and 7 lb/hr methanol.

2. Water 1 stream: 100 gpm Water with 2 percent acetaldehyde.

3. Water 2 stream: 100 gpm water with 3 percent ethylene glycol.

Current Facilities

1. The air stream is vented to the atmosphere.

2. The water wastes are sent to a bio-pond. The waste chemicals are oxidized to CO
2
and
H
2
O. The pond is sparged with air to provide oxygen for the bacteria. The pond is at
capacity. The holdup time for the complete oxidation of the wastes is 36 hours.

Specifications

1. > 90% removal of all contaminants from the waste streams. This includes any new vent
streams which may be created in the waste facility.

2. If solvents are recovered for reuse, the purity must be at all times > 99.5% pure with water
as the major impurity.

3. The waste-handling system must never shut down the production plant.

Upset Conditions

1. The air flow can decrease by as much as 50% in 30 seconds. The total contaminant load
will stay the same.
CD-A-II-67

2. The Water 1 stream has shown short-term flow rate fluctuations of 10% with no change in
contaminant concentration.

3. The Water 2 stream has shown short term fluctuations of as much as 50% with a 2 ×
increase in the contaminant concentration.

Expansion Plans for the Polymer Facility

1. There is a high probability that the air stream will double in size, but the contaminants will
increase by 50%.

2. The Water 1 stream will most likely have the same flow rate, but the concentration may be
as high as 5% acetaldehyde.

3. The Water 2 stream will most likely double, but the concentration will be cut to 2%
ethylene glycol.

Assignment

Design a facility that will meet the above specifications. Include in your study:

1. A discussion of alternatives to your final process.
2. A detailed development of your selected process.
3. A demonstration that the process is operable, using a model that shows the process can be
started up, operated, and shut down.
4. A demonstration of the process sensitivity to changes in feed conditions.


A-II.9 ENVIRONMENTAL – SOIL TREATMENT


A-II.9.1 Phytoremediation of Lead-Contaminated Sites
(Robert M. Busche, Bio-en-gene-er Associates, January 1995)

A large chemical company quartered on the East Coast spends about $400 million annually to
remediate contaminated aquifiers and sites associated with past manufacturing operations. Much of
this is spent on sites contaminated with lead from the manufacture of tetraethyl lead, lead-based
paints, and lead cartridges. For example, the soil of a 25-acre site within a large plant located in
New Jersey contains as much as 2,000 ppm of lead as inorganic salts to a depth of 2 feet. The
distribution is as follows: at the surface, 2,000 ppm; 6”, 1,000 ppm; 12”, 500 ppm; 24”, 0 ppm.

A straightforward, albeit expensive way, to remediate this site would be to excavate the top 2 feet
of soil and replace it with uncontaminated fill, then mix the contaminated material with cement to
stabilize the lead, and dump it into a landfill. The cost of the remediation alone was estimated to
CD-A-II-68
amount to about $9 million. An additional $1.8 million would also be required for documentation,
sampling, analytical tests, decontamination, etc.

Alternatively, Dr. Scott Cunningham, of Central Research's Environmental Remediation Services,
has been experimenting with hyperaccumulating plants that can absorb lead and other heavy metals
at up to 2% of the dry biomass weight. Such plants can produce 20 tons (dry basis) per acre per
harvest of vegetative matter. Cunningham has identified as candidate crops a perennial plant, hemp
dogbane, which yields a single annual crop, and two annual plants, brassica (Indian mustard) and
common ragweed. Brassica can be planted in the spring and fall to yield two crops annually.
Ragweed is planted in early summer and harvested in the fall before blooming. Operators involved
in the planting, harvesting, and handling of the biomass are required to wear Level C personnel
protective equipment (PPE), e.g., hooded, unlined Tyvek coveralls, goggles, and masks.

After harvest the biomass can be treated in a number of ways:

1. It can be incinerated to reduce its volume by 75%. The ash is then stabilized with cement
and landfilled; or

2. It can be chopped, dried, and then fed pneumatically to a flame reactor as developed by the
Horsehead Resource Development Company of Monaca, Pennsylvania. Natural gas and
oxygen-enriched air (40 to 70% oxygen) are fed to the reactor with the biomass to produce a
very hot reducing gas at 2,000°C. Under reducing conditions the biomass is consumed to
produce carbon monoxide while the lead compounds are reduced to elemental lead vapor.
Small amounts of biomass minerals and dirt from the harvest operation are melted into slag,
which flows down into a horizontal separator where it is separated from the lead vapor. The
nonhazardous slag is tapped, cooled, and disposed of in a landfill. The lead vapor is passed
into a combustion chamber, where it is converted into the oxide, cooled with cold air,
collected in a bag house, and stored. (It is extremely difficult and expensive to quench lead
vapor without converting to the oxide.) The crude oxide is sold to a lead smelter at about
50% of the price for pure lead (currently 38 to 40 cents per pound); or

3. It can be chopped and fed with suitable nutrients to an anaerobic digester wherein 95% of
the carbohydrate is converted to a mixture of carbon monoxide and carbon dioxide. In the
process the lead precipitates as lead sulfide and is centrifuged to separate it from the
residual carbohydrate and water. The aqueous layer is recycled to the digester after taking a
suitable purge to bleed off salts. The aqueous waste can be treated with lime to precipitate
the salts. As with alternative 2, the lead sulfide can be sold to a lead smelter at 50% of the
price for pure lead.

As a member of your corporate plans department, you have been asked to evaluate the
technoeconomic position of phytoremediation and recommend an appropriate plan of action for
remediating the site to the plant manager. Cunningham has promised to provide additional
information and, perhaps, a tour of his laboratory. John Pusateri of Horsehead will perhaps provide
a tour of his pilot facilities.

CD-A-II-69
References

Baker, A.J.M., and R.R. Brooks, “Terrestrial Higher Plants Which Hyperaccumulate Metallic
Elements - A Review of Their Distribution, Ecology and Phytochemistry,” Biorecovery, 81-126,
Academic Publishers, Great Britain (1989).

Berti, W.R., and S.D. Cunningham, Remediating Soil Lead with Green Plants, Int'l. Conf. Soc.
Environ. Geochem. and Health, New Orleans, LA (July 25-27, 1993).

Cunningham, S.C., and W.R. Berti, “Remediation of Contaminated Soils with Green Plants: An
Overview,” In Vitro Cell. Dev. Biol., 29, 207-212 (October 1993).

Farago, M.E., A.J. Clark, and M.J. Pitt, “The Chemistry of Plants Which Accumulate Metals,”
Coord. Chem. Rev., 16, 1-8 (1975).


A-II.9.2 Soil Remediation and Reclamation
(1993 Environmental Design Contest Problem)

A large area (hundreds of square miles) in an arid region of the Pacific Northwest has been
contaminated with fallout from a neighboring manufacturing region. The site is to be both
remediated and reclaimed. Remediation will be defined as reducing the concentration of identified
contaminants below the threshold values listed below. Reclamation will include the use of a water
harvesting system to enhance the growth of natural vegetation or agricultural crops on the site.

Water harvesting is an ancient concept that has been applied to increase biomass production in arid
and semi-arid lands. Water harvesting concepts currently applied in arid lands continue to be
somewhat primitive technically and small in scale. The desire to improve the technical state of
water harvesting by finding, selecting, designing and/or testing sealants for catchment areas and by
developing equipment that can apply the sealants on very large areas (hundreds of miles) in
relatively short times (a few years) in a cost effective manner. These water harvesting catchments
(sealed areas) may be tied into no drainage growing strips.

The design team is given the following three tasks:

1. Develop and demonstrate a bench scale process to remove the identified contaminants from a 5-
kg sample of the soil. Develop a conceptual design of the process applicable to the field-scale
project.

2. Develop and demonstrate a non-geomembrane, UV-resistant, water-repellent, erosion-resistant,
sealant that can be applied to the soil surface as an aid in water harvesting.

3. Develop a conceptual design for a machine capable of applying the sealant developed in task 2
to the surface of the remediated area.


Regional and Soils Description

The area to be remediated is located adjacent to a large river in an arid climate. Natural vegetation
is desert shrub and bunch grasses. Soil material is the result of catastrophic flooding followed by
CD-A-II-70
deposition of river alluvium. The resulting material is a mixture of cobbles and sandy loam soil
material. The following particle size description is typical of the material at the remediation site.


SOIL

Component


______________
Size (mm)


______________
Weight Basis
(%)

______________
Weight Basis
(%)
< 2mm
______________
Large cobbles 305 15 None
Small cobbles 152 30 None
Fine pebbles 8.5 5 None
Very course sand 2.000 10 20
Course sand 1.000 7 14
Medium sand 0.500 7 14
Fine sand 0.250 5 10
Very fine sand 0.106 4 8
Silt and clay 0.050 17 34
TOTAL 100 100

To approximate this material with a soil from New Mexico, we have chosen the soil series Casito
(Petrocalcic Ustollic Paleargrid). This soil is formed in alluvium at the base of mountain
watersheds. It is found on alluvial fans and terraces. It contains a similar mixture of cobbles and
fines as the remediation site; however, the source of the alluvium is storm runoff rather than
catastrophic flooding and river deposition. Provided below is some additional information on the
contaminants in this soil.


Contaminants:
Concentration
Category per kg of soil

1. Pesticides, herbicides, insecticides
Lindane (C
6
H
6
Cl
6
) 150 mg
Methoxychlor (Cl
3
CCH (C
6
H
4
OCH
3
)
2
) 150 mg
Endrin (C
12
H
8
OCl
6
) 150 mg

2. Metals
Cadmium (Cd) 350 mg
Silver (Ag) 100 mg
Copper (Cu) 100 mg


3. Organic Compounds
Ethyl Benzene (C
6
H
5
C
2
H
5
) 75 mg
Methyl isobutyl ketone
CH
3
-CO-CH
2
-CH-(CH
3
)
2
100 mg

4. Halogenated compounds
CD-A-II-71
Chloroethene (CH
2
CHCl) 75 mg
Tetra Chloroethylene (C
2
Cl
4
) 100 mg

The contamination is a surface type contamination (<1' deep) and must be removed to the following
levels:

1. Pesticides, herbicides, insecticides
Lindane (C
6
H
6
Cl
6
) 10 mg
Methoxychlor (Cl
3
CCH (C
6
H
4
OCH
3
)
2
) 10 mg
Endrin (C
12
H
8
OCl
6
) 10 mg

2. Metals
Cadmium (Cd) 15 mg
Silver (Ag) 15 mg
Copper (Cu) 15 mg

3. Organic compounds
Ethyl benzene (C
6
H
5
C
2
H
5
) 10 mg
Methyl isobutyl ketone
CH
3
-CO-CH
2
-CH-(CH
3
)
2
10 mg

4. Halogenated compounds
Chloroethene (CH
2
CHCl) 14 mg
Tetrachloroethylene (C
2
Cl
4
) 14 mg

See the complete problem statement (1993 Environmental Design Contest Problem), which
contains a detailed discussion of the tasks and the evaluation criteria.



A-II.10 ENVIRONMENTAL – MISCELLANEOUS


A-II.10.1 Fuel Processor for 5 KW PEM Fuel Cell Unit
(Jianguo Xu and Rakesh Agrawal, Air Products and Chemicals, January 2002)

Fuel cell technology is considered to be a disruptive energy technology. Fuel cells use fuel in an
electrochemical combustion process that converts the chemical potential of the fuel with respect to
the combustion product directly into electrical power. They are more efficient and more
environmentally friendly than conventional energy technologies. Fuel cells, especially the proton
exchange membrane (PEM) fuel cell, are being considered for distributed power generation (DG).
Using a fuel cell for DG reduces the energy loss due to power transmission, and can eliminate
power outages due to weather-related or other causes. It also allows for efficient use of the low-
level waste heat from the power generation process. This low-level heat can be used for producing
hot water, and for room heating. Since the PEM fuel cell uses hydrogen gas as fuel, a supply of
hydrogen gas has to be installed for a fuel-cell power generator to work.

Hydrogen for use in residential fuel cells can be produced from pipeline natural gas using a fuel
processor. Assume that a residential, fuel-cell, electric-power generator with 5 kW electricity
output has an efficiency of 50% (the electricity output from the fuel cell is 50% of the lower
CD-A-II-72
heating value of the hydrogen consumed in the fuel cell). The desired hydrogen pressure is 0.5
barg. Note that the CO content in the hydrogen supplied to the fuel cell must be below 10 ppm, and
the sulfur content must be less than 0.1 ppm. Nitrogen, carbon dioxide, methane, water vapor, and
other inert gases are not poisonous to the fuel cell. For design purposes, a fuel gas with less than 3
vol% of hydrogen cannot be used to fuel the fuel cell.

A possible approach: Natural gas can be converted at a high temperature into hydrogen, CO, CO2
(syngas) in a steam reformer or partial-oxidation reactor, or autothermal reformer which is a
combination of the first two. Most of the CO in the syngas is typically converted into carbon
dioxide at a lower temperature in a water-gas shift reactor. The remaining small amount of CO
must be removed to below 10 ppm level. This can be done using adsorption, or membrane
separation, or catalytic preferential oxidation (at about 90°C with an air stream), or other practical
means. Also, there are designs with membrane reformers in the literature.

Natural gas composition and pressure: use that available at the sight of your plant. If no data can be
found, use the data below:

vol%
methane 95
ethane 2.0
propane 1.5
butane 0.65
pentane 0.35
nitrogen 0.5

organic sulfur 2 ppm

5 barg

References

Chemical Engineering, July 2001, pp. 37-41
AIChE Journal, July 2001, perspectives article.


A-II.10.2 Combined Cycle Power Generation
(William B. Retallick, Consultant, January 2001)

The wave of the future in power generation is the combined cycle, in which gas turbines are
combined with steam turbines, with the hot exhaust from the gas turbine used to generate steam.
The combined cycle is a cascade of heat engines operating over temperatures from 1200-1300°C to
about 30°C. This broad temperature range renders the combined cycle efficient.

A gas turbine is comprised of three main parts. The compressor compresses the inlet air to the
pressure in the combustor, with fuel injected into the latter. Hot combustion gases are expanded in
CD-A-II-73
the turbine, which drives the compressor, with the bulk of the power produced by the turbine
consumed by the compressor.

The final stage(s) in the turbine comprise a “free” turbine. These stages are mounted on the shaft
of an electric generator, rather than the shaft of the main turbine. To generate 60-cycle power, the
free turbine rotates at 3,600 RPM. Note that the main turbine rotates at 8,500 RPM. The exhaust
gas from the free turbine is sent to the steam generator.

There are two kinds of steam turbines. In a condensing turbine, the exhaust steam is condensed
using cooling water, at a pressure determined by the temperature of the cooling water. In an
extraction turbine, the exhaust steam is not condensed, rather it is exhausted at an intermediate
pressure to be reheated and used in a condensing turbine.

The efficiency of the combined cycle is determined almost entirely by four parameters:

• The temperature of the combustion gas entering the turbine, here
assumed to be 1,250°C.
• The efficiency of the compressor, here assumed to be 89%.
• The efficiency of the turbine, here assumed to be 90%.
• The efficiency of a steam turbine, here assumed to be 89%.

The gas turbine is operated at a compression ratio that maximizes the work produced per weight of
air, as explained in the first reference. Your turbine is equivalent or similar to the W501G turbine
described in the second reference. Its electrical power output is 230 MW, which fixes the size of
your combined cycle. You are to configure a set of steam generators and steam turbines that
provides the economic-optimum amount of electric power from the heat in the exhaust from the
free turbine.

Design Basis

The fuel gas composition (mol %) is:

Methane 96
Ethane 3
Propane 1

The gas is delivered at 400 psig.
The ambient air is 25°C and 40% relative humidity.
Cooling water for the condensing turbine is at 30°C.
The efficiency of an electric generator is 98%.
The plant is located in Pennsylvania.

CD-A-II-74
Your report should include:

The plant efficiency, kwh of fuel per kwh of electrical power.
A graph of the investor’s rate of return (IRR) as it varies with
the selling price of power, for different costs for the fuel gas.

References

Chem. Eng. Prog., May, 2000, page 69.
Diesel and Gas Turbine Worldwide, July-August, 2000, page 42.


A-II.10.3 Production of Low-Sulfur Diesel Fuel
(Matthew J. Quale, Mobil Technology Company, January 2000)

There is a trend in recent environmental legislation to lower sulfur specifications in both gasoline
and diesel fuels. You work for a refinery in the Delaware Valley that anticipates a new diesel
specification requiring an order of magnitude lower sulfur than currently allowed. In fact,
legislation is already in the works in Europe to lower the allowable sulfur to this new level by the
year 2005. To achieve these low sulfur levels, you are to design a new catalytic hydro-
desulfurization (HDS) system. This type of reactor has been in use in industry for a long time, but
never for such severe service.

This unit will require just two feeds: a liquid feed blend from your refinery, and hydrogen. Since
your refinery does not have a reforming unit (common hydrogen source within a refinery) or a
hydrogen plant, you will have to buy the necessary hydrogen from a third party. Fortunately, a
group similar to yours (1998/1999 Penn Senior Design Group – Khandker et al., 1999) recently
designed a new hydrogen plant for the Delaware Valley that should be on-stream shortly before
your unit and they are looking for new long-term supply agreements. Use the conclusions from
their published report for information on the hydrogen purity and price. (I would recommend
researching current contract hydrogen prices to ensure they are charging a reasonable price,
however.)

Your R&D department has done substantial pilot plant work on this new process and has
determined the following correlations to assist you in designing the HDS reactor. You also have
processing data available from an older HDS unit within your company to use as a baseline.

Processing Conditions

A common value to track while designing a HDS unit is the percent hydrodesulfurization (%HDS):

% 100
) S wt% (
) S wt% (
1 HDS % ×
(
(
¸
(

¸

− =
feed
product


Different catalysts have different intrinsic activities, aging rates, and processing
abilities/robustness. For your particular feedstock, the R&D department found the following
CD-A-II-75
correlations based on a reference catalyst. Terms denoted with a “
0
” are the baseline data provided
in Table 2. The start-of-cycle (SOC) temperature is given by

( ) ( )
(
¸
(

¸

× −
(
(
¸
(

¸

× −
(
(
(
(
(
¸
(

¸

|
|
.
|

\
|

|
|
.
|

\
|

× +
|
|
.
|

\
|
× + =
0 2
2
0
0
0
0
Circ. H
Circ. H
ln D
P
P
ln C
1
S
S
1
S
S
ln B
SV
SV
ln A T T
2
2
H
H
product
feed
product
feed
SOC


where T
SOC
and T
0
are in °F. The aging rate is given by

( )
|
|
.
|

\
|

×
(
(
¸
(

¸

× =
SOC 0
2
2 T
1
T
1
F
E
0
0
e
H
H
P
P
AR AR
where T
SOC
and T
0
are in °R.

The values for constants (A – F) and the base and proposed operating parameters are given in the
following tables. Please note that the equation and constants are Mobil Corporation internal
numbers and should be cited as such.

Table 1
Constant Value
A 45
B 44
C 20
D 30
E 1.7
F 18,000

Table 2
Base
Operation
Proposed
Operation
Target Product Sulfur wt% 0.05 0.005
Feed Sulfur wt% 1.9 1.9

Reactor Conditions
Feed Rate TBD 35 35
SpaceVelocity (SV) hr
-1
1.0 ??
H
2
Circulation scf/bb
l
800 1,000 (min.)
H
2
Partial Pressure psia 630 800 (min.)
SOC Temperature °F 632 ??
Aging Rate °F/mo 4.7 ??

CD-A-II-76
The circulation and pressure values for the proposed operation are given as minimums to
achieve the necessary product specifications. Increasing these values will improve the
catalyst life, but result in higher capital and operating costs. It is left to you to determine the
optimum values from an economic standpoint. To determine the catalyst cycle length, take
750°F as the maximum average bed temperature because higher values will produce product
which has a color greater than ASTM 2.0 (the current spec).

Feed and catalyst information along with a brief overview of catalytic hydroprocessing
(HDS in particular) will be presented to your group prior to beginning the project.

References

Grancher, P., Hydrocarbon Processing, July, 1978, p. 155; September 1978, p. 257.

Khandker, D., A. Lam, and M. Molloy, “Hydrogen Production Using Steam Reforming and
Water Gas Shift Technologies,” University of Pennsylvania, Towne Library (1999).

Satterfield, C. N., Heterogeneous Catalysis In Practice, 1980; Section 9.8, p. 259.

U.S. Patent 5,011,593 to Mobil Oil Corporation

U.S. Patent 5,474,670 to Exxon Research and Engineering

U.S. Patent 5,454,933 to Exxon Research and Engineering


A-II.10.4 Waste Fuel Upgrading to Acetone and Isopropanol
(Robert Nedwick and Leonard A. Fabiano, ARCO Chemical, January 1997)

Your plant produces two byproduct streams from an existing process. Currently, these streams are
being sent to the on-site steam boiler where they are burned to produce high-pressure steam for the
complex. A recent change in the environmental regulations have put the major components of
these streams (acetone and isopropanol) on an environmental listing, which will require you to
spend capital to upgrade the existing boiler and storage tanks if you continue burning. You have
been asked to determine the optimum disposition of these streams among the following options:

1. Continue burning these streams. The capital required to upgrade the boiler and storage
tanks is $10.0 MM.

2. Build a unit to produce specification grade acetone product.

3. Pay to have the streams taken off site for proper disposal at the rate of 5.0¢/lb.

The following information is available:

CD-A-II-77
Feed Composition and Quantity

Waste Waste
Components, wt% Acetone Isopropanol

Acetone 80.0 12.0
Isopropanol (IPOH) 1.0 58.0
Methanol (MeOH) 10.0 7.0
Isobutylene (iC
4
=
) 2.0 0.0
Methyl ethyl ketone (MEK) 0.5 0.0
Acetic acid 2.5 3.5
Heavies 1.0 1.5
Water (H
2
O) 3.0 18.0
100.0 100.0

Quantity, lb/hr 15,000 18,000

Heating Value, BTU/lb (water free) 12,000 12,000


Acetone Product Specification

Acetone 99.5 wt% min
Isopropanol (IPOH) 500 wt ppm max
Methanol (MeOH) 500 wt ppm max
Acetic Acid 50 wt ppm max
Water (H
2
O) 0.5 wt% max

The isopropanol can be dehydrogenated to acetone per the referenced patents. The reaction is
highly endothermic and at 90% conversion does result in coking of the catalyst, which requires a
one-week regeneration burnout every two months. At 80% conversion, the catalyst run length can
be extended to six months. Expected catalyst life is four regenerations after which the catalyst
must be replaced at $6/lb.

Purification of the acetone product will require overcoming some azeotropes, acetone/methanol
being the most important.

Your plant would be situated in an existing complex where much of the infrastructure is available.

The following is the situation with the Outside Battery Limit (OBL) components:

Site Development: Everything provided except:
• Site Clearing/Prep ($500M).
• Control Room Upgrade ($250M).


CD-A-II-78


Utilities
• Firewater/N
2
/Air/demineralized water/potable water are all available.
• Boilers are available to provide as much as 200 M lb/hr of 600-psig steam at $4.50/Mlb.
• Cooling Water is at its limit and a whole new system will be required.
• Electrical power is available at 4¢/kW.
• All utility and electrical tie-ins are required ($1,000 M).

Storage
• One fuel tank sized for the two waste fuels for 7days is available. (The acetone and IPOH
streams are currently fed to a single tank before being sent to the boiler.)
• Product Storage for 14 days is required.
• Two Product Day Tanks for testing product quality before sending to the larger product tank
are required.
• Any other new fuel, product, solvent, chemical, etc., storage associated with this process is
required.
• Pipe runs from IBL to Storage and Loading areas are required ($500 M).
• Truck Loading upgrade is required ($350 M).

Environmental
• Waste water to the bio-pond can be treated for $2.00/Mgal.
• The flare system can handle 150,000 lb/hr extra load upon CW failure. If higher, an
additional flare will be required.
• Tie-ins to these systems are required ($150 M).

Of the three options identified, only the acetone recovery has the potential for positive returns, but
at the highest capital. The projected price of acetone is 25¢/lb in 2000, the target startup date for
this unit. However, acetone has experienced large pricing swings being as low as 15¢/lb and as
high as 30¢/lb for extended periods. Acetone is also a new product line for the company and there
is some reluctance on management’s part to get involved. Your company’s philosophy is that a
project must achieve a minimum economic hurdle rate of 12% investor’s rate of return (IRR).

What do you recommend to your management?

References

“Catalytic Dehydrogenation of Alcohols to Carbonyl Compounds,” U. S. Patent 2,586,694
(February 19, 1952).

“Dehydrogenation Catalyst,” U.S. Patent 2,549,844 (April 24, 1951).


CD-A-II-79
A-II.10.5 Conversion of Cheese Whey (Solid Waste) to Lactic Acid
(Robert M. Busche, Bio-en-gene-er Associates, January 1993)

It is now January 1993, and the public is perceiving that the United States is burying itself in solid
waste materials. ConAgra, Inc., has approached DuPont with a proposal for a joint venture to
produce lactic acid for conversion to biodegradable polylactide plastics to be used in packaging and
other markets that might help to alleviate the solid waste problem.

Under the proposal, the United States Ecological Chemical Products Company (Ecochem) will
build a 20-million-pound acid plant based on cheese whey as a raw material at Adell, WI, where
the Adell Whey Company will collect whey from producers within a 100-mile radius and supply it
to the lactic acid plant via pipeline.

Key to the proposal appears to be the use of new technology being developed at the Oak Ridge
National Laboratory under Dr. Brian Davison. The new process is based on a three-phase,
biparticle, fluidized-bed bioreactor, in which lactic acid, produced continuously in a fluidized bed
of immobilized Lactobacillus delbreuckii, is simultaneously adsorbed onto a solid
polyvinylpyridine resin moving countercurrent to the fermenter beer. In this way, the pH can be
maintained at the optimum 5.5 and product inhibition of the fermentation is minimized. As a
result, fermentation rates have been increased 4- to 10-fold higher than the conventional
fermentation process and the acid product can be recovered by methanol extraction.

As the Planning Manager for Chemicals, you have been asked to evaluate the techno-economics of
the proposal as compared with the alternative conventional fermentation process and advise the
Executive Committee of the financial expectations for the venture. It appears that if the design and
financial evaluation can be completed by May 1993, the plant can be constructed for start-up in
January 1996.

References

Anon., Dupont Mag., 18 (July/August 1992).

Atkinson, B., and F. Mavituna, Biochemical & Biotechnology Handbook, Nature Press, London,
440-442, 1044-1048 (1983).

Bajpai, R., J.E. Thompson, and B.H. Davison, Appl. Biochem. & Biotech., 24/25, 485-496 (1990).

Chisti, Y., “Assure Bioreactor Sterility,” Chem. Eng. Prog., 80-85 (September 1992).

Davison, B.H., “Dispersion and Holdup in a Three-phase Fluidized-bed Bioreactor,” Appl.
Biochem. & Biotech., 20/21, 449-460 (1989).

Davison, B.H., “Biochemical Engineering,” Ann. N.Y. Acad. Sci., 589, 670-677 (1990).

Davison, B.H., and T.L. Donaldson, in Biotechnology Processes, C.S. Ho and J.Y. Oldshue, Eds.,
254-258 (1987).
CD-A-II-80

Davison, B.H., and C.D. Scott, Biotech. & Bioeng., 39, 365-368 (1992).

Davison, B.H., and J.E. Thompson, Appl. Biochem. & Biotech., 34/35, 431-439 (1992).

Potera, C., Genetic Eng. News, 1 (November 1, 1992).

Scott, C.D., Enzyme Engineering VIII, Ann. N.Y. Acad. Sci., 501, 487-493 (1987).


A-II.10.6 Ethanol for Gasoline from Corn Syrup
(Kamesh G. Venugopal, Air Products and Chemicals, January 1990)

In its environmental program, the Bush administration is evaluating clean-burning, low-volatile
fuels for automobiles. One alternative is to convert a farm product, corn syrup, to motor-grade
ethanol.

Your consulting company is requested to design a 100,000-metric tons/year, automobile-grade
ethanol plant using corn syrup as the feedstock. After designing the process and determining its
total cost, the price subsidy to make ethanol competitive with current gasoline prices should be
determined.

In creating your design, give special consideration to processes that reduce the energy expenditure
of the plant. In one such process, pervaporation membranes are used to dehydrate ethanol.
Pervaporation is a membrane separation process in which the feed and residue streams are liquid,
but the permeate is a vapor. The combination of permeation and evaporation in the membrane
gives rise to separation factors much greater than can be accomplished by distillation and can be
used to break azeotropes.

References

Fong, W.-S., Ethanol for Gasohol, Stanford Research Institute, Process Economics Program, SRI
PEP 149 (1982).

Milton, M.L., Gasohol Economic Feasibility Study: Final Report, Energy Research and Dev.
Center, Univ. Nebraska (1978).



CD-G-1
General Algebraic Modeling System (GAMS)

Prepared by James R. Phimister
University of Pennsylvania
Department of Chemical Engineering
Philadelphia, PA 19104/6393

The General Algebraic Modeling System (GAMS) is a programming language that provides a
flexible framework for formulating and solving linear, nonlinear and mixed-integer optimization
problems. Among other attributes, its syntax allows for declaring associations among variables,
constants, and constraints in the form of sets. Through this syntax, input files are written
compactly and similarly to the typical formulations of optimization problems. In addition, GAMS
provides a wide array of solvers to optimize a variety of problem formulations including linear
programs (LPs), nonlinear programs (NLPs), mixed-integer linear programs (MILPs, but referred
to as MIPs by GAMS), and mixed-integer nonlinear programs (MINLPs).
Here, it is possible only to provide a limited overview of the capabilities of GAMS.
Examples discussed in the text are presented to illustrate the structure of input files for an LP, an
NLP, and an MIP. These input files can be copied from the CD-ROM that accompanies this
book. It is recommended that the reader copy and run the GAMS input files, and observe the
results. The files can be modified and rerun to observe how the optimal solutions change. As
with many software applications, one of the best means for learning GAMS is through hands-on
experience.
For interested readers a detailed presentation of GAMS is provided in GAMS: A User’s
Guide: Release 2.25 (Brook, A., D. Kendrick, and A. Meeraus, Scientific Press, San Francisco,
1992). The solvers available in GAMS are presented in GAMS - The Solver Manuals (GAMS
Development Corporation, Washington, DC, 1996).
In its simplest form, GAMS operates on a user-supplied input file (normally denoted with
a .gms or .number extension to the filename), which encodes the mathematical formulation of
the optimization problem being examined. Selection of the word processor for use in editing the
input file is left to the discretion of the user. Note, however, that files should be saved in ASCII


CD-G-2
or TEXT format. Thus, the Notepad word processor included in the Windows operating system
is a good choice. GAMS is not likely to be able to run files saved in another format (e.g. that of
.doc files in WORD) since the default save options of many word processors add formatting
codes to the saved file.
GAMS operates on a variety of platforms, with execution of the program initiated from
the command prompt line. GAMS is run using the executable (GAMS) followed by the name of
the input file at the command prompt, that is:

GAMS filename.extension

In the WINDOWS operating system, GAMS is run through the Run window, shown in Figure 1,
which is obtained by left clicking the Start window and then clicking Run. In this case, the
executable (GAMS) and the input file (CASC.1) are located in the directory C:\GAMS. The
output file, CASC.lst, is placed in the same directory as the GAMS executable, not the directory
of the input file.

GAMS operates on an input file in two stages:

1. Compilation. This stage ensures that the input file is understood by GAMS. The
compiler checks for errors in the input file, ensuring that the file abides to a specific
format, does not contain syntax errors, and uses an appropriate solver. The compiler
does not solve the problem or indicate that a solution exists. When the compiler
locates errors in the input file, the errors are flagged and written in the output file (e.g.,

Figure 1. GAMS run from WINDOWS or NT.


CD-G-3
CASC.lst) before GAMS terminates. The user must then correct the input file. When
the compilation is successful, GAMS proceeds to stage 2.

2. Execution. With the input file readable, GAMS proceeds to carry out the
optimization using an appropriate solver for the problem formulation (e.g., LP, NLP,
and MIP). Note that the solver declared by the user must be applicable to the
formulation. For instance, an LP solver cannot be used to solve an NLP. GAMS
writes to the output file, providing information on whether the solution was obtained,
and if so, the solution values. Output can be controlled using display options in the
input file.


1. INPUT FILE

Consider Example 10.4 in which the minimum utilities for a HEN are determined by solving a
linear program:
1
1 2
2 3
3 4
4
Min
30 0
2 5 0
82 5 0
75 0
15 0
− + =
− + =
− − =
− + =
− − =
steam
steam
Q
steam
cw
Q
s.t.
Q R
R R .
R R .
R R
R Q


where Q
steam
, Q
cw
, and R
1
, R
2
, R
3
, R
4
are all non-negative real numbers. The GAMS input file,
CASC.1, in Figure 2 contains this LP formulation. Note that it closely resembles the written
problem formulation and is equivalent to the input file in Example 10.4.



CD-G-4
Figure 2. GAMS input file CASC.1 to determine minimum utilities for a HEN.


The output file, CASC.lst, contains a wealth of information. Of particular interest is the Solve
Summary:


that shows normal completion of the linear program (LP) by the solver MINOS5 to one optimal
solution; that is, Z = 50.0.


Statements


Although much of the input file, CASC.1, is self-explanatory, it is important to understand the
structure of a GAMS input file and its statements. In its simplest form, an input file must consist
of statements for:
VARIABLES
Qs, Qcw, R1, R2, R3, R4, Z ;

EQUATIONS
OBJ,T1,T2,T3,T4,T5,B1,B2,B3,B4,B5,B6;

OBJ .. Z =E= Qs;
T1.. Qs-R1+30 =E= 0;
T2.. R1-R2+2.5 =E= 0;
T3.. R2-R3-82.5 =E= 0;
T4.. R3-R4+75 =E= 0;
T5.. R4-Qcw-15 =E= 0;

B1.. R1 =G= 0;
B2.. R2 =G= 0;
B3.. R3 =G= 0;
B4.. R4 =G= 0;
B5.. Qs =G= 0;
B6.. Qcw =G= 0;

MODEL CASCADE /ALL/;
SOLVE CASCADE USING LP MINIMIZING Z;
S O L V E S U M M A R Y

MODEL CASCADE OBJECTIVE Z
TYPE LP DIRECTION MINIMIZE
SOLVER MINOS5 FROM LINE 38

**** SOLVER STATUS 1 NORMAL COMPLETION
**** MODEL STATUS 1 OPTIMAL
**** OBJECTIVE VALUE 50.0000


CD-G-5
1. Variable declarations and assignments
2. Equation declarations
3. Equation definitions
4. A model declaration, with an appropriate solve statement
Initially, it is recommended that all statements be ended with a semicolon, as statements without
semicolons may cause compiler errors.

Variable Declaration Statement. Each variable must be declared in the input file. Note that a
variable for the objective function must also be declared. In Figure 2, the objective function
variable is denoted as Z.

Equation Declaration Statement. Each constraint as well as the objective function must be
defined with a name.

Equation Definition Statement. For every declared equation name, a corresponding equation
must be defined. To define the equation:
1. Every equation name is restated as written in the declaration followed by two periods and
at least one space.
2. The equation is stated using the declared variables and constants, the operators (+, -, ≥,
etc.) and GAMS functions (sine, sum, etc.).
3. Each equation is defined as a statement, and hence, is ended with a semi-colon.

The following relational operators are defined:

Relation Syntax
Equality constraint (=) =E=
Less than or equal to (≤) =L=
Greater than or equal to (≥) =G=

Note there is no definition for the strict inequalities less than (<) or greater to (>). This omission
is intentional and does not result in any loss of generality by GAMS.
The most commonly used arithmetic operators are:


CD-G-6

Operator Syntax
Addition +
Subtraction -
Multiplication *
Division /
Exponent (to the power of) **

In addition, several built-in functions are available, including:
Function Syntax
exponential (e
x
) exp(x)
natural log log(x)
log base 10 log10(x)
sine sin(x)
cosine cos(x)

Model Declaration Statement. The model declaration statement defines a user-specified name
for the model and declares the equations to be included in the model. For novice GAMS users, it
is recommend that all equations be included. Hence, the model declaration statement is:

MODEL MODEL_NAME /ALL/;

Solve Statement. The solve statement defines the:
1. Model to be optimized (defined previously in the model declaration statement).
2. Type of solving procedure (LP, MIP, etc.).
3. Type of optimization; that is, minimization or maximization.
4. Variable to be optimized.
It has the form:

SOLVE MODEL_NAME USING PROBLEM_TYPE MINIMIZING OBJEC_FUNC_VARIABLE;

The key words ‘SOLVE’ and ‘USING’ must be present in the statement, as well as either
‘MINIMIZING’ or ‘MAXIMIZING’



CD-G-7
In Figure 2, the model name is CASCADE, the type of solving procedure is LP since only
linear constraints and a linear objective function appear. The objective function variable, Z, is
minimized, and consequently, the solve statement is:

SOLVE CASCADE USING LP MINIMIZING Z;

There are several optimization formulations that can be solved, the most common being:

Formulation GAMS Syntax
Linear program LP
Mixed integer linear program MIP
Nonlinear program NLP


2. EXPANDED FEATURES - DOCUMENTATION, VARIABLE
REDECLARATION, AND DISPLAY

Using the basic features of GAMS, a large array of optimization problems can be solved. There
are, however, several features that greatly improve the ease of formulation and the readability of
the input and output files.

Syntax. The GAMS compiler does not distinguish between upper and lower case characters.
Hence, to allow for more readable text, both cases may be used interchangeably in an input file.

Documentation. It is important to add documentation to the input file to simplify debugging as
well as to clarify the formulation of the optimization problem. Documentation can be interspersed
throughout the file by placing an asterisk (*) in the first column of a documentation line. Note
that the asterisk alerts the compiler to overlook the line. Documentation can also be included
within declaration statements. Any character string placed after a variable or equation has been
declared, but prior to a comma or semi-colon, is considered to be documentation attributed to the
variable or equation. These character strings also appear in the output file.



CD-G-8
Variable Redeclaration. It is often desirable to re-declare a variable with bounds provided. For
example, variables w and x are re-declared such that bounds greater than or equal to zero are
applied using the statement

POSITIVE VARIABLES w,x;

Alternatively, for real-valued variables, this can be accomplished by defining equations that
incorporate the bounds on the variables. However, the use of re-declared variables provides for a
more concise input file. The key words to define the bounds on a variable are

GAMS Syntax Range on Variable
FREE (default) -∞ to ∞
POSITIVE
0 to +∞
NEGATIVE
-∞ to 0
BINARY
0 or 1 only
INTEGER
0, 1, …, 100

Note that binary and integer variables must be re-declared for mixed-integer programming. To
define the binary variable, y, this is accomplished using the statement:
BINARY VARIABLE y;
Variable Display. After computing a solution, GAMS displays the variable values in the output
file. In addition, GAMS can redisplay values in tabular form toward the end of the output file.
To accomplish this, a DISPLAY statement is added following the MODEL statement. While a
range of possible outputs can be displayed, the level (or final) outputs (denoted with a ‘.L’
extension to the variable) are often of most concern. For example, the final values for R1, …, R4,
Qcw, and Qs, are requested in tabulated form in the output file, using the input statement:
DISPLAY R1.L,R2.L,R3.L,R4.L,Qcw.L,Qs.L

Subsequently, these are displayed in the output, as shown in Figure 3.

Expanded Input File for Example 10.4. An improved input file for Example 10.4, named
CASC.2, is shown in Figure 4.



CD-G-9

Bounds and Initial Conditions. When the bounds using variable re-declaration statements are
inadequate, additional statements are available. To set a lower bound for x, use:
x.lo = 10.0;
and to set an upper bound for x, use:
x.up = 100.0;
An initial starting point for the solver is supplied by the user with the level (‘.l’) extension:
x.1 = 50.0;
Bounding and initialization statements appear after the variable declaration statements, but prior
to the equation declaration statements.
For nonlinear programs (NLPs) it is important to provide bounds and initial conditions
where possible. This is often necessary because:
1. It is often difficult for a nonlinear solver to locate a feasible solution (one that satisfies the
constraints), especially when the initial guessed values are poor. When the user provides a
feasible starting point, the likelihood of successful convergence to an optimal solution is
greatly improved.
2. Nonlinear programs are often multi-modal; that is, the surface of the objective function
contains numerous local minima. With physical insights, the user may be able discern where
the global minimum is likely to exist, and hence, provide initial conditions near this point.
Likewise, the user may be able to discern where a solution cannot exist, and hence provide
tighter bounds on the search space. GAMS does not seek all local minima.
3. GAMS defaults initial variable values to zero. When a variable appears alone in a
denominator, or is the argument of a log function, the solver may abort.

VARIABLE R1.L = 80.000
VARIABLE R2.L = 82.500
VARIABLE R3.L = 0.000
VARIABLE R4.L = 75.000
VARIABLE QCW.L = 60.000
VARIABLE QS.L = 50.000

Figure 3. Displayed values requested in input file CASC.1


CD-G-10

Figure 5 provides the input file for the nonlinear program discussed in Example 10.16, in
which an optimal network for a hot stream being matched with two cold streams is determined.
Note that the Chen approximation to the log-mean temperature difference:
3 / 1
2 1
2 1
2
(
¸
(

¸

|
.
|

\
| ∆ + ∆
∆ ∆ = ∆
T T
T T T
LM

* This is the input file for Example 10.4
* The GAMS file formulates an LP to be solved for minimum utilities

* Declare the variables
* Note that Z (used for the objective function)
* 1. must be declared
* 2. should not be made positive

VARIABLES

Qs, Qcw, R1, R2, R3, R4
Z minimum utilities ;
* Remember the semi-colons !!!

* Declare non-negative variables
POSITIVE VARIABLE Qs, Qcw, R1, R2, R3, R4;

* If desired, specify additional bounds on variables
* or initial values could be specified here.

* Now declare the equations in the problem!
EQUATIONS
COST this defines the objective function
T1,T2,T3,T4,T5 ;

* and define the equations just declared
COST .. Z =E= Qs;
T1.. Qs-R1+30 =E= 0;
T2.. R1-R2+2.5 =E= 0;
T3.. R2-R3-82.5 =E= 0;
T4.. R3-R4+75 =E= 0;
T5.. R4-Qcw-15 =E= 0;

* Nearly done! Place all of the above in the model CASCADE
MODEL CASCADE /ALL/;

* and solve it using an LP solver
SOLVE CASCADE USING LP MINIMIZING Z;

* Let’s display these variables at the solution
* at the end of the output file
DISPLAY R1.L,R2.L,R3.L,R4.L,Qcw.L,Qs.L

Figure 4. Expanded input file for LP in Example 10.4.


CD-G-11
is used, as recommended by Floudas (1995), because numerical difficulties arise due to division
by zero. Here, ∆T T T
in
H
out
C
1
= − and ∆T T T
out
H
in
C
2
= − . Consequently, the input file provides a
solution which deviates slightly from that reported in Chapter 10. The GAMS input file, COST.1,
is provided on the accompanying CD-ROM.

* Define variables
VARIABLES
Ah1c1, Ah1c2, F1, F2, F3, F4, F5, F6, F7, F8,
T3, T4, T56, T78, DELh1c1, DELh1c2,
Z heat exchanger cost ;

* Declare total variables strictly non-negative
POSITIVE VARIABLES Ah1c1, Ah1c2,F1, F2, F3, F4, F5, F6, F7, F8 ;

* For NLPs, providing initial conditions and bounds can improve the solver's
* likelihood of finding feasible solutions, as well as avoiding numerical
* difficulties

DELh1c1.L = 20 ; DELh1c1.LO = 10 ; DELh1c1.UP = 100 ;
DELh1c2.L = 20 ; DELh1c2.LO = 10 ; DELh1c2.UP = 100 ;
Ah1c1.L = 100.0 ; Ah1c2.L = 100.0 ;
T3.L = 440 ; T3.LO = 330 ; T3.UP = 440 ;
T4.L = 440 ; T4.LO = 330 ; T4.UP = 440 ;
T56.L = 330 ; T56.LO = 330 ; T56.UP = 440 ;
T78.L = 330 ; T78.LO = 330 ; T78.UP = 440 ;

* Specify equations.
EQUATIONS

OBJ defines the objective function,
MBALSPL1,MBALSPL2,MBALSPL3, MBALMIX1, MBALMIX2,
EBALMIX1, EBALMIX2, EBALEX1, EBALEX2,
FEAS1, FEAS2, FEAS3, FEAS4, AREA1, AREA2, DELTAC1, DELTAC2;

OBJ.. Z =E= 1300*(Ah1c1**0.6)+1300*(Ah1c2**0.6);

MBALSPL1.. F1+F2 =E= 22;
MBALSPL2.. F3-F5-F6 =E= 0;
MBALSPL3.. F4-F7-F8 =E= 0;
MBALMIX1.. F3-F1-F8 =E= 0;
MBALMIX2.. F4-F2-F6 =E= 0;

EBALMIX1.. 440*F1+T78*F8-T3*F3 =E= 0;
EBALMIX2.. 440*F2+T56*F6-T4*F4 =E= 0;
EBALEX1.. F3*(T3-T56) =E= 1620;
EBALEX2.. F4*(T4-T78) =E= 360;

FEAS1.. T3-430 =G= 10;
FEAS2.. T56-349 =G= 10;
FEAS3.. T4-368 =G= 10;
FEAS4.. T78-320 =G= 10;

AREA1.. Ah1c1*DELh1c1 =E= 1620;
AREA2.. Ah1c2*DELh1c2 =E= 720;

*Chen LMTD approximation
DELTAC1.. DELh1c1=E=((T3-430)*(T56-349)*(1/2)*((T3-430)+(T56-349)))**0.333;
DELTAC2.. DELh1c2=E=((T4-368)*(T78-320)*(1/2)*((T4-368)*(T78-320)))**0.333;

MODEL COST /ALL/;
SOLVE COST USING NLP MINIMIZING Z;

DISPLAY Z.L, Ah1c1.L, Ah1c2.L, DELh1c1.L, DELh1c2.L, T3.L,T4.L, T56.L, T78.L;
DISPLAY F1.L, F2.L, F3.L, F4.L, F5.L, F6.L, F7.L, F8.L;

Figure 5. Input file for NLP in Example 10.16 using Chen approximation.



CD-G-12
3. EXPANDED FEATURES: SETS, TABLES, PARAMETERS AND SCALARS,
EQUATION GROUPING

GAMS has a powerful feature which allows sets to be declared. Sets allow for subscripted
variables used in variable and constant declarations, as well as equation definitions. As an
example of the utility of declaring sets, an optimization problem might contain the five
constraints:

x
i
≤ 10 ∀i, where i∈{1,2,…, 5}

Likewise, by employing sets in GAMS, input files can be written with subscripted constraints
written in a single line. Note any input file that incorporates sets can be written in GAMS
without defining sets. However, input files with defined sets can be written concisely, and are
often easier to debug and update.
To illustrate the definition of sets and how they are employed, Example 10.8 is
considered. In this example, it is desired to determine the least number of matches between hot
and cold streams while providing maximum heat recovery. Note that the problem has been
restated in Figure 6. The GAMS input file, MATCH.1, is shown in Figure 7, and provided on the
accompanying CD-ROM.

Set Declarations. In Example 10.8, variables are defined with reference to whether there is a
match between a hot stream and a cold stream, and if a match exists, over which interval in the
heat cascade. Hence, y
H2,C2
is a binary variable representing whether hot stream 2 is matched to
cold stream 2, and Q
H1,C1,3
is a continuous variable that represents the heat transferred between
hot stream 1 and cold stream 1 in interval 3.
In formulating the input file, H2 is a member of the set of hot streams, termed HOT,
where:
HOT= {H1, H2, S}



CD-G-13
Minimize z = y
S,C2
+ y
H1,C1
+ y
H1,C2
+

y
H1,W
+ y
H2,C1
+ y
H2,C2
+ y
H2,W
ST: (MILP)
S: R
S,1
+ Q
S,C2,1
= QH
S,1
H2: R
H2,2
+ Q
H2,C1,2
+ Q
H2,C2,2
= QH
H2,2

R
H2,3
- R
H2,2
+ Q
H2,C1,3
+ Q
H2,C2,3
= QH
H2,3

R
H2,4
- R
H2,3
+ Q
H2,C1,4
+ Q
H2,W,4
= QH
H2,4

- R
H2,4
+ Q
H2,W,5
= QH
H2,5

H1: R
H1,3
+ Q
H1,C1,3
+ Q
H1,C2,3
= QH
H1,3

R
H1,4
- R
H1,3
+ Q
H1,C1,4
+ Q
H1,W,4
= QH
H1,4

- R
H1,4
+ Q
H1,W,5
= QH
H1,5

C2: Q
S,C2,1
= QC
C2,1

Q
H2,C2,2
= QC
C2,2

Q
H1,C2,3
+ Q
H2,C2,3
= QC
C2,3

C1: Q
H2,C1,2
= QC
C1,2

Q
H1,C1,3
+ Q
H2,C1,3
= QC
C1,3

Q
H1,C1,4
+ Q
H2,C1,4
= QC
C1,4

W: Q
H1,W,4
+ Q
H2,W,4
= QC
W,4

Q
H1,W,5
+ Q
H2,W,5
= QC
W,5

S-C2: Q
S,C2,1
- y
S,C2
U
S,C2
≤ 0
H1-C1: Q
H1,C1,3
+ Q
H1,C1,4
- y
H1,C1
U
H1,C1
≤ 0

H1-C2: Q
H1,C2,3
- y
H1,C2
U
H1,C2
≤ 0
H1-W: Q
H1,W,4
+ Q
H1,W,5
- y
H1,W
U
H1,W
≤ 0
H2-C1: Q
H2,C1,2
+ Q
H2,C1,3
+ Q
H2,C1,4
- y
H2,C1
U
H2,C1
≤ 0
H2-C2: Q
H2,C2,2
+ Q
H2,C2,3
- y
H2,C2
U
H2,C2
≤ 0
H2-W: Q
H2,W,4
+ Q
H2,W,5
- y
H2,W
U
H2,W
≤ 0

where
QH
S,1
= 127.68 QC
C2,1
= 127.68
QH
H1,3
= 298.86 QC
C2,2
= 541.12
QH
H1,4
= 290.07 QC
C2,3
= 206.72
QH
H1,5
= 0 QC
C1,2
= 76.2
QH
H2,2
= 938.95 QC
C1,3
= 259.08
QH
H2,3
= 232.1 QC
C1,4
= 426.72
QH
H2,4
= 0 QC
W,4
= 125.07
QH
H2,5
= 0 QC
W,5
= 125.07

Furthermore, the upper bounds, U
ij
, for the potential matches are:

S-C2: U
S,C2
= min{127.68, 127.68} = 127.68
H1-C1: U
H1,C1
= min{762, 588.93} = 588.93
HI-C2: U
H1,C2
= min{875.52, 588.93} = 588.93
H1-W: U
H1,W
= min{250.14, 588.93} = 250.14
H2-C1: U
H2,C1
= min{1171.05, 762} = 762
H2-C2: U
H2,C2
= min{1171.05, 747.84} = 747.84
H2-W: U
H2,W
= min{1171.05, 250.14} = 250.14

where Q
i,j,k
≥ 0, R
i,j
≥ 0 and y∈[0,1]

Figure 6. MILP for Example 10.8.


CD-G-14

* Define cold, hot and interval sets
SETS HOT hot streams / H1, H2, S /
COLD cold streams / C1, C2, W /
INT interval / 1,2,3,4,5 /;

TABLE U(HOT,COLD) upper bound on heat transfer between streams
C1 C2 W
H1 588.93 588.93 250.14
H2 762.00 747.84 250.14
S 0.00 127.68 0.00 ;

* Define a table having more than 2 dimensions
* Remember defaults are taken as 0.0!!

TABLE QH(HOT,INT) Hot side heat transferred
1 2 3 4 5
S 127.68
H1 298.86 290.07
H2 938.95 232.10 ;

TABLE QC(COLD,INT) Cold side heat transferred
1 2 3 4 5
C1 76.20 259.08 426.72
C2 127.68 541.12 206.72
W 125.07 125.07 ;

VARIABLES
Q(HOT,COLD,INT), R(HOT,INT), Y(HOT,COLD)
Z minimum no of matches ;
* Declare variables non-negative
POSITIVE VARIABLES Q(HOT,COLD,INT), R(HOT,INT);
* and those which are binary
BINARY VARIABLES Y(HOT,COLD)

EQUATIONS
OBJ defines the objective function
S, H2a, H2b, H2c, H2d, H1a, H1b, H1c
CSIDE(COLD,INT), QMATCH(HOT,COLD);

OBJ.. Z =E= SUM(HOT,SUM(COLD,Y(HOT,COLD)));

S.. R("S","1")+Q("S","C2","1") =E= QH("S","1");
H2a.. R("H2","2")+Q("H2","C1","2")+Q("H2","C2","2") =E= QH("H2","2");
H2b.. R("H2","3")-R("H2","2")+Q("H2","C1","3")+Q("H2","C2","3") =E= QH("H2","3");
H2c.. R("H2","4")-R("H2","3")+Q("H2","C1","4")+Q("H2","W","4") =E= QH("H2","4");
H2d.. -R("H2","4")+Q("H2","W","5") =E= QH("H2","5");
H1a.. R("H1","3")+Q("H1","C1","3")+Q("H1","C2","3") =E= QH("H1","3");
H1b.. R("H1","4")-R("H1","3")+Q("H1","C1","4")+Q("H1","W","4") =E= QH("H1","4");
H1c.. -R("H1","4")+Q("H1","W","5") =E= QH("H1","5");

CSIDE(COLD,INT).. SUM(HOT,Q(HOT,COLD,INT)) =E= QC(COLD,INT);
QMATCH(HOT,COLD).. SUM(INT,Q(HOT,COLD,INT)) =L= U(HOT,COLD)*Y(HOT,COLD);

MODEL MATCH /ALL/;
SOLVE MATCH USING MIP MINIMIZING Z;

DISPLAY R.L,Q.L,Z.L

Figure 7. MIP input file for matching heat exchangers.


CD-G-15
Likewise, a set COLD is defined as the cold streams {C1, C2, W} and the set INT = {1,2,3,4,5}
defines the intervals in the heat cascade. These sets are defined by the statement:
SETS

HOT hot streams / H1, H2, S /
COLD cold streams / C1, C2, W /
INT interval / 1,2,3,4,5 /;


Note that the elements in the set are defined within the slashes (/). The set name is the first word
in the line. Any character strings following the set name and preceding the first slash are
documentation.

Data Statements: Scalars, Parameters and Tables. It is often desired to declare constants,
which can be referred to in the equation definitions. For instance, a constant UPPER is declared
and assigned the value 100.0 using the GAMS statement:

Scalar UPPER defines an upper bound /100.0/;


Similarly an array of scalars, termed a parameter can be declared. Parameters are defined for sets
whose elements are the names in the array. For example, when the feed temperatures for the set
of cold streams {C1, C2, W} are 60, 116, and 38°C, respectively, a parameter TENTER is
declared using the statement:

Parameter TENTER entering cold stream temp /60, 116, 38/;

Tables have a dimension of two or greater and declare inter-related parameters. In
Example 10.8, a variable U is declared. On inspection, U can be declared as a 2-dimensional
table whose elements are entered in GAMS using the TABLE statement:

TABLE U(HOT,COLD) upper bound on heat transfer between streams

C1 C2 W
H1 588.93 588.93 250.14
H2 762.00 747.84 250.14
S 0.00 127.68 0.00 ;


CD-G-16

The format for the table declaration is flexible; spacing between the elements is greater or equal
to one space. It is recommended that the TAB key not be used when constructing tables as text
editors save tab spaces differently, often creating parsing problems for the compiler. When table
cells are left blank, they are assigned the default value of zero.

File Format. Input files that include either set and data statements must be organized as follows:
1. Set declarations and assignments
2. Data (or constant) declarations and assignments
3. Variable declarations and assignments
4. Variable bound declarations (optional)
5. Equation declarations
6. Equation definitions
7. A model declaration, with an appropriate solve statement
8. Display statements (optional)

Variable Declarations. Variables can be declared over sets (that is, with sets as their elements).
In Example 10.8, the variable R
i,k
is declared R(HOT,INT), Q
i,j,k

is declared
Q(HOT,COLD,INT), and the binary variable y
i,j
is declared Y(HOT,COLD).

Equation Declarations. Sets allow equations to be declared for all (∀) elements in a set. For
example, rather than declare nine equations and define each equation to express the maximum
heat transferred between its match (H1-C1, H1-C2, H1-W, H2-C1, etc.), the set of equations,
QMATCH(HOT,COLD) can be declared, and subsequently, defined to encompass all matches
between the elements in HOT and COLD.

Equation Definitions. The first term in an equation definition statement is the equation name.
Hence, when the declaration specifies that the equation utilizes sets, the equation definition must
do so as well. This is shown for the set of equations, QMATCH(HOT,COLD), with an equation
defined to provide an upper bound on heat transferred in a match:


CD-G-17

QMATCH(HOT,COLD).. SUM(INT,Q(HOT,COLD,INT))=L= U(HOT,COLD)*Y(HOT,COLD);

When it is necessary to refer to a specific element in a set, quotation marks are used. For
example, the following statement defines constraint S in Figure 7:

S.. R("S","1")+Q("S","C2","1") =E= QH("S","1");

which defines the heat balance for the stream of steam in interval 1.
A number of set specific functions are available in GAMS. The most commonly used
function is SUM, which sums over all of the elements in a given set. This is shown in the
objective function Z:

OBJ.. Z =E= SUM(HOT,SUM(COLD,Y(HOT,COLD)));

The above statement sums y over all of the elements in both sets HOT and COLD.


4. DEBUGGING

Two types of errors are encountered: errors during compilation and errors during execution. All
errors are written in the output file.

Compilation errors. Many errors are usually reported in the output file the first time an input file
is run. Since errors further down in the input file are often a result of an error earlier in the file, it
is recommended that one proceed from the top of the file downwards, rerunning the input file
after several errors have been corrected.
Compilation errors indicate that the input file contains statements that are not recognized
by the compiler. Common compilation errors include:
1. Syntax errors, such as failure to end a statement with a semi-colon.
2. Left and right parentheses not matching.
3. Incorrect references to a variable name.
Until the compilation errors are corrected, GAMS is unable to execute the model.


CD-G-18
During compilation, GAMS copies the input file to the output file, adding row numbers in
the left-hand column. When compilation errors are encountered, a dollar sign ($) followed by an
error number is indicated. At the end of the file, a brief description of the errors is provided.
Consider the input file CASC.1 in Figure 2 with the following modifications:
1. Qs is omitted in the variable declaration statement.
2. The semi-colon following the statement defining equation B1 is omitted.
In the corresponding output file, shown in Figure 8, three errors are flagged. The flags are
normally directly below the statement at which GAMS anticipates that the error occurs. In this
case, GAMS detects and flags the undeclared variable Q
s.
However, the error occurs because Q
S

is omitted from the variable declaration. In addition, because the semi-colon is omitted, GAMS
is unable to parse statement B1 from statement B2. Finally, GAMS does not check the solve
statement because the other errors are identified.

Execution errors. Execution errors occur when the program compiles successfully and a solver
is attempting to locate the optimum solution. It is usually more difficult to correct these errors
because they are related to the optimization algorithm. When trying to resolve execution errors, it
is recommended that the user:
1. Check the optimization formulation and its transcription into the GAMS input file. Is the
formulation correct? Has the formulation been copied correctly to the input file? Are all of
the variables and equations that use sets correctly stated?
2. Consider adding or altering the bounds.
3. When the solver performed an illegal operation, such as a divide by zero, check whether the
equations can be modified/transformed to avoid this error. Inspect whether different initial
conditions or stricter bounds avoid premature termination of the algorithm.
4. When the solver reports the problem is infeasible, check whether the problem is an LP or an
MILP. If so, the formulation is likely to be inconsistent and the model should be re-
examined. If not, consider slackening or removing some of the constraints, and re-running
GAMS until a feasible solution is obtained. Then, re-introduce constraints that have been
removed or slackened, attempting to discern why infeasibility is reported. Also, for an NLP,
the solver may not be able to locate a feasible solution. Examine equations shown to be


CD-G-19
infeasible in the output file. Check whether these equations can be modified or removed to
improve the likelihood of convergence. Try to provide an initial feasible solution.

It may be useful to observe the level (final) values for specific variables after the first
iteration. To stop the solver after one iteration, the following statement is added to the input file,
immediately before the solve statement:

OPTION iterlim = 1

In addition, after the solve statement, add appropriate display statements for those variables to be
tabulated in the output file.


1 VARIABLES
2 Qcw, R1, R2, R3, R4, Z ;
3
4 EQUATIONS
5 OBJ,T1,T2,T3,T4,T5,B1,B2,B3,B4,B5,B6;
6
7 OBJ .. Z =E= Qs;
**** $140
8 T1.. Qs-R1+30 =E= 0;
9 T2.. R1-R2+2.5 =E= 0;
10 T3.. R2-R3-82.5 =E= 0;
11 T4.. R3-R4+75 =E= 0;
12 T5.. R4-Qcw-15 =E= 0;
13
14 B1.. R1 =G= 0
15 B2.. R2 =G= 0;
**** $409
16 B3.. R3 =G= 0;
17 B4.. R4 =G= 0;
18 B5.. Qs =G= 0;
19 B6.. Qcw =G= 0;
20
21 MODEL CASCADE /ALL/;
22 SOLVE CASCADE USING LP MINIMIZING Z;
**** $257

140 Unknown symbol
257 Solve statement not checked because of previous errors
409 Unrecognizable item - skip to find a new statement
looking for a ';' or a key word to get started again

**** 3 ERROR(S) 0 WARNING(S)

Figure 8. Output file generated from incorrect input file for Example 10.4.


CD-G-20
REFERENCES

Brook, A., D. Kendrick, and A. Meeraus, GAMS: A User’s Guide: Release 2.25. Scientific Press
(1992).
Floudas, C. A. Nonlinear and Mixed-Integer Optimization: Fundamentals and Applications.
Oxford University Press, Oxford (1995).
GAMS-The Solver Manuals. GAMS Development Corporation, Washington, DC (1996).

CD-16.7-1
16.7 EQUIPMENT SIZING AND CAPITAL COST ESTIMATION USING THE
ASPEN ICARUS PROCESS EVALUATOR (IPE)

The Aspen Icarus Process Evaluator (IPE) is a software system provided by
Aspen Technology, Inc., for evaluation of capital expenditures, operating costs, and
profitability of a process design. Aspen IPE has an automatic, electronic expert system
which links to process simulation programs. It is used to (1) extend the results of process
simulations, (2) generate rigorous size and cost estimates for processing equipment, (3)
perform preliminary mechanical designs, and (4) estimate purchase and installation costs,
indirect costs, the total capital investment, the engineering-procurement-construction
planning schedule, and profitability analyses. This section concentrates on capital cost
estimation, with profitability analysis covered in Section 17.8.

Aspen IPE uses five key steps in the evaluation of process designs:

1. Simulation results are loaded into Aspen IPE

2. Process simulation units (that is, blocks, modules, or subroutines) are mapped into
more descriptive models of process equipment (e.g., mapping a HEATX simulation
unit into a floating-head, shell-and-tube heat exchanger; mapping a RADFRAC
simulation unit into a tray tower, complete with reboiler, condenser, reflux
accumulator, etc.) and associated plant bulks, which include installation items, such
as piping, instrumentation, insulation, paint, etc.

3. Equipment items are sized and re-sized when modified.

4. Capital costs, operating costs, and the total investment are evaluated for a project.

5. Results are presented to be reviewed, with modifications as necessary and re-
evaluation.


CD-16.7-2
Aspen IPE begins with the results of a simulation using one of the major process
simulators. The program accepts results from ASPEN PLUS, HYSYS.Plant,
CHEMCAD, PRO/II, and other simulators. To estimate equipment sizes and costs, it is
necessary to prepare simulation results for loading into Aspen IPE. This is normally
accomplished by augmenting the simulation file in two ways. First, to estimate
equipment sizes, Aspen IPE usually requires estimates of mixture properties not needed
for the material and energy balances, and phase equilibria calculations performed by the
process simulators. For this reason, it is necessary to augment the simulation report files
with estimates by the simulator of mixture properties, such as viscosity, thermal
conductivity, and surface tension for each of the streams in the simulation flowsheet.
Second, Aspen IPE estimates equipment sizes using the simulation results computed by
the more rigorous, rather than approximate, simulation subroutines. Consequently, when
the approximate DISTL and RSTOIC subroutines are used in ASPEN PLUS, these must
be replaced by more rigorous subroutines, such as the RADFRAC and RPLUG
subroutines. This replacement can be viewed as the first step in computing equipment
sizes and costs.

After the simulation file is augmented, the revised simulation is run and the
results are sent to Aspen IPE. Note that the ASPEN PLUS and HYSYS.Plant simulators
contain menu entries to direct the results to Aspen IPE. For details, the reader is referred
to course notes prepared at the University of Pennsylvania (Nathanson and Seider, 2003),
which are provided in the file, Aspen IPE Course Notes.pdf, on this CD-ROM. This
section presents estimates of equipment sizes and purchase and installation costs using
Aspen IPE for two examples involving: (1) the depropanizer distillation tower presented
on the CD-ROM (either HYSYS → Separations → Distillation or ASPEN PLUS →
Separations → Distillation), and (2) the monochlorobenzene (MCB) separation process
introduced in Section 4.4, with simulation results using ASPEN PLUS provided on the
CD-ROM (ASPEN → Principles of Flowsheet Simulation → Interpretation of Input and
Output → Sample Problem). Just the key specifications and results are presented here.
The details of using Aspen IPE for these two examples are presented in the file, Aspen
IPE Course Notes.pdf.

CD-16.7-3

Example 16.18 Depropanizer

The depropanizer distillation tower in Figure 16.16 is designed and simulated
using the procedures described on the CD-ROM (either HYSYS → Separations →
Distillation or ASPEN → Separations → Distillation). In summary, for the pressures
shown, using the DSTWU subroutine for the specification R = 1.75R
min
, the reflux ratio,
number of equilibrium stages, and the feed stage are estimated to be: R = 6.06, N = 14,
and N
Feed
= 7. When the tower is simulated with these specifications and D/F = 0.226, to
achieve the desired distillate purity, the RADFRAC subroutine adjusts the reflux ratio to
8.88. In this example, it is desired to estimate the total permanent investment, C
TPI
, using
Aspen IPE. The material of construction throughout is carbon steel.

Figure 16.16 Specifications for design of the depropanizer
distillation tower


CD-16.7-4
SOLUTION

For the depropanizer system, Aspen IPE performs mechanical designs, and
estimates sizes, purchase costs, and associated installation materials and labor costs for
the distillation tower, condenser, reflux accumulator, reflux pump, and reboiler. The
designer can add a reboiler pump (to pump liquid from the sump to the reboiler), as was
done in obtaining this solution. Aspen IPE uses many parameters to estimate equipment
sizes and to specify the characteristics of utilities, with default values built in that can be
replaced by user-specified values. Particular attention should be paid to the IPE Design
Basis parameters, such as the design pressure and temperature, the overdesign
allowances, the residence times in the process vessels, and the tower specifications. For
the depropanizer complex, a few changes were made to the default parameters, including
the tray efficiency (0.8), bottom sump height (10 ft), and vapor disengagement height
(above the top tray, 4 ft). The other default parameters are listed in Appendix II of the
file, Aspen IPE Course Notes.pdf, on the CD-ROM.

For the condenser, Aspen IPE uses the cooling water utility. However, its default
inlet and outlet temperatures were changed from 75 and 95°F to 90 and 120°F. Also,
Aspen IPE has three built-in utilities for steam at 100, 165, and 400 psia. Because 100
psia steam condenses at 377.8°F and the bubble point temperature of the bottoms product
at 252 psia is 260.8°F, when 100 psia steam is used in the reboiler, ∆T = 117°F, which
often results in undesirable film boiling as discussed in Section 13.1 of the book. To
reduce the approach temperature difference, and assure nucleate boiling, a low pressure
steam utility, at 50 psia, is defined.

After the parameters for estimating equipment sizes and the utility parameters are
adjusted, and a new steam utility is defined, the simulation units (blocks, modules, or
subroutines) are mapped into Aspen IPE. In this case, there is only one distillation unit,
D1, to be mapped. The default mapping results in: (1) a tray tower, (2) a shell-and-tube
heat exchanger with a fixed tube sheet for the condenser, (3) a horizontal drum for the
reflux accumulator, (4) a centrifugal reflux pump, and (5) a kettle reboiler with U tubes.

CD-16.7-5
To use a kettle reboiler with a floating head, or one of the other built-in reboilers, the
default mapping is deleted and replaced with the preferred mapping. Similarly, the
default mapping for the condenser, a shell-and-tube heat exchanger with a fixed tube
sheet, can be replaced with a shell-and-tube heat exchanger having a floating head.
When the mapping for the simulation unit, D1, is completed, sizes have been estimated
by Aspen IPE for all of the equipment items. Note that for this distillation complex a
reboiler pump is added by the designer and mapped separately by Aspen IPE. Note also
that the equipment sizes can be adjusted by the designer before Aspen IPE estimates
equipment costs, although no adjustments have been made here for the distillation
system.

In the next step, Aspen IPE estimates the purchase and installation costs. Before
proceeding, the designer can (1) apply one of six engineering contractor profiles, which
determine the engineering execution procedure, and (2) adjust the standard basis, which
defines the nature of the site and workforce. Here, the default values may correspond to
inappropriate costs for the following reasons. When designing small plants, the Plant
Engineer or Local Contractor profiles are preferable. For this distillation system, which
is the only system in the plant, it is important to replace the default project type (grass
roots/clear field) with plant addition – suppressed infrastructure. The latter instructs
Aspen IPE to omit items involving electrical switchgear and transformers, which are not
needed when adding this distillation system to an existing process facility. After the
standard basis has been adjusted, Aspen IPE evaluates all of the equipment items in the
project. During the evaluation, purchase and installation costs are estimated. For this
purpose, Aspen IPE utilizes design, work-item, and cost models that have been developed
and updated annually, in accordance with industry design codes and costs for numerous
process plants, since the mid-1970s. Given the broad spectrum of Aspen IPE users
worldwide, Aspen IPE purchase cost estimates are based upon an extensive data base of
material and construction labor costs and detailed, though preliminary, design methods.

For installation costs, Aspen IPE does not use bare module factors as discussed in
Section 16.3 of the book. Rather, rigorous methods are used to estimate the costs of

CD-16.7-6
materials, labor, and construction equipment. These methods are based upon detailed
design calculations for foundations, platforms, piping, instrumentation, electrical
connections, insulation, and painting, among other items involved in the installation. For
example, for concrete foundations, the dimensions of the foundation and the amount of
concrete are estimated based upon the height and weight of the tower, soil conditions,
wind velocity, and seismic zone. For piping and instrumentation types, quantities, and
sizes, Aspen IPE uses self-contained, user-adjustable, P&ID templates that are unique to
each type of equipment. Aspen IPE uses its library of piping and instrumentation models,
mechanical design methods, and equipment and stream information, to develop lists of
materials for piping and instruments, with associated material costs and installation
hours. Consequently, the installation cost estimates by Aspen IPE are more accurate than
those obtained using bare-module or factored-cost methods.

For the six equipment items in the depropanizer distillation system, including the
added reboiler pump, the key equipment sizes and cost estimates are shown in Table
16.33. Note that Aspen IPE designed the condenser to be a shell-and-tube heat exchanger
with two parallel units, each having two tube passes and a correction factor, F
T
= 0.64. It
should be possible to improve this design by re-sizing the unit to obtain a correction
factor close to unity, eliminating one of the parallel units. Figure 16.17 shows more
details for the tray tower from the Capital Estimate Report. For details of the other
equipment items, see Appendix III of the file, Aspen IPE Course Notes.pdf, on the CD-
ROM. Also, these results can be reproduced by accessing the DEC3RP folder (on the
CD-ROM in the Aspen Eng. Suite folder) from within Aspen IPE. Note that the DEC3
folder does not include the reboiler pump. The calculations were carried out using Aspen
IPE, Version 11.1, with the design and cost basis date being the First Quarter 2000.


CD-16.7-7
Total Permanent Investment

Aspen IPE also computes the total permanent investment, C
TPI
, as defined in
Table 16.9 of the book. However, here, the total permanent investment is computed by
the spreadsheet, Profitability Analysis-1.0.xls, which is discussed in Section 17.8. When
using the Aspen IPE option in the spreadsheet, the user enters the following values,
which are obtained from Aspen IPE:

Total Direct Materials and Labor Costs $757,500
Material and Labor G&A Overhead and Contractor Fees 61,200
Contractor Engineering Costs 383,700
Indirect Costs 365,700

Note that the total direct materials and labor costs, $757,500, includes items not
chargeable to the individual equipment items in Table 16.33. For the details of obtaining
these values from Aspen IPE, see the file, Aspen IPE Course Notes.pdf, on the CD-ROM.



CD-16.7-8





Table 16.33 Aspen IPE estimates of equipment sizes,
purchase costs, and direct materials and
labor costs for installation of the
depropanizer distillation complex



Equipment Sizes

Purchase Cost,
C
P
, $
Direct Materials
and Labor Cost,
C
DML
, $
Tray tower
No. of trays = 14 64,100 192,600
Tangent-to-tangent height = 42 ft
Diameter = 5 ft
Vessel weight = 31,500 lb
Condenser
Heat-transfer area =11,100 ft
2

(5,550 ft
2
/shell)
139,400 229,600
Reflux
accumulator

Volume = 2,350 gal 19,000 74,400
Diameter = 5 ft
Length =16 ft
Vessel weight = 9,600 lb
Reflux pump
Fluid head = 50 ft

5,200 35,200
Driver power = 5 Hp
Reboiler
Heat-transfer area = 3,580 ft
2
52,600 115,000
Reboiler pump
Fluid head = 20 ft

7,000 44,700
Driver power = 3 Hp

TOTAL

$287,300

$691,500


CD-16.7-9





















C O M P O N E N T L I S T


=======================================================================================================================
: : : : : PURCHASED:
:ORIGIN : ITEM TYPE : I T E M :--------------------- D E S I G N D A T A ----------------: EQUIPMENT:
: : : D E S C R I P T I O N : : COST USD :
=======================================================================================================================
Equipment mapped from 'D1'.
TW - 10 TRAYED D1-tower Shell material A 515 64100
CODE OF ACCOUNT: 111 Number of trays 15
TAG NO.: D1-tower Vessel diameter 5.000 FEET
Vessel tangent to tangent height 42.00 FEET
Design temperature 310.80 DEG F
Design gauge pressure 262.30 PSIG
Application DISTIL
Tray type SIEVE
Tray spacing 24.00 INCHES
Tray material A285C
Tray thickness 0.188 INCHES
Base material thickness 0.625 INCHES
Total weight 31500 LBS

I T E M :--- M A T E R I A L ---:********* M A N P O W E R *********:--- L/M ---:
: FRACTION : FRACTION : RATIO :
: USD OF PE : USD OF PE MANHOURS : USD/USD :
EQUIPMENT&SETTING: 64100. 1.0000 : 1877. 0.0293 92 : 0.029 :
PIPING : 20847. 0.3252 : 14937. 0.2330 651 : 0.716 :
CIVIL : 1572. 0.0245 : 2153. 0.0336 127 : 1.370 :
STRUCTURAL STEEL : 7021. 0.1095 : 3924. 0.0612 218 : 0.559 :
INSTRUMENTATION : 36315. 0.5665 : 16719. 0.2608 729 : 0.460 :
ELECTRICAL : 1678. 0.0262 : 909. 0.0142 45 : 0.542 :
INSULATION : 10270. 0.1602 : 8250. 0.1287 423 : 0.803 :
PAINT : 643. 0.0100 : 1376. 0.0215 88 : 2.141 :
-------------------------------------------------------------------------
SUBTOTAL : 142445. 2.2222 : 50145. 0.7823 2373 : 0.352 :
TOTAL MATERIAL AND MANPOWER COST =USD 192600. INST'L COST/PE RATIO = 3.005

======================================================================================================================



Figure 16.17 Estimates of equipment sizes and purchase
and installation costs for the depropanizer
tray tower.

CD-16.7-10


Example 16.19 Monochlorobenzene (MCB) Separation Process

The monochlorobenzene (MCB) separation process in Figure 16.18 is designed
and simulated using the procedures described in Section 4.4 and on the CD-ROM
(ASPEN PLUS → Principles of Flowsheet Simulation → Interpretation of Input and
Output → Sample Problem). In this example, it is desired to estimate the total permanent
investment, C
TPI
, using Aspen IPE.


Figure 16.18 Process flowsheet for the MCB separation
process.


CD-16.7-11
SOLUTION

The simulation results were computed initially using the DISTL subroutine in
ASPEN PLUS. When this is replaced by the RADFRAC subroutine, prior to using
Aspen IPE, the reflux ratio is adjusted from 4.29 to 3.35 and the stream flow rates differ
slightly (< 1%).

Because the absorber has a tray efficiency of 20%, while the tray efficiency of the
distillation column is 60%, the two towers must be mapped separately. Also, the heat
exchanger, H1, is too small to be mapped as floating-head, shell-and-tube heat exchanger.
Consequently, this mapping is replaced by a double-pipe heat exchanger. Finally, the
units, M1, S1, and T1, are mapped as Quoted Items having zero cost by Aspen IPE.

After the mapping and sizing are completed (i.e., the equipment sizes are
computed), as for the depropanizer in Example 16.18, the MCB separation process can be
viewed as representing an addition to an existing plant. Consequently, the standard basis
profile is selected to be Local Contractor and the project type is selected as plant
addition – suppressed infrastructure. This is because a full grass roots/clear field
installation would provide an unnecessary supporting power distribution substation and
control system equipment for this small separation plant, which typically would be
supported as a neighboring facility and not built as a separate entity. After the standard
basis has been adjusted, Aspen IPE evaluates all of the equipment items in the mapping.
During the evaluation, purchase and installation costs are estimated. For 11 equipment
items, the key equipment sizes and cost estimates are shown in Table 16.34, with details
of the equipment items provided in Appendix IV of the file, Aspen IPE Course Notes.pdf,
on the CD-ROM. Also, these results can be reproduced by accessing the MCB folder (on
the CD-ROM in the Aspen Eng. Suite folder) from within Aspen IPE. The calculations
were carried out using Aspen IPE, Version 11.1, with the design and cost basis date being
the First Quarter 2000.


CD-16.7-12
Total Permanent Investment

Aspen IPE also computes the total permanent investment. However, in this
textbook, the total permanent investment is computed by the spreadsheet, Profitability
Analysis-1.0.xls, which is discussed in Section 17.8. When using the Aspen IPE option
in the spreadsheet, the user enters the following values, which are obtained from Aspen
IPE:

Total Direct Materials and Labor Costs $785,700
Material and Labor G&A Overhead and Contractor Fees 69,700
Contractor Engineering Costs 558,300
Indirect Costs 482,600

Note that the total direct materials and labor costs, $785,700, includes items not
chargeable to the individual equipment items in Table 16.33. For the details of obtaining
these values from Aspen IPE, see the file, Aspen IPE Course Notes.pdf, on the CD-ROM.

References

Nathanson, R. B., and W. D. Seider, Aspen Icarus Process Evaluator Course
Notes, University of Pennsylvania, Philadelphia, 2003.

CD-16.7-13
Table 16.34 Equipment sizes and purchase costs for the
MCB separation process.



Equipment Sizes

Purchase Cost,
C
P
, $
Direct Materials
and Labor Cost,
C
DML
, $
Tray Tower, D1
No. of trays = 30 53,500 179,200
Tangent-to-tangent height = 72 ft
Diameter = 3 ft
Vessel weight = 21,400 lb
Condenser, D1
Heat-transfer area =155 ft
2
12,200 50,600
Reflux accumulator,
D1

Liquid volume = 238 gal 7,500 51,300
Diameter = 3 ft
Length = 4.5 ft
Vessel weight = 1,500 lb
Reflux pump, D1
Fluid head = 70 ft

3,300 24,000
Driver power = 1.0 Hp
Reboiler, D1
Heat-transfer area = 921 ft
2
23,500 71,800
Absorber, A1
No. of trays = 15 16,000 110,000
Tangent-to-tangent height = 42 ft
Diameter = 1.5 ft
Vessel weight = 6,400 lb
Flash Vessel, F1
Liquid volume = 264 gal

7,100 54,200
Diameter = 3 ft
Length = 5 ft
Vessel weight = 1,400 lb
Heat Exchanger, H1
Heat-transfer area = 160 ft
2
16,100 58,100
Heat Exchanger, H2
Heat-transfer area = 196 ft
2
12,400 52,900
Pump, P1
Fluid head = 62.1 ft

2,800 19,800
Driver power = 1.5 Hp

TOTAL

$154,400

$671,900



CD-17.8-1
17.8 PROFITABILITY ANALYSIS SPREADSHEET

This section shows how to use purchase and installation cost estimates from
Aspen IPE, and other sources, together with an economics spreadsheet by Holger
Nickisch (2003) to estimate profitability measures for the monochlorobenzene (MCB)
separation process, which was introduced in Section 4.4. In Section 16.7, IPE was used
to estimate the total permanent investment for this process. The economics spreadsheet,
Profitability Analysis-1.0.xls, is on the CD-ROM that accompanies this textbook.

Holger Nickisch, a graduate of the University of Pennsylvania, with dual degrees
in chemical engineering and business, designed the spreadsheet for use with Chapters 16
and 17 of Product and Process Design Principles: Synthesis, Analysis, and Evaluation
(Seider, Seader, and Lewin, Wiley, 2004). It replaces Version 3.0 of an earlier
spreadsheet, entitled HNP.xls.

The spreadsheet utilizes extensive Visual BASIC (VBA) programming to reduce
the most common sources of error when setting up a complicated spreadsheet in
Microsoft EXCEL. The use of VBA makes it possible to avoid common mistakes in
entering specifications, allows the output to be formatted into presentable pages, and
ensures that the output is not altered inadvertently after specifications have been entered.
The user of the spreadsheet is not required to know VBA.


General Instructions for Use of Profitability Analysis-1.0.xls

Depending on the version of EXCEL being used, the procedures to activate
“Macro Code” differ. In EXCEL 97, when the spreadsheet is loaded, the user is asked
whether macros should be enabled. An affirmative response is necessary, after which
EXCEL loads the complete file, which contains many worksheets most of which are
hidden. In EXCEL 2000, and later versions, three security settings under the Tool,
Macros menu are offered. The highest setting does not allow VBA code to be opened.

CD-17.8-2
The intermediate setting causes the user to be prompted, as in EXCEL 97, and the lowest
setting causes VBA code to be opened without user approval. The latter is
recommended.

After the spreadsheet is started with the “Macro Code” activated, the introductory
page is displayed briefly. Then, the Login dialog box appears in which a user name and
password must be entered. For students, the user name is ‘student’ and the password is
‘engineer’ (which can be altered). When proper entries have been provided, the
Save/New dialog box appears in which the user selects either Start New Analysis or Load
Existing Analysis and clicks on the OK button.

When a new analysis is initiated, the Step 1 dialog box is displayed, into which
input specifications are entered. The user provides entries for the title of the process, the
name of the product, the location of the plant site, and the site factor (which is obtained
from Table 16.13). Then the annual operating hours are entered, either hr/yr, day/yr, or
the operating factor (fraction of hours in operation per year). Finally, the timelines and
investment distribution are provided for the total permanent investment, C
TPM
, and the
working capital, C
WC
. When the Timelines button is depressed, the Timelines dialog box
appears. Entries are provided for the starting year, the number of years of design and
construction, and plant life in years. When the Investment Distribution is pressed, the
Investment Distribution dialog box appears, in which percentage distribution in each year
can be adjusted for C
TPM
and C
WC
. Note that when the percentages sum to 100%, the sum
is displayed with a green background. Otherwise the background is red, signaling to the
user that corrections must be made. Specific entries are shown below in Example 17.32,
in which a profitability analysis for the MCB separation process is completed. After
these specifications are completed, the OK button is depressed and the Input Summary
form is displayed. By scrolling down on this form, the following sections appear:

General Information
Chronology
Product Information

CD-17.8-3
Raw Materials
Equipment Costs
Total Permanent Investment
Working Capital
Utilities
Byproducts
Other Variable Costs
Fixed Costs

Note that the specifications just entered in the General Information section are displayed.
Associated with each section heading is a blue button: CLICK HERE FOR MENU.
When pressed, the spreadsheet menu appears at the top of the screen. To enter the
specifications in any section, point anywhere within the section, except for the section
heading. This produces a dialog box that guides the specification of many of the required
inputs. Other entries are provided in dialog boxes produced by pressing the Menu
buttons. Note that for most entries default values are provided. These are displayed on
the Input Summary form and remain unaltered unless new entries are provided. The
default values are those recommended in Chapters 16 and 17. Next, the entries in each
section are described.

General Information

These entries have been discussed above. To produce the Step 1 dialog box, point
to the General Information section and left click.

Chronology

This section lists each year during the life of the project, beginning with the
starting year. The Action in each year is indicated as Design, Construction, or Production.
As discussed above, these specifications are entered using the Step 1 dialog box, which is
obtained by pointing to the Chronology section and left-clicking. To change the

CD-17.8-4
Production Capacity (i.e., the percent of design capacity) in each year and the MACRS
tax-basis depreciation schedule, on the Menu, press the Options button, which produces
the Options dialog box. Press the Production Capacity tab to enter Production Capacity
at full production (the percent of design capacity at full production) and information to
ramp-up to full production, that is, the years to achieve full production, and the Start
Production percentage (the percent of design capacity during the first year of production.)
Note that a linear ramp is computed. Also, the number of operator shifts per week is
specified. Using the Depreciation Schedule tab, the number of years in the MACRS Tax-
basis Depreciation schedule is specified. Note that 5, 7, 10, and 15 year schedules are
displayed.

Product Information

When left-clicking within this section, the Product Units dialog box is displayed.
In this box, the unit in which the primary product is specified is entered in five characters
or less (e.g., lb). This produces the Capacity and Product Price dialog box in which the
capacity of the plant is entered (e.g., lb/hr of MCB) and the product price is entered in
$/unit (e.g., $/lb MCB).

Raw Materials

Similar entries are provided for each raw material. When left-clicking within the
Raw Materials section, the Raw Materials dialog box is produced. To add a raw material,
press the Add button. This produces the Raw Materials: NEW dialog box, in which the
raw material name and unit of measure are entered (e.g., FEED and lb). This produces
the Raw Materials: ‘FEED’ dialog box, within which the units of the raw material per
unit of product (e.g., lb FEED/lb MCB) and the price per unit of raw material (e.g., $/lb
FEED) are entered. Subsequently, this entry can be edited by displaying the Raw
Materials dialog box and selecting an existing raw material using the pull-down menu.
The entries for this raw material can be edited by pressing the Edit button or the raw
material can be deleted by pressing the Delete button.

CD-17.8-5

Equipment Costs

When left-clicking within the Equipment Costs section, the Equipment Costs
dialog box is produced. Herein, equipment items are identified to be in one of five
categories: Fabricated Equipment, C
FE
; Process Machinery, C
PM
; Spares, C
spare
; Storage,
C
storage
; or Catalysts, C
catalyst
; as grouped in Table 16.9 and discussed in Section 16.3.
Entries in each category can be entered, edited, and deleted. After one of the categories
is selected, a dialog box, with the name of the category, appears. In this box, the user
chooses to add, edit, or delete an equipment item. When pressing the Add button, the
New Equipment Item dialog box appears. The user chooses to enter (1) the purchase cost
only, (2) the purchase cost and bare module factor, or (3) the bare module cost. For the
first option, the Entering Purchase Costs Only dialog box appears, in which the
equipment name and purchase cost are entered. In this case, a default bare module factor,
3.21, is used. Note that to alter the default bare module factor, on the Menu, press the
Options button to produce the Options dialog box. Select the Derived Bare Module
Factor tab. On this form, the factors in Table 16.10 are entered, as fractions of the
purchase cost to compute the cost of installation materials, C
M
; labor, C
L
; freight,
insurance, and taxes, C
FIT
; construction overhead, C
O
; and contractor engineering, C
E
.
These factors are summed to give the total bare module factor. For the second option, the
Entering Purchase Cost and Bare Module Factor dialog box appears, in which the
equipment name, purchase cost, and bare module factor are entered. Bare module factors
for a number of types of equipment are given in Table 16.11. Alternatively, for the third
option, the Entering Bare Module Cost dialog box appears. Here, just the equipment
name and bare module cost are entered.

Aspen IPE Specifications. When Aspen IPE is used to estimate purchase and
installation costs for the entire plant, or a portion of the plant, click the Options entry in
the Menu and check the Allow IPE Entries box at the bottom of the dialog box that
appears. This produces the IPE Specifications subsection in the Equipment Costs section.
Then left-click within the IPE Specifications subsection to produce the IPE Specifications

CD-17.8-6
dialog box. The entries, Total Direct Materials and Labor Costs, Material and Labor
G&A Overhead and Contractor Fees, Contractor Engineering Costs, and Indirect Costs,
are obtained from the Aspen IPE Capital Estimate Report, as discussed in Section 16.7.
Other costs can be entered (e.g., for pipe racks and sewers/sumps) under Miscellaneous
Installation Costs, if desired. The entries are summed and added to the Total Bare
Module Cost.

Total Permanent Investment

When left clicking within the Total Permanent Investment section, the Direct
Permanent Investment dialog box appears. For each of the pertinent entries in Table
16.9, the default entry can be altered. Either a percentage value or an absolute dollar
amount is entered.

Working Capital

When left-clicking within the Working Capital section, the Working Capital
dialog box appears, on which the numbers of days are provided for the product, accounts
receivable, cash reserves, and accounts payable, as discussed in Section 17.3, with
defaults for each. If desired, additional entries can be made for any or all of the raw
materials.

Utilities

When left-clicking within the Utilities section, the Utilities dialog box appears.
An entry is provided for six default utilities in the spreadsheet: high pressure steam, low
pressure steam, process water, cooling water, natural gas, and electricity. Additional
utilities can be entered by pressing the Options button in the Menu, selecting the Utilities
tab, pressing the Add button to produce the Add a Utility dialog box, entering the name of
the utility (e.g., medium pressure steam), and pressing the Add button. The additional
utilities appear in the Utilities dialog box. Then check the box for each utility in the

CD-17.8-7
process and press the OK button, to produce a box into which its unit of measure is
entered (e.g., kWhr for electricity). This produces a named utility dialog box in which
the units of utility per unit of product is entered (e.g., lb high pressure steam/lb MCB), as
well as the price of the utility (e.g., $/kWhr). By pressing the next button, a similar
dialog box is produced for the next utility, until this information is entered for all utilities
in the process. Representative prices for many utilities are listed in Table 17.1.

Byproducts

When left-clicking within the Byproducts section, the Byproducts dialog box
appears. As in the specification of raw materials, byproducts are added individually, with
a specification of the unit of measure, the unit of byproduct per unit of product, and the
price per unit of byproduct.

Other Variable Costs

When left-clicking within the Other Variable Costs section, the General Expenses
dialog box appears, which permits the specification of percentages of product sales
charged for selling/transfer expenses, direct research, allocated research, administrative
expenses, and management incentives compensation. The defaults shown are those in the
cost sheet of Table 17.1 and discussed in Section 17.2.

Fixed Costs

The entries under Fixed Costs appear in six subsections: Operations,
Maintenance, Operating Overhead, Property Taxes and Insurance, Straight-line
Depreciation, and Depletion Allowance. When left-clicking within each subsection, the
appropriate dialog box appears, in which the default entries can be replaced when
desired. Note that the default entries are those in Table 17.1. However, under
Operations, entries must be made for (1) the number of operators per shift, (2) technical

CD-17.8-8
assistance to manufacturing, and (3) control laboratory, for which see page 576 and Table
17.1. If a depletion allowance applies, see pages 606-608 for estimating it.

Financial Information

In addition to the above entries, it is necessary to specify financial information for
calculation of the return on investment (ROI), the net present value (NPV) and the
investor’s rate of return (IRR), also known as the discounted cash flow rate of return
(DCFRR). To accomplish this, select the Options button in the Menu, and the Financial
Information tab. Then enter the income tax rate, the cost of capital (for the NPV
calculation) and the inflation rate. Note that a general inflation rate can be specified,
applicable to all operating costs, or by checking the Different Inflation Rate box, separate
inflation rates can be specified for fixed and variable costs.

Running the Analysis and Creating a Report

To initiate the profitability analysis, on the Menu, press the Create Report button
to produce the Create Report dialog box. After entering the Report Name, to which the
word “Report” is automatically appended, and the directory into which the report file is
to be stored (i.e., the report path), press the Create Report button. The results, which are
placed in an EXCEL report file, include sections on the Investment Summary, which
presents cost estimates for all entries associated with the total permanent investment, the
working capital, and the total capital investment (i.e,, the entries shown in Table 16.9).
Also included are sections on the Variable Costs at design capacity (not production
during a specific year) of operations and for the Fixed Costs. These correspond to the
entries shown in Table 17.1. Then, a section on the cash flows, and the elements that
contribute to them, is displayed for each year during the life of the project. Finally, a
section on the NPV and the IRR is provided. Each section is accessed by clicking on the
appropriate tab at the bottom of the frame.


CD-17.8-9
It is also possible to have the ROI (during the third operating year) estimated and
to carry out sensitivity studies. This is accomplished by pressing the Choose Custom
Analyses button, which produces the Custom Analyses dialog box, and checking the ROI
(Third Year) entry. In addition, the IRR can be computed as a function of a single
variable or as a function of two variables. These variables are the product price, variable
cost, fixed cost, initial investment, and the rate of inflation.

Saving or Loading an Analysis

At any point when entering specifications or after completing an analysis, the
contents of the worksheet can be saved in a file. Alternatively, an existing file can be
loaded into the spreadsheet. To accomplish this, on the spreadsheet Menu, press the
Save/New button to produce the Save/New dialog box. To save a file, check the Save
Current Analysis button and press OK. On the Save As dialog box, enter a file name and
a file path. To load a file, check the Load Existing Analysis button and press OK, which
produces the Browse for Folder dialog box, within which the file is located. Note that the
Save/New dialog box also permits the user to start a new analysis.

Having described the details of data entry into the spreadsheet, Profitability
Analysis-1.0.xls, Example 17.32 is provided to illustrate its use for the MCB separation
process.

Example 17.32
It is desired to carry out a profitability analysis for the monochlorobenzene
(MCB) separation process using (a) purchase costs and bare module factors, (b)
purchase and installation costs estimated by Aspen IPE. In Section 16.7, the latter
estimates were computed, beginning with the ASPEN PLUS simulation in the
file, MCB.bkp. Plant location is the Gulf Coast. The design time is estimated to
be one year, the construction time at one year, and the total operating life of the
project at 15 years. Assume that 5% of the total permanent investment is

CD-17.8-10
allocated to engineering during the design year. The cost of capital is taken to be
15% annually.

SOLUTION:
From the simulation results:

MCB production rate =
yr
day
330
day
hr
24
hr
lb
1 . 572 , 5 × ×
=
yr
lb
000 , 131 , 44

The MCB product (stream S14) is valued at $0.54/lb. Furthermore, from the
simulation results:

S14 lb
S01 lb
636 . 1
S14/hr lb 5,572.1
S01/hr lb 1 . 117 , 9
=
and the price of the feed stream (S01) is $0.30/lb.
The utility costs are estimated as follows, with the quantities per pound of product
determined based upon the simulation results.
High Pressure Steam –
lb
$
004 . 0
lb 1,000
$
00 . 4 =


S14 lb
steam lb
2451 . 0
S14/hr lb 5,572.1
steam/hr lb 1,365.5
=

Cooling Water -
lb
$
10 6
gal
$
10 5
gal 000 , 1
$
05 . 0
6 5 − −
× = × =


S14 lb
O H lb
2 . 23
S14/hr lb 5,572.1
O/hr H lb 10 2927 . 1
2 2
5
=
×


Electricity -
KWhr
$
04 . 0


S14 lb
kWh
00172 . 0
S14/hr lb 5,572.1
kW 60 . 9
=
The byproduct benzene (stream S11) is valued at $0.15/lb and the quantity per
pound of product is determined from the simulation results:

CD-17.8-11

S14 lb
S11 lb
5622 . 0
S14/hr lb 5,572.1
S11/hr lb 3,132.7
=

Results from the Profitability Analysis Spreadsheet – Part (a) – Purchase Costs
and Bare Module Factors

The pages that follow contain the:

1. Input Summary. Note that all specifications are shown, with the default
values used in most cases.

2. Investment Summary.

3. Variable Cost Summary. These costs are estimated for the third operating
year.

4. Fixed Cost Summary.

5. Cash Flow Summary.

6. Profitability Measures. As seen, the IRR is 27.9%, the ROI is 34.0%, and the
NPV is $2,888,500.

7. Sensitivity Analyses. Here, the IRR is studied as the product price and
variable costs are adjusted.

Note that the results are displayed sometimes as 0.00, having just two decimal
places. To avoid this, the user can adjust the units of measure.

CD-17.8-12
1. Input Summary - Part (a) – Purchase Costs and Bare Module Factors


General Information
Process Title: Monochlorobenzene Separation Process
Product: Monochlorobenzene
Plant Site Location: Gulf Coast
Site Factor: 1.00
Operating Hours per Year: 7,920
Operating Days per Year: 330
Operating Factor: 0.9041
Chronology
Year Action
Start Year 2003 Design
2004 Construction
2005 Production
2006 Production
2007 Production
2008 Production
2009 Production
2010 Production
2011 Production
2012 Production
2013 Production
2014 Production
2015 Production
2016 Production
2017 Production
2018 Production
End Year 2019 Production
Product Information
The Process will yield: α 5,572 lb of Monochlorobenzene per hour.
α 133,730 lb of Monochlorobenzene per day.
α 44,131,032 lb of Monochlorobenzene per year.
The Price per lb of Monochlorobenzene is: $ 0.54
Raw Materials
Raw Material Unit of Measure Ratio to Product Cost of Raw Material
FEED lb 1.6400 lb per lb of Monochlorobenzene $0.3000 per lb
Equipments Costs
Fabricated Equipment Purchase Cost Bare Module Factor Bare Module Cost
Absorber $ 29,900 4.16 $ 124,384
Distillation Column $ 115,600 4.16 $ 480,896
Heat Exchangers $ 11,900 3.17 $ 37,723
Flash Vessels and Storage Tanks $ 87,200 4.16 $ 362,752
Process Machinery Purchase Cost Bare Module Factor Bare Module Cost
Pumps $ 5,000 3.3 $ 16,500
*Derived Bare Module Factor
Input Summary
90.0%
90.0%
90.0%
90.0%
90.0%
90.0%
90.0%
Distribution of Total
Permanent Investment
Distribution of Total
Working Capital
5.0%
95.0%
90.0%
0.0%
100.0%
45.0%
67.5%
90.0%
90.0%
Production Capacity (%
of Design Capacity)
Percentage of Total
Capital Investment for
Depreciation
0.0%
0.0%
90.0%
90.0%
90.0%
20.0%
32.0%
19.2%
11.5%
11.5%
5.8%

CD-17.8-13














































Total Permanent Investment
Cost of Site Preparations: 5.0% of Total Bare Module Costs
Cost of Service Facilities: 5.0% of Total Bare Module Costs
Allocated Costs for utility plants and related facilities: $0
Cost of Contingencies and Contractor Fees: 18.0% of Direct Permanent Investment
Cost of Land: 2.0% of Total Depreciable Capital
Cost of Royalties: $0
Cost of Plant Start-Up: 10.0% of Total Depreciable Capital
Working Capital
Monochlorobenzene α Inventory: 4 Days α 534,921.60 lb
FEED α Inventory: 2 Days α 438,635.71 lb
Accounts Receivable α 30 Days
Cash Reservces α None
Accounts Payable α None
Utilities
Utility Unit of Measure Ratio to Product Cost of Utility
High Pressure Steam lb 0.2500 lb per lb of Monochlorobenzene $0.0040 per lb
Cooling Water Mlb 0.0232 Mlb per lb of Monochlorobenzene $0.0060 per Mlb
Electricity kWhr 0.0017 kWhr per lb of Monochlorobenzene $0.0400 per kWhr
Byproducts
Byproduct Unit of Measure Ratio to Product Price of Raw Byproduct
Benzene lb 0.5600 lb per lb of Monochlorobenzene $0.1500 per lb
Other Variable Costs
General Expenses
Selling / Transfer Expenses: 3.00% of Sales
Direct Research: 4.80% of Sales
Allocated Research: 0.50% of Sales
Administrative Expense: 2.00% of Sales
Management Incentive Compensation: 1.25% of Sales
Fixed Costs
Operations
Operators per Shift: 1 (Assuming 5 Shifts)
Direct Wages and Benefits: $30.00 per Operator Hour
Direct Salaries and Benefits: 15.00% of Direct Wages and Benefits
Operating Supplies and Services: 6.00% of Direct Wages and Benefits
Technical Assistance to Manufacturing: $0.00 per year, for each Operator per Shift
Control Laboratory: $0.00 per year, for each Operator per Shift
Maintenance
Wages and Benefits: 3.50% of Total Depreciable Capital
Salaries and Benefits: 25.00% of Maintenance Wages and Benefits
Materials and Services: 100.00% of Maintenance Wages and Benefits
Maintenance Overhead: 5.00% of Maintenance Wages and Benefits
Operating Overhead
General Plant Overhead: 7.10% of Maintenance and Operations Wages and Benefits
Mechanical Department Services: 2.40% of Maintenance and Operations Wages and Benefits
Employee Relations Department: 5.90% of Maintenance and Operations Wages and Benefits
Business Services: 7.40% of Maintenance and Operations Wages and Benefits
Property Taxes and Insurance
Property Taxes and Insurance: 2.00% of Total Depreciable Capital
Straight Line Depreciation
Direct Plant: 8.00% of Total Depreciable Capital, less1.18 times the Allocated Costs for Utility Plants and Related Facilities
Allocated Plant: 6.00% of 1.18 times the Allocated Costs for Utility Plants and Related Facilities
Depletion Allowance
Annual Depletion Allowance: $0.00

CD-17.8-14
2. Investment Summary - Part (a) – Purchase Costs and Bare Module Factors




































May, 2003
Bare Module Costs
Fabricated Equipment
Absorber $124,400
Distillation Column $480,900
Heat Exchangers $37,700
Flash Vessels and Storage Tanks $362,800
Total Fabricated Equipment: $1,005,800
Process Machinery
Pumps $16,500
Total Process Machinery: $16,500
Total Bare Module Costs:
Direct Permanent Investment
Cost of Site Preparation: $51,100
Cost of Service Facilities: $51,100
Allocated Costs for utility plants and related facilitie$0
Direct Permanent Investment:
Total Depreciable Capital
Cost of Contigencies and Contractor Fees: $202,300
Total Depreciable Capital:
Total Permanent Investment
Cost of Land: $26,500
Cost of Royalties: $0
Cost of Plant Start-Up: $132,600
Total Permanent Investment:
Working Capital
Inventory
Monochlorobenz α 481,000 lb $260,000
FEED α 395,000 lb $118,400
Total Inventory: $378,400
Accounts Receivable: $2,166,400
Cash Reservces: $0
Accounts Payable: $0
Total Working Capital: $2,544,800
TOTAL CAPITAL INVESTMENT
$1,124,000
$1,326,000
$1,485,000
$4,029,800
Investment Summary
Monochlorobenzene Separation Process
TOTAL
$1,022,000

CD-17.8-15
3. Variable Cost Summary - Part (a) – Purchase Costs and Bare Module Factors















May, 2003
Raw Materials
FEED
Total Raw Materials:
Utilties
High Pressure Steam
Cooling Water
Electricity
Total Raw Materials:
Byproducts
Benzene
Total Byproducts:
General Expenses
Selling / Transfer:
Direct Research:
Allocated Research:
Administrative Expense:
Management Incentives:
Total Byproducts:
TOTAL
0.06 per lb of Monochlorobenzen $2,752,500 $20,811,300
0.47 per lb of Monochlorobenzen $20,811,200 $20,811,200
$0.01 per lb of Monochlorobenzene $476,600
$0.01 per lb of Monochlorobenzene $297,900
$0.03 per lb of Monochlorobenzene $1,143,900
$0.00 per lb of Monochlorobenzene $119,200
$18,058,800
$0.02 per lb of Monochlorobenzene $714,900
0.08 per lb of Monochlorobenzen -$3,707,000
$0.08 per lb of Monochlorobenzene -$3,707,000
0.00 per lb of Monochlorobenzen $53,300 $21,765,800
$0.00 per lb of Monochlorobenzene $3,000
$21,712,500
$0.00 per lb of Monochlorobenzene $44,100
0.49 per lb of Monochlorobenzen $21,712,500
Variable Cost Summary
Monochlorobenzene Separation Process
Per lb Monochlorobenzene
$0.00 per lb of Monochlorobenzene $6,100
TOTAL
$0.49 per lb of Monochlorobenzene $21,712,500

CD-17.8-16
4. Fixed Cost Summary - Part (a) – Purchase Costs and Bare Module Factors



















May, 2003
Operations
Direct Wages and Benefits: $312,000
Direct Salaries and Benefits: $46,800
Operating Supplies and Services: $18,720
Technical Assistance to Manufacturing: $0
Control Laboratory: $0
Total Operations: $377,520
Maintenance
Wages and Benefits: $46,410
Salaries and Benefits: $11,603
Materials and Services: $46,410
Maintenance Overhead: $2,321
Total Maintenance: $106,744
Operating Overhead
General Plant Overhead: $29,594
Mechanical Department Services: $10,004
Employee Relations Department: $24,592
Business Services: $30,844
Total Operating Overhead: $95,034
Property Insurance and Taxes
Total Property Insurance and Taxes: $26,520
TOTAL
$484,264
$579,298
$605,818
$605,818
Fixed Cost Summary
Monochlorobenzene Separation Process
TOTAL
$377,520

CD-17.8-17
5. Cash Flow Summary - Part (a) – Purchase Costs and Bare Module Factors











6. Profitability Measures - Part (a) – Purchase Costs and Bare Module Factors













May, 2003
Year
Percentage
of Design
Capacity
Sales Capital Costs Working Capital Variable Costs Fixed Costs
Depreciation
Allowance
Depletion
Allowance
Taxable Income
Income Tax
Costs
Net Earnings
Annual Cash
Flow
Cumulative Net
Present Value at
15.0%
2003 0.0% Design -$74,300 $0 -$74,300 -$74,300
2004 0.0% Construction -$1,410,800 -$2,544,800 -$3,955,600 -$3,514,000
2005 45.0% $10,723,800 -$9,365,000 -$605,800 -$265,200 $0 $487,800 -$180,500 $307,300 $572,500 -$3,081,100
2006 67.5% $16,085,800 -$14,047,600 -$605,800 -$424,300 $0 $1,008,100 -$373,000 $635,100 $1,059,400 -$2,384,500
2007 90.0% $21,447,700 -$18,730,100 -$605,800 -$254,600 $0 $1,857,200 -$687,200 $1,170,000 $1,424,600 -$1,570,000
2008 90.0% $21,447,700 -$18,730,100 -$605,800 -$152,800 $0 $1,959,000 -$724,800 $1,234,200 $1,387,000 -$880,400
2009 90.0% $21,447,700 -$18,730,100 -$605,800 -$152,800 $0 $1,959,000 -$724,800 $1,234,200 $1,387,000 -$280,800
2010 90.0% $21,447,700 -$18,730,100 -$605,800 -$76,400 $0 $2,035,400 -$753,100 $1,282,300 $1,358,700 $230,000
2011 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $664,900
2012 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $1,043,100
2013 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $1,372,000
2014 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $1,658,000
2015 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $1,906,700
2016 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $2,122,900
2017 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $2,310,900
2018 90.0% $21,447,700 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $1,330,400 $2,474,400
2019 90.0% $21,447,700 $2,544,800 -$18,730,100 -$605,800 $0 $2,111,800 -$781,400 $1,330,400 $3,875,200 $2,888,500
Cash Flow Summary
Monochlorobenzene Separation Process
May, 2003
The Investor's Rate of Return (IRR) for this Project is: 27.86%
The Net Present Value (NPV) at 15% for this Project is: $2,888,500
ROI Analysis (Third Production Year)
Annual Sales:
Annual Costs:
Depreciation:
Income Tax:
Net Earnings:
Total Capital Investment:
ROI: 34.0%
-$106,100
-$742,100
$1,369,700
$4,029,800
Profitability Measures
Monochlorobenzene Separation Process
$21,447,700
-$19,335,900

CD-17.8-18
7. Sensitivity Analyses - Part (a) – Purchase Costs and Bare Module Factors













Results from the Profitability Analysis Spreadsheet – Part (b) – Purchase and
Installation Costs Estimated by Aspen IPE

The pages that follow contain the:

1. Input Summary. Note that all specifications are shown, with the default
values used in most cases.

2. Investment Summary.

3. Variable Cost Summary. These costs are estimated for the third operating
year.

4. Fixed Cost Summary.

5. Cash Flow Summary.

6. Profitability Measures. As seen, the IRR is 21.0%, the ROI is 25.0%, and the
NPV is $1,625,500.

7. Sensitivity Analyses. Here, the IRR is studied as the product price and
variable costs are adjusted.

Note that the results are displayed sometimes as 0.00, having just two decimal
places. To avoid this, the user can adjust the units of measure.


May, 2003
Product Prices vs Variable Costs
$17,689,500 $18,209,800 $18,730,100 $19,250,400 $19,770,600 $20,290,900 $20,811,200 $21,331,500 $21,851,800 $22,372,000 $22,892,300 $23,412,600
0.46 $ 24.98% 18.44% 11.26% 3.06% Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range
0.47 $ 31.49% 25.51% 19.12% 12.14% 4.25% Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range
0.49 $ 37.46% 31.87% 26.01% 19.77% 12.99% 5.38% Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range
0.50 $ 43.01% 37.73% 32.24% 26.50% 20.40% 13.79% 6.43% Out of Range Out of Range Out of Range Out of Range Out of Range
0.51 $ 48.22% 43.18% 37.99% 32.60% 26.97% 21.00% 14.56% 7.43% -0.75% Out of Range Out of Range Out of Range
0.53 $ 53.14% 48.31% 43.35% 38.24% 32.95% 27.42% 21.58% 15.30% 8.38% 0.52% Out of Range Out of Range
0.54 $ 57.81% 53.16% 48.40% 43.52% 38.49% 33.29% 27.86% 22.13% 16.00% 9.29% 1.70% Out of Range
0.55 $ 62.27% 57.76% 53.17% 48.48% 43.67% 38.73% 33.61% 28.28% 22.67% 16.68% 10.15% 2.82%
0.57 $ 66.52% 62.15% 57.71% 53.18% 48.56% 43.83% 38.96% 33.93% 28.69% 23.19% 17.33% 10.97%
0.58 $ 70.60% 66.35% 62.04% 57.66% 53.20% 48.64% 43.98% 39.18% 34.23% 29.08% 23.69% 17.95%
0.59 $ 74.51% 70.38% 66.19% 61.93% 57.61% 53.21% 48.72% 44.12% 39.40% 34.53% 29.47% 24.17%
0.61 $ 78.28% 74.25% 70.16% 66.03% 61.83% 57.56% 53.22% 48.79% 44.26% 39.61% 34.81% 29.84%
0.62 $ 81.91% 77.97% 73.98% 69.95% 65.87% 61.73% 57.52% 53.23% 48.87% 44.40% 39.81% 35.09%
IRR Analysis - Two Variable
Monochlorobenzene Separation Process
Variable Costs
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CD-17.8-19
General Information
Process Title: Monochlorobenzene Separation Process
Product: MCB
Plant Site Location: Gulf Coast
Site Factor: 1.00
Operating Hours per Year: 7,920
Operating Days per Year: 330
Operating Factor: 0.9041
Chronology
Year Action
Start Year 2003 Design
2004 Construction
2005 Production
2006 Production
2007 Production
2008 Production
2009 Production
2010 Production
2011 Production
2012 Production
2013 Production
2014 Production
2015 Production
2016 Production
2017 Production
2018 Production
End Year 2019 Production
Product Information
The Process will yield: α 5,572 lb of MCB per hour.
α 133,730 lb of MCB per day.
α 44,131,032 lb of MCB per year.
The Price per lb of MCB is: $ 0.54
Raw Materials
Raw Material Unit of Measure Ratio to Product Cost of Raw Material
FEED lb 1.6400 lb per lb of MCB $0.3000 per lb
Equipments Costs
IPE Specifications
Total Direct Materials and Labor Costs: $785,700
Miscellaneous Installation Costs: $0
Material and Labot G&A Overhead and Contractor Fees: $69,700
Contractor Engineering Costs: $558,300
Indirect Costs: $482,600
*Derived Bare Module Factor
Input Summary
90.0%
90.0%
90.0%
90.0%
90.0%
90.0%
90.0%
Distribution of Total
Permanent Investment
Distribution of Total
Working Capital
5.0%
95.0%
90.0%
0.0%
100.0%
45.0%
67.5%
90.0%
90.0%
Production Capacity (%
of Design Capacity)
Percentage of Total
Capital Investment for
Depreciation
0.0%
0.0%
90.0%
90.0%
90.0%
20.0%
32.0%
19.2%
11.5%
11.5%
5.8%

1. Input Summary - Part (b) – Purchase and Installation Costs Estimated by
Aspen IPE



CD-17.8-20

Total Permanent Investment
Cost of Site Preparations: 5.0% of Total Bare Module Costs
Cost of Service Facilities: 5.0% of Total Bare Module Costs
Allocated Costs for utility plants and related facilities: $0
Cost of Contingencies and Contractor Fees: 18.0% of Direct Permanent Investment
Cost of Land: 2.0% of Total Depreciable Capital
Cost of Royalties: $0
Cost of Plant Start-Up: 10.0% of Total Depreciable Capital
Working Capital
MCB α Inventory: 4 Days α 534,921.60 lb
FEED α Inventory: 2 Days α 438,635.71 lb
Accounts Receivable α 30 Days
Cash Reservces α None
Accounts Payable α None
Utilities
Utility Unit of Measure Ratio to Product Cost of Utility
High Pressure Steam lb 0.2500 lb per lb of MCB $0.0040 per lb
Cooling Water Mlb 0.0232 Mlb per lb of MCB $0.0060 per Mlb
Electricity kWhr 0.0017 kWhr per lb of MCB $0.0400 per kWhr
Byproducts
Byproduct Unit of Measure Ratio to Product Price of Raw Byproduct
Benzene lb 0.5600 lb per lb of MCB $0.1500 per lb
Other Variable Costs
General Expenses
Selling / Transfer Expenses: 3.00% of Sales
Direct Research: 4.80% of Sales
Allocated Research: 0.50% of Sales
Administrative Expense: 2.00% of Sales
Management Incentive Compensation: 1.25% of Sales
Fixed Costs
Operations
Operators per Shift: 1 (Assuming 5 Shifts)
Direct Wages and Benefits: $30.00 per Operator Hour
Direct Salaries and Benefits: 15.00% of Direct Wages and Benefits
Operating Supplies and Services: 6.00% of Direct Wages and Benefits
Technical Assistance to Manufacturing: $0.00 per year, for each Operator per Shift
Control Laboratory: $0.00 per year, for each Operator per Shift
Maintenance
Wages and Benefits: 3.50% of Total Depreciable Capital
Salaries and Benefits: 25.00% of Maintenance Wages and Benefits
Materials and Services: 100.00% of Maintenance Wages and Benefits
Maintenance Overhead: 5.00% of Maintenance Wages and Benefits
Operating Overhead
General Plant Overhead: 7.10% of Maintenance and Operations Wages and Benefits
Mechanical Department Services: 2.40% of Maintenance and Operations Wages and Benefits
Employee Relations Department: 5.90% of Maintenance and Operations Wages and Benefits
Business Services: 7.40% of Maintenance and Operations Wages and Benefits
Property Taxes and Insurance
Property Taxes and Insurance: 2.00% of Total Depreciable Capital
Straight Line Depreciation
Direct Plant: 8.00% of Total Depreciable Capital, less1.18 times the Allocated Costs for Utility Plants and Related Facilities
Allocated Plant: 6.00% of 1.18 times the Allocated Costs for Utility Plants and Related Facilities
Depletion Allowance
Annual Depletion Allowance: $0.00

CD-17.8-21
2. Investment Summary - Part (b) – Purchase and Installation Costs Estimated by
Aspen IPE

May, 2003
Bare Module Costs
IPE Specifications
Total Direct Materials and Labor Costs: $785,700
Miscellaneous Installation Costs: $0
Labot G&A Overhead and Contractor Fees: $69,700
Contractor Engineering Costs: $558,300
Indirect Costs: $482,600
Total from IPE: $1,896,300
Total Bare Module Costs:
Direct Permanent Investment
Cost of Site Preparation: $94,800
Cost of Service Facilities: $94,800
Allocated Costs for utility plants and related facilitie$0
Direct Permanent Investment:
Total Depreciable Capital
Cost of Contigencies and Contractor Fees: $375,500
Total Depreciable Capital:
Total Permanent Investment
Cost of Land: $49,200
Cost of Royalties: $0
Cost of Plant Start-Up: $246,100
Total Permanent Investment:
Working Capital
Inventory
MCB α 481,000 lb $260,000
FEED α 395,000 lb $118,400
Total Inventory: $378,400
Accounts Receivable: $2,166,400
Cash Reservces: $0
Accounts Payable: $0
Total Working Capital: $2,544,800
TOTAL CAPITAL INVESTMENT
Investment Summary
Monochlorobenzene Separation Process
TOTAL
$1,896,300
$2,086,000
$2,461,000
$2,756,000
$5,300,800

CD-17.8-22
3. Variable Cost Summary - Part (b) – Purchase and Installation Costs Estimated
by Aspen IPE
May, 2003
Raw Materials
FEED
Total Raw Materials:
Utilties
High Pressure Steam
Cooling Water
Electricity
Total Raw Materials:
Byproducts
Benzene
Total Byproducts:
General Expenses
Selling / Transfer:
Direct Research:
Allocated Research:
Administrative Expense:
Management Incentives:
Total Byproducts:
TOTAL
TOTAL
$0.49 per lb of MCB $21,712,500
Variable Cost Summary
Monochlorobenzene Separation Process
Per lb MCB
$0.00 per lb of MCB $6,100
$21,712,500
$0.00 per lb of MCB $44,100
$0.49 per lb of MCB $21,712,500
$21,765,800
$0.00 per lb of MCB $3,000
-$0.08 per lb of MCB -$3,707,000
$0.00 per lb of MCB $53,300
$18,058,800
$0.02 per lb of MCB $714,900
-$0.08 per lb of MCB -$3,707,000
$0.03 per lb of MCB $1,143,900
$0.00 per lb of MCB $119,200
$0.01 per lb of MCB $476,600
$0.01 per lb of MCB $297,900
$0.06 per lb of MCB $2,752,500 $20,811,300
$0.47 per lb of MCB $20,811,200 $20,811,200

CD-17.8-23

4. Fixed Cost Summary - Part (b) – Purchase and Installation Costs Estimated by
Aspen IPE



May, 2003
Operations
Direct Wages and Benefits: $312,000
Direct Salaries and Benefits: $46,800
Operating Supplies and Services: $18,720
Technical Assistance to Manufacturing: $0
Control Laboratory: $0
Total Operations: $377,520
Maintenance
Wages and Benefits: $86,135
Salaries and Benefits: $21,534
Materials and Services: $86,135
Maintenance Overhead: $4,307
Total Maintenance: $198,111
Operating Overhead
General Plant Overhead: $33,119
Mechanical Department Services: $11,195
Employee Relations Department: $27,522
Business Services: $34,519
Total Operating Overhead: $106,355
Property Insurance and Taxes
Total Property Insurance and Taxes: $49,220
TOTAL
Fixed Cost Summary
Monochlorobenzene Separation Process
TOTAL
$377,520
$575,631
$681,986
$731,206
$731,206

CD-17.8-24
5. Cash Flow Summary - Part (b) – Purchase and Installation Costs Estimated by
Aspen IPE




6. Profitability Measures - Part (b) – Purchase and Installation Costs Estimated
by Aspen IPE


May, 2003
Year
Percentage
of Design
Capacity
Sales Capital Costs Working Capital Variable Costs Fixed Costs
Depreciation
Allowance
Depletion
Allowance
Taxable Income
Income Tax
Costs
Net Earnings
Annual Cash
Flow
Cumulative Net
Present Value at
15.0%
2003 0.0% Design -$137,800 $0 -$137,800 -$137,800
2004 0.0% Construction -$2,618,200 -$2,544,800 -$5,163,000 -$4,627,400
2005 45.0% $10,723,800 -$9,365,000 -$731,200 -$492,200 $0 $135,400 -$50,100 $85,300 $577,500 -$4,190,700
2006 67.5% $16,085,800 -$14,047,600 -$731,200 -$787,500 $0 $519,500 -$192,200 $327,300 $1,114,800 -$3,457,700
2007 90.0% $21,447,700 -$18,730,100 -$731,200 -$472,500 $0 $1,513,900 -$560,100 $953,800 $1,426,300 -$2,642,200
2008 90.0% $21,447,700 -$18,730,100 -$731,200 -$283,500 $0 $1,702,900 -$630,100 $1,072,800 $1,356,300 -$1,967,900
2009 90.0% $21,447,700 -$18,730,100 -$731,200 -$283,500 $0 $1,702,900 -$630,100 $1,072,800 $1,356,300 -$1,381,500
2010 90.0% $21,447,700 -$18,730,100 -$731,200 -$141,800 $0 $1,844,600 -$682,500 $1,162,100 $1,303,900 -$891,300
2011 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 -$482,200
2012 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 -$126,500
2013 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 $182,800
2014 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 $451,800
2015 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 $685,700
2016 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 $889,100
2017 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 $1,066,000
2018 90.0% $21,447,700 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $1,251,400 $1,219,800
2019 90.0% $21,447,700 $2,544,800 -$18,730,100 -$731,200 $0 $1,986,400 -$735,000 $1,251,400 $3,796,200 $1,625,500
Cash Flow Summary
Monochlorobenzene Separation Process
May, 2003
The Investor's Rate of Return (IRR) for this Project is: 20.95%
The Net Present Value (NPV) at 15% for this Project is: $1,625,500
ROI Analysis (Third Production Year)
Annual Sales:
Annual Costs:
Depreciation:
Income Tax:
Net Earnings:
Total Capital Investment:
ROI:
Profitability Measures
Monochlorobenzene Separation Process
$21,447,700
-$19,461,300
25.0%
-$196,900
-$662,100
$1,324,300
$5,300,800

CD-17.8-25

7. Sensitivity Analyses - Part (b) – Purchase and Installation Costs Estimated by
Aspen IPE

May, 2003
Product Prices vs Variable Costs
$17,689,500 $18,209,800 $18,730,100 $19,250,400 $19,770,600 $20,290,900 $20,811,200 $21,331,500 $21,851,800 $22,372,000 $22,892,300 $23,412,600
0.46 $ 17.98% 12.43% 6.18% -1.20% Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range
0.47 $ 23.51% 18.52% 13.10% 7.04% -0.04% Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range
0.49 $ 28.55% 23.94% 19.04% 13.74% 7.86% 1.06% Out of Range Out of Range Out of Range Out of Range Out of Range Out of Range
0.50 $ 33.21% 28.88% 24.35% 19.54% 14.36% 8.64% 2.09% Out of Range Out of Range Out of Range Out of Range Out of Range
0.51 $ 37.58% 33.47% 29.21% 24.74% 20.03% 14.96% 9.39% 3.06% Out of Range Out of Range Out of Range Out of Range
0.53 $ 41.71% 37.78% 33.73% 29.52% 25.13% 20.50% 15.53% 10.10% 3.98% Out of Range Out of Range Out of Range
0.54 $ 45.64% 41.86% 37.97% 33.98% 29.83% 25.51% 20.95% 16.09% 10.79% 4.86% -2.05% Out of Range
0.55 $ 49.39% 45.74% 42.00% 38.17% 34.22% 30.13% 25.87% 21.39% 16.62% 11.45% 5.69% -0.95%
0.57 $ 52.99% 49.44% 45.83% 42.14% 38.35% 34.45% 30.42% 26.23% 21.82% 17.14% 12.08% 6.48%
0.58 $ 56.44% 53.00% 49.49% 45.92% 42.27% 38.53% 34.68% 30.71% 26.57% 22.24% 17.65% 12.70%
0.59 $ 59.77% 56.42% 53.01% 49.54% 46.01% 42.40% 38.71% 34.91% 30.98% 26.91% 22.64% 18.13%
0.61 $ 62.99% 59.71% 56.39% 53.02% 49.59% 46.10% 42.53% 38.88% 35.13% 31.26% 27.24% 23.04%
0.62 $ 66.10% 62.90% 59.66% 56.37% 53.03% 49.64% 46.19% 42.66% 39.05% 35.34% 31.52% 27.56%
IRR Analysis - Two Variable
Monochlorobenzene Separation Process
Variable Costs
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After studying this chapter. recycle ratio. Be able to determine the best location for the separation section. This chapter extends that introduction to give a more detailed treatment of reactor-separator-recycle networks. included a few examples of the interaction between the reactor and separation sections. one or more of the streams leaving the separation section(s) is (are) recycled to the reactor. either before or after the reactor. and raw material loss. 3. the reader should 1. Understand the need to determine the optimal reactor conversion.Chapter 8 Reactor-Separator-Recycle Networks 8.0 OBJECTIVES The presence of at least one chemical reactor and one or more separation sections for the separation of the effluent mixture leaving the reactor(s) characterizes many chemical processes. the design of reactors and reactor networks was considered without regard for the separation section(s) and possible recycle there from. CD-8-1 . 2. involving the tradeoff between the cost of the reactor section and the cost of the separation section(s) in the presence of recycle. In almost all cases. Understand the tradeoffs between purge-to-recycle ratio. which dealt with the synthesis of the entire process. In Chapter 6. Chapter 5. even when chemical equilibrium greatly favors the products of the reaction. when dealing with inert or byproduct chemicals that are difficult to separate from the reactants. Chapter 7 was concerned with the design of separation sections in the absence of any consideration of the reactor section.

as shown in Figure 7.1. and inert chemicals.3 (Example 20. effluents may contain reactants. Recycle streams are intended to contain only unconverted reactants of the desired reaction(s).5 (Case Study 21. they may contain inert chemicals. catalyst poisons. 5. Reactor effluents are almost never products that meet purity specifications. which is presented in Sections 20. This chapter presents many of the considerations involved in that optimization. and products of the desired reaction(s). products of undesired side reactions. However. Besides the products. Fresh reactor feeds rarely contain only the reactants for the desired reaction. more commonly. Besides the reactants. multiple reactor sections are sometimes required. A major challenge of process design is to devise an optimal scheme for uniting the reaction and separation functions of a process. and feed impurities. Thus. Understand the conditions under which the recycle of byproducts to extinction can be employed to reduce waste and increase yield. potential reactants for side reactions. products of undesired side reactions. Although Figure 7. almost every chemical process that involves a chemical reaction section also involves one or more separation sections in addition to one or more recycle streams. with separation sections located between each pair of reactor sections CD-8-2 . recycle streams also contain products of the desired reaction(s).4.3).1 shows only one reactor section. Be aware of the snowball effect in a reactor-separator-recycle network and the importance of designing an adequate control system.11) and 21. 8.1 INTRODUCTION The feed to a reactor section of a chemical process almost always is a combined feed consisting of a fresh feed mixed with one or more recycle streams. inerts.

chemical processes. a process involving reactions with unfavorable chemical equilibrium constants. a separation section is located after the reaction section. overall process conversions of 100% are approached.8. N 2 + 3H 2 ↔ 2NH 3 and the hydrogenation of carbon monoxide to methanol. decrease with increasing temperature according to the van’t Hoff equation: o ∆H rx  ∂ ln K c  =   2  ∂T  P RT (8. but practical considerations limit the operating pressure. Because both reactions involve shrinkage in the number of moles (4 to 2 for the ammonia reaction and 3 to 1 for the methanol reaction). the chemical equilibrium constants are both less than unity and reactor conversions are less than 50% at temperatures high enough to achieve reasonable reaction rates. perhaps most. In this separation section. with the recovery and recycle of unconverted reactants. In this manner. as shown in Figure 7. CO + 2H 2 ↔ CH 3OH both of which are exothermic reactions. Kc. therefore. CD-8-3 . whose chemical equilibrium constants.2 LOCATING THE SEPARATION SECTION WITH RESPECT TO THE REACTOR SECTION In many.1. However. at reactor conditions can achieve high overall process conversions to desired products. Important industrial examples are the hydrogenation of nitrogen to ammonia. products are purified and unconverted reactants are recovered for recycle back to the reactor.1) In these two examples. the reactor conversion can also be increased by increasing the pressure.

61. Cumene Manufacture. A more complex example is the manufacture of cumene (isopropyl benzene) by the alkylation of benzene with propylene. Water from the main reaction must be treated to the extent required for disposal to a sewer or for another use. Example 8. and because they are recycled they need not be purified to a high degree. Methanol and toluene are recovered and recycled. when distillation is used. relative volatility) are separated by the product(s). recycle streams rarely require a significant degree of purification with respect to recycled reactants.. therefore. Typically. the recycle stream might contain 5% ethylbenzene plus styrene. as shown in the next two examples.g.2. Cumene is widely used to make acetone and phenol. In this process. they need not be separated. They are adjacent in relative volatility and. In the styrene manufacture process of Figure 10. When two or more reactants are involved. CD-8-4 . taken from the 1997 National Student Design Competition of the AIChE.Although product purification may require extreme measures to achieve product specifications. the main reaction is Methanol + Toluene → Styrene + Hydrogen + Water The following side reaction also occurs: Methanol + Toluene → Ethylbenzene + Water The reactor effluent contains appreciable percentages of unreacted methanol and toluene.1 Styrene Manufacture. they do not have to be recovered separately for recycle unless their separation indexes (e. where the benzene feed is nearly pure. The fresh feeds are as follows. Example 8. both styrene and ethylbenzene are products and must be purified to meet strict specifications. but a refinery cut of a propylene-propane mixture is used rather than a more expensive feed of nearly pure propylene.

including the large amount of propane in the propylene feed. are essentially inert.5130 0.Component Water Ethane Propylene Propane 1-Butene Isobutane Methylcyclopentane.3135 Benzene feed. with the exception of 1Butene.029.6127 0.2075 465.1270 The main reaction.2030 0.6440 1. MCP Benzene Methylcyclohexane.1800 4. conducted with a catalyst.4-methyl Benzene (p-Cymene) CD-8-5 . is: Propylene + Benzene → Isopropylbenzene (Cumene) A number of undesirable side reactions involving the main reactants also occur. including: Propylene + Benzene → n-Propylbenzene Cumene + Propylene → m-Diisopropylbenzene (m-DIPB) Cumene + Propylene → p-Diisopropylbenzene (m-DIPB) Other reactions that produce alkylation heavies All of the impurities in the propylene and benzene fresh feed streams.0300 0. MCH Toluene Propylene feed. lbmol/hr 1.1570 997. lbmol/hr 0. which enters into the following undesirable side reactions: 1-Butene + Benzene → t-Butylbenzene (t-BB) 1-Butene + Benzene → 1-isopropyl.

ppm (by wt) Others.1. two remedies are applied.2: (1) the use of a large excess of benzene in the combined feed to the alkylation reactor. inert aromatic compounds. one for alkylation and one for trans-alkylation.01 wt%. The cumene product must meet the following specifications: Cumene purity. ppm (by wt) Toluene. inert light hydrocarbons. for example. The process consists of one separation section. The separations are all distillations. p-cymene.0 molar ratio of benzene to propylene to reduce the DIPB formation reactions.Potential products and byproducts include cumene. t-BB. Experimental alkylation data show that the two reactions above that produce DIPBs can result in a serious loss (> 10%) of potential cumene product. and (2) the addition of a trans-alkylation reactor where the DIPBs are reacted with benzene to produce cumene according to the reaction: DIPB + Benzene → 2 Cumene Other reactions that produce trans-alkylation heavies Solution A preliminary block flow diagram. ppm (by wt) 99. However. wt% Butylbenzenes. the first of which is related to Heuristic 2 in Table 5. is shown in Figure 8. propane. DIPBs. and water. it can contain water and light hydrocarbons. ppm (by wt) Cymene. A main objective of the process is to maximize the production of cumene and minimize the amounts of byproduct and waste streams. Thus. situated between two reactor sections. ppm (by wt) Benzene and paraffins. consisting of three columns. To reduce this loss. where approximate measures for the ease of distillation. CD-8-6 . suggested for the cumene process. the aromatic content cannot exceed 0.97 40 15 10 10 225 minimum maximum maximum maximum maximum maximum The propane byproduct is used as either fuel gas or LPG. a 4.

3 162.16 78.1 100.6 152. oC 100 -88. are the differences between the normal boiling points of the components in the alkylation reactor effluent: Component Water Ethane Propylene Propane Isobutane 1-Butene Methylcyclopentane Benzene Methylcyclohexane Toluene Cumene n-Propylbenzene t-Butylbenzene p-Cymene m-DIPB p-DIPB Trans-alkylation heavies Alkylation heavies Formula H2 O C2H6 C3H6 C3H8 C4H10 C4H8 C6H12 C6H6 C7H14 C7H8 C9H12 C9H12 C10H14 C10H14 C12H18 C12H18 Molecular weight 18.2 120.2 134.07 42.16 120.7 206.6 -47.3 278.13 56.3 201.4 -42.3 261.12 84.1 -11.3 71.11 58.2 210.08 44.4 159.12 98.0 177.8 CD-8-7 .02 30.9 110.assuming ideal liquid solutions.4 Normal boiling point.2 169.1 203.19 92.2 162.2 134.8 80.7 -6.

CD-8-8 .1 Cumene process.Benzene Recycle Benzene Benzene feed Propane Cumene Benzene Alkylation Reactor C1 C2 C3 Trans-alkylation Reactor Recycle Propylene feed Figure 8.

However. cumene product is recovered as the distillate in distillation column. Propane can be removed in a separation section before or after the alkylation reactor. However. a difficult separation between propane and propylene is required. Heuristic 3 of Table 5. Finally.2.2 should be considered. In the trans-alkylation reactor. the difference in boiling points between the key components is 112.Note that the fresh propylene feed contains approximately 31 mol% propane. the benzene recycle to the alkylation reactor can contain up to 10 mol% impurities. a 4.3). as discussed in Section 7. C2. Following the depropanizer is a benzene-recovery distillation column. CD-8-9 . as well as all of the 1-butene. In the alkylation reactor. which are more volatile than propane. comprised of DIPBs. is to provide exits from the process for all inert species that enter the process as impurities in the fresh feed(s) or are formed in irreversible side reactions. MCP.3oC (relative volatility > 5). and n-propylbenzene. no net production of DIPBs is incurred. are easily removed from the excess benzene in the reactor effluent in the depropanizer. In the cumene process. tBB. these species include water and ethane. is sent to the trans-alkylation reactor to be converted to cumene. C3. which are more volatile than cumene. MCH. propylene is not present to be separated from propane. together with water and small amounts of inert light hydrocarbons in the propylene feed. The main separation is between benzene and cumene with a boiling-point difference of 72. after the reactor. because the boilingpoint difference is only 5.3oC (relative volatility < 1. the combined feed to the alkylation reactor must not contain more than 1.2. that must be adhered to when developing a process flowsheet. if removed before the reactor. essentially all of the propylene. are reacted. Because propane is inert. with a portion recycled to the alkylation reactor and the remainder sent to the trans-alkylation reactor. implied in Heuristic 4 of Table 5. A cardinal rule. where benzene is removed.0 molar ratio of benzene to total DIPBs is used. Instead. but the conversion of DIPBs is only 50%. isobutane. By recycling the effluent from the trans-alkylation reactor. C1. and p-cymene.3 mol% cumene. and toluene. Here. where the bottoms product. Therefore.2oC (relative volatility > 10). Based on laboratory experiments and other considerations. the propane.

suggested in Heuristic 4 of Table 5. Inclusion of drag streams and the resulting material balance calculations are the subjects of Exercise 8. wherever the separation index is more favorable. fluorides. Based on the product specifications for the propane and cumene products. Consequently. resulting in the loss of reactant(s). two alternatives. moisture must be removed from the entering air to avoid corrosion and allow the use of carbon steel. Two drag streams. and the third reaction is the absorption of SO3 in water to form sulfuric acid. The feed stocks are air and either sulfur or sulfide ores. or both. consider the manufacture of sulfuric acid. may require a feed separation section. Before entering the second reactor. However. dust. product(s). What should be done when the fresh feed contains an appreciable percentage of product chemicals? This occurs most frequently in isomerization reactions involving CD-8-10 .2. a larger reactor is required because of the higher flow rate and lower reactant concentrations. that may enter into undesirable side reactions in the reactor section. The first is to add separators to the process flowsheet. one from the distillate of the benzene recovery column and one from the bottoms of the cumene recovery column. leading to a benzene loss of about 2% and a cumene loss of less than 1%. when removed after the reactor.1. other than reactants for the main reaction(s). where the first reaction is the oxidation of sulfur or sulfide to sulfur dioxide.which are more volatile than the DIPBs. to purify the fresh feed before it enters the reactor. catalyst poisons are removed as well as components. calculations show that the total amounts of these species produced do not leave with one or both products. In this separation section. As an example. the second includes one or more purge or drag streams. When too expensive. inert chemicals can be removed in separation sections either before or after the reactor. as shown in Figure 7. In general. and arsenic and vanadium compounds must be removed from the feed gas to prevent catalyst poisoning.1 at the end of this chapter. especially those utilizing a catalyst in the chemical reactor. Before the first reactor. as discussed above for the cumene process. must be evaluated. the second reaction is the catalytic oxidation of SO2 to SO3. are used. Chemical processes.

Thus. in most processes where a chemical reactor is required.000) at reactor conditions of temperature and pressure provide an opportunity for approaching 100% conversion during a single pass through the reactor. It is the manufacture of anhydrous hydrogen chloride gas from pure. > 10. Exercise 8. the optimal reactor conversion is less than 100% and a separation section is necessary. electrolytic hydrogen by the reaction: H2 + Cl2 → 2 HCl The only pieces of equipment required are a reactor. with A recovered and recycled. it is important to remove the product B from the fresh feed before it enters the reactor so as to increase the rate of reaction and achieve the highest equilibrium conversion possible. Such a process is rare. because reactor conversion is usually incomplete for isomerization reactions. CD-8-11 .3 TRADEOFFS IN PROCESSES INVOLVING RECYCLE Reactions with very large chemical equilibrium constants (e. then in principle no separation section is needed. with the resulting separator placed before the reactor. In addition.light paraffin hydrocarbons. Unless other chemicals formed in the reactor interfere with the A-B separation. A is commonly separated from B.. One such situation exists. as illustrated in Example 5. evaporated chlorine and a stoichiometric amount of pure.2 considers separator placement for a pentane isomerization process.g. and heat exchangers. consideration must be given to the tradeoffs between the cost of the reactor section and the cost of the separation section that follows it.2. Suppose the reaction is A ↔ B. the two A-B separators are combined. when the feed contains stoichiometric proportions of the reactants with no impurities and the reaction leads to only one product. The main reason for this is the rapid decline in reaction rate as the reacting mixture is depleted of reactants. 8. In this case. Even when 100% reactor conversion is theoretically possible. compressors. However.

in conjunction with optimization. entering temperature. This reduces the cost of the separation system. programmed temperature profile. as discussed in Chapter 18. Reactor pressure. but at the higher cost of gas compression. diluent ratio. Use of a gas or liquid purge stream to avoid difficult separations. many of which were introduced in Chapters 3-7. 5. but results in the loss of reactants and may increase the cost of the reactor section. This affects heating and/or cooling costs and reactor effluent composition when side reactions are possible. In this case. Use of an excess of one reactant to minimize side reactions and/or increase the rate of reaction. and purge-to-recycle ratio. allows one to determine optimal values of reactor conversion. molar ratio of reactants in a combined reactor feed. This increases the cost of the separation system. depending on the purge-to-recycle ratio (ratio of purge flow rate to recycle flow rate).) for the reactor. 6. This directly affects the need for and cost of the separation section. 2. These include 1. The entering temperature to and mode of operation (adiabatic. The use of process simulation. This increases the cost of the separation system. etc.A number of factors affect the tradeoff between the reactor and separation sections. The fractional conversion in the reactor of the limiting reactant. CD-8-12 . mode of operation. particularly for gas-phase reactions where the number of reactant molecules is greater than the number of product molecules. Use of an inert diluent in an adiabatic reactor to reduce the change in temperature. 3. reaction kinetics may favor a higher pressure. isothermal. pressure. 4.

Next. time. kf.2. Also. as a function of temperature is taken from the paragraph below Eq. (6. are shown in Figure 8. psia (0 pressure drop) Component flow rates. to avoid carbon formation.3. is in sec. t.500 500 The calculations can be performed with any process simulator. concentrations. the reverse reaction is considered to be negligible and Eq. Thus. For the isothermal case. lbmol/hr: Hydrogen Toluene 1. 000  1/2 1/2 = k f CH2 Ctoluene = 6.2) where R = 1. oF Pressure.8. To illustrate the effect of achieving a high conversion on reactor size.200 500 2.2. assume a molar ratio of hydrogen to toluene of 5 for the combined feed to the reactor.3 × 1010 exp   CH 2 Ctoluene dt  RT  rf = − (8.31). with the adiabatic case in Figure 8. the volume of both isothermal and adiabatic PFRs is computed for a series of conversions from 1% to 99%. dCtoluene  −52.31) gives the forward reaction rate. plotted as reactor volume against fractional conversion of toluene. where the Arrhenius equation for the rate constant. At typical reactor conditions. (6. the reactor volume increases almost linearly as CD-8-13 .4 OPTIMAL REACTOR CONVERSION Return to the toluene hydrodealkylation process in Section 4. rf.987 cal/mol-K. are in kmol/m3. simplify the combined reactor feed by eliminating methane and neglect biphenyl formation. with the reaction kinetics in Example 6.3. Ci. and temperature. Using the CHEMCAD program. for the following feed conditions: Temperature. the results for the isothermal case. is in K. T.

2 0 0 0.8 0. the difference in reactor volumes widens as the conversion is increased.4 0.8 0.080 ft3 at a conversion of 0.2 1 0.3.5 0.1 0.conversion increases to 0. As seen in Figure 8. the volume turns up sharply. conversion. the effect of conversion on reactor volume for the adiabatic case is very different from the isothermal case in Figure 8.3 0.1 0.99. For example.3 0.2 0. the reactor volume is less for the adiabatic case. The volume then increases more rapidly until at conversions near 0. Reactor Volume [1.9 1 Fractional Conversion of Toluene Figure 8.000 ft3] 8 6 4 2 0 0 0.4.4 0.25 times that of the adiabatic reactor.6 0. Furthermore.8 0.2 Required reactor volume for toluene hydrodealkylation in an isothermal PFR.7 0. Reactor Volume [1.3 Required reactor volume for toluene hydrodealkylation in an adiabatic PFR. At a 99% The adiabatic case benefits by the increase in CD-8-14 .2 0.9 1 Fractional Conversion of Toluene Figure 8.6 0. the isothermal reactor volume is 2. At all conversions.8.5 0.2. at a 50% conversion.000 ft3] 1. the ratio becomes 8.7 0.6 0.4 0. The reactor volume is 4. but twice that at a conversion of 0.9.

This is the case for the hydrodealkylation of toluene. the concentration of toluene in Eq.000 Btu/lbmol of toluene reacted.3 for the adiabatic case. it may be necessary to consider the reverse reaction even when the reaction is considered to be irreversible.temperature with increasing conversion. Thus. given by Eq. unlike the isothermal case. CD-8-15 . However. Only beyond a conversion of 90% does the reactor volume turn up sharply. the temperature increases by approximately 2. Thus. (8. the decrease in toluene concentration with conversion is offset by the increase in the rate constant with temperature because the activation energy is moderately high at 52.000 cal/mol. the reactor outlet temperature is 1. in Figure 8.2oF per 1% increase in conversion.000 and 22. (8. This results in an approximate doubling of the rate constant with every 50oF increase in temperature. The decrease of the hydrogen concentration is not nearly as pronounced because of its large excess in the reactor feed. by assuming that the two rate equations are consistent with the chemical-reaction equilibrium constant. the chemical equilibrium constant can be expressed in terms of concentrations and equated to the ratio of the rate constants by: Kc = CCH4 Cbenzene CH2 Ctoluene = kf kb (8. As the conversion increases. causing the rate of reaction to decrease.423oF. Therefore. the large excess of hydrogen acts as a heat carrier.2). Assume that the gas reacting mixture is ideal at the high temperature of the reaction. Then. curtailing the adiabatic rise in temperature. Nevertheless.2). at 99% conversion. the increase in reactor volume is less than linear up to an inflection point at a conversion of approximately 50%. When striving for high reactor conversions.3) But in chemical equilibrium. with an as yet undetermined dependence of component concentrations on the backward rate. In the adiabatic case. (8. from Eq. A rate equation for the reverse reaction can be derived from the rate equation for the forward reaction.2) decreases. the rate of the forward reaction is equal to the rate of the backward reaction. The exothermic heat of reaction is considerable at between 21.

3) and (8. an expression for Kc as a function of temperature is needed. β. α β γ δ CH 2 CtolueneCCH4 Cbenzene kf kb = 1/ CH 22Ctoluene = CCH 4 Cbenzene CH 2 Ctoluene (8. as a function of the absolute temperature.4) To determine the exponents. and δ.5).5) By equating exponents in Eq. the o standard Gibbs free energy of reaction.3). β = 0.8) CD-8-16 . α = -1/2. (8. (8. combine Eqs. α. in cal/mol.7) o From thermodynamics. for the hydrodealkylation of toluene. (8.4). T. in K.1/2 α β γ δ k f CH 2 Ctoluene = kbCH2 CtolueneCCH4 Cbenzene (8.1 T (8. 200 − 2. the form of the rate equation for the backward reaction is -1/2 rb = kbCH2 CCH 4 Cbenzene (8. ∆Grx is related to the chemical-reaction equilibrium constant by the equation: o  −∆Grx  K c = exp    RT  (8. H2 + C7H8 → CH4 + C6H6 is given by: o ∆Grx = −11. Therefore. γ = 1. ∆Grx . γ. Based on the correlations of Yaws (1977).6) To determine the Arrhenius expression for kb from Eq. and δ = 1.

636  K c = exp  + 1. using the temperature-dependent expressions for kf in Eq.  −52.3). (8. the rate law for the backward reaction becomes  −63. gives:  5. conversion decreases to 97. when only the stoichiometric quantity of hydrogen is used in the feed. taking into account the reverse reaction.8) and substituting 1. (8. (8. (8.057  = 2.6) and (8. When the main reaction is irreversible or has a large CD-8-17 . Reaction equilibrium calculations for this example give a 99.11) When the reactor calculations are repeated for up to 99% conversion of toluene. 200  -1/2 rb = 2. (8. case and a 99. 000  6.5 RECYCLE TO EXTINCTION In many chemical processes. 636   RT  2.7) and (8. This is largely due to the large concentration of hydrogen. 200  kb = f =   Kc  5.96% conversion for the adiabatic case.987 for R.878exp    T  Combining Eqs.878exp    T   T  (8.19 × 1010 exp   CH2 CCH4 Cbenzene  RT  (8. 636   5.98% conversion for the isothermal However. (8. the main reaction is accompanied by one or more side reactions that produce byproducts.19 × 1010 exp  −63. which according to Eq. reactor volumes for both isothermal and adiabatic cases increase only slightly (< 1%).Combining Eqs.9) From Eq.2) and Kc in Eq. the equilibrium isothermal 8.10) (8.11) decreases the rate of the reverse reaction.3%.9).3 ×1010 exp   k  RT  = 2.10).

This is accomplished by applying a concept sometimes referred to as recycle to extinction. the main reaction is the hydrogenation of toluene to the main product. The recycle to extinction concept is introduced briefly in Example 5. a further reaction to triphenyl also occurs. but one or more of the side reactions are socalled reversible reactions with chemical-reaction equilibrium constants on the order of one or less. this reaction. while not completely irreversible at typical reactor operating conditions.4. Two alternatives are considered: (1) production of the byproduct. in the absence of a catalyst. The concept must be applied with care and must be supported by reaction rates that are sufficiently high. In this process. it is accompanied by the following side reaction that produces the Kc = C H 2 C biphenyl 2 C benzene (8.1. Experimental verification is essential. and (2) recovery and recycle to extinction of the byproduct.3. This is particularly true when the main reaction is catalyzed because the catalyst may not support the side reaction(s).chemical-reaction equilibrium constant.4 and in Section 7.12) Although not always considered. CD-8-18 . benzene. byproduct. biphenyl: 2 C6H6 ↔ H2 + C12H10 The chemical-reaction equilibrium constant for this reaction is written as: When the main reaction is carried out thermally. and methane: H2 + C7H8 → CH4 + C6H6 As shown in Section 8. has a chemical-reaction equilibrium constant high enough to give conversions greater than 99%. illustrated for the toluene-hydroalkylation process in Figure 7. the possibility of increasing the overall yield of the desired product(s) from the main reaction by eliminating the net production of byproduct(s) exists.

(8. with a chemical-reaction equilibrium constant written as: Kc = C H 2 C triphenyl C benzene C biphenyl (8.13). such that no net production of either biphenyl or triphenyl occurs.23 to 0. This occurs in the toluene hydrodealkylation process in which the biphenyl and triphenyl are recovered with toluene. as determined from Eqs.045 to 0. When the biphenyl and triphenyl byproducts are recovered and recycled to the reactor.12) and (8. (8.32 over a temperature range of 700 to 1. the byproducts are recycled to extinction. the production of undesirable byproducts is eliminated and the overall yield of the main product(s) is increased. (8. A second example in which recycle to extinction should be considered is the hydrolysis of ethylene to ethyl alcohol: C2 H 4 + H 2 O → C 2 H5OH which is accompanied by a reversible side reaction that produces diethylether and water.13). the chemical-reaction equilibrium constant for Eq.13) From Hougen and Watson (1947).12) ranges from 0. In this manner.C6H6 + C12H10 ↔ H2 + C18H14 . while for Eq. the cost of the separation system downstream of the reactor may be reduced when the byproducts are recovered together with one or more of the reactants in a single recycle stream.400oF. the constant increases from 0.46 over the same temperature range. In effect. 2 C2H5OH ↔ (C2H5)2O + H2O CD-8-19 . they build to their equilibrium concentrations at the reactor outlet. However. A disadvantage of recycling the byproducts to extinction is that the byproducts and unconverted reactants increase the cost of recycling.

or methanol. is the overall yield of synthesis gas increased? This is the subject of Example The fresh feed to a steam reformer is 13.3.2.929. a number of side reactions occur as discussed by Rase (1977). an intermediate that can be used to produce acetic acid. However.5 kmol/hr of methane and 86. the chemical-reaction equilibrium constant for this reaction is 0. In the presence of the catalyst.8.3. which limits the extent of the reaction to that of chemical equilibrium. The main reaction is: CH4 + H2O ↔ CO + 3 H2 Typically. Example 8. with compositions in partial pressures in atm. By recovering and recycling diethylether and water. A third example is the steam reforming of methane (or natural gas) in the presence of a nickel-supported catalyst to produce synthesis gas (CO + H2).2 atm and CD-8-20 . with compositions in partial pressures in atm. with an equilibrium constant of 126. ammonia. Steam Reforming of Naphtha. gasoline. the reactor operation at adiabatic conditions gives an outlet temperature of approximately 800oC. the overall yield of alcohol is increased.for which the chemical-reaction equilibrium constant at typical reactor conditions is 0. 8. the only one of significance is the water-gas shift reaction: CO + H2O ↔ CO2 + H2 At 800oC.5 kmol/hr of steam. When CO2 is recovered and recycled to extinction. If the outlet conditions of the reactor are 800oC and 12. Reactor pressure is generally set by the available pressure of the methane and may be as high as 30 atm.

5 = nCH 4 + nCO + nCO2 2(86. Solution (a) At 800oC.5) + 4(13.5) = 227. kmol/hr 13. Since these two equations contain five unknowns.791 CD-8-21 .chemical equilibrium is achieved for both the steam reforming and water-gas shift reactions.521 7.929 where P = 12.5 86.605 66. and O in the fresh feed. determine the kmol/hr of synthesis gas produced when: (a) the CO2 produced is not recovered and recycled. They are: Carbon balance: Hydrogen balance: Oxygen balance: 13.5 = nH 2O + nCO + 2 nCO2 where the left-hand sides are in kg⋅atom/hr of the elements. H. (b) the CO2 is recovered from the reactor effluent and recycled to extinction.8 nCH 4 nH2O  ntotal  nCO2 nH 2 nCO nH2O = 0. three atom-balance equations are needed.0 Reactor Effluent.5 0 0 0 100. C.375 125. Solving these five equations gives: Component Methane Water Hydrogen Carbon monoxide Carbon dioxide Total Fresh Feed. kmol/hr 0.2 atm and ni are in kmol/hr.229 46.061 5. the two chemical equilibrium equations are: 2 3 nCO nH2  P    = 126.0 = 2nH2 + 4nCH4 + 2nH 2O 86.

0 = 2nH2 + 4nCH4 + 2nH 2O 86. less H2 is produced.763 122. with the production of synthesis gas slightly increased to 12.544 38.859 = 51. The percent conversion of methane is slightly greater at 95. kmol/hr 0. by eliminating the net production of CO2.5% of the methane is reacted. (b) For recycle of CO2 to extinction. The production of synthesis gas is 5.661 Observe that there is no net production of CO2. The usual benefit of the increased yield of the main product(s) by recycle to extinction is not achieved CD-8-22 .946 22.5) + 4(13.5 86.521 + 46.061 = 51.5) = 227. the production of CO2 from CO by the water-gas shift reaction gives an additional mole of H2 for every mole of CO2 produced.549 73. At chemical equilibrium.5 + 2 nCO2 = nH2O + nCO + 2 nCO2 Solving the revised equations gives: Component Methane Water Hydrogen Carbon monoxide Carbon dioxide Total Combined Feed.5 + nCO2 = nCH 4 + nCO + nCO2 2(86. Thus. Note that in case (a). kmol/hr 13.5 0 0 22. the CO2 in the reactor effluent is recycled and added to the fresh feed to give a combined feed.763 148.From these results. the flow rate of CO2 in the reactor effluent is the same as that in the combined feed. but the three atom balance equations become: Carbon balance: Hydrogen balance: Oxygen balance: 13. The two chemical equilibrium equations remain the same.9%.859 12.582 kmol/hr.805 kmol/hr. 95.763 Reactor Effluent.946 + 38.

for example. causes a very large change in the flow rate of the recycle stream. Understand the considerations in determining the best locations. the majority of chemical processes involve recycle.in this case. which is the subject of Sections 20. However. of the separation sections. This is due to the possibility of the so-called snowball effect. in the fresh feed rate to a reactor. chemical engineers engaged in process design in industry have become increasingly aware of the need to understand the interaction of process design and process control when developing a control system for an entire chemical plant. with respect to the reactor section.3 (Example 20. particularly for a reactor-separator-recycle network. is not at all straightforward. in case (b). may not be able to handle the increased load.3). the development of the control system is relatively straightforward because the process can be treated in a sequential manner.5 (Case Study 21.11) and 21. Whether or not the snowball effect occurs depends on the design of the control system. Mulholland and Dyer (1999). When the process does not involve recycle. for which the development of a feasible and efficient control system.6 SNOWBALL EFFECTS IN THE CONTROL OF PROCESSES INVOLVING RECYCLE In recent years. when designing reactor-separator-recycle networks. or both. which refers to a situation where a small disturbance. However. CO2 is not emitted to the atmosphere where it contributes to global warming. either the reactor or the separation system. the reader should 1. 8. CD-8-23 . This is considered in more detail by 8.7 SUMMARY Having studied this chapter. When this occurs.

Case Studies and Design Data. C. Chemical Process Principles. that flowsheet does not provide for the removal of water. Pollution Prevention: Methodology. EXERCISES 8. MCH. MCP. The flowsheet for the process is given in Figure 8. Watson. L. Know that the optimal fractional conversion of the limiting reactant in the reactor section is usually less than 100% of the equilibrium conversion. Technologies and Practices. 5. New York (1947). 4.. New York (1999). CD-8-24 . AIChE. REFERENCES Hougen. Wiley-Interscience. A. tBB. and J. New York (1977). Be aware that the snowball effect can occur in a reactor-separator-recycle network.. Part Three. Chemical Reactor Design for Process Plants. isobutane. Be aware of the many tradeoffs between the reactor section and the separation section(s) when recycle is used. K. New York (1977). O. toluene. Dyer. For their removal. ethane. In Section 8. 2. Mulholland.2. it is proposed to add two drag (purge) streams to the flowsheet: one from the distillate of the benzene recovery column. a process for producing cumene by the alkylation of benzene with propylene is described. However. n-propylbenzene. H. Kinetics and Catalysts. and K. and p-cymene. A.1. John Wiley & Sons. Physical Properties. Yaws. F. Be able to apply the concept of recycle to extinction to reduce waste and increase the yield of the main product. M.1 Cumene process with drag (purge) streams. 3. Rase. Vol.2. L. McGraw-Hill.

4953 -16.0039 -168.0025 -0.1 does not provide for an exit for the heavies produced in the alkylation and trans-alkylation reactors in the event that their amounts are too large to be included in the allowable impurity in the cumene product. If so.7652 0. Most of the data for the cumene process is given in Section 8.C2. Also.0000 These are as follows from Propylene 1-Butene Benzene Toluene Cumene n-Propylbenzene p-Cymene t-BB m-DIPB p-DIPB Alkylation Heavies Trans-alkylation Heavies Total change CD-8-25 . C4. C3.0000 0 0.0080 20. following C3.1. it may be necessary to add a fourth distillation column.3314 14.3570 Change in pounds per 100 pounds of propylene in the combined feed to the Alkylation Reactor 0.3227 0.0306 0. with the distillate from C4 fed to the trans-alkylation reactor and the bottoms from C4 being a heavies product. missing are the product distributions for the two reactors. the flowsheet in Figure 8.0007 -20.0346 0. However.7797 0.0214 232.3121 0 50. the heavies must not contain more than 5% of the DIPBs and lighter entering C4.2323 -14. laboratory studies: Trans-alkylation Reactor Alkylation Reactor Component Change in pounds per 100 pounds of propylene in the combined feed -100.0000 -0.1835 -0. Thus.7018 0. the other from the bottoms of the cumene recovery column.0087 -0.

revise the flowsheet in Figure 8. Repeat the material balance calculations and the design of the distillation column if the separation system is placed after the reactor. and the bottoms product from the distillation column. what could it be used for? 8.5 moles of isopentane for every mole of n-pentane. Based on your results and without determining any capital or operating costs. the combined feed to the reactor.1 and produce a complete material balance with the component flow rates in lbmol/hr for each stream in your flowsheet. which separation system placement is preferred? CD-8-26 . produced by separating isopentane from n-pentane by distillation. is to contain only 2 wt% npentane and the separation system is to be placed before the reactor. again. Be sure to add two drag streams for removal of byproducts.95. The catalyst prevents the formation of neopentane.Note. Try to maximize the production of cumene. and a fourth distillation column. The effluent from the catalytic isomerization reactor will contain 6.2 The feed to a pentane isomerization process consists of 650 kmol/hr of n-pentane and 300 kmol/hr of isopentane. if necessary.1. Using the above data and that in Section 8. that the conversion of DIPBs in the trans-alkylation reactor is only 50%. If the isopentane product. Compute the overall percent conversion of benzene to cumene and the annual production of cumene in lb/yr if the operating factor is 0. Design the distillation column. If a heavies product is produced. calculate the total flow rate and composition of the reactor effluent.

.

chemical engineers need to spend more effort in improving energy efficiency. 2. Understand the causes of lost work and how to remedy them. 6. 3. but are readily carried out with a process simulation program. a better process should be sought. 7.Chapter 9 Second-Law Analysis 9. calculations with the second law or a combined first and second law can determine energy efficiency. 5. After studying this chapter. Understand the usefulness of the second law and a combined statement of the first and second laws. CD-9-1 . Understand the limitations of the first law of thermodynamics. Be able to derive and apply a combined statement of the first and second laws for the determination of lost work or exergy. the reader should 1. Be able to specify a system and surroundings for conducting a second-law analysis. As shown in this chapter. Be able to use a process simulation program to perform a second-law analysis. Therefore. When the second-law efficiency of a process is found to be low. Much less used are the entropy balances based on the second law of thermodynamics. Be able to determine the second-law efficiency of a process and pinpoint the major areas of inefficiency (lost work). Although the first law can determine energy transfer requirements in the form of heat and shaft work for specified changes to streams or batches of materials. it cannot even give a clue as to whether energy is being used efficiently. 4. The average second-law efficiency for chemical plants is in the range of only 20-25%.0 OBJECTIVES The first law of thermodynamics is widely used in design to make energy balances around equipment. The calculations are difficult to do by hand.

9. Compressors K-1 and K-2 bring CD-9-2 . Table 9. turbine.1 lists the types of operations that are most widely used. other undesirable side reactions such as C7H8 + H2 → C6H6 + CH4 occur and produce light paraffins. or cyclically. absorption. compressor. where benzene and a mixture of xylene isomers are produced by the disproportionation of toluene. continuously.1. heat-integrated process that illustrates batchwise. light paraffin gases are removed in fractionator C-1. Hydrogen is recovered for recycle by partial condensation in exchanger E-2 with phase separation in flash drum D-1. and mixed xylenes are recovered and purified. the process is conducted A continuous. expander Heat exchanger. several of the operations in Table 9. and unreacted toluene is recovered for recycle in fractionator C-3. benzene is recovered and purified in fractionator C-2. valve.1 is shown in Figure 9. R-1.1 Common Operations in Chemical Processing Operation Change in chemical species Separation of chemicals Separation of phases Pressure change Temperature or phase change Mixing Dividing Size enlargement of solids Size reduction of solids Separation of solids by size Examples of Equipment Used Reactor Distillation. liquid-liquid extraction Settler Pump. However. The heart of the process is a fixed-bed catalytic reactor. Chemicals in the reactor effluent are separated from each other as follows. Depending on the production rate and the operations used.1 INTRODUCTION A chemical process uses physical and/or chemical operations to transform feed materials into products of different composition. in-line mixer Pipe tee Pellet mill Jaw crusher Screen This reaction is conducted in the presence of hydrogen to minimize the undesirable formation of coke by condensation reactions. where the main chemical change is the reaction 2C7H8 → C6H6 + C8H10 isomers Table 9. condenser Agitated vessel.

1 Process for disproportionation of toluene to benzene and xylenes.Figure 9. CD-9-3 .

and E-9. and steam is used in reboilers E-5. corresponding to a second-law thermodynamic efficiency of 100%.2 Overall process streams for toluene disproportionation. and steam for reboilers is produced from coal-fired power plant B-1. Pump P-1 brings fresh toluene to reactor pressure. Benzene and xylene products are cooled by water in coolers E-8 and E-11 (not shown in Figure 9. respectively. such a process would be uneconomical because of excessive capital investment in equipment. E-7. respectively.1) before being sent to storage. respectively. and to design new processes to operate at higher CD-9-4 . which would have to be essentially infinite in size to minimize transport gradients. Even if this were technically feasible. Pumps P-3 and P-6 deliver benzene and xylene products. Electricity for all pumps and compressors.2. and pump P-5 recycles toluene. Furnace F-1 uses the combustion of fuel oil with air to bring reactants to reactor temperature. E-6. after preheater E-1 has recovered a portion of the thermal energy in the reactor effluent.fresh hydrogen and recycled hydrogen. Exchanger E-3 preheats feed to fractionator C-1 with bottoms from the same fractionator. P-3. to reactor pressure. The overall input to and output from the process is represented schematically in Figure 9. Nevertheless. Cooling water is supplied mainly by recycle from cooling tower T-1 by pump P-7. and C-3. to storage. and P-4 deliver reflux to fractionators C-1. C-2. respectively. Ideally. Cooling water is used in overhead condensers E-4. and C-3. it is economical to modify existing processes to reduce energy consumption. each operation in a process would be conducted in a reversible manner to achieve the minimum energy input or the maximum energy output. C-2. and E-10 of fractionators C-1. Pumps P-2. Figure 9.

and open or closed to the transfer of matter between the system and the surroundings. They refer to the boundary of the control volume as the control surface across which matter can flow.3 Common methods of processing.3. so that the process engineer can direct his or her efforts to conserving energy. Batch. rigid or movable. 9.thermodynamic efficiencies. a process is divided into a system and surroundings. CD-9-5 . The boundaries of the system may be real or imaginary. Some references call a closed system simply a system. Batch and cyclic processes are usually divided into a closed system (or simply a system) and surroundings. continuous processes are divided into an open system (or control volume) and surroundings. The system is the matter contained in the operating unit(s) on which the engineer wishes to focus. and an open system. Figure 9. A second-law thermodynamic analysis identifies inefficient processes and the operations within these processes that are the most wasteful of energy. Everything not in the system is in the surroundings.2 THE SYSTEM AND THE SURROUNDINGS To conduct a second-law analysis. into and/or out of which matter can flow. cyclic. and continuous processes are shown schematically in Figure 9. a control volume.

Finally. and so forth.Figure 9.can be the system and everything else the surroundings. For example. Any individual operation in the process . the steam power plant and cooling-water system) are considered separately from the rest of the process. one tray in fractionator C-2. fractionator C-2 . The division of a process into system and surroundings is the choice of the one performing the thermodynamic analysis.1.g.for example. or infinite heat reservoir) and the storage tanks for the raw materials and products. CD-9-6 .. a portion of a single operation can be the system . in Figure 9.for example. water. with the surroundings being the ambient air.4 Partitioning of the toluene disproportionation plant. surrounding the equipment (commonly referred to as the infinite surroundings.5. This is shown schematically in Figure 9. where the process is divided into three systems. utility plants (e. The benzene-mixed xylenes plant is sufficiently complex that it is advisable to divide it into a reaction section and a separation section. as shown in Figure 9. the system can be the complete process. dead state. Many choices are possible for a chemical process. More commonly.4.

consider Figure 9.001 m3/kg is pumped continuously at a rate m of CD-9-7 . V. can be transferred across the boundaries of closed or open systems. As an example of energy transfer by work. is heat transfer.6(a). If no heat is transferred across its boundaries. of 0. Less useful. it gains energy and the surroundings lose energy. compressors. which occurs when the temperatures of the system and the surroundings differ. blowers. A motor converts electrical work to shaft work. it loses energy and the surroundings gain energy. and fans convert shaft work into fluid energy for the main purpose of increasing fluid pressure. but more common. the system is said to be adiabatic or thermally isolated. 9. where an incompressible liquid at 25oC having a specific volume. a rotating or reciprocating shaft at the boundary of a system causes shaft work. For example. and if the system is at the lower temperature. If the system is at the higher temperature. and if neither work nor heat is transferred. causing fluid pressure to decrease. A generator converts shaft work to electrical work. Turbines and expanders take energy from a fluid. the system is said to be totally isolated.5 Partitioning of the toluene disproportionation process. A number of devices are used in processes to transfer work between a system and its surroundings. or both.Figure 9. Pumps. The most useful kind of energy transfer is work. and convert the energy to shaft work for use elsewhere.3 ENERGY TRANSFER Heat or work.

isopotential energy increase of liquid = W = mV ( P2 − P ) = 10(0. and fluid friction. shaft friction. with no change in kinetic or potential energy. electrical resistance may permit only a 95% transfer of electrical work to the motor shaft. Electrical work input to the electric motor = shaft work delivered to the pump by the motor = shaft work delivered to the liquid by the pump = isothermal.000.95) Winput = CD-9-8 .39 kW (0.000 . by a rotating shaft driven by an electrical motor.6(b)). and fluid friction may cause a rise in fluid temperature equivalent to a 5% loss of the shaft work. shaft friction may permit only a 90% transfer of shaft work to the fluid. For the same increase in fluid pressure.0 MPa.95)(0.001)(2.1 MPa to a pressure P2 of 2.100.000) 1 = 19 kN-m/s (kJ/s or kW) Figure 9. In the absence of electrical resistance.10 kg/s from a pressure P1 of 0. isokinetic.6 Comparison of reversible and irreversible pumping operations. the electrical work input to the electric motor is then 19 = 23.90)(0. In actual equipment (as shown in Figure 9.

oil. chilled water.The difference. ammonia. which are designed to operate at certain desired temperatures. For each of these reservoirs. This excess power causes temperatures in the system and/or the surroundings to rise. such as a point on the surface of the earth. oceans. It is also convenient to distinguish between finite-sized heat reservoirs. (2) location in a gravitational field (potential energy). such as atmospheric air. it is convenient to assign a temperature.4 THERMODYNAMIC PROPERTIES When work and/or heat is transferred to or from a system. atoms.00 = 4. 23. and electrons. and vibrational motions of molecules. Ti. energy changes occur. Dowtherm. and the essentially infinite heat reservoirs that exist in the natural environment. If the temperature of a system or a part of the surroundings remains reasonably constant when heat transfer between these two regions occurs. and other refrigerants. and cooling media such as air. between the rate of electrical work input to the motor and the rate of energy required to increase the fluid pressure is the power not used in accomplishing the desired goal. In most chemical processes. and large lakes or rivers at temperatures designated as T0. hot water.39 . The first two forms of energy are taken relative to some arbitrary reference. such as steam.19. changes to these two forms of energy are relatively small and are often ignored. and nuclei. An exception is the combustion chamber and nozzle of a rocket engine. 9. CD-9-9 . atoms. where the heat of reaction (internal energy) is converted to kinetic energy. together with the potential energy due to forces acting between molecules. electrons. rotational. Internal energy is most important in chemical processing and is taken relative to some arbitrary reference condition. propane. molten salts. Heat reservoirs include heating media. and (3) internal energy due to translational. mercury. and flue gases produced by combustion.39 kW. water. The most common forms of energy are those associated with (1) macroscopic motion (kinetic energy). then the system or the part of the surroundings is called a heat reservoir.

Another state property. and the reference condition. By contrast. Cl2 (gas). the enthalpy is 3. which is determined by temperature. defined by the relation (9. for a reference condition of saturated liquid water at 0oC. O2 (gas). but only a fraction of heat can be converted to work. S. N2 (gas). into a system.1) H = U + PV This property is particularly convenient for continuous processes because the two terms on the right-hand side frequently appear together in energy balance equations.3 kJ.051. composition. is enthalpy. The most desirable reference conditions for internal energy and enthalpy in processes where chemical reactions take place are 0 K or 25oC. pressure. work transfer (shaft work) is not accompanied by entropy transfer. rather than the chemical species themselves that are in the mixture. Work can be completely converted to heat. internal energy and enthalpy changes automatically take into account heat of reaction. heat transferred from the system becomes less useful and less of the heat can be converted to work. As an example. Felder and Rousseau (2000) discuss this reference condition. because its value depends on the state or condition of the substance. closely related to internal energy. zero pressure. When heat is transferred at a rate Q from a surrounding heat reservoir at a constant temperature.The internal energy of a substance is a state property. such as C (graphite). A state property that accounts for the differences between heat and work is entropy. Treservoir. (1994). as the temperature of a system is decreased. phase (if more than one phase is possible). and standard chemical elements.209. the heat reservoir experiences a decrease in entropy given by CD-9-10 . Alternatively. H2 (gas). the enthalpy of 1 kg of superheated steam at 300oC and 1 MPa relative to the elements H2 (gas) and O2 (gas) at 0 K and 0 Pa is determined to be -12. It is well known from thermodynamic principles that energy transferred as work is more useful than energy transferred as heat.2 kJ/kg. from the steam tables in van Wylen et al. With this reference condition. Furthermore. the entropy of the system increases because entropy transfer accompanies heat transfer. When heat is transferred into a closed system at temperature T. Changes in internal energy are independent of the path employed in moving from one state to another. and S (rhombic sulfur).

3) 1 T Using Eq. Accordingly. the rate of heat transfer to the differential section. when heat is transferred to a nonisothermal system. only temperature affects U and H. ideal gas. dQ . Typical Entropy Changes In general. is: dQ = mdH = mc p dT where m is the mass flow rate and cp is the heat capacity. Consider the stream at constant P in Figure 9. S is the specific entropy. Substituting in Eq. At a reference temperature of 0 K. that is. the entropy of a crystalline substance is zero. According to the first law of thermodynamics.3). (9. is: dQ (9. the reference pressure for U and H is usually taken as zero. For S. ∆S .4) ∆S1→ 2 = ∫ T2 c p dT (9. S / m .7 Isobaric flow through a pipe. The lower the value of T. by the third law of thermodynamics.2) where ∆S is the entropy change in Btu/hr-oR. S. entropy changes can be computed for several common systems. the greater the decrease in entropy.∆Sreservoir = −Q Treservoir (9. as illustrated next. the reference pressure is usually taken as 1 atm to avoid a value of S equal to minus infinity. CD-9-11 .6) T1 dQ Figure 9. its entropy change.5) ∆S1→ 2 = c p ln T2 T1 T2 (9. of an ideal gas is affected by both temperature and pressure. (9. the entropy.7. For constant cp: T1 (9. However. ∆S = ∫ 2 Isobaric Heat Transfer.3): T Here. For a pure.

10) P1 P2 Figure 9. the change in the entropy flow rate is given by Eq. as illustrated in Figure 9.7) (9. and m j is its molar flow rate. When C species are mixed at constant pressure and temperature.13) CD-9-12 . the differential change in the specific enthalpy is: dH = TdS + VdP = cpdT = 0 where V is the specific volume.12) or ∆S1→ 2 = −∑ x j R ln x j j =1 C (9. Figure 9.Ideal Gas at Constant Temperature.8 Isothermal flow through a pipe Ideal Gas Mixing.8) Substituting for an ideal gas. V = RT/P: dS = − R (9. Summing over all of the species. (9.10).8 shows the isothermal flow of an ideal gas. applied separately for each species j: m j ∆S1→ 2 j = m j R ln P Pj (9. the change in the enthalpy flow rate for the mixing process is: m∆S1→2 = ∑ m j R ln j =1 C P Pj (9. For this system. Rearranging: dS = − V dP T dP P P 1 P2 (9. and xj is its mole fraction.9) and integrating: ∆S1→ 2 = R ln (9. with a decrease of pressure from P1 to P2.11) where Pj = xjP is the partial pressure of species j.9.

composition.. The first law cannot be used to determine the maximum or minimum amount of useful work. while producing shaft work at the rate. Thermodynamic Availability When matter is taken from state 1. P0. at T1 and elevated pressure. m = ∑ mj j =1 C P xj = mj m Figure 9. to state 2. mC P . T0. T. and P. it is of interest to determine the maximum amount of useful work that can be extracted or the minimum amount of work that is needed. elevation. which operates adiabatically and reversibly. The maximum or minimum is achieved only if the process is reversible. The effluent stream from turbine I is expanded isothermally (non-adiabatically) and reversibly in turbine II to the environmental pressure.10. The path is shown in the P-V and T-S diagrams. Ws I . m . in bringing a stream to equilibrium with its surroundings. To determine the maximum rate at which work is performed.where xj = Pj/P = m j / m. A stream at molar flow rate. as illustrated in Figure 9. at a given velocity. Ignoring kinetic energy and potential energy differences and referring enthalpies to the elements. P1. is fed to turbine I. which depends on the details of the process used to effect the change in state. It is expanded to P2 and the environmental temperature. m1 P 1 2 m2 P . composition.9 Isothermal mixing of C ideal gas species. at a different velocity. elevation. and pressure P. CD-9-13 . which is simply the change in enthalpy. in state 1. Wmax . a reversible path can be selected. the second of which shows the isentropic behavior of turbine I. the first law of thermodynamics can be used to determine the net amount of energy transferred by heat and/or work in moving from state 1 to state 2. temperature T.

10 Reversible path. (9.14): CD-9-14 . P2 II T0 . T1 . For turbine 2. and W s is the sum of the shaft work rates delivered by the two turbines. P0 QII P T1 P1 P2 P0 V Figure 9.WsI WsII m.3): mdS = and integrating: Q = m ∫ T0 dS = T0 m∆S1→0 dQ T0 (9. the first law of thermodynamics. applying the differential form of Eq. applied to the overall process is: m∆H1→0 = Q − Ws (9. (9.14) where Q is the rate of heat transfer to turbine 2. P1 I QI = 0 T0 .16) Substituting in the first law. Eq.15) (9. T0 S1 S2 Ignoring kinetic and potential energy changes.

P2 A2 Figure 9. is: ∆A1→2 = A2 − A1 = ∆H1→2 − T0 ∆S1→ 2 (9.18) and rearranging: Ws = Ws1 + Ws 2 = − m(∆H1→ 0 − T0 ∆S1→ 0 ) This reversible work is the maximum work “available” in bringing the feed stream to the environmental conditions. Typical Availability Changes In this subsection. when it is converted from state 1 to state 2 in a chemical process. but dependent on the temperature. Ws is the maximum rate of obtaining work. T1. which can be written mA1→0 .m∆H 1→0 = T0 m∆S1→0 − Ws (9.11 Availability change upon processing. A1→0 . independent of path. the environmental (dead-state) temperature in the following examples is taken as 298 K = 537oR. that is. as shown in Figure 9. P1 A1 T2. A is a state function. and pressure. the change in the maximum work available from the stream is a function solely of its changes in enthalpy and entropy. If chemical reactions occur. who presents many other excellent examples. P0. availability changes are computed for several simple processes to show the significant impact of the change in entropy. including three that take into account chemical reaction. These are taken from the monograph by Sussman (1980). It follows that the change in availability of a stream. Like H and S. and the environmental temperature. of the dead state. The concept of availability was first developed in detail by Keenan (1951).11. The intensive property. was initially referred to as the thermodynamic availability and is commonly referred to as the exergy.19) That is. the availability also depends on the composition of the dead state. one of which deals with a complete methane reforming process. CD-9-15 . In all cases. T0.17) (9.

saturated steam at 250 psia and 401°F is superheated isobarically to 600°F. As shown in Figure 9.12. (9.11) − 298(0 − 0. with the enthalpy and entropy values taken from the steam tables. Substituting in Eq.5 = 51.37 + 275.6502 Btu/lb°R H1 = 1. Although the enthalpy of the stream is increased by 117. Liquefying Air.1 Btu/lb S1 =1.74 − 127.319 Btu/lb S2 = 1.201.13. which equals the heat transferred to the stream. Substituting in Eq. which is less than 50 % of the heat transferred.6 kcal kg CD-9-16 .95 = 174.1) − 537(1. (9.5264) = 117. the maximum work that can be obtained from stream 2.6502 − 1. As shown in Figure 9.5264 Btu/lb°R Figure 9.12 Steam superheater. if it is taken to the environmental conditions. air at 25°C and 1 atm is condensed isobarically to a saturated liquid at -194.4 Btu lb Sat’d.9 − 66.9 Btu/lb.319 − 1.4 Btu/lb. 201.19): ∆A1→ 2 = ∆H1→2 − T0 ∆S1→ 2 = (25.Superheating Steam. is increased by only 51. because the entropy term increases so significantly.19): ∆A1→ 2 = ∆H1→2 − T0 ∆S1→ 2 = (1.5°C. Steam 250 psia 401°F 1 Superheater 2 250 psia 600°F H2 = 1.9260) = −101.

14. the entropy change is sufficiently negative to cause the entropy to be about three times more positive than the negative enthalpy change. -101. 174. the entropy term is the maximum loss of the ability of the stream to do work in transferring to its environmental (dead) state. Substituting in Eq. Throttling.19): ∆A1→ 2 = ∆H1→2 − T0 ∆S1→2 = 0 − 537(1. where the reference state is saturated liquid air at 25°C. is the heat removed from the condenser. Liquid -194. (9. and consequently. Stated differently. Air 25°C 1 atm 1 Condenser 2 Sat’d. This causes a large increase in the availability of the liquid air. As considered subsequently in CD-9-17 . In this case. superheated steam is throttled adiabatically across a valve from 600°F and 250 psia to 100 psia.19).Note that the enthalpy and entropy data are obtained from the air tables. A1 is computed to be 434. using a refrigerator that requires considerable compression work.11 kcal/kg S1 = 0. 12% of its “available” work is lost in throttling.68 = −52.68 Btu lb When throttling.9 Btu/lb. Stated differently. (9. Using the steam tables.6502) = 0 − 52.6502 Btu/lb-°R to 1.37 kcal/kg. The change in enthalpy. As shown in Figure 9. for this isenthalpic process.9260 kcal/kg-K Figure 9. the entire change in availability is due to the negative change in entropy. its temperature is reduced to 578°F and its entropy is increased from 1.13 Condensation of air.7483 − 1.6 kcal/kg is the maximum work obtained from the liquid air in returning it to the environmental state.7483 Btu/lb-°R.74 kcal/kg S2 = 0 H1 =127. and is the minimum work of refrigeration in liquefying air. Using Eq.5°C 1 atm H2 = 25.

319 Btu/lb S1 = 1.6502 Btu/lb-°R S2 = 1.7483 Btu/lb-°R Figure 9.3 cal of work are the minimum required to separate air into nitrogen and oxygen gases. (9. Isothermal Mixing. Stated differently.21 ln0.79 mol N2 0.19) applies.21) 1.79 ln0. In Figure 9.14 Throttling steam.21 mol O2 CD-9-18 .15 Isothermal mixing to air. N2 Ideal gases O2 Figure 9.3 cal mol air The positive entropy change upon mixing results in the negative change in availability. with Eq.15.13) substituted to give ∆A1→ 2 = ∆H1→2 − T0 ∆S1→2 = 0 + T0 ∑ x j R ln x j j =1 2 To obtain the change in = 0 + 298(0.79 + 0. nitrogen and oxygen gases are mixed isobarically and adiabatically to give concentrations proportional to those in air. Steam 600°F 250 psia 1 2 578°F 100 psia H1 = H2 = 1. 304. (9.this chapter. Eq. availability. the possibility of replacing the valve with a turbine to recover power should be considered when the pressure of a stream must be reduced.987 = −304. 25°C 1 atm 0.

Sussman (1980) makes extensive use of availability flow diagrams like that in Figure 9.61 kcal/s. and 3.5 kg/s State 2 50°C Figure 9. this is divided into 0. the availability change upon thermal mixing is: ∆( mA)1→2 = (1)(0. 0.99) − (0. as shown in Figure 9. which leaves in the mixed effluent stream.11) = −3.6) substituted.1 kcal/kg and A2. In the mixer.11 kcal/kg. Consequently.17. (9. the availability of the mixed stream is computed:   T  A2 = − (∆H 2→0 − T0 ∆S 2→0 ) = − c p (T0 − T2 ) − T0c p ln  0    T2    298   = − (1)(298 − 323) − 298(1) ln 323    = − [−25 + 24. where the widths of the arrows are approximately proportional to the availability flow rates.5)(8.62 kcal/s.17.5 kg/s of water at 0°C and 1 atm.5 kg/s of water at 100° and 1 atm is mixed adiabatically and isobarically with 0.05 + 0.cold = 1. approximately 78% of the availability to do work is lost upon thermal mixing. (9.16 Thermal mixing of water.5)(1.62 kcal s 100°C 0. In Figure 9. The availability change upon thermal mixing is illustrated conveniently in an availability flow diagram. which is lost to the environment.Thermal Mixing.1) − (0. that is.01] kcal = 0. Combining the availability flow rates for the hot and cold streams. the availability flow rate entering the mixer is 4.555 = 4. Using Eq. this loss decreases as the temperatures of the hot and cold streams approach each other. CD-9-19 .5 kg/s H2O 0° C 0. Clearly. with Eq.99 kg Similarly.16.hot = 8. the availabilities of the hot and cold feed streams are computed: A1.99 kcal/s. The resulting temperature is 50°C.19).

the first and second laws of thermodynamics are used to derive useful equations for computing the lost work of any process. Streams at certain fixed states flow at fixed rates into or out of the control volume. matter within the control volume undergoes changes in amount and state. ∆ ( mH )flowing streams is the sum of ∆ ( mU )sys where ∆ ( mU )sys enthalpy flows leaving the system minus the sum of those entering the system. Q0 is positive for heat transfer from the infinite surroundings at T0 to the control volume.99 kcal/s Mixer 0.05 kcal/s 0.18. and Qi is positive for heat transfer to the control volume from a heat reservoir at temperature Ti different from T0. is (9. and work resulting from the expansion (or contraction) of the control volume itself against the surroundings ( Psurr ∆Vsys ) . Eq. and the boundaries of the control volume expand or contract. ∆t.20) ignores changes in kinetic energy and potential energy for both the system and the flowing streams.20) + ∆ ( mH )flowing streams = Q0 − ∑ Qi − ∑ Wi ∆t i i is the change in internal energy of the system.17 Availability flow diagram for thermal mixing of water. (9. electrical work.Hot Cold 4. The energy balance for such a control volume over a period of time.62 kcal/s Figure 9. A general energy balance (first law of thermodynamics) can be written for a system bounded by the control volume shown in Figure 9. 9. CD-9-20 . The term ∑ Wi is positive for work done by the system on the surroundings and includes i mechanical shaft work. heat and work are transferred at fixed rates across the boundaries of the control volume.555 kcal/s 3.5 EQUATIONS FOR SECOND-LAW ANALYSIS In this section.

it is preferred by chemical engineers to use a CD-9-21 .18 Control volume for open system. chemical potential. that are used to transfer heat into the system.18 can be written in a manner analogous to that used for the energy balance. The term ∆Sirr is the increase in entropy of the universe due to the process. As with another fundamental thermodynamic quantity. Unlike energy.20).Figure 9. The result is ∆ ( mS )sys ∆t + ∆ ( mS )flowing streams − Q0 Q − ∑ i = ∆Sirr T0 i Ti (9. Although ∆Sirr is a fundamental quantity. and −∑ Qi Ti ( ) is the sum of the rates of entropy decrease in the various heat reservoirs at various temperatures. Eq.21) where ∆ ( mS )sys is the change of entropy of the system. An entropy balance for the system in Figure 9. entropy is not conserved. Ti. (9. it is of limited practical use because of the difficulty in interpreting the significance of its magnitude. Otherwise. it is positive and is a measure of the irreversibility of the process. It is zero only for a reversible process. − Q0 T0 is the rate of decrease in entropy of the infinite surroundings when heat is transferred from the infinite surroundings at T0 to the system in the control volume. except that here we prefer to write an entropy balance for both the control volume and the surroundings. ∆ ( mS )flowing streams is the sum of entropy flows leaving the system minus the sum of those entering the system.

however. (9. If one is interested in the maximum useful work that can be extracted from a material that is brought to equilibrium with the dead state.20) and (9. CD-9-22 . T0. When evaluating a process. by substituting Eq. for ∆Sirr . (9. by contrast.23) We now define an availability function. The result is ∆  m ( H − T0 S − PV )  sys   ∆t  T  + ∆  m ( H − T0 S )  flowing streams − ∑ Qi  1 − 0  + ∑ Wi + T0 ∆Sirr = 0   i  Ti  i (9.23): B = H – T0S (9. we will use ∆B. In the second-law analysis of a process. is important. the change in availability function is exactly equal to the change in availability. that quantity is fugacity.1). T.surrogate property. can be referenced to any state and is not an absolute quantity. A. the first term on the left side can be rewritten to give the same combination.23). it is availability (exergy). (9. ∆A or ∆B. is of importance.19) differ from each other in that the availability is referenced to a dead state at T0.21) by eliminating Q0 . as will be shown next. (9. By their definitions. for the internal energy. However. the entropy is multiplied by the dead-state temperature. the definition of enthalpy. respectively. For chemical potential. (9. The result is ∆  m (U − T0 S )  sys   ∆t  T  + ∆  m ( H − T0 S )  flowing streams − ∑ Qi 1 − 0  + ∑ Wi + T0 ∆Sirr = 0   i  Ti  i (9. H − T0 S .22) In this equation. then the availability.24) and availability in Eq. an absolute quantity. only the change in availability function appears. instead of the stream temperature. In addition. (9.24) The availability function in Eq. P0. for the combination of enthalpy and entropy in Eq. B. when the first and second laws of thermodynamics are combined. therefore. and a composition for every element in the periodic table) and is. To derive availability. combine Eqs. only the change in availability or availability function. which was defined earlier and arises naturally. The availability function. in the second term on the left-hand side. we see that the enthalpy and entropy appear together to form a combined factor that is similar to the Gibbs free energy. In Eq.

work will have to be transferred from the surroundings to the processing system. then ∑W i i is the maximum work that can be extracted from the decrease in availability. (9. are zero.27) For a reversible process. it is given the name lost work. (9.25) into Eq. we also note in Eq. Thus. if the lost work is greater than the decrease in availability.23) gives ∆  m ( B − PV )  sys   ∆t  T  + ∆  m ( B )  flowing streams − ∑  1 − 0 Qi + ∑ Wi + LW = 0   Ti  i  i (9. (9. For an irreversible process. ∆Sirr and. That decrease will be converted to useful work done on the surroundings and/or lost work.24) and (9. adiabatic process.      ∑ Wi  = −∆  m ( B )  flowing streams . Consider a continuous. The lost work represents the energy flow (power) lost because of irreversibilities in the process.22) that ∆Sirr is multiplied by T0 and that their product has the units of energy flow. (9.28) will be a negative quantity. then the right-hand side of Eq. T0 ∆Sirr and LW .28) If the process decreases the availability function for the flowing streams.29) If the process increases the availability function for the flowing streams. (9. If the process is also reversible. for such a reversible process.28) will be a positive quantity. The lost work is much easier to relate to than ∆Sirr .In addition. That increase will require work to be done by the CD-9-23 . ∆Sirr and LW are positive. (9. then the right-hand side of Eq. therefore. (9. Accordingly. where Eq.26) may be rearranged to the following form: ∑Wi + LW = − i ∆  m ( B − PV )  sys   ∆t  T  − ∆  m ( B )  flowing streams + ∑ 1 − 0 Qi   Ti  i  (9. Eq.  i  max for ∆B = (−) (9.27) is best illustrated by a simple case. steady-state.26) Alternatively. (9. or loss of availability or exergy: LW = T0 ∆Sirr (9. The significance of Eq. LW . However.25) Substitution of Eqs.27) simplifies to ∑W + LW = −∆  m ( B )   i i flowing streams (9.

The left-hand side of Eq. according to Eq. the left-hand side is positive and availability is not conserved. an equivalent amount of additional work must be done on the process by the surroundings to satisfy the change in availability function. (9.27) are availability balances. (9.. That is.26) for the availability balance. some availability is lost. Thus. in the following forms.    ∑ Wi  = −∆  m ( B )  flowing streams . energy is conserved. (9. let us compare an energy balance to an availability balance. a negative value for ∑W i i ).30) Eqs. If lost work (a positive quantity) occurs in the process because of irreversibilities. steady-state process.surroundings on the process (i. where work and heat terms are all positive because they are labeled into or out of the system: Energy balance: 0= ∑ ( mH ) − ∑ ( mH ) +∑ W − ∑ W +∑ Q − ∑ Q in in out in out out (9. CD-9-24 . we note the following: 1. The heat and the work terms are transfers of availability to or from the process.20) for the energy balance and Eq. (9. then. The comparison is facilitated by rewriting Eq. then ∑W i i is the minimum work required for the increase in availability. If the process is reversible.26) and (9. Otherwise.31) is zero. respectively.31) Availability balance: LW = ∑ ( mB ) − ∑ ( mB ) +∑ W − ∑ W in in out out   T    T  + ∑  Q  1 − 0   − ∑ Q  1 − 0     T   in   T   out By comparing these two equations. (9. For a continuous.32) is zero only for a reversible process. In an irreversible process.    i  min for ∆B = (+ ) (9. (9. for such a reversible process. (9.e.28).32) The left-hand side of Eq.

the energy balance cannot be used to compute the minimum or maximum energy requirements when taking material from inlet to outlet states. T0. but is the temperature of the heat source or sink outside the system. (9. which is valid whether the process is reversible or not. CD-9-25 . All work input increases the availability of material flowing through the process.32) can be used to determine the maximum or minimum energy requirements to cause a change in availability. Regardless of whether a net availability of heat or work is transferred to or from a process. the energy balance must be satisfied. work and heat are counted the same.2.6 EXAMPLES OF LOST-WORK CALCULATIONS Before proceeding with a discussion of the second-law thermodynamic efficiency in the next section. In the energy balance. that is a measure of irreversibility. The more efficient a process. 3. the energy and availability balances are used together to determine energy requirements and irreversibilities that lead to lost work. When the lost work is zero. This coefficient is precisely the Carnot cycle efficiency for a heat engine that takes heat from a source at temperature. two examples are provided to illustrate the calculation of lost work for chemical processes. The heat is degraded by a coefficient equal to 1 − (T0 / T ) . work and heat are not counted the same. Note that in the availability balance. T is not the temperature of the process stream within the system. the process is reversible and Eq. The availability balance does have a term. LW . In the availability balance. and converts a portion of it to useful work. Thus. Thus. Only a portion of heat transferred into a system is available to increase the availability of flowing streams. T. The energy balance. 9. discharging the balance to a sink at a lower temperature. has no terms that take into account irreversibility. the smaller the lost work.

consider the continuous two-stage compression of nitrogen gas shown in Figure 9.19.3 kW and T0 is given as 536. The enthalpies and entropies of the entering and exiting nitrogen gas. T0. which is based on actual plant operating conditions.5758 Btu/lb.32) reduces to LW = ( mB )1 − ( mB )2 + Welectrical in where B = H – T0S. computed from a modified Benedict-Webb-Rubin (BWR) equation of state. The system or control volume is selected to exclude the electric power generation plant and cooling-water heat sink.6335 Btu/lb. Figure 9. SOLUTION For this process. (9.49 Btu/lb S2 = 1.46 Btu/lb S1 = 1.7oR. of the cooling water is essentially equal to the dead-state temperature.o R The electrical work input is given as 107.1 For the first example. Assume that the temperature.19 Continuous process for compression of nitrogen. Eq.33) H 2 = 182.EXAMPLE 9. are H1 = 132. T. The entering and exiting availability functions are CD-9-26 .R o (9. Calculate the lost work.

Therefore. separate second-law analyses are needed for each of the two compressors and the intercooler.132.9 kW or 29. Eq.600 lb/hr.24)] = 291.46 − (536. Thus.24 . (9. How can we apply the first law of thermodynamics to the nitrogen compression problem? We can apply an energy balance to calculate how much heat must be transferred from the nitrogen to cooling water in the intercooler: Welectrical in = Qout + m ( H 2 − H1 ) Therefore.400 .B1 = 132. and the work input into the availability balance.3 kW is equivalent to 366. which represents the minimum energy input corresponding to a reversible process.34) Qout = 366.46) = 366. 400 = 74.24 Btu/lb B2 = 182. Where does the irreversibility occur? To answer this. substitute the change in availability of the nitrogen.300 Btu/hr CD-9-27 .600 Btu/hr Because the availability increases. 600 + 366.7)(1.600)(182.33). This is greater than the availability increase. data on the nitrogen leaving the first compressor and leaving the intercooler are not provided.180.4 hp.100 = 186. for the lost work: LW = ( mB )1 − ( mB ) 2 + Welectrical in = −291.400 Btu/hr. The electrical power input of 107. To determine the extent of the irreversibility.49 .(3. the compression process has irreversibility.600[-663.5758) = −663.49 − (536. energy must be transferred into the system.400 .7)(1. the change in availability of nitrogen is 3. Therefore.800 Btu/lb This is equivalent to 21.24 Btu/lb The flow rate of nitrogen through the process is 3.(-744. these separate analyses cannot be made. (9.6335) = −744. Unfortunately.

20 for a propane refrigeration cycle.600 Btu/hr that must be added. EXAMPLE 9. consider the plant operating data shown in Figure 9. The cycle is completed by passing the propane through the refrigerant evaporator. Figure 9.100 Btu/hr is far less than the minimum amount of energy of 291. thus completing the cycle.7oF and 185 psia. Even if the compressors and the intercooler were reversible.400 lb/hr is compressed to superheated vapor (state 2) at 187 psia and 113oF.180.37 psia for a flow rate of 5. Saturated propane vapor (state 1) at 0 oF and 38.20 Operating conditions for propane refrigeration cycle. where the propane absorbs heat from the matter being refrigerated and from which it emerges as a saturated vapor (state 1). Calculate the lost work.Note that the enthalpy increase of 180.300 Btu/hr for the actual process.500 Btu/hr of energy would have to be transferred out of the system.2 As a second example. it is still a large amount. CD-9-28 . The propane is then condensed with cooling water at 77oF in the refrigerant condenser to state 3 at 98.600 .100 = 111. 291. Although this is considerably less than the 186. Reducing the pressure across the valve to 40 psia causes the propane to become partially vaporized (state 4) at the corresponding saturation temperature of 2oF.

35) For a reversible cycle. would therefore indicate that no energy is required to run the cycle.35). and heat is transferred to the system from the matter being refrigerated at the evaporator. it is emphasized that the first law of thermodynamics cannot be used to determine minimum or maximum energy transfer to or from a system. we take the deadstate temperature. The lost work then reduces to  T0 LW = Win + 1 −  T Evaporator    Qin   (9.36) Substitution of this equation into the lost-work equation. we must use the second law or the availability balance (combined first and second laws). TCondenser. T0. (9.32) simplifies to  T0 LW = Win +  1 −  T Evaporator    T0   Qin −  1 −  Qout   TCondenser   (9. the lost work would be zero. The heat transferred in the evaporator is obtained most readily from an energy balance on the propane as it flows from state 3 CD-9-29 . For the propane refrigeration cycle. To prove this.38) The electrical work input is given in Figure 9.20 as 70 kW. Eq. Again. energy input is required at the compressor. so as to eliminate Qout . Instead. to be the cooling-water temperature. the first law gives Win + Qin = Qout (9. but not the cooling water used in the condenser or the matter being refrigerated in the evaporator. The energy balance. of course. and this form of the availability balance is the classical result for the refrigeration (reverse Carnot) cycle. (9. For each pass through the cycle. First.SOLUTION Let the system be circulating propane and the electric motor drive of the compressor.37) The lost work for the cycle is computed in the following manner. the sum of these two energy inputs is transferred out of the system to cooling water at the condenser. the availability balance of Eq. there is no net enthalpy change for the propane. gives the following widely used equation for the coefficient of performance (COP) of a refrigeration cycle: COP = TEvaporator Qin = Win TCondenser − TEvaporator (9. if applied incorrectly. But. with LW = 0 . By an energy balance.

(-797. which gives H1 = -686.7  The lost work is LW = 70 + ( −24.37 psia).7 oR and H3 = H4 = -797. It is  536. with LW = 0. For CD-9-30 .2 Btu/lb The second term on the right-hand side of the lost-work equation.9 = −24. 9.7  1 − 174. noting that no enthalpy change occurs across the valve: Qin = mpropane ( H1 − H 4 ) = mpropane ( H1 − H 3 ) (9. Eq. Goals differ from application to application. Qin = 5.7 THERMODYNAMIC EFFICIENCY The thermodynamic efficiency of an operation or an entire process depends on its main goal and the work lost in accomplishing that goal.95 kW of electrical work input would be required. we estimate enthalpies and entropies from a modified Benedict-Webb-Rubin (BWR) equation of state. for the propane refrigeration cycle is the reversible work input that corresponds to the heat input.7 = 469.6) .38).2)] = 597.05 kW In a reversible cycle. the propane circulation rate is 5.05 or 24.400 lb/hr.45.9 kW The temperatures are T0 = 77 + 459.6 Btu/lb Thus. only 70 .400[(-686.7 = 536.200 Btu/hr = 174.(saturated liquid at 185 psia) to state 1 (saturated vapor at 38.39) From above. Again.7 oR and TEvaporator = 10 + 459.95 ) = 45. (9.95 kW  469.

2.example.40). The thermodynamic efficiency is computed from one of two equations. the main goal of an adiabatic turbine operating continuously might be to produce work. (9. If the sign is positive. the thermodynamic efficiency is given by η( + )goal = main goal − LW main goal (9.26). we write Eq. For a complex batch chemical process.40) Main Goal −W Explanation Work transfer Change in availability function of flowing streams −∆ ( mB )  T0  1 −  Qi  T1  − ∆  m ( B − PV )  sys   ∆t Work equivalent of heat transfer Change in batch availability function of system Each of the terms on the right-hand side of Eq.41) CD-9-31 .40) represents a possible main goal.2 Possible Main Goals of an Operation or Process (9.PV) of the system. (9. (9. heat exchangers. in the form ∆  m ( B − PV )  sys  T    LW = −∑ Wi − ∆ ( mB )flowing streams + ∑  1 − 0  Qi − ∆t Ti  i i  Table 9. separators. the main goal is the increase or decrease of the batch availability function m(B . To derive general expressions for thermodynamic efficiency. The availabilities of some main goals are listed in Table 9. The main goal of a refrigeration cycle might be the transfer of heat from the stream being refrigerated to the refrigerant. the main goal is the increase or decrease of the availability function of the streams flowing across the boundaries of the system. and shaft-work devices. In continuous chemical processes that involve reactors. depending on the sign of the term that represents the main goal on the right-hand side of Eq. the combined energy and entropy balance.

For example.42) The application of Eq. the thermodynamic efficiency is given by η( − )goal = main goal main goal − LW (9. CD-9-32 . steady-flow. (9. Thermodynamic efficiencies greater than unity are impossible.41) and (9. consider a continuous process in which the main goal is to decrease the availability function of the flowing streams. work must be done on the system by the surroundings.796 or 79.600 Btu/hr LW = 74. however. the main goal is to change the availability function of the nitrogen gas. steady-state. we apply Eq. and Eq. (9.800 This is consistent with the previous calculation of 20.41) will yield a negative efficiency. −∆ ( mB )flowing streams . If.e.4% for the loss of input electrical energy. because the main goal has a negative sign and the lost work is greater than or equal to zero. (9.If the numerical value of the main goal selected is negative. then LW = 0 and work could be done on the surroundings. 600 − 74. two-stage compression process shown in Figure 9. the process is so irreversible that.6% −291. On the other hand.19.42) for the calculation of thermodynamic efficiency may be illustrated by considering the two examples in the preceding section.42) always results in a positive efficiency that is equal to or less than unity (i. then LW will be greater than the main goal. instead. (9.42) to obtain η= −291.. The calculations previously presented give Main goal = − m( B2 − B1 ) = −291.800 Btu/hr Because the main goal has a negative value. A negative efficiency results when the lost work is greater than the absolute value of the main goal. For the continuous. 100%). Eq. (9.41) can give values ranging from less than zero up to unity. The application of Eqs. 600 = 0. If the process is reversible and exchanges heat only with the infinite surroundings.

8 CAUSES OF LOST WORK Lost work is caused by irreversibilities. This work was accompanied by 45 kW of lost work. such mixing can be avoided when recycling material. the smaller the driving forces. Quenching a hot stream with a cold stream increases entropy. Reducing the velocity or streamlining the shape of the object can reduce form drag for flow of fluid past submerged objects. Mixing of two or more streams or batches of material that differ in temperature.the transfer of heat from the matter being refrigerated at 10oF to the propane refrigerant . small driving forces are best achieved with countercurrent flow of vapor and liquid at reflux ratios close to minimum.357 or 35.In the refrigeration cycle of Figure 9. In distillation. 3. Finite driving forces for transport processes. Significant decreases in skin friction for flow of fluids in pipes can be achieved by increasing pipe diameter. which was calculated to be -25 kW.requires the work of a reversible Carnot cycle. their major causes are: 1. Eq. finite driving forces are needed for heat transfer and mass transfer. but may be unavoidable when preparing a composite feed for chemical reaction.42) gives η= −25 = 0. Often. Thus. For heat exchangers. CD-9-33 . and/or composition. However. the smaller is the lost work.20. thereby reducing fluid velocity. 2. For reasonable-size processing equipment. small temperature-driving forces are achieved with countercurrent flow and small temperature approaches at either end of the exchanger. however. the main goal .7% −25 − 45 9. (9. Fluid friction and drag. pressure. Such mixing leads to significant increases in entropy.

6. and turbines. especially when that heat is available at an elevated temperature. Economic analyses have shown that it is worthwhile to seek ways to improve this efficiency to at least 60%. with minimal side reactions.6 and 9. it is best carried out at high temperature to maximize the usefulness of the energy produced. Now. The examples involve (1) the propane refrigeration cycle introduced in Section 9. three detailed examples of second-law analysis are presented for chemical processes. and (3) a process for the hydrogenation of benzene to cyclohexane. (2) the separation of a mixture of propylene and propane by distillation. compressors.20. Each example includes the calculation of lost work. 9. Machinery is available with efficiencies of 80% and higher. Second-law thermodynamic efficiency of the majority of chemical processes is in the range of 25 . the determination of where the lost work occurs. Transferring heat to cooling water. EXAMPLE 9. reactions should be carried out with little or no dilution. and at maximum yields to avoid separations and byproduct formation. is calculated. If the reaction is exothermic.30%. To minimize lost work. shown in Figure 9. The third example is computed with ASPEN PLUS. the total rate of lost work and overall thermodynamic efficiency of a propane refrigeration cycle. If the reaction is endothermic. it is best carried out at below ambient temperature to utilize heat from the dead state.7. and consideration of how the lost work can be reduced.3 A Refrigeration Cycle In Sections 9. consider this cycle in detail CD-9-34 .9 THREE EXAMPLES OF SECOND-LAW ANALYSIS In this section. Chemical reactions occurring far from equilibrium. This is best achieved by using selective catalysts. Mechanical friction in machinery such as pumps. Good uses should be found for waste heat. 6.4. 5.

17 kW { } This represents 20. The rate of lost work in kilowatts is LW1− 2 = ( 2. so LW2 −3 = ( 2.60 − ( 536.8% of the total lost work for the cycle. SOLUTION Compressor: State 1 to State 2 For this step.929 × 10−4 ) (5. Although the overall process is a cycle.67 )(1. each separate step in the cycle can be treated as a continuous process so that Eq. LW2 −3 = m ( H 2 − T0 S 2 ) − ( H 3 − T0 S3 )    State 3 is a saturated liquid.83/45.3507 )  −  −655. T0.929 ×10−4 ) (5. 400)  −686. Then. This lost work results because of motor and compressor irreversibilities. Refrigerant Condenser: State 2 to State 3 For heat rejection from the propane refrigerant to cooling water at the temperature of the infinite surroundings.448.67 )(1. or 19.41 − ( 536.2 − ( 536.05 = 0.05 = 0. (9. Note that states 1 and 2 are both vapor.27) applies. 400)  −655.83 + 70 = 20.3501)  −  −797.67 )(1.67 )(1.to determine where the lost work occurs with respect to each of the four steps in the cycle.17/45. This lost work results because of a frictional pressure drop of 2 psi through the heat exchanger and the rather large temperature driving force for heat transfer.0963)      = 8. CD-9-35 . attempt to improve the efficiency of the cycle by concentrating on those steps where most of the lost work occurs.6% of the total lost work for the cycle.83 kW { } This represents 8. or 44.41 − ( 536.3501)  − ( −70 )     = −49.196. LW1− 2 = m ( H1 − T0 S1 ) − ( H 2 − T0 S 2 )  − Welec   The thermodynamic properties of propane are obtained from a modified BWR equation as above.

2 − (−855.0.929 ×10−4 ) (5. The weight fraction vaporized can be determined by noting that H 3 = H 4 = ψ ( H 4 )V + (1 − ψ )( H 4 ) L and by solving for ψ to obtain ψ= Therefore. the heat transfer rate in the refrigerant evaporator is Qi = m ( H1 − H 4 ) Therefore. if ψ is the weight fraction vaporized. This lost work occurs because of the frictional pressure drop across the valve.37/45. From the energy balance.1 − (−855.7oR). or 25.67 )(1.345)(1.345)(0.Valve: State 3 to State 4 Assume that this step is adiabatic with H3 = H4.252.7) = 0.345 −686.1097 Btu/lb-oR and thus LW3− 4 = ( 2.37 kW { } This represents 11.1097 )      = 11. Refrigerant Evaporator: State 4 to State 1 For this step. Then LW3− 4 = m ( −T0 S3 ) − ( −T0 S 4 )    Because state 4 is a partially vaporized condition.05 = 0. CD-9-36 . then S4 = ψ ( S4 )V + (1 − ψ )( S4 ) L where V and L represent vapor and liquid.  T  LW4 −1 = m ( H 4 − T0 S 4 ) − ( H1 − T0 S1 )  + 1 − 0  Qi    Ti  where Ti. respectively.3501) + (1 .0963)  −  − ( 536. is 10oF (469. 400)  − ( 536. That is.2% of the total lost work for the cycle. the temperature of the matter being refrigerated. ( H 4 )V − ( H 4 ) L H 3 − ( H 4 )L = −797. the fractions of vapor and liquid must be determined to obtain S4.7) S4 = (0.9831) = 1.67 )(1.

Some improvements can be made by maintaining the same basic cycle. Reduce the frictional pressure drop in the refrigerant condenser.60 ) − ( −797. 2.67   = 4. 400 )( 536. Increase the efficiency of the compressor. with moderate losses in the refrigerant condenser and the valve. but adjusting the operating conditions and changing the equipment to accomplish the following: 1.3 shows that the major loss is due to the compressor. or 10.68 45.104. Use a higher-temperature coolant for the refrigerant condenser or reduce the compressor discharge pressure to lower the temperature of the refrigerant at states 2 and 3.05 Percentage of Total LW 44.0 How can the thermodynamic efficiency of this refrigeration cycle by improved? Table 9.68/45.4 100.6 25.83 11. Table 9.1097 ) −  469. Table 9.2 10.8 19. CD-9-37 .3 Lost Work for Propane Refrigeration Cycle Step in Cycle Compressor Refrigerant condenser Valve Refrigerant evaporator State to State 1-2 2-3 3-4 4-1 LW ( kW ) 20.67 ) (1.20 )  = ( 2.68 kW This represents 4. This lost work occurs because of frictional pressure drop through the heat exchanger and the small but finite temperature driving force for heat transfer. but only a small loss in the refrigerant evaporator.3507 − 1. T  LW4 −1 = m ( H 4 − T0 S 4 ) − ( H1 − T0 S1 )  + 1 − 0  m ( H1 − H 4 )    Ti  Simplifying.  H − H4  LW4 −1 = mT0 ( S1 − S 4 ) − 1  Ti    ( −686.4% of the total lost work for the cycle.929 × 10−4 ) ( 5.3 summarizes the preceding analysis.17 8.37 4.05 = 0.

Figure 9.4).0 - 38. 3. A revised cycle that incorporates these improvements is shown in Figure 9. Reduce the frictional pressure drop in the refrigerant evaporator.185) to 0. The valve is replaced by a power-recovery turbine that supplies a portion of the power required by the compressor.20 shows the following: 1.5 psi (44. 4.154.63 psi (40. Comparison of the cycle with the original one in Figure 9.35). Increase the pressure at state 4 to reduce the temperature-driving force in the refrigerant evaporator. The frictional pressure drop in the refrigerant evaporator is reduced from 1. Replace the valve with a power-recovery turbine. 2.9 .21. The frictional pressure drop in the refrigerant condenser is reduced from 2 psi (187 .44.5 psi (154.21 Revised propane refrigeration cycle.3.37) to 0.85 . CD-9-38 .

0 8.7 77) to 8oF (85 .85 44. Next.90 154.9899 1.0805 1. as calculated above). Also note that (S4)V > 1.493. Therefore.35 psia and from 187 psia to 154.40 44.0 1.37 psia to 44.4.874 to 3. The corresponding changes in refrigerant temperature cause reductions in the minimum temperature-driving forces in the condenser and evaporator from 21.77) and from 8oF (10 .0 8.8).4 100.85 44. respectively. If ψ is the weight fraction vaporized. thus reducing the compression ratio from 4. where the known heat duty permits us to determine the propane flow rate.0 154. The compressor inlet and discharge pressures are changed from 38. note that since the power-recovery turbine is assumed to operate isentropically.3485 0.1 -663.4 -852.0 90. From State 4 to State 1 Qi = m ( H1 − H 4 ) Therefore.7oF (98.1 -684. Also.6 − H 4 To obtain H4.0 7. S4 = S3 = 1.0805 > (S4)L.0805 Btu/lb-oR.2) to 2oF (10 .3431 It is worthwhile to begin calculations with the refrigerant condenser. 200 = H1 − H 4 −684. liquid Sat’d. the rate of heat transfer in the refrigerant evaporator is assumed to be the same as for the original cycle (597. m= Qi 597.200 Btu/hr. vapor Sat’d liquid Sat’d vapor Vapor Vapor -806.90 Sat’d. state 4 is partially vaporized propane.3 -684. the lost work is calculated assuming that the power-recovery turbine and the compressor operate isentropically. respectively.6 -658.3518 1. CD-9-39 . Required thermodynamic properties of propane for the revised cycle are Temperature ( F) o Pressure (psia) Phase Enthalpy (Btu/lb) Entropy (Btu/lb-oR) 85.3486 1.9 psia.35 154.

4 ) + (1 − 0.6 − ( −809.2526 )( −852. −WC = m ( H 2 − H1 ) The enthalpy. From the thermodynamic data given. H2.9 Btu/lb Thus. 720 Btu/hr   CD-9-40 .9 − ( −684. (S 100o F V ) > (S ) > (S ) 2 V 90o F V By interpolation.32 °F and H2 = -659.0805 − 0.6 )  = −117.1)  = −18. T2 = 96.9 − ( −806.9 Btu/lb. 766  −659. depends on the temperature of the propane leaving the compressor.9899 = 0.2526 1.9899 597.3) = −809. It can be obtained by noting that S2 = S1 = 1. m= From State 3 to State 4 ψ= = 1.9 ) Letting WT = rate of work transferred from the propane by the turbine. 200 = 4.110 Btu/hr From State 1 to State 2 Letting −WC = rate of work transferred by the compressor to the propane. WC = −4. Therefore.110 Btu/hr   or WT = 18.S4 = S3 = ψ ( S 4 )V + (1 − ψ )( S 4 ) L and therefore. 766  −809.3486 Btu/lb-oR because of the isentropic compression assumption.2526 ( −684.3485 − 0. −WT = m ( H 4 − H 3 ) = 4. 766 lb/hr −684. S3 − ( S 4 ) L ( S4 )V − ( S4 ) L H 4 = ψ ( H 4 )V + (1 − ψ )( H 4 ) L = 0.

steady-state.14 for conditions at the top of the fractionator to conditions at the bottom of the fractionator. respectively. The relative volatility of propylene to propane is quite low. a large external reflux ratio of 15. WE . 720 + 18.9 is required at operation near the minimum reflux.67  or (14. 610 + 597.22. EXAMPLE 9. 200 stages are required at 100% tray efficiency. The reduction is so large because isentropic compression and expansion has been assumed unrealistically for the revised cycle. Total pressure drop for the two columns is 20 psi. Conventional distillation is used with a bottoms pressure of 300 psia so that cooling water can be used in the partial condenser to provide reflux.Of this amount. Therefore.67  = 99. is Therefore.110 = −99. 610 Btu/hr For the cycle. the WE = −117.0544) = 4.  T  LW = −WE + Qi 1 − 0   Ti   536.110 Btu/hr is supplied from the power-recovery turbine. tray spacing. refer to Exercise 9. Because of high product purities. two columns in series are needed because a single column would be too tall. varying from 1. With 24-in. 200 1 −  = 14. an intercolumn pump is shown in addition to the reflux pump.05 kW computed for the original cycle. the system is chosen so that it does not include the 77oF cooling water used as the coolant in the partial condenser or the 220oF saturated steam used as the heating CD-9-41 . 600 This rate of lost work represents a large reduction from the value of 45.22 kW 3.08 to 1. theoretical electrical power input. as well as the low average relative volatility.22. To account for irreversibilities in compression and expansion. 420 Btu/hr  469. As shown in Figure 9. thus.22. 420)(1. 18.4 Separation of a Propylene-Propane Mixture by Distillation The initial design of a distillation operation for the continuous. steady-flow separation of a propylene-propane mixture is shown in Figure 9.

239.8 50. LW (in kilowatts) is given by CD-9-42 .81 51.7 116.medium in the partial reboiler.0 135.4 Properties for Propylene-Propane Separation State Stream Phase Condition T(oF) P(psia) m (lbmol/hr) H (Btu/lbmol) S (Btu/lbmol-oR) 1 2 3 Feed Distillate Bottoms Saturated liquid Saturated vapor Saturated liquid 125. Thus.133.22 Distillation system for propylene-propane separation.16 The rate of lost work is  T  LW = −∑ Weleci +  m1 ( H1 − T0 S1 ) − m2 ( H 2 − T0 S 2 ) − m3 ( H 3 − T0 S3 )  + 1 − 0  Qreboiler   i  Tstm  where the work equivalent of the heat transferred to the condenser is zero because the temperature of the cooling water is assumed to be T0.4 20.92 57. Figure 9.7 -31.4.8 294 380 300 600 351 249 -4. Entropies given are referred to 0oR and 1 atm.218. with reference to the elements H2 (gas) and C (graphite) at 0oR and 0 psia using the Soave-Redlich-Kwong (SRK) equation of state with standard heats of formation. Table 9. Enthalpies of the feed stream and the two product streams are given in Table 9.

8 − (536.67)(50. elaborate schemes for reducing the reboiler heat duty in distillation have been devised. Liquid leaving the bottom tray is flashed across an expansion valve to a pressure corresponding to a saturation temperature lower than the saturation temperature of the overhead vapor so that the partial condenser can be used as a reboiler.33 = 1.300)  679. as in most continuous separation operations.81 − 1.4 − (536.133.89% −∆ ( mB ) − LW −140.81 + 1. The feed is reduced in pressure to 108 psia by a power-recovery turbine and then distilled in a single column operating at a bottoms pressure of 112 psia. In this example. as discussed in Section 10. using reboiler-liquid flashing. such as adsorption.23.81 kW Thus.92)]    + ( 2. Therefore.9.929 ×10 −4 ) −351[ 20. but typical of conventional distillation of mixtures with a low relative volatility because of the large energy expenditures required in the reboiler.362.67  = 49. giving η= −∆ ( mB ) −140. 239. The large reduction in reboiler steam is somewhat offset by the power requirement of the compressor. the availability function of the flowing streams has been increased.55) 600 [ −4.67)(57.902.58 kW The thermodynamic efficiency is computed from Eq. One such alternative scheme. CD-9-43 .902. which is −∆ ( mB )flowing streams = −140. including multieffect distillation and operation at lower pressures using heat pumps. Also. have been explored for this application.81 = = 0.929 ×10−4 ) 1 −  (32.7 − (536. the increase is brought about mainly by the transfer of heat in the reboiler.41) because the main goal is to change the availability function of the streams.58 This is a very low efficiency. Because the required reboiler duty is somewhat larger than the required condenser duty.06 − 140. other separation methods. (9.67  + ( 2. 218.67)(51.16) ]  536. for the separation of propylene from propane is shown in Figure 9.81)]    −249 [ −31. an auxiliary steam-heated reboiler is needed.LW = −(−1.0689 or 6. A compressor is needed to return the reboiled vapor to the bottom of the column.55 − 23.994.96 − 23.

133. 682.133.67  = 366.929 × 10 −4 ) −351[19.40) ]    −249 [ −33.6 -33.67)(50.67  + ( 2.Figure 9.1 − (536.92 58.92) ]    + ( 2.4 19.2 + 173.682. 672.67)(46.6 − (536.23. Stream Feed Distillate Bottoms Phase Saturated liquid Saturated vapor Saturated liquid Enthalpy (Btu/lbmol) -4.23 Low-temperature distillation with reboiler-liquid flashing for propylene-propane separation.6 kW   Qreboiler  CD-9-44 .672.820.0 − 38. The following enthalpy and entropy data apply to Figure 9.4 − (536. 000)  679.1 Entropy (Btu/lbmol-oR) 50.929 × 10−4 ) 1 −  (2.87) ]  536.87 The rate of lost work for the system is given by  T LW = −∑ Weleci +  m1 ( H1 − T0 S1 ) − m2 ( H 2 − T0 S2 ) − m3 ( H 3 − T0 S3 )  + 1 − 0   i  Tstm = −(29 − 14 − 381) 600 [ −4.40 46.67)(58.8 = 501.

heat exchangers. CD-9-45 .2 kW . at elevated temperature and pressure. A continuous. η= −∆ ( mB ) − LW −∆ ( mB ) = −38.24 Process flow diagram and design basis for hydrogenation of benzene to cyclohexane. EXAMPLE 9.Since −∆ ( mB )flowing streams = −38. steady-state.58 kW computed for the system in Figure 9. a process is considered that involves a chemical reactor as well as separators. The two cases are not really comparable because the product conditions are not the same. and pumps. The heart of the process is a reactor in which liquid benzene from storage. steady-flow process for manufacturing approximately 10 million gallons per year of high-purity cyclohexane by the catalytic hydrogenation of high-purity benzene. take part in the reaction C6 H6 + 3H2 → C6 H12 Figure 9.22. together with makeup hydrogen and recycle hydrogen in stoichiometric excess.902.07 or 7.2 − 501.0% −38. the thermodynamic efficiency is still low.2 = 0. is shown in Figure 9.5 A Process for Converting Benzene to Cyclohexane Here.24.6 Although the lost work is much lower than the value of 1.

That flowsheet is shown in Figure 9.24. R1. specifications can be entered interactively in the ASPEN PLUS program.24. The top name. The information given in Figures 9. e. F1. 62% of the liquid (S10) from flash drum F1 is sent in stream S14 to a low-pressure adiabatic flash drum.25 is sufficient to prepare the input for a simulation. The remaining liquid S13 from F1 is recycled by pump P2 to reactor R1 to control the pressure of the saturated-vapor reactor effluent. Specifications entered on input forms are converted by ASPEN PLUS to a compact listing that can be displayed if desired. at 15 psia.. with the remaining vapor (S12) recycled to the reactor. a particular operation can be simulated with two or more models. D2. is a unique user-specified unit name or so-called block i. refers to the selected ASPEN PLUS model. and then separated at these conditions in the high-pressure flash drum. or subroutine.g. the same as or similar to that shown in Figure 9. This effluent is reduced in temperature to 120oF at 300 psia by the cooler.86% of the benzene in stream S6 is hydrogenated to produce the saturated-vapor reactor effluent (S7) at 392oF and 315 psia. in many cases.14 lbmol/hr of pure liquid benzene feed (S1) at 100oF and 15 psia is pumped by P1 to 335 psia and mixed in-line and adiabatically at M1 with impure hydrogen makeup gas (S3) containing 0. RSTOIC for the reactor. Thermodynamic properties are computed by option SYSOP1. e. It is convenient to use computer simulation to perform mass and energy balance calculations automatically for continuous-flow. F2. R1.24 includes all major equipment and streams together with a set of operating conditions for making a preliminary design and second-law analysis. Each operation is a simulation unit within which two names appear.24 and 9. in which each stream has a unique name..3. For this example. ASPEN PLUS is used. 92. steady-state processes like the one in Figure 9. 99. At the line tee. A total of 8.296 mol% nitrogen at 120oF and 335 psia. Gas from F2 is vented to stream S15.26.Figure 9. This requires that the process flow diagram be converted to a simulation flowsheet as discussed in Section 4. The listing is given in Figure 9. gas recycle (S4). to provide an excess of hydrogen. R1 for the reactor. As discussed earlier. H1.d. while liquid is taken as cyclohexane product S16. In the cooled reactor. As shown.g.25. and a cyclohexane recycle (S5) to produce the combined reactor feed (S6). which is the Chao-Seader CD-9-46 . into a hydrogen-rich vapor and a cyclohexane-rich liquid. for the operation.166% of the vapor from this flash drum is purged to stream S11 at line tee D1. The bottom name. As discussed earlier. where the flowsheet topology is followed by the list of components with user-selected names followed by data bank names.

molar entropy. it is seen that an overall excess of CD-9-47 . S1 and S3. Figure 9. the tear streams. molar vapor and liquid fractions. temperature. for a selected value of T0. and a convergence method.1400 or 99. initial component flow rates of zero for the tear streams. where component and total molar flow rates. The ASPEN PLUS program concludes with the operating conditions for each simulation unit.27.method with the Grayson-Streed constants for estimating K values and the Redlich-Kwong equation of state for obtaining the departure functions for the effect of pressure on enthalpy and entropy. density. B. The availability function. is readily computed from its definition. it is seen that the overall yield of cyclohexane from the process is 91. However. All mixture enthalpies and entropies are referenced to the elements at 25oC.26 are given in Figure 9. and average molecular weight are listed.24). ASPEN PLUS selects. pressure. no recycle convergence method is specified in the ASPEN PLUS program. In Figure 9. two recycle loops are clearly seen. follow. (9. Specifications for the two inlet streams. molar enthalpy. by default.25. Accordingly. energy and entropy balances automatically account for enthalpy and entropy changes due to chemical reaction.25 ASPEN PLUS flowsheet for the cyclohexane process. By comparing streams S3 and S16.2899/92. Therefore. By comparing streams S1 and S16. This greatly simplifies the calculations when chemical reactions occur as in this cyclohexane process. The converged results of the simulation for the ASPEN PLUS program in Figure 9. Eq.08%. and the flowsheet does not show the convergence units.

5 Net Energy Transfer Rate for the Simulation Units in the Cyclohexane Process Operation R1 H1 K1 P1 P2 Net Energy Transfer Rate 4.26 ASPEN PLUS input in paragraph form for the cyclohexane process. H1.457.2899] .230 Bhp in 3.[(282. The energy balance results are summarized in Table 9. where the net energy transfer rates are listed for each operation. Figure 9.288 Bhp in CD-9-48 . Examination of stream S4 or S12 shows that relatively little N2 is recycled.32% H2 is used. and the partial condenser.5.9599/3)/91.0 or only 3. The amount of cyclohexane recycle in stream S5 or S13 is considerable compared to the benzene feed S1.200 Btu/hr out 3. Table 9.704.1.455 Bhp in 0.300 Btu/hr out 5. and are considerable for the reactor. although the amount is large relative to the N 2 in the makeup hydrogen. R1.

Figure 9.27 Converged results for process streams of the cyclohexane process. CD-9-49 .

CD-9-50 .Figure 9.28 Second-law analysis of the cyclohexane process.

The fraction of the total lost work for each operation is as follows: Operation % of Total Lost Work Feed pump P1 Recycle pump P2 Recycle compressor K1 Mixer M1 – Reactor R1 Cooler H1 – Flash F1 Flash F2 with valve Total 0.00 This table shows clearly that the reactor and cooler are.52 24. The overall efficiency is only 25. the largest contributors to the inefficiency of the process. as shown in Figure 9.7%.23 0. The dead-state temperature is taken as 100oF. The calculation of lost work for the entire process and the corresponding second-law efficiency is carried out conveniently on a spreadsheet by transferring results from ASPEN PLUS.55 0.02 0. Some reduction in lost work can be achieved by replacing the partial condenser with two or three heat exchangers operating with coolants at different temperature levels. by far. CD-9-51 .The results in Figure 9. But what can be done with the reactor? Would it be better to operate it at a lower or higher temperature? Should a larger excess of hydrogen be used? Clearly.27 and Table 9.56 100. Note that the availability function for each stream can be computed and printed by ASPEN PLUS. See Exercise 9.12 74. Similar analyses are carried out readily for the separate operations in the process.28. there is room for considerable improvement in the reactor operation.23.5 are used to perform a second-law analysis.

3rd edition. J.. Elementary Principles of Chemical Processes. Wiley. Sonntag.. ‘Ein Neues Wort Fur Technische Arbeitfahrigkeit”. British Journal of Applied Physics. 2. Know the differences between and the limitations of the first and second laws of thermodynamics. Wiley. the reader should 1.J. New York (1994). T. Winter (2001).. Availability (Exergy) Analysis – A Self Instruction Manual. “Analysis and Simulation of a Solar-powered Refrigeration Cycle. 22. New York (2000). Fundamentals of Classical Thermodynamics. M. and R.M. and C. Eng.” Chem. Sommerfeld.9.W. 4th edition. R.. 4.10 SUMMARY Having studied this chapter. van Wylen. 3. V. Keenan . Exergie. Sussman. Rousseau. REFERENCES Felder. CD-9-52 . Z. Be able to use a process simulator to compute lost work and second-law efficiency. Borgnakke. Forschung Ing-Wes. H. G. Understand the concepts of the irreversible change in entropy and lost work or exergy.E. J.. Educ. 36-37 (1956). 2. “Availability and Irreversibility in Thermodynamics”. Be able to pinpoint major causes of lost work in a process and determine ways to improve the efficient use of energy. 1. R.. Tufts University (1980). Rant.. 183-192 (1951).

compute the temperature of Reservoir B.1 kW.1 A stream of hot gases at 1.EXERCISES 9. compute its a. having a specific heat of 6. Compute the lost work. is compressed from 1 to 50 atm while its temperature rises from 25 to 150 oC. How much does its availability change per mole? 9.000 Btu/hr. ∆TAB.5 The rate of heat transfer between Reservoir A at 200oF and Reservoir B at 180oF is 1. Thermodynamic efficiency 9. and 100 lb/hr is compressed to 200 psia.9 cal/mol-oC.000oC. The electrical work is 4.6 Nitrogen gas at 25oC and 1 atm. What is the maximum work per mole that can be obtained when the gas is returned to 25oC and 1 atm? CD-9-53 . Lost work b. a. For the same heat duty and lost work. Assuming an ideal gas. Adjust the temperature of Reservoir A to 10oF. with Cp = 7 cal/mol-oC. Lost work b. is used to preheat air fed to a furnace. Isentropic efficiency 9.3 Superheated steam at 250 psia and 500oF is compressed to 350 psia. compare? How do the approach temperatures. 9. the hot gas cools to 700oC before it enters the air preheater. Because of insufficient insulation. For the compressor. The isentropic efficiency of the compressor is 70%. calculate the minimum work per mole required for cooling.4 Steam at 400oF. How much availability per mole does it lose? 9. Thermodynamic efficiency c. Determine the a. b.2 An ideal gas. with Cp = 7 cal/mol-K. is cooled to -100oC at 1 atm. 70 psia.

5 lb/hr steam at 550 psia. are mixed as shown: a. Lost work c.7 An equimolar stream of benzene and toluene at 1. each containing 0.9.8 and 4.000 lb/hr of saturated water at 600 psia is superheated to 650oF and expanded across a turbine to 200 psia. Assume that the heat is transferred to an infinite reservoir of cooling water at 77 oF.9 Two streams. determine the lost work associated with the cooler.10 1. 9. Change of availability upon mixing b. a. b. 9. CD-9-54 .8 Consider the cooler.3 lbmol/hr and 50oF. Thermodynamic efficiency 9. as discussed in connection with Figures 4. Compute the lost work and thermodynamic efficiency.9. Using the enthalpy and entropy values in the results for the sample problem in the ASPEN PLUS section of the CD-ROM that accompanies this textbook.24. b. in the monochlorobenzene separation process in Figure 4. H2. Let the reservoir be at 100oF and repeat (a). Assuming ideal vapor and liquid mixtures. Compute the heat loss to an environmental reservoir at 77oF.000 lbmol/hr and 100oF is mixed with a toluene stream at 402. use a process simulator to compute the a. as illustrated.23 and 4.

9 kW of shaft work are produced. Isentropic efficiency of the turbine b.12 Calculate the minimum rate of work in watts for the gaseous separation at ambient conditions indicated in the following diagram. The turbine exhaust is cooled by a 77oF reservoir to its dew point at 400 psia. Isentropic efficiency of the turbine c. 0. Flow rate of steam in lb/hr b. Determine the a. Thermodynamic efficiency of the process 9. Lost work for the process c. Thermodynamic efficiency 9. CD-9-55 .Calculate the a.11 Superheated steam at 580 oF and 500 psia is expanded across a turbine. as shown below. to 540oF and 400 psia. Lost work d.

Lost work c.95 0.920 0.27 0.9 15 -3.98 0.14 For the adiabatic flash operation shown below.05 4.13 Calculate the minimum rate of work in watts for the gaseous separation at ambient conditions of the feed indicated below into the three products shown.642. calculate the a. 1.08 91.03 0.78 4.000 Btu/hr-oR 0.22 0.69 Stream 2 119. 1. psia Enthalpy.860 CD-9-56 .08 91. lbmol/hr Stream 1 Stream 2 Stream 3 H2 N2 Benzene Cyclohexane Temperature.000 Btu/hr Entropy.627.21 0.92 Stream 1 120 300 -3.00 0.23 Stream 3 119.094 0.9 15 -14. oF Pressure. Change in availability function (T0 = 100 oF) b. 9. Thermodynamic efficiency Flow rate.9.01 0.

Rate of heat addition b. Calculate the a. Thermodynamic efficiency CD-9-57 .15 Consider the results of an ASPEN PLUS simulation of the following flash vessel: Heat is obtained from a large reservoir at 150oF. Lost work c.9.

84 3.29 14.80 0.68 241.05 4.61 0.60 0.13 21.00 Stream 1 392 315 Stream 2 65.15 7.05 56.62 0.02 -3.00 0.9. 1. Condenser duty b. 1. Lost work d.76 2.01 0.231.000 Btu/hr Entropy. oF Pressure.13 0. Thermodynamic efficiency Flow Rate.92 Stream 5 120 300 -2.53 7. Assuming that T0 = 70oF.98 0.19 -2.303.22 0.000 Btu/hr-oR Stream 1 72.92 CD-9-58 .13 150.00 1.642.14 Stream 3 120 300 Stream 4 0. psia Enthalpy.08 91.98 0. Change in availability function c. lbmol/hr H2 N2 Benzene Cyclohexane Temperature.33 Stream 4 120 300 Stream 5 0.61 Stream 2 120 300 Stream 3 5. calculate the a.16 A partial condenser operates as shown below.

9. Change in availability function in Btu/hr c. and a reboiler steam temperature of 250oF. as shown in Figure 9. and Hp d. use ASPEN PLUS with the RADFRAC distillation model to simulate the column operation. with T0 = 80oF. Thermodynamic efficiency Figure 9. Irreversible production of entropy.29. into ethane-rich and propane-rich fractions. CD-9-59 . Lost work in Btu/hr. Using the results of the simulation. Btu/hr-oR b. Based on the specifications given and use of the Soave-Redlich-Kwong equation for thermodynamic properties.29 Distillation process for Exercise 9. a condenser refrigerant temperature of 0oF. calculate the a. kW.17.17 A light-hydrocarbon mixture is to be separated by distillation.

Change in availability function in Btu/hr c. calculate the a. Lost work in Btu/hr.30 Thermally coupled distillation process for Exercise 9. together with use of the Peng-Robinson equation for thermodynamic properties. Irreversible production of entropy.30.18.9. as shown in Figure 9. use ASPEN PLUS with the MULTIFRAC distillation model to simulate the column. kW. and Hp d. Using the results of the simulation.18 A mixture of three hydrocarbons is to be separated into three nearly pure products by thermally coupled distillation at 1 atm. Figure 9. with T0 = 100oF. Btu/hr-oR b. Thermodynamic efficiency CD-9-60 . Based on the specifications given and other specifications of your choice to achieve reasonably good separations.

(b) reboiler.55.9.19 Consider the hypothetical perfect separation of a mixture of ethylene and ethane into pure products by distillation as shown in Figure 9. at which the average relative volatility is 1. Thermodynamic efficiency Other thermodynamic data are Latent Heat of Vaporization (Btu/lbmol) 4. Calculate for each scheme: a. Change in availability function (T0 = 100oF) b.31 Distillation process and data for Exercise 9.751 5. In both cases the column will operate at a pressure of 200 psia. is to be used. A reflux ratio of 1.19: (a) distillation. Two schemes are to be considered: conventional distillation and distillation using a heat pump with reboiler liquid flashing. as computed from the Underwood equation.10 times minimum. Lost work c.473 Ethylene at 200 psia Ethane at 200 psia Ethane at 90 psia CD-9-61 .31. Other conditions for the scheme using reboiler liquid flashing are shown below.348 4. Figure 9.

determine the shaft work delivered by the turbine. a. 2. at 550 K and 1. Compute the lost work for the turbine. 9. The reaction is very exothermic. Compute the thermodynamic efficiency for the turbine. What is the temperature of the feed to the turbine? c. b.20 Consider a steam engine that operates in a Rankine cycle. b.1 bar. as illustrated below: The turbine exhaust is a saturated vapor. Adiabatic reaction.21 (Example 9. and 0. The fractional conversion of sulfur dioxide is 50%. Compute the a.9.058 kmol/s of oxygen.219 kmol/s of nitrogen.7. 3. respectively. consists of 0. CD-9-62 . Three cases are to be considered: 1.22 For the revised propane refrigeration cycle in Figure 9. Thermodynamic efficiency of the cycle.9 and 0. 0.3). d. compute the lost work in kW. Isothermal reaction with the heat of reaction transferred to boiler feed water at 200oC. 9. with excess oxygen from air. Find the saturation temperature of the turbine exhaust.21 A reactor is to be designed for the oxidation of sulfur dioxide. to sulfur trioxide. Isothermal reaction with the heat of reaction transferred to boiler feed water at 100oC. For an isentropic efficiency of 90 percent. The entering feed. let the isentropic efficiencies of the turbine and compressor be 0. For each case. Lost work for the four process units and the entire cycle.028 kmol/s of sulfur dioxide.

determine the refrigerant flow rate and the brake horsepower for the compressor. as well as the lost work for each piece of equipment. a portion of the condensate is pumped to an elevated pressure. Assume that the ambient air is at 100°F and 95% humidity on a hot summer day and is rejected at 100% humidity. CD-9-63 . Assuming an isentropic efficiency of 70% for the compressor. The condensing medium is water at 85°F. In addition to the conventional refrigeration loop. where it is vaporized using solar energy or low-temperature waste energy in a chemical complex. 9.000 tons.9. Calculate the lost work and thermodynamic efficiency.5 to reduce the lost work and increase the thermodynamic efficiency. Use a simulation program to complete the material and energy balances. c. and compute the entropies and availability functions for all of the streams. Select a refrigerant and its operating pressures. which was proposed by Sommerfeld (2001). 9. the cooling capacity is 20.32. Calculate the flow rates of the chilled water and condenser water in gal/min.23 Alter the design of the cyclohexane process in Example 9. which is heated to 95°F as it absorbs heat rejected from the refrigerant. For Phase I of the plant. in which it is sprayed over a stream containing ambient air. b. A refrigerant is vaporized in the refrigerant condenser at 38°F. as it removes heat from warmed water. The refrigerant is condensed to a saturated liquid at 98°F.24 The chilled-water plant at the University of Pennsylvania sends chilled water to the buildings at 42°F and receives warmed water at 55°F. a. The warmed condenser water is cooled in a cooling tower.25 Consider the solar or waste-heat refrigeration cycle in Figure 9. Its saturated vapor effluent is expanded to recover power in a turbine and mixed with the gases from the compressor.

the three operating pressures. lost work.saturated liquid at 125°F Solar or waste-heat available at 220°F Solar or waste-heat collector effluent . Determine the flow rates of refrigerant in both loops. and thermodynamic efficiency for the refrigerator. the condenser and collector heat duties. pump. Vary the condenser effluent temperature to determine its effect on the solution in part a.Figure 9.saturated vapor at 40°F Condenser heat rejected to environment at 77°F Condenser effluent . the power consumed or generated by the compressor. b.saturated vapor at 200°F Isentropic efficiency of the compressor = 70% Isentropic efficiency of the turbine = 90% Isentropic efficiency of the pump = 100% a.32 Solar or waste-heat refrigeration cycle. and turbine. CD-9-64 . Use a process simulator to solve the material and energy balances for the following specifications: R-134a refrigerant 4-ton refrigeration load at 20°F Refrigerant evaporator effluent . the coefficient of performance.

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ASPEN ICARUS PROCESS EVALUATOR (IPE) Equipment Sizing and Costing Using ASPEN PLUS to Initiate Evaluation Notes prepared by: Robyn B. Nathanson Warren D. Seider University of Pennsylvania May 2003 Previous versions were coauthored with: Holger Nickisch Maizatul Zain University of Pennsylvania Robert Nedwick Pennsylvania State University .

ASPEN IPE CAPITAL ESTIMATE REPORT FOR THE DEPROPANIZER APPENDIX IV .DEPROPANIZER – ASPEN PLUS REPORT APPENDIX II .CONTENTS INTRODUCTION PREPARING AN ASPEN PLUS SIMULATION FOR ASPEN IPE Additional Mixture Properties INVESTMENT ANALYSIS USING ASPEN IPE DEPROPANIZER Initial Setup Mapping Process Simulation Units into Aspen IPE Standard Basis Equipment Costing Total Permanent Investment Adding Equipment Applying Alternative Utilities MONOCHLOROBENZENE SEPARATION PROCESS Initial Setup Mapping Process Simulation Units to Aspen IPE Standard Basis Equipment Costing Total Permanent Investment ASPEN IPE FOLDERS AND FILES REFERENCES APPENDIX I .ASPEN IPE CAPITAL ESTIMATE REPORT FOR THE MONOCHLOROBENZENE SEPARATION PROCESS 1 2 3 3 3 3 8 17 19 25 25 34 37 37 39 45 45 50 51 51 52 58 61 70 CD-IPE-i .DESIGN CRITERIA SPECIFICATIONS APPENDIX III .

and (4) estimate purchase and installation costs. Aspen IPE is a software system provided by Aspen Technology. Aspen IPE usually begins with the results of a simulation from one of the major process simulators (e. After completing these notes. and the profitability of proposed designs.4 of the textbook (Seider et al.bkp.4 and 17. CHEMCAD. alternatively. as shown in Figure 1.g. and profitability analyses. Version 11. all of the calculations were carried out using Aspen IPE. Aspen IPE has an automatic. Inc. and for improvements in new versions of the software system. Instructions are provided to prepare an ASPEN PLUS simulation for use with Aspen IPE. electronic expert system which links to process simulation programs. explanations. for economic evaluation of process designs. In these notes. The depropanizer is a distillation tower to recover propane and lighter species from a normal-paraffins stream. Additional features of Aspen IPE are introduced for a more complete process.21 in the textbook. 3. only results from ASPEN PLUS are used to initiate Aspen IPE evaluations and only capital cost estimation is emphasized. A copy of the simulation file. It determines the capital expenditure. and PRO/II). It is used to (1) extend the results of process simulation. the monochlorobenzene (MCB) separation process.. is provided on the CD-ROM. MCB. is provided on the CD-ROM that contains these notes. provide equipment specifications and request investment analysis without using the process simulators.. the total capital investment. Also. 2. it being noted that users can. ASPEN PLUS. A depropanizer example is provided to illustrate the use of Aspen IPE. to practice estimating capital costs using Aspen IPE. Readers should refer to the Aspen IPE User’s Guide (press the Help button in Aspen IPE) for detailed instructions. operating costs. with the design and cost basis date being the First Quarter 2000. (2) generate rigorous size and cost estimates for processing equipment. indirect costs. a copy of the file. which is discussed in Sections 4.bkp. RADFRAC. In these notes.. the engineering-procurement-construction planning schedule.INTRODUCTION These notes are prepared to provide a step-by-step procedure for estimation of the total capital investment using the Aspen Icarus Process Evaluator (Aspen IPE). CD-IPE-1 . HYSYS. The simulation flowsheet and selected results are shown in Appendix I and in the multimedia tutorial on the CD-ROM that contains these course notes (ASPEN → Tutorials → Separation Principles → Flash and Distillation). you may wish to solve Exercises 16. (3) perform preliminary mechanical designs. 2004). These notes are organized as follows: 1.1.

For the steps when using the other process simulators. While this is accomplished in a similar manner for most of the major process simulators.Figure 1 Depropanizer PREPARING AN ASPEN PLUS SIMULATION FOR ASPEN IPE To estimate equipment sizes and costs using Aspen IPE for a process simulated with ASPEN PLUS. such as viscosity. it is necessary to augment the simulation report files with estimates of mixture properties. it is necessary to prepare the simulation results for use with Aspen IPE. It is normally necessary to adapt the simulation file in two ways. to estimate equipment sizes. the reader should refer to the Aspen IPE User’s Guide (press the Help button in Aspen IPE). For this reason. Aspen IPE usually requires estimates of mixture properties not needed for the material and energy balance. and phase equilibria calculations performed by the process simulators. these notes focus on the steps to prepare ASPEN PLUS simulations. CD-IPE-2 . thermal conductivity. First.

a copy of which is on the CD-ROM that contains these notes. for example. the Import entry and the PROPSETS. RADFRAC. select Setup and then Report Options. Aspen IPE requires specifications to estimate equipment sizes that are not computed by some of the approximate simulation models.bkp (which is available on the CDROM that contains these course notes). Aspen IPE automatically adds three new property sets.apt file on the CD-ROM that contains these course notes. This Aspen Icarus from the File pull-down menu in is accomplished by selecting Send To ASPEN PLUS. To accomplish this. DEPROPANIZER This example involves the single distillation column shown in Figure 1. INVESTMENT ANALYSIS USING ASPEN IPE In this section. Additional Mixture Properties Estimates for the additional stream properties are added using the PROPSETS.g.. Note that it is also possible to provide specifications for computing equipment sizes without using ASPEN PLUS. using the Data pull-down menu. display the Streams page by selecting the appropriate tab and click the Property Sets button. Second. Observe that all three Aspen IPE property sets have been entered into the Selected Property Sets box. To check that this has been accomplished. after which the file can be saved as RADFRAC-IPE. e. Now that the Aspen IPE property sets have been added.apt file are selected. Under the File pull-down menu.and surface tension. This replacement can be viewed as the first step in computing equipment sizes and costs. These must be replaced by more rigorous models. the ASPEN PLUS simulation file is opened first. with its simulation flowsheet and selected results shown in Appendix I and on the multimedia tutorial on the CD-ROM that contains these course notes (ASPEN → Tutorials → Separation Principles → Flash and Distillation). This is the case. Initial Setup Having sent the ASPEN PLUS simulation file to Aspen IPE. Then. the use of Aspen IPE for equipment sizing and costing is illustrated for a depropanizer and for the monochlorobenzene separation process. it is necessary to re-run the simulation.bkp. for the streams in the simulation flowsheet. such as the RADFRAC and RPLUG models. The simulation results are loaded automatically into Aspen IPE. when the DISTL and RSTOIC models are used in ASPEN PLUS. It remains to transfer the ASPEN PLUS simulation results into Aspen IPE. it is opened automatically and the Create New Project dialog box appears: CD-IPE-3 .

The narror Project Explorer. Note that the underscore and space characters are permitted. however punctuation marks are not allowed. The first is the Project Properties dialog box. A units of measure set is also chosen. The Project Name RADFRAC-IPE is assigned automatically from the ASPEN PLUS file name. appear. Double-click on Design Criteria to cause the Design Criteria-IP form to appear in the Main window: CD-IPE-4 . Palette and Property. and a wider Main window. not shown here. This form allows the user to customize the units of measure that will appear on input specification forms. can be opened using the View pulldown menu.The user can either select an existing project in which to start a new scenario. Aspen IPE now opens two windows shown below. press the OK button. the Load Simulator Data? dialog box is displayed. Note that the Design Criteria and Utility Specifications entries under the Process Design heading are the most relevant when estimating equipment sizes and costs. Since no adjustments are needed in this example. is in Project View mode. so enter the Project Name DEC3 instead. Fourth. This can be done by selecting the Project Basis View tab in the Project Explorer. or enter a new Project Name. The first step in completing this simulation is to examine the project Design Criteria. the Input Units of Measure Specifications dialog box is displayed. These are the basis for sizing the equipment and for specifying its utilities. Third. in which a Project Description and further remarks may be entered. on the left. which for this example is the Inch-Pound (IP) units set. the General Project Data dialog box appears. After pressing the OK button. the first of four dialog boxes. is on the right. initially blank. Aspen IPE allows the user to specify many parameters for equipment sizing or to accept default values. Enter Yes to do so. Click the Close button to accept the default settings. Note that two additional windows. Second.

For this purpose. For implementation details.Default values are provided for many of the entries. as well as to other tower information. but they can be modified as necessary. the Utility Specifications entry under the Process Design heading is selected to produce the Develop Utility Specifications dialog box: CD-IPE-5 . see the Aspen IPE User’s Guide. The user must be careful to check all of the relevant specifications that apply to the equipment under study. Note also that design criteria files can be created for use with other design projects. Particular attention should be paid to the design pressure and temperature. to the overdesign factors. with the values specified for the depropanizer process shown in Appendix II (Defining the Project Basis → Process Design → Design Criteria). which can be accessed using the Help button in Aspen IPE. and missing entries can be entered. it is usually important to examine the default values associated with the utilities. Also. to the residence times in the process vessels. Note that the design criteria are defined in the Aspen IPE User’s Guide.

double-click on the Cooling Water entry. For example. CD-IPE-6 . because the textbook recommends that process designs accept cooling water at 90°F and heat it to 120°F. Other default values can be changed similarly. the inlet and exit temperatures are changed to 90 and 120°F. Click OK when finished. and missing utilities should be added. Default values should be examined and modified. which produces the Utility Specifications dialog box: Then.Note that all existing utilities to be used by Aspen IPE are listed. it is necessary to replace the temperatures associated with the cooling water utility. To modify these temperatures.

the Close button is pressed to return to the IPE Main window. click on the Create option on the Develop Utility Specifications dialog box. When complete. low-pressure steam is added as a utility. where the entries have already been made from the steam tables of Smith et al. After the Create button is pressed. (2001). the new utility is displayed as shown below. Note that utility files can be created for use on other design projects.To add a utility not in the existing utility list. see the Aspen IPE User’s Guide. CD-IPE-7 . For implementation details. As shown below. Then. the OK button is pressed to return to the Develop Utility Specification dialog box. which is named Steam @50PSI and has the Steam Fluid Class.

with just one tower. it may be preferable to map each process unit independently. After pressing OK. the Default and Simulator Data button should be selected. if two distillation towers differ in tray efficiency. Note that the mapping and equipment sizing steps are accomplished in sequence. all items are mapped and sized in sequence. To begin the mapping step in the IPE Main window. For example. Also. blocks. After Aspen IPE completes the mapping and reserves storage for the installation items. condenser. or subroutines) into more descriptive models of process equipment (e. as shown. insulation. More information and definitions are provided in the Aspen IPE User’s Guide (Defining the Project Basis → Process Design). the Project Component Map Preview dialog box is produced: CD-IPE-8 . Mapping Process Simulation Units into Aspen IPE Having completed the initial setup. mapping a HEATX simulation unit into a floating-head. equipment sizes are computed. the next step is to map the process simulation units (that is.Other specifications can be changed in a manner similar to those described for the utilities and design criteria. with sizes and costs of the installation items estimated during the Equipment Costing step. the Map Simulator Items button on the toolbar is pressed to produce the Map dialog box: For the depropanizer. Under Basis. which include installation items. reflux accumulator. paint. etc. modules. when there are multiple process units of a certain type.g. In this case. such as piping. it is simplest to press the Map all Items button under Source. etc..) and associated plant bulks. only the mapping step is completed. instrumentation. mapping a RADFRAC simulation unit into a tray tower. since the Size ICARUS Project Components button is checked. it is necessary to map them separately and change the tray efficiency under Design Criteria before each tower is mapped. shell-and-tube heat exchanger. When this button is not checked.

the configuration is switched from Standard-Total to Full-Single. Furthermore. In this example. each equipment item has a specific type assigned by Aspen IPE that can be modified. a reboiler pump will be added. a distillate pump. five equipment items are included: TW-TRAYED (tower). the RB U-TUBE reboiler is deleted by highlighting it and pressing Delete One Mapping: CD-IPE-9 . Note also that to include a reboiler (bottoms) pump. and two product heat exchangers. To begin. For this example. and RB U-TUBE (reboiler). Note that the two C entries denote stream splitters. Standard-Total. HT HORIZ-DRUM (reflux accumulator).For each Simulator Item (unit or block). highlight the item to be modified. HE FIXED T-S (condenser). CP CENTRIF (reflux pump). the Current Map List shows all corresponding equipment items in Aspen IPE. Observe that for the default configuration. the kettle reboiler with U-tubes is replaced by a kettle reboiler with a floating head. To modify the equipment type. as discussed in the section on Adding Equipment.

Heat Exchangers. CD-IPE-10 . heaters is highlighted on the ICARUS Project Component Selection dialog box that appears. Next.New Mapping is pressed and reb is highlighted on the screen that appears. OK is pressed. Then. Reboiler is chosen from the dialog box that appears. and finally a Kettle type reboiler with floating head is selected as the last step of the replacement procedure. and OK is pressed.

press OK to continue and wait for the equipment mapping and sizing to be completed.After these steps are completed. CD-IPE-11 . When the desired changes are completed. for the condenser. For example. the modified mapping should appear on the Project Component Map Preview dialog box: Other mappings can be altered in a similar fashion. the mapping is altered from a shell-and-tube heat exchanger with a fixed tube sheet to one with a floating head.

the equipment items have been sized by Aspen IPE (because the Size ICARUS Project Components button was checked in the Map dialog box). it is possible to view the IPE Process Flow Diagram. As each equipment item is sized. This is accomplished using the View pulldown menu and clicking on Process Flow Diagram to produce: CD-IPE-12 . Also note that user-inputted equipment items. alerting the user to provide a specification(s) so that the equipment-sizing step can proceed. The yellow arrows inside the boxes indicate that the equipment item was obtained from the mapping of a process simulation unit. Note that the Project Explorer window displays the Process View: The blue boxes to the left of each item in the list indicate the Project Components. whose calculations are based upon the simulator data. as well as the default values specified earlier. such as a reboiler pump (not included in the above frame). The OK in the Status column of the Workbook indicates that the minimum required information for costing the equipment is available. Note that by default Aspen IPE lists all of the equipment items in the Workbook Mode.At this point. To add these equipment items. that is. The List tab at the bottom of the Main window denotes that the equipment items are listed in the Workbook Mode. are represented in the Workbook by blue boxes without the yellow arrow. see the section Adding Equipment. When one or more items are missing. the List window. it appears in the Aspen IPE Main window as a list. In addition. a question mark appears instead. as shown above. whose name appears after its box.

It is also possible to view a list of the process streams utilized by Aspen IPE. Using the View pulldown menu. that is.Note that the unit icons and streams have been repositioned using “drag and drop” facilities. click on Streams List to produce: CD-IPE-13 . a list of all streams and their physical properties in the Process Flow Diagram.

For example. it is a good practice to estimate equipment sizes independently for comparison with the Aspen IPE results. and chemical reactors. compressors. and consequently. it is prudent to check the results. especially for major equipment items such as towers. These items are usually very expensive. is obtained for the depropanizer tower. which contains some of the sizing results. CD-IPE-14 . It is displayed using the View pulldown menu and clicking on Block Flow Diagram to give: Mapping Results. After Aspen IPE has mapped and sized the equipment items.Finally. the following component specification form. double click on the item on the IPE Workbook window or on its icon in the Process Flow Diagram. the IPE Block Flow Diagram shows the simulation flowsheet. To view the Aspen IPE results for an equipment item.

Aspen IPE calculated a design temperature and pressure in accordance with the Design Criteria specifications. A more detailed report can be obtained in two ways. Alternatively. With a 2-ft tray spacing. which is 12/0.8 = 15. a high-strength alloy. alloy types. As changes are made. Material codes. A285C (which is for carbon steel plates in pressure vessels that have low and intermediate strength). and maximum service temperatures are tabulated in the chapter on Materials Selection in the ICARUS Reference Manual (press the Help button in Aspen IPE and follow the path Aspen Icarus Process Evaluator 11. used the default shell material. Changes can be made to any of the equipment sizes computed by Aspen IPE or to the default values used by Aspen IPE. as shown by Aspen IPE. excluding the condenser and reboiler) divided by the tray efficiency (0. In some cases.1 → Icarus Reference). First. Furthermore. Note that the number of trays is the number of equilibrium stages (12 = 14 – 2.Observe that the depropanizer tower was designed by Aspen IPE to have a 5 ft diameter and a 42 ft (tangent-to-tangent) height using sieve trays.8). may have thinner walls and be less expensive than a low-strength material that is less expensive per pound. Also. a 4-ft high disengagement region at the top and a 10-ft high sump at the bottom. right click on the equipment item in the Process Flow Diagram and select Item Report in the menu that appears. the effect of material on size and cost can be determined easily. A515 (which is carbon steel for pressure vessels at intermediate and higher temperatures). dependent results are adjusted by Aspen IPE. right click on the equipment item in the Project View of the CD-IPE-15 . the nominal vessel tangent-to-tangent height is 2 × 14 + 4 + 10 = 42 ft. that is more expensive per pound. and used the default tray material.

a portion of which is illustrated here for the condenser: Note that only a small portion of the Item Report is shown above. 12. shell-and-tube heat exchanger in parallel for condensing the overhead vapor. At this pressure. Using cooling water heated from 90 to 120°F. at a higher pressure the separation would become somewhat more difficult. These steps produce the Item Report. is quite large because the log-mean temperature difference. CD-IPE-16 . resulting in more trays. It might be preferable to increase the column pressure to increase the log-mean temperature difference and reduce the condenser area. It might be possible to improve the condenser design by resizing the unit with different numbers of shell and tube passes to give a correction factor close to unity. the distillate enters the condenser at 125°F and leaves as a saturated vapor at 115°F. However. Note that Aspen IPE can easily compare the capital costs at various pressures. The raw surface area. 9. (13.7°F.7)] of 0.Project Explorer in the Main window (or in the List View) and select Item Report in the menu that appears.635. is relatively small. The number of tube and shell passes for each exchanger can be seen on the report produced by double clicking on the condenser in the IPE Workbook window or on the condenser icon in the Process Flow Diagram. This is related to the condenser pressure which was set at 248 psia. the small logmean temperature difference is obtained. Note also that Aspen IPE used two floating-head.652 ft2. Each condenser has two tube passes with a temperature correction factor [FT in Eq.

and the other three are for projects to be executed by Engineering and Construction firms (3. and 2). wage rates. To select a standard basis profile for a project. right-click on the Basis for Capital Costs. Default values are provided for all entries. Double-click the General Specs entry under the Basis for Capital Costs heading to produce the Standard Basis-IP dialog box: CD-IPE-17 . For the small depropanizer project of this example. The Basis for Capital Costs includes specifications for process controls. When modifying the Basis for Capital Costs. depending on the size of the project. and contractor profiles. plant location.Standard Basis Six standard basis profiles are available within Aspen IPE for estimating the capital cost. most of which need not be adjusted. changes can be made to the General Standard Basis Specifications or to the Construction Workforce and Indexing. Three of the profiles are for projects to be executed by an Owner company (0. These model the nature of the contractor to execute the project. units of measure. 4. and 5). Click Select to choose the most appropriate profile. To view the General Standard Basis Specifications. currency. in the Project Basis view. as shown below. 1. the Project Basis tab is selected in the Project Explorer. the LOCAL CONTRACTOR is appropriate.

the default values and items included or omitted can be observed. Typically. these include a new control system and electrical substation components. the Project Type would not be selected as Grass Roots/Clear field. CD-IPE-18 . are not provided. already provided at the site. costs can be computed for each option. Because a single distillation system would be installed normally on an existing plant site. most of the default values are acceptable. if desired. and transformers. items involving the new control system.For the depropanizer column. electrical switchgear. This Project Type would cause new items. These are not needed for the addition of the depropanizer column to an existing process. Through examination of the results. click on the Value field to produce a pulldown menu that displays the options: Grass Roots/Clear field Plant addition – adjacent to existing plant Plant additions – inside existing plant Plant addition – suppressed infrastructure Plant modification/Revamp While guidelines are not provided concerning the selection of Project Type. When selecting Plant addition – suppressed infrastructure. using utilities provided by the site. Under Project Type. to be included in the design and cost estimates.

which includes the cost of the tower and setting it in place on its foundation (civil). structural steel (e. It does not include: (1) the fractional cost of buildings. For the depropanizer tower. guard houses.600. the entire project) using a single command.100 and an Installed Direct Cost of $192. freight to the site. and (3) taxes. chemical and storm sewers and drains. by scrolling about a third of the way down the report. pipe racks.. fences. the project control system or electrical substations. etc. royalties.Equipment Costing Aspen IPE estimates the purchase and installed cost of each equipment item individually or provides estimates for all of the equipment items (i. electrical lighting. the foundation to support the tower. right click on the unit in the List View and select Evaluate Item. piping. Be aware that the Total Material and Manpower Cost is the cost of the equipment item and the direct cost of installation materials and labor (directly related to the equipment item).. and to manage the engineering process. These include the piping and field instruments that bring the process streams to and from the tower. and fireproofing. the designer can observe the effects of modifications in the design specifications on these costs for the unit. heat tracing. etc. fire control systems. ladders and platforms attached to the tower). treatment systems. to procure all project components. and local components.. Aspen IPE produces a detailed item report for the unit. For an individual unit. At this point. insulation. CD-IPE-19 .g. the following summary of the cost estimates appears: Observe that the tower designed by Aspen IPE has a Purchased (Equipment and Setting) Cost of $64. cable.e. permits. (2) the work required to perform basic and detail engineering.

To have Aspen IPE estimate the capital costs of all the units at once (i. CAP_REP. cost of pipe racks and intra-plant piping. and Run Summary spreadsheets. mark the Evaluation Reports checkbox and press the OK button. If you prefer a different name.3 of the textbook. Utility Summary (available in Version 12. the total material and manpower cost is not the total bare module cost discussed in Section 16. Note that when the Interactive Reports checkbox is pressed. Furthermore. charges for instrument testing. press the Evaluate Project button on the IPE Main window. e. which can be added to the project as additional items. These costs are accumulated for each area that contains project components and are summed for the entire project. For the details of these spreadsheets. and the cost of sumps and sewers. CD-IPE-20 . indirect costs. the Aspen ICARUS Reporter dialog box is produced. The Evaluate Project dialog box appears. Aspen IPE displays a window that contains an executive summary of its results.g.. To view a detailed report of the capital costs. Executive Summary. enter it in the Report File field. because the report focuses on an equipment item and its associated installation items and costs. see the Aspen IPE User’s Guide (press the Help button and follow the path Aspen Icarus Process Evaluator User’s Manual → Evaluating the Project → Reviewing Investment Analysis).Consequently. Aspen IPE is activated to prepare several spreadsheets.. DEC3 as shown below. selects Options. This permits the user to select individual items to be examined rather than entire reports as discussed below. access the ICARUS Editor by pressing the Capital Costs ($) button on the IPE Main window.CCP. including the Equipment Summary. as discussed later in this section. The dialog box shows the default report file name. the entire project). and then View Spreadsheet in Excel. On the Select Report Type to View dialog box. The contents of this report are viewed in the ICARUS Editor.e. Note that when the user presses the Tools pulldown menu. materials and manpower items not typically charged to the tower (e. and equipment grounding) are excluded.. The estimate reported by Aspen IPE does not include contractor engineering costs. ProjSum. pipe testing. When finished with its evaluation.1). This window is not shown here.g.

working capital.xls. CD-IPE-21 .e. the List of Equipment and Bulk Material by Area portion of the report is displayed when the Equipment List is accessed. though necessary for obtaining accurate cost estimates. Equipment List 2. This provides the Purchased (Equipment & Setting) and Installed Direct Costs (i. Furthermore. Of greatest interest to process engineers. is the information in the following two sections: 1.8 of the textbook. These notes discuss capital cost estimation only because the spreadsheet.g. for whom these course notes are intended. is far too detailed for most estimates during the conceptual design stage. the reboiler as shown next. It is recommended that just small portions of the report be printed.0. 1 PRIME CONTRACTOR which are accessed by double-clicking on these titles in the left-hand window. e. Total Material and Manpower Cost or Total Direct Materials and Labor Cost) for each piece of equipment. This is achieved by pressing the Select Font button on the toolbar.The ICARUS Editor displays the report in two adjacent windows.. As shown below. as well as a complete profitability analysis. CONTRACTOR NO. is used to compute operating costs. Most of this information. Note that the right-hand window below is displayed using a 7point font. Aspen IPE computes annual operating costs. Profitability Analysis-1.. It is often preferable to print in landscape format. and profitability measures. with the major subject headings listed in the left-hand window. and hence. When the appropriate specifications are made. This is accomplished by highlighting the desired section and pressing the Print button on the toolbar. which is discussed in Section 17. the results of which appear in this Investment Analysis spreadsheet. portions of the complete printed output are provided in Appendix III of these notes. is normally not printed by process engineers.

000 $280.600 139.800 The Contract Summary section of the Capital Estimate Report is displayed when the CONTRACT NO.200 115.350 gal TOTAL Purchase Cost 64.0 ft diam. The entries shown below are in a 6-point font and are totals for all of the equipment items (i.300 Total Material and Manpower Cost 192.000 229. 1 PRIME CONTRACTOR is accessed. purchase costs.600 74.100 ft2 5.550 ft2/shell 2.600 35. 42 ft height 5 Hp 3. CD-IPE-22 . and total material and manpower cost for the depropanizer system (without the reboiler pump) are as follows: Simulation Unit D1 Equipment Item Tower Reflux pump Reboiler Condenser Reflux accumulator Size 5.200 52.400 $646. Note that selected portions of the complete printed output are provided in Appendix III of these notes.In summary..e.580 ft2 11.100 5. the entire project). the equipment sizes.400 19.

100. charges for instrument testing.500) and the Warehouse Spares ($370).300. These sum to $757.Note that the entry for the purchased equipment.200.400 and $152. pipe testing. Note that the installed costs of the equipment items are displayed on the List View: CD-IPE-23 . $289.. from line 1. is approximately the sum of the entries for the pieces of equipment provided above. Item Allowance ($8. as shown in line 11.500 and include items that cannot be charged to the individual equipment items (e. $280. and equipment grounding). The difference is due to the Misc.) The total direct material and manpower costs for construction of the plant are $605.g. These additional items are in Code of Accounts 105 and 107 and appear in the Code of Accounts Summary section of the Capital Estimate Report (just below the Contract Summary.

4564.TRAYS. is referred to in Chapter 16 of the textbook as the Total Direct Materials and Labor Cost. $108.JBOX. 2979. 192 127 4564. 3086. 7534. RUNS. 185.500. 2648. CDML. 138 2341. 8807. that is. 2124. $757. 16 0 344. 4352.700 less than the total direct cost of materials and manpower for installation of the plant. AREA AREA AREA AREA AREA AREA CD-IPE-24 . 10182. 231. 344. 14 0. 50.800.000 FEET 0. 0. Finally. 95 60 11 83 2124. 370. 370.The installed costs sum to $646. This Installed Direct Cost. CDI. the materials and manpower items that are not chargeable to the individual equipment items are displayed in the Area Bulk Report within the Capital Estimate Report: A R E A B U L K R E P O R T ================================================================================================================================= : : : : : M A N P O W E R : TOTAL : : : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT : :ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD: ================================================================================================================================= AREA MISC CONCRETE ITEMS 638. 416. 1266. EQUIPMENT GROUNDING PILED FOUNDATION Number of piles ELECTRICAL TESTING ROTATING EQP SPARE PARTS 0. 1407. AREA GRADE PIPE TESTING UNPAVED AREA Area length Area width INSTRUMENT TESTING INSTR. 10214.000 FEET 50.

These non-chargeable items add to $35. these are added to the total direct installed equipment costs. BASE TOTAL.500. material and manpower costs associated with G and A (General and Administrative) Overheads. Profitability Analysis-1.200 383. $56. Suite folder) from within Aspen IPE. from line 14. with the exception of the IPE-generated utility streams.300 (which is sufficiently close to $108.900 and $16.700 CD-IPE-25 . CTBM.e. The contractor engineering and indirect costs are in row 15.. $21. Also. all of the Aspen IPE results can be reproduced using the DEC3 folder (on the CD-ROM in the Aspen Eng. for equipment contingencies to allow for design changes. under DESIGN ENG’G AND PROCUREMENT K-USD. Total Permanent Investment The total permanent investment is computed by the spreadsheet. These are: Contractor Engineering Costs Indirect Costs $383.xls. all of the equipment items have originated with the simulation units from an ASPEN PLUS simulation.500. the difference reported above). $18.0. yellow arrows are placed in the blue boxes associated with each equipment item in the Aspen IPE Main window.700.200 and $4. and Code of Accounts item 105. and material and manpower charges associated with Contract Fees. $8.500 61.700 365.8 of the textbook. Returning to the Capital Estimate Report. these sum to approximately $100.300. under CONSTRUCTION INDIRECTS K-USD. the user enters: Total Direct Materials and Labor Costs Material and Labor G&A Overhead and Contractor Fees Contractor Engineering Costs Indirect Costs Adding Equipment Thus far. When it is desirable to add a piece of equipment that is not in a simulation or has not been created during the mapping of simulation units by Aspen IPE.600. Together with the Other item on line 10 of the Contract Summary.700 $365. and in the fifth column. Finally. These sum to $61. are obtained from line 13. the following steps are taken.200. press the Project View tab at the bottom of the left-hand window (i. in the Process Flow Diagram. all of the streams are yellow. the Project Explorer window) to give: $757.700 Together with the fees for materials and manpower G and A Overheads and Contract Fees. From the IPE Main window. After the mappings have been completed. discussed in Section 17. CDI. in the first column. When using the Aspen IPE option.545. to give the IBL Total Bare Module Cost. which are green.

CD-IPE-26 . a 50’x 50’ area is reserved and used to estimate piping lengths.. right click. Note that the original area for the plant. etc. Press OK and the new area. This is adequate for most applications. New Item) is entered with its dimensions. appears on the Project View (left window) of the IPE Main window. which is named New Item.g. and press Add Area to produce the Area Information dialog box in which an Area Name (e.Then. which was named Miscellaneous Flowsheet Area by Aspen IPE. is also 50’ x 50’ by default. highlight Main Project. Here.

highlight the New Item area. right click. and click on Add Project Component to produce the ICARUS Project Component Selection dialog box. enter Reboiler Pump as the Project Component Name.Next. highlight Process equipment and press the OK button. Continue through the appropriate menus until the desired equipment type is obtained. which in this example is a centrifugal pump. For the addition of a reboiler pump. CD-IPE-27 .

CD-IPE-28 .

After the OK button is pressed. CD-IPE-29 . the pump specification form is displayed.

the Process Flow Diagram appears as follows: CD-IPE-30 . After the streams are realigned. Observe that the Reboiler pump appears in the New Item area on the Project View. drag the Reboiler pump over the ICP-BE stream. press the Edit Connectivity button and place the cursor over the Reboiler pump. ICP-BE. it was brought to our attention that reboiler pumps are used normally with vertical reboilers. Before proceeding. or any other equipment item. to the mapping. To insert the Reboiler pump into the liquid stream from the sump. after completing this example. as shown in the IPE Process Flow Diagram: The Reboiler pump is positioned in the upper-left-hand corner of the Process Flow Diagram in the New Item area. Release the mouse and click with the left-mouse button to insert the Reboiler pump.Note that the specifications are incomplete because the Reboiler pump has not been connected into the main process. independent of the Miscellaneous Flowsheet Area. not with kettle reboilers. after which the cursor becomes a hand. the procedures in this section should be followed. When appropriate to add a reboiler pump. which resides in the Miscellaneous Flowsheet Area. Keeping the left-mouse button depressed.

To move it into the Miscellaneous Flowsheet area.Note that a new stream. has been created and named ICP-BE_2 by Aspen IPE. which appears in white. it remains in the New Item area. Although the Reboiler pump has been inserted into the process. in the Project View. drag and drop the Reboiler pump from the New Item Area to the Miscellaneous Flowsheet area. This results in: CD-IPE-31 .

double-click on it: CD-IPE-32 .5 gpm. After the pump is sized. a fluid head of 20 ft is entered.Next. double click on the pump icon to display the component specification form: Note that the design capacity of the Reboiler pump has been adjusted to 765. which should be sufficient to convey the bottoms liquid to the reboiler. At this point. a default specification in the Design Criteria. right click on the Reboiler pump and select Size Item on the menu that appears. which is 10 percent higher than the flow rate leaving the sump. To obtain the variables for the ICP-BE stream.

the total permament investment can be reestimated as discussed in the prior section. The detailed report appears in the Capital Estimate Report in the List of Equipment and Bulk Material by Area section. is clicked on.700. Finally. which is equivalent to the liquid mass flow rate. When the effluent stream. This discussion is not repeated here. the stream report does not display the stream properties because the stream has been referenced to the ICP-BE stream. Then. Having added the Reboiler pump. This procedure is repeated to add other equipment items. ICP-BE_2. This is accomplished by pressing the Evaluate Project button and requesting that all equipment items be re-evaluated. select Evaluate Item. It can be accessed by selecting Equipment List under Miscellaneous Flowsheet in the left-hand window: Note that no equipment items remain in the New Item section of the report. $44.5 gpm is 10 percent higher than 695.Observe that 765. can be accessed by highlighting Reboiler pump in the Project View and pressing the List tab to obtain the Workbook. all of the Aspen IPE results can be reproduced using the DEC3RP folder (on the CD-ROM in the Aspen Eng. A brief report that contains the installed cost. Suite folder) from within Aspen IPE. 160.645 lb/hr. which may be added to the New Item area or to other new areas. either right click on Reboiler pump in the Project View or on its icon in the Process Flow Diagram.9 gpm. To estimate the installed cost of the Reboiler pump. A complete report is obtained by re-evaluating the capital estimates for the process. CD-IPE-33 .

the steam utility can be replaced with steam at a higher pressure to reduce the area. when the resulting surface area of a reboiler is too large due to a small logmean-temperature-difference. This produces the Interactive Sizing dialog box. in this case. the default utility applied by Aspen IPE can be altered interactively for a particular equipment item. This is illustrated for the reboiler of the depropanizer as an example. For example. respectively. the items for Hot Inlet Stream and Hot Outlet Stream are ICUST-IN and ICUST-EX. after it has been mapped. delete the Final Surface Area. To change to steam at 100 psi. Aspen IPE uses steam at 50 psi as the default utility.Applying Alternative Utilities When desired. say at 100 psi. as shown below: In the Item 1 column that contains the values. which correspond to the default utility. such as a condenser or reboiler. steam at 50 psi. right click on the appropriate cells and select Steam @ 100 PSI – IPE Utility from the pull-down menu that appears. previously computed. since it must be re-sized by Aspen IPE: CD-IPE-34 . the following steps are taken. right click on the reboiler and select Re-Size Item from the menu that appears. For this reboiler. Next. To change to higherpressure steam. being careful to stay in the nucleate boiling region. In the Process View or Process Flow Diagram.

After the reboiler is re-sized. In the Sizing Data section. right click on the reboiler again and select Item Report from the pop-up menu. the reboiler is re-sized.When OK is pressed. the new results for the reboiler are displayed: CD-IPE-35 .

the surface area is 1. This can be accomplished for condensers. Furthermore. reduced from 3. storage vessels.7°F. They are accessed by selecting Equipment List under Miscellaneous Flowsheet in the left-hand window: These steps are repeated when it is desired to change the default utilities for other equipment items in the process. refer to the chapter on Sizing Project Components in the Aspen IPE User’s Guide (Aspen Icarus Process Evaluator User’s Manual → Sizing Project Components).Using steam at 100 psi. while the log-mean-temperature-difference is 72. This is accomplished by pressing the Evaluate Project button on the toolbar and selecting Evaluate All Items. and compressors. The results appear in the Capital Estimate Report in the List of Equipment and Bulk Material by Area section. increased from 25. CD-IPE-36 . flash drums.7°F. other specifications can be adjusted using interactive sizing. Note. however. reboilers. that interactive sizing is not possible for reactor vessels. For a complete listing of equipment items that can be sized interactively.262 ft2. Finally. the capital cost of the entire process is re-evaluated since the cost of the smaller reboiler is lower.580 ft2. pumps. reflux accumulators. for most equipment items.

the user is ready to use Aspen IPE. which is discussed in Section 4. Aspen IPE is opened automatically and the Create New Project dialog box appears. MCB-IPE. is replaced with the RADFRAC subroutine. the Inch-Pound (IP) unit set is selected in the Project Properties dialog box. MCB. the IPE Main window appears: CD-IPE-37 . After the Project Name MCB is entered.bkp and MCB-IPE. When completed. Initial Setup After sending the file.29 computed using the approximate DISTL subroutine.35.bkp. are on the CDROM. used to model the D1 distillation column. additional mixture properties are added and the DISTL subroutine. Also.MONOCHLOROBENZENE SEPARATION PROCESS In this section. as compared with 4.4 of the textbook and in the multimedia portion of the CD-ROM (ASPEN → Principles of Flowsheet Simulation → Interpretation of Input and Output → Sample Problem) that contains these course notes. which is available on the CD-ROM. MCB-IPE. Beginning with the file. The reflux ratio computed using the RADFRAC subroutine is 3. Both of the files.rep. the stream flow rates differ slightly (< 1%). Aspen IPE loads the information associated with each process model in ASPEN PLUS.rep to Aspen Icarus. After OK is pressed. equipment sizes and costs are estimated for the monochlorobenzene (MCB) separation process.

No other changes to the default values are necessary. at roughly 20%. such as the cooling water temperatures.2 (or 20%) is entered. an absorber and a distillation column. with the appropriate efficiency specified in the Design Criteria prior to each mapping. Changes to the Utility Specifications. This difference must be taken into account when proceeding with Aspen IPE. are made at this point. the parameters for trayed towers. including the tray efficiency are near the bottom of the list: To size the absorber column (A1-block). Absorber efficiencies are normally low. it is necessary to map and size each of the columns separately. while efficiencies for distillation columns are considerably higher. in this case at about 60%.The MCB separation process has two types of columns. Note that in the Design CriteriaIP dialog box. each having a distinct tray efficiency. CD-IPE-38 . Because Aspen IPE allows only one specification for the tray efficiency. a tray efficiency of 0.

as shown below: CD-IPE-39 . select Map Selected Item(s). Since the Current Map List does not need to be altered. the A1 unit has been added to the list of Project Components.Mapping Process Simulation Units to Aspen IPE To map a single process unit. In the Map dialog box. select OK to map the A1 unit. When the mapping and equipment sizing has been completed. and use Default and Simulator Data as the basis: Press OK to produce the Project Component Map Preview dialog box (not shown here). right-click on the selected item on the Aspen IPE Main window. and choose Map.

and then heaters to give: CD-IPE-40 .6 in the Design Criteria. D1. which is more appropriate for this application. Heat exchangers. each of the remaining equipment items is mapped and sized. Consequently. select New Mapping. select HE FLOAT-HEAD in the Current Map List and press the Delete One Mapping button: Then. the tray efficiency is changed to 0. Subsequently. Note that the unit H1 is too small to be mapped as a floating-head heat exchanger. one at a time. To change the mapping.Before mapping the distillation unit. as described above. it is necessary to change the default equipment type to a Double-pipe heat exchanger.

67. the Current Map List is modified in the Project Component Map Preview dialog box: Note that when the sizing calculations are being carried out for the flash vessel.From the next dialog box. two Message dialog boxes appear. The first indicates that the diameter is calculated to be 2.0 from the Design Criteria.007 ft. select Heat exchanger and finally choose the Double-pipe heat exchanger: After these steps are completed. rather than 3. but that the user-specified minimum value of 3 ft is used instead. The second indicates that the L/D ratio is 1. CD-IPE-41 . F1.

After all of the equipment items have been mapped and sized successfully. On the Map dialog box. The unit T1 represents a treater. the IPE Main window is displayed: Note that the three C entries represent Quoted Items having zero cost. In the Project View. right click on T1. a 1-degree difference between the inlet and outlet temperatures of the hot stream is assumed. which is not being considered at this point in the design of the MCB separation process. The default mapping for the treater T1 is a VT CYLINDER. The unit M1 is a mixing junction between two pipes and the unit S1 is a simple pipeline splitter. H1. and click OK. to produce the ICARUS Project Component Selection dialog box. with size and cost estimates computed. select Quoted equipment. then on Map. Size and cost estimates are not needed for these units. This default mapping is replaced with a Quoted Item having zero cost. click on OK to produce the Project Component Map Preview dialog box. The associated Process Flow Diagram is: CD-IPE-42 .Also. Delete the VT CYLINDER mapping and click on New Mapping. This places the unit T1 into the List View with a C. Aspen IPE maps the mixer M1 and splitter S1 as Quoted Items with zero cost. to indicate that it is a Quoted Item having zero cost. delete the mapping for T1. Click on Project Components. for the heat exchanger. To accomplish this.

and chemical reactors. To view the Aspen IPE result for an equipment item. especially for major equipment items such as towers. this produces the following results: CD-IPE-43 . compressors.When the mapping and sizing are completed it is prudent to check the equipment sizes computed by Aspen IPE. For the absorber. the two towers are of particular interest. large heat exchangers. For the MCB separation process. double click on the item of interest in the IPE Main window.

and 15 trays.5 ft diameter. CD-IPE-44 . 2004). Because of the small diameter. but is not considered here.23 of the textbook (Seider et al.Note that the column is designed to have a 1.. in accordance with the specifications in Figure 4. a 42 ft (tangent-to-tangent) height. a packed column would be preferred.

it is convenient to have Aspen IPE estimate the costs for the entire project at once. Estimates for contractor engineering and indirect costs are listed as well.23 in the textbook (Seider et al. a 72 ft (tangent-to tangent) height. 2004).Similarly. MCB. Most of this information. the standard basis profile is selected to be LOCAL CONTRACTOR and the Project Type is selected as Plant addition – suppressed infrastructure. After pressing the Evaluate Project button on the IPE Main window. Aspen IPE prepares the Capital Estimate Report.. also in accordance with Figure 4. is far too detailed for most estimates made in the conceptual design stage. Of greatest interest to process engineers. and hence. which contains detailed listings of the items to be procured to install the equipment (classified in the areas of piping. and 30 trays. Equipment Costing Aspen IPE estimates purchase and installed costs for the equipment units individually or for the entire project using a single command. is normally not printed by process engineers. for whom these notes are intended. The ICARUS Editor displays the report in two adjacent windows. Standard Basis As for the depropanizer discussed earlier. and an installation schedule. with a listing of the major subject headings listed in the left-hand window. structural steel. is the information in the following two sections: CD-IPE-45 . Consequently.ccp. instrumentation. estimates of the man-hours required for installation. electrical. though necessary for obtaining accurate cost estimates. the MCB separation process can be viewed as representing an addition to an existing plant. estimates of the costs. the Evaluate Project dialog box appears: As discussed for the depropanizer. For the MCB separation process. and insulation). the distillation column is designed to have a 3 ft diameter.

1 PRIME CONTRACTOR which are accessed by double-clicking on these titles in the left-hand window.e. This is achieved by pressing the Select Font button on the toolbar. It is often preferable to print in landscape format. This provides the Purchased (Equipment & Setting) and Installed Direct Costs (i.. Note that the right-hand window below is displayed using a 7-point font. Furthermore. This is accomplished by highlighting the desired section and pressing the Print button on the toolbar.1. portions of the complete printed output are provided in Appendix IV of these notes. the List of Equipment and Bulk Material by Area portion of the report is displayed when the Equipment List is accessed. CONTRACTOR NO. purchase costs. In summary. for the absorber. As shown below. and total material and manpower cost for the MCB separation process are tabulated below: CD-IPE-46 . Equipment List 2. Total Material and Manpower Cost or Total Direct Materials and Labor Cost) for each piece of equipment. the equipment sizes. It is recommended that just small portions of the report be printed.

600 51.500 12. 42 ft height 3.300 23.400 Total Material and Manpower Cost 19.800 16.0 ft diam.100 52.500 3.500 16.200 24.000 53.5 ft diam.900 54.24 kW 921 ft2 155 ft2 238 gal 161 ft2 196 ft2 264 gal TOTAL Purchase Cost 2.800 50. The entries shown below are in a 6-point font and are totals for all of the equipment items in the project. 1 PRIME CONTRACTOR is accessed.800 110. 72 ft height 2. Note that portions of the complete printed output are provided in Appendix IV of these notes.400 7.000 179.000 71.12 kW 1. CD-IPE-47 .200 7.Simulation Unit P1 A1 D1 Equipment Item Pump Tower Tower Reflux pump Reboiler Condenser Reflux accumulator Size 1.100 12.900 H1 H2 F1 Heat exchanger Heat exchanger Flash vessel The Contract Summary section of the Capital Estimate Report is displayed when the CONTRACT NO.200 $671.300 58.100 $154.

Item Allowance ($4.) The total direct material and manpower costs for construction of the plant are $536. pipe testing.400. The difference is due to the Misc.g. as shown in row 11.700 and include items that cannot be charged to the individual equipment items (e.500.Note that the entry for the purchased equipment. $154.. $159. Note that the installed costs of the equipment items are displayed on the List View: CD-IPE-48 . These sum to $785. from line 1. charges for instrument testing.500.200 and $249.700) and the Warehouse Spares ($430). is approximately the sum of the entries for the pieces of equipment provided above. These additional items are in Code of Accounts 105 and 107 and appear in the Code of Accounts Summary section of the Capital Estimate Report (just below the Contract Summary. and equipment grounding).

179 68 23 131 4012. 0. $113. is referred to in Chapter 16 of the textbook as the Total Direct Materials and Labor Cost.000 FEET 50. the materials and manpower items that cannot be charged to the individual equipment items are displayed in the Area Bulk Report within the Capital Estimate Report: A R E A B U L K R E P O R T ================================================================================================================================= : : : : : M A N P O W E R : TOTAL : : : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT : :ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD: ================================================================================================================================= AREA MISC CONCRETE ITEMS 916.800 less than the total direct cost of materials and manpower for installation of the plant. 831. 198 3358. 22 0. CDI. 369. 4274. 20 0 430.900. 2211. 4012. 462. RUNS.TRAYS. 50. 2648. CDML.JBOX.These installed costs sum to $671. 7771. 7534. that is. EQUIPMENT GROUNDING PILED FOUNDATION Number of piles ELECTRICAL TESTING ROTATING EQP SPARE PARTS 0. 3471. 430. 1450. This Installed Direct Cost. AREA GRADE PIPE TESTING UNPAVED AREA Area length Area width INSTRUMENT TESTING INSTR. 13840.700. $785. 4921. 328 127 7771. 16051. 430. 430. 10182. Finally. AREA AREA AREA AREA AREA AREA CD-IPE-49 .000 FEET 0.

and in the fifth COLUMN. and material and manpower charges associated with Contract Fees. in the first column.8 of the textbook. BASE TOTAL.xls. all of the Aspen IPE results can be reproduced using the MCB folder (on the CD-ROM in the Aspen Eng. When using the Aspen IPE option.500 (which.600 CD-IPE-50 .100 and $7.700.600 Together with the fees for materials and manpower G and A Overheads and Contract Fees.0. CTBM. These are: Contractor Engineering Costs Indirect Costs $558. for equipment contingencies to allow for design changes.700.800. material and manpower costs associated with G and A (General and Administrative) Overheads. Total Permanent Investment The total permanent investment is computed by the spreadsheet. for profitability analysis in the conceptual design stage. from line 14.700 558. is sufficiently close to $113.500. are obtained from line 13. The contractor engineering and indirect costs are in row 15.400 and $25. the difference reported above). to give the IBL Total Bare Module Cost. Profitability Analysis-1. these are added to the total direct installed equipment costs. $20. Returning to the Contract Summary. Together with the Other item on line 10 of the Contract Summary.These additional costs sum to approximately $48. discussed in Section 17. Finally.700 69. These sum to $69. these sum to approximately $103. $16. $49. the user enters: Total Direct Materials and Labor Costs Material and Labor G&A Overhead and Contractor Fees Contractor Engineering Costs Indirect Costs $785.700.900. and Code of Accounts item 105. $4. under CONSTRUCTION INDIRECTS K-USD.300 482.902. CDI. under DESIGN ENG’G AND PROCUREMENT K-USD. Suite folder) from within Aspen IPE.300 $482.

and M. and D. B. This produces the Select Report Type To View dialog box. N. D. M. Van Ness.. J.. Nathanson. D. W. Seider. Analysis. Select one of the two options to have Aspen IPE display the capital cost report as an HTML file or in the ICARUS Editor. that is. Sixth Edition. Process Design Principles: Synthesis. from which the appropriate report file is selected.. 1999. Wiley. Lewin. the Select Capital Cost Report File dialog box is produced. J. As work with Aspen IPE proceeds. 2003. This produces the Process/Project View window. Wiley. This produces the Open an IPE Project dialog box. in its associated project folder. Lewin.. and Evaluation. J. H. which has a browser icon. Fucci. Version 2. D. 2001.ccp file.ASPEN IPE FOLDERS AND FILES When a new project is created within Aspen IPE. Note that when more than one report file exists. CD-ROM. When returning to work with Aspen IPE. Analysis. Seader.1\ Data\Archive_IPE folder. Seader. various files are created and stored in this project folder. Seider. R. Second Edition. J. Abbott. It is also possible to examine a . D. using the File pulldown menu. to examine any portion of the Capital Estimate Report (which is automatically stored in your Projects folder after it has been generated). which contains the Capital Estimate Report for the depropanizer. Each item in the contents that is produced provides a link to its section of the Capital Estimate Report. DEC3) is created in the Program Files|Aspen Tech\ Aspen Icarus 11. This produces the Capital Estimate Report. Select the Project Name and press the OK button. press OK.ccp file using the NETSCAPE or EXPLORER browser by double-clicking on the appropriate file. Seider.0. 2004. J. CD-IPE-51 . E. Smith. W. W. D. Golbert. Goldberg. J. R. press the Capital costs button ($) on the toolbar. REFERENCES Lewin. McGraw-Hill. D. open the folder having the appropriate project name. and D. Wiley. M. Product and Process Design Principles: Synthesis. Then.g. Dassau. C. a folder having the project name (e. Seader. the DEC3. for example. R. and Evaluation. the IPE Main window.. D. Introduction to Chemical Engineering Thermodynamics. and R. D. M. When working in the Process/Project View window. Using Process Simulators in Chemical Engineering: A Multimedia Guide for the Core Curriculum.

APPENDIX I DEPROPANIZER ASPEN PLUS Report CD-IPE-52 .

0 BPVAL C3H8 C5H12-1 .0 BPVAL C4H10-1 C5H12-1 .0156000000 BPVAL C3H8 C4H10-1 0.0204000000 BPVAL C4H10-1 C6H14-1 -.0204000000 BPVAL C5H12-1 C2H6 5.70000000E-3 BPVAL C2H6 C5H12-1 5.60000000E-3 BPVAL C2H6 C6H14-1 -.0233000000 BPVAL C3H8 C6H14-1 -2.bkp on the CD-ROM DIS D1 FEED BOT ASPEN PLUS Program IN-UNITS ENG DEF-STREAMS CONVEN ALL DATABANKS PURE93 / AQUEOUS / SOLIDS / INORGANIC / & NOASPENPCD PROP-SOURCES PURE93 / AQUEOUS / SOLIDS / INORGANIC COMPONENTS C2H6 C2H6 / C3H8 C3H8 / C4H10-1 C4H10-1 / C5H12-1 C5H12-1 / C6H14-1 C6H14-1 FLOWSHEET BLOCK D1 IN=FEED OUT=DIS BOT PROPERTIES RK-SOAVE USER-PROPS DRUSR2 1 2 3 PROP-DATA RKSKIJ-1 IN-UNITS ENG PROP-LIST RKSKIJ BPVAL C2H6 C3H8 -2.ASPEN PLUS Flowsheet .2000000E-3 BPVAL C2H6 C4H10-1 6.60000000E-3 STREAM FEED SUBSTREAM MIXED TEMP=225 PRES=250 MOLE-FLOW C2H6 30 / C3H8 200 / C4H10-1 370 / C5H12-1 350 / C6H14-1 50 & CD-IPE-53 .0111000000 BPVAL C4H10-1 C2H6 6.simulation results can be reproduced using the file RADFRAC.0233000000 BPVAL C5H12-1 C4H10-1 .2000000E-3 BPVAL C3H8 C2H6 -2.70000000E-3 BPVAL C5H12-1 C3H8 .2000000E-3 BPVAL C4H10-1 C3H8 0.

0282 4.0000 226.9894 -66.1178 -951.0000 C4H10-1 365.4772 BTU/LB-R -1.0 0.0 0.0000 VFRAC 0.7856+04 BTU/LB -932.9682 3.7619 BTU/HR -4.1876 4228.06 SPEC 1 MOLE-FLOW 191 PHASE=V STAGE=1 COMPS=C3H8 VARY 1 MOLE-RR 3 9 STREAM-REPOR MOLEFLOW Stream Variables BOT DIS FEED -----------STREAM ID FROM : TO : BOT D1 ---DIS D1 ---FEED ---D1 SUBSTREAM: MIXED PHASE: LIQUID VAPOR MIXED COMPONENTS: LBMOL/HR C2H6 3.226 DP-COL=4 MOLE-RR=6.9964 30.1173+04 9615.0000 LB/HR 5.4407 STATE VARIABLES: TEMP F 260.0000 248.0000 C5H12-1 349.7738+07 -9.7950 AVG MW 66.4405 5.5473 60.6799-06 50.5871 DENSITY: LBMOL/CUFT 0.1817-02 350.4212+04 -5.5584 -1.5935-03 29.DIS STAGE 1 BOT STAGE 14 PROPERTY OPTION SET: RK-SOAVE STANDARD RKS EQUATION OF STATE CD-IPE-54 .3064 -96.6886 6.0748 225.1220 2.BLOCK D1 RADFRAC PARAM NSTAGE=14 COL-CONFIG CONDENSER=PARTIAL-V FEEDS FEED 7 PRODUCTS BOT 14 L / DIS 1 V P-SPEC 1 248 COL-SPECS D:F=.1282 LB/CUFT 29.0000 191.7169 SFRAC 0.0000 TOTAL FLOW: LBMOL/HR 774.1148 42.0000 C3H8 9.0000 1000.0 ENTHALPY: BTU/LBMOL -6.0 1.0000 250.3452-02 0.0 0.2831 LFRAC 1.8017 115.9918+06 -5.0000 PRES PSI 252.0955 7798.0000 C6H14-1 50.FEED STAGE 7 OUTLETS .7885 Process Unit Output BLOCK: D1 MODEL: RADFRAC ------------------------------INLETS .0000 5.0789+04 CUFT/HR 1757.2742 7.1678+04 -4.8868 -1039.7856+07 ENTROPY: BTU/LBMOL-R -105.0000 200.0000 0.9718 370.6031 -1.0000 0.

11360E-06 *** SUMMARY OF KEY RESULTS TOP STAGE TEMPERATURE F BOTTOM STAGE TEMPERATURE F TOP STAGE LIQUID FLOW LBMOL/HR BOTTOM STAGE LIQUID FLOW LBMOL/HR TOP STAGE VAPOR FLOW LBMOL/HR BOTTOM STAGE VAPOR FLOW LBMOL/HR MOLAR REFLUX RATIO MOLAR BOILUP RATIO CONDENSER DUTY (W/O SUBCOOL) BTU/HR REBOILER DUTY BTU/HR **** PROFILES **** *** 115. -0.263325E-14 -0.11978E-03 .29 774. FOR THE FIRST STAGE.45000E-01 .000 1.115854+08 0.802 2. OF INSIDE LOOP ITERATIONS MAXIMUM NUMBER OF FLASH ITERATIONS FLASH TOLERANCE OUTSIDE LOOP CONVERGENCE TOLERANCE **** MOLAR VAPOR DIST / TOTAL DIST MOLAR REFLUX RATIO DISTILLATE TO FEED RATIO **** *** COL-SPECS 14 STANDARD NO STANDARD NO BROYDEN NESTED 25 10 50 0.13437E-01 .5 -0.006.99988 .000100000 0.06000 0.217615E-02 ) **** INPUT DATA NUMBER OF STAGES ALGORITHM OPTION ABSORBER OPTION INITIALIZATION OPTION HYDRAULIC PARAMETER CALCULATIONS INSIDE LOOP CONVERGENCE METHOD DESIGN SPECIFICATION METHOD MAXIMUM NO.000 226.13927 -0.22600 RESULTS **** *** COMPONENT SPLIT FRACTIONS OUTLET STREAMS -------------BOT .79 8. CD-IPE-55 .113687E-15 -0.577303E+08 **** RELATIVE DIFF.00 60788. THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW.00000 6.*** TOTAL BALANCE MOLE(LBMOL/HR) MASS(LB/HR ) ENTHALPY(BTU/HR MASS AND ENERGY BALANCE *** IN OUT 1000.95500 .578562E+08 1000.117112+08 **NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS FROM THE STAGE EXCLUDING ANY SIDE PRODUCT.075 260.000100000 **** 1.98656 . FOR THE LAST STAGE.0000 DIS COMPONENT: C2H6 C3H8 C4H10-1 C5H12-1 C6H14-1 .00 60788.87737 2.99991 1. THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW.90906E-04 .655. OF OUTSIDE LOOP ITERATIONS MAXIMUM NO.5 -0.

75943E-01 0.31913 0.42 248. -48372.64599E-01 CD-IPE-56 . 1560. 0.54 249.15681 0.41399E-05 0. -59970.71663E-03 0.9810E+05 0.65 209.36784E-06 0.61454 0. -61678.88845E-02 0.26424E-01 0. 1542.45216 C6H14-1 0.27216E-01 0. -45507.1523E+06 0.9845E+05 0.29446 0.56594 0. -52686.15547 0.11585+08 .66748E-02 0. 2372. HEAT DUTY BTU/HR -. 1864.56268E-01 0.8829E+05 0.31 248.20293 0. -47215.57253E-01 0.28601 0.6153 774. 1677.48005 0.15740+05 .37366 0. -60295.1544E+06 0.1382E+06 0.56172E-01 0. 1989.1047E+06 LIQUID MIXED .38453E-01 0.40998E-02 0. -53340.9759E+05 0.9838E+05 0. -44928.62 249. 1600. -51780.12085 0.1032E+06 0.08 251. 2453.39505E-04 0.38 251.11628E-01 0. 2454. 2334.24609 0.38791E-04 0. 226.10271E-03 0. 1680.1558E+06 0.28 235.80 PRESSURE PSI 248.21933E-01 0.99 260.23898 0.45048+05 .63050 0.1425E+06 0.0 1955.16827E-02 0.47161 0.10340E-01 0.88576 0. 1661.0000 1 2 3 5 6 7 8 11 12 13 14 FLOW RATE LBMOL/HR LIQUID VAPOR 2006. -59293.62 241. 2232.38 217.0 1656.18785E-02 0. -52692.36411E-01 0.25942E-01 0.00 ENTHALPY BTU/LBMOL LIQUID VAPOR -50783.51173+05 STAGE 1 2 3 5 6 7 8 11 12 13 14 C2H6 0. -52207. 774.5117E+05 0.23 249.15 251. -51581.84979 0.29880E-01 0.74938 0.0000 MASS FLOW PROFILES FEED RATE LB/HR VAPOR **** PRODUCT RATE LB/HR LIQUID VAPOR 9615.07 125.22597 0. -50212.52813 0. -55843.28 136.69 252.8848E+05 9616. 2181.8384E+05 0.1012E+06 0. 1679. -60816.14274E-01 0.6886 STAGE 1 2 3 5 6 7 8 11 12 13 14 FLOW RATE LB/HR LIQUID VAPOR 0.43455 0.39 190. -57560.75715E-02 0.STAGE TEMPERATURE F 1 2 3 5 6 7 8 11 12 13 14 STAGE 115.14072E-04 0.8996E+05 0.8897E+05 0.00 248. -59032.56948 0. 1903.46428E-05 **** MOLE-X-PROFILE **** C3H8 C4H10-1 C5H12-1 0.9859E+05 0.25864E-01 0.85 250. FEED RATE LBMOL/HR VAPOR -44212.53451 0. **** LIQUID MIXED 283.29316E-02 0.8877E+05 0. 2430.11711+08 PRODUCT RATE LBMOL/HR LIQUID VAPOR 226.3846 716. -49521.57 170.8706E+05 0.

27279E-03 0.88165 0.48332 0.25783 0.32189 0.14792E-03 0.38744E-03 0.26750E-01 0.42565 0.20941 0.69553 0.52798E-01 0.84513 0.64894E-01 0.25132E-07 0.13273 0.37152 0.13882E-01 0.65833E-03 0.11540 0.**** STAGE 1 2 3 5 6 7 8 11 12 13 14 C2H6 0.12031 0.21999E-01 0.76709E-01 0.33697 C6H14-1 0.11061 0.60259E-02 0.14670E-01 0.18479E-04 MOLE-Y-PROFILE **** C3H8 C4H10-1 C5H12-1 0.47830E-01 0.26231E-01 CD-IPE-57 .27326E-01 0.48748 0.66941E-01 0.37136E-05 0.70375 0.99812E-02 0.37438E-01 0.14078E-03 0.84931 0.61003 0.26424E-02 0.13318 0.29788 0.66399E-02 0.54526E-04 0.22436E-01 0.18013 0.23512E-01 0.61322E-02 0.33314E-06 0.68040 0.62700 0.16554E-02 0.55617 0.85532E-02 0.

APPENDIX II DESIGN CRITERIA SPECIFICATIONS CD-IPE-58 .

CD-IPE-59 .

CD-IPE-60 .

APPENDIX III ASPEN IPE CAPITAL ESTIMATE REPORT FOR THE DEPROPANIZER Selected portions of the List of Equipment and Bulk Material by Area and the Contract Summary CD-IPE-61 .

0 31. 710.0 289.3 9.0 2. ================================================================================================================================= : : : DESIGN : C O N S T R U C T I O N : MISC.4 18.5 34. 343.0 0.0 33.2 -------204.0 -----------1568.7 0.5 56.9 24.0 65.7 289.0 -------152.9 7.4 0.4 9.7 0.0 ------383.9 33.5 -------173.8 1.9 25.8 --------645.4 7.8 0. 2599. DIRECT SUBCONTRACTS G AND A OVERHEADS CONTRACT FEE -------------------BASE TOTAL ESCALATION CONTINGENCIES SPECIAL CHARGES -------------------TOTAL 350.6 -------0.6 3.6 59.2 21.0 0.8 ----100.2 0.0 32.3 5.6 0. 5.0 116.0 ----118.3 --------605.3 7.7 0.6 34.0 0. AND : : PERCENT : :NO.4 0. 1455.6 152.0 0.0 -------0.0 -----------1850.6 16.0 ================================================================================================================================= * NO SUBCONTRACTS CD-IPE-62 .0 0. 218.0 0.: I T E M : ENG'G AND :-------------------------------------------------: ALL *: AMOUNT : OF : : : :PROCUREMENT: MATERIAL : MANHOURS : MANPOWER : INDIRECTS :SUBCONTRACTS : : CONTRACT : : : : K-USD : K-USD : : K-USD : K-USD : K-USD : K-USD : TOTAL : ================================================================================================================================= 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 PURCHASED EQUIPMENT EQUIPMENT SETTING PIPING CIVIL STEEL INSTRUMENTATION ELECTRICAL INSULATION PAINT OTHER -------------------SUBTOTAL.0 3.8 -------365.2 5.2 0.1 4.5 ----91.6 17.5 10.9 27.2 15.8 0.5 46. 380.4 0.8 1.0 89.9 122.0 282.7 7.2 0.5 58.3 -------321.Depropanizer Without the Reboiler Pump (see DEC3 Folder) C O N T R A C T S U M M 1) A R Y PRIME CONTRACTOR (CONTRACT NO. 1242.3 321.1 ------452.2 18.3 -----------1429.7 ------350.2 93.8 -------431.2 --------761.1 6.6 265.0 18.0 69. --------7210.0 -------0.4 106.0 0.7 2.7 12.9 728.0 0.

426 : TOTAL MATERIAL AND MANPOWER COST =USD 35200. 0. 0. 1. INST'L COST/PE RATIO = 6.031 : PIPING : 14291. QUOTE EQP5 D1-overhead split Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO.000 : INSTRUMENTATION : 6262. 4.8743 : 4684.1005 31 : 3. 0. 0.: D1-cond acc Vessel diameter 5.0312 29 : 0.00 FEET Design temperature 250. 0.0000 : 0.4918 : 1928.9007 204 : 0.0736 89 : 1. 1.0000 : 593.7452 : 10512.0835 : 2031.748 : ------------------------------------------------------------------------SUBTOTAL : 57633.754 : PAINT : 144.M A T E R I A L ---:********* M A N P O W E R *********:--.00 DEG F Speed 3600.: D1-reflux pu Fluid head 50.280 : STRUCTURAL STEEL : 0. 0.30 PSIG Driver type MOTOR Seal type SNGL Total weight 530 LBS I T E M :--. 0. 1.0000 : 0.0000 0 : 0.23 GALLONS TAG NO. 0. 0.174 : ELECTRICAL : 0.0673 22 : 2.0421 : 1399.1147 : 898.1555 : 3823.00 DEG F Design gauge pressure 258.0000 0 : 0. 0.625 INCHES Total weight 9600 LBS I T E M :--.4712 391 : 0. CP 4 CENTRIF D1-reflux pump Casing material CS 5200 CODE OF ACCOUNT: 161 Liquid flow rate 401.0276 : 350.0737 19 : 0. 0.0000 : 0.00 FEET Design temperature 250.0000 0 : 0.M A T E R I A L ---:********* M A N P O W E R *********:--.291 : TOTAL MATERIAL AND MANPOWER COST =USD 74400. 0. 0. 0.000 HP Design gauge pressure 258.481 : CIVIL : 170.0333 : 16799.1727 42 : 1.8842 793 : 0. 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 19000. 0.769 ========================================================================================================================== Equipment mapped from 'D1'.074 : PIPING : 9746. 0.1069 120 : 1.30 PSIG Application CONT Base material thickness 0. 0. 0.437 : ------------------------------------------------------------------------SUBTOTAL : 24675. 1.0216 492 : 0.916 ========================================================================================================================== =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.000 : INSTRUMENTATION : 21954. 0.626 : CIVIL : 1587.279 : ELECTRICAL : 596.3359 76 : 0.0327 : 523.99 GPM TAG NO. 0. 0. HT 3 HORIZ DRUM D1-cond acc Shell material A 515 19000 CODE OF ACCOUNT: 114 Liquid volume 2350.3708 98 : 0.0000 : 0. INST'L COST/PE RATIO = 3. 0.7522 : 8952.506 : INSULATION : 2557.: D1-overhead ========================================================================================================================== CD-IPE-63 .2012 164 : 0. 0. 0.0000 : 383. 0.0000 0 : 0.2042 : 1747.000 : PAINT : 801. 2.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 5200.000 : INSULATION : 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'. 1. 3. 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'.00 RPM Driver power 5.000 FEET Vessel tangent to tangent length 16.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------. 0.077 : STRUCTURAL STEEL : 0.

55 SF TAG NO. 0. 0.: D1-tower Vessel diameter 5.000 : INSTRUMENTATION : 13153. 1.310 : STRUCTURAL STEEL : 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 52600.0056 : 736.0612 218 : 0.00 PSIG Shell design temperature 310.0142 45 : 0. 1. 0.0293 92 : 0. INST'L COST/PE RATIO = 2. 0. 0.519 : ------------------------------------------------------------------------SUBTOTAL : 89412.0895 205 : 0. 0. 0. 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'. 0. RB 7 KETTLE D1-reb Tube material A 214 52600 CODE OF ACCOUNT: 262 Heat transfer area 3579.0000 0 : 0. 0.141 : ------------------------------------------------------------------------SUBTOTAL : 142445.0262 : 909.0000 : 1877.2330 651 : 0.0100 : 1376.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'. 2. 0.625 INCHES Total weight 31500 LBS I T E M :--.000 FEET Vessel tangent to tangent height 42.2222 : 50145. 0. 0. 0. 0. 0.000 INCHES Tube length extended 20.0140 47 : 2.2600 : 11432.716 : CIVIL : 1572.0273 : 1881. TW .000 : INSULATION : 8253.00 INCHES Tray material A285C Tray thickness 0. QUOTE EQP6 D1-bottoms split Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO.803 : PAINT : 643.: D1-reb Shell material A285C TEMA type BKT Shell design gauge pressure 262.10 TRAYED D1-tower Shell material A 515 64100 CODE OF ACCOUNT: 111 Number of trays 15 TAG NO. 0. 0.00 DEG F Tube outside diameter 1. 0. INST'L COST/PE RATIO = 3.1080 291 : 0. 0. 0.3252 : 14937.1569 : 5679.022 : PIPING : 13678.80 DEG F Design gauge pressure 262. 0.0000 0 : 0. 0.005 ========================================================================================================================== CD-IPE-64 .5665 : 16719.1095 : 3924.30 PSIG Application DISTIL Tray type SIEVE Tray spacing 24.0000 : 1152. 0.4864 1201 : 0. 0. 0.30 PSIG Tube design temperature 331.029 : PIPING : 20847. 0. 0.00 INCHES Tube design gauge pressure 60.0358 111 : 1.00 FEET Tube port diameter 36.M A T E R I A L ---:********* M A N P O W E R *********:--.0219 52 : 0.: D1-bottoms s ========================================================================================================================== Equipment mapped from 'D1'.7823 2373 : 0.286 : TOTAL MATERIAL AND MANPOWER COST =USD 115000.0336 127 : 1.0000 : 0.2501 : 4707. 0.2608 729 : 0.M A T E R I A L ---:********* M A N P O W E R *********:--. 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 64100.00 FEET Design temperature 310.0000 : 0.2173 495 : 0. 0.370 : STRUCTURAL STEEL : 7021.688 : PAINT : 292.542 : INSULATION : 10270. 0.460 : ELECTRICAL : 1678.0215 88 : 2.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.1287 423 : 0. 1.559 : INSTRUMENTATION : 36315.0245 : 2153.80 DEG F Shell diameter 54.836 : CIVIL : 1436.352 : TOTAL MATERIAL AND MANPOWER COST =USD 192600.00 FEET Total weight 34300 LBS I T E M :--.1602 : 8250.00 INCHES Shell length 25.188 INCHES Base material thickness 0.6999 : 25587.186 ========================================================================================================================== =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.358 : ELECTRICAL : 0.

0000 0 : 0. 0. 0. 0.00 FEET Tube design gauge pressure 60.30 PSIG Tube design temperature 250.0089 : 1693.011 : PIPING : 34630. 0. INST'L COST/PE RATIO = 1.0108 96 : 2.00 DEG F Tube outside diameter 1.2243 1489 : 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'.619 : PAINT : 636.438 : CIVIL : 1237.0634 : 2876.2484 : 15175.00 INCHES Shell length 23.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.00 SF Shell material A285C TEMA type BES Shell design gauge pressure 258. 0. 0.0000 : 1601. HE .0121 100 : 1.0975 : 8413.0115 73 : 0.0000 : 0. 0.M A T E R I A L ---:********* M A N P O W E R *********:--.000 : INSTRUMENTATION : 8835.0000 : 0. 0.0206 125 : 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 139400.0604 430 : 0.158 : TOTAL MATERIAL AND MANPOWER COST =USD 229600.000 INCHES Tube length extended 20.000 : INSULATION : 13585. 0.647 ========================================================================================================================== CD-IPE-65 . 0.0000 0 : 0. 1.00 DEG F Shell diameter 46.: D1-cond Area per shell 5551.4227 : 31270. 0. 1.326 : ELECTRICAL : 0. 0.13 FLOAT HEAD D1-cond Tube material A 214 139400 CODE OF ACCOUNT: 261 Number of shells 2 TAG NO. 0.377 : ------------------------------------------------------------------------SUBTOTAL : 198323. 0.1089 665 : 0. 0.369 : STRUCTURAL STEEL : 0.61 PSIG Shell design temperature 250.00 FEET Total weight 89200 LBS I T E M :--. 0.0046 : 1512.

50. 1407.A R E A B U L K R E P O R T ================================================================================================================================= : : : : : M A N P O W E R : TOTAL : : : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT : :ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD: ================================================================================================================================= AREA MISC CONCRETE ITEMS 638. 4564.TRAYS. 231. 192 127 4564. 185. 10182. RUNS. 0. EQUIPMENT GROUNDING PILED FOUNDATION Number of piles ELECTRICAL TESTING ROTATING EQP SPARE PARTS 0. 2979. 370. 14 0. 10214. 7534. 416. 16 0 344. 2648. 4352. AREA AREA AREA AREA AREA AREA CD-IPE-66 . 95 60 11 83 2124. 2124. 344.000 FEET 50. 1266. 8807. 138 2341.JBOX. 3086.000 FEET 0. 370. AREA GRADE PIPE TESTING UNPAVED AREA Area length Area width INSTRUMENT TESTING INSTR.

7 ----100.0 0.2 110.0 8.0 0.0 0.9 17. DIRECT SUBCONTRACTS G AND A OVERHEADS CONTRACT FEE -------------------BASE TOTAL ESCALATION CONTINGENCIES SPECIAL CHARGES -------------------TOTAL 371.: I T E M : ENG'G AND :-------------------------------------------------: ALL *: AMOUNT : OF : : : :PROCUREMENT: MATERIAL : MANHOURS : MANPOWER : INDIRECTS :SUBCONTRACTS : : CONTRACT : : : : K-USD : K-USD : : K-USD : K-USD : K-USD : K-USD : TOTAL : ================================================================================================================================= 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 PURCHASED EQUIPMENT EQUIPMENT SETTING PIPING CIVIL STEEL INSTRUMENTATION ELECTRICAL INSULATION PAINT OTHER -------------------SUBTOTAL.9 107.2 287.0 2. 6.0 34.0 0.6 7.3 -------447. ================================================================================================================================= : : : DESIGN : C O N S T R U C T I O N : MISC.4 -----------1656.1 --------807.5 --------684.0 ------478.9 1.0 296.9 4.6 3.0 73.0 -----------1954.0 -------164.9 12.9 6.5 296.0 68. --------7805.7 28.0 ----118.0 95.6 3.0 35.1 0.5 0.1 8.7 59.1 65.2 0. 426.0 33.3 19. AND : : PERCENT : :NO.0 -------0. 374.7 -------221.6 764.3 0.0 0.0 34.0 0.9 35.4 10.0 ------371.1 6.5 0.7 7.5 ------405.9 0.9 131.9 26.1 173.5 1.4 10.6 0.9 0.1 65.0 298.0 123.7 --------642.0 ================================================================================================================================= * NO SUBCONTRACTS CD-IPE-67 . 1355.5 2.7 -------187.0 0.0 18.0 -------0.8 15.3 17.7 -------379.4 -------333.2 10.9 0.2 0.5 46.1 ----91. 1536.2 38.7 0.1 -----------1511.3 22.0 0. 2865.Depropanizer With the Reboiler Pump (see DEC3RP Folder) C O N T R A C T S U M M A R 1) Y PRIME CONTRACTOR (CONTRACT NO.2 333. 218.4 -------0.9 18.0 0.0 27.5 5. 744.

2495 76 : 0.8141 248 : 0.420 : ------------------------------------------------------------------------SUBTOTAL : 32680.0287 : 487. 0. 0.390 : CIVIL : 160. 1.000 : INSTRUMENTATION : 6277.00 PSIG Driver type MOTOR Seal type SNGL Total weight 630 LBS I T E M :--. 0.5465 : 2219. 2.0000 0 : 0.386 ========================================================================================================================== CD-IPE-68 .066 : PIPING : 14619. 0.0884 : 5699.99 DEG F Speed 3600.506 : INSULATION : 3826. INST'L COST/PE RATIO = 6.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== CP 8 CENTRIF reboiler pump Casing material CS 7000 CODE OF ACCOUNT: 161 Liquid flow rate 756. 0. 0. 0. 0.0000 : 0.0662 23 : 0. 1. 4.0000 : 463. 0. 0.M A T E R I A L ---:********* M A N P O W E R *********:--.368 : TOTAL MATERIAL AND MANPOWER COST =USD 44700. 0. 0.00 FEET Design temperature 298.0229 : 504.146 : STRUCTURAL STEEL : 0.00 RPM Driver power 3.278 : ELECTRICAL : 596.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 7000. 0.52 GPM Fluid head 20.0720 30 : 3.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.0852 : 898.3170 113 : 0.7166 563 : 0.580 : PAINT : 201. 0.000 HP Design gauge pressure 262.0695 31 : 2.6685 : 12016.1283 42 : 1.8967 : 1747.

8807. RUNS. 5002. 3086. 2242.TRAYS. AREA GRADE PIPE TESTING UNPAVED AREA Area length Area width INSTRUMENT TESTING INSTR. 1407. 10214. 3070. 499. 4352. 860. AREA AREA AREA AREA AREA AREA CD-IPE-69 . 2648. 0. 7534. 50.A R E A B U L K R E P O R T ================================================================================================================================= : : : : : M A N P O W E R : TOTAL : : : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT : :ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD: ================================================================================================================================= AREA MISC CONCRETE ITEMS 657. 1266. 277. 10182. 222.000 FEET 50. 14 0. 142 2413.000 FEET 0. 100 60 14 83 2242.JBOX. 860. 376. EQUIPMENT GROUNDING PILED FOUNDATION Number of piles ELECTRICAL TESTING ROTATING EQP SPARE PARTS 0. 17 0 376. 211 127 5002.

APPENDIX IV ASPEN IPE CAPITAL ESTIMATE REPORT FOR THE MONOCHLOROBENZENE SEPARATION PROCESS Selected portions of the List of Equipment and Bulk Material by Area and the Contract Summary CD-IPE-70 .

0 44.0 0.5 ------658.0 36.9 -------333.6 425.6 41.0 0.0 -------0.3 0.1 1. 8.9 10.1 37.0 0.7 159.9 -------482.3 0.0 103.6 0.3 0.4 --------572.0 86.1 0.9 23.6 8.0 11.1 --------675. 485.0 159.6 209.2 1.3 0.0 100.6 147.9 --------536.0 0.7 5.6 4.4 9.0 ================================================================================================================================= * NO SUBCONTRACTS CD-IPE-71 .9 -----------1724.0 0.4 0.1 ----100.0 18.0 -----------2237.2 16.0 -------0. DIRECT SUBCONTRACTS G AND A OVERHEADS CONTRACT FEE -------------------BASE TOTAL ESCALATION CONTINGENCIES SPECIAL CHARGES -------------------TOTAL 513.5 8. 1924.7 0.8 0.5 25.9 390.1 12. 1086.3 101.2 -----------1896.0 0.1 82.8 0.4 52.0 61.7 -------282.8 43.0 ----118.6 18.1 20.5 76.0 0.6 30. 346.9 -------569.5 18.1 ----91.: I T E M : ENG'G AND :-------------------------------------------------: ALL *: AMOUNT : OF : : : :PROCUREMENT: MATERIAL : MANHOURS : MANPOWER : INDIRECTS :SUBCONTRACTS : : CONTRACT : : : : K-USD : K-USD : : K-USD : K-USD : K-USD : K-USD : TOTAL : ================================================================================================================================= 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 PURCHASED EQUIPMENT EQUIPMENT SETTING PIPING CIVIL STEEL INSTRUMENTATION ELECTRICAL INSULATION PAINT OTHER -------------------SUBTOTAL.4 0.9 7. 4404.7 20.5 7.4 2. --------11672.4 135.3 49. AND : : PERCENT : :NO.0 7.1 ------513.0 -------249.0 341.3 178. 333.7 988.3 2.0 50.2 ------558.0 0.9 12. ================================================================================================================================= : : : DESIGN : C O N S T R U C T I O N : MISC.0 45.C O N T R A C T S U M M A R 1) Y PRIME CONTRACTOR (CONTRACT NO.9 -------425.4 -------0.4 6.0 1. 2704.

350 ========================================================================================================================== CD-IPE-72 . 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 53500. 0.480 : ELECTRICAL : 2230. 0.0116 : 1350. 0.0045 2522 : 0.188 INCHES Average wall thickness 0. 4.00 FEET Design temperature 353. INST'L COST/PE RATIO = 6.0720 : 696. 1.00 FEET Design temperature 320.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.0449 729 : 0. 0.5304 : 14966. 1.: A1-tower Vessel diameter 1. 1.482 : INSTRUMENTATION : 35223. 0. 0.178 : ------------------------------------------------------------------------SUBTOTAL : 125452.875 ========================================================================================================================= =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.0238 : 860. 0.2869 : 2162.30 PSIG Application DISTIL Tray type SIEVE Tray spacing 24.00 INCHES Tray material A285C Tray thickness 0.0896 84 : 1.264 : ------------------------------------------------------------------------SUBTOTAL : 67980.428 : TOTAL MATERIAL AND MANPOWER COST =USD 179200. 0.000 FEET Vessel tangent to tangent height 72. 2. TW 3 TRAYED D1-tower Shell material A 515 53500 CODE OF ACCOUNT: 111 Number of trays 30 TAG NO.417 INCHES Total weight 21400 LBS I T E M :--.500 FEET Vessel tangent to tangent height 42.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'A1'.032 : PIPING : 13675.619 : TOTAL MATERIAL AND MANPOWER COST =USD 110000. 0. INST'L COST/PE RATIO = 3. 0.0000 : 512.2074 : 9098. 0.0719 213 : 0. 0. 0.0538 55 : 2.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'.30 PSIG Application DISTIL Tray type SIEVE Tray spacing 24. TW 2 TRAYED A1-tower Shell material A 515 16000 CODE OF ACCOUNT: 111 Number of trays 15 TAG NO.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 16000.0000 : 1727.0568 : 1434.0320 25 : 0. 0.0435 34 : 0.00 DEG F Design gauge pressure 60.0315 99 : 1.0252 86 : 2.535 : INSULATION : 11094.3449 : 53740. 0.2938 240 : 0.2488 : 42051.: D1-tower Vessel diameter 3.0323 84 : 0. 0. 0. 0.604 : INSULATION : 4921. 0. 1.032 : PIPING : 8486.3075 : 4701. 0.500 INCHES Total weight 6400 LBS I T E M :--.484 : STRUCTURAL STEEL : 7974.2556 : 17933.311 : CIVIL : 1136. 0.1491 : 3845. 0.764 : CIVIL : 909.6584 : 16909.02 DEG F Design gauge pressure 35. 0.9714 : 16719.188 INCHES Base material thickness 0.00 INCHES Tray material A285C Tray thickness 0. 0.578 : STRUCTURAL STEEL : 4590.M A T E R I A L ---:********* M A N P O W E R *********:--.1701 466 : 0.530 : ELECTRICAL : 1152.3161 737 : 0. 0.6282 1934 : 0.0417 : 1193. 0.1351 120 : 0. 2.9354 647 : 1.471 : INSTRUMENTATION : 31542. 0.0212 : 1685.0223 59 : 0. 1.820 : PAINT : 620.3352 778 : 1.M A T E R I A L ---:********* M A N P O W E R *********:--.955 : PAINT : 380.

0689 38 : 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'.5329 : 17263. INST'L COST/PE RATIO = 4. 0.7876 : 8169.000 : INSULATION : 3692.000 : INSTRUMENTATION : 7741. 0.0000 : 0.069 : PIPING : 9609.673 : STRUCTURAL STEEL : 0.M A T E R I A L ---:********* M A N P O W E R *********:--. 2. 0.215 : ELECTRICAL : 0. 0. 0.2449 152 : 0.0000 : 511. 1.3298 : 2678.96 GALLONS TAG NO.840 ========================================================================================================================== CD-IPE-73 . 0. 0.000 FEET Vessel tangent to tangent length 4.3017 800 : 0.71 SF TAG NO. INST'L COST/PE RATIO = 6. 0.0000 : 0.508 : TOTAL MATERIAL AND MANPOWER COST =USD 51300.642 : ------------------------------------------------------------------------SUBTOTAL : 33997.: D1-cond Shell material A285C TEMA type BEM Shell design gauge pressure 35.000 INCHES Shell length 20.0000 0 : 0. 0. 0. 0. 0.7988 : 8621.461 : STRUCTURAL STEEL : 0.083 : PAINT : 142.0000 0 : 0. 0.1495 373 : 1.0000 : 841.2527 : 3624.419 : ------------------------------------------------------------------------SUBTOTAL : 34124.000 : INSTRUMENTATION : 16896.439 : CIVIL : 995. 0.483 : TOTAL MATERIAL AND MANPOWER COST =USD 50600.0000 0 : 0.00 FEET Tube design gauge pressure 60.0189 : 376.30 PSIG Shell design temperature 255.0000 : 0.0549 : 1120. 1.3518 772 : 0. 0.1937 86 : 1.0423 33 : 2. 0. 0. 0. 0.1326 : 1453.6696 358 : 0.0000 0 : 0. 0. 0.6345 : 2859. 0.98 DEG F Design gauge pressure 35. HT 5 HORIZ DRUM D1-cond acc Shell material A 515 7500 CODE OF ACCOUNT: 114 Liquid volume 237. 2.30 PSIG Application CONT Base material thickness 0.0681 25 : 0. 0.000 : INSULATION : 2474. 1. 0. 4.068 : PIPING : 5991.7971 : 16492.000 INCHES Tube length extended 20.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'. 1.369 : ELECTRICAL : 0. 0.809 : PAINT : 213.M A T E R I A L ---:********* M A N P O W E R *********:--.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 7500. 2.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 12200.0501 24 : 2.39 DEG F Shell diameter 8.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.30 PSIG Tube design temperature 255.500 FEET Design temperature 254.: D1-cond acc Vessel diameter 3.0000 : 0.0175 : 516.3026 : 2988.313 INCHES Total weight 1500 LBS I T E M :--.850 : CIVIL : 669. 0.4832 156 : 0.2344 125 : 0. 0.148 ========================================================================================================================= ========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------. 0.00 FEET Total weight 1800 LBS I T E M :--.39 DEG F Tube outside diameter 1.0918 66 : 1. HE 4 FIXED T S D1-cond Tube material A 214 12200 CODE OF ACCOUNT: 261 Heat transfer area 154.3571 136 : 1.

030 : PIPING : 8327. 0.0462 463 : 0.0000 0 : 0. 0. 0.00 FEET Total weight 9100 LBS I T E M :--.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 23500. 0.0000 : 0.151 : CIVIL : 1067. 0.2181 : 10052.0000 0 : 0.0000 0 : 0. 0.1540 : 21210.2218 : 4266.536 : ------------------------------------------------------------------------SUBTOTAL : 50618.0661 14 : 2. 0. RB 9 U TUBE D1-reb Tube material A 214 23500 CODE OF ACCOUNT: 262 Heat transfer area 921. 1.9704 : 4783.0303 32 : 0.5106 : 1734.494 : CIVIL : 141.431 : STRUCTURAL STEEL : 0. 0. 0. 0.30 PSIG Driver type MOTOR Seal type SNGL Total weight 200 LBS I T E M :--.2721 42 : 1.30 PSIG Shell design temperature 353.5256 88 : 1.: D1-bottoms s ========================================================================================================================== Equipment mapped from 'D1'.3543 : 9585.377 : ELECTRICAL : 0.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------. 3.355 : ELECTRICAL : 596. 0.5243 : 4641.000 : INSTRUMENTATION : 12322. 0.00 RPM Driver power 1. 0.0000 : 0. QUOTE EQP8 D1-bottoms split Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO. INST'L COST/PE RATIO = 3.0000 : 0. 0.98 DEG F Speed 3600.30 PSIG Tube design temperature 377.0000 : 713.: D1-overhead ========================================================================================================================== ========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.1815 218 : 0.818 : PAINT : 189. 0.4896 : 1747. 0.0429 : 468.0621 10 : 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'. 0. 0. 0.1417 27 : 3.0241 : 218. 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'D1'.00 FEET Tube port diameter 26. 0.: D1-reflux pu Fluid head 70.746 : ------------------------------------------------------------------------SUBTOTAL : 13920.000 INCHES Tube length extended 20. 0. 4. 0.419 : TOTAL MATERIAL AND MANPOWER COST =USD 71800.000 HP Design gauge pressure 35. 0. 1.0454 : 1526.000 : INSTRUMENTATION : 4916.306 : STRUCTURAL STEEL : 0. 1.00 FEET Design temperature 254. 2.000 : INSULATION : 5213.1975 203 : 0. 1.722 : TOTAL MATERIAL AND MANPOWER COST =USD 24000. 0. 0.20 SF TAG NO.0204 31 : 2.506 : INSULATION : 1685.9026 990 : 0.M A T E R I A L ---:********* M A N P O W E R *********:--.44 GPM TAG NO. INST'L COST/PE RATIO = 7.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 3300. 0.00 INCHES Shell length 13.00 INCHES Tube design gauge pressure 110.5293 76 : 0.4079 416 : 1.055 CD-IPE-74 .02 DEG F Shell diameter 39.1807 : 898. 0. 0.4493 206 : 1.M A T E R I A L ---:********* M A N P O W E R *********:--. QUOTE EQP7 D1-overhead split Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO.0649 90 : 1.029 : PAINT : 79.: D1-reb Shell material A285C TEMA type BKU Shell design gauge pressure 35.0081 : 480.273 ========================================================================================================================== Equipment mapped from 'D1'.80 DEG F Tube outside diameter 1.062 : PIPING : 3202. CP 6 CENTRIF D1-reflux pump Casing material CS 3300 CODE OF ACCOUNT: 161 Liquid flow rate 37.0000 : 205.

1203 : 2415.1459 : 17670. 0.1937 922 : 0.209 : ELECTRICAL : 0.3589 : 4314.0000 : 0.M A T E R I A L ---:********* M A N P O W E R *********:--. 2.0000 : 0. 0. 1.000 : INSULATION : 3291.4887 817 : 0.0631 29 : 2.0000 : 512. VT .M A T E R I A L ---:********* M A N P O W E R *********:--. 1. 0.290 : ELECTRICAL : 0.0000 0 : 0. 0. 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 7100.247 : STRUCTURAL STEEL : 0. 0. 0.2680 220 : 0. INST'L COST/PE RATIO = 3.930 : PAINT : 172. 1.========================================================================================================================== C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------. INST'L COST/PE RATIO = 7.0721 25 : 0.1554 65 : 1.0000 : 2195. 1. 2.10 CYLINDER F1 Shell material A 515 7100 CODE OF ACCOUNT: 113 Liquid volume 264. 0. 0.3507 : 1635.00 DEG F Design gauge pressure 35.747 : PAINT : 213.00 FEET Number of tubes per shell 1 Design gauge pressure 60.5266 161 : 0.419 : ------------------------------------------------------------------------SUBTOTAL : 38867.886 : CIVIL : 1937.634 ========================================================================================================================== =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 16100.0000 : 0.494 : TOTAL MATERIAL AND MANPOWER COST =USD 58100.0132 : 516.072 : PIPING : 7383.30 PSIG Application CONT Base material thickness 0.: F1 Vessel diameter 3.000 FEET Design temperature 320.193 : CIVIL : 659.313 INCHES Total weight 1400 LBS I T E M :--.5709 : 8144. 0. 0. 1. 0. 0.609 ========================================================================================================================== CD-IPE-75 .4141 : 19219.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'F1'. 0.1016 69 : 0.1500 143 : 1. 0.0929 : 1103.11 SF TAG NO.484 : TOTAL MATERIAL AND MANPOWER COST =USD 54200.5059 357 : 0.1363 100 : 0. 0.0242 : 448. 0.0320 33 : 2.0000 0 : 0.0000 0 : 0.4635 : 3060. 0. 0.2406 381 : 1.5255 : 3739. 2.: H1 Tube length 20.30 PSIG Temperature 331.00 DEG F Number of sections 8 Total weight 7280 LBS I T E M :--. 0. 0.136 : PIPING : 9192.0000 0 : 0. 0.000 : INSTRUMENTATION : 17931.605 : ------------------------------------------------------------------------SUBTOTAL : 36536. 5.000 : INSULATION : 5778.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'H1'.000 : INSTRUMENTATION : 5647.0000 : 0. 0.000 FEET Vessel tangent to tangent height 5. 0. 0. 0.11 JACKETED H1 Material CS 16100 CODE OF ACCOUNT: 263 Heat transfer area 160. 0.40 GALLONS TAG NO.0398 : 8809.673 : STRUCTURAL STEEL : 0.4309 156 : 0. HE .

0.00 FEET Total weight 2500 LBS I T E M :--.02 DEG F Tube outside diameter 1.0547 : 1132.0418 33 : 2.4967 71 : 1.10 FEET Design temperature 250. INST'L COST/PE RATIO = 4.0000 0 : 0.30 PSIG Shell design temperature 353.0171 : 139. 0.80 SF TAG NO.14 M1 Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO.246 : STRUCTURAL STEEL : 0.0000 : 0.926 : TOTAL MATERIAL AND MANPOWER COST =USD 19800.3207 42 : 1.: M1 ========================================================================================================================== Equipment mapped from 'S1'. INST'L COST/PE RATIO = 7.370 : ELECTRICAL : 0. 1.00 DEG F Speed 3600.5102 : 1747. 0.C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.071 CD-IPE-76 .903 : ------------------------------------------------------------------------SUBTOTAL : 10261.30 PSIG Tube design temperature 353.7763 : 8205.02 DEG F Shell diameter 10.5146 : 4641.2129 : 898. 0. 0. 0.506 : INSULATION : 999.852 : CIVIL : 679.000 INCHES Tube length extended 20.00 INCHES Shell length 22. 0.669 : STRUCTURAL STEEL : 0.15 S1 Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO. HE . QUOTE EQP.500 HP Fluid viscosity 0.073 : PIPING : 1441.221 : CIVIL : 148. 0.12 FLOAT HEAD H2 Tube material A 214 12400 CODE OF ACCOUNT: 261 Heat transfer area 195.477 : TOTAL MATERIAL AND MANPOWER COST =USD 52900. 1. 1.0000 : 205. 0.413 : ELECTRICAL : 596. 0.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'H2'.0173 : 519. 0. 0.2313 125 : 0.6243 : 2868. 0.0495 9 : 2. 3.6239 76 : 0.: S1 ========================================================================================================================== Equipment mapped from 'P1'.D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'M1'.0913 67 : 1.8863 : 17087. 2.6576 200 : 3.070 : PIPING : 9626. 0.73 GPM TAG NO.M A T E R I A L ---:********* M A N P O W E R *********:--.0000 0 : 0.00 RPM Driver power 1. CP . 3. 1. 0.000 : INSTRUMENTATION : 7742.M A T E R I A L ---:********* M A N P O W E R *********:--. 0.0000 : 0.3780 802 : 0.266 ========================================================================================================================== ========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------. 0.0529 : 481. 0. 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 12400.6645 : 9501.0000 0 : 0.6617 360 : 0.30 PSIG Driver type MOTOR Seal type SNGL Total weight 210 LBS I T E M :--. 0.18 CENTRIF P1 Casing material CS 2800 CODE OF ACCOUNT: 161 Liquid flow rate 22.000 : INSULATION : 5130.0705 40 : 0.1717 28 : 3. 0. 0. 0. 0.0732 10 : 0.4137 : 3490.680 : PAINT : 215.00 FEET Tube design gauge pressure 60.392 : PAINT : 48. 0. 1.: P1 Fluid head 62.417 : ------------------------------------------------------------------------SUBTOTAL : 35791.: H2 Shell material A285C TEMA type BES Shell design gauge pressure 35.000 : INSTRUMENTATION : 4228.2814 177 : 0. QUOTE EQP.0000 : 874.0000 : 0. 0.3933 436 : 0.583 CPOISE Design gauge pressure 60.3569 : 1391. 0. 0.L/M ---: : FRACTION : FRACTION : RATIO : : USD OF PE : USD OF PE MANHOURS : USD/USD : EQUIPMENT&SETTING: 2800.

========================================================================================================================== C O M P O N E N T L I S T =========================================================================================================================== : : : : : PURCHASED: :ORIGIN : ITEM TYPE : I T E M :--------------------.: T1 ========================================================================================================================== CD-IPE-77 .D E S I G N D A T A --------------------: EQUIPMENT: : : : D E S C R I P T I O N : : COST USD : =========================================================================================================================== Equipment mapped from 'T1'.19 T1 Number of identical items 1 0 CODE OF ACCOUNT: 100 TAG NO. QUOTE EQP.

000 FEET 50. 7771. 2211. 16051. AREA AREA AREA AREA AREA AREA CD-IPE-78 . 4921.JBOX. 0. 430. 22 0. 430. 2648. 831. 430. EQUIPMENT GROUNDING PILED FOUNDATION Number of piles ELECTRICAL TESTING ROTATING EQP SPARE PARTS 0. 198 3358. RUNS.A R E A B U L K R E P O R T ================================================================================================================================= : : : : : M A N P O W E R : TOTAL : : : ITEM : D E S C R I P T I O N :------------------------------------: MATERIAL :------------------: DIRECT : :ORIGIN : SYMBOL :---------: D E S I G N D A T A : COST-USD : MANHOURS:COST-USD: COST-USD: ================================================================================================================================= AREA MISC CONCRETE ITEMS 916. 13840. 50. 7534. 3471. 462. AREA GRADE PIPE TESTING UNPAVED AREA Area length Area width INSTRUMENT TESTING INSTR. 4274. 369. 328 127 7771. 20 0 430. 1450.TRAYS. 179 68 23 131 4012.000 FEET 0. 10182. 4012.

1.1.2.1.10 A-II.2 A-II.4 A-II.9 A-II. A-II.DESIGN PROBLEM STATEMENTS A-II.1.1.1.1.8 A-II.7 A-II.1.1.1.3 A-II.1.1 A-II.12 A-II.0 CONTENTS AND INTRODUCTION Petrochemicals Batch Di (3-pentyl) Malate Process Acetaldehyde from Acetic Acid Ethylene by Oxidative Dehydrogenation of Ethane Butadiene to n-Butyraldehyde and n-Butanol Methacrylic Acid to Methylmethacrylate Coproduction of Ethylene and Acetic Acid from Ethane Methylmethacrylate from Propyne Mixed-C4 Byproduct Upgrade Hydrogen Peroxide Manufacture Di-tertiary-butyl-peroxide Manufacture Vinyl Acetate Process PM Acetate Manufacture Propoxylated Ethylenediamine Petroleum Products Fuel Additives for Cleaner Emissions A-II.1 Problem No.1.11 A-II.5 A-II.6 A-II.1.13 CD-A-II-1 .

5.5 A-II.6.6.5.2 A-II.2 A-II.2 A-II.1 A-II.3 A-II.3.1 A-II.3 A-II.1 A-II.7.3.5 CD-A-II-2 .3.3.3 A-II.6.2 A-II.4.2 A-II.1 A-II.4 A-II.4 A-II.Gas Manufacture Nitrogen Rejection Unit (from natural gas) Ultra-pure Nitrogen Generator Nitrogen Production Krypton and Xenon from Air Ultra-High-Purity Oxygen Foods Monosodium Glutamate Polysaccharides from Microalgae Alitame Sweetener Pharamaceuticals Generic Recombinant Human Tissue Plasminogen Activator (tPA) Penicillin Manufacture Novobiocin Manufacture Polymers Polyvinyl Acetate Production for Polyvinyl Alcohol Plant Butadiene to Styrene Biodegradable PHBV Copolymer Xantham Biopolymer Rapamycin-Coated Stents for Johnson & Johnson Environmental – Air Quality R134a Refrigerant Biocatalytic Desulfurization of Diesel Oil A-II.4.6.3.4.3 A-II.6.1 A-II.5.7.

2 A-II.10.7.3 A-II.2 A-II.3 A-II.8.8.10.6 A-II.1 A-II.Sulfur Recovery Using Oxygen-Enriched Air California Smog Control Zero Emissions Volatile Organic Compound Abatement Recovery and Purification of HFC by Distillation Carbon Dioxide Fixation by Microalgae for Mitigating the Greenhouse Effect Hydrogen Generation for Reformulated Gasoline Environmental – Water Treatment Effluent Remediation from Wafer Fabrication Recovery of Germanium from Optical Fiber Manufacturing Effluents Solvent Waste Recovery Environmental – Soil Treatment Phytoremediation of Lead-Contaminated Sites Soil Remediation and Reclamation Environmental – Miscellaneous Fuel Processor for 5 KW PEM Fuel Cell Unit Combined Cycle Power Generation Production of Low-Sulfur Diesel Fuel Waste Fuel Upgrading to Acetone and Isopropanol Conversion of Cheese Whey (Solid Waste) to Lactic Acid Ethanol from Corn Syrup A-II.7.3 A-II.7 A-II.1 A-II.5 A-II.4 A-II.6 CD-A-II-3 .10.7.10.9.7.7.1 A-II.7.7.9 A-II.10.9.2 A-II.8.8 A-II.5 A-II.4 A-II.10.

In the spring.pdf. this was accomplished in each of the problems included herein. the industrial consultants strive to create process opportunities that lead to designs that are timely. and Environmental. each prepared for design teams of three students at the University of Pennsylvania by chemical engineers in the local chemical industry. Polymers. these problem statements should be useful to students and faculty in several respects. Some provide relatively little information. Gas Manufacture. they should provide a basis for similar design projects to be created for their courses. The reader should recognize that. as the design team proceeded to assess the primitive problem statement and carry out a literature search. whereas others are fairly detailed concerning the specific problems that need to be solved to complete the design. and spends the spring semester completing the design. in nearly every case. As seen in the contents. the projects have been assigned to one of the following areas. Still. In this respect. challenging. furthermore. they should help to show the broad spectrum of design problems that chemical engineers have been tackling in recent years. each team selects its design project during the first lecture course in the fall. Petroleum Products. successful designs were completed by a student design team for most of these problems. to report on its progress and gain advice. on the CD-ROM are in their original forms. as they were presented to the student design teams on the date indicated. including the individual who provided the problem statement.This appendix contains the problem statements for 50 design projects. Foods. each group meets regularly with its faculty advisor and industrial consultants. Every effort is made to formulate problems that can be tackled by chemical engineering seniors without unduly gross assumptions and for which good sources of data exist for the reaction kinetics and thermophysical and transport properties. At Penn. In formulating design problem statements. and offer a reasonable likelihood that the final design will be attractive economically. For the faculty. the specific problems it formulated were somewhat different than stated herein. Pharmaceuticals. in some cases arbitrarily: Petrochemicals. CD-A-II-4 . For students. Design Problem Statements. The problem statements in the file.

Brengel Robert M.Credit is given to each formulator on his problem statement. Busche Leonard A. Pillarella William B. as their contributions in preparing these design problems have been crucial to the success of the design course. DE CDI Corporation (formerly ARCO Chemical and Lyondell) Air Products and Chemicals Air Products and Chemicals DuPont DuPont Pennsylvania State University (formerly ARCO Chemical and Lyondell) Air Products and Chemicals Air Products and Chemicals Consultant. Tyreus Kamesh G. Farrell Mike Herron F. In addition. Wilmington. the names of the contributors are listed below with many thanks. PA Air Products and Chemicals Bio-en-gene-er Associates. Venugopal Bruce Vrana Andrew Wang Steve Webb John Wismer Jianguo Xu Air Products and Chemicals Environex. Retallick Matthew J. Wayne. Robert Becker David D.R. Short Peter Staffeld Albert Stella Bjorn D. Miller Robert Nedwick Frank Petrocelli Mark R. Rakesh Agrawal E. West Chester. PA Mobil Technology Company University of Delaware (formerly DuPont) Exxon/Mobil General Electric (formerly AlliedSignal) DuPont Air Products and Chemicals DuPont Air Products and Chemicals Air Products and Chemicals Atochem North America Air Products and Chemicals CD-A-II-5 . Miles Julian Ralph N. Fabiano Brian E. Quale David G.

A-II. When the desired conversion is achieved.1. the rest of the time the reactor is idle. bottom). using 0. Water and 3-pentanol form a low-boiling azeotrope (see CRC Handbook for data) that forms two liquid phases upon condensation. Your marketing team has projected the following sales estimates for this product: Anticipated Sales (in thousands of pounds) 1 Sales @ $6.600 1.000-pound batches that require 36 reactor hours per batch and is sold at a profit of $0.200 4 and beyond 3. January 2002) Your company.1 weight percent of an acid catalyst such as sulfuric acid (see reaction above). This reactor is jacketed for heating and uses 175 psig saturated steam.00/lb 100 75 2 600 450 3 1. This approach can be used with your existing reactor. which is sufficiently corrosionresistant for producing the new product as well. 1. A typical process scheme would be to carry out the batch reaction above the azeotrope temperature while condensing the overhead vapors into a decanter.1 PETROCHEMICALS Batch Di (3-pentyl) Malate Process (Frank Petrocelli and Andrew Wang. Water is produced as a co-product and must be removed to drive the reaction to completion.000 2. A more sophisticated approach would involve interposing a distillation column between the reactor and the condenser.1 A-II. recycling the organic layer to the reactor and removing the aqueous layer (Figure 1.88 per pound. Air Products and Chemicals.50/lb Sales @ $8.000-gallon batch reactor that is used to manufacture another product (Product X). 100 such batches are produced annually (not expected to change). Product X is made in 6. the product must be treated with aqueous sodium hydroxide to neutralize the residual acidity (due both to the catalyst and the unreacted malic acid). The jacket has a heat-transfer area of 88 ft2 and an estimated overall heat-transfer coefficient of 100 Btu/ft2hr°F. allowing the alcohol-rich vapors off the reactor to strip water out of the organic recycle (Figure 1. a small specialty chemicals manufacturing operation. top). O OH OH OH OH O + 2 ROH Acid Catalyst O OR OR O + 2 H2O Di(3-pentyl) malate is made by batch reaction of malic acid with an excess of 3-pentanol. is considering producing di(3-pentyl) malate for the additives market.250 You currently have a fully depreciated. The residual 3-pentanol must be stripped off CD-A-II-6 . This reactor is made of 316SS.

filtration. 3. 2. Assume that the Henry’s law constant for 3pentanol in the product is 1.37 <0. This will itemize the individual steps the operator will follow to produce the batch.076 5 0. Finally.? What kind of vacuum system should you purchase? CD-A-II-7 .1N <0.1 wt.% 1.min) kLa (1/hr) The required product specifications are: Residual acidity (prior to neutralization) Residual 3-pentanol Purity (moles ester / total moles) You are being asked to provide the following: 2 0. Your R&D group has come up with the mass-transfer estimates given in Table 1.% >98 wt. estimated duration of each step and the safety procedures and precautions that must be followed.using vacuum (50 mm Hg) with nitrogen sparge at 120°C. Your company currently has no vacuum or filtration equipment. A recommendation to management on whether/when to build the dedicated equipment or use the existing reactor. time)? How does the composition of the vapor from the reactor change with time? What ratio of alcohol to malic acid should be charged? What types of process control systems are required to ensure product quality? What are you going to do with the aqueous byproduct and the recovered excess alcohol? Is it worth buying any additional vessels for post-treatment. Mass Transfer Data Superficial Gas Velocity (scf/ft2.200 mm Hg. supported by appropriate financial information. and y is the vapor phase mole fraction of 3-pentanol. including a capital cost estimate for both process options shown in Figure 1. y* is the dt vapor phase mole fraction of 3-pentanol in equilibrium with x.12 10 0. dx = k L a y * − y where x is the mole fraction of 3-pentanol in the liquid . An equipment design for a dedicated batch-reactor system to produce dibutyl malate. including amounts of materials being added. storage.17 20 0.24 50 0. etc. Key process determinations: Which process option should you use for a new design – with or without the distillation column? How much heat-transfer surface is required and what heating medium (assume you have saturated steam available at 175 psig for $5 per million Btu)? What type of agitation is needed (horsepower and impeller design)? How long will the reaction take? What is the reaction profile (concentrations and temperature vs. It should also specify when samples must be taken and what the criteria are for proceeding to the next step. ( ) Table 1. A batch ticket for a typical production batch. the product must be filtered to remove the salts of neutralization.

000 exp[-15. Assume that the reaction occurs at atmospheric pressure. $2. Cooling water. use market price Electricity. Residual alcohol and product purity are measured by chromatography.000.000 exp[-23. $0. Use the following reaction rate expressions in your model.00211*exp(2. requiring 45 min from the time the sample is taken.600/T).000.000/RT]*[Ester][Water] Byproduct (Dimer) Reaction: Rate (mol/L-min) = 10. Assume that all products of neutralization are insoluble.03 g/cc. No additional equipment must be purchased to transport or charge the solid malic acid.50/1.000/RT]*[Acid][BuOH] Back-Reaction: Rate (mol/L-min) = 1.95/lb Sulfuric Acid.50 Btu/lb°F throughout the process. 90°F. The heat capacity of the reactor contents is 0. 1. Residual acidity can be measure by titration. requiring 15 minutes to obtain a measurement from the time the sample is taken.000 exp[-16.55/lb. where T is in Kelvin.750 each. 5000 gal tank truck @ $1.000.05 per KWH. Assume that this is also the density of the reactor contents at every point in the reaction.000 kg supersacks.What equipment will be needed for filtration? What will your overall batch cycle time be? Costs: Malic Acid. 50 lb bags. 55 gal drums. $78 each 3-pentanol. $0.000/RT]*[Ester]2 Make the following additional assumptions (and be sure to document additional assumption you make): Malic acid completely dissolves in 3-pentanol at 70°C. Product density is 1. CD-A-II-8 . Assume that during filtration only the resistance of the cake itself is significant. $2.000 gal Data & Additional Information: The viscosity (cP) of the reactor contents can be estimated using the equation 0. treating the two acid groups on each malic acid molecule as if they are two separate molecules: Acid + 3-Pentanol = Ester + Water 2Ester = Dimer + 3-Pentanol Formation of ester: Rate (mol/L-min) = 1.

Reaction Schemes for Di(3-pentyl) Malate Manufacture CD-A-II-9 .VENT Org Aqu AQUEOUS BYPRODUCT VENT Org Aqu AQUEOUS BYPRODUCT Figure 1.

and make appropriate recommendations. that price might drop to $0.12/lb. Your company has asked your group to determine whether this new technology should be used in your Gulf Coast plant. DuPont.95% pure. That process is very corrosive. Based on past experience. Eastman Chemical has developed a selective palladium catalyst that gives acetaldehyde with selectivity of up to 86% at 46% conversion. you know that you will have to defend any decisions you have made throughout the design.S. Acetic acid.2 Acetaldehyde from Acetic Acid (Bruce Vrana. And like all oxidations. if 99. can be sold (on an excise tax-free basis) for $2. if MTBE is legislated out of gasoline. there may be a worldwide glut of methanol. Hydrogen can be purchased over the plant fence for $0. requiring expensive materials of construction. water and ethanol. according to your marketing organization. Gulf Coast location on the same site as a large chemical plant. which is available on the site.50/lb at 200 psig. However. But the reduction of acetic acid to acetaldehyde is notoriously difficult. would be a good feedstock.1. It is commercially made via the Wacker process.50/gal. Ethanol.A-II. the partial oxidation of ethylene. January 2002) Acetaldehyde is a versatile chemical intermediate. so any chemicals that use methanol may become much more economically attractive. And the acetic acid-water and acetone-water mixtures are famous for their tangent pinches. However. the ethanol-water azeotrope can also be sold into the CD-A-II-10 . over-oxidation of the ingredient and the product reduce the yield. produced from inexpensive methanol. Acetaldehyde can be sold for $0. Byproducts formed include ethanol. however. Acetic acid is available on your site for $0. and the best defense is economic justification. CH 3 − COOH + H 2 → CH 3 − CHO + H 2O (main reaction) CH 3 − COOH + 2 H 2 → CH 3 − CH 2OH + H 2O CH 3 − COOH + CH 3 − CH 2OH ↔ CH 3 − COO − CH 2 − CH 3 + H 2O 2 CH 3 − COOH + 2 H 2 → CH 3 − CO − CH 3 + CH 4 + H 2O Distillation of the product will be complicated by the existence of azeotropes between ethanol and ethyl acetate. Test your economics with both prices. acetone and ethyl acetate. Your job is to design a process and plant to produce 100 MM lb/yr of acetaldehyde from acetic acid. and water and ethyl acetate. Because of the possible legislation of MTBE out of gasoline. because aldehydes are easier than acids to reduce. all of which can be sold after purification.16/lb. Rigorous distillation simulations with thermodynamics that accurately predict each of these azeotropes and pinches will be required to have confidence in the design.48/lb. Assume a U. if a selective route to acetaldehyde could be found. and convert expensive ethylene into carbon oxides.

which may require significantly less investment. The selectivity is similar to that in the conventional steam cracking process. The plant design should be as environmentally friendly as possible.60/lb. All prices listed are in 2002 dollars. Your company has 1 MMM pounds per year of ethane. ethane is passed over a catalyst at very high space velocity (100. The fluidized bed has a slightly higher selectivity. depending on which is most economical to produce. according to Dow. Recover and recycle process materials to the maximum economic extent. Dow Chemical has recently applied for a patent on a new process. The plant design must also be controllable and safe to operate. truck or railcar loading stations.fuel market for $1. Dow has patented both a fixed bed supported catalyst and a fluidized bed reactor. It is normally produced by steam cracking of ethane or heavier hydrocarbons. with world production over 50 billion pounds per year. and discuss this major decision in your report. January 2001) Ethylene is the largest volume organic chemical product. etc. Patent 6. Because the reaction with oxygen is exothermic. A-II.1.3 Ethylene by Oxidative Dehydrogenation of Ethane (Bruce Vrana.121. In this process. to the extent economically justified. Your job is to determine the economic optimum design. the expensive furnaces of the steam cracking process should not be required. maximizing the net present CD-A-II-11 . for each byproduct that you sell. but the conversion is higher. DuPont. Hydrogen in the feed improves the conversion while minimizing the amount of over-oxidation of the feedstock. and reacts with oxygen (exothermically!).498 to Eastman Chemical. which should result in a much more operable plant. Remember that you will be there for the start-up and will have to live with whatever design decisions you have made. Acetone can be sold for $0.000/hr or higher). This process is quite energy and capital intensive. You may sell either or both grades of ethanol. producing ethylene in good selectivity (greater than 80% under some conditions) and high conversion. References: U. S. Your team has been asked to evaluate the economic viability of the Dow process for your plant.. You will need storage tanks.07/lb in 2000. which is currently being produced at your Gulf Coast plant and sold for $0. energy consumption should be minimized. and would probably be easier to manage the heat load than the less expensive fixed bed reactor.60/gal. Ethyl acetate can be sold for $0. as a way of upgrading your product and increasing your sales revenue. Byproducts sold must also meet normal purity specs for that chemical. You should use economics and technical criteria to guide your decision about which reactor technology to use in the plant design.20/lb. Much less coke is produced in this reactor system. Also. or you may burn them in the boiler for fuel value.

25/lb in 2001 dollars. which is available. or hydrogenated and hydrolyzed to n-butanol using the same Ru catalyst. nBB will then react with more nbutanol to produce the acetal. and the best defense is economic justification. energy consumption should be minimized. Pipeline oxygen in your area costs $0. Reference World Patent Applications 00/14035 and 00/14180 to Dow.4 Butadiene to n-Butyraldehyde and n-Butanol (Bruce Vrana. The n-butyraldehyde is used to make 2-ethyl hexanol via aldol condensation as well as n-butanol. You may consume all or part of the ethane. with all recycle loops closed.1. an important consideration with oxygen and hydrocarbons.value (NPV) of the project. DuPont. The plant design must also be controllable and safe to operate. Remember that you will be there for the start-up and will have to live with whatever design decisions you have made. The acetal can be hydrolyzed to n-butyraldehyde. They found that a homogeneous palladium acetonylacetonate catalyst with phosphine ligands would allow butadiene to react with n-butanol to produce 1-n-butoxy-2-butene (nBB). you know that you will have to be able to defend any decisions you have made throughout the design. BASF has applied for a patent on a new route to n-butyraldehyde and/or n-butanol starting from butadiene.02/lb. CH2=CHCH=CH2 + BuOH → BuO-CH2CH=CHCH3 [nBB] nBB + BuOH → (BuO)2CHCH2CH3 [Acetal] Acetal + H2O → O=CHCH2CH2CH3 + 2 BuOH Acetal + H2 + H2O → 3 BuOH CD-A-II-12 . Because propylene is frequently quite expensive and in short supply. It would be a good idea to test the sensitivity of the optimum plant design and economics to uncertainty in the selling prices of the product and the raw material. using a homogeneous phosphine modified ruthenium catalyst. Based on past experience. Recover and recycle process materials to the maximum economic extent. Your plant design must be backed up with a rigorous simulation of the entire process. in either the alcohols or ester form. These oxo alcohols are frequently used. January 2000) n-Butyraldehyde is conventionally produced from propylene and highly toxic synthesis gas in the so-called oxo process. Also. A-II. The plant design should be as environmentally friendly as possible. to the extent economically justified. Your marketing organization believes they can sell ethylene for $0. as solvents.

As an alternative. both in 2001 dollars. to the extent economically justified. you could purchase pure butadiene for $0. Based on past experience.Unfortunately. The butenes in the C4 cut are inert under the reaction conditions. or some combination of the two. one possible feedstock would be the butadiene contained in the crude. The plant design must also be controllable and safe to operate. and n-butanol for $0. you could produce n-butyraldehyde or n-butanol. a side reaction produces 2-butoxy-3-butene (iBB). energy consumption should be minimized. which would result in smaller vessels. the C4 olefin cut from an ethylene cracker. Your company has asked your group to determine whether this new technology should be used in your Gulf Coast plant. and if so. Reference World Patent Application 98/41494 to BASF CD-A-II-13 . Thus. this isomerization reaction is likely to be equilibrium limited. The goal is to maximize the net present value (NPV) of the project. and complicate the separation train. The plant design should be as environmentally friendly as possible.40/lb. The iBB can be isomerized to nBB using an acid ion exchange resin or a Pd catalyst. which has already passed through your MTBE plant to react away the isobutylene. you know that you will have to be able to defend any decisions you have made throughout the design. in the first reactor. so you would only have to pay fuel value for the butadiene you actually consume in the process. Also. and the best defense is economic justification. BASF also found that while this reaction works well with pure butadiene. The composition of your plant's C4 cut.40/lb also. the inert C4's will dilute the reactor contents. You would receive a credit for the unused C4's in the stream. Your marketing organization believes they could sell the aldehyde for $0. which is currently being burned for fuel value. Of course.15/lb in 2001 dollars. is: 43% BD 28% 1-butene 10% cis-2-butene 10% trans-2-butene 6% n-butane 3% isobutene For a product. making it larger. it will also work with "crude" butadiene. what the economic optimum feedstock and product would be. Recover and recycle process materials to the maximum economic extent. Unfortunately. Your company has 200 MM lb/yr of crude butadiene.

it is not often produced from methacrylic acid.