Professional Documents
Culture Documents
The Industrial Practice of Chemical Process Engineering
The Industrial Practice of Chemical Process Engineering
of
Chemical Process Engineering
Samuel W. Bodman
The present text seeks to combine some aspects of the Practice School
program with elements of Professor Sherwood's case-study approach to in
struction in engineering design. It is hoped that the result of this combination
will not only be useful as a text for academic process design instruction but
will also serve as a reference book for the young engineer embarking on a
career in industry.
iii
iv Preface
A great deal of emphasis has been placed on the use of the digital
computer in the analysis and presentation of design problems; computer
programs are presented for three of the cases discussed. These programs
and others like them have proven to be particularly stimulating when used in
a "computerized classroom, " wherein the student can communicate directly
with the machine. In preparing portions of the text, it has been assumed that
the reader has at least some knowledge of the FORTRAN coding language.
The present volume was written while the author served as Director of
the Bound Brook Station of M. I.T.'s School of Chemical Engineering Practice.
This station is located with the Organic Chemical Division of the American
Cyanamid Company, Bound Brook, New Jersey. The data used in the prep
aration of Chapter 3 were gathered by a student group as a part of a project
at the Bound Brook Station. The author is grateful to American Cyanamid for
its permission to use these data as well as for the company's hospitality during
the 1965-66 and 1966-67 academic years.
S. W. Bodman
Cambridge, Massachusetts
March, 1968
Contents
Preface iii
1. Introduction 1
Appendix 199
Index 229
1. Introduction
1
2 Chapter 1
In his text, Sherwood (41) states quite appropriately that the de
signer must be willing to make assumptions. Once sufficient informa-
Table 1-1. Useful Methods of Evaluating and Correlating Chemical Engineering Expe rimental Data
Bases for Evaluation or Literature
Process Operation Required Design Parameter Correlation of Data References
Fluid transportation Friction factor 1/2 F(NHe)
= (3-1)
Fluid heating or cooling Heat-transfer coefficient j /IF(N He)
= (31)
Chemical reaction Chemical-kinetic constant Arrhenius correlation (46)
Chemical-equilibrium constant van't Hoff correlation (.52)
Catalytic chemical Effectiveness factor Thiele modulus (10)
reaction
Mass-transfer coefficient from jo = F(Nl<e) (10)
fluid to catalyst pellet surface
Slurry reaction Mass-transfer coefficient (rom kL = F(D. N.D p.ll. Ap) (19)
liquid to catalyst pellet surface
Sparged reaction Mass-transfer coefficient at the kL = F(D, N) (27)
bulk liquid surface
Mass-transfer coefficient from kLa = F(D, N, Vs) (45)
a gas bubble to bulk liquid
Absorption Solubility of gas in a liquid Henry's law or Raoult's law (21)
Boiling or Vapor pressure Clausius-Clapeyron equation (52)
condensation
Distillation Vapor-liquid equilibrium Gibbs-Duhem equation (37) �
(relative volatility)
-
�
c
Tray efficiency Murphree efficiency relationship (37) �
<=;
Crystallization Solubility and supersolubility Clapeyron-type correlation (U) -
-.
Extraction Distribution (partition) Nernst's law (1·1) g
coeffiCient
�
10 Chapter 1
SUMMARY
NOTATION
D Diffusion coefficient
Dp Catalyst pellet diameter
Introductioll 15
f Friction factor
jD Mass-transfer j-factor
jJJ Heat-transfer j-factor
IlL Liquid-phase mass-transfer coefficient
N Rotational speed of impeller
NRe Reynolds number
Vs Superficial gas velocity
J.l Dynamic viscosity
Ap Density difference between solid and liquid
REFERENCES
1 8. Happel, J., Chemical Process Economics, John Wiley & Sons, Inc.,
New York (1958) .
23. Hunter, W. G., and A. C. Atkinson, Chern. Eng. 7 3, No.12 ,159 (1966).
35. Peters, M. S., Plant Design and Economics for Chemical Engin
eers, McGraw-Hill Book Co., Inc., New York (1958).
36. Ravicz, A. E., and R. L. Norman, Chern. Eng. Progr. 60, No. 5, 71
(1964).
38. Rosen, E. M., Chern. Eng. Progr. 58, No. 10,69 (1962).
Introduction 17
(1963).
This case deals ll'ith the design of a process for the chlorillatioll of
bellzelle, Initial ellljJ/wsis is placed on tlie jJroj)er correlation of
laboratory data that describe the ldnetics of tlie three sequential
chlorinatioll reactions, Set'eral /)rocess schellles, illeluding bolh batch
and COl1til1llOUS oj)erations, are examil1ed ami each is oj)tilllized econo
mically, The most attraeth'e j)rocess is selected by })leallS of examin
il1g the result s of tlie financial emll/atioll, Filially, the thermal stabil
ity of IIle O/JtiJlIIIIII jJ}"ocess is inl'estigated alld the desigll is lIlodified
apjJro/)riately ill order to ellsure stable operation,
Tile cha/)ter j)roL'ides all opportllnity for tlie invelltioH alld analysis
of mriOl/s process schemes, Set'eral altenzatil'e designs are available
It'llicll might offer certain adml/lages o/'er those cases cOllsidered in
tlie /)resellt text, These alleY/lath'es quite j)ro/)erly could forlll tlie
basis for fllrllier designs alld ecollolllic emillaliolls, Tlie effectil'eness
of litis c/w/)ter lzillges Oil the deterwinatioll of the appro/)riate design
jJarallleler such Ihal tlie ecollomies of mriolls ty/)es of reactor desiglls
call be cOllljJared ill a meal/ingful u'ay,
18
R eactor Desigll, OjJtilllizatiOll, alld COl/trol 19
quested to evaluate the feasibility of this proj ect under the assump
tion that both benzene and chlorine would have to be purchased .
T h e three reactors a r e equipped with coils for heating and cooling
and with gas distributor s to a s sure that the chlorine is well dispersed
so as to keep the liquid saturated with chlorine. The reactors are
necessarily ope rated at atmospheric pres sure. Each has a reflux
conden ser, a chlorine gas r ecycle system, an agitator, and 5 5 0 sq ft of
cooling surface in the form of a double helical coil of O. 5-in. o. d.
tubing. With the agitator in op eration, ove r - all heat transfe r coef
ficients o f 1 5 0 Btu/(h r) (sq ft) (OF) have been obtained for benzene at
60°C with cooling wate r in the coil . During operation, with chlorine
being fed, each reactor will hold 400 gallons of liquid. Adequate dis
tillation capacity is available to s eparate the unconverted benzene and
the chlorinated products: technical - grade monochlorobenzene and a
mixture of di- and trichlorobenz ene s . It is anticipated that this latter
mixture cannot be sold and that it will have to be di scarded.
The kinetics of the liquid-phase chlorination of benzene have been
investigated by the Res earch Department; their re sults confirm the
lite rature reports that the chlorination of benz ene, monochlorobenzene,
and dichlorobenzene is in all cas e s first -order and irreversible, bas ed
on rate equations in which mole fractions (instead of mole s per unit
volume) are employed. The laboratory tests were carried out in a 2-
liter flask equipped with a r eflux condenser that returned everything
but exc e s s chlorine. The liquid was well agitat ed by the bubbling
chlorine, which was fed through a fritted glass bubbler. Small amounts
of ferric chloride were used as a cataly st.
The re sults of the laboratory tests are summarized as follows:
Mole Fraction
Time Mole Fraction Benzene Monochlorobenzene
---
Physical Data
Suggested Nomenclature:
Before study ing the different pos s ible r eactor flow plans , the
chemical kinetics for the chlorination r eactions must be derived by
refe rring to pertinent literature reference s (6) and by examining the
available laboratory data. The chemical reactions to be considered
are
C 6H6 + Cl2 __ C 6H5CI + HCI
dXA
= !ZlxA (2. 1)
elt
(LYB
= k 1 x A - k 2 xB (2. 2)
dt
dx
k t
- � = k lX A ; xA =e- l (xA = 1 . 0 at t = 0) (2 . 3 )
tit
k1
xB = (e-k2t _ eklt) (2. 4)
kl -k2
10 .------r---r--
1---t-O
--t---iT--J'--t---l .1 ..
�
::>
o
.<:.
N
...
...-
O. 1 I---Tf-f-t---t---t---l 0.01
30 60
Temperature.oC
k 2 , hr- 1 0. 0045 0. 0 5 5 0. 4 5
Figure 2 - 1 shows the se re sults graphically and may b e used t o inter
palate between data pOints. Figure 2 -2 is a check on the calculations;
the data are compared with curves calculated by the use of Eqs. 2 . 3
and 2 . 4 and the tabulated rate constant s .
e 10 12 14 16
Time. hours
Legend
Symbol Mole Fraction Temperature, OC
t:,. XA 40
+ XA 55
A. XA 70
0 XB 40
x XB 55
• XB 70
Benzene recycle
Tt Tz T5
X At XAZ Xu
Benz_ x .. X.Z
fHd F xl5
OiChloro- and
'richlaro
benzene
First Reacto r
1
xA - ----
l -
1+K 11
Second Reactor
- x.<l1 1
x
:.4.2 -1 +K1 = (----
1 +Ku (1 +K12)
)
--
2
F(XB2 - xB1) = NR (1l1 xA2 - k2 xB2 )
K1 2
xB2 = -=-==--
(1+K11) (1+K 1 2 ) (1+K22 )
------- -----
Third Reacto r
XA2 1
XA3
1 +-K--
=-- 13 (2. 5)
R eacto1' Design, OpLimizat.:oJl, and ConLml 27
(2 . 6)
1
x - ----
- (I +K ) 3 (2 . 7)
A3 1
and
( 2 . 8)
Costs
The annual co sts for the required production rate of 8 million
lbs/year of monochlorobenzene are expressed in term s of xA3 and xB3•
�
_
_
400 x
7. 4 8
62. 3
x 78
x 0. 88
-
_
37. 6 lb mo I es
8 ----8 X 1 06
1 1 2. 6 FXB 3
-
7 1 , 000
FXB 3
hr/year
8 X 1 06 x 78
x 0. 03 4 = $1 89, 000/year
112. 6
(b)
X 3
Benzene for dichlorobenzene: $1 89, 000 C year
xB3
!
28 Clza/)ter 2
8 X 106 X 71 x 0. 045
---- = $2 27, 400/year
1 12. 6
By summing items a through It, the total annual operating cost for
this process is established; this parameter is a function of F, 1'" T 2'
and T 3' The total costs will evidently pass through a minimum as the
feed rate F is varied. At low flow rates, with U approaching 7000, the
conversion is high and the cost of chlorine and benzene for the un
wanted dichlorobenzene becomes large. At very high flow rates the
conversion is low and the cost of benzene recycle becomes excessive.
For the particular case when all the reactors are operated at 5 5°C,
Eqs. 2 . 7 and 2. 8 may be applied. In this instance:
(0. 0 5 5) (3 7 . 6) 2. 07
[(2 =
F F (2. 1 0)
Using Eqs. 2 . 7 to 2 . 1 0, calculations have been carried out in order to
optimize Case I when all the reactors are operated at 55°C. The re
sults are summarized in Table 2 - 1 .
Table 2-1 indicates that a minimum annual cost is achieved for
Case I when the feed rate is about 55 Ib moles/hr and the reactor sys
tem is operated approximately 2660 hrs/year. It is to be noted that
the minimum in the total cost curve is a very broad one. Therefore,
Table 2-1. Results of the Design Calculations for Case I
De sign parameter s
F 10 20 30 40 50 60 70 1 00
1(1 1. 55 0. 7 5 5 0. 5 1 6 0. 3 87 0.3 1 0 0. 2 5 9 0. 2 2 1 0. 1 5 5
[(2 0 . 2 07 0.1 03 0 . 069 0. 0 5 1 8 0. 041 4 0.0345 0 . 02 96 0. 0207
::;:,
�
xA3 0. 0603 0. 1 79 0. 2 8 8 0. 3 74 0. 446 0. 502 0. 549 0. 649 �
<)
....
xn3 0. 5 8 6 0. 652 0. 6 1 4 0. 560 0. 5 1 0 0. 464 0. 424 0. 3 3 8 c
"'(
xC3 0. 3 54 0. 1 69 0. 098 0. 066 0 . 044 0. 034 0. 02 7 0. 013 tJ
�
CJ)
9 1 2, 100 5, 440 3 , 860 3 , 1 70 2, 780 2 , 540 2 , 400 2 , 1 00 riC"
..'t:f.
Costs,dollars /year
�"-
a+c+g+h 5 3 8, 400 53 8, 400 53 8, 400 53 8,400 5 3 8, 400 538, 400 53 8,400 �-..
b 1\1
49,000 3 0,200 2 2 , 3 00 16,300 1 3 , 800 12 , 1 00 7,3 00 t:I
"-
-
tl 1 1 8, 2 00 72 , 600 53, 600 3 9 , 200 3 3 , 400 29, 000 1 7, 500 .
g
e 22,800 3 9, 000 5 5,500 72 , 700 90, 000 1 07, 3 00 1 5 9, 3 00 e
i5..
f 1 52, 000 1 0 8, 000 88, 500 77, 600 71 , 000 67, 000 5 8, 600 (')
Total 880, 400 788, 200 758, 3 00 744, 2 00 746, 600 753 , 800 781 , 100 g....
cl
.....
�
10
30 Chapter 2
wide variations in the operation of the thre e reactor s for this p ro
c e s s can be tolerated since the total conve r s ion cost is only slightly
affe cted. This characte ristic should make it convenient to schedule
other products for manufacture in the same three reacto r s .
I t i s now approp riate to proceed with the inve stigation o f Case s II
and Ill, so that the effect of other typ e s of recycle can be ascertained.
This proce s s case is the same as that shown in Fig. 2-3 , except
that the recycle stream is now mixed with the product from the fir st
reactor. The combined stream is fe d at a rate of (F + R) lb mole s /hr
to the se cond reactor . The analysis of this case proceeds as follows :
First Reactor
The material balances follow dire ctly from Case I, whereby:
Second Re actor
A mate rial balance on benzene around the junction of the recycle
and the line between reactor s 1 and 2 give s
FXA l + R == (F + R)xAl
Solving fo r xA1' the composition of the stream ente r ing the second
reactor, one obtains
where /(3 = R/F. A benzene balance around the second reacto r re
sults in
Kl K IK3
XB2 -
- + ---=--=---- -
2
(1+K2+K3) (1+K1) (1+ K2+K3) 2
Kl
+ ----- �--------
(1+K1) (1+K 2) (1 + K 2+K3)
Third Reacto r
Mate rial balan c e s on benzene and mono chlorobenzene aroun d the
third reactor re sult in
1 + K3 (1+ K 3) K3
x 3- + ------==--=-
-- -
<4. - (1 + K1) (1 + Kl + K3)2 (1+ /(1+ K3)2 (2.11)
K1(1 + K3)
x 3 --------- � -- ��--------------
B - (1 +K + K3)2 (1 + Kl + K3) (1 + K1)
2
Kl (1 + K3) -----
+ .
--------=:...;.,.-- .
--=:...;.,.--
(1 + K1) (1 + K2) (1 +K
2 + Ka)2
/(1 (1+K3)
+ ...-
------�:...- �---
/( I K3(1+/(3)
+ ---��---�---- (2.12)
(1+Kl+K3) 2 (1+K2+K3)
One more relation may be obtained by noting that for the re cycle
R = (F+ R)x A 3
Therefore,
and
(2.13)
32 Chapter 2
Equation 2 . 1 3 can be solved by trial and error so that one may obtain
1(1 as a function of 1(3' The only re maining equation needed is that
which relate s the flow rate and convers ion to 0:
7 1 , 000
e= ----
(F+ R)xB3 (2 . 1 4)
(2. 1 5 )
and
1(1
X - -------'''-----------
-
B3 2
(1 +1( 1) (1+K1 +K3) (1+K2+K3)
K 11(3
+ ------"-"------
(1 +](1+](3) (1+](2+](3)
+ -- ](1
---=-- -
(1 +]( 1)2 (1+1(2) (1+](2+1(3)
-- - -----
](1
( 2. 16)
1
]( 3 - ------
(1 + I( 1)3 - (1 +]( 1)2 - 1 (2 . 1 7)
1
x - ---
(2 . 1 8)
A 1 +K1
and
(2 . 1 9)
3( 1 1 2 . 6)Fx B FXB (2 . 2 0 )
3 NR 1 12. 8
F= -- = --
t t (2.2 1 )
where t repres ents the time each batch is allowed to react. If the time
for loading and unloading is conside red negligible, the annual reactor
u sage follows directly a s
8 x l06 63 0e
8= = --
( 1 1 2.6)FxB xB (2 . 2 2 )
From E q s . 2 . 3 , 2 . 4, 2 . 2 1 , and 2 .22 the ideal operating c o s t s f o r the
hat.r.h rp.ar.t.nr havp. hp.p.n C'.alr.1I1at.p.rl anrl arp. !'lummari7.p.rl in Tahlp. 2-5.
The re sults of the de s ign s for the five reactor cas e s are com
pared in Fig. 2 - 4, which shows the annual ope rating cost for the
t.J
<:l'I
Table 2-4. Results of Design Calculations for Case IV
C")
::::-
Design parameters %
-
�
F 10 15 20 30 40 60 "':
I\l
Kl 1.55 1.032 0.775 0.516 0.387 0.259
K2 0.207 0.138 0.103 0.069 0.0518 0.0345
xA 0.392 0.493 0.563 0.659 0.72 0.795
xB 0.502 0.448 0.395 0.318 0.264 0.199
Xc 0.106 0.059 0.042 0.023 0.016 0.006
e 4,730 3,520 3,000 2,480 2,240 1,970
Costs! dollars/year
a + c +g+ h 538,400 538,400 538,400 538,400 538,400 538,400
b 39,800 24,800 20,100 13,700 11,500 5,700
d 96,000 59,800 48,400 33,000 27,600 13,800
e 64,600 91,500 108,300 172,000 226,500 332,000
f 132,000 98,300 83,900 69,200 62,500 55,000
Total 870,800 812,800 799,100 826,300 866,500 944,900
Table 2-5. Results of Design Calculations for Ca se V
Design parameters
t , hrs 1 2 2. 5 3 4 5 6
F, Eq. 2 . 2 1 11 2 . 8 56. 4 45. 1 37.6 27.2 22. 5 1 8. 8
XA, Eq. 2 . 3 0. 663 0. 434 0. 3 5 6 0. 291 0. 1 92 0. 1 2 8 0. 083 ::;;::
�
i::l
XB, Eq. 2 . 4 0. 3 27 0. 534 0. 5 9 5 0 . 645 0. 706 0. 73 0. 73 5 r,
e-
xc 0. 0 1 0 0. 032 0. 049 0. 0 64 0. 1 02 0 . 1 42 0. 1 82 ,'"
b
0, Eq. 2. 2 2 1 , 92 5 2 , 3 60 2, 650 2 , 930 3 , 570 4, 3 1 0 5, 150 �
'"
\/:"
C o sts, dollar s /year ;::
Q
a + c +g + It 538, 400 �
53 8, 400 538, 400 5 3 8 , 400 538, 400 53 8, 400 53 8, 400 -.
b 5, 800 1 1 , 300 1 5, 500 1 9, 700 27, 2 00 3 6, 900 4 6, 700 �.
-.
N
d 1 3 , 900 27, 3 00 37, 300 44, 700 65, 400 89, 800 1 1 2, 300 �
-
.
e 1 68, 000 67, 600 49, 800 37, 500 2 2 , 600 14, 500 9, 500 g
�
f 53, 700 6 5, 900 73, 800 8 1 , 600 99, 500 1 2 0, 000 1 44, 000 �
Total 779, 800 71 0, 500 714, 800 72 1 , 900 753, 1 00 799, 600 8 5 0, 900 ()
�
�
""
�
38 Clzapler 2
t
"
i900
., I---+---++--+-�-*-+--I-
i
'g
§800 r-�����+__r�--+_-r_�
§ ,,;
!
Calculations of the type shown in Table 2-1 have been carried out
fo r the case of three re actor s in serie s w ith recycle to the fir st.
Figure 2 - 5 sum marizes the r e sults of these calculations and pre sents
40 Chapter 2
�� !! !!..(OCI
AA 40 40 40
BB 50 50 50
CC 55 55 55
00 60 60 60
EE 70 70 70
FF 70 60 50
the annual costs as functions of feed rate fo r five cases in which the
temperatu res in all reacto r s are the sa me . The optimum feed rate
and the minimum annual costs are approximately as follows:
Tl = T 2 = T 3 6 0°C
F, lb moles/hr 80
Costs, dollar s/year 945, 000 773, 000 744, 000 743, 000 760, 000
kl = 5. 1 x 1 01 2 e-19600fRT (2 . 2 3 )
1 1.70 + 0 = 2 . 50 -- 22 . 0 6 - MI
Ml = - 3 1 . 26 Kcal
(b) C6HsCI + Cl2 = C6H4Cl2 + HCI
2 . 5 0 +0 = -4 . 90 - 22 . 0 6 - MI
MI = -29 . 46 Kcal
The rate of heat e volution in a single reactor may now be computed
as
Qn = 3 1 , 2 6 0 ( 1 . 8) (NJl1xA) + 2 9 , 4 6 0 ( 1 . 8 ) (NRk1 xB )
= 2, 1 2 0, 000 k1 xA +2, 000, 000 1<2xn Btu/hr (2 . 2 5 )
XA xB
Mole fraction Mole fraction
First reactor 0.7 60 0 . 22 8
Second reacto r 0 . 578 0. 389
Third reactor 0.440 0 . 50 1
of chlorine is about the same for each of the two step s of the chlorin
ation sequence, it is clear that the cooling load is greatest in the first
reactor.
At 6 0°C, k l is 0. 6 5 hr-1 and k2 is 0 . 1 1 3 hr- 1 ; therefore
Q1 = 2, 1 20, 000 (0. 65) (0. 7 6) +2, 000, 000 (0. 1 1 3) (0. 228)
= 1 , 1 00, 000 Btu/hr
The benzene, if fed at 20°C, would absorb (60 - 20) (1 . 8) (80) (3 3 . 4) =
1 93 , 000 Btu/hr. The heat to be removed from the fir st reactor is then
1 , 1 00, 000 - 1 93,000 = 907, 000 BtU/hr.
The feed to the second reacto r absorbs no heat, but the heat trans
fer to the cooling coil is still les s than in the first reactor (see Ap
pendix) . Excess chlorine pas sing to the condenser provides some re
flux cooling, but this will be neglected in order to make a conservative
estimate of the adequacy of the cooling coil s .
Under the assumption that cooling water i s available at 75°F and
that a temperature rise of 40°F may be allowed, the appropriate tem
perature driving force for heat transfer is computed as
A Tave = 60 ( 1 . 8) +3 2 - 9 0 = 5 0°F
9 07, 000
(VA)required = = 1 8, 1 0 0 Btu/(hrWF)
50
but the available VA product was specified as
The coil is evidently more than adequate to handle the cooling load
for cooling water averaging 90°F.
There remains the question of reacto r stability. Will a small upset,
causing the temperature to rise slightly, so inc rease the reaction rate
(and hence the rate of heat evolution) that the coo ling coil c annot re
turn the temperature to the control point of 60°C? If the temperature
does not return, the rate of heat evolution will continue to inc rease,
and the contents will boil over. There is a serious safety hazard due
to benzene and chlorine, and also the pos sibility of damage to the
equipment. If the reactor is inherently unstable, it may still be pos
sible to provide controls so as to maintain it at 60°C . Expenses for
control eqUipment will of course be much lower if the operation is
inherently stable.
If the rate of heat release goes up because the temperature rises,
the inc reased cooling due to the larger temperature difference fo r
heat transfer should cause the temperature to return to the desired
60°C . To determine whether this will happen, the heat release in the
first reactor is calculated as a function of temperature. At 50°C, for
example, J( 1 and J{ 2 co rresponding to a feed rate of 80 lb moles/hr
are 0.1 2 1 and 0.0 1 2 1 , respectively; thus, xA1 i s 0. 892 and xB1 is 0 . 1 07.
44 Cliapter 2
The heat release QJ' calculated by the procedure desc ribed earlie r, i s
then 4 9 4 , 0 0 0 Btu/hr.
Part of the heat generated by the chemical r eaction is used to pre
heat cold benzene feed, and the r e st must be tran sfe rred to the cool
ing medium. Let Tn represent the tempe rature of the liquid in the
reacto r, and assume the benzene to be supplied at 2 0°C. The heat
absorbed by the feed is then
The diffe rence Q1 - qF repre sents the heat to be transfe rred to the
cooling coil. At 5 0°C , for example, this amounts to 494, 000 - 4, 820
( 5 0 - 2 0) = 3 8 8, 000 Btu/hr . Corre sponding values at other te mpera
tures versus Tn are shown as line I on Fig. 2-6. The points used in
plotting this line have been calculated from value s of Q1 obtained from
Eq. 2 . 25, with value s of XA1 and XB1 for steady-state operation of the
first reacto r at F = 80.
2.0 ,--.,---,-----r---.--,
r:eecJ fole ' 80lb moles I hr
QuantIfy
� plotted
I 0. - QF
0, - QF
III 0,) - QF
';; 1.5 A Qc
iii S Qc
C Qc
D Qc
2
c:
0-
�
� 1.01----+---1---+--
'0 0.5f---+--+r'-----LfIL-i-j+---t--j
s/
,
,
,
40 50 60 70 80
Reactor temperature I °C
9 07, 000
Tc = 60 - = 60 - 6. 1 = 53. goe
1 4 8, 500
increase at least 8 per cent per degree. The t::. T must therefo re not
be greater than about 1 2 °e . For an elabo ration of this point, see
Boynton, Nichols, and Spurlin (2) .
In case cold water were supplied for cooling ( e . g., 20°C), the
Tc =
cooling line qc would pass through the 60° point P if the UA product
had a value of 22, 600 instead of the available 82, 500 Btu/hr OF. Line
B on Fig. 2 - 6 rep resents the qc cooling line in this situation. The
operation is now seen to be unstable at 600e , since an increase in
reactor temperature from 60 to 6 1 °e would cau se the rate of heat
generation to increase more than the rate of cooling: The reaction
would " run away . "
A t this point it seems c lear that the stability question has been
dispo sed of: The c riterion of stability discussed by Van Heer den ( 7 )
and many other writers i s satisfied. A t the operating point P , the
cooling line A is steeper than line I, the curve rep resenting the net
rate of heat generation. The latter curve, however, rep resents
(Ql - qp ) under steady-state conditions at TR • In calculating Ql' the
compositions employed were obtained from the equation s fo r steady
state operation at each TR • As reaction proceeds isothermally, the
benzene disappears and Q1 decrease s . It follows that ( Ql qF ) would
-
and since
qF = 4 82 0 (Tn - 5 3 . 9)
then,
o (Q 1 - qF ) dk l dll 2
= 1 , 6 1 0, 000 _ + 4 5 6, 000 _ - 4820
o TR dTR dTR
dink 1 dl nll 2
= 1 , 6 1 0, 000 k 1 -- + 4 5 6 , 000 k 2 -- - 4820
( )
dTR dTR
1 9, 600
= 1 , 6 1 0, 000 (0. 65)
R Tf
+4 5 6, 000 ( 0 . 1 1 3)
( )3 2 600
- ' -
RT�
- 4 820
o (Q 1 - q )
F = 9 3 , 000 + 7, 650 _ 4820 = 9 5, 830 Btu/ ( hr) (OC).
o TR
Since UA is the same in each reactor, the cooling lines for the
second and third reactor s will have the same slopes as that for the
fir st reacto r. These are shown as lines C and D on Fig 2 - 6 . The
mean coolant temperatures in the three reactor s are seen to be 53 . 9 ,
54.0, and 5 5 . 1 °C. The mean temperatures fo r reacto rs I and II are
approximately equal, because the lower reaction rate in the second
reactor is almo st exactly balanced by the la ck of a cooled feed stream
in the second reactor . In order to avoid confusion, curves A and C
have been superimpo sed in Fig. 2 - 6.
In designing the process, part of the cooling water leaving the fir st
reactor can be used in the second reactor and part of that from the
second can be used in the third. Part of that leaving the third can
then be mixed with cold water so as to provide warm water to cool
the first reactor .
If the temperature rise o f the cooling water in the first reactor is
1 0°F, some ( 1 , 1 00, 000 - 1 93 . 000)/1 0. or 90. 700 lb/hr will be needed .
If all of this were to be put through a single O. 5 -in. coil with O . 4-in.
L d., the mean water velocity would be 460 ft/sec. This is obviously
exces sive, and it will be necessary to connect the coil so as to handle
a numbe r of water streams in parallel short coil sections.
There are many questions to be explored fu rther if the project is
pur sued. Regarding stability, it i s evident that a factor of safety
could be introduced by operating at 5 5 ° instead of 60°C. Figure 2 - 6
shows that the slopes of the cooling line and the heat- generation
curve would then differ markedly at the control point. Operation of
all reacto rs at 5 5 ° instead of 60°C would increase the annual costs by
only a very slight amount (see Fig. 2 - 5) .
The subject of control has not been discussed. What contingencies
mu st the control instruments handle? Power failure? Lo ss of cooling
water? Unexpected increase in cataly st activity? Variation in feed
rate? Perhaps the quickest way to stop a runaway is to cut the chlo
rine supply . But if cooling water were cut off, would the dis solved
chlo rine continue the reaction far enough to boil over benzene? All of
these questions should be treated in some detail before the final de
sign is approved. Consideration of these types of problem during the
design phase of a project can save many hours of difficulty during
plant start -up and subsequent operation.
It has been shown that the cooling coils in the existing reacto r s
are adequate t o take care o f the heat o f reaction under the conditions
of the proposed operation at 60°C and a feed rate of 8 0 lb moles/hr of
benzene. However, stability con siderations indicate that operation at
5 5°C and at a somewhat reduced feed rate would be preferable, even
though the total annual costs would be slightly increased.
Water can be used as a cooling medium, but it is essential to em
ploy relatively hot water fo r this purpo se. If the temperature dif
ference between reacting liquid and water is small, the increased rate
of cooling due to a s mall increase in reactor temperature may be
48 Chapter 2
made large r than the increase in rate of heat gene ration. This will
cause the temperature to fall and to stabiliz e at the control tempe ra
ture. The use of hot wate r a s a cooling medium would undoubtedly
cause scaling p roble m s . The po s sibility of using treated water or
some other heat-transfe r medium should be evaluated.
Since the ave rage te mperature difference must be small (11 OF) ,
the water temperature can ri se only perhaps l O°F in pas sing through
the coil. This means that the wate r rate must be rathe r high, and it
will be nece s sary to modify the coil connections so that seve ral coil
sections can be used in parallel.
Finally, if the propo sed proj ect is to be unde rtaken, a careful study
to dete rmine the best type of control equipment will be necessary.
R eactor De sign, Op tim ization, and Control 49
APPENDIX TO CHAPTER 2
5 0°C
xA 1 0 . 804 0. 861 0. 892 0. 9 1 1 0. 9 2 5
xB l 0. 1 9 0 0. 1 3 7 0. 1 0 7 0. 088 0. 072
Q1 4 50, 000 4 78, 000 494, 000 50 2, 000 5 1 0, 000
xA2 0 . 646 0. 741 0 . 795 0 . 83 1 0. 856
xB2 0. 3 3 9 0. 2 53 0. 2 0 1 0. 1 6 7 0. 1 42
Q2 3 70, 000 4 1 8, 000 445, 000 4 64, 000 475, 000
xA3 0. 520 0. 63 8 0. 7 1 0 0. 757 0. 792
xB3 0. 454 0. 3 5 1 0. 2 83 0. 238 0. 2 0 5
Q3 3 0 7, 000 3 6 7, 000 402, 000 42 6, 000 443 , 000
60°C
XA 1 0 . 621 0 . 71 1 0 . 760 0. 804 0. 850
XB 1 0. 343 0. 2 71 0. 2 2 8 0. 1 88 0. 1 63
Q1 933, 000 1 , 040, 000 1 , 1 00, 000 1 , 1 4 8, 00 0 1 , 1 92 , 000
xA2 0. 3 8 5 0. 506 0. 5 7 8 0. 64 5 0. 689
xB 2 0. 523 0. 445 0. 3 89 0. 3 3 2 0. 2 9 4
Q2 648, 000 797, 000 885, 000 963, 000 1 , 01 6, 000
xA3 0. 239 0. 3 6 0 0. 440 0. 5 1 9 0. 5 72
50 Chapter 2
F ( lb
moles/
hr ) 40 60 80 1 00 1 20
xB 3 0. 6 1 6 0. 5 5 3 0. 501 0. 43 9 0. 3 9 6
Q3 4 6 8, 000 620, 000 71 9, 000 8 1 6, 000 876, 000
70°C
REF ERENCES
Tlds case is based uj)OIl [abomtoJ)' data obtained ill ({II industrial
laboratory />riOl" to lite design of a contillllOus extractiol! /n'ocess. Tile
names of tile actual c/lemicals being cOllsidered lI(u'e been c/I(mged for
/mr/JOses of comme1'cial security. Some discussioll is directed to
lW1"d IIle use of faclorially designed eX/.Jerimellts ill gathering and
analyzing cltemical engineering data. The im/J01"t(IIICe of utilizing tile
/Jroper /01'111 of inde/Jelldent variables ilZ tile fOl'lnulalioll of designed
eX/Je1"imelll s is also em/J/Ulsized
Tile design computations in lids clla/Jte1' lead /0 a classical/ill(JIl
cial emluatioll in ll'hicll ca/.Jital and operating costs are balallced in
the determination of all optimum design. III tills case only a prelimi
nary desigl/ is required, al/d liberal use of appmximations greatly
simplifies the calculation effm'l. An ol'er-all underslandillg of lite
process economics is obtained by all allalysis of a limiting case in
zclliell all illfillite lIumber of ext1'aclion slages is used.
51
52 C/wple y 3
added to the mixture to produce the stable sodium salt of Fenway aCid;
this neutralization is necessary to prevent hydrolysis of the sulfonate
group. The salt is extracted into water and then amidated to the
sodium salt of Brighton acid, the desired end product.
Since the aromatic solvent lowers the yield of the amidation step,
it must be removed before the reaction can proceed. Moreover, a
highly pure aromatic solvent is necessary for the recycle to the sul
fonator, because water reacts with the monochlorosulfonic acid. This
separation is at present achieved by a cumbersome and costly series
of washing and stripping operations carried out on each batch of pro
duct.
Since the batch extraction process is currently operated at peak
capacity and increases in product demand are anticipated, it is de
sired to investigate the possibility of a continuous extraction opera
tion. Your design group is requested to complete a preliminary pro
cess design that will allow the extraction of Fenway acid to be carried
out on a continuous basis. The present batch operation is carried out
at 70°C, with a PH in the aqueous phase of 8. Since only a preliminary
design is requested, you may wish to restrict your attention to these
same conditions. However, the manufacturing technical group has ob
tained sufficient data to allow consideration of temperatures between
20° and 70°C and of pH values from 8 to 12.
The plant has available several agitated kettles that could easily
be adapted to a continuous mixer-settler operation for the proposed
extraction. Since this eqUipment is currently idle,you are requested
to direct at least some attention to a continuous mixer-settler opera
tion; however, any ideas you may have about other types of processes
would also be appropriate.
The design requirements for other sections of the process specify
the following:
Molecular Weights
Although both the Fenway acid and the aromatic solvent are com
posed of mixtures of several components,the following average mole-
Process im/JYocemellt for Liquid-Liquid Extractioll 53
Molecular
Compound weight
Suggested Nomenclature
A Refers to the sodium salt of Fenway acid
B Flow rate of the bottoms or product stream, lb moles/hr
C Capacity of a process unit, cu ft
D Diameter of a fractionating column, in.
f Fugacity, atm
F Feed rate to a fractionating column, lb moles/hr
J( Distribution or partition coefficient,dimensionless
L Liquid flow rate in a fractionating column, lb moles/hr
nz Mass flow rate of a process stream, lb/hr; or quantity of
material present, lb.
n Molal flow rate of a process stream, lb moles/hr; or quantity
of material present, lb moles
S Refers to the aromatic solvent
T Temperature, °C
V Vapor flow rate, lb moles/hr or lb/hr
W Refers to water
x Mole fraction in a liquid phase
y Mole fraction in a vapor phase
(3 Per cent of the total Fenway acid salt appearing in the aqueous
phase
"y Activity coefficient
Superscripts
Subscripts
AS Refers to component A in the solvent phase
Aw Refers to component A in the aqueous phase
D Refers to the solvent content of the bottoms stream from a frac-
tionating column
s Refers to the aromatic solvent
sw Refers to the aromatic solvent in the aqueous phase
ss Refers to the aromatic solvent in the organic phase
v Refers to the solvent content of the overhead product from a
fractionating column
w Refers to water
ws Refers to water in the organic phase
ww Refers to water in the aqueous phase
Factor Levels
where mw/m s represents the ratio of the mass of water to the mass
of solvent in each batch extraction and {3 denotes the percentage of the
total Fenway acid which is found in the aqueous phase. According to
the statistics group, this equation is valid within 90 per cent confidence
limits for the ranges of the variables over which the data were taken.
0.008
I I
0.00
7_S),mbol 'AW IpH :/
/f
. 0_0117 8
d 0.0197 8
0.006 c-- 0.0117 12
0.0197 12
•
/
°
0.00 5
Ys
0.004
V
V
0.003
/.
./
.
0.002 /
0.00 1 //
0.0002 0.0004 0.0006 0.0008 0.001
'SW
Experiment Temp.oC pH nl /m s
w
x
sw
x
ws
The data at 20°C reveal that the presence of the acid salt and the
variations in pH have only a modest effect on the mutual solubilities
of the two solvents. At constant temperature, the variations in pH and
salt concentration do not appear to produce any Significant or consis
tent changes in the mutual solubilities. The scatter in the data ob
tained at 70°C may arise from difficulties in maintaining accurate
temperature control at the higher levels of temperature. For the pur
pose of a preliminary design, the effects of PH and salt concentration
will be neglected, and average values of the mutual solubilities will
60 CI/(/pter 3
Temperature xs w xws
0.00059 0.0256
0.00093 0.0275
After the design has been completed, it will be important to inves
tigate the effect of variations in the values of x sw and xws on the
estimated process economics. If variations of the magnitude shown in
Table 3-2 are found to affect the estimated financial return signifi
cantly, a more exact experimental determination of the mutual solu
bilities would be required.
have gone unnoticed if the equation had been combined with other alge
braic expressions. In view of these observations it is worthwhile to
search for a more satisfactory basis of expressing the experimental
results before proceeding with the design considerations.
In a thermodynamic system in which a solute is distributed between
two immiscible solvents, equilibrium will be obtained when the chemi
cal fugacity of the component in one phase becomes equal to the fugac
ity of the same component in the other phase. When this concept is
applied to the present case,
(3. 2)
(3.3)
(3.4)
Experiment Temperature,OC pH K /
= XAW XAS
I 20 8 0. 655
II 20 8 0. 656
III 20 12 0. 699
IV 20 12 0. 647
V 70 8 0. 661
VI 70 8 0. 411
VII 70 12 0.782
VIII 70 12 0. 503
Aqueous
recycle
Aqueous
exlract
Organic
phose
Organic
phose
RofflOQle streom
(Solvent recycle)
A' 141b Ihr
W'
S' 2 ,994.4lb/hr
mixer. The effluent from the mixer is separated into organic and
aqueous phases in the settler. The small amount of dissolved organic
solvent in the aqueous phase is removed by a stripper from which the
final desired product is removed. It is important to note that the
aqueous stream fed to the stripper is saturated with organic solvent,
and further that the mutual solubility of the water and solvent is quite
insensitive to temperature variations. Therefore, if a rectifying sec
tion were added to the stripper, all the plates in such a section would
contain a two-phase liquid and no enrichment could be effected. For
this reason, the process will have to be designed so that the desired
product purity can be achieved by using only a stripping section. The
overhead product from the stripper is condensed and separated. The
64 Chapter 3
No over-all balance in water is yet pOSSible, since the flow rate of the
make-up water stream has not yet been determined.
Focusing attention on the mixer-settler unit, if equilibrium is at
tained, the relationship summarized by Eq. 3-4 may be assumed valid:
( . nAIV )
0 . 63
xAW nAIV + nslV + nlVlV
-= = (3.5)
xAS /lAS
(nAS
+ /lws + nSS )
The quantities designated by /l represent the molal flow rates of the
streams leaving the mixer-settler combination.
As a first approximation, the mutual solubilities of water and solvent
may be assumed to be negligible. The validity of this approximation
will be determined by a second iteration on the calculation. Equation
3. 5 may be rewritten as:
(3. 6)
Process Improvement for Liquid-Liquid Extraction 65
where
ns s = 3,000/123 = 24. 4 lb moles/hr
nAW = 666/24 6 2. 71
n
AS
= 14/24 6 = 0. 057
Therefore,
nw w = 2. 71 (429
0. 63
- 1)
= 1, 841 lb moles/hr
or mw w = 33,200 lb/hr
Xsw = O. 00093
xws = 0. 0275
A 2. 71 666
W 1840 33,100
S 1. 72 212
A o o
W 1729 31,200
S 1. 68 206. 4
Now that the approximate flow rates of all streams have been estab
lished, a second iteration in the calculations should establish the flow
rates with sufficient validity for a preliminary economic evaluation.
First, the amount of solvent in the organic phase is recomputed, taking
into account the solvent in the recycle water stream:
And the water flow rate in the aqueous phase is established as:
Ilw w =
[1 + (24. 3/0. 057)
- 1. ] 0 2. 71 = 1, 832 lb moles/hr
0. 63
= 33, 000 lb/hr
Il ws = (24. 3 + 0. 057)
(0.--
0275 )
= O. 688 lb moles/hr
0. 9725
111W S = 12. 4 Ibs/hr
Process /1II/JrOL'Clllelll for Liq/lid-Liquid Exlraction 67
Stripper Design
The feed to the stripper is specified by Table 3 -4, and the minimum
requirement for product purity is shown in Fig. 3-2. Since most of the
aromatic solvent will be taken overhead, the following molal flow rates
are readily established:
F = L = 1835. 4 lb moles/hr
V = 1721. 7 lb moles/hr
B = 113. 7 lb moles/hr
Now, there are limits to the values that can be assumed by xB• The
maximum tolerable value of x B is specified as 0. 0004, and from
Eq. 3. 7 the corresponding value of)' v is 0. 000965. At the other
extreme, if infinite stages were used, x B would be 0 and)' v would rise
to 0. 00099. Clearly this range of concentrations does not allow a sig
nificant variation in the usage of steam; the boil-up rate is essentially
fixed by an over-all stripper balance which in turn results from the
specification of a one-stage extraction process. This being the case,
the stripper in this instance is designed to minimize its capital cost;
i.e., only one ideal stage is utilized. Based upon one stage and an
L/V ratio of 1,835.4/1, 721. 7 1.06 7,the McCabe-Thiele diagram for
=
0.008
0.006
0.005
Ys
0.004
0.003
0.002
O.OOIc.d:t��ZIJ
0 0008 0 01)10
The following compositions were derived by trial and error from this
figure and from Eq. 3. 7:
XB = 0. 000105
Yv = 0. 000983
Q ualitatively this result means that the large amount of water that
must be removed and the high relative volatility of the system cause
virtually all the aromatic solvent to be taken overhead in the stripper.
Actually, the material balance for the mixer-settler units might be
modified to include this change in flow rate, but such a computation is
probably not worthwhile.
Aqueous extract
Mixer·
sellier
NO.t
Mlxer
sertler
No.2
Mixer
sertler
NO.3
Aqueous
recycle
Condensole
sellier
Roffinote stream
(Solvent recycle)
Stripper
Auxiliary
water
Product stream
1 + (3,000/123)/(680/246)
------ = 0.63
1 + nww/ (666/246)
Solving this equation shows that a minimum water flow rate of
39. 6 lb moles/hr or 713 lb/hr is required to complete the separation,
even if an infinite number of stages is utilized. Since this value is
less than that required in the final product, it is clear that the amount
of auxiliary water will have to be reduced when the use of larger num
bers of stages is to be examined. In such instances, make-up water
could be added to the product stream after the stripping has been com
pleted. It may be shown quite easily that, if more than three extraction
stages are used, a water flow rate of less than 2007 lb/hr will be re
quired and a corresponding decrease in the auxiliary flow must be
effected.
72 ClwjJ/er 3
In both systems, the water flow rate is reduced far below that re
quired in the final product stream. The present calculations assume
that the solubility of Fenway acid salt is not being exceeded. The
validity of this assumption will have to be checked if any processes
having a large number of stages appear economically significant.
Since direct operating expenses are negligible for the four- and
eight-stage operations, the financial evaluation for them is straight
forward. Combining these evaluations with those summarized in
Table 3-6, the process economics have been optimized according to
Fig. 3-5, which shows that either a three- or a four-stage unit could
be used with comparable economic results. In order to avoid any
problems that may result from exceeding the solubilities of the Fen
way acid salt, the three-stage unit is a good selection for this pre
liminary design.
il. � �
!
<t
�
'"
!
N
�
� + +
-
+ ...
- - -
1------.,1--1--(0••
+--- --
''''.''-. c.,,,
I
___ Steam and coollng"wa,er
costs
$88, 000, and the computed annual operating cost for the extraction
process is about $15, 000, which corresponds to $0. 003/lb of acid
salt. As mentioned previously, this operating cost does not include
several important items, such as labor, overhead charges, equipment
maintenance, and solvent losses. In particular, the cost of solvent
losses is often quite an important contributor to the operating costs
of an extraction operation. If the additional cost items were included,
the resulting total conversion cost probably would approach $O. Ot /lb
-a value close to those usually incurred for the type of extraction
operation being considered in the present case. Since most of the
additional costs are quite insensitive to the number of extraction
stages, it is unlikely that the inclusion of these factors would cause a
significant alteration in the optimum process design that has been
selected.
Since only three mixer-settler stages are required, it is doubtful
that a liquid-liquid extraction column would have any significant ad
vantages over the proposed design. However, Table 3-6 shows that
the cost for controlling the mixer-settler operation represents a
large fraction of the total capital investment. This investment might
well be reduced by use of an extraction column; this possibility should
be examined in subsequent design calculations.
Some assumptions made in the preliminary design analysis should
also be investigated in later,more detailed design efforts. First of
all, the residence-time values used in sizing the mixing equipment
should be recalculated. The values used are thought to be reasonable,
but they and the corresponding estimates for efficiency should be re
estimated using literature values of the mass-transfer coefficients
and settling times that are correlated for equipment of the type pro
posed for the present process. Such calculations would bp. !lartir1l1�r
ly important because depreCiation charges constitute a major portion
of the total conversion cost. A second assumption, implicit in the siz
ing of the mixing and settling equipment, was that little or no difficulty
would be encountered in separating the phases; i.e., the two phases
are not easily emulsified. Evidently no difficulty of this type was
encountered in the laboratory. However, small amounts of surfactants
in the plant water system could cause substantial difficulties in the
commercial operation. This possibility needs to be studied thorough
ly before finalizing the design specifications.
A third assumption was that of constant mutual solubilities of the
two solvents. If solvent losses prove to be an important economic
factor,it may be worthwhile to establish these values more accurately .
However, since both the capital and operating costs for the stripper
are quite small in the optimum process, there does not appear to be
much justification for further experimental work at this stage in the
design.
In summary, it is felt that the preliminary economic evaluation
calculations summarized in Fig. 3-5 have very likely established the
optimum design scheme. The clarification of some of the assumptions
and the inclusion of some of the costs not yet determined may alter
the size of the equipment and the operating costs for the ultimate pro
cess. However, it is unlikely that any of these factors will cause the
74 Chapter 3
REFERENCES
Chern-Fiber Corporation
Houston, Texas
75
76 Cliapler 4
For the time being it will not be necessary for you to complete
an economic evaluation of the process. The Market Research group
is currently negotiating with raw-material suppliers as well as with
possible outside sources of cyclohexane. When this group has assem
bled the appropriate market information,the process recommended
by your group will be evaluated. In this way a decision regarding the
in-house manufacture of cyclohexane can be made.
The Research Laboratory has come up with a new catalyst that
seems to be as good as or better than any we might buy or license.
This catalyst is basically nickel on alumina and would be provided in
the form of 3/16-in. pellets at a cost of $1. 40/lb ( bulk density 88 lb/
cu ft ) . It is rugged and can be regenerated by burning off the carbon
in inert gas containing about 1 to 2 per cent oxygen.
The laboratory has made a thorough study of the performance of
this catalyst,using bench-scale flow reactors. The results obtained
confirm the literature reports for platinum,palladium,and nickel
(1,4, 7, 8); the hydrogenation has been found to be first-order in
hydrogen pressure and zero-order in both benzene and cyclohexane.
The activation energy is found to be 12 Kcal/mole,confirming the
literature data. Results from a representative laboratory test are
attached.
The reaction proceeds readily to clean and complete conversion of
the benzene to cyclohexane,with only small amounts of byproducts,
such as methylcyclopentane. The design problem hinges on the fact
that the reaction is highly exothermic and must not be allowed to
"run away." Designs must be developed to maintain stable operation
at an appropriate temperature; your group is asked to determine the
best approach to the deSign.
The Process Development group recommends that the tempera
ture of the reacting gases be held to a maximum of 6000K because
hydrocarbon decomposition resulting in excessive carbon deposition
occurs at higher temperatures. Carbon deposition also appears to
result from high pressures,although high pressure helps the con
version. For the present,plan on a maximum pressure of 150 psia.
The Research Laboratory suggests that the work of Amane and Par··
ravano (1), Kassel (5), and Smith (7) be consulted in order to provide
additional insight into the reaction kinetics for the vapor-phase hydro
genation of benzene. In addition, the work of Smith and Meriwether
(8) is helpful in that it presents results for the liquid-phase hydro
genation. Finally, the text of Griffith and Marsh (4) provides an excel
lent discussion of the hydrogenation mechanism in terms of the geo
metrical characteristics of various catalysts.
Thermodynamic Data
(From American Petroleum Institute, "Selected Values of Physical
and Thermodynamic llroperties of Hydrocarbons, " Project 44,
Carnegie Press, Pittsburgh, Pa.1953.)
Cyclohexane
Allf W-lI�
T, oK Kcal/g mole gcal/g mole loglO/(/
0 -20. 01 0
298 -29.43 4, 237 5.5 605
400 -31. 70 7,352 -11.28 61
500 -34.08 11,425 -14.8932
600 -35. 57 16, 404 -17.4318
700 -3 6.59 22, 148 -19.3103
Benzene
0 24.00 0
298 19. 82 3, 401 -22. 7143
400 18.554 5, 762 -19.1271
500 17.536 8, 750 -17.1521
600 1 6.711 12, 285 -15.9040
700 16.040 1 6,2 67 -15.0519
78 Clzaptey 4
Hydrogen
0 0
298 2,024
400 2, 731
500 3,430
600 4, 130
700 4, 832
Heats of Vaporization
Raw-Material Values
The raw-material costs are subject to the results of current
negotiations. However,the following approximate prices may be use
ful:
Benzene: $0.04/lb
Hydrogen: $0.40/MSCF
Operation
Suggested Nomenclature
E Activation energy for the hydrogenation reaction, equal to
12 Kcal/ g mole
Equal to exp (12, OOO/RT) evaluated at absolute tempera
ture T
h Temperature interval used in the evaluation of an integral
by Simpson's Rule, oK
Molal enthalpy of component i, g cal/g mole
Molal enthalpy of a compound or element in the gas phase at
any temperature when the molal enthalpy of the compound or
element is taken to be zero at a temperature of OOK, g cal/g
mole
All! Isothermal enthalpy change for the formation of a pure com
pound from its elements at any temperature, g cal/g mole
k Reaction rate constant, lb mole/(hr) (atm) (cu ft of catalyst
bed)
Catalytic Reactor Desib'71 79
Subscripts
B Refers to benzene
c Refers to cyclohexane
F Refers to a condition in the feed stream to a reactor
II Refers to hydrogen
Refers to a condition in the product stream from a reactor
tube of length L
L
Superscripts
, (prime) Refers to an intermediate feed stream as shown in Fig.
4-4.
80 Clwp/er 4
O+3H2�O ( .1)
4
0.9091-0.(1-Ct'2727) Ct'
0.9091 0.0909
+
(W Jl�) II
Hydrogen -
Benzene 0.0909 (W - W
+
AIlj}B
0.0 0.0909 (Ir -lr J C
AIr)
Cyclohexane Ct'
Total °
1.000 1. - 0.2727Ct'
An approximate calculation of the compressibility factor for the
gas mixtures under consideration indicates that the ideal gas law may
be used with negligible error. Therefore, at any position x in the
reactor tube the partial pressure of hydrogen may be expressed as
(4.2)
For the particular conditions of the laboratory experiment,wherein
a hydrogen/benzene molal feed ratio of
to
10
was used, Eq.4. reduces 2
P/I
[0.9091 - 0.2727 Ct'J 71 (4.3)
=
1.0- 0.2727Ct'
Ct'
where denotes th� degree of conversion of benzene to cyclohexane.
It is useful to evaluate the hydrogen partial pressure of the inlet and
outlet streams of the laboratory reactor. Since Ct' has a value of unity
Catalytic Reactor Design 81
for the feed and a value of O.202 for the product stream, the hydrogen
partial pressures are computed as
Since the hydrogen partial pressure varies only slightly through the
reactor, an average value of O.9061T may be used for PJI and may be
assumed to be constant for purposes of calculation.
In order to proceed with an analysis of the laboratory data, it is
helpful to visualize the experimental apparatus as shown in Fig. 4-1.
Writing a material balance on the differential element, one obtains
(4.5)
-dN B = kp II (dV)
da
k PIl
= dV (4.6)
(4.8)
and
1
L IIix�x = (0.9091 - 0.2727 (II) (Ir - It;,) H
NTF
+ 0.0909 (1 - (II) (Ir - H� + All,) B
+ O. 0909 (II (Ir - Il� + AIIf) c (4.9)
O! = 0.002016 ( T - 500)
dO! = 0.002016 dT (4.11)
The results of the energy balance may now be combined with the
material balance by substituting Eq. 4. 11 into Eq. 4. 7:
v � H ('1/] ( : )
[-
[ 4
d . 0[53 'q It
620
NBF = = O. 0175 Ib moles/ hr
(78) (454)
1 600 e12,000/RT h
dT = - [1500 + 1600 + 4(fs10 + 15 3 0 + .. 1590)
.
500 3
+ 2(fs20 + fS40 +
...
IS80)]
10
= -- [201,823 + 4(358,192) + 2 (266,839)]
3
10
= -- [2,168,269]
3
= 7,227,563°K
(7,227,5 63) (2.016 x 10-3 ) (0.0175)
- ------
ko -
9.0 6 (0.0153)
k [1 1]
..!:.... = e12,0001R TF - T
kF L (4.1 3)
kL 600 - 500
= e12,000/1.98S (600)(500)
[ ] = e2•02 =
7.5
kF
T 12,000/RT iT = e12,OOO/RT
¥
line T,·K n
�
• 500 7
8 500 5
O.ll---\'\"""J----\'\\"'�--_t_--
C SOO 3
AS C DEF G
�
_
0
E
600
600
GO
7
F 600 5
j G 600 3
5
"0
] 0.01�---\'.
-\\----+-\\ ..._-_+--""'_c__+---___l
'"
,
0.001 L---'-LW..J.J..1.ll.---'-''---_-'-_-->..>.-'---'-
- __-.30.--'-___--''
0.1 10 100 1000 10,000
7r t 10101 pressure. aIm
V
( 40 X 106 )( 0.0153 ) 258 cu ft
x x
= =
1838
k = 1838 e-1 2,OOO/600R =
23,742
and
V
( 40 X 106 )( 1
) 77 cu ft
x x
= =
8000 84 10 0.0774
This value constitutes the lowest attainable limit for the catalyst
volume under the restrictions of the specified design criteria.
88 Chapter 4
k
1838
= = 0.01033 lb moles/(hr) (cu ft) (atm)
178, 081
and
V = 77
(-
10
x
0.0774 ) = 825 cu ft
7 0.01033
c,.-..
product
600·,,;
.---,---+ Recycle H 2
Bleed stream
Recycle benzene
(ossumed small)
(4.14)
Since the benzene is assumed to react completely in each section of
the reactor, it is noted that
(4.15)
With the basis selected,the analysis of the reactor system follows
directly.
First Reactor
Pill N IlO::
-::.
3 N BO
. -:.- ---=
--- - - � = 0.7
1f
Nllo - 3NBO+ N co+ NBO
and,from Eq. 4.14,
Making use of the enthalpy quantities given in Table 4-2, Eq.4.8 may
be applied to the first reactor as follows:
or
Second Reactor
Applying material balances around the first mixing point and the
second reactor,one obtains
33.54 + �;l
O. 7
50.21+ �!l + Nell
= ---- -=-='-- -
or
(4.20)
An enthalpy balance on the second reactor yields the final required
equation:
92 CI/{{pler 4
(4.21)
Note that the specific enthalpy quantities used in Eq.4.21 have been
obtained from Table 4-2. As mentioned previously,it is anticipated
that the use of a linear average to obtain the enthalpy values of 5500K
should be quite accurate. By combining Eqs.4.18 to 4.21, the values
for Ndl' �:l' NC2' and �I2 have been obtained and are tabulated in
Table 4-4.
Other Reactors
3
L:
J=1
(Nil + �2)lIi = 158,785 -1177 (600 - T2 , inlet )
Since the flow rate, composition, and temperature of the stream leav
ing the second reactor have already been established, the total enthalpy
in that stream is computed in a straightforward manner to be 106, 400
g cal. Because the reactor is operated adiabatically with no work
interactions with the surroundings, the enthalpies of the inlet and out
let streams may be equated, and the entrance temperature for the
second reactor is obtained:
T2, inlet
. = (
600 - 52. 385
1177
) = 555.5°K
(4.22)
f1 e12,OOO/RT dOl
o
Reactor 5: = 3 1, 168
Since a basis of one mole of benzene feed to each reactor has been
used in the present analysiS, the appropriate value of NSF for use in
Eq. 4.22 is computed as
40 X 106
----- = 11.9 lb moles/hr
(8 000) (84) (5)
94 Chapter 4
IleQIee of -.ion. a
0.2 0.4 0.6 0.8 1.0
By use of this feed rate, the hydrogen partial pressure values from
Table 4-4, and the values from the graphical integration, the volumes
required for the first and fifth reactors may now be evaluated as
follows by means of Eq. 4. 22:
(11.9) (38,308)
V1 = = 35.1 cu ft
(1838) (7.07)
(11.9) (31,168)
V5 = = 28.6 cu ft
(1838) (7.05)
These two values are not greatly different, and it is clear that the
volumes required for the second, third, and fourth reactors will be
distributed approximately linearly between these two extreme values.
Therefore, with reasonable accuracy, the total reactor volume for the
design shown in Fig. 4-4 may be computed as
6-10'
\1'\:"0' I
5-10 5
-
I
a::
"-
'"
§� 4-10 5
"
......�IOr5
'"
i'--
I'...
�
3-105
I'-....r-.. �
...."" ..:::: �
,
2.?-IO 5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Degree of conversion I a
This is a substantial reduction from the 258 cu ft that was obtained by scal
ing up the conditions from the laboratory experiments. Table 4 -4 shows
that the hydrogen partial pressure deviates only slightly from 7.0
atm.
900�-��-+--�-4---4
800'�-�--1�-T---r-�
7001---+---4---Po..---+---I
a6001--4---4--+---+��
�
�500'�-�--1--+---r-�
bOlhtrmol ,tOC
600·K
,:",,::.,;-!r-==:;::=:j
9
O �-�-�--�-�-�
5 6 7 8 10
Average hydrogen portlol pressure. aim
REFERENCES
100
Sill/ur Trw/sportalioll Techniques 101
Alternative No.1
Alternative No.2
Alternative No.3
Alternative No.4
Alternative No. 5
CONCLUSIONS
Suggested Nomenclature
Suggested Costs
1. Steel costs $250 per tOll plus $60 per ton for delivery t o site,
unloading, placement, etc.
2. Engineering, surveying, etc., may be taken as $10,OOO /mile
3. Ditching, welding, installation of expansion bends, backfilling,
cleanup may be taken as BOOD, $ /mile
4. First cost of a pumping station is $25, 000 plus $345 per bhp
5. Labor, supervision, and salaries are $2, 600 per month for a
400-bhp station; assume $600 of this independent of station size
and the rest proportional to station bhp
6. The annual maintenance cost of a pumping station may be taken
as 20 per cent of the first cost of the station
7. Insulation costs $14. 70/ cu ft ( installed cost)
B. Steam costs $0. BO/1000 lb (total cost including fixed plus
variable costs)
9. Electrical power is available at $0. 0 1 / kwh
Sulfur Transportation Teclzniques 105
Suggested Assumptions
0.04
� 0.03
r\
.... \-.;;
';;�,..;
�
0.02
1\
:>
'\ \.
"
0.0 I
"'-
I'-..
I'--.r-
- r-'
o
140 160 180 200 220 240 260 280 300 320
Temperature I °C
70
h\
60
50 �
'"
, 1\
u
.,
� 40
\
D
,..
;;; 30
§
:>
20
\
10
''\
�oo
) 400
'
500
,,--- 600
Temperature 1°C
DESIGN COMPUTATIONS
_ Insulation
.-
02
Steam annulus
D, Ds
Sulfur pipe
x
7. 5 108
The sulfur flow rate has been fixed at lb/year or
85, 500lb/hr. Thus the velocity and Reynolds number are given, res
pectively, by
85,500(144)
=
U 3600(112) (0. 78 5D2) 38.9 D2
------ = / fps
J1.
12 D2 0.005 D
If it is assumed that the gauge pressure in the sulfur line drops to
zero just as the sulfur reaches each new pumping station, the Fanning
equation may be written as
�
p
=
41 (U2)(�
2gc D )
11 0 Chapter 5
W vdP vP
=
J° =
Hence,
o85, 500 50
w=
144 x-x Px ------
3600 L
112(550)(0. 75)
3. 70P/ 074P
= L hp (�O. hp per station )
Cpower
3.70P (0.745) (8750) (0.01) 241 P/
= --
L
= L dollars/ year
t
DP 30,000
=
DP- = --- in.
2S
and theweight of sulfur pipe is computed as
WI 0.0460 D2p
= tons
Heat-Transfer Considerations
1
Dj
!
where steam is condensing on the inner wall of the steam pipe having
a diameter Ds'
For steady-state conduction from a buried pipe,McAdams (4) gives
the relation
Q= Btu/hr
1 4Z
In-
Di
Btu/hr
Btu/hr
112 Cl[{[pter 5
Btu/hr (5.2)
Making use of the foregoing analyses and the cost data given in the
problem statement, the costs for the pipeline project are computed
as
CFixed, S t eel
= 0. 15(310) [0. 046D 2p + 275(D + 2. 4)]
= 2. 14D2p + 1 2, 800(D + 2. 4)
Ciixed, Eng.
= 0. 15(50) (10, 000) = 75, 000
( ) ( ) --
1. 49 X 108 1 0. 80
Cs team = -- 8750
288 D; 1000 1000
In - + 8 ln -
D; Ds
1. 04 X 106
288
( ) ( :)
D.
In
D;
+ 8 In
D
1T D.2 - Ds2
= - ' (50) (5280) (14.70) (0.15)
CFixed,lnsul.
4 144
= 3. 18 X 103(D;2 - Vs2)
Cpump Power
= 241 P/L (see Eqs.5. 3Jf.)
Sulfur Trallsportation Techniques 113
7. 97 X 105 910 P
CT = 105, 700 + 2. 14 D2p + 18, 800 D + + --
L L
1. 04 X 106
+ 3. 18 X 103 (D,2 - Ds2) dollars/year
(288
In \
) + 8 In
(D.\�) (5. 3)
Di
Equation 5.3 expresses the total annual cost of operating the pipe
line as a function of D, Ds' Di, and L. Some of these latter variables
P,
are dependent upon each other; for example, Eq. 5. 1 relates and L. P
In addition, a I-in. steam annulus has been specified for the design.
Thus, assuming a value for t of about 0. 1 in. , we get
(5.4)
Di � D + 5.6 (5. 5)
114 Chapter 5
2. 18 X 1010
CT == 183,900 + 2. 14 D2p + 37,900 D +
+
2. 48 X 107
+ -------
1.04 X 106
5. 67 + 7 In(D + 5. 6) 8 In(D + 2. 6) - (5. 6)
By use of the methods illustrated by Sherwood (7), Eq. 5.6 may be dif
ferentiated partially with respect to each independent variable and the
resulting partial derivatives set equal to zero. Following this pro
cedure to find the condition of minimum cost, one obtains
2. 18 X 1 010
2.1 4 D2 - 0
p2 D4.8
=
1. 10 X 105
:. P
D3.4 (5. 7)
and
aCT
aD
= 4.28 DP + 37, 900 - ----
10. 51010
P D5.8
x 11. 9 X
D5.8
107
+
1. 04
------
X 106 (\D 7+ 5. 6
� � ----
) (� �)
---
_
D +
8
----
2.6
= 0
[5.67 + 7 In (D + 5. 6) - 8 In (D + 2. 5) ]2 (5. 8)
37, 900 -
6.08
-- ---:---:-1-
D2. 4
X
- 05 1 1. 9
D5.8
X 107
1. 04 X 1 06 (
\.0 +
8
2. 6
____
D +
7
5. 6
)
+
[5.67 + 7 ln(D + 5.6) - 8 ln(D + .
2 6) ]2
=0
D = 4. 1 in.
P = 840 psi
L = 27 miles
Sulfur Transportation Tecliniques 115
L = 25 miles
P = 990 psia
D = 3. 9 in.
Capital costs
Item Cost
Steel pipe,3. 9-in.diam x 50 miles (sulfur) $2 14, 500
Steel pipe,6. 5-in.diam x 50 miles (steam) 537,500
Engineering and survey 500, 000
Ditching costs 156, 000
Pumping-station costs,2 @ $ 50,300 100,600
Insulation, tl-2-in thick x 50 miles 1,0 18, 000
Subtotal 2, 526,000
Contingency,20 per cent 505, 200
Total capital estimate $3, 031,200
ing cost ( depreciation . Since the cost optimization was carried out
)
in order to minimize the total annual operating expense, it is clear
that the optimization essentially reduces to a minimization of the
capital requirement.
The capital cost estimate shown in Table 5-1 shows that the cost
for insulation is by far the largest contributor to the capital outlay.
Since an arbitrary insulation thickness was assumed, designs using
other insulation thicknesses should likewise be examined. In par
ticular, the use of a thinner insulation layer might lead to a more
economic over -all design.
FORTRAN
Item Symbol Formula
In -
(288) (D.) +81n '
Di D+2. 6
CPUMP = 7. 97 X 105 L -1
- -+ 2. 48 X 107 D-4.8
[ ( ) (\D
CINSU = 3. 18 X 103 (D;2 - D2 5. 2 D 6. 76)
6)J\l
288 D
CSTM 1. 04 x l06/ ln + 8 In i
+
=
Di 2.
where
I
f-
•
�
10•
- ��
\VV "':::""
i.--
� I-
..:::;::: --s_
b;:::::: �
....- -
�r<:�
, \
\
�
E.._"_
-..,-
".,.
-
I
100 2 4 6 B 10 � � � � OO� � � �
Sulfur-pIpe dIameter. Inches
10•
• I I
• 5_ t_
T SlOt.. .lIIlian
.L! !
To...
S _II
•
-�
NuIotion co.tI -
r-
j" COIfs
•
•
• i\..
T E--. ....
•
"- .....,-
s
"" I
•
• It=:-
o 10 20 30 40 50 60
..... mtles
DIstance bet_ l'UtnPong stat
minimum cost is only about $3000 per year less than the cost that
would be incurred if no intermediate pumping stations were used.
The preliminary cost estimate in Table 5-1 indicates that insula
tion costs constitute a major contribution to the total cost. Calcula
tions carried out to determine the effect of insulation thickness on
the economics of the design are plotted in Fig. 5-5. An optimum in
sulation thickness of about one third of an inch is found, with de
creasing insulation costs being offset by increasing steam costs as
the pipe diameter is decreased. The figure shows that the balance be
tween these factors is nearly exact and that the effect of insulation
thickness having the specified conductivity is not particularly critical.
It would be interesting to investigate the effect of more expensive
types of insulation having lower thermal conductivities.
10 "
•
•
•
•
_ -..
"
o
'"
�
'
I
I'---� -
E
�
�
� ./
"
�IO•I
'"
o
-.... ./
GIld
-�
o
• ./ EJ9oNrio
....,-t
o
• /
o • -.....
�
• /'
o
U
4
"
I I=-
I
( 0.5 1.0 1.5
Insulahon IhiCllne ,
. inches
Figure 5-5. Effect of insulation thickness
on costs for D 4.0 in.; L 25 miles.
= =
If consideration is limited to insulation having a conductivity of
0. 05 Btu/(hr)(tt)(q F ), then Fig. 5-5 indicates that the use of insulation
should probably be eliminated in order to simplify construction. Cal
culations have been carried out in order to optimize the pipe diameter
for the case when only one pumping station is used (L 50 miles) and
=
Totol --
10 ,
�-
l\�--
•
I ----
9
7
:.---
•
Sl�om
...--
,
�- ��V-
2 � pe
(0$15
y
2
9
• \
7 Enqlneennq and
• 'I survey coslS
•
4
\
,
2 p"mp
"""- COo;I5
10 ,
o 4 8 12 16 20 24 28
Sulfur·pJpe dlomeler. inches
Insulation costs
Subtotal 1,585,900
2oo r-------�--_r--_,
IOOO�------+_--�--�
Deslon Case I
� 3.9-ln pipe diameter
.,
...
....
..
g
o
800�----+_--�7�--���
"0
"0
�
E
§
o
..
600
On. �umplnQ sialion
s
u
5
'"
� 400�--��--+_----_r-
�
Both the conveyor belt and the pipeline appear to show substantial
economic benefits over more conventional transportation methods.
The use of a conveyor system undoubtedly would result in higher
material-handling charges than would the pipeline system. These
charges would tend to equalize the economics of the two methods. For
convenience, the pipeline would probably be preferred. Further work
should be done to ascertain the feasibility of operating a long-diS
tance conveyor system in the humid climate found on the Gulf Coast.
The application cited in reference (2) is located in a comparatively
dry region. The mechanical difficulties of operating a conveyor de
vice in the geographical area contemplated in the present design
would probably eliminate this method from consideration. However,
in other parts of the world it may well be worthy of further investi
gation.
One additional fact should be pointed out: the possibility that the
rail or trucking firms would reduce their rates when faced with the
competition from a pipeline. In any event, a preliminary design such
as the one illustrated here is quite valuable as a preliminary means
of comparing a pipeline system with alternative transportation methods.
REFERENCES
This is tile firs t of tlCO cases dealing ICi/1t the /JroductiOIl of s tyrene
Iil 0/10111er from e thylbellzene. This chapter describes tlte design of a
frac tionating colulIlll for the separa tion of s tyrene and e thylbellzelle,
wllile C/w/)ter 7 lcill deal wi th the dehydrogenatioll reactor for the
COil version of e tllylbellzene to s tyrene.
In tile presen t chapter several allenzalive techniques are used ill
tlte COlUlIl1l design. Since the distillation mus t be carried Ollt llnder
mcuul/2, special cOllsidera tion is directed to the mechanical problems
engendered by this type of opera/iOIl. A cOIll/mter program is pre
sented to complete the design calculations by Sorel's me thod. This
/Jrogram accollliis for tile s/Jecial equi/)lJ1en t limitation illl/}osed by
mClllllll o/Jeratioll alld allon·s tile o/) til/2l1l/2 distilla tion s).'stem to be
selected for any specified se t of feed conditions.
125
126 Clzapter 6
(6.1)
(6.2)
(6.3)
(6.4)
r2 = k2PE (6.5)
r3 =ll�EP/l (6.6)
Table 6-l. Chemical Kinetic Data for the Dehydrogenation of Ethylbenzene by Means of the Type A Catalyst
of Wenner and Dybdal (10)
Catalyst Conversion Byproducts Based on Perfect
Entrance Feed Rate Nitrate Bed Based on Recovery, lb moles per
Run Pressure (lb. mole/ Bath Temp. Temp. Perfect !b mole ethyJbenzene fed
No. (atm) h r) (OC) (OC) Recovery Benzene Toluene Tad % Yield
R-228 1.02 0.0207 556 552 0.225 0.00540 0.00636 0.00492 82.4
R-229 1. 00 0.0141 557 555 0.227 0.00948 0.00825 0.00473 80.7
R-227 1.02 0.0219 557 555 0.226 0.0063 0.00689 0.00455 82.5
R-230 1.00 0.0131 557 556 0.227 0.00604 0.00936 0.00473 81. 9
R-237 1.04 0.0243 604 598 0.246 0.00587 0.00817 0.00362 82.2
-0::::
�
R-239 1. 00 0.0128 604 600 0.269 0.00534 0.0189 0.00452 81.0
R-252 1.20 0.0238 681 676* 0.366 0.0377 0.0447 0.01211 73.1 i
'"'l
R-254 1.20 0.0235 681 676* 0.360 0.0396 0.0412 0.01328 73.0 "(
�
R-242 1.00 0.00640 604 598 0.260 0.0106 0.0135 0.00396 80.6 ::
R-240 1.27 0.0321 654 650 0.310 0.0167 0.0204 0.00606 79.4 g'
�
R-251 1.20 0.0227
0-
677 671* 0.355 0.0430 0.0459 0.0114 72.2 "(
t::::I
R-255 1.00 0.0131 674 668* 0.372 0.0561 0.0696 0.0168 68.2 �
'"
R-232 1.00 0.00689 557 555 0.195 0.00298 0.0177 0.00365 79.1 CJ"O'
;:i
* Estimated
t Assumed molecular weight 180. ......
I\)
"l
128 Clzapter 6
,-----r---,--r--,---. 107
!---r-+-
-r"----t- +-
---1- ---+--i106
E
(; :::
!!!
'"
N c
o
�
'"
E
i5
(Reaction 6 I)
'"
�
'C-�-+--J�+--r-+----+--4--�105c
o
;;;
S
=-+----+---I---�104
t::-J-t-"I,-
---t-
C2H5 CH3
O+H2- O+CH4
(Reaction 6.3)
0
�0 :----:-40�0
1 ·�0 :----:500
-!- ::---- --:- ----..l- --'!..-8..l0-0 --
6.L 00 9c23
---l
Temperature,OC
Making use of the data of Table 6-1 and rate equations 6.4,6.5, and
6.6they obtained the following expressions for Ill, Il 2' and Il3:
-11,370
log IO'.?1 = + 0.883 (6.7)
4.575T
-50, 800
log IOk 2 = + 0.883 (6.8)
4.575T
-21,800
logIO'.?3 = + 9.13 (6.9)
4.575T
The data points used in determining Eq. 6.7 are shown in Fig. 6-2.
All of the kinetic data gathered by Wenner and Dybdal were obtain
ed using an alumina catalyst whose particle size ranged from 4- to 8-
mesh standard Tyler screen size. The bulk catalyst density was
61 lb/cu ft.
Vacuum Fractiol1ator Desigll 129
10-I
•
•
•
•
5
2 ......
�,
•
•
•
'" •
• .......
......
• """
5
......
•
1.0 1.1 1.2 1.3
IOOO/T with T in oK
XB = 0. 01
where X refers to the mole fraction of ethylbenzene. Common in
dustrial practice might dictate a limit of 0. 003 for X B (1). As in the
case of the tray hydraulics, the design computer program may be
130 Chaptel' 6
Subscripts
ACT Refers to the actual number of trays
H Refers to the bottoms stream; HI refers to the bottoms stream
of column 1, etc
C Refers to the critical vapor velocity in a distillation column as
limited by entrainment consideration
D Refers to a distillate stream; DI refers to the distillate stream
of column 1, etc
E Refers to ethylbenzene
F Refers to the feed stream
H Refers to hydrogen
Refers to component i
Feed
stream
Reactor
Ethylbenzene
to recycle
Styrene
product
Reboiler
132 Clwpter 6
The vapor pressure data for ethylbenzene and for styrene which
are necessary for the column design are tabulated in Perry's Hand
book (7). These data may be checked for consistency when it is re
membered that the data for each pure component must be well cor
related by the Clausius-Clapeyron relationship. Thus,Fig. 6-3 was
prepared by plotting the logarithm of the vapor pressure for each
component against the reciprocal of absolute temperature. The data
fall on a straight line, and the heats of vaporization as computed
from the slopes of these lines agree well with experimental values
VacuulIl Fractiollator Design 133
-,
� t':�enzene
"
"' ......
.� -,
�.
4
Styrene� '"' .
1"'·'\..
"
z �'\
-"
10 I
2.70 2.80 2.90 3.00
10001 T with
3.10
T In oK
3.20
�f'.
3.30
given in the literature (7). Therefore, the vapor pressure data shown
in the figure will be used in the design.
Since the molecular structures of ethylbenzene and styrene are
very similar and since both materials are reasonably nonpolar,one
might anticipate that liquid mixtures of these two components would
be ideal. Fortunately, the validity of this supposition can be verified
by referring to the paper of Chaiyavech and Van Winkle (2), who per
formed a very extensive study of styrene-ethylbenzene vapor-liquid
equilibria at reduced pressures. For variations in the total pressure
of 10 to 200 torr and at temperatures from 26° to 97°C,these investi
gators have shown that the vapor-liquid system is an ideal one. The
nvpr-�l1 rlp.viation from idealitv. as measured by the activity coeffi
cients, was less than 2 per cent,and this discrepancy was within the
limits of probable experimental error. From the assumption of
ideality and the vapor-pressure data of Fig. 6-3, the relative vola
tility of the styrene-ethylbenzene system may be computed as a
function of temperature. This calculation has been carried out for
temperatures ranging up to 90°C,the maximum allowable tempera
ture for liquid styrene in the present process, and is summarized
in Table 6-2.
134 Chapter 6
40
(OC)
313 3.19
s
16.4
E
22.0
a
. ,- ,
1.34
. _ . _-- --
[( �:J C �:B)]
log
1
N + 1 = ----"'
- -------
log a
0. 8 0.
[( ) ( )J
log 9
0.02
99
0.01
N + 1=
log 1. 37
N+ 1 = 27
ex (XF)
where Y* = -----
(ex -l)XF + 1
(1. 37)(0.70)
Y* =
(0.37)(0.70) + 1
Y* = 0.762
Therefore,
0 . 98 - 0.762
(a/V) un
. =
0.98 - 0.70
= 0.778
From this value, the minimum reflux ratio, (O/D)lIlin' can be cal
culated as follows:
(O/V)min 0.778
(a/D)min = = -- =3 50
1 _ (O/V)min 0.222 .
Once the minimum number of trays and the minimum reflux ratio
for the desired separation have been established, there are several
available methods for computing the number of trays required as a
function of reflux ratio. Since these methods vary in their complexity
and in the accuracy of the resulting answers, two of them will be
illustrated here. In addition,the results of a third one will be pre
sented.
1. Gilliland Method. Using normalized, dimensionless variables,
Gilliland has plotted the number of fractionation stages versus reflux
ratio. Using his correlation, we may find the number of stages re
quired at 1. 3 times the minimum reflux ratio by the following com
putations:
5 - Smin
= 0. 44
5+1
27. 44
and 5= -- = 49 theoretical stages
0. 56
Erbar and Maddox have presented a correlation which for some sys
tems appears to be more accurate than that of Gilliland. Oliver (6)
provides an excellent discussion of this new correlation,which may
be used to provide additional insight into the present problem.
2. McCabe-Thiele Method. For a binary system for which the
equilibrium data are well known,the most accurate technique for
computing the number of trays in a column is the McCabe-Thiele
method,which is merely a graphical representation of the Lewis
Matheson computational technique.
With equilibrium data computed using a constant value for a of
1. 37,Fig. 6-4 was prepared to illustrate the McCabe-Thiele method
for the case of (a/D) 1. 3 (O/D)min. As can be seen,this method
=
1.0.
0..9
0..8
>--
g
o
0.7
0.6
I
� 0.5
<;
: 0.4
S?
OJ
g 0..3
lower po' lion of
"
::;;(; 0.2
SIFlPo.nq seCllon
O.os 010
Number of Number
Method Theoretical Stages Actual Stages
Gilliland 49 70
McCabe-Thiele 44 63
Lewis 46 66
N = S -l = 65
138 Chap ter 6
= 2
( 760 ) = 3. 7 torr
34 X 12
Since the pressure at the top of the column is 40 torr, that in the
reboiler is computed as
To vocuum
system 01 +-------r::----------,
40 lorr To vacuum
Feed
stream
Bottoms
stream 10
of tercooler
end SloroQe
PB2
Assumed LV>1 PEl = XE at 0.7 N = 205XE
l
=
Assumed
po o
Temp. oC E
ps O. 54 p� 0.46 p� PD2 = �Pi
Since the XE at the bottom of the second column is 0. 01, PB2 may
be compared with P so, which is 154 torr at 93. 5°C. Therefore, at a
reflux ratio of 1. 3 (0/D) m in three towers would be required to com
plete the separation without exceeding the maximum temperature
specification of 90°C.
140 Chapter 6
The results for other reflux ratios are shown in Table 6-5,
1. 2 4. 20 77 3
1. 3 4. 55 66 3
1. 4 5 5. 07 63 2 or 3
1. 70 5. 95 60 2
which makes clear that for all (O/D)/(O/D)min > 1. 45 two columns
will be required, while for all such ratios < 1. 45 three columns are
needed. For the purpose of this design,the number of columns will
be arbitrarily limited to a maximum of three,although more than
three columns obviously would be necessary at very low OlD ratios.
At the other end of the spectrum the minimum number of theoretical
trays in the system is 26; this corresponds to 37 actual trays. Thus,
it is clear that at least two columns will be required to carry out
the desired fractionation,regardless of the reflux ratio.
V
c
( Pv
) 1/2 = 0. 13
PL - PV
V = 0. 13
( 49. 9 )1/2 = 5. 5 ft / sec
c
0. 0279
174
f
�
=
;.
35
��------��
En'halpy (e," lib I -+
Since the (O/V)min ratio in the column may be taken very roughly
as unity, the heat exchanger shown in Fig. 6-5 may be used to cool
the hot liquid from the first column by heating the condensed vapor
from the top of the second column. Clearly, however, this heat ex
changer can account for only the sensible heat changes of the two
streams, and a vaporizer must be supplied to boil the feed to the
bottom of the first column. Hence, when two columns are required
for the separation, the reboiler and condenser duties are effectively
doubled. This is a good assumption, since for liquid ethylbenzene
styrene mixtures the enthalpy of vaporization is an extremely weak
function of temperature and composition.
Thus, for (O/D)/(O/D)min ;;. 1. 45, the reboiler and condenser
duties will be taken as twice those for a single column. For
,
(O/D)(O/D)m in < 1. 45 these duties will be assumed to be three
times those for a single column.
Optimization Computations
Restrictions XF = O. 70
XD = 0. 98
X B= 0. 01
(1 - XB)B = 20 x 106 lb/year
(8 x
v = D( O/D + 1)
where D = F - B, and FX F = D XD + BX
B •
Hence,in general,
and V = B
( XB -XF
XF -XD
)
(O/D + 1)
Vacuum FracLionalor Design 143
V = (24. 3)
( 0. 01 - 0. 70 ) (O/D + 1)
0. 70 - 0. 98
= 60. 0 (O/D + 1)
NOw, the velocity to be used in the specification of a column dia
meter is to be computed at an average pressure of 90 torr. Thus,
(760)(326 )
(60. O) (O/D + 1)(359) 90 273 76. 9 (O/D + 1)
v =
3600 (1T / 4) d2
=
- - - -
d2::-- -
Note that the capital cost for the column system is taken to be
a function of the number of trays only and not of the number of
columns. This assumption is obviously a great simplification of
the true situation.
For styrene, from Fig. 6-3,
boH a In pO In 200 - In 20
= - -=
- = 47900K
-
R a (l/T) (2. 67 - 3. 15) X 10-3
Now all costs for the distillation system are known in terms of
the reflux ratio and the number of trays required for the separation.
The computed costs for typical reflux ratios are shown in Table 6-6.
These costs may be plotted versus reflux ratio in order to obtain the
optimum reflux ratio for this system ( Fig. 6-7) .
Because o f the increased heating and cooling duties required in
the three-column system, a discontinuity in the total cost curve fixes
the optimal point at (OlD) 5. 07. In the actual design,a reflux ratio
=
160
'- ...../·1,
,
,,
140
, .,/"
b/
� &
� 120 ,,
2
�
"
"
/
V ,,
I
,
""
".100
E
.� 80
V �......
is
o
�60 \
u
\r--.. e_ I--e
-�
40
20
o
1.0 1.2 1.4 1.6 1.8 2.0
(0/0)/(0/0) ....
Input
Material
balance
Establish
operating lines
InitialIZe
variables
------------------,
compute number
of trays by
Lewis -Matheson method
compute actual
number of trays
and costs
RRMI�, F, XF, XD
Pr int output RRCNINl, ANTINl
FTINl,COSTINl,
CPCOSINl, STCDS INl,
CWCOS INl
equations in their binary form (8). Also, since the general shape of
the optimization curves (Fig. 6-7) is already known, the computing
effort could be reduced to a narrow range of (O/D) /(O/D) min and
the slopes of the cost curves could be tested to determine the opti
mum. Either of these approaches would constitute desirable design
projects.
Next the program enters a "DO-loop" in which the required num
ber of trays and number of columns are computed for each specified
value of the reflux ratio. Actually, the calculation is carried out for
a wide range of values for the variable RRCN(I) ,which represents
the ratio of the operating reflux ratio to the minimum reflux ratio.
For each value of RRCN,the equations of the upper and lower operat
ing lines are first developed. Then,starting from the top of the
column,plate-to-plate calculations are made using the method of
Lewis and Matheson (8). Since constant molal overflow has been
assumed,this method merely involves alternate applications of the
equilibrium relationship and the material balance (operating line)
expressions. At the conclusion of this calculation, the number of
theoretical trays and the feed plate location have been specified.
As a final step in the "DO-loop," the column diameter is computed,
the required number of columns and the actual number of trays are
calculated, and the capital and operating costs are specified. In
these calculations the maximum number of trays per column has
been set arbitrarily at 33. This of course is an approximation, but
it seems sufficiently accurate for the purposes of the present work.
As the last step in the machine program,a table is printed which
shows the number of trays,the feed tray,and the operating and capi
tal costs as functions of RRCN. The Appendix contains the actual
FORTRAN program used as well as the output from this program,
which corresponds to a feed stream flow rate of 71 x 106 lb/year
having an ethylbenzene composition of 70 mole per cent. The rela
tive volatility has been taken as 1. 37 for this computation. The re
sults shown in the output table compare well with the manually com
puted results shown in Fig. 6-7.
FORTRAN Notation
REFERENCES
This case foclises 011 the design of a yeactoy for tile catalytic dehydro
genatioll of ethylbenzelle to /)Yoduce styrene. Initial elllphasis is placed
011 tlle analysis of laboratory Idlletic data and on asce rtailling Ille iu
151
152 Chapter 7
It is now desired that your design group proceed with the reactor
design . After completing consideration of the reactor it should be
possible to optimize the reactor-fractionator process unit. Most of
the information necessary for the reactor design is ava ilable in my
original memorandum, entitled "Styrene Production from Ethylbenzene. "
For the phase of the design involving the reactor, you may find some
useful information in the references listed. In addition, some data and
notes are given that pertain to the experimental work done in studying
the chemical kinetics for the catalytic dehydrogenation of ethyl
benzene.
NOTATION
Subscripts
FORTRAN Nomenclature
4 mesh'" 4 . 70 mm '" O.
185 in .'" 3/16 in .
8 mesh'" 2 . 36 mm '" 0. 093 in. '" 3/ 2 in.
3
As an average pellet diameter we may then take
cl'j> =
1
-
( 3
-+
3
- ) = %4 in. = O. 1 4 0 in. = 0 . 0 1 1 7 ft
2 16 32
Sg = 240 m2 /g
e = 0. 5 9
Pp = 1 . 3 3 g/cm3
=
PT 3 . 2 5 g/cm3
Vg = e /pp =
1
-
Pp
1
- -
PT
= O. 5 9 / 1. 3 3 = 0 . 443 c m3/g catalyst
Now consider a container of volume VB' packed full with one gra m of
catalyst pellets. If the pellets are assumed to be spheres, it is reason-
160 Chapter 7
able to take the void volume between pellets, Vy, as O. 38 of the total
volume of the container.
To find the total volume of the container:
Vy = 0.38 VB
Vr = 1/Pr = 0.308
Hence,
VB = 1. 21 cm3/g catalyst
(:. )
or the bulk density of the catalyst bed is
e = 0.50
Pp = 1.57
Pr = 3.15
Values of J( 1 are shown in Fig . 6-1. If the side reactions are neglec
ted for the moment, the conversion of ethylbenzene may be calculated
as
y'2
S
---
1 - Ys
3 .1O·'':::-----l...:----.L,----...J
1.0 1.1 1.2 1.3
fOOOl T with T In ·K
(7. 1)
(7.3)
Therefore,
dpG
---,-�
- ��--
(0.0117)(0.0613)
- - --
N - = 56
Re - -;; (0.02)(6.72 x 10-4)
jD = 1.82(56)-0.51 = 0.234
a1 2 = 0.833 Vl /3
E/k = O. 77Tc
[ 104+106 1 /2
DES =
0.00 1858(871)3/2
104 X 106 J :"-00.168 cm2/sec
(1.0)(5.92)2 (1.109)
0.0191
= = =
Ns c Jl/p DES 0.772
102 (1.47 x 10-3)(0.168)
(0.234)(0.0613) lb moles
kg = = 1.73 X 10-4 -----
(105)(0.9)(772)2 /3 sq ft-atm-sec
(0.62)(71')(0.0117)2
a = = 5.12 sq ft/lb catalyst
1/671'(0.0117)361
166 Chapter 7
3600(0.749) lb catalyst-sec
6.19 X 10-7
(P,If -p,.) = = 7.00 X 10-4 atm
(1.73 x 10-4){5. 12)
The catalyst used in this work has most of its effective area within
the interior of the porous pellets. Thus, limitations due to diffusion
within the pores must be considered. The effect of pore diffusion is
evaluated in terms of the dimensionless parameter 1), the effective
ness factor. The parameter 1) is equal to the ratio of the actual reac
tion rate to the reaction rate that would have been observed if all the
interior catalyst surface were exposed to a reactant of the same con
centration and temperature as found at the outer surface of the cata
lyst pellet. For a first-order irreversible reaction , 7] is found to
[1 IJ
be (9)
3
1)=- -- --
cp tanh cp ¢ (7.5)
where
(7.6)
The variable ct> is conventionally termed the Thiele modulus; it may
be thought of as the ratio of the chemical reaction rate to the diffu
sion rate within the pellet . To facilitate calculations , Eq. 7.5 has
been presented graphically in Fig . 7-2.
Process Elytiualioll jor Styrene Prodllction 167
1.0
0.9 \
0.8
\
1\
\ \
1\
0.4
\
"'"i'-
0.3
......
'-....
0.2
o 2 4 6 8 10 12
Thiele modulus t cP
1 1 1
-- = +
Deff (D12)eff (DKn)eft (7.7)
(7.8)
where the factor 20/S Pp may be thought of as the mean pore radius
in the pellet, re' Equation 7.8 has been derived from the kinetic
theory of gases for cases when re is less than the mean free path of
the gas under consideration.
From Eqs. 7.5 through 7. 8 the value of 1/ may be computed for
each experimental point of Wenner and Dybdal . This trial-and-error
computation is illustrated in the following section.
168 Chapter 7
(0.16�(0.5� 0.084
(D12)eff = = -- cm2 /sec
7 7
29 2(0.59)
re = -- = -,------..,,--
Sg P p
-:- ----,.
(240 x 104)(1.33)
= 3.70 X 10-7 cm = 37 A
And the Knudsen number is found to be
2 re 2(37)
f.kn - = -- = 0.0793
L
=
933
With NKn < 0.1, Knudsen diffusion should be the controlling mecha
nism of diffusion . This calculation checks the previous result.
USing 8 as a typical value for the tortuosity, the effective diffusi
vity becomes
0.0061 2
Deff = ---= 0.00076 cm /sec
8
With this information, the following general relation for the Thiele
modulus may now be developed:
cf> = 0.178
�F = 6.45.JkF
-
0.00076 (7 .9 )
Process Evaluation for styYene Pyoducti on 1 69
g moles
(7. 10)
T = 871°K
= 1. 10 X 10 -2 ( Fig. 7-1)
kl
(kF)exp = 0.343 secl (Eq.7.10)
� ,r--.r��----_+--�
.K"3
i:e 4
�::::
" E
H'z�-
&� ----4_--��_+-
�
E!
lO-rL-___...I.___
.- --':___---,J
'\
1_0 1.1 1.2 1.3
10001 T with T in eK
19,100 +
In kl = 7.30
RT ( 7. 11)
Ethylbenzene -----,
feed
----- - 2
_Flue gas
:-ll
l..:-1LlLll � -'7- - - - - - 3
____
u..
L-__ -+ Reaction
product
Lb Moles at
Lb Moles Position L
Compound in Feed Catalyst Tube
Hydrogen 0 x-z
Benzene 0 y
Ethylene 0 y
Toluene 0 z
Methane 0 z
1.0 1 + x + y
Fx - [FX
Input - Output = Accumulation
+
d
: (Fx) dL - r1A(dL)PB ] = 0
or
dx
F- = ApBr1
dL (7.12)
( )
Substituting from Eq. 6. 4, there results
dx
dL -
_ APBk1
F
PE
_ PSPH
[(1 (7.13)
(7.14)
(7. 15)
Process Emillatioll for Styrene Prorillclio}/ 173
dT U7felave APBbJ/(dX)
=
F1J; M Cp (G
_
T T
) 1J; MC p
_
elL dL (7. 1 6)
(7.17)
and
Position, I 0 1
XI 0 0.237
YI 0 0.0011
ZI 0 0
TI,of 1022 962
(TG)I' of 1600 1618
PI(l in ear),atm 3.79 2.97
1 -(X+Y+Z)I 1.0 0.752
(x-z) I 0 0.237
iz1,Eq.7.23 0.00925 0.00794
k ,Eq.6.5 4.3 x 10-5 1.5 X 10-5
2
k3 ,Eq.6.6 10-3 0.6 X 10- 3
J{l' F ig .6 -1 8.4 x 10-2 3.8 X 10-2
1.35 k1P(1 - X-Y -z) I 0.0473 0.0168
1.35 k1P2xix-Z)I/K1 0 0.097
1.35 k P(l-x-y -2 ) I 2.2 X 10-4
2
1. 35iz3 P2 (l-x-y -z) I
(X-Z)I 0
0.0422(TG-T)I 25.5
792 61(x)I 37.5
O. 00615(TG-T) I 3.55
xI+1, Eq. 7.18 0.237 -0.163
dx
- =f(T,x,y,z )
dL
Process EI:aluatioll 10 1' Sty ren e Produ c t i on 1 77
XI+l + XI
---- = II = l(x I
6.L
� = (1 + I( 6.L) (7 . 2 4)
-2
6.L <
I( (7 . 2 5)
=( aa/x ) [1 - Z)]
the numerical solution. To implement it, 1( is first calculated as
I( = -1. 3 5 1l 1 P +� (2x
1( 1
[
The largest value of K would be found when
( 6.L) m a x = --2
1. 14
= 1. 7 5 ft
1 78 Chapter 7
5
Since a 6.L value of ft was used in the calculations sum m arized in
Table 7- 5, the app roxim ate analysis just carried out would indicate
that this value is too high. Sm aller value s of M will therefore have
to be used to m ake a stable and ac curate solution to the problem
pos sibl e . It was probably intuitively obvious that 6.L was too large
5
in the cal culations shown in Table 7 ; however , the fo regoing ana
-
(�)
the final design calculations is that given in reference {l) :
dP 3 5 p v2
= . ( 7 . 2 6)
dL dp 1 - €
Xr + l - Xr
---- = f ( Tr+ 1 / 2 • x r+1 /2 ' " /+ 1 / 2 ' z / + 1 /2 )
6.L ( 7 . 27)
Process EI'([lllalioJl for Sty rene Producli(}// 179
Analogous equations m ay be written fo r the other dependent variabl e s .
)
B y u s e o f m ethods sim ilar t o tho se previously illustrated, t h e growth
factor for the num erical s olution to E q . 7 . 27 m ay be shown to be
(
L
J( t:.
� = 1 + J( t:.L 1 + --
( 7 . 2 8)
2
With a value of -1 . 1 4 for K, the m aximum value of t:.L that will en
sure stability i s found to be 1 . 75 ft . Thus , the stability c riterion has
remained unchanged from that for the simple r mar ching technique ;
however , use of the improved Euler m e thod should re sult in a m arked
improvem ent in the ac curacy of the solution .
A FORTRAN program m ay now be prepared so that design cal cu
lations can be carried out for wide range s of the param ete r s th<l t
characterize the system . The improved Euler m e thod is used for
the solution of the finite difference equations.
The computer program for car rying out the design calculations
is quite straightforward. T o facilitate the inte rp retation of the pro
gram , a flow diagram for the programm ing logic i s shown on Fig . 7 - 5 .
The program first makes provision for reading the necessary
input data, including the flow rate , feed tempe ratur e , and exit pres
sure of the ethylbenzene feed stream , the r ate and exit temperatur e
of the flue gas stream and the lengh and diam eter of the tube s to be
used in the reactor. In addition, the program requi r e s value s of the
catalyst bulk density and poro sity , catalys t pellet diam ete r , and the
effectiven ess factor for the dehydrogenation reaction as carried out
using catalyst pellets of the sp ecified diam eter. Finally , the number
of distance inc rem ents to be used in the finite diffe rence calculations
must be supplied in the input data.
As a first step in the calculation , the program e stimates the pre s
sure drop through the bed. This value i s computed from E q . 7 . 2 6
with use o f ave rage values of the gas density and velocity. B y adding
thi s approxim ate value of the p r e s sure drop to the spe cified exit
pressure, the entrance pressure is esti m ated. Since the technique of
estimating is not exact, an ite rativ,= procedure is inc o rporated into the
p rogram . By this proc edure the initial e stimate of the ent rance pres
sure is used and the enti re p roblem is solved to yield valu es of tem
p e rature, p ressure, and c omposition at the downstream end of a reac
tor tube . If the value of the exit pressure is sufficiently close to the
specified exit pressure ( 5 ± 2 . 5 psig) , then the finite differenc e c alcu
lations are assumed complete and the program moves on to the next
portion of the c alculation . If the indicated agree m ent on the down
stream pressure is not aChieved, the entrance pressure is re - es tima
ted and the problem is solved repeatedly until conve rgenc e is
obtained.
The actual finite diffe rence calculations follow directly from the
m ethods pr eviously discussed. In all the c ompute r calculations , 1 00
distan ce in crem ents we r e used; even with thi s relatively large num
ber the program requir e s only a m ode st am ount of m achine tim e .
1 80 Chapter 7
loilion.. ..,10"'.'
IZ I K I = IZ I I I + TDEL / X l o F2 1 � 1
TEMPI K I • TEMP I I I + TDEL / X I . F4I� 1
PRESS I K I. PRESSI I I - TDEL/XI . 'I I � I
Dill", fraclionotion
... ilt ot __
re'lua r.t ..
Multiplying F, the ethylbenzene feed rate per tub e , with the value
of x found at the r eactor exit yields a value for the styrene produc
tion rate per reacto r tube. Then by dividing thi s value into the total
required production rate, values for the number of tube s needed in
the reactor and the required catalyst volum e are e stablished. The se
quantitie s are of course neces sary in sizing the reactor and in e sti
m ating the capital require m e nts for the proce s s . In order to allow
for losses in th e fractionato r , a styrene production rate 5 per cent
Process Eualualion jo r Sty rene Production 1 81
greater than the required 20 x 106 lb/year has been used to e stab
lish the reactor size. This i s an important assumption, and its effe ct
on the ove r - all design should be subsequently exam ined.
In o rder to consider the e stim ation of costs for the dehydrogena
tion of ethylbenzene , it is assum e d that F lb moles/year of fresh feed
must be m ixed with 'R lb moles/year of a recycle stream and then
fed to the reactor . For purposes of illustration, the costs of carrying
out the ope ration wer e computed on two different bas e s :
First Basis -Optimization o f the Reactor Only. O n the first baSiS ,
the costs of operating the reactor wer e evaluated by taking a fixed
price for completing the separation of the reaction m ixture ; i. e . , the
economics of the distillation operation was not considered. On this
basis the operating cost was assum ed to be compo sed of the sum of
two factor s :
1. CR , the cost of separating and r ecycling the unconverted
e thylbenzene, taken as $0.01 per lb of unc onverted ethyl
benzene.
2. Cy, the cost of ethylbenzene converted to by -products that
were assum ed to be valuel e s s , taken as $ 0.12 per lb of
ethylbenzene lost.
All ethylbenzene was assum e d to have been r ecove red in the separa
( : +2)L
tion step . With the definitions given, it i s easily de m onstrated that
+
F .
x
(1 -.:, -z).
�
(20 10')/(104)
(7.29)
� �
(20 x 10 ')/(104)
(7.30)
In addition to the running costs, the capital cost for the reactor and
catalyst also had to be e stim ated. Here it was assum ed that two
r eactor units would be requir e d and we re to be op e rated in tandem
with one unit on stream while the cataly st in the other is being r e
generated. T h e capital c o s t for the se units was e stim ated b y fitting
an analytical exp r e SSion to the cost data for stainl e s s steel, shell
and- tube reacto r s given by Chilton (3) . A corre ction fo r the E NR
price index was applied to the se data to update the costs to an E NR
index of 980; the result of the se operations was
Cc a p = 2340 Ao . 57 1 (7.33)
T ube l ength 1 0 , 1 5 , 2 0 ft
Tube diam eter 1 , 2 , 4 in.
Inlet tempe rature 842, 9 3 2 , 1 02 2 , 1 1 22°F
With the specified value s for the param e ters shown in T able 7 - 7 ,
the reactor de sign was completed [or all 3 6 cases sum m arized in
Table 7 - 6. After the calculations were completed for e ach case , the
costs of carrying out the reaction in each reacto r was computed on
each of the two cost base s previously de scribed.
63 1 7
483 5
1239203
939526
0. 83 7
0. 785
0. 991
0. 987
2 . 990
3 . 1 76
1 . 45
1 . 40
66
66
66340
54836
1 5861 9
1 1 5477
841 9
6129
2333 79
1 76442
�-..
�
15 1 0634 1 3 93424 0. 855 0. 992 2 . 93 1 1 . 45 66 713 5 1 1 79085 9505 259942 g"
15 8281 1 077802 0. 813 0. 989 3 . 075 1 . 40 66 59777 1 33334 70'17 2001 88 2'
�
15 6680 858999 0. 765 0. 986 3 . 2 54 1 . 40 65 51 03 1 1 05076 5577 1 6 1 684
-
..z
"
15 5540 6981 78 0. 71 1 0. 981 3 . 486 1. 35 66 44587 81 799 4342 130728
20 9766 946996 0. 787 0. 987 3. 1 69 1 . 40 66 551 1 0 1 1 6442 61 80 1 77732 g
'"'
20 82 1 0 784683 0. 743 0. 984 3 . 346 1 . 35 66 48053 92666 4 91 8 14563 7
:?
20 701 7 655551 0. 692 0. 979 3 . 574 1 . 35 66 4281 2 76442 4057 1233 1 1 C;;
�
20 6095 550063 0. 633 0. 973 3 . 882 1 . 30 66 3 7469 61 213 3249 1 01931
8:
g
......
C:
'=>
1 90 Cllap ter 7
To illu strate the effect of the thre e c ritical var iables upon the
maj or costs assoc iated with the reactor, one typical set of cas e s was
selected for p re sentation. In this example, a base case of a 1 5 -ft x
2 - in. reactor tube with a feed-gas temperature of l 022°F was sele c
ted; subsequent case s were e stablishe d by varying the de s ign para
mete r s both above and below the values used in the bas e case . C o st s
we re computed o n the fir st basis where independent cons ide ration i s
given t o the reactor; the depreciation charge s w e r e found t o be negli
gible compare d to the yield and recycle costs and were not con side r
ed i n the optimization. The r esults o f the s e calculations ar e shown in
Fig. 7 - 6, 7 - 7, and 7 - 8 . In addition, a plot of ethylbenzene conve rsion
ve rsus styr ene yield for all 36 de sign cas e s is p r e s ented in Fig. 7 - 9 .
1,200
�
h
t\
IpOO �\ ,
\
'\ \, Total oprr01ln9 COS!,. ... #' ...
� \ ,
, "
1-" "
� \ ... ..
� 800
. _ -- "",, -- '
� \
,
� \ Y ield cost . C y
�
E
o
600
\ /'
8
\ /
\.
� 400
;;
'/
1/ ' .....
�
o
/" �
e,e" e... . CR
......
- -
-
200
o
o
/1/ 2 3
Nominal tube d lometer I Inches
4
In Fig. 7-6 the effect of tube diameter upon operating cost is illu s
trated. While the c o s t o f yield lo s s decrea s e s with increasing tube
diamete r, the effect of diameter upon re cycle cost is just the oppo site .
The explanation of the se effects lie s in the fact that for a given tube
length and inlet tempe rature the heat supplied per unit volume of
reacting gas de cr ease s with incre asing tube diame te r . The reaction
temperatur e i s the refore lowe r at large r tube diameter s . Since the
conve r s ion increases with increasing temperature , it can be c onclud
ed that as the tube diameter inc reas e s , the c onversion is lowe r and the
Process Em[/(utioll for Sty rene Prod/(ctioll 1 91
r ecycle cost is higher . The effec t upon the c o st of yield los s is the
opposite because , as illustrated in Fig. 7 - 9 , conver s ion and yield are
inve r sely related .
The effec t of t h e reactor tube length on the ope rating cost i s plot
ted in Fig. 7 - 7, indicating that for a given tube diameter and inlet
temperature, e thylbenzene conversion incr eas e s with tube length. It
therefo r e follows directly that recycle costs decrease with increas
ing tube len gth . Si milarly , it i s obvious that yield loss due to side
reactions must inc rease as tube length inc reas e s .
',200
I I
TOlol optrofln9 cost
,
.
I
'
'poo ,
I
,
," ,
.. , ,
, I
..
o
" .
.0" /
�
.. .. ... -
"
g
�
800
.g
/
\ Y'tld COSt , C y A
" 600
�
\ 1/
o I
o
"'
\ /
�V·
�
:3
'"
S 400
�
"
o
/
,/
i'., � co" , c .
./
200
-, -
o
8 '0 ,2 '4 '6 '8 20 22
Tube length , feet
lpoo
I
TOIOI optrohnq C01':" , 0 ...
...
_0 ... ... � �
�
!2
�
.'"
� 600 Ylt.d COi. ,:,;. .... �-
� ./
"
�
", . '/
o
o
.; 400
;;;
8
....��..c:../. '"
-'
", . .......
.-
..... . �
'"
�
8 200
o
800 9 00 1000 1 1 00
Feed temperat ure , of
100 1--�-.d--+---I--_1f--__I
8o 1----+--�---I--_1--__I
�
0.
g
� 60 f---+--+�H-!---If---l
�
8
20'f---�----�--+--��,-�
�_L--��--7L--��--
O 60 O 80 9�0-�1 00
SI yrene Y i e l d . per cent
r e sult s are plotted in Fig. 7 - 1 0, which shows the total operatin g co sts
for each diamete r -length combination ver sus inlet temperature . The
total ope rating costs were computed by adding the yield-loss cost
and the re cycle cost, the latter compute d on the fir st baSiS, an assum
ed cost of $ 0 . 0 1/lb of e thylbenzene recycled. On the fir st baS is for
e stimation, the optimum reactor is one having 2 4 9 tubes, each ten feet
by one inch, and is ope rated with an inlet feed temperature of approxi
mately 9 00°F . The effec t of inlet tempe rature on operating cost is
quite s mall; this obse rvation should have importan t ramifications in
the control of the r eacto r .
2,600 .----::---,--,.---,
2,200 f-----\--+---1--l
o
�
�
,
�
E
"0
i 1,800
"0
E
°
(';
g
§ 1 ,400
'"
c
l
o
60��00�-----:�---��-�-�
Feed tempera t ure . O F
.8oo t-------t---+--=- . �
(;
�
"
g 1 ,400t-----t--i---l
'"
o
"0
�
E
o
80 1.000
"0 _e
�
g 600 r-----�-
:::� __--r
:e2�?
=�=:::::=:;;:::
2 0� 0�0�---��---��---�1�10�0-�
Feed t e m p e r a t u r e . o f
Total
Ite m Number Unit Cost Installed
Cos t
Reactor, shell an d tube 2 $ 51 , 598 $ 1 03, 196
1 60 tubes; 10 ft x 2 in.
stainless steel
Catalyst 1 754 lb 3 5 , 262
Fractionation column 2 145, 1 1 2 290, 224
33 -tray vacuum column
Column diameter-S. 75 ft
Reboiler and condenser 1 00, 000
Pumps 20, 000
Instruments (10 per cent of 51, 870
above)
$ 570, 552
Item Material Labor
Insulation $ 47, 000 $ 70, 500
Piping 23, 000 23, 000
Foundations 23, 000 34, 500
Structures 1 9, 000 3, SOO
Fireproofing 4, 700 28, 200
Electrical 28, 000 42, 000
Painting and cleanup 4, 700 23, 500
Subtotals 1 49, 400 225, 500 $ 3 74, 900
Estimated costs of equipment and material, installed 945, 452
(A)
Overhead, 30 per cent of A 2 83, 63 6
Total erected cost �, 229, 08S
Engineering Fee, 13 per cent of A 122, 909
Contingencies, 13 per cent of A 1 22, 909
Total capital for process unit $ 1 , 474, 906
Manufacturing buildings $ 33 , 000
1 96 C /Zap t e r 7
plex, which would utilize a raw petroleum feed stock and would pro
duce, among other things, a final poly styrene product.
It is helpful to compare the r e sult s of the pre sent study with the
cur rent industrial practic e s for styrene manufacture (2, 6). The com
pe titive economic s of the petrochemical industry dictate s that styr ene
be made in ve ry large equipment, and usually in a s ingle train (5) .
The capital costs for reactor construction can be greatly reduced by
u sing a self-regenerative cataly st that requires steam to be added to
the ethylbenzene feed. This type of operation eliminate s the need for
two parallel reacto r s; this can be very impo rtant in modern, large
volume installations. Thu s it is in the selection of a c atalyst that the
pre sent de sign departs most significantly from cur rent industrial
practic e . Also, in the modern, large - scale operations the value s of the
by -produc ts from c racking become ve ry significant econo mic facto r s .
In the pre sent study i t wa s a s sumed that benzene , toluene, and hydro
gen were to be discarded because they we re produc ed only in small
quantitie s . The value of the se mate rials generated from a large - scale
proce s s cannot, howeve r , be neglected. Furthe r more, it has been point
ed out that the as sumed value fo r ethylbenzene of $ O. 1 2 /lb is high
(5) and that the effect of a reduction in this cost should be inve stiga
ted in subsequent studi es. The sugge sted change s in the se factors
would tend to yield an optimum pro c e s s that op erate s at h igher ethyl
benzene conver sions but lower styrene yields . This trend is in agree
ment with the point made in Chapte r 6 that the majority of industr ial
ethylbenzene - styrene fractionator s ope rate w ith fee d concentrations
in the range of 45 to 60 mole per c ent ethylbenzene . The se value s are
to be contrasted with the 82 mole per cent feed interpolated from
Table 7 - 8 for the optimum system selected in the pre sent study.
As a final i s sue, it has been pointed out that standard commercial
practice dictate s the use of reactor pressur e s as low as pO SSible , with
values seldom exceeding 20 p s ig (5) . The late st designs appear to
have reduced this even furthe r. This reduction in reactor p r e s sure
is probably one of the advantage s realiz ed from the development of
more active catalysts for the conve r s ion of ethylbenzene to styrene.
The optimum proc e s s sele cted in the pre sent study require s p r e s
sure s as high as 3 8 pSig.
Returning to the optimization calculations summarized in Fig.
7 - 1 1 , it is clear that a number of critical assumptions have entered
into the selection of the " optimum" proce s s unit. Fir st, the assumed
temperature and flow rate of the flue ga s and the as sumed o ve r -all
heat -transfer coefficient we re c r itical in obtaining the r e sult s pre
sented here. By using the program given in the appendix, variations
in the se paramete r s would be inve stigated readily. The cataly st pel
let diameter and effectivne s s factor used were important in deter
mining the re sults pr eviously pre sented. The effect of varying the s e
parameter s should a l s o be inve stigated b y further use o f the p r o
g r a m provided. F o r example, the economics o f trying t o develop a
bette r catalyst could be studied; this type of inve stigation would
i llu st rate the ki nd of work that must be c ompleted by a d i rector of
re search in attempting to place prio r itie s on the diffe rent re search
proj ects he must evaluate and manage .
198 Process Evaluation fo r Styrene Production
RE FERENC ES
201
202
Appendix
PIPF nll,lNCI! f'lr.INEERING PIDF. COST ,UM, COST I"SUl A TlON STU" COST TOrAL COST
1."'" 7�"CI).rQ 1'l"5(1!).0l' 24115"'6,0" -0.0 2 37 " J.06 2101"60.00
l'5"nl"."'" 411""".'" "('6\111.12 -".n 251 1 " ' .6'1 111171 !I.OO
70nI5.56
,-.nf\-
1.1"f' 7')O"(\.,,r- 72136:1.44 14Jl'16.75 -�.(' 26''146. J8
4."('1 7'5"(""',nl'" 16'111" ... . 44 478'16.1'1 -".0 2754 J\ .6'I 564225.00
').�" 7'5(\�".n(' 156120.12 26 1 "' . '15 -� .o Zl6lU.OO 5448) 1.62
" ."" 7-;n/,,'.I"1'" 16l1111.1I 21'50'4 •• " -".n 2'161'95.1'1 5 54411.25
T.n!" 7"1"(''','''' lT4"".44 18117.62 -� .
(' 105114.62 51)712.6'1
A.nn 75f'\/"It"',"(\ 111 '1 714 . 1 5 1 7017. 1 5 -D.!' )14'150.50 5'16752.)7
7�CN'.N' '060'14.'56 165'11.76 -l).(' 32''''O.JI 621476 . 62
646'91.62
'1.1'1'
7C;('Int".nt:' UHI2."C 16131.(''5 -0.0 ))2146.62
67 Z 1 U . I '
I�."r
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Il.ne' 7'MC.on ""7112.11 16051.56 -0.1' ,'6691.0 0 725054.11
rc;"nn.",.. 2956.".'" 16011.17 -�.n J64451.)I 751 1 7). 1 '1
771262.""
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-".(\
n.""
7,0,.,'.(\('1 """'6.'14 1'5'181. II )7'15" '.1 1 80 n 0 1.11
12.'01.1'1
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Hroo."� "'1'18'1.44 1596"'9 -1'.0 ' .42 17.44 855 240.25
.11125.44
'1',,,,,
75('1":'0."0 J"I664.5D 15'151.'" -('.(1 40 15 0 2 .'14
'06.'1.""
lq.!"If'I
1".1"1/"1 7I1i/"lnn."" 4 " 7 1117 . 1 " 1'5.54.11 -o.� 408642.6.
�UIFUR PIPELINE DESIGN CALCULATlnNS
"rPF r:tfa,r".c ... ��t;'NEfqING PIPf COST PUMP COST INSULATION STEAM COST TOUL COST
1,"'(" 15t'\O('l."'�
7 2'15'15('r:>.(ll' 2481'936.CO 261'15.98 !T0551.CO 280"70..0.00
486B'I. '7 H435.9q 1 886 1 5.06
1)""
]."" ". QO'IAI.\? 1688370.00
1"'11'''
1."" 7�f'\t"f"'.nf\ 221362.44 143�76. H 3 9 79 '.9 9 2(431)'1.75 6IZ54.. . 87
4."'''' 71;,(\(\('.("'1'" 16� �'1� .44 4189�.A9 4�1�5.9q 21832'1.63 552278.87
C;.�� 71i,�nt'.�r 15682". 1 2 7.�A8q.,S � 15 1'.9q 211105.61 5"1331.19
6."''' 7C;"''''''',''''' lf0277R.l1 2f'51"�.�n �1 8 n .0 4 242'122.44 559080.50
7.f)� 75(,"'(".':'''' 174�2(\.44 tell1.�? 642H.99 253'178.'14 58615Z.'14
R."'''' l,\t"II"f"!."'" IA'I714.7� 171"R7.tCi 705q�.q4 264418.31 61 6.16.12
q.�"" 71S"�r.(\'" 1�6�?4.56 I �S9 1 . 16 1695,.94 27434'.'14 6U'I91.1'I
1", .... (': 7",.."'''','''' nHP."1' lA3�J."S RBlS.94 283.52.6'1 681.13.62
11."'" 715('('I�.n" 2411'�1.7'l 1 6 1 A 8 . 1S 8q67S.94 292'1'14.87 7lU'I1.31
I? • "" 11)("1('''','''''' 1"'11'68.12 1 6 10 3. 8 2 Q6!'35.94 301827.06 14803".'1"
1 1.rn HI'OI'.t'!' 277312.)1 1 � 0 5 1.�6 102394.69 310392.00 781150.56
14.1"" 711\('f"\"."'" 'Q'i6q".7� IhI'18.17 II'R75S.RI 318722.31 814 "".QIl
t5.�'" 75""C .CC' 314181.94 IS996.13 l 1S 115.81 3268.. 8.81 847142.69
" . "" 71i."nt'."" H2736.'14 l�q81.18 12 1475.81 1347'15.37 87'1'18'1.25
11. "" 7�l'r"-."o 1513H.�1 I S 91n . 1 A lZ18��.S6 3425'3.56 9 12734.69
l�.(\" 7-;('1('1(\."'" 36'1'1ft'l.44 15963.39 13419S.81 35022'1.69 945378.31
19,"(' "�('f'I('.�('I 38R664.5C I,Q58.CS 1405SS.81 3577"'1.50 '177'127.11
7" • no 7'11'''1'.''1' 41'7162.1'I 15qS4. 1 1 146'HS.8 1 365157.44 101038'1.50
FORTRAN IV Program and Sample Printout for Chapter 5
203
204
PIPE f1U.INCW F'I(;''IHRINr. PIPE CIl�T PUMP COST INSULATION STEAM COST TOTU COST
1.0" nc"('.�I' 29�qlli(,!,'I.n,t;o 24el�93�.",! 91307.88 120'10.06 21061304.00
'- . "''' 7S('Il"'n.M" 4Rftt"�.37 '1"H81.12 116387.94 U5920.25 1 ,,9627.00
3.�(, 15'1�C'."t;' 22136?44 143076.75 135467.94 149717.62 7246.... 75
4.�'" 7c;n,..�.,..,.. 1�5�9�.44 47"96.89 1"45"8."" 1 6 2 511.94 605ln. 2 5
Ij."'" 1t;t:'�C'."''' 1�6R2r.12 26�e<l.�5 1 H628.(\/l 1 74187.00 606724.62
ft."''' 7151"I'Ir.f"'!(' 16277R.31 2r�C3.8C' 19270R.OO 1 1 5 5 11.94 636509.00
t.en 71)�('IC'.':'('I 17482�.44 I �117.62 211787.94 196051.37 67577 7.31
�."" 7';"t:'n.,,1' 1 R"714. 75 17(\�7.15 23"�67.94 206071.1 1 711741.62
CJ.'"'' 751"('0.1''':- 7C6C'''4.�6 16591.76 H9947.94 215615.13 T6n09.'1
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11.1'1' 7-;""''''.'''('1 241�'1.7� 16188.75 2R81(,6.69 UlIOI.17 154129.06
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1�."!'" H""".C'C' '77312.31 16C'51.�6 326266.37 250"1.75 945419.00
14."'''' 7':'t:'''r.'''f' 2"56"7.7� 16"IA.17 345347.50 2'''9)5.62 990999.00
l'i."1"! 71)t""('.�n 314l!1.94 15996.13 364428.25 266815.50 In649l.11
t-..�'" 7,,(,,:,1"'.(," H2n6.'14 15"°1.1. 3B1�n8.25 2 74651.'" 10111.4.00
11.C'r 715"'''('1.(,''' 351341.8 I 15970. n 4C258e.25 2IZZ7)._4 1127176.00
1'1."'1"1 7-;"""."'" '''QQ''CJ.44 \.,q6�.3q 421667.50 ZIl974'S. 50 1172)65.00
1Q.I''' 715��".�� 388664.5r. 1595A.O� 44e7H.5/) 2970 ...94 lZ I 74".00
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g
;j
�
�ULfUR P I PfL IN f DESIGN CAlCULATIONS
�
....
�
NUMBER OF PUIIPING STATIONS . Z.O
INSULATION THICKNESS IN INCHES • 0.0 4'
ANNUAL COSTS ARE SHOWN BELOW AS FUNCTIONS OF SULFUR PIPE DIAMETER
��
�
DIA.lNrH ENGINfERING PIPE CnST PUMP COST INSULATION STEAM COST TOUL COST �
PIPE
231333.06 2664 .....00
;:!
1.'10 75 � 0 (\.() 0 15()�500.()O 210831872."0 -0.0
R.
2.(''' 7�nO(l.O(l 277219.69 922121.12 -C).O 251395 . 69 1'25"" .00
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SULFUR PIPFlI�E DESIGN CALCULATIONS �.
NU�"FR nF PUMPI�G STATIONS = z.r
INSlIlATlO"l THlfK"lFSS I� INCHFS • 1.5
ANNUAL COSTS ARE SHOWN BELOW AS FUNCTIONS OF SULFUR PIPE DIAMETER
9 J PF r'\ t A • f NC'" F'ICINHRING PIPf COST PU"P COST INSULATION SfEAM COST fOUL COST
1.�'" 75"�".�r: 1504�o�.n r 248316H.OO 97307.B8 120580.06 2662'232.00
'.1'\1"1 7snn,.., n� 277ZI9. 6 9 '1721ZI.12 116381.94 135'ZO.25 15266.1.00
1.rr 7S('I"('I.O('l 154231.19 159C16.75 135467.94 H97IT.62 6U503.50
4.('1'- 715"'("1(\.('1" n�aq".lq �,"36.89 154548.00 162531.9. 5'1815.00
-;.�,.. 71)t:'':.'r:'.t:'o 140160.1)6 42829.55 173628.00 1 7.,87.00 60660•• 56
6 . "" 7c;on".l"In 1510'1.12 36443.8" 19270�.(,(, 1855U.9� 6U80'.1I
7."'(' 750('(1.':'''' 16"56".19 34C57.62 211787.94 1'6051.31 6".51.12
�.n,.. 7",..n('l,(\" lAS4t'11.31 31(121.15 23n867.94 206078.81 U0311.25
q .r·r 7500D.O(, 202997.25 32531.76 249947.94 215615.13 116152.06
In.,..,.. 71;nl\I'\.n" 171"n6."� '2271.n� 269027.94 22.900.116 822201.00
11.('0 75('''C.(,0 23qz6�. 87 32128.75 288106.1>9 213801.87 868303.1.
1,..",,", 7""'''''',('11) 2571>84.06 3Zt)43.a2 3C7186.56 ZU.ZO.OO ."'33 •.••
11.(\/"1 7500(,.1'� 276206.12 31991.56 326266.37 250788.75 960Z52.81
14.1"'It:' 7snnn.(\n 7Q47'1�.R7 31958.1 7 345347.50 258935.6Z 10060.0.12
Pi .�� 75�CC.l'n 313440.94 31936.13 364428.25 266885.50 1051690.00
ll1J."'I" 15nnc.�� �31IlR.44 3 1'121.18 3835nR.25 27.658." 10'7206.00
17.0(' 75D�t'. N' 350811.87 31HO.78 4C2588.25 2822U ••• 11425'•• 00
lR."f\ 115'" ('In , ru:, 16'1544.6'1 319('3.1'1 4Z1667.50 2897.5.50 1187861.00
lCJ.I"'''' 750D('.or 3RR282.75 318'18.1)5 4�OH7.50 2970".94 1233016.00
7"'."'1\ 7-;f"Inl".n(, 4r70JI."6 31"94.11 45'1827.50 304315.62 1278061.00
�ULFLJR PIPFLINF nFSlr.� CALCULATIONS
ANNUAL COSTS ARE S�OWN BELOW AS FUNCTIONS OF SUL FU� PIPE 01 A�ETER
PIPF nIA.rNC� FN(;rNf:�� I�r. PI.� tO�T PU"P COST INSUlATION STEAII COST TOTAL COST
I.�n 7';1)0':1.t){" 15(!.50�.O(! 24�3187?.Ory 25U55.9. 92.62.25 26755648.00
,.nn 1Ii/"lI"H"I.('\(\ H1?19.('9 "nI21.1? 290('15.9. IOU01.31 1668558.00
3.�":' 1151"1')1' .. �� 154ZlI.19 l�qnI6.75 32817'.94 11'1071.44 Ul4n.il
4.1"" 71)"'nr.or;" 115898.19 61R��. A9 366315.94 125266.8l 1663n.8l
'3.
"'''' 1r:;r;o�C.f)" 14"1(1).1'6 4 2 8 Z 9. 5 5 40.495.94 13.910.12 198005.62
6."" 7'5f"1('O."1'\ 1'I1U9.11 1�441.RO 4.26'1�.94 1••123.9. 851362.15
7.t:''':' 7'i(lf'\�.f'\(' 1 68 5 6" . 19 34�'I7 .62 U/)8l'l.9. 152946.15 911380.50
tl.t'\1"1 7,)1"\1'\,...(\1'\ IM."1.H nnn.t'l 518914.62 161442.06 91)851.19
9.0" 750/"1('1."('1 2CZ'I91.25 3 2 5 31 . 76 551U • • 5" 16 965 1.6. 1037315.19
1".l"n 7C;/"Inn."'f' 721""6.(1" 3nn.�5 5952<14.31 117610." 1101183.00
tt."'!'" 7r;('IC'r.cr 23926'1.81 32IZ8.75 633.54.19 18n.6.?5 11651.5.00
I z.n" 7C;l'InO./"I/"I Z�7M4.1'6 32"43.R2 67161 •• 81 19288 •• 69 1229227.00
11.0<' 7c;rr'lO. rf' 11621'6.12 319QI.'I6 7(!9174.69 200244 •• 4 12.3216.00
t4.nl'\ 1'l""l(\."f" 7'1479�.81 3 1 "5 R .1 7 1479H.81 207.44.62 13571]6.00
1'I.rn 7Sf'''O.('\{'\ 311.41'.'14 31936.13 786095.8l 21H9'1.56 1420.71.00
1"."'''' 7&:;('\('\".n('o 131I1A.44 31nt. 1 8 !l2415 5.8l 221U3.06 IU.718.oo
17.r." 7r:;(H,,,.f'l" 3501111.87 3t91�.78 8U415.81 228227.00 154un.OO
Jf'.t'l1"I 1'5('\r'I('.(I'" 16Q'l44.69 3 IQOJ.H 900575.06 234921.6. 1611944.00
,q.l"!'" 7";('I!"If'.!"r 3 �8 2 112. 25 31896.05 9387]5.1!6 2U516.50 1615.11.00
7.n."" 115"('('\.1'1'" 4n71'31.!'6 3 1 M4. 11 '176895.81 2480 20.1. 1738840.00
FORTRAN IV Program and Sample Printout for Chapter 5
207
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1"'�UlATln'" THICK"'FSS I'" INCHFS • I."
AN�UAL cnSTS ARE SHOWN B E lOW AS FUNCT IONS OF SULFUR PIPE DIAMETER
""F OU, INCH FNGINfF.RING PIPE C�q PUMP COST I NSULAT I O N STUN COST TO TAL COST
l.fIr 7�1'0('.or 1�lq49 � . H 2484 79C9. CO 58511.93 139133.12 26139920.00
2.�" 71J""t"I."� 2n7579.69 9lAn61.t2 7l231.9� 156062.56 1��79n,oo
1."''' '5(,4lt'.�� 131854.12 174956.75 6)951.94 171112.15 1>36815.56
4 ."" 7�I)"O.(," 12�.9�.RI 79776.87 9 6 671.94 18�766.12 562113.15
t; ."''' "O"O.(I� l'541"16.6Q 5e769.�7 11)9392.(10 191)39.12 515901.31
", .'''' l�(l M. n" 14QQ'"aC''' �2183. �2 12l112.00 209052.19 60Ml�,06
1.�t' 15,,(10.(''' IM4n.44 49991. �� 134831 .94 22006�.�� 6�U61."
fl."'''' ''5"n"."" IAH71.% 48967.t � 147�51.94 230496.38 685911.00
CI.nl'l 1'.I0oc.rf! 2rt 964. A I 48471.79 16 0 27 1.94 240440.06 72 6 1 48.56
I"."'" 'IJ�";'.I'I" '2°2H.'1 487.1,.n. 172991.94 2�9968.06 76MIO.3 1
II."" 7�f"'Il'I"."t'! 7.H�77.]� 4AOAA.18 185711.94 259138.69 806596.62
t? .�,. 7�"'''r..''1' 25n?? �9 479 ' l . 9 � 1 984 3� .69 268000.06 8466'J7.25
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1'."" l�Ono./)r. 1.1 '\lQ3.Q4 4 7876. 1 6 236591.69 293083.75 9651U.50
16."''' .",,"t.I"II'" 33 19 12 . 1 1 47 66 1 . 2 0 2�HI2.�4 101038.15 1005124.69
17.nt' l�I'''O.(,1' l�n 647. 94 47850. 81 262032.44 308827.15 1044358.11
, ... nt'" l"l'nn.(l1' 369396.44 47843.47. 2 74 15 1. 1>9 316461.50 1083459.00
19."1' nl'l'O.l'n 'ARI'4.Al 4183A.r7 287471.69 323913.62 lL22438,OO
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FORTRAN IV Program and Sample Printout for Chapter 6
209
Ff�D .aT�- 11�r����. F, �R.rTl"N I� FEEO. r.l0� E! FRACTION IN DISTILLATE-O.916 "INI� R- 3.�66 t\)
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1.4" �"."" 76."" �111�."" IOlU.(,6 4'-53.59 125769.69
l.�. �l.�" Z!'."" �142 •• '6 1251".19 4379.54 128320.56
1.tI" �•• f"I" 2".1)" �1'15"."1 141111.25 4505.49 130148.8\
1.5. !I�.�� '"."� �on2." 81261.31 4611.45 132625.31
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1.6" �6.1)t' 2'3."" ��91.ll nOOT.56 �883.36 13H88.69
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216 Appendix
21 7
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TUBE LENGTH = 1 0 . 0 0 0U O FT
OU T S I D E T U S f 1l 1 A ... n R = 1 . 3 1 50 0 I�
I � S I Il E TUdE uI A"E T � R 1 . 04900
= IN
f � EU RAT E ' L B E T H Y L B E N l E �E / H � / T U S E
28 . 7 9 b
I N I T I AL fEt� n MP E k A T U R E . 9 3 2 . 00 O � G � F. E S F �
A S S UM E D
CATALYST
t x U T E MP OF f l U E G A S =
Pt L LE T D I AMeT e R
1 6 00 . 0 0 0
=
DEGR E E S F
0 . 0 1 04 0 F T
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CATALYSI d UL K D E N S I T Y ' 6 1 . 00 0 � 0 L B /C U F T ::!
E f F E C T I V E N E S ) F AC T O R = 0 .44 �
VU I D �K AC T I UN U F P AC K e D B E D = 0 . 38000 �.
O V t � - A L l H E A T I R A � S F E R C G E F F I C IE � T . 8 . 00 0 0 0 B IU /HK/ SQ F T/ F
HE AT CAPAC I T Y U f E T H YL B t N 1 E �E
= O . 6 350C BTU/L8/F
H E Al CAP A C I T Y U F F L U E GA S = 0. 30000 B T U / L � /F
FLUE G A S F L � � R AT E ' 556. 7b7 L 8 F L UE G AS / H R / TU 8E
A S SU M t U tX1 1 P�tSSJK E = 5 . CO O O O PSIG
NU"d E R O F I NCk E ME N I S ' 100
I NCR E ME NT L ENuTH E T HY L S T YR E NE 6ENZ E �E T OL UE N E H Y U � OG E N R E AC T I O N f lU E GAS PR E S S J R E Y I EL D
NUM d E ot FT I H N l E NE E TH Y l E N E M E T H A lli E T E �P TEMP PS [ G L a MOL E S STY ,
L8 MUL E S fORMEO PER L B " U L E Of E T HY L 8 E N l E � E F ED DEG f DEG F L I MOL E EI RE AC T E D
0 0.0 I . OOOOC C .O 0.0 0 .0 0.0 932 . 00 1 60 0 . 0 0 41 .287 0. 0
10 1 . J v l" " . 9 80 7C C . O I 'l l l 0 . 00 006 0 . 0 00 1 l 0 . 0 1 �0 0 1 01 1 .93 1 6 1 0 .42 3 9 . 3 65 98 . 989
20 l . �OO 0 . 9 �O0 7 0 . 04d 7 1 0. 00041 0 . 0 00 1 5 0 . 0 480? 1014.28 1 6 1 9 . 82 37.220 97. 614
30 3 . 0 0� 0 . 90�d 3 0 . 08&52 0.00125 0 .00240 0 . 0 �4 1 3 1 121.21 1 62 8 . 4 7 34 . 8 1 9 9 5 . 95 3
40 4 . 11 00 v . 862 8 1 0 . 1 2 8 "4 0 . 00288 0 . 005 31 0 . 1 2 16 3 1 1 6 3. 0 5 1636.53 32. 1 1 7 94 . 02 7
50 5 . 0 (, (; 0 . 8 1 1 90 0 . 1 7 3 20 0 .005�1 0 . 009 4 0 0 . 1 6 3 80 1 191.08 1 64 4 . 1 1 29.058 92 . 0 7 7
60 & . (; 0 0 O. 7�905 0 . 2 1 74 1 0 . 0092 5 0 .0 1429 0.20H2 1227.H 1 6 5 1 . 7. 9 2 5 . 5 56 90 . 2 3 1
70 7.UOO 0 . 70& 1 5 0 . 2 & .1 2 5 0.01413 0 . 0 1 9 46 0 . 2 4 0 79 1 25 5 . 5 3 1 65 8 . 1 0 2 1 . 4 85 8 8 . 567
80 8 . �v O ;; . 6 5 � 0 0 0 . 300�9 0 . 0 2 006 0 . J2435 0 . 2 76 2 4 1 2 8 2 . 49 1664 .57 1 6 .6 2 5 87 . 1 2 8
90 9 . 0 0 (; � . 6U762 0 . 3 3 7 06 O . C 2 6 1� o.na �8 0 . J Od68 1 30 9 . 44 1 6 7 0 . 1> 9 1 0 .5 2 9 8 5 . 9H
9� � . 900 J. H1 81 0 . 3 6 4 ,2 0 . 0 32 8 7 0 . 030dO 0. 3 Hll 1 3350 1 8 1675 . 9 1 2.983 85 . 1 3 0
0 0 . ", 1 . 0 0 .1 0 0 0.0 0.0 0.0 0.0 932.00 1 1> 0 0 . 0 0 42.28 1 0.0
10 1 . 00C .. . 9 00 3 1 0 . (; 1 9 4 3 0. 0 0008 0 . 0 00 1 2 0.0 1931 1 0 1 1 . 1> 9 161 0.42 40.400 9 8 . 970
20 2 . 0 0 1) 0 . � 49 3 1 0 . 04 9 4 '1 0 . 0 0 0 42 0 .00079 0 . 0 4 HO 1 0 7 3 . 18 1619.83 38.296 9 7 . 1> 1 3
3(; ) . U I.I O 0 . 90859 0 . 087b3 0 . 0 0 1 26 0 .0 02 5 2 0.085 1 1 1 1 2 2 . 50 1 62 8 . 49 3 5 . 94 5 9 5 . 864
40 4 . uJO J . 6b 1 1 b 0 . 1 3036 o . O C 2 �O 0 .005 5 1 0 . 1 2 4 79 1 162. 2 1 1 1> 3 6 . 5 1> 33 .305 9 3 . 895
50 , . (lUU J . 80968 0 . 1 7� 90 0 . 00555 0 . 009 8 1 0. 1 6�03 1 196. 1 5 1 1>4 4 . 1 6 30 . 3 2 3 9 1 . 898
1> 0 o . O vO 0 . 756 2 2 0 . 2 1 �� 1 0 . 0 0 '1 3 3 0 . 0 1 504 0 . 2 04 3 7 1 2 2 b . 42 165 1 . 35 2 1> . 9 2 5 90 . 00 3
70 1 . 0uO v . 702 52 0 . 262b4 0.0 1428 0 . 02056 0 . 2 42 0 8 1 2 5 4 . 39 1658. 1 8 2 2 . 997 88. 288
80 8 . t O (; u . 6 �028 0. 30355 0. 02032 0 . 02585 0 . 2 7 1 10 1 28 1 . 10 1 6 1> 4 . 6 7 1 8 . 35 2 86. 791
90 � . � O" 0 . 6 0 1 49 0 . 34095 0 . 0 2 72 1 0 . 0 30 34 0 . 3 1061 1 3 0 7 . 51> 1670.83 1 2 . 6 33 85. 551
100 1 0. O L O 0 . 5 5 '1 2 4 0 . Hl d 1 0 . 0 3 4 40 0 . 0 3 3 50 0. \ 3937 1 3 3 5 . 25 1 6 7 1> . 6 4 4.935 8 4 . 596
N U M B � � ut T U B E � = 249 . 1 8 1
A � N U AL CU � T a t � E C YC L ' � G E T H Y L B E Nl E N t A T O . O I C ' / L � = 32 1 0 1 8 . "YR
A N N U A L C O S T U F U H YL B � N L E N E C ON V E R T E D Tel B Y- P R O DU C T S A T O o l 2 0 H L B = 4676 73. HYR
T O T AL A N N U AL u P � R A T I N G C U S T = 78d6Q2 . HYR
S U � f AC E A R � A U F R E A C T U R = 85 1 . 04 4 SO F T
C O S T Of T w O R E Ae T U K , Of A BO V . S I l E = 1 0 9 96 0 . 0 0 'l1
CO S T UF L A T A L V , ' A T 3.00 $ / L B = 2 7 30 . 7 9 8 $ 0
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T U B I: L E N � T H = 1 5 . COOOO FT
O U T , I U E T U � E U I A M I: TER . 4 . 5000 0 IN
I N , I U E T Ude UI A ME T ER ' 4. 02600 IN
H E U �AI E ' 4 2 4 . 1 5. La E THYl B ENlE"IE I HoI I TUBE
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C A T A L Y S T P I: L l t r U l lMETER . 0 . 0 1 04 0 FT
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H l A T C A P A C I T Y OF " THYl BENZENE ' 0 •• 3500 BTU I LB l f
H I: A T C A P A C I T Y O f F L Uk G AS . 0 . 30000 B TUIL BI F
F L UE GAS FLUW tl A l t . 1> 5 2 0 . 000 LII f l UE GU/HRI TUIIE
A > S U M I: U eXI T P R t S � UR E ' 5 . 00000 P SIG
N U MB E k �F I N C� " M E N T S ' 100
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NUM8ER FT 8 t N l EN � E TH Y L E N E OI U HANE T E IIP TE M P PSIG L B MOL E S STY I
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Appendix
Chapters 5, 6, and 7
Index
229
230 The Industrial P rac t ic e of Clzemical Process Engineering