CHAPTER III

PRODUCTION DESIGN CONCEPT

3.1 PROCESS OVERVIEW

There are two process happens in the production of formic acid. First process is the
hydrolysis of cellulose by using solid acid catalyst. The second process is
hydrothermal oxidation of glucose by using solid alkali catalyst. The desired product,
formic acid has 95% purity. The raw materials for this plant are biomass (sugarcane
bagasse), water and oxygen.

Sugarcane bagasse is fed at room temperature and standard pressure and the
size of sugarcane bagasse is reduced by using ball mill (M-101) to speed up the
reaction. Then, it is fed into packed bed reactor (PBR), R-101 along with water for
hydrolysis process with the aid of sulfonated silica/carbon nanocomposite solid
catalyst. The operating condition is at 190˚C at 1 atm. The main product of this
reaction are glucose with un-reacted cellulose, hemi-cellulose and water. The by-
products of this process are lignin, 5-hydromethylfulfural (5-HMF), oligosaccharides
and fructose.

The lignin, cellulose, hemi-cellulose are called biosolids are separated by using
rotary drum filter (F-101) with small amount of water and removed from the process.
Glucose, fructose, oligosaccharides and 5-HMF then are fed into phase separator 1 (S-
101) by using pump (P-101) to separate 5-HMF in gas phase from the others
 23

Component that in liquid phase. The 5-HMF gas are then cooled down to 60 ˚C by using
cooler (H-102) and pump out by using pump (P-109), removed from process at liquid
phase.

The other components that are in liquid phase coming from S-101 (fructose,
glucose and oligosaccharides) flow through pump P-103 and entering filter F-102. The
permeate which is oligosaccharides. The retentate (fructose and glucose) are fed into
moving-bed chromatography separator (S-102) with the addition of water. Glucose is
separated from fructose at S-102. Fructose will be removed from the process and sell to
customers.

The glucose is the main intermediate product, will be fed into packed-bed reactor
(PBR), R-102 for hydrothermal oxidation with pure oxygen to form the desired product
which is formic acid. The reaction will be operating at 250˚C at 11 atm with potassium
hydroxide (KOH) as the solid catalyst. The by-products that will formed are carbon
dioxide and water with un-reacted glucose and oxygen. The bottom products is un-reacted
glucose in liquid phase are then will be 90% recycled back to R-102 by using pump P-107.
The un-recycled glucose will be removed from the process by using pump P-108 and sell
to customers.

The components in gas phase (carbon dioxide, oxygen, formic acid and water)
from R-102 are then will be cooled down to 60˚C by using condenser (H-101). The
formic acid and water are in liquid phase are separated from carbon dioxide and oxygen
in gas phase by using phase separator 2 (S-102). The carbon dioxide and oxygen are
cooled down to 25˚C and removed from the process. The formic acid and water are
cooled down to 25˚C. The desired product formic acid has 95% purity at the end of
stream.
 24

3.2 PROCESS DESIGN LEVEL 1

In the hierarchy of process design developed by Douglas (1988), process selection is the
first level before starting the process. This level will cover the information of process
design involved such as chemical reaction, details for raw material and product, design
constraint, site location and physical and chemical properties of the material involved.

3.2.1 Chemical Reaction

The chemical reaction that involved in the production of Formic acid is involve two
reaction which is hydrolysis of cellulose is the first reaction to form glucose as an
intermediate product with presence of sulfonated silica/carbon nano composite solid
catalyst as an catalyst while the second reaction is hydrothermal oxidation of glucose with
the presence of catalyst potassium hydroxide. During the second reaction, there are three
component is form which is formic acid is the main product while water and carbon
dioxide is a side product.

3.2.2 Reaction Stoichiometry

The stoichiometric equation of these reaction

3C12H20O10 + 2H2O 3C6H12O6 + C6H6O3 + C12H22O11 (3.1)
2C6H12O6 + 9 O2 6HCOOH + 6CO2 + 6H2O (3.2)

Since the name of the component is too long, therefore a symbol will be given to simplify
and address each component in the following equations and calculations.

Cellulose = cel
Water =w
Glucose =g
5-HMF =h
Oligosaccharide (maltose) =m
 25

Oxygen =o
Formic Acid = fa
Carbon dioxide = cd

To determine either the stoichiometric equations is balance or not, we need to perform the
stoichiometric balance.
From the stoichiometric equation, we can simplify by using the equation below:

∑𝑆𝐾=1 ∝𝐾 𝐶𝐾 = 0 (3.3)

Where,
S = total number of component
αk = molecular weight

From equation (3.1)

3(180) + 126 + 342 - 3(324)- 2(18) = 0 (balanced)

From equation (3.1)

6(46) + 6(44) + 6(18) - 2(180) - 9 (32) = 0 (balanced)
Beside, element balance also can determined the stoichiometric equation is balanced or
not which is total element in reactants is equal to the total element in the product of the
stoichiometric equation.
∑𝑆𝐾=1 ∝𝐾 𝑚𝐾𝐿 (3.4)

Where,
mkl = number of element atom in a molecule of component k
For reaction 1, each of the element is balance as shown as below
Balance on C : 3mg + mh +mm-3mg -2mw
3(6) + 1(6)+1(12)-3(12)-2(0) = 0
0 = 0 (Balanced)
 26

Balance on H : 3mg + mh +mm-3mg -2mw

3(12)+1(6)+1(22)-3(20)-2(2) = 0
0 = 0 (Balanced)
Balance on O : 3mg + mh +mm-3mg -2mw
3(6)+1(3)+1(11)-3(10)-2(1) = 0
0= 0 (Balanced)
For reaction 2, each of the element is balance as shown as below
Balance on C : 6mfa + 6mcd -2 mg = 0
6(1) + 6(1) - 2(6) = 0
0 = 0 (Balanced)
Balance on H : 6mfa + 6mw -2 mg = 0
6 (2) + 6(2) - 2(12) = 0
0 = 0 (Balanced)
Balance on O: 6mfa + 6mcd + 6mw - 2mg - 9 mo = 0
6(2) + 6(2) + 6(1) - 2(6) -9 (2) = 0
0 = 0 (Balanced)

Hence, the stoichiometric coefficient for each of the component is

For reaction 1,
αCellulose, C12H20O10 = -3
α Water, H2O = -2
α Glucose, C6H12O6 = +3
α 5-HMF, C6H6O3 = +1
α Oligosaccharide, C12H12O11 = +1

For reaction 2,
α Glucose, C6H12O6 = -2
α Oxygen, O2 =-9
α Formic Acid, HCOOH = 6
α Carbon Dioxide, CO2 = 6
α Water, H2O =6
 27

3.2.3 Reaction Condition

Heterogeneous reaction is involved in the first reactor which cellulose and water combine
to form glucose, 5-HMF, fructose and oligosaccharide in liquid form will react together
inside the packed bed reactor (PBR) with the presence of solid catalyst, sulfonated
silica/carbon nano composite which is a solid catalyst for acid. Operating temperature and
pressure inside the reactor is 190 °C and 3 atm respectively. According to the
stoichiometric equation, 3 mole of cellulose will react with 2 mole of water to form 3
mole of glucose and 1 mole of 5-HMF and Oligosaccharide

The reaction involved inside the second reactor is heterogeneous reaction in which
glucose in liquid state will react with oxygen in gas state inside the packed bed reactor
with the presence of potassium hydroxide, KOH as a catalyst to produce main product
which is formic acid while side product is carbon dioxide and water.

Operating temperature and pressure inside the reactor is 250 °C and 11 atm
respectively. Based on the stoichiometric equation above, 2 mole of glucose react with 9
mole of oxygen to form 6 mole of each of the component for the main product and side
product which is formic acid, carbon dioxide and water.

The presence of potassium hydroxide, KOH in the reaction as a catalyst is to

enhance the purity of the formic acid. According to (Akiya et al. 2002; An et al. 1997;
Ikushima et al. 2000), they figured out that hydrothermal oxidation of carbohydrates or
glucose can obtained a high yield of formic acid. The high yield of formic acid can be
achieved by include the alkali catalyst. It shown that the process without addition of alkali
into the reaction, formic acid yield around 60% while addition of alkali can achieved
purity higher than 95% with the same operating temperature and pressure (Jin, &
Enomoto 2009)
 28

3.2.4 Kinetic Rate Law

The relative rate of reaction of the various species involved in a reaction can be obtained
from the ratio of stoichiometric coefficients. For example equation below:
𝑏 𝑐 𝑑
𝐴 +𝑎𝐵 → 𝑎𝐶 + 𝑎𝐷 (3.5)

Based on the equation (3.2), species A is taken as a basis of calculation, where one
of the reactant that is disappearing as a result of reaction. In addition, the rate of
disappearance of A, -rA depends on temperature and composition which also can be
written as a function of the concentration of the various species involved in the reaction:

−𝑟𝐴 = [𝑘𝐴 (𝑇)][𝑓𝑛(𝐶𝐴 , 𝐶𝐵 , … )]

Therefore, rate law is the product of concentrations of the individual reacting

species where each of it is raised to a power.

𝛽
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴𝛼 𝐶𝐵 (3.6)

The power which concentration are raised in the kinetic rate law in equation (3.6) indicate
the order of a reaction. Based on the equation (3.6), α indicate order for reactant A while
β indicate order for reactant B. Unit of rA are always in terms of concentration per unit
time or ( mol/ m3/s) while the unit of specific reaction rate, ki will vary with the order of
reaction. (Elements of Chemical Reaction Engineering 2006):

(𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)1−𝑛
𝑘𝑖 = (3.7)
𝑇𝑖𝑚𝑒

Rate law is corresponding to a zero-, first-, second-, and third-order reaction.

Based on equation (3.1) and (3.2), the derived kinetic rate laws of each reaction involved
are given as below:
 29

3
𝑟1 = 𝑘1 𝐶𝑐𝑒𝑙 𝐶𝑤2 (3.8)
𝑟2 = 𝑘2 𝐶𝑔2 𝐶𝑜9 (3.9)

Where,
k1 = 90 s -1 (L.Kupianien 2012)
k2 = 0.116 s -1(Zhimin.T et al. 2009)
Ccel = Concentration of cellulose
Cw = Concentration of water
Cg = Concentration of glucose
Co = Concentration of oxygen

3.1.5 Selectivity

Selectivity is an indicator show how one product favour over another when got multiple
reaction. Basically, selectivity is almost similar with reaction yield which can also be
defined as ratio of moles of product formed at the end of the reaction to the number of
moles of the key reactant.

Based on the stoichiometric equation for reaction 1 and reaction 2, the changes of
concentration with time to the net rate law of each component can be formed as below:

𝑑(𝐶𝑐𝑒𝑙 ) 3
Cellulose : = −𝑟𝑐𝑒𝑙 = −𝑟1 = 𝑘1 𝐶𝑐𝑒𝑙 𝐶𝑤2 (3.10)
𝑑𝑡
𝑑(𝐶𝑤 ) 3
Water : = −𝑟𝑤 = 6𝑟2 − 2𝑟1 = 6𝑘2 𝐶𝑔2 𝐶09 − 2𝑘1 𝐶𝑐𝑒𝑙 𝐶𝑤2 (3.11)
𝑑𝑡
𝑑(𝐶𝑔 ) 3
Glucose : = 𝑟𝑔 = 3𝑟1 − 2𝑟2 = 3𝑘1 𝐶𝑐𝑒𝑙 𝐶𝑤2 − 2𝑘2 𝐶𝑔2 𝐶09 (3.12)
𝑑𝑡
𝑑(𝐶ℎ ) 3
5-HMF : = 𝑟ℎ = 𝑟1 = 𝑘1 𝐶𝑐𝑒𝑙 𝐶𝑤2 (3.13)
𝑑𝑡
𝑑(𝐶𝑚 ) 3
Oligosaccharide : = 𝑟𝑚 = 𝑟1 = 𝑘1 𝐶𝑐𝑒𝑙 𝐶𝑤2 (3.14)
𝑑𝑡
𝑑(𝐶𝑜 )
Oxygen : = −𝑟0 = −9𝑟2 = −9𝑘2 𝐶𝑔2 𝐶09 (3.15)
𝑑𝑡
𝑑(𝐶𝑓𝑎 )
Formic Acid : = 𝑟𝑓𝑎 = 𝑟2 = 6𝑘2 𝐶𝑔2 𝐶09 (3.16)
𝑑𝑡
 30

𝑑(𝐶𝑐𝑑 )
Carbon dioxide : = 𝑟𝑐𝑑 = 𝑟2 = 6𝑘2 𝐶𝑔2 𝐶09 (3.17)
𝑑𝑡

𝑑(𝐶𝑐𝑒𝑙 ) 𝑑(𝐶𝐶𝑒𝑙,𝑜 (1 − 𝑋)) 𝑑𝑋 3

= = 𝐶𝑐𝑒𝑙,𝑜 = −𝑘1 (𝐶𝑐𝑒𝑙,𝑜 (1 − 𝑋)) 𝐶𝑤2
𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑𝑋 2
= 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1 − 𝑋)3 )𝐶𝑤2 (3.18)
𝑑𝑡

By substitute the expression for cellulose concentration in terms of its conversion, Ccel =
Ccel, o (1-X) and equation (3.6) in equations (3.10) until (3.17), then

Cellulose :
𝑑(𝐶𝑐𝑒𝑙 ) 𝑑(𝐶𝑐𝑒𝑙 ) 𝑑𝑡
= 𝑥 = −𝐶𝑐𝑒𝑙,𝑜 (3.19)
𝑑𝑋 𝑑𝑡 𝑑𝑋

Water :
3
𝑑(𝐶𝑤 ) 𝑑(𝐶𝑤 ) 𝑑𝑡 6𝑘2 𝐶𝑔2 𝐶09 − 2𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤
2
= 𝑥 = 2 2
𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

6𝑘2 𝐶𝑔2 𝐶09

=𝑘 2 3 2
− 2𝐶𝑐𝑒𝑙,𝑜 (3.20)
1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋) )𝐶𝑤

Glucose :
3 2 −2𝑘 𝐶 2 𝐶 9
𝑑(𝐶𝑔 ) 𝑑𝑡 𝑑(𝐶𝑔 ) 𝑑𝑡 3𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤 2 𝑔 0
= = 𝑥 = 2 2
𝑑𝑋 𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

2𝑘2 𝐶𝑔2 𝐶09

= 3𝐶𝑐𝑒𝑙,𝑜 − 𝑘 2 3 2
(3.21)
1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋) )𝐶𝑤

5-HMF :
3
𝑑(𝐶ℎ ) 𝑑𝑡 𝑑(𝐶ℎ ) 𝑑𝑡 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤
2
= = 𝑥 = 2 2
𝑑𝑋 𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

= Ccel, o (3.22)

Oligosaccharide :
3
𝑑(𝐶𝑚 ) 𝑑𝑡 𝑑(𝐶𝑚 ) 𝑑𝑡 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤
2
= = 𝑥 = 2 2
𝑑𝑋 𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

= Ccel, o (3.23)
 31

Oxygen :
𝑑(𝐶0 ) 𝑑(𝐶0 ) 𝑑𝑡 −9𝑘2 𝐶𝑔2 𝐶09
= 𝑥 = 2 2 (3.24)
𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

Formic Acid :
𝑑(𝐶𝑓𝑎 ) 𝑑(𝐶𝑓𝑎 ) 𝑑𝑡 6𝑘2 𝐶𝑔2 𝐶09
= 𝑥 = 2 2 (3.25)
𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

Carbon dioxide :
𝑑(𝐶𝑐𝑑 ) 𝑑(𝐶𝑐𝑑 ) 𝑑𝑡 6𝑘2 𝐶𝑔2 𝐶09
= 𝑥 = 2 2 (3.26)
𝑑𝑋 𝑑𝑡 𝑑𝑋 𝑘1 ((𝐶𝑐𝑒𝑙,𝑜 )(1−𝑋)3 )𝐶𝑤

Next, the selectivity of the intermediate product, main product and side product
for reaction 1 and reaction 2 can be shown as below:
Selectivity of glucose:
𝐶𝑔
𝑆𝑔 = 𝐶 (3.27)
𝑐𝑒𝑙,𝑜 𝑋

Selectivity of 5-HMF:
𝐶ℎ
𝑆ℎ = 𝐶 (3.28)
𝑐𝑒𝑙,𝑜 𝑋

Selectivity of Oligosaccharide:
𝐶𝑚
𝑆𝑚 = 𝐶 (3.29)
𝑐𝑒𝑙,𝑜 𝑋

Selectivity of formic acid:

𝐶𝑓𝑎
𝑆𝑓𝑎 = 𝐶 (3.30)
𝑐𝑒𝑙,𝑜 𝑋

Selectivity of carbon dioxide:

𝐶𝑐𝑑
𝑆𝑐𝑑 = 𝐶 (3.31)
𝑐𝑒𝑙,𝑜 𝑋

Selectivity of water:
𝐶𝑐𝑤
𝑆𝑤 = 𝐶 (3.32)
𝑐𝑒𝑙,𝑜 𝑋
 32

Equation (3.19) to (3.32) are solved using Polymath software using RungeKutta
algorithm (RKF45). The result of polymath is shown below
 33

Figure 3.1 Result of polymath.

 34

Figure 3.2 Graph of change in concentration of each component against conversion.

40

35

30

25 Sd
Se
Selectivity,S 20
Sh
15 Sg

10 Sb
Sc
5

0
0.00E+00 2.00E-01 4.00E-01 6.00E-01 8.00E-01 1.00E+00
Conversion,X

Figure 3.3 Graph of selectivity against conversion.

 35

Where the symbol represent

a = Cellulose
b = Water
c = Glucose
d = 5-HMF
e = Oligosaccharide
f = Oxygen
g = Formic Acid
h = CO2

3.2.6 Catalyst Used For Reaction

Catalyst is the substance that increase the rate of chemical reaction without itself
undergoing any permanent chemical change. Catalyst that has been used in the production
of formic acid is sulfonated silica/carbon nano composite which is the solid acid catalyst
and potassium hydroxide.

The hydrolysis of cellulose into sugar with solid acid has received increasing
attention. Solid acid catalysts have various advantages over liquid acid catalyst such as
ease of product separation, recyclability, less damage to the reactor. Besides, the use of
solid catalyst can reduce the pollutant which will have a minimal impact on environment.

In the production of glucose, 6% of sulphuric acid required for hydrolysis of

cellulose which cellulose react with water to produce glucose as an intermediate product
before further reaction to form formic acid as a main product. By using sulphuric acid as
a catalyst, about 50% of glucose yield can be obtained (Y.Huang et al. 2013). Table 3.1
below show some properties of the solid catalyst.
 36

Table 3.1 The properties of sulfonated silica/carbon nano composite catalyst

Parameters Description

Physical State Solid

PH Acidic

Melting Point 3500 °C

Chemical Stability Stable

Source: Material Safety Data Sheet (MSDS) 2013

There is a few method that can be used to produce formic acid such as hydrolysis
of methyl formate, hydrolyzing of formamide with sulphuric acid and oxidation of
glucose. Oxidation of glucose process has been used to produce formic acid since the
alkali catalyst, potassium hydroxide, KOH can increased the purity of formic acid more
than 95% which is the most important for the purpose of selling the product.

One of the possible reason that we choose potassium hydroxide, KOH as a

catalyst since the melting point of the potassium hydroxide, KOH is 360 °C which is
higher than the operating temperature inside the reactor which is 250 °C. Table 3.2 below
show some properties of the alkali catalyst, potassium hydroxide:

Table 3.2 The properties of potassium hydroxide, OH as a catalyst.

Parameters Description

Physical State Solid

Appearance White or yellow

PH 13.5

Boiling Point 1320 °C

 37

Melting Point 360 °C

Chemical Stability Stable

Source: Material Safety Data Sheet (MSDS) 2000

3.2.7 Design Constraint

Design constraint is one of the important component during designed a plant by

understand and alert on the limitation of the process. Therefore, some precaution need to
be taken from during designed for safety of the equipment and environment.

Catalyst must be used in the reaction which potassium hydroxide which in alkali
state since from the previous is stated that the high yield of formic acid can be achieved
by include the alkali catalyst. The process without addition of alkali into the reaction,
formic acid yield around 60% while addition of alkali can achieved purity higher than 95%
with the same operating temperature and pressure (Jin, & Enomoto 2009). The higher the
purity, the higher the cost to sell the product.

However, the price of the alkali catalyst, potassium hydroxide, KOH in market is
quite expensive around USD 420-520 which is in Malaysia is around RM 2000-2300 per
metric tonne with purity 90% (Alibaba, 2015). This can be overcome since our purity of
product which is formic acid is above 95% which in the market price can sell around
USD 500-800 in Malaysia is around RM 2200- RM 3520 per metric tonne with 99%
purity (Alibaba, 2015). Catalyst only been replaced in a certain time and not continuous,
hence the production of product with high purity of formic acid can cover the cost of
catalyst.

3.3 PROCESS DESIGN LEVEL 2

According to the hierarchy of Douglas 1988, in level 2 it focuses on the input-output

structure of a process for the raw material and the product involved.
 38

3.3.1 Synthesis of input-output structure

Synthesis of input-output structure is the overall reaction between raw materials and the
products. In process design, there have rule of thumb which is the recovery of the high
value of the valuable component more than 99%.

In the production of formic acid, the reaction involve of hydrolysis of biomass to

get the glucose and the oxidation of glucose to produce formic acid. The raw material in
this process is biomass which is sugar cane bagasse, oxygen and water. Figure 3.4 shows
the input and output for the production of formic acid.

Figure 3.4 input-output structure for production of formic acid.

In this process the components from output flow are formic acid, water, glucose,
oligosaccharide, fructose, water, biosolid and carbon dioxide. These components have
been listed in the overall process output destination. The analysis of each output is been
compared by boiling water of propylene to determine the component is light or heavy.
Propylene is used the reference point, and the component with lower boiling point than
propylene (-48oC) is considered as light component and vice-versa.
 39

Table 3.3 Overall process output destination

Components Boiling point (oC) Heavy/light Destination

Formic acid 100.8 Heavy Main product

Carbon dioxide -78.5 Light Purge out

Fructose 440 Heavy By-product
Oligosaccharides 150 Heavy By-product

Water 100 Heavy Waste

Bio solid 350 Heavy Waste

From table 3.3 it shows the destination of the component in output process.
Formic acid have high boiling point than propylene and it comes as product of this
process. Water, carbon dioxide and bio solid from this plant are flow as the waste of these
plant while oligosaccharide and fructose produce as the by-product.

3.3.2 Design capacity

The formic acid plant capacity is set to produce 1518 kg/hr of production of formic acid
which operating for 24 hours through 350 days per year.

3.3.3 Mass balance

The stoichiometry equations of overall reaction are:

Hydration
Cellulose + 2 water → 2 glucose (3.27)
Oxidation
2Glucose + 9oxygen → 6 formic acid + 6 carbon dioxide + 6 water (3.28)
Let assume n1 as reaction (3.27) and n2 as reaction (3.28).
Cellulose : FC = n1 (3.29)
Oxygen : FO = 9n2 (3.30)
 40

Water : FW = 2n1 (3.31)

Water : PW = 6n2 (3.32)
Glucose : PG = 2n1 – 2n2 (3.33)
Formic acid : PF = 6n2 (3.34)
Carbon dioxide: PC = 6n2 (3.35)
Based on the selectivity for each product:
Glucose : PG = SGFc (3.36)
Formic acid : PF = SFPG (3.37)
Carbon dioxide: PC = SCPG (3.38)
Water : P W = S CPG (3.39)

Solving FO:
Let (3.30) is multiply by2/3 ,
22/3 FO = 6 n2 (3.40)
Then (3.40) minus (3.34),
2/3 FO - PF= 6 n2 - 6 n2
2/3 FO - PF = 0
FO =3/2 PF (3.41)
Substitute (3.37) into (3.41)
FO = 3/2 SFPG (3.42)
Substitute (3.36) into (3.42)
FO =3/2 SF SGFc (3.43)
Solving for FC:
Let (3.33) is multiply by 3
3 PG = 6n1 – 6n2 (3.44)
Equation (3.29) is multiply by 6
6 FC = 6n1 (3.45)
By minus (3.45) and adding (3.34) from (3.44)
3 PG - 6 FC + PF = 6n1 – 6n2 - 6n1 + 6n2 (3.46)
=0
3PG = PF -6 FC
 41

PG =1/3 PF -2 FC (3.47)
By substitute (3.37) and (3.36) into (3.47)
PG =2 FC -1/3 SFPG
PG =2 FC - 1/3 SF SGFc
PG = (2- 1/3 SF SG) FC
𝑃𝐺
FC= 1 (3.48)
(2− 𝑆𝐹 𝑆𝐺 )
3

Solving for Pg.:

Substitute (3.48) into (3.36)
PG = SGFC
𝑃𝐺
PG = S G 𝑥 1 (3.49)
(2− 𝑆𝐹 𝑆𝐺 )
3

Solving for PF:

Substitute (3.48) into (3.37)
PF = SFFC
𝑃𝐺
PF = S G X S F 𝑋 1 (3.50)
(2− 𝑆𝐹 𝑆𝐺 )
3

Solving for PC:

Substitute (3.48) into (3.38)
PC = SCFC
𝑃𝐺
P C = S G X SC 𝑋 1 (3.51)
(2− 𝑆𝐹 𝑆𝐺 )
3

Solving for PW:

Substitute (3.48) into (3.39)
PW = SWFC
𝑃𝐺
P W = S G X SW X 1 (3.52)
(2− 𝑆𝐹 𝑆𝐺 )
3

Solving for FW:

Multiply (3.29) with 2, then minus by (3.31).
FW – 2FC = 2n1 - 2n1
FW = 2FC (3.53)
Substitute (3.48) into (3.53)
 42

𝑃𝐺
FW = 2 1
(2− 𝑆𝐹 𝑆𝐺 )
3

Solving for FO:

Substitute (3.50) into (3.41)
FO =3/2 PF
𝑃𝐺
FO =3/2 SG X SF 𝑋 1 (3.54)
(2− 𝑆𝐹 𝑆𝐺 )
3

From the plant capacity of 1518 kg/hr, the flow of formic acid is,
1518kg 8400hr kmol
PF = × × 46.03kg = 277019.34 kmol/year
hr yr

3.3.4 Economy Potential Analysis Level 2.

The economy potential for production of formic in level 2 is

fEP2 =CF PF -C𝐶 PC -C𝑤 P𝑤 -CO2 P02

Where Ci is the cost for material i in RM/kg.

The cost of each component involved in the input-output structure is shown in

table 3.4 shows the price of the flow rate of each stream in the term of selectivity and the
final product.

Table 3.4 Price of component involved

Component Price (MYR)/kg Source

Cellulose 0.07 ICIS

Formic acid 3.92 ICIS

Oxygen 6.17 ICIS

Water 0.0027 ICIS

 43

Table 3.5 Flow rate of each component of level 2

Number Component Flow Rate

𝑃𝐺
1 Cellulose 1
(2− 𝑆𝐹 𝑆𝐺 )
3

𝑃𝐺
2 Oxygen 3/2 SG X SF 𝑋 1
(2− 𝑆𝐹 𝑆𝐺 )
3

2𝑃𝐺
3 Water 1
(2 − 3 𝑆𝐹 𝑆𝐺 )
𝑃𝐺
4 Formic acid S G X SC 𝑋 1
(2− 𝑆𝐹 𝑆𝐺 )
3

𝑃𝐺
5 Carbon dioxide S G X SC 𝑋 1
(2− 𝑆𝐹 𝑆𝐺 )
3

𝑃𝐺
SG 𝑥 1
6 Glucose (2− 𝑆𝐹 𝑆𝐺 )
3

7 Water 𝑃𝐺
2 1
(2− 𝑆𝐹 𝑆𝐺 )
3

200

150
economic potentiol (RM million/year)

100

50

0
conversion
0.05

0.15

0.25

0.35

0.45

0.55

0.65

0.75

0.85

0.95
0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-50

-100

-150

-200
conversion

Figure 3.5 Graph of fep2 (RM million/year) against conversion

 44

Table 3.6 Data for economic potential of process design level 2

FEP2
X FC FW PF FO2 (RM
Million/Year)

0.05 8557.395316 17114.79063 0.016625592 0.024938 3.62E-06

0.1 17225.25209 34450.50418 0.200206155 0.300309 6.426E-05

0.15 27139.89981 54279.79962 1.9928938 2.989341 0.0004345

0.2 38299.5814 76599.1628 8.781253866 13.17188 0.0019146

0.25 52890.9722 105781.9444 36.51581781 54.77373 0.0079617

0.3 66745.33245 128699.5583 88.40882263 132.6132 0.022765

0.35 81848.05237 163696.1047 266.5050046 399.7575 0.058107

0.4 98211.66416 196423.3283 622.340099 933.5101 0.135691

0.45 118932.967 237865.934 1528.484733 2292.727 0.333261

0.5 141491.3304 276302.6501 3096.165918 4644.249 0.755565

0.55 158811.5975 324809.4432 6638.269217 9957.404 1.447366

0.6 188884.3246 362138.4209 13529.0226 20293.53 2.949782

0.65 209414.9061 427419.5606 22011.7321 36339.41 4.799299

0.7 236308.0554 472616.1109 38967.14812 113985.3 9.340397

0.75 272110.7542 544221.5084 75990.19252 187216.6 16.568422

0.8 302435.5858 632711.3478 153655.3968 457044 33.502054

0.85 369674.9321 739349.8642 304696.0051 930593 58.75191

0.9 471117.207 942234.4141 737338.4858 1106008 135.26709

0.95 823762.9 4504650 1362051 2813531 194.31082
 45

3.4 PROCESS DESIGN LEVEL 3

In level 3, design of reactor and synthesis of recycle stream will be considered more in
detail in order to determine the higher accuracy of product distribution. The design
variables that will be considered will be discuss in this subtopic.

The structure of recycle stream for the production of formic acid by using
hydrothermal oxidation of sugarcane bagasse is shown in Figure 3.6.
5-HMF

Oxygen

Carbon Dioxide
Water

Hydrothermal
Pre-treatment
Biomass Separation Glucose Oxidation of Separation
of biomass
Glucose

Formic Acid
Water

Cellulose
Hemi-cellulose
Lignin
Oligosaccharide
Fructose

Figure 3.6 Recycle structure of hydrothermal oxidation of sugarcane bagasse.

3.4.1 Number of Reactors

For this production of formic acid, there are two reactions will occur. Thus, two reactors
are needed. The first reactor, R-101 is needed to convert cellulose to glucose while the
second reactor, R-102 is used to produce formic acid. Type of reactor for R-101 is
packed-bed reactor with addition of sulfonated silica/carbon nanocomposite solid catalyst
and for R-102 is packed-bed reactor (PBR) with potassium hydroxide solid, KOH will be
used as the solid catalyst. The operating conditions for R-101 is 190˚C, 1 atm and for R-
102 is 250˚C, 11 atm.
 46

2.4.2 Number of Recycle Streams

From Figure 3.6, the reactant biomass in the form of cellulose will be fed together with
water with the addition of sulfonated silica/carbon nanocomposite catalyst to the reactor
R-101 where the hydrolysis of biomass takes place. The product is glucose, with by-
products fructose, 5-hydromethylfurfural and oligosaccharides. The glucose then will be
fed in reactor R-102 for hydrothermal oxidation reaction with oxidation. The product is
formic acid with by-product carbon dioxide and water.
The selectivity to formic acid will be drop drastically at high conversion of
glucose, at conversion higher than 90% and the production of by-products that will
produces at high conversion of glucose. Thus, the conversion of glucose must be control.

Glucose then is separated from other by-products by using rotary drum filter, filter
and simulated moving-bed chromatography separator. The final stream after separation
process need to be recycled back to ensure the quality of glucose before entering R-102.
After the reaction, the un-reacted glucose coming from output of R-102 must be recycled
back to the reactor to prevent wastage of glucose.

Formic acid obtained from reaction in R-102 need to be recycled back to ensure
the purity of formic acid in order to obtain 95% purity. Thus, three recycle stream is
needed. The summary of the classification and destination of the output of reactor is on
Table 3.7.

Table 3.7 Classification and destination of reactor output

Component Normal Boiling Light/Heavy Destination
Point (˚C)
Cellulose Not applicable Heavy Waste treatment
facility
Water 100 Heavy Waste water
treatment facility
 47

5-HMF 114 Heavy Waste water

treatment facility
Fructose Not applicable Heavy Sell

Oligosaccharide Not applicable Heavy Sell

Glucose Not applicable Heavy Sell
Oxygen -183 Light Waste treatment
facility
Carbon Dioxide -78.5 Light Waste treatment
facility

3.4.3 Limiting Reactant Balance

For the first reaction which is hydrolysis of cellulose to glucose, the limiting reactant is
the limiting reactant. For the second reaction, the hydrothermal oxidation of glucose to
formic acid, glucose is the limiting reactant.

The molar flow rate of un-reacted glucose is NG (1-XG). Since all of the un-reacted
glucose will be recycled, the mole balance at the mixing point is

NG = NG (1-XG) + NG’ (3.55)

Where NG is the total molar flowrate after mixed with recycled glucose and N G’ is
the molar flowrate of glucose before mixed with recycled glucose. Equation (2.4.1) can
be solved for the molar flowrate of feed that enters reactor, so

𝑁𝐺′
NG = (3.56)
𝑋𝐺

Table 3.8 shows the amount that need to be fed NG as a function of conversion
with NG’ = 10.77524 kmol/hr (FG’ = 1941.225 kg/hr).
 48

Table 3.8 NG as a function of conversion

XG NG (kmol/h)

0.05 215.5049

0.1 107.7524

0.15 71.83496

0.2 53.87622

0.25 43.10098

0.3 35.91748

0.35 30.78641

0.4 26.93811

0.45 23.94499

0.5 21.55049

0.55 19.59135

0.6 17.95874

0.65 16.5773

0.7 15.39321

0.75 14.36699

0.8 13.46905

0.85 12.67676

0.9 11.97249

0.95 11.34236

1 10.77524
 49

250

200
Molar Flowrate of Glucose, Ng (kmol/hr)

150

100

y = 17178x6 - 60729x5 + 85180x4 - 60318x3 + 22698x2 - 4377.4x + 380.65

R² = 0.9951
50

0
0 0.2 0.4 0.6 0.8 1 1.2
Conversion of Glucose, Xg

Figure 3.7 Molar flowrate of glucose as a function of conversion

Figure 3.7 shows the trend of molar flowrate of feed glucose that is needed to be
fed as a function of conversion of glucose. The molar flowrate of glucose decrease with
the increase of conversion of glucose. The equation that is compatible to the above graph
is

NG (kmol/hr) = 17178x6G - 60729x5G + 85180x4 G - 60318x3 G + 22698x2 G - 4377.4x G

+ 380.65 (3.57)

3.4.4 Reactor Selection

The type of reactor used for both reactions is PBR. The material of construction of the
both PBR is stainless steel.
 50

3.4.5 Heat Effect of Reactor

The hydrolysis of cellulose and the hydrothermal oxidation of glucose are both
exothermic reaction. Thus, heat will be released during both reactions. The heat of both
reaction can be managed either adiabatically or isothermally. If the reaction is carried out
adiabatically, no heat will be added into the reactor and no heat will be removed from the
reactor during the reaction. In contrast, heat will be added into the reactor for isothermal
condition in order to keep the constant temperature of contents inside the reactor. In order
to decide whether the reactions are suitable to be carried out in adiabatic or isothermal
condition, adiabatic temperature of the both reactions need to be calculated.

3.4.5.1 Adiabatic Temperature of Reactor

Energy balance in a reactor at adiabatic condition with the assumption that average
specific heat can be used and reference temperature is Tin is shown below:

𝑖𝑛
∑𝑁 𝑀 𝐾
𝑗=1 𝑛𝑗 ∆𝐻𝑟𝑥𝑛,𝑗 + ∑𝑖=1 𝑃𝑖 𝐶𝑝𝑖 (𝑇𝑎 − 𝑇𝑖𝑛 ) − ∑𝑘=1 𝐹𝑘 𝐶𝑝𝑘 (𝑇𝑖𝑛 − 𝑇𝑖𝑛 ) = 0 (3.58)

Where,
𝑖𝑛
∆𝐻𝑟𝑥𝑛,𝑗 = Heat of reaction at inlet temperature for reaction j
𝐶𝑝𝑖 = Specific heat for each product i which includes reactants and impurities
𝑇𝑎 = Adiabatic temperature of reactor
𝐶𝑝𝑘 = Specific heat for each feed component k which includes reactants, feed impurities,
and recycled reactants

Equation (3.58) can be simplified to an easier form:

∑𝑀 𝑖𝑛
𝑗=1 𝑛𝑗 ∆𝐻𝑟𝑥𝑛,𝑗
𝑇𝑎 = 𝑇𝑖𝑛 − ∑𝑀
(3.59)
𝑖=1 𝑃𝑖 𝐶𝑝𝑖
 51

𝑖𝑛
The heat of reaction for hydrolysis of cellulose, ∆𝐻𝑟𝑥𝑛,𝑐 is 4491.295 kJ/mol. The
𝑖𝑛
heat of reaction for hydrothermal oxidation of glucose, ∆𝐻𝑟𝑥𝑛,𝑔 is -2066903.53 kJ/mol.
The results of adiabatic temperature for R-101 is shown Table 3.8 and for R-102 in Table
3.9.

Table 3.9 Adiabatic Temperature for R-101

X Ft (kmol/hr) Sigma Pi Cpi Sigma nHrxn Temperature (˚C)

1.00E-05 25201.02 1.82E+02 1.11E-02 6.1181E-05

0.023923 25215.95 4.36E+05 6.68E+04 0.15335428

0.031843 25221.19 5.80E+05 1.20E+05 0.2072043

0.039763 25226.6 7.25E+05 1.90E+05 0.26258628

0.055603 25237.87 1.01E+06 3.83E+05 0.37794552

0.063523 25243.75 1.16E+06 5.07E+05 0.43792278

0.071443 25249.79 1.30E+06 6.51E+05 0.49943078

0.079363 25256 1.45E+06 8.14E+05 0.56246952

0.095203 25268.93 1.74E+06 1.20E+06 0.69313862

0.103123 25275.65 1.88E+06 1.43E+06 0.76076774

0.111042 25282.55 2.03E+06 1.68E+06 0.82992639

0.118962 25289.64 2.17E+06 1.96E+06 0.90061455

0.134802 25304.37 2.46E+06 2.58E+06 1.04657454

0.142722 25312.01 2.61E+06 2.93E+06 1.12184636

0.150642 25319.84 2.76E+06 3.30E+06 1.19864525

0.158562 25327.88 2.90E+06 3.70E+06 1.27696998

 52

0.174402 25344.54 3.19E+06 4.59E+06 1.43819822

0.182322 25353.17 3.34E+06 5.08E+06 1.52109927

0.190242 25362.03 3.49E+06 5.60E+06 1.60552495

0.198162 25371.1 3.63E+06 6.14E+06 1.69147341

0.214001 25389.89 3.92E+06 7.33E+06 1.86793869

0.221921 25399.64 4.07E+06 7.97E+06 1.95845368

0.229841 25409.6 4.22E+06 8.65E+06 2.05048962

0.237761 25419.81 4.37E+06 9.36E+06 2.14404529

0.253601 25440.98 4.66E+06 1.09E+07 2.33571214

0.261521 25451.94 4.81E+06 1.17E+07 2.43382209

0.269441 25463.15 4.96E+06 1.26E+07 2.53344872

0.277361 25474.64 5.10E+06 1.34E+07 2.63459141

0.293201 25498.44 5.40E+06 1.53E+07 2.84141944

0.301121 25510.77 5.55E+06 1.64E+07 2.94710357

0.30904 25523.4 5.70E+06 1.74E+07 3.05430008

0.31696 25536.34 5.85E+06 1.85E+07 3.16300837

0.3328 25563.16 6.15E+06 2.08E+07 3.38495476

0.34072 25577.06 6.29E+06 2.20E+07 3.49819165

0.34864 25591.3 6.44E+06 2.33E+07 3.61293663

0.35656 25605.9 6.59E+06 2.46E+07 3.7291885

0.3724 25636.19 6.90E+06 2.74E+07 3.96621165

0.38032 25651.92 7.05E+06 2.88E+07 4.0869811

 53

0.38824 25668.04 7.20E+06 3.03E+07 4.20925498

0.39616 25684.57 7.35E+06 3.18E+07 4.33303207

0.411999 25718.92 7.65E+06 3.51E+07 4.58509649

0.419919 25736.75 7.81E+06 3.68E+07 4.71338199

0.427839 25755.06 7.96E+06 3.85E+07 4.84316886

0.435759 25773.85 8.11E+06 4.04E+07 4.97445771

0.451599 25812.94 8.42E+06 4.41E+07 5.24153832

0.459519 25833.25 8.57E+06 4.61E+07 5.37732946

0.467439 25854.13 8.73E+06 4.81E+07 5.51462198

0.475359 25875.56 8.88E+06 5.02E+07 5.65341464

0.491199 25920.17 9.20E+06 5.46E+07 5.93550104

0.499119 25943.39 9.35E+06 5.69E+07 6.07879599

0.507038 25967.24 9.51E+06 5.92E+07 6.22359293

0.514958 25991.75 9.67E+06 6.16E+07 6.36988819

0.530798 26042.78 9.99E+06 6.66E+07 6.66698771

0.538718 26069.35 1.01E+07 6.92E+07 6.81778586

0.546638 26096.64 1.03E+07 7.18E+07 6.97009518

0.554558 26124.68 1.05E+07 7.46E+07 7.1238973

0.570398 26183.08 1.08E+07 8.02E+07 7.4360228

0.578318 26213.47 1.10E+07 8.32E+07 7.59434618

0.586238 26244.69 1.11E+07 8.62E+07 7.75416848

0.594158 26276.76 1.13E+07 8.93E+07 7.91549583

 54

0.609997 26343.5 1.16E+07 9.57E+07 8.24267178

0.617917 26378.21 1.18E+07 9.90E+07 8.40852038

0.625837 26413.85 1.19E+07 1.02E+08 8.57587402

0.633757 26450.44 1.21E+07 1.06E+08 8.74473883

0.649597 26526.54 1.24E+07 1.13E+08 9.08698358

0.657517 26566.08 1.26E+07 1.17E+08 9.26036964

0.665437 26606.65 1.28E+07 1.21E+08 9.43526687

0.673357 26648.27 1.30E+07 1.25E+08 9.61166913

0.689197 26734.73 1.33E+07 1.33E+08 9.96900716

0.697117 26779.61 1.35E+07 1.37E+08 10.1499368

0.705036 26825.62 1.37E+07 1.41E+08 10.3323715

0.712956 26872.79 1.38E+07 1.46E+08 10.5163234

0.728796 26970.66 1.42E+07 1.55E+08 10.8887425

0.736716 27021.42 1.44E+07 1.59E+08 11.0772096

0.744636 27073.41 1.46E+07 1.64E+08 11.2671879

0.752556 27126.67 1.47E+07 1.69E+08 11.4586712

0.768396 27237.08 1.51E+07 1.79E+08 11.8461468

0.776316 27294.29 1.53E+07 1.84E+08 12.0421391

0.784236 27352.86 1.55E+07 1.90E+08 12.2396304

0.792156 27412.82 1.57E+07 1.95E+08 12.4386267

0.807995 27537.05 1.61E+07 2.06E+08 12.8410977

0.815915 27601.36 1.63E+07 2.12E+08 13.0445724

 55

0.823835 27667.2 1.65E+07 2.18E+08 13.2495338

0.831755 27734.58 1.67E+07 2.24E+08 13.4559819

0.847595 27874.17 1.71E+07 2.37E+08 13.8733137

0.855515 27946.43 1.73E+07 2.43E+08 14.0841852

0.863435 28020.42 1.75E+07 2.50E+08 14.296525

0.871355 28096.16 1.77E+07 2.57E+08 14.5103148

0.887195 28253.15 1.81E+07 2.71E+08 14.9422198

0.895115 28334.52 1.83E+07 2.78E+08 15.1603106

0.903034 28417.89 1.85E+07 2.85E+08 15.3798025

0.910954 28503.35 1.88E+07 2.93E+08 15.600677

0.926794 28680.9 1.92E+07 3.08E+08 16.0464272

0.934714 28773.21 1.94E+07 3.16E+08 16.2712234

0.942634 28868.03 1.97E+07 3.24E+08 16.4972065

0.950554 28965.52 1.99E+07 3.33E+08 16.7242786

0.966394 29169.26 2.04E+07 3.50E+08 17.180919

0.974314 29275.84 2.06E+07 3.59E+08 17.4097225

0.981412 29374.06 2.08E+07 3.67E+08 17.6140721

0.99 29494.83 2.11E+07 3.77E+08 17.8570757

 56

Table 3.10 Adiabatic Temperature for R-102

X Ft (kmol/hr) Sigma Pi Cpi Sigma nHrxn Temperature (˚C)

1.00E-05 10239.07 1.30E+02 0.00E+00 0.00E+00

0.023923 10655.67 3.23E+05 2.62E+03 8.11E-03

0.031843 10793.68 4.35E+05 6.51E+03 1.49E-02

0.039763 10931.71 5.51E+05 1.34E+04 2.42E-02

0.055603 11207.81 7.90E+05 4.05E+04 5.13E-02

0.063523 11345.89 9.13E+05 6.36E+04 6.97E-02

0.071443 11483.99 1.04E+06 9.53E+04 9.17E-02

0.079363 11622.12 1.17E+06 1.38E+05 1.18E-01

0.095203 11898.44 1.44E+06 2.64E+05 1.84E-01

0.103123 12036.64 1.57E+06 3.53E+05 2.24E-01

0.111042 12174.86 1.71E+06 4.64E+05 2.71E-01

0.118962 12313.11 1.86E+06 6.01E+05 3.24E-01

0.134802 12589.71 2.15E+06 9.70E+05 4.51E-01

0.142722 12728.05 2.30E+06 1.21E+06 5.27E-01

0.150642 12866.43 2.46E+06 1.50E+06 6.11E-01

0.158562 13004.83 2.61E+06 1.84E+06 7.06E-01

0.174402 13281.75 2.94E+06 2.72E+06 9.27E-01

0.182322 13420.27 3.10E+06 3.27E+06 1.06E+00

0.190242 13558.83 3.27E+06 3.91E+06 1.20E+00

0.198162 13697.43 3.44E+06 4.65E+06 1.35E+00

 57

0.214001 13974.76 3.79E+06 6.49E+06 1.71E+00

0.221921 14113.49 3.97E+06 7.61E+06 1.92E+00

0.229841 14252.27 4.15E+06 8.90E+06 2.14E+00

0.237761 14391.09 4.34E+06 1.04E+07 2.39E+00

0.253601 14668.9 4.71E+06 1.39E+07 2.95E+00

0.261521 14807.87 4.91E+06 1.60E+07 3.27E+00

0.269441 14946.9 5.10E+06 1.84E+07 3.61E+00

0.277361 15085.98 5.30E+06 2.11E+07 3.98E+00

0.293201 15364.31 5.71E+06 2.75E+07 4.83E+00

0.301121 15503.56 5.92E+06 3.13E+07 5.30E+00

0.30904 15642.87 6.13E+06 3.56E+07 5.81E+00

0.31696 15782.24 6.34E+06 4.03E+07 6.36E+00

0.3328 16061.15 6.77E+06 5.13E+07 7.58E+00

0.34072 16200.7 6.99E+06 5.78E+07 8.26E+00

0.34864 16340.3 7.22E+06 6.49E+07 8.99E+00

0.35656 16479.97 7.45E+06 7.28E+07 9.78E+00

0.3724 16759.48 7.91E+06 9.11E+07 1.15E+01

0.38032 16899.33 8.14E+06 1.02E+08 1.25E+01

0.38824 17039.23 8.38E+06 1.13E+08 1.35E+01

0.39616 17179.19 8.62E+06 1.26E+08 1.46E+01

0.411999 17459.3 9.11E+06 1.55E+08 1.70E+01

0.419919 17599.43 9.36E+06 1.72E+08 1.83E+01

 58

0.427839 17739.61 9.62E+06 1.90E+08 1.97E+01

0.435759 17879.85 9.87E+06 2.09E+08 2.12E+01

0.451599 18160.49 1.04E+07 2.54E+08 2.45E+01

0.459519 18300.87 1.07E+07 2.80E+08 2.62E+01

0.467439 18441.3 1.09E+07 3.07E+08 2.81E+01

0.475359 18581.78 1.12E+07 3.37E+08 3.01E+01

0.491199 18862.86 1.17E+07 4.04E+08 3.44E+01

0.499119 19003.45 1.20E+07 4.42E+08 3.68E+01

0.507038 19144.08 1.23E+07 4.83E+08 3.93E+01

0.514958 19284.75 1.26E+07 5.27E+08 4.19E+01

0.530798 19566.15 1.32E+07 6.26E+08 4.76E+01

0.538718 19706.89 1.35E+07 6.81E+08 5.06E+01

0.546638 19847.66 1.37E+07 7.40E+08 5.39E+01

0.554558 19988.44 1.40E+07 8.04E+08 5.73E+01

0.570398 20270.06 1.46E+07 9.47E+08 6.46E+01

0.578318 20410.89 1.50E+07 1.03E+09 6.86E+01

0.586238 20551.73 1.53E+07 1.11E+09 7.28E+01

0.594158 20692.58 1.56E+07 1.20E+09 7.72E+01

0.609997 20974.3 1.62E+07 1.41E+09 8.67E+01

0.617917 21115.17 1.65E+07 1.52E+09 9.19E+01

0.625837 21256.04 1.69E+07 1.64E+09 9.73E+01

0.633757 21396.91 1.72E+07 1.77E+09 1.03E+02

 59

0.649597 21678.66 1.78E+07 2.06E+09 1.15E+02

0.657517 21819.53 1.82E+07 2.22E+09 1.22E+02

0.665437 21960.4 1.85E+07 2.39E+09 1.29E+02

0.673357 22101.27 1.89E+07 2.58E+09 1.37E+02

0.689197 22383 1.95E+07 2.99E+09 1.53E+02

0.697117 22523.86 1.99E+07 3.23E+09 1.62E+02

0.705036 22664.72 2.02E+07 3.48E+09 1.72E+02

0.712956 22805.58 2.06E+07 3.74E+09 1.82E+02

0.728796 23087.3 2.13E+07 4.35E+09 2.04E+02

0.736716 23228.16 2.17E+07 4.69E+09 2.16E+02

0.744636 23369.03 2.20E+07 5.05E+09 2.29E+02

0.752556 23509.9 2.24E+07 5.45E+09 2.43E+02

0.768396 23791.67 2.32E+07 6.36E+09 2.74E+02

0.776316 23932.58 2.35E+07 6.87E+09 2.92E+02

0.784236 24073.5 2.39E+07 7.43E+09 3.11E+02

0.792156 24214.44 2.43E+07 8.05E+09 3.31E+02

0.807995 24496.41 2.51E+07 9.47E+09 3.77E+02

0.815915 24637.44 2.55E+07 1.03E+10 4.04E+02

0.823835 24778.52 2.59E+07 1.12E+10 4.33E+02

0.831755 24919.63 2.63E+07 1.22E+10 4.65E+02

0.847595 25202.05 2.71E+07 1.46E+10 5.40E+02

0.855515 25343.36 2.75E+07 1.60E+10 5.84E+02

 60

0.863435 25484.77 2.79E+07 1.77E+10 6.34E+02

0.871355 25626.27 2.83E+07 1.95E+10 6.90E+02

0.887195 25909.66 2.91E+07 2.41E+10 8.28E+02

0.895115 26051.6 2.95E+07 2.70E+10 9.14E+02

0.903034 26193.73 3.00E+07 3.04E+10 1.02E+03

0.910954 26336.11 3.04E+07 3.45E+10 1.14E+03

0.926794 26621.79 3.13E+07 4.57E+10 1.46E+03

0.934714 26765.27 3.17E+07 5.36E+10 1.69E+03

0.942634 26909.32 3.21E+07 6.38E+10 1.98E+03

0.950554 27054.14 3.26E+07 7.76E+10 2.38E+03

0.966394 27347.45 3.35E+07 1.27E+11 3.78E+03

0.974314 27497.33 3.39E+07 1.76E+11 5.19E+03

0.981412 27635.32 3.44E+07 2.60E+11 7.55E+03

0.99 27812.9 3.49E+07 5.36E+11 1.54E+04

 61

20

18

16
Adiabatic Temperature (˚C)
14

12

10

0
1.E-05
6.E-02
1.E-01
1.E-01
2.E-01
2.E-01
3.E-01
3.E-01
3.E-01
4.E-01
4.E-01
5.E-01
5.E-01
5.E-01
6.E-01
6.E-01
6.E-01
7.E-01
7.E-01
8.E-01
8.E-01
8.E-01
9.E-01
9.E-01
1.E+00
Conversion of Cellulose, X

Figure 3.8 Adiabatic Temperature for R-101

1.80E+04

1.60E+04

1.40E+04
Adiabatic Temperature (˚C)

1.20E+04

1.00E+04

8.00E+03

6.00E+03

4.00E+03

2.00E+03

0.00E+00
0.00E+00 2.00E-01 4.00E-01 6.00E-01 8.00E-01 1.00E+00 1.20E+00
Conversion of Glucose, X

Figure 3.9 Adiabatic Temperature for R-102

 62

From Figure 3.8, the adiabatic temperature increase linearly with conversion of
cellulose. This is because, high temperature will affect the reaction of hydrolysis of
cellulose to glucose. From Figure 3.9, the adiabatic temperature increases at high
conversion of glucose. The second reaction occurred at R-102, which is hydrothermal
oxidation of glucose need high reaction temperature in order to achieve the best
conversion of glucose to the desired product which is formic acid. Thus, we can conclude
that the best condition for the both reactions in order to get high conversion of limiting
reactants are by operating the reaction at isothermal condition.

3.4.6 Reactor Sizing

By referring to the stoichiometric equation,

C12H20O10 + 2H2O  2C6H12O6 (3.60)
2C6H12O6 + 9O2  6HCOOH + 6CO2 + 6H2O (3.61)

Rate laws: refers equation (3.60) and (3.61)

Net rate law for formic acid
r1 = k1CcelCw2 (3.62)
r2 = k2Cg2Co9 (3.63)
Total net rate law for these equation are:
r = r1 + r2
r = k1CcelCw2 + k2Cg2Co9 (3.64)

The design equation for catalytic reaction for PBR:

𝑑𝑋
𝐹𝐴0 = - r’A (3.65)
𝑑𝑊

The design equation for catalytic reaction for PBR

𝑑𝑋
𝐹𝐴0 𝑑𝑊 = - r’A
 63

These equations are implemented into Microsoft Excel to find the volume of for
reactor based on conversion of glucose. The Microsoft Excel graphical output is shown in
Figure 3.10 and Figure 3.11.

2000
1800
1600
1400
Fa0/ra (m^3)

1200
1000
800
600
400
200
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
conversion, X

Figure 3.10 Volume of reactor PBR as a function of Cellulose

20000
18000
16000
14000
Fa0/ra (m^3)

12000
10000
8000
6000
4000
2000
0
0.25
0.05
0.10
0.15
0.20

0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95

conversion, X

Figure 3.11 Volume of reactor PBR as a function of Glucose

 64

The dimension for reactor is estimated between the ratios of length to diameter:
LR/D ≈ 3 (3.66)

Table 3.11 Volume of reactor R-101 PBR based on conversion

Conversion Xcel Volume (𝒎𝟑 ) Diameter (m) Length (m)

0.05 0.00 0.00 0.00

0.10 0.00 0.00 0.00

0.15 0.00 0.00 0.00

0.20 0.00 0.00 0.00

0.25 0.00 0.00 0.00

0.30 0.02 0.00 0.00

0.35 0.04 0.00 0.02

0.40 0.09 0.02 0.04

0.45 0.17 0.04 0.07

0.50 0.31 0.07 0.01

0.55 0.54 0.11 0.23

0.60 0.94 0.20 0.40

0.65 1.58 0.33 0.67

0.70 2.65 0.60 1.12

0.75 4.46 0.95 1.89

0.80 7.66 1.63 3.25

0.85 13.80 2.92 5.85

0.90 27.40 5.81 11.6

 65

0.95 71.50 15.2 30.4

Table 3.12 Volume of reactor R-102 PBR based on conversion

Conversion Xg Volume (𝒎𝟑 ) Diameter (m) Length (m)

0.05 0.02878 0.00611 0.01221

0.10 0.23700 0.05029 0.10057

0.15 0.38740 0.08220 0.16440

0.20 0.61560 0.13062 0.26123

0.25 0.88168 0.18707 0.37415

0.30 1.19104 0.25271 0.50543

0.35 1.55075 0.32904 0.65807

0.40 1.97019 0.41803 0.83607

0.45 2.46221 0.52243 1.04486

0.50 3.04475 0.64603 1.29206

0.55 3.74375 0.79435 1.58869

0.60 4.59813 0.97563 1.95125

0.65 5.66901 1.20284 2.40569

0.70 7.05829 1.49762 2.99524

0.75 8.94940 1.89888 3.79775

0.80 11.70915 2.48444 4.96887

0.85 16.19348 3.43592 6.87184

0.90 24.97019 5.29815 10.59630

 66

0.95 50.87827 10.79530 21.59061

3.4.7 Cost of Reactor

Annual cost of a reactor (Krt) can be estimated by the following equation (Daud 2002):
𝐼𝑀𝑆𝑘 7775.3
Krt =( )( ) 𝐷1.066 𝐿𝑅 0.82 (2.18 + 𝐹𝑚 𝐹𝑝 )𝐹𝐼   (3.67)
𝐼𝑀𝑆𝑑 3


Where
D = Diameter of reactor
𝐿𝑅 = Length of reactor
𝐹𝑚 = Design of material’s factor
𝐹𝑝 = Pressure factor
𝐹𝐼 = Installation factor = 1.5
𝐼𝑀𝑆𝑘 = Recent Marshall and Swift index
𝐼𝑀𝑆𝑑 = Early Marshall and Swift index = 280

The Marshall and Swift equipment cost index is shown in Table 3.13 below:

Table 3.13 Marshall and Swift equipment cost index

Year Marshall and Swift index

2005 1244.5

2006 1302.3

2007 1373.3

2008 1449.3
 67

2009 1468.3

2010 1457.4

2011 1515.70

2012 1532.37

2013 1546.16

2014 1577.08

2015 1581.81

Source: American Appraisal 2014 & 2015

Design material factor, 𝐹𝑚 for stainless steel is 3.75 and the pressure factor 𝐹𝑝 is assumed
to be 1. Table 3.14 shows the annual cost of reactor as a function of conversion.

Table 3.14 Annual cost of reactor R-101 PBR based on conversion

Conversion Xg Volume (𝒎𝟑 ) Diameter (m) Length (m) Krt (RM/year)

0.05 7.31E-07 1.55E-07 3.10E-07 0.00

0.10 8.05E-05 1.71E-05 3.42E-05 0.00

0.15 6.00E-04 1.27E-04 2.55E-04 0.01

0.20 2.45E-03 5.20E-04 1.04E-03 0.15

0.25 7.44E-03 1.58E-03 3.16E-03 1.20

0.30 1.89E-02 4.01E-03 8.01E-03 6.92

0.35 4.24E-02 8.99E-03 1.80E-02 31.83

0.40 8.72E-02 1.85E-02 3.70E-02 123.92

0.45 1.68E-01 3.56E-02 7.12E-02 426.43

 68

0.50 3.08E-01 6.53E-02 1.31E-01 1337.02

0.55 5.43E-01 1.15E-01 2.31E-01 3909.88

0.60 9.35E-01 1.98E-01 3.97E-01 10873.23

0.65 1.58E+00 3.35E-01 6.70E-01 29269.54

0.70 2.65E+00 5.62E-01 1.12E+00 77663.87

0.75 4.46E+00 9.47E-01 1.89E+00 207520.57

0.80 7.66E+00 1.63E+00 3.25E+00 575209.06

0.85 1.38E+01 2.92E+00 5.85E+00 1737848.93

0.90 2.74E+01 5.81E+00 1.16E+01 6352691.70

0.95 7.15E+01 1.52E+01 3.04E+01 38839725.29

Table 3.15 Annual cost of reactor R-102 PBR based on conversion

Conversion Xcel Volume (𝒎𝟑 ) Diameter (m) Length (m) Krt (RM/year)

0.05 0.02878 0.00611

0.01221 15.33
0.10 0.23700 0.05029
0.10057 817.54
0.15 0.38740 0.08220
0.16440 2065.45
0.20 0.61560 0.13062
0.26123 4947.14
0.25 0.88168 0.18707
0.37415 9740.87
0.30 1.19104 0.25271
0.50543 17176.82
0.35 1.55075 0.32904
0.65807 28255.50
0.40 1.97019 0.41803
0.83607 44379.92
0.45 2.46221 0.52243
1.04486 67574.32
 69

0.50 3.04475 0.64603

1.29206 100860.60
0.55 3.74375 0.79435
1.58869 148936.46
0.60 4.59813 0.97563
1.95125 219468.10
0.65 5.66901 1.20284
2.40569 325730.30
0.70 7.05829 1.49762
2.99524 492483.32
0.75 8.94940 1.89888
3.79775 770596.43
0.80 11.70915 2.48444
4.96887 1279330.11
0.85 16.19348 3.43592
6.87184 2358084.78
0.90 24.97019 5.29815
10.59630 5336805.53
0.95 50.87827 10.79530
21.59061 20429783.27

3.4.8 Economy Potential Analysis of Level 3

The economy potential for level 3 is given:

𝑓𝑃𝐸3 = 𝑓𝑃𝐸2 – 𝐾𝑟𝑡 (3.68)

Thus, the economy potential of level 3 is shown in Table 3.16. and Figure 3.12.

Table 3.16 Data for Economy Potential of Process Design Level 3

Conversion X fpe2 (RM/year) fpe3 (RM/year)

0.05 3.62 -11.71

0.10 64.26 -753.28

0.15 434.52 -1630.95

 70

0.20 1914.61 -3032.68

0.25 7961.68 -1780.39

0.30 22765 5581.26

0.35 58107 29819.67

0.40 135691 91187.16

0.45 333261 265260.25

0.50 755565 653367.38

0.55 1447366 1294519.66

0.60 2949782 2719440.67

0.65 4799299 4444299.16

0.70 9340397 8770249.81

0.75 16568422 15590305.00

0.80 33502054 31647514.84

0.85 58751910 54655976.28

0.90 135267093 123577595.77

0.95 194310816 135041307.44

 71

160000000.00
140000000.00

Economy Potential, RM/year

120000000.00
100000000.00
80000000.00
60000000.00
40000000.00
20000000.00
0.00

0.75

0.85

0.95
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70

0.80

0.90
-20000000.00

Conversion, X

Figure 3.12 Potential Economy Curve for Level 3

3.5 PROCESS DESIGN LEVEL 4

3.5.1 Preliminary Design of Rotary Drum Filter F-101

Figure 3.13 PFD of Rotary Drum Filter F-101

The design of rotary drum filter is based on the filtrate flow rate based on conversion in
stream 10. Given that the density of stream 10 as 7.1349 kg/m3, the data is shown in
Table 3.17.
 72

Table 3.17 Mass and volumetric flow rate based on conversion of stream 10.
Conversion Mass flow rate (kg/hr) Volumetric flow rate
(m3/hr)
0.05 316.65 44.38044

0.1 432.74 60.65117

0.15 548.28 76.84481

0.2 663.26 92.95996

0.25 777.68 108.9966

0.3 891.55 124.9562

0.35 1004.86 140.8373

0.4 1117.61 156.6399

0.45 1229.81 172.3654

0.5 1341.45 188.0124

0.55 1452.53 203.581

0.6 1563.05 219.071

0.65 1673.02 234.484

0.7 1782.43 249.8185

0.75 1891.29 265.0759

0.8 1999.59 280.2548

0.85 2107.33 295.3552

0.9 2214.51 310.3772

0.95 2321.14 325.322

 73

Assume a total membrane area, the open-tube velocity is given as:

V
u=A (3.68)

Where u = open-tube velocity

V = Volumetric flow rate

Given viscosity of stream 10 as 0.00025114 Pa.s and pressure drop of 2.0265 Pa. From
Poiseuille's law, the length of drum is given as:
∆𝑝𝐷 2
𝐿= (3.69)
32𝜇𝑢

Where D = diameter of drum

u = viscosity of filtrate
∆𝑝 = pressure drop
𝜇 = filtrate viscosity

For 2 m area of filter, the value of u from excel calculation is 155 m/hr.
recalculate the value of area, diameter and length using Eq. (3.68) and Eq (3.69). The
economic potential analysis is given as follow:

𝐼 7775.3
𝐾𝑟𝑡 = 𝐼𝑀𝑆𝐾 3
𝐷1.066 𝐿0.82 (2.18 + 𝐹𝑀 𝐹𝑃 )𝐹𝐼 (3.70)
𝑀𝑆𝐷

Where D = Column diameter

L = Height of column
Fp = Pressure factor
FI = Installation factor
FM = Material of construction factor
IMSD = Latest Marshall & Swift Index (1567 for year 2012)
IMSK = Previous Marshall & Swift Index (280)
 74

Table 3.18 Economic analysis for Rotary Drum Filter F-101

Conversion Radius (m) Diameter (m) Length (m) Krt (RM)

0.05 0.301834 0.603667 0.592849 75581.21

0.1 0.352851 0.705702 0.810199 104104.4

0.15 0.397172 0.794345 1.02652 134690.5

0.2 0.436837 0.873675 1.241791 167052.3

0.25 0.473019 0.946037 1.456015 200976.7

0.3 0.506467 1.012933 1.669208 236291.2

0.35 0.537688 1.075377 1.881353 272857.2

0.4 0.567052 1.134104 2.09245 310562.9

0.45 0.594836 1.189671 2.302517 349306.7

0.5 0.621248 1.242496 2.511535 389003.9

0.55 0.646458 1.292916 2.719505 429579.9

0.6 0.670601 1.341202 2.926427 470972.7

0.65 0.693791 1.387581 3.132319 513119.6

0.7 0.716117 1.432234 3.337162 555971.4

0.75 0.737661 1.475322 3.540976 599476

0.8 0.758487 1.516975 3.743741 643589.3

0.85 0.778653 1.557307 3.945457 688270.8

0.9 0.798209 1.596418 4.146126 733487.3

0.95 0.8172 1.634401 4.345764 0

 75

3.5.2 Preliminary Design of Ultrafiltration Membrane F-102

Figure 3.14 PFD of Ultrafiltration Membrane F-102

The design of ultrafiltration membrane is based on the conversion of oligosaccharide on

permeate stream 12 as shown in Table 3.19. The density of stream 12 is given as
1513.2140 kg/m3.

Table 3.19 Flow rates based on conversion of stream 12

Conversion Mass flow rate (kg/hr) Volumetric flow
rate (m3/hr)
0.05 94.27 0.062297864

0.1 89.14 0.058907729

0.15 84.62 0.055920709

0.2 80.7 0.053330197

0.25 77.38 0.051136191

0.3 74.67 0.049345301

0.35 72.55 0.047944309

0.4 71.05 0.046953042

 76

0.45 70.14 0.046351673

0.5 69.84 0.046153419

0.55 70.14 0.046351673

0.6 71.05 0.046953042

0.65 72.55 0.047944309

0.7 74.67 0.049345301

0.75 77.38 0.051136191

0.8 80.7 0.053330197

0.85 84.62 0.055920709

0.9 89.14 0.058907729

0.95 94.27 0.062297864

Assume a total membrane area, superficial fluid velocity of stream 12 is given as

Darcy's Law.

𝑉
J=𝐴 (3.71)

Where v = Volume flow rate

A = Area of filter

In terms of bulk flow permeability, the pressure on downstream side of membrane is

given as Kozeny (1927) and Carman (1938).

2𝐽(1−∈)2 𝜏𝑎𝑣2 𝜇𝑙𝑀

PL = PO (3.72)
∈3

Where Po = Pressure on the upstream side of membrane

 77

∈ = Porosity of membrane
𝜏 = Tortuosity factor
av = Specific surface area
𝑙𝑀 = Membrane thickness
𝜇 = Viscosity

Given that the porosity of membrane as 0.85, tortuosity factor of 0.25, and
membrane thickness of 0.001 m and viscosity of 0.030611Pa.s, the pressure on
downstream side of membrane is 1.15 bar when the area is 0.5203 m2 from trial and error
calculation. The economic potential analysis is given as follow:

𝐼 7775.3
𝐾𝑟𝑡 = 𝐼𝑀𝑆𝐾 𝐷1.066 𝐿0.82 (2.18 + 𝐹𝑀 𝐹𝑃 )𝐹𝐼 (3.73)
𝑀𝑆𝐷 3

Where D = Column diameter

L = Height of column
Fp = Pressure factor
FI = Installation factor
FM = Material of construction factor
IMSD = Latest Marshall & Swift Index (1567 for year 2012)
IMSK = Previous Marshall & Swift Index (280)

Table 3.20 Economic analysis for Ultrafiltration Membrane F-102.

Conversion Radius (m) Diameter (m) Length (m) Krt (RM)

0.05 1.348098 2.696197 5.392394 1492727

0.1 0.406866 0.813732 1.627464 155865.7

0.15 0.396416 0.792833 1.585665 148401.8

0.2 0.387126 0.774251 1.548502 141910.3

 78

0.25 0.379079 0.758157 1.516315 136398.3

0.3 0.372382 0.744763 1.489526 131889.1

0.35 0.367057 0.734114 1.468229 128355.1

0.4 0.363243 0.726486 1.452971 125851.1

0.45 0.360909 0.721818 1.443637 124330.5

0.5 0.360137 0.720273 1.440546 123829

0.55 0.360909 0.721818 1.443637 124330.5

0.6 0.363243 0.726486 1.452971 125851.1

0.65 0.367057 0.734114 1.468229 128355.1

0.7 0.372382 0.744763 1.489526 131889.1

0.75 0.379079 0.758157 1.516315 136398.3

0.8 0.387126 0.774251 1.548502 141910.3

0.85 0.396416 0.792833 1.585665 148401.8

0.9 0.406866 0.813732 1.627464 155865.7

0.95 0.41841 0.836819 1.673639 164310.9

3.5.3 Preliminary Design of Simulated Moving Bed Chromatography (S-101)

Chromatography is one of the few separation techniques that can separate a multi-
component mixture into nearly pure components in a single device, generally a column
packed with a suitable sorbent. The degree of separation depends upon the length of the
column and the difference in component
 79

Proper selection of the separator type is important in the design process. In this
system, liquid chromatography in simulated moving bed (SMB) has been use for
separation of multi-component mixtures especially high yields and purities are required.
In this area, the simulated moving bed chromatography (SMB) has been used to separate
glucose from fructose to produce high purity of glucose before feed to reactor (R-102) to
produce formic acid.

Sizing of the chromatography is important to know the size of chromatography

and costing to design the chromatographer. However, sizing of chromatography is
depends on the height and diameter of the chromatography.

First of all, we need to calculate the diameter of the chromatography. The

parameter such flow rate, density volumetric flow rate and velocity is required to
calculate the diameter of chromatography. However, all the value we can get from iCON
software which can be tabulated as shown in table 3.21 which depends on the conversion.

Table 3.21 Parameter required to calculate diameter of chromatography.

X F(kg/h) ρ(kg/m3) Q(m3/s) Ut(m/s)

0.05 122.38 1434.28 2.37014E-05 0.0233

0.1 243.60 1441.67 4.69363E-05 0.0324

0.15 363.66 1449.8 6.96763E-05 0.0387

0.2 482.56 1457.36 9.19776E-05 0.0439

0.25 600.30 1465.01 0.000113822 0.0483

0.3 716.88 1472.73 0.000135214 0.0519

0.35 832.30 1481.23 0.000156083 0.0547

0.4 946.56 1489.14 0.000176567 0.0575

 80

0.45 1059.67 1499.15 0.000196346 0.0597

0.5 1171.61 1507.27 0.000215918 0.0618

0.55 1282.39 1516.18 0.000234945 0.0632

0.6 1392.01 1525.85 0.000253412 0.0652

0.65 1500.47 1535.00 0.000271529 0.0661

0.7 1607.77 1544.26 0.000289202 0.0669

0.75 1713.91 1555.06 0.000306153 0.0678

0.8 1818.89 1563.82 0.000323085 0.0688

0.85 1922.71 1574.9 0.000339124 0.0694

0.9 2025.37 1586.15 0.000354697 0.0699

0.95 2126.87 1596.07 0.000370157 0.0699

The volumetric flow rate can be calculated using the formula below:

4𝑄
𝐷 = √𝜋𝑣 𝑥 3600𝑠 (3.74)

Where
D = Diameter of chromatography, m
Q = Volumetric flow rate, m3/s
v = Velocity, m/s

Based on the standard ratio, the height of the chromatography can be determine
using the ratio of 4 : 1 which height is 4 times the value of diameter.
 81

The annual cost of gas liquid separator can be calculated by this formula:

𝐼 7775.3
𝐾𝑟𝑡 = (𝐼𝑀𝑆𝐾)( )𝐷1.066 𝐿0.82
𝑅 (2.18 + 𝐹𝑚 𝐹𝑝 )𝐹𝐼 (3.75)
𝑀𝑆𝐷 3

Where,
IMSK = Present Marshall and Swift Index
IMSD = Past Marshall and Swift Index
D = Diameter of chromatography
LR = Length / Height of chromatography
Fm = Design material factor
Fp = Pressure factor
FI = Installation factor

Table 3.22, 3.23, 3.24 and 3.24 is the list of Marshall and Swift index, design
material factor, pressure factor and design variables of Simulated Moving Bed (SMB)
Chromatography (S-101) respectively.

Table 3.22 Marshall and Swift index

Year Marshall and Swift index

2005 1244.5

2006 1302.3

2007 1373.3

2008 1449.3

2009 1468.6

2010 1457.4

2011 1515.70
2012 1532.37
 82

2013 1546.16
2014 1577.08
2015 (July) 1581.81
Source: American Appraisal 2014 & 2015

Table 3.23 Material design factor list

Fm Construction material

1.00 Carbon steel

2.15 Stainless steel (Chromium-molybdenum)

3.75 Stainless steel

Source: Daud 2002

Material that has been choose to construct the simulated moving bed
chromatography (S-101) is stainless steel Type 316L. Stainless steel Type 316L have
high resistance to corrosion since molybdenum is added to improved anti-corrosion and it
can be used in severe corrosive environments. The main composition inside the stainless
steel Type 316 is chromium, molybdenum and nickel (American Metal Company 2012).
Hence, the construction material that has been chosen is stainless steel (chromium-
molybdenum) with material design factor 3.75.

Table 3.24 Pressure factor list

P(Bar) 1.6 6.8 13.6 20.4 27.2 34.0 40.8 47.6 54.4 61.2 68.0

Fp 1.00 1.05 1.15 1.20 1.35 1.45 1.60 1.80 1.90 2.30 2.50

Source: Daud 2002

 83

Table 3.25 Value for design variables on gas liquid separator (S-101)

Variables Value

𝐼𝑀𝑆𝐾 1581.81

𝐼𝑀𝑆𝐷 280

𝐹𝑚 3.75

𝐹𝑝 0.85

𝐹𝐼 1.50

Based on the equation 3.75, the annual cost of simulated moving bed
chromatography (S-101) can be calculated by inserting the diameter, length or height on
the table 3.5.7. Hence, table 3.26 below shows the annual cost of the gas liquid separator
(S-101) as a function of conversion.

Table 3.26 Annual cost of the gas liquid separator (S-101) as a function of conversion.

X Q(m3/s) D (m) H (m) Krt (RM)

0.05 2.37014E-05 0.359885 1.079656 42229.94

0.1 4.69363E-05 0.429474 1.288422 58940.54

0.15 6.96763E-05 0.478787 1.43636 72350.71

0.2 9.19776E-05 0.516492 1.549477 83470.54

0.25 0.000113822 0.547765 1.643294 93257.43

0.3 0.000135214 0.575946 1.727838 102512.1

0.35 0.000156083 0.602752 1.808257 111695.8

0.4 0.000176567 0.625282 1.875847 119700.1

 84

0.45 0.000196346 0.647112 1.941336 127703.3

0.5 0.000215918 0.666969 2.000907 135194.2

0.55 0.000234945 0.687987 2.06396 143341.1

0.6 0.000253412 0.703469 2.110408 149485.6

0.65 0.000271529 0.723207 2.169621 157494.0

0.7 0.000289202 0.741895 2.225685 165257.4

0.75 0.000306153 0.758245 2.274734 172193.0

0.8 0.000323085 0.773249 2.319747 178675.6

0.85 0.000339124 0.788777 2.366332 185503.1

0.9 0.000354697 0.803795 2.411385 192220.2

0.95 0.000370157 0.821126 2.463378 200111.3

3.5.4 Preliminary Design of Phase Separator S-102

Phase separator S-102 is a gas-liquid separator which is used to separate the carbon
dioxide and oxygen (gas state) from formic acid and water (liquid state).The material
used for this separator is stainless steel. Vertical separators are only requires of lower
space requirement and easy to install control systems. The phase separator is designed to
be vertically orientation. The advantages of vertical separator are liquid entrainment is
reasonably constant, it requires a smaller footprint area and easier to install level
instruments, alarms, and shutdown systems. Sizing is very important to know the
dimension of the phase separator, diameter and height will be calculated.

For conversion X=0.90, the operating condition for S-102 as shown at table below.
 85

Table 3.27 Operating condition for phase separator S-102.

Parameter Value

Temperature 60 oC

Pressure 2 atm

Flowrate: Inlet 1692.86 kg/hr

Top Stream 175.00 kg/hr

Bottom Stream 1517.86 kg/h

𝜌𝐿 , Liquid density 1158 kg/m3
𝜌𝑣 , Vapour density 1.833 kg/m3

QL, Liquid volumetric flow-rate 0.00025 m3/s

QV, Vapour volumetric flow rate 0.01356 m3/s

For calculation of vertical separator sizing:

Vv is determined on the basis of liquid residence time, t which should be at least 25 min,
with the vessel half full of liquid:

2 𝐿 𝑀𝐿 𝑡
Vv = (3.76)
𝜌𝐿

2(1517.86)(25)
=
(60)(1158)
= 1.093 m3

Where L is the molar liquid flow rate leaving flow rate leaving the vessel. LML is
the total flow rate of the liquid outlet stream. Based on the vertical, cylindrical vessel and
neglecting the volume associated with the heads, the height, H of the vessel is:

4 𝑉𝑣
H= (3.77)
𝜋 𝐷2
 86

However, if H > 4DT, it is generally preferable to increase DT and decrease H to

give H = 4D. Then:
1
𝐻 𝑉 ⁄3
D= = = 0.98 𝑚 (3.78)
4 𝜋

H = 4D = 3.92 m (3.79)

Where D = Minimum allowable vessel diameter, m

VV = Volume separator, m3
t = residence time
H = Height of vessel, m

The installation cost can be approximated by:

𝑀𝑆𝐼
𝐾𝑚 = ( 280 ) [7775.3𝐷1.066 𝐿0.82 (2.18 + 𝐹𝑚 𝐹𝑝 )]𝐹𝑙 (3.80)

= RM 628376

The annual cost:

Kmt = Km / 3 = RM 209458

Where
D =Diameter of the distillation column
L =Height of the distillation column
Fm=Construction factor = 3.75
Fp=Pressure Factor =1.04
FI = Malaysia’s installation column factor = 1.5
MSI = Latest plant cost index for distillation column = 1518.81
 87

The result of each parameter for all conversion are the same due to the flowrate
the same. The annual costs for separator S-102 are same for all the conversion.

3.5.5 Potential Economic Analysis for Level 4

Table 3.28 Fpe 3 and Fpe 4 with conversion.

X Fep3 Fep 4

0.05 -11.71 -1820007.86

0.1 -753.28 -529121.92

0.15 -1630.95 -566531.96

0.2 -3032.68 -604923.82

0.25 -1780.39 -641870.82

0.3 5581.26 -674569.14

0.35 29819.67 -692546.43

0.4 91187.16 -674384.94

0.45 265260.25 -545538.25

0.5 653367.38 -204117.72

0.55 1294519.66 387810.16

0.6 2719440.67 1763673.27

0.65 4444299.16 3435872.46

0.7 8770249.81 7707673.91

0.75 15590305 14472779.7

0.8 31647514.84 30473881.64

0.85 54655976.28 53424342.58

 88

0.9 123577595.8 122286564.6

0.95 135041307.4 133678906.2

Figure 3.15 The graph of Fep 4 versus conversion.

3.6 MASS BALANCE

The mass balance for whole process is shown in table 3.27 in kg/hr and table 3 in kmol/hr.
The variable for this calculation are:

Production rate of formic acid: 1518 kg/hr

Conversion of cellulose to glucose: 90%
Conversion of glucose to formic acid: 90%
Yield of formic acid: 75%
Purity of desired formic acid: 95%
 89

The molecular weight of each component as in table 3.27. below.

Table 3.29 Molecular weight of each component

Component Molecular Weight (g/mol)

Glucose 180.156

Oxygen 32

Formic Acid 46.025

Carbon Dioxide 44.01

Water 18.015

Cellulose 324

Hemi-cellulose Not applicable

Lignin Not applicable

Fructose 180.16

5-hydromethylfurfural 126.11

Oligosaccharides Not applicable

Source: VMGSim v7.0

The mass balance is calculated by using equation (3.81) below:

Rate of mass accumulation = Total rate of mass in – total rate of mass out
𝑑𝐹
= ∑ 𝐹𝑖𝑛 − ∑ 𝐹𝑜𝑢𝑡
𝑑𝑡
(3.81)
𝑑𝐹
Where at steady state, =0
𝑑𝑡

So, the equation (3.81) can be simplify as

∑ 𝐹𝑖𝑛 = ∑ 𝐹𝑜𝑢𝑡

(3.82)
 90

Table 3.28 below summaries the overall mass balance. From the table below, it
can be concluded that the input mass flowrate equals to the output mass flowrate, thus the
overall mass balance is achieved.

Table 3.30 Overall mass balance of the process

Stream Input Mass Flowrate (kg/hr) Output Mass Flowrate (kg/hr)

1 3082.28 -

2 3127.30 -

3 270.28 -

11 - 2482.14

13 - 1486.79

17 - 115.56

20 - 429.38

35 - 37.08

37 - 411.06

40 1517.86

Total 6479.87 6479.87

3.7 ENERGY BALANCE

The information used for this calculation by using specific heat capacity in table below,
the heat of reactions obtained from VMGSim v7.0 and rate of reactions from mass
balance of both reactors.
 91

Heat of reaction for R-101: -858918.1855 kJ/kmol

Rate of reaction for R-101: 5.563205325 kmol/hr
Heat of reaction for R-102: -2066903.53 kJ/kmol
Rate of reaction for R-102: 5.201285468kmol/hr

The enthalpy of component,Hij is calculated by using equation (3.83) below,

Hij = Cpij∆T (3.83)
Where ∆T = Tstream– Treference with Treference= 25℃
And Cpij is the specific heat capacity of component
Energy balance in reactor is calculated by using the equation (3.84) below
Q = ∑ 𝐻𝑖𝑗 𝑁𝑖𝑗 − ∑ 𝐻𝑜𝑗 𝑁𝑜𝑗 + 𝑟𝐻°𝑟𝑥𝑛 (3.84)

Where Q is the output energy

Hij is the input enthalpy of component
Nij is the input molar flowrate of component
Hoj is the output enthalpy of component
Noj is the output molar flowrate of component
r is the rate of reaction
and H˚rxn is the standard enthalpy of reaction

3.8 COMPARISON MANUAL MASS AND ENERGY BALANCE WITH iCON

There is no much difference in mass flowrate for both calculation. However, there is
different in the calculation of energy balance. This is due to several assumptions that has
been made in order to calculate the energy balance manually compared to iCON that used
more accurate data and equation to solve the energy balance. The comparison for energy
balance calculation is shown on table 3.29.
 92

Table 3.31 Energy balance by manual calculation and iCON result

Equipment Manual EB iCON EB Error (%)

R-101 PBR -1324938.32 -725357 0.004525

P-101 Pump 0.00 0.267521 0.009988

P-102 Pump 0.00 0

H-101 Condenser -628.71 777635.3 0.010008

P-103 Pump 0.00 0

P-104 Pump -1.20 -347.592 0.009965

P-105 Pump 1.19 346.0807 0.009966

H-102 Condenser -652.49 778223.9 0.010008

H-103 Cooler 4.39 5572.391 0.009992

H-104 Cooler 118.10 115.237 0.000243

H-105 Cooler 13.94 17432.67 0.009992

P-106 Expander 0.00 5.454782 0.010002

R-102 PBR -2985426.59 -2938189 0.000158

P-107 Pump 0.01 2.751664 0.009958

H-106 Cooler -42.92 80.47874 0.015333

P-108 Pump 0.00 0.303196 0.01

H-107 Cooler 6.18 11075.25 0.009994

 93

S5 S11
S1 S4
SP1 P1
S23

S2

S7 S6 M S22
S18 S21
SP3
P5
S8 S10
C1 MSepLV1
9_12_p P3 S19 S20
P2 S9
C3
CRx1 S24
S15

S16 S17
S12 S14 C2
SP2 P4
E-209 S13

S25 S32
M1

S28 S36 S37

C6

S40
25_3_r 26_30_p S26 S27 S29 S38 S39
S3
C4 SP5 C7
M2 SP4 S30 P8
Sep1
CRx2

S31
SP6 P6

S33 S34 S35

C5
P7

Figure 3.16 iCON simulation