Industial Chemical Process PDF

CHEMICAL DEPARTMENT
Industrial Chemical Process
Prepared by: NGET Sovannmony

Lectured by KONG Sela
INTRODUCTION TO INDUSTRIAL CHEMICAL PROCESS
Chemical processing industries manufacture and process

chemicals. The chemical industry is divided into four categories:
1. Basic chemicals
• Petrochemicals (derived from oil and natural gas) – examples:
methanol, ethylene, butadiene and toluene
• Polymers – examples: polyethylene (PE), polycarbonate,
polyamide (nylon) and polyaramide
• Basic inorganics – examples: chlorine, sulfuric acid (H2SO4),
and hydrochloric acid (HCl)
2
2. Specialty chemicals – examples: adhesives, agrichemicals,

construction chemicals, flame-retardants.
3. Consumer chemicals – alcohol, cosmetics, cleaners, paints,
pesticides, herbicides and foods.
4. (Biobased chemicals and polymers) – ethanol,
polysaccharides, poly lactic acid, bioaromatics, and
furandicarboxylic acid
3
Source: Global Chemicals Outlook – Towards Sound Management of Chemicals, Synthesis Report for Decision-
Makers, pub by the United Nations Environment Program, 2012
4
• In chemical process, quantitative analysis is an important tool

for chemical engineer.
• The basic concept of chemical engineering, such as
thermodynamics, heat and mass transfer, and reaction kinetics,
are commonly expressed by mathematical equations based on
calculus to be in form of algebraic or differential equation,
which can be solved.
• In the analysis of chemical engineering phenomena, non-
uniform conditions, such as time dependent and position
dependent, or both are commonly encountered. The common
approach of these situations are the concept of element, known
as volume element, time element, and population distribution
element.
5
1. CONCEPT OF VOLUME ELEMENT
• Volume element: dV = dx.dy.dz

or dV = S.dz
• The volume element approach is an idea
used determine the whole volume from
the smallest volume.
• Ex 1. flowing of liquid in the pipe inside radius of R. The non-
uniform velocity of liquid is v (cm/s) = 10(1- 0.25r2 ), Radius
of pipe is 2cm. Calculate debit 𝑐𝑚!/𝑠and average velocity.
6
• Generally, 𝑄 = 𝑣×𝐴, this formula can be applied

when v is uniform velocity.
• The cross section of the pipe is divided into many small area (area
element). Hence, the velocity at each small area can be assumed to be
constant.
• Let dQ = the debit at the area element
dA = the area of element
Then,
𝑑𝑄 = 𝑣×𝑑𝐴
The velocity distribution in the pipe does not depend on length of pipe: dA=2𝜋𝑟𝑑𝑟
𝑑𝑄 = 10 1 − 0.25𝑟 ! . 2𝜋𝑟𝑑𝑟
7
# $
% 𝑑𝑄 = % 20𝜋. 𝑟 − 0.25𝑟 ! 𝑑𝑟
" "
𝑅% 0.25 &
𝑄 = 20𝜋 − 𝑅
2 4
𝑄 = 62.8 𝑐𝑚!/𝑠
# (%.*
• Average velocity: 𝑣 = ' = +$" = 5𝑐𝑚/𝑠
• Maximum velocity: 𝑣,-.:01" = 10𝑐𝑚/𝑠
8
Ex 2. Solid sphere with radius of R contains water with non-

uniform concentration. Determine the total mass of water and
average concentration of water in sphere.
C(mg/ml 𝑜𝑟 𝑚𝑔/𝑐𝑚!) = C0 + 3.r + 4r2.
Initial concentration C0 = 120
Radius of sphere = 5cm.
9
• The general calculation

• Mwater = C x V
• This formula can’t apply to non-uniform
concentration distribution.
• dmwater = C. dV, dV is the smallest volume imaginable
• This formula is applicable, because the concentration of water
will be uniform in a very small volume.
, 2
• Thus, ∫" 𝑑𝑚 = ∫" 𝐶. 𝑑𝑉 , dV = S.dr , S = 4πr2,
10
3 $
Þ∫" 𝑑𝑚 = ∫" 𝐶(𝑟). 4πr2𝑑𝑟, C = C0 + 3r + 4r2
3 $
Þ ∫" 𝑑𝑚 = ∫" ( 𝐶" + 3𝑟 + 4𝑟 %) 4πr2𝑑𝑟
$# $$ $%
Þ M = 4π( C0 ! + 3 & + 4. 4 )= 100087.5 mg=100,0875g
! $# $$ $%
• Average concentration Cav = M/V = ( C0 +3 + 4. )
$# ! & 4
56 $ $"
Cav = 3 (! +3 &
+ 4. 4 )
• Maximum concentration: 𝐶,-.;01$ = 𝐶" + 3𝑅 + 4𝑅%
11
• Homework 1
1. Example at least 3 private companies or SMEs and their
products in Cambodia related to the chemical industry.
2. Fowing of liquid in the pipe inside radius of R. The non-
uniform velocity of liquid is v = 10(1- 4r2 ). The radius of
pipe is R=0.5 cm. Calculate debit and average velocity.
3. Solid sphere with radius of R= 2 cm contains water with non-
uniform concentration C = 0.3(1- 0.25r2 ). Determine the total
mass of water and average concentration of water inside the
sphere.
12
• Time element
• Ex1: A pipe delivered sugarcane juice into a clarification tank
with flow rate which is function of time: Q(t) = -3t2 + 30t.
Calculate the volume of sugarcane juice collected after 10 min.
Note that the tank was initially empty.
• Analysis:
𝑉(𝐿) = 𝑄(𝐿@𝑚𝑖𝑛). 𝑡(𝑚𝑖𝑛)
This formula can be applied if Q is constant but in this problem
the debit (flow rate) is not constant. It is considered to divide time
element into a very small-time interval (dt→ 0). Then, we can
assume that each very small time is constant.
Let dV: volume collected in the time interval of dt
13
• 𝑑𝑉 = 𝑄. 𝑑𝑡=(-3t2 + 30t)dt
8 9
• ∫" 𝑑𝑉 = ∫" −3𝑡 % + 30𝑡 𝑑𝑡
• 𝑉 = 500L
14
• Assignment 1. A grain of substance A has a cone shape ϕ = 300.

The bag of substance A was accidentally cut open. The grain of
substance A absorb the moisture in the air into the grain. The
moisture distribution in the grain is C (mg/ml) = C0 + 0.026r +
0.015r3 . Calculate the amount of pure substance A remained in
the bag since we know that substance A react with the water.
• Mass of grain : m= 80g and n=1.22 mole
• 20 grains/bag
• r = 5cm, h = 8.66cm, Co = 0.025mg/ml
• A + H 2O à B
15
2. POPULATION DISTRIBUTION
• Example: GPA of students in Chemical Engineering Department
These are very common representation of population distribution. However, you

cannot answer how many student having GPA between 2.75-3.0 from this graph?
These mean that those representation cannot be applied for mathematical operation.
16
𝑁%.:4;!." ≈ 504 − 400 ≈ 104
17
• If N = F(x) is the cumulative fraction or density function.
ΔNx1,x2 = Nx2 - Nx1
18
• However, the last diagram cannot give visual information on the

population distribution.
• Actually, the next graph can also show the density of the
𝒅𝑵
population distribution by the slope of curve 𝒅(𝑮𝑷𝑨)
• N is number of population
𝒅𝑵
• The next graph, inform of the slop of curve versus GPA
𝒅(𝑮𝑷𝑨)
can satisfy both of the need (interpolation and population
density as well as other mathematical operation.
19
In general, the representation of population distribution is mathematically in form of:

!"
𝑝 𝑥 = ; N = population number
!#
x = the independent varriable of distribution
20
• The interpolation of function:

#%
𝜕𝑁 = P(x) 𝜕x or ΔN = ∫#$ 𝑃(𝑥)𝜕𝑥
21
• It is very common that the number of population is expressed by fraction.

]
• Let: 𝑛=]
!
• n = fraction
• 𝑁& = total number of population
• 𝑁= number of population
'(
• The population distribution will be: p 𝑥 = =𝑓 𝑥
')
• dN = 𝑁& . 𝑑𝑛
• 𝐝𝐍 = 𝑵𝒕 . 𝒑 𝒙 . 𝒅𝒙 [ dN = number total x fraction function]
𝒙 𝒎𝒂𝒙
• Normalization: ∫𝒙 𝒎𝒊𝒏 𝒑(𝒙)𝝏𝒙 = 1
22
• P(x) is the probability of distribution of a function in the

variation of x.
• Example of some probability distribution
P(x) = 𝜆𝑒 &# P(x) =
23
• Ex 1. Flowing of liquid in the pipe. The velocity of liquid is

V(r) = 10(1- 0.25r2 ), Radius of pipe is 2cm. Calculate debit and average velocity using
population distribution.
ü Analysis
• We image that the cross section of pipe is form by
very large number of areas.
• The total number is Nt and each is having area of dA.
• The debit of an area is: dQ=v(r).(dA)
• Velocity in element depends on the distance in the centre
of pipe. The larger distance, the smaller velocity would be.
24
The population distribution of areas related to velocity is

function of r.
"#
Recall: 𝑝 𝑟 = = 𝑓(𝑟)
"$
• Suppose: P(r) = βr
% &(%
• Recall: ∫% &'# 𝑃(𝑥)𝜕𝑥 = 1
$)+ β+! ,
∫$)* 𝑃(𝑟)𝜕𝑟 = 1, =>
,
=1; => β =
+!
Thus, 𝑝 𝑟 = "!!$
25
• Consider now the element of population distribution of dr

(between r to r + dr):
The number of population between r and r + dr: 𝑑𝑁 = 𝑁- . 𝑝 𝑟 . 𝑑𝑟
Then, the debit through those element would be:
𝑑𝑄 = 𝑣. 𝑑𝐴. 𝑑𝑁
𝑣. 𝑑𝐴 = 𝑑𝑒𝑏𝑖𝑡 𝑜𝑓 𝑒𝑎𝑐ℎ 𝑎𝑟𝑒𝑎
𝑑𝑁 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑟𝑒𝑎
𝑑𝑄 = 𝑣. 𝑑𝐴. 𝑁- . 𝑝 𝑟 . 𝑑𝑟
𝑇𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎: 𝑁- . 𝑑𝐴 = 𝜋𝑅,
26
𝑑𝑄 = 𝜋𝑅, . 𝑣(𝑟). 𝑝 𝑟 . 𝑑𝑟
𝑑𝑄 = 𝜋𝑅, . 10 1 − 0.25𝑟 , . +,!$𝑑𝑟
. +
F 𝑑𝑄 = F 20𝜋. 𝑟 − 0.25𝑟 / 𝑑𝑟
* *
𝑅, 0.25 0
𝑄 = 20𝜋 − 𝑅
2 4
27
• Ex2. Solid sphere with radius of R contains water with non-uniform

concentration. Determine the total mass of water and average
concentration of water in sphere.
C(mg/ml) = C0 + 3.r + 4r2.
Initial concentration C0 = 120 mg/ml
Radius of sphere = 5cm.
• Solution:
• m = c.v
• dm = c.dv
• Concentration in element depends on the distance to the centre of
sphere. The population of area related to concentration is a function
of r.
• Then, we can write population distribution: p(r)=dN/dr
28
• Suppose: 𝑝 𝑟 = 𝛽𝑟 ,
$)+ β+# /
• ∫$)* 𝑃(𝑟)𝜕𝑟 = 1, =>
/
=1; => β =
+#
/
• 𝑝 𝑟 = # 𝑟,
+
• The number population between r and r + dr:
𝑑𝑁 = 𝑁- . 𝑝 𝑟 . 𝑑𝑟
Then,
𝑑𝑚 = 𝑐 𝑟 . 𝑑𝑣. 𝑑𝑁
𝑑𝑚 = 𝑐 𝑟 . 𝑑𝑣. 𝑁- . 𝑝 𝑟 . 𝑑𝑟
0
• But 𝑁- . 𝑑𝑣 = 𝜋𝑅/
/
• Thus,
4 /
𝑑𝑚 = 𝜋𝑅 𝑐 𝑟 . 𝑝 𝑟 . 𝑑𝑟
3
29
4 ! %
3 %
𝑑𝑚 = 𝜋𝑅 𝐶" + 3𝑟 + 4𝑟 . ! 𝑟 𝑑𝑟
3 𝑅
𝑑𝑚 = 4𝜋 𝐶" + 3𝑟 + 4𝑟 % . 𝑟 %𝑑𝑟
, $
∫" 𝑑𝑚 = 4𝜋 ∫" ( 𝐶"𝑟 % + 3𝑟 ! + 4𝑟 &)𝑑𝑟
$# $$ $%
m = 4π( C0 +3 + 4. )
! & 4
30
3. CONCEPT OF AVERAGE
• If a population have distribution of P(x) each population have

different value of Y in which Y = F(x);
• Average of Y is
`,-.
• < Y> = ∫`,ab 𝑃 𝑥 . 𝑦 𝑥 𝑑𝑥
• Ex1: Calculate the debit and average velocity in Ex1 (Chapter2)

by using Concept of average.
31
• Solution: we have V(r) = 10(1- 0.25r2 ) and R= 2 cm

• Population distribution: 𝑝 𝑟 = ('' !
The debit can be calculated by:
𝑄 = 𝑉"# . 𝐴
𝑄 = 𝑉"# . 𝜋𝑅$
!%'
𝑉"# = , 𝑝 𝑟 . 𝑣 𝑟 . 𝑑𝑟
!%&
!%'
𝑉"# = , 𝑝 𝑟 . 𝑣 𝑟 . 𝑑𝑟
!%&
32
$)+
,
𝑉(1 = F +!
$. 10(1− 0.25r2 )𝑑𝑟
$)*
20 $)+
𝑉(1 = , F (r − 0.25𝑟 / )𝑑𝑟
𝑅 $)*
20 𝑅, 𝑅0 1 0.25𝑅,
𝑉(1 = , − 0.25 = 20( − )
𝑅 2 4 2 4
2 *.,4+!
𝑄 = 𝑉(1 . 𝜋𝑅, = 20( − ) 𝜋𝑅,
, 0
+! *.,4+$
Hence, 𝑄= 20𝜋( , − 0
)
33
• Ex 2. Calculate Ex 2 (Chapter 2) by using Concept of average.
34
HOMEWORK 2
• Homework 2: Solve the problem by using the concept of

population distribution and concept of average
1. Fowing of liquid in the pipe inside radius of R. The non-
uniform velocity of liquid is v = 10(1- 4r2 ). The radius of
pipe is R=0.5 cm. Calculate debit and average velocity.
2. A Solid sphere with radius of R= 2 cm contains water with
non-uniform concentration C = 0.3(1- 0.25r2 ). Determine the
total mass of water and average concentration of water inside
the sphere.
3. A Long cylinder with R= 2 cm and L=200 cm contains water
with non-uniform concentration C =0.3(1- 0.25r2 ). Determine
the total mass of water and average concentration of water
inside the cylinder.
35
CHAPTER 4. MOLE BALANCE
• Reactor:
an equipment in which reactions occur.
• Chemical Identity:
A chemical species is said to have reacted when it has lost its
chemical identity.
• Reaction Rate:
the rate at which a species looses its chemical identity per unit
volume.
36
CHAPTER 4. MOLE BALANCE
1. General mole balance concept
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑨 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑨
𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑜𝑓 𝑨 𝑏𝑦 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
- 𝑜𝑢𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒 =
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
𝑜𝑓 𝑨 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
"𝑚𝑜𝑙𝑒/𝑡𝑖𝑚𝑒" "𝑚𝑜𝑙𝑒/𝑡𝑖𝑚𝑒"
"𝑚𝑜𝑙𝑒/𝑡𝑖𝑚𝑒"
c]F
FAo + GA - FA = (e.q 1)
c9
&567
• GA (mole/time) = rA ( -'&7.1568&7 ).V (volume) (e.q 2)
37
4. GENERAL MOLE BALANCE CONCEPT
• E.q 2 into e.q 1

8 c]F
F0A + ∫ 𝑟' 𝑑𝑉- FA = c9
• Batch reactor
Assumption: the reaction is perfectly mixed.

c]F K! LK!
c9
= 𝑟' 𝑉 or 𝑡 = ∫K M N
!" !
38
- Constant volume batch reactor

h c]F c5F
8 c9
= rA , c9
= rA
- Constant pressure batch reactor,

NA = CAV ,
h c]F h c(5F 8) c5F 5F c8
8 c9
=8 c9
= c9
+ 8 c9 = rA
c5 5 cib8
rA = c9F + Fc9
39
• Continuous-flow Reactors
+ CSTR (Continuous Stirred Tank Reactor)
1. Assumption: the reaction is perfectly mixed.
H
∫G 𝑟I 𝑑𝑉 = 𝑟I 𝑉
2. The conditions in the exit stream (e.g. concentration, temperature) are identical
to those in the tank.
𝑑𝑁I
𝐹IG − 𝐹I + 𝑟I 𝑉 =
𝑑𝑡
• At steady state:
𝑑𝑁I
=0
𝑑𝑡
• We get:
𝐹IG − 𝐹I + 𝑟I 𝑉 = 0
Or
𝐹IG − 𝐹I
𝑉=
−𝑟I
40
+ Tubular reactor or plug flow reactor (PFR):

• At steady state:
'& FA0 FA,exit
𝐹% |& + ∫ 𝑟% 𝑑𝑉 − 𝐹% |&('& = 0
V
𝐹% |& + 𝑟% 𝛥𝑉 − 𝐹% |&('& = 0
FA│ ∆V FA│V+∆V
kF |JKLJ ;kF |J
• Then,
l8
= 𝑟' V)
• limit ∆V→0:
𝑑𝐹%
= 𝑟%
𝑑𝑉
• Or
)!
𝑑𝐹%
𝑉=.
)!" 𝑟%
41
+ Pack Bed reactor (PBR)
FA (w)in – FA(w+∆w) + r’A (∆w) = 0
ckF
cm
= r’A
42
43
Ex. 1.1. First –order reaction:

A B
Is carried out in a tubular reactor in which the volume
metric flow rate v, is constant. Derive the equation relating the
reactor volume. Determine the reactor volume necessary to
reduce the existing concentration to 10% of the entering
concentration when the volume metric flow rate is 10dm3/min,
and the specific reaction rate K 0.23 min-1.
44
• Solution: Determine the reactor volume necessary

ckF
• Tubular reactor, c8
= rA ,
• Constant volumetric flow rate FA = CA vo
• First order reaction – rA = kCA
c5F
• Thus, 𝑣6 c8 = - kCA ; 𝐶' = 10%𝐶'"
2M 5FN
V= n
ln 5
F
V=100 dm3
45
• Ex 1.2. The reaction A B

is to be carry out isothermally in a continuous-flow reactor.
Calculate both the CSTR and PFR reactor volume necessary to
consume 99% of A (CA = 0.01CA0) when the entering molar flow
rate is 5 mol/h, assuming the reaction rate is –rA :
a, -rA = k with k = 0.05 mol/h/dm3
Answer Key:P1-6B
b, -rA = kCA with k = 0.0001s -1 Essential of Chemical
Engineering
c, -rA = kCA 2 with k = 3 dm /mol/h;
3
The entering volumetric flow rate is 10 dm3/h. For a constant

volumetric flow rate v = vo then FA = CAvo . Also, CA0 = FA0/v0
= (5mol/h)/(10dm3/h) = 0.5 mol/dm3.
46
• Ex 1.3.
47
2. Conversion and reactor sizing

• Conversion:
a measure of a reaction's progress toward completion.
• Consider the general equation
aA + bB à cC + dD
• The basis of calculation is always the limiting reactant. We will

choose A as our basis of calculation and divide through by the
stoichiometric coefficient to put everything on the basis of "per
mole of A".
48
• The conversion X of species A in a reaction is equal to the

number of moles of A reacted per mole of A fed.
Batch Flow
49
What is the maximum value of conversion?

• For irreversible reactions, the maximum value of conversion, X,
is that for complete conversion, i.e. X=1.0.
• For reversible reactions, the maximum value of conversion, X,
is the equilibrium conversion, i.e. X=Xe.
50
• Reactor Sizing:
By sizing a chemical reactor, we mean we're either deterring the
reactor volume to achieve a given conversion or determine the
conversion that can be achieved in given reactor type and size.
kFM
• For;0F
vs. X, the volume of a CSTR and the volume of a PFR
can be represented as the shaded areas in the Levenspiel Plots
shown below:
51
• Numerical Evaluation of Integrals

Simpson’s One-Third Rule:
52
Ex 2.1. Consider the liquid phase reaction
which is to take place in a PFR. The following

data was obtained in a batch reactor.
X 0 0.4 0.8
-ra(mol/dm3.s) 0.01 0.008 0.002
If the molar feed of A to the PFR is 2 mol/s,

what PFR volume is necessary to achieve 80%
conversion under identical conditions as those
under which the batch data was obtained?
53
FA0 (XXX(out
dX
dX t )outdX- X in )
VN=AA=00NFAA00ò=
tF ò= 0- -
) rrAAV
dt (- r-A-)rout
XX(in
dV rAAV
Solution:
Apply Simson’s rule:
,6i
• 𝐹'" = 2 o
`O ;`P
• ∆𝑋 = b
, 𝑛 = 0,1,2 … , 𝑘
".*;"
• ∆𝑋 = %
= 0.4
V=???
• Ex 2.2.
Repeat Ex 2.1. if the reaction takes place in a CSTR.
54
• Consider a PFR between two CSTRs:
FAi = FA 0 (1 - X i )
F X
V1 = A0 1
(- rA )1
X 2 dX
V2 = FA0 òX
1 -r
A
F -F F (1 - X 2 ) - FA 0 (1 - X 3 )
V3 = A 2 A3 = A 0
- rA3 - rA3
F (X - X 2 )
= A0 3
- rA3
55
56
• Ex 2.3. The isothermal gas-phase decomposition reaction

A → B+C
occurs at temperature of 422.2 K and total pressure of 10 atm (1013 kPa) in a
CSTR. The initial charge is an equimolar mixture of A and inert. The
volumetric feed, v0 = 6,0 L/s and gas constant, R=0.082057 L.atm.K-1.mol-1.
Calculate the volume necessary to achieve 80% conversion.The experimental
data:
• Ex 2.4. Repeat Ex 2.3 if the reaction is carried out in an isothermal PFR.
57
Some definition
1. Relative rate of reaction
Reaction: 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
−𝑟9 −𝑟: 𝑟; 𝑟<
= = =
𝑎 𝑏 𝑐 𝑑
2. Space Time = holding time = mean residence time, τ
Definition:
𝑉 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝜏= =
𝑣* 𝑡ℎ𝑒 𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑒𝑒𝑑
= - "= = - "=
• For PFR: 𝑉 = 𝐹9* ∫* = 𝐶9* 𝑣* ∫*
>$* >$*
= -
𝑉 𝑑𝑋
𝜏= = 𝐶9* F
𝑣* * −𝑟9
58
If v = v0 (for example, in a liquid phase reaction):
𝐹9* − 𝐹9 𝐶9* 𝑣* − 𝐶9 𝑣 𝐶9* − 𝐶9

𝑋= = =
𝐹9* 𝐶9* 𝑣* 𝐶9*
−𝑑𝐶9
𝑑𝑋 =
𝐶9*
;*
𝑑𝐶9
𝜏=F
;*+ 𝑟9
• Space time is the time necessary to process one volume of reactor fluid at
the entrance conditions. This is the time it takes the amount of fluid that
takes up the entire volume of the reactor to either completely enter or
completely exit the reactor.
59
Sample Industrial Space Times

Pressure Space
Reaction Reactor Temperature
atm Time
(1) C2H6 → C2H4 + H2 PFR 860°C 2 1s
CH3CH2OH +
HCH3COOH →
(2) CSTR 100°C 1 2h
CH3CH2COOCH3 +
H2O
1s<τ
(3) Catalytic cracking PBR 490°C 20
< 400 s
C6H5CH2CH3 →
(4) PBR 600°C 1 0.2 s
C6H5CH = CH2 + H2
(5) CO + H2O → CO2 + H2 PBR 300°C 26 4.5 s
C H + HNO3 →
(6) 6 6 CSTR 50°C 1 20 min
C6H5NO2 + H2O
3. Space Velocity, SV
# )
• Definition: 𝑆𝑉 = ) =
( *
60
3. Rate laws and stoichiometry

• If we combine:
−𝑟' = 𝑘𝑓 𝐶' , 𝐶p , … and 𝐶' = 𝑔 𝑋
Then, we get −𝑟' = 𝑓 𝑋
3.1. Stoichiometry
+ Stoichiometric Table for A Batch System
• Reaction: 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
• For A is the limiting reactant:
𝑏 𝑐 𝑑
𝐴+ 𝐵→ 𝐶+ 𝐷
𝑎 𝑎 𝑎
61
62
In general:
𝑁q = 𝑁'" 𝛩q + 𝜈q 𝑋
nj = stoichiometric coefficients j → negative for reactant and
positive for product. Thus: nA = -1; nB= -b/a; nC= c/a; nD= d/a;
and nI= 0.
]
Concentration of i for a batch system: 𝐶a = 8P
]F ]FM h;`
e.g.: 𝐶' = =
8 8
63
• Constant-Volume Reaction System (= constant density

reaction system):
1. Liquid phase reaction
2. Gas phase reaction in a constant volume batch reactor
3. Isothermal-isobaric gas phase reaction where the number of
moles of product equals the number of moles of reactant, and
compressibility factors of reactants are the same as those of
products.
For a constant volume reaction system, V=V0, thus:

𝐶q = 𝐶'" 𝛩q + 𝜈q 𝑋
64
Ex 3.1. Liquid phase reaction:
3NaOH(aq) + (C17H35COO)3C3H5 → 3C17H35COONa +C3H5(OH)3
Letting X represent the conversion of NaOH, set up a

stoichiometric table for a batch system.
Ex.3.2. Write the rate law for the elementary liquid phase
reaction.
solely in terms of conversion. The feed to the batch reactor is

equal molar A and B with CA0 = 2 mol/L and kA= 0,01 (L/mol)4/s.
65
+Stoichiometric Table for A Flow System
66
𝐹+& 𝐶+& 𝑣& 𝐶+& 𝑦+&

𝛩+ = = = =
𝐹,& 𝐶,& 𝑣& 𝐶,& 𝑦,&
And in general:
𝐹- = 𝐹,& 𝛩- + 𝜈- 𝑋
.*
• Concentration of i for a flow system: 𝐶+ =
#
.+ .+) )/0
• e.g.: 𝐶, = =
# #
For liquids, volume change with reaction is negligible when no phase
changes are taking place. Consequently,
• 𝑣 = 𝑣& =constant
• And 𝐶- = 𝐶,& 𝛩- + 𝜈- 𝑋
67
• However, for gas phase reactions, the volumetric flow rate most
often changes during the course of the reaction due to several
reasons, such as:
- A change in the total number of moles
- A change in temperature
- A change in pressure (such as due to pressure drop in a PFR or
PBR)
68
q Volume Change with Reaction

Variation of V in a batch system or v in a flow system during reaction.
Gas phase batch system:

𝑃𝑉 = 𝑍𝑁? 𝑅𝑇
where:
T = temperature, K
P = total pressure, atm
Z = compressibility factor
R = universal gas constant = 0,08206 L.atm/gmol.K
V = volume of a batch system, L
NT = total mol of gas in the system, gmol
69
• At t=0: 𝑃D 𝑉D = 𝑍D 𝑁ED 𝑅𝑇D

•
F1 E G H2
• Thus: 𝑉 = 𝑉D F E1 G1 H21
From stoichiometric table:
𝑁3 = 𝑁3& + 𝛿𝑁,& 𝑋
4, 4+)
• or =1+𝛿 𝑋 = 1 + 𝛿𝑦,& 𝑋
4,) 4,)
• where:
yA0 = mole fraction of A at t =0
• If all the species in the generalized reaction are in the gas phase, then:
5 6 7
• 𝛿 = + − −1
" " "
70
• Let:
𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑛 𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑓𝑜𝑟 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛
𝜀=
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑓𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝜀 = 𝛿𝑦,&
• Combine with the previous equation, we have:
𝑃& 𝑇 𝑍
𝑉 = 𝑉& 1 + 𝜀𝑋
𝑃 𝑇& 𝑍&
• For Z0 @ Z,
𝑃& 𝑇
𝑉 = 𝑉& 1 + 𝜀𝑋
𝑃 𝑇&
71
• Concentration of gas j for a variable volume batch reaction as a

function of X:
𝑁q 𝑁'" 𝛩q + 𝜈q 𝑋
𝐶q = =
𝑉 𝑉 1 + 𝜀𝑋 𝑃" 𝑇
" 𝑃 𝑇"
𝛩q + 𝜈q 𝑋 𝑃 𝑇"
= 𝐶'"
1 + 𝜀𝑋 𝑃" 𝑇
72
• Gas phase flow system:

𝑃𝑣 = 𝑍𝐹r 𝑅𝑇
• For a negligible change in Z,

kQ sM r
• 𝑣= 𝑣" k s rM
QM
• From stoichiometric table:

• 𝐹r = 𝐹r" + 𝛿𝐹'"𝑋
• or:
kQ k
• kQM
= 1 + 𝛿 kFM 𝑋 = 1 + 𝛿𝑦'"𝑋 = 1 + 𝜀𝑋
QM
73
• Then:
sM r sM r
• 𝑣 = 𝑣" 1 + 𝛿𝑦'"𝑋 s rM
= 𝑣" 1 + 𝜀𝑋 s rM
• Concentration of j in a flow system as a function of X:
𝐹q 𝐹'" 𝛩q + 𝜈q 𝑋
𝐶q = =
𝑣 𝑣 1 + 𝜀𝑋 𝑃" 𝑇
" 𝑃 𝑇"
= 𝐶'"
1 + 𝜀𝑋 𝑃" 𝑇
74
• Then:
sM r sM r
• 𝑣 = 𝑣" 1 + 𝛿𝑦'"𝑋 s rM
= 𝑣" 1 + 𝜀𝑋 s rM
• Concentration of j in a flow system as a function of X:
𝐹q 𝐹'" 𝛩q + 𝜈q 𝑋
𝐶q = =
𝑣 𝑣 1 + 𝜀𝑋 𝑃" 𝑇
" 𝑃 𝑇"
= 𝐶'"
1 + 𝜀𝑋 𝑃" 𝑇
75
• Relation between CA and XA (aA + bB rR)

• Case 1, constant density batch and flow system:
• .
76
• εA is expansion factor, fractional volume change on complete

conversion of A.
• Case 2: Batch and flow system of gases of changing density but

with T and ᴨ (total pressure) constant, V = V0(1+ εA XA)
77
• Case 3. Batch and flow system for gas in general ( varying ρ, T,

π)
78
79
80
• Batch reactor
81
82
83
• Space time and space velocity
84
85
• Steady state Mixed flow Reactor.
FA0XA = (-rA)V
86
87
88
• Ex: Pure gaseous reactant A (CAo = 100 millimole/lliter) is fed

at a steady rate into a mixed flow reactor (V = 0.1 liter) where it
dimerizes (2A à R). For different gas feed rates the following
data are obtained.
• Find a rate equation for this reaction.
89
• εA = (1-2)/2 = -0.5
90
• EX. Calculate the flow rate of each

stream
A +2B =R
• Before reaction: After reaction

CA0 = 1.4 mol/lliter CA = 1.4 - 0.6/2 = 1.1 mol/liter
CB0 = 0.8 mol/lliter CB = 0.8 - 0.6 = 0.2 mol/liter or
75% conversion
CR0 = 0 CR = 0.3 mollliter.
91
92
• Plug flow reactor
93
94
• Ex:
95
96
97
98
• Solution 1: Mix flow reactor

• A+ BàR
• Fao Xa = (-rA) V; -rA = 200 CACB ; CB = CB0 - CB0 XB;
• CA = CA0 - CA0Xa; CB0Xa = CA0Xa ; CB0 = 2CA0
• V = Fao Xa /(200CA0 .(1- Xa)(2- XA)); CA0 = FA0/q
99
• Solution 2: A à B + C; changing density

• FA0dXA= (-rA)dv; -rA = 10 CA ;
• dv = FA0dXA /(10 CA) ; CA = CA0 (1-XA)/(1+εAXA)
• dv = FA0 (1+εAXA)dXA/CA0 (1-XA); FA0 = CA0 q;
• dv = q (1+εAXA)dXA/(1-XA) ; εA= ¾;
100
• Solution 3: 3A à R, density changing

• Fao dX = (-rA)dv; -rA = 54
• dv = Fao dX/54; Xf = Caf /CA0.
101
• 4. We plan to replace our present mixed flow reactor with one

having double the volume. For the same aqueous feed (10 mol
Alliter) and the same feed rate find the new conversion. The
reaction kinetics are represented by
present conversion is 70%.
102
5. A mixed flow reactor (2 m3) processes an gas feed (100

liter/min) containing reactant A (CA0 = 100 mmole/liter) with inert
35% of feed. The reaction is reversible and represented by
+B, 𝐶-
• What is the equilibrium conversion and the actual conversion in

the reactor?
103
• 6. A specific enzyme acts as catalyst in the fermentation of

reactant A. At a given enzyme concentration in the aqueous feed
stream (25 liter/min) find the volume of plug flow reactor
needed for 95% conversion of reactant A (CA0 = 2 mol/liter).
The kinetics of the fermentation at this enzyme concentration is
given by
104
• 7. A gaseous feed of pure A (2 mol/liter, 100 mol/min)

decomposes to give a variety of products in a plug flow reactor.
The kinetics of the conversion is represented by
• Find the expected conversion in a 22-liter reactor.
105
• 8. A gaseous feed of pure A (1 mollliter) enters a mixed flow

reactor (2 liters) and reacts as follows:
• Find what feed rate (liter/min) will give an outlet concentration

CA = 0.5 mol/liter.
9. Gaseous reactant A decomposes as follows:
• Find the conversion of A in a 75% A-25% inert feed (q, = 180

liter/min, CAo = 300 mmol/liter) to a 1 m3 mixed flow reactor.
106
4. MONTE CARLO SIMULATION
• Monte Carlo simulation is a computational algorithm that rely

on repeated random sampling to get a numerical result.
• History: It was developed Since 1930s. The modern version was
developed in 1940s in los alamos project which is related to the
atomic bomb development. Later, the Monte Carlo is an
important method for development of hydrogen bomb.
• In this lesion, you will learn two type of Monte Carlo
simulation:
- Integral method
- Neuman Method
107
• The ideas is to create a lot of random sample in order to get a

stable result with calculation.
X ]u,vw0 6x y6ab9 ab zu-c0-b9

= 969-i bu,vw0 ab ozu-0w
Y
108
• Chemical domain:
. ,-.
∫. ,ab 𝑃(𝑥)𝜕𝑥 = 1;
.
Thus, ∫. ,ab 𝑃(𝑥)𝜕𝑥 = γ; [ 0 < γ < 1]
֍ The ideas is to generate random value of γ and calculate P(x);
109
• This chapter, we will learn two method of monte carlo

- Integral method
- Neuman method
110
• Ex1. Solve Ex1 in Chapter 1.

• Integral method
Φ (generated) r V
Rand() (excel) Cal. From P(x) Cal.
Using r
rand(1,n) (Mathlab) Cal.
V(av)
• Cal. q using V(av) .
111
• Ex.2. Determine the amount of water, and average

concentration of water in a non-uniform sphere. Water
distribution
C = C0 + 3.r + 4r2.
Initial concentration C0 = 120 mg/ml,
Radius of sphere = 5dm.
Φ (generated) R V
Rand() (excel) Cal. From P(x) Cal.
Using r
rand(1,n) (Mathlab) Cal.
C(av)
112
• Ex. 3. A grain of substance A has a cone shape ϕ = 300. The bag

of substance A was accidentally cut open. The grain of
substance A absorb the moisture in the air into the grain. The
moisture distribution in the grain is C (mg/ml) = C0 + 0.026r +
0.015r3 . Calculate the amount of pure substance A remained in
the bag since we know that substance A react with the water.
• Mass of grain : 80g or 1.22 mole, 20 grains/bag
• r = 5cm, h = 12cm, Co = 0.025mg/ml
• A + H 2O à B
113
• Neuman method
1. Find the maximum value of P(xmax)
2. Generate random first value of ϕ1
3. Find X position by using X = Xmin + ϕ1( Xmax –Xmin)
4. Calculate β by using β = P(x)/P(xmax)
5. Generate random second value of ϕ2
6. Compare ϕ2 and β
- if ϕ2 ≤ β the sample is accepted
- if ϕ2 > β the sample is rejected and back to step 2
1. Calculate average F(x) which P(x) distributed for.
114

distribution
C = C0 + 3.r + 4r2.
115
• Ex. 2. Calculate the surface of powder of a chemical product in

(Cm2/g). The grain of powder was assumed as in cubic shape
with X is the edge of cubic. Assume the size distribution is P(x)
= 2 βx exp(- βx2). β = 300cm-2, ρ = 2.1g/cm3.
116

distribution
C = C0 + 3.r + 4r2.
117
6. CATALYSTS AND CATALYZED REACTION
vClassification of Catalysts
• Alkylation and Dealkylation Reaction
It is the addition of an alkyl group to an organic compound. This
type of reaction is commonly carried out in the present of Friedel-
crafts catalysts, ALCl3 along with a trace of HCl.
118
• Isomerization reaction
It’s important to be able to convert from linear chain hydrocarbon
to branch chain hydrocarbon. The catalysts of this reaction is acid
promoted Al2O3. it’s commonly used in refinery application.
119
• Hydrogenation and Dehydrogenation Reaction

The bonding strength between hydrogen and metal surface
increases in vacant d-orbitals. Maximum catalytic activity will
not be realized if the bonding is too strong and the product are not
readily released. Consequently, the this maximum in catalytic
activity occurs when there is approximately one vacant d-orbitals
per atom. The most active metal for this reaction is Co, Ni, Rh,
Ru, Os, Pd, Ir, and Pt.
120
121
122
• Oxygenation
• Transition group are used extensively in oxidation reaction, Ag,
Cu, Pt, Fe, Ni, and their oxide generally good oxidation
catalysts such as V2O5, and MnO2.
123
• Hydration and Dehydration Reaction:

• A common catalysts for this reaction is Al2O3. which is used in
the dehydration of alcohol to form olefins.
• Halogenation and Dehalogenation Reaction
124
• Surface reaction of catalysts
125
• Chemisorption
126
• Adsorption rate
• Desorption rate
• Overall
127
128

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CHEMICAL DEPARTMENT

Industrial Chemical Process

Prepared by: NGET Sovannmony

Chemical processing industries manufacture and process

2. Specialty chemicals – examples: adhesives, agrichemicals,

• In chemical process, quantitative analysis is an important tool

• Volume element: dV = dx.dy.dz

• Generally, 𝑄 = 𝑣×𝐴, this formula can be applied

• Maximum velocity: 𝑣,-.:01" = 10𝑐𝑚/𝑠

Ex 2. Solid sphere with radius of R contains water with non-

• The general calculation

• Assignment 1. A grain of substance A has a cone shape ϕ = 300.

• Example: GPA of students in Chemical Engineering Department

These are very common representation of population distribution. However, you

𝑁%.:4;!." ≈ 504 − 400 ≈ 104

• If N = F(x) is the cumulative fraction or density function.

ΔNx1,x2 = Nx2 - Nx1

• However, the last diagram cannot give visual information on the

In general, the representation of population distribution is mathematically in form of:

• The interpolation of function:

• It is very common that the number of population is expressed by fraction.

• 𝐝𝐍 = 𝑵𝒕 . 𝒑 𝒙 . 𝒅𝒙 [ dN = number total x fraction function]

• P(x) is the probability of distribution of a function in the

P(x) = 𝜆𝑒 &# P(x) =

• Ex 1. Flowing of liquid in the pipe. The velocity of liquid is

The population distribution of areas related to velocity is

• Consider now the element of population distribution of dr

𝑇𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎: 𝑁- . 𝑑𝐴 = 𝜋𝑅,

𝑑𝑄 = 𝜋𝑅, . 10 1 − 0.25𝑟 , . +,!$𝑑𝑟

• Ex2. Solid sphere with radius of R contains water with non-uniform

• If a population have distribution of P(x) each population have

• Ex1: Calculate the debit and average velocity in Ex1 (Chapter2)

• Solution: we have V(r) = 10(1- 0.25r2 ) and R= 2 cm

• Ex 2. Calculate Ex 2 (Chapter 2) by using Concept of average.

• Homework 2: Solve the problem by using the concept of

1. General mole balance concept

• E.q 2 into e.q 1

Assumption: the reaction is perfectly mixed.

- Constant volume batch reactor

- Constant pressure batch reactor,

+ Tubular reactor or plug flow reactor (PFR):

+ Pack Bed reactor (PBR)

FA (w)in – FA(w+∆w) + r’A (∆w) = 0

Ex. 1.1. First –order reaction:

• Solution: Determine the reactor volume necessary

• Ex 1.2. The reaction A B

The entering volumetric flow rate is 10 dm3/h. For a constant

2. Conversion and reactor sizing

• The basis of calculation is always the limiting reactant. We will

• The conversion X of species A in a reaction is equal to the

What is the maximum value of conversion?

• Numerical Evaluation of Integrals

Ex 2.1. Consider the liquid phase reaction

which is to take place in a PFR. The following

If the molar feed of A to the PFR is 2 mol/s,

4. GENERAL MOLE BALANCE CONCEPT

• Consider a PFR between two CSTRs:

• Ex 2.3. The isothermal gas-phase decomposition reaction

• Ex 2.4. Repeat Ex 2.3 if the reaction is carried out in an isothermal PFR.

𝐹9* − 𝐹9 𝐶9* 𝑣* − 𝐶9 𝑣 𝐶9* − 𝐶9

Sample Industrial Space Times

3. Rate laws and stoichiometry

• Constant-Volume Reaction System (= constant density