Chemical Reactor Design Chemical Reactor Design: Y W L Youn-Woo Lee

Chemical Reactor Design
Y
Youn-Woo
W L Lee
School of Chemical and Biological Engineering
Seoul National Universityy
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea  ywlee@snu.ac.kr  http://sfpl.snu.ac.kr
Chapter 4
Isothermal Reactor Design
Chemical Reactor Design
化學反應裝置設計
Seoul National University

Objectives
j
• Describe
ib the
h algorithm
l i h thath allows
ll the
h reader
d to solve
l chemical
h i l
reaction engineering problems through logic rather than
memorization.
• Size batch reactors, semibatch reactors, CSTRs, PFRs, and PBRs
for isothermal operation given the rate law and feed conditions.
• Studying
Study g a liquid-phase
qu d p ase batch
batc reactor
eacto to dete
determinee the
t e specific
spec c
reaction rate constant needed for the design of a CSTR.
• Design of a tubular reactor for a gas-phase
gas phase pyrolysis reaction.
reaction
• Account for the effects of pressure drop on conversion in packed
b d tubular
bed b l reactors andd in
i packed
k d bed
b d spherical
h i l reactors.
Fig. 4-1
Isothermal
Reaction
Design
Algorithm
for Conversion

Algorithm for isothermal reactor design
1. Mole balance and design equation

2. Rate law
3
3. Stoichiometry
4. Combine
5
5. Evaluate
E al ate
We can solve the equations in the
combine step either
A. Graphically (Chapter 2)
B N
B. Numerical
i l (Appendix
(A di A4)
C. Analytical (Appendix A1)
D. Software packages (polymath)
French Menu Analogy

French Algorithm for isothermal reactors
Menu
Analogy

4.2.1 Batch Operation
p
For constant volume batch reactor,, the mole balance can be written
in terms of concentration
1  dN A  1 dN A 1 dN A d N A / V0  dC A
   rA     rA
V  dt  V dt V0 dt dt dt
Generally, when analyzing laboratory experiments, it is best to

process the data in terms of the measured variable. Because
concentration is the measured variable for most liquid
liquid-phase
phase
reactions, the general mole balance equation applied to reactions
in which there is no volume change becomes
dC A
   rA
dt
This is the form we will use in analyzing reaction rate data in Chap 5.
Reaction time in Batch Operation
Algorithm for isothermal reactor design A

 B
1. Mole balance dX
N A0   rAV0
& Design equation dt
2. Rate law  rA  kC A2 irreversible, 2nd order in A
3. Stoichiometry C A  C A0 (1  X )
dX
4 Combination
4. C bi ti  kC A0 (1  X ) 2
dt 2nd order
Isothermal
Liquid-phase
dX
  kC A0 dt Batch reaction
(1  X ) 2
5. Analytical Evaluation
t X 1  X 
 
1 dX
dt   t  
0 kC A0 0 (1  X ) 2 kC A0 1 X 
Reaction time in Batch Operation
Typical cycle times for a batch polymerization process

tt = tf + te + tR + tc
Activity Time (h)
1. Charge feed to the reactor and agitate, tf 1.5-3.0
2. Heat to reaction temperature, te 0.2-2.0
3. Carry out reaction, tR V i
Varies
4. Empty and clean reactor, tc 0.5-1.0
Total cycle time excluding reaction 30 60

3.0-6.0
Batch polymerization reaction times may vary between 5 and 60 hours. hours
Decreasing the reaction time with a 60-h reaction is a critical problem. As the
reaction time is reduced (e.g. 2.5 h for a 2nd-order reaction with X=0.9 and
kCA0=1010-3 s-1),
) it becomes important to use se large lines and pumps
p mps to achieve
achie e
rapid transfer and to utilize efficient sequencing to minimize the cycle time.
Batch Reaction Times
A
 B
Mole balance dX  rA
 V
dt N A0
First - order Second order
Rate law
 rA  kC A  rA  kC A2
NA
Stoichiometry (V=V0) CA   C A0 (1  X )
V0
dX dX
Combine  k (1  X )  kC A0 (1  X ) 2
dt dt
1 1 X
Integration t  ln t
k 1 X kC A0 (1  X )

1st - order (X  0.9, k  10 -4 s 1 ) 2nd order (X  0.9, kC A0  10 3 s 1 )

1 1 X
tR  ln tR 
k 1 X kC A0 (1  X )
1 1 0 .9
 ln 
k 1  0 .9 kC A0 (1  0.9)
2. 3 9
 
k kC A0
2 .3
  4 1 
9
10 s 10 3 s 1
 23,000 sec  9,000 sec
 6.4hr  2.5hr
Table 4-3
The order of magnitude of time
to achieve
hi 90% conversion
i
For first- and second-order irreversible batch reactions
1st-order 2nd-order Reaction time

k (s-1) kCA0 (s-1) tR
10-4 10-3 Hours
10-22 10-11 Mi t
Minutes
1 10 Seconds
1,000 10,000 Milliseconds

Design a Reactor to Produce of ethylene glycol
Design a CSTR to produce 200 million pounds of ethylene glycol per year
by hydrolyzing ethylene oxide. However, before the design can be carried
out, it is necessary to perform and analyze a batch reactor experiment to
determine the specific reaction rate constant (kA). Since the reaction will be
carried out isothermally,
isothermally kA will need to be determined only at the reaction
temperature of the CSTR. At high temperature there is a significant by-
product formation, while at temperature below 40oC the reaction does not
proceed at a significant rate; consequently, a temperature of 55oC has been
chosen. Since the water is usually present in excess, its concentration may
be considered constant during the course of the reaction.
reaction The reaction is
first-order in ethylene oxide.
O CH2-OH
OH
H2SO4
CH2-CH2 + H2O CH2-OH
A + B C
Catalyst
Example 4-1 Determining k from Batch Data
In the lab experiment, 500mL of a 2 M solution (2 kmol/m3) of EO in

water was mixed with 500mL of water containing 0.9
0 9 wt % sulfuric acid
catalyst. At T=55oC, the CEG was recorded with time. Determine the
specific reaction rate at 55oC.
C
Time Concentration of EG EO + H2O → EG

(min) (kmol/m3) A + B → C
0.0 0.000
0.5 0.145
1.0 0.270
1.5 0.376
2.0 0.467
3.0 0.610
4.0 0.715
60
6.0 0 848
0.848
10.0 0.957
Problem Solving Algorithm
A. Problem statement. Determine the kA D. Assumptions and approximations:

B Sketch
B. Assumptions
C. Identify 1. Well mixed
C1. Relevant theories A, B, C batch 2. All reactants enter at the same time
Rate law:  rA  k AC A 3. No side reactions
4. Negligible filling and emptying time
dN A
Mole balance:  rAV 5. Isothermal operation
C2. Variables dt Approximations
pp
Dependent: concentrations, Ci 1. Water in excess (CH2O~constant)
Independent: time, t CB~ CBO
C3. Knowns and unknowns E. Specification. The problem is neither
Knowns: CEG = f(time) overspecified nor underspecified.
Unknowns:
1. CEO = f(time) F. Related material. This problem uses the
2. kA mole balances developed in Chap. 1
3. Reactor volume for a batch reactor and the
C4. Inputs and outputs: reactant fed stoichiometry and rate laws developed
allll at once a batch
b h reactor i Chap.
in Ch 3
3.
C5. Missing information: None G. Use an Algorithm.(figs 4-1 & 4-2)
1 dN A
1. MOLE BALANCE   rA Batch reactor that is well-mixed
V dt
Since water is present in such excess, the
concentration of water at any time t is virtually
2 RATE LAW
2.  rA  kC A the same as the initial concentration and the rate
law is independent of the concentration of H2O.
(CB~CB0)
3. STOICHIOMETRY
Species symbol Initial Change Remaining Concentration
CH2CH2O A NA0 - NA0X NA=NA0(1-X) CA=CA0(1-X)

H2O B ΘBNA0 - NA0X NB=N
NA0(ΘB-X)
X) CB=C
CA0(ΘB-X)
X)
CB~ CA0 ΘB = CB0
(CH2OH)2 C 0 NA0X NC =NA0X CC=CA0X
NT0 NT =NT0 - NA0X

1 dN A
  rA
V dt
dC A dC A
4 COMBINING
4.   rA ,  rA  kC A   kC A
dt dt
Mole balance Rate law
5. EVALUATE
For isothermal operation,

operation k is constant:
CA dC A t t C A0
 C A0 CA
  kdt  k  dt
0 0
ln
CA
 kt
C A  C A0 e  kt
The concentration of EG at any time t can be obtained from the reaction stoichiometry
A+B C
N C  N A0 X  N A0  N A
NC NC
CC    C A0  C A  C A0 (1  e  kt )
V V0
CC  C A0 (1  e  kt )
C A0  C C
l
ln   kt
k
C A0
Rearranging and taking the logarithm
of both side yields  rA  (0.311 min 1 )C A
C A0  C C
ln   kt The rate law can now be used in the design
C A0
of an industrial CSTR. Note that this rate
We see that a plot ln[(CA0-C CC)/CA0] as law was obtained from the lab-scale batch
a function of t will be a straight line with reactor (1000 mL).
a slope –k.
1
ln 10 2 .3
k   0.311 min 1 0.6
t 2  t1 8.95  1.55
Time C A0  CC
A0
CA
((CA0-CC)/C
(min) C A0
0.0 1.000 0.1
0.5 0.855 0.06

10
1.0 0 730
0.730
1.5 0.624
2.0 0.533
3.0 0.390
0.01
4.0 0.285 0 2 4 6 8 10 12
6.0 0.152 1.55 t ( min) 8.95
10.0 0.043 Seoul National University
4.3 Design of CSTR
Design Equation for a CSTR
FA0 X
Mole balance V
(rA ) exit
FA0  v0 C A 0 v0 C A0 X V C A0 X
V   the space time
 rA v0  rA
For a 1st-order irreversible reaction, the rate law is

Rate law  rA  kC A
1  X  C A0 X
C bi
Combine   
k 1 X  kC A
g g
Rearranging
k CSTR relationship
X  between space time and
1  k conversion for a 1st-order
liquid-phase rxn

4.3.1 A single CSTR
We could also combine Eq (3-29) and (4-8) to find the exit

concentration
t ti off A,
A CA:
 k  k
C A  C A0 (1  X )  C A0 1   X 
1  k
 1  k 
 1  k  k  C A0
 C A0  
 1  k  1  k
C A0
CA 
1  k
C A0
exit concentration of A CA 
1  k

4.3.2 CSTRs in Series
CA0 CA1, X1
v0
CA2, X2
-rA1, V1 -rA2, V2
For 1st-order irreversible reaction with no volume change (v=v0) is carried out in
two CSTRs placed in series. The effluent concentration of A from reactor 1 is
C A0
C A1 
1  1k1
From a mole balance on reactor 2,
FA1  FA2 v0 C A1  C A2 
V2  
 rA2 k 2 C A2
CSTRs in Series
Solving for CA2, the concentration exiting the second reactor, we get
C A1 C A0 C A0
C A2   C A1 
1   2 k 2 1   2 k 2 1  1k1 
1  1k1
If instead of two CSTRs in series we had n equal-sized CSTRs connected in

series (1 = 2 = … = n = i = (Vi/v0)) operating at the same temperature (k1 =
k) the
k2 = … = kn = k), th concentration
t ti leaving
l i th
the llastt reactor
t would
ld b
be
C A0 C A0
C An  
1  k n
1  Da n
The conversion and the rate of disappearance of A for these n tank reactors
in series would be
1 kC A0
X  1  rAn  kC An 
1  k  n
1  k n
Conversion as a function of reactors in series
for different Damköhler numbers for a first-order reaction
k=1
k=0.5
k=0.1
rA0V
Da 
FA0
Da  1,, 90% conversion is achieved in two or three reactors;;
thus the cost of adding subsequent reactors might not be justified
Da ~0.1, the conversion continues to increase significantly with each reactor added
Reaction Damköhler number
 rA0V Rate of Reaction at Entrance " a reaction rate"

Da   
FA0 Entering Flow Rate of A " a convection rate"
The Damköhler is a dimensionless number that can give us a quick

estimate of the degree of conversion that can be achieved in continuous-
flow reactor.
 rA0V kC A0V
For 1st-order irreversible reaction Da    k
FA0 v0 C A0
 rA0V kC A2 0V
For 2nd-order irreversible reaction Da    kC A0
FA0 v0 C A0
RULE OF THUMB
Da  0.1 will usually give less than 10% conversion.
Da  10.0 will usually give greater than 90% conversion.
4.3.4 A Second-Order Reaction in a CSTR
For a 2nd-order liquid-phase reaction We solve the above eq. for X:

being carried out in a CSTR, the
combination of the rate law and the
design equation yields 1  2kC A0   1  2kC A0 2  2kC A0 2
X 
2kC A0
V
FA0 X FA0 X
 (4-14) 1  2kC A0   1  4kC A0

 rA kC A2 2kC A0

1  2Da   1  4Da
For const density v=v0, FA0X=v0(CA0-CA) (4-16)
2Da
V C A0  C A
 
v0 kC A2 The minus sign must be chosen in the
quadratic equation
q q because X cannot
be greater than 1.
Using our definition of conversion, we
have

X
(4 15)
(4-15) X 
1  2Da   1  4Da
kC A0 (1  X )
2
2Da
A Second-Order Reaction in a CSTR
rA0V
Da 
FA0
0.88
0.67
At high conversion, a 10-fold
increase in Da will increase the
conversion only to 88% due to
lowest value of reactant
concentration in CSTR.
CSTR
6 60
Example 4-2: Producing 200,000,000 lb/yr in a CSTR
~91 ton/yr
CA0=1 vA0=vB0
produce 200 x 106 p
It is desired to p pounds pper yyear
of EG. The reactor is to operated isothermally.
A 1 lb mol/ft3 solution of ethylene oxide (EO) in
water is fed to the reactor together with an equal
volumetric solution of water containing 0.9 wt%
of the catalyst H2SO4. The specific reaction rate
0 311 min-1 as determined in Ex 4-1.
constant is 0.311 4-1
(a) If 80% conversion is to be achieved, determine

th necessary CSTR volume.
the l
(b) If two 800-gal reactors were arranged in parallel,

what is the corresponding conversion?
(c) If two 800-gal reactors were arranged in series,

what is the corresponding conversion?

M.W. of EG=62
M.W. of EO=58

v0 = vA0 + vB0
=1
3m 10’
~2 gps 5’
1.5m
5 gal~19.8L
1 ga
gal ~3.78
3 8L

Producing 200,000,000 lb/yr of EG in a CSTR
one CSTR two equal-sized CSTRs in parallel two equal-sized CSTRs in series
X=0.81
800gal
800gal 800gal
X=0.8
X=0.81 X1=0.68 X2=0.90
1480gal
800gal
Conversion in the series arrangement is greater than in parallel for CSTRs.

The two equal
equal-sized
sized CSTRs in series will give a higher conversion than
two CSTRs in parallel of the same size when the reaction order is greater than zero.
4.4 Tubular Reactors
-2nd-order liquid-phase rxn Rate law:  rA  kC A

2
(A Products)
X

-Turbulent, dX
- No dispersion V  FA0
- No radial gradients in T, u, or C
0 kC A2
St i hi
Stoichiometry
t for
f liq.
li phase
h rxn
PLUG-FLOW REACTOR T & P = constant
PFR mole balance C A  C A0 (1  X )

dX
FA0   rA Combination
dV
The differential form of PFR design F X 1 v0  X 
equation must be used when there is a V  A20
kC A0 0 (1  X ) 2
dX   
kC A0  1  X 
P or heat exchange between PFR &
th surrounds.
the d InI the
th absence
b off P
P or
heat exchange, the integral form of the kC A0 Da2
PFR design equation is used. X 
1  kC A0 1  Da2
X

dX
V  FA0 Da2 is the Damkohler number
0  rA for a second-order reaction
-2nd-order gas-phase rxn Rate law:  rA  kC A2

(A Products)
-Turbulent,
- No dispersion X

dX
- No radial gradients in T, u, or C V  FA0
0 kC A2
PLUG-FLOW REACTOR
PFR mole balance Stoichiometry for gas phase rxn

dX T & P = constant
FA0   rA
dV FA FA0 (1  X ) (1  X )
The differential form of PFR design CA    C A0
v v0 (1  X ) (1  X )
equation must be used when there is a
P or heat exchange between PFR &
th surrounds.
the d InI the
th absence
b off P
P or Combination
heat exchange, the integral form of the
X (1  X ) 2
PFR design equation is used.
V  FA0  dX
X 0 kC A0 (1  X )
2 2

dX
V  FA0
0  rA Seoul National University
X (1  X ) 2
V  FA0  0 kC 2 (1 
A0 X) 2
dX
CA0 is not function of X;; k=constant ((isothermal))
FA 0 X (1  X ) 2
V
kC A2 0  0 (1  X ) 2
dX FA0  C A0 v0
Integration yields (see Appendix A.1 Eq. (A-7) @ page1009)
v0  (1   ) 2
X
V 2(1  ) ln(1  X )   X 
2

kC A0  1  X 
Reactor length will be
v0  (1   ) 2
X V  Ac L
L 2(1  ) ln(
l (1  X )   X 
2

kC A0 Ac  1  X 
Cross sectional area Seoul National University
Conversion as a function of distance down the reactor
1.2
A  0.5B (=-0.5)
1
A  B (=0)
( 0)
onversion (X)
0.8 A  2B (=1)
A  3B (=2)
0.6
0.4
Co
v0
0.2  2.0dm 3
kC A0
0
0 2 4 6 8 10 12 14
L (m)

The reaction that has a decrease in the total number of moles
will have the highest conversion for a fixed reactor length.
length
v  (1  0.5 X )v0
the reactant spends more time
v  (1  2 X )v0
the reactant spends less time
The volumetric flow rate decreases with increasing conversion,

conversion
and the reactant spends more time in the reactor
than reactants that produce no net change in the total number of moles.
Change in Gas-Phase Volumetric Flow Rate Down the Reactor
v0  (1   ) 2 X 
v=vo(1+X) V 2 (1   ) ln(1  X )   X 
2

kC A0  1 X 
=1 : (A→2B)
v = vo((1+X))
 = 0 : (A→B)
( )
v = vo
 =0.5 : (2A→B)
Complete
conversion v = vo(1-0.5X)
When there is a decrease in the number of moles in the gase phase,

the volumetric flow rate decreases with increasing conversion,
conversion
and the reactant spends more time in the reactor
than reactants that produce no net change in the total number of moles.
Example 4-3: Determination of a PFR Volume
Determine the PFR volume necessary to produce 300 million

pounds
d off ethylene
h l a year from
f cracking
ki a feed
f d stream off pure
ethane. The reaction is irreversible and follows an elementary rate
law We want to achieve 80% conversion of ethane,
law. ethane operating the
reactor isothermally at 1100K at a pressure of 6 atm.
C2H6  C2H4 + H2
A  B+C
FB = 300x106 lb/year
lb/ = 0.340
0 340 lb-mol/sec
lb l/
FB = FAoX
FAo = FB/X = 0.340/0.8 = 0.425 lb-mol/sec
.2)
Ind. Eng. Chem. Process Des. Dev., 14, 218 (1975)

Ind. Eng. Chem., 59(5), 70 (1967)
C2H6  C2H4 + H2

4.5 Pressure Drop in Reactors
 In liquid
liquid-phase
phase reaction
- the concentration of reactants is insignificantly affected by even
relatively large change in the total pressure
- ignore the effect of pressure drop on the rate of reaction
when sizing liquid-phase chemical reactors
- that
th t is,
i pressure drop
d i ignored
is i d for
f liquid-phase
li id h ki ti calculations
kinetics l l ti
 In gas-phase
gas phase reaction
- the concentration of the reacting species is proportional to total pressure
- the effects of p
pressure dropp on the reaction system
y are a keyy factor
in the success or failure of the reactor operation
- that is, pressure drop may be very important for gas-phase reactions
(Micro-reactors packed with solid catalyst)

Pressure drop
p and the rate law
기상반응에서는 반응 성분
• for an ideal gas
gas, 의 농도가 반응압력에 비례
Fi FA0  i  vi X  하므로 압력강하에 대한
Ci   고려가 필수적이다.
v v0 (1  X )( P0 / P)(T / T0 )
• For isothermal operation
  i  vi X  P
Ci  C A0   i 
Fi 0
  y A0
 1  X  P0 FA0
 A  1,  B  b / a
- determine the ratio P/P0 as a function of V or W

- combine the concentration, rate law, and design equation
- the differential form of the mole balance (design equation) must be used
Pressure drop
p and the rate law
• For example,
example
- the second order isomerization reaction in a packed-bed reactor
2A  B + C
-the mole balance (differential form)
The differential form of
dX  gmoles 
FA0   rA   PFR design equation
dW  g catalyst  min  must be used when
there is a P
- rate law
 rA  kC A2
- stoichiometry for gas-phase reactions

 1 X  P T0
C A  C A0  
 1  X  P0 T
Pressure drop
p and the rate law
• Then, the rate law
2
  1 X  P T0 
 rA  k C A0    (4-20)
  1  X  0 
P T
- the larger the pressure drop from frictional losses, the smaller the reaction rate
• Combining
C bi i with
ith th
the mole
l bbalance
l ((assuming
i iisothermal
th l operation:
ti T T0)
T=T
2
 P 
2
dX  C (1  X ) 
FA 0  k  A0   
P 
dW  1  X   0 
• Dividing by FA0(=v0CA0)
2
 1  X   P 
2
dX kC A0
    
 1  X   P0 
dW v0 

Pressure drop
p and the rate law
2
 1  X   P 
2
dX kC A0
    
dW v0  1  X   P0 
-The right-hand side is a function of only conversion and pressure
dX (4-21)
 f ( X , P)
dW
-Another equation is needed to determine the conversion as a function of

catalyst
l weight:
i h that
h iis, we need
d to relate
l the
h pressure d
drop to the
h catalyst
l
weight dP
P  f (W ) We need
dW
Flow through
g ap
packed bed

dP
Flow through
g ap
packed bed We need
dW
• The majority of gas-phase reactions are catalyzed by passing the reactant

through a packed of catalyst particles
• Ergun equation: to calculate pressure drop in a packed porous bed
ddP G  1    150(1   ) 
  3   1.75G  (4-22)
dz g c D p     Dp 
laminar turbulent
G=u=superficial mass velocity [kg/m2s]; u=superficial velocity [m/s]; Dp=diameter of particle

in the bed [m]; =porosity=volume of void/total bed volume; 1- 1  =volume of solid/total bed
volume, gc=1.0 [m/s2]; =viscosity [kg/ms]
• The gas density () is the only parameter that varies with pressure on the right-
right
hand side. We are now going to calculate the pressure drop through the bed.
Flow through
g ap
packed bed


dP
Flow through
g ap
packed bed We need
dW
• Equation of continuity
m 0  m
 0 v0  v
- The reactor is operated at steady state, the mass flow rate at any point is equal to
the entering mass flow rate
• Gas-phase volumetric flow rate
P0 T  FT v0
v  v0 
T


  0
P  0  FT 0 v
• Then,
v0 P  T0  FT 0
  0  0  
v P0  T  FT

Pressure drop in a packed bed reactor
• then, Ergun equation
dP G (1   ) 150(1   )  P0 T  FT
   1.75G   
0 g c D p  3 T F
dz  Dp  P  0  T0
• Simplifying dP P0  T  FT
  0   (4-24)
dz P  T0  FT 0
G (1   ) 150(1   ) 
0    1.75G  ((4-25))
We need
dP dP dP dz

 0 g c D p  
3
Dp 
dW dW dz dW
Ac
• The catalyst weight, W  (1   ) Ac z   c z
Volume of Density of
solid solid catalyst
dW   c (1   ) Ac dz (4-26)
Pressure drop in a packed bed reactor
dz 1
dP 0 P0  T  FT 
dW  c (1   ) Ac
   dP dP dz

dW Ac (1   ) c P  T0  FT 0 dW dz dW dP P T  F
  0 0   T
dz P  T0  FT 0
dP  T P0  FT 
• Simplifying    (4-28)
F 
dW 2 T0 P / P0  T0 
2 0
 (4-29)
Ac  c (1   ) P0
 F  FT FA0
FT  FT 0  FA0X  FT 0 1  A0 X   1  X   y A0   
 FT 0  FT 0 FT 0
dP  T P0
 (1  X ) (4 30)
(4-30)
dW 2 T0 P / P0
Pressure drop
p in a p
packed bed reactor
dP  T P0
 (1  X ) (4-30)
(4 30)
dW 2 T0 P / P0
ε <0
0, the
th pressure d
drop (P) will
ill b than ε = 0
be lless th
ε > 0, the pressure drop (P) will be greater than ε = 0
• For isothermal operation
dP dX
 f ( X , P) and  f ( X , P) (4-31)
dW dW
• The two expressions are coupled ordinary differential equations.

We can solve them simultaneously using an ODE solver such as Polymath.
• For the isothermal operation and ε = 0, we can obtain an analytical solution.
• Polymath will combine the mole balance, rate law and stoichiometry
Pressure drop
p in a p
packed bed reactor
1 0
For the isothermal operation and ε = 0,
dP  T P0
 (1  X ) (4-30)
dW 2 T0 P / P0
Analytical Solution
If ε = 0 or ε X ≪ 1, we can obtain an analytical solution to Eq. (4-30) for isothermal

operation (i.e., T=T0). For isothermal operation with ε = 0, Eq. (4-30) becomes
Isothermal with dP  P0

ε=0 dW 2 ( P / P0 )
Rearranging gives us
 P  d ( P / P0 ) d ( P / P0 ) 2
2 
 dW    
 P0  dW
Taking P/P0 inside
(4-32) the derivative
Pressure Drop
p in a Packed Bed Reactor
d ( P / P0 ) 2
 
dW
Integrating with P=P0 @ W=0
( P / P0 ) 2  1  W
P
ε=0  1  W (4-33)
T = T0 P0

Pressure drop
p in a p
packed bed reactor
If ε = 0 or ε X ≪ 1, we can obtain an analytical solution to Eq. (4-30)

(4 30) for isothermal
operation (i.e., T=T0). For isothermal operation with ε = 0, Eq. (4-30) becomes
Pressure ratio P
 1  W (4-33)
only for ε = 0 P0
2 0

Ac (1   ) c P0 2 0 z
W 
W  (1   ) Ac z   c P0
G (1   ) 150(1   ) 
0    1.75G 
 0 g c D p  
3
Dp 
Pressure as a P 2 z
function of  1 0 (4-34)
P0 P0
reactor length, z
4.5.3 Pressure Drop in Pipes
Pressure drop for gases along the length of the pipe w/o packing
dP du 2 fG 2 u G/
P dP 2 dP 2 fG 2
 G  0 G  0
dL dL D   0
P P0 dL PdL D
P0
Integrating with P=P0 at L=0, and assuming that f = constant
0
P02  P 2 P  L P 
 G2 0 2 f  ln 0 
2 0  D P
Rearranging, we get
P0 4 fG 2
 1   pV p 
P  0 P0 Ac D
Example 4
4-4:
4: 1½”
1½ schedule 40 x1000
x1000-ft =0 018) P<10%
ft L (p=0.018),
However, for high volumetric flow rates through microreactors,
the P may be significant. Example 4-4 Seoul National University
4.5.4 Analytical Solution for Reaction with Pressure Drop
For gas phase reactions, as the pressure drop increases, the concentration decreases,
resulting in a decreased rate of reaction,
reaction hence a lower conversion when compared to
a reactor without a pressure drop.

Reaction with Pressure Drop
Conversion as a function of catalyst
y weight
g
2nd-order isothermal reaction
A B Combining
Mole balance:
dX
dX
dW

kC A2 0
FA 0

(1  X ) 2 1  W 1/ 2 2
F A0  r A
dW
Separating variable and Integrating
Rate law:
 rA  kC A2
 1  W dW
FA 0 dX
kC A2 0 (1  X ) 2
S
Stoichiometry: Gas-phase isothermal with =0
at X  0, W  0 and FA0  C A0 v0
P
C A  C A0 (1  X )
P0 v0  X   W 
   W 1  
P kC A0  1  X   2 
 1  W
P0
C A  C A0 (1  X )(1  W )1/ 2 (4-37)

Reaction with Pressure Drop
Conversion as a function of catalyst weight
Conversion for 2nd-order isothermal reaction in PFR with P
kC A0W  W 
1  
v0  2 
X  (4-38)
kC W  W 
1  A 0 1  
v0  2 
Catalyst weight for 2nd-order isothermal reaction in PFR with P
1  1  ( 2 v 0  ) / kC A 0 X /(1  X ) 1 / 2 (4-39)

W 


The Optimum Catalyst Particle Diameter
Pressure drop
dominant Internal diffusion
Conversion inside catalyst k ~ 1/Dp
dominant
X
Dp, optt
Particle Diameter, Dp
Why
y not p
pack the catalyst
y Problems with largeg diameter tubes:
into a large diameter (1) Bypassing or Channeling
to reduce P? (2) Little efficient of heat transfer rate
Example 4-6 Production of ethylene glycol
H 2, C 2H 4
402 million
lbC2H6 /yr
1 C2H6  C2H4 + H2 2
separator
V=81 ft3, X=0.8 C2H6
O2, C2H4, N2, C2H4O
 rA  kPA1/ 3 PB2 / 3 k  0.0141
lbmol
@ 260o C
Ag atm  lb  cat  h
C2H4+ ½ O2  C2H4O C2H4
3
6 5 260oC, 10bar
4 Air
separator
W=45,440 lb, X=0.6
H 2O C2H4O
7 8 H2O, 0.9wt% H2SO4
C2H4O(aq)
O( )
200 million
9
lb EG/yr
197 ft3, X
V=197
V X=0
0.8
8
absorber
CH2OH
C2H4O + H2O Cat.

CH2OH Seoul National University
Example 4-6 Calculating X in a Reactor with Pressure Drop
dX k  1 X 
  y
dW FA0  1  X 
dy  (1  X )

dW 2y





Negligible Pressure Drop in Pipes
Pressure drop along the length of the pipe
dP d 2 fG 2 P dP 2 dP 2 fG 2
 G  0 G  0
dL dL D P0 dL PdL D
Integrating with P=P0 at L=0, and assuming that f = constant
0
P02  P 2 P  L P 
 G2 0 2 f  ln 0 
2 0  D P
Rearranging, we get
P0 4 fG 2
 1   pV p 
P  0 P0 Ac D
Example 4-4: 1½” sch. 40 x1000-ft L (p=0.018), P<10%

4.6 Synthesizing
y g a Chemical Plant
 Always challenge the assumptions, constraints, and

boundaries of the problem
 The profit from a chemical plant will be the difference
between income from sales and the cost to produce the
chemical
Profit = value of products – cost of reactants

– operating costs – separation costs
 The operating cost: energy, labor, overhead, and

depreciation of equipment

Production of ethylene glycol
H 2, C 2H 4
402 million
lbC2H6 /yr
1 C2H6  C2H4 + H2 2
separator
V=81 ft3, X=0.8 C2H6
O2, C2H4, N2, C2H4O
Ag
C2H4+ ½ O2  C2H4O C2H4
3
6 5
4 Air
separator
W=45,440 lb, X=0.6
H 2O C2H4O
7 8 H2O, 0.9wt% H2SO4
C2H4O(aq)
O( )
200 million
9
lb EG/yr
197 ft3, X
V=197
V X=0
0.8
8
absorber
CH2OH
C2H4O + H2O Cat.

CH2OH Seoul National University
Production of ethylene glycol
lb mol
M.W. bp(oC) 1 2 3 4 5 6 7 8 9 $/lb
$/ b
s
C2H6 0.425 0.040
C2H4
H2
O2
N2
EO
EG 0.102 0.380
H2SO4 - 0.043
H2O
Total 0.425 0.102
Synthesizing
y g a Chemical Plant
 $0 38/lb (2x108 lb/yr)

Ethylene glycol = $0.38/lb
Ethane = $0.04/lb (4x106 lb/yr)
S lf i acid
Sulfuric id = $0.043/lb (2 26 108 lb/yr)
$0 043/lb (2.26x10 lb/ )
Operating cost = $8x106/yr
 Profit = $0.38/lb x 2x108 lb/yr - $0.04/lb x 4x108 lb/yr

-$0.043/lb x 2.26x106 lb/yr - $8x106/yr
=$
$52 million
 How the profit will be affected by conversion,

conversion separation,
separation recycle
stream, and operating costs?
Fig. 4-1
Isothermal
Reaction
Design
Algorithm
for Conversion

4.11 The Practical Side
A practical guidelines for the operation of chemical reactors have been

presented over the years, and tables and some of these descriptions are
summarized and presented on the CD-ROM and web. The articles are
s ed in Table
listed ab e 4-7.
For example, Mukesh gives relationships between the CSTR tank diameter,
p
T, impeller size diameter, D, tank height,g H, and the liquidq level, l. To scale
up a pilot plant (1) to a full scale plant (2), the following guidelines are given
D 2 T2  2 H 2
   R
D1 T1  1 H1
And the rotational speed, N2, is
N 2  N1R  n
Where values
Wh l off n for
f different
diff t pumping
i capacities
iti and
d Froude
F d numbers
b are
given in Mukesh’s article.
Closure
After completing this chapter, you should be

able to apply the algorithm building blocks
Evaluation
Combine
Stoichiometry
Rate Law
Mole Balance
To batch reactor,, CSTR,, PFR,, PBR.

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Chemical Reactor Design

Chemical Reactor Design

Seoul National University

Seoul National University

1. Mole balance and design equation

Seoul National University

Seoul National University

Generally, when analyzing laboratory experiments, it is best to

Algorithm for isothermal reactor design A

Typical cycle times for a batch polymerization process

Total cycle time excluding reaction 30 60

Seoul National University

1st - order (X  0.9, k  10 -4 s 1 ) 2nd order (X  0.9, kC A0  10 3 s 1 )

1st-order 2nd-order Reaction time

10-4 10-3 Hours

1,000 10,000 Milliseconds

Seoul National University

In the lab experiment, 500mL of a 2 M solution (2 kmol/m3) of EO in

Time Concentration of EG EO + H2O → EG

A. Problem statement. Determine the kA D. Assumptions and approximations:

Species symbol Initial Change Remaining Concentration

CH2CH2O A NA0 - NA0X NA=NA0(1-X) CA=CA0(1-X)

(CH2OH)2 C 0 NA0X NC =NA0X CC=CA0X

NT0 NT =NT0 - NA0X

For isothermal operation,

0.5 0.855 0.06

For a 1st-order irreversible reaction, the rate law is

Seoul National University

We could also combine Eq (3-29) and (4-8) to find the exit

Seoul National University

From a mole balance on reactor 2,

If instead of two CSTRs in series we had n equal-sized CSTRs connected in

 rA0V Rate of Reaction at Entrance " a reaction rate"

The Damköhler is a dimensionless number that can give us a quick

For a 2nd-order liquid-phase reaction We solve the above eq. for X:

(a) If 80% conversion is to be achieved, determine

(b) If two 800-gal reactors were arranged in parallel,

(c) If two 800-gal reactors were arranged in series,

Seoul National University

Seoul National University

Seoul National University

Conversion in the series arrangement is greater than in parallel for CSTRs.

-2nd-order liquid-phase rxn Rate law:  rA  kC A

PFR mole balance C A  C A0 (1  X )

-2nd-order gas-phase rxn Rate law:  rA  kC A2

PFR mole balance Stoichiometry for gas phase rxn

CA0 is not function of X;; k=constant ((isothermal))

Integration yields (see Appendix A.1 Eq. (A-7) @ page1009)

Reactor length will be

Seoul National University

The volumetric flow rate decreases with increasing conversion,

When there is a decrease in the number of moles in the gase phase,

Determine the PFR volume necessary to produce 300 million

Ind. Eng. Chem. Process Des. Dev., 14, 218 (1975)

Seoul National University

Seoul National University

• For isothermal operation

- determine the ratio P/P0 as a function of V or W