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Design of Chemical Reactors

Ways of processing a chemical transformation undergone into a fluid:


• in a single batch reactor;
• in a single semi-continuous reactor;
• constant/pre-programmed feed;
• constant/pre-programmed withdrawal;
• in a single flow reactor:
• perfectly mixed;
• plug flow;
• in a chain of reactors possibly with interstage feed injection or
heating;
• in a reactor with recycle of the product stream using various feed
ratios and conditions
• in a network of reactors;
• ….
June 5, 2008 FILS – Chemical Reactors 1
Design of Chemical Reactors
Design of Chemical Reactors
Factors to be considered
• reaction type;
• planned scale of production;
• cost of equipment and operations;
• safety;
• stability and flexibility of operation;
• equipment life expectancy;
• length of time that the product is expected to be manufactured;
• ease of convertibility of the equipment to modified operating
conditions or to new and different processes.

June 5, 2008 FILS – Chemical Reactors 2


Design of Chemical Reactors
Design of Chemical Reactors
Selecting a reasonably good design is based upon:
• experience;
• engineering judgment;
• sound knowledge of the characteristics of the various reactor
systems
• thorough economic analysis of the over-all process, which will
dictate the final solution – the reaction system could not be optimal
but the over-all process should be.
The reaction system influences the process economics by:
• dictating the size of units needed (may well vary a hundredfold
among competing designs);
• fixing the products distribution (this is of prime consideration where it
can be varied and controlled).
June 5, 2008 FILS – Chemical Reactors 3
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

Single reaction chemical processes


The chemical process can be abstracted by a single stoichiometric
equation; its progress can be described and followed adequately by
using one and only one rate expression coupled with the necessary
equilibrium expressions.
For such reactions product distribution is fixed; hence, the important
factor in comparing designs is the reactor size.
The size comparison of various single and multiple ideal reactor
systems will give the possibility of choosing the best variant.

June 5, 2008 FILS – Chemical Reactors 4


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

Single volume reactors

June 5, 2008 FILS – Chemical Reactors 5


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
BR vs. CSTR or PFR
BR (batch reactor)
• advantages
• small instrumentation cost
• flexibility of operation
• disadvantages
• high labor and handling costs
• considerable shutdown time to empty, clean out, and refill
• poorer quality control of the product.
The BR is well suited to produce small amounts of material or many
different products from one piece of equipment.
For the chemical treatment of materials in large amounts the
continuous process is nearly always found to be more economical.
June 5, 2008 FILS – Chemical Reactors 6
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
BR vs. CSTR

A   q Q, rA  k C An , V  ct
k

A performance comparison may be made in terms of the size of


vessel required in each case to achieve the same rate of production
for the same conversion at the same temperature and initial/inlet
composition.
q C A0 X Af VBR q C A0 X Af VBR
PQ , BR   PQ ,CSTR  FV q C A0 X Af  q rA  X Af  VCSTR
t  taux X Af
dX A 1 42 43
taux  C A0 
0
rA  X A 
CQ

X Af
dX A taux high CSTR
VBR
taux  C A0  rA  X A 
 0

VCSTR X Af
C A0 
rA  X Af  XAf high BR

June 5, 2008 FILS – Chemical Reactors 7


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
BR vs. PFR

A   q Q, rA  k C An , V  ct
k

The performances of a BR and of a PFR are similar in many respects,


since an element of fluid, of arbitrary size, acts as a closed system
(i.e., a batch) in moving through a PFR. The residence time in a PFR,
the same for all elements of fluid, corresponds to the reaction time in
a BR, which is also the same for all elements of fluid. Depending on
conditions, these quantities, and other performance characteristics,
may be the same or different.
X
Af
For an isothermal first-order reaction taking
dX A place in a constant-volume BR but at varying
taux  C A0 
VBR rA  X A  density in a PFR, the time of reaction is equal
 0

VPFR D to the residence (space) time; this is not the


case for other orders of reaction.

June 5, 2008 FILS – Chemical Reactors 8


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
PFR vs. CSTR

A   q Q, rA  k C An , V  ct
k

The comparison is made in terms of the size of vessel required in


each case to achieve the same rate of production for the same
conversion at the same temperature and inlet composition.
q VPFR X Af
PQ , PFR  FV q C A0 X Af  PQ ,CSTR  FV q C A0 X Af  q rA  X Af ,   VCSTR
1 42 43 X Af
dX A 1 42 43
CQ

0
rA  X A ,  
CQ

X Af
VCSTR rA  X Af ,    1   X Af 
 X Af
VPFR dX A

0
rA  X A ,  

June 5, 2008 FILS – Chemical Reactors 9


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

PFR vs. CSTR

June 5, 2008 FILS – Chemical Reactors 10


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
PFR vs. CSTR
1. For any particular duty and for all positive reaction orders the mixed
reactor is always larger than the plug flow reactor. The ratio of volumes
increases with order. For zero-order reactions reactor size is independent
of the type of flow.
2. When conversion is small, the reactor performance is only slightly
affected by flow type, the volume ratio approaching unity as conversion
approaches zero. The ratio increases very rapidly at high conversion;
consequently a proper representation of the flow becomes very important
in this range of conversion.
3. Density variation during reaction affects design; however, it is normally
of secondary importance compared to the difference in flow type.
Expansion (or density decrease) during reaction increases the volume
ratio, in other words, further decreases the effectiveness of the mixed
reactor with respect to the plug flow reactor; density increases during
reaction has the opposite effect.
June 5, 2008 FILS – Chemical Reactors 11
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
PFR vs. CSTR
– second order reactions with variable composition
A + B → prod

It is usually more economical in


1
cost of reactants and
Any rate curve
equipment (reactor size) to use
rA ( X A , M BA ) unequal molar quantities of the
Area=τ CSTR/CA0
two active feed components.
This factor also influences the
Area=τ D/CA0 cost of separating products
from unused reactants. It is
important then to include the
XAi XA XAf molar feed ratio as a variable in
the search for optimum overall
operations.

June 5, 2008 FILS – Chemical Reactors 12


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
The recycle reactor (RR)
In certain situations it is found to be advantageous to divide the
product stream from a plug flow reactor and return a portion of it to
the entrance of the reactor.

(F’A0 )
Plug flow
FA1
XA1
FA0 XA2 (β+1)Fvf Fvf
K Fv 1
Fv0 V
L
XAf
XA0 = 0

Fv r = βFvf

volume of fluid returned to the reactor entrance



volume leaving the system

June 5, 2008 FILS – Chemical Reactors 13


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Characteristic equation
X A 2  X Af
V dX A
FA0
 
X A1
rA  X A 

The flow entering the reactor includes both fresh feed and the
recycle stream. The recycled flow is measured at the split
point L
 A which would enter in an   A entering in 
FA0        FA0  FA0     1 FA0
 unconverted recycle stream   fresh feed 
1  C A1 / C A 0 FA1 FA 0  FAr  1    X A f 
X A1  C A1    CA0 
1   C A1 / C A0 FV 1 FV 0   FVf  1     X A f 

 

  
X A1   X A f
   1 

June 5, 2008 FILS – Chemical Reactors 14


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Characteristic equation
X Af
V dX A
    1 
FA 0   
rA  X A 
 X Af
  1 

For the special case where density changes are negligible


C Af
C A 0V dC A
 RR       1 
FA 0 C A 0   C Af rA  C A 
 1

 0  

X Af
V dX A V X Af
FA 0
 
0
rA
PFR 
FA 0 rAf  X Af 
CSTR

June 5, 2008 FILS – Chemical Reactors 15


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

June 5, 2008 FILS – Chemical Reactors 16


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

June 5, 2008 FILS – Chemical Reactors 17


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

June 5, 2008 FILS – Chemical Reactors 18


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case

Multiple volume reactors

June 5, 2008 FILS – Chemical Reactors 19


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
PFRs in Series and/or in Parallel
Consider N plug flow reactors connected in series, and let
XA1, XA2, . . . , XAN be the conversion of component A leaving
reactor 1, 2, . . . , N.
X
Vi Ai
dX A
 
FA0 X Ai1 rA  X A 

For the series of N reactors


N X X X X AN
V Vi A1
dX A A2
dX A AN
dX A dX A
     L    
FA0 i 1 FA0 X A 0 rA  X A  X A1 rA  X A  X AN 1 A 
r X A 0
rA  X A 

For parallel or any parallel-series combination – the system could be seen as a


single plug flow reactor of volume equal to the total volume if the feed is
distributed in such manner that fluid streams which meet have the same
composition. Thus for reactors in parallel  must be the same for each parallel
line. Any other way of feeding is usually less efficient.
June 5, 2008 FILS – Chemical Reactors 20
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Equal-size CSTRs in Series

Consider a system of N mixed C A,in

reactors connected in series. N >30

Though the concentration is


Plug flow
uniform in each reactor, there
is nevertheless a change in
Five mixed reactors, N = 5
concentration as fluid moves
from reactor to reactor.
This stepwise drop suggests Single mixed reactors, N = 1

that the larger the number of


units in series the closer C A,out

should the behavior of the Volume through

system approach plug flow.

June 5, 2008 FILS – Chemical Reactors 21


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Equal-size CSTRs in Series

C A0, XA0 = 0 C A1, XA1 C A2, XA2 CAi-1, XAi-1 C Ai, X Ai C AN-1 , XAN-1

FA0

1 2 i CAN , XAN
N

V0 , τ R0 V0, τR0 V0, τR0 V0 , τ R0

Density changes will be assumed to be negligible


(ε = 0). Also, the temperature of reaction will be
assumed the same for all reactors.
As a rule, with mixed reactors it is more convenient
to develop the necessary equations in terms of
concentrations rather than conversions.
June 5, 2008 FILS – Chemical Reactors 22
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Equal-size CSTRs in Series
First order processes
C A0V0 V0 C A0  X Ai  X Ai 1  C A0  X Ai  X Ai 1 
 R0    
FA0 FV ri  X Ai  k C Ai

Rewrite the equation, in terms of concentrations ratio:


C Ai 1
 1  k  R 0
C Ai
The CSTRs are equal, so they have the same residence time.
C A0 1 C C C
 A0 A1 L AN 1   1  k  R 0 
N

C AN 1  X AN C A1 C A 2 C AN

N   C  1N  N  1 C A0
 R  N R 0    A0   1 D  ln
k   C AN   k CA

June 5, 2008 FILS – Chemical Reactors 23


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
30
(CA0n V / FA0)N reactors First order reaction
(CA0n V / FA0) plug N=1

k= 50

10 20

10
=

N=2
τRN

5
τRN =

N=3
=

N=4 2
τD
τRN

N=6 k= 1
N = 10
1 N=

0.01 0.1 1.0


1 - XA = CA / C A0

June 5, 2008 FILS – Chemical Reactors 24


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Equal-size CSTRs in Series
Second order processes A→prod; A+B→prod, MBA=1
C A0V0 V0 C A0  X Ai  X Ai 1  C A0  X Ai  X Ai 1 
 R0    
FA0 FV ri  X Ai  k C Ai2

Rewrite the equation for the first reactor in series:


C A1 
1
4k R 0
2  2 1  4C A0 k R 0 
Apply the same procedure, knowing that CSTRs are equal:

C AN 
1 
2  2
M  N 
4k R 0  1L  2 1  2 1  4C A0 k R 0 
 

C A0
Plug flow solution:  1  C A0 k D
CA
June 5, 2008 FILS – Chemical Reactors 25
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
100

(CA02 V / FA0) D
(CA02 V / FA0)N
N =1
Second order reaction

kC A0τR = 1000
=

500
(τCA0)N
(τCA0)D

200

100
10
50
N=2
20

N=3 10

5
N=4
2
N=6
1
N = 10

1 N= (plug flow)

0.01 0.1 1.0


1 - XA = CA / CA0

June 5, 2008 FILS – Chemical Reactors 26


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Unequal-size CSTRs in Series

C A0, XA0 = 0 C A1, XA1 C A2, XA2 CAi-1, XAi-1 C Ai, X Ai C AN-1 , XAN-1

FA0

1 2 i CAN , XAN
N

V1 , τ R1 V2, τR2 Vi, τ Ri VN , τ RN

For arbitrary kinetics in CSTRs of different size two types of


questions may be asked:
• how to find the outlet conversion from a given reactor system
• how to find the best set-up to achieve a given conversion.

Different procedures are convenient for these two problems.

June 5, 2008 FILS – Chemical Reactors 27


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Unequal-size CSTRs in Series
Finding the Conversion in a Given System
1 r C 
  A Ai
 Ri C Ai  C Ai 1

Rate versus
concentration M
rA

curve
r A(C A1) 1
Slope =
cA1-cA0= τR1
P
rA(C A2) 1
Slope = =
cA2-cA1 τR2

N L
C A3 CA2 CA1 CA0
Reactant concentration
June 5, 2008 FILS – Chemical Reactors 28
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Unequal-size CSTRs in Series
Determining the Best System for a Given Performance

XA = 0 XA1 XA2 XA = 0 XA1 XA2


C A0 CA0
F A0 τR1 τ R2 τR1 τ R2
F A0
V1 V2 V1 V2

1 Arbitrary
r curve
K L K L

τR2 V2 Area measure of


= N M
cA0 F A0 first unit

N M Of second unit

0 XA1 XA2 0 XA1 XA2


τR1 V1
cA0 = FA0

June 5, 2008 FILS – Chemical Reactors 29


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Unequal-size CSTRs in Series
Determining the Best System for a Given Performance

Diagonal of
1 rectangle
rA
K L
Maximum
area
Slope of
curve at M

N M
Second
First reactor reactor
area area
0 XA1 XA2 XA
June 5, 2008 FILS – Chemical Reactors 30
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Reactors of Different Types in Series
F A0
C A0 X A1 X A2 X A3
V2
X A0 = 0 V1 V3
V1 X  X A0
 A1
FA0 rA  X A1 
1
rA Rate conversion
dependent curve
X A2
V2 dX A
FA0
  r XA
X A1 A 

V3
V3 X  X A2 V2 FA0
 A3 V1
FA0 rA  X A3  FA0
FA0
X2
June 5, 2008 FILS – Chemical Reactors 31
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Best Arrangement of a Set of Ideal Reactors
1) For a reaction whose rate-concentration curve rises monotonically (any
nth-order reaction, n > 0) the reactors should be connected in series.
They should be ordered so as to keep the concentration of reactant as
high as possible if the rate-concentration curve is concave (n > 1), as
low as possible if the curve is convex (n < 1). For the previous case, the
ordering of units should be PFR, small CSTR, large CSTR; the reverse
ordering should be used when n < 1.
2) For reactions where the rate-concentration curve passes through a
maximum or minimum the arrangement of units depends on the actual
shape of curve, the conversion level desired, and the units available. No
simple rules can be suggested.
3) Whatever may be the kinetics and the reactor system, an examination of
the 1/rA versus CA curve is a good way to find the best arrangement of
units.

June 5, 2008 FILS – Chemical Reactors 32


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Autocatalytic reactions, A+R → R+R
In an autocatalytic reaction the rate at the start is low because
little product is present; it increases to a maximum as product
is formed and then drops again to a low value as reactant is
consumed.
rA 1
Some R rA
in feed

Point of
No R maximum
in feed rate

Progress
of reaction
Progress
of reaction

CA XA

June 5, 2008 FILS – Chemical Reactors 33


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Autocatalytic reactions, A+R → R+R
PFR Versus CSTR, No Recycle
Plug
flow
Mixed flow
- r1A
Plug flow is better
Mixed flow is better Mixed and plug flow
equaly good

0 XAf 0 XAf 0 XAf

1. At low conversions the mixed reactor is superior to the plug


flow reactor.
2. At high enough conversions the plug flow reactor is superior.

June 5, 2008 FILS – Chemical Reactors 34


Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Autocatalytic reactions, A+R → R+R
Recycle Reactor
Recycle too Recycle just Recycle too
high right low
1
rA Average
rate
P K
K

Average Average
rate rate
P
K P

L L L
XA0 XAi XAf Q XA0 XAi XAf Q XA0 X Ai XAf Q

When material is to be processed to some fixed final conversion


XAf in a recycle reactor, reflection suggests that there must be
a particular recycle ratio β which is optimum in that it
minimizes the reactor volume or space-time.
June 5, 2008 FILS – Chemical Reactors 35
Design of Chemical Reactors
Design of Chemical Reactors
Single Reaction Case
Autocatalytic reactions, A+R → R+R
Recycle Reactor
 
d   RR / C A 0  d   1
X Af

d
0   d 

 X Af rA  X A 
dX A  0

X Ai  
  1 
b  
dF  f  X A,   db da
  dX A  f  b,    f  a,  
d  a    d d

d   RR / C A 0  X Af
dX A   1 dX Ai 1. For conversions smaller
d
0  rA  X A 
0
rA X { d
than the point of maximum
X Ai Ai rate the CSTR performs better
X Af
  1 2
than any RR.
X Af
dX A 2. For conversions higher than

1
 rA  X A 
the point of maximum rate the

X Ai
RR with the proper β is better
rA X Ai
X Af  X Ai to either PFR or CSTR
June 5, 2008 FILS – Chemical Reactors 36
Design of Chemical Reactors
Design of Chemical Reactors

Multiple reactions chemical processes

June 5, 2008 FILS – Chemical Reactors 37


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case

Multiple reactions chemical processes


When a multiple reactions chemical process should be done at
industrial scale, both the size requirement and the distribution of
reaction products are affected by the pattern of flow within the
reactors network (the distinction between single reaction and
multiple reactions is that the former requires only one rate
expression to describe its kinetic behavior whereas the latter require
more than one rate expression).
In general, all multiple reactions can be abstracted as combinations of
two primary types: parallel and series reactions, so these two primary
reaction types are the building blocks or components for more
involved reaction schemes, the series-parallel reactions.

June 5, 2008 FILS – Chemical Reactors 38


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case
Multiple reactions chemical processes:
• It is more convenient to deal with concentrations than conversions
or, better, with degree of advancements;
• In examining product distribution the procedure is to eliminate the
time variable by dividing one rate equation by another, getting
equations relating the rates of change of certain components with
respect to other components of the system → two distinct
analyses (a – reactor size, b – product distribution);
• The two requirements, small reactor size and maximization of
desired product, may run counter to each other (an economic
analysis will yield the best compromise). Generally, product
distribution controls;
• The volume change is ignored (ε = 0). This means that the terms
mean residence time, reactor holding time, space time, and
reciprocal space velocity are interchangeable.

June 5, 2008 FILS – Chemical Reactors 39


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case
Product Distribution and Reactor Size – Quantitative Treatment

1) the instantaneous fractional yield of R


moles R formed dCR
' 
moles A reacted  dC A

2) the over-all fractional yield of R


all R formed CRf  CR 0 CR f  CR 0
     in reactor
all A reacted C A0  C Af C A

PFR
C Af
CSTR
1
D  
C A C A 0
 dC A 
 R  evaluated at C Af

C Af
 d PFR  1
C A CA 0
CSTR   &  PFR  CSTR dC A
 dC A  at C Af

June 5, 2008 FILS – Chemical Reactors 40


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case

CRf  CR 0    C A0  C Af 
Plug flow Mixed
Staged reactors
flow

η’ CRf C Rf CRf

CAf CA0 (- ∆ CA) CAf CA2 C A1 CA0

June 5, 2008 FILS – Chemical Reactors 41


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case

The contacting pattern with the largest area produces most R

CSTR up to CA1 then


PFR is best CSTR is best
PFR is best
CR, PFR CR, CSTR

η' η' η'


CR, PFR PFR CSTR

CR,CSTR

CR, total

CAf CA0 CAf CA0 CAf CA1 CA0


a) b) c)

June 5, 2008 FILS – Chemical Reactors 42


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case
BR vs. PFR A  R 
k1
 S
k2

Replacing reaction time by the space time, the equations relating


concentration with time, valid for BR, apply equally well for PFR.
CA
C A0
k 
e 1
CR

k1
C A0 k2  k1
k  k 
e 1 e 2   CS  C A 0  C A  C R

The maximum concentration of intermediate and time at which it occurs

k2 /  k2  k1 
CR , max  k  ln  k2 / k1 
 1   opt 
C A0  k2  k2  k1

June 5, 2008 FILS – Chemical Reactors 43


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case
BR vs. PFR A  R 
k1
 S
k2

1 1
CA A R S CA
CA 0
0.8 CA0 Plug flow
0.1
CB k2 CS
0.6
CA0
for
k1
=0 0.1
C/CA0

C A0
k2
0.4 Locus of CR, max =1
k1

0.2 CR
1 C A0
10 10
0 0
0 1 2 3 4 5 0 1
k1τ XA = 1 - CA/CA0

June 5, 2008 FILS – Chemical Reactors 44


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case
CSTR A  R 
k1
 S
k2

Writing the mass balance for each species of interest, for the whole
CSTR, their dependencies upon residence time are found.
CA 1 CR k1 CSTR CS k1k2 CSTR
2
  
C A0 1  k1 CSTR C A0  1  k1 CSTR   1  k2 CSTR  C A0  1  k1 CSTR   1  k2 CSTR 

The maximum concentration of intermediate and time at which it occurs

CR ,max 1 1
 2  opt 
C A0   k2 / k1  1/ 2  1 k1k2
 

June 5, 2008 FILS – Chemical Reactors 45


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case
CSTR A  R 
k1
 S
k2

1 1
CA k2
CA for =0 A R S
CA0 k1 Mixed flow CA
0.8 CA0 C A0

0.6 0.1 0.1


C/CA0

0.4 Locus of CR, max CS


C A0
k2 =1
0.2 CR k1 0
1 C A0 1
10
0 0
0 1 2 3 4 5 0 1
k1τ XA = 1 - CA/CA0

June 5, 2008 FILS – Chemical Reactors 46


Design of Chemical Reactors
Design of Chemical Reactors
Multiple Reactions Case

Parallel reactions

Homework!

June 5, 2008 FILS – Chemical Reactors 47


Design of Chemical Reactors
Design of Chemical Reactors

Non-ideal flow & the performance


of the chemical reactors

June 5, 2008 FILS – Chemical Reactors 48


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow

Micro-mixing Use flow models developed


based on tracer experiments

Ideal zones network


Time scale
of mixing Axial dispersion

Macro-mixing Use directly the age distribution function


computed from tracer experiments
 
C A   CA , element  t  E  t  dt   CA , element    E    d
0 0

June 5, 2008 FILS – Chemical Reactors 49


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
Ideal zones network
Cholette – Cloutier Model

The chemical process


(1-β)∙FV, Overall Volume V
CA0 A  P
k

rA  k C An
FV, XAR β∙FV, FV,
m
Steps in design:
CA0 α∙V XAR XA
2. Apply CSTR characteristic
Active Zone equation to the active zone
3. Take the mass balance in
the mixing point, m
Dead Zone
4. Write the residence time
with respect to the reactor
performance
June 5, 2008 FILS – Chemical Reactors 50
Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
Apply CSTR characteristic equation to the active zone
VR X AR  X Ain X AR 1 X AR
R   C A0  C A0 
FVR rA  X AR  k C An 0  1  X AR 
n
k C An 01  1  X AR  n
 V 1 X AR

 FV k C An 01  1  X AR  n
Take the mass balance in the mixing point, m
 1    FV C A0   FV C A0  1  X AR   FV C A0  1  X A 
X
X AR  A

Write the residence time with respect to the reactor performance
V 1 XA
 
FV  k C An 01  XA 
n

 1  
 
June 5, 2008 FILS – Chemical Reactors 51
Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
Axial Dispersion Model

Closed vessel The chemical process


Plug flow, Plug flow,
Dg = 0 Dg = 0 A  P
k

rA  k C An

Steps in design:
2. Write the mass balance for
dispersion zone, taking into
Change in flow pattern at
boundaries account the chemical process
3. Write the boundary conditions
4. Solve analytically or numerically
the model

June 5, 2008 FILS – Chemical Reactors 52


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
Write the mass balance for dispersion zone, taking into account the chemical process
CA0 CA,l CA,l + ∆ l CAf
l=0 ∆l l=L

A entering by A leaving by
bulk flow bulk flow

A entering by A leaving by
dispersion dispersion

Accumulation of A
Cross - sectional (= 0 for steady state )
area = S
Disappearance of A

The material balance for reactant A reads:

 out-in  bulk flow   out-in  axial dispersion  dissapearance by reaction  accumulation=0

June 5, 2008 FILS – Chemical Reactors 53


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
The individual terms are as follows, in moles A/time:

 moles A   volumetric   moles A   flow   cross-sectional 


entering by bulk flow=   =     =C A,l uS
 volume   flow rate   volume   velocity   area 
leaving by bulk flow  C A,l l uS

dN A  dC A 
entering by axial dispersion     DL S 
dt  dl l
dN A  dC A 
leaving by axial dispersion     DL S 
dt  dl  l l
dissapearance by reaction  rA V  rA S l
Note the inclusion of two dispersion terms, because material enters and leaves
the differential section not only by bulk flow but by dispersion as well

June 5, 2008 FILS – Chemical Reactors 54


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
Entering individual terms and dividing by S∙∆l gives:

  dC A   dC A  

u
 C A,l l  C A ,l 
 DL
  dl 

 
 l l  dl  l 
 rA  0
l l
Taking the limits as ∆l→0 reads:

d 2C A dC A
DL 2
 u  kC A 0
n

dl dl
The dimensionless form is:

DL d 2 X A dX A  z l L
 k C A 0  1  X A   0 
n 1 n

dz 1 2 3    L u  V FV
2
uL dz
{ *
Dg 

June 5, 2008 FILS – Chemical Reactors 55


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
Analytical solution for first order processes and closed
vessels:  dX A
 z  0  0  X A  Dg
d 2 X A dX A  dz
Dg  2    * 1 X A   0 
dz dz  dX A
z 1 0
 dz
The solution is of the form: m1 & m2 given as solutions of
the characteristic equation
1  X A  A1 e m1 z  A2 e m2 z Dg m 2  m   *  0

m1,2 
1
2 Dg
 
1  1  4  * Dg 
1
2 Dg
 1 a 

  1 a  z  1 a  z 
X A  1   A1 e 2 Dg
 A2 e 2 Dg

 

June 5, 2008 FILS – Chemical Reactors 56


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)
A1 and A2 result from boundary conditions – first take the derivative
 A1  1  a   1 a  z  1 a  z 
d XA A2  1  a 
  e 2 Dg
 e 2 Dg

dz  2 Dg 2 Dg 

Then solve the system:


  A1  1  a  A2  1  a  
 1   A1  A2   Dg    0
  2 Dg 2 Dg 
 A1  1 a  A2  1 a 
 A1  1  a  2Dg
A2  1  a  2Dg
 e  e 0
 2 Dg 2 Dg
1

4 a e 2 Dg
1 X A z 1
 a a

 1 a    1 a  e
2 2 Dg 2 2 Dg
e
June 5, 2008 FILS – Chemical Reactors 57
Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)

June 5, 2008 FILS – Chemical Reactors 58


Design of Chemical Reactors
Design of Chemical Reactors
Non-ideal Flow: Micro-mixing (microfluid)

June 5, 2008 FILS – Chemical Reactors 59


Design of Chemical Reactors