REACTION ENGINEERING UTILIZES

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• CHEMICAL KINETICS AND THERMODYNAMICS
• TRANSPORT PHENOMENA
• MATHEMATICAL MODELING AND OPTIMIZATION

MAJOR UNCERTAINTIES

• REACTION NETWORK
• REACTION RATE
• FLOW FIELD (TRICKLE BED, BUBBLE COLUMN,
FLUIDIZED BED)
• INTERACTION BETWEEN TRANSPORT AND
KINETICS
Gas-Liquid Reaction
Gas-Solid Reaction

The main principle of reaction engineering modeling is to

follow Einstein¶s advice ³Keep things as simple as possible
but not too simple´.
This approach has led to many useful engineering
applications.

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For example, in the design of heat exchangers, we use the
relation
ƦT1 - ƦT2
q = UA
ln(ƦT1 ƦT2 )

r 


r
 r 

However, this assumes plug-flow in both compartments,

which is not the case.

Calculations of heat and mass transfer are often done

based on the film model which assumes a linear profile
next to the wall and uniform condition at •
. This
however is not what a rigorous analysis or experiments
reveal.

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 CONVENTIONAL PARADIGM FOR PROCESS
DEVELOPMENT

• Chemist finds reaction with reasonable yield in

desirable product
• Process is developed in a relatively sequential mode:
microreactor benchscale
pilot plant commercial plant
• Process design is based on experimental selectivity
vs. conversion data
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BASIC DATA

ANALYSIS OF MECHANISMS
CHOICE OF TECHNOLOGY
CONSTRUCTION OF A MODEL

LABORATORY PILOT PLANT MOCK-UPS

MODEL VALIDATION
EXTRAPOLATION

INDUSTRIAL PLANT
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CONCURRENT PROCESS DEVELOPMENT

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cccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccccc
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MULTIPLE OBJECTIVES IN PROCESS ENGINEERING
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ù Process and Product Safety

ù Environmentally Compatible Products

ù Minimization of Waste Generation

ù Minimization of Investment

ù Operability and Control

ù Minimization of Energy Consumption

DESIGNER NEEDS TO DETERMINE IMPACT OF

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(not only on reactor but on the whole
process, e.g., separation unit, heat
exchangers«. )

• Changes in feed

• Changes in temperature

• Changes in reactor configuration

• Deactivation

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 EXPERIMENTAL OPTIMIZATION OF REACTOR

• Throughput
• Feed composition
• Feed temperature
• Cooling temperature
• Pressure

EXPERIMENTAL ± COMPUTATIONAL

REACTOR: Diameter
Length
Cooling Profile

CATALYST: Sequence of different types

Operation under decay
Catalyst shape design

USE OF PILOT PLANT

Gain confidence in design procedure

Determine adjustable parameters
Explore regions of operation

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Contain essential features
Enable determination of parameters
Be able to check predictions

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ECONOMIC INCENTIVES
REQUIRED ACCURACY
AVAILABLE DESIGN INFORMATION

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 USE OF MODEL
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Scale-up, optimization
Check sensitivity of design
Improve performance of existing reactor
Control and start-up policies
Determine impact of unknowns
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• Temperature of feed, coolantc

• Pressurec
• Recyclec
• Residence timec
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Consider | 0 0

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 DESIGN PROBLEMS
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Totally constrained trajectory design
Only one reaction occurs, or several occur but only one is
fast.

Focal point design

Outlet composition close to equilibrium. Can over design.

Minimax design
Desired composition removed from equilibrium.
Ex - C 2 H 6 + O 2 C 2 H 4 O + H 2 O CO 2

Try to transform minimax to focal point design.

1 w
CH 4 + O 2 CH 3 OH

Ex: 2  minimax
CH 3 OH + 1.5O 2 CO 2 + 2H 2 O


Instead,
1
CH 4 + O 2 CO + 2H 2 Synthesis gas
2
Reduce temperature and carry out
CO + 2H 2 CH 3 OH

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 TWO TYPES OF TRAJECTORIES
Averageable trajectories  Here the effluent composition
of a CSTR can always be written as the flow averaged
composition from plug flow reactors using same feed.
Ex: All first-order reactions: plug flow optimal

Nonaverageable trajectories : CSTR may give

composition that is Non-attainable by any plug flow
reactor combination.
Ex: Alkylation
iC 4 H 10 + C 4H 8 iC 8H 18
C 4 H8 n ÚC 4 H 8

Here, neither plug-flow nor CSTR may be optimal.


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Me en te a c e ical reacti n • t e eq ati n

S

i Ai ~0
i ~1

A i cc e ical s ecies

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 csti c i etric c efficients
i

i ·c cc0r ct
i  c creactant

2 2 â 2 2 2

1 2 3 i
2
2 1  2 â2 3
0  2
1
3
2

M en t ere are R c e ical reacti ns, t en eac reacti n

satisfies t e relati n:
S
  ji i
0 ccccccccccc
ccccccc
i
1
c
 ji csti c i etric c efficient f s0ecies i in j-t eq ati ncccccccccccc

It is i 0
rtant t
kn

 an•
f t e reacti
ns are

in e0en ent an n
t si 0le linear c
inati
ns
f t e
in e0en ent
ne. An• 
el
f t e s•ste as t
acc
nt
f
r t e kinetics
f t e set
f t e ine0enent reacti
ns (
r
f
r a lar er ner
f reacti
ns).

C
nsier t e set
f reacti
ns

{ CO
2H 2  CH 3OH
Ú1 Ú2 Ú3
c c 1-
(2) CO 2
H 2  H 2 O
CO
Ú4 Ú2 (5) Ú1
(3) CO 2
3H 2  CH 3 OH
H 2 O
(4) (2) (3) (5)

S0ecies CO c 2 c CH3 OH c CO 2 c H2 O c
r  { { { {
{
1 -1 -2 1 0 0
2 1 -1 0 -1 1
3 0 -3 1 -1 1

Me can eterine t at in t is case, t e rank
f t e

sti
c i
etric c
efficients is jst 2.
T is eans t at e nee
nl• t
reacti
ns t
eterine
t e relati
ns a
n t e five s0ecies.
T e t ir reacti
n (
r relati
n) is jst a linear c
inati
n

f t e ine0enent
nes. T e c
ice
f t e ine0enent
reacti
n is aritrar•.

In t is case, e can easil• see t e rank. T is a• e 
re

ifficlt in s•stes it an• s0ecies an reacti
ns.
Can anser t is • ins0ecti
n
f t e at
ic atri
f t e
s0ecies.
c c 1å
 S0ecies CH 3 OH c H2O c CO c CO 2 c H2 c
at
s c c c c c
C 1 0 1 1 0
H 4 2 0 0 2
O 1 1 1 2 0

T e rank
f t is at
ic atri is t ree. In eneral, t e rank

is eqal t
t e ner
f istinct at
s in t e s0ecies.
T s, at
ic alances 0r
vie 3 linear relati
ns
(c
nservati
n) a
n t e s0ecies. T e ner
f
ine0enent reacti
ns (relati
ns) a
n t e five s0ecies is
t s 5 ² 3 = 2.

Me c
ncle t at
Ner
f ine0enent c eical reacti
ns =
Ner
f s0ecies ² rank
f at
ic atri

T e c
ice
f t e ine0enent reacti
ns is n
t niqe. One

can c
nstrct t ese • c

sin an• set
f n ine0enent
vect
rs (s0ecies)
f t e at
ic atri an se t e t

c
nstrct t e linear relati
ns efinin an
t er vect
r
(s0ecies).
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Use

aCH 3 OH â H 2 â cCO 2
CO
1
0
1
1

 $  $  $  $
a 4 $ â  2 $ â c 0 $
 0 $
1$ 0$ 2$ 1$
   

a + 0 + c = 1
4a + 2 + 0c c c

cc cc ccc
c

cccccc cc c

c c 1Ë