1 ) NUMBER OF REACTOR SYSTEMS

If sets of reactions take place at different T and P, or if they require

different catalysts, then we use different reactor systems for these
CHEMICAL PROCESS DESIGN reaction sets.

Acetone  Ketene + CH4

CHAPTER 3. SELECTING REACTOR Ketene  CO + 1/2C2H4
OPERATING CONDITIONS 700C, 1atm
Ketene + Acetic Acid  Acetic Anhydride
80 C, 1atm

2) Number of Recycle Streams

LEVEL 3 DECISIONS TABLE 3.1
Destination codes and component classifications

Destination code Component classifications

1 ) How many reactors are required ?
1. Vent Gaseous by-products and feed impurities
2. Recycle and purge Gaseous reactants plus inert gases and/or gaseous by-products
3. Recycle Reactants
2 ) How many recycle streams are required ? Reaction intermediates
Azeotropes with reactants (sometimes)
Reversible by-products (sometimes)
3 ) Should we use excess reactant / use inert to maximize selectivity ? 4.None
5.Excess - vent
Reactants-if complete conversion or unstable reaction intermediates
Gaseous reactant not recovered or recycles
6.Excess - vent Liquid reactant not recovered or recycled
7.Primary product Primary product
4 ) Should the reactor be operated adiabatically or with direct 8.Fuel
9.Waste
By-products to fuel
By-products to waste treatment should be minimized
heating or cooling ? A ) List all the components that are expected to leave the reactor. This list includes all
Is a diluent or heat carrier required ? the components in feed streams, and all reactants and products that appear in every
reaction.
What are the proper operating temperature and pressure ?
B ) Order the components by their normal boiling points.
C) Classify each component in the list according to Table 3.1 and assign a destination
code to each.
D) Group neighboring components with the same destination
E) Identify the recycle streams accordingly
 2 ) NUMBER OF RECYCLE STREAMS
EXAMPLE HDA Precess
Component NBP , C Destination 3. REACTOR CONCENTRATION
H2 -253 Recycle + Purge Gas (3-1) EXCESS REACTANTS
CH4 -161 Recycle + Purge Recycle
Benzene 80 Primary Product  shift product distribution
Toluene 111 Recycle liq. Recycle
Diphenyl 255 By-product  force another component to be close to complete

CH4 , H2 (Purge) conversion

(Gas Recycle)
Compressor
 shift equilibrium
Benezene
(PrimaryProduct) ( molar ratio of reactants entering reactor )
(Feed)H2 , CH4
Reactor Separator is a design variable
(Feed) Toluene
Diphenyl
(By-product)
Toluene (liq. recycle)

2 ) NUMBER OF RECYCLE STREAMS ( 1a ) Single Irreversible Reaction

force complete conversion
EXAMPLE
Acetone  Ketene + CH4 700C ex. C2H4 + Cl2  C2H4Cl2
Ketene  CO + 1/2C2H4 1atm excess
Ketene + Acetic Acid  Acetic Anhydride
ex. CO + Cl2  COCl2
80 C, 1atm
excess
Component NBP , C Destination
CO -312.6 Fuel By-product ( 1b ) Single reversible reaction
CH4 -258.6 “
C2H4 -154.8 “
shift equilibrium conversion
Ketene -42.1 Unstable ex. Benezene + 3H2  Cyclohexane
Acetone 133.2 Reactant excess
Acetic Acid 244.3 Reactant
Acetic Anhydride 281.9 Primary Product

Acetic Acid (feed) CO , CH 4 , C2H4

(By-product)

Acetone
(feed) R1 R2 Separation
Acetic Anhydride
(primary product)
Acetic Acid (recycle to R2)
Acetone (recycle to R1)
 ( 3 ) Multiple reactions in series producing byproducts
( 2 ) Multiple reactions in parallel producing byproducts
Shift product distribution
shift product distribution
ex. CH3

A  R (desired) and A  S (waste) O + H2  O + CH4

excess 5:1
rR k1 a1  a2 2O O O + H2
 CA 
rS k 2
( 4 ) Mixed parallel and series reactions  byproducts

 if a1 › a2  keep CA high : high pressure, eliminate inerts, Shift product distribution

avoid recycle of products, use plug flow reactor
ex. CH4 + Cl2  CH3Cl + HCl Primary
 if a1 < a2  keep CA low : low pressure, add inerts, excess 10:1
recycle of products, use CSTR CH3Cl + Cl2  CH2Cl2+ HCl
CH2Cl2+ Cl2  CHCl3 + HCl Secondary
CHCl3 + Cl2  CCl4 + HCl

( 3-2 ) FEED INERTS TO REACTOR ( REDUCE REACTION PRESSURE)

( 2 ) Multiple reactions in parallel producing byproducts
( 1b ) Single reversible reaction
shift product distribution
FEED PROD1 + PROD2
A + B  R (desired) and A + B  S (waste) Cp1Cp2
Cinert   Xfeed  keq =
CF
rR k1 a1  a2 b1 b2 FEED1 + FEED2 PRODUCT
 C A CB
rS k 2 CP
Cinert   Xfeed1 or Xfeed2  keq =
CF1CF2
 if a1 › a2 and b1 › b2  keep CA & CB high
( 2 ) Multiple reactions in parallel  byproducts
 if a1 < a2 and b1 › b2  keep CA low, CB high
FEED1 + FEED2  PRODUCT
 if a1 > a2 and b1 < b2  keep CA high, CB low FEED1 + FEED2 BYPRODUCT
 if a1 < a2 and b1 < b2  keep CA & CB low Cinert   Cbyproduct 
FEED1 + FEED2  PRODUCT
FEED1  BYPROD1 + BYPROD2
Cinert   Cbyprod1-2 
Single reversible reaction
Some of the decisions involve introducing a new component into
A  B + C
the flowsheet, e.g. adding a new component to shift the product
Initial: CA0 0 0 distribution, to shift the equilibrium conversion, or to act as a heat
React: CA0X CA0X CA0X carrier. This will require that we also remove the component from
At equilibrium: CA0(1-X) CA0X CA0X the process and this may cause a waste treatment problem.
n P Example Ethylene production
C 
V RT
C2H6 = C2H4 +H2 Steam is usually used as the
(C X )(C A0 X ) C A0 X 2
K eq  A0 
C A0 (1  X ) (1  X ) C2H6 + H2 = 2CH4 diluent.
Example: CA0=1, Keq = 4, then X = 0.828 Example Styrene Production
If we increase the pressure (2 times) by reducing the EB = styrene +H2
volume of reactor V (2 times) OR increasing the
number of moles nA0 (2 times), then CA0 = 2 EB  benzene +C2H4 Steam is also used.

CA0=2, Keq = 4, then X = 0.732 EB + H2  toluene + CH4

That is: P then X 

A  B + C ( 3-3 ) PRODUCT REMOVAL DURING REACTION

Initial: PA0 0 0 to shift equilibrium + product distribution
React: PA0X PA0X PA0X ( 1b ) single reversible reaction
At equilibrium: PA0(1-X) PA0X PA0X ex. 2SO2 + O2 = 2SO3
H 2O
n P H 2O
C  ; Pt  ( n) RT
V RT SO2
( P X )( PA0 X ) PA0 X 2 REACT ABSORB REACT ABSORB
K eq  A0 
PA0 (1  X ) (1  X ) O2 + N2
H2SO4
H2SO4
Example: Pt = PA0=1, Keq = 4, then X = 0.828
( 2 ) multiple reactions in series  byproduct
If we maintain the same initial pressure: Pt = 1, but
use inert with molar ratio nI FEED  PRODUCT
remove
1
n A0 PRODUCT = BYPRODUCT
remove
then PA0 = yA0*Pt = 0.5*1 = 0.5 .
PA0=0.5, Keq = 4, then X = 0.9
That is: P then X 
( 3-4 ) RECYCLE BYPRODUCT
to shift equilibrium + product distribution

CH3

O + H2  O + CH4

2 O = O O + H2

Heat transfer to and from stirred tanks

( 4-1 ) REACTOR TEMPERATURE

T   k   V
T  400C  Use of stainless steel is severely
 Single Reaction :
limited !
- endothermic
AHAP ! T  250C  High pressure steam ( 40~50 bar)
provides heat at 250-265 C
- exothermic
T  35C  Cooling water Temp 25-30C
* irreversible AHAP !
* reversible
continuously decreasing as conversion increases.
 Multiple Reaction
max. selectivity

Heat transfer arrangements for fixed-bed catalytic reactors

( 4-3 ) REACTOR PRESSURE ( usually 1-10 bar )
 VAPOR-PHASE REACTION
- irreversible as high as possible
P    V 
r
- reversible single reaction
* decrease in the number of moles
AHSP
* increase in the number of moles
continuously decreases as conversion increases
- multiple reactions
 LIQUID-PHASE REACTION
prevent vaporization of products
allow vaporization of liquid so that it can be condensed and refluxed as a
means of removing heat of reaction.
allow vaporization of one of the components in a reversible reaction.