CHEMICAL PROCESS DESIGN

CHAPTER 3. SELECTING REACTOR

OPERATING CONDITIONS
LEVEL 3 DECISIONS

1 ) How many reactors are required ?

2 ) How many recycle streams are required ?

3 ) Should we use excess reactant / use inert to maximize selectivity ?

4 ) Should the reactor be operated adiabatically or with direct

heating or cooling ?
Is a diluent or heat carrier required ?
What are the proper operating temperature and pressure ?
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
reaction sets.

Acetone → Ketene + CH4

Ketene → CO + 1/2C2H4
700C, 1atm
Ketene + Acetic Acid → Acetic Anhydride
80 C, 1atm
 2) Number of Recycle Streams
TABLE 3.1
Destination codes and component classifications

Destination code Component classifications

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
Reaction intermediates
Azeotropes with reactants (sometimes)
Reversible by-products (sometimes)
[Link] Reactants-if complete conversion or unstable reaction intermediates
[Link] - vent Gaseous reactant not recovered or recycles
[Link] - vent Liquid reactant not recovered or recycled
[Link] product Primary product
[Link] By-products to fuel
[Link] By-products to waste treatment should be minimized

A ) List all the components that are expected to leave the reactor. This list includes all
the components in feed streams, and all reactants and products that appear in every
reaction.
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
H2 -253 Recycle + Purge Gas
CH4 -161 Recycle + Purge Recycle
Benzene 80 Primary Product
Toluene 111 Recycle liq. Recycle
Diphenyl 255 By-product

(Gas Recycle) CH4 , H2 (Purge)

Compressor

Benezene
(PrimaryProduct)
(Feed)H2 , CH4
Reactor Separator
(Feed) Toluene
Diphenyl
(By-product)
Toluene (liq. recycle)
2 ) NUMBER OF RECYCLE STREAMS
EXAMPLE
Acetone → Ketene + CH4 700C
Ketene → CO + 1/2C2H4 1atm
Ketene + Acetic Acid → Acetic Anhydride
80 C, 1atm
Component NBP , C Destination
CO -312.6 Fuel By-product
CH4 -258.6 “
C2H4 -154.8 “
Ketene -42.1 Unstable
Acetone 133.2 Reactant
Acetic Acid 244.3 Reactant
Acetic Anhydride 281.9 Primary Product

Acetic Acid (feed) CO , CH4 , C2H4

(By-product)

Acetone
(feed) R1 R2 Separation
Acetic Anhydride
(primary product)
Acetic Acid (recycle to R2)
Acetone (recycle to R1)
3. REACTOR CONCENTRATION
(3-1) EXCESS REACTANTS
 shift product distribution
 force another component to be close to complete
conversion
 shift equilibrium
( molar ratio of reactants entering reactor )
is a design variable
( 1a ) Single Irreversible Reaction
force complete conversion
ex. C2H4 + Cl2 → C2H4Cl2
excess
ex. CO + Cl2 → COCl2
excess
( 1b ) Single reversible reaction
shift equilibrium conversion
ex. Benezene + 3H2  Cyclohexane
excess
( 2 ) Multiple reactions in parallel producing byproducts
shift product distribution

A → R (desired) and A → S (waste)

rR k1 a1 −a2
= CA
rS k2

▪ if a1 › a2  keep CA high : high pressure, eliminate inerts,

avoid recycle of products, use plug flow reactor
▪ if a1 < a2  keep CA low : low pressure, add inerts,
recycle of products, use CSTR
( 2 ) Multiple reactions in parallel producing byproducts
shift product distribution

A + B → R (desired) and A + B → S (waste)

rR k1 a1 −a2 b1 −b2
= C A CB
rS k2

▪ if a1 › a2 and b1 › b2  keep CA & CB high

▪ if a1 < a2 and b1 › b2  keep CA low, CB high
▪ if a1 > a2 and b1 < b2  keep CA high, CB low
▪ if a1 < a2 and b1 < b2  keep CA & CB low
( 3 ) Multiple reactions in series producing byproducts
Shift product distribution
ex. CH3

O + H2 → O + CH4
excess 5:1
→
2O O + H2
 O
( 4 ) Mixed parallel and series reactions → byproducts

Shift product distribution

ex. CH4 + Cl2 → CH3Cl + HCl Primary

excess 10:1
CH3Cl + Cl2 → CH2Cl2+ HCl
CH2Cl2+ Cl2 → CHCl3 + HCl Secondary
CHCl3 + Cl2 → CCl4 + HCl
( 3-2 ) FEED INERTS TO REACTOR ( REDUCE REACTION PRESSURE)
( 1b ) Single reversible reaction
=
FEED PROD1 + PROD2
Cp1Cp2
Cinert  → Xfeed  keq =
CF
=
FEED1 + FEED2 PRODUCT
CP
Cinert  → Xfeed1 or Xfeed2  keq =
CF1CF2
( 2 ) Multiple reactions in parallel → byproducts

FEED1 + FEED2 → PRODUCT

=
FEED1 + FEED2 BYPRODUCT
Cinert  → Cbyproduct 
FEED1 + FEED2 → PRODUCT
FEED1 = BYPROD1 + BYPROD2
Cinert  → Cbyprod1-2 
Single reversible reaction
A  B + C
Initial: CA0 0 0
React: CA0X CA0X CA0X
At equilibrium: CA0(1-X) CA0X CA0X
n P
C= =
V RT
(C A0 X )(C A0 X ) C A0 X 2
K eq = =
C A0 (1 − X ) (1 − X )

Example: CA0=1, Keq = 4, then X = 0.828

If we increase the pressure (2 times) by reducing the
volume of reactor V (2 times) OR increasing the
number of moles nA0 (2 times), then CA0 = 2
CA0=2, Keq = 4, then X = 0.732
That is: P then X 
 A  B + C
Initial: PA0 0 0
React: PA0X PA0X PA0X
At equilibrium: PA0(1-X) PA0X PA0X
n P
C= = ; Pt = ( n) RT
V RT
( PA0 X )( PA0 X ) PA0 X 2
K eq = =
PA0 (1 − X ) (1 − X )

Example: Pt = PA0=1, Keq = 4, then X = 0.828

If we maintain the same initial pressure: Pt = 1, but
use inert with molar ratio nI
=1
nA0
then PA0 = yA0*Pt = 0.5*1 = 0.5
PA0=0.5, Keq = 4, then X = 0.9
That is: P then X 
Some of the decisions involve introducing a new component into
the flowsheet, e.g. adding a new component to shift the product
distribution, to shift the equilibrium conversion, or to act as a heat
carrier. This will require that we also remove the component from
the process and this may cause a waste treatment problem.
Example Ethylene production
C2H6 = C2H4 +H2 Steam is usually used as the
C2H6 + H2 = 2CH4 diluent.
Example Styrene Production
EB = styrene +H2
EB → benzene +C2H4 Steam is also used.
EB + H2 → toluene + CH4
( 3-3 ) PRODUCT REMOVAL DURING REACTION
to shift equilibrium + product distribution
( 1b ) single reversible reaction
ex. 2SO2 + O2 = 2SO3
H2O
H2O
SO2
REACT ABSORB REACT ABSORB
O2 + N 2
H2SO4
H2SO4
( 2 ) multiple reactions in series → byproduct
FEED → PRODUCT
remove
PRODUCT = BYPRODUCT
remove
.
( 3-4 ) RECYCLE BYPRODUCT
to shift equilibrium + product distribution

CH3

O + H2 → O + CH4

2 O = O O + H2
( 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 to and from stirred tanks
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.