Hierarchy of decisions

1. Batch versus continuous

2. Input-output structure of the flowsheet
Ch. 4
3. Recycle structure of the flowsheet
4. General structure of the separation system Ch.5
a. Vapor recovery system
b. Liquid recovery system
5. Heat-exchanger network Ch.6, Ch.7, Ch.16
LEVEL I Decision: Batch vs. Continuous
Favor batch operation, if

1. Production rate
a ) less than 5000 ton/year (sometimes)
b ) less than 500 ton/year (usually)
c ) multi-product plants
2. Market force
a ) seasonal production
b) short production lifetime
3. Scale-up problems
a ) very long reaction times
b ) handling slurries at low flow rates
c ) rapidly fouling materials.
 LEVEL I Decision: Batch vs. Continuous

• Flexibility
– Batch can handle many different feeds and
products – more flexible
– Continuous is better for smaller product
slate and fewer feeds
 LEVEL I Decision: Batch vs. Continuous

• Other Issues
– Accountability and quality control – FDA
requires batch accountability
– Seasonal demands – e.g., antifreeze, food
products
 Hierarchy of decisions
1. Batch versus continuous
2. Input-output structure of the flowsheet
Ch. 4
3. Recycle structure of the flowsheet
4. General structure of the separation system Ch.5
a. Vapor recovery system
b. Liquid recovery system
5. Heat-exchanger network Ch.6, Ch.7, Ch.16
 Input – Output Structure
(Process Concept Diagram)

Toluene Benzene
Toluene + H2  Benzene + CH4 CH4
H2 2 Benzene ↔ Diphenyl + H2

Diphenyl ?

Hydrodealkylation of toluene to produce benzene

HDA Process
HDA Process configuration – Alternative 1
 H2 Recycle By-product
CH4

H2 Benzene
Toluene Dipheny1

Toluene Recycle

Input-Output Structure of the HDA

Process – Alternative 1
Toluene + Diphenyl
Recycle

HDA Process configuration – Alternative 2

HDA Process configuration – Alternative 2
 H2 Recycle By-product
CH4

H2
Benzene
Toluene

Toluene + Diphenyl
Recycle

Input-Output Structure of the HDA

Process – Alternative 2
HDA Process configuration – Alternative 3
 Recycle Purge

H2 + CH4

H2 + CH4
Benzene
Toluene

Toluene + Diphenyl
Recycle

Input-Output Structure of the HDA

Process – Alternative 3
What Information Can Be Determined Using the Input/Output
Diagram for a Process?
• Basic economic analysis on profit margin
• What chemical components must enter with the feed and leave
as products
• All the reactions, both desired and undesired, that take place

=> The potential profitability of a proposed process can be

evaluated and a decision whether to pursue the process can be
made.
Disproportionation or transalkylation of toluene to produce
benzene and a mixture of para-, ortho-, and meta-xylene:
Generic Block Flow Process Diagram
Purge
Generic Block Flow Process Diagram
(Process Requiring Multiple Reactors)
Purge
Heuristics:
Recover more than 99% of all valuable materials.
assume

Completely recover and recycle all

valuable reactants
DECISIONS FOR THE INPUT/OUTPUT STRUCTURE
 Flowsheet Alternatives

(1)
Feed streams Process Products
by-products
no reactants
(2) Purge
Products
Feed streams Process
By-Products
reasons:
a. inexpensive reactants, e.g. Air, Water.
b. gaseous reactants + (inert gaseous feed impurity or inert gaseous
reaction by-product)
A HIERARCHICAL APPROACH

Toluene + H2  Benzene + CH4

2 Benzene Diphenyl + H2
1150  F ～ 1300  F
500 psia
LEVEL 2 DECISIONS:

1 ) Should we purify the feed streams before they enter the process?
2 ) Should we remove or recycle a reversible by-product?
3 ) Should we use a gas recycle and purge stream?
4 ) Should we not bother to recover and recycle some reactants?
5 ) How many product streams will there be?
6 ) What are the design variables for the input/output structure?
What economic trade-offs are associated with these variables?

 
Products
Feeds 
 PROCESS 

&
By products
OR
Purge
 
Products
Feeds 
 PROCESS 

&
By products
Purify Feed ?
• Feed purity and trace components
– Small quantities and “inerts” – do not separate
Example H2 in feed contains CH4
CH4 does not react
so – do not remove
• If separation of impurities is difficult – Do
not separate
– Azeotrope – (water and ethanol)
– Gases – (requires high P and low T)

How would you remove CH4 from H2?

• If impurities foul or poison catalyst then separate
– Sulfur – Group VIII Metals (Pt, Pd, Ru, Rh)
– CO in platinum PEM fuel cells

Note: S and CO may be present in very small

amounts (ppm)
• If impurity reacts to form difficult-to-separate material
or hazardous product then separate
Phosgene Example
CO + Cl2 COCl2
(phosgene + amine isocyanates polyurethanes
Produce CO by steam reforming of natural gas:
CH4 + H2O CO + 3H2
If H2 is not removed from CO, then
H2 + Cl2 2HCl
HCl is difficult to remove from the phosgene, is highly
corrosive, and is detrimental to the isocyanate product
=> separate H2 from CO
• Impurity in large quantities then purify –
why?

A notable exception is air

3 ) Gas Recycle and Purge
“Light” reactant 
“Light” feed impurity, or
“Light” by-product produced by a reaction

Whenever a light reactant and either a light feed impurity or a light by-
product boil lower than propylene (-55ºF), use a gas recycle and purge
stream.

Lower boiling components normally cannot be condensed at high pressure

with cooling water.
4 ) Do not recover and recycle some reactants which are
inexpensive, e. g. air and H2O.
We could try to make them reacted completely, but often we feed them as an excess
to try to force some more valuable reactant to completion.
 5 ) Number of Product Streams
TABLE 5.1-3
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)
4.None Reactants-if complete conversion or unstable reaction intermediates
5.Excess - vent Gaseous reactant not recovered or recycles
6.Excess - vent Liquid reactant not recovered or recycled
7.Primary product Primary product
8.Fuel By-products to fuel
9.Waste 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 ) Classify each component in the list according to Table 5.1-3 and assign a destination
code to each.
C ) Order the components by their normal boiling points and group them with
neighboring destinations.
D ) The number of groups of all but the recycle streams is then considered to be the
number of product streams.
 EXAMPLE
b.p. A Waste
A + B to waste 
B Waste
C Recycle
D Fuel
D + E to fuel stream # 1 
E Fuel
F Primary product F to primary product 
G Recycle (storage for sale)
H Recycle
I Valuable By-product I to valuable by-product (storage for sale) 
J Fuel J to fuel stream # 2 

EXAMPLE
b.p.
-253C H2 Recycle and Purge
CH4 Recycle and Purge 
-161
80 Benzene Primary Product
111 Toluene Recycle 
253 Diphenyl Fuel 
 Purge : H , CH
2 4

H2 , CH4  Benzene
Toluene Process
 Diphenyl
Alternatives for the HDA Process
1. Purify the H2 feed stream.
2. Recycle diphenyl
3. Purify H2 recycle stream.
 REACTOR PERFORMANCE
Conversion (x)
= (reactant consumed in the reactor)/(reactant
fed to the reactor)
Selectivity (S)
=[(desired product produced)/(reactant
consumed in the reactor)]*SF
Reactor Yield (Y)
=[(desired product produced)/(reactant fed to
the reactor)]*SF
 STOICHIOMETRIC FACTOR
(SF)

The stoichiometric moles of reactant

required per mole of product
Material Balance of Limiting Reactant in Reactor

Toluene
unconverted recycle
(1-x) mole

Toluene Benzene
feed produced
(1 mole) Sx mole
Toluene
converted
x mole
Diphenyl
produced
(1-S)x / 2
 Gas recycle Purge
H2 , CH4
Toluene 1  x
Benzene Sx
1 Benzene
Diphenyl (1  S) x
H2 , CH4 Reactor 2
Separation Sx
Toluene system system
Dipheny1
x 1
(1  S ) x
1 x
2

Toluene recycle
Material Balance of the Limiting
Reactant (Toluene)
Assumption: completely recover and recycle the limiting reactant.