Hierarchy of decisions

1. Batch versus continuous

2. Input-output structure of the flowsheet
3. Recycle structure of the flowsheet
4. General structure of the separation system
a. Vapor recovery system
b. Liquid recovery system
5. Heat-exchanger network

Ch.6, Ch.7, Ch.16

Ch. 4
Ch.5

LEVEL I Decision: Batch vs. Continuous

Favor batch operation, if
1. Production rate
a ) less than 10106 lb/yr (sometimes)
b ) less than

1106 lb/yr

(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.

Hierarchy of decisions
1. Batch versus continuous
2. Input-output structure of the flowsheet
3. Recycle structure of the flowsheet
4. General structure of the separation system
a. Vapor recovery system
b. Liquid recovery system
5. Heat-exchanger network

Ch.6, Ch.7, Ch.16

Ch. 4
Ch.5

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

(2)
Feed streams

Products
by-products
no reactants

Process

Purge
Process

Products
By-Products

reasons:
a. inexpensive reactants, e.g. Air, Water.
b. gaseous reactants + (inert gaseous feed impurity or inert gaseous
reaction by-product)

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
&
PROCESS
Feeds
By products

OR

Feeds

PROCESS

Purge
Products
&
By products

1 ) Purification of Feeds (Liquid/Vapor)

1 ) If a feed impurity is not inert and is present in significant quantities,
remove it.
2 ) If a feed impurity is present in large amount, remove it.
3 ) If a feed impurity is catalyst poison, remove it.
4 ) If a feed impurity is present in a gas feed, as a first guess, process the
impurity.
5 ) If a feed impurity is present as an azeotrope with a reactant, often it is
better to process the impurity.
6 ) If a feed impurity is inert, but it is easier to separate from the product than
the feed, it is better to process the impurity.
7 ) If a feed impurity in a liquid feed stream is also a byproduct or a product
component, usually it is better to feed the process through the separation
system.

Heat

Compressor

H2, CH4
H2

CH4

1150 ~ 1300
Reactor
Toluene

Coolant

Heat

H2, CH4

Benzene
Product

Toluene

Flash

500 psia

Recycle

Heat

95F

Dipheny1
Toluene

Stabilizer

Heat

Purge

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 byproduct boil lower than propylene (-55F), use a gas recycle and purge
stream.
Lower boiling components normally cannot be condensed at high pressure
with cooling water.

A HIERARCHICAL APPROACH

Toluene + H2 Benzene + CH4

2 Benzene
Diphenyl + H2
1150 F 1300 F
500 psia

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
1. Vent
2. Recycle and purge
3. Recycle

4.None
5.Excess - vent
6.Excess - vent
7.Primary product
8.Fuel
9.Waste

Component classifications
Gaseous by-products and feed impurities
Gaseous reactants plus inert gases and/or gaseous by-products
Reactants
Reaction intermediates
Azeotropes with reactants (sometimes)
Reversible by-products (sometimes)
Reactants-if complete conversion or unstable reaction intermediates
Gaseous reactant not recovered or recycles
Liquid reactant not recovered or recycled
Primary product
By-products to fuel
should be minimized
By-products to waste treatment

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
B
C
D
E
F
G
H
I
J

Waste
Waste
Recycle
Fuel
Fuel
Primary product
Recycle
Recycle
Valuable By-product
Fuel

A + B to waste

D + E to fuel stream # 1
F

to primary product
(storage for sale)

I
to valuable by-product (storage for sale)
J to fuel stream # 2

EXAMPLE
b.p.
-253C
-161
80
111
253

H2
CH4
Benzene
Toluene
Diphenyl

Recycle and Purge

Recycle and Purge
Primary Product
Recycle
Fuel

Purge : H , CH
2
4

H2 , CH4
Toluene

Process

Benzene
Diphenyl

5
H2 , CH4
1
Toluene

Purge
H2 , CH4
3

Process

Benzene
Diphenyl

Production rate = 265

Design variables: FE and x
Component
H2
CH4
Benzene
Toluene
Diphenyl
Temperature
Pressure

1
FH2
FM
0
0
0
100
550

0
0
PB/S
0
100
15

0
PB
0
0
100
15

where S = 1 - 0.0036/(1 -x)1.544

FIGURE 5.2-1
.

5
FE

0
FM + PB/S
0
0
0
0
PB(1 - S)/(2S) 0
100
100
15
465

FH2 = FE + PB(1 + S)/2S

FM = (1 - yFH)[FE + PB(1 + S)/S]/ yFH

Stream table

FG = FH2 + FE

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
(1-x) mole
Toluene
feed
(1 mole)

Toluene
converted
x mole

recycl
e
Benzene
produced
Sx mole

Diphenyl
produced
(1-S)x / 2

Gas recycle

Purge
H2 , CH4

Toluene 1 x
Benzene
Sx

H2 , CH4
Toluene

Reactor
system

1
2

Diphenyl (1 S) x

Benzene
Separation
system

Sx

Dipheny1

1 x
Toluene recycle

Material Balance of the Limiting

Reactant (Toluene)
Assumption: completely recover and recycle the limiting reactant.

1
(1 S ) x
2

POSSIBLE DESIGN VARIABLES FOR LEVEL 2

For complex reactions:
Reactor conversion (x), reaction temperature (T) and pressure (P).

If excess reactants are used, due to reactant not recovered or gas recycle and purge, then
the excess amount is another design variable.

PROCEDURES FOR DEVELOPING OVERALL

MATERIAL BALANCE
1 ) Start with the specified production rate.
2 ) From the stoichiometry (and, for complex reactions, the correlation for product
distribution) find the by-product flows and the reactant requirements (in terms of the
design variables).
3 ) Calculate the impurity inlet and outlet flows for the feed streams where the reactant are
completely recovered/recycled.
4 ) Calculate the outlet flows of reactants in terms of a specific amount of excess for streams
where reactants are not recovered and recycled (recycle and purge, or air, or H2O)
5 ) Calculate the inlet and outlet flows for the impurities entering with the reactant streams
in Step 4).

Normally, it is possible to develop expressions for overall MB in terms of design

variables without considering recycle flows.

EXAMPLE

Purge ; H2 , CH4 , PG

FG , H2 , CH4
FFT , Toluene

relation
known

Benzene , PB
Diphenyl , PD

Process

design variable

given

SS( x )
= selectivity = given
PBB( mol/hr ) = production rate of Benzene =given
P
FFT( mol/hr ) = toluene feed to process ( limiting reactant ) = PB/S
PR , CH4

= diphenyl produced in reaction = FFT (1 - S/2) = (PB/S)(1 - S/2)

PD
design
variable

= methane produced in reaction = FFT = PB/S

F
Let FEE = excess amount of H2 in purge stream= PH2
y
( PB/S ) - [( PB/S )( 1 - S )/2]
FHFG
y
FE +
= FHFG
purge rate
of H2

disapp. in reaction

where

FG = make-up gas stream flowrate (unknown)

y

FH

= mole fraction of H2 in FG
( known )

methane in purge stream

Let PCH4 = purge rate of CH4

( 1 - yFH ) FG + PB/S = Pmethane

CH4
product in reaction

methane in feed

FH2

 PG = total purge rate = PH2 + PCH4 = FE + (1 - yFH) FG + PB/S

= FG + ( PB/S )[( 1 - S )/2]
Define
y

design
variable

PH

= purge composition of H2 = PH2/PG = FE/PG

It can be derined that

FG = PB [ 1- (1- yPH)(1-S)/2 ]
design variable

Known :

S (yFH - yPH)
Design Variable :

S (x)

FH

PB

PB/S

(PB/S)[(1-S)/2]

FE
PCH4

FCH4+PB/S

[(1- yFH)/ yFH]FH2

FCH4
FH2

PCH4+FE
PG

FN2+FCH4

FFT

FG

FE+[PB(1+S)/2S]
PD

Known : yFH
PB
Design Variables :
x,

S(x)

PB/S

FFT

FFT(1-S)/2

PD
PB[1-(1- yPH)(1-S)/2

PH

S(yFH - yPH)

FCH4

FH2
1- yPH

FCH4+PB/S

PCH4

FE+PB(1+S)/2S

FE
(PH2)

FH2

PG

FG
FG+(PB/S)(1-S)/2

PG yPH

PH

6 ) ECONOMIC POTENTIAL AT LEVEL 2

EP2 = Annual profit if capital costs and utility costs are excluded
= Product Value + By-product Value - Raw-Material Costs
[EXAMPLE] HDA process
4 10^6
2 10^6
$/yr
-2 10^6
-4 10^6

0.1

0.3

0.5

0.1

PH

0.1
0.7
0.9

Douglas, J. M., Process Synthesis for Waste

Minimization. Ind. Eng. Chem. Res., 1992, 31, 238-243
If we produce waste by-products, then we have negative byproduct values.
Solid waste : land fill cost / lb
Contaminated waste water :
- sewer charge : $ / 1000 gal. (e.g. $0.2 / 1000 gal)
- waste treatment charge :
$ / lb BOD lb BOD / lb organic compound (e.g. $0.25 /lb BOD)
Solid or liquid waste to be incinerated :
$ 0.65 / lb

BOD - biological oxygen demand