BITS Pilani

Pilani Campus

Level-2 Decisions: Input-output structure

CHE F314 Process Design Principles I

Decisions for the Input-Output

Structure
• To fix the input-output structure of a flow sheet
– We merely draw a box around the total process

• Focus mainly on what raw materials are fed to the

process and what products and by-products are
removed

• Raw materials costs fall normally in the range of

33-85% of the total processing costs

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CHE F314 Process Design Principles I

Contd..

Douglas, J. M. AIChE J., 31: 353, 1985

Fig. Input-output structure of flowsheet

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CHE F314 Process Design Principles I

Flow Sheet Alternatives

• For initial design calculations

– It is assumed that desirable to recover more than 99% of
all valuable materials
– is equivalent to requiring
• That we completely recover and then recycle all valuable
reactants
– Thus Fig. 1(a) indicates that no reactants leave the
system

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CHE F314 Process Design Principles I

Contd..

• If Air & water are reactants in a process

– Sufficiently inexpensive compared to organic materials

– Cheaper to lose them in an exit stream rather than to

recover & recycle them

– Hence, in a few rare cases, Fig. 1(a) might not be

complete

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CHE F314 Process Design Principles I

Contd..

• The other situation in which commonly reactants

have been lost from a process occurs
– When we have a gaseous reactant, and
– Either a gaseous feed impurity
– Or a gaseous by-product produced by one of the
reactions

• We want to recycle the gaseous reactant

• But the inert-gas components must be purged

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CHE F314 Process Design Principles I

Contd..

• In the past, it was so expensive to separate

gaseous mixtures that some reactant was allowed
to leave the process in a gas-recycle and purge
stream [Fig. 1(b)]

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CHE F314 Process Design Principles I

Contd..

• Presence of a gas recycle and purge stream adds a

design degree of freedom to the design problem
– reactant composition of the purge stream,
– or the excess gaseous reactant fed to the process
becomes a new design variable

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CHE F314 Process Design Principles I

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. How many product streams will be there?
5. What are the design variables for the input-output
structure, and what economic trade-offs are
associated with these variables?

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CHE F314 Process Design Principles I

Level-2 Decisions:
I. Purification of Feeds
• If a feed impurity is not inert and is present in
significant quantities

Remove it
• otherwise it will lead to raw material losses,
• and usually a much more complicated
separation system is required to recover the
additional by-products

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CHE F314 Process Design Principles I

• If the impurities are not present in large

quantities (say, <10-20%), and these impurities
do not react to form by-products

Do not separate them, Process it

• If the feed impurity foul or poison the catalyst

Purity the feed (Remove it) before

Process

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CHE F314 Process Design Principles I

• If the impurity reacts to form difficult-to-separate

or hazardous products

Purity the feed (Remove it) beofore

Process

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CHE F314 Process Design Principles I

Contd..

• If a feed impurity is present in a gas feed

As a first guess process the impurity
i.e., allow it to go to the process step

• If a feed impurity is present in large amounts

Remove it
• There is no quantitative criterion available to indicate
how “large” is large

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CHE F314 Process Design Principles I

Contd..

• If a feed impurity is present as an azeotrope

with a reactant
Often it is better to process the impurity

• If a feed impurity is inert but is easier to

separate from the product than the feed

It is better to process the impurity

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CHE F314 Process Design Principles I

Level-2 Decisions: II. Remove or

Recycle Reversible By-products
• The reactions to produce Benzene from Toluene
are:
Toluene + H2 → Benzene + CH4
2 Benzene → Diphenyl + H2

• Since the 2nd reaction is reversible

– We could recycle the diphenyl back to the reactor
– And let it build up in the recycle loop
• Until it eventually reached an equilibrium level
• i.e., the recycled diphenyl would decompose to form
benzene at the same rate as benzene producing diphenyl
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CHE F314 Process Design Principles I

Contd..

Recycle diphenyl to extinction

• Trade-off
– Over sizing of all the equipment in recycle loop
Vs.
Paying economic penalty because of the increased raw
material cost of reactant (toluene) that was converted to
reversible by product (diphenyl)
– i.e., (raw material cost of toluene – fuel value of diphenyl)

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CHE F314 Process Design Principles I

Level-2 Decisions: III. Gas

Recycle & Purge
• Gas Recycle & Purge
– If we have a light reactant & either a light feed impurity
or a light by-product produced by a reaction
• It used to be common practice to use a gas recycle and a purge
stream
• i.e., we want to recycle the reactant, but we must purge one or
more components from the process

– Light component: It is one which boils lower than

propylene (-55 0F; -48 0C)

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CHE F314 Process Design Principles I

Contd..

• Propylene as a break-point
– lower b.p. components normally cannot be
condensed at high pressure with cooling water

– i.e., both high pressure and refrigeration would be

required

– Which is very expensive indeed

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CHE F314 Process Design Principles I

Contd..

• Gaseous reactants normally are less expensive

than organic liquids, and
– Since refrigeration is one of the most expensive
processing operations

– It is usually was cheaper to lose some of the gaseous

reactants from a gas recycle & purge stream than it was
to recover & recycle pure reactant

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CHE F314 Process Design Principles I

Contd..

Heuristic
Whenever a light reactant and either a light feed
impurity or a light by-product boil lower than
propylene (- 55 0F; -48 0C), use a gas recycle and
purge stream

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CHE F314 Process Design Principles I

Level-2 Decisions: V. Number

of Product Streams
• List all the components that are expected to leave
the reactor

• This component list include

– All the components in the feed streams
– All the reactants & products that appear in every
reaction

• Classify each component in the list & assign a

destination code to each

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CHE F314 Process Design Principles I

Table: Destination codes and component classifications

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CHE F314 Process Design Principles I

Contd..

• Order the components by their normal boiling

points
• Group neighbouring components with the same
destination
– No of product streams = (No of all groups – No of
recycle streams)
– This procedure for determining the no of product
streams is based on the common sense design
guideline:
It is never advantageous to separate two streams and
then mix them together
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CHE F314 Process Design Principles I

Suppose we have the 10 components

listed in order of their boiling points and
with the destination codes indicated.
How many product streams will be
there?

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CHE F314 Process Design Principles I

Contd..

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CHE F314 Process Design Principles I

Answer

The product streams are:

No of all groups – No of recycle streams = 7–2 = 5
1. A+B to Waste
do not separate them and then mix them in the sewer
2. D+E to Fuel
do not separate them and then mix them
3. F is a primary product
to storage for sale
4. I is a valuable by-product
to storage for sale
5. J to Fuel
J must be separated from D & E to recover components F, G, H and
I, so we treat J as a separate product stream

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CHE F314 Process Design Principles I

Product Streams in HDA

Process
• For HDA Process (where diphenyl is a by-product
fuel)

Table 5.1-4: Toluene to Benzene

Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 122

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CHE F314 Process Design Principles I

Contd

 1 & 2 (one group) boil at lower temperature than

propylene, and hence we decided to use recycle & purge
(one recycle group & one purge group)

 4 – unconverted toluene to be recycled

 No of product streams = (5 – 2) = 3
 (one purge, one primary product, and one fuel)

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CHE F314 Process Design Principles I

Contd..

Fig 5.1-2: Input-output of HDA Process

Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 123

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CHE F314 Process Design Principles I

Design variables, Material

Balances, Stream Costs
• To calculate overall process material balances and
the stream costs
– first assess whether the problem definition is complete

– or, whether there are any degrees of freedom that must

be specified

• In general, the problem definition is not complete

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CHE F314 Process Design Principles I

Contd..

• It is impossible to develop a unique set of material

balances for a process
– with a single reaction & with no loss of reactants from
the process and has no degrees of freedom
– Of course, when the material balances are not unique,
then the stream costs will also not be unique

• Develop the material balances and the stream

costs in terms of the unknown design variables to
find optimum Economic Potential (EP)

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CHE F314 Process Design Principles I

Design Variables

• The variables we select to complete the definition

of the design problems are called degrees of
freedom
• Possible design variables for Level-2:
1. For complex reactions, the product distribution is
a function of
– Conversion of the limiting reactant x vs. space
– Molar ratio of reactants
– Reaction Temperature
– Reactor Pressure

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CHE F314 Process Design Principles I

Contd..

2. Excess Reactants
– If we use an excess amount of air in a
combustion reaction
• We must specify the amount of excess
– Similarly, if we have a gas recycle & purge
stream present
• We must specify the excess amount of gas reactant fed (i.e., the
excess of the reaction requirements) which is lost in the purge
stream, or
• The reactant composition in the purge stream

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CHE F314 Process Design Principles I

Procedure for developing

overall material balances
Start with the specified production rate

From the stoichiometry, find the by-product flows and the

reactant requirements

Calculate the impurity inlet & outlet flows for the feed streams
where the reactants are completely recovered & recycled

Calculate the outlet flows of reactants in terms of a specified

amount of excess (above the reaction requirements)

Calculate the inlet & outlet flows for the impurities entering with
the reactant streams in Step 4
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CHE F314 Process Design Principles I

Selectivity & Reaction

Stoichiometry
• For HDA Process:
Toluene + H2 → Benzene + CH4
2 Benzene → Diphenyl + H2
S = selectivity= moles of benzene at reactor outlet/moles of toluene
converted

• Hence, for a production of PB moles/hr of Benzene

• Toluene fed to the process (FFT)

PB
FFT  Eqn(1)
S
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CHE F314 Process Design Principles I

Contd..

• Also, from stoichiometry, the amount of CH4

produced P
PR ,CH 4  B
Eqn(2)
S
• If a fraction S of toluene is converted to benzene, a
fraction (1-S) must be lost to diphenyl
• From stoichiometry,
1  S PB 1  S Eqn(3)
PD  FFT  .
2 S 2

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CHE F314 Process Design Principles I

Contd..

• Toluene stream contains no impurities

• Total fresh feed rate of toluene
• and the diphenyl by-product flow rate in terms of
selectivity from the reaction stoichiometry and given
production rate

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CHE F314 Process Design Principles I

Contd..

Purge:
• If we feed an excess amount of H2 (as some H2
goes into purge), FE into the process, this H2 will
leave with the purge stream
• The total amount of H2 fed to the process

FH 2  FE 
PB
1  S  ?yFH .FG Eqn(4)
2S

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CHE F314 Process Design Principles I

Contd..
PB
• Required H2  In 1st Rxn
S
• H2 Produced  PB . 1  S In 2nd Rxn
S 2

• H2 Fed  PB   PB 1  S 
  .
 S   S 2 
 PB   PB 
     .S
 2S   2S 
 PB  
  .1  S 
 2 S  
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CHE F314 Process Design Principles I

Contd..

• yFHFG = amount of H2 in the make-up gas stream

• (1-yFH)FG = amount of CH4 in the make-up gas
stream
• Similarly, the methane flow rate leaving the
process =
(amount of methane entering the process +
amount of methane produced)

 1  y FH FG 
PB
PCH 4 Eqn(5)
S

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CHE F314 Process Design Principles I

Contd..

• The total purge flow rate PG

PG  FE  Total Methane (i.e. PCH 4 )

PG  FE  1-y FH FG 
PB Eqn(6)
S
• Normally use the purge composition of the
reactant, yPH as design variable

FE H 2 moles in purge
yPH   Eqn(7)
PG purge flow rate
BITS Pilani, Pilani Campus
CHE F314 Process Design Principles I

Contd..

• From Eqs. (4) & (7), we get

PB PB 1  S Eqn(8)
y FH FG   .  y PH PG
S S 2

• And the methane in the feed plus the methane

produced must all leave with the purge

1  yFH FG   1  yPH PG

PB Eqn(9)
S

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Contd..

• Adding Eqs. (8) & (9)

PB 1  S
PG  FG  . Eqn(10)
S 2
• Solve for FG
(make-up gas rate, i.e. CH4+ H2 entering)
  1  S 
PB 1  (1  y pH ) 
  2  Eqn(11)
FG 
S ( y FH  y PH )

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Contd..

• If we are given the values of PB, S and either FE or

yPH, the following can be calculated:
– Fresh feed rate of toluene, FFT (Eq. 1)
– The production rate of diphenyl, PD (Eq. 3)
– The make-up gas rate, FG (Eq. 4 or 11)
– The purge flow rate, PG (Eq. 6 or 10)

• All the input & output flows in terms of

– unknown design variables
– i.e., S & either FE or yPH

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Material Balances In Terms of

Extent of Reaction
• Common practice to describe material balances in
terms of extent of reaction (ξ) or fractional extent of
reaction
• For HDA process,
Toluene + H2 → Benzene + CH4 ξ1
2 Benzene → Diphenyl + H2 ξ2
• ξ1 mol (or moles/hr) of toluene reacts with ξ1 mol
(or moles/hr) of H2
• to produce ξ1 mol (or moles/hr) benzene
• and ξ1 mol (or moles/hr) of CH4

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Contd..

• 2ξ2 mol (or moles/hr) of benzene produces

• ξ2 mol (or moles/hr) diphenyl
• and ξ2 mol (or moles/hr) of H2
Net benzene produced = ξ1 - 2ξ2 Eqn(12)
Methane produced = ξ1 Eqn(13)
Diphenyl produced = ξ2 Eqn(14)
Toluene consumed = ξ1 Eqn(15)
Hydrogen consumed = ξ1 – ξ2 Eqn(16)

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Contd..

• Selectivity can be defined as,

moles of desired product 1  2 2

S 
moles of limiting reactant converted 1

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CHE F314 Process Design Principles I

Example

Develop the expressions relating the extents of

reaction to production rate and selectivity for the
HDA process

Toluene + H2 → Benzene + CH4 ξ1

2 Benzene → Diphenyl + H2 ξ2

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Solution

• From Eqs. 15 & 1,

PB
1 
S

• From Eqn. 12, 1  2 2  PB

• So,
PB  1  S 
 2  1  PB   
1

2 2  S 

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CHE F314 Process Design Principles I

Stream Tables

• Report material balance calculations in terms of

stream tables
– i.e., the streams are numbered on a flow sheet, and
– Then a table is prepared that gives the component flows
in each of these streams
• which correspond to a particular set of values of the design
variables
– The temperature, pressure, and enthalpy of each stream
also are normally listed
• In the present case, we do not consider energy balances until
the end of the synthesis procedure

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CHE F314 Process Design Principles I

Stream Table for HDA Process

Fig. HDA Process

Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 130
BITS Pilani, Pilani Campus
CHE F314 Process Design Principles I

Stream Table of HDA Process

Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 130

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CHE F314 Process Design Principles I

Stream Costs: Economic

Potential
• Best values of the design variables depend on the
process economics
• we want to calculate the stream costs
– i.e., the costs of all raw materials & product streams in
terms of design variables

– Normally combine these costs into a single term, which

we call the Economic Potential (EP)

EP2 = (Product value + By-product value – Raw material costs), Rs/yr

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CHE F314 Process Design Principles I

Stream Costs: Economic

Potential
• The economic potential is the annual profit we
could make

• If the economic potential is negative

• i.e. raw materials are worth more than the products and
by-products
• We need to terminate our design project

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CHE F314 Process Design Principles I

EP2 for HDA Process

EP2 (Rs/yr)  Benzene value  Fuel value of Diphenyl  Fuel Value of Purge
- Toluene cost - Makeup Gas Cost
- Annualized capital and Operating Cost of Feed Compressor (optional)

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CHE F314 Process Design Principles I

Thank You

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