BITS Pilani

Pilani Campus

Module 2: Flowsheet synthesis

Lecture-5
Input - Output structure of flowsheet
Course: Process Plant Design CE 1705/1701

Nandana Chakinala
Department of Chemical Engineering
Revisit

Hierarchy of decisions for process design

• Batch or continuous
• Input/output structure of flowsheet
• Recycle structure of flowsheet
• Structure of separation system
• HEN or Energy Integration

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Typical input-output structure

• HDA

In many petro chemical processes and also other processing industries, the processing
cost is about 30 to80 or, even 100% of raw the materials cost
Thumb rule: Recover 99% of all valuable material
Some reactant could be lost – air, water → Cheap reactants
Purge and recycle streams – Gaseous reactants with impurities, gaseous by-product
Gaseous reactant are fed in excess to force complete higher conversion of toluene
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Contd..

• Loss of H2 occurs in purge stream

• Recycle and purge streams add degree of freedom
to design
– Recycle to purge ratio
– Composition of purge stream
– Molar ratio or excess of gaseous reactant fed to
the process

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Decisions to be made at I/P-
O/P structure
1. Do we need to purify feed stream?
2. Should we remove a reversible by-product
from reactor effluent?
3. Is a recycle or purge stream needed?
4. How many product streams are required?
5. Should we recover and recycle unreacted
reactants?
6. Listing and identification of design variables
and economic trade off associated with these
variables
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1. Purification of feed streams
– Designing of pre-purification systems
– We may not know the kind of separation for purification
– Is a recycle or purge stream needed?
• Guidelines for decision
– Feed impurity not an inert, and present in large quantities,
remove it
– Feed impurity in gas feed: consider feeding the process
– If impurity in liquid streams and also a by-product, feed the
process through separations
– If impurity in liquid stream and form azeotrope, feed the
process with impurity
– If impurity is easy to be separated from products than
reactants, feed it to process
– If impurity is catalyst poison, remove it

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Economic trade off with feed
purification
– Design a separation system : capital and operating cost
– Better selectivity, better yield, reduction of load and
hence cost of separations
– Process specific no general guideline

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2. Recovery and recycle of by-products

– If diphenyl is recovered and recycled, it will build to an

equilibrium level
– Oversize all pipelines and reactor and separations
– Savings: The cost of equipment used for separation of by-
product, loss of reactant in the form of by-product
– Toluene loss in the form of diphenyl is eliminated
– The column separating unreacted toluene from diphenyl is
eliminated
– Diphenyl is used as fuel – alternate fuel required
– Oversize the equipment and pipeline

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3. Gas recycle and Purge
– What reactants can be characterized as gas- light ends criterion
for light end
– To liquefy a gas/vapor stream – compress and cool (refrigeration)
– Definition: Light component is one which condenses using cooling
water when compressed at moderate pressures
– Propylene is basis for light ends (B.P is -48oC)
– If any component boils at temperature lesser than b.p of
propylene , we call it as light end and we go for recycle and purge
streams
– No recovery and recycle if reactant is cheap (water/air)
– Excess of these components are used – specify excess. Use of
necessarily large quantities could cause burden on equipment and
increasing processing cost

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4. Number of product streams
– What is the destination of products/by-products?
– What is ultimate fate?
• Thumb rule: Never separate and remix two streams
• List all the components that leave the reactor
• Component classification
• Gaseous by products and feed impurities
• Gaseous unreacted reactants/inerts
• Reaction intermediates, azeotropes with reactants, reversible by-products
• Primary products
• Valuable by-products
• By- products (Fuel) – Furnace
• By products (waste treatment) – ETP
• Gaseous / liquid reactants not recovered / recycled – exit the process

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CE 1705/1701 Process Plant Design

Example

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Evaluation of the flowsheet
• Thumb rule: Make certain that all products/by-products/inerts
leave the process
• Thumb rule: Never separate and remix two streams
• List all the components that leave the reactor
• Component classification
• Gaseous by products and feed impurities - vent
• Gaseous unreacted reactants/inerts –Recycle and purge
• Reaction intermediates, azeotropes with reactants, reversible by-products - Recycle
• Primary products – Packing and further processing
• Valuable by-products - Packing and further processing

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Decisions to be made at I/P-
O/P structure- Revisit
1. Do we need to purify feed stream?
2. Should we remove a reversible by-product
from reactor effluent?
3. Is a recycle or purge stream needed?
4. How many product streams are required?
5. Should we recover and recycle unreacted
reactants?
6. Listing and identification of design variables
and economic trade off associated with these
variables
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6. Design variables, overall material
balance and stream costs
• To achieve total material balance, and get stream costs, we must
assess whether problem definition is complete or some
information is missing (design variables)
• Design variables add “degrees of freedom” to process design
• Hypothetical process: Single product, complete conversion of
reactants
• If material balance is not unique- stream costs will also be not
unique
• Do material balance and develop stream costs model in terms of
unknown design variables and eventually look for optimum value
of these variables
• In case of processes with multiple/ complex reactions, there will
always be a correlation of the product distribution in terms of
process variables
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Design variables
• Conversion of limiting reactant
• Molar ratio of reactants
• Reactor T
• Reactor P
• Catalyst
• Temperature: if the activation energies of all the reactants are
similar, the product distribution will not be influenced by T
• Pressure: Liquid phase reactions are relatively insensitive to
variation in pressure
• Gas phase reactions are also insensitive to P, provided_____
• Plug flow reactor: the correlation of limiting reactant conversion is
w.r.t space velocity which helps in deciding size of reactor
• Reactor configuration: For preliminary designs, use same
configuration as chemist
• Kinetic data: we cannot evaluate at initial stage the variation in
product distribution with reactor configuration

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Design variables
• Preliminary calculation should warrant additional effort for reactor
design
• Other variables: whether all reactants recovered and recycled?
Use of gas recycle/purge stream
• % recovery: Molar ratio of reactants → excess reactant fed→
amounts of inerts→ recycle to purge ratio → molar composition
of recycle/purge

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Summary
• Level-2 variables: Reactor conversion, molar ratio of reactants,
reactor T, P, excess reactants, recycle/purge

Procedure for developing material balance:

– For grass root plants, product rate of desired product is starting
point
– In case of expansion, the feed rate of raw material (waste of
existing process) is starting point

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Procedure for developing
overall material balances
Start with the specified production rate

From basic reactions, determine reactant , by product flow

rates

Calculate impurity levels at reactor inlet and outlet, if we

recover all unreacted reactants and recycle them

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
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Limitations
• Assume 100% recovery of all valuable materials
• Find neighbourhood or group of optimum values of design
variables that decide inlet/outlet flows then to determine the
losses
• Processes having multiple valuable products
• Eg: chlorination of methane
• Amine process

• Product distribution is the starting for such reactions, which is

governed by market demand

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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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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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Contd..

• Toluene stream contains no impurities

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

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CE 1705/1701 Process Plant Design

H2 balance

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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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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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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 − yFH )FG +
PB Eqn(5)
PCH 4
S

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Contd..

• The total purge flow rate PG

PG = FE + Total Methane (i.e. PCH 4 )

PG = FE + (1-yFH )FG +
PB Eqn(6)
S
• Normally use the purge composition of the
reactant, yPH as design variable

FE H 2 moles in purge
y PH = = Eqn(7)
PG purge flow rate
Contd..

• From Eqs. (4) & (7), we get

PB PB 1 − S Eqn(8)
yFH FG = − . + yPH 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
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 )
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
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
Stream Table for HDA Process

Fig. HDA Process

Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 130
Stream Table of HDA Process
Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 130

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 Thank You

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Back up slides
CE 1705/1701 Process Plant Design

Numerical Problem on
Selectivity vs Conversion
• The 1967 AIChE student contest problem gives
data showing how the selectivity (S = moles of
benzene at reactor exit per mole of toluene
converted) depends on the reactor conversion.

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CE 1705/1701 Process Plant Design

Contd..

1. Plot the data on arithmetic paper, and

2. Make a log-log plot of (1-S) vs (1-x)
3. Develop correlation for both sets of data
4. Why is it better to correlate (1-S) vs (1-x)?
5. Also use the correlation 0.0036
S = 1− ; ( x  0.97)
(1 − x)
1.544

to calculate the yield of Benzene (Y = mol Benzene at

reactor exit/mole of toluene fed to reactor = Sx) as a
function of conversion.
6. Estimate the conversion corresponding to the
maximum yield.

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CE 1705/1701 Process Plant Design

Solution

• 1 - s vs 1 – x

• log (1 – s) vs log (1 – x)

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CE 1705/1701 Process Plant Design

S vs x in Arithmetic Graph

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CE 1705/1701 Process Plant Design

1-S vs 1-x on Arithmetic Graph

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CE 1705/1701 Process Plant Design

S vs x on Logarithmic Graph

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CE 1705/1701 Process Plant Design

1-S vs 1-x on Logarithmic

Graph

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CE 1705/1701 Process Plant Design

Analysis of Graphs

• Graphs:
1. S vs x Nonlinear
2. (1-S) vs (1-x) Nonlinear
3. log S vs log x Nonlinear and Small Range
(Not accurate)
4. log(1-S) vs log(1-x) Linear and Wider Range
(Accurate)

Selectivity should be correlated with conversion as (1-S)

vs (1-x) rather than S vs x, when the range covered is less
(in this problem S ranges from 0.93 to 0.99 only for x
range of 0.5 to 0.85)
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CE 1705/1701 Process Plant Design

Contd..

• It widens the range and hence more accurate

• Also when plotted as log-log graph, it becomes
linear

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CE 1705/1701 Process Plant Design

Contd..

For the 3rd Graph (log S vs log x): (i.e., S vs x on

log-log plot):
• Slope = -0.10274 and Intercept = -0.0311
• For y = m xn ; log y = log m + n log x
• So log m = -0.0311; m = 0.9694 and n = -0.10274
• So the final relation is −0.10274
S = 0.9694x

But , the given correlation is S = 1 −

0.0036
• ; ( x  0.97)
(1 − x)1.544

• It indicates that the proposed

• Correlation is not good

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CE 1705/1701 Process Plant Design

Contd..

For the 4th Graph log (1-S) vs log (1-x): (i.e., 1-S
vs 1-x on log-log plot):
• Slope = -1.59602 and Intercept = -2.47319
• For y = m xn ; log y = log m + n logx
• So, log m = -2.47319; m = 3.3636 x10-3 and n = -1.59602
• So the final relation is (1 − S ) = 3.3636 10 −3 (1 − x) −1.59602
0.0033636
 S = 1−
(1 − x)1.59602

• Which is almost very close to the 0.0036

S = 1− ; ( x  0.97)
given correlation (1 − x)1.544

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CE 1705/1701 Process Plant Design

Contd.

• How to calculate conversion

corresponding to maximum yield?
1. By finding dY/dx, equating it to zero (dY/dx=0) and
solving it for conversion corresponding to maximum
Yield

2. By generating data on Y vs x, plotting it on a graph

sheet and taking the conversion corresponding to
maximum yield from the graph

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CE 1705/1701 Process Plant Design

Contd..

By following the Method-2.

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CE 1705/1701 Process Plant Design

Enlarged View

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