BITS Pilani

Pilani Campus

Level-3 Decisions: Recycle structure of

Flowsheet
CHE F314 Process Design Principles I

Level-3 Decisions: Determination

of Recycle Structure
• Number of reactor systems required
– Is there any separation between the reactor systems?
• Number of recycle streams required
• Use of an excess of any one reactant at the reactor
inlet
• Gas compressors are required?
– What are the costs?
• Should the reactors be
– Operated adiabatically, or
– With direct heating or cooling, or
– Is a diluent or heat carrier required?

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Contd..

• Is shift in equilibrium conversion required? If so

how?
• Effect of reactor cost on Economic Potential.

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CHE F314 Process Design Principles I

L3 Decisions: 1. Number of
reactor systems
HDA process:
Toluene + H2 → Benzene + CH4 1150-1300 0F, 500 psia
2 Benzene → Diphenyl + H2 1150-1300 0F, 500 psia

– Both the above reactions take place at the same

temperature and pressure without a catalyst

– Hence, there is only one reactor required for this case

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CHE F314 Process Design Principles I

Contd..

Consider another process:

Acetone → Ketene + CH4 700 0C, 1 atm
Ketene → CO + ½ C2H4 700 0C, 1 atm
Ketene + Acetic Acid → Acetic Anhydride 80 0C, 1 atm

– The first two reactions take place at a higher

temperature, whereas the third reaction takes place at a
lower temperature

– Hence, two reactor systems would be required for this

case

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CHE F314 Process Design Principles I

Contd..

• If sets of reactions take place

– at different temperatures
– or pressures
– or if they require different catalysts

then we use different reactor systems for these

reaction sets

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CHE F314 Process Design Principles I

L3 Decisions: 2. Number of
recycle streams
• Associate reaction steps with a reactor number
(R1, R2, etc.)
• Then associate feed streams with the reactor
number where feed component reacts
• Similarly, associate the components in recycle
streams with the reactor number
• Now, list all the components leaving the reactor
and order them by their normal boiling points
• List the reactor number as the destination code for
each recycle stream
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CHE F314 Process Design Principles I

Contd..

• Next, group recycle components having

neighbouring boiling points if they have the same
reactor destination
• (Number of recycle streams) = (number of groups)

Heuristic
Do not separate two components and
then remix them at a reactor inlet

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CHE F314 Process Design Principles I

Contd..

• Distinguish between gas- and liquid-recycle

streams
– Because gas-recycle streams require compressors,
which are always expensive

– Consider a stream to be a gas-recycle stream if it boils

at a lower temperature than propylene

– Liquid recycle streams require only pumps

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CHE F314 Process Design Principles I

Contd..

Example: Anhydride Process

Acetone → Ketene + CH4 700 0C, 1 atm
Ketene → CO + ½ C2H4 700 0C, 1 atm
Ketene + Acetic Acid → Acetic Anhydride 80 0C, 1 atm

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

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CHE F314 Process Design Principles I

Component List and

Destination codes
Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 140

• There are 2 product streams:

– (CO+CH4+C2H4) & Acetic Anhydride
– 2 liquid recycle streams returned to different reactors:
– Acetone recycled to R1 & Acetic Acid recycled to R2
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CHE F314 Process Design Principles I

Contd..

Example: HDA Process

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

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CHE F314 Process Design Principles I

Contd..
Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 140

• 3 Product streams: Purge, Benzene, and

Diphenyl
• 2 Recycle streams: 1. Gas (H2+CH4) & 2. Liquid
(Toluene)
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CHE F314 Process Design Principles I

L3 Decisions: 3. Use of Excess

Reactant
• In some cases, the use of an excess reactant can
shift the product distribution
Butene + Isobutane → Isooctane (desired)
Butene + Isooctane → C12 (undesired)
• If the kinetics match the stoichiometry (elementary
reaction)
– then the use of excess of isobutane leads to an
improved selectivity to produce Isooctane
– The larger the excess
• The greater the improvement in selectivity
• But larger the cost to recover & recycle the Isobutane

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Contd..

• Thus, an optimum amount of excess must be

determined from an economic analysis
• Molar ratio of reactants at the reactor inlet is
often a design variable

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CHE F314 Process Design Principles I

Contd..

• The use of an excess component can also be used

– To force another component to be close to complete
conversion
– For example, in the production of Phosgene:
CO + Cl2 → COCl2 → di-isocyanate (NCO)

• The product (NCO) must be free of Cl2

• Thus, an excess of CO is used to force the Cl2

conversion to be very high

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CHE F314 Process Design Principles I

Contd..

• Similarly, the use of an excess can be used to shift

the equilibrium conversion
– For example, in the production of Cyclohexane:
Benzene + 3H2 → Cyclohexane
– We want to obtain equilibrium conversions very close to unity
• So that we can obtain a high conversion of benzene and
• Avoid a benzene-cyclohexane distillation separation
• As the boiling points of benzene (80.1 0C) and cyclohexane
(80.74 0C) are very close to each other
– We can shift the equilibrium conversion to the right by using an
excess of H2 at the reactor inlet

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CHE F314 Process Design Principles I

Contd..

• Thus, the molar ratio of reactants (MR) at the

reactor inlet is often a design variable

• Normally, the optimum amount of excess to use

involves an economic trade-off between
– Some beneficial effect &
– The cost of recovery and recycling the excess

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CHE F314 Process Design Principles I

L3 Decisions: 4. Use of A Gas

Compressor
• Compressor design (for a centrifugal gas
compressor) equation for the theoretical
horsepower (hp)

 3.303 10    Pout 
5 
hp    PinQin    1
    Pin  
RG
Qin  where,  m  mole/ft 3
60  m
and RG  Gas recycle flow rate, mol/hr

where,  
C C  1 p v Tout  Pout 
 


 ; Pin  lbf/ft 2 ; Qin  ft 3 /min

C C  ;
p v Tin  Pin 
BITS Pilani, Pilani Campus
CHE F314 Process Design Principles I

Contd..

Efficiency
• For first design, assume compressor efficiency of
90% to account for fluid friction in suction and
discharge ports, valves, fluid turbulence etc.
• Also, assume, driver efficiency of 90% to account
for the conversion of the input energy to shaft work

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

Installed and Purchased Costs

of Compressor
M &S
Installed cost of compressor, $  (517.5)(bhp) 0.82 (2.11  FC )
280

hp
where, bhp 


For centrifugal compressor FC = 1.0

M &S
Purchased cost of compressor, $  (517.5)(bhp ) 0.82 ( FC )
280

BITS Pilani, Pilani Campus

CHE F314 Process Design Principles I

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CHE F314 Process Design Principles I

Recycle Material Balances:

Other Reactants
• After estimating the limiting reactant
– the specified molar ratio at the reactor inlet is used to
calculate the recycle flows of the other components
• For example, in HDA process:
Total amount of H 2entering the reactor  Fresh feed H 2  Recycle H 2
 yFH FG  y PH RG

FFT
Amount of limiting reactant (Toluene) entering the reactor 
x
FH 2
Thus, Molar ratio H 2 to Toluene at reactor inlet  MR 
FT
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CHE F314 Process Design Principles I

Contd..

• Thus,
 MRFT  MR
FFT
FH 2
x
 FFT   PB   PB 
y FH FG  y PH RG  MR   MR ;   FFT  
 x   Sx   S 

  1  S  From Input-output
1  1  y PH 
PB
FG    structure of HDA
S  y FH  y PH    2  case study

PB  MR y FH 
RG      f ( x, y PH , MR)
SyPH  x y FH  y PH 
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CHE F314 Process Design Principles I

Level-3 Decisions: 5. Reactor

Heat Effects
• A decision needs to be made whether the reactor
can be operated
1. adiabatically (without heat entering or leaving), or
2. with direct heating or cooling, or
3. whether a heat carrier is needed
• We need to introduce an extraneous component as
a heat carrier
– Then our recycle material balances, and overall material
balances will have to be changed

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CHE F314 Process Design Principles I

Contd..

– Moreover, we need to make this decision

• before specifying the separation system
• because it will affect the design of separation system

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CHE F314 Process Design Principles I

Reactor Heat Load

• For single reactions all fresh feed of limiting

reactant gets converted in the process (if per pass
conversion is low, then large recycle is favored)
Reactor Heat Load  Heat of Reaction  Fresh Feed Rate

• For HDA case study, QR  H R   FFT

(∆HR) = negative for exothermic reactions

(∆HR) = positive for endothermic reactions

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CHE F314 Process Design Principles I

Contd..

• For complex reactions

– The extent of each reaction will depend
• On design variables (such as x, MR (mole ratio), T and/or P)

– Once we select the design variables, the extent of each

reaction and the heat load corresponding to the side
reactions can be calculated

– Hence, it is a simple matter to calculate the reactor heat

loads as a function of design variables

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CHE F314 Process Design Principles I

Adiabatic Temperature
Changeontd..
• Adiabatic temperature change
– Once, we know the reactor heat load (QR), and the flow
rate through the reactor (F) as a function of design
variables
– The adiabatic temperature change can be calculated by
using the equation

QR  FCp TR,in  TR,out 

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CHE F314 Process Design Principles I

Adiabatic Temperature
Change in HDA Case Study
• Ex. HDA process (if the amount of diphenyl
produced is very small)

• The flows and heat capacities of the reactor feed

stream for a case where Conversion (x) = 0.75
and yPH= 0.4 are given below:
– ΔHR (at 1200 0F) = -21, 350 Btu/mol
– CpH2= 7 Btu/mol.oF , CpCH4= 10.1 Btu/mol.oF, CpToluene=
48.7 Btu/mol.oF, PB= 265 mol/hr
Calculate adiabatic temperature change (TR,out).

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CHE F314 Process Design Principles I

Contd..

• We can neglect the second reaction (since the

amount of diphenyl produced is very small)

Table: HDA Case Study: Stream flow rate and Cp values

(10.1)=7.16

48.7
48.7
Douglas, J. M. Conceptual Design of Chemical Processes, 1988, pp. 147
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CHE F314 Process Design Principles I

Contd..

• So heat load
QR  H R  FFT   21530 273  5.878 10 6 Btu/hr

QR  FC p TR ,in  TR ,out ; TR ,in  1150  F

QR  5.878 10 6
 273  9148.7  49671.6  33718.86 TR ,in  TR ,out 


TR ,out  1150  115  1265 F
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CHE F314 Process Design Principles I

Contd..

• This value is below the constraint on the reactor

exit temperature of 1300 0F
– (if TR,out>1300 0F hydrocracking takes place which is
undesirable)

• Calculation is not very sensitive to the Cp values or

to the flows

• The relatively small temperature rise (1265-1150 =

115 0F) is due to the large gas recycle flow which
contains methane

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CHE F314 Process Design Principles I

Adiabatic Temperature
Change in IPA Case Study
IPA Process
• Acetone can be produced by dehydrogenation of
Isopropanol (IPA)
– (CH3)2CHOH → (CH3)2CO + H2
• If we desire to produce 51.3 mol/hr of acetone, then
51.3 mol/hr of IPA is required. The heat of reaction
at 570oF and 1 atm is 25,800 Btu/mol,
• So the reactor heat load is
Q• R positive
H Rand.FFTheatis25 ,800 
. 51.3  1.324 10 Btu/hr
6
consumed by the endothermic reaction

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CHE F314 Process Design Principles I

Contd..

• If the feed stream in IPA process is an IPA – H2O

mixture (Cp,mix= 22 Btu/mol)

• 22 mol/hr of H2O enters with the feed to the reactor

• The recycle stream contains 2.1 mol/hr of IPA and

0.9 mol/hr of water

• If reactor inlet temperature is 572 0F, what is the

outlet temperature of reactor?
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CHE F314 Process Design Principles I

Solution

• Using the reactor heat load values calculated

earlier,
Q R  1.324 10 6 Btu/hr  51.3  22.0  2.1  0.922.0272  TR ,out 

TR ,out  572  788  216 0 F

• Clearly, this is an unreasonable result
• Thus, instead of using an adiabatic reactor, we
attempt to achieve isothermal operation by
supplying the heat of the reaction to the process

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CHE F314 Process Design Principles I

Heuristic for Heat Loads

• For direct heating or cooling

If adiabatic operation is not feasible, as in IPA process,
then we attempt to use direct heating or cooling

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CHE F314 Process Design Principles I

Heuristic of Heat Loads:

Limitations
• There is a limit to the amount of heat transfer
surface area that we can fit into a reaction
• To get some ‘feeling’ for the magnitude of this area:
– case of a high temperature gas phase reaction and we
let U = 20 Btu/ (hr.ft2 .oF) and ΔT = 50oF
• Then for heat load of 1 x 106 Btu/hr

Q 110 6
A   1000 ft 2
UT (20)(50)

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CHE F314 Process Design Principles I

Contd..

• The maximum heat transfer area that fits into the

shell of a floating head heat exchanger in the
range of 6000- 8000 ft2

• Thus to use a single heat exchanger as a reactor,

when we are attempting to remove or supply the
heat of reaction by direct heating or cooling, the
reactor heat loads are limited to the range of
6.0 x 106 to 8.0 x 106 Btu/hr

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CHE F314 Process Design Principles I

Contd..

• Important Heuristic
For endothermic processes, with a heat load upto
8x106 Btu/hr, we use an isothermal reactor with direct
heating

• For larger heat load use heat carrier

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CHE F314 Process Design Principles I

Heat Carriers

• The reactor load is often fixed by the fresh feed

rate of the limiting reactant
• if only a small amount of by product is produced so that
the secondary reactions are unimportant
• The adiabatic temperature change depends
primarily on the flow through the reactor
• Hence, we can always moderate the temperature
change through the reactor by increasing the flow rate
• If we desire to moderate the temperature changes,
we prefer to do this by recycling more of a reactant
or recycling a product or by-product
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CHE F314 Process Design Principles I

Contd..

• However, where this is not possible, we may add

an extraneous component
• Addition of an extraneous component may make the
separation system more complex, and so we normally
try to avoid this situation

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CHE F314 Process Design Principles I

Contd..

• In HDA process, the methane in the gas recycle

stream (60% methane) acts as a heat carrier
• Thus, if we do not purify the H2-recycle stream
• If this exit temperature exceeded the constraint of
1300 0F, we would no longer use an adiabatic
reactor
• Instead, we would have to cool the reactor, increase the
H2 recycle flow, or introduce an extraneous component
as a heat carrier

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CHE F314 Process Design Principles I

Problem

Ethanol is produced via hydration of ethylene by the following

reactions. C 2 H 4  H 2 O  C 2 H 5 OH
2C 2 H 5 OH  (C 2 H 5 ) 2 O  H 2 O
The reactions take place in the batch reactor at 3000 C and 882 psia.
The production rate of ethanol is 200 moles per hour. The feed of
ethylene is 98% pure containing 2% methane as an inert. Assume
cost of process steam is negligible and diethyl ether is completely
recycled back. Develop the recycle structure for ethanol production
process and calculate the stream flow rates (inputs, outputs, recycle
flows, reactor inlet) in terms of design variables. Selectively is
defined as moles of Ethanol produced per mole of ethylene
converted.
Given Data: The boiling points of ethylene, water, ethanol, diethyl ether,
and methane are – 103.4 oC, 100 oC, 78.4 oC, 34.6 oC and – 161 oC
respectively.
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CHE F314 Process Design Principles I

Thank You

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