BITS Pilani

Pilani Campus

Module 2: Flowsheet synthesis

Lecture-6
Input - Output & Recycle structure of flowsheet
Course: Process Plant Design CE 1705/1701

Nandana Chakinala
Department of Chemical Engineering
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
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)
Contd..

• Selectivity can be defined as,

moles of desired product 1 − 2 2

S= =
moles of limiting reactant converted 1

4
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
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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 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)
EP at level -2 of design is the annual profit if there are no capital costs and no
utilities cost
EP if negative indicates non-profitable
Alternate raw material or alternate process itself with different chemistry

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

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 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)

At higher per pass conversion, process is unprofitable

At high purge compositions, we lose money
8
Decisions for HDA

Not to purify H2 feed stream

To remove diphenyl from process
To use gas recycle and purge streams

Alternatives can be generated if any of these decisions change

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Production of Cyclohexane:
Case Study
Cyclohexane is produced by following reaction:
C6H6 + 3 H2 ↔ C6H12 at 392oF and 370 Psia

Benzene used in the feed is pure, but the hydrogen stream

contains 2% methane. The desired production rate is 100
mol/hr and the costs are:
C6H6 = Rs. 260/mol, H2 = Rs. 52.8 /mol, C6H12 = Rs. 481.20
/mol and fuel at Rs. 160 /106 Btu. The fuel value for H2 and
CH4 are 0.123 x 106 Btu/mol and 0.383 x 106 Btu/mol
respectively.
Draw the input-output flow sheet and plot the economic
potential for various parametric values of purge composition.
10
Solution: Input-Output
Flowsheet

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Fresh Feed Rate of Benzene

12
Hydrogen Balance

13
Methane Balance

14
EP-2

15
Contd..

• We can get EP-2 as a function of x and ypH

• Fix ypH at 0.1 (Case I), 0.7 (Case II) and 0.9 (Case III)
CASE-I

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Contd..

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EP-2 at ypH =0.1

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 EP-2 vs x

50000

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-50000

-100000

EP-2 -150000
(Rs./yr)
-200000

-250000

-300000

-350000
Conversion, x

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 BITS Pilani
Pilani Campus

Module 2: Flowsheet synthesis

Lecture-6
Recycle structure of flowsheet
Course: Process Plant Design CE 1705/1701

Nandana Chakinala
Department of Chemical Engineering
 Recycle structure
Product distribution as a function of conversion
Reactor design governs the extent of reaction or conversion and thus
influences the recycle structure
Gas recycle – needs expensive equipment with high operating cost

Decisions that govern recycle structure

1. How many reactor systems required? Should there be separation in b/w?
2. No of recycle streams?
3. Should excess reactant be used at reactor inlet?
4. Gas compressor required? Its capacity and capital cost?
5. Mode of operation? Isothermal/Adiabatic or direct heating/cooling, heat
diluent required?
6. How to shift equilibrium conversion?
7. How do reactor cost effect EP?

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 Example : Acetic anhydride mfg.

• We need two reactors for this process

• Associate feed streams with reactor number
• Associate components in recycle stream to reactor number
• No of recycle streams: Same thumb rule as in case of no of product streams
NEVER SEPARATE TWO COMPONENTS AND REMIX THEM (AT REACTOR
INLET)
• How to decide no of streams?
– Determine phase of the component – can be identified from B.P – Determine destination
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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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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Contd..

Example: HDA Process

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

25
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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2. No of recycle streams
Component Destination NBP (oC)
H2 Recycle or purge -213
CH4 Recycle or purge -161
Toluene Recycle to reactor 110
Benzene Primary product 80
Diphenyl Full by-product 265
Acetone Recycle-R1
Acetic acid Recycle-R2
Acetic anhydride Primary product
CO, CH4, C2H4 Fuel by-products

2 product streams 2 recycle and 2 product streams

2 recycle streams
1 purge stream

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3. Excess reactants
Production of isooctane

▪ Isobutane fed in excess to improve selectivity towards

isooctane formation
▪ The larger the excess, the higher the selectivity
▪ Recovery and recycle of isobutane becomes cost
intensive. Therefore, determination of optimum excess is
essential

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3. Excess reactants
HDA
▪ H2 fed in excess
▪ Forces higher conversion of toluene
▪ Supresses diphenyl formation
▪ Burning of coke deposited on reactor wall due to thermal decomposition
▪ Helps limit the T surge

Phosgene manufacture CO +Cl2 → COCl2

CO fed in excess to force Cl2 to conversion

Cyclohexane manufacture
Excess of H2 to force conversion of benzene to completion

Bottom line: Molar ratio of reactants becomes an important design variable.

“Excess” has an optimum.
No thumb rules Heat effects → Equilibrium limitation
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Material balance with recycle streams

In this case, we assume complete recovery and recycle of limiting

reactant
In some cases, limiting reactant may leave with the product or purge,
hence we slightly modify material balance. The general relation b/w
total feed30of limiting reactant and fresh feed remains same
CE 1705/1701 Process Plant Design

Ethanol mfg

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 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 2 entering the reactor = Fresh feed H 2 + Recycle H 2
= y FH 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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Contd..

• Thus,
= (MR)FT = (MR)
FFT
FH 2
x

 FFT   PB   PB 
y FH FG + y PH RG = MR  = MR ;   FFT = 
 x   Sx   S 

PB  MR y PH 
RG =  −  = f ( x, y PH , MR)
SxyPH  x y FH − y PH 

34
Recycle Material Balances:
Recycle By-products
• If we recycle a by-product formed by a reversible
reaction
– and let the component build up to its equilibrium level
– such as Diphenyl in HDA process
2 Benzene ↔ Diphenyl + H2
– Then, we find the recycle flow by using the equilibrium
relationship at the reactor exit
– At the reactor exit, K = (Diphenyl )(H 2 )
eq
(Benzene )2
– H2 and Benzene flows have been determined by using
the first reaction and the purge calculations
35
Contd..

• So we can use the equilibrium expression to calculate

the Diphenyl flow at the reactor exit

36
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
– Moreover, we need to make this decision
• before specifying the separation system
• because it will affect the design of separation system
37
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

38
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

39
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 )

40
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).

41
Contd..

PB 265
FFT = = = 273 mol/hr
x 0.75
• 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
42
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

43
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

44
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 = H R .FFT = (25,800 )(
. 51.3) = 1.324 10 6 Btu/hr
• positive and heat is consumed by the endothermic reaction

45
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?
46
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

47
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

48
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)

49
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

50
Important Heuristics
• 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

• For exothermic processes, we use an adiabatic

reactor if the Adiabatic Temperature Rise is less than
10-15% of the inlet temperature
• If the Adiabatic Temperature Rise exceeds this value,
we use direct cooling if the reactor heat load is less
than 8x106 Btu/hr
• Otherwise, we introduce a diluent or a heat carrier

51
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
52
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

53
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

54
Equilibrium Limitations

• In numerous industrial processes, equilibrium

limitations are important
• Equilibrium Conversion
– We can use our previous procedure for calculating the
process flows as a function of the design variables
(conversion, molar ration of reactant etc)

– Substitute these flows into the equilibrium relationship to

see whether the conversion we selected is above or
below the equilibrium values

55
Contd..

• Necessary to determine the exact values of the

equilibrium conversion (as a function of the design
variables)

56
Case Study: HDA

57
Reactor heat effect: Isothermal or adiabatic?

Reactants enter at 1150oF

Per pass conversion 75% yPH = 0.4 Component Cp (Btu/mol oF)
Reactor effluent H2 7
benzene: 265 mol/h
CH4 10.1
Toluene: 91 mol/h → Toluene 273 mo/h
Toluene 48.7
Diphenyl: 4 mol/h
Make up gas : 496 mol/h
Recycle gas: 3371 mol/h
Now do a heat balance
Q = mCp∆T

58
Reactor heat effect: Isothermal or adiabatic?

Tout = 1265oF which is within the limits of 1150-1300oF

Max T reached is 1265oF if reactor is operated adiabatically
we have not considered here the various loses that occur
due to radiation, convection, so on and so forth

59
Reactor heat effect: Isothermal or adiabatic?

In some cases heat is to be supplied

Eg: Dehydrogenation of isopropanol to acetone
• Heat of reaction 25800 Btu/mol
• Rate of production of acetone=51.3 mol/h
• Heat required to be supplied to reactor = 1.324 MMBtu/hr
• Entry T of reactants (Fresh + Recycle) = 576oF

Fixed Bed

Reactor Design Moving bed Bubbling bed

Fluidized Bed
Circulating
fluid bed

60
Reactor heat effect: Isothermal or adiabatic?

If reactor is fixed bed, typical heat transfer area = 6000-8000ft2

𝑄 = 𝑈𝐴∆𝑇
LMTD
Overall HT coeff.

Reactor being vapor phase U = 20 Btu/hr.ft2.oF

Assume ∆T = 50oF, Q = 1 MMBtu
A = 1000ft2
Total heat duty in a reactor = 6-8 MMBtu
This helps in determining molar flow rates of limiting reactants
HDA process, Q = -5.8 MMBtu which implies single reactor
However, the amount of reactant that can be processed in the
single reactor is limited by the heat of reaction
61
Heat carriers
▪ The reactor heat load is fixed by fresh feed rate of limiting
reactants.
▪ Now, if the other reactants is fed in excess then we have a
very large amount of unreacted reactant at the reactor outlet
▪ Control of T can be achieved by recycling of unreacted
reactant or by-product
▪ Addition of extraneous component

Eg: Oxidation systems → N2 as inert

HDA process → Methane

62
 Thank You

63