Chapter 6

Principles of Chemical Engineering Processes

By the end of this chapter you should

be able to:
Drawandlabelaprocessflowsheetforproblems

involverecycle,bypassandpurge.
Explainthepurposeofarecyclestream,abypass
stream,andapurgestream.
Usethesinglepassandoverallconversioninsolving
recycleproblemsinvolvingchemicalreactions.
Writeasetofindependentmaterialbalancesfora
complexprocessinvolvingchemicalreactionsand
morethanoneunit.
Solveproblemsinvolvingmultiplesystems.
Principles of Chemical Engineering Processes

A recycle stream is introduced to recover

and reuse unreacted reactants.
Two definition of reactant conversion
are used in the analysis of chemical
reactors with product separation and
recycle the unconsumed reactants.

Principles of Chemical Engineering Processes

Figure 6.1 Single pass and overall conversion

in the presence of recycle

OverallConversion

reactant input to process reactant output from process

reactant input to process

reactantinput to reactor reactantoutputfromreactor

Single- PassConversion
reactantinput to reactor
Principles of Chemical Engineering Processes

Problem that can occur in processes that involve recycle

Material that enters the process in feed stream may remain entirely in it.
To prevent this
Portion of recycle stream is withdrawn as purge stream( simple splitter in flowchart)

Purge stream bleeds material out of recycle stream

The accumulation is avoided

Remark : the purge point have the same composition and only one independent
material balance.

Principles of Chemical Engineering

Processes

Figure 6.2 Single pass and overall conversion

in the presence of recycle and purge

Principles of Chemical Engineering Processes

Figure below Shows a process flow sheet where unreacted

compounds are recycled for further processing.

Principles of Chemical Engineering

Processes

Example: polyethylene production

Nitrogen in the feed in the polyethylene reactor is inert and is used as a

diluents carrier gas for the ethylene and comonomers.

Principles of Chemical Engineering Processes

Example 6.1 Methanol production

CO2 +3H2

CH3OH +H2O

The fresh feed to the process contains H2 , CO2 and -.4 mole % inerts(I). The
reactor effuent passes to a condenser that removes essentially all the
methanol and water formed and none of the reactants or inerts. The latter
substances are recycled to the reactor. To avoid buildup of the inerts in the
system, a purge stream is withdrawn from the recycle. The feed to the
reactor (not the fresh feed to the process).Contains 28 mole% CO2 , 70 mole
% H2, and 2 mole % inerts. The single-pass coversion of H2 is 60%.
Calculate the molar flow rates and molar compositions of fresh feed, the total
feed to the reactor, the recycle stream, and the purge streams for a methanol
production rate of 155 mol CH3OH /h.

Principles of Chemical Engineering

Processes

This figure explains example 6.1

Methanol production process flow sheet

10

Principles of Chemical Engineering

Processes

Systems
Mixing

Reactor Condenser

Overall
process

Number of unknowns

6+1

7+1

Number of independent
equation

Number of auxiliary relations

Df

Degree of freedom Analysis

11

Principles of Chemical Engineering

Processes

Basis: 100 mole of feed to the rector

System :reactor
CO2 +3H2

CH3OH +H2O

Material balance uasing the extent of reaction approach:

nCO2,2 = 0.28(100)
nH2,2 =0.7(100) - 3
nCH3OH,2 =0.0 +
nH2O,2 =0.0 +
nI,2 = nI,1 = 0,012(100)
Knowing the conversion,
0.6 = (0.7(100)-nCO2,2)/0.28(100)

12

Principles of Chemical Engineering

Processes

SolutionusingEZSolve
nCO2,2 = 22.4 mol nH2,2 =53.2 mole
nH2O,2 = 5.6 mole nI,2 = 2 mole

nCH3OH,2 = 5.6 mole

= 5.6 mole

This figure shows the results algebraic material balance equations.

Principles of Chemical Engineering Processes

13

Scaling up
nCO2,2 = nCO2,4 = 22.4 mole
nH2,2 = nH2,4 = 53.2 mole
nI,2 = nI,4 = 2 mole
nCH3OH,2 = nCH3OH,3 = 5.6 mole
nH2O,2 = nH2O,3 = 5.6 mole

The composition of the recycle and purge

XCO2,4 = XCO2,5 = XCO2,6 = 22.4/ (22.4 +53.2+2)= 0.29
XH2,4 = XH2,5 = XH2,6 = 53.2/ (22.4 +53.2 +2) = 0.685
XI,4

= XI,5

= XI,6 = 2/ (22.4+53.2+2)= 0.025

Principles of Chemical Engineering Processes

14

BALANCE AROUND THE MIXING POINT

Total balance: nCO2,2 + n6 = 100
Inter balance : 0.004 x n0 + 0.025 x n6 =0.02 x100
The answer can be rounded as: n0 = 23.8 mole, n6 = 76.2 mole
Other component can be determined as follows
nCO2,0 + 0.029 x 76.2 = 0.28 x 100
nH2, 0 + 0.685 x 76.2 = 0.7 x 100
nCO2,0 = 5.9 mole , nH2, 0 = 17.8 mole nI,0 = 0.095 mole

Amount of fresh feed required to produce 155 mole of methanol

155 mole CH 3OH produced

23.8 mole of fresh feed

658.75 mole of fresh feed
5.6 mole of CH 3OH produced

A fresh feed of 658.75 mole/h id required to produce 155 mole/h

Principles of Chemical Engineering Processes

15

 In solving problems where multiple-unit steady state processes involve

chemical reaction:

1. Some system contain reaction ands some wont , in this case:

Use individual component flows around the reactor not composition.
Include stoichiomertry and generation /consumption on molar

balances.
In subsystems without reaction (such as mixers, splitter and separators):

Input= output (moles are conserved, no generation/consumption terms).

More flexibility as to stream specification (component flows or composition).

2. Reactions combined with product separation and recycle:

recycle stream is introduced to recover and reuse unreacted

reactants.

Recycle allows operation of reactor at low single-pass conversion, and

have a high overall conversion for the system.
Principles of Chemical Engineering Processes

16

3. Subsystem involving reactions with recycle and purge:

The purge is introduced to prevent build of inerts ( or incompletely

separated products) in the system.

purge point is a simple splitter, only one independent material

balance does exist.

Principles of Chemical Engineering Processes

17

Example 6.2 Ammonia synthesis

N2 +3H2

2NH3

Nitrogen gas and hydrogen gas are fed to a reactor in stoichiometric quantities
to react to from ammonia. The conversion of nitrogen to ammonia is to
ammonia is 25%. How much nitrogen is required to make 100 metric tons/day
of ammonia?
Note that the inlet mole of nitrogen and hydrogen are in stoichiometric
quantities
N 2 in 1

H 2 in 3
18

Principles of Chemical Engineering

Processes

This figure explains example 6.2

Ammonia synthesis reactor

Principles of Chemical Engineering Processes

19

The basis of 100 tones/day of ammonia

Since we have a chemical reaction
Covert to moles

tonnes 103 kg kgmol NH 3

100
5882 kgmol NH 3
day tonne 17 kgNH 3
moles N 2CONVERTED moles N 2 IN moles N 2OUT

Conversion X A
moles N 2 IN
moles N 2 IN
2.

vfrom the problem statement we knowing that 25% of the entering nitrogen
has been converted to ammonia. Knowing the definition of conversion to be:

5882
0.25

kgmol NH 3 kgmol N 2
day
2kgmol NH 3
n1
x N 2 n1

Principles of Chemical Engineering Processes

20

Sincestream1ispurenitrogen,hencexN 1.0
2

n 1 11 , 764

kgmol N 2
day

m 1 11 , 764

kgmol

m 2 35,292

2
2

N tonne
kgmol N 10 kg
28 kg

day

n2 1kmol H
N
3kmol

329

tonne

day

11,764kmol N 2
kmol H 2 fed
x[
] n
35,292

2
fed
day
day
fed

kmol H 2 fed

2kgH

day

1kmol

tonnes H 2
1tonne
70.584
1000 kg
day

Principles of Chemical Engineering Processes

21

since the single pass in the previous example was wasteful,

separation of the product stream and recycling the unwanted

gases will be drawn.
Amount of nitrogen and mass flow rate of the recycle stream
should be known.

Principles of Chemical Engineering Processes

Figure E6.3a Ammonia synthesis with recycle

22

 Basis of 100 tons/day will be used.

Conversion of mass to moles should be done here also

because there is a chemical reaction taking place to get

5882 kmol nitrogen per day.
The method of solving the system here was the analysis of
the degree of freedom.
Let us start by zero degree of freedom.

Principles of Chemical Engineering Processes

23

Degree of freedom Analysis

Systems within control volume
Degree of freedom Analysis

Reactor

Distillation
Column

Overall
process

Number of unknowns

7+1()

2+1()

Number of independent equation

Number of auxiliary relations

Df

24

Principles of Chemical Engineering

Processes

 Since the control volume above includes a chemical reaction, the number

of moles may not be conserved and switch from one molecule to another.
Mass in= mass out
Atoms in = atoms out
Overall atomic balance:

x N 2 n1 x N 2 n2 x N 2 n4 ;

x N 2 n2 0

x N 2 n1 x N 2 n4
1.0n1 (1.0)5882
2941

kgmol NH 3 kgmol N 2
kgmol N 2
2941
day
day
2kgmol NH 3

kgmol N 2 28kg N 2 tonne

tonne N 2

82
.
3
day kgmol N 2 103 kg
day
25

Principles of Chemical Engineering

Processes

 It has been known that 25% of the entering nitrogen

has been converted to ammonia. Knowing the

definition of conversion to be:
Conversion=

xA

molesN 2 reacted molesN 2 fed molesN 2out

molesN 2 fed
molesN 2 fed

0 . 25

n 1 X
X

n R X

n 1 X

kgmolN
day
0 . 25
kgmolN
2941
day

2941

Rearranging:

x
N

n 3

n R
n R X

n 3

n R

So far, two unknowns are present if the equation

Another independent equation will be the nitrogen balance in the separator.
No reactions in the separator so moles are conserved.
26

Principles of Chemical Engineering

Processes

x N 2 n3 x N 2 n4 x N 2 n R ; x N 2 n4 0
x N 2 n3 x N 2 n R
By substituting 2 in 1 and solve:
.

kgmolN 2
R x N n R
2941
xN n
2
2
day
0 . 25
kgmolN 2
2941
x N n R
2
day

2941
0 . 25
2941

kgmolN
day

kgmolN
day

x n R
N2

x n R 8823
N2

8823

kgmolN
day

kgmolN 2 28kgN 2 tonne

tonneN 2

247
day kgmolN 2 103
day
27

Principles of Chemical Engineering

Processes

 Hydrogen is fed stoichiometrically so the amount of

hydrogen fed is 3 times greater than the amount of

nitrogen in every stream.
3 xN

n R x n R
H2

kgmolN 2
kgmolH 2
3x8823
24,469
day
day
26,469

kgmolH 2 2kgN 2 tonne

tonneH 2

52
.
9
day kgmolN 2 103
day

tonneH2
tonneN2
ton
52.9
247
300
day
day
day
28

Principles of Chemical Engineering

Processes

Example 6.4 Ammonia reaction with inert in the

feed stream

1.
2.

Suppose that nitrogen stream in the previous example has 0.2%

argon as an impurity.
With recycling only the argon concentration will build up and block
the reaction.
A purification should take place to maintain a 0.7% of argon in the
recycle stream.

Draw the process flow sheet and choose the basis.

Perform balances around: Overall system, separator, reactor and
splitter.
Principles of Chemical Engineering Processes

29

Figure E6.4a blow Ammonia synthesis process with

Argon (Ar) in the nitrogen stream

The basis chosen was 100ton/day of ammonia which converts

5882 kgmol/day of ammonia.

Principles of Chemical Engineering Processes

30

Degree of freedom Analysis

Systemswithincontrolvolume
DegreeoffreedomAnalysis

Reactor

Separator

Splitt
er

Overall
process

Numberofunknowns

9+1()

3+1()

Numberofindependent
equation

Numberofauxiliary
relations

1(conversion) 1

Df

31

Principles of Chemical Engineering

Processes

x
x

N2

NH 3

Ar

x H x Ar x NH 1.0
2

0 in stream R

0 . 07 in stream R

3 xN
2

H2

Solving:

N2

3 x N 0.07 1.0, x N 0.2325,3 x N xH 0.697

2

32

Principles of Chemical Engineering

Processes

 Since stream 5 splits into R and P where the composition is the

same in all streams.

We will start by balancing the system since the composition of
streams 1,2,4 and P are known and the DOF is 0.

Figure E6.4b Ammonia synthesis process with recycle and

purge (system
: overall
process
) Processes
Principles
of Chemical
Engineering

33

 Three unknowns are present, therefore three independent equations can

be written to solve the molar flow rates of 1,2 and P.

Individual or overall atom balances can be also written for N, H and Ar.
Overall atomic balances for the system:
Ar balance
n
n
n
n
x

Ar

Ar

n 4

n 2 x H n 4
Simplification of the above equations
Argon atomic balance

N balance

Ar

n 1

x
x

x n 2 x

Ar

n 4

Ar

x n 2 0 and
Ar

n 2 x

Ar

n 1

H balance

x n 1

x Ar n 4

x n P
Ar

x Ar n 1 x Ar n P

0.002n1 0.07
n
34 P

Principles of Chemical Engineering

Processes

Ar

Nitrogen atomic balance:

x N 2 n1 x N 2 n2 x NH 3 n4 N 2 / 2 NH 3 x N 2 n P

x N 2 n 2 0
x N 2 n 1 x NH 3 n 4 N 2 / 2 NH

x N 2 n P

0.998n1 5882kgmol NH3 N2 / 2 NH3 0.233nP

Principles of Chemical Engineering Processes

35

Hydrogen atomic balance

x n 2
H

1 . 000

n 2

0 . 998

n1

NH

n 4 ( 3 H

3)

2 NH

5882 kgmol

NH

5882 kgmol NH

x n P
H

3 H 2

3 H

/ 2 NH

/ 2 NH

0 . 697 n P

0 . 233 ( 00. .002

) n
1
07

0 . 002
n 1 0 . 998 0 . 233
5882 kgmol
0
.
07

NH

N
2 NH

n 1

2967

kgmol
day

Then by substituting the flow rate of 1 in equation 1 and the results in equation 3:
1 . 000

n 2 5882 kgmol

0 . 002 [ 2967

NH

kgmol
] 0 . 07
day

3H
2 NH

2
3

kgmol
0 . 697 84 . 8
day

84 . 8

kgmol
day

Principles of Chemical Engineering Processes

36

 Streams 3,5 and R should be solved also.

The following figure shows the control volume around the

separator. The borders of the control volume crosses

streams 3 and R.
No chemical reaction so moles are conserved.
Nitrogen balance:

x n3 x n 4 x n p x n R
N2

N2

N2

N2

x n4 0
N2

kgmol
x N 2 n 3 0 . 233 84 . 8
n R
day

37

Principles of Chemical Engineering

Processes

Figure E6.4c Ammonia synthesis process (system

: distillation column

Principles of Chemical Engineering Processes

38

 The last equations has three unknowns so four other equations are

needed.
We can write the molecular formulas for nitrogen, hydrogen, argon and
ammonia.
Hydrogen balance:

x H 2 n3 x H 2 n 4 x H 2 n P x H 2 n R , x H 2 n 4 0
84 . 8 kmol
x H 2 n 3 0 . 697
day

n R

X Ar n3 X Ar n 4 X Ar n P X Ar n R , x Ar n 4 0
Argon balance:

kmol
n R
x Ar n 3 0 .07 84 .8
day

NH3 balance:

x n
R
n3 xof Chemical
n 4 Engineering
x Principles
x n P Processes
NH 3

NH 3

NH 3

NH 3

39