Mass & Energy Balance

CheEng HCMUT

MATERIAL BALANCES WITH MULTIPLE-UNIT PROCESSES

Reference: Chapters 4.4 to 4.5 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical
Processes, 3rd ed. 2005 (Wiley).
A typical chemical engineering process contains more than a single piece of equipment or unit
operation

The law of conservation of mass still holds for multiple-unit processes.

Material balance problems are best attacked by dividing whole process into sub-systems
Output
Input
Sub-systems
Streams
Streams

Only consider streams crossing the system boundary or control volume

Material balance calculations are needed over as many sub-systems as necessary to determine
the unknown variables

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Important Notes
1. Basis

a basis of calculation should be chosen, which may be general to the whole process or specific to a
sub-system

if different bases are used for different sub-systems, results must be converted to the appropriate
basis

it may be necessary to use a global or common basis for the whole process to facilitate conversion
from sub-system bases

2. Selection of Sub-Systems for Calculations

an overall balance on the entire process helps identify unknown process streams and indicate which
sub-systems to select

sub-systems chosen should be based on those process units which involve as few unknown
variables as possible

3. Common Sub-Systems
Mixing Point (Mixer)
composition of stream C is not necessary the same as that of A or B
a mixing point is considered as a sub-system

Separation Point (Splitter)

composition of streams B & C is same A

considered as a sub-system

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Evaporator
water 100%
2
solid 40%

solid 80%

water 60%

water 20%
Evaporator
3

Condenser
air 98%
water 2%

air 40%
water 60%
Condenser

water 100%

Absorber
Inlet liquid stream

Outlet gas stream

Absorber

Inlet gas stream

Outlet liquid stream

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Total Condenser

D (Distillate) and R (Reflux) are liquid with same

composition

D and R have same composition as vapour V

Partial Condenser

D is vapour, R is liquid, both having different

compositions and different from V

Total Reboiler

B (Bottoms) and L are liquid with same

S is vapour with same composition as L

composition

Partial Reboiler

L is liquid, B is liquid, S is vapour

L, B and S have different compositions

RECYCLE

Part of product is returned and mixed with fresh feed, or put back to some earlier stage

Main reasons: recovery of catalyst, dilution of a process stream (slurry process), control of a process
variable and circulation of a working fluid (see page 112 of textbook for more information).

Overall aim: to improve efficiency of a unit operation within process.

EXAMPLE - Chemical reactor

Why recycle in this process? To recover unreacted material

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EXAMPLE Distillation

Why recycle in this distillation column?

Recycled liquid (Reflux) and recycled vapour (Reboil) maintain continuous flows of liquid and vapour
in the column.

High reflux ratio (=reflux/distillate) high purity of products

MASS BALANCE CALCULATIONS INVOLVING RECYCLE

Recycled material

Feed

Process

Separation

Net Product

The steady-state condition of the process is maintained: no accumulation takes place inside system
due to recycle stream.

Recycle stream is treated as any other process stream

A combined feed is made up of the fresh feed and the recycled material

The gross product leaving system consists of the net product and the recycle

PURGE

Used to prevent inerts or unwanted material from accumulating in the recycle stream
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BYPASS

A fraction of the feed to a process unit is diverted around the unit and combined with the output stream
from the unit (i.e., bypass stream skips one or more stages)
By varying the fraction of the feed that is bypassed, we can vary the composition and properties of the
product.
e.g. used when only a small change of the feed is desired, ie product not drastically different from feed

THE SYSTEM BOUNDARY

A system boundary is an arbitrary line we draw around a region of interest.
We can place the system boundary wherever is most appropriate to suit our purposes. We might draw the
system boundary around a whole process, or we might draw system boundaries around different sections
of a process - in the latter case the overall system would be composed of a number of subsystems.

(Figure 4.4-1, page 105)

EXAMPLE
Problem statement: A waste treatment plant operating under steady-state conditions processes an
aqueous waste liquor containing 500 ppm of a noxious impurity. The impurity is removed with practically no
loss of water. The treating process can remove the impurity down to a level of 10 ppm. By local ordinance,
a maximum of 100 ppm is allowed in the discharge of the processed effluent to a nearby river. You have
been asked to calculate the fraction of the waste liquor that must be sent through the waste treatment unit,
and the fraction that can be bypassed. Draw a fully labelled block diagram of the process and analyze the
system.

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Block diagram:
Your first task is to work out the basic structure of the block diagram. Note that the description does not
give a detailed description of streams and processing units. You will need to use your judgement. However,
it should be clear that you have an aqueous waste liquor and that some of it passes through a waste
treatment unit, and some of it is bypassed. It is implicit in the problem statement that these two streams are
mixed together before they are discharged into the river. Also don't forget that you were told that the
impurity is removed from the waste liquor in the treating process. Therefore you should be able to draw the
following structure

To finish the block diagram you need to annotate it. You are told that the waste liquor contains 500 ppm
impurity. Since it is aqueous, it will also contain water. There is no indication in the problem statement that
the waste liquor contains anything other than impurity and water. Note that the flow splitter simply sends a
fraction of the flow one way and the remainder the other - so both of the streams exiting the flow splitter will
also have 500 ppm of impurity. You are told that the treatment unit can remove the impurity with practically
no loss of water, so you can label the waste impurity stream (W) as 100% impurity. You are also told that
the treated water contains 10 ppm impurity, and that the final discharge contains 100 ppm impurity.
Therefore the fully annotated block diagram will look like this:

Analysis of system
the system consists of three subsystems - the flow splitter, the treatment process and the mixer
there are six streams - their compositions are shown on the block diagram
the system boundaries are the walls of the vessels - they are real and rigid
material flows into and out of each subsystem so all subsystems are open
the process description indicates it is continuous - all subsystems are continuous
the process description says that it operates at steady-state - therefore there will be no accumulation of
either water or impurity in any of the processing units over time.
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HOW TO DETERMINE THE NUMBER OF INDEPENDENT EQUATIONS (NE) FOR MULTIPLE-UNIT

PROCESSES
1.

if there are C common components and N independent process units, then

NE = N.C

2.

if the number of components is not the same in all N process units, then, in general

where (NE,i) is number of independent equations for process unit i.

EXAMPLE Determine the number of independent equations for the process below

F =100 kg

P ? kg

xA = 0.5

xA = 0.9

xB = 0.5

xB = 0.1

Q ? kg
xA = 0.2
xB = 0.8
Solution:
N = 3; C = 2; Hence NE = 3 x 2 = 6
Balance on individual system
Overall system:

Sub-system #2:

F.xA,F = P. xA,P + Q. xA,Q

(1)

J. xA,J = Q. xA,Q + K. xA,K

(5)

F.xB,F = P. xB,P + Q. xB,Q

(2)

J. xB,J = Q. xB,Q + K.xB,K

(6)

Sub-system #1:

Sub-system #3:

F. xA,F = I. xA,I + J. xA,J

(3)

I. xA,I + K. xA,K = P. xA,P

F. xB,F = I. xB,I + J. xB,J

(4)

I. xB,I + K. xB,K = P. xB,P (8)

Only 6 equations are independent

(7)

can solve for 6 unknown variables

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PROBLEM EXAMPLE 1 - Mass Balance on Multiple-Unit Process

A waste gas containing 98.5 mole% air and 1.5% acetone (CH3COCH3) is scrubbed at a rate of 250 kmol/h
with clean water supplied at 1200 kg/h. In the absorber, the acetone in the gas is completely absorbed into
the water, producing only air in the exit gas. The liquid output from the absorber is pumped to a still
whereby partial evaporation occurs. The overhead vapour from the still containing 99 wt% acetone is
completely condensed in a condenser. The bottom liquid from the still contains 5 wt% acetone and is
removed as waste.
Calculate the flow rates (in kg/h) and compositions of all process streams.
Solution:
(1),(2),(3)
100% Air

% Ac ?
% H2O ?

Condenser

S3?

S7?

S1 = 1200 kg/h
Absorber

99 wt% Ac
1 wt% H2O

S6?

100% H2O
S4?

S2 = 250 kmol/h

Still

1.5 mole% Ac

% Ac ?

98.5 mole% Air

% H2O?

S5?
5 wt% Ac
95 wt% H2O

(4) Convert S2 stream from mole fraction to mass fraction

Basis: 100 mol waste gas (F)
Component

mol

MW

gram

wt%

Acetone

1.5

58

87

3.0

Air

98.5

29

2857

97.0

Total

100.0

2944

100.0

Average MW of waste gas = 29.44 g/mol

Also, since stream S6 has same composition as S7
Acetone:

yacetone,S7 = 0.99

Water:

ywater,S7= 0.01

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(5)

Basis : 1 hour of operation

(6)

SYSTEM I : Entire (overall) process

100%
S3?
S7?

S1 = 1200 kg
100% H2O

99 wt% Ac
1 wt% H2O

SYSTEM I

S2 = 7539 kg

S5?

3 wt% Ac
5 wt%
95 wt% H2O

97 wt%
Stream mass balance:
S1 + S2

= S3 + S5 + S7

7359 + 1200

= S3 + S5 + S7

8559 = S3 + S5 + S7

(1)

Component mass balances:

Ac:

(7359) (xacetone,S2) +1200 (0) = S3 (0) + S5 (xacetone,S5) + S7(xacetone,S7)

220.8 =

Air:

7359(0.97) = S3 (1.0)

H2O:

7359(0) + 1200 (1.0) = S7 (xwater,S7) + S5 (0.95)

1200

(7)

= (0.01)S7 + (0.95)S5

(2)
(3)
(4)

4 equations but only 3 are independent

3 Unknowns: S3, S5, S7

(8)

(0.99)S7 +(0.05)S5

ND = 3 - 3 = 0

Solve
from eq (3):

S3 = 7138.2 kg

Subst. into (1):

8559 7138.2 = S5 + S7
1420.8 = S5 + S7

(5)

Solving equations (2) and (5) simultaneously:

(9)

S5 =

1261.5 kg

S7 =

159.3 kg

Check, using (4):

0.01* 159.3 + 0.95 * 1261.5 = 1200

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SYSTEM II: Absorber

S1 = 1200kg

S3 = 7138 kg
100% air

100% H2O
SYSTEM II

S4=?
S2 = 7359 kg

?%

3 wt%

?% H2O

97 wt%
Stream balance:
S1 + S2= S3 + S4
1200 + 7359 = 7138 + S4

(6)

Acetone balance:
1200(0) + 7359(0.03) = 7138(0) + S4 (xacetone,S4)

(7)

Water balance:
1200(1.0) + 7359(0) = 7138(0) + S4 (xwater,S4)

(8)

2 independent equations + 2 unknowns ND = 2 2 = 0

From equation (6)

S4 = 1421 kg

From equation (7)

xacetone,S4 = 0.155 (15.5wt% acetone)

SYSTEM III: Still

S6? kg
SYSTEM III
S4 = 1421 kg

S5= 1261.5 kg
5 wt%
95 wt% H2O

15.5 wt% Ac
84.5 wt% H2O

Stream balance:
S4
= S5 + S6
1421 = 1261.5 + S6

99 wt% Ac
1 wt% H2O

(9)

S6 = 159.5 kg (= S7)

This is also done as a check.

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Alternative method: (will demonstrate during lecture)

S1

S2

Acetone

(7359)(0.03)
=
221

Water

1200

Air

(7359)(0.97)
=
7138

Total
(kg/h)

1200

7359

S3

S4

S5

S6

S7

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Mass & Energy Balance

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PROBLEM EXAMPLE 2
A continuous distillation column is used to separate a liquid mixture containing 50 wt% alcohol and 50%
water. The overhead vapour from the column is condensed in a total condenser at a rate of 150 kg/h. Part
of the liquid condensate is withdrawn as the distillate product containing 95% alcohol; the remainder is
recycled to the column as reflux, with a reflux to distillate ratio of 1:1.
The bottoms product leaves as saturated liquid containing 96% water.
Calculate the product flow rates.
Solution:
V = 150kg/h
?% Al
?% H2O

F?

Condenser

D?
95 %
5% H2O

Distillation

50 wt% Al

R?

50 wt% H2O

? % Al
B?
4 % Al

? % H2O

96 % H2O

Basis: 1 hour (V=150 kg)

System I:

Condenser + Separation Point

Note condenser is a total condenser

Stream balance:
V = D + R = 150 kg

(1)

Since R/D = 1.0 (reflux ratio)

2D = 150

D = 75 kg
R = 75 kg

System II: Entire Process

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xA,D= 0.95
xW,D = 0.05
D

F = ? kg
System II

B?

xA,F = 0.5
xW,F = 0.5

xA,B= 0.04
xW,B = 0.96

Stream Balance:
F = 75 + B

(2)

Alcohol balance:
F (0.5)

= 75 (0.95) + B (0.04)

(3)

Solving using (2) and (3):

F=

148.37 kg

B=

73.37 kg

Check, using stream mass balance on distillation column:

F

+ R

148.37 + 75 =
Answers:

+ B

150 + 73.37 = 223.37

F= 148.37 kg/h
D= 75 kg/h
B= 73.37 kg/h

Complete the below table by performing mass balance

F

Alcohol

Water

Total (kg/h)

(0.95) (150)

(0.95) (75)

142.5

71.25

(150) (142.5)

(75) (71.25)

7.5

3.75

150

71.25

3.75

(150) / (2)

(150) (75)

75

75

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PROBLEM EXAMPLE 3
A process employed for producing brine with 4.0% salt is shown below.
W

W = 1000kg/h

4.0% salt

Mixing II

Water

P
W

Product
Brine

15.0% salt

Mixing
Salt

Calculate
1.
2.
3.

rate of the brine product

amount of salt required per tonne of water consumed
rate of the bypassing water fed to mixing tank I.

Solution:
Basis: 1 hour operation, W=1000kg
System 1:

Entire (Overall) process

W = 1000 kg/h

Mixing II

4.0% salt

Water

P
W

Product
Brine

15.0% salt

Mixing
Salt
Stream:
Salt:
Water:

S
W

+S

1000 + S

(1)

= P(0.04)

(2)

W(0) + S(1)
W(1) + S(0)

= P(0.96)

1000 + S(0) = P(0.96)

(3)

Three equations but only two independent equations

Using (3) & (1) P = 1041.7 kg
S = 41.7 kg

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System 2: Mixing tank I

Stream:

S + W2

41.7 + W2
Salt:

41.7(1.0) + W2(0)

From (5)

B = 277.8 kg

From (4)

W2 = 236.1 kg

(4)

= B (0.15)

(5)

Check: using system 3 Mixing tank II:

W1 + B = P

(6)

But from balance around point of separation:

W1 = W - W2 = 1000 236.1 = 763.9 kg
Thus from (6):LHS = 763.9 + 277.8 = 1041.7 kg = P
Answers:
1.
2.
3.

Rate of brine product: 1041.7 kg/h

Salt required: 41.7 kg salt/tonne water used
Rate of bypassing water: 236.1 kg/h

Water

Salt

Total (kg/h)

W1

W2

1000

1000

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Mass & Energy Balance

CheEng HCMUT

PROBLEM EXAMPLE 4 (From Example 4.4-2, page 107)

Take a basis of calculation of 100 kg acetone-water feed, calculate the masses and compositions
(component weight percentages) of the Stage 1 raffinate and extract, the Stage 2 extract, the combined
extract, and the distillation overhead and bottoms products.
Solution:
Systems Boundary

Analysis of system
1. Balances around Two-Extractor subsystem
3 components = 3 independent equations
3 unknowns: m1, m3 and xM1
Degree of freedom = 0
2. Balances around Extract Mixing point
3. Balances around first Extractor

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PROBLEM EXAMPLE 5 (From Example 4.5-1, page 110)

Fresh air containing 4.00 mole% water vapour is to be cooled and dehumidified to a water content of 1.70
mole% H2O. A stream of fresh air is combined with a recycle stream of previously dehumidified air and
passed through the cooler. The blended stream entering the unit contains 2.30 mole% H2O. In the air
conditioner, some of the water in the feed stream is condensed and removed as liquid. A fraction of the
dehumidified air leaving the cooler is recycled and the remainder is delivered to a room. Taking 100 mol of
dehumidified air delivered to the room as a basis of calculation; calculate to the moles of fresh feed, moles
of water condensed, and moles of dehumidified air recycled.
Solution:
BLOCK DIAGRAM

5
2

4
6

1
3

DA

WATER

Total (mol)

100

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PROBLEM EXAMPLE 6 (From Example 4.5-2, page 112)

Forty-five hundred kilograms per hour of a solution that is one-third K2CrO4 by mass is joined by a recycled
stream containing 36.4% K2CrO4, and the combined stream is fed into an evaporator. The concentrated
stream leaving the evaporator contains 49.4 % K2CrO4; this stream is fed into a crystallizer in which it is
cooled (causing crystals of K2CrO4 to come out of solution) and then filtered. The filter cake consists of
K2CrO4 crystals and a solution that contains 36.4% by mass; the crystals account for 95% of the total mass
of the filter cake. The solution that passes through the filter, also 36.4% K2CrO4 , is the recycle stream.
1. Calculate the rate of evaporation, the rate of production of crystalline K2CrO4, the feed rates that
the evaporator and the crystallizer must be designed to handle, and the recycle ratio (mass of
recycled)/(mass of fresh feed).
2. Suppose that the filtrate were discarded instead of being recycled. Calculate the production rate
of crystals. What are the benefits and costs of the recycling?
Solution:
Block diagram

Fresh
Feed

Recycle
stream

Filter
Cake stream

K2CrO4

WATER

Total (kg/h)

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Mass & Energy Balance

CheEng HCMUT

MATERIAL BALANCES WITH CHEMICAL REACTIONS

Reference: Chapters 4.6 to 4.7 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical
Processes, 3rd ed. 2005 (Wiley).

IMPORTANT DEFINITIONS AND CONCEPTS IN CHEMICAL REACTION STOICHIOMETRY

Stoichiometric equation
Chemical reaction equation which states the relative number of molecules or moles of reactants and
products that participate in the reaction.
Stoichiometric ratio
Ratio of the stoichiometric coefficients of two molecular species participating in a chemical reaction.
Limiting reactant
The reactant that presents less than its stoichiometric proportion relative to every other reactant.
Excess reactant
Present in excess of the limiting reactant, based on 100% complete reaction.

Tie components
If one component passes unchanged through a process unit, it can be used to tie the inlet and outlet
compositions, such a substance is called tie component.
Incomplete Reaction
Chemical reactions do not take place instantaneously, and indeed often proceed rather slowly. In such
cases, it is not practical to design the reactor for complete conversion of the limiting reactant; instead, the
reactor effluent emerges with some of the limiting reactant still present and is then usually subjected to a
separation process to remove the unconverted reactant from the product. The separated reactant is then
recycled to the reactor inlet.
Fractional conversion

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Percentage Conversion of any Reactant

Extent of reaction
CH4 + 2O2 CO2 + 2H2O
80 mol CH4
Reactor
60 mol CO2
200 mol O2

120 mol H2O

20 mol CH4
80 mol O2

Component

Initially, ni

Finally, nf

Amount of reacted or produced,

CH4

80

20

20 - 80 = - 60 (- )

O2

200

80

80 200 = - 120 (-2 )

CO2

60

60 0 = 60 ( )

H 2O

120

120 0 = 120 (2 )

In equation form
n (CH4)f = [n (CH4)]i -
n (O2)f = [n (O2)]i - 2
n (CO2)f = [n (CO2)]i +
n (H2O)f = [n (H2O)]i + 2
GENERALISED EQUATION FORM FOR

nf = ni + i
where:

ni
nf

= number of moles of substance i initially present

= number of moles of substance i after an arbitrary amount of reaction

= extent of reaction

i is i, stoichiometric coefficient
i = + i ; if i is a product;

i = - i ; if i is a reactant

i = 0 ; if i is a non-reactive component

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EXAMPLE 4.6-1 (PG 120) REACTION STOICHIOMETRY

Acrylonitrile is produced by the reaction of propylene, ammonia, and oxygen.
C3H6 + NH3 + 3/2 O2 C3H3N + 3H20
The feed contains 10 mole% propylene, 12% ammonia, and 78% air. A fractional conversion of 30% of the
limiting reactant is achieved in the reactor. Taking 100 mol of feed as a basis,
(i)

determine which reactant is limiting,

(ii)

the percentage by which each of the other reactants is in excess,

(iii) and the molar amounts of all product gas constituents

SOLUTION
Basis: 100 mol Feed
1

(i)

Determine the limiting reactant

Since NH3 and O2 are in excess, hence C3H6 is a limiting reactant

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(ii)

Determine the percentage excess of other reactants

(iii)

Outlet stream

CheEng HCMUT

Fractional conversion

NH3 - balance: O2
- balance: C3H3N
- balance: H2O balance:
N2 balance:

MULTIPLE REACTIONS
In most chemical processes, reactants are brought together with the object of producing a desired product
in a single reaction. Unfortunately, reactants can usually combine in more than one way, and the product
once formed may react to yield something less desirable. The result of these side reactions is an economic
lost: less of the desired product is obtained for a given quantity of raw materials, or a greater quantity of raw
materials must be fed to the reactor to obtain a specified product yield.
For example, ethylene can be produce by the dehydrogenation of ethane:

Once some hydrogen is produced, it can react with ethane to produce methane:

Moreover, ethylene can react with ethane to form propylene and methane:

Since the object of the process is to produce ethylene, only the first of these reactions may be regarded as
desirable; the second one consumes the reactant without yielding the desired product and the third
consumes both reactant and desired product.
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The terms yield and selectivity are used to describe the degree to which a desired reaction predominates
over competing side reactions.
Yield

Selectivity

The concept of extent of reaction can be extended to multiple reactions, only now each independent
reaction has its own extent. If a set of reaction takes place in a batch or continuous steady-state reactor
and i,j is the stoichiometric coefficient of substance i in reaction j (negative for reactants, positive for
products), we may then write

EXAMPLE 4.6-3 (PG 124) YIELD AND SELECTIVITY IN A DEHYDROGENATION REACTOR

The reactions
C2H6 C2H4 + H2

(1)

C2H6 + H2 2CH4

(2)

take place in a continuous reactor at steady state. The feed contains 85.0 mole% ethane (C 2H6) and the
balance inert (I). The fractional conversion of ethane is 0.501 and the fractional yield of ethylene is 0.471.
Calculate the molar composition of the product gas and the selectivity of ethylene to methane production.
SOLUTION
Basis: 100 mol Feed

Let

1 be extent of reaction for reaction 1

2 be extent of reaction for reaction 2

Fractional conversion of C2H6 = 0.501

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C2H6 YIELD = 0.471

C2H4 - balance:
C2H6 - balance:

H2 - balance:
CH4 - balance:
I - balance:
Total amount in product stream:

Product composition:

Molecular Species Balances

Component balance
Mol IN + Mol Generated = Mol OUT + Mol Consumed
Atomic Species Balances
Atoms can neither be generated nor destroyed

INPUT = OUTPUT

no generation or consumption terms will be present in atomic balance

atomic balances can be used when

single chemical reaction takes place
several simultaneous reactions takes place

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MATERIAL BALANCE CALCULATIONS INVOLVING CHEMICAL REACTIONS

Summary of procedure - in addition to the general procedure for mass balance calculations.
1.

Write correct stoichiometric equations for chemical reactions involved.

2.

Identify limiting and excess reactants, inerts,..

3.

Perform all calculations using molar basis. Convert all mass quantities into molar quantities.

4.

Write down the necessary material balance equations, assuming steady-state with a specified
system.
a.

Extent of reaction method

b.

Molecular species balance

c.

Atomic species balanced

EXAMPLE 4.7-1 (PG 131) INCOMPLETE COMBUSTION OF METHANE

Methane is burned with air in a continuous steady-state combustion reactor to yield a mixture of carbon
monoxide, carbon dioxide, and water. The reactions taking place are
CH4 + 3/2 O2 CO + 2H2O
CH4 + 2O2 CO2 + 2H2O
The feed to the reactor contains 7.80 mole% CH4, 19.4% O2, and 72.8% N2. The percentage conversion
of methane is 90.0%, and the gas leaving the reactor contains 8 mol CO2/mol CO. Calculate the molar
composition of the product stream using (1) molecular species balances, (2) atomic species balances, and
(3) extents of reaction.
SOLUTION
Basis: 100 mol Feed

nN2 = (0.728) (100) = 72.8 mol N2

nCH4 = (0.1) (0.078) (100) = 0.78 mol CH4
METHOD 2: ATOMIC SPECIES BALANCES
C balance:

(0.078) (100) = (1) nCH4 + (1) nCO + (1) nCO2

7.8 = nCH4 + nCO + (8) nCO = 0.78 + 9 nCO nCO = 0.78 mol CO
nCO2 = 8 x 0.78 = 6.24 mol CO2
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H balance:

CheEng HCMUT

(4) (0.078) (100) = (4) nCH4 + (2) n H2O

31.2 = (4) (0.78) + (2) n H2O n H2O = 14 mol H2O

O balance:

(2) (0.194) (100) = (1) nCO + (2) (8) nCO + (1) n H2O + (2) nO2
38.8 = (1) (0.78) + (2) (8) (0.78) + (1) (14) + (2) nO2 n O2 = 5.75 mol O2

REFER TO PAGES 131-134 FOR COMPLETE SOLUTION

PRODUCT SEPARATION AND RECYCLE

S2

Recycled material

S
Feed

Process

Separation
S4

Net Product
S5

Single-pass conversion (of A) or Conversion per pass:

Overall conversion (of A) or Fresh-feed conversion:

Overall conversion = single-pass conversion if there is no recycle of the reactant.

By recycling all the unreacted reactant it is possible to achieve 100% conversion for the process as a
whole, although the reaction may be incomplete in the reactor.

If product separation is not complete, overall conversion will be less than 100% but is always greater
than single-pass conversion.

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ILLUSTRATION 1
Consider the block diagram below

Determine
1.
Recycle ratio
2.
Single pass conversion
3.
Overall conversion
Solution:
1.
Since all products from reactor are passed through a Separator where unreacted C4H10 is completely
separated and recycled to the reactor.
C4H10 Recycled
=
Combined C4H10 Feed =
Fresh C4H10 Feed
=

2.

3.

2 mol C4H10
10 mol C4H10
10 2 = 8 mol C4H10

Single-pass conversion
C4H10 : (10 2 ) / 10 = 0.8

H2O : (50 18 ) / 50 = 0.64

80% conversion
64% conversion

Overall conversion
C4H10 : (10 2 ) / 8 = 1.0

H2O : (50 18 ) / 50 = 0.64

100% conversion
64% conversion

EXAMPLE 4.7-2 (PG 135) DEHYDROGENATION OF PROPANE

Dehydrogenation of propane produces propylene in a catalytic reactor:
C3H8
C3H6 +
H2
The process aims to achieve an overall conversion of 95%. The effluent from the reactor is separated into
two streams:
i.
Net product stream containing C3H6 , H2 and 0.555% of the unreacted C3H8 leaving the reactor
ii.
Recycle stream to reactor containing 5% of C3H6 in the product stream
Calculate:
1.
composition of the final (net) product
2.
recycle ratio (mol recycled/ mol fresh feed)
3.
single-pass conversion
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Solution:
Basis: 100 mol fresh feed (F= 100 mol C3H8)

Overall conversion of C3H8 = 0.95

mol C3H8 consumed = 0.95 x 100 = 95 mol
System 1 : Entire Process
C3H8 balance: Mol IN + Mol Generated = Mol OUT + Mol Consumed

IN
= 100 mol C3H8
Generated
= - 95 mol C3H8
n6 (C3H8), OUT = 100 95 = 5 mol C3H8

C3H6 balance: Mol IN + Mol Generated = Mol OUT + Mol Consumed

IN = 0
Generated

n7 (C3H6), OUT = 0 + 95 = 95 mol C3H6

H2 balance:

Mol IN + Mol Generated = Mol OUT + Mol Consumed

IN = 0
Generated

n8 (H2), OUT = 0 + 95 = 95 mol H2

(i)

Net Product Composition:

Component
C3H8
C3H6
H2
Total

IN
100
0
0
100

GEN
-95
95
95
95

OUT
5
95
95
195

Mole%
2.56
48.72
48.72
100.00
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System 2: Separator (no chemical reaction)

Given relations among separator variables
n6 = 5 = (0.555/100) n3

n3 = 900 mol C3H8

n10 = (0.05) n7 = (0.05) 95 n10 = 4.75 mol C3H6

C3H8 balance:
IN
= OUT
n3
= n6 + n9

2)

n9 = n3 - n6 = 900 5 = 895 mol C3H8

Recycle ratio?
Recycle ratio based on total stream
=

3) Single-pass conversion of C3H8?

System 3:

Mixing point

C3H8 balance:
IN
= Fresh feed + recycled =
n1
= 100 + n9 n1 = 100 + 895= 995 mol C3H8

Single-pass conversion of C3H8

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EXAMPLE 4.7-3 (PG 139) RECYCLE AND PURGE IN THE SYNTHESIS OF METHANOL
Methanol is produced in the reaction of carbon dioxide and hydrogen:
CO2 + 3H2 CH3OH + H2O
The fresh feed to the process contains hydrogen, carbon dioxide, and 0.400 mole % inerts (I). The reactor
effluent passes to a condenser that removes essentially all of 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 28.0 mole% CO2, 70.0 mole% H2, and
2.00 mole% inerts. The single-pass conversion of hydrogen is 60.0%. Calculate
(i)
(ii)
(iii)
(iv)

the molar flow rates and molar compositions of the fresh feed,
the total feed to the reactor,
the recycle stream,
and the purge stream for a methanol production rate of 155 kmol CH3OH/h.

Solution
SP

SR

Basis: 100 mol combined Feed to the reactor

In Stream 3:

CO2: (0.280) (100) = 28 mol

H2: (0.700) (100) = 70 mol
I : (0.020) (100) = 2 mol

Reactor Analysis
Single pass conversion of H2 = 60%
0. 6 = (70 n1) / 28 n2 = 28.0 mol H2
H2 consumed = (0.6) (70) = 42 mol H2
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Mass & Energy Balance

CO2 balance:

CheEng HCMUT

Mol IN + Mol Generated = Mol OUT + Mol Consumed

IN = 28
Consumed

n1 (CO2), OUT = 28 - 14 = 14 mol CO2

CH3OH balance:

Mol IN + Mol Generated = Mol OUT + Mol Consumed

IN = 0
Produced

n3 (CH3OH), OUT = 0 + 14 = 14 mol CH3OH

H2O balance:

Mol IN + Mol Generated = Mol OUT + Mol Consumed

IN = 0
Produced

n4 (H2O), OUT = 0 + 14 = 14 mol CH3OH

Condenser Analysis
To determine flow rate and composition in Stream 5
(CO2 + H2 + I ) in stream 4 = (CO2 + H2 + I ) in stream 5

Composition in stream 5 = composition in purge stream = composition in recycle stream

Fresh Feed-Recycle Mixing Point Analysis
Total Mole Balance:

Input = Output
n0 + nr = 100
I Balance:
(0.00400) n0 + (0.04545) nr = 2
Solving these two equations simultaneously yields
n0 = 61.4 mol fresh feed, nr = 38.6 mol recycle

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Mass & Energy Balance

CO2 Balance:

CheEng HCMUT

(xOC) n0 + (0.3182) nr = 28
(xOC) (61.4) + (0.3182) (38.6) = 28
xOC = 0.256 mol CO2 / mol
xOH = 1 - 0.256 0.004 = 0.740 mol H2 / mol

Recycle-Purge Splitting Point Analysis

Total Mole Balance:

Input = Output
n5 = nr + np np = 44 38.6 = 5.4 mol purge

Flowchart scaling

ANS Variable

Basis Value

Scaled Value

(i)

61.4 mol

681 kmol/h (61.4 x 11.1)

25.6 mole% CO2

25.6 mole% CO2

74.0 mole% H2

74.0 mole% H2

0.400 mole% I

0.400 mole% I

100 mol

1110 kmol/h (100 x 11.1)

28.0 mole% CO2

28.0 mole% CO2

70.0 mole% H2

70.0 mole% H2

2.0 mole% I

2.0 mole% % I

38.6 mol

428 kmol/h (38.6 x 11.1)

28.0 mole% CO2

28.0 mole% CO2

70.0 mole% H2

70.0 mole% H2

2.0 mole% I

2.0 mole% % I

5.4 mol

59.9 kmol/h (5.4 x 11.1)

31.8 mole% CO2

31.8 mole% CO2

63.6 mole% H2

63.6 mole% H2

4.6 mole% I

4.6 mole% I

(ii)

(iii)

(iv)

Fresh Feed

Feed to the reactor

Recyle

Purge

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LECTURE
COMBUSTION REACTIONS
Reference: Chapter 4.8 of R.M. Felder & W. Rousseau, Elementary Principles of Chemical Processes, 3rd
ed. 2005 (Wiley).
MATERIAL BALANCE CALCULATIONS INVOLVING COMBUSTION REACTIONS

Combustion is the rapid reaction of a fuel with oxygen

Combustion reactions are industrially significant:
Large amounts of heat released
Environmental impact of combustion products
Fuels:
Solid: eg coal (carbon, hydrogen, some sulfur, and various minerals)
Liquid: eg fuel oil (heavy hydrocarbons, some sulfur)
Gas: eg natural gas (mainly methane) or LPG (propane and butane)

Combustion Chemistry
Combustion is basically an oxidation reaction. When a fuel is burned, C reacts with O2 to form CO or CO2;
H forms H2O; S forms SO2.
In Complete combustion CO2 is produced.
EXAMPLES
C
CH4
C4 H8
CS2

+
+
+
+

O2
2O2
6O2
3O2

CO2
CO2
4CO2
CO2

+
+
+

2H2O
4H2O
2SO2

In Incomplete (partial) combustion CO is produced.

EXAMPLES
C
CH4
C4 H8

+
+
+

1/2O2
3/2O2
8O2

CO
CO
4CO

+
+

2H2O
4H2O

In combustion, hydrogen present in fuel always reacts with O2 to form water vapour

Oxygen/Air Requirement
Oxygen demand for a particular combustion reaction can be determined from stoichiometry.
For economical reason, air is the source of O2 in most combustion processes.
Air has the following composition:
Component
N2
O2
Ar
CO2
H2, He, Ne

%mol
78.03
20.99
0.94
0.03
0.01

Average molecular weight = 29.0 g/mol

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In most combustion calculations, air can be assumed to consist of 79 mole %N2 and 21 mole %O2 or
76.7%N2 and 23.3%O2 (by mass).

If air is used as a source of O2, must take into account N2 in the feed, i.e.
21 mol O2

79 mol N2
Unless the combustion temperature > 1800oC, where N2 reacts with O2 to form NO or NO2, nitrogen is
considered as inert.
Flue or stack gas
All the gases resulting from combustion process including the water vapour, sometimes known as a wet
basis.
Orsat analysis or dry basis
All the gases resulting from a combustion process not including the water vapour. Orsat analysis refers to
a type of gas analysis apparatus in which the volumes of the respective gases are measured over and in
equilibrium with water. The net result of the analysis is to eliminate water as a component being measured.
Composition on a wet basis
- is used to express component mole fraction of a flue gas that contains water
Composition on a dry basis
- is used to express component mole fractions of the same gas without water
Example 1: Composition on Wet and Dry Bases
A stack gas contains 33.3 mole% CO2, 33.3 mole% N2 and 33.3 mole% H2O. Express the composition on
wet and dry basis.
Solution: (To be covered in lecture)

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Example 2:
A gas contains 5 wt% C3H8, 5 wt% C4H10, 16 wt% O2, 38 wt% N2, and the balance H2O. Calculate the
molar composition of this gas on both a wet and a dry basis.
Solution: (To be covered in lecture)

Theoretical and Excess Air

Although combustion is very rapid, it may not be instantaneous and complete due to insufficient time
or poor mixing.

Usually, air is supplied in excess, ie more than needed based on stochiometry of complete
combustion reaction.
Theoretical Oxygen:
The moles (batch) or molar flow rate (continuous) of O2 needed for complete combustion of all the fuel fed
to the reactor, assuming that all C is oxidized to CO2 and all H is oxidized to H2O.
Theoretical Air:
Quantity of air that contains the theoretical oxygen
Excess Air:
The amount by which the air fed to the reactor exceeds the theoretical air
= actual air supplied theoretical air

EXAMPLE
If 50% excess air is supplied, then (moles air) fed = 1.5 (moles air)theoretical
NOTES:
1.
2.
3.

The theoretical air required to burn a given quantity of the fuel does not depend on how much it
is actually burned, or whether the combustion is incomplete
the percent excess air depends only on the theoretical air and the air feed, and not on how
much O2 is consumed or whether the combustion is complete or partial.
if the fuel contains some O2, then this must be subtracted from the theoretical oxygen amount
used for calculating excess air.

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Example 3:
Partial combustion and excess air
100 mole of propane (C3H8) are burned with 3000 mol of air to produce 240 mol CO2 and 60 mol CO.
1. calculate the percentage excess air
2. determine the composition of the flue gas on both wet and dry bases
Solution
Air 3000 mol
2

Flue Gas
Combustor

N2 ??
C3H8 ??
CO2 240 mol
CO 60 mol
H2O ??

C3H8 100 mol

Stoichiometric equations:
C3H8
C3H8

+
+

5O2

7/2O2

3CO2
3CO

+
+

4H2O
4H2O

(1)
(2)

a) Percentage excess air ?

Theoretical oxygen = O2 required by reaction (1) to burn completely all 100 mol of C3H8

Theoretical air
xcess air = supplied theoretical
= 3000 2381= 619 mol air
%Excess air
b)

= 100 (619/2381) = 26%

Composition of Flue Gas?

O2 balance:
IN =

3000 x 21/100 = 630 mol O2

Consumed in complete combustion (1):

Consumed in partial combustion (2):

Total O2 consumed = 400 + 70 = 470 mol O2

OUT = 630 470 = 160 mol O2

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CheEng HCMUT

C3H8 balance:
IN = 100 mol
Consumed in (1):

Consumed in (2)

Total C3H8 consumed = 80 + 20 = 100 mol

OUT = 100 100 = 0 (none in flue)

H2O balance:
IN = 0
Produced in complete combustion (1):

Produced in partial combustion (2):

Total H2O produced = 320 + 80 = 400 mol

OUT = 400 mol H2O

N2 balance:
IN =
=

OUT
3000 (79/100) = 2370 mol N2

Composition of Flue Gas:

Component
CO2

mol
240

%mol(wet)

%mol(dry)

CO

60

7.43
1.86

8.48
2.12

O2

160

4.95

5.65

N2

2370

H 2O

400

83.75
-

Total

3230

73.37
12.38
100.00

100.00

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Example 4: Adopted from EXAMPLE 4.8-3 of recommended text

Ethane (C2H6) is burned with 50% excess air. The percentage conversion of the ethane is 90%; of the
ethane burned, 25% reacts to form CO and the balance to form CO2. Calculate the composition of the flue
gas and the ratio of water to dry flue gas.
Solution: (To be covered in lecture)

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Mass & Energy Balance

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Example 5: Adopted from EXAMPLE 4.8-4 of recommended text

A hydrocarbon gas is burned with air. The dry-basis product gas composition is 1.5 mole% CO, 6.0% CO2,
8.2% O2, and 84.3% N2. There is no atomic oxygen in the fuel. Calculate the ratio of hydrogen to carbon in
the fuel gas and speculate on what the fuel might be. Then calculate the percent excess air fed to the
reactor.
Solution: (To be covered in lecture)

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Example 6:
A fuel oil contains 87 wt% as C, 11% H and 1.4% S, and the remainder non-combustible matter. It is
burned with 20% excess air. The oil burns completely, but 5% of the carbon forms CO.
Determine the composition of the stack gas.

Solution:
Combustion reactions:
(1)
C
(2)
C
(3)
2H
(4)
S

+
+
+
+

O2
0.5O2
0.5O2
O2

CO2
CO
H 2O
SO2

Reactions (1), (3) and (4) are used for calculating %excess air.
Basis: 100 g fuel oil

Theoretical oxygen:
From (1):

From (3):

From (4):

Total theoretical O2 = 10.044 mol

Theor. air = 10.044(1/0.21) = 47.828 mol

Actual air @ 20% excess = 1.2 x 47.828 = 57.394 mol

O2 supplied = 0.21 x 57.394 = 12.053 mol

N2 supplied = 0.79 x 57.394 = 45.341 mol

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Mass & Energy Balance

CheEng HCMUT

95% of total C reacts in (1):

=
0.95 x 7.25 =

6.888 g-atom C

5% of total C reacts in (2):

=
0.05 x 7.25 =

0.362 g-atom C

O2- balance:
IN = 12.053 mol
Consumed =

= 9.863 mol O2

O2 OUT = 12.053 9.863 = 2.190 mol O2

CO2- balance:
IN = 0 mol
Produced

CO2 OUT = 6.888 mol

CO- balance:
IN = 0 mol
Produced

CO OUT = 0.362 mol

H2O- balance:
IN = 0 mol
Produced

H2O OUT = 5.5 mol

SO2- balance:
IN = 0 mol
Produced

SO2 OUT = 0.044 mol

N2 Balance:
OUT = IN

= 45.341 mol N2

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Mass & Energy Balance

CheEng HCMUT

Composition of stack gas

Basis: 100 g fuel oil
Component
CO2
CO
O2
N2
H 2O
Total

mol
6.888
0.362
2.19
45.341
5.5
60.281

%mol(wet)
11.43
0.60
3.63
75.22
9.12
100.00

%mol(dry)
12.57
0.66
4.00
82.77
100.00

Solid Fuel: Coal

Composition: C, H, O, N, S, moisture, mineral matter
Combustion of coal
C
C
2H
S

+
+
+
+

O2
O2
O2
O2
2O
2N

CO2
CO
H2O
SO2
O2
N2

Moisture
Moisture (water) content in coal can be significant depending on coal rank
During combustion, moisture is evaporated as steam and leaves with flue gas. This must be included in
wet analysis
Minerals
Consist of various inorganic and organic matters
Most will not be burned during combustion and constitute the ash content of coal
Some combustible minerals:
- Iron pyrites (FeS2)
FeS2 + 11/2 O2 Fe2O3 (s) + 4SO2 (g)
- Carbonates, e.g. CaCO3, FeCO3, MgCO3
- May decompose under furnace condition to form metal oxides and CO2
CaCO3 CaO (s) + CO2 (g)
- Also
CaO + O2 + SO2 CaSO4 (s)
Analyses of Coal
i. Proximate analysis
Arbitrarily defined analysis as a means for specification of coal for commercial purposes

Moisture content: loss in weight on heating at 105oC for 1 hour. Expressed in wet or dry basis
Volatile matter: loss in weight in 7 minutes on heating at 960oC
Fixed Carbon content: amount of combustible material left after test on volatile materials
Ash content: amount of residue remaining after ordinary combustion of coal

Volatile matter + Fixed C content = Total combustible content

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Mass & Energy Balance

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EXAMPLE - Proximate coal analysis

Moisture
Volatiles
Fixed C
Ash
Total
Total combustibles

Brown coal
(wet)
(dry)
65.0
17.2
49.1
16.5
47.1
1.3
3.8
100.0
96.2
33.7

Black coal
(wet)
(dry)
9.6
33.2
36.7
46.0
50.9
11.2
12.4
100.0
79.2
87.6

ii. Ultimate analysis

Chemical analysis in terms of elemental constituents on dry and ash-free basis (DAF)
analysis of the Total Combustible content
Necessary for combustion calculations

EXAMPLE
Brown coal
Carbon
C
64.9
Hydrogen
H
4.3
Nitrogen
N
0.7
Sulphur
S
0.2
Oxygen
O
29.9*
Total
100.0
* determined by difference

Black coal
84.2
5.2
1.1
1.4
8.1
100.0

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