METTU UNIVERSITY

FACULTY OF ENGINEERING AND TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING

Plant Design and Economics: ChEg 5132

By: Abdisa R.
 Lecture 3
Material And Energy Balances

Contents

1. Fundamental of Material balance

2. Fundamental of energy balance
3. Degree of freedom analysis

2
 Why material and energy balance?

The basic purpose of material and energy balance is to:

 Quantify all the material, energy and waste streams in a process or a system.
 Check performance against design
 Extend the often limited data available from the plant instrumentation
 Check instrument calibrations;
find out the difference between calculated/designed values and measured/actual values
thereby making it possible
 Locate sources and identify previously unknown of material loss and emissions.

3
 FUNDAMENTAL OF MATERIAL BALANCE
 Material balances are the basis of process design.

Material balance

Over complete process Over individual process unit

To determine the quantities of raw materials To set the process stream flow rates and
required and product produced compositions
Provide basic equation for sizing equipment

 4
Chemical processes may be classified into as batch, continuous, or semi batch, or either
 Fundamentals of Material Balance
2. Process Classification:
 Batch process
 No mass crosses system boundaries between the time feed is charged and the time product is removed.
 Typically used for making small quantities, particularly those products that have high value.
 Used when some flexibility is wanted in production rate and product specifications.
 Continuous process
Feeds and effluents continuously flow across the system boundary through the duration of the process.
Suited for the production of large quantities.
 Semi-batch process
Any process that is neither batch nor continuous.

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 FUNDAMENTAL OF MATERIAL BALANCE
3. Process Operation
Steady state

 There is no change in the value of all process variables (temperature, pressure, flow

rates, heat-transfer rates) except for minor fluctuations about the mean value

 Continuous processes may be steady-state.

Transient (Unsteady State)

 The values of process variables change with time.

 Batch and semi-batch process are transient by nature.

 Continuous processes may be transient.

6
 CONT’D…
4. Conservation of Mass:
 The general conservation equation for any process system can be written as

input + generation – output – consumption = accumulation

 If the balanced quantity is total mass,
 set generation =0 and consumption = 0
Rules of Material Balance  If the balanced substance is a nonreactive species,
simplification:  set generation =0 and consumption = 0
 If a system is at steady state,
 set accumulation = 0

 A balance equation can be written for each separately identifiable species present, elements,
compounds, or radicals; and for the total material.
 Balances can be written for mass or for number of moles.
7
 CONT’D…
Continuous steady-state system:
0

input + generation – output – consumption = accumulation

input + generation = output + consumption

 If the balance is for a nonreactive species or on total mass, the generation and

consumption terms equal zero, and the balance reduces as

 continuous process
input = output
 steady-state operation
 no reactions occurring
input = output
 Toluene balance Benzene balance
500 kg T/h = m1 + 475 kg T/h 500 kg B/h = 450 kg B/h + m 2
m1 = 25 kg T/h m 2 = 50 kg B/h 8
 EXAMPLE: BENZENE/TOLUENE
DISTILLATION
5. Basis of calculation:

 A basis of calculation is an amount or flow (mass or molar) of one stream or component in a process.

 The first step in balancing a process is to chose a basis of calculation; all unknown quantities are then determined to be

consistent with this basis.

 If a stream amount or flow is given in a problem statement, it is usually the most convenient basis to use.

 If no stream amounts or flows are known, assume a value of 1, preferably for a stream of known composition.

 If mass fractions are known, set a total mass or flow of that stream (i.e., 100 kg or 100 kg/h) as the basis.

 If mole fractions are known, chose a total number of moles or molar flow rate (i.e., 100mol or 100mol/h).

 When a composition is specified as a percentage, it is important to state clearly the basis: weight, molar, or volume.

 The abbreviations w/w, wt%, and %wt are used for mass (weight) basis.

9
 Volume basis is usually abbreviated vol%, LV%, or v/v.
 6. Degree of Freedom Analysis:
 Process used to determine if a material balance problems has sufficient specifications to be solved .

a) draw and completely label the flowchart

b) count the unknown variables on the chart

c) count the independent equations relating these variables

d) calculate degrees of freedom by subtracting (c) from (b)

ndf = nunknowns – nindep_eqns

 If ndf = 0, problem can be solved (in principle).

 If ndf > 0, problem is underspecified and at least ndf additional variables must be specified before the
remaining variable values can be determined.

 If ndf < 0, the problem is over-specified with redundant and possibly inconsistent relations.
10
 General Procedure for Material Balance Problems
The best way to tackle a problem will depend on the : •Information given;
•Information required from the balance; and
•Constraints that arise from the nature of the
problem

The standard procedures for material balances are:

1) Make any necessary assumptions (E.g. steady state, no rxn, etc.)

2) Draw a flowchart for the process & fill in all known variables and values. Label unknown stream
variables on the chart. Include either:
 Total mass & stream composition
 Total mole & stream composition
 The mass or molar flow rate of each stream components.

3) Choose as a basis of calculation an amount or flow rate of one of the process stream.

11
4) Express what the problem statement asks you to determine in terms of the labeled variables.
Cont’d….

5) If you are given mixed mass and mole units for a stream, convert all quantities to one basis.
6) Do the degree of freedom analysis. Count the unknowns and identify equations.

Number of df = number of unknown – number of independent equations

• If ndf = 0, the problem can in principle be solved

• If ndf > 0, the problem is underspecified
• If ndf < 0, the problem is over specified
ndf = nunknown – nindp. equ

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Cont’d…

Sources of equations relating unknown process stream variables include the following:

  Physical properties and laws

Material balances
  Physical constraints
Energy balances
 Stoichiometric relations
 Process specifications

7) If the number of unknowns equal the number of equations then start solving
the equation.

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EXAMPLE

14
 SOLUTIONS
2a. Flowchart drawn from description
1. basis is given as a
2b. Convert mole to mass fractions
volumetric quantity

2c. no stream information known

write in terms of species flows
2d. confirm every component mass flow in every 2e. process
process stream can be expressed in terms of labeled specification
quantities and variables.
15
 CONT’D…
3. write expressions for quantities requested in problem statement

 2 m
m 1m
3

 3 m
m  B3  m
 T3
4. Convert mixed units in
overhead product stream
95.0 kmol B 78.11 kmol
kg B

B 7420 kg B

5.0 kmol T 92.13 kmol

kg T

T 461 kg T

7420 kg B  461 kg T  7881 kg mixture  B3 m

x B m  3 ; x T 1  x B
y B 2 7420 kg B  7881 kg mixture  0.942 kgkgB
yT 2 1  0.942 0.058 kgkgT

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CONT’D…
5. Perform degree of freedom analysis

4 unknowns
-2 material balances
-1 density relationship
-1 process specification
0 degrees of freedom
17
CONT’D…
6. Write system equations
7. Solve
i. volumetric flow
conversion
 1 2000 hL 0.872 kgL 1744 kgh
m

ii. benzene split fraction

 B3 0.08 0.45m
m  1 62.8 kghB

iii. benzene balance iv. toluene balance

0.45m 1 m 2 yB2  m B3
 2 766 kghB
m 0.55m 1 m 2 1  yB2  m T3
 T 3 915 kghT
m 18
 Exercise

Problem 1.

A binary mixture consists of 35 % benzene and 65 % toluene are continuously

fed to the distillation column at a rate of 1000 kg/hr. Whereas, the distillate

flow rate was 10% from the feed flow rate. The distillate (top product) contains

85 % benzene. Calculate quantity and compositions of the waste stream.

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EXAMPLES

20
 Balances On Multiple Unit Operations
 A system is any portion of a process that can be enclosed within a hypothetical box (boundary).
 It may be the entire process, a single unit, or a point where streams converge or combine.

 Boundary A encloses the entire process.

• inputs: Streams 1, 2, and 3
• products: 1, 2, and 3
• Balances on A would be considered overall balances
• internal streams would not be included in balances
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CONT’D…
 B: an internal mixing point (2 inputs, 1 product)
 C: Unit 1 (1 input, 2 products)
 D: an internal splitting point (1 input, 2 products)
 E: Unit 2 (2 inputs, 1 product)

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 7. RECYCLE
 It is seldom cost effective to waste reactant fed that does not react to product.
 More often, this material is separated (recovered), and recycled (returned to its point of
origin for reuse).

Reasons to recycle:
 recover catalyst:- typically most
expensive chemical constituent
 dilute a process stream: -
• To reduce slurry concentration
 control a process variable: control heat
produced by highly exothermic reaction
 Circulation of a working fluid:
 refrigerant

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EXAMPLE

process cools and dehumidifies feed air

unknowns: n1, n2, n3, n4, n5 (requested by problem)
degree-of-freedom analysis is critical to solution

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BALANCES ON AN AIR CONDITIONER
 Overall system
 n = 2 variables (n , n ) – 2 balances = 0
df 1 3

25
CONT’D…
 Mixer
 n = 2 variables (n , n ) – 2 balances = 0
df 2 5

26
CONT’D…
 Cooler
 n = 2 variables (n , n ) – 2 balances = 0
df 2 4

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CONT’D…
 Splitter
 n = 2 variables (n , n ) – 1 balances = 1
df 4 5
 only 1 independent balance can be written on the splitter because the streams
entering/leaving have the same composition.

0.983n4 0.983n5  0.983100 

0.017n4 0.017n5  0.017100 

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 CONT’D…
 Overall: n = 2 variables (n , n ) – 2 balances=0 To find requested unknowns,
df 1 3 solve overall balances followed
 Mixer: n = 2 variables (n , n ) – 2 balances = 0 by mixing balances.
df 2 5
 Cooler: n = 2 variables (n , n ) – 2 balances =0 There is no need to solve the
df 2 4 cooler or splitter balances.
 Splitter: n = 2 variables (n , n ) – 1 balances =1
df 4 5

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CONT’D…
 Overall dry air balance
0.960n1 0.983100 n1 102.4mol
 Overall mole balance n1 n3  100 n3 2.4 mol H 2O condensed



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CONT’D…
 overall mole balance n1  n5 n2
 water balance
 solved simultaneously:
0.04 n1  0.017n5 0.023n2
n2 392.5 mol; n5 290 mol

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8. BYPASS STREAM
 Similar to a recycle, but a fraction of a stream is diverted around
a process unit, rather than being returned to it.
 Calculation approach is identical.

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 9. PURGE
 It is usually necessary to bleed off a portion of a recycle stream to prevent the build up of unwanted
material.
 For example, if a reactor feed contains inert components that are not separated from the recycle stream
in the separation units, these inerts would accumulate in the recycle stream until the stream eventually
consisted almost entirely of inerts.
Under steady-state conditions:
Loss of inert in the purge = Rate of feed of inerts into the system
 The concentration of any component in the purge stream is the same as that in the recycle stream at the
point where the purge is taken off. So the required purge rate can be determined from the following
relationship:

( [Feed stream flow rat𝑒¿ ×

) ( )
[ Purge stream flow rate ]
¿ [Feed stream inert concentration] = ×
[ Specified ( desired ) recycle inert concentration ]

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 EXAMPLE
In the production of ammonia from hydrogen and nitrogen, the conversion, based on either raw material, is limited to 15%. The
ammonia produced is condensed from the reactor (converter) product stream, and the unreacted material is recycled. If the feed
contains 0.2% argon (from the nitrogen separation process), calculate the purge rate required to hold the argon in the recycle
stream below 5.0%. Percentages are by volume.
Solution:
 Basis: 100 moles feed (purge rate will be expressed as moles per 100 mol feed, as the production rate is not given).

Process diagram:

 Volume percentages are taken as equivalent to mol%.

Argon entering system with feed = 100x0.2/100 = 0.2 mol.

Let purge rate per 100 mol feed be F.
Argon leaving system in purge = F x 5/100 = 0.05 F.
At the steady state, argon leaving = argon entering
0.05F = 0.2; F = 4mol
Purge required: 4mol per 100mol feed. 34
 BALANCES ON REACTIVE SYSTEMS
 Material balance no longer takes the form

INPUT = OUTPUT
 Must account for the disappearance of reactants and appearance of products
through stoichiometry
Stoichiometric Equations:
 The stoichiometric equation of a chemical reaction is a statement of the relative
amounts of reactants and products that participate in the reaction.
2 SO2 + O2 → 2 SO3
 A stoichiometric equation is valid only if the number of atoms of each atomic
species is balanced.
2S→2S
4O+2O→6O

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 CONT’D…
 A stoichiometric ratio of two molecular species participating in a reaction is
the ratio of their stoichiometric coefficients:
2 mol SO3 generated / 1 mol O2 consumed
2 mol SO3 generated / 2 mol SO2 consumed
C4H8 + 6 O2 → 4 CO2 + 4 H2O
 Is this stoichiometric equation balanced?
 What is the stoichiometric coefficient of CO ?
2

 What is the stoichiometric ratio of H O to O ?

2 2

 How many lb-mol O react to form 400 lb-mol CO ?

2 2
6 lbmol O 2
400 lbmol CO 2  600 lbmol O 2
4 lbmol CO 2

 100 lbmol/min C H is fed and 50% reacts. At what rate is water formed?
4 8
lbmol C 4H8 4 lbmol H2O lbmol H2O
100 0.50  200
min 1 lbmol C 4H8 min 36
 LIMITING AND EXCESS
REACTANTS/REAGENTS
 Two reactants are said to be in stoichiometric proportion if the ratio (moles A
present/moles B present) equals the stoichiometric ratio from the balanced
reaction equation.
2 SO2 + O2 → 2 SO3
 the feed ratio that would represent stoichiometric proportion is n /n = 2:1
SO2 O2

 If reactants are fed in stoichometric proportion, and the reaction proceeds to

completion, all reactants are consumed.
 Stoichiometric Proportion – Reactants are present in a ratio equivalent to
the ratio of the stoichiometric coefficients.
 Limiting reactant – A reactant is limiting if it is present in less than
stoichiometric proportion relative to every other reactant
 Excess reactant – All other reactants other than the limiting reactant.
 to promote the desired reaction, to maximize the use of an expensive
reagent, or to ensure complete reaction of a reagent, as in combustion.

37
 CONT’D…
 The percentage excess reagent is defined by the following equation:

Example:
To ensure complete combustion, 20% excess air is supplied to a furnace
burning natural gas. The gas composition (by volume) is methane 95%,
ethane 5%.
Calculate the moles of air required per mole of fuel.
Solution:
 Basis: 100 mol gas, as the analysis is volume percentage.

Reactions:

Stoichiometric moles of O required= 95x2 + 5x3.5=207.5

2

38
 CONT’D…
With 20% excess, moles of O required = 207.5 x1.2 = 249
2

Moles of air (21% O )

2

Air per mole of fuel

CONVERSION, SELECTIVITY AND YIELD:

 Conversion is to do with reactants; yield with products.

Conversion:
is a measure of the fraction of the reagent that reacts.
is often less than 100%; to optimize reactor design and minimize by-product
formation.
If more than one reactant is used, the reagent on which the conversion is based
must be specified.
Is defined as:

39
 CONT’D..

The definition gives the total conversion of the particular reagent to all products.
 Example:

In the manufacture of vinyl chloride (VC) by the pyrolysis of dichloroethane

(DCE),the reactor conversion is limited to 55% to reduce carbon formation, which
fouls the reactor tubes. Calculate the quantity of DCE fed to the reactor to
produce 5000 kg/h of VC.
Basis: 5000 kg/h VC (the required quantity).
Reaction:C2H4Cl2 C2H3Cl + HCl
Molar weights: DCE 99, VC 62.5
kmol/h VC produced
From the stoichiometric equation, 1 kmol DCE produces 1 kmol VC. Let X be
DCE feed in kmol/h.
40
 CONT’D…

Note: In this example, the small loss of DCE to carbon and other products has
been neglected. All the DCE reacted has been assumed to be converted to VC.
Selectivity:
is a measure of the efficiency of the reactor in converting reagent to the
desired product.
It is the fraction of the reacted material that was converted into the desired
product.
100%, If no by-products are formed.
decreases If side reactions occur and by-products are formed.
is always expressed as the selectivity of feed A for product B.

41
 CONT’D..
 Defined as;

Stoichiometric factor = moles of B produced per mole of A reacted in the reaction

stoichiometric equation.
 is usually improved by operating the reactor at low conversion.
 At high conversion, the reactor has low concentrations of at least one reagent and
high concentrations of products, so reactions that form by-products are more
likely to occur.
 Reagents that are not converted in the reactor can be recovered and recycled.
 Reagents that become converted to by-products usually cannot be recovered, and
the by-products must be purified for sale or else disposed as waste

42
 CONT’D…
 The optimum reactor conditions thus usually favour low reactor conversion to

give high selectivity for the desired products when all of these costs are taken into
account.

Yield:
is a measure of the performance of a reactor or plant

Several different definitions of yield are used, and it is important to state clearly
the basis of any yield numbers.
The yield of product B from feed A is defined by:

For a reactor, the yield is the product of conversion and selectivity:

43
 CONT’D…
 With industrial reactors, it is necessary to distinguish between ‘‘Reaction yield’’ (chemical

yield), which includes only chemical losses to side products; and the overall ‘‘Reactor yield,’’
which also includes physical losses, such as losses by evaporation into vent gas.

 If the conversion is near 100%, it may not be worth separating and recycling the unreacted

material; the overall reactor yield would then include the loss of unreacted material.

 If the unreacted material is separated and recycled, the overall yield taken over the reactor

and separation step would include any physical losses from the separation step.

 Plant yield is a measure of the overall performance of the plant and includes all chemical

and physical losses.

44
 CONT’D…

 Plant yield (applied to the complete plant or any stage)

 Where more than one reagent is used, or product produced, it is

essential that product and reagent to which the yield refers is clearly
stated.

 The plant yield of B from A is the product of the reactor selectivity of

feed A for product B and the separation efficiency (recovery) of each

separation step that handles product B or reagent A.

45
 EXAMPLE
In the production of ethanol by the hydrolysis of ethylene, diethyl ether is produced
as a by-product. A typical feed stream composition is 55% ethylene, 5% inerts, 40%
water; and product stream: 52.26% ethylene, 5.49% ethanol, 0.16% ether, 36.81%
water, 5.28% inerts. Calculate the selectivity of ethylene for ethanol and for ether.
Solution:
Reactions:

Basis: 100 moles feed (easier calculation than using the product stream)

46
 CONT’D…
 Note: The flow of inerts will be constant, as they do not react; and it can
thus be used to calculate the other flows from the compositions.
Feed stream: ethylene 55 mol
inerts 5 mol
water 40 mol
Product stream

47
 CONT’D…
As 1 mol of ethanol is produced per mol of ethylene, the stoichiometric factor
is 1.

The stoichiometric factor is 0.5, as 2 mol of ethylene produce 1 mol of ether.

Note that the conversion of ethylene, to all products, is given by

 The selectivity based on water could also be calculated but is of no

real interest, as water is relatively inexpensive compared with

ethylene. Water is clearly fed to the reactor in considerable excess.
The yield of ethanol based on ethylene is

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 EXAMPLE
In the chlorination of ethylene to produce dichloroethane (DCE), the conversion of ethylene is
reported as 99.0%. If 94 mol of DCE are produced per 100 mol of ethylene reacted, calculate the
selectivity and the overall yield based on ethylene. The unreacted ethylene is not recovered
Solution:
Reactions:
The stoichiometric factor is 1.
Selectivity
Overall yield (Including physical losses)
Therefore, 99 moles of ethylene are reacted for 100 moles fed, so
Overall yield
Note that:
 we get the same answer by multiplying the selectivity (0.94) and conversion (0.99).

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End of chapter 2