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Material balance

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Material balance

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MATERIAL BALANCES

Chapter Contents

2.1. Introduction 2.11. Tie Components

2.2. The Equivalence of Mass and 2.12. Excess Reagent

Energy 2.13. Conversion, Selectivity, and Yield

2.3. Conservation of Mass 2.14. Recycle Processes

2.4. Units Used to Express 2.15. Purge

Compositions 2.16. Bypass

2.5. Stoichiometry 2.17. Unsteady-State Calculations

2.6. Choice of System Boundary 2.18. General Procedure for Material-

2.7. Choice of Basis for Calculations Balance Problems

2.8. Number of Independent 2.19. References

Components 2.20. Nomenclature

2.9. Constraints on Flows and 2.21. Problems

Compositions

2.10. General Algebraic Method

& How to use mass balances to understand process flows

& How to select a system boundary and design basis

& How to estimate reactor and process yields

49

50 CHAPTER 2 FUNDAMENTALS OF MATERIAL BALANCES

2.1. INTRODUCTION

Material balances are the basis of process design. A material balance taken over the

complete process will determine the quantities of raw materials required and products

produced. Balances over individual process units set the process stream flows and

compositions, and provide the basic equations for sizing equipment.

A good understanding of material balance calculations is essential in process design.

In this chapter the fundamentals of the subject are covered, using simple examples to

illustrate each topic. Practice is needed to develop expertise in handling what can often

become very involved calculations. More examples and a more detailed discussion of

the subject can be found in the numerous specialist books written on material and

energy balance computations. Several suitable texts are listed in the ‘‘Bibliography’’

section at the end of this chapter.

For complex processes, material balances are usually completed using process

simulation software, as described in Chapter 4. Significant time and effort can be

wasted in process simulation if the fundamentals of material and energy balances are

not properly understood. Careful attention must be paid to selecting the best basis and

boundaries for material and energy balances; to predicting yields; and to understand-

ing recycle, purge, and bypass schemes. Shorthand calculations, of the type illustrated

in this chapter, should always be used to check process simulation results. Short

calculations can also be used to accelerate convergence of flowsheet simulations by

providing good initial estimates of recycle and make-up streams.

Material balances are also useful tools for the study of plant operation and

troubleshooting. They can be used to check performance against design, to extend

the often limited data available from the plant instrumentation, to check instrument

calibrations, and to locate sources of material loss. Material balances are essential to

obtaining high-quality data from laboratory or pilot plants.

Einstein showed that mass and energy are equivalent. Energy can be converted into

mass, and mass into energy. They are related by Einstein’s equation:

E ¼ mc2 (2:1)

where

E ¼ energy, J,

m ¼ mass, kg,

c ¼ the speed of light in vacuo, 3 108 m=s.

The loss of mass associated with the production of energy is significant only in

nuclear reactions. Energy and matter are always considered to be separately conserved

in chemical reactions.

2.4. UNITS USED TO EXPRESS COMPOSITIONS 51

The general conservation equation for any process system can be written as

Material out ¼ Material in þ Generation Consumption Accumulation

processes, mass is neither generated nor consumed; but if a chemical reaction takes

place, a particular chemical species may be formed or consumed in the process. If

there is no chemical reaction, the steady-state balance reduces to

Material out ¼ Material in

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.

Example 2.1

2000 kg of a 5% slurry of calcium hydroxide in water is to be prepared by diluting a

20% slurry. Calculate the quantities required. The percentages are by weight.

Solution

Let the unknown quantities of the 20% slurry and water be X and Y, respectively.

Material balance on Ca(OH)2

In Out

20 5 (a)

X ¼ 2000

100 100

Balance on water

(100 20) (100 5)

X þ Y ¼ 2000 (b)

100 100

From equation (a), X ¼ 500 kg.

Substituting into equation (b) gives Y ¼ 1500 kg

Check material balance on total quantity:

X þ Y ¼ 2000

500 þ 1500 ¼ 2000, correct

basis: weight, molar, or volume.

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

basis is usually abbreviated vol%, LV%, or v/v.

52 CHAPTER 2 FUNDAMENTALS OF MATERIAL BALANCES

Example 2.2

Technical grade hydrochloric acid has a strength of 28% w/w. Express this as a mole

fraction.

Solution

Basis of calculation 100 kg of 28% w/w acid.

Molecular mass: water 18, HCl 36:5

Mass HCl ¼ 100 0:28 ¼ 28 kg

Mass water ¼ 100 0:72 ¼ 72 kg

28

kmol HCl ¼ ¼ 0:77

36:5

72

kmol water ¼ ¼ 4:00

18

Total mols ¼ 4:77

0:77

mol fraction HCl ¼ ¼ 0:16

4:77

4:00

mol fraction water ¼ ¼ 0:84

4:77

Check total 1:00

Within the accuracy needed for technical calculations, volume fractions can be

taken as equivalent to mole fractions for gases, up to moderate pressures (say 25 bar).

Trace quantities are often expressed as parts per million (ppm). The basis, weight

or volume, needs to be stated, for example, ppmw or ppmv.

quantity of component

ppm ¼ 106

total quantity

Note: 1 ppm ¼ 104 percent.

Minute quantities are sometimes quoted in parts per billion (ppb). This refers to an

American billion (109 ), not a UK billion (1012 ).

2.5. STOICHIOMETRY

The stoichiometric equation for a chemical reaction states unambiguously the number

of molecules of the reactants and products that take part, from which the quantities

can be calculated. The equation must balance.

With simple reactions it is usually possible to balance the stoichiometric equation

by inspection, or by trial-and-error calculations. If difficulty is experienced in balanc-

ing complex equations, the problem can always be solved by writing a balance for

each element present. The procedure is illustrated in Example 2.3.

2.6. CHOICE OF SYSTEM BOUNDARY 53

Example 2.3

Write out and balance the overall equation for the manufacture of vinyl chloride from

ethylene, chlorine, and oxygen.

Solution

Method: Write out the equation using letters for the unknown number of molecules of

each reactant and product. Make a balance on each element. Solve the resulting set of

equations.

A(C2 H4 ) þ B(Cl2 ) þ C(O2 ) ¼ D(C2 H3 Cl) þ E(H2 O)

Balance on carbon

2A ¼ 2D, A ¼ D

on hydrogen

4A ¼ 3D þ 2E

A

substituting D ¼ A gives E ¼

2

on chlorine

A

2B ¼ D, hence B¼

2

on oxygen

E A

2C ¼ E, C¼ ¼

2 4

putting A ¼ 1, the equation becomes

C2 H4 þ 1=2Cl2 þ 1=4O2 ¼ C2 H3 Cl þ 1=2H2 O

4C2 H4 þ 2Cl2 þ O2 ¼ 4C2 H3 Cl þ 2H2 O

The conservation law holds for the complete process and any subdivision of the

process. The system boundary defines the part of the process being considered. The

flows into and out of the system are those crossing the boundary and must balance

with material generated or consumed within the boundary.

Any process can be divided up in an arbitrary way to facilitate the material balance

calculations. The judicious choice of the system boundaries can often greatly simplify

what would otherwise be difficult and tortuous calculations.

No hard and fast rules can be given on the selection of suitable boundaries for all types

of material balance problems. Selection of the best subdivision for any particular process

54 CHAPTER 2 FUNDAMENTALS OF MATERIAL BALANCES

is a matter of judgment, and depends on insight into the structure of the problem,

which can only be gained by practice. The following general rules serve as a guide:

1. With complex processes, first take the boundary around the complete process

and if possible calculate the flows in and out. Raw materials in, products and

byproducts out.

2. Select the boundaries to subdivide the process into simple stages and make a

balance over each stage separately.

3. Select the boundary around any stage so as to reduce the number of unknown

streams to as few as possible.

4. As a first step, include any recycle streams within the system boundary (see

Section 2.14).

Example 2.4

The diagram shows the main steps in a process for producing a polymer. From the

following data, calculate the stream flows for a production rate of 10,000 kg/h.

slurry polymerization 20 wt% monomer/water

conversion 90% per pass

catalyst 1 kg/1000 kg monomer

short stopping agent 0.5 kg/1000 kg unreacted monomer

Filter wash water approx. 1 kg/1 kg polymer

Recovery column yield 98% (percentage recovered)

Dryer feed 5% water, product specification 0.5% H2 O

Polymer losses in filter and dryer 1%

Reactor

Monomer

water M

catalyst Wash

Short stop water

Polymer

Dryer

Filter

Recycle

monomer Recovery

column

Effluent

2.6. CHOICE OF SYSTEM BOUNDARY 55

Solution

Only those flows necessary to illustrate the choice of system boundaries and method

of calculation are given in the solution.

Basis: 1 hour

Take the first system boundary around the filter and dryer.

Filter Product

Input and 10,000 kg polymer

dryer 0.5% water

Water

+ monomer

Losses

10,000

¼ ¼ 10,101 kg

0:99

Take the next boundary around the reactor system; the feeds to the reactor can

then be calculated.

Short stop

Water

10,101 kg

Reactor

Monomer polymer

Cat.

Recycle

10,101

At 90% conversion per pass, monomer feed ¼ ¼ 11,223 kg

0:9

Unreacted monomer ¼ 11,223 10,101 ¼ 1122 kg

11,223

0:2 ¼

F1 þ 11,223

11,223(1 0:2)

F1 ¼ ¼ 44,892 kg

0:2

Now consider filter-dryer subsystem again.

56 CHAPTER 2 FUNDAMENTALS OF MATERIAL BALANCES

10,101 0:05

¼ ¼ 532 kg

0:95

monomer, unreacted monomer ¼ 1122 kg

Column

Water Monomer

54,461 kg

monomer

1122 kg

Effluent

¼ 0:98 1122 ¼ 1100 kg

Consider reactor monomer feed

Fresh Reactor

feed feed

Recycle

1100 kg

¼ 11,223 1100 ¼ 10,123 kg

Note that this 12-line calculation would have required setting up a recycle and

three stream-adjusts in a process simulator, illustrating that simple problems can often

be solved more easily by hand or spreadsheet calculations if the boundaries for mass

balances are chosen carefully.

The choice of the basis for a calculation often determines whether the calculation

proves to be simple or complex. As with the choice of system boundaries, no all-

embracing rules or procedures can be given for the selection of the right basis for

2.8. NUMBER OF INDEPENDENT COMPONENTS 57

any problem. The selection depends on judgment gained by experience. Some guide

rules are

A. Time: Choose the time basis in which the results are to be presented; for

example kg/h, metric tons/y, unless this leads to very large or very small

numbers, where rounding errors can become problematic.

B. For batch processes, use one batch.

C. Choose as the mass basis the stream flow for which most information is given.

D. It is often easier to work in moles, rather than weight, even when no reaction is

involved.

E. For gases, if the compositions are given by volume, use a molar basis, remembering

that volume fractions are equivalent to mole fractions up to moderate pressures.

A balance equation can be written for each independent component. Not all the

components in a material balance will be independent.

Physical Systems, No Reaction

If there is no chemical reaction, the number of independent components is equal to

the number of distinct chemical species present.

Consider the production of a nitration acid by mixing 70% nitric and 98% sulfuric

acid. The number of distinct chemical species is three: water, sulfuric acid, nitric acid.

H2SO4/H2O H2O

HNO3 Nitration

Mixer

H2SO4 acid

HNO3/H2O

If the process involves chemical reaction, the number of independent components is

not necessarily equal to the number of chemical species, as some may be related by the

chemical equation. In this situation the number of independent components can be

calculated by the following relationship:

Number of independent components ¼ Number of chemical speciesNumber of

independent chemical equations (2:2)

Example 2.5

If nitration acid is made up using oleum in place of the 98% sulfuric acid, there will be

four distinct chemical species: sulfuric acid, sulfur trioxide, nitric acid, water. The

sulfur trioxide will react with the water producing sulfuric acid, so there are only

three independent components.

Oleum

H2SO4/H2O/SO3 H2O

HNO3 Nitration

HNO3/H2O H2SO4 acid

58 CHAPTER 2 FUNDAMENTALS OF MATERIAL BALANCES

Solution

Reaction equation SO3 þ H2 O ! H2 SO4

No. of chemical species 4

No. of reactions 1

No. of independent equations 3

It is obvious, but worth emphasizing, that the sum of the individual component flows

in any stream cannot exceed the total stream flow. Also, the sum of the individual

molar or weight fractions must equal 1. Hence, the composition of a stream is

completely defined if all but one of the component concentrations are given.

The component flows in a stream (or the quantities in a batch) are completely

defined by any of the following:

A. Specifying the flow (or quantity) of each component.

B. Specifying the total flow (or quantity) and the composition.

C. Specifying the flow (or quantity) of one component and the composition.

Example 2.6

The feed stream to a reactor contains ethylene 16%, oxygen 9%, nitrogen 31%, and

hydrogen chloride. If the ethylene flow is 5000 kg/h, calculate the individual com-

ponent flows and the total stream flow. All percentages are by weight.

Solution

5000

Percentage ethylene ¼ 100 ¼ 16

total

100

hence total flow ¼ 5000 ¼ 31,250 kg=h

16

9

so, oxygen flow ¼ 31,250 ¼ 2813 kg=h

100

31

nitrogen ¼ 31,250 ¼ 9687 kg=h

100

44

hydrogen chloride ¼ 31,250 ¼ 13,750 kg=h

100

General rule: The ratio of the flow of any component to the flow of any other

component is the same as the ratio of the compositions of the two components.

The flow of any component in Example 2.6 could have been calculated directly

from the ratio of the percentage to that of ethylene and the ethylene flow.

44

Flow of hydrogen chloride ¼ 5000 ¼ 13,750 kg=h

16

2.10. GENERAL ALGEBRAIC METHOD 59

Simple material-balance problems involving only a few streams and with a few

unknowns can usually be solved by simple, direct methods. The relationship between

the unknown quantities and the information given can usually be clearly seen. For

more complex problems, and for problems with several processing steps, a more

formal algebraic approach can be used. The procedure is tedious if the calculations

have to be done manually, but should result in a solution to even the most intractable

problems, providing sufficient information is given for the problem to have a solution.

Algebraic symbols are assigned to all the unknown flows and compositions. Bal-

ance equations are then written around each subsystem for the independent compon-

ents (chemical species or elements).

Material-balance problems are particular examples of the general design problem

discussed in Chapter 1. The unknowns are compositions or flows, and the relating

equations arise from the conservation law and the stoichiometry of the reactions. For

any problem to have a unique solution, it must be possible to write the same number

of independent equations as there are unknowns.

Consider the general material balance problem where there are Ns streams each

containing Nc independent components. Then the number of variables, Nv , is given by

Nv ¼ Nc Ns (2:3)

Nd , that must be specified for a unique solution, is given by

Nd ¼ (Ns Nc ) Ne (2:4)

1

2 Mixer 4

3

Let Fn be the total flow in stream n, and xn,m the concentration of component m in

stream n. Then the general balance equation can be written

F1 x1,m þ F2 x2,m þ F3 x3,m ¼ F4 x4,m (2:5)

A balance equation can also be written for the total of each stream:

F1 þ F 2 þ F 3 ¼ F 4 (2:6)

but this could be obtained by adding the individual component equations, and so is

not an additional independent equation. There are m independent equations, the

number of independent components.

This problem has 4m variables and m independent balance equations. There will be

a unique solution to the problem if we specify 3m variables, for example, the molar

flows of all m components in the three feeds or in two feeds and the product.

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