CHAPTER TWO

Flow Diagram and Material Balances

Flow Diagram (Flow-sheeting).

2.1. Introduction:
The flowsheet is the key document in process design. It shows the
arrangement of the equipment selected to carry out the process; the
stream connections; stream flow-rates and compositions; and the
operating conditions. It is a diagrammatic model of the process. The
flow-sheet will be used by the specialist design groups as the basis for
their designs. This will include piping, instrumentation, equipment
design and plant layout. It will also be used by operating personnel for
the preparation of operating manuals and operator training. During plant
start-up and subsequent operation, the flow-sheet forms a basis for
comparison of operating performance with design. The flow-sheet is
drawn up from material balances made over the complete process and
each individual unit. Energy balances are also made to determine the
energy flows and the service requirements.
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2.2. Drawing of Flow sheets.

Flow-sheets may be drawn by hand at preliminary stages of a project, but
with process simulators and CAD software packages, it is a simple
matter to develop flow-sheets with a consistent set of intricate
configuration often is represented simply by a circle or rectangle. Since a
symbol does not usually speak entirely for itself but also may carry a
name and a letter-number identification, the flow-sheet can be made clear
even with the roughest of equipment symbols. The letter-number
designation consists of a letter or combination to designate the class of
the equipment and a number to distinguish it from others of the same
class, as two heat exchangers Operating conditions such as flow rate,
temperature, pressure, enthalpy, heat transfer rate, and also stream
numbers are identified with symbols called flags.

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On a process flow-sheet, distillation towers, furnaces, reactors, and large

vertical vessels often are arranged at one level, condenser and
accumulator drums on another level, re-boilers on still another level, and
pumps more or less on one level but sometimes near the equipment they
serve in order to minimize excessive crossing of lines. Streams enter the
flow-sheet from the left edge and leave at the right edge.
2.2.1. Block diagrams
A block diagram is the simplest form of presentation. Each block can
represent a single piece of equipment or a complete stage in the process.
They are useful for showing simple processes. With complex processes,
their use is limited to showing the overall process, broken down into its
principal stages; as in Example 2.1 (Vinyl Chloride). In that example
each block represented the equipment for a complete reaction stage: the

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Process Flowsheet (Block Diagram)

A process flowsheet is a collection of icons

to represent process units and arrows to
represent the flow of materials to and from
the units.
Fresh feed

Distillation

steam

Reactor
Heater
Flash

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Product
5

Example 1: Input and Output diagram

Water

Raw material

Energy

Auxiliary materiales

Unit
Operation

Product
(expected)

byproduct
(usable)

Waste

Waste easily
assimilated by
the
environment
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Inert waste
always available

toxic/dangerous
waste
6

Example 2: Input and Output

Raw
materials

Gaseous emissions

Plant, Process
or Unit
Operacin

Catalyst

Air/Water
Energy

Recycle

Products
By-products

Wastewater
Liquid waste

Reusable residues in other

operation
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Solid waste

reactor, separators and distillation columns. Block diagrams are useful for representing
a process in a simplified form in reports and textbooks, but have only a limited use as
engineering documents. The stream flow-rates and compositions can be shown on the
diagram adjacent to the stream lines, when only a small amount of information is to be
shown, or tabulated separately. The blocks can be of any shape, but it is usually
convenient to use a mixture of squares and circles, drawn with a template.
Example 2.1
The block diagram shows the main steps in the balanced process for the production of
vinyl chloride from ethylene. Each block represents a reactor and several other
processing units. The main reactions are:

Block A, chlorination
C2H4 + Cl2 C2H4Cl2.

yield : on ethylene 98 %

Block B, oxyhydrochlorination
C2H4 + 2HCl + 1/2O2 C2H4Cl2 + H2O.

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yield: on ethylene 95%

on HCl 90%

Block C, pyrolysis
C2H4Cl2 C2H3Cl + HCl.

yield: on DCE 99%, on HCl 99.5%

The HCl from the pyrolysis step is recycled to the oxyhydrochlorination step. The flow
of ethylene to the chlorination and oxyhydrochlorination reactors is adjusted so that the
production of HCl is in balance with the requirement. The conversion in the pyrolysis
reactor is limited to 55 per cent, and the unreacted dichloroethane (DCE) separated and
recycled.

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Using the yield figures given, and neglecting any other losses, calculate the flow of
ethylene to each reactor and the flow of DCE to the pyrolysis reactor, for a production
rate of 12,500 kg/h vinyl chloride (VC).
Solution
Molecular weights: vinyl chloride 62.5, DCE 99.0, HCl 36.5.
12.500
VC per hour = ---------------- = 200 Kmol/h
62.5
Draw a system boundary round each block, enclosing the DCE recycle within the
boundary of step C.
Let flow of ethylene to block A be X and to block B be Y, and the HCl recycle be Z.
Then the total moles of DCE produced = 0.98X + 0.95Y, allowing for the yields, and
the moles of HCl produced in block C
(0.98X + 0.95Y) 0.995 = Z
Consider the flows to and product from block B

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2.2.2. Pictorial representation

On the detailed flow-sheets used for design and operation, the
equipment is normally drawn in a stylized pictorial form. For tender
documents or company brochures, actual scale drawings of the
equipment are sometimes used, but it is more usual to use a simplified
representation.
2.3. Material Balance; 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. Material
balances are also useful tools for the study of plant operation and trouble
shooting. 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.
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2.4. The Equivalence of Mass and Energy.

Einstein showed that mass and energy are equivalent. Energy can be converted into
mass, and mass into energy. They are related by Einsteins equation:

E = mc2

(2.1)

where E = energy, J,
m = mass, Kg
c = the speed of light in vacuum, 3 X 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

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Classification Based on Spatial Homogeneity

Lumped Parameter System
A system wherein process variables are spatially
homogeneous (do not vary in spatial dimension)
but may vary with time.

Distributed Parameter System

A system wherein process variables are spatially
heterogeneous (vary with space) and may vary
with time.
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Classification Based on Temporal Variation

Steady-State System
Chemical processes that operate at steadystate conditions, i.e. the inputs and the
outputs of the process(es) or process
variables do not change with time.
Dynamic System
Chemical processes for which inputs and
the outputs of the process(es) change with
time, i.e. they have a dynamic behavior.
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e.g. batch reactors for pharmaceutical

chemicals

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Steady State

Dynamic

Balance at equilibrium condition

Time dependent results

Equilibrium results for all unit

operations

Equilibrium conditions not

assumed for all units

Equipment sizes not needed

Equipment sizes needed

Amount of information required: Amount of information required:

small to medium
medium to large
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Types of System and Resulting Equations

Lumped Parameter System

Steady State
Algebraic
Equations

Linear

Distributed Parameter System

Dynamic

Steady State

Dynamic

Differential
Equations

Differential
Equations

Partial
Differential
Equations

Non-Linear

Single
Variable

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MultiVariable

17

Differential and Integral Balance Equations

Differential Balance Equations
Equations are derived by considering what is happening in
a system at any instance in time. Each term of the equation
is a RATE (rate of input, output etc.)

Integral Balance Equation

Equations are derived by considering the state of a system
at two distinct time. Each term of the equation is an
AMOUNT of the balance quantity

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Differential Balance Equation General Form

Rate of

Rate of

Rate of

Rate of

Rate of

INPUT + GENERATION OUTPUT CONSUMPTION = ACCUMULATION

Output
Input
Control Volume = V

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Mass Conservation: Material Balance Equation

Output
Input
Control Volume = V

Rate of
Rate of
INPUT OUTPUT

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Rate of
ACCUMULATION

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Mole Balance Equation

Output
Input
Control Volume = V

Rate of

Rate of

Rate of

Rate of

Rate of

INPUT + GENERATION OUTPUT CONSUMPTION = ACCUMULATION

Question: Is mole balance equation a conservation equation ?

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Mass and Energy Balances

Balance Equation
Input + generation Output =
Accumulation

Control
Volume

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Mass and Energy Balances

For non-reacting systems Generation = 0
For systems operated at steady state
Accumulation = 0
Mass and Energy Balances reduce to
Input = Output
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Separations Calculation
V moles
40% C2H5OH

100 moles
10% C2H5OH
90% H2O

Magic
Separating
Machine

80 moles
x % C2H5OH
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Separation Calculation
V moles

40% C2H5OH

Magic

100 moles

10% C2H5OH

Separating

Machine

90% H2O
80 moles
x % C2H5OH

Conservation of total Moles 100 (V+80) = 0

V =20
Conservation of moles of C2H5OH 100*.1 (.4*V+x*80) = 0
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x = 2.5%

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2.5. CONSERVATION OF MASS

The general conservation equation for any process system can be written
as:
Material out = Material in +Generation _ Consumption _ Accumulation

For a steady-state process the accumulation term will be zero. Except

in nuclear 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 = Material in

A balance equation can be written for each separately identifiable

species present, elements, compounds or radicals; and for the total
material.

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Example 2.2
2000 kg of a 5 per cent slurry of calcium hydroxide in water is to be prepared by diluting a 20 per cent 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
20

___
100

Out
5

= 2000 *

___

(a)

100

(100 20)
(100 5)
X ________ + Y = 2000 * _______
100
100
From equation (a) X = 500Kg
Substituting into equation (b) gives Y = 1500Kg
Check material balance on total quantity
X + Y = 2000
500 + 1500 = 2000 correct
Balance on water

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(b)

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2.6. UNITS USED TO EXPRESS COMPOSITIONS

When specifying a composition as a percentage it is important to state
clearly the basis: weight, molar or volume.
The abbreviations w/w and v/v are used to designate weight basis and
volume basis.
Example 2.3
Technical grade hydrochloric acid has a strength of 28 per cent w/w,
express this as a mol fraction.

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2.7. NUMBER OF INDEPENDENT COMPONENTS

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 per cent nitric and 98 per cent sulphuric acid. The number of distinct
chemical species is 3; water, sulphuric acid, nitric acid.

Chemical systems, reaction

If the process involves chemical reaction the number of independent components will
not necessarily be 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 = Number of chemical species _
Number of independent
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chemical equations

(2.2)

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Example 2.4
If nitration acid is made up using oleum in place of the 98 per cent sulphuric acid, there
will be four distinct chemical species: sulphuric acid, sulphur trioxide, nitric acid, water.
The sulphur trioxide will react with the water producing sulphuric acid so there are only
three independent components

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2.8. GENERAL PROCEDURE FOR MATERIAL-BALANCE

PROBLEMS
The best way to tackle a problem will depend on the information given; the information
required from the balance; and the constraints that arise from the nature of the problem.
No all embracing, best method of solution can be given to cover all possible problems.
The following step-by-step procedure is given as an aid to the efficient solution of
material balance problems. The same general approach can be usefully employed to
organise the solution of energy balance, and other design problems.
Procedure
Step 1. Draw a block diagram of the process.
Show each significant step as a block, linked by lines and arrows to show the stream
connections and flow direction.
Step 2. List all the available data.
Show on the block diagram the known flows (or quantities) and stream compositions.
Step 3. List all the information required from the balance.
Step 4. Decide the system boundaries.

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Step 5. Write out all the chemical reactions involved for the main products and
byproducts.
Step 6. Note any other constraints,
such as: specified stream compositions,
azeotropes,
phase equilibria,
tie substances.
Step 7. Note any stream compositions and flows that can be approximated.
Step 8. Check the number of conservation (and other) equations that can be written, and
compare with the number of unknowns. Decide which variables are to be design
variables; This step would be used only for complex problems.
Step 9. Decide the basis of the calculation.
The order in which the steps are taken may be varied to suit the problem.

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2.9.Methods of material balance

2.9.1 GENERAL ALGEBRAIC METHOD
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 involved, and often 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 known.
Algebraic symbols are assigned to all the unknown flows and compositions. Balance
equations are then written around each sub-system for the independent components
(chemical species or elements). Material-balance problems are particular examples of
the general design problem. 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.

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2.9.1.1. STOICHIOMETRY
Stoichiometry (from the Greek stoikeion element) is the practical application of the
law of multiple proportions. 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 balancing complex
equations, the problem can always be solved by writing a balance for each element
present.
The chemical equation and stoichiometry
1.Write and balance chemical reaction equations.
2.Know the products of common reactions given the reactions.
3.Calculate the stoichiometric quantities of reactants and products given the chemical
reaction.
4.Define excess reactant, limiting reactant, conversion, degree of completion,
selectivity, and yield in a reaction.
5.Identify the limiting and excess reactants and calculate the percent excess reactant(s),
the percent conversion, the percent completion, and yield for a chemical reaction
with the reactants being in non-stiochiometric proportions.
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Problem 2.5
A solution composed of 50% ethanol (EtOH), 10% methanol (MeOH), and 40% water
(H2O) is fed at the rate of 100 kg/hr into a separator that produces one stream at the rate
of 60 kg/hr with the composition of 80% EtOH, 15% MeOH, and 5% H2O, and a
second stream of unknown composition. Calculate the composition (in %) of the three
compounds in the unknown stream and its flow rate in kg/hr.
Solution
We will follow the steps in the analysis and solution of this problem.

Step 1
The problem is to calculate the percent of the three components in the unknown stream
and its flow rate. Assume the process in the steady state over a sufficiently long period
of time.

Steps 2, 3, and 4
The figure is shown with all known values entered as numbers (with units) and all
unknown values entered as symbols.

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Step 5
Four mass balances can be written for each set of variables, one total and three component balances, but only three of the balances are independent.

In addition you know one more independent equation holds for the components in W

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Step 6
Because the equations involving the product of w and W are nonlinear, the equations
involving m are often selected for solution of the problem, but if W is calculated first,
then both sets of equations are linear and uncoupled (can be solved independently).

Step 7
The solution of the equations is (using the total and first two component balances)

Problem 2.6
A liquid adhesive, which is used to make laminated boards, consists of a polymer
Dissolved in a solvent. The amount of polymer in the solution has to be carefully
controlled for this application. When the supplier of the adhesive receives an order for
3000 kg of an adhesive solution containing 13 wt % polymer, all it has on hand is (1)
500 kg of a 10 wt % solution, (2) a very large quantity of a 20 wt % solution, and (3)
pure solvent. Calculate the weight of each of the three stocks that must be blended
together
to fill the order. Use all of the 10 wt % solution.
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Solution

Steps 1, 2, 3 and 4 This is a steady state process without reaction.

Step 5 Basis: 3000 kg 13 wt % polymer solution

Step 6 Two unknowns: B and C . (A is not an unknown since all of it must be used).
Step 7 and 8 Two component balances and one total balance can be made. Only 2 of the
balances are independent.
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We will use equations (1) and (2).

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