CT 206 INDUSTRIAL TECHNOLOGY

A. CHEMICAL PROCESS INDUSTRY

 A Chemical Process Industry is one in which the raw materials undergo

chemical conversion during their processing into finished products, as well
as (or instead of) the physical conversions common to industry in general.
 In the chemical process industry the products differ chemically from the
raw materials as a result of undergoing one or more chemical reactions
during the manufacturing process.
 The chemical process industries broadly include the traditional chemical
industries, both organic and inorganic; the petroleum industry; the
petrochemical industry, which produces the majority of plastics,
synthetic fibers, and synthetic rubber from petroleum and natural-gas
raw materials; and a series of allied industries in which chemical
processing plays a substantial part.
 While the chemical process industries are primarily the realm of the
chemical engineer and the chemist, they also involve a wide range of other
scientific, engineering, and economic specialists.

B. TECHNOLOGICAL ECONOMICS

BASIC COST CONCEPTS

Concept of Cost

 In general, cost means the amount of expenditure (actual or notional)

incurred on, or attributable to a given thing.

However, the term cost cannot be exactly defined. Its interpretation depends
upon the following factors:

 The nature of business or industry

 The context in which it is used
 The cost may be factory cost, office cost, cost of sales and even an item
of expense. For example, prime cost includes expenditure on direct
materials, direct labor and direct expenses. Money spent on materials is
termed as cost of materials just like money spent on labor is called cost
 of labor and so on. Thus, the use of term cost without understanding the
circumstances can be misleading.

Different costs are found for different purposes. The work-in-progress is

valued at factory cost while stock of finished goods is valued at office cost.

ELEMENTS OF COST

Following are the three broad elements of cost:

1. Material is the substance from which a product is made. It may be in a

raw or a manufactured state. It can be direct as well as indirect.
 Direct Material is when the material becomes an integral part of a
finished product and can be conveniently assigned to specific physical
units. It can also be described as process material, prime cost
material, production material, stores material, constructional material
etc.
 Following are some of the examples of direct material:
 All material or components specifically purchased, produced
or requisitioned from stores
 Primary packing material (e.g., carton, wrapping, cardboard,
boxes etc.)
 Purchased or partly produced components

 Indirect Material is a material which is used for purposes ancillary to

the business and cannot be conveniently assigned to specific physical
units. Indirect material may be used in the factory, office or the
selling and distribution divisions.
 Some of the examples of indirect material are:
 Consumable stores
 oil and waste
 printing and stationery material etc.

2. Labour is human effort needed for conversion of materials into finished

goods. Labour can be direct as well as indirect.
 Direct Labour is labor which actively and directly takes part in the
production of a particular commodity. Direct labour costs are,
 therefore, specifically and conveniently traceable to specific
products. Direct labor can also be described as process labour,
productive labour, operating labour, etc.
 Indirect Labour is labour employed for the purpose of carrying out
tasks incidental to goods produced or services provided. Such labour
does not alter the construction, composition or condition of the
product. It cannot be practically traced to specific units of output.
Indirect labour may relate to the factory, the office or the selling
and distribution divisions.
 examples of indirect labour costs:
 Wages of storekeepers, Foremen, Timekeepers
 directors’ fees
 salaries of salesmen etc

3. Expenses -Expenses may be direct or indirect.

 Direct Expenses are the expenses that can be directly, conveniently
and wholly allocated to specific cost centers or cost units. Direct
expenses are sometimes also described as chargeable expenses.
 Examples of such expenses are as follows:
 Hire of some special machinery required for a particular
contract
 Cost of defective work incurred in connection with a
particular job or contract etc.
 Indirect Expenses are the expenses that cannot be directly,
conveniently and wholly allocated to cost centers or cost units.
 Examples of such expenses are:
 Rent
 Lighting
 insurance charges etc.

CLASSIFICATION OF COST

Cost may be classified into different categories depending upon the purpose of
classification. Some of the important categories in which the costs are
classified are as follows:
1. Fixed, Variable and Semi-Variable Costs
 Variable costs these are costs which vary directly in proportion with
every increase or decrease in the volume of output or production.
 Some of its examples are as follows:
 Wages of laborers
 Cost of direct material
 Power
 Fixed cost is the cost which does not vary but remains constant within
a given period of time and a range of activity inspite of the
fluctuations in production.
 Some of its examples are as follows:
 Rent or rates
 Insurance charges
 Management salary
 Semi-variable cost is the cost which does not vary proportionately but
simultaneously and does not remain stationary at all times. It can also be
named as semi-fixed cost.
 Some of its examples are as follows:
 Depreciation
 Repairs

2. Direct and Indirect Costs

 Direct costs are expenses incurred on material and labour and are
economically and easily traceable for a product, service or jobs. In the
process of manufacturing of production of articles, materials are
purchased, labourers are employed and the wages are paid to them.
Certain other expenses are also incurred directly. All of these take an
active and direct part in the manufacture of a particular commodity and
hence are called direct costs.

 Indirect costs are expenses incurred on those items which are not
directly chargeable to production. All of these cannot be conveniently
allocated to production and hence are called indirect costs.
 for example:
 salaries of timekeepers, storekeepers and foremen
  certain expenses incurred for running the administration

3. Production, Administration and Selling and Distribution Costs

A business organization performs a number of functions, e.g., production,

illustration, selling and distribution, research and development. Costs are to be
curtained for each of these functions. The Chartered Institute of Management
accountants, London, has defined each of the above costs as follows:

 Production Cost is the cost of sequence of operations which begins with

supplying materials, labour and services and ends with the primary packing
of the product. Thus, it includes the cost of direct material, direct
labour, direct expenses and factory overheads.
 Administration Cost is the cost of formulating the policy, directing the
organization and controlling the operations of an undertaking which is not
related directly to a production, selling, distribution, research or
development activity or function.
 Selling Cost is the cost of selling to create and stimulate demand
(sometimes termed as marketing) and of securing orders.
 Distribution Cost is the cost of sequence of operations beginning with
making the packed product available for dispatch and ending with making
the reconditioned returned empty package, if any, available for reuse.
 Research Cost is the cost of searching for new or improved products,
new application of materials, or new or improved methods.
 Development Cost is the cost of process which begins with the
implementation of the decision to produce a new or improved product or
employ a new or improved method and ends with the commencement of
formal production of that product or by the method.
 Pre-Production Cost is the part of development cost incurred in making a
trial production as preliminary to formal production.

A manufacturing organization can broadly be divided into the following three

divisions:

 Factory or works, where production is done

 Office and administration, where routine as well as policy matters are
decided
  Selling and distribution, where products are sold and finally dispatched to
customers

OVERHEADS

All indirect costs are overheads. The term overhead includes indirect material,
indirect labor and indirect expenses.

 Overheads may be incurred in a factory or office or selling and

distribution divisions. Thus, overheads may be of three types:

a. Factory Overheads
 They include the following things:
 Indirect material used in a factory such as lubricants, oil, consumable
stores etc.
 Indirect labor such as gatekeeper, timekeeper, works manager’s salary
etc.
 Indirect expenses such as factory rent, factory insurance, factory
lighting etc.

b. Office and Administration Overheads

 They include the following things:
 Indirect materials used in an office such as printing and stationery
material, brooms and dusters etc.
 Indirect labor such as salaries payable to office manager, office
accountant, clerks, etc.
 Indirect expenses such as rent, insurance, lighting of the office

c. Selling and Distribution Overheads

 They include the following things:
 Indirect materials used such as packing material, printing and stationery
material etc.
 Indirect labor such as salaries of salesmen and sales manager etc.
 Indirect expenses such as rent, insurance, advertising expenses etc.
BREAK-EVEN ANALYSIS AND FORECASTING

Break-even analysis depends on the following variables:

1. Selling Price per Unit:The amount of money charged to the customer for
each unit of a product or service.

2. Total Fixed Costs: The sum of all costs required to produce the first
unit of a product. This amount does not vary as production increases or
decreases, until new capital expenditures are needed.

3. Variable Unit Cost: Costs that vary directly with the production of one
additional unit.

 Total Variable Cost The product of expected unit sales and variable unit
cost, i.e., expected unit sales times the variable unit cost.

 Forecasted Net Profit: Total revenue minus total cost.

 Each of these variables is interdependent on the break-even point

analysis. If any of the variables changes, the results may change.

 Total Cost: The sum of the fixed cost and total variable cost for
any given level of production, i.e., fixed cost plus total variable
cost.
 Total Revenue: The product of forecasted unit sales and unit
price, i.e., forecasted unit sales times unit price.

Break-Even Point: Number of units that must be sold in order to produce a

profit of zero (but will recover all associated costs). In other words, the break-
even point is the point at which your product stops costing you money to
produce and sell, and starts to generate a profit for your company.

The graphic method of analysis (below) helps you in understanding the concept
of the break-even point. However, the break-even point is found faster and
more accurately with the following formula:

Q = FC / (UP - VC)

where:
Q = Break-even Point, i.e., Units of production (Q),

FC = Fixed Costs,

VC = Variable Costs per Unit

UP = Unit Price

Therefore,

Break-Even Point Q = Fixed Cost / (Unit Price - Variable Unit Cost)

Gross Profit is a term to describe the money left over from the sale of
products after subtracting the cost of goods sold without taking out the money
needed to pay operating expenses. Knowing how much is left from each sale to
pay salaries and other fixed expenses helps leaders determine the financial
health and viability of the operation.

BASIC CHEMICAL DATA

Chemical conversion is a chemical manufacturing process in which chemical

transformation takes place, that is, the product differs chemically from the
starting materials.

 Most chemical manufacturing processes consist of a sequence of steps,

each of which involves making some sort of change in either chemical
 makeup, concentration, phase state, energy level, or a combination of
these, in the materials passing through the particular step.
 If the changes are of a strictly physical nature (for example, mixing,
distillation, drying, filtration, adsorption, condensation), the step is
referred to as a unit operation.
 If the changes are of a chemical nature, where conversion from one
chemical species to another takes place (for example, combustion,
polymerization, chlorination, fermentation, reduction, hydrolysis), the
step is called a unit process.
 Some steps involve both, for example, gas absorption with an
accompanying chemical reaction in the liquid phase. The term chemical
conversion is used not only in describing overall processes involving
chemical transformation, but in certain contexts as a synonym for the
term unit process.

Another usage of the term chemical conversion is to define the percentage of

reactants converted to products inside a chemical reactor or unit process. This
quantitative usage is expressed as percent conversion per pass, in the case of
reactors where unconverted reactants are recovered from the product stream
and recycled to the reactor inlet.

Yield : the fraction of raw materials recovered as the main or desired

product

- it can be improved through recycling or multipass so that

multiconversion improves yield.

Conversion: the fraction of raw materials changed to something else- products

or by products.

It also indicates the amount changed by a single pass through an

operation when multipasses are present.

It is also an reflection of the equilibrium position thus can be

changed by optimising environmental conditions such as pressure,
temperature and reaction time and improved catalysts. Usually
costs go up in doing so.
Efficiency: the ratio of moles of reactants converted to desired product to
the moles of reactants chemically converted.

For catalytic reactions, the term selectivity may be used instead of

efficiency.

Selectivity: the ratio of moles of desired product formed to the moles of

reactants chemically converted.

C. MATERIAL BALANCES

Material Balance Fundamentals

Material balances (mass balances) are based on the fundamental “law of

conservation of mass (not volume, not moles)”. In particular, chemical
technologists are concerned with doing mass balances around chemical
processes.

Doing a ‘mass balance’ is similar in principle to accounting. In accounting,

accountants do balances of what happens to a Company’s money. Chemical
technologists do a mass balance to account for what happens to each of the
chemicals that is used in a chemical process.

Whats important is to learn how to

a) Specify a process stream
b) Specify a process unit
c) Do a mass balance on a process unit
d) Do a mass balance on a sequence of process units.

Classification of Processes

A. Based on how the process varies with time.

a. Steady-state process is one that does not change with time. Every
time we take a snapshot, all the variables have the same values as
in the first snapshot.
 b. Unsteady-state (Transient) process is one that changes with
time. Every time we take a snapshot, many of the variables have
different values than in the first snapshot.

B. Based on how the process was built to operate.

a. A Continuous process is a process that has the feed streams and

product streams moving chemicals into and out of the process all
the time. At every instant, the process is fed and product is
produced. Examples are an oil refinery, a power grid and a steady
salaried job.

b. A Batch process is a process where the feed streams are fed to

the process to get it started. The feed material is then processed
through various process steps and the finished products are
created during one or more of the steps. The process is fed and
products result only at specific times. Examples are making a batch
of a product, like soup or a specialty chemical.

c. A Semi-batch process (also called semi-continuous) is a process

that has some characteristics continuous and batch processes.
Some chemicals in the process are handled batch-wise. Some
chemicals are processed continuously.

Types of Balances

a. Differential Balance is a balance taken at a specific instant in time. It is

generally applied to a continuous process. If the process is at steady
state, a differential balance applied at any time gives the same result.

 We will apply differential balances to steady-state continuous

processes.
  Each term in a differential balance represents a process stream
and the mass flow rate of the chemical(s) in that stream.

b. Integral balance is a balance taken at two specific instants in time. It

describes what has happened over the time period between the two
points. An integral balance is generally applied to the beginning and the
end of a batch process. It accounts for what happens to the batch of
chemicals.

 We will apply integral balances to batch processes.

 Each term in an integral balance represents a process stream and

the mass of the chemical(s) in that stream.

The Mass Balance Equation

The law of ’conservation of mass’ states that mass cannot be created or

destroyed. We will use this law in the form of a general mass balance equation
to account for the total mass all of the chemicals that are involved in the
process. The total mass balance equation can be written as

INPUT  OUTPUT = ACCUMULATION

I  O = A

If the process is at steady-state, there is no accumulation of mass within the

process. We will deal only with steady-state processes. Thus

INPUT = OUTPUT
I = O
When we apply this equation to a process, it is best to write it as

Masses entering via feed streams = Masses exiting via product

streams
We understand that we must include the mass of every chemical in every
stream. The above equation can applied to batch and continuous processes as

Mass in = Mass out for a batch process, and

Mass in by flow = Mass out by flow for a continuous process.

If the process involves chemical reaction(s), we must account for the formation
of product chemicals and the consumption of feed chemicals. We must remind
ourselves that the law of conservation of mass means total mass. For this case,
we must write a mass balance for each chemical and account its formation and
consumption as follows

Mass in + Mass formed by reaction = Mass out + Mass used by

reaction

Or, written more simply as

in + formed = out + consumed

What balances can one write?

1. A mass balance can be written using the total mass in each process
stream. This is called a total balance.
2. A separate mass balance can be written for each chemical component
involved. These are called component balances.

Example: A process unit involves 3 chemical components. How many mass

balances can be written?

Solution: We can write 4 balances. We can write a total balance and 3

component balances.

Independent balances: Not all balances are independent since the total balance
in the sum of all of the component balances.
Thus, the number of independent balances we can write = the number of
components.

Which of the following must be conserved in a chemical process?

-Total mass
-Mass of a chemical
-Total moles
-Moles of a chemical
-Mass of a specie (eg. SO2)
-Moles of a specie
-Mass of an element
-Moles of an element
 You need to develop skill at using a systematic approach to solving mass
balance problems. And later, skill at using a systematic approach to
solving mass and energy balance problems.
To answer the first question, you need to:
1. Read, study and understand the problem.
2. Draw a flow sheet for the process.
3. Label it with all given information, including symbols for the unknowns
4. Note any special relationships.

To accomplish this step, you need to learn

1. The information needed to specify a stream.
2. How to use symbols to represent the required stream data.
3. How to determine the mass of each component in a stream (each mass will
be a term in a mass balance)

Required Stream Information

1. Stream name & symbol (1)
2. Component masses/ stream composition (n)
3. Stream temperature and pressure (these are needed only when an energy
balance is being done, phase behaviour is included or to specify chemical
properties.
How to represent the required information

1. Specify each stream and total mass --- Select a stream name & symbol
a) Use a single Capital letter to represent the total mass of the stream.
b) Select a stream name to clearly identify the stream, by the location or
purpose of the stream on the flow sheet.
c) Put the mass on the flow sheet using an equation symbol = value (if the
mass is known) or symbol = ? (if the value is unknown)

Example: The reactor is fed with 25 kg/s of a hot feed stream and a
recycle stream. Label the reactor inputs.

Solution: The reactor has two input streams. We draw and label them as

Hot Reactor Feed, H =25 kg/s

Reactor
Recycle, R=?

NOTE:The total mass balance will be written using the symbols selected for the
stream names.

Next we must learn how to represent the component masses so we can write the
component balances.

2. Component masses/ stream composition- A component mass can be

represented directly, using a lower case letter and a subscript, or indirectly
using the fractional composition times the stream total (use and reserve
x,y,z for fractional composition).
3. Note that a component mass can be calculated as the product of the
total and the fractional composition.

Example1: Stream F contains 500 kg of O2 and 700 kg of CH4. Label the stream.
Solution: Note that the component masses must add to the total. The total mass
in F is 1200 kg. Thus,

Stream F F=1200 kg
m O2 = 500 kg
m CH4 = 700 kg

Example 2: 1200 kg of a mixture of O 2 , N2 and CH4 are fed to a process. The

stream has 20% O2 by mass. Label the stream.
( Note the Mass of i in the stream is F x i )

Solution: The composition is partially known. Note that the fractional

compositions must add to 1.0. Thus, we can write two alternatives

Using fractional composition

Feed Stream F, F=1200 kg

xO2 = 0.2
xN2 = ?
xCH4 = 1. – 0.2 - xN2 = 0.8 - xN2

or using component masses

Feed Stream F, F=1200 kg

mO2 = 240 kg
mN2 = ?
mCH4 = 1200 - 240 - mN2 = 960 - mN2

Some Suggestions for Component Labeling

 1. If the stream composition is unknown (or if some of the component
masses are known) represent the component masses directly and use a
lower case letter for each chemical.
Eg. If stream F contains chemicals a, b and c, label the flow rates
as F, aF, bF and cF=F- aF - bF
2. If the stream composition is known from fractional compositions,
represent the component masses directly and label as in 2.

3. If stream composition is partially known with fractional compositions and

the total is known, represent the component masses indirectly and use
lower case x,y,z for each fractional composition.
4. Avoid the creation of a product of two unknowns—this will result in a
non-linear equation.

EXAMPLE

An equimolar mixture of propane and butane is fed to a distillation column at

the rate of 67mols-1 . 90% of the propane is recovered in the top product which
has a propane mole fraction of 0.95. Calculate the flowrates of the top and
bottom products and the composition of the bottom product.

SOLUTION
1. Flowsheet
2. Basis : 10 mol of feed , ie F=10 mol
3. Conversion of units- not necessary since all units are molar.
4. Equations- there are no reactions and the steady state balance equation
for the total flow is Input = output.

i. Total material balance

F= D+B………………(1)
{ where D=distillate; B=bottom prdt}

ii. Component balances

Propane: FxF= DxD +BxB……………...(2)
Butane:F(1-xF)= D(1-xD)+ B(1-xB)……………(3)
 {where XF is mol fraction of propane in F, X D is mol fraction of
propane in D and XB is mol fraction in B}.

Inserting values into the first two equations gives

10= D+ B………………………….(4)
5= 0.95D+BxB………………(5)

iii. A third independent equation is provided by the specification on

propane
xDD= 0.90FxF
0.95D= 0.90*10*0.50
hence 0.95D= 4.5………….(6)
D=4.74mol

Substituting in (4)
10= 4.74+ B
B= 5.26mol

Equation (5) can now be solved for the bottom stream composition
5= 0.95D+ BxB
5= 0.95(4.74)+ 5.26xB
XB= 0.095 (mol fraction of Propane)

Scaling – compositions are unchanged by the choice of . the

quantities obtained above must be scaled by:
67mols-1/ 10mol= 6.7s-1
Bottom flowrate= 5.26 x 6.7= 35.2mols-1
Top flow rate= 4.74 x 6.7= 31.8mols-1

CHEMICAL REACTIONS

 The treatment of material balances for the systems in which chemical

reactions take place involves the inclusion of generation and consumption
 terms for molecular species as well as observance of stoichiometric
constraints
 The stoichiometric equation of the reaction of a reaction defines the
ratios in which the molecules of different species are consumed or
formed in the reaction.
e.g. C2H6+ 7/2O2 2CO2+ 3H2O
 for defining stoichiometric coefficients ν i, the stoichiometric equation is
written with all species on the right hand side
i.e. 0= 2CO2+ 3H2O- C2H6-7/2O2
 the stoichiometric coeeficients are

 νCo2 =2
 νH2O= 3
 νC2H6= -1
 νO2= -7/2
 a general stoichiometric equation can be written as
 ∑ ν iAi = 0
i

 Where Ai are the participating species and ν i is negative for

reactants and positive for products, and zero for inerts.
 The extent of the reaction is a measure of the material consumed or
produced in a reaction.
 If the material balance for the chemical reactor is considered, then the
extent ξ, is defined by the equation:
fi out= fi in+ νi ξ
 Where fi out= number of moles of species i leaving the reactor
fi in= number of moles of species i entering the reactor
hence ξ = fi out- fi in/ νi
 most chemical reactions do not result in complete conversion of reactants
to products
 the maximum possible extent depends on the equilibrium constant, but it
is more convenient to define a fractional conversion based on quantities
present in the feed
fractional conversion of species= fi in- fi out/ fi in

EXAMPLE
200mol of ethane are burnt in a furnace with 50% excess air. A conversion of
95% is achieved. Calculate the composition of stack gases.

SOLUTION

furnace

fC2H6 in= 200mol fC2H6 out

fO2 in= 1050mol fO2 out
fN2 in= 3948mol fN2 out
fCO2 out
fH2O out

stoichiometric equation

C2H6+ 7/2O2 2CO2+ 3H2O

A stoichiometric feed would require 200 * 7/2= 700mol of O 2, thus 50% excess
air provides 1050mol O2.

Taking air to be 21%(molar) O2 and 79% N2 gives 3.76mol N2/mol O2, i.e.
3948mol N2 in the feed.

The conversion is 95%, since no reactant is specified we assume that it refers

to the limiting reactant- ethane in this case.

Conversion = (fc2H6 in- fc2H6 out)/ fc2H6 in = 0.95

Hence, fc2H6 out = 10mol

Extent ξ = (fc2H6 out- fc2H6 in)/ νc2H6

= (10- 200)/-1

=190mol

The Material balance is summarized in the table below;

In mol mol Out mol Mol fraction

C2H6 200 200- ξ 10 0.0019
O2 1050 1050- 7/2 ξ 385 0.0727
 N2 3948 3948 3948 0.7459
CO2 0 2ξ 380 0.0718
H2O 0 3ξ 570 0.1077
5198+ 1/2 ξ 5293 1.0

ENERGY BALANCES

 Based on the principle of conservation of energy

 An energy balance is used to determine the energy requirements of a
process or unit in terms of heating, cooling or work
 For many purposes it is possible to cary out material and energy balances
independently but it is not always the case , for example in the design of
a chemical reactor the extent is strongly dependent on the temperature
and the two balances must be solved simultaneously.

Energy balance equations

 The general balance equation may be applied to energy but the generation
and consumption terms are always zero
 Energy is neither created nor destroyed in chemical reactions- there is
merely a difference in energy associated with chemical bonds in
reactants and products.

[ENERGY IN]- [ENERGY OUT]= [ACCUMULATION OF ENERGY WITHIN

SYSTEM]

 The types of energy that go in and out of a system are internal energy
(fu), flow work (fPv), potential energy (fP’), kinetic energy (fk’).
 The internal energy term includes both chemical energy of bonding and
thermal energy due molecular motion and intermolecular interactions.
 The flow work term represents the work done by the surroundings or
system in transferring material across system boundaries.
 For a system at steady state,

[ENERGY IN]= [ENERGY OUT]

Hence:

∑ f ( u+ Pv + P' + K ' ) + Q+ W = ∑ f (u+ Pv+ P ' + K ')

inlet streams outlet streams
Where f=the flow work

P= the pressure

and u, v, P’ and K’ are specific, internal energy, volume, potential

energy and kinetic energy.

 The difference between kinetic and potential energy terms in inlet and
outlet streams is usually small as compared with the remaing terms.

In such cases:

∑ f ( u+ Pv )−∑ f ( u+ Pv ) =Q+ W
outlet inlet

Or in terms of enthalpy, h=u+ Pv

∑ fi h i−∑ fi h i=Q+W
outlet inlet

Hence, ∆ H =Q+W

 this is the form of an energy balance equation most frequently used in

continuous process
 for a close (batch) system which has no flow of matter in or out, the
change in internal energy of the system is due solely to heat flow and
work done. Hence :

Ufinal−Uinitial=Q+W

Or ∆ U =Q+W

Where U = total internal energy

 Heat capacities can be used to estimate enthalpy changes

 The change in enthalpy at constant pressure due to a change in
T1

temperature from T0 to T1 is given by ∆ h=∫ CpdT

T0

where Cp is the isobaric temperature.

EXAMPLE
Determine the heat load required to heat a stream of nitrogen, flowing at
50molmin-1 from 20℃ to 100 ℃ given that the heat capacity of nitrogen is
represented by:

Cp= 29.0+ 2.2x10-3T+ 5.7X10-6T2- 2.87x10-9T3 JK-1mol-1

Where T is in ℃

SOLUTION

This is steady state flow, hence, ∆ H =Q+W

Assuming work done is negligible, ∆ H ≈ Q

100
∆ H =∫ Cp ( T ) d T ¿
20 ¿

integration gives ∆ H =2332 J mol−1

flow rate is 50molmin-1

Q= 50* 2332

=116.6KJmin-1

=1.94KW

 For the purposes of energy balances the enthalpy of a substance, I, at a

pressure P and temperature T may be evaluated by expressing it in the
formhi ( P ,T )=( hi ( P , T )−hi ) + ∆ h f ,i
θ θ

Where ∆ hf , i is the standard enthalpy change of formation of i from its

θ

elements and hi =hi= (101325Pa, 298K)
θ

 The above equation is based on the convention that enthalpies of

elements at 101325Pa, 298K are zero.

HEAT TRANSFER

WHAT IS HEAT?

 Heat is energy in transit from warmer systems to colder systems.

  Heat is associated with the internal potential and kinetic energy (an
apparently disorganized molecular motion) of a system.

What is Heat Transfer?

Thermal energy is related to the temperature of matter. For a given material

and mass, the higher the temperature, the greater its thermal energy. Heat
transfer is a study of the exchange of thermal energy through a body or
between bodies which occurs when there is a temperature difference. When
two bodies are at different temperatures, thermal energy transfers from the
one with higher temperature to the one with lower temperature. Heat always
transfers from hot to cold.

Table 1 shows the common SI and English units and conversion factors used for
heat and heat transfer rates. Heat is typically given the symbol Q, and is
expressed in joules (J) in SI units. The rate of heat transfer is measured in
watts (W), equal to joules per second, and is denoted by q. The heat flux, or the
rate of heat transfer per unit area, is measured in watts per area (W/m 2), and
uses q" for the symbol.

Table 1. Units and Conversion Factors for Heat Measurements

  SI Units English Units

Thermal Energy (Q) 1J 9.4787×10-4 Btu

Heat Transfer Rate (q) 1 J/s or 1 W 3.4123 Btu/h

Heat Flux (q") 1 W/m2 0.3171 Btu/h ft2

1.2 Three Modes of Heat Transfer

There are three modes of heat transfer: conduction, convection, and radiation.
Any energy exchange between bodies occurs through one of these modes or a
combination of them. Conduction is the transfer of heat through solids or
stationery fluids. Convection uses the movement of fluids to transfer heat.
Radiation does not require a medium for transferring heat; this mode uses the
electromagnetic radiation emitted by an object for exchanging heat.

1.2.1 Conduction

CONDUCTION: It is the flow of heat through solids and liquids by vibration

and collision of molecules and free electrons .
 The molecules of a given point of a system which are at higher
temperature vibrate faster than the molecules of other points of the
same system -or of other systems- which are at lower temperature.
 The molecules with a higher movement collide with the less energized
molecules and transfer part of their energy to the less energized
molecules of the colder regions of the structure. For example, the heat
transfer by conduction through the bodywork of a car.

 Formula to calculate the conductivity gradient for a given system:

q = - kA (Δ T/Δ n)

Where Δ T/Δ n is the temperature gradient in the direction of area A, and k is

the thermal conductivity constant obtained by experimentation in W/m.K.

Conduction is at transfer through solids or stationery fluids. When you touch a

hot object, the heat you feel is transferred through your skin by conduction.
Two mechanisms explain how heat is transferred by conduction: lattice vibration
and particle collision. Conduction through solids occurs by a combination of the
two mechanisms; heat is conducted through stationery fluids primarily by
molecular collisions.

In solids, atoms are bound to each other by a series of bonds, analogous to

springs as shown in Figure 1.1. When there is a temperature difference in the
solid, the hot side of the solid experiences more vigorous atomic movements.
The vibrations are transmitted through the springs to the cooler side of the
solid. Eventually, they reach an equilibrium, where all the atoms are vibrating
with the same energy.

Solids, especially metals, have free electrons, which are not bound to any
particular atom and can freely move about the solid. The electrons in the hot
side of the solid move faster than those on the cooler side. This scenario is
shown in Figure 1.2. As the electrons undergo a series of collisions, the faster
electrons give off some of their energy to the slower electrons. Eventually,
through a series of random collisions, an equilibrium is reached, where the
electrons are moving at the same average velocity. Conduction through electron
collision is more effective than through lattice vibration; this is why metals
generally are better heat conductors than ceramic materials, which do not have
many free electrons.

Figure 1.1 Conduction by lattice vibration

Figure 1.2 Conduction by particle collision

The effectiveness by which heat is transferred through a material is measured by

the thermal conductivity, k. A good conductor, such as copper, has a high
conductivity; a poor conductor, or an insulator, has a low conductivity. Conductivity
is measured in watts per meter per Kelvin (W/mK). The rate of heat transfer by
conduction is given by:
   (Eq. 1.1)

where A is the cross-sectional area through which the heat is conducting, T is the
temperature difference between the two surfaces separated by a
distance Δx (see Figure 1.3). In heat transfer, a positive q means that heat is
flowing into the body, and a negative q represents heat leaving the body. The
negative sign in Eqn. 1.1 ensures that this convention is obeyed.

Figure 1.3: Heat transfer by conduction

Steady State and Transient State

 If you heat a pan on a stove, it takes a while for the pan to heat up to
cooking temperature, after which the temperature of the pan remains
relatively constant. The latter state is called the steady state, where there
is no temporal change in temperatures. When the system is still changing
with time, it is in transient state. The rate of conduction through an object
at steady-state is given by:

  (Eq. 3.1)

 where k is the conductivity of the material, A is the cross-sectional area

through which the heat is conducting, and ΔT is the temperature
difference between two surfaces separated by a distance Δx.
In fluids, conduction occurs through collisions between freely moving molecules.
The mechanism is identical to the electron collisions in metals.

1.2.2 Convection

CONVECTION: Flow of heat through currents within a fluid (liquid or gas).

 Convection is the displacement of volumes of a substance in a liquid or
gaseous phase.
 When a mass of a fluid is heated up, for example when it is in contact
with a warmer surface, its molecules are carried away and scattered
causing that the mass of that fluid becomes less dense.
 For this reason, the warmed mass will be displaced vertically and/or
horizontally, while the colder and denser mass of fluid goes down (the
low-kinetic-energy molecules displace the molecules in high-kinetic-energy
states).
 Through this process, the molecules of the hot fluid transfer heat
continuously toward the volumes of the colder fluid.

For example, when heating up water on a stove, the volume of water at the
bottom of the pot will be warmed up by conduction from the metallic bottom of
the pot and its density decreases. Given that it gets lesser dense, it shifts
upwards up to the surface of the volume of water and displaces the upper
-colder and denser- mass of water downwards, to the bottom of the pot.

 Formula of Convection:

q = hA (Ts - T ∞)

Where h is for convective heat transfer coefficient, A is the area implied in the
heat transfer process, Ts is for the temperature of the system and T ∞ is a
reference temperature.

Convection uses the motion of fluids to transfer heat. In a typical convective

heat transfer, a hot surface heats the surrounding fluid, which is then carried
away by fluid movement such as wind. The warm fluid is replaced by cooler fluid,
 which can draw more heat away from the surface. Since the heated fluid is
constantly replaced by cooler fluid, the rate of heat transfer is enhanced.

Natural convection (or free convection) refers to a case where the fluid

movement is created by the warm fluid itself. The density of fluid decrease as
it is heated; thus, hot fluids are lighter than cool fluids. Warm fluid surrounding
a hot object rises, and is replaced by cooler fluid. The result is a circulation of
air above the warm surface, as shown in Figure 1.4.

Figure 1.4 Natural convection

Forced convection uses external means of producing fluid movement. Forced

convection is what makes a windy, winter day feel much colder than a calm day
with same temperature. The heat loss from your body is increased due to the
constant replenishment of cold air by the wind. Natural wind and fans are the
two most common sources of forced convection.

Convection coefficient, h, is the measure of how effectively a fluid transfers

heat by convection. It is measured in W/m2K, and is determined by factors such
as the fluid density, viscosity, and velocity. Wind blowing at 5 mph has a
lower h than wind at the same temperature blowing at 30 mph. The rate of heat
transfer from a surface by convection is given by:

  (Eq. 1.2)

where A is the surface area of the object, Tsurface is the surface temperature,

and T∞ is the ambient or fluid temperature.

1.2.3 Radiation
RADIATION: It is heat transfer by electromagnetic waves or photons. It does
not need a propagating medium. The energy transferred by radiation moves at
the speed of light

The formula to know the amount of heat transferred by radiation is:

q = e σ A [(ΔT) ^4]

Where q is the heat transferred by radiation, E is the emissivity of the system,

σ is the constant of Stephan-Boltzmann (5.6697 x 10^-8 W/m^2.K^4), A is the
area involved in the heat transfer by radiation, and (ΔT)^4 is the difference of
temperature between two systems to the fourth or higher power.

Radiative heat transfer does not require a medium to pass through; thus, it is
the only form of heat transfer present in vacuum. It uses electromagnetic
radiation (photons), which travels at the speed of light and is emitted by any
matter with temperature above 0 degrees Kelvin (-273 °C). Radiative heat
transfer occurs when the emitted radiation strikes another body and is
absorbed. We all experience radiative heat transfer everyday; solar radiation,
absorbed by our skin, is why we feel warmer in the sun than in the shade.

The electromagnetic spectrum classifies radiation according to wavelengths of

the radiation. Main types of radiation are (from short to long wavelengths):
gamma rays, x-rays, ultraviolet (UV), visible light, infrared (IR), microwaves, and
radio waves. Radiation with shorter wavelengths are more energetic and
contains more heat. X-rays, having wavelengths ~10-9 m, are very energetic and
can be harmful to humans, while visible light with wavelengths ~10 -7 m contain
less energy and therefore have little effect on life. A second characteristic
which will become important later is that radiation with longer wavelengths
generally can penetrate through thicker solids. Visible light, as we all know, is
blocked by a wall. However, radio waves, having wavelengths on the order of
meters, can readily pass through concrete walls.

Any body with temperature above 0 Kelvin emits radiation. The type of radiation
emitted is determined largely by the temperature of the body. Most "hot"
objects, from a cooking standpoint, emit infrared radiation. Hotter objects,
 such as the sun at ~5800 K, emits more energetic radiation including visible and
UV. The visible portion is evident from the bright glare of the sun; the UV
radiation causes tans and burns.

The amount of radiation emitted by an object is given by:

  (Eq. 1.3)

where A is the surface area, T is the temperature of the body, σ is a constant

called Stefan-Boltzmann constant, equal to 5.67×10-8 W/m2K4, and ε is a material
property called emissivity. The emissivity has a value between zero and 1, and is
a measure of how efficiently a surface emits radiation. It is the ratio of the
radiation emitted by a surface to the radiation emitted by a perfect emitter at
the same temperature.

The emitted radiation strikes a second surface, where it is reflected,

absorbed, or transmitted (Figure 1.5). The portion that contributes to the
heating of the surface is the absorbed radiation.

Figure 1.5 Interaction between a surface and incident radiation

The percentage of the incident radiation that is absorbed is called the

absorptivity, α. The amount of heat absorbed by the surface is given by:

  (Eq. 1.4)

where I is the incident radiation. The incident radiation is determined by the

amount of radiation emitted by the object and how much of the emitted
radiation actually strikes the surface.
 
SHELL AND TUBE HEAT EXCHANGERS

 A shell and tube heat exchanger is a class of heat exchanger design.

 It is the most common type of heat exchanger in oil refineries and other
large chemical processes, and is suited for higher-pressure applications.
 As its name implies, this type of heat exchanger consists of a shell (a
large pressure vessel) with a bundle of tubes inside it. One fluid runs
through the tubes, and another fluid flows over the tubes (through the
shell) to transfer heat between the two fluids.
 The set of tubes is called a tube bundle, and may be composed by several
types of tubes: plain, longitudinally finned, etc.

Theory and Application

 Two fluids, of different starting temperatures, flow through the heat

exchanger. One flows through the tubes (the tube side) and the other
flows outside the tubes but inside the shell (the shell side).
 Heat is transferred from one fluid to the other through the tube walls,
either from tube side to shell side or vice versa.
 The fluids can be either liquids or gases on either the shell or the tube
side.
 In order to transfer heat efficiently, a large heat transfer area should
be used, leading to the use of many tubes. In this way, waste heat can be
put to use. This is an efficient way to conserve energy.
 Heat exchangers with only one phase (liquid or gas) on each side can be
called one-phase or single-phase heat exchangers.
 Two-phase heat exchangers can be used to heat a liquid to boil it into a
gas (vapor), sometimes called boilers, or cool a vapor to condense it into a
liquid (called condensers), with the phase change usually occurring on the
shell side.
 Boilers in steam engine locomotives are typically large, usually
cylindrically-shaped shell-and-tube heat exchangers.
 In large power plants with steam-driven turbines, shell-and-tube surface
condensers are used to condense the exhaust steam exiting the turbine
 into condensate water which is recycled back to be turned into steam in
the steam generator.

Shell and tube heat exchanger design

 There can be many variations on the shell and tube design. Typically, the
ends of each tube are connected to plenums (sometimes called water
boxes) through holes in tubesheets. The tubes may be straight or bent in
the shape of a U, called U-tubes.

 In nuclear power plants called pressurized water reactors, large heat

exchangers called steam generators are two-phase, shell-and-tube heat
exchangers which typically have U-tubes. They are used to boil water
recycled from a surface condenser into steam to drive a turbine to
produce power.
 Most shell-and-tube heat exchangers are either 1, 2, or 4 pass designs on
the tube side. This refers to the number of times the fluid in the tubes
passes through the fluid in the shell.
 In a single pass heat exchanger, the fluid goes in one end of each tube
and out the other.
 Surface condensers in power plants are often 1-pass straight-tube heat
exchangers. Two and four pass designs are common because the fluid can
enter and exit on the same side.

 There are often baffles directing flow through the shell side so the fluid
does not take a short cut through the shell side leaving ineffective low
flow volumes.
 Counter current heat exchangers are most efficient because they allow
the highest log mean temperature difference between the hot and cold
streams. Many companies however do not use single pass heat exchangers
because they can break easily in addition to being more expensive to
build. Often multiple heat exchangers can be used to simulate the
counter current flow of a single large exchanger.
Selection of tube material

 To be able to transfer heat well, the tube material should have good
thermal conductivity.
 Because heat is transferred from a hot to a cold side through the tubes,
there is a temperature difference through the width of the tubes.
 Because of the tendency of the tube material to thermally expand
differently at various temperatures, thermal stresses occur during
operation. This is in addition to any stress from high pressures from the
fluids themselves.
 The tube material also should be compatible with both the shell and tube
side fluids for long periods under the operating conditions (temperatures,
pressures, pH, etc.) to minimize deterioration such as corrosion.
 All of these requirements call for careful selection of strong, thermally-
conductive, corrosion-resistant, high quality tube materials, typically
metals, including copper alloy, stainless steel, carbon steel, non-ferrous
copper alloy, Inconel, nickel, Hastelloy and titanium.
 Poor choice of tube material could result in a leak through a tube between
the shell and tube sides causing fluid cross-contamination and possibly
loss of pressure.

CO-CURRENT AND COUNTER CURRENT FLOW ARRANGEMENTS

 A heat exchanger utilizes the fact that heat transfer occurs when there
is a difference in temperature.
 In a heat exchanger, there is a cold stream and a hot stream. The two
streams are separated by a thin, solid wall. The wall must be thin and
conductive in order for heat exchange to occur. Yet the wall must be
strong enough to withstand any pressure by the fluid. Copper seems to be
one of a common choice for construction.
 Here is a simple flow diagram showing how heat transfers in a heat
exchanger.
  This flow arrangement is called co-current. If the direction of one of the
stream is reversed, the arrangement is called counter-current flow.
 Here are the temperature profiles along the heat exchanger. Note that
the temperature profiles are different for co-current flow and for
counter-current flow.

The area between the curve is the heat transfer rate (Q). We can see that the
heat transfer rate for counter-current flow is larger than the rate for co-
current flow.

Counterflow heat exchanger provides more effective heat transfer. Most of

the industrial heat exchangers are counter-current flow design.

The performance of a heat exchanger depends on:

 heat transfer area

 fluid flow velocity
  temperature gradient

based on the equation for heat transfer rate of a heat exchanger, which is:

Q=U*A*dTlm

where

Q = Heat transfer rate between the fluids

U = Overall heat transfer coefficient
A = Heat transfer area
dTlm = Log mean temperature difference of the system

a) Heat transfer area

 As the equation shown above, the heat transfer area (or contact area)
is directly proportional to the heat transfer rate. If the heat
transfer area increases, heat transfer rate increases as well.
 A common way to increase heat transfer area is adding fins to the
surface. It is cheap to put fins to the heat transfer area but fins also
increase fouling, especially in bio-process.
b) Fluid flow rate
 The importance of the fluid flow in a heat exchanger is that it
changes the overall heat transfer coefficient, U.
 the velocity of the cooling fluid is directly proportional to the overall
transfer coefficient.
 ∴ ,as the cooling fluid velocity increases, the cooling fluid is able to
dissipate heat more effectively.
c) Temperature gradient
 Temperature gradient is certainly an important part of heat transfer.
It is the driving force for heat transfer.
 If we can introduce fluids with greater temperature difference into
the heat exchanger, the heat transfer rate (Q) will be greater.
 If we go back to the temperature profiles of the co-current and
counterflow, we can see that the driving force is great for co-current
 at the beginning but decreases drastically as it moves along the heat
exchanger.
 The counter-current flow provides relatively consistent driving force
and therefore performs better than co-current flow.

SEPARATION PROCESSES

Separation processes are essential to the chemical, petroleum refining, and

materials processing industries. The word "separation," however, refers to
different processes and functions for different industries. Separation
processes comprise a large portion of the activity in the chemical and
petrochemical industries. In the forest products industry, separation ranges
from separating wood chips of different sizes to converting black liquor for
reuse. In the aluminum and steel industries, as well as the metal casting and
glass industries, the most important area of separation technology is separation
of different types of scrap, sand, and cullet. Finding common ground among
these definitions of separation processes or technologies is a difficult task. For
the purposes of this report, however, separation processes are defined as
processes using physical, chemical, or electrical forces to isolate selected
constituents from a mixture.

Separation processes can be thought of in general terms as performing similar

functions in all industries. Figure 1-1 is a schematic illustration of these
functions and their relationships. The materials streams may be composed of
homogeneous solids, liquids, gases, or supercritical fluids, or they may be
composed of heterogeneous mixtures containing any combination of these
phases. The functions of separation processes include the removal of impurities
from raw materials, products, and by-products; the separation of recycle
streams; and the removal of contaminants from air and water waste streams.

For the chemical, petroleum refining, and materials processing industries as a

group, separation technologies are critical for reducing waste, improving energy
efficiency, and increasing the efficiency of raw material use. For example,
separation technologies have the potential to reduce waste and increase
productivity by separating valuable materials that can be used or sold as by-
products from waste streams.
Figure 1.1: Separation in manufacturing processes. Adapted from Humphrey and
Keller, 1997.

As environmental regulations become increasingly stringent, the costs

associated with waste management are expected to rise. By reducing these
costs, separation technologies can contribute to the competitiveness of U.S.
industries. Similar examples can be given for energy efficiency and raw
materials efficiency. Research that increases the fundamental knowledge
necessary to improve existing separation processes and develop new ones can,
therefore, have a large impact on these industries. Separation technologies are
critical for the productivity and global competitiveness of U.S. industries.

Traditional Chemical Engineering Separation Processes

Chemical products are made by a combination of processes that include

synthesis, separation, and purification. The traditional chemical engineering
methods of separation and purification include distillation, crystallization,
adsorption, membrane processes, absorption and stripping, and extraction.
These technologies are briefly described below.

Distillation

Distillation and its companion processes, azeotropic and extractive distillation,

are by far the most widely used separation processes for mixtures that can be
vaporized. Distillation is a process for isolating components from a mixture
based on differences in boiling points. Vapors are generated from liquids or
solids by heating and are then condensed into liquid products. In azeotropic
distillation, a compound is added to form an azeotrope with at least one of the
components of the mixture. That component can then be more readily separated
from the mixture because of the increased difference between the volatilities
of the components. Extractive distillation combines continuous fractional
distillation with absorption. A relatively high-boiling solvent is used to
selectively scrub one or more of the components from a mixture of components
with similar vapor pressures. Distillation processes are widely used for the
separation of organic chemicals and for the separation of gases, usually at
cryogenic temperatures, as in the production of oxygen and nitrogen from air.

DISTILLATION

 Most widely used separation process in the chemical industry

 Also known as fractional distillation or fractionation
 Normally used to separate liquid mixtures into two or more vapour or
liquid products with different compositions
 It is an equilibrium stage operation
 In each stage, a vapour phase is contacted with a liquid phase and mass is
from vapour to liquid and fro liquid to vapour.
 The less volatile, “heavy” or “high boiling” components concentrate in the
liquid phase; the more volatile “light”, components concentrate in the
vapour.
 By using multiple stages in series, separation can be accomplished.
  The distillation column is divided into a series of trays (also called plates
or stages).
 Liquid flows down the column from stage to stage, and is contacted by
vapour flowing upwards.
 As vapour bubbles through the liquid on a tray, ther is mass transfer
between phases and their compositions approach equilibrium.
 Vapour passing up the column becomes enriched in the more volatile
component (mvc) whilst the liquid is enriched in less volatile component
(lvc) as it passes downwards.
 At the top of the column vapour is condensed and part is returned to
provide a liquid reflux
 Part of the liquid at the bottom is evaporated in the reboiler to provide a
vapour phase.
 The separating agent is the heat supplied in the boiler.
 The product leaving the top of the column is called the overhead product,
the overhead, the “top product”, the distillate or “ distillate product”.
 The distillate flow rate is assigned the symbol D and the composition x D
or yD.
 The product leaving the bottom of the column is called the bottom
product or “bottoms” and given the symbol B with composition x B.

Distillation column design

Designed using vapour- liquid equilibrium data.

Vapour- liquid equilibrium characteristics of the mixture will determine the

number of stages hence the number of stages the number of trays or plates
required for separation.

The number of theoretical stages/ plates can be determined by the graphical

McCabe-Thiele method.

Procedure for determining number of theoretical plates

Given xB, xD, xF and r information on state of feed and equilibrium data

i. Draw equilibrium line and x= y line

r
ii. Draw top operating line through point (xD, y=xD) with gradient
r +1
iii. Determine q and draw line through point (x F, y= xF) with gradient
q
q−1
iv. Draw bottom operating line from point (x B, y=xB) to intersection of
top operating line and q line
v. Step off theoretical plates between operating lines and equilibrium
lines, transferring from top to bottom operating line after the
intersection point.

Crystallization

Crystallization is one of the oldest unit operations in the portfolio of separation

techniques used for industrial and laboratory processes. Crystallization is used
to achieve several functions: separation, purification, concentration,
solidification, and the production of a crystal that can be used to determine
molecular structure. Because the heat of crystallization is typically much lower
than the heat of vaporization, considerable energy savings can be realized in
applications where crystallization is an effective means of separation.

Solutes can be recovered from solutions by reducing the solubility through

cooling, heating, evaporation, chemical reaction, or by adding a nonsolvent to the
mixture. Alternatively, separation of a chemical species from a mixture of
similar compounds may be achieved by melt crystallization. In such operations,
the mixture is cooled and the species allowed to solidify differentially according
to their melting points. Melt crystallization is an important means of
separating para-xylene from ortho-and meta-xylene. An example of the
purification of a chemical species is the manufacture of L-isoleucine, in which
the material crystallized from a fermentation broth that has been filtered and
subjected to ion exchange may contain undesirable impurities. The crystals are
then redissolved and recrystallized to enhance purity. Concentration of a
solution can be accomplished by crystallization of the solvent. For example,
fruit juice is concentrated via the crystallization of ice.

Product requirements are the criteria for determining the success of the
crystallization process. These requirements are based on how the product will
be used and the processing steps between crystallization and the recovery of
the final product. Key determinants of product quality are size distribution
(including mean and spread), morphology (including habit and polymorphic form),
and purity. Crystal size distributions determine several important processing
and product properties, including appearance, the separation of crystals from
liquor, reactions, dissolution, and other processes and properties involving
surface area, transportation, and storage.

Adsorption

Adsorption is a method of fractionating mixtures using microporous solids

(adsorbents) that have strong affinities for one or more of the components in
the mixture (adsorbates). The adsorbates held by the adsorbent solid are
subsequently desorbed and the adsorbent freed for further adsorption. The
process is necessarily cyclic, alternating between adsorption and desorption.
Desorption involves weakening the bonds between the adsorbates and the
adsorbent or reducing the driving force for adsorption. Desorption can be
accomplished by increasing the temperature, reducing the pressure, adding
another component that competitively adsorbs with the adsorbate, or a
combination of these strategies.

Membrane Processes
Separation processes involving membranes require two bulk phases that are
physically separated by a third phase, the membrane. In all membrane
processes, the feed is separated into two phases: the permeate (the materials
that go through the membrane) and the retentate (the portion of the feed
retained by the membrane). The transport of materials between the permeate
and retentate phases is controlled by the membrane and the operating
conditions. One or more of the species in the feed mixture are allowed to pass
through the membrane in preference to others, that is to say, the membrane is
selective for these species. The permeate phase is enriched in these species as
the retentate phase is depleted of them.

Most commercial membranes consist of thin, selective, active layers or skins

(about 0.1 to 5μm) on porous support layers that provide mechanical strength.
The active and support layers can be formed in a single operation from a given
polymeric material. In the case of composite membranes, the active layer can be
a coating on the support layer. The transport of any species across the
membrane relies on one or more forces, such as those created by a gradient in
chemical potential or electrical potential. Membrane processes typically do not
involve a phase change and therefore do not involve a specific heat of
vaporization (like distillation) or a specific heat of crystallization (like
crystallization). Because there is no phase change, highly selective membranes
can, in a number of circumstances, accomplish separations with considerably less
energy than other methods.

In addition to gas separation, a number of membrane separation processes are

used. Dialysis is the transfer of solute molecules across a membrane by
diffusion from a concentrated solution to a dilute solution. In the
electrodialysis process (e.g., the concentration of brine) a typical electrodialysis
stack consists of a series of anion-exchange and cation-exchange membranes
arranged in an alternating pattern between an anode and a cathode to form
individual cells. A reverse osmosis membrane separates the various low-
molecular-weight molecules and ions from the solvent by forcing the solvent or
major component to pass selectively through the membrane by applying pressure
greater than the normal osmotic pressure. Separation occurs based on the size,
solubility, and/or charge of the various species. Ultrafiltration is another
pressure-driven membrane process capable of separating somewhat larger
solution components on the basis of molecular size and shape. Under an applied
pressure difference across the membrane, the smaller molecules pass through
the membrane and are collected as permeate while the larger molecules are
retained by the membrane. The microfiltration process is similar to the
ultrafiltration process, except its effective separation range is from 1,000 Å to
100,000 Å in molecular size whereas the ultrafiltration range is from 10 Å to
1,000 Å.

Absorption and Stripping

Absorption refers to the transfer of one or more components of a gas phase to

a liquid phase in which the gas phase is soluble. Stripping is exactly the reverse,
the transfer of a component from a liquid phase in which it is dissolved to a gas
phase. There are three types of absorption processes: separation based on
physical solution; separation based on reversible chemical reaction; and
separation based on irreversible chemical reaction. Absorption processes
require the generation of extensive areas of liquid surfaces in contact with gas
phases.

Extraction

Liquid-liquid extraction is a separation technique involving two immiscible liquid

phases. During liquid-liquid extraction, one of the two phases, the solvent phase,
extracts the solutes from the other liquid phase. Solvent recovery and
raffinate cleanup follow the separation. There is usually more than one possible
method of purifying the solvent and raffinate phases, so process design is
important. Solvent selection is based on liquid-liquid interfacial tension.

CHARACTERISTICS OF SEPARATION PROCESSES

 A separation process takes one or more feed streams containing mixtures

and transforms these into product streams which differ in composition.
 This is achieved by the addition of a separating agent which may be
energy or another stream of material.
 Separation usually involves the formation of more than one phase by the
addition of the separating agent.
 The components of a mixture will be distributed unequally between the
phases.
  The separation of phases of different density is easily accomplished by
mechanical means, e.g. a liquid feed is passed through a pressure reducing
valve into a vessel (a flash drum) where it separates into separate two
phases of different composition. Vapour is taken off the top of the drum
and liquid at the bottom. The sepating agent is energy- introduced as
work of compression of the feed.
 The driving force for interphase mass transfer is always the
thermodynamic chemical potential but in some processes, the
thermodynamic equilibrium is not approached, and the degree of
separation is dependent on the rate of mass transfer.

COOLING TOWERS

 Cooling towers are a very important part of many chemical plants. They
represent a relatively inexpensive and dependable means of removing low
grade heat from cooling water.

Figure 1: Closed Loop Cooling Tower System

 The make-up water source is used to replenish water lost to evaporation.

Hot water from heat exchangers is sent to the cooling tower. The water
exits the cooling tower and is sent back to the exchangers or to other
units for further cooling.

Types of Cooling Towers

Cooling towers fall into two main sub-divisions:

 natural draft and

 mechanical draft.
 a. Natural draft designs use very large concrete chimneys to introduce air
through the media.
 Due to the tremendous size of these towers (500 ft high and 400
ft in diameter at the base) they are generally used for water
flowrates above 200,000 gal/min.
 Usually these types of towers are only used by utility power
stations in the United States.
b. Mechanical draft cooling towers are much more widely used.
 These towers utilize large fans to force air through circulated
water.
 The water falls downward over fill surfaces which help increase
the contact time between the water and the air.
 This helps maximize heat transfer between the two.

Types of Mechanical Draft Towers

Figure 2: Mechanical Draft Counterflow Tower Figure 3: Mechanical Draft

Crossflow Tower

 Mechanical draft towers offer control of cooling rates in their fan

diameter and speed of operation. These towers often contain several
areas (each with their own fan) called cells.

Cooling Tower Theory

  Heat is transferred from water drops to the surrounding air by the
transfer of sensible and latent heat.

Figure 4: Water Drop with Interfacial Film

Type of reactors

Chemical reactors are vessels designed to contain chemical reactions. The

design of a chemical reactor deals with multiple aspects of chemical engineering.
Chemical engineers design reactors to maximize net present value for the given
reaction. Designers ensure that the reaction proceeds with the highest
efficiency towards the desired output product, producing the highest yield of
product while requiring the least amount of money to purchase and operate.
Normal operating expenses include energy input, energy removal, raw material
costs, labor, etc.

There are a couple main basic vessel types:

 A tank
 A pipe or tubular reactor (laminar flow reactor (LFR)

Both types can be used as continuous reactors or batch reactors. Most

commonly, reactors are run at steady-state, but can also be operated in a
transient state. When a reactor is first brought back into operation (after
 maintenance or in operation) it would be considered to be in a transient state,
where key process variables change with time. Both types of reactors may also
accommodate one or more solids ( reagents, catalyst, or inert materials), but
the reagents and products are typically liquids and gases. There are three main
basic models used to estimate the most important process variables of
different chemical reactors:
 Batch Reactor
 Continuous Stirred-Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)

Key process variables include

Residence time (τ) , Volume (V) , Temperature (T) , Pressure (P) , Concentrations
of chemical species (C1, C2, C3, ... Cn) ,Heat transfer coefficients (h, U)

Chemical reactions occurring in a reactor may be exothermic, meaning giving off

heat,
or endothermic, meaning absorbing heat. A chemical reactor vessel may have a
cooling
or heating jacket or cooling or heating coils (tubes) wrapped around the outside
of its
vessel wall to cool down or heat up the contents

Type of Reactor Characteristics

Simple Batch Reactor is charged via two holes in the top of the tank;
while reaction is carried out, nothing else is put in or
taken out until the reaction is done; tank easily heated or
cooled by jacket

Kinds of Usage Advantages Disadvantages

Phases
Present

1. Gas 1. Small scale 1. High 1. High

 phase production conversion operating cost
per unit
2. Liquid 2. volume for 2. Product
phase Intermediate one pass quality more
or one shot variable than
3. Liquid production 2. with
Solid Flexibility continuous
3. of operation
Pharmaceutical operation-
same
4.
reactor can
Fermentation
produce one
product one
time and a
different
product the
next

3. Easy to
clean

Type of Reactor Characteristics

Plug flow Arranged as one long reactor or many short reactors in a

reactor(PFR) tube bank ; no radial variation in reaction rate
(concentration); concentration changes with length down
the reactor

Kinds of Usage Advantages Disadvantages

Phases
Present

1. 1. Large Scale 1. High 1. Undesired

Primarily Conversion thermal
Gas 2. Fast per Unit gradients may
 Phase Volume exist
Reactions
2. Low 2. Poor
3. operating temperature
Homogeneous (labor) control
Reactions cost)
3. Shutdown
4. 3. and cleaning
Heterogeneous Continuous may be
Reactions Operation expensive

5. Continuous 4. Good
Production heat
transfer
6. High
Temperature

Type of Reactor Characteristics

Continuously Stirred Run at steady state with continuous flow of reactants and
Tank Reactor (CSTR) products; the feed assumes a uniform composition
throughout the reactor, exit stream has the same
composition as in the tank

Kinds of Usage Advantages Disadvantages

Phases
Present

1. Liquid 1. When 1. Continuous 1. Lowest

phase agitation is operation conversion per
required unit volume
2. Gas- 2. Good
liquid 2. Series temperature 2. By-passing
 rxns configurations control and channeling
for different possible with
3. Solid- concentration 3. Easily poor agitation
liquid streams adapts to
rxns two phase
runs

4. Good
control

5. Simplicity
of
construction

6 Low
operating
(labor) cost

7. Easy to
clean

Packed bed reactor

Characteristics

Is essentially a tubular reactor that is packed with solid catalyst particles

Advantages

 Most reactions give the highest conversion per weight of catalyst of any
catalytic reactor

Disadvantages

 Difficulties with temperature control

 Catalyst is usually troublesome to replace
  Channelling of the gas or liquid flow occurs, resulting in ineffective use of
part of the reactor bed.

CATALYSTS AND CATALYSIS

 catalysis refers to chemical processes in which chemical reaction rates

are subjected to the influence of a catalyst.
 Basically a catalyst is considered to form an intermideate compound with
some of the reactants which in turn interacts with other reactants to
form desired products and to degenerate the catalyst.
 In this way a catalyst enables a reaction to proceed at a faster rate by a
mechanism that requires a lower activation energy than that for the
uncatalysed one.
 Catalysis is customarily classified into two major categories namely
homogeneous and heterogeneous catalytic reactions.
 In the former the catalyst forms a homogeneous phase with the reaction
mixture whereas in the latter, the catalyst exists as a phase dinstinct
from the reaction mixture.

Basic characteristics of catalysis

i. In a catalytic reaction, the catalyst is unchanged at the conclusion of the

reaction; but it may participate in the intermediate steps so as to
increase the reaction rate.
ii. When more than one mechanism is feasible for a reaction, a catalyst may
exhibit selectivity favouring one mechanism over others.
 This situation usually results in a product distribution different from
those by other mechanisms. Proper application of catalyst selectivity
would enable the desired reaction to be accelerated while the undesired
reactions were retarded.
iii. The rate of reaction is generally proportional to the catalyst
concentration. For a solid- catalysed reaction, the surface area of the
catalyst and the concentration of the so called active centers or catalyst
sites become important.
iv. In a reversible reaction the catalyst accelerates the reverse reaction as
well as the forward one. Thus the equilibrium composition of the reacting
system would be the same as that of the uncatalysed system.
 v. In an autocatalytic reaction where one of the reaction products functions
as a catalyst, a small amount of the product must be present to initiate
the reaction.

Homogeneous catalysis

 This has the catalyst in the same phase as the reactants

 Take place either in the gas phase or liquid phase

Gas phase catalysis: e.g.

 Oxidation of SO2 to SO3 catalyzed by nitric oxide in the lead chamber

sulphuric acid process.
The presence of nitric oxide promotes normally very slow oxidation process by
the following mechanism:
2 NO+O2 →2 NO2
SO2+ NO 2 → SO3 + NO
Liquid phase catalysis: e.g.
 acid- base catalysis is the type of liquid- phase catalytic reaction that
has been most extensively studied.
Examples of organic reactions, the rates of which are controlled by acid- base
catalysis include:
a. Inversion of sugars
b. Hydrolysis of esters and amides
c. Halogenation of acetone and nitroparaffins
d. Mutarotation of glucose
e. Esterification of alcohols
f. Enolization of aldehydes and ketones
 For general acid or general base catalysed reactions, the relationship
between the catalyst effectiveness (in terms of the rate constant) and
the strength of the acid or base (ionization constant) has been frequently
expressed by the Bronsted equation.
k =CK a
Where k represents the rate constant (or catalytic constant),
K is the ionization constant of either acid or base,
C and a are empirical constants governed by the type of reaction the
temperature and the solvent.
  The observed values of a lie in the range 0.3 to 0.9
 According to the general concept of acids and bases proposed by
Bronsted and Lowry, undissociated acids and bases are just as effective
as catalysts as are H+ or OH- ions.
 Thus acid catalysis involves transfer of H + to the reactant being
catalysed, whereas acceptance of H + by the base prevails in the case of
base catalysis.
 This implies that the reactant functions as a base in acid catalysis while
it serves as an acid in base catalysis.

Heterogenous catalysis

 In this catalytic reaction system, the catalyst is present in a phase

different from those of the reactants.
 Many important industrial reactions are catalysed by the surfaces of
special solid solid materials.
 Heterogeneous catalysts are often composed of metals or metal oxides
 The greater the surface area of a heterogeneous catalyst, the more
reactions can take place.
 The initial step is heterogeneous catalysis is the adsorption of reactants
onto the surface of a catalyst at active sites.
 Then there is interaction between the surface of the surface of the
catalyst and reactant molecules which makes them more reactive. This
might involve an actual reaction with the surface or some weakening of
the bonds in the attached molecules.
 The reaction then happens to form products. At this stage, both the
reactants molecules might be attached to the surface.
 The product molecules are desorbed.
 The product molecules break away, leaving the active site available for a
new set of molecules to attach and react.
 A good catalyst needs to adsorb the reactant molecules strongly enough
for them to react, but not so strongly that the product molecules stick
more or less permanently to the surface.
 Silver for example isn’t a good catalyst because it does not form strong
enough attachments with reactant molecules.
  Tungsten on the other hand isn’t a good catalyst because it adsorbs too
strongly.
 Metals like Pt and Ni make good catalysts because they adsorb strongly
enough to hold and activate the reactants but not so strongly that the
products cannot break away.

Examples of heterogeneous catalysts

 The hydrogenation of a Carbo-carbon double bond.

 The simplest example of this is the reaction between ethane and
hydrogen in the presence of a nickel catalyst.
CH 2=CH 2+ H 2 →¿ CH 3 CH 3
1. one important industrial use is in the hydrogenation of vegetable oils to
make magarine, which also involves the reaction of a C-C double bond in
the vegetable oil with hydrogen in the presence of a nickel catalyst.

The mechanism of hydrogenation

1. The hydrogen molecules are adsorbed onto the surface of the nickel
 When this happens, the relatively strong H-H sigma bond is broken
and replaced with two weak metal-H bonds
2. The pi bond of the alkene interacts with the metal catalyst surface
weakening the bond.
 A hydrogen atom is transferred from the catalyst surface to one of
the C atoms of the double bond.
3. The pi bond of the alkene interacts with the metal catalyst weakening
the bond.
 A second hydrogen atom is transferred from the catalyst surface
forming the alkane.
4. The alkane is released from the catalyst’ surface allowing the catalyst to
accept additional hydrogen and alkene molecules.