I.

LECTURE NOTES

MODULE I
Lecture No.: 1 Date: 14/07/2015 Hour: 6

Objective: Introduction to chemical process industries

Key points: Transfer operation, reaction etc.

Explanation:

Chemical processes usually have three interrelated elementary processes

Transfer of reactants to the reaction zone
Chemical reactions involving various unit processes
Separation of the products from the reaction zone using various unit operations
Processes may involve homogeneous system or heterogeneous systems. In homogeneous system,
reactants are in same phase-liquid, gases or solids while heterogeneous system include two or
more phases; gas liquid, gas solid, gas-gas, liquid liquid, liquid solid etc. Various type reactions
involve maybe reversible or irreversible, endothermic or exothermic, catalytic or non-catalytic.
Various variables affecting chemical reactions are temperature pressure, composition, catalyst
activity, catalyst selectivity, catalyst stability, catalyst life, the rate of heat and mass transfer. The
reaction may be carried out in batch, semi batch or continuous. Reactors may be batch, plug
flow, CSTR. It may be isothermal or adiabatic. Catalytic reactors may be packed bed, moving
bed or fluidised bed
Along with knowledge of various unit processes and unit operation following information are
very important for the development of a process and its commercialization [Austin,1984]
Basic Chemical data: Yield conversion, kinetics
Material and energy balance, raw material and energy consumption per ton of product,
energy changes
Batch vs Continuous, process flow diagram
Chemical process selection: design and operation, pilot plant data, Equipment required,
material of construction
Chemical Process Control and Instrumentation
 Chemical Process Economics: Competing processes, Material and, Energy cost, Labour,
Overall Cost of production
Market evaluation: Purity of product and uniformity of product for further processing
Plant Location
Environment, Health, Safety and Hazard
Construction, Erection and Commissioning
Management for Productivity and creativity: Training of plant personals and motivation
at all levels
Research, Development and patent
Process Intensification
In order to improve productivity and make the process cost effective and for improving overall
economy, compact , safe, energy efficient and environmentally sustainable plant, process
intensification has become very important and industry is looking beyond the traditional
chemical engineering.

Lecture No.: 2 Date: 14/07/2015 Hour: 7

Objective: unit operations and unit process

Key points: Chemical processes

Explanation:

UNIT PROCESSES AND UNIT OPERATIONS IN CHEMICAL

PROCESS INDUSTRIES

Chemical process is combination of unit processes and Unit operation. Unit process involves
principle chemical conversions leading to synthesis of various useful product and provide basic
information regarding the reaction temperature and pressure, extent of chemical conversions and
yield of product of reaction nature of reaction whether endothermic or exoexothermic, type of
catalyst used. Unit operations involve the physical separation of the products obtained during
various unit processes. Various unit processes in chemical industries are given in Table M-I 3.1.
Various chemical reactions and its application in process industries are given in Table M-I 3.2.
UNIT OPERATIONS IN CHEMICAL INDUSTRIES
Unit operations are very important in chemical industries for separation of various products
formed during the reaction. Table M-I 3.3 give the details of unit operation in chemical process
industries.

Lecture No.: 3 Date: 21/07/2015 Hour: 6

Objective: Processing of producer gas and water gas

Key points: syn gas , coal gasification

Explanation:

Syngas
Syngas is a mixture of Carbon Monoxide and Hydrogen which is the product of steam or
oxygen gasification of organic material such as biomass. After clean up, syngas can be used to
produce organic molecules such as synthetic natural gas (SNG-methane (CH4)) or liquid biofuel
such as synthetic diesel. Syngas is the term generally used for mixture of combustible gases. So
typically a syngas mixture will constitute of only hydrogen and carbon monoxide, with
possibility of having carbon dioxide content sometimes. If the gasification product contains
significant amount of non-combustible gases such as nitrogen and carbon dioxide, the term used
for such mixtures is 'Producer Gas'.
Producer Gas
Producer gas is a mixture of combustible (Hydrogen, Methane and Carbon Monoxide) and non-
combustible (Nitrogen, Carbon dioxide) gases. The heating value of producer gas varies from 4.5
to 6 MJ/m3 depending upon its constituents. Similar to syngas, producer gas is also produced
by gasification of carbonaceous material such as coal or biomass. When atmospheric air is used
as gasification agent, the producer gas consist mostly of carbon monoxide, hydrogen ,nitrogen,
carbon dioxide and methane.
18-22 %

13-19 %

1-5 %

0.2-0.4 %

9-12 %

45-55 %

4%

Table 1 - Typical composition of producer gas

Water Gas
Actually a mixture of only Carbon Monoxide and hydrogen is called water gas. Water gas is
generally used for production of hydrogen. Since both constituents of water gas are combustible
gases, they can be used as input to gas turbine for power production. Water gas shift reaction
(Lowe's gas Process) CO+H2 2+H2is used to remove carbon monoxide from water gas to
get pure hydrogen for the fuel cell applications. Water gas shift reaction is very sensitive
to temperature and increasing temperature reverses the direction of the reaction. This process
also known as Lowe's Gas Process is often done in two stages one at high temperature shift
3500C and another at low temperature shift 190-2100C. Industrial catalyst for this reaction is iron
oxide promoted with chromium oxide for the high temperature shift and copper mixed with zinc
oxide and aluminum oxide for low temperature shift.
Carbon monoxide is produced from reduction of carbon dioxide and it is generally 18-22% on
volume basis. Its octane number is 106 but its burning velocity is low. It is very toxic in nature.
Hydrogen is also the product of reduction process in gasification. Its octane number is in the
range of 60-66 but its burning velocity is very high. Hence it increases the burning velocity of
producer gases. Methane and hydrogen are mostly responsible for high heating value of the
gases. Nitrogen and carbon dioxide are non combustible gases in the producer gases. High
percentage of carbon dioxide indicates incomplete reduction inside the gasifier.

Applications of Syngas
Syngas is used as an intermediate in the industrial synthesis of hydrogen and ammonia.
Syngas has 50% of the energy density of natural gas.
It can be burnt and is used as a fuel source.
Syngas is used as a fuel in power generation using IGCC power plant.
Applications of Producer Gas
Producer gas can fuel hot-air generators of the kind used to produce hot air in industries such
as those involved with production of fertilizer and cement.
Producer gas can also be used for heating water in a number of industrial applications.
Another benefit of producer gas is its suitability for melting of glass in the production of
artifacts.
In addition, producer gas can be employed in food processing industry to provide heat for
drying vegetables, seeds and to heat ovens in bakeries.
Applications of water Gas
Water gas consists of combustible carbon monoxide and hydrogen and hence can be used as a
feed to gas turbines in power generation.
Primarily water gas is used for hydrogen production using water gas shift reaction also

CO2+H2 is used to remove carbon monoxide from water gas to get pure hydrogen for the
fuel cell applications. Water gas shift reaction is very sensitive to temperature and increasing
temperature reverses the direction of the reaction. Lowe's Gas Process is often done in two
stages one at high temperature shift 3500C and another at low temperature shift 190-2100C.
Industrial catalyst for this reaction is iron oxide promoted with chromium oxide for the high
 temperature shift and copper mixed with zinc oxide and aluminum oxide for low temperature
shift.
Process flow sheet:
Lecture No.: 4 Date: 22/07/2015 Hour: 3

Objective: Coke oven gas production and its uses

Key points: coal gasification

Explanation:

Upgraded coal for coking purpose is fed to a byproduct coke oven which uses producer gas for
heating the batch chamber to 1000 0C for 12-20 hrs. gas is removed continuously and put
through a series of purification steps as shown in the process flow sheet.

Major engineering problems:

1. Obtaining suitable grades of coking coal in India. Washing, pre-roasting, and solvent
extraction are some of the schemes used.
2. Choice of scrubbing liquors for CO2 and CO.
Lecture No.: 5 Date: 23/07/2015 Hour: 4
Objective: Acetylene production by partial combustion

Key points: Partial oxidation

Explanation:

Chemical reactions:

Exothermic heat supply

CH4 +2O2 CO2+2H2O

Endothermic production reaction

2CH4 C2H2+3H2

Undesirable side reaction

C2H2 2C+H2

Raw material:
Low purity natural gas or higher mol.wt hydrocarbons.

Hydrocarbon feed and low purity oxygen are heated separately to 550 0C and fed to an acetylene
production burner which can be designed for one stage or two staged operation. The hydrocarbon
is cracked to acetylene at the 1500 0C operating temperature the product gases are quenched
immediately to avoid undue pyrolysis of acetylene. The residence time is less than 100
milliseconds.

Major engineering problems:

1. Thermodynamic and kinetic consideration

2. Burner design

Lecture No.: 6 Date: 27/07/2015 Hour: 3

Objective: Acetylene production by pyrolysis

Key points: electric arc process

Explanation:

Wulff Process:

Chemical reactions:

Propane

C3H8 C2H2+C2H4+CH4+CO+H2+CO2

Ethylene

C2H4 C2H2+H2+CO+CO2+CH4

Methane

2CH4 C2H2+ 3 H2+ CO+ CH4

Hydrocarbon feed plus diluents steam to improve the equilibrium yield is fed to a set of
regenerative furnace operating in pairs on a 1-1.5 minute cycle.
The furnace is designed with refractory walls and internal check work. The furnace is heated on
air mixture. After this heat- up period, the valves are switched to the
-
1.5 minute period. The cycle is repeated again using the other end of the furnace in the paired
system operates on staggered cycle.

Lecture No.: 7 Date: 28/07/2015 Hour: 6

Objective: Hydrogen production

Key points: Hydrogen uses and commercial production

Explanation:

Hydrogen can be produced from a variety of feed stocks. These include fossil resources, such as
natural gas and coal, as well as renewable resources, such as biomass and water with input from
renewable energy sources (e.g. sunlight, wind, wave or hydro-power). A variety of process
technologies can be used, including chemical, biological, electrolytic, photolytic and thermo-
chemical.
Hydrogen is used to process crude oil into refined fuels, such as gasoline and diesel, and for
removing contaminants, such as sulphur, from these fuels. Total hydrogen consumption in oil
refineries is estimated at 12.4 billion standard cubic feet per day, which equates to an average
hydrogen consumption of 100-200 standard cubic feet per barrel of oil processed. Low sulphur
in diesel fuel regulations - hydrogen is used in refineries to remove
sulphur from fuels such as diesel. Increased consumption of low quality 'heavy' crude oil, which
requires more hydrogen to refine.

Hydrogen production:

Large-scale, industrial hydrogen production from all fossil energy sources can be
considered a
commercial technology for industrial purposes, though not yet for utilities. Hydrogen
production
at a large scale has the potential for relatively low unit costs, although the hydrogen
production
 cost from natural gas in medium sized plants may be reduced towards the cost of large-
scale
production. An important challenge is to decarbonise the hydrogen production process.
CO2 capture
and storage options are not fully technically and commercially proven. They require
R&D on absorption
or separation processes and process line-up, as well as acceptance for CO2 storage. It is
also important
to increase plant efficiency, reduce capital costs and enhance reliability and operating
flexibility.

Lecture No.: 8 Date: 29/07/2015 Hour: 6

Objective: Oxygen and nitrogen production

Key points: Cryogenic Process

Explanation:

Raw material : Air

Process description:
Air is compressed to 4-5 atms, cooled with water and passed to regenerative
exchangers
 Cylindrical pressure vessels are packed with aluminium spirals and operating in
pairs
Air is cooled in one, while the cool product (O2&N2) gas is removing sensible
heat in others.
After 2-4 minutes the cycle is reversed
Air entering the cold exchanger contains liquifing impurities like water and CO2
is removed at -183 0C to -195 0C
The air is then admitted in the reboiler section of the double column where further
cooling takes place.
The double column is a two distillation column with low pressure (1.4 atm)
column standing on the top of high pressure (5.7 atm)
The rebolier of the upper column works as the condenser for lower column
In high pressure more volatile nitrogen will vaporizes and is condensed in the
reboiler section of the low pressure column.
And the liquid oxygen surrounding the tubes
This condensed nitrogen is then sprayed in to the top of the low pressure column
as reflux.
Less volatile oxygen is pumped to low pressure column for further rectification.

Major Engineering problems:

Complete removal of H2O, CO2 and hydrocarbon to prevent the plugging in

low temperature sections of the plant.
Developing effective low temperature insulation and lubricants
Complex heat balancing design
Prevention of explosive mixture in the oxygen rich regions.
Lecture No.: 9 Date: 04/08/2015 Hour: 6
Objective: Oxygen and nitrogen production by pressure swing adsorption

Key points: Non cryogenic process

Explanation:

PSA Process

In operation each vessel cycles between absorption and regeneration. Impurities are rejected
during deprusization
 Non cryogenic process.
Using molecular sieves as adsorbent to separate the O2 from ambient temperature
compressed air.
This process produces O2 of low purity 90-95%
It uses three vessel in operation each vessel cycles between two stages, adsorption and
regeneration. One vessel adsorbes and other regenerates.
When the adsorbing vessel achieves its capacity for impurities the compressed air feed is
automatically switched to another vessel.
The first vessel then begins its regeneration cycle, which is accomplished by three
successive steps : depruserizing, purging with product oxygen and partial
depressurization after which the vessel is ready for adsorption.

MODULE II

Lecture No.: 10 Date: 05/08/2015 Hour: 6

Objective: To deliver on Hydrochloric acid manufacture

Explanation:

Obtained by burning chlorine in hydrogen.

Hydrogen Chloride is gas at ordinary temperature and pressure.