Basic Principles of Unit Processes and Unit Operations

in Organic Chemical Industries

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, gassolid, gas-gas, liquidliquid, 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.
Basic Chemical data:
Yield conversion, kinetics
Material and energy balance, raw material and energy consumption per tone 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.

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 exothermic, 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.
NITRATION

Nitration involves the introduction of one or more nitro groups into reacting molecules using
various nitrating agents like fuming, concentrated, aqueous nitric acid mixture of nitric acid and
sulphuric acid in batch or continuous process.
Nitration products find wide application in chemical industry as solvent, dyestuff,
pharmaceuticals, explosive, chemical intermediates.
Typical products: TNT, Nitrobenzene, m-dinitrobenzene, nitroacetanilide, alpha
nitronaphthalene, nitroparaffins.

Example Preparation of TNT (trinitrotoluene)

TNT is produce in a three-step process: First, toluene is nitrated with a mixture of sulfuric acid
and nitric acid to produce mono-nitrotoluene or MNT.
The MNT is separated and then renitrated to dinitrotoluene or DNT.
In the final step, the DNT is nitrated to trinitrotoluene or TNT using an anhydrous mixture of
nitric acid and oleum.
HALOGENATION
Halogens involve introduction of one or more halogen groups into a organic compound for
making various chlorine, bromine, iodine, fluorine organic derivatives.
All though chlorine derivatives find larger application, however some of the bromine and
fluorine derivatives are also important.
Various chlorinating agents are chlorine, HCl, phosgene sulfuric chloride, hypochlorite,
bromination, bromine, hydrobromic acid, bromide, bromated, alkaline hypobromites. In
iodination iodine, hydroiodic acid and alkali hypoiodites.

Example
Typical important chemicals are chlorinated products: Ethylene dichloride, chlorinated
methanes Chloroform, Carbon tetra chloride etc) Chlorinate ethane, Chloro propane, chloro
butanes, chloroparaffins, chlorination of acetaldehyde (Chloral), alkyl halhides, Chlorobenzene,
Ethylene diiodide, Chloroflurocarbon (CFCs).

Preparation of chloroform and chloroflurocarbon (CFCs)

SULPHONATION AND SULPHATION

Sulphonation involves the introduction of sulphonic acid group or corresponding salt like
sulphonyl halide into a organic compound while sulphationinvolves introduction of -OSO2OH or
-SO4-.
Various sulphonating agents are sulphur trioxide and compounds, sulphurdixide,
sulphoalkylating agents.
Some of the sulphaming agents are sulphamic acid.
Apart from sulfonation and sulphamate sulpho chlorinated, sulfoxidation is also used.
Typical application of sulphonation and sulphation are production of lingo sulphonates, linear
alkyl benzene sulphonate, Toluene sulphonates, phenolic sulphonates, chlorosulphonicacd,
sulphamates for production of herbicide, sweetening agent (sidiumcyclohexysulphamate).
Oil soluble sulphonate, saccharin.

Preparation of Saccharin
The industrial synthesis entails the reaction of hydrogen chloride with a solution of sulfur
trioxide in sulfuric acid.
Sulfonation by chlorosulfonic acid gives the ortho and para substituted chlorosulfones.
The ortho isomer is separated and converted to the sulfonamide with ammonia.
Oxidation of the methyl substituent gives the carboxylic acid, which cyclicizes to give saccharin.
HCl + SO3 ClSO3H

OXIDATION
Oxidation used extensively in the organic chemical industry for the manufacture of a large
number of chemicals.
Oxidation using oxygen, are combinations of various reactions like oxidation via
dehydrogenation using oxygen, dehydrogenation and the introduction of oxygen and
destruction of carbon, partial oxidation, peroxidation, oxidation in presence of strong oxidizing
agent like KMnO4, chlorate, dichromate, peroxides H2O2, PbO2, MnO2; nitric acid and nitrogen
tertra oxide, oleum, ozone.
Some of the important product of oxidation are aldehyde, ketone, benzyl alcohol, phthalic
anhydride, ethylene oxide, vanillin, bezaldehyde, acetic acid, cumene, synthesis gas from
hydrocarbon,, propylene oxide, benzoic acid, maleic acid, benzaldehyde, phtathalic anhydride.
Oxidation maybe carried out either in liquid phase or vapour phase.

Preparation of synthesis gas from hydrocarbon

By using the FischerTropsch process, or FischerTropsch synthesis, is a collection of chemical
reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons.

HYDROGENATION
Hydrogenation involves the reaction of a substance with hydrogen in the presence of a catalyst.
Some of the other reaction involving hydrogen are, hydrodesulphurisation, hydrcracking, hydro
formylation, oxosynthesis, hydroammonylsis, synthesis of ammonia.

Preparation of aldehyde (Hydro-formylation):

ESTERIFICATION
Esterification is an important unit process in the manufacture of polyethylene terephathalate,
methyl metha acrylate, cellulose ester in viscose rayon manufacture (xanthation of alkali
cellulose with carbon disulphide), nitroglycerine.
HYDROLYSIS
Hydrolysis is used both in inorganic and organic chemical industry.
Typical application is in oil and fats industry during soap manufacture where hydrolysis of fats
are carried out to obtain fatty acid and glycerol followed by addition of sodium hydroxide to
form soap. Other application is in the manufacture of amyl alcohols.
Some of the major product using hydrogen is ethylene from acetylene, methanol, propanol,
butanol, production of alcohol from olefins (eg. Ethanol from ethylene).
Various types of hydrolysis reaction may be pure hydrolysis, hydrolysis with aqueous acid or
alkali, dilute or concentrated, alkali fusion, hydrolysis with enzyme and catalyst.

Preparation of ethanol from ethylene:

ALKYLATION
Alkylation involves the introduction of an alkyl radical into an organic compound by substitution
or reduction. Products from alkylation find application in detergent, lubricants, high octane
gasoline, photographic chemicals, plasticizers, synthetic rubber, chemicals etc.
Some of the alkylating agents are olefins, alcohols, alkyl halides. Although sulphuric acid and
phosphoric acid were commonly used as catalyst in alkylation process, however due to the
corrosive nature of these acid now solid acid catalyst is finding wide application in new
alkylation processes.

Preparation of toluene
Alkylation is the transfer of an alkyl group from one molecule to another.

POLYMERIZATION
Polymerization is one of the very important unit processes which find application in
manufacture of polymer, synthetic fibre, synthetic rubber, polyurethane, paint and petroleum
industry for high octane gasoline.
Polymerisation maybe carried out either with single monomer or with comonomer.
Polymerisation reaction can be addition or condensation reaction.
Various Polymerisation methods may be bulk, emulsion, solution, suspension.
Typical important product from polymerization are, Polyethyelene, PVC, poly styrene, nylon,
polyester, acryicfibre, poly butadiene, poly styrene, phenylic, urea, melamine and alkyd resins
epoxy resin, silicon polymers, poly vinyl alcohol etc.

Preparation of Polyethylene or polythene

It is the most common plastic.
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.
DISTILLATION
Distillation has been the king of all the separation processes and most widely used separation
technology and will continue as an important process for the foreseeable future.
Distillation is used in petroleum refining and petrochemical manufacture Distillation is the heart
of petroleum refining and all processes require distillation at various stages of operations.

MEMBRANE PROCESSES
Membrane processes have emerged one of the major separation processes during the recent
years and finding increasing application in desalination, wastewater treatment and gas
separation and product purification.
Membrane technology is vital to the process intensification strategy and has continued to
advance rapidly with the development of membrane reactors, catalytic membrane reactor,
membrane distillation, membrane bioreactors for wide and varied application.
Membrane process classified based on driving force.
Various type of membrane process and driving force are given in Table M-I 3.4.

Based on lower operating costs, comparable capital cost and only slightly product loss
(including fuel), membranes have demonstrated a flexible, cost, effective alternative to amine
treating for some natural gas processing applications.
Gas membrane and its application areas are mention in Table M-I 3.5.
Membrane distillation is a membrane separation process, which can overcome the limitation of
more traditional membrane process.
Membrane distillation has significant advantage over other processes, including low sensitivity
to feed concentration and the ability to operate at low temperature.
Various type of membrane processes are mention in Table M-I 3.6.
ABSORPTION
Absorption is the one of the most commonly used separation techniques for the gas cleaning
purpose for removal of various gases like H2S, CO2, SO2 and ammonia.
Cleaning of solute gases is achieved by transferring into a liquid solvent by contacting the gas
stream with liquids that offers specific or selectivity for the gases to be recovered. Unit
operation and is mass transfer phenomena where the solute of a gas is removed from being
placed in contact with a nonvolatile liquid solvent that removes the components from the gas.
Solvent: Liquid applied to remove the solute from a gas stream.
Solute: Components to be removed from entering streams.
Some of the commonly used solvents are:
Chemical Absorption
Amine Processes: Mono-ethanol amine (MEA), di-ethanol amine (DEA), tri-ethanol amine
(TEA), diglycol amine (DGA), methyl diethanol amine (MDEA)
Carbonate Process: K2CO3, K2CO3 + MEA, K2CO3 + DEA, K2CO3 + arsenic trioxide
Physical Absorption
Polyethylene Glycol Dimethyl Ether (Selexol), N-methyl pyrrolidine,NMP (Purisol), Methanol
(Rectisol), Sulphonane mixed with an alkanolamine and water (sulfinol).

ADSORPTION
Adsorption technology is now used very effectively in the separation and purification of many
gas and liquid mixtures in chemical, petrochemical, biochemical and environmental industries
and is often a much cheaper and easier option than distillation, absorption or extraction.
Some of the major applications of adsorption are gas bulk separation, gas purifications, liquid
bulk separation, liquid purifications. One of the most effective method for recovering and
controlling emissions of volatile organic compounds is adsorption Some of the commercial
adsorbent s are silica gel, activated carbon, carbon molecular sieve, charcoal, zeolites molecular
sieves, polymer and resins, clays, biosorbents. some of the key properties of adsorbents are
capacity, selectivity, regenerability, kinetics, compatibility and cost. Some of the methods used
for regeneration of adsorbent are thermal swing, pressure swing, vacuum (special case of
pressure swing), purge and gas stripping, steam stripping.
Commercial adsorption processes is given in Table M-I 3.7.

Some of the important criteria of good adsorbent are ;

(1) it must selectivity concentrate one or more components called adsorbate to from their fluid
phase levels
(2) the ability to release adsorbate so that adsorbent can be reused,
(3) as high as possible delta loading the change of weight of adsorbate per unit weight of
adsorbent between adsorbing and desorbing steps over a reasonable range of pressure and
temperature
Pressure swing adsorption (PSA) is based on the principle of relative adsorption strength, is a
milestone in the science of gas separation. Some of the commercial application of PSA are air
drying, hydrogen purification, bulk separation of paraffins, air separation for oxygen and
nitrogen production,
Chromatography is a sorptive separation process. in choromatography feed is introduce in
column containing a selective adororbent( stationary phase) and separated over the length of
the column by the action of a carrier fluid (mobile phase)that is continually supplied to the
column following the introduction of the feed.
The separation occurs as a result of the different partitioning of the feed solutes between the
stationary phase.
The separated solutes are recovered at different time in the effluent from the column.

CRYSTALLIZATION PROCESS
Crystallization processes are used in the petroleum industry for separation of wax. The process
involves nucleation, growth, and agglomeration and gelling.
Some of the applications of crystallization is in the separation of wax, separation of p-xylene
from xylenes stream.
Typical process of separation of p-xylene involves cooling the mixed xylene feed stock to a
slightly higher than that of eutectic followed by separation of crystal by centrifugation or
filtration.

LIQUID LIQUID EXTRACTION

Liquid liquid extraction has been commonly used in petroleum and petrochemical industry for
separation of close boiling hydrocarbons.
Some of the major applications are:
Removal of sulphur compound from liquid hydrocarbons
Recovery of aromatics from liquid hydrocarbon
Separation of butadiene from C4 hydrocarbons
Extraction of caprolactam
Separation of homogenous aqueous azeotropes
Extraction of acetic acid
Removal of phenolic compounds from waste water
Manufacture of rare earths
Separation of asphaltic compounds from oil
Recovery of copper from leach liquor
Extraction of glycerides from vegetable oil
Some of the important property of a good solvent
 High solvent power/capacity
High selectivity for desired component
Sufficient difference in boiling points of the solvent and the feed for effective
separation
Low latent heat of evaporation an specific heat to reduce utility requirement
high thermal an chemical stability
Low melting point
Relatively inexpensive
Non toxic and non corrosive
Low viscosity low interfacial tension

Technological development in unit operations

Distillation, Azeotropic, extractive distillation, reactive distillation, membrane distillation
Random packing to Structured Packing
Single and two pass to Multiple down comer
Rasching rings and berl saddles to Intalox sadles, pall rings, nutter rings, half rings, super
rings,Fleximax
Pan park to Wire gauge packing, Goodloe, Mellpark, Flexipack, Gempack, Intalox
Fixed bed to Fluidised bed reactor
Conventional reactor to Micro reactor
Ball mill grinding to Vertical roller mill and press roll Mill
Open circuit grinding to Closed circuit grinding
Batch digester to continuous digester
Low speed and low capacity cipper to High speed chipper and high capacity chipper
Low speed Paper machine to high speed machine
Drum displacer, Pressure diffuser, Displacement presses, Combined deknotting and Fine
screening,
High temperature screening before washing, Reverse cleaners
Adsorption(Olex, Parex and Molex), Crystallisation and Membrane separation processes
 Solvent extraction processes and New solvents
Conventional distillation Short path distillation, divided wall column
Conventional bubble cap, sieve plate to valve tray
Random packing to structured packing
Axial flow reactor to radial flow reactor
Conventional instrumentation to smart (intelligent) instrumentation