4th Stage/Chemical Industries 1

Asst. Professor: A. Al-Mosawi

Chapter 1. Chemical Processes

1.1 Introduction
Chemical processes usually have three interrelated steps:
1. Transfer of reactants to the reaction zone.
2. Chemical reactions involving various unit processes.
3. 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, liquid-
solid. Various type reactions involve may be reversible or irreversible, endothermic
or exothermic, catalytic or non-catalytic.
Various variables affecting chemical reactions are temperature, pressure, reactants
composition, catalyst activity, and the rate of heat and mass transfer.
The reaction may be carried out in batch, semi batch or continuous reactor.
Reactors may be batch, plug flow (PFR), CSTR. It may be isothermal or adiabatic.
Catalytic reactors may be packed bed, moving bed or fluidized bed.
The most important factors for chemical processes are: basic data, yield, conversion,
and kinetics.
Basic data: are the physical and chemical properties of reactants and products.
Yield is that fraction of raw material recovered as the main product.
Conversion is that fraction of material changed to another desired product.
The yield is frequently above 90 percent, whereas the conversion is limited by
equilibrium, changing the operating conditions, the equilibrium can be shifted and the
conversion enhanced.
Kinetics: is the study of reaction rates. Such information is essential for plant design,
since reaction rate determines equipment size. Catalysts are materials that increase
reaction speed.
Along with knowledge of various unit processes and unit operation, the following
information and requirements are very important for the development of a
commercial process:
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1. Material and Energy Balances, and Process Flow and Piping and Instruments
Diagrams (PFD and P& ID).
2. Raw Material and Energy Consumption per Ton of Product.
3. Batch vs. Continuous.
4. Chemical Process Selection: design and operation, pilot plant data, equipment
required, material of construction.
5. Chemical Process Control and Instrumentation.
6. Chemical Process Economics: Material and Energy Cost, Labor, Overall Cost of
Production.
7. Market Evaluation: Purity and Uniformity of Products for Further Processing.
8. Plant Location.
9. Environment Protection, Health, Safety and Hazardous Material.
10. Construction, Building and Commissioning.
11. Management for Productivity and Creativity, Training of Plant Personals.
12. Research and Development (R&D).
The chemical process is a combination of unit process and unit operation:
1.2 Unit Processes
Unit process involves principle chemical conversions leading to synthesis of
various useful products and provide basic information regarding;
1. the reaction temperature and pressure, 2. the extent of chemical conversions, 3.
the yield of product of reaction, 4. the nature of reaction whether endothermic or
exothermic, 5. and the type of catalyst.
Various unit processes in chemical industries are given in Table 1.1
Nitration
Nitration involves the insertion of one or more nitro groups into reacting molecules
using various nitrating agents such as nitric acid or 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.
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Asst. Professor: A. Al-Mosawi

Table 1.1: Unit Processes in Chemical Industries

Halogenation
Halogenation is the replacement of one or more hydrogen atoms in an organic or
inorganic compound by a halogen (fluorine, chlorine, bromine or iodine) for
making various halogen derivatives. Although chlorine derivatives find larger
application, however some of the bromine and fluorine derivatives are also
important. Various chlorinating agents are; Cl2, HCl, phosgene (COCl2),
hypochlorite (NaOCl). For bromination; bromine Br2, hydrobromic acid HBr,
bromide Br−, bromated (NaBrO3), alkaline hypobromites BrO−. In iodination;
iodine I2, hydroiodic acid HI and alkali hypoiodites NaIO. In fluorination: fluorine
F2, hydrofluoric acid HF, and silver tetrafluoroborate AgBF4.
Sulfonation and Sulfation
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Sulfonation involves the replacement of H atom of an organic compound with a

sulfonic acid group -SO3H or corresponding salt like sulfonyl halide.
Sulfation involves the replacement of H atom of an organic compound with a
sulfate -OSO2OH or -SO4-. Various sulfonating agents are SO3 and its compounds,
SO2, sulfoalkylating agents. Sulfonation and sulfation are major industrial chemical
processes used to make a diverse range of products, including dyes and color
intensifiers, pigments, medicines, pesticides and organic intermediates. Typical
application of sulfonation and sulfation are production of lingo sulfonates, linear
alkyl benzene sulfonate, Toluene sulfonates, phenolic sulfonates, chlorosulfonic
acid, sulfamates for production of herbicide.
Oxidation
Oxidation used extensively in the organic and inorganic chemical industry for the
manufacture of a large number of chemicals. Oxidation using O2 are combinations
of various reactions like oxidation via dehydrogenation using O2, dehydrogenation
and the introduction of O2 and destruction of carbon, partial oxidation,
peroxidation, oxidation in presence of strong oxidizing agent like potassium
permanganate KMnO4, sodium chlorate NaClO3, potassium dichromate K2Cr2O7,
hydrogen peroxide H2O2, lead dioxide PbO2, MnO2, nitric acid, oleum, and O3.
Oxidation maybe carried out either in liquid phase or vapor phase. Some of the
important products of organic oxidation are aldehyde, ketone, benzyl alcohol,
phthalic anhydride, ethylene oxide, vanillin, benzaldehyde, acetic acid, cumene,
synthesis gas from hydrocarbon, propylene oxide, benzoic acid, maleic acid, etc.
Hydrogenation
Hydrogenation is a chemical reaction between hydrogen gas (H2) and another
compound or element, usually in the presence of a catalyst such as nickel,
palladium or platinum. Some reactions with H2 gas are: hydrodesulfurization,
hydrocracking, hydroformylation (is an industrial process for the production of
aldehydes from alkenes), hydroammonolysis (is a process in which NH3-H2 mixture
is made in the presence of a hydrogenation catalyst), synthesis of ammonia NH3,
hydrogenation of vegetable oils.
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Asst. Professor: A. Al-Mosawi

Hydration
Hydration is the process of combining a substance chemically with water
molecules. Hydrate, a term used to indicate that a substance contains water, many
minerals and crystalline substances are hydrates. In organic chemistry, water is
added to an unsaturated substrate, which is usually an alkene or an alkyne. This type
of reaction is employed industrially to produce ethanol, isopropanol, and 2-butanol.
Hydrolysis
Hydrolysis is the chemical breakdown of a compound due to reaction with water.
The reaction mainly occurs between an ion and water molecule and often changes
the pH of a solution. 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 NaOH to form soap. Various types of hydrolysis reaction may be
pure hydrolysis, hydrolysis with aqueous acid or alkali, dilute or concentrated.
Electrolysis
Electrolysis is a chemical decomposition produced by passing an electric current
through a liquid or solution containing ions. Electrolysis is a technique that uses a
direct electric current (DC) to drive non-spontaneous chemical reaction.
Electrolysis is commercially important as a stage in the separation of elements from
naturally occurring sources such as ores using an electrolytic cell.
Esterification
Esterification is the conversion of carboxylic acid into an ester by combination with
an alcohol and removal of a molecule of H 2O. It is an important process in the
manufacture of polyethylene terephthalate, methyl meta acrylate, cellulose ester in
viscose rayon manufacture, nitroglycerine.
Alkylation
Alkylation is the transfer of an alkyl group from one molecule to another
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,
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alkyl halides. Although sulfuric acid and phosphoric acid were commonly used as
catalyst in alkylation process.
Polymerization
Polymerization is a process of reacting monomer molecules together in a chemical
reaction to form polymer chains or three-dimensional networks. Polymerization is
one of the very important unit processes which find application in manufacture of
polymer, synthetic fiber, synthetic rubber, polyurethane, paint and petroleum
industry for high octane gasoline. Polymerization may be carried out either with
single monomer or with co-monomer. Polymerization reaction can be addition or
condensation reaction. Various Polymerization methods may be bulk, emulsion,
solution, suspension. Typical important product from polymerization are,
polyethylene, PVC, polystyrene, nylon, polyester, acrylic fiber, polybutadiene,
polystyrene, vinyl compounds, urea, melamine and epoxy resin, etc.
Pyrolysis
Pyrolysis is a thermochemical decomposition of hydrocarbon at elevated
temperatures in the absence of oxygen (or any halogen). It involves the
simultaneous change of chemical composition and physical phase, and is
irreversible. Application involves plastic and tire pyrolysis at temperature of 400-
450 °C, in absence of oxygen to break down into smaller molecules of oil and gas.
The pyrolysis of coal is the first step of gasification. Biomass pyrolysis include
biochar, bio-oil and gases of CH4, H2, CO, and CO2 production.
Carbonization is the term for the conversion of an organic substance into carbon or
a carbon-containing residue through pyrolysis or destructive distillation.
Carbonation
Carbonation is created by adding dissolved CO2 and carbonic acid into the liquid.
Carbonation is added to soft drinks to give the soft drinks a "bite" to them.
Methanation
Methanation is the reaction by which carbon oxides COx and hydrogen H2 are
converted to methane CH4 and water. The reaction is catalyzed by nickel catalysts.
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Asst. Professor: A. Al-Mosawi

1.3 Unit Operations

Unit operations are very important in chemical industries for separation of various
products formed during the reaction. Table 1.2 give some details of unit operation
in chemical process industries.
Table 1.2 Unit Operations in Chemical Process Industries

Distillation
Distillation is the process of separating the components or substances from a liquid
mixture by successive evaporation and condensation steps and most widely used
separation technology. 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 Technology
Membrane technology is a generic term for a number of different, very
characteristic separation processes. These processes are of the same kind, because
in each of them a membrane is used. Membranes are used more and more often for
the creation of process water treatment. Membrane technology has finding
increasing application in desalination, wastewater treatment and gas separation and
product purification. Membrane separation processes operate without heating and
therefore use less energy than conventional thermal separation processes such as
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Asst. Professor: A. Al-Mosawi

distillation, sublimation or crystallization. The separation process is purely physical

and both fractions (permeate and retentate) can be used.
Absorption
Absorption is a physical or chemical a process in which molecules or ions of
gaseous stream enter another absorbing bulk phase of gas or liquid. Absorption is
the most commonly used separation technique for the gas cleaning purpose to
remove pollutants such as H2S, CO2, SO2 and NH3. Cleaning of solute gases is
achieved by transferring to a liquid solvent with good contact of the gas stream and
liquid stream which offers specific or selectivity for the gases to be recovered. The
absorption is mass transfer phenomena where the solute of a gas is removed from
being fed in contact with a nonvolatile liquid solvent that absorbs the components
from the gas.
Solvent: Liquid applied to remove the solute from a gas stream.
Solute: Components to be removed from entering streams.
Adsorption
Adsorption is the adhesion of molecules of gas, liquid, or dissolved solids to a
surface based adsorbent. This process creates a film of the adsorbate (the molecules
or atoms being accumulated) on the surface of the adsorbent. Adsorption is present
in many natural, physical, biological, and chemical systems, and is widely used in
industrial applications such as heterogeneous catalysts, activated charcoal, air
conditioning and other process requirements (adsorption chillers), synthetic resins,
and water purification. Adsorption process is often a much cheaper and easier
option than distillation, absorption or extraction. One of the most effective method
for recovering and controlling emissions of volatile organic compounds is
adsorption. Some of the commercial adsorbents 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.
Crystallization
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Crystallization is a chemical solid–liquid separation technique, in which mass

transfer of a solute from the liquid solution to a pure solid crystalline phase occurs.
Crystallization occurs in two major steps. The first is nucleation; the appearance of
a crystalline phase from either a supercooled liquid or a supersaturated solvent. The
second step is known as crystal growth, which is the increase in the size of particles
and leads to a crystal state. The most important application 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.
Solvent Extraction
Solvent extraction is a method to separate compounds based on their relative
solubilities in two different immiscible liquids, usually water and an organic
solvent. It consists of transferring one (or more) solute(s) contained in a feed
solution to another immiscible liquid (solvent). The solvent that is enriched in
solute(s) is called extract. The feed solution that is depleted in solute(s) is called the
raffinate. 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 sulfur compound from liquid hydrocarbons,
recovery of aromatics from liquid hydrocarbon, separation of butadiene from C4
hydrocarbons, extraction of acetic acid, removal of phenolic compounds from
wastewater, recovery of copper from leach liquor, and extraction of glycerides from
vegetable oil. Some of the important property of a good solvent are:
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.
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Asst. Professor: A. Al-Mosawi

1.4 Engineering Flowsheets

For a chemical process in general, equipment, operating details, and all reactions as
that occurred, which should include data covering not only materials, but labor and
utilities as well.

Fig. 1.1 Typical flowsheet symbols

Process Flow Diagrams (PFD) are usually prepared when the design is completed and
are used to coordinate all the data from the drawings of individual plant items, which
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must be prepared separately. It is conventional to show pipes with flanges, heat

exchangers with supports, flanges and nozzles and so on, each item being given a
code number, various companies have their own ideas on this, but E for exchangers,
C for columns, V for vessel and so on seems to be generally accepted. Some useful
and generally accepted symbols are shown in Figure 1.1.
Piping and Instrument Diagrams (P&ID) are mechanical flow diagrams allied to the
engineering flowsheets. These include all pipe sizes, size and type of valves, pipe
fittings, etc., and are necessary where this information, which is required by
mechanical, electrical and instrument engineers, is too complicated to be included in
the process flowsheet. A portion of a typical piping flow diagram is shown in Fig.1.2.
In such diagrams it is conventional to number the various pipelines and branches as
an aid to clarity and also in locating lines once the plant is completed. There are a
multitude of systems, though the following coding is fairly widespread: nominal pipe
size/material code/sequence number.

Fig. 1.2 Part of a typical piping flowsheets

For example, `2-Cl-6a'-represents a 2 in. diameter, number 6a carrying chlorine,

whilst `4-S150-21' refers to pipe 21, which is 4 in. diameter carrying steam at
1501b/in2 g. Other material codes are fairly obvious and a matter of personal
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reference. In numbering pipes, letters are often used to indicate branches. Useful
symbols for incorporation in such diagrams are as in Figure 1.3.

Fig. 1.3 Symbols used in piping flowsheets

1.5 Chemical Process Design

The process engineer is a specialist in current aspects of chemical process design.
Practical experience is a necessity if the senior design engineer is to be able to
foresee and solve plant problems of a less obvious nature, such as maintenance,
safety, and conformation to government environmental controls. Experienced
consultants, either individuals or professional consulting firms, are available to
advise, design, and/or erect chemical process plants.
1.5.1 Pilot Plants
Pilot plants are small-scale units designed to allow experiments that obtain design
data for larger plants and sometimes to produce significant quantities of a new
product to permit user evaluation of it. Pilot plant development experiments are
expensive but frequently essential. Where possible, current practice is to calculate
more and use pilot plants less. The design engineer should plan pilot plant runs
carefully by using statistical analysis of the procedures necessary to determine the
data required for design. Particularly in completely new operations, the pilot plant
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should be constructed with equipment identical in material with that to be used by the
commercial plant in order to ascertain the effects of corrosion and "to commit
blunders on a small scale and make profits on a large scale."
Corrosion data from the pilot plant are much more reliable than small-scale tests with
pure chemicals, and the other aspect of corrosion, the effect of corrosion products on
the chemical reaction and final products, generally appears here first.
1.5.2 Equipment
Equipment is emphasized in conjunction with descriptions of the various processes
and with flowcharts representing these processes. Any chemical engineer should start
early to become familiar with industrial equipment such as pumps, filter presses,
distillation towers, nitrators, evaporators, sulfonators, electrolyzers, and fuel cells.
The Chemical Engineering Catalog includes convenient information concerning the
actual equipment that can be supplied by various manufacturers.
1.5.3 Corrosion, Materials of Construction
Successful operation of chemical plants depends not only on the original strength of
the materials of construction but also upon proper selection to resist corrosion.
Mechanical failures are seldom experienced unless there has been previous corrosion
or weakening by chemical attack. Erosion is occasionally a factor in the deterioration
of equipment; it can be reduced by avoiding sudden changes in flow direction.
Corrosion cannot be prevented; it can only be minimized. Advances in materials
science have provided many corrosion-resistant materials: rubber-covered steel,
resin-bonded carbon, and tantalum to resist hydrochloric acid; stainless steel to resist
the action of aqueous nitric acid and organic acids even under pressure; and nickel or
nickel-clad steel to resist caustic solutions, hot or cold. Polymeric organic materials
have become important in the fight against corrosion. Among the construction
materials used by chemical engineers are many of the commonest substances and
some of the rarest-brick, cast iron, steel, wood, cement, platinum, tantalum, and
silver. Corrosion testing must be done with commercial chemicals rather than pure
laboratory chemicals since it frequently happens that a small amount of a
contaminant in a commercial raw material affects corrosion appreciably.
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1.6 Instrumentation and Process Control

1.6.1 Instruments are the essential tool for modern processing. Automatic and
instrument controlled chemical processes are common and essential. Data processing
and computing instruments actually take over the running of complex chemical
processing systems. Some instruments can even optimize plant conditions to meet
changing feed conditions. Instruments should be chosen simply to record process
variables and to assure:
(1) Quality, usually by sensing.
(2) Controlling.
(3) Recording.
(4) Maintaining desired operating conditions.
In large-scale continuous operations, the function of the workers and the supervisory
chemical engineer is to maintain the plant in proper running order. Batch sequences
require few instruments, hence more supervision on the part of the workers and the
process engineer because conditions or procedures usually differ from start to finish.
Even these problems can be solved by programmed instruments if the expense can be
justified.
Instrumentation has been forced into this position of importance by the increase in
continuous procedures, by the increased cost of labor and supervision, by the relative
unreliability of human actions, and by the availability of many types of instruments
and monitors at decreasing price and increasing reliability. Instrument types include:
1. Indicating instruments-presenting current data, value, or deviation from a norm
2. Recording instruments-permit study and analysis
3. Indicating/ recording and controlling instruments.
Two types of instruments are currently used, analog and digital:
Analog instruments such pressure spring, thermometers and Bourdon pressure gages,
that show results by mechanical movement of some type of device which is
proportional to the quantity being measured.
Digital devices generally utilize a "transducer" a device to convert the quantity being
measured into some type of signal (usually electrical or pneumatic) and electronic
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circuitry to this signal to readable numerical figures (digits) which are displayed
and/or recorded.
Instruments are indicated by appropriate symbols with the following typical
abbreviations:
RTC recording temperature controller
RFM recording flowmeter
ILC indicating level controller
ORFM orifice for recording flowmeter
PG pressure gauge
HPA high pressure alarm
In most designs, diagrams of instrumentation lines, power supplies, and so on, have
to be prepared. Instruments and control lines should be presented on the piping flow
diagram and on the drawings of the plant items together with full mechanical.
1.6.2 Chemical analytical control has been used in factory procedures for analysis of
incoming material and outgoing product, but generally conventional procedures are
too slow, expensive, and dependent on frequently questionable sampling procedures.
With the advent of fast, reliable, and sensitive procedures capable of automation,
control based on analysis within the process has become economically feasible.
Quality devices are produced far more reliably than when human analyses are used.
Chromatographic systems, pH sensors, conductivity meters, even mass spectroscopy
have been automated and used industrially.