Chemical Process

Industries
Eduardo O. Hernandez, Jr.
2018
 The Chemical Process
• What is a Chemical Process?
 A chemical process is the combination of unit processes
and unit operations.

 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.
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 The Chemical Process
• 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

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 The Chemical Process

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 The Chemical Process
• Chemical processes may involve:
• homogeneous or heterogeneous systems.

• various type of reactions (reversible, irreversible, endothermic,

exothermic, catalytic, etc.).

• various variables affecting chemical reactions (temp. pressure,

composition, catalyst activity, the rate of heat and mass transfer, etc.).

• carrying the reaction in batch, semi batch or continuous way.

• using reactors that may be batch, plug flow, or CSTR and it may be
isothermal or adiabatic.

• catalytic reactors that may be packed bed, moving bed or fluidized bed.

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 The Chemical Process
• Important Unit Processes in the Chemical Process Industries

Oxidation Reduction Hydrogenation

Dehydrogenation Hydrolysis Hydration
Dehydration Halogenation Nitrification
Sulfonation Ammoniation Alkaline fusion
Alkylation Dealkylation Esterification
Polymerization Polycondensation Catalysis

and many more...

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 Development of a Chemical Process
• Important information for the development of a chemical
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, Labor, Overall Cost of production

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 Development of a Chemical Process
• Important information for the development of a chemical
process and its commercialization (cont..).
 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

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 Chemical Reaction and their Application in CPI
• Inorganic Chemical Reactions
Reaction Description
Kraft Process Manufacture of paper from pulp employing the Foudrinier machine
Bosch Process Method of recovering hydrogen from water gas; carbon monoxide is
reacted with steam at 500°C in the presence of catalyst to form carbon
monoxide and hydrogen.
Hoepener Process Recovering copper from its sulfide ores by leaching with cupric and
sodium or calcium chloride solution and electrolyzing the resulting
cuprous chloride liquor in cells with impure copper anodes protected by
diaphragms; the electrolytic by product, cupric chloride, is returned for
further leaching.
Holloway Process Copper or iron sulfides fused and blown with air to burn out sulfur
content
Barff Process Formation of rust resistant coating on iron; base metal by oxidation with
superheated steam
Carinthian Process Process for reduction of lead ores; small charge is roasted slowly at a
low temperature, the lead being collected outside the furnace by means
of heat
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 Chemical Reaction and their Application in CPI

Reaction Description
Cyanidation Method of recovering gold and silver from their ores into a soluble from
Process by treatment with cyanides.
Banbury Process Rubber reclaiming process in vulcanized scraps are introduced into a
mixer (Banbury) where in the presence of air it is worked under pressure
and at high temperature for a very short time.
Dennis Bull Sulfonation and extraction process in the manufacture of phenol.
Process
Solvay Process Soda ash ma nufacture.
Haber-Bosch Production of ammonia by direct combination of nitrogen and hydrogen
Process at 600°C and under 200 – 300 atmopheric pressure in the presence of
catalyst.
Frasch Process Process of recovering sulfur from buried porous cap rock of a salt dome
and delivering it above ground as a product of suitable purity and
condition for use.
Hall’s Process Extraction of aluminium from bauxite.

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 Chemical Reaction and their Application in CPI
• Organic Chemical Reactions

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Chemical Reaction and their Application in CPI

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Chemical Reaction and their Application in CPI

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 Unit Operations in Chemical Industries
• Unit operations are very important in chemical industries for
separation of various products formed during the reaction.

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 Unit Operations in Chemical 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.

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 Unit Operations in Chemical Industries
Membrane Process
• 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 is classified based on driving force.

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 Unit Operations in Chemical Industries
Membrane Process
• Various type of membrane process and driving force.

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 Unit Operations in Chemical Industries
Membrane Process
• 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.

• 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.

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 Unit Operations in Chemical Industries
Membrane Process
• Gas membrane application areas:

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 Unit Operations in Chemical Industries
Membrane Process
• Various types of membrane process:

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 Unit Operations in Chemical Industries
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.

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 Unit Operations in Chemical Industries
Absorption
• 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
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 Unit Operations in Chemical Industries
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.

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 Unit Operations in Chemical Industries
Adsorption
• 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.

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 Unit Operations in Chemical Industries
Adsorption
• Commercial Adsorption Processes:

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 Unit Operations in Chemical Industries
Crystallization
• 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.
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 Unit Operations in Chemical Industries
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 sulfur 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
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 Unit Operations in Chemical Industries
Technological Development in Unit Operation

• 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

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 Unit Operations in Chemical Industries
Technological Development in Unit Operation

• Fixed bed to Fluidized 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 chipper to High speed chipper

and high capacity chipper

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 Unit Operations in Chemical Industries
Technological Development in Unit Operation
• 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
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 Unit Operations in Chemical Industries
Technological Development in Unit Operation

• 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

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 Chemical Process Industries

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 Chemical Process Industries
The Alkali Industry
• Sodium hydroxide is used in many industries: in the
manufacture of pulp and paper, textiles, drinking
water, soaps and detergents, and as a drain cleaner.

• Sodium hydroxide is industrially produced as a 50% solution by

variations of the electrolytic chloralkali process. Chlorine gas is
also produced in this process. Solid sodium hydroxide is
obtained from this solution by the evaporation of water.

• Solid sodium hydroxide is most commonly sold as flakes, prills,

and cast blocks.

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 Chemical Process Industries
The Alkali Industry

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 Chemical Process Industries
The Alkali Industry
• Lime Soda Process
 Used for manufacturing caustic soda
 Lime and soda ash as raw materials
 Chemical Reactions:
CaO + H2O  Ca(OH)2
Ca(OH)2 + Na2CO3  CaCO3 + 2NaOH

• Solvay Process
 Used for manufacturing soda ash
 Limestone and salt as raw materials
 Chemical Reaction:
CaCO3 + NaCl  CaCl2 + Na2CO3
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 Chemical Process Industries
The Electrochemical Industry
 The electrochemical industry includes industrial water
electrolysis, electrolysis, electrosynthesis, electroplating, fuel
cells, flow batteries, decontamination of industrial effluents,
electrorefining, electrowinning, etc.

 The main example of an electrolysis based process is

the chloralkali process for production of caustic soda and
chlorine. Other inorganic chemicals produced by electrolysis
include: chlorine, fluorine, Sodium chlorate, Sodium chlorate,
ammonium persulfate, Sodium persulfate, Sodium
hypochlorite, potassium permanganate, Potassium dichromate,
hydrogen peroxide, ozone, manganese dioxide, silver nitrate.

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 Chemical Process Industries
The Electrochemical Industry
• Industries that heavily rely on oxidation-reduction reactions
 Two types: energy-requiring and energy-storing

• Energy-requiring
 Electrolytic cells
 Production of metal from salt solutions
 Formation of metal at the cathode
 Production of gases

• Energy-storing
 Batteries (wet cell, dry cell)

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 Chemical Process Industries
Sulfuric Acid Production
• Sulfuric acid’s principal uses include fertilizer manufacturing
(and other mineral processing), oil refining, wastewater
processing, and chemical synthesis.

• Wide range of end applications including in domestic acidic

drain cleaners, as an electrolyte in lead-acid batteries and in
various cleaning agents.

• Sulfuric acid is produced from sulfur, oxygen and water via the
conventional contact process (DCDA) or the wet sulfuric acid
process (WSA).

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 Chemical Process Industries
Sulfuric Acid Production
• Contact Process:
S (s) + O2 (g) → SO2 (g)
2 SO2 (g) + O2 (g) ⇌ 2 SO3 (g) (in presence of V2O5)
H2SO4 (l) + SO3 (g) → H2S2O7 (l)
H2S2O7 (l) + H2O (l) → 2 H2SO4 (l)
SO3 (g) + H2O (l) → H2SO4 (l)

• Wet Sulfuric Acid Process:

2 H2S + 3 O2 → 2 H2O + 2 SO2
2 SO2 (g) + O2 (g) ⇌ 2 SO3 (g) (in presence of V2O5)
SO3 + H2O → H2SO4(g)
H2SO4(g) → H2SO4(l)

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 Chemical Process Industries
Paper Industry
• Paper comes from the word “papyrus”

• Matted or felted sheet usually composed of plant fibers

• Paperboard are heavier and rigid paper with grammage higher

than 250 gsm

• Steps in Paper Production

 Fiber preparation – 1% fiber
 Forming – 20% solids (use of foudrinier or cylinder)
 Pressing – 40% solids (also called “calendering”)
 Drying - remaining water evaporated in steam-heated
cylinders
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 Chemical Process Industries
Clays and Ceramics
• Clays
 consist primarily of Al2O3 and SiO2 (aluminosilicates)
 typical formula is Al2O3 . 2SiO2 . 2H2O

• Ceramics
 heated clay
 interlocked SiO2-Al2O3 network

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 Chemical Process Industries
Fermentation Industry
• Conversion of sugar to alcohol and/or acid with the aid of
microorganisms

• Examples of fermented products are:

 Wine
 Beer / Lager
 Vinegar
 Yogurt

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 Chemical Process Industries
Fermentation Industry
• Beer Production
 Anaerobic conversion of sugar to alcohol with the aid of
Saccharomyces cerevisiae

• Vinegar Production
 Conversion of sugar to acetic acid
 Chemical Reactions:
1a. C6 H12O6  2C2H5OH + 2CO2
1b. C6 H12O6  3CH3COOH
2. C2H5OH + O2  CH3COOH + H2O

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 Chemical Process Industries
Glass Industry
• Glass
 Normally a colorless, transparent solid
 Acquires color from other elements present
 Made of SiO2, Na2O, and CaO
 Has low thermal stability and easily breaks on impact
 Partial replacement of Na2O and CaO with B2O3 gives
rise to borosilicate glass, which has greater heat and
mechanical resistance

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 Chemical Process Industries
Ammonia Production

• Production of ammonia from atmospheric nitrogen was

developed by Fritz Haber (Nobel Prize Winner)

• Chemical Reaction:
N2 + 3H2  2NH3

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 Chemical Process Industries
Metallurgical Industry

• Mining of ores, followed by refining process

 Bauxite / Cryolite – aluminium
 Hematite/Pyrite – iron
 Sphalerite – zinc
 Galena – lead

• Aluminum Production
 Wöhler process – isolation of aluminium from aluminium
chloride using potassium
 Deville process – modified Wöhler process; used sodium
instead of potassium
 Faraday – extracted aluminium from bauxite thru electrolysis

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 Chemical Process Industries
Metallurgical Industry

• Baeyer’s process
 Process of refining bauxite to pure Al2O3

• Hall-Heroult Process
 Extraction of aluminium thru electrolysis with the use of
carbon electrodes

Al2O3 + NaOH  NaAlO2 + H2O

NaAlO2 + H2O  NaOH + Al(OH)3
Al(OH)3  Al2 O3 + H2O
Al2O3 + 3C  2Al + 3CO

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 Chemical Process Industries
Industrial Gases

• Industrial gases are usually stored as liquid (pressurized)

• Thru a process called liquefaction

 Carried out in three ways:
 Heat exchange at constant pressure
 Expansion process
 Throttling

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 Chemical Process Industries
Fertilizer
• Earliest fertilizers were natural organic materials such as
manure and waste materials

• Primary nutrients needed for plant growth are: CHONPK

 CHO are readily available in the atmosphere
 NPK come exclusively from the soil

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 Chemical Process Industries
Fertilizer
• Ammonium nitrate
 An excellent nitrogen fertilizer

 Synthesized shortly after Fritz Haber discovered ammonia

production from atmospheric nitrogen

 Chemical Reactions:
N2 + 3H2  2NH3
NH3 + 2O2  HNO3 + H2O
HNO3 + NH3  NH4NO3

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 Chemical Process Industries
Fertilizer
• Superphosphate fertilizer
 Treatment of phosphate rocks with sulfuric acid

• N-P-K blends
 Combination of nitrogen, phosphorus and potassium
(listed in order)

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 Chemical Process Industries
Fats and Oils
• Soaps and Detergents

 Soap: a natural surfactant made from salt of fatty acid; a

good cleaning agent in soft water, but not in hard water

 Detergent: a synthetic surfactant patterned after soap’s

structure; first commercially developed detergent is a
fatty alcohol sulfate

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 Chemical Process Industries
Paints and Pigment
• Paints are dispersions of
 Binder – polymer
 Solvent – water or organic liquid
 Pigment – compound that either
 Gives color (prime)
 Makes the paint last longer (inert)

• Two kinds:
 Oil-based paints
 Latex paints – aqueous polymer dispersion

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 Chemical Process Industries
Paints and Pigment
• Typical prime pigments
 Titanium dioxide (TiO2)
 Iron oxides (Fe2O3 / Fe3O4)
 Phthalocyanines

• Typical inert pigments

 Talc
 Clay
 Calcium carbonate

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 Chemical Process Industries
Petroleum Industry
• Petroleum and petrochemical products are produced from the
distillation of crude oil

• Petroleum fractions include:

 Fuel gas (C1 - C4)
 Gasoline (C5 - C12)
 Kerosene (C10 - C16)
 Diesel (C12 - C20)
 Fuel Oil (C15 - C20)
 Lubricating Oil (C16 - C24)
 Asphalt (C20+)

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 Chemical Process Industries
Petroleum Industry
• Catalytic cracking
 Splitting of large molecule to smaller molecules

• Catalytic reforming
 Conversion of one hydrocarbon to another hydrocarbon,
typically from lower octane HC to higher octane HC

• Octane Rating
 Based on the combustion of n-heptane (Octane 0) and
2,2,4-trimethylpentane (Octane 100)
 Gasoline’s “burning characteristic” is measured against
mixture of n-heptane and isooctane
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 Chemical Process Industries
Rubber Industry
• Natural Rubber (rubber latex)
 Sourced from the sap of the tree Hevea brasiliensis
 Made up of units of isoprenes
 White, sticky material
 Very difficult to use

• Vulcanization
 Accidentally discovered by Charles Goodyear by mixing
rubber with sulfur, creating a cross-linked structure that is
stronger, more elastic, less sticky

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 Chemical Process Industries
Plastic Industry
• Properties of Plastics
 Thermal behavior
 Thermoplastic
 Thermosetting

• Structure
 Linear
 Branched
 Cross-linked

• Preparation Method
 Addition Polymerization
 Condensation Polymerization
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 Chemical Process Industries
Plastic Industry

• The “Big Six” of Plastics

 PET
 HDPE
 PVC
 LDPE
 PP
 PS

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 Chemical Process Industries
Mass Balance Problem

• A 20% aqueous solution of Na2CO3 and 25% aqueous solution

of Ca(OH)2 were reacted caustic soda solution. The precipitate
which formed was analyzed to contain 5% H2O, 1% NaOH, 94%
CaCO3. The concentration of NaOH solution produced is

a. 98.67%
b. 15.68%
c. 20.97%
d. 10.97%

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 Chemical Process Industries
Mass Balance Problem
Ca(OH)2 soln
• Given: 25% Ca(OH)2
Na2CO3 soln 75% H2O NaOH
20% Na2CO3 H2 O
80% H2O

Sludge:
94%CaCO3
1% NaOH
5% H2O

• Required: Concentration of NaOH produced

• Assumption:
A. ) 100% conversion
B. ) Materials input are in accordance with their stoichiometry for
NaOH production
• Na2CO3 + Ca(OH)2  2NaOH + CaCO3
94 kg
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 Chemical Process Industries
Mass Balance Problem
99.64 kg Na2CO3
398.51 kg H2O 75.2 -1 = 74.2 kg NaOH
398.51+208.68-5 = 602.24 kg H2O

69.56 kg Ca(OH)2
208.68 kg H2O

94 kg CaCO3
1 kg NaOH
5 kg H2O

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 Common Board Exam Questions
• Identify the process given its description

• Identify the industrial process given the reaction

• Identify the product/s from a given industrial process / reaction

• Identify the type of industry, given the equipment or raw

material used

• Identify the person who invented/discovered the chemical /

process

• Mass balance problems

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We all need people who will give us
feedback. That’s how we improve.
— Bill Gates

Thank you for listening.