CHEMICAL ENGINEERING

REVIEW
ENGR. LYLE MELAD
26 SEPTEMBER 2019
 BRIEF HISTORY OF CHEMICAL
ENGINEERING

• 1880s: The Issue

• Chemical products and processes discovered in the lab have to
be scaled up for the industrial plant in order to give them
commercial importance.
• With the rapid growth of the chemical industry, there was an
increasing gap between laboratory processes and full-scale
industrial production
 BRIEF HISTORY OF CHEMICAL
ENGINEERING

• The Solution:
• Hire a research or industrial chemist and work with a
mechanical engineer to scale up lab bench to factory
floor

• The Challenges:
• Limited output for scaled-up (batch) processes.
• Limited knowledge of chemists on continuous processes
• Complex engineering is required
 BRIEF HISTORY OF CHEMICAL
ENGINEERING
• Realizations:
• "From their experience in chemical plants, both
chemists with an instinct for engineering and engineers
with a taste for chemistry grew into chemical
engineers without realizing it and indeed without
being willing to admit it." - Sir Harold Hartley (1880)
• "It is very difficult to find a manager who has a
knowledge of engineering combined with a
knowledge of chemistry. Such men must be educated,
and it is only now that we are beginning to follow in
[this] path." - E. K. Muspratt (1886)
 THE FIRST CHEMICAL ENGINEER

• Generally credited for initiating the

concept of chemical engineering
• In 1887, gave a series of 12 lectures at
the Manchester School of England, which
formed the basis of his two-volume
George E. Davis. Courtesy
"Chemistry & Industry" (1981).
Handbook of Chemical Engineering

"The object of this handbook is not to enable anyone to erect works of special
character ... but to illustrate the principles by which a plant of any kind may be
designed and erected when certain conditions and requirements are known. We
cannot make the best use of our abilities unless we are taught to investigate the
principles underlying the construction of the appliances with which we have to
work." (early recognition of the need to understand underlying physical and
chemical principles in chemical engineering)
 THE CHEMICAL ENGINEERING
EDUCATION
• “Course X” launched by Massachusetts Institute of
Technology in 1888
• Arranged to meet the needs of students who desire a
general training in mechanical engineering and to
devote a portion of their time to the study of the
application of chemistry to the arts, especially to those
engineering problems which relate to the use and
manufacture of chemical products
• “What central theme could chemical engineering
education rally around?”
 THE BIRTH OF UNIT OPERATIONS
• In 1915, in a letter to the President of MIT, Arthur
Little stressed the importance of "Unit Operations" in
distinguishing chemical engineering from all other
professions and giving chemical engineering
programs a common focus.
• The concept was developed to emphasize the
underlying unity among seemingly different
operations. For example, the principles are the same
whether one is concerned about separating alcohol
Arthur D. Little in 1922. from water in a fermenter, or separating gasoline
Courtesy MIT Museum.
from diesel in a refinery, as long as the basis of
separation is generation of a vapor of a different
composition from the liquid. Therefore such
separation processes can be studied together as a
unit operation (in this case called distillation).
 DEFINITION OF CHEMICAL
ENGINEERING
“… a branch of chemical engineering concerned with the development and
application of manufacturing processes in which chemical or certain physical
changes of materials are involved.”

“Processes are resolved into a coordinated series of unit

physical operations and unit chemical processes”

“The work of a chemical engineer is concerned primarily with the design,

construction and operation of equipment and plants in which these unit
operations and processes are applied”

“Chemistry, physics and mathematics are the underlying sciences of chemical

engineering, and economics its guide in practice”
 WHERE DO THEY NEED US?
• Biochemical engineering
• Biomedical engineering
• Biomolecular engineering
• Biotechnology
• Chemical process modeling
• Chemical Technologist
• Chemical reactor
• Chemical weapons
• Cheminformatics
• Computational fluid dynamics
• Corrosion engineering
• Cost estimation
• Electrochemistry
• Environmental engineering
• Food engineering
• Fuel cell
• Gasification
• Industrial gas
• Materials science
• Metallurgy
• Mineral processing
• Molecular engineering
• Nanotechnology
• Natural environment
• Natural gas processing
• Nuclear reprocessing
• Oil exploration
• Oil refinery
• Pharmaceutical engineering
• Plastics engineering
• Process control & design
• Process development
• Process engineering
• Process miniaturization
• Paper engineering
• Safety engineering
• Semiconductor device fabrication
• Crystallization processes
• Distillation processes
• Membrane processes
• Syngas production
• Textile engineering
• Water technology
Chemical engineering unit operations and chemical engineering
unit processes form the main principles of all kinds of
chemical industries and are the foundation of
designs of chemical plants, factories,
and equipment used.
Chemical Process
Industries
Prepared by:
Engr. Lyle M. Melad
31 August 2019
 The Chemical Industry
• Air, water, various minerals
• Hydrocarbons (coal, natural gas, petroleum, plant
Raw Material materials)

• NH3, HCl, H2, HNO3, O2, NaOH, H2SO4

Primary and
Secondary
• C2H2, C6H6, C2H6, C2H5OH, C2H4, CH4, C6H5OH
Products

• Explosives, Fertilizers, Paints, Pharmaceuticals

Tertiary
(Finished
• Plastics, Rubber, Soaps, Detergents
Products)
 Chemical Process Industries
Primary and Secondary Tertiary Products
Products • Fertilizers
• Sulfuric Acid • Soaps and Detergents
• Ammonia • Paints and Pigments
• Alkalis • Plastics
• Fats and Oils • Rubber
• Petroleum and • Batteries
Petrochemical Products • Metals (Aluminum)
• Electrochemical Industry • Paper and Paperboard
• Alcohol • Glass and Ceramics
• Wines and spirits
 Water as a raw material
• Purity and quantity as consideration
• Impurities in water
– Physical (turbidity)
– Microbiological (pathogenic microorganisms)
– Chemical (hardness, dissolved solids, organic
matter)
• Water treatment (conditioning) is
necessary
 Water as a raw material
• Hardness – amount of dissolved calcium
and magnesium salts, calculated as
calcium carbonate equivalent, CaCO3,
usually expressed in ppm
• Carbonate hardness = temporary
hardness (caused by lime and magnesia)
• Non-carbonate hardness = permanent
hardness (caused by sulfates and
chlorides)
 Water Conditioning
• Softening – removal of hardness
• Purification – removal of organic matter
and microorganisms
 Water Softening
Ion-exchange
• a process where the Ca++ and Mg++ are
exchanged with Na+ from the cation
exchange system, composed of hydrated
alkali-alumina-silicates (usually zeolite -
Na2Al2Si3O10·2H2O)

Regeneration of zeolite is done by adding salt in the

pH range between 6 to 8
 Sulfuric Acid

• How important is sulfuric acid?

– Very important commodity chemical, an indicator
of industrial strength or economic prosperity
– Used in fertilizers, detergents, resins, dyestuffs,
pharmaceuticals, petroleum catalysts, pigments,
insecticides, batteries
 Sulfuric Acid

• History:
– Medieval period: Sulfuric acid prepared by roasting green vitriol in
an iron retort
– 18th century: increasing demand for sulfuric acid
– 1736: Joshua Ward began the first large-scale production of sulfuric
acid by burning sulfur together with saltpeter in the presence of
steam
– 1749: England begins a Lead-Chamber Method to produce sulfuric
acid.
– 1831: Peregrine Phillips, a British vinegar merchant, patented the
contact process
– 1875: Industrial scale for contact process by Rudolf Messel
 Sulfuric Acid

• Contact Process
Chemical Reactions:
• S + O2  SO2
• SO2 + O2  SO3
• SO3 + H2SO4  H2S2O7 (oleum)
• H2S2O7 + H2O  2H2SO4
 Ammonia
• 1910: Production of ammonia from atmospheric nitrogen
was developed by Fritz Haber, and was scaled up to
industrial production by Carl Bosch
• 1918: Fritz Haber received Nobel Prize for the ammonia
synthesis
Chemical Reaction:
N2 + 3H2  2NH3

• Today, Haber process is widely used to make fertilizers (in

the form of ammonia, ammonium nitrate and urea), nitric
acids and explosives
 Fertilizers
• 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
 Fertilizers
• 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
 Fertilizers
• Superphosphate fertilizer
– Treatment of phosphate rocks (fluoroapatite)
with sulfuric acid
Chemical Reaction:
2Ca5(PO4)3F + 7H2SO4 + 3H2O  7CaSO4 + 3Ca(H2PO4)2 . H2O + 2HF

• Potassium
– Main source is coming from KCl, which comes
from sylvinite (sylvite, KCl and halite, NaCl) and
langbeinite (K2SO4-MgSO4)
– Manufacture via Trona Process
 Fertilizers
• N-P-K blends
– Combination of nitrogen, phosphates (P2O5) and
soluble potash (K2O), listed in order)
 Alkalis

• How important are alkalis?

– Vital chemicals in the glass, textile, soap and
paper industries
• As flux for silica, to produce soda glass
• As a fixative or activator for textile dyeing
• As a water softener for soaps and detergents
• Kraft pulping in the paper industry
• pH regulator
• Other sodium chemicals
 Alkalis
• History:
– Before 18th century: alkalis are obtained from wood
ashes and other plant sources
– 1791: Nicholas Le Blanc develops his process for
converting sea salt into soda ash with the aid of sulfuric
acid, limestone and coal
– Early 19th century: soda works as a target of lawsuits and
legislations due to environmental issues
– 1861: Ernest Solvay perfects his method for producing
sodium bicarbonate from ammonia.
 Alkalis
• Le Blanc Process
Main issues:
- Gaseous HCl released in the environment
- Calcium sulfide as waste releases H2S

*Image under license by creativecommons.org

 Alkalis
• Solvay Process
Key features:
- Ammonia recovery
- Calcination of baking soda
produces soda ash

*Image under license by creativecommons.org

 Alkalis
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 + NaOH
 Fats and Oils
What is the difference between fat and oil?

• A fat is solid or semi-solid at ambient

temperature.
• An oil is liquid at ambient temperature.
 Fats and Oils
Fatty acid 1
OH
Esterification
OH

OH
Glycerol Fatty acid 3
Fatty Acid 1
Fatty acid 2

Glycerol
Fatty Acid 2

Fatty Acid 3

Triglyceride or Triacylglycerol
 Fats and Oils
Fatty acids with 18 carbon atoms
• Length of the carbon chain: Functional group:
carboxyl group (acid)
– 4 to 24 carbon atoms
Stearic acid: no DB O
• Degree of unsaturation:
– Saturated Fatty Acids (SFA): OH

no double bonds O
Oleic acid: 1 DB
– Unsaturated Fatty Acids: OH
• Monounsaturated Fatty 9
Acids (MUFA): Linoleic acid: 2 DB O
– 1 double bond
OH
• Polyunsaturated Fatty 12
Acids (PUFA): a-Linolenic acid: 3 DB O
– 2 to 6 double bonds
OH
15
 Fats and Oils
Selection of Fatty Acids Occurring in Fats and Oils
Trivial name of fatty acid Carbons Double Type Bioche- Nutritionall Main
bonds mical type y essential Sources
Butyric acid 4 0 SFA n.a. no MF

Lauric acid 12 0 SFA n.a. no CNO, PKO

Palmitic acid 16 0 SFA n.a. no PO, POo

Oleic acid 18 1 MUFA n-9 no All fats and oils

Linoleic acid (Li or LA) 18 2 PUFA n-6 yes CO, SFO, SBO

a-Linolenic acid (Lin or 18 3 PUFA n-3 yes RSO, SBO

ALA)
Arachidonic acid (ARA) 20 4 PUFA n-6 ?* ARASCO

Eicosapentaenoic acid (EPA) 20 5 PUFA n-3 ?* FO

Docosahexaenoic acid 22 6 PUFA n-3 ?* Tuna FO,

(DHA) DHASCO

*: depends on age and health status of the person

CNO: coconut oil, CO: corn oil, FO: fish oil, MF: milk fat, PKO: palm kernel oil
PO: palm oil, POo: palm olein, RSO: rapeseed oil, SBO: soybean oil, SFO: sunflower oil
 Fats and Oils
Oil seeds

Oil seed cleaning

Flaking

Cooking Solvent

Pressing Oil cake Deoiled cake

Solvent

Crude press oil + Extraction oil Crude oil

(to be refined)
 Fats and Oils

Crude oil

Acid
Degumming Gums
Water
Caustic
soda Neutralisation Free Fatty Acids
as soaps
Bleaching
earth Bleaching Pigments

Steam Deodorization off-taste

off-odours

Finished oil

The RBD Process

 Hydrogenation
• Conversion of various unsaturated fatty
glycerides into more highly or completely
saturated glycerides by the addition of
hydrogen in the presence of a catalyst.
• The objective of the hydrogenation is not
only to raise the melting point but greatly
to improve the keeping qualities, taste,
and odor of many oils.
 Soaps and Detergents
• Soap
– a natural surfactant made from salt of fatty
acid
– Allows insoluble particles to become soluble
in water, due to formation of micelles
 Soaps and Detergents
History of Soap
• Ancient times: a Babylonian clay tablet dated 2200 BC
records an earlier formula consisting on water, alkali and
cassia oil
• Before Industrial Revolution: soapmaking was limited to
small scale production
• Late 18th century: Awareness campaigns on soap
launched industrial production of soap
 Soaps and Detergents
Soapmaking Process
• Cold Process
– Reaction takes place at near room temperature (i.e. does not
require excessive heating)
– Requires exact measurements of alkali (lye) and fats
• The saponification value of oil/fat is used to calculate the exact amount of
sodium hydroxide that will react with the fat to form soap.
• Hot Process
– Reaction takes place at 80 to 100 degrees Celsius
• Fully Boiled Process
– Mix is boiled above 100 degrees Celsius
– After saponification has completed, soap is precipitated by
adding salt
 Soaps and Detergents
History of Detergent
• Development of detergent is mainly driven
by:
– Shortage of fats for making soaps during
World War I
– Need for a cleaning agent that would not react
with mineral salts in water
 Soaps and Detergents
• Detergent
– a synthetic surfactant patterned after soap’s
structure
– First commercially developed detergent is a
fatty alcohol sulfate
 Soaps and Detergents
Three Types of Detergents
• Anionic detergents
– Alkyl sulfates
– Alkylbenzenesulfonates
– Phosphates
– Carboxylates
• Cationic detergents
– Quaternary ammonium salts
• Non-ionic detergents
– PEG
– Ethoxylates
 Paper and Paperboard

• Paper
– From the word “papyrus”, a tall reed growing
along Nile River
– Matted or felted sheet usually composed of plant
fibers

• Paperboard
– Heavier and rigid paper with grammage higher
than 250 gsm
 Paper and Paperboard

History of Papermaking
- Early industry
- Rags as raw material
- Washing and stamping into pulp
- Wooden frame with wire-screen bottom dipped
into the pulp, excess liquor drained and forming
sheet
- Stacking, pressing, and hanging to dry
- Final product: rag paper
 Paper and Paperboard

History of Papermaking
- Breakthroughs
- 1799: Louis Robert invented a process for forming a sheet on a
moving wire screen
- Invention was sold to M. Didot and John Gamble, and additional
improvements were made
- 1804: Invention was sold to Fourdrinier brothers
- 1809: John Dickinson invented the cylinder machine
- 1830’s: combination of Fourdrinier and cylinder machines increased
production of paper, and developed scarcity for rags
 Paper and Paperboard

History of Papermaking
- Breakthroughs
- 1841: Invention of mechanical process of making pulp from wood
- 1853: Development of soda process
- 1866: Invention of sulfite process
- 1879: Development of sulfate (kraft) process
 Paper and Paperboard

Steps in Paper Production

1. Fiber preparation / Pulping Process (Kraft
Process)
– Impregnation of wood chips with steam and liquor
– Digestion (delignification) in pressurized vessels
– Blowing & Screening & Washing
– Bleaching
 Paper and Paperboard
Pulp Chips
Cooking and
Washing
Black liquor
Lignin White liquor
Na2CO3 NaOH + Na2S
Na2SO4
Inorganic salts

Green liquor
Evaporation
Na2CO3 + Na2S
Causticizing
and burning
 Paper and Paperboard

Steps in Paper Production

2. Forming – 20% solids
• Wet web of fiber
3. Pressing – 40% solids
4. Drying - >90% solids
• Remaining water evaporated in steam-heated cylinders
5. Calendering
• Smoothening of paper
 Starch Industry
• Various sources of starch include:
– Corn
– Tapioca (Cassava)
– Potato
– Wheat
– Rice
• Widely used as a raw material in the food industry
• Used as a raw material to derive simple carbohydrates (e.g.
glucose and maltodextrin)
Glucose Syrup Production
Starch Slurry

NaOH and
Liquefaction
enzymes

Cooking Steam

HCl and enzymes

Saccharification
(amylase/amylopectinase)

Drum Filtration Diatomaceous earth

Decolorization Activated Carbon

Ion Exchange Activated Carbon

For HFS, a second

Evaporation saccharification using glucose
isomerase converts glucose
Glucose syrup to fructose
 Sugar Industry
• Sugar  Sucrose
• Cane as raw material
• Raw cane sugar - partially purified sucrose,
which is crystallised from partially purified cane
juice, which is characterised by sucrose crystals
covered with a film of cane molasses
• White sugar (or refined sugar) – purified and
crystallized sucrose with a polarization not less
than 99.5oZ
• Molasses as by-product
 Fermentation

• Conversion of sugar to alcohol and/or acid

with the aid of microorganisms
• Examples of fermented products are:
– Wine
– Beer / Lager
– Vinegar
– Yogurt
 Fermentation

Other Fermentation Products

• Food
– Bread, cheese, cocoa
• Pharmaceutical
– Vitamins (B1, B2, B12)
– Antibiotics (Penicillin, Terramycin)
• Industrial
– Acids (Citric Acid, Malic Acid, Lactic Acid)
– Glycerine
 Fermentation
Beer Production
– Anaerobic conversion of sugar to alcohol with the aid of
Saccharomyces cerevisiae
Vinegar Production
– Conversion of sugar to acetic acid with the aid of
Acetobacter / Acetobacterium / Clostridium
Chemical Reactions:
1a. C6H12O6  2C2H5OH + 2CO2
1b. C6H12O6  3CH3COOH
2. C2H5OH + O2  CH3COOH + H2O
3. 2C6H12O6 + H2O  C2H5OH + CH3COOH + 2CO2 + 2C3H8O3
 Fermentation
Citric Acid Production
– Aerobic conversion from sugar by Aspergillus niger

Chemical Reactions:
C12H22O11 + H2O + 3O2  2C6H8O7 + 4H2O
 Fermentation
Lactic Acid Production

Cream
Casein
Raw Milk
Skimmed
Milk Whey Protein
Whey
Lactose

C12H22O11 + H2O  C6H12O6 (glucose) + C6H12O6 (galactose)

C6H12O6 (presence of Streptococcus lactis)  2CH3CHOHCOOH

Other fermenting microorganisms: L. delbrueckii (bulgaricus)

 Alcohols and Spirits
• In the production of spirits, fermentation is
followed by distillation
• Type of spirit depends on the source of
fermentable sugar
– Barley and grain (corn) – whisky and gin
– Grapes and berries – wine and brandy
– Molasses –rum
– Succulents – tequila
– Potatoes – vodka
 Electrochemical Industries
• Industries that heavily rely on oxidation-
reduction reactions
• Two types:
– energy-requiring
– energy-producing
 Electrochemical Industries

• Energy-requiring
– Electrolytic cells
– Production of metal from salt solutions
• Formation of metal at the cathode (e.g. Aluminum from bauxite)
– Production of gases (e.g. decomposition of water to
hydrogen and oxygen gases)
• Energy-producing
– Batteries
• Wet cell
• Dry cell
 Electrochemical Industries
• Batteries
– 1748: Benjamin Franklin described multiple
Leyden jars to a “battery of cannon”
– 1800: Alessandro Volta built the first
electrochemical battery, the voltaic pile
– 1836: Daniell cell, the first practical source
of electricity, was invented
 Electrochemical Industries
• Principle:
 Metallurgical Industries
• Mining of ores, followed by refining process
– Bauxite/Cryolite - aluminum
– Hematite/Pyrite – iron
– Sphalerite – zinc
– Galena - lead
 Metallurgical Industries

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

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

Al2O3 + NaOH  NaAlO2 + H2O

NaAlO2 + H2O  NaOH + Al(OH)3
Al(OH)3  Al2O3 + H2O

• Hall-Heroult Process
– Extraction of aluminum thru electrolysis with the
use of carbon electrodes
2Al2O3 + 3C  4Al + 3CO2 ΔH = 6.34 kWh / kg Al
 Paints and Pigments, Lacquers
and Varnishes
• Paint Constituents
– Film-forming materials (to form the protective film through
oxidation and polymerization of the unsaturated constituents of the
drying oil)
– Thinners (to suspend pigments, dissolve film-forming material,
better handling)
– Driers (to accelerate drying)
– Antiskinning agents (to prevent gelling before application)
– Plasticizers (to give elasticity to film, minimizing or preventing
cracking)
– Pigment
 Paints
• Paint Failure
– Chalking
– Flaking
– Alligatoring
– Checking
 Pigments
History of Pigments
• Ancient times: use of naturally-occurring
pigments
– Earth and mineral pigments
– Biological pigments
 Pigments
History of Pigments
• Industrial Revolution: Development of
synthetic pigments due to expensive cost
of natural pigments
– Prussian blue discovered in 1704
– First aniline dye (mauveine) discovered in
1856
– BASF discovered synthesis of alizarin red
from anthracene
 Pigments
Metal-based Pigments
• Cadmium (yellow, orange, red)
• Chromium (yellow, green)
• Cobalt (violet, blue)
• Copper (blue, green)
• Iron (red)
• Lead (yellow)
• Manganese (violet)
• Mercury (orange)
• Titanium (white)
• Zinc (white)
 Varnish and Lacquers
• Varnish - a colloidal dispersion or solution
of synthetic and/or natural resins in oil
and/or thinner used as protective and/or
decorative coating for various surfaces
• Lacquer – a colloidal dispersion or solution
of nitro-cellulose or similar film-forming
compound, resins and plasticizers in
solvents and diluents, which is used as a
protective and/or decorative coating
 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+)
 Petroleum Industry

• Fuel gas (C1-C4)

– Natural gas (mainly CH4) and liquefied
petroleum gases
• Gasoline (C5-C12)
– Light fraction of petroleum which burns rapidly,
produced via cracking of naphtha
• Kerosene (C10-C16)
– The very first important petroleum fraction used
in lamps
 Petroleum Industry

• Diesel (C12-C20)
– Used in compression-ignition engines
• Fuel Oil (C15-C20)
– Used for domestic and industrial heating
• Lubricating Oil (C16-C24)
– Fraction which cannot be vaporized under
normal pressure
• Asphalt or Pitch (C20+)
– Thick, black, sticky material
 Refining Process
• Catalytic reforming
– Conversion of one hydrocarbon to another hydrocarbon, typically
from lower octane HC to higher octane HC

Ex: n-heptane  toluene + 4H2

Heated at 500 degrees C, with
the aid of platinum catalyst

• Alkylation
– Produces high octane gasoline at low temperature and pressure,
using acid catalyst
 Refining Process
• Catalytic cracking
– Breaks long molecules into smaller molecules, under extreme heat

Ex: C16H34  2C8H17

• Hydroprocessing
– Includes hydrocracking and hydrotreating
• Hydrotreating involves addition of hydrogen atoms without breaking the
hydrocarbon (at 325 degrees C, 50 atm)
• Hydrocraking involves temperatures of over 350 degrees C and
pressures up to 200 atm

Ex: C32H66 + 3H2 4C8H18

 Rubber Industry
Natural Rubber (rubber latex)
• Sourced from the sap of the tree Hevea
brasiliensis
• Made up of units of isoprenes (2-methyl-
1,3-butadiene), or cis-poly(isoprene)
• White, sticky material
• Very difficult to use
 Rubber Industry
Vulcanization
• Accidentally discovered by Charles Goodyear by
mixing rubber with sulfur, creating a cross-linked
structure that is stronger, more elastic, less sticky
 Rubber Industry
• Years after discovery of vulcanization
– 1844: Goodyear’s vulcanization was given a patent
– 1852: Goodyear’s patent was challenged by Thomas Hancock, who
secured a British patent three weeks ahead of Goodyear’s patent
– 1869: Goodrich secured a licensing agreement with Charles
Goodyear, Jr.
– 1870: BF Goodrich Corporation was established
– 1888: John Boyd Dunlop invented pneumatic tires
– 1898: Goodyear Tire & Rubber Company founded by Frank
Seiberling
 Rubber Industry
• Styrene-butadiene rubber (SBR)
– A major synthetic rubber used widely for tires, conveyor belts, and
other commercial and industrial products
– A copolymer made by polymerizing benzene and ethylene, by-
products of crude oil refining

Styrene
Styrene-butadiene rubber

Butadiene
Plastic Industry
 Main Polymers Used
THERMOSETTING RESINS
• Molecules cross-links during polymerization –
but once polymerized or hardened, the material
cannot be softened by heating without degrading
some linkages.

• Usually purchased as liquid monomer and polymer

mixtures.

• Formed to the finished shape with or without pressure

and polymerized or hardened with chemicals or
heat.

• Examples: Melamine, Urea, Phenol Formaldehyde

• Uses: plastic plates, pots, ash trays
Plastic Manufacturing Process
Thermosets
COMPRESSION MOULDING

Application of pressure to a material that has

been placed in a cavity between the heated
plates of a hydraulic press.

The powdered plastic compound (phenolic,

urea or melamine) is introduced into the
cavity where it closes under great pressure.

The material or compound becomes semi-

fluid and is held in the mould until it has
polymerized and becomes infusible. When
curing is completed, the mould cavity and
plunger are split so that the finished article
can be ejected.
 Main Polymers Used
THERMOPLASTIC RESINS
• Consist of long molecules, either linear or
branched, having side chains or groups that are
not attached to other polymer molecules

• Usually, thermoplastic resins are purchased as

pellets or granules that are softened by heat
under pressure so they can be formed, then
cooled and hardened into the desired, final
shape

• Examples: PP, PS, PE, PET

 Plastic Preparation
• Addition Polymerization
– Poly(ethylene)
– Poly(styrene)
– Poly(vinyl chloride)
– Poly(propylene)
• Condensation Polymerization
– with byproduct
– Poly(esters)
– Poly(amides)
– Poly(carbonates)
The Big Six
The Big Six
The Big Six
The Big Six
The Big Six
The Big Six
INSTRUMENTATION AND
PROCESS CONTROL
TYPES OF PROCESS

• Batch
• Continuous
• Semi-Batch / Semi-Continuous (Hybrid)
WHAT IS PROCESS CONTROL?

• Application of control engineering and chemical

engineering which uses industrial control systems
in order to achieve a production level of
consistency, economy and safety, which could not
be achieved by pure human control
ELEMENTS OF A CONTROL SYSTEM

• Measuring element (e.g. sensor)

• Transmitter
• Signal converter (transducer)
• Controller
• Final control element
EXAMPLES OF CONTROLLER

• ON-OFF Controller (simplest type of controller)

• PID Controller
• Advance Controllers
PID CONTROLLER
• Continuously computes the error (SP - PV) and applies
correction based on proportional, integral and derivative of
the error
• Controller minimizes the error by adjusting a control variable
to a value determined by the weighted sum of the control
terms
• P – related to the present value of the error
• I – related to past values of the error and integrates them over time
• D – related to future trends based on current rate of change
(anticipatory control)
Plant and Equipment
Design
 Our role as chemical
engineer
• To design
– New plants
– Expansion lines
• To modify
– Existing lines / processes
• To develop
– New technologies
• To maximize
– Resources
 Plant and Equipment Design
• Feasibility Study
• Development of Design
• Final economic evaluation (optimum
economic design)
• Detailed engineering design
• Procurement
• Commissioning
• Start-up
• Commercial production
 Feasibility Study contains…
• Market Study
– Present and future demand
– Present buying habits
– Price range
– Possible switchers and new buyers
– Present and future uses
– Competition
 Feasibility Study contains…
• Technical Study
– Raw materials
– Process technology
– Finished product
 Feasibility Study contains…
• Economic Study
– Plant location
– Facilities and equipment (available and to be
procured)
– Raw materials (availability, cost)
– Labor
– Total investment
– Estimated COP
 Feasibility Study contains…
• Financial Study
– Return on investment
– Payback period
– Profit
 Types of Designs
• Preliminary (quick-estimate)
– Rough cost estimates
• Detailed-estimate
– Cost-benefit
– No exact specifications
• Final Process Design
– Final plant design
– Detailed drawings of equipment
– Piping diagrams and other construction details
 Pre-requisites for Detailed-
estimate
• Manufacturing process
• Material and energy balances
• Temperature and pressure ranges
• Raw material and product specifications
• Yields, reaction rates and time cycles
• Materials of construction
• Utilities requirements
• Plant site
 Flow Diagrams
• Qualitative
– General flow of materials, unit
operations/processes involved, equipment,
operating temperature and pressure
• Quantitative
– Shows the quantities of materials required for
the process
• Combined-Detail
 Considerations for Location
• Raw Material Availability
• Markets
• Energy availability
• Climate
• Transportation
• Water supply
• Water disposal
• Labor
• Taxation and legal restrictions
• Community factors
 Equipment Sizing and
Selection
• During early stages of design
• Factor of safety
• Material of construction
 Material of Construction
• Classified into two categories:
– Metals
• Iron and Steel (including stainless steel)
• Hastelloy
• Copper and alloys
• Nickel and alloys
• Aluminum
– Non-metals
• Glass
• Plastics
• Rubber
• Stoneware
• Wood
 Considerations for MoC
• Compatibility
• Working Temperature range
• Working Pressure range
 Compatibility
Carbon Stainless Nickel Monel Brass Aluminum Glass Plastic
Steel Steel

Acetic Acid X C C A X A A A

Benzene A A A A A A A C

Chlorine X X X X X X A A

Ethanol A A A A A A A A

Hydrochloric X X C C X X A A
Acid

Nitric Acid X C X X X C C C

Sodium A A A A C X A A
Hydroxide

Sulfuric A C X X X C A X
Acid, fuming

Sulfuric X C C C C C A A
Acid, dilute

Sodium A C A A C C A A
chloride
 Steel
• An alloy of iron and carbon in which the
carbon content does not exceed 1.7%
• Contains some amount of sulfur,
phosphorus, manganese and silicon
• Steel which contain elements which are
intentionally added is called alloy steel
 Effect of Impurities on Steel
• Sulfur
– No effect if content is less than 0.05%
– Reacts with iron, making the steel brittle and
unworkable at high temperature
– Increases machinability of steel
• Phosphorus
– The most undesirable impurity, affecting
toughness, shock resistance and ductility
 Effect of Impurities on Steel
• Silicon
– Increases elastic limit and ultimate strength of
the steel without reducing ductility
• Manganese
– Increases strength of steel
 Steel Alloys
• Purpose of alloying steels
– Increase hardenability
– Increase resistance to softening on tempering
– Increase resistance to corrosion
– Improve high temperature properties
– Increase resistance to abrasion
– Strengthen ferrite
 AISI Steel Series
1. Carbon Steel
2. Nickel Steel
3. Nickel-Chromium
4. Molybdenum
5. Chromium
6. Chromium-Vanadium
7. Tungsten
8. Nickel-Chromium-Molybdenum
9. Silicomanganese
 Effects of Alloying Element
• Nickel
– Increases strength and toughness
• Chromium
– Increase corrosion-resistance
• Tungsten
– Increases hardness
• Molybdenum
– Increases resistance to repeated stress
• Vanadium
– Increases tensile strength
 Stainless Steel
• Steel alloy which contains high chromium
or chromium/nickel
• More than 100 different types
• 18-8 stainless steel – most commonly
used SS
• 300 series and above – food-grade
stainless steels
 Passivation and Passivity
Oxidant agent

Passive film in the surface rich in Chrome Cr2O3

thickness 3 – 5 x10-7mm

Base Metal
>11% Cr

This film is thin, uniform, continuous, resistant and highly stable.

Passivity: State in which steel has lost its chemical reactivity

Passivation: Chemical oxidation using Nitric Acid
 Stainless Steel Groups
Austenitic: AISI 304,
304L, 316, 316L, 317L,
321
Cr18 %, Ni 8 %,
Mo 2–3 % C 0.03-0.03%

Martensitic AISI* Ferritic: AISI

410, 420, 431 430, 409, 434
Cr 12 to 18 %
Cr 12 to 18 %
C 0.2 %
C 0.2 to 1.2 %

Duplex
Interrelation of austenitic SS
 Other Metal Alloys
• Hastelloy
– 56% Ni, 17% Mo, 16% Cr, 5% Fe, 4% W
– Expensive, but high corrosion-resistance and
strength
• Copper Alloys
– Resistant to corrosion, but not suited for acids
• Monel
– 67% Ni, 30% Cu
• Inconel
– 77% Ni, 15% Cr
 Non-Metal MOCs
• Glass
– Excellent resistance to chemicals; subject to
attack only by HF and hot alkaline solutions
– Main disadvantage is brittleness and damage
by thermal shock
• Stoneware and Porcelain
– About as resistant to acids and chemicals as
glass, but with advantage of greater strength
– Very susceptible to damage by thermal shock
 Non-Metal MOCs
• Brick and Cement Materials
– Used for severely corrosive conditions, where
high alloys would fail
• Plastics
– Generally have excellent resistance to weak
mineral acids and are affected by inorganic
salt solutions
– Less resistant to mechanical abuse and have
high expansion rate, low strength and fair
resistance to solvents
 Non-Metal MOCs
• Rubber and Elastomers
– Used as linings
– Resistant to dilute mineral acids, alkalis and
salts, but not to oxidizing media, oils, benzene
and ketones
• Wood
– Chemically inert, but shrinks when subjected
to concentrated solutions
 Pressure Vessel Design
• Working Pressure as main consideration
for the following:
– Shell thickness
– Head design
– Type of joint
 Welding Joints
Type of Joint Joint Efficiency, Shell Thickness,
E ts
Single butt 0.70 1/16” to 1/8”

Double butt 0.80 1/8” to ¼”

Single V-butt 0.70 ¼” to 5/8”

Single V-butt with 0.80 5/8” to 1 ¼”

backing strip
Double V-butt 0.90 5/8” to any
thickness
 Design Equation for Welded
Vessel
PD
ts  C
2SwE  P
ts =thickness of the shell
P =internal pressure
D =inside diameter
E =joint efficiency
Sw =working stress
 Head Selection
• Standard Ellipsoidal
PD
t
2SE
• Standard Dished
PLW
t
2SE
• Conical
PM
t
2(cos A) SE
• Hemispherical
PD
t
4SE
 Vessel Design Selection
• Cylindrical Shell
PR
t
SE  0.6 P
• Spherical Shell
PR
t
2SE  0.2 P
• Hemispherical Head
PL
t
2SE  0.2 P
• Torispherical Head
0.885 PL
t
SE  0.1P
 Cost Estimation
• Factors Affecting Investment and
Production Costs
– Sources of equipment (brand new vs. second
hand)
– Price fluctuations
– Company policies
– Operating time and rate of production
– Governmental policies
 Cost Estimation
• Cost Index
– Present cost = original cost (index value at
present time / index value at time original cost
was obtained)
– Index value – take into account the cost of:
materials, labor, equipment and
instrumentation
 Cost Estimation
• Scaling
– Cost of equip. A = cost of equip. B (cap. A / cap. B)n
– n = (refer to Table, otherwise use 0.6 in the absence
of other information)
• Purchased Equipment Installation
• Insulation, Piping, Instrumentation, Electrical
Installations, Buildings (including services), Yard
improvements, Service facilities, Land,
Engineering and Supervision, Construction
Expense, Contractor’s Fee, Contingencies
 Cost Estimation
• Direct costs = material and labor involved in actual installation of complete facility (70-
85% of fixed-capital investment)
– Equipment + installation + instrumentation + piping + electrical + insulation + painting (50-
60% of fixed-capital investment)
• Purchased equipment (15-40% of fixed-capital investment)
• Installation, including insulation and painting (25-55% of purchased equipment cost)
• Instrumentation and controls, installed (6-30% of purchased equipment cost)
• Piping, installed (10-80% of purchased equipment cost)
• Electrical, installed (10-40% of purchased equipment cost)
– Buildings, process and auxiliary (10-70% of purchased equipment cost)
– Service facilities and yard improvements (40-100% of purchased equipment cost)
– Land (1-2% of fixed-capital investment or 4-8% of purchased equipment cost)
• Indirect costs = expenses which are not directly involved with material and labor of
actual installation of complete facility (15-30% of fixed-capital investment)
– Engineering and supervision (5-30% of direct costs)
– Construction expense and contractor’s fee (6-30% of direct costs)
– Contingency (5-15% of fixed-capital investment)
• Fixed-capital investment = direct costs + indirect costs
• Working capital (10-20% of total capital investment)
• Total capital investment = fixed-capital investment + working capital
 Product Costing
Cost Components of Total Product Cost
• Manufacturing Cost
– Direct Production Cost
– Fixed Charges
– Plant Overhead Cost
• General Expense
– Administrative Expense
– Distribution and Marketing Expense
– Research and Development
– Financing Expense
– Gross Earning Expense