Engg
Engg
REVIEW
ENGR. LYLE MELAD
26 SEPTEMBER 2019
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
"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.”
• 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
• 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
Chemical Reactions:
• CaO + H2O Ca(OH)2
• Ca(OH)2 + Na2CO3 CaCO3 + NaOH
Fats and Oils
What is the difference between fat and oil?
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
Linoleic acid (Li or LA) 18 2 PUFA n-6 yes CO, SFO, SBO
Flaking
Cooking Solvent
Crude oil
Acid
Degumming Gums
Water
Caustic
soda Neutralisation Free Fatty Acids
as soaps
Bleaching
earth Bleaching Pigments
Finished oil
• 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
Green liquor
Evaporation
Na2CO3 + Na2S
Causticizing
and burning
Paper and Paperboard
NaOH and
Liquefaction
enzymes
Cooking Steam
Chemical Reactions:
C12H22O11 + H2O + 3O2 2C6H8O7 + 4H2O
Fermentation
Lactic Acid Production
Cream
Casein
Raw Milk
Skimmed
Milk Whey Protein
Whey
Lactose
• 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
• 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
• 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
• 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
• 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
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.
• Batch
• Continuous
• Semi-Batch / Semi-Continuous (Hybrid)
WHAT IS PROCESS CONTROL?
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
thickness 3 – 5 x10-7mm
Base Metal
>11% Cr
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”