REVIEW IN CHEMICAL PROCESS INDUSTRIES

Prepared by: Y. E. Fernandez

COAL CHEMICALS
Carbonization or Destructive distillation or thermal decomposition or pyrolysis of
coal - heating to decompose coal in the absence of oxygen through the use of
steam or electric-heating coils.
- Includes
1.) Low temperature carbonization - 850oF to 1300oF
- produces relatively large liquid products than gaseous
products.
2.) High temperature carbonization – 1650oF
- produces relatively low liquid products than gaseous
products.

Sir William Perkin (1856) – synthesized the first coal-tar color and laid foundation
of the coal-dye industry.

Processes of Coking Coal :

1.) Coproduct Process - for large production capacity
2.) Beehive Process - older method of coking

Common Products of Carbonization of coal

1.) Coke
2.) Tar
3.) Oils
4.) coal gas
5.) Coal chemicals

FUEL GASES & INDUSTRIAL GASES

Common Types of Fuel Gases
1.) Natural Gas – high methane – content
2.) Coke-Oven Gas - High H2 – content; produced as a by-product for
Coproduct Process Coking
3.) Blue Gas or Water Gas – high CO – H2 content; produced by reaction of
steam and coal/coke.
Reaction Involved:
C(s) + H2O(g) ======= CO + H2
4.) Carbureted water gas - high CO – H2 content
5.) Producer gas - produced by passing air and steam through thick bed of hot
fuel
6.) LPG
7.) SNG
Methods for Desulfurization of fuel gases:
1.) Girbotol or Monoethanolamine process
2RNH2 + H2S ======= (RNH3)2S
2.) Caustic Soda Process
2NaOH + H2S ======= Na2S + 2H2O

Common Types of Industrial Gases

1.) CO2 - used for carbonation, fire-retardant, refrigeration and preservative.
- Raw material for soda ash and salicylic acid.
- Method of production
a.) CO2 recovery from combustion
b.) CO2 recovery from fermentation

2.) H2 - used for hydrogenation of fats/oils, etc.

- as raw material for NH3 production (Haber-Bosch Process)
- Method of production
a.) Electrolytic Method
b.) Steam – Hydrocarbon Reforming
Involves a WATER –GAS Shift Reaction: CO + H2O ===== CO2 +
H2
c.) Coal Gasification
c.1) Lurgi Process - uses a moving bed gasifier at 30 atm
with temp at 1150 to 1600oF and more economical.
c.2) Koppers-Totzek Process – uses horizontal, cylindrical
gasifier at 3500oF
c.3) Winkler Process – uses fluidized bed at atmospheric
pressure

NOTE: The Lurgi process is the only one which operates under
pressure and provides process operating economy and requires
sized coal and cannot handle coking coal. Kopper-Totzek process
uses all types of coal. Winkler process has difficulty handling
coking of coal unless it is pretreated.

3.) Synthesis Gas - contains a mixture of H2, CO and N2 used for ammonia and
methanol synthesis.
4.) O2 and N2 - produced by liquefaction and rectification of air.
5.) Helium
6.) Acetylene –commonly produced by the Carbide Process
Ex: How many grams of pure calcium carbide is needed to produce
500liters of acetylene at STP?
7.) SO2
8.) CO
9.) N2O
CERAMIC INDUSTRIES – also known as Clay Products Industries or Silicate
Industries
Types of Ceramic Products
1.) Whitewares
2.) Structural clay products/ building bricks
3.) Refractories/firebricks
4.) Specialized ceramic products
5.) Enamels and enameled metal

Raw Materials Used

1.) Clay
2.) Feldspar - includes potash feldspar (K2O.Al2O3.6SiO3), soda feldspar
(Na2O.Al2O3.6SiO3) and lime feldspar (CaO.Al2O3.6SiO3)
3.) Sand/silica
4.) Refractory ingredients – contribute to the acidic part of the melt and give
body to the ceramic/glass. Include quartz, feldspar and clay.
5.) Fluxing agents – give the basic character and reacts with acidic refractories
to form glassy properties. Include borax, soda ash, cryolite and fluorspar.
6.) Opacifiers – give the white opaque appearance of enamels. Include TiO2,
SnO and ZrO.

Vitrification – progressive reduction in porosity up to a glass-like structure.

Calcination – heating of calcium- containing mineral forming lime (CaO)
Like CaCO3 + heat ===== CaO + CO2
Glaze – a thin coating of glass melted onto the surface of a more or less porous
ceramic ware.
Glost firing – technical term for firing of the glaze.

Molding/Shaping Processes for Ceramic Products:

1.) Casting like “sand –casting”
2.) Extrusion
3.) Jiggering for “ceramic plates”
4.) blow molding

CEMENT INDUSTRIES

Cement = it is a binder, a material that sets and hardens as it dries and also reacts
with CO2 in the air independently, and can bind other materials together usually
used as a basic material for concrete buildings, roads, etc. The word “cement”
traces to the Romans, who used the term “opus caementicium” to describe
masonry resembling modern concrete.

Argillaceous materials = materials or minerals that contains Al2O3

Calcareous materials = materials or minerals that contain CaO

Clinker = product mixture obtained in the burning of argillaceous materials,

calcareous materials, silica and other inorganic oxides.
= solid material obtained after kilning of cement raw materials (except
gypsum)
Calcination = reaction involving the decomposition by heat of CaCO3 forming CaO
and CO2.

Pozzolan = a material which is not cementitious(binder) by itself but becomes so

upon admixture with lime. Natural pozzolan are usually volcanic tuffs while
artificial pozzolan include fly ash.

Portland Cement – a pulverized mixture of clinker and or Calcium Sulfate (gypsum;

CaSO4.2H2O)

Pozzolan Cement – admixture of pozzolan (volcanic tuffs, fly ash) with lime.

Clinker compounds:
C2S - Dicalcium Silicate 2CaO.SiO2 = responsible for long term setting and
hardening time of cement
C3S - Tricalcium Silicate 3CaO.SiO2 = responsible for the short term or
early setting or hardening time of cement
C3A - Tricalcium Aluminate 3CaO.Al2O3
C4AF - Tetracalcium Alumniferrite 4CaO. Al2O3. Fe2O3
MgO - Magnesium Oxide

Raw Materials for Portland Cement:

- Refer to calcareous and argillaceous materials
1.) Cement rock
2.) limestone
3.) marl
4.) clay/shale
5.) blast furnace slag
6.) gypsum
7.) sand
8.) iron materials
NOTE: Setting and Hardening of Cements are due to hydrolysis and hydration.

Raw Materials for Cement Manufacture:

A. Clinker Materials
 a.) Argillaceous Materials
b.) Calcareous Materials
c.) Silica
d.) Iron Oxides
B. Gypsum = refers to CaSO4.2H2O

Classification of Cement:
A. According to the water involved in using cement for concrete mix:
1.) Non-Hydraulic Cement = a cement that will not set in the presence of
water or wet condition. (Ex: slaked lime)
2.) Hydraulic Cement = a cement that not only hardens by reacting with
water but also forms water-resistant products (Ex: Portland cement, gypsum
plaster)

B. According to Composition:
1.) Portland Cement = product obtained by pulverizing clinker with gypsum.
2.) Pozzolan Cement = mixture of pozzolan and lime
3.) High-Alumina Cement = essentially calcium aluminate cement made by
mixing limestone and bauxite(mineral or impure Al2O3)
4.) Other special cements

Formulation of Cement:
A. For Portland Cement

Portland Cement = Clinker + Gypsum

B. For Pozzolan Cement

Pozzolan Cement = Pozzolan + lime

Clinker Production and Reactions involved:

- Clinker Production is achieved by burning the clinker raw materials in the
horizontally-inclined rotary kiln with sections at varying temperatures with
lowest temperature on top as entry of raw materials. Reactions taking place
are shown in the table below:
Reaction Taking Place Type of Heat Change
Temperature
(oC)
100 Evaporation of free water Endothermic
or moisture
500 and Evolution of combined Endothermic
 above water from clay

900 and Crystallization of

above amorphous dehydration
products of clay
900 - 1200 Main reaction between lime
( CaO) and clay (SiO2)
1250 - 1280 Commencement of liquid
formation
1280 - above Further formation of liquid
and complete formation of
clinker compounds
NOTE: C3S or tricalcium silicate, the chief strength – producing
constituent of cement is formed at the last reaction.

GLASS INDUSTRIES
Glass – can be defined
1.) physically, as a rigid, undercooled liquid having no definite melting
point and sufficiently high viscosity.
2.) Chemically, as the union of the nonvolatile inorganic oxides resulting
from decomposition and fusing of alkali and alkaline earth compounds,
sand and other glass constituents.

Raw Materials for Glass-making:

1.) Sand/SiO2
2.) Lime
3.) Soda ash
4.) Feldspar
5.) Borax
6.) Saltcake = impure Na2SO4 = removes impurities as scum in the molten glass
7.) Cullet = waste broken glasses = helps to lower the melting point of glass raw
materials.

Methods of Window or Flat-glass making:

1.) Fourcault Process - drawing chamber (debiteuse) is filled with glass from
melting tank and is drawn vertically from the kiln by means of a drawing
machine where the flattened glass melt is drawn vertically upward.
2.) Colburn Process - drawing is started vertically from the furnace and after
travelling about 3ft is heated and bent over a horizontal roller.
3.) Continuous Process
4.) Float Process
 Common Equipment for Glass Manufacture
1.) Furnace
2.) Debiteuse - drawing unit of molten glass
3.) Lehr or annealing oven

Common Methods for Molding or Shaping of Glass Products

1.) Casting
2.) Extrusion
3.) Glass blowing
4.) injection molding
5.) etc.

MISCELLANEOUS CHEMICALS INDUSTRIES

Method of Production of Caustic Soda (NaOH)
1.) Le Blanc Process – old method
Na2CO3 + Ca(OH)2 ===== 2NaOH + CaCO3

2.) Solvay Process or Ammonia –Soda Process – new method

NH3 + Na2CO3 ==== NaOH + other products

Method of Production of Chlorine

1.) Deacon Process - uses air with copper chloride catalyst
2HCl + ½ O2 ===== Cl2 + H2O
2.) Weldon Process- oxidation conducted with MnO2

Method of Ammonia Production

1.) Haber-Bosch Process
N2 + 3H2 ======== 2NH3

Method of Manufacture of Urea

1.) Wohler Synthesis
NH4CNO ===== NH3 + CO(NH2)2
NOTE: FRiedrich Wohler discovered urea and the first person to synthesize
an organic compound from an inorganic compound.

SULFUR AND SULFURIC ACID INDUSTRIES

Frasch Process - a method of mining elemental sulfur or brimstone.
Concentrated Sulfuric Acid also known as Oil of Vitriol - 93.19% H2SO4 by weight
and 1.835oBe at 60oF
Oleum - solution containing SO3 dissolved in H2SO4

Main Reactions of H2SO4 Manufacture

1.) Formation of SO2 ( in 1st converter)
 S + O2 ===== SO2
2.) Conversion of SO2 to SO3 ( in 2nd converter)
SO2 + O2 ======= SO3
3.) Hydrolysis
SO3 + H2O ====== H2SO4

Method of Production of Sulfuric Acid:

1.) Contact Process - first patented by Philips; uses a column with a catalyst
bed of Platinum or Vanadium for the oxidation of SO2 to SO3.
2.) Chamber Process

HCl & MISCELLANEOUS INORGANIC CHEMICALS

Basilius Valentinius - discovered HCl in the 15th Century.

Method of Production of HCl

1.) By-product in the chlorination of hydrocarbons
CnH2n+2 + Cl2 ==== CnH2n-1Cl + HCl
2.) Salt Process or Reaction with salt and sulfuric acid
2NaCl + H2SO4 ====== 2HCl + Na2SO4
3.) Synthetic Process or Combustion of hydrogen and chlorine
H2 + Cl2 ===== 2HCl
4.) Hargreave’s Process
4NaCl + O2 + 2H2O === 2Na2SO4 + 4HCl

SURFACE-COATING INDUSTRIES
Products of Surface-coating industries :
1.) Paint
2.) Pigments
3.) Varnish
4.) Lacquers

Raw Materials for Paint Production

1.) Resins – film formers
2.) Solvent or vehicle – dissolves paint ingredients
3.) Pigments - colorant
4.) Extenders – increase hiding capacity (like CaCO3)
5.) Plasticizers/ emulsifiers
6.) Driers

NOTE: Refer to Table 24.3 for list of the different coloring pigments

TiO2 - best selling white pigment

Carbon – major black pigment
Modes of Paint Failure
1.) Chalking
2.) Erosion
3.) Flaking
4.) Alligatoring
5.) Checking

FRAGRANCES, FLAVORS & FOOD ADDITIVES

Perfume comes from the Latin Word “Perfumare” which means “to fill with
smoke”
Perfume – any mixture of pleasantly odorous substances incorporated in a suitable
vehicle.

Components of Perfume
1.) Vehicle - solvent used for blending and holding perfume material together
usually refined ethyl alcohol.
- Prefixation of alcohol refers to the deodorizing process of alcohol
involving the addition of gum benzoin or resinous fixatives to the alcohol
and allowing it to mature for a week or two.
2.) Fixatives – substances of lower volatility than perfume oils which retards and
even up the rate of evaporation of various odorous constituents.
- Includes animal, resinous, essential oils and synthetic fixatives
3.) Odorous substances – include essential oils, isolates and synthetic/semi-
synthetic chemicals.

Method of Essential Oils Recovery from Plants:

1.) Expression = mechanical pressing
2.) Steam distillation
3.) Solvent extraction
4.) Enfleurage – cold fat extraction process
5.) Maceration – extraction with hot fat

OILS, FATS & WAXES

See Table 28:1 p.465 Shreve’s for list of fatty acid –content of various oils and fats

Fatty acid - refers to long – chain carboxylic acid usually containing even number
of carbons from 8 carbons up. = RCOOH
Fats or oils – refer to esters of fatty acids.
= triglycerides

Common Types of Fatty Acid:

 1.) Saturated fatty acid – contains single bonds for its carbon-linkage
2.) Unsaturated fatty acid – contains a double bond for its carbon-linkage

SOAP & DETERGENTS

Soap - contains sodium or potassium salts of fatty acids formed by saponification
reaction.
Detergent – complex mixtures of several substances usually involving sulfonation
and other reactions.

Cleansing action of soap and detergents – based on the opposing pulling effect of
the hydrophobic and hydrophilic ends of soap or detergent – usually known as
“micelle formation”.

Raw Materials for Production of Detergents:

1.) Surfactants – any compound that affects or reduces the surface tension
when dissolved in water or water solutions.
2.) Suds regulator
3.) Builders – boost detergent power.
4.) Additives – may include corrosion inhibitors, bluings, antimicrobial agents,
fabric brighteners etc.

Saponification Reaction:
Fat/oil + Caustic Soda ====== Sodium Salt of fatty acid + glycerol

Raw Materials for Soap Production:

1.) Fat or tallow or oil
2.) Caustic soda
3.) Builders

Scheele - discovered glycerin in 1779

SUGAR & STARCH INDUSTRIES

Major Processes in Sugar Manufacture:
I. Raw Sugar Manufacture
1.) Cane crushing
2.) Coagulation by liming
3.) Evaporation
4.) Crystallization
5.) Centrifugation
6.) Packaging

II. Sugar - Refining

1.) Affinition
2.) Clarification or defecation
 3.) Carbonation
4.) Evaporation
5.) Crystallization
6.) Centrifugation
7.) Drying
8.) Packaging

FERMENTATION INDUSTRIES
Five basic prerequisites of a good fermentation process:
1.) Microorganism that forms the desired product.
2.) Cheap raw materials as substrate
3.) Acceptable yields
4.) Rapid fermentation
5.) Product that is recoverable or can be purified.

Ethanol Production by Fermentation:

1.) Raw materials
a.) Molasses or other substrate
b.) Yeast
c.) Nutrients
2.) Steps involved in Production of Ethanol
a.) Growth of inoculating cultures
b.) Fermentation
c.) Recovery of by-product CO2
d.) Distillation and rectification

Beverage Beer-Production
1.) Raw Materials
a.) Barley or other grains
b.) Malt adjuncts
c.) Yeast
d.) Nutrients
e.) hops
2.) Steps in Beer Production
a.) Steeping of barley for pre-germination to facilitate enzyme
formation
b.) Mashing by mixing ground barley/malt adjuncts with water in a
mash tun.
c.) Brewing or boiling of mash ( water with steeped barley/ adjuncts)
producing the wort.
d.) Wort is cooked with hops.
e.) Fermentation of mixed wort with yeast forming the beer.
f.) Pasteurization of beer.
g.) Bottling of beer
Other Fermentation Products:
1.) Acetic acid
2.) MSG
3.) antibiotics

PULP & PAPER INDUSTRIES

Robert - invented the Fourdrinier machine
Keller of Saxony - invented the method mechanical process for wood-pulping

Raw Materials for Paper Production

1.) Wood pulp or other cellulosic material
2.) Bleaching agent
3.) Additives

Method of Pulping:
1.) Kraft or Sulfate Process - an alkaline process of pulping using cooking liquor
containing strong bases like NaOH, etc.
2.) Soda Pulp Method – developed by Watt and Burgess, comparable to Kraft
process but not readily used.
3.) Sulfite Pulp Method – patent given to Tilghman; uses dissolved SO2

For Self- Review :

PLASTIC INDUSTRIES
RUBBER INDUSTRIES
PETROCHEMICALS
PHARMACEUTICAL INDUSTRY