CEMENT

• Cement is a generic name for powdered material which initially have plastic
flow when mixed with water or other liquid but form a solid structure in
several hours with varying degree of strength and bonding properties which
continue to improve with age
• Portland cement is the basis for a number of cement products. It is defined
as finely ground calcium aluminates and silicates of various compositions
which hydrate when mixed with water to form a rigid continuous structure
with good compressive strength
• Constituents of cement are
• Portland: 2Cao.sio2 (c2s), 3Cao.sio2 (C3s), 3Cao.Al2o3 (C3A), 4cao.Al2o3
Fe2o3 (C4AF) and Mgo
• High Alumina: 3Cao.Al2o3 (c3A), 2cao.sio2 (c2s) and 2Cao.Al2o3.sio2 (c2As)
• Hydraulic hydrated lime: Ca(oH)2, 2Cao.sio2 and 3Cao.Al2o3
Types of Portland cement
• Varying the % of constituents changes the rate of setting heat
evolution and strength characteristics
• Type I regular: 40-60% C3s, 10-30% C2s and 7-13% C3A. Hardens to
full strength in 8 days
• Type II Modified : Higher c2s/c3s to resist sulfate attack
• Type III High energy strength: Attains strength of type II in only 3
days, high heat rates. Useless in massive structure. Higher C3s and
c3A% with finer grinding to increase hydratum rate
• Type IV Low Heat : Designed for massive structure lurk, low C3s and
C3A which are largest contributors to heat of hydration
• Type V Surface resistant: Good for sea water contact C3A < 4%
Other types of cement
High alumina:
❖Manufacture by fusing limestone and bauxite
❖Rapid rate of strength development to high values but with high values but with high heat
rate liberation, superior resistance to sea and sulfate waters
Pozzolona:
• Mixture of volcanic ash, burnt clay or shade in 2-4 packets with hydrated lime
• Mixed with Portland cement as a cheap extender
Hydraulic lime:
❑Used only for brick mortar composition
❑Low price & strength
Magnesium chloride:
✓Lightly calcined Mgo mixed with Mgcl2 forms
✓Excellent high-strength, spark proof
✓Water resistant flooring
✓High bonding strength to wood fibers so useful in forming indoor construction material with
only fair resistance to water
Relative compressive strength characteristics
• Cement when mixed with other ingredients such as sand and gravel is
used for structural purposes under compressive loading since it has very
poor tensible strength
• High Alumina: 3Cao.Al2o3 (c3A), 2cao.sio2 (c2s) and 2Cao.Al2o3.sio2
(c2As)
• Hydraulic hydrated lime: Ca(oH)2, 2Cao.sio2 and 3Cao.Al2o3
TYPES 1 DAY 3 DAYS 28 DAYS
Portland Type I 37 120 340
Portland Type II 28 83 260
Portland Type III 103 240 440
Portland Type IV 20 49 177
Portland Type V 28 88 214
Hydrated lime - 14 30
Aluminous 280 480 690
Contd..
• India ranks as the fourth largest producer of cement in the world after
china, Japan & USA
• The first bag of cement was picked in the year 1914 at Porbundar. A
mere 945 mts was produced in that year throughout India compared to
the production of 48.75M tons in the year 1990-91
• Cement factories are in M.P, TN, A.P, Rajasthan, Gujarat, Bihar and
Karnataka. Location of cement factory near limestones resources has its
own advantages
• Different varieties of cements produced in India are Portland,
Pozzolana, Portland blast furnace slag, Special high strength cement, low
heat cement, oil well cement, coloured cement and white cement
Contd..
Cement rock beneficiation:
Most of the locally available limestone has to high a silica and iron content for
direct use in cement manufacture.
These undesirable constituents can be removed by ore dressing or
beneficiation methods which are based on fluid mechanics and adsorption
Quantitative requirements:
Basis: 1 ton of low-grade limestone
Water -3 tons, Reagents 50-200 grams and Electricity – 2.5 KwH
Process Description:
The operators are grinding, classification, flotation and thickening.Rock is
wet-ground,fed to a hydro separator where the overflow goes directly to the
final thickener, being of satisfactory composition. If not, it is subjected to
floatation separation which must be floated to remove Silica, mica and talc
Contd…
Major Engineering problems:
Choice of flotation agents, old type is oleic acid 200gm/ton, New types
of detergents have better selectivity and lower consumption, Grinding
which includes optimizing particle size range with power input
Portland Cement Process
Basis: 1 ton of type I content
MATERIAL QUANTITY

Clay 0.1-0.3 tons

Lime stone 1.2 -1.3 tons
Gypsum 0.03 – 0.05 tons
Coal 0.25 – 0.40 tons
Water 3 tons
Electricity 80 KWH
Contd..
• Chemical reactions:
Caco3 Cao + Co2
Cao + Al2o3 + sio2 Mixture of C3s, C2s, C3A
Process description:
Cement grade limestone + clay + sand + Iron containing materials + gypsum
and coal are ground together. Grinding may be a wet or dry process. Dry
process predominates because of savings in heat and accurate control possible.
The sequence may include rough crushing followed by gyratory and hammer
mills then drying and fine grinding in tube mills followed by air separation
and pneumatic blending. The cement compounds (c2s, c3s, c3A). The hot
clinker (3-10mm size) is dropped to a rotary cooler which preheats
combustion air for the kiln. The product from tube milling the clinker is a
powder of which 90% passes 200 mesh .It is bagged or stored and shipped
Rough crushing Gyratory Hammer mills Drying

Air separator Fine grinding

Pneumatic blending

Rotatory Kiln Decarbonator and

fired to form
Contd..
Major Engineering Problems:
Types of Grinding : Wet or dry grinding may be used with dry grinding
being used in most new plants
80% of the total power is consumed for crushing, grinding and blending
operations.
Kiln design:
✓Calcining involves decomposition of Caco3 to Cao and firing at 1400-
1500oc to promote compound formation.
✓Heat is required for water evaporation, oxidizing organic materials,
partial volatilization of sulfates, chlorates and alkalies.
✓Wet process requires 90-170m length kiln with 2.5-6m diameter.
✓Dry process includes 50m length with 2.5-m diameter and speed of 2-1/2
rpm
Cont..
Heat economy:
❖Minimizing fuel consumption is an economic balance between fuel cost and
addition of waste heat boiler and air preheater
❖Theoretical heat required is 430 Kcal/kg of Portland cement
❖Wet grinding releases 1300-1800 kcal/kg of cement
❖Dry grinding releases 700-1000 Kcal/kg of cement
Quality control
Product performance is quite sensitive to rock composition, particle size and
degree of calcining. Instrumentation and automatic control of the calcining
kiln has improved the cement quality
Economics of cement industry
High grade and beneficiated circuit rock will have to be supplemented by
blending with burnt clays and blast furnace slag to conseive native
limestone.The sludge from fertilizer industry is used for the manufacture of
cement
PROBLEMS
▪ Shortage of capital
▪ Power shortage
▪ Locatorial problems
Western & southern produces 71%, consumes 57%
East & North produces 29% , consumes 43%
▪ Shortage of coal
▪ Non-availability of Railway wagons
▪ Defective method of transport
▪ Negligible share in world trade
▪ Technological obsolescence
▪ Mini cement plant
▪ Research includes flyash blending, cement from paddy husk
LIME
• Quick lime: Cao
• M.pt 2570oc, Density 3.32 g/cc, soluble in water and acid
• Hydrated or slaked lime Ca(oH)2 , density = 2.2 gm/u, slightly soluble in water
and decomposition to Cao at 580oc
• Commercial lime is not 100% Cao or Ca(oH)2 but mixtures with Mgo and or
Mg(oH)2
• Quick lime: high calcium (>90% cao), low magnesium (5-25%mg),dolomite (25-
40%Mgo)
• Hydraulic lime and slaked lime : Ca(oH)2 plus Mgo-Mg(oH)2 in varying
percentage
• Lime is used s a basic flux in the manufacture of steel. Sio2 is a common impurity
in iron ore which cannot be melted unless it combines with another substance first
to convert it to a more fluid lava called slag
• Sio2 is a lewis acid and reacts with Lewis base lime.The molten silicate slag is less
dense than the molten iron and collects at the top of the reactor, where it can be
drawn off.Over 100 lbs of lime must be used to manufacture a ton of steel
Contd..
• Cao + Sio2 Casio3
• The uses of lime in chemical industries are numerous over 150 chemicals
are made with this basic material. Five other raw materials are salt, coal,
sulfuric acid and water
• Classification of process: calcining limestone to yield quick lime,
Hydration of quicklime
• Quicklime process: Caco3 Cao + Co2
• Basis: limestone 1.87 tons, coal 0.3 ton
• Process description:
Lime stone is quarried or mixed and put on conveyors feeding the mill
crushing unit. Lime stone of several sizes is produced. Jaw or gyratory
crushes are used for hard rock. Hammer or roll mill used for soft rock
The size depends on type of calcines as follows:
Vertical shaft 10-20 cm, Moving bed 1-10cm, Rotary kiln 0.5-5cm and
Fulidized bed 0.5-0.05cm
Contd…
✓Vertical shaft or Rotary kilns are usually specified
✓A vertical shaft kiln is 3-8mts in dia and 10-25m height lined with refractory brick
and covered with sheet steel outside for strength and prevention of gas leakage
✓Operation is of two types:
✓Unmixed coal is fixed in separate combustion chamber and flue gases supply heat
of decomposition
✓Mixed coal is mixed with limestone lump, simplifies kiln design but coal ash is
added to product.
✓Feed is from top of furnace where combustion gas preheats the stone it gradually
slides down the shaft into the calcining zone. This section of the shaft kilns
operates at 100-1100oc (Caco3 decomposes at 898oc)
✓The lime dump moves to the cooling section where heat exchanger occurs
between the secondary air and hot lime particles.
✓After further cooling in a conveyor, the lime is either packaged as lump lime or
crushed and screened to yield pulverized lime containers are jute bags with inner
seal lining of polyethylene to prevent moisture contact.
Hydrated Lime Process
Cao + H2o Ca(oH)2
1 ton of Ca(oH)2 require quicklime 0.787 ton, water 0.242 ton
Process description:
Quick lime lump crushed to 2cm or less is added along with water or
steam to a vertical cylindrical pug mill containing 18-24 extended
horizontal arms. Product from complete rxn is light, dry slaked lime
which is classified by screen or air seperators to remove any over buried
lime that did not hydrate. The finely divided product is packaged in bags
for shipping. Steam under pressure is used to more rapidly convert Mgo
where dolomite lime is used. The product is known as hydraulic lime
Contd..
Major Engineering Problems:
➢Large production rates of Quality product
➢Degree of calcining is controlled
➢Produce porous solid structure
➢Over buried lime require high temperature resistance time to produce unreacted
Mgo-cao for refractory sals.
➢Beneficiated limestone slurry or precipitated calcium carbonate sludges as from
caustizing ammonium sulfate, paper and sugar plants can only be handles with
rotary kilns. For smaller capacity vertical kilns are used
Heat transfer operations:
Optimization of Particle size, residence time, gas temperature, velocity profile
and heat economy in kilns
Economics of lime industry:
Lime production is very dependent on the steel industry which in turn fluctuates
directly with automobile and housing demand. Lime being an energy intensive
chemical because of the high temperature required
Glass industries
❑Glass may be defined physically, a rigid, undercooled liquid having no
definite melting point and a sufficiently high viscosity to prevent
crystallization and chemically as the union of non-volatile inorganic
oxides resulting from the decomposition and fusion of alkali and
alkaline earth compounds, sand and other glass contituents ending in a
product with random atomic structure
❑Glass has many uses because of its transperancy high resistance to
chemical attack, effectiveness as an electrical insulator and ability to
contain a vaccum.
❑Glass is a brittle material and exhibits greater compressive strength
than tensile strength. 800 different glass compositions are produced.
Contd..
History
➢Glass is discovered when cooking a meal in a vessel upon a mass of tuna at
the sea-shore. The union of the sand and alkali caught the man’s attention
and led to subsequent efforts at imitation
➢As early as 6000 or 5000 B.C Egyptians were making jewels of glass.
Window glass was made by A.D 290.
➢Glasswares started by 1608.
➢In 1914, the Fourcault process for drawing a sheet of glass continuously was
developed in Belgium.
➢Types of glass and glasswares are Flat glass, Pressed and Blown glass and
Glass containers
COMPOSITION
Lime, silica, soda fors 90% of all glasses. There have been minor changes in
major ingredients and major changes in minor ingredients.
Lime ,soda,sand are major ingredients
 Contd…
CLASSIFICATION
Commercial glasses fall into several classes
Fused silica:
• Made by the high temp pyrolites of silicon tetrachloride or by fusion of Quartz or pure
sand.
• Also or fused as Quartz glass and is characterized by low expansion and a high softening
point which have high thermal resistance and permit to be used beyond temperature range
of other glasses.
• Transparent to ultra violet radiation
Alkali silica:
• Sand & soda melted together simply called sodium silicate.
• Composition ranging from Na2osio2 to Na2o.4sio2. Equilibrium btwn in the two
components determine the behavior of complicated system.
• Silicate of soda ash also known as water glass
• It is usd as an adhesive for paper manufacture
• Used as detergents and soap builders
 Contd…
Soda-lime glass:
❑It is used for containers of all kinds, flat glass, automobile and other
windows, tumblers and tableware
❑Composition lies Sio2 (70-74%), Cao (8 to 13%), Na2o (13 to 18%)
❑Difficult to melt, chemically resistant, better colour
❑Selerium is used as a decolorizer of raw materials
Lead glass:
• By stabilizing leas oxide for calcium oxide in the glass melt, lead glass is
obtained
• High index of refraction and dispersion for optical work
• When lead content is 92% (RI=2.2)
• The brilliance of good “cut glass” is due to its lead bearing composition
• Because of its high electrical resistance, its used for construction of electric
light bulbs, neon-sign tubing and radiations.
Contd..
Special glasses
❑Colored and coated, opal, translucent, safety, optical, photometric glasses,
glass ceramics and special glasses.
❑Varying compositions depending upon the final products
Glass Fibers
• Resistant to weather conditions
• Low in silica about 85%
• Low in alkali
Raw materials:
Soda ash, salt cake & lime stone are required to flux this silica.In addition lead
oxide, pearl ash (potassium carbonate) salt peter, borax, boric acid, arsenic
trioxide, field space, fluoroscope together with great variety of metallic oxides,
carbonates and other reuired for coloured glass. In furnishing operations,
abrasives and hydro fluoric acid are consumed
Contd…
Sand for glass manufacture should be pure quartz.
• Should not exceed 0.45% Iron for tableware or 0.015% for optical glass
• Iron affects the color of most glass adversely
Field spares have formula R2o.Al2o3.6sio2 where R2o corresponds to Na2o or
K2o or mixture of these two
• It is a source of aluminate.
• Cheap, pure & fabric
• Composed of glass forming oxides
Burax for lower expansion value & high refractive index for optical ware. Salt
cake is to remove troublesome scum from tank furnaces. Carbon is used to
reduce sulfates to sulfites. Arsenic trioxide added to remove bubbles. Nitrates
of Na or K used to oxidise iron and make it less notification in the finished
glass. Cullet is crushed glass from imperfect articles, time and other waste glass.
It facilitates melting & utilizes waste material. 10 to 80% is added
Refractory blocks
To serve for severe conditions,

• sintered zirum, alumina, mullite, mullite-alumina, electrocast zirconia-alumina-silica,

chronic alumina are typical for glass tanks
• The reactions
Na2CO3 + aSiO2 Na2O.SiO2 + CO2
CaCO3 + bSiO2 CaO.bSiO2 + CO2
Na2SO4 + cSiO2 Na2OaSiO2 + SO2 + CO
The last rxn may be take place by following
Na2SO4 + C Na2SO3 + CO
2Na2SO4 +C 2Na2SO3 + CO2
Na2SO3 + cSiO2 Na2O.cSiO2 + SO2
Typical manufacturing sequences
1. Transportation of raw materials to the plant
2. Sizing of some raw materials
3. Storage of raw materials
4. Conveying, weighing and mixing raw materials and feeding them into
the glass furnace
5. Burning of the fuel to serve temperature needed for glass formation
6. Reactions in the furnace to form glass
7. Saving of heat by regeneration or recuperation
8. Shaping of glass products
9. Annealing of glass products
10. Finishing of glass products
Melting
Pot furnaces with capacity of 2tons or less are used for the small production of
special glasses
✓Employed for optical and art glass by the casting process
✓Made of clay or platinium
✓It is very difficult to melt glass in the vessels without contaminating the
product or partly melting the container itself, except when platinium is used
Tank furnaces
Batch materials are changed into one end of a large “tank” built of refractory
blocks
• Capacity is 1350 tons
• The glass forms a pool in the hearth of the furnace, across which the flames
play alternately from oneside and the other. The fined glass is worked out of
the opposite end of the tank
• The wall may gets corrode under the action of the hot glass
Shaping or Forming
• Glass may be shaped by either machine or hand molding machine molding should
be completed in a very few seconds. Relatively short time the glass changes from a
viscous liquid to a clear solid
• Design problem should solve the flow of heat, stability of metals and clearance of
bearings
• Machine shaped glasses are window glass, plate glass, float glass, bottles, light,
bulbs and tubing
• Window glass is made by Fourcault process, where the melted glass is drawn
vertically from the kiln through “debiteuse” by means of drawing machine
• The debit use consist of a refractory boat with seat in the center through which the
glass flows continuously upward when the boat is partly submerged. A metal bait
lowered into the glass through the slot at the same line
• The glass is drawn upward in ribbon form as faster, it flows up through slot and its
surface is chilled by adjacent water coils.
• The ribbon still travelling vertically and pass through a 7.5m long annealing
chimney or then it is cut into sheets of desired size and sent for grading or cutting
Annealing
To reduce strain, it is necessary to anneal all glass objects.
It involves two operations
1. Holding a mass of glass above a certain critical terms long enough to reduce
internal strain by plastic flow to less than a predetermined maximum

2. Cooling the mass to room temperature slowly enough to hold the strain below
the maximum
This is a heating chamber in which rate of cooling is controlled
Establish the relationship between stress & strain to meet the mechanical or thermal
stress of glass
Finishing:
This includes cleaning, grinding, polishing, cutting, sand blasting, enameling,
grading and gaging
Surface-coating industries
• Preservation of architecture structures, including factories from attack of weather
• Uncoated wood & metal are susceptible to detoriation
• Protective action & aesthetic appeal of a community of homes and their interiors
• Industrially coating used in metals, textiles, rubber, paper and plastics as well as wood
Paint:
Liquid paint is a dispersion of a finely divided pigment in a liquid composed of a resin or
binder and a volatile solvent. The liquid portion is known as vehicle
Surface coating should posses the following properties:
1. Hiding power or covering power
2. Colour
3. Weather resistance
4. Glass
5. Anticorrosive properties
6. Consistency suited to application (brushing, dipping, spraying or roller coating)
7. Non-toxicity
8. Low-cost
Components of paints
Pigment & extenders
❑Inorganic substance, insoluble organic dye known as tonee, or an organic
dye precipitated on an organic carrier such as aluminium hydroxide, barium
sulfate or clay this constituting a lake.
❑Pigment extenders or filters reduce the cost of paint and increases its
durability.
❑It gives colour and aesthetic appeal. The solid particle in the paint reflect
many of the destructive light rays which help to prolong the life of the paint
❑Pigment should be opaque to ensure good covering and chemically inert to
secure stability
❑Pigment should be non-toxic or low toxicity
❑Must be wet by the film forming constituents and be of low cost
Solvents (air or water)
• Oil serve a dual purpose in surface coating formulations
• Serves as carriers for the pigments and as formers of the films
• Oil paint films are formed by the drying of varying unsaturated oils.
• Drying is a chemical change involving oxidation and polymerization.
• It is hastened by pre-treatment of the oil and by adding driers or catalyst
predominantly heavy metallic soaps, which are oxygen carriers usually
soluble in oil.
• Reactive oils are linseed, soybean, castor, safflower are used
Film formers:
This may be synthetic resin known as alkyds and may be made from fatty
acids or oils, polybasic acids and polyhydric resins
Driers:
In drying, these oils first absorb oxygen from air forming peroxides or
hydroperoxides at the olefinic binds. Heavy metal salts of carboxylic acids
such as cobalt, naphthenate are used in conjunction with drying oils.
Contd..
Resins:
➢Oil based paints use no resins. Water based paints contain no oil and depends on
vinyl-acetate, acrylic or butadiene-styrene polymer resins as the film forming
materials.
➢Varnishes contain variety of natural or synthetic resins.These may be phenolic, alkyl,
urea-formaldehyde, acrylate, vinyl or silicone resins as well as such natural resins as
African copal or resin.
➢Lacquers contained nitrocellulose as the resin constituent
Diluents:
• Diluents or thinners for paint varnish composition may include aliphatic or aromatic
napthe fractions or may contain turpentine
• Lacquers employ aliphatic chemicals such as ethers, esters, ketones and alcohols to
provide the desired controlled volatility
White pigments:
❖Oldest and most important white pigment
❖white-lead – now not permitted as a constituent of paint
❖Zinc oxide – another white pigment
Lithopone
• Lithopone is mixed zinc-sulfide barium sulfate pigment that contains
about 30% zinc sulfide
• The original light sensitiveness has been overcome by raw material
purification and by the addition of such agents as polythionates and
cobalt sulfate
• Brilliant white, extremely cheap, well adopted to interior coatings
• The barium sulfide solution is prepared by reducing barite ore Baso4 with
carbon and leaching the resulting mass
• Baso4 +4C Bas + 4CO
• Scrap zinc or concentrated zinc ores are dissolved in sulfuric acid.The
two solutions are reacted, and a heavy mixed and 72-70% barium sulfate
• Znso4 + Bas Zns + Baso4
Contd..
• This precipitate is not suitable for a pigment until it is filtered, dried, crushed, heated
to a high temperature and quenched in cold water.
• The second heating in a muffle furnace at 725oc produces crystals of the right optical
size
• Lithopores are used in water-based paints because of their excellent alkali resistance.
Also used as a whitener and reinforcing agent for rubber and as a filler
• Basis: 1 ton of lithopore and whitener for paper
MATERIALS QUANTITY
Barytes 0.85 tons
Coal 1.1 tons
Zinc ore 0.4 tons
H2So4 0.5 tons
Electricity 400 M
Titanium dioxide
• Two crystalline forms- Anatase and rutile
• Anatase can be converted to rutile by heating to 700-750oc
• Widely used in exterior paints and also in enamels and lacquers
• Typical white paint contains 60% pigment of which 20% Tio2, 60% tale and
20% mica
• Consumed in paint, varnishes and lacquers and paper and coloring of
plastics
Manufacturing method:
Sulfate process – uses the cheaper, domestic ore, ilmenite as a raw material.
Chloride process – require more expensive rutile
In batch ore dissection core, sulfuric acid is reacted with ilmenite.This
reaction is violent and causes the entrainment of So2 and H2so4 in water
vapour and they are subsequently emitted to atmosphere in large quantity then
are allowed by clean air standards.
Contd..
• The chloride process utilizes rutile with cl2 gas and coke to produce
titanium tetrachloride. Ticl4 is distilled to remove impurities and then
reacted with oxygen or air in a flame at 1500oc to produce cl2 gas and
very fine particle Tio2 . Cl2 gas is recycled. The waste products are
easier to dispose of than those formed by the sulfate process.
• Tio2 (ore) + H2so4 Tioso4 + Feso4.H2o
• Tioso4 + H2o Tio2.xH2o
• Tio2 .xH20 Tio2 @ 800-1000 oc
Pigments volume concentration
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑝𝑖𝑔𝑚𝑒𝑛𝑡 𝑖𝑛 𝑝𝑎𝑖𝑛𝑡
PVC = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑝𝑖𝑔𝑚𝑒𝑛𝑡 𝑖𝑛 𝑝𝑎𝑖𝑛𝑡+
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑛𝑜𝑛𝑣𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑣𝑒ℎ𝑖𝑐𝑙𝑒 𝑐𝑜𝑛𝑠𝑡𝑖𝑡𝑢𝑒𝑛𝑡𝑠 𝑖𝑛 𝑝𝑎𝑖𝑛𝑡

Flat paints 50-75%, Exterior house paint 28-30%, semi-glass paints 35-45%, Metal primers 25-40%,
Glass paints 25-35%, wood primers 35-40%
PVC largely controls such factors as gloves, rheological properties, refractive, washability and
durability
Paint failure:
Chalking is a progressive powdering of the paint film from the surface inward that is caused by
continued and destructive oxidation of the oil after original drying of the paint. Thermal erosion is very
rapid chalking. Flaking, calleel peeling is due to poor attachment of paint to the surface. Alligatoring is
a form of peeling, is due to poor attachment of paint to the surface. Checking denotes a very film type
of sulfur eracting.
Industrial gases
✓Industrial gases are oxygen, nitrogen, hydrogen and carbon di oxide
✓Nitrogen preserves the flavor of packaged foods by reducing chemical
action leading to immediately of cannel fats
✓Many of the gases, their liquids & solids have a common application in
creating cold by absorbing heat upon evaporation by performinf work,
or by melting such as liquid carbon dioxide & dry ice
✓Cryogenic techniques have been worked out, reducing the cost of
liquification and improving and simplifying theequipment used for
storage, handling and shipment of very cold liuid and gases
✓Cryogenic or supercold temps cause fundamental changes in properties
of materials. Cryogenic is being applied to rocket propulsion, infrared
photoptics, electronic data processing, magnetic & light vaccum
pumping, manufacture of nitogen and in metallurgy
Carbon dioxide
Uses:
❖Refrigrating and freezing ice cream, meat and other foods
❖Reduces meat and food bacteria spoilage
❖For carbonated beverages
❖Chilling aluminium rivets
❖Shrink-filtering machine parts
❖Fire-extinguishing material
❖Has advantages over ordinary acids in neutralizing alkalies
❖Shipped in solid form, is non-corrosive in nature
❖Light in weight
❖Chemically equivalent more than twice its shipping wt in H2so4 and five times its wt in Hcl
❖pH control of waste water
❖Transport refrigerant for food materials
❖40% in production of ores, 35% for pressurizing of oil wells, 10% for refrigration., 5% for
beverage carbonation, 10% for others
Manufacture of pure co2
1. Recovery from synthesis gas in ammonia production
2. Recovery from the production of ethanol by fermentation
3. Recovery from natural wells
Manufacture of co2 from fuel oil or natural gas
1. Oil, natural gas or coke is burned giving heat for 1380kpa steam and furnishing 10
to 15% Co2 at 345oc
2. Flue gas cooled, purified and washed by passing through two water scrubbers
3. Co2 is removed by counter current selective absorption into an aqueous solution of
ethanolamines
4. Co2 – ethanolamines solution is pumped to a steam-heated reactivator
5. Co2 and steam leave the top of the reactivator passing through a Co2 cooler to
condense the steam, which returns to the tower of reflux
6. Co2 at about 200kpa is purified from traces of H2s and amines in a permagnate
scrubber and dried
7. Co2 is compressed, cooled and liquefied
8. For “liquid” draw off from Co2 receiver
Contd…
Co2 from fuel oil or natural gas
For dry ice:
Liquid Co2 is reduced to atmospheric pressure with consequent partial
solidification. The evaporated gas returns through the precooler and is
recirculated with compression and the recooling of co2. Co2 snow is
compressed to form a cake. Dry ice cakes are generally caked to 25cm
cubes of 3kg wt.
Co2 recovery from fermentation
❖Purification consist of oxidation of organic impurities and dehydration by means of
chemicals in liquid form
❖The gas from fermentor is passed through three scrubbers containing storeware spiral
packing and on to the gasometer
❖The first scrubber contains weak alcohol which remove most of alcohol carried by the gas.
❖The next two scrubbers contain deaerated water to remove all the water soluble impurities
❖The scrubbing liquid is pumped to fermentor for alcohol recovery
❖From gasometer, the gas is conducted to a scrubber containing K2cr2o7 solution which
oxidises the aldehydes, alcohols in the gas and is then cooled
❖Second scrubber which contains H2so4 which dehydrate the gas.
❖The co2 leaving the acid scrubber may contain some entrained acid which is removed in
packed tower over which a Na2co3 solution is circulated
❖When the acid is neutralized, the co2 is released
❖Before going to the compressor, the gas passes through scrubber containing glycerin,
which absorbs the oxidized products and delivers an odorless gas to the compressor
❖The H2so4, after being used for deodorization and drying is pumped to the distillery, where
it serves for pH control
ACETYLENE
❑M.wt 26.02
❑Acetylene, either as liquid or gas is highly explosive .
❑Since it is an endothermic compound and decomposition into the
elements (C2H2 2C + H2 ) can be intiated even in the absence
of air by heat or mechanical shock
❑Gas cylinder storage requires the addition of a mutual solvent such as
acetone and a porous inert materials such as asbestos as a safe release
carrier
Methods of Production
From petroleum hydrocarbons:
1. Partial or stage wise combustion
2. Pyrolysis
3. Arc process
From calcium carbide:
This is known as recuperative heat exchangers. The reversing principle is used to remove
co2 and Ho from the incoming air stream by switching the flow of the N product stream and
the air stream.A catalytic oxidation chamber insulin after the intial compression to 70 psig to
convert hydrocarbons to Co2 and H2o. Silica gel filter ahead of the double column
Major Engineering Problems:
1. Complete removal of H2o, Co2 and hydrocarbons to prevent plugging in the time,
temperature sector
2. Low temperature insulation & lubricants development
3. Complex heat balancing design
4. Prevention of explosive mixtures in oxygen- rich regions
 Manufacture of acetylene
1. O2 & natural gas are preheated to 50oc using fuel gas.
2. Mixed in a burner in a ratio of 0.6:100 for oxygen-methane.
3. After burner quenched in quench chamber with quench oil or water spray.
4. Methane conversion is 90-95%
5. O2 conversion is 100%
6. The acetylene and gases are cooled rapidly to 38oc.
7. The soot is removed in a carbon filter
8. Acetylene is removed in a column by using dimethylformamide
9. Acetylene is employed with oxygen to give high welding temperature and
in the manufacture of vinyl chloride, acrylonitrilite, polyvinylpyrolidone,
trichloroethylene and acetic acid
10. Chloroprene and neoprene is made from acetylene such as
CaC2 + 2H2o Ca(oH)2 + C2H2
Acetylene from calcium carbide
❖Lime is produces in a fuel fired limestone kiln.
❖The lump product is ground with coke in a 60/40 ratio to about 5 cm
lump size and reacted in an electric furnace at 2100 oc.
❖The gaseous effluent mostly Co is recovered for lime kiln fuel.
❖ The molten Cac2 is solidified and ground under nitrogen to avoid
explosion of acetylene released by moist air.
Two methods for release of acetylene from CaC2 by water
➢Wet process
➢Pyrolysis process
Wet Process
1. Pulverized carbide is added through a gas-tight hipper valve
arrangement to the acetylene gas generator in which the quantity of
water used is sufficient to discharge the calcium hydroxide as a lime
slurry containing 85-90% water which is usually Lagooned.
2. The lump is kept below 90oc.Traces of NH3, sulfides and phosgene
is scrubbed with acid solution and then purified and dried with iron
oxide and alumina or silica gel.
Pyrolysis Process
▪ Hydrocarbon feed lus diluent steam (7H2o/1 ratio) to improve equation yield is fed to a
set of regenerative furnaces operating in pairs on a 1-1.5 minute cycle.
▪ The furnace is designed with brick refractory walls and internal check work.
▪ The furnace is heated on the “blow run” with fuel air mixture.
▪ After this heat-up period, the valves are switched to the make run positive and pyrolysis
feed-stock is vaporized into the same end of the furnace for the 1-1.5 minute period.
▪ The cycle is repeated again using the other end of the furnace so all flows are reversed
from the previous cycle.
▪ The other furnaces with paired system operates on a staged cycle so continuous
production of acetylene is possible.
▪ Pressure maintained in the furnace is 0.5-0. atm by measure of vaccum pumps after the
quench tower.
▪ Residence time in the furnace is 0.02-0.04 second.
Partial combustion
Exothermic Heat supply:
CH4 + 2o2 Co2 + 2H2o
Endothermic Heat supply:
2CH4 C2H2 + 3H2
Side reaction:
C2H2 2C + H2
Pyrolysis of hydrocarbons:
Propane:
C3H8 CH=CH + C2H4 + CH4 + Co +H2 + Co2
Ethylene
C2H4 CH=CH + H2 + Co + Co2 +CH4
Methane
2CH4 CH=CH + 3H2 + Co + CH4
Major Engineering problems for stage wise
combustion
➢Thermodynamic and kinetics consideration
➢The rate of pyrolysis reaction is favourable at high temperature at 1300oc.
➢Provides rapid heat up for inducing pyrolysis and quenches low
temperature before the back and side reaction
➢Burner design
➢Seperation of polymer and purification of acetylene
➢Design of explosion proof plant
➢Alcohol and co2 are produced in fermentation of yeast
➢H2 & co2 are produced by certain microorganisms
➢From 50kg starting material such as corn, 17L ethyl alcohol & 14kg of Co2
are obtained
HYDROGEN
❑Hydrogen is derived from carbonaceous materials
❑These materials are decomposed by the application of energy, which
may be electrical, chemical or thermal such as electrolysis of water,
steam reforming of hydrocarbons, thermal dissociation of natural gas
❑Hydrogen is also produced by partial oxidation of hydrocarbons
❑Steam-iron process, water gas and produce gas processes
❑Seperation from coke-oven gas and refinery off gas streams
❑Diffusion through a palladium-silver alloy furnishes very high purity
hydrogen
ELECTROLYTIC METHOD
• Passing direct current through an aqueous solution of alkali and
decomposing the water according to the following equation
• 2H2o 2H2 + o2
• Theoretical decomposition voltage for this electrolysis is 1.23v at room
temperature but because of over voltage of H2 and cell resistance it
requires 2 to 2.25v
• A typical cell electrolyzes a 15% NaoH solution, uses an Iron cathode and
a Nickel- plated-iron anode, has an asbestos diaphragm separating the
electrode compartments and operates at 60 to 70oc.
• Most types of cell produces about 56L hydrogen and half as much oxygen
per mega Joule
• The gas is about 99.7% pure and is suitable for hydrogenating edible oi
Contd..
• The cells are of two types:
• The Bipolar or Filter press- each plate is an individual cell
• Unipolar or tank type- containing two anode compartments with a
cathode compartment between them
• In most installation o2 is washed unless it can be used locally
• Hydrogen is also obtained from other electrolytic process such as
electrolysis of salt brine
Steam- hydrocarbon reforming process:
This process consists of catalytically reacting a mixture of steam and
hydrocarbons at an elevated temperature to form a mixture of H2 and
oxides of carbon
Contd…
Reaction
CnHn + nH2o nCo + (m/2 + n) H2
Co + H2o Co2 + H2
Generally light hydrocarbons such as propane, butane (LPG) are used.
Naphthane is also a suitable feed stock. These two reactions occur
together in the steam-reforming furnace at temperature of 760 to 980 oc.
The composition depends upon the process condition including temp,
pressure and excess steam.
Typical product contains 75% H2, 8% Co and 15% Co2 the remainder
consist of nitrogen and uncorrected methane. The first stage may
operate at high temperature to obtain high reaction rates and the second
at lower temperature to obtain good conversion.
Contd…
❖Propane is vaporized by steam.
❖Propane vapor is desulfurized by contact with activated carbon to prevent deactivation of the
catalyst.
❖Propane vapor mixed with steam is reformed over a nickel catalyst at about 815oc in alloy tubes in
a combustion furnace.
❖The gases H, Co & Co2 are cooled to about 370oc and the partial pressure of water increased by
addition of steam or condensate and passed over a iron oxide catalyst in the first stage co-convertor
(where 90 to 95 % Co is converted to Co2 with more H2).
❖This is called water gas shift reaction.The hot gases cooled by heat exchangers and by water to
about 38oc.
❖The cooled gases are scrubbed with a monoethanolaminic solution in the first stage Girbotol
absorber to remove essentially all the Co2.
❖The gases low in Co2 & Co are heated about 315oc and passed to the methanator over a nickel
catalyst to convert all the carbon oxides to methane by reaction with H2.
❖The product gas from the methanator is cooled to 38oc., leaving it pure except for saturated with
water.
❖The Co2 at 55kg/100 m3 H2 can be removed.
Partial oxidation process:
Non-catalytic partial combustion of the hydrocarbon feed with oxygen in the
pressure of steam in a combustion chamber at flame temperature between
1300 to 1500 oc.
When methane is feed stock, reactions are
CH4 + 2o2 Co2 + 2H2o
CH4 + Co2 2Co + 2H2
CH4 + H2o Co + 3H2
The first reaction is highly exothermic and produces enough heat to sustain
the other two reactions, which are endothermic
CH4 + ½ o2 Co + 2H2
The product gas has a composition that depends upon the carbon/hydrogen
ratio in the feed and the amount of steam added. The remaining process steps
for conversion of the partial oxidation product gas to hydrogen are the same
as for the steam-hydro carbon reforming process: water-gas shift reaction,
Co2 removal via monoethanolamine scrubbing and methanation.
Coal Gasification
Cracked ammonia:
1. A mixture of nitrogen, 1 vol and hydrogen, 3 vol may be prepared
from cracking or dissociation of ammonia.
2. The mixed gas can be used for hydrogenation because the nitrogen is
inert.
3. This process consists of vaporizing the liquid ammonia from
cylinders, heating it to 870oc, passing it over an active catalyst and
then cooling it in heat exchanger where the incoming gas may be
vaporized.
4. A single 8kg cylinder of anhydrous ammonia will produce 190m3 of
cracked ammonia.
5. This is equivalent to the contents of about 33 hydrogen cylinders.
Hydrogen Purification
• Carbon-monoxide removal by water-gas-shift reaction
• Co2 & H2s Removal-absorbed by Monoethnolamine (MEA) or Girbol
process
• Absorbed by hot potassium carbonate process in which
1. Co2 down to 0.1% by vol
2. Ecnomical at purity level of 1% or greater
3. Useful for removing large quantites of Co2
 Contd..
Physical solvent process
✓Reetisol process – cold methanol
✓Fluor solvent process – propylene carbonate
✓Sulfinol process – sulfonate (tetra hydrothiophene dioxide)
✓Slexol process – dimethyl ether of polyethylene glycol
✓Purisol process – 2-methyl-2-pyrrolidene
Adsorptive purification:
Fixed bed adsorption remove such impurities as Co2, H2o, CH4, C2H6, Co, Ar and N2.
Thermal-swing process impurity adsorbed at low temperature described at high temperature
Pressure-swing process which adsorbed at high pressure,desorbed at low pressure at same
temperature
Cryogenic Liquid Purification:
Purified by cooling to cryogenic temperature impurity will combine and can be removed as
liquid stream.
OXYGEN & NIROGEN
Oxygen:
Low grade (90 to 95% O2, 4 to 5% Ar, Balance N2,Co2,H2o)
High grade (99.5% O2,0.5% Ar)
Nitrogen:
99% N2, Balance O2
Uses of oxygen:
1. High purity O2 used for welding and cutting of metals open hearth steel purification,
medicinal purposes.
2. Low purity used for blast furnace operation such as chemical oxidation process.
Uses of Nirogen:
1. To prevent oxidation in metal working and food preservation
2. Captive usage in NH3 and nitrogen chemicals
3. Liquid N2 used for refrigration cooling in temperature industry
Production methods are based on liquefaction and subsequent fractionation of air. Variations
in compression, purification and refrigration cycles
Linde-Frankle cycle (Joule Thomson cooling)
Claude refrigration by adiabatic expansion of compressed air
Reaction: 2NaoH + Co2 Na2co3 + H2o
Raw material:
Air composition such as N2 = 78.03%, H2 = 10-4, O2 =20.97,
Co2 = 0.02 to 0.07%, Ar = 0.94, H2o = 0.01 to 0.03
Minor quantities of NaoH, NH3 and silica gel
Basis: 1ton of 95% oxygen in 300 tons/day
Air = 3600 Nm3 , Steam = 1.75 tons, cooling water = 5 tons,
Electricity=450 to 480 KWH
Process:
1. Air is compressed to 4-5 atm, cooled with H2o and passed to refrigrative exchangers.
2. These are cylindrical pressure level packed with aluminium spirals and operating in pair.
3. Air is cooled in ore while cold product (O2, N2) is removing sensible heat from the
packing in the other.
4. After 2 to 4 min, the cycle is reversed by automatic valves.
5. Air entering cold exchangers contain both H2o & Co2 which must be removed before
entering the fractionation section operated at -183 to -195oc to prevent drying.
6. These impurities removed on the cold packing throughout the exchangers and the
reevaporated.
7. The air having the regeneration heat exchanger is cooled to -170oc and fed to the reboiler
section of the double colour when further cooling takes before.
8. The distillation column with low pressure (1.4 atm) and high pressure (5.7atm)
Cycles for high oxygen (Kellogg process)
This uses recuperation –reversing heat exchangers. These are built in a concentric triple tuber
design with high purity oxygen reversing through the inner tube never contacting the
incoming air