1. INORGANIC AND FINE CHEMICALS
Chapter 5
INORGANIC AND FINE CHEMICALS

2. Contents Sulfuric Acid The Chlor-Alkali Industry Cement Industry
Glass Industry
Fertilizer

3. Sulfuric Acid Largest tonnage Raw material is sulfur Sources:
Direct mining of underground deposits
Desulfurization of oil and gas (off-gases containing H2S or SO2)
By-product of metal extraction (copper process, ore such CuFeS2)
Produced in various strengths

4. Sulfuric Acid Manufacturing Process
Three major steps in sulfuric acid manufacturing:
Burning of sulfur in air:
S + O2 SO2
Reaction of SO2 and O2:
2 SO2+ O2 2SO3
Absorption of SO3 into water to produce a sulfuric acid (H2SO4)

6. Oxidation of Sulfur Oxidation of Sulfur Process:
Air
93% H2SO4
Sulfur
10-12% SO2
Steam
Water
molten
Process:
- Air drying tower with acid
- Air and sulfur are injected into burner
- Reaction temperature 2000°F
- Exothermic reaction must be cooled
- Steam is produced from recovered heat
Primary Generation of SO2
79% Combustion of Sulfur
9% Recovery from Metallurgic Processes
- 5% Regeneration of Spent Acids

7. Oxidation of Sulfur Dioxide
SO ½ O SO3
Because of the large effect temperature plays on the reaction, multiple catalyst layers are used (vanadium pentoxide catalyst), with cooling between each step.
As the partial pressure of SO3 increases, further reaction is limited. This is overcomed by removing the SO3 after the third stage to drive the reaction to completion.
Air
Gas
Cooling
SO3 Gas
SO2 Gas
93% H2SO4
Oleum 7

8. Oxidation of Sulfur Dioxide
Kinetic Effects
- Oxidation of sulfur dioxide is slow and reversible
- The reaction requires a catalyst and 426.7°C temperatures
The reaction is exothermic and sensitive to excessive heat
Equilibrium Constant (The degree at which the reaction proceeds is temp. dependent)
log Kp = T
T = absolute temp. in kelvin
Kp = equilibrium constant as a function of partial pressure of gases
Kp = ( PSO3 )
PSO2 PO2
0.5

9. Dilution of absorber acids
Absorption of SO3
Sulfuric acid is obtained from the absorption of SO3 and water into H2SO4 (with a concentration of at least 98%).
The efficiency of the absorption step is related to:-
– The H2SO4 concentration of the absorbing liquid ( %)
– The range of temperature of the liquid (normally 70°C-120°C)
– The technique of the distribution of acid
Dilution of absorber acids
The acid produced, normally 95.5%-96.5% or 98.5%-99.5%, is diluted with water or steam condensate down to the commercial concentrations:
25%, 37%, 48%, 78%, 96% and 98% H2SO4.
The dilution can be made in a batch process or continuously through
in-line mixing.

10. Manufacture of Sulfuric Acid
Oxidation of SO2 is thermodynamically favored by low temperatures
All SO2 must be converted for environmental reasons
Catalytic oxidation in adiabatic fixed bed reactors
Multiple catalyst beds with intermediate cooling
Heat from combustion of sulfur is recovered as HP steam

11. Modern Sulfuric Acid Plant

12. Oleum Production Oleum Production
Oleum is produced in the contact process, where sulfur is oxidized to sulfur trioxide which is subsequently dissolved in concentrated sulfuric acid. Sulfuric acid itself is regenerated by dilution of part of the oleum.
20% Oleum contains 20% SO3 by weight in the oleum
Common strengths of oleum are 20, 30, 40, 65 percent.
To produce 20 and 30 percent oleum, only requires an additional absorption tower.
Oleum is used in reactions where water is excluded
SO3 + H2SO H2S2O7 (disulfuric acid)

13. Uses of H2SO4 Manufacture of phosphoric acid for fertilizer
Production of ammonium sulfate
Production of ethanol from ethylene
One method of producing TiO2
Production of hydrofluoric acid from calcium fluoride
Aluminum sulfate

14. The Chlor-Alkali Industry

15. The Chlor-Alkali Industry
Sodium hydroxide, sodium carbonate, and chlorine are substances
produced on a large scale by the chemical industry.
The term CHLOR-ALKALI PROCESS refers to the industrial
production of (alkali sodium hydroxide, NaOH, and chlorine, Cl2 from
the common salt (sodium chloride, NaCl).
The importance of these chemicals, produced in the millions of tons
annually, is illustrated by the table next slide. However, this part includes:
NaOH (Caustic Soda)
Chlorine
HCl
Sodium Hypochlorite (NaOCl)

16. Uses for NaOH, NaOCl, Na2CO3 and Cl2
Manufacture of    Soap    Ceramics    Numerous organic chemicals    Various sodium salts
NaOCl
Manufacture of
dairies
Paper and laundries as a bleaching agent
Manufacture of    Paper    Glass    Various sodium salts
Manufacture of:    Plastics    Paper industry    Insecticides    Hydrochloric acid    Numerous organic chemicals Used for:    Bleaching    Water purification

18. Electrolysis of sodium chloride:
Sodium hydroxide and chlorine are produced industrially by the electrolysis of brine, which is a near-saturated solution of sodium chloride, NaCl. The reactions involved are
When a current is passed through brine (an aqueous solution of sodium chloride), hydrogen gas is produced at the cathode, since H+ ions are more easily discharged than Na+ ions. The depletion of H+ ions near the cathode means that hydroxide(OH-) ions, as sodium hydroxide, accumulate in the cathode compartment. Chlorine gas is produced at the anode. Three processes are used, 1- the MEMBRANE CELL,
2- the DIAPHRAGM CELL,
3- the MERCURY PROCESS.

20. Electrolysis HCl Product Hydrogen Handling HCl Production HCl Storage
Sulphuric Acid
Carbon Dioxide
NaOH
Chlorine
Product
Chlorine
Drying
Chlorine
Compression
Chlorine
Liquefaction
Chlorine
Storage
Chlorine
Packing, Filling
Vaporization
Salt
Brine
Saturation
Primary
Treatment
Secondary
Treatment
Demin. Water
Sulphuric Acid
Hypo
Storage
Hypo
Product
Hypo
Production
Sodium Sulphite
To Hypo
Sulphate
Removal
Caustic
Product
HCl
Electrolysis
Caustic
Concentration
Caustic
Storage
NaOH
Brine
Dechlorination
Chlorate
Destruction
Demineralized Water
HCl
AC Power Supply DC
Rectification
Hypo
Destruction

21. Sodium Hypochlorite Production
The most common method for manufacturing sodium hypochlorite is by the treatment of sodium hydroxide solution with gaseous chlorine.
2NaOH + Cl2 → 2NaOCl + NaCl + H2O
Sodium hypochlorite is employed as:
a disinfectant and deodorant in dairies, creameries, water supplies, sewage disposal, and households.
It is also used as bleach in laundries. As a bleaching agent, it is very useful for cotton, linen, jute, rayon, paper pulp, and oranges.

22. Cement Industry

23. WHAT IS CEMENT???? Material with adhesive and cohesive properties
Any material that binds or unites - essentially like glue
Cement is a basic material for building and civil engineering construction.

24. FUNCTION OF CEMENT to bind the sand and coarse aggregate together
to fill voids in between sand and coarse
aggregate particle
to form a compact mass

25. Types of Cement
Two types of cement normally used in building industry are as follows:
a) Hydraulic Cement
b) Non-hydraulic Cement

26. Hydraulic Cement
Hydraulic Cement sets and hardens by action of water. Such as Portland Cement
In other words it means that hydraulic cement are:
“ Any cements that turns into a solid product in the presence of water (as well as air)
resulting in a material that does not
disintegrate in water.”

27. Non-hydraulic Cement
Any cement that does not require water to transform it into a solid product.
2 common Non-hydraulic Cement are
a) Lime derived from limestone / chalk b) Gypsum

28. PORTLAND CEMENT Chemical composition of Portland Cement:
a) Tricalcium Silicate (50%)
b) Dicalcium Silicate (25%)
c) Tricalcium Aluminate (10%)
d) Tetracalcium Aluminoferrite (10%)
e) Gypsum (5%)

29. FUNCTION :TRICALCIUM SILICATE
Hardens rapidly and largely responsible for
initial set & early strength
The increase in percentage of this compound
will cause the early strength of Portland
Cement to be higher.
A bigger percentage of this compound will
produces higher heat of hydration and
accounts for faster gain in strength.

30. FUNCTION :DICALCIUM SILICATE
Hardens slowly
It effects on strength increases occurs at ages
beyond one week .
Responsible for long term strength

31. FUNCTION :TRICALCIUM ALUMINATE
Contributes to strength development in the
first few days because it is the first compound
to hydrate .
It turns out higher heat of hydration and contributes to faster gain in strength.
But it results in poor sulfate resitance and increases the volumetric shrinkage upon drying.

32. Sulphate attack on concrete

33. Cements with low Tricalcium Aluminate
contents usually generate less heat, develop higher strengths and show greater
resistance to sulfate attacks.
It has high heat generation and reactive
with soils and water containing moderate
to high sulfate concentrations so it’s least
desirable.

34. FUNCTION: TETRACALCIUM ALUMINOFERRITE
Assist in the manufacture of Portland Cement
by allowing lower clinkering temperature.
Also act as a filler
Contributes very little strength of concrete
eventhough it hydrates very rapidly.
Also responsible for grey colour of Ordinary
Portland Cement

35. FUNCTION: GYPSUM
gypsum is used to assist in retard the setting time of cement when it is mixed with water.

36. MANUFACTURING OF PORTLAND CEMENT
The 3 primary constituents of the raw materials used in the manufacture of Portland Cement are:
a) Lime b) Silica c) Alumina
Lime is derived from limestone or chalk
Silica & Alumina from clay, shale or bauxite

37. There are four main steps for cement manufacturing
1- Quarry,
2- raw grinding,
3- burning, grinding,
4- storage & packing

38. THE CEMENT MANUFACTURING PROCESS
quarry
dumper
loader
Quarry face
1. BLASTING
2. TRANSPORT
crushing
storage at the plant
conveyor
3. CRUSHING & TRANSPORTATION
1. BLASTING : The raw materials that are used to manufacture cement (mainly limestone and clay)
are blasted from the quarry.
2. TRANSPORT : The raw materials are loaded into a dumper
3. CRUSHING AND TRANSPORTATION : The raw materials, after crushing, are transported to the
plant by conveyor. The plant stores the materials before they are homogenized.

39. THE CEMENT MANUFACTURING PROCESS Raw grinding and burning
storage at the plant
Raw mill
conveyor
Raw mix
1. RAW GRINDING
preheating
kiln
cooling
clinker
2. BURNING
RAW GRINDING : The raw materials are very finely ground in order to produce the raw mixture.
mostly, using raw mill.
2. BURNING : The raw mix is preheated, using cyclone, before it goes into the kiln, which is heated by a flame that can be as hot as 2000 °C. The raw mix burns at 1500 °C producing clinker which, when it leaves the kiln, is rapidly cooled with air fans. So, the raw mix is burnt to produce clinker : the basic material needed to make cement. Natural gas, petroleum or coal are used for burning.

40. THE CEMENT MANUFACTURING PROCESS Grinding, storage, packing, dispatch
Gypsum and the secondary additives are added to the clinker.
clinker storage
Finish grinding
1. GRINDING
silos
dispatch
bags
2. STORAGE, PACKING, DISPATCH
1.GRINDING : The clinker and the gypsum are very finely ground , using ball mill , giving a “pure
cement”. Other secondary additives materials can also be added to make a blended cement.
2. STORAGE, PACKING, DISPATCH :The cement is stored in silos before being dispatched either in
bulk or in bags to its final destination.

41. CEMENT CLINKERS

43. 1.  The cement manufacturing process begins when limestone,
the basic raw material used to make cement, from the
limestone quarry is transported to the cement plant.
   2.  The limestone is combined with clay, ground in a crusher and
fed into the additive silos. Sand and iron are then combined
with the limestone and clay in a carefully controlled mixture
which is ground into a fine powder in a 2000 hp roller mill.
   3.  Next, the fine powder is heated as it passes through the
Pre-Heater Tower into a large kiln, which is about 100 meters length and up to 4 meters in diameter. In the kiln, the powder is heated to 1500oC, and the created new product is called clinker.

44. 4.  The clinker is combined with small amounts of gypsum and limestone and finely ground in a finishing mill.
5. The cement is, then, stored in silos before being dispatched either in bulk or in bags to its final destination.
The mill is a large revolving cylinder containing 250 tones of steel balls that is driven by a 4000 hp motor. The finished cement is ground to a fine product.
Fuel: Natural gas, petroleum or coal are used for burning. High fuel requirement may make it uneconomical compared to dry process.

45. Process Type
There are two main process that can be used in manufacturing of Portland Cement, the raw material process and the clinker burning process are each classified into:
i) wet process
ii) dry process

46. Wet Process Raw materials are homogenized by crushing,
grinding and blending so that approximately
80% of the raw material pass a No.200 sieve.
The mix will be turned into form of slurry by
adding % of water.
It is then heated to about 1510ºC in
horizontal revolving kilns (76-153m length
and m in diameter).

47. Dry Process Raw materials are homogenized by crushing,
grinding and blending so that approximately
80% of the raw material pass a No.200 sieve.
Mixture is fed into kiln & burned in a dry state
This process provides considerable savings in
fuel consumption and water usage but the
process is dustier compared to wet process
that is more efficient than grinding
Dry process kilns may be as short as half in length of that in wet process.

48. Dry Process & Wet Process-kiln Reactor
In the kiln, water from the raw material is
driven off and limestone is decomposed into
lime and Carbon Dioxide.
limestone lime + Carbon Dioxide
In the burning zone, portion of the kiln, silica
and alumina from the clay undergo a solid
state chemical reaction with lime to produce
calcium aluminates.
silica & alumina + lime calcium aluminates

49. The rotation and shape of kiln allow the
blend to flow down the kiln, submitting it to
gradually increasing temperature.
As the material moves through hotter regions
in the kiln, calcium silicates are formed
These products, that are black or greenish
black in color are in the form of small
pellets, called cement clinkers
Cement clinkers are hard, irregular and ball
shaped particles about 18mm in diameter.

50. The cement clinkers are cooled to about 51ºC and stored in clinker silos.
When needed, clinker are mixed with 2-5%
gypsum to retard the setting time of cement
when it is mixed with water.
Then, it is grounded to a fine powder and
then the cement is stored in storage bins
or cement silos or bagged.
Cement bags should be stored on pallets in
a dry place.

51. KILN
                                                                                                                                                          

52. CEMENT SILO

53. Glass Industry

54. What is Glass? Chemistry
Glass is a manufactured material formed when a mixture of sand, soda, and lime is heated to a high temperature and assumes a molten, or liquid, state.
Chemistry
Common Name
Chemical Name
Chemical Formula
Glass Component
Sand
Silica or Silicon Dioxide
SiO2
Soda Ash
Sodium Carbonate
Na2CO3
Na2O
Limestone
Calcium Carbonate
CaCO3
CaO

55. Glass Manufacturing
Commercially produced glass can be classified as soda-lime glass, since it constitutes 77 percent of total glass production.
The manufacture of such glass is carried out in four phases:
(1) preparation of raw material,
(2) melting in a furnace,
(3) forming and
(4) finishing.
See diagram for typical glass manufacturing, next slide

57. Glass production
involves two main methods –
The float glass process, which produces sheet glass, and
The glassblowing which produces bottles and other containers.
Glass container production
Modern glass container factories are three-part operations:
1- batch house : handles the raw materials
2- hot end : handles the manufacture proper: in which the molten glass is formed into glass products, beginning when the batch is fed into the furnace at a slow, controlled rate. The furnaces are natural gas- or fuel oil-fired, and operate at temperatures up to 1,575°C. then, to the annealing ovens, and forming machines;
3- Cold end
The role of the cold end is to inspect the containers for defects, package the containers for shipment and label the containers.

58. Annealing
As glass cools it shrinks and solidifies. Uneven cooling causes weak glass due to stress. Even cooling is achieved by annealing. An annealing oven (known in the industry as a Lehr)
The glass cools to approximately 600 oC by the time it actually enters the annealing lehr. Inside the lehr, the glass undergoes a controlled cooling process, depending on the glass thickness, over a 20 – 6000 minute period

59. Float Glass In 1952 Alistair Pilkington invented the float glass
process. The float glass process is the most common
method of flat glass production in the world.
This process involves melting recycled glass, silica
sand, lime, potash and soda in a furnace and floating
it onto a large bed of molten tin. This mass slowly
solidifies over the molten tin as it enters the
annealing oven where it travels along rollers under a
controlled cooling process.
From this point the glass emerges in one continuous
ribbon where it is then cut and further processed to
customer's needs.

60. Float Glass Process1/4 Batching of raw materials
The main components of Soda Lime glass:
Silica sand (73%),
Calcium oxide (9%),
Soda (13%) and
Magnesium (4%),
All are weighed and mixed into batches
to which recycled glass (cullet) is added.

61. Float Glass Process2/4 Melting of raw materials in the furnace
The batched raw materials pass from a mixing silo to a five-chambered furnace where they become molten at a temperature of approximately 1500°C. Every operation is carefully monitored.
Drawing the molten glass onto the tin bath
The molten glass is "floated" onto a bath of molten tin at a temperature of about 1000°C. It forms a ribbon with a working width of 3210mm which is normally between 3 and 25mm thick. The glass which is highly viscous and the tin which is very fluid do not mix and the contact surface between these two materials is perfectly flat.

62. Float Glass Process3/4 Cooling the molten glass in the annealing lehr
On leaving the bath of molten tin, the glass - now at a temperature of 600°C - has cooled down sufficiently to pass to an annealing chamber called a lehr.
The glass is now hard enough to pass over rollers and is annealed, which modifies the internal stresses enabling it to be cut and worked in a predictable way and ensuring flatness of the glass.
As both surfaces are fire finished, they need no grinding or polishing.

63. Float Glass Process4/4 Quality checks, automatic cutting, storage
After cooling, the glass undergoes rigorous quality checks and is washed. It is then cut into sheets up to 6000mm x 3210mm which are in turn stacked and stored ready for transport.
The entire production process from the batching of raw materials to cutting and stocking is fully automatic controlled.

64. Glass Recycling
The used glass containers which you recycle at curb-side or take to your local recycling station are easily recycled into new containers at the glass factory.
Glass companies depend upon local communities and various glass recyclers, usually located near our manufacturing facilities, to supply quality used glass, known as cullet, for their factories.
Already separated by color, the cullet is placed into a hopper and fed onto a belt. The belt carries the cullet through a powerful magnet to remove bottle tops and other metals. It then passes through picking stations to remove contaminants such as ceramic, Pyrex, and other items that cannot be removed mechanically. The final step in processing cullet is to crush the cullet into finer glass particles which will then be added to the Raw Materials as they are fed into the glass furnace.

65. Fertilizer Industry

66. Fertilizer

67. Fertilizer
Most producers of compound fertilizers in the world are producing nitrate based mineral compound fertilizers under the product name “NP” or “NPK”. These products contain nitrogen in ammoniacal (NH4) and nitrate (NO3) form, phosphorus expressed as P2O5, and normally also potassium expressed as K2O.
The content of nutrients (N + P2O5 + K2O) will normally be between 40 and 50%. In addition the fertilizers may contain magnesium, boron, sulphur and micro-nutrients.
These compound fertilizers are made by one of the two following important production routes:
1– The nitric acid route or nitro-phosphate process,
2– The sulfuric acid route or mixed-acid process,
The two processes are based on different technologies, having different investment costs, economic impact, energy consumptions, emission values and process integration
Sources for the three primary nutrients are given in Figure next two slide.

70. Manufacturing of Fertilizer
Fertilizers are composed of several solid chemical compounds.To make fertilizer easy to use, each of these
compounds must first be granulated. One method of granulating these materials is to put them into rotating drum that has an inclined axis. As the drum rotates pieces of solid fertilizer take on small spherical shapes
The small pieces passed through a
screen, which separates out the
adequately sized particles.

71. After the components are granulated, they are mixed
together according to the manu-
facturer’s recipe producing
composite fertilizer
A coating of inert dust is applied to the particles.
The dust keeps the particles from sticking to each
Other and inhibits moisture retention. Then the
particles are dried.

72. The finish fertilizer is loaded into a hopper,
Which releases a designated amount into
large bags. The bags are sealed closed
and shipped to distribution

73. Fertilizer Materials

74. 1- Direct Applications

75. 2-Mixed Fertilizers
The primary advantage of mixed fertilizers is that they contain all three primary nutrients—nitrogen, phosphorus, and potassium—and require a smaller number of applications. They can be liquids or solids.
The overall percentage of the three nutrients must always be stated on the container. The grade designation is %N-%P2O5-%K2O. It is commonly called the NPK value.
Note that it is an elemental percentage only in the case of nitrogen. Phosphorus and potassium are expressed as oxides. Thus an NPK value of means that 6% by weight is elemental nitrogen, 24% is phosphorus pentoxide, and 12% is potash.

76. LIQUIDS VS. SOLIDS
There are many different types of liquid and solid fertilizers but we give only some generalizations about advantages of each.
Liquid fertilizers:
Are a clear solution, a suspension of a solid in a liquid (aided by a suspending agent), or a simple slurry of a solid in a liquid, account for 20% of all NPK mixed fertilizers
Solid fertilizers:
Contain no liquid, Mixed solid fertilizers can be made by either direct granulation methods or bulk blending.
Bulk blending is made by mechanical mixing of the separate granular intermediate materials. It is usually done in small plants near the point of use. This technique is employed because the fertilizer can be "tailor-made" to fit the exact requirements of the user.
Table next slide summarizes the advantages of liquids and solids