Inorganic

Sulphuric acid

Pure 100%
H2SO4

Video clip by Royal Society of Chemistry: https://www.youtube.com/watch?v=mym1rRPX6F4

 Sulphuric acid
Methods of Production:
• Contact Process
• Lead Chamber Process
Both processes are based on SO2. Chamber process was developed first in 1746 but produced acid
of concentration less than 80%. Contact process yields 98% H2SO4 and higher which can be
diluted, if necessary. Chamber process has become obsolete.
 Sulphuric acid
SO2 is obtained via:
 Sulphuric acid
Catalyst:
Most widely used catalyst is vanadium pentoxide dispersed on a porous carrier in pellet form.
Platinum catalyst was previously used but suffers from easy poisoning, fragility, rapid heat
deactivation, high initial investment.
Characteristics of catalysts

• Porous carrier having large surface area controlled pore size, and resistance to process gases
at high temperature: in pellet form if used in fixed beds, powdered form for fluidized beds.
Examples-alumina, silica gel, kieselguhr, zeolite.

• Active catalytic agent-V2O5 in this case. Preparations are secret for competitive reasons; usually
consist of adding H₂O soluble compounds to gels or porous substrates and firing at temperatures
below sintering point.

• Promoter-alkali, and/or metallic compounds added in trace amounts to enhance activity of

catalytic agent.
 Sulphuric acid
Catalyst:
Advantages of V2O5 catalyst:
• Relatively immune to poisons (stable)
• Low initial investment and only 5% replacement per year (cheap)
• Requires only 10 kg of catalyst mass containing 7-8% V₂O5 per daily ton of 100% acid
(effective)

Disadvantages of V2O5 catalyst

• Must use dilute SO2 input (7-10%); as catalyst is less active and requires high O2/SO2 to
give economic conversion. Larger converters are necessary.
 Sulphuric acid
Process Description:
• Air-SO2 gas containing 7-10% SO2 and 11-14% O2 is preheated by converter gas, if necessary, and
sent to first stage reactors of steel construction.

• This is the high temperature (500-600°C) stage, contains 30% of total catalyst and converts about 80% of
SO₂.

• The converter product is cooled by heat exchanger at 300°C and fed to a second stage where total yield
is increased to 97% by operating at 400-450°C for favorable equilibrium.

• High yield product gases are cooled to 150°C by water and air heat exchangers and absorbed in oleum
fed at a rate to allow not over a 1% rise in acid strength. Final scrubbing is done with a lower strength
(97%) acid. Oleum concentrations up to 40% can be made by tower absorption. Higher strength oleum
up to 65% is prepared by distilling 20% oleum.
Sulphuric acid
 Sulphuric acid
Major Engineering Problems:

• Design of multistage catalytic converter for a highly exothermic reaction: Some designs
contain 3 or 4 stages rather than the conventional two-stage operation for large capacity
plants.

• Optimization of space velocity in catalyst chamber: Pumping costs versus fixed charges
of reactor.

• Corrosion problems: Optimization studies show that equilibrium yield can be increased by
square root of system pressure PT at a given temperature:
YSO3 = Kp Yso2 (Yo₂)1/2 (PT)1/2
but increasing compression costs & corrosion problems dictate low pressure (1 atm.)
operation.
 Sulphuric acid
Major Engineering Problems:

• Adaptation of process to various types of gas feeds.

• As the result of considering problems (a) and (b) above, thin catalyst beds result (30-50 cm
height). Yield can drop due to longitudinal mixing if the convective gas velocity through the
bed is too low.

• Removal of heat of absorption of SO3 in acid. Pipe coolers with water dripping over external
surface have been replaced by cast iron pipe with internal fins to promote better heat
transfer. Pressure drop must be low so 8 cm stacked packing is often used.
Sulphuric acid
 Sulphuric acid
Double contact double absorption:
• The next step to the contact process is double contact double absorption (DCDA).

• In this process the product gases (SO2) and (SO3) are passed through absorption towers twice
to achieve further absorption and conversion of SO2 to SO3 and production of higher grade
sulfuric acid.

• SO2-rich gases enter the catalytic converter, usually a tower with multiple catalyst beds, and are
converted to SO3, achieving the first stage of conversion.

• The exit gases from this stage contain both SO2 and SO3 which are passed through intermediate
absorption towers where sulfuric acid is trickled down packed columns and SO3 reacts with
water increasing the sulfuric acid concentration. Though SO2 too passes through the tower it
is unreactive and comes out of the absorption tower.
 Sulphuric acid
Double contact double absorption:

• This stream of gas containing SO2, after necessary cooling is passed through the catalytic
converter bed column again achieving up to 99.8% conversion of SO2 to SO3.

• The gases are again passed through the final absorption column thus achieving not only high
conversion efficiency for SO2, but also enabling production of a higher concentration of
sulfuric acid.

• The industrial production of sulfuric acid involves proper control of temperatures and flow
rates of the gases as both the conversion efficiency and absorption are dependent on these.
 Sulphuric acid
Economics:

• Prior to 1947, a number of chamber process plants were installed. Since that date only
contact plants are being licensed with minimum capacity set at 50 tons per day.

• The superiority of the contact process results from:

• Engineering improvement to contact plant, particularly the catalyst performance

• High strength acid which reduces costs & increases the economic allowable market area

• High SO3 acids applicable to newer uses such as sulfonation and sulfation reactions
 Sulphuric acid
Economics:

• Sulfuric acid is generally made in India at locations near to acid consumption, often in small
plants.

• Initially, plants were built near seaports but it is more economical to transport sulfur from
the seaport to an inland plant adjacent to the point of consumption, then to transport acid
from a plant near a seaport.
Read Chapter 7 of Chemical Process Technology (Processes for the Conversion of
Biomass):
Jacob A. Moulijn
Michiel Makkee
Annelies E. Van Diepen

Specifically → Bioethanol, Biobutanol and biorefinery

 Sulphuric acid
Lead Chamber Process:

• In 1746 John Roebuck developed the lead chamber process for the manufacture of sulfuric acid.
Prior to this time, sulfuric acid had been produced in glass bottles several pounds at a time. But the
lead chamber process could produce sulfuric acid by the ton.

• In the original lead chamber process, sulfur and potassium nitrate are ignited in a room lined
with lead foil. Potassium nitrate, or saltpeter is an oxidizing agent oxidizes the sulfur to sulfur
trioxide according to the reaction:

6 KNO3(s) + 7 S(s) -----> 3 K2S + 6 NO(g) + 4 SO3(g)

• The floor of the room was covered with water. When the sulfur trioxide reacted with the water,
sulfuric acid was produced:

SO3(g) + H2O(l) -----> H2SO4(aq)

 Sulphuric acid
• This process was a batch process and resulted in the consumption of potassium nitrate.

• In 1835, Joseph Lussac invented a process for recovering the nitrogen in nitrogen monoxide and
recycling it to replace the saltpeter as a source of nitrogen.

4 NO(g) + O2(g) + 2 H2O(l) -----> 4 HNO2(l)

4 HNO2(l) + 2 SO2(g) -----> 2 H2SO4(aq) + 4 NO(g)

• This accomplished two things simultaneously: it reduced the dependence on expensive saltpeter and at
the same time sharply reduced nitrogen monoxide emissions. The only requirement now for saltpeter
was to make up for the lost nitrogen monoxide.
 Sulphuric acid
• The classic lead chamber process consists of 3 stages; Glover tower, lead chambers and Lussac Tower.

• The process starts with hot sulfur dioxide gas entering the bottom of a reactor called a Glover tower
where it is washed with nitrous vitriol (sulfuric acid with NO and NO2 dissolved in it) and mixed with
nitric oxide and nitrogen dioxide gases.

• The Glover tower serves two functions; concentration of the chamber acid and stripping of nitrogen
oxides from the liquid to the gas or denitration.

• Concentration of the chamber acid (62% to 68% H2SO4) is achieved by the hot gases entering the tower
which evaporate water from the acid.

• Some of the sulfur dioxide is oxidized to sulfur trioxide and dissolved in the acid wash to form tower
acid or Glover acid (about 78% H2SO4). The dissolved nitrogen oxides are stripped from the acid and
carried with the gas out of the Glover tower into the lead chambers.
 Sulphuric acid
• From the Glover tower a mixture of gases (including sulfur dioxide and trioxide, nitrogen oxides,
nitrogen, oxygen, and steam) is transferred to a lead-lined chamber where it is reacted with more water.

• The chamber may be a large, boxlike room or an enclosure in the form of a truncated cone.

• Sulfuric acid is formed by a complex series of reactions; it condenses on the walls and collects on the
floor of the chamber. There may be from three to twelve chambers in a series; the gases pass through
each in succession.

• The acid produced in the chambers, often called chamber acid or fertilizer acid, contains 62% to 68%
H2SO4.
 Sulphuric acid
• NO + ½ O2 -----> NO2

• NO2 + NO + H2O -----> 2 HNO2

• SO2 + H2O -----> H2SO3

• 2 HNO2 + 2 H+ -----> 2 NO + 2 H2O

• H2SO3 -----> HSO3- + H+

• NO+ + HSO3- -----> NOSO3- + H+

• NO+ + NOSO3- -----> 2NO + SO3

• SO3 + H2O -----> H2SO4

• Overall Reaction: SO2 + ½ O2 + H2O -----> H2SO4

 Sulphuric acid
• After the gases have passed through the chambers they are passed into a reactor called the Lussac tower
where they are washed with cooled concentrated acid (from the Glover tower); the nitrogen oxides
and unreacted sulfur dioxide dissolve in the acid to form the nitrous vitriol used in the Glover tower.

• The waste gases exiting the Lussac tower are usually discharged into the atmosphere.

• Product acid at a concentration of 78% H2SO4 is drawn from the cooled acid stream that is circulated
from the Glover tower to the Lussac tower.

• Nitrogen losses are made up with nitric acid which is added to the Glover tower.
Sulphuric acid
 Sulphuric acid
• The oxidation of sulfur dioxide is thermodynamically
favored by low temperature.
• The conversion is (nearly) complete up to
temperatures of about 700 K. As with all exothermic
equilibrium reactions, however, the ideal temperature
must be a compromise between achievable
conversion (thermodynamics) and the rate at which
this conversion can be attained (kinetics).
• With the current sulfur dioxide oxidation catalysts
this means a minimum temperature of 680–715 K.
• Elevated pressure is thermodynamically favorable,
but the effect of pressure is small.
• Figure shows the influence of the
temperature on the equilibrium conversion of
sulfur dioxide.
Nitric Acid
 Nitric Acid

• Methods of Production
 Nitric Acid
• Ammonia Oxidation Process
 Nitric Acid
• Process Description: Compressed air is mixed with anhydrous ammonia; fed to a shell
and tube converter designed so that the preheater and a steam heat recovery boiler-
superheater are within the same reactor shell.

• The converter section consists of 10-30 sheets of Pt-Rh alloy in the form of 60-80 mesh
wire gauge packed in layers inside the tube. Gas passes downward with a velocity
designed to give a contact time of about 2.5 x 10-4 sec in the catalyst zone at 800°C.

• Product gases from the reactor, containing 10-12% NO, are sent through heat recovery
units, a quench unit for rapid cooling to remove a large fraction of the product heat, and
into the oxidizer-absorber system. Air is added to convert NO to NO2 at the more
favorable low temperature (40-50°C) environment of the absorption system.

• The equipment in the absorption train may be a series of packed or sieve tray vertical
towers or a series of horizontal cascade absorbers. The product from this water
absorption system is 57-60% HNO3 solution which can be sold as is or concentrated.
 Nitric Acid
• Process Description: Concentration of the nitric acid to 95% can be done by one of
several processes:

• Concentration by H₂SO4 :Rectification by 93% H₂SO4 (66°Be) in silicon-iron or stoneware

towers produces concentrated nitric acid and 70% H₂SO4 which can be reevaporated to 93%
or used elsewhere in the plant.

• Concentration by Mg(NO3)2 :Developed in 1958 by Hercules Powder Company. Magnesium

nitrate solution containing 70-75% Mg(NO3)2 is fed to a dehydrating tray tower along with
the dilute HNO3 from the absorption system. The salt solution acts as an extractive
distillation agent, removing water at 100°C or higher, thus allowing rectification without
azeotropic formation. The dilute Mg(NO3)2 solution is reconcentrated by evaporation.
Advantages of Mg(NO3)2 presess are:

• (1) Operating costs about half of those encountered with H₂SO, concentration
• (2) Capital requirements are only 70% as great
• (3) Acid quality and yield is improved
Nitric Acid
 Nitric Acid
• Major Engineering Problems:

• Thermodynamic and Kinetic Consideration: There is a slight equilibrium

advantage to operation at low pressure (1 atm.). This is more than offset by
increased capacity in a given reactor volume with subsequent catalyst and reactor
savings when operating at higher pressures (3-8 atms.).

• The NO oxidation reaction 2 does not have as large an equilibrium constant.

Hence, this reaction predominates in the water cooling and absorption portions of
the process, which operate at 40-50°C. All of the NO which is liberated on
absorption of NO2 must also be reoxidized in the absorption tower
 Nitric Acid
• Reaction kinetics in the NH3 oxidation stage can be summarized as:
• The reaction to form NO is favored by increasing temperature until an optimum is reached which increases
with higher gas velocities. This results from the prevention of back diffusion of NO into the higher NH3
concentration region. If this occurs, reaction 6 is quite probable and should be avoided for high NO yield.

• Alloying platinum with rhodium improves yield at a given set of conditions.

• Rate of NO formation very nearly corresponds to diffusional transport of NH3 molecules to the catalyst
surface.

• Reaction rate is directly proportional to the system pressure. The absorption of nitrogen oxides from gaseous
mixtures by chemical reaction with water has the following design criteria:

• Low temperatures are beneficial for absorber operation efficiency.

• Increasing pressure favors physical absorption rates and shifts chemical equilibrium to produce higher acid strengths.

• The rate of absorption is dependent on concentration of NO₂ in gas phase. In commercial absorbers where the
concentration of NO, is greater than 5%, the controlling reaction is solution of N2O4 accompanied by hydrolysis to
HNO3 and HNO₂.
 Nitric Acid
• Process design modification: Most plants use intermediate (3-4 atms.) or high
pressure (8 atms.) processes rather than the complete atmosphere process or a
combination of 1 atm. pressure oxidation and high pressure absorption. Top
pressure is limited by pressure vessel costs.

• The reasons for elevated pressure processes are:

• High reaction rates and lower volumes in both oxidation and absorption equipment
• Higher acid strength
• Lower investment costs

• The disadvantages of higher pressures:

• Lower oxidation yields
• Higher catalyst losses unless good filtering procedures are used
• High power requirements if power recovery units are not specified
 Nitric Acid
• Economics:
Nitric acid finds its largest end use in the fertilizer industry, both as an acidulant for phosphate
rock to produce nitrophosphate for mixed fertilizers and in the production of ammonium
nitrate, a synthetic nitrogen fertilizer containing 35% N.

This is expected to increase in line with the population growth and increased standard of
living.

New uses have been found for ammonium nitrate-oil mixtures as a cheap open-pit explosive
for quarrying, mining, and construction. The market for other nitrate-base explosives is
considered stable with very little growth.

Rocket propellant compositions may ultimately provide a small but increasing market for such
products as fuming red nitric acid (conc: HNO3 with N₂O4 solubilized), N₂O4 and
monopropellants such as tetranitromethane.
Phosphoric Acid
Phosphoric Acid
Phosphoric Acid
 Phosphoric Acid
Raw Materials:

• The high grade of imported ore is necessary to avoid solubilization of mined rock
impurities such as aluminium, silicon, iron oxides, and alkali minerals.

• In USA a beneficiation process is used on low-grade ore which involves milling,

screening, hydroseparation, classification, and floatation.

• The only other raw material required is strong sulfuric acid which comes from a
contact sulfuric acid plant located at or near the phosphoric acid plant.
 Phosphoric Acid
Process:

• Phosphate rock ground to 65%-200 mesh and fed to a chute where a recycle stream
of weak H3PO4 washes it into a reaction tank. Strong H2SO4 is metered with
automatic control which keeps the acid and rock feed ratio at the desired setting.

• A single reactor can be designed by proper baffling and residence time capacitance
to permit a 98% conversion in 4-6 hours. In other designs, a series of 4-5 continuous
mixing tanks can be used with slightly better efficiency of extraction by minimizing
backmixing. Heat of reaction is controlled by pulling cooling air across.

• The gypsum-phosphoric acid slurry goes to a travelling pan vacuum filter where the
40% acid is removed and the cake washed with water. Filtrate from the latter is
returned to the reactor.
 Phosphoric Acid
Process:
• The gypsum is free-filtering and cake thicknesses of about two inches can be readily
obtained.

• The gypsum; can either be dried for use in plaster, paints and cements, or reacted
with ammonium carbonates to give ammonium sulfate (fertilizer ingredient) and
calcium carbonate (Merseberg process).

• The dilute acid is concentrated in a single effect evaporator to any grades > 50%
acid. Most of the wet process acid is being converted to high concentration chemical
fertilizers.

• Pyrophosphoric acid (H4P2O7) can be made by heating the orthophosphoric acid to

250°C. By increasing the temperature to red heat (-900°C), metaphosphoric
acid(HPO3) results.
 Phosphoric Acid
Major Engineering Problems:
• Process Design:
• Fineness of the grind: Economic balance between grinding costs and reactor fixed
charges
 Phosphoric Acid
Major Engineering Problems:

• Temperature: If the temperature is kept above 100°C, undesirable semi hydrate

(CaSO4.1/2H₂O) and anhydrate (CaSO4) crystals are formed which are
difficult to filter. By digesting at 80°C, the gypsum (CaSO4.2H₂O) rhombic
crystals predominate and these can be filtered and washed easily.

• Control of sulfuric acid-1-1.5% residual H2SO4 is left in the slurry going to

the filter, again to produce a more filterable gypsum. Small percentages of
sulfuric acid can be tolerated for fertilizer-grade acid. If a purer product is
desired, the excess H₂SO4, is eliminated with a slower filtration rate.
 Phosphoric Acid
Major Engineering Problems:
• Materials of construction
• Reaction tanks constructed of steel and lined with acid-proof brick.

• All air vent systems are polyvinyl chloride (PVC) coated steel

• Filter is Type 316 stainless steel with polypropylene filter cloth and rubber lined
vacuum receivers of steel

• Storage tanks of rubber-lined steel

Phosphoric Acid
 Phosphoric Acid
• Capital Investment Comparison for Acid Versus Electric Furnace Processes

• After losing out to the electric furnace process for nearly 35 years, both the acid
processes are now used almost exclusively for new additions to the growing demand for
phosphoric acid, particularly in fertilizers. The reasons are:
• Capital investments compared to an electric furnace plant. This more than offsets the price differential
for the high grade rock required by the wet process.

• The lack of need for the high purity acid produced by the electric furnace method in the fertilizer
market.

• Possibility of producing ammonium sulfate from gypsum by-product in the H2SO4 process.

• Use of cheap HCI or excess Cl₂ in India.

 Phosphoric Acid
• The HCI process is only economical where there is excess chlorine and a
scarcity of native sulfur. Such is the case for India. Since the processing costs
are approximately the same for either process, the selection can be made on the
basis of parity price of HCI versus H₂SO4.
 Phosphoric Acid
• Plant Location Comparison
• With the exception of acid produced from P4 at or near consumer plants, both wet
process and electric furnace acid plants are located in the region of phosphate rock, i.e.,
USA-Southeastern and Rocky Mountain states.

• Rock beneficiation is required for upgrading low P₂O5 rock in the wet process where
high purity acid is required for all uses except triple superphosphate fertilizer.
 Phosphoric Acid
• By-product Usage
• The extraction of uranium at rates of 0.1-0.2 kg per ton of rock is potentially attractive
for the wet process. This appears as an impurity salt in the H3PO4 liquor from the
gypsum filter and can be extracted by precipitation or solvent extraction methods. To
date, the Atomic Energy Establishment has found more economic sources of supply for
uranium.
 Phosphoric Acid
• Hydrochloric acid leaching

Phosphate rock of high P2O5 content (>30%) is preferred to avoid excessive acid consumption.
Hydrogen chloride gas or concentrated aqueous HCI (>30%) as waste or by-product acid is used.
Organic C4 and/or C3 alcohol solvents are used to extract H3PO4 from CaCl2 solution.
 Phosphoric Acid
• Process Description

• Phosphate rock is ground to pass a 20 mesh screen and fed into a dissolver where an acid
stream of conc. HCl plus make-up wash water from the counter-current decantation system is
added.

• Fumes of CO₂, HF and HCI are scrubbed for acid recovery.

• The mixture is fed to a series of decantation units with overflow from the first settler moving
to the counter current solvent extraction operations. The solids underflow goes to 2-3
washing thickeners.
Phosphoric Acid
• Extraction of H3PO4 plus some free HCl is done in a battery of mixer-settlers (a) with CaCl₂ + CaF2
retained in aqueous phase.

• The extract is again passed through several more mixer-settlers (b) for removal of trace impurities of
Ca2+ which are co extracted.

• The extractant is aqueous reflux from the next unit-transfer extractors (c) where water extracts
H3PO4 and HCI from solvent phase.

• The washed solvent is recycled to a final series of mixer-settlers (d) where the balance of HCl is
extracted from raffinate phase of extractors (a). The acid-free brine is sent to steam stripping for
solvent recovery. The aqueous acid raffinate from (c) is separated and concentrated in a triple effect
evaporator to give three different overhead streams:
• (1) Alcohol-water overhead flash from the first effect which is condensed and returned to extractors (a)
• (2) Dilute HCl from the second effect
• (3) Conc. HCl from the third effect.

• The HCl is returned to acid make-up. The bottoms from the third effect is product phosphoric acid
(80% H3PO4).
 Phosphoric Acid
• Engineering Problems:

• Solvent recovery: The use of relatively expensive solvent in producing low-cost acid
means careful attention to design and operation of solvent-handling equipment.

• Materials of construction: All sections of the plant must be HCl resistant which requires
rubber-lined or PVC-lined mild steel or rigid PVC equipment. The latter is
recommended. For evaporation and steam stripping equipment, impervious graphite (e.g..
Karbate, Diabon) is specified.

• Waste disposal: Problems of disposing of CaCl2 aqueous effluent and siliceous rock
residue become acute.
Dry process(es) - Phosphoric acid

Electric furnace process

– Direct conversion at
plant site

Electric furnace process

– Oxidation and
hydration of elemental
phosphorus
 Hydrochloric acid
• Hydrochloric acid (HCl), also known as muriatic acid, is a solution of hydrogen chloride in water.

• HCl exists in solid, liquid, and gaseous states and is water soluble in all proportions.

• The first hydrochloric acid was prepared through heating common salt and sulfuric acid by
Benedictine Monk and Basil Valentine in 15th century. Also, Libavius prepared free hydrochloric
acid by heating salt in clay crucibles in 16th century. In the 17th century, Johann Rudolf Glauber
used NaCl and H2SO4 for the preparation of sodium sulfate in the Mannheim process, releasing
hydrogen chloride gas as a by-product. Joseph Priestley prepared pure HCl in 1772, and chemical
composition includes hydrogen and chlorine was proven by Humphry Davy in 1818.

• Demand for alkaline substances increased during the Industrial Revolution in Europe, Nicolas
Leblanc developed cheap large-scale production of sodium carbonate (soda ash). Using common salt,
sulfuric acid, limestone and coal which release HCl as a by-product.

• Until the British Alkali Act 1863 and similar legislation in other countries, the excess HCl was
vented to air.
 Hydrochloric acid
• After the passage of the act, waste gas is absorbed in water, producing hydrochloric acid
on an industrial scale.

• In the twentieth century, the Leblanc process was effectively replaced by the Solvay process
without hydrochloric acid by-product.

• Since hydrochloric acid was already fully settled as an important chemical in numerous
applications, the commercial interest initiated other production methods, some of which are
still used today.

• Currently, hydrochloric acid is mostly made by absorbing by product hydrogen chloride

during a chemical manufacturing process such as chlorination of hydrocarbons.
 Hydrochloric acid
• MANUFACTURE
HCl is manufactured by various methods as follows:

• Synthesis from hydrogen and chlorine

• From salt and sulfuric acid

• As by-product from chemical processes

• From incineration of waste organics

• Hydrochloric acid solutions

 Hydrochloric acid
• Process:
• Sources of raw material: Both hydrogen and chlorine can be obtained during electrolysis of
brine for manufacturing of NaOH. Also, hydrogen can be synthesized from any one methods
of following:
• Lane process or iron steam process
• Steam hydrocarbon process
• Liquefaction of coal gas and coke oven gas
• Bosch process or water gas-steam process
• Reaction H2 + Cl2 → 2HCl ΔH = - 43.9kcals
The plant consists of combustion chamber of structural carbon
or lined with silica bricks provided with cooling device which
may consist even of cold-water circulation in the shell. To
ensure all the chlorine reacts with hydrogen, excess of 10%
hydrogen compare to chlorine is charged from the bottom of
combustion chamber. Also, care should be taken that the
combustion chamber and length of ducting which leads the gas
to absorber should be sufficiently spacious, otherwise
hydrochloric acid will contain free chlorine.
 Hydrochloric acid
• The burning of hydrogen is started by igniting the burner with an external air-hydrogen
torch.
• Dry chlorine is passed into the combustion chamber, where hydrogen burns in an atmosphere
of chlorine to produce HCl.
• The exothermic nature of the direct combination of both gases (H2 and Cl2) is such as to raise
the temperature of the reagents, and the reaction products to a point where they are
incandescent.
• The reaction is carried out at 2400oC with greenish flame. The gases are always kept above
dew point to avoid corrosion.
• The combustion chamber is then cooled externally by water and gastight lid is fitted at the
top of the reactor which suddenly opens to allow the gases to escape in case of emergency.
• Hydrochloric acid gas is cooled absorbed in water or dilute HCl solution by passing through
cooler and absorber through the connecting pipe. The strength of acid produced is generally
32-33 %.
• The heat of absorption of HCl in water is removed by spray of cold water outside the
absorber. The solution of HCl flows into a storage tank.
The dew point is the temperature to which air must be cooled to become saturated with water vapor, assuming constant air pressure and water content.
When cooled below the dew point, moisture capacity is reduced and airborne water vapor will condense to form liquid water known as dew.
 Hydrochloric acid
• Anhydrous: Hot gases originating from combustion chamber are passing over anhydrous
CaCl2 or washing them with 98% sulfuric acid and then cooled and compressed to 60atm
pressure. The cooled and compressed gas having 99.9% purity is filled in steel cylinders.

• In another process, absorb the combustion gas into water and distill it to 36% concentration
of HCl (sounds familiar?).

• If one is to obtain 97% HCl at the top of the column, the 35% acid is cooled to -120 deg C
and aqueous liquid containing 50% HCl is left to condense, while residual gases, when they
have been de nebulized as compressed to 60atm are of purity exceeding 99.5%.
 Thermodynamics and kinetics
• On account of the existence of large energy barrier to the reaction, mixture of molecular H2
and Cl2 is stable at ambient temperatures and in absence of suitable wavelengths. Photons
with frequencies which are able to furnishing the activation energy can be produced by
creating an electrical spark in a mixture of molecular H2 and Cl2 or by first burning mixture
of H2 with air and then gradually replacing air with chlorine.

The combustion chamber and ducting to absorber should be

sufficiently specious for avoiding wall effect. From
physicochemical point of view if the walls of reactor in which
chain reactions takes place by their varying nature,
development, shape and orientation as to affect the chain
carriers is called wall effect. In the present case wall tends to
interrupt the process by promoting the chain breaking reaction
(termination reactions). Physico chemically, chain terminators
act as a third body in a system which already consists of the
reactant bodies.
 Salt Sulphuric Acid
• Salt (NaCl) and sulfuric acid are charged to the furnace. It is desirable to keep one of the
components in the reaction mixture in a liquid form in both steps. The first step is carried out
at the lower temperature compared to second step. Even so, for liquefaction of NaHSO4,
which is required to carry out in second step, material is heated up to 4000 C. Sodium
sulfate in form of sludge is collected from the bottom of the furnace. The product and
unconverted sulfuric acid is sent to further processing in which recovery of sulfuric acid and
nitric acid in cooling tower and absorber respectively.

Reaction:
• NaCl + H2SO4 → NaHSO4 + HCl
• NaCl + NaHSO4 → Na2SO4 + HCl
 Uses
• Anhydrous HCl is consumed for its chlorine value, whereas aqueous hydrochloric acid is
often utilized as a non-oxidizing acid.
• Used in metal cleaning operations, chemical manufacturing, petroleum well activation,
and in the production of food and synthetic rubber.
• Used for the manufacture of chlorine and chlorides, e.g. Ammonium chloride used in dry
cell.
• In the manufacture of glucose from corn starch.
• For extracting glue from bones and purifying boneblack.
• A saturated solution of zinc chloride in dilute HCl is used for cleaning metals before
soldering or plating
• It is also used in medicine and as laboratory reagent.
• Aqua regia used for dissolving metal.
 Cement
Cement is a generic name for powdered materials 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.

The most common is Portland cement which is the basis for a number of
cement products.

Specifically, Portland cement is defined as finely ground calcium aluminates and

silicates of varying compositions which hydrate when mixed with water to form
a rigid continuous structure with good compressive strength.
Cement
Cement
 Cement
• In the heart of the process of cement manufacturing →
https://www.youtube.com/watch?v=5Jbdk7DBm74

• Portland Cement Production Process →

https://www.youtube.com/watch?v=JlQWD2RUslU&t=29s
 Cement
• India ranks as the fourth largest producer (can anyone guess the current status?) of cement in the
world after China, Japan and the United States and is poised to emerge as a leader among cement
producing countries.

• The cement industry has come a long way since the first bag of cement was packed in the year 1914 at
Porbandar. A mere 945 mts, was produced in that year throughout India compared to the production of
about 48.75 million tons in the year 1990-91 as against the target of 49.00 million tons from an
installed capacity of 63.96 million tons

• Broadly the progress of cement industry falls into five phases. The first period beginning from 1947
till 1980 is the period during which government exercised strict control over the entire industry by
various policies and legislations. The cement industry experienced a period of price and distribution
controls. The years from 1980 to 1989 mark the second phase of partial decontrol.

• The third period could be considered as beginning from 1989 to 1992 when the industry functioned
free from price and distribution controls, but remained still under a regime of controlled economic
decision making. The fourth period beginning from 1992 onward is the period when cement industry
has been free from all price, distribution and licensing controls.
 Cement
• However, it would still have to face pangs of transitional period of structural reform process.

• The fifth and decisive period will commence from 1995 onwards when free market conditions in
cement would work within a reformed economic system.

• Cement factories in India are mainly concentrated in Madhya Pradesh, Tamil Nadu, Andhra Pradesh,
Rajasthan, Gujarat, Bihar and Karnataka.

• The limestone reserves of these states account for 90 percent of the reserves in India. Location of a
cement factory near limestone resources has its own advantages.

• The different varieties of cement produced in India may be described as ordinary portland, portland,
pozzolana, portland blast furnace slag, special high strength cement, low heat cement, oil well cement,
colored cement and white cement.
 Cement
• However, it would still have to face pangs of transitional period of structural reform process.

• The fifth and decisive period will commence from 1995 onwards when free market conditions in
cement would work within a reformed economic system.

• Cement factories in India are mainly concentrated in Madhya Pradesh, Tamil Nadu, Andhra Pradesh,
Rajasthan, Gujarat, Bihar and Karnataka.

• The limestone reserves of these states account for 90 percent of the reserves in India. Location of a
cement factory near limestone resources has its own advantages.

• The different varieties of cement produced in India may be described as ordinary portland, portland,
pozzolana, portland blast furnace slag, special high strength cement, low heat cement, oil well cement,
colored cement and white cement.
Cement
 Cement
Process Description:
• The operations are grinding, classification, floatation and thickening.

• Rock is wet-ground, fed to a hydroseparator where the overflow directly goes to the final thickener,
being of satisfactory composition.

• If not, it is subjected to flotation separation as well as the coarse material which must be floated to
remove silica, mica and tale.

• Flotation is based on the ability of a collecting agent to wet certain minerals causing these to be
entrained in an air froth which rises to the surface and overflows the flotation cell into the thickener
cascade.

• In these latter units the flotation liquor is recycled and the beneficiated cement rock slurry is fed
directly to cement kilns.
Cement
 Cement
Major engg problems:
• Choice of flotation agents-necessary for selective wetting.

• Oldest type is oleic acid @ 200 gm/ton.

• Newer types of detergents have better selectivity and lower consumption.

• Grinding-optimizing particle size range with power input.

 Portland Cement Process

Process Description:
• Cement-grade limestone (and possibly oyster shells) plus clay or shale, sand, iron containing materials (such as
blast furnace slag), gypsum and coal (especially in India where it is more plentiful than oil or gas for heating)
are ground together.

• Grinding may be a wet or dry process, but dry process plants now predominate because of savings in heat (less
water to evaporate) 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 dry powdered feed (or wet slurry) is then fed to a direct-fired counter-current rotary kiln. The residence time
is 1-3 hours and the feed mixture is decarbonated and fused to form the cement compounds (C2S, C3S, C3A).
The hot clinker (3-10 mm size) is dropped to a rotary cooler which so 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 bulk stored and
shipped.
 Portland Cement Process
Major Engineering Problems:
• Type of grinding: Wet or dry grinding may be used with dry grinding being used in most new plants.
The importance of good design here is emphasized by the fact that about 80% of the total power
consumed in the manufacture of cement is used in the crushing, grinding and blending operations.

• Kiln design: Calcining involves decomposition of CaCO3 to CaO and firing at 1,400-1,500°C to
promote compound formation. Heat duty is also required for water evaporation, oxidizing organic
material, partial volatilization of sulfates, chlorides, and alkalies. A typical performance graph is
given:

Wet process feed requires 90-170 m length kilns

of 2.5-6 m diameter; rotating at corresponding
speeds of 2 rpm-½ rpm. Dry process kilns may be
as short as 50 m.
 Portland Cement Process
Major Engineering Problems:

• Heat economy: Minimizing fuel consumption is an economic balance between fuel costs and addition
of waste-heat boiler and air preheater with the equipment usually specified because of favorable
incremental investment. The theoretical heat requirement is 430 Kcal/kg of Portland cement clinker.
Actual heat requirements vary from 1,300-1,800 Kcal/kg for processes using wet grinding down to
700-1,000 Kcal/kg for processes using dry grinding.

• 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 proven a worthwhile
investment in improving Indian cement quality so that it now stands high in world market
comparisons.
 Portland Cement Process
Economics

• High grade and beneficiated circuit rock will have to be supplemented by blending with burnt clays
and blast furnace slag to conserve native limestone.

• Another example of substituted raw materials is at Fertilizer Corp. of India Ltd., Sindri, where
calcium carbonate sludge is utilized in producing 600 tons/cement per day via an adjacent plant of the
Associated Cement Companies Ltd. The sludge comes from the reaction:

• CaSO4 + (NH4)2CO3 → (NH4)2SO4 +CaCO3

Fertilizer grade
sludge
ammonium sulfate

• Still another example of substituted raw materials involves cement production as a co-product in the
production of sulfuric acid from gypsum. See Section IIA on Sulfur and Sulfuric Acid for further
discussion. This process produces cement clinker and a gas containing 9% SO2 as co-products. The
process is carried out by heating gypsum, coke and shale in a coal-fired kiln at 2,500°F.
 Portland Cement Process
Economics

• The following are some of the reactions which occur:

 Factors to be considered in cement industry
• Process technology
• Industry problems including
• Capital availability
• Power
• Locational problems
• Raw material problems
• Transport problems
• Export problems
• The advent of mini-plants
• The impact of research and development
• Future market influences and trends
 Factors to be considered in cement industry
• A review of the cement industry has been provided in "Kothari's Industrial Directory of India"
published in Madras in 1994 which could serve as a pattern for the consideration of many industrial
chemical processes-sort of an outline for considering processes in general.

• It is a good case history of the factors involved in considering an industry. Several salient features
characterize the cement industry. It is a core sector industry and cement is an infrastructural product.
Any increase in its price would have a cascading effect on many other sectors, especially that of
construction.

• It is a capital-intensive industry. A new one million ton plant would cost between Rs. 180-200 crore,
with its gestation period ranging between 2 and 3 years. It is also a power-intensive industry and is
therefore highly susceptible to power cuts.

• Incidentally power is considered to be a major cost of production in the manufacture of cement.

Besides it is an industry which depends heavily on the policies of the government.
 Factors to be considered in cement industry
• Production Global cement production has surpassed one thousand million tons and the Indian cement
industry has reached 340 million in the production capacity as of 2021.

• Cement may be manufactured employing three alternative technologies: (a) the largely outmoded wet
process technology, (b) the more modern dry process that requires only 19 percent coal utilization (as
against 30 percent for the wet process) and (c) the latest precalcinator technology through which
optimum power utilization may be achieved.

• Here the calcination of raw material is partly or completely carried out before the feed enters the
rotary kiln, thus reducing the thermal load on the kiln. Precalciners can be fitted on to existing dry
process kiln. Besides saving power, the adoption of this technology enables an increase in installed
capacity by 30-50 percent.
 Factors to be considered in cement industry
• Modernization provides the key to the problem of technology obsolescence in the industry. This may
be done by closing down uneconomic units and converting the others to semi-dry or completely dry
process.

• Process conversion costs less than the cost associated with the setting up of green field units of similar
capacity. Modernization and rehabilitation by way of conversion of wet to dry process and addition of
precalciners to existing dry process units are long overdue in the country.

• The conversion program in all would require an investment of Rs. 1,500 crore. Since the cement units
are not in a position to generate funds of this dimension from their own resources, the government
should think in terms of a modernization fund as has been done for the textile industry.

• Financial institutions should also dovetail their soft loan schemes to meet the cost of modernization
and companies should earmark adequate funds for R and D programs for improving existing
technologies and adapting foreign knowhow to Indian conditions. The industry's present commitment
to R and D is almost negligible.
 Problems
• Shortage of capital
• Power shortage
• Locational problems
• Shortage of coal
• Non-availability of railway wagons
• Defective method of transport
• Negligible Share in the world trade
• Technological obsolescence