CHAPTER 2

CHEMICAL INDUSTRIES
1. SULPHURIC ACID
Sulfuric acid (H2SO4) is a basic raw material used in a wide range of industrial processes and
manufacturing operations. Almost 70% of sulfuric acid manufactured is used in the production of
phosphate fertilizers. Other uses include copper leaching, inorganic pigment production,
petroleum refining, paper production, and industrial organic chemical production. Sulfuric acid is
manufactured commercially by following two methods.
 Lead chamber process
(Produce relatively dilute H2SO4 (62%-78%))
 Contact process
Because of economics, all of the sulfuric acid produced in the U. S. is now produced by the
contact process. U. S. facilities produce approximately 42 million megagrams (Mg) (46.2 million
tons) of H2SO4 annually. Growth in demand was about 1% per year from 1981 to 1991 and is
projected to continue to increase at about 0.5% per year.
Raw material:
Sulphur is the raw material used in the manufacturing of Sulphuric acid.
Frasch process: is a method to extract sulphur from the underground deposits. It is the only
industrial method which is used in recovering the sulphur from elemental deposits.
Elemental sulphur is found in the deposits in the ground. There are two properties of sulphur that
are used in its extraction process. These are its low melting point and low density. The extraction
of sulphur is done by a process known as the Frasch process. In this process, superheated water
is pumped into the sulphur deposit. The sulphur then melts and is then extracted by lifting it to
the surface with compressed air. There are a few steps in this process for sulphur to be extracted.
First, a well is drilled into the soil for mineral deposits. Then after this, the superheated water is
pumped into the deposit (this water was approximately heated to 170 degrees Celsius).
As a result of this, the sulphur in the deposit melts. It melts so easily because sulphur has a low
melting point. Remember that, although the sulphur is melted, it is still in the deposit and we
need to extract it. Now, besides with the water pumped into the well, compressed air is also
pumped in it.
We know that sulphur has a low density and due to this reason, the molten sulphur comes to the
surface. The low density of sulphur allows the compressed air to push it to the surface.
Now, the sulphur can cool down and solidify since it is on the surface.
From here, sulphur forms a rhombic crystal. Hence, in this way sulphur is extracted through the
Frasch process.
This extracted sulphur also contain dirt particles and As 2S3 which on reacting with oxygen
convert to As2O3 (Acid fog).
2 As2S3 + 9 O2 = 2 As2O3 + 6 SO2
Contact process:
Since the contact process is the only process currently used. In this process the Iron pyrite
(Silicon free FeS2 containing about 53.4% of sulphur), Elemental sulphur and air are used as raw
materials.
This process involves the following steps:
1 ST STEP: PREPARATION OF SO 2 GAS: In the 1st step sulphur or iron pyrite (FeS 2) is
burnt with air in pyrite burner to produce sulphur dioxide gas (SO2).
S + O2 SO2
4FeS2 + 11O2 2FeS3 + 8SO2
2ND STEP: PURIFICATION OF SO2 GAS: SO2 gas obtained from pyrite burner contains
many impurities such as a sulphur, dust particles, arsenic oxides (As 2O3) etc which make the
catalyst ineffective. To remove these impurities, mixture of SO 2 and air is passed through special
dust filter chamber, washing tower and then drying tower as shown in figure.
3RD STEP: PREPARATION OF SO3 GAS: Mixture of purified SO2 gas and air is heated at
450°C under 1.5 – 1.7 atmospheric pressure in the presence of vanadium pentaoxide (V 2O5) or
platinum (Pt) as catalyst in contact tower. In this tower SO2 gas is oxidized to SO3 gas.

2SO2 + 3O2 ⇌ 2SO3 ∆H (–ve)

This reaction is slow, reversible and exothermic.
4 TH STEP: PREPARATION OF OLEUM (H2S2O7): Sulphur trioxide gas (SO3) produced in contact tower is
absorbed in 97% sulphuric acid and in absorption tower to form very thick liquid called oleum or
pyrosulphuric acid.

SO3 + H2SO4 H2S2O7

5 TH STEP: PREPARATION OF H2SO4: The oleum or pyrosulphuric acid is dissolved in calculated amount
of water to obtained sulphuric acid of any desired concentration.

H2S2O7 + H2O 2H2SO4

100% pure sulphuric acid can be obtained by this process.

PHYSICAL PROPERTIES OF H2SO4:

1. Pure sulphuric acid is a colorless, odorless and viscous oily liquid often known as oil of vitriol.
2. When concentrated sulphuric acid is mixed with water, it produces large amount of heat energy.
3. Its melting point is 10.5°C, boiling point is 338°C and specific gravity is 1.84.
Emissions of sulfur Dioxide:
Nearly all sulfur dioxide emissions from sulfuric acid plants are found in the exit stack gases.
Extensive testing has shown that the mass of these SO 2 emissions is an inverse function of the
sulfur conversion efficiency (SO2 oxidized to SO3). This conversion is always incomplete, and is
affected by the number of stages in the catalytic converter (V 2O5, 400-450°C), the amount of
catalyst used, temperature and pressure, and the concentrations of the reactants (sulfur dioxide
and oxygen). For example, if the inlet SO 2 concentration to the converter were 9% by volume (a
representative value), and the conversion temperature was 430°C (806°F), the conversion
efficiency would be 98%. At this conversion, the uncontrolled emission factor for SO 2 would be
13 kilograms per megagram (kg/Mg) (26 pounds per ton [lb/ton]) of 100 percent sulfuric acid
produced. While according to new source performance standard [NSPS] it should be 2 kg/Mg (4
lb/ton) of 100 percent acid produced, maximum 2 hour average. To achieve this standard
requires a conversion efficiency of 99.7% in an uncontrolled plant, or the equivalent SO 2
collection mechanism in a controlled facility. Dual absorption, as discussed above, has generally
been accepted as the best available control technology for meeting NSPS emission limits. There
are no byproducts or waste scrubbing materials created, only additional sulfuric acid. Conversion
efficiencies of 99.7% and higher are achievable, whereas most single absorption plants have SO 2
conversion efficiencies ranging only from 95 to 98%. Furthermore, dual absorption permits
higher converter inlet sulfur dioxide concentrations than are used in single absorption plants,
because the final conversion stages effectively remove any residual sulfur dioxide from the
interpass absorber. In addition to exit gases, small quantities of sulfur oxides are emitted from
storage tank vents and tank car and tank truck vents during loading operations, from sulfuric acid
concentrators, and through leaks in process equipment. Few data are available on the quantity of
emissions from these sources.
USES OF SULPHURIC ACID(H2SO4):
1. It is used in the manufacture of fertilizers specially in ammonium sulphate [(NH 4)2SO4]
and calcium super phosphate[Ca(H2PO4)2]
2. It is very useful chemical in dyeing, paper, iron and steel, leather and textile industries.
3. It is used in the manufacture of rayon, plastics detergents, paints and pigments.
4. It is used for refining of petroleum and in the preparation of all kinds of man-made
fabrics.
5. It is used in the manufacture of highly explosive materials and as drying agent.
 2. NITRIC ACID:
In 1991, there were approximately 65 nitric acid (HNO 3) manufacturing plants in the U. S. with a
total capacity of 11 million tons of HNO 3 per year. The plants range in size from 6,000 to
700,000 tons per 3 year. About 70 percent of the nitric acid produced is consumed as an
intermediate in the manufacture of ammonium nitrate (NH 4NO3), which in turn is used in
fertilizers. The majority of the nitric acid plants are located in agricultural regions such as the
Midwest, South Central, and Gulf States because of the high demand for fertilizer in these areas.
Another 5 to 10 percent of the nitric acid produced is used for organic oxidation in adipic acid
manufacturing. Nitric acid is also used in organic oxidation to manufacture terephthalic acid and
other organic compounds. Explosive manufacturing utilizes nitric acid for organic nitrations.
Nitric acid nitrations are used in producing nitrobenzene, dinitrotoluenes, and other chemical
intermediates. Other end uses of nitric acid are gold and silver separation, military munitions,
steel and brass pickling, photoengraving, and acidulation of phosphate rock.
In the production of HNO3, ammonia is used as raw material. This ammonia is synthesized by
Haber’s process.
Synthesis of NH3:

The Haber Process is an industrial method of reacting nitrogen and hydrogen gas to produce
ammonia. Stoichiometrically, this involves one mole of diatomic nitrogen and three moles of
diatomic hydrogen per two moles of ammonia.

N2 + 3H2 → 2NH3

Many chemists call the Haber Process a form of “nitrogen fixation,” meaning the conversion of
nitrogen gas to a more chemically useful form. In nature, microorganisms called diazotrophs
perform nitrogen fixation, which helps cycle nitrogen through ecological systems. Nitrogen, of
course, serves as one of the fundamental elements of biological life, forming an important part
of proteins and nucleic acids. Nitrogen, in the form of ammonia, also has importance in research
and industrial applications. However, despite diatomic nitrogen serving as the most abundant
atmospheric gas, its lack of reactivity made it hard for chemists to harness.

In 1909, German chemist Fritz Haber made scientific history when he demonstrated synthesizing
ammonia from atmospheric nitrogen and hydrogen. Later in 1911, the method was significantly
improved by another German chemist Carl Bosch, which made the reaction more efficient for
industry. As a result, when performed today, many refer to the method as the Haber-Bosch
Process. Due to the work of Haber and Bosch, ammonia can now be readily synthesized for a
variety of important purposes, such as fertilizer, explosives, refrigeration technology, and
pharmaceuticals.

The Kinetics of the Haber Process

If nitrogen gas is so inert, how did Fritz Haber manage to get it to react? To get past the un-
reactivity of nitrogen, the Haber Process involves two important factors. The first factor is an
effective catalyst.

Transition metals are almost always used to catalyze the Haber Process. Most often, industrial
chemists use magnetite, an iron oxide (Fe 3O4), with smaller amounts of potassium hydroxide
(KOH). Other common catalysts include chromium and osmium oxides. Mechanistically, the
catalyst must bind to nitrogen gas. This allows hydrogen to add across the nitrogen bonds until
the nitrogen fully saturates, yielding ammonia. Without this crucial binding of the catalyst,
nitrogen remains inert and unreactive, producing virtually no ammonia.

The second factor to get nitrogen to react relates to pressure. Specifically, higher pressures
indicate more molecular collisions, which increases the rate of reaction. As a result, industries
tend to perform the Haber Process at the highest pressures possible, often higher than 200
atmospheres.

The Equilibrium Properties of the Haber Process

As we just covered, the Haber Process is exothermic and increases spontaneity at lower
temperatures. With this information, chemists can increase the yield of the reaction by lowering
temperatures. The explanation for this phenomenon involves the principles of chemical
equilibrium. Due to exothermicity, we could say that heat serves as a “product” of the reaction.
According to L’Chatelier’s Principle, we can shift the equilibrium of a reaction mixture by
placing stress on the system. The reaction then responds in the direction to counteract the stress.
By cooling the mixture, we “remove” heat, and the system counteracts this stress by producing
more products. Thus, we get more ammonia under lower temperatures. However, if we decrease
the temperature too much, the kinetics of our reaction decrease since the molecules don’t move
as fast. To compromise, industrial chemists usually set the reaction temperature of the Haber
Process at 450-500°C.

Complete process:

One thing you may notice is that dihydrogen gas is not directly inputted into the system. Instead,
methane (1) and water (2) react to produce hydrogen within the system (3). Later, oxygen and
nitrogen gas enter the system (4), which further generates hydrogen from methane (5). In both
reactions, carbon monoxide forms as a by-product.

Further water vapor enters the system, oxidizing carbon monoxide to carbon dioxide (6). This
carbon dioxide then leaves (8), producing a mixture of nitrogen and hydrogen gas.

This gas mixture becomes compressed to more than 200atm (7) and pre-heats to ~500°C (9).
Then, the heated and pressurized mixture enters the reaction chamber, fitted with the transition
metal catalyst (10). A certain amount of ammonia is produced, which is distilled by running a
cold water jacket over the reaction mixture (11). This condenses the ammonia gas to a liquid,
which drains out of the system (13).

Importantly, on the first run, only about 15% of the nitrogen and hydrogen will have reacted. The
unreacted gas separates from the liquid ammonia (12) and enters the reaction chamber again.
Eventually, about 98% of the original gas mixture reacts to form ammonia after enough runs.

Ostwald Process for HNO3 manufacturing:

Nitric acid is produced by 2 methods. The first method utilizes oxidation, condensation, and
absorption to produce a weak nitric acid. Weak nitric acid can have concentrations ranging from
30 to 70 percent nitric acid. The second method combines dehydrating, bleaching, condensing,
and absorption to produce a high-strength nitric acid from a weak nitric acid. High-strength nitric
acid generally contains more than 90 percent nitric acid. The following text provides more
specific details for each of these processes.
1st method (Weak Nitric Acid Production):
Nearly all the nitric acid produced in the U. S. is manufactured by the high-temperature catalytic
oxidation of ammonia as shown in figure. This process typically consists of three steps:
1. ammonia oxidation,
2. nitric oxide oxidation
3. absorption
Each step corresponds to a distinct chemical reaction.
Ammonia Oxidation: First, a 1:9 ammonia/air mixture is oxidized at a temperature of 1380 to
1470oF as it passes through a catalytic convertor, according to the following reaction:
4NH3 + 5O2 4NO + 6H2O
The most commonly used catalyst is made of 90% platinum and 10% rhodium gauze constructed
from squares of fine wire. Under these conditions the oxidation of ammonia to nitric oxide (NO)
proceeds in an exothermic reaction with a range of 93 to 98% yield. Oxidation temperatures can
vary from 1380 to 1650oF. Higher catalyst temperatures increase reaction selectivity toward NO
production. Lower catalyst temperatures tend to be more selective toward less useful products:
nitrogen (N2) and nitrous oxide (N2O). Nitric oxide is considered to be a criteria pollutant and
nitrous oxide is known to be a global warming gas. The nitrogen dioxide/dimer mixture then
passes through a waste heat boiler and a platinum filter.
Nitric Oxide Oxidation: The nitric oxide formed during the ammonia oxidation must be
oxidized. The process stream is passed through a cooler/condenser and cooled to 100 OF or less at
pressures up to 116 pounds per square inch absolute (psia). The nitric oxide reacts non-
catalytically with residual oxygen to form nitrogen dioxide NO 2 and its liquid dimer, nitrogen
tetroxide:
2NO + O2 2NO2 ⇌ N2O4
This slow, homogeneous reaction is highly temperature- and pressure-dependent. Operating at
low temperatures and high pressures promotes maximum production of NO 2 within a minimum
reaction time.
Absorption: The final step introduces the nitrogen dioxide/dimer mixture into an absorption
process after being cooled. The mixture is pumped into the bottom of the absorption tower, while
liquid dinitrogen tetroxide is added at a higher point. Deionized water enters the top of the
column. Both liquids flow countercurrent to the nitrogen dioxide/dimer gas mixture. Oxidation
takes place in the free space between the trays, while absorption occurs on the trays. The
absorption trays are usually sieve or bubble cap trays. The exothermic reaction occurs as follows:
3NO2 + H2O 2HNO3 + NO
A secondary air stream is introduced into the column to re-oxidize the NO that is formed in the
above Reaction.
This secondary air also removes NO2 from the product acid. An aqueous solution of 55 to 65%
(typically) nitric acid is withdrawn from the bottom of the tower. The acid concentration can
vary from 30 to 70% nitric acid. The acid concentration depends upon the temperature, pressure,
number of absorption stages, and concentration of nitrogen oxides entering the absorber.
There are two basic types of systems used to produce weak nitric acid:
1. Single-stage pressure process: In the past, nitric acid plants have been operated at a
single pressure, ranging from atmospheric pressure 14.7 to 203 psia. However, since
Reaction 1 is favored by low pressures and Reactions 2 and 3 are favored by higher
pressures, newer plants tend to operate a dual stage pressure system.
2. Dual-stage pressure process: incorporating a compressor between the ammonia oxidizer
and the condenser. The oxidation reaction is carried out at pressures from slightly
negative to about 58 psia, and the absorption reactions are carried out at 116 to 203 psia.
In the dual-stage pressure system, the nitric acid formed in the absorber (bottoms) is
usually sent to an external bleacher where air is used to remove (bleach) any dissolved
oxides of nitrogen. The bleacher gases are then compressed and passed through the
absorber.

High-Strength Nitric Acid Production:

A high-strength nitric acid (98 to 99% concentration) can be obtained by concentrating the
weak nitric acid (30 to 70% concentration) using extractive distillation. The weak nitric acid
cannot be concentrated by simple fractional distillation. The distillation must be carried out
in the presence of a dehydrating agent. Concentrated sulfuric acid (typically 60% sulfuric
acid) is most commonly used for this purpose. The nitric acid concentration process consists
of feeding strong sulfuric acid and 55 to 65% nitric acid to the top of a packed dehydrating
column at approximately atmospheric pressure. The acid mixture flows downward,
countercurrent to ascending vapors. Concentrated nitric acid leaves the top of the column as
99% vapor, containing a small amount of NO2 and oxygen (O2) resulting from dissociation of
nitric acid. The concentrated acid vapor leaves the column and goes to a bleacher and a
countercurrent condenser system to effect the condensation of strong nitric acid and the
separation of oxygen and oxides of nitrogen (NOx) byproducts. These byproducts then flow
to an absorption column where the nitric oxide mixes with auxiliary air to form NO 2, which
is recovered as weak nitric acid. Inert and unreacted gases are vented to the atmosphere from
the top of the absorption column. Emissions from this process are relatively minor. A small
absorber can be used to recover NO2.

Emissions and Controls:

Emissions from nitric acid manufacture consist primarily of NO, NO 2 (which account for
visible emissions), trace amounts of HNO3 mist, and ammonia (NH3). By far, the major
source of nitrogen oxides (NOx) is the tail gas from the acid absorption tower. In general, the
quantity of NOx emissions is directly related to the kinetics of the nitric acid formation
reaction and absorption tower design. NOx emissions can increase when there is
1. insufficient air supply to the oxidizer and absorber,
2. low pressure, especially in the absorber,
3. high temperatures in the cooler-condenser and absorber
4. production of an excessively high-strength product acid,
5. operation at high throughput rates,
 6. faulty equipment such as compressors or pumps that lead to lower pressures and
leaks, and decrease plant efficiency.
The 2 most common techniques used to control absorption tower tail gas emissions are extended
absorption and catalytic reduction. Extended absorption reduces NO x emissions by increasing the
efficiency of the existing process absorption tower or incorporating an additional absorption
tower. An efficiency increase is achieved by increasing the number of absorber trays, operating
the absorber at higher pressures, or cooling the weak acid liquid in the absorber. The existing
tower can also be replaced with a single tower of a larger diameter and/or additional trays. See
Reference 5 for the relevant equations.
3. FORMIC ACID
Formic acid (HCOOH) is a colorless liquid with a pungent odor, which is completely miscible
with water and many polar solvents but only partially miscible with hydrocarbons. Formic acid
derived its name from the red ant, Formica rufa, in which it was discovered around 1670. Formic
acid has been detected in the poison or defense systems of ants, bees, and other insects.
Formic acid is used primarily in dyeing, in the textile and leather industries; in rubber
production; and as an intermediate in the chemical and pharmaceutical industries. The use of
formic acid as an aid in the ensilage of green forage has increased sharply. The worldwide
production of formic acid is about 260000 t/a in 1987 and 390000 t/a in 1995. Formic acid is
produced by hydrolysis of methyl formate or formamide or from its salts. In addition, formic
acid is a byproduct of acetic acid production by liquid-phase oxidation of hydrocarbons.
Formic acid is more easily ionized than acetic acid. Therefore, formic acid is expected to be
more corrosive than acetic acid. Indeed, formic acid attacks many common metals and alloys.
Steel corrodes rapidly in this acid at all concentrations, even at ambient temperatures. Stainless
alloys have some serious limitations. Nickel-based alloys may corrode at high rates in the acid
with the presence of certain impurities like halides and under heat-transfer conditions. Titanium
and its alloys are not consistent due to factors such as aeration and water content. Compared to
the mentioned alloys, zirconium is versatile and corrosion resistant in most formic acid solutions.
Zirconium has played a key role in the commercialization of the Leonard–Kemira process.
In the industrial manufacturing of formic acid by following Leonard–Kemira process, methanol
is used as a raw material. It is produced by using syngas by following Lurgi process.
Production of raw material (Methanol):

Commercially, methanol is produced from coal or natural gas via synthesis gas (syngas), mainly
containing carbon monoxide and hydrogen along with a small amount of carbon dioxide.
Processes have been developed by Lurgi, ICI, Topsoe and MGG among others during the last
century. Synthesis gas is a key intermediate in the chemical industry.

Synthesis gas is a mixture of hydrogen and carbon monoxide. It can be used in a number of
syntheses of a wide range of fuels and chemicals, and as a source of pure carbon monoxide and
hydrogen. It can be produced by gasification or reforming from almost any carbon-containing
source ranging from natural gas and oil products to biomass and coal. At present, natural gas is
the dominant feedstock for the production of synthesis gas. From industrial and environmental
perspective, there is a growing interest in utilizing alternative raw materials.

Commercially, methanol is produced from coal or natural gas via synthesis gas (syngas), mainly
containing carbon monoxide and hydrogen along with a small amount of carbon dioxide.
Processes have been developed by Lurgi, ISI, Topsoe and MGG among others during the last
century. The potential use of most important greenhouse gas, CO 2, as an alternative feedstock
replacing CO in the methanol production has received attention as an effective way of CO 2
utilization. Currently, more than 75 % of methanol is produced from natural gas. The methanol
production is based on three steps of natural gas reforming in order to produce synthesis gas,
conversion of synthesis gas into crude methanol and distillation of crude methanol to achieve the
desired purity. BASF started synthetic methanol production with zinc-chromium oxide catalyst
in 1923. The activity of this catalyst required high pressure 250 – 350 bar and temperatures
between 320 – 450°C. This high pressure process suffered from high capital and compression
energy cost and poor catalyst selectivity. ICI developed in 1960s a more active copper – zinc –
alumina catalyst that operates at 50 – 100 bar and 210 – 270 °C with higher stability and
selectivity.

Currently, several companies, including ICI, Mitsubishi and Lurgi, offer commercial technology
solution for methanol synthesis. There is an argument about many important factors related to
kinetics, catalyst and the reaction mechanism of the commercial methanol synthesis reaction.
The main question is whether CO or CO2 is the main source for methanol. Commercially,
methanol is produced from syngas mainly containing H2 and CO along with a small amount of
CO2, which have been developed by ICI, Lurgi, MGC and Topsoe in the last century. The
CuO/ZnO/Al2O3 catalyst has long been used in industrial methanol synthesis because of its high
catalytic activity, high poison resistance, long durability and relatively low reaction pressure and
temperature of 50 – 100 bar and 200 – 250°C.

High pressure process

Methanol synthesis process is generally categorized in two classification according to the

pressure used. The process developed by BASF is known as the high pressure process which
operated at 250 – 300 bar and 320 – 450°C with relatively poison resistant ZnO/Cr 2O3 catalyst.
The disadvantages of high pressure process are related to the significant investment in the plant
design and operating costs.
Low Pressure process:
Currently, the only process which is used in a methanol market is low pressure process which
operated at about 50 – 100 bar and 200 - 300°C. The current catalyst used in low pressure
processes are composed of copper oxide and zinc oxide on a carrier of aluminium oxide.
Currently, the two important technology providers for the low pressure methanol processes are
Lurgi and ICI. Lurgi offers a methanol synthesis concept based on the quasi-isothermal reactor
design in which the mechanism of temperature control is achieved via boiling water-stream
generation inside the reactor’s shell. ICI offers a methanol synthesis reactor concept that is based
on the adiabatic quench converter design in which a portion of the fresh and recycled synthesis
gas is injected along the bed to control the reaction. The main advantages of the low pressure
process are lower investement and production costs, greater flexibility in the choice of plant size,
and improved operational reliability.

The methanol synthesis loop with Lurgi reactor:

Industrial methanol production can be subdivided into three main steps which include production
of synthesis gas, synthesis of methanol and processing of crude methanol. Many improvements
have been made to early methanol processes, and now the current technology is a low-pressure
process using copper-based catalyst. The synthesis gas needed as a feedstock is usually produced
by catalytic steam reforming of hydrocarbon feedstock or by non-catalytic partial oxidation of
coal or hydrocarbons. Carbon dioxide is used in the feedstock to adjust the feed compositions.
The methanol synthesis from synthesis gas containing carbon monoxide and carbon dioxide can
be described by the reactions 1 and 2. The reaction 1 is the main reaction and the reaction 2
occurs as a side reaction.
CO + 2H2 CH3OH (1)
CO2 + 3H2 CH3OH + H2O (2)
Reactions 1 and 2 are exothermic and accompanied by a decrease in volume. Formation of
methanol is thus favored by decreasing temperature and increasing reaction pressure.
Fresh synthesis gas is compressed and mixed with the un-reacted, recycled synthesis gas comes
from the reactor effluent. This stream is sent to the methanol synthesis reactor to be reacted to
produce methanol. Three reactions CO 2 hydrogenation, CO hydrogenation and reverse water-gas
shift reactions are responsible for the methanol synthesis inside the reactor. Lurgi fixed-bed
reactor is operated at low pressure region with copper and zinc oxide catalyst on an alumina
carrier (Cu/ZnO/Al2O3).The heat from the methanol synthesis reactions is transferred to the
boiling water where steam will be generated. Typical operation conditions are 250°C and 80 bar.
The product from the reactor effluent is cooled and fed to a flash drum where the un-reacted
synthesis gas and crude methanol are separated. The crude methanol is then sent to the methanol
distillation section for further purification. The un-reacted synthesis gas is compressed, recycled
and mixed with the fresh synthesis gas before introduced back to the reactor. To avoid the
thermodynamic limitation and low single-pass conversion, the synthesis loop is usually operated
with high synthesis gas recycle rate.
Kemira-Leonard Process:
A 20,000 ton per year formic acid plant based on a method developed by the Leonard Process
Co. was built at Kemira in Finland and put into operation in 1982. The plant was built at Kemira
in Finland and it started operation in 1982. The process has been developed further by Kemira. In
the Kemira-Leonard process methyl formate and carbonylation is performed at approximately 40
bar and temperature of about 80 °C with additive-containing alkoxides as a catalyst. Hydrolysis
is carried out in two reactors with different reaction conditions. Hydrolysis is carried out at the
reaction conditions about 9 bar and 120 °C. The formic acid is dehydrated by distillation.
Methanol and carbon monoxide are converted into methyl formate in reactor (a).
CO + H2 CH3COOH
Catalyst is fed into reactor in a methanol solution. The discharge from reactor (a) is flashed and
fed into the methyl formate column (b) from which methyl formate is drawn off as the distillate.
Dissolved catalyst and methanol are returned to the reactor (a). Waste gas from reactor (a) and
exhaust gas from column (b) are burned. In the preliminary reactor (c) the methyl formate reacts
partially with water and discharge from reactor (c) is fed into the main reactor (d) along with
recycled methyl formate, water and methanol. Reactor discharge is flashed to about atmospheric
pressure in the flash tank (e), where methanol, methyl formate and small amount of formic acid
are evaporated and recycled to the main reactor. Methanol and methyl formate are distilled in
vacuum in the acid separation column (g). In the recycle column (f) the distillate is separated into
methyl formate and methanol. Formic acid can be concentrated under pressure in a column; 85 %
formic acid is drawn off as the bottom product if the pressure is about 3 bar. In the first product
column (h) water is distilled overhead and the bottom product is concentrated further in the
second product column (i) and formic acid with a maximum concentration of about 98 wt % is
drawn off as distillate. The bottom product from the second product column is recycled to the
first product column. The problems associated with metyl formate hydrolysis are unfavourable
hydrolysis equilibrium and because methyl formate is a highly volatile chemical. These problems
are eliminates in Kemira-Leonard process using two reactors placed in series to each other after
which a flash distillation is carried out in order to takeaway very quickly unconverted ester and
distillation. Other processes which use methyl formate hydrolysis to the synthesis of formic acid
are BASF Process, USSR Process and Scientific Design – Bethlehem Steel Process. In the BASF
Process carbonylation stage is quite much identical to that of Kemira – Leonard Process, but the
hydrolysis and the dehydration of formic acid are significantly different. In the BASF process,
hydrolysis is carried out with an excess of water.

3. OXALIC ACID

Oxalic acid, or ethanedioic acid, is a colorless crystalline compound with the chemical formula
(COOH)₂. Due to its two carboxylic acid functional groups, it belongs to the family of organic
acids and is classified as a dicarboxylic acid. Oxalic acid is highly soluble in water and has a
sour taste. It is naturally found in various plants, such as spinach, rhubarb, and sorrel, as well as
in some vegetables, fruits, and nuts. As a relatively strong organic acid, oxalic acid acts as a
cleaning and bleaching agent, pharmaceutical intermediate, and a vital component in the leather,
tanning, and rare earth industries. Its chelating ability, derived from its chemical structure, is
particularly noteworthy as it enables it to bind with metal ions, thereby facilitating processes
such as rust removal and the extraction of rare earth elements. It also work as a strong reducing
agent.

Oxalic acid was discovered by Scheele in 1776. He prepared oxalic acid by the oxidation of
sugar by using nitric acid
Production Processes and Raw Materials
There are many industrial processes for the production of oxalic acid, which have been carried
out by a large number of companies and are in part still used today. In recent years both the
number of firms producing oxalic acid and the number of starting materials used for its
production have been reduced. Generally, only three classes of compounds are employed as raw
materials for the production of oxalic acid. These are:
 carbohydrates (including ethylene glycol and molasses)
 olefins (The scope and limitations of this process are restricted by safety problems
because the nitrates of α-hydroxy-carboxylic acids that are formed as intermediates from
α-olefins and NO2 are unstable and lead to uncontrollable decomposition and violent
explosions.
 carbon monoxide
Nevertheless, three out dated methods, which have been abandoned in important industrial
nations for economic reasons, are described briefly, because in the third world small firms might
exist that still employ these production methods:
1) The sodium formate method, which is also based on carbon monoxide as the raw
material, but involves very cumbersome procedures of questionable technical safety that
are no longer economically feasible (heating to 400 ◦C, elimination of hydrogen, calcium
precipitation, and precipitation with sulfuric acid). Nevertheless, this process is probably
still being used in China.
2) The alkali fusion of cellulose, which is the oldest production method. Although cellulose-
containing material from every source can be used in this method, this process has been
discontinued because of the low yields, large amounts of required alkali and sulfuric acid,
and the large amounts of wastewater.
3) The isolation of oxalic acid as a byproduct of carbohydrate fermentation, for example, in
the synthesis of citric acid. The process involves the biotechnical exploitation of the
tricarboxylic acid cycle through enzymatic cleavage of sugars. The intermediary formed
oxalacetic acid esters and oxalosuccinic acid (1-oxopropane-1,2,3-tricarboxylic acid)
esters are cleaved by hydrolases. Especially because of the handling of large amounts of
water, this process is no longer economically feasible.
Production of oxalic acid by Oxidation of Carbohydrates:
This method, the oldest of chemical productions, was in principal discovered by Scheele more
than 200 years ago (1776). He oxidized sugar with concentrated nitric acid to oxalic acid.
However, it was not until ca. 1940 that this process gained industrial importance when the
nitrogen oxides produced in the reaction could be recovered and recycled. In Germany, I.G.
Farben produced 2000t of oxalic acid per year by this method until 1944. This process is
employed in Brazil, China, and in several Eastern European countries. Raw materials employed
in this process include sugar, glucose, fructose, corn starch, wheat starch, reclaimed starch,
potato starch, corncobs, tapioca, and molasses. Choice of starting material depends on
availability and price and on optimization of the reaction process involved. Molasses and other
agricultural waste have gained increasing importance as raw materials. These materials are not
only inexpensive, but must be further processed in any case due to environmental reasons.
Molasses contains, as a production residue of sugar refinement, many nitrogen-containing
compounds, which are, however, for the most part removed during the nitric acid oxidation. This
explains the difficulties encountered with excessive foam formation during production that must
be overcome. If starch products are used as raw materials they must be hydrolyzed to glucose in
an extra batch wise step prior to the actual oxidation. This is carried out by boiling the starch
suspension in the presence of oxalic acid or sulfuric acid for about six hours.
Allied Chemical Process:
The Allied Chemical process is schematically presented in Figure. The concentration of the
glucose solution obtained by hydrolysis of starch is approximately 50–60wt%. This material,
along with the recycled supernatent from the crude centrifugation, is placed in a reactor with ca.
50% sulfuric acid, vanadium pentoxide (0.001 – 0.05wt%) and iron (III) sulfate (0.39– 0.8wt%),
based on the total mass of the mixture. Nitric acid (65%) is then added slowly under vigorous
stirring in a tightly controlled temperature range around 70 ◦C the temperature range differs
according to the raw material being used.

The strongly exothermic reaction must be well cooled. Air is simultaneously blown into the
reactor to support the reaction and to remove NO and other nitrogen oxides of low oxidation
number. The nitrogen oxides expelled are collected in an adsorption system and are recycled
after oxidation. Crude oxalic acid is obtained after cooling and centrifugation of the reaction
mixture. The crude acid is again dissolved in hot water, put through a grease separator and
recrystallized. After a second centrifugation and drying, oxalic acid di-hydrate is obtained with a
purity >99%. Precise control of the reaction parameters is critical for a good yield. For good
quality raw materials ca. 65% of the theoretical yield is obtained. The absent ca. 35% of the yield
mainly results from losses through CO2 formation. This process is employed today in Spain,
Brazil, The People’s Republic of China, Taiwan, Korea, and India.
Uses and Applications of Oxalic Acid in Industry

Cleaning and Household Products: Oxalic acid is used as a cleaning agent to remove rust and
mineral stains. It is commonly found in rust removers, stain removers, and wood cleaning
products. Oxalic acid can effectively remove rust from metals, clean mineral deposits, and
brighten wood surfaces. Oxalic acid’s utility in rust removal agents is attributed to its ability to
form a stable and water-soluble salt with ferric iron, known as ferrioxalate ion. When oxalic acid
comes into contact with rust, it reacts with the rust’s ferric iron oxide (Fe₂O₃), converting it into
a soluble compound.

Tooth Whitening Products: Oxalic acid is sometimes used as an ingredient in tooth-whitening

products. Oxalic acid’s bleaching properties effectively remove stains and discoloration from
teeth surfaces. In tooth whitening products, oxalic acid is typically used in low concentrations
and combination with other ingredients. It helps break down and dissolve surface stains on the
teeth, resulting in a brighter and whiter appearance.

Descaling Agent in Boilers: Oxalic acid is a descaling agent to remove calcium and magnesium
deposits from boilers and other equipment. These deposits, called lime scale or scale, can
accumulate over time and reduce equipment efficiencies like boilers, heat exchangers, and pipes.
Oxalic acid’s ability to dissolve and chelate calcium and magnesium ions effectively remove
these mineral deposits. When oxalic acid comes into contact with lime scale, it reacts with the
calcium and magnesium ions, forming soluble complexes easily rinsed away.

Mordant in Dyeing: Oxalic acid can be used as a mordant in dyeing processes. A mordant is a
substance that helps fix dyes onto fabrics, improving color fastness and enhancing the bonding
between the dye and the fibers. It helps create a chemical bond between the dye molecules and
the fibers, promoting better adhesion and color retention.

Wood Bleaching: Oxalic acid is commonly used as a wood bleach to remove stains,
discoloration, and dark spots from wood surfaces. It is particularly effective in lightening the
color of tannin-based stains, water stains, and rust stains on wood. Oxalic acid is typically used
in its crystalline form, which is then mixed with water to create a solution of the desired
concentration for wood bleaching. The solution is applied to the wood surface, and the oxalic
acid works by breaking down and removing the pigments responsible for the discoloration.

Semiconductor Industry: Oxalic acid is used in the electronic and semiconductor industries,
particularly in the fabrication process of semiconductor devices. One of its applications is in
copper layers’ electrochemical-mechanical planarization (ECMP). ECMP is a crucial step in
the manufacturing process of integrated circuits and semiconductor devices. It involves removing
excess copper and planarizing the copper surface to ensure uniformity and smoothness. Oxalic
acid is used as a complexing agent in the slurry during the ECMP process.
Paper & Pulp Industry: In the pulp and paper industry, oxalic acid is used in the bleaching
process to brighten and whiten paper products. It helps to remove lignin and other impurities
from the pulp, resulting in a higher-quality and more visually appealing paper. Oxalic acid is
often combined with other bleaching agents and processes, such as chlorine dioxide or hydrogen
peroxide, to achieve the desired bleaching effect.

Textile Industry: Oxalic acid is a bleaching agent for fabrics and fibers in the textile industry. It
helps to remove natural colorants, stains, and impurities from the textile materials, resulting in a
lighter and brighter appearance. Oxalic acid is beneficial for bleaching natural fibers such as
cotton, linen, and silk.
Caustic soda
Caustic soda is the most typical of the strong alkalis. Although there is no danger of it exploding
or igniting, it reacts with various acids, such as hydrochloric acid, and is neutralized and
generates considerable exothermic heat of neutralization. It corrodes metals, such as aluminum,
tin, and zinc. During this process, it generates hydrogen, which has the potential to behave as an
explosive gas. It is highly hygroscopic, and absorbs the moisture, carbon dioxide, or sulfur
dioxide in the air. It is also highly deliquescent and absorbs moisture to form an aqueous
solution. When liquid caustic soda is diluted, it generates a considerable amount of heat of
dilution. Since this rapidly generates strong heat and the resulting solution may spatter if the
water is carelessly poured into it, care must be taken. Caustic soda easily decomposes animal
fibers. Although plant fibers are also decomposed, they have a higher resistance than animal
fibers. Although materials resistant to corrosion by caustic soda include stainless steel, steel-
epoxy resins, and fiber-reinforced plastics, steel and rubber-lined steel are the most frequently
used.

Raw material for manufacturing of caustic soda:

Brine is the primary raw material necessary to make chlorine and caustic soda using a chlor-
alkali process discovered more than 200 years ago. About 90% of the companies’ brine is used in
chlor-alkali production. This brine is supplied by pipeline directly from the producing salt
domes. The remainder is used in a wide range of essential U.S. industries, including refineries,
power plants, aquariums, oils field services and hospital systems. This brine is supplied by truck
and barge.

Depending on the customer’s needs, there are three types of brine supply: raw brine, treated
brine and evaporated salt. Brine has been produced commercially using the solution mining
process for more than 100 years. After a well is drilled into the salt dome, fresh water is pumped
down the well. This water dissolves the underground salt until it becomes a fully saturated brine
solution, which is collected at the surface.
Sodium Hydroxide Solutions are produced by three different technologies:

 Mercury cells
 Membrane cells
 Diaphragm cells

Mercury Cell

In the Mercury Cell Process saturated brine voyages down a steel trough roughly 15 meters in
length and one meter wide between a streaming film of mercury (the cathode) and titanium
plates (the anodes). Direct current is connected between the anode and cathode. Chlorine freed at
the anodes gathers above the brine and is begun as a hot, wet and corrosive gas.
Sodium ions are released at the surface of the streaming mercury cathode, forming an amalgam
of low concentration with the mercury, which streams out of the cell without reacting with the
water or chlorine. The mercury cell thus has two products 1. Hot, wet chlorine 2. Sodium
amalgam.

The soda cell or decomposer is a cylindrical steel trough loaded with graphite balls or graphite
electrodes. The sodium amalgam is passed, along with pure water, into the decomposer, where it
reacts to transform Sodium hydroxide as a controlled 50 percent aqueous solution and hydrogen
gas, liberating fee mercury, which is reused again to the electrolytic cell. The graphite provides a
surface that expedites this reaction. The following two types of reactions called brine cell and the
soda cell respectively.

Brine Cell
2Cl Cl2 + e

Na + e Na

Na + Hg Na/Hg

Soda Cell
2 Na/Hg + 2 H2O 2NaOH + H2 + 2Hg

This method produces 71 percent of Sodium hydroxide.

Diaphragm Cell

Diaphragm Cell process utilizes asbestos or alternate substitutes to asbestos, to separate the co-
products Sodium Hydroxide (Caustic Soda) and Chlorine. The production of 50 percent NaOH
occurs primarily outside of the electrolytic cell. The diaphragm cell produces a very weak ‘cell
liquor,’ that contains 12-14 percent, by weight, NaOH and the constant volume of NaCl salt. The
cell liquor is subsequently evaporated in a three or four ‘effect’ evaporation method to a final
nominal concentration of 50 percent NaOH by weight. The surplus salt is precipitated and
filtered through the evaporation method for subsequent reuse/recycle. This method produces the
lowest quality electrochemical NaOH solutions.

The quality considerations with respect to the diaphragm cell produced Caustic solutions include
comparatively high salt, chlorates, carbonates, and sulfates. Salt, as NaCl, concentrations are
typically 1.0 percent, with maximums ranging from 1.1 to 1.3 weight percent, counting on the
producer.

The diaphragm cell created Caustic Soda (NaOH) is usually referred as Diaphragm Cell Grade. It
is conjointly known as Commercial Grade, Technical Grade, and occasionally Technical
Diaphragm or other similar combinations.
An additional ‘grade’ of Caustic Soda (NaOH) produced by the diaphragm cell method is the
sublimate grade. The production of sublimate Grade involves the further evaporation of the 50
percent Diaphragm Grade NaOH solution to cut back the salt concentration. The higher
concentration solution is then re-diluted to the 50% concentration that is commercially available
as sublimate grade Caustic Soda.
Common uses include process and sewer water neutralization, textiles production, soaps and
detergents, and aluminum production. These uses and applications typically can confer with the
Caustic Soda as any of the varied grades.
Membrane Cell
This method produces approximately 13 percent of Sodium Hydroxide. The membrane cell
method utilizes a selective membrane that separates the Chlorine and Sodium ions. The
membrane permits the Sodium ion to migrate across the membrane whereas keeping the
Chlorine gas and salt (brine) solution in a compartment on the opposite facet of the membrane.
The Sodium ion is reacted with refined water as within the mercury cell to provide the Caustic
Soda (NaOH). Evaporation is employed, as within the diaphragm method, to lift the
concentration up to the nominal 50 weight percent solution. The salt concentrations are not
targeted as considerably during this evaporation method attributable to the selective diffusion
nature of the membranes as well as the reduced quantity of evaporation needed during this
method as opposed to the diaphragm evaporation. The Caustic Soda produced by the membrane
cell process is most typically brought up as Membrane Grade. It conjointly contains a growing
acceptance as a Rayon Grade product in all areas outside of rayon fiber production.
Washing Soda
Washing soda is indeed a white powder with no odour. It is also called sodium carbonate and has
the chemical formula Na2CO3. It collects moisture from the air because it is hygroscopic. It has a
high water solubility and produces a powerful alkaline water solution. The washing soda is made
using Solvay’s technique, which involves the combination of sodium chloride, CO 2, and
ammonium in water. The carbon dioxide is produced by the calcium carbonate, as well as the
calcium oxide is utilised to separate ammonia from ammonium chloride. The following are some
uses of washing soda:
 For eliminating burnt-on oil from kitchen equipment, by using washing soda.
 It’s popular in the soap, glass, and paper industries.
 It also aids in the elimination of the water’s persistent hardness.
Raw material used for manufacturing of washing soda are NH3 (Haber’s process), NaCl (Brine
solution by solution mining) and CaCO3 (by mining of minerals).

Raw material (Calcium Carbonate) Manufacturing Process:

Natural mineral sources are necessary to make commercially usable calcium carbonate.
Manufacturing processes are used to improve specific properties and reduce the size of particles
within the material. Calcium carbonate is mined from open pits or underground, then drilled,
blasted, and crushed. After this, the crushed stone is sized and washed, removing much of the
colored impurities within the material.

From there, calcium carbonate goes through either dry or wet processing. The wet process
involves a chemical synthesis that uses carbon dioxide, with wet processing often following dry
processing to increase purity. This method also works in reverse, as when calcium carbonate
reacts with acids, it produces carbon dioxide. This enables geologists to reliably test a mineral to
determine whether it contains calcium carbonate.
The Step-By-Step Manufacturing Process

 Raw Material Preparation: The first stage in the manufacturing process of calcium
carbonate involves the preparation of raw materials. The primary raw material used is
limestone, which is a sedimentary rock composed mainly of calcium carbonate. Limestone
is usually obtained from quarries or mines. It is then crushed and screened to obtain the
desired particle size. The quality and characteristics of the limestone used can have an
impact on the properties of the final calcium carbonate product.
 Calcination: The next step in the manufacturing process is calcination. Calcination refers to
the heating of the crushed limestone at high temperatures to convert it into lime (calcium
oxide) and carbon dioxide. This process is carried out in a kiln, which can be a vertical shaft
kiln or a rotary kiln. The limestone is heated to a temperature of around 900-1000°C,
causing the calcium carbonate to decompose and release carbon dioxide. The resulting
product is quicklime or burnt lime.
 Hydration: After calcination, the quicklime obtained is hydrated to produce slaked lime
(calcium hydroxide). Hydration is achieved by adding water to the quicklime in a process
called slaking. The reaction between quicklime and water is highly exothermic, releasing a
large amount of heat. The slaked lime produced can be in the form of a fine powder or a
suspension in water, depending on the desired application.
 Carbonation: The slaked lime is then subjected to carbonation, where it reacts with carbon
dioxide to form calcium carbonate. This process is known as precipitation or carbonation.
Carbon dioxide can be obtained from various sources, such as industrial flue gases, the
atmosphere, or by burning fossil fuels. The reaction between calcium hydroxide and carbon
dioxide is as follows:
Ca(OH)2 + CO2 → CaCO3 + H2O
The carbonation reaction can be carried out in different types of reactors, such as a batch reactor
or continuous stirred-tank reactor (CSTR). The reaction is typically carried out under controlled
conditions of temperature, pressure, and pH to optimize the precipitation of fine calcium
carbonate particles.

 Separation and Drying: After the carbonation process, the calcium carbonate precipitate
needs to be separated from the liquid phase. This can be done through various methods,
such as filtration, centrifugation, or sedimentation, depending on the desired particle size
and purity. The separated calcium carbonate is then washed to remove any impurities or
residual chemicals. Once separated, the calcium carbonate is dried to remove the moisture
and obtain a free-flowing powder. The drying process can be achieved through various
methods, such as air drying, spray drying, or using rotary dryers. Drying is crucial to ensure
the stability and usability of the final product.
Leblanc process:
In the first step, sodium chloride is treated with sulfuric acid in the Mannheim process. This
reaction produces sodium sulfate (called the salt cake) and hydrogen chloride:

2 NaCl + H2SO4 → Na2SO4 + 2 HCl

This chemical reaction had been discovered in 1772 by the Swedish chemist Carl Wilhelm
Scheele. Leblanc's contribution was the second step, in which a mixture of the salt cake and
crushed limestone (calcium carbonate) was reduced by heating with coal. This conversion entails
two parts. First is the carbo-thermic reaction whereby the coal, a source
of carbon, reduces the sulfate to sulfide:

Na2SO4 + 2C → Na2S + 2CO2

In the second stage, is the reaction to produce sodium carbonate and calcium sulfide. This
mixture is called black ash.

Na2S + CaCO3 → Na2CO3 + CaS

The soda ash is extracted from the black ash with water. Evaporation of this extract yields solid
sodium carbonate. This extraction process was termed lixiviation. In response to the Alkali Act,
the noxious calcium sulfide was converted into calcium carbonate:

CaS(s) + CO2(g) + H2O(l) → CaCO3(s) + H2S(g)

The hydrogen sulfide can be used as a sulfur source for the lead chamber process to produce
the sulfuric acid used in the first step of the Leblanc process. The Leblanc process plants were
quite damaging to the local environment. The process of generating salt cake from salt and
sulfuric acid released hydrochloric acid gas, and because this acid was industrially useless in the
early 19th century, it was simply vented into the atmosphere. Also, an insoluble smelly solid
waste was produced. For every 8 tons of soda ash, the process produced 5.5 tons of hydrogen
chloride and 7 tons of calcium sulfide waste. This solid waste had no economic value, and was
piled in heaps and spread on fields near the soda works, where it weathered to release hydrogen
sulfide, the toxic gas responsible for the odor of rotten eggs.

Solvay process:
This process uses sodium chloride to provide the sodium ions and calcium carbonate for the
carbonate ions in sodium carbonate. Salt and limestone are cheap and plentiful raw materials.
Salt is found in underground deposits in Cheshire. It is extracted by solution mining as brine
which is pumped to the Northwich site and treated to precipitate out calcium and magnesium
ions. The calcium carbonate is quarried as limestone near Buxton in Derbyshire and arrives on
site by rail. At first sight, the reaction below seems to be the obvious way to prepare sodium
carbonate from sodium chloride and calcium carbonate.

2NaCl(aq) + CaCO3(s) Na2CO3(aq) + CaCI2(aq)

Unfortunately salt and limestone do not react together. In fact the reverse reaction actually takes
place between calcium chloride and sodium carbonate to give the original starting materials, so
an indirect route must be found. Furthermore, the overall reaction is endothermic and so a
significant energy input is required. This is provided by burning coke which thus becomes the
third raw material. This is transported to the site by road.
The key reaction is that between sodium chloride solution and carbon dioxide in the presence of
ammonia. This is a reversible reaction forming ammonium chloride and sodium bicarbonate. It
occurs in 25 metre high Solvay towers.
 NaCl(aq) + NH3(aq) + H2O(I) + CO2(g) NH4Cl(aq) + NaHCO3(s)
Energy is provided by burning coke, and the heat generated is used to decompose the calcium
carbonate to provide carbon dioxide for the process.
CaCO3(s) CaO(s) + CO2(g)
Returning to the key reaction.
NaCl(aq) + NH3(aq) + H2O(I) + CO2(g) NH4Cl(aq) + NaHCO3(s)
At low temperatures the sodium bicarbonate is much less soluble than ammonium chloride and
crystallises out. This moves the equilibrium in the Solvay tower reaction to the right. The sodium
hydrogencarbonate is filtered out and heated to form sodium carbonate.
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
The calcium oxide from the decomposition of the limestone is slaked with water to form calcium
hydroxide.
CaO(s) + H2O(I) Ca(OH)2(s)
The calcium hydroxide is used to regenerate the ammonia.
Ca(OH)2(s) + 2NH4Cl(aq) CaCl2(aq) + 2NH3(aq) + 2H2O(I)
The overall process is shown in a simplified form in Figure 1 and more pictorially in Figure 2. It
operates as two cycles, an ammonia cycle and a carbon dioxide cycle. In theory, no ammonia is
used up; it is all recycled. In practice, a little is required to make up losses.
 CEMENT INDUSTRY

Introduction:
The cement-making process, from crushing and grinding of raw materials, through roasting of
the ground and mixed ingredients, to final cooling and storing of the finished product. Cement, in
general, adhesive substances of all kinds, but, in a narrower sense, the binding materials used in
building and civil engineering construction. Cements of this kind are finely ground powders that,
when mixed with water, set to a hard mass. Setting and hardening result from hydration, which is
a chemical combination of the cement compounds with water that yields submicroscopic crystals
or a gel-like material with a high surface area. Because of their hydrating properties,
constructional cements, which will even set and harden under water, are often called hydraulic
cements. The most important of these is portland cement.

Applications of cement:
Cements may be used alone (i.e., “neat,” as grouting materials), but the normal use is in mortar
and concrete in which the cement is mixed with inert material known as aggregate. Mortar is
cement mixed with sand or crushed stone that must be less than approximately 5 mm (0.2 inch)
in size. Concrete is a mixture of cement, sand or other fine aggregate, and a coarse aggregate that
for most purposes is up to 19 to 25 mm (0.75 to 1 inch) in size, but the coarse aggregate may also
be as large as 150 mm (6 inches) when concrete is placed in large masses such as dams. Mortars
are used for binding bricks, blocks, and stone in walls or as surface renderings. Concrete is used
for a large variety of constructional purposes. Mixtures of soil and portland cement are used as a
base for roads. Portland cement also is used in the manufacture of bricks, tiles, shingles, pipes,
beams, railroad ties, and various extruded products. The products are prefabricated in factories
and supplied ready for installation.

The manufacture of cement is extremely widespread, as concrete is the most widely used of all
construction materials in the world today.

Raw materials:
1. Composition:

Portland cement consists essentially of compounds of lime (calcium oxide, CaO) mixed with
silica (silicon dioxide, SiO2) and alumina (aluminum oxide, Al2O3). The lime is obtained from a
calcareous (lime-containing) raw material, and the other oxides are derived from an argillaceous
(clayey) material. Additional raw materials such as silica sand, iron oxide (Fe 2O3), and bauxite
containing hydrated aluminum, Al(OH)3 may be used in smaller quantities to get the desired
composition. The commonest calcareous raw materials are limestone and chalk, but others, such
as coral or shell deposits, also are used. Clays, shales, slates, and estuarine muds are the common
argillaceous raw materials. Marl, a compact calcareous clay, and cement rock contain both the
calcareous and argillaceous components in proportions that sometimes approximate cement
compositions. Another raw material is blast-furnace slag, which consists mainly of lime, silica,
and alumina and is mixed with a calcareous material of high lime content. Kaolin, a white clay
that contains little iron oxide, is used as the argillaceous component for white portland cement.
The magnesia (magnesium oxide, MgO) content of raw materials must be low because the
permissible limit in portland cement is 4 to 5%. Other impurities in raw materials that must be
strictly limited are fluorine compounds, phosphates, metal oxides and sulfides, and excessive
alkalies.

Another essential raw material is gypsum, some 5% of which is added to the burned cement
clinker during grinding to control the setting time of the cement. Portland cement also can be
made in a combined process with sulfuric acid using calcium sulfate or anhydrite in place of
calcium carbonate. The sulfur dioxide produced in the flue gases on burning is converted to
sulfuric acid by normal processes.

2. Extraction and processing

Raw materials employed in the manufacture of cement are extracted by quarrying in the case of
hard rocks such as limestones, slates, and some shales, with the aid of blasting when necessary.
Some deposits are mined by underground methods. Softer rocks such as chalk and clay can be
dug directly by excavators.

The excavated materials are transported to the crushing plant by trucks, railway, conveyor belts,
or ropeways. They also can be transported in a wet state or slurry by pipeline. In regions where
limestones of sufficiently high lime content are not available, some process of beneficiation can
be used. Froth flotation will remove excess silica or alumina and so upgrade the limestone, but it
is a costly process and is used only when unavoidable.

Manufacturing of cement
There are four stages in the manufacture of portland cement:

1. crushing and grinding the raw materials,

2. blending the materials in the correct proportions,

3. burning the prepared mix in a kiln, and

4. grinding the burned product,

known as “clinker,” together with some 5% of gypsum (to control the time of set of the cement).
The three processes of manufacture are known as the wet, dry, and semidry processes and are so
termed when the raw materials are ground wet and fed to the kiln as a slurry, ground dry and fed
as a dry powder, or ground dry and then moistened to form nodules that are fed to the kiln.

It is estimated that around 4–8% of the world’s carbon dioxide (CO 2) emissions come from the
manufacture of cement, making it a major contributor to global warming. Some of the solutions
to these greenhouse gas emissions are common to other sectors, such as increasing the energy
efficiency of cement plants, replacing fossil fuels with renewable energy, and capturing and
storing the CO2 that is emitted.
 1. Crushing and grinding

All except soft materials are first crushed, often in two stages, and then ground, usually in a
rotating, cylindrical ball, or tube mills containing a charge of steel grinding balls. This grinding
is done wet or dry, depending on the process in use, but for dry grinding the raw materials first
may need to be dried in cylindrical, rotary dryers. Soft materials are broken down by vigorous
stirring with water in wash mills, producing a fine slurry, which is passed through screens to
remove oversize particles.

2. Blending

In the dry process these mixes are stored in silos; slurry tanks are used in the wet process.
Thorough mixing of the dry materials in the silos is ensured by agitation and vigorous circulation
induced by compressed air. In the wet process the slurry tanks are stirred by mechanical means
or compressed air or both. The slurry, which contains 35-45% water, is sometimes filtered,
reducing the water content to 20-30%, and the filter cake is then fed to the kiln. This reduces the
fuel consumption for burning.
 3. Burning

The earliest kilns in which cement was burned in batches were bottle kilns, followed by chamber
kilns and then by continuous shaft kilns. The shaft kiln in a modernized form is still used in some
countries, but the dominant means of burning is the rotary kiln. These kilns up to 200m (660
feet) long and 6m in diameter in wet process plants but shorter for the dry process consist of a
steel, cylindrical shell lined with refractory materials. They rotate slowly on an axis that is
inclined a few degrees to the horizontal. The raw material feed, introduced at the upper end,
moves slowly down the kiln to the lower, or firing, end. The fuel for firing may be pulverized
coal, oil, or natural gas injected through a pipe. The temperature at the firing end ranges from
about 1,350-1,550°C, depending on the raw materials being burned. Some form of heat
exchanger is commonly incorporated at the back end of the kiln to increase heat transfer to the
incoming raw materials and so reduce the heat lost in the waste gases. The burned product
emerges from the kiln as small nodules of clinker. These pass into coolers, where the heat is
transferred to incoming air and the product cooled. The clinker may be immediately ground to
cement or stored in stockpiles for later use.

4. Grinding

The clinker and the required amount of gypsum are ground to a fine powder in horizontal mills
similar to those used for grinding the raw materials. The material may pass straight through the
mill (open-circuit grinding), or coarser material may be separated from the ground product and
returned to the mill for further grinding (closed circuit grinding). Sometimes a small amount of a
grinding aid is added to the feed material. For air-entraining cements (discussed in the following
section) the addition of an air-entraining agent is similarly made. Finished cement is pumped
pneumatically to storage silos from which it is drawn for packing in paper bags or for dispatch in
bulk containers.
 Petroleum Industry
The refining of crude petroleum owes its origin to the successful drilling of the first oil wells in
Ontario, Canada, in 1858. Prior to that time, petroleum was available only in very small
quantities from natural seepage of subsurface oil in various areas throughout the world. With the
discovery of “rock oil” in northwestern Pennsylvania, crude oil became available in sufficient
quantity to inspire the development of larger-scale processing systems. The earliest refineries
employed simple distillation units, or “stills,” to separate the various constituents of petroleum
by heating the crude oil mixture in a vessel and condensing the resultant vapours into liquid
fractions. Initially the primary product was kerosene, which proved to be a more abundant,
cleaner-burning lamp oil of more consistent quality than whale oil or animal fat.

The lowest-boiling raw product from the still was naphtha, a partly refined or unrefined crude oil
product (petrol). Its initial commercial application was primarily as a solvent. Higher-boiling
materials were found to be effective as lubricants and fuel oils, but they were largely novelties at
first.

Petroleum refineries convert (refine) crude oil into petroleum products for use as fuels for
transportation, heating, paving roads, and generating electricity and as feedstocks for making
chemicals. Refining breaks crude oil down into its various components, which are then
selectively reconfigured into new products. Petroleum refineries are complex and expensive
industrial facilities. All refineries have three basic steps:

 Separation

 Conversion

 Treatment

1. Separation

A) Fractional distillation:
The primary process for separating the hydrocarbon components of crude oil is fractional
distillation. Crude oil distillers separate crude oil into fractions for subsequent processing in such
units as catalytic reformers, cracking units, alkylation units, or cokers.
The principles of operation of a modern crude oil distillation unit are shown in the figure. Crude
oil is withdrawn from storage tanks at ambient temperature and pumped at a constant rate
through a series of heat exchangers in order to reach a temperature of about 120 °C (250 °F). A
controlled amount of fresh water is introduced, and the mixture is pumped into a desalting drum,
where it passes through an electric field and a saltwater phase is separated. The desalted crude oil
passes through additional heat exchangers and then through steel alloy tubes in a furnace. There
it is heated to a temperature between 315 and 400 °C (600 and 750 °F), depending on the type of
crude oil and the end products desired. A mixture of vapour and unvaporized oil passes from the
furnace into the fractionating column, a vertical cylindrical tower as much as 45 metres (150
feet) high containing 20 to 40 fractionating trays spaced at regular intervals. The most common
fractionating trays are of the sieve or valve type. Sieve trays are simple perforated plates with
small holes about 5 to 6 mm (0.2 to 0.25 inch) in diameter. Valve trays are similar, except the
perforations are covered by small metal disks that restrict the flow through the perforations under
certain process conditions. The oil vapours rise up through the column and are condensed to a
liquid in a water- or air-cooled condenser at the top of the tower. A small amount of gas remains
uncondensed and is piped into the refinery fuel-gas system. Typical boiling ranges for various
streams are as follows: light straight-run naphtha (overhead), 20–95 °C (70–200 °F); heavy
naphtha (top sidestream), 90–165 °C (195– 330 °F); crude kerosene (second sidestream), 150–
245 °C (300–475 °F); light gas oil (third sidestream), 215–315 °C (420–600 °F).
b) Conversion
The separation processes described above are based on differences in physical properties of the
components of crude oil. All petroleum refineries throughout the world employ at least crude oil
distillation units to separate naturally occurring fractions for further use, but those which employ
distillation alone are limited in their yield of valuable transportation fuels. By adding more
complex conversion processes that chemically change the molecular structure of naturally
occurring components of crude oil, it is possible to increase the yield of valuable hydrocarbon
compounds.
Naphtha reforming
The most widespread process for rearranging hydrocarbon molecules is naphtha reforming. The
initial process, thermal reforming, was developed in the late 1920s. Thermal reforming
employed temperatures of 510–565°C at moderate pressures about 40 bars, or 600 to obtain
gasolines (petrols) with octane numbers of 70 to 80 from heavy naphthas with octane numbers of
less than 40. The product yield, although of a higher octane level, included olefins, diolefins, and
aromatic compounds. It was therefore inherently unstable in storage and tended to form heavy
polymers and gums, which caused combustion problems.
By 1950 a reforming process was introduced that employed a catalyst to improve the yield of the
most desirable gasoline components while minimizing the formation of unwanted heavy
products and coke. (A catalyst is a substance that promotes a chemical reaction but does not take
part in it.) In catalytic reforming, as in thermal reforming, a naphtha-type material serves as the
feedstock, but the reactions are carried out in the presence of hydrogen, which inhibits the
formation of unstable unsaturated compounds that polymerize into higher-boiling materials.
In most catalytic reforming processes, platinum is the active catalyst; it is distributed on the
surface of an aluminum oxide carrier. Small amounts of rhenium, chlorine, and fluorine act as
catalyst promoters. In spite of the high cost of platinum, the process is economical because of the
long life of the catalyst and the high quality and yield of the products obtained. The principal
reactions involve the breaking down of long-chain hydrocarbons into smaller saturated chains
and the formation of isoparaffins, made up of branched-chain molecules. Formation of ring
compounds (technically, the cyclization of paraffins into naphthenes) also takes place, and the
naphthenes are then dehydrogenated into aromatic compounds (ring-shaped unsaturated
compounds with fewer hydrogen atoms bonded to the carbon). The hydrogen liberated in this
process forms a valuable by-product of catalytic reforming. The desirable end products are
isoparaffins and aromatics, both having high octane numbers.

Purification:
Before petroleum products can be marketed, certain impurities must be removed or made less
obnoxious. The most common impurities are sulfur compounds such as hydrogen sulfide (H2S)
or the mercaptans (“R”SH)—the latter being a series of complex organic compounds having as
many as six carbon atoms in the hydrocarbon radical (“R”). Apart from their foul odour, sulfur
compounds are technically undesirable. In motor and aviation gasoline they reduce the
effectiveness of antiknock additives and interfere with the operation of exhaust-treatment
systems. In diesel fuel they cause engine corrosion and complicate exhaust-treatment systems.
Also, many major residual and industrial fuel consumers are located in developed areas and are
subject to restrictions on sulfurous emissions.
Most crude oils contain small amounts of hydrogen sulfide, but these levels may be increased by
the decomposition of heavier sulfur compounds (such as the mercaptans) during refinery
processing. The bulk of the hydrogen sulfide is contained in process-unit overhead gases, which
are ultimately consumed in the refinery fuel system. In order to minimize noxious emissions,
most refinery fuel gases are desulfurized.
Other undesirable components include nitrogen compounds, which poison catalyst systems, and
oxygenated compounds, which can lead to colour formation and product instability. The
principal treatment processes are outlined below.

Sweetening
Sweetening processes oxidize mercaptans into more innocuous disulfides, which remain in the
product fuels. Catalysts assist in the oxidation. The doctor process employs sodium plumbite, a
solution of lead oxide in caustic soda, as a catalyst. At one time this inexpensive process was
widely practiced, but the necessity of adding elemental sulfur to make the reactions proceed
caused an increase in total sulfur content in the product. It has largely been replaced by the
copper chloride process, in which the catalyst is a slurry of copper chloride and fuller’s earth. It
is applicable to both kerosene and gasoline. The oil is heated and brought into contact with the
slurry while being agitated in a stream of air that oxidizes the mercaptans to disulfides. The
slurry is then allowed to settle and is separated for reuse. A heater raises the temperature to a
point that keeps the water formed in the reaction dissolved in the oil, so that the catalyst remains
properly hydrated. After sweetening, the oil is water washed to remove any traces of catalyst and
is later dried by passing through a salt filter.