Industrial Chemistry I
Industrial Chemistry I
Industrial Chemistry I
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Difference between Chemistry and Industrial Chemistry
Desired product is produced at Desired product is produced at large
small scale in the lab scale in the industry
The parameters such as The parameters such as Temperature
Temperature Pressure and Pressure and Concentration etc are
Concentration etc are set through monitored by sophisticated instrument
usual methods such as computers.
Different equipment and Different equipment and instruments
instruments may not be required are used in industrial process.
to use Material balance and energy balance
Material balance and energy must be considered.
balance may not be considered Cost effective production is to be
Cost of production may not be considered
considered Along with Chemist, chemical,
Only chemist can perform the electrical, mechanical engineers
chemical process(reaction) experts required to carry out the
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Definition:-
Industry is a general term that refers to all economic activities that
deal with production of goods and services.
Industrial Chemistry is the study of different chemical process
involved in the industry for the manufacture of synthetic products
like; Cement, Plastics, Glass, Paints, Medicines, Fertilizers, Food, and
other industrial products.
Industrial chemistry as the branch of chemistry which applies
physical and chemical procedures towards the transformation of
natural raw materials and their derivatives to products that are
benefit to humanity.
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Every industrial process is designed to produce a desired product
extraction
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It is combination of unit processes and Unit operation
The layout of a chemical process indicates areas where:
entry and exit points of services such as cooling water and steam
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Characteristics of the Chemical Industry
Basic objective - make a profit
Very competitive
Highly dependent on science and technology
Spends large amounts of money on designing of reactor
Large capital requirements - to construct, expand and maintain
production facilities
Low labor requirements - BUT needs highly qualified personnel
Industry Growth - generally through integration rather than
diversification
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Unit process and unit operations
Unit processes: are the chemical transformations or conversions
that are performed in a process.
involves principle chemical conversions leading to synthesis of
various useful product
provide basic information regarding the reaction temperature and
pressure, extent of chemical conversions
and yield of product of reaction nature of reaction whether
endothermic or exothermic, type of catalyst used
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Examples of
unit processes
Unit operations
Unit operations are the physical treatment steps applied in chemical
processes to transform raw materials and products into required
forms.
These are the physical treatment steps, which are required to:
put the raw materials in a form in which they can be reacted
chemically
put the product in a form which is suitable for the market
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Examples of unit operations
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Benefits of continuous reactors
Continuous reactors are generally able to cope with much higher
reactant concentrations due to their superior heat transfer capacities.
The small size of continuous reactors makes higher mixing rates
possible.
The output from a continuous reactor can be altered by varying the run
time. This increases operating flexibility for manufacturers.
Reduces waste
Increases productivity-more units completed in less time.
Improves quality by making it easier to spot and correct errors.
• Examples,
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production of ammonia by Haber process, and sugar
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Figure : a continuous reactor
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Process variables
Process variables are parameters which determine the rate of
kinetics and mechanism of reaction in the unit process.
These are reaction temperatures, pressures, Residence time, volume
of reactor, concentration of reacting species, and others.
Variables can be either independent variable or dependent variable
based on relations each other.
Example Fertilizer used to stimulate for the growth of plant.
From this fertilizer is independent variable where as growth of plant
is dependent variable.
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Material and Energy balance
One ton of total material input will only give one ton of total output,
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Mass balance calculations serve the following purposes:
in the process.
process.
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In mass balance calculations, we begin with two assumptions
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General mass balance equation
Input (enters through system boundaries) + Generation (produced
within system boundaries)
− Output (leaves through system boundaries) − Consumption
(consumed within system) = accumulation (buildup within system)
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The concept of energy conservation as expressed by an energy
balance equation is central to chemical engineering calculations.
Energy balances can be calculated on the basis of external energy
used per kilogram of product, or raw material processed, or on dry
solids or some key component.
Non isothermal operations energy balances must be used in
conjunction with material balances.
Energy balance =
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Energy In = Energy Out + Energy Stored
ΣER= ΣEP+ ΣEW+ ΣEL+ ΣES
Where
ΣER= ER1+ ER2+ ER3+ ……. = Total Energy Entering
ΣEp= EP1+ EP2+ EP3+ ……. = Total Energy Leaving with
Products
ΣEW= EW1+ EW2+ EW3+ … = Total Energy Leaving with Waste
Materials
ΣEL= EL1+ EL2+ EL3+ ……. = Total Energy Lost to Surroundings
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general flow chart about Mass and Energy Balance
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A “system” is an object or a collection of objects that an analysis is
done on
The system has a definite boundary, called the system
boundary, that is chosen and Specified at the beginning of the
analysis
Once a system is defined, through the choice of a system
boundary, everything external to it is called the surroundings.
All energy and material that are transferred out of the system enter
the surroundings, and vice versa
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system
Input = Output
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The general procedure for carrying out mass balance calculations is as
follows:
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Example 2. An aqueous solution of sodium hydroxide contains 20%
NaOH by mass. It is desired to produce an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure water.
Water is by far the most common liquid on the Earth’s surface, and
its unique properties enable life to exist.
Water is usually regarded as a public resource a common good
because it is essential for human life and society.
Water is an essential constituent of all animal and vegetable matter
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Water molecule attracted to each other and to many solutes by
moderately strong “hydrogen bonds.
The hydrogen bonds in ice and liquid water,∼21 kJ/mol,14 are much
weaker than the O-H bond of water (464 kJ/mol),
but they are stronger than London-van der Waals forces (<4 kJ/mol).
Dissolved and suspended solid in water
Total dissolved solids (TDS) are inorganic salts and small amounts
of organic matter present in solution of water.
dryness, and then finding the mass of the dry residue per liter of
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A second method uses a Vernier Conductivity Probe to determine
the ability of the dissolved salts and their resulting ions in an unfiltered
varies
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between 0.55 and 0.8. 41
However, the tests described here will not tell you the specific ion
responsible for the increase or decrease in TDS (electrical
conductivity).
TSS will not pass through a filter, where as dissolved solids can pass
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The latter represent a transport mechanism rather than an ultimate
source
The human source may be comes from effluent of inorganic
chemical industries, mining and other manufacturing sector.
Weathering dissolution of mineral as Congruent and Incongruent
Congruent :- solid phase dissolves to form only soluble species, and
no new solid phase is formed. Dissolution of simple salts, including
metal sulfates and carbonates, behaves this way.
For example, limestone (impure calcium carbonate) dissolves to form
only calcium and bicarbonate ions:
CaCO3(s) + H2O+CO2 (aq) → Ca2+ (aq) +2HCO3- (aq)
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Incongruent:- Primary silicate minerals such as feldspars and secondary
alumino silicate clay minerals dissolve incongruently, forming a
secondary mineral phase, in addition to releasing ions to solution.
basic rocks/minerals +acidic rain → base cations + alkalinity +silica +
clay minerals
For example, albite, a sodium feldspar, reacts as follows:
NaAlSi3O8(s) + H2O+CO2 (aq) → Na+ +HCO3 +
2Si(OH)4(aq) + Al2Si2O5(OH)4(s) all in solution kaolinite
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Hardness and alkalinity are usually closely correlated because they
are derived in large part from a common source dissolution of
limestone (CaCO3)
Hard waters tend to be high in total dissolved solids (TDS) and have
relatively high pH (>7).
Waters often are classified according to hardness as follows:
Hardness meq/L mg/L as CaCO3
Soft <1 <50
Moderately hard 1–3 50–150
Hard 3–6 150–300
Very Hard >6 >300
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The process of removing divalent cations from water is called
softening of water
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Requisites of water for industry
The importance of suitably preparing water for chemical industry is
now well recognized and various processes for purification.
If free from mineral salts ,should be soft water
Water should be
It should not be turbid, Turbidity should be less than 10 ppm on silica
scale.
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It should be colorless.
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The various important factors which are responsible for
color, odor and taste are :
Presence of iron and maganese in appreciable concentration impart
colour to water.
Presence of algae in water during collection, which multiply during
storage.
Electrolytic corrosion of the metal of the water pipe.
Presence of bacteria in water being stored. These bacteria reduce
sulphates to sulphides which produce H2S by hydrolysis.
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Water treatment
Water treatment transforms raw surface and groundwater into safe
drinking water and for industrial applications.
Water treatment involves two major processes:
physical removal of solids and
chemical disinfection.
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Distribution
Sedimentation
The simplest way to clarify muddy water is to allow the suspended
material in it to settle.
This process, known as sedimentation, takes place when water is
allowed to stand in a reservoir or to flow through a series of settling
tanks.
Removal of coarse, dispersed and colloidal impurities from water is
known as clarification.
The suspended and colloidal impurities are separated in
sedimentation tanks by gravitation.
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The main principle of sedimentation is to allow water to rest or flow
at a very slow velocity so that heavier particles settle down due to
gravity.
Sedimentation takes a long time, requires large capacity settling
tanks and can not ensure complete removal of coarse dispersed
impurities from water
Filtration of water is done in order to remove colloidal and
suspended matter remaining after sedimentation and to remove
bacterial load.
The process of filtration usually consists in allowing the water to
pass through thick layers of sand, called media which act as
strainers.
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The chemical characteristics of water get altered and the number of
bacteria present in water is considerably reduced.
Types of Filtration
Rapid filtration - uses gravity (faster flow).
Slow filtration - uses gravity [slower flow].
Pressure sand filters-use water pressure.
Micro straining - uses fine steel fabric (sometimes used prior to other
filtrations).
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Filter media should be:
Coagulation of water
Sedimentation alone is not sufficient to remove all the suspended
mater.
The process of coagulation is used to remove colloidal particles
from water.
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The process of consolidation of colloidal particles, terminating in
precipitation of the substance removed from the treated water by
settling or filtration is called coagulation.
Use reagents so as to remove colloidal and coarse dispersed
impurities.
Since, colloidal particles of a given substance carry same charges,
they are very stable and cannot be easily coagulated or consolidated
into coarse formations.
In water treatment technology ferrous sulphate (FeSO 4.7H2O),
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6FeSO4 + 3Cl2→2Fe2(SO4)3 + 2FeCl3
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Flocculants
The process of coagulation can be intensified by adding
special reagents known as flocculants.
These are the substances, forming colloidal dispersed systems with
water.
Flocculants work by neutralizing the charge on the colloidal
particles of the coagulant and by destroying the protective
properties of some colloids.
Flocculants are used to coagulate fine dispersed particles and reduce
the consumption of coagulant 2-3 times.
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Starch, sodium polyalginate, polyacrylamide, a copolymer of
vinyl acetate and maleic anhydride, activated silica etc are used as
flocculants.
Polyacrylamide has widely been used as a flocculants. Small
quantities of this additive (up to 1mg/litre) accelerate 10-20 times
coagulation by aluminumsulphate.
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Membrane process
In a membrane separation process, a feed consisting of a mixture of
two or more components is partially separated by means of a semi
permeable barrier through which one or more species move faster
than the other species. Used as:
Desalting seawater
Holding back seawater intrusion
Treating brackish groundwater
Water softening
Waste water recovery
Removing color, odor, and other organic contaminants
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Reverse osmosis and electro dialysis
In osmosis, if a semi-permeable membrane separates two solutions,
solvent from the lower concentration passes to the higher
concentration to equalize the concentration of both.
But in the reverse osmosis, pressure higher than osmotic pressure is
applied from the higher concentration side so that the path of the
solvent is reversed, i.e. from higher concentration to lower
concentration.
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Reverse osmosis
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Reverse osmosis removes the ionic and non-ionic substances in the
Large metallic ions with higher + charge cannot pass easily (Ni, Zn,
Cu, Cd)
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After some time, the water in middle chamber become pure and is
taken out. When outer chambers become more concentrated with
brine, they are also changed.
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Ion exchange process
Ion exchangers are two types. Anionic & Cationic.
These are co-polymers of styrene & divinylbenzene.i.e., long chain
organic polymers with a micro porous structure
Cation exchange resins: containing acidic functional groups such
as -COOH,-SO3H etc. are capable of exchanging their H+ ions with
other cations are called cation exchange resins, represented as RH+
Anion exchange resins: The resins containing amino or quaternary
ammonium or quaternary phosphonium or tertiary sulphonium groups,
treated with “NaOH solution becomes capable of exchanging their OH -
ions with other anions. These are called as Anion exchange resins,
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Sterilization and Disinfection of Water
Coagulation and filtration of water through sand purify it from
suspended solids and partly decrease its bacteriological
contamination.
Complete disinfection is attained by chemical reagents which kill
pathogenic bacteria or microorganisms.
Chlorine gas and chlorine compounds, such as chlorinated lime,
chloramines, chlorine dioxide, hypochlorite's, as well as ozone, and
salts of heavy metals are effective against microorganisms.
Ultraviolet radiation, ultrasound and other physical factors also
kill pathogenic organisms.
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But, the most important and common disinfecting agent used to
treat water is chlorine and chlorine compounds
For chlorination, chlorine may be used directly in the liquid
form or as bleaching powder.
The chemical action of chlorine is that it reacts with water to
form hypochlorous acid and nascent oxygen. Both these are
powerful germicides.
Cl2 + H2O → HOCl (Hypochlorous acid)+HCl
HOCl→HCl + [Nascent oxygen]
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Chapter 3
Manufacture of Hydrochloric acid ,
Hydrofluoric acid and Sulphuric acid
Hydrochloric acid
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Burner Process
Chlorine and hydrogen react exothermally to form hydrogen chloride
gas as follows:
Cl2(g) + H2 (g) 2HCl (g)
Both gases pass through a burner nozzle, and are ignited inside a
graphite combustion chamber, which is cooled by water.
The hydrogen chloride gas produced is cooled, and absorbed into
water to give hydrochloric acid at the desired concentration.
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Organic By-product Synthesis
Hydrochloric acid is made during chlorination of organic products as
follows:
where R stands for organic products and RCl stands for chlorinated
organic products such as methyl chloride, methylene chloride, alkyl
chloride, etc.
RCl + HF RF + HCl
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where RCl stands for chloroform, trichloroethane, etc and RF
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Cont..
•Reaction of metallic chlorides, particularly sodium chloride (NaCl),
with sulfuric acid(H2SO4) or a hydrogen sulfate
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Thermal decomposition of the hydrated heavy-metal chlorides
from spent picklen Liquor in metal treatment
Characteristic of HCl
HCl is a non-flammable transparent and colorless or light
yellow liquid
It reacts with a chromate, permanganate, or per sulfate to
generate chlorine; and
reacts
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with a metal peroxide to form its chloride and chlorine
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It has a strong pungent odor, and is highly corrosive.
It is harmful to humans and animals. The inhalation of a large
quantity of hydrochloric acid will cause intoxication and result in
death
The shipping containers used for hydrochloric acid are those rail
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Use of HCl
It is a strong inorganic acid that is used in many industrial processes
Pickling of steel
To remove rust or iron oxide scale from iron or steel before
subsequent processing, such as extrusion, rolling, galvanizing, and
other techniques
The steel pickling industry has developed hydrochloric acid
regeneration processes, such as the spray roaster or the fluidized
bed HCl regeneration process
Production of organic compounds
2CH2=CH2 + 4HCl + O2 → 2 ClCH2CH2Cl + 2 H2O (dichloroethane
by oxychlorination)
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Wood + HCl + heat → activated carbon (chemical activation)
Production of inorganic compounds
eg. Fe2O3 + 6HCl → 2 FeCl3 + 3 H2O (iron (III) chloride from
magnetite)
CaCO3 + 2HCl → CaCl2 + CO2 + H2O (calcium chloride from
limestone)
pH Control and neutralization
OH− + HCl → H2O + Cl−
Regeneration of ion exchangers
HCl is used to rinse the cations from the resins. Na + is replaced with
H+ and Ca2+ with 2 H+
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Other
such as leather processing,
purification of common salt,
household cleaning, and building construction.
Hydrofluoric acid
HF is a weak inorganic acid used primarily in industrial processes:
glass etching, metal cleaning, electronics manufacturing, laboratory
reagent, etc
Anhydrous hydrogen fluoride is manufactured by the action of
sulfuric acid on calcium fluoride.
The gaseous hydrogen fluoride that leaves the reactor is condensed
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purified by distillation 87
CaF2 + H2SO4 CaSO4 +2HF
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Some Feature of HF
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Causes lung injury-effects may be delayed. corrosive to the eyes
and skin.
May cause blindness and permanent scarring.
Absorbed fluoride can cause metabolic imbalances with irregular
heartbeat, nausea, dizziness, and vomiting.
Long-term exposure may cause skeletal fluorosis (weakened bone
structure)
HF etches glass by forming strong bonds between the fluoride
anions and the silicon molecules in glass
HF is reactive with concrete, enamels, glazes, rubber and many
organic compounds
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Use of HF
It used for the production of fluorine and hydrogen gas.
Fluorine is produced commercially by electrolyzing anhydrous HF
containing dissolved potassium fluoride to achieve adequate
conductivity.
Potassium fluoride and hydrogen fluoride form potassium bifluoride
(KHF2 or KF·HF).
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Sulphuric acid (H2SO4)
Sulfuric acid (H2SO4) is a highly corrosive strong mineral acid.
It is a colorless to slightly yellow viscous liquid which is soluble in
water at all concentrations
Manufacturing of sulfuric acid
The commonly used raw materials are:
Elemental sulphur
Sulphides such as pyrites
Hydrogen sulphide from petroleum refineries
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Chamber Process and Contact Process of
Manufacturing of H2SO4
Lead chamber process:
This process employs as reaction vessels large lead-sheathed brick
towers.
In these towers, sulphur-dioxide gas, air, steam, and oxides of
nitrogen react to yield sulphuric acid as fine droplets that fall to the
bottom of the chamber
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Sulphuric acid produced in this way is only about 62 to 70 percent
H2SO4
The chamber process has become obsolete and has been replaced by
the contact process due to the following reasons:
i. An increased demand for strong, pure acid and oleum.
ii. Contact process plants are cheaper and more compact.
Contact process:
The contact process, which came into commercial use about 1900,
depends on oxidation of sulphur dioxide to sulphur trioxide, SO3,
under the accelerating influence of a catalyst.
The first contact plants (before 1920) were built using platinum
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catalysts.
This platinum catalysts has two Limitation
it is very expensive, and
it is deactivated by certain impurities in ordinary sulphur dioxide.
In the middle of 1920s, vanadium catalysts started being used and
have since then replaced platinum.
By 1930, the contact process could compete with the chamber
process and Because it produces high strength acid, it has almost
replaced the chamber process.
divided
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S + O2 --------- SO2 or
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The efficiency of the absorption step of is SO3 related to:-
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Application of H2SO4
Most of its uses are actually indirect in that the sulphuric acid is
used as a reagent rather than an ingredient.
The largest single sulphuric acid consumer by far is the fertilizer
industry
Substantial quantities are used as an acidic dehydrating agent in
organic chemical and petrochemical processes, as well as in oil
refining
used for pickling and desaling steel; for the extraction of copper,
uranium and vanadium from ores; and in non-ferrous metal
purification and plating.
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In the inorganic chemical industry, it is used most notably in the
lubricants and the manufacture of food acids such as citric acid and
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lactic acid
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Environmental impact
The resulting water can be highly acidic and is called Acid Rock
Drainage (ARD).
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Chapter 4
The Common Salts and Chlor-alkali Industries
• Common salts and its resource
Salt is most widely distributed inorganic compound throughout the
world.
Sodium chloride (NaCl), also known as salt, common salt, table salt
or halite, is an ionic compound.
It is a part of human food and life without salt is impossible
It is responsible for the salinity of the ocean and the
extracellular fluid of many multi-cellular organisms
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Salt is the basic raw material for the production of caustic soda,
chlorine, soda ash (sodium carbonate), sodium sulfate, hydrochloric
acid etc
It can be formed by the reaction of hydrochloric acid and sodium
hydroxide
HCl + NaOH → H2O + NaCl
As a solid, sodium chloride is crystalline and forms a cubic lattice
The bonding of the sodium and chlorine atoms is one of the classic
examples of ionic bonding.
Lattice structure of
sodium chloride
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SOURCES OF SODIUM CHLORIDE
The main source of sodium chloride salt is:
Sea Water, Salt Lakes, Sub Soil Water, and Rock Salt
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Due to evaporation of water from brine the solution gradually
concentration as follows
At the 25 °Be brine from the condensers is now passed on to the
impurities
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Artificial evaporator
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Artificial evaporation was carried out in open pans but it is now
Then brine sent to settling tank and it is treated with dilute solution
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ferric ions. 113
Freezing Method
In some countries, salt is also manufactured by freezing the brine, but
it is not a common method.
Salt water usually takes short time to freeze as compare to free water.
This is due to freezing point depurations than pure solvent.
4.2. Chlor-alkali industry introduction
The caustics chain begins with sodium chloride (NaCl) and forms the
environment.
The process of generating salt cake from salt and sulfuric acid
because this acid was industrially useless in the early 19th century, it
For every 8 tons of soda ash, the process produced 5.5 tons of
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This solid waste had no economic value, and was piled in heaps.
reclaiming the sulfur in the calcium sulfide waste had been discovered,
by Henry Deacon.
but the Leblanc process remained more wasteful and more polluting
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the Solvay process 120
Deacon process
The Deacon process was a secondary process used during the
manufacture of alkalis (the initial end product was sodium carbonate)
by the Leblanc process.
Hydrogen chloride gas was converted to chlorine gas which was
then used to manufacture a commercially valuable bleaching powder,
and
At the same time the emission of waste hydrochloric acid was
reduced.
Invented by Henry Deacon in 1874. The process was based on the
oxidation of Hydrogen Chloride:
4HCl(g)+
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O2(g) → 2Cl2(g) + 2H2O (aq) 121
The reaction takes place at about 400 to 450 °C in the presence of a
copper chloride (CuCl2) catalyst.
Three companies developed commercial processes for producing
chlorine based on the Deacon reaction:
The Kel-Chlor process developed by the M.W. Kellogg Company in
the United States.
The Shell-Chlor process developed by the Shell Oil Company in the
Netherlands.
The MT-Chlor process developed by the Mitsui Toatsu Company in
Japan
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Solvay process
ash, Na2CO3).
The ingredients for this are readily available and inexpensive: salt
brine (from inland sources or from the sea) and limestone (from
quarries)
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Main steps
Ammonia absorption. NH3 in the recycled gases is dissolved
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Calcination. The NaHCO3 product is heated at approximately 150 ~
to expel excess CO2, and then lime from the kiln is added to
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Applications
A large part of the sodium carbonate consumed is utilized in the
glass industry, of which ca. 40% is used in the manufacture of bottle
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glass.
It serves both as a raw material and as a flux for the glass melt to
dissolve the sand. A further 19% is utilized in the manufacture of
chemicals, of which ca. 10% is for the production of :
sodium phosphates, mainly Penta sodium triphosphate, in addition to
silicates (sodium meta silicate pentahydrate and sodium orthosilicate),
chromate, sodium dichromate, sodium hydrogen carbonate, sodium
nitrate etc.
13.5% is utilized in the soap and detergent industry and 2.5% in the
paper and pulp industry
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