SULFURIC ACID (contact process) Purification unit

Raw materials - Sulfur, Pyrites (FeS2), CuS ,ZnS, PbS, MoS2. This includes the dusting tower, cooling pipes, washing tower, drying tower, arsenic purifier and
testing box. Sulfur dioxide has many impurities such as vapours, dust particles and arsenous oxide.
Sources of raw material - Sulfur from mines, Sulfur recovered from petroleum desulfurization, Recovery Therefore, it must be purified to avoid catalyst poisoning . In this process, the gas is washed with
of sulfur dioxide from coal or oil-burning public utility stack gases, Recovery of sulfur dioxide from the water, and dried by sulfuric acid. In the dusting tower, the sulfur dioxide is exposed to a steam
smelting of metal sulfide ores (2PbS + 3O2 = 2PbO + 2SO2), Isolation of SO2 from pyrite. which removes the dust particles. After the gas is cooled, the sulfur dioxide enters the washing
Reactions - S + O2 = SO2 ; 2SO2 + O2 = 2SO3 ; SO3 + H2O = H2SO4 tower where it is sprayed by water to remove any soluble impurities. In the drying tower sulfuric
acid is sprayed on the gas to remove the moisture from it. Finally, arsenic oxide is removed when
Steps in the Contact Process - Burning of sulfur, Catalytic oxidation of SO2 to SO3, Hydration of SO3 the gas is exposed to ferric hydroxide.

Process - The process can be divided into five stages: combining of sulfur and oxygen, purifying sulfur DCDA
dioxide in the purification unit, adding excess of oxygen to sulfur dioxide in presence of
The next step to the Contact Process is DCDA or Double Contact Double Absorption. In this
catalyst vanadium pentoxide, with temperatures of 450 °C and pressure of 1-2 atm, sulfur
process the product gases (SO2) and (SO3) are passed through absorption towers twice to achieve
trioxide formed is added to sulfuric acid which gives rise to oleum (disulfuric acid), the oleum then is
further absorption and conversion of SO2 to SO3 and production of higher grade sulfuric acid. SO2-
added to water to form sulfuric acid which is very concentrated.
rich gases enter the catalytic converter, usually a tower with multiple catalyst beds, and are
converted to SO3, achieving the first stage of conversion. The exit gases from this stage contain
both SO2 and SO3 which are passed through intermediate absorption tower where sulfuric acid is
trickled down packed columns and SO3 reacts with water increasing the sulfuric acid concentration.
Though SO2 too passes through the tower it is unreactive and comes out of the absorption tower.
This stream of gas containing SO2, after necessary cooling is passed through the catalytic converter
bed column again achieving up to 99.8% conversion of SO2 to SO3 and the gases are again passed
through the final absorption column thus resulting not only achieving high conversion efficiency
for SO2 but also enabling production of higher concentration of sulfuric acid.

The industrial production of sulfuric acid involves proper control of temperatures and flow rates of
the gases as both the conversion efficiency and absorption are dependent on these. Because of the
large effect temperature plays on the reaction, multiple catalyst layers are used, with cooling
between each step. Additionally, as the partial pressure of SO3 increases, further reaction is limited.
This is overcome by removing the SO3 after the third stage to drive the reaction to completion.

CATALYST: MOST WIDELY USED CATALYST IS VENADIUM PENTOXIDE DISPERSED ON A

POROUS CARRIER IN PELLET FORM.

Oleum Production - Sulfuric acid with additional SO3 absorbed, 20% Oleum contains 20% SO3
by weight in the oleum, Common strengths of oleum are 20, 30, 40, 65 percent. Oleum is used in
reactions where water is excluded - SO3 + H2SO4 = H2S2O7 (disulfuric acid). Metal corrosion is
a big issue in the manufacture of sulfuric acid. Special alloy metals must be used to guard against
excessive corrosion. Nickel, chromium, molybdenum, copper, a silicon are the most important
elements that enhance corrosion resistance of alloys.

Burning of sulfur USES

Burning of sulfur in presence of dry air is carried out in sulfur pyrite burner. As SO2 is needed for • The largest single use is in the fertilizer industry.
the catalytic oxidation and prevention of corrosion, dry air is used in the combustion process. If
sulfur contains carbonaceous impurities, the molten material has to be filtered to avoid poisoning • Mostly in production of phosphoric acid, which in turn used to manufacture fertilizers such as triple
the catalyst and forming water from burning hydrogen. superphosphate, mono and diammonium phosphates

Catalytic oxidation of SO2 to SO3 • Used for producing superphosphate and ammonium sulfate.

Catalyst - vanadium pentoxide (V2O5), pressure - 1.2-1.5 atmospheres temperature - 450oC. • Used as an acidic dehydrating reaction medium in organic chemical and petrochemical processes
involving such reactions as nitration, condensation, and dehydration, as well as in oil refining, in
If it rises above 450oC, the equilibrium is displaced away from SO3. Temperature should reach which it is used for refining, alkylation, and purification of crude-oil distillates
around 450oC for the catalyst to be activated. This process is strongly exothermic. The catalytic
reactor is designed as a four-stage fixed-bed unit. The gas has to be cooled between each step. Four • In the inorganic chemical industry e.g. in the production of TiO2 pigments, hydrochloric acid, and
passes, together with "double absorption, are necessary for overall conversion of 99.5-99.8% (three hydrofluoric acid
passes, 97-98%). The temperature rises to over 600oC with the passage of the gas through each
• In the metal processing industry e.g. for pickling and descaling steel, for leaching copper, uranium,
catalyst bed. The doubled absorption consists of cooling the gases between each bed back to the
and vanadium ores in hydrometallurgical ore processing, and in the preparation of electrolytic baths
desired range by sending them through the heat exchanger and then back through the succeeding
for nonferrous-metal purification and plating
beds. Between the third and fourth beds, the gases are cooled and sent to an absorption tower. This
is to shift the equilibrium to the right by absorbing SO 3. The gases are then sent to the heat • Certain wood pulping processes in the paper industry require sulfuric acid, used in textile and
exchanger to warm them to 410-430oC and then on to the fourth catalyst bed. chemical fiber processes and leather tanning

Hydration of SO3 • In manufacture of explosives, detergents and plastics

After the catalytic oxidation process, the resulting SO3 is hydrated by absorption in packed towers • In production of dyes, pharmaceuticals
filled with 98-99% sulfuric acid. SO2 has a low solubility in 98% H2SO4. The absorption acid
concentration is kept within the desired range by exchange as needed between the H 2SO4 in the
drying acid vessel that precedes the combustion chamber with the H2SO4 in the absorption tower.
The acid strength can be adjusted by controlling the streams of H 2SO4 to give acid of 91 to 100%
H2SO4 with various amounts of added SO3 and water. The conversion of sulfur to acid is over
99.5%.

Major engineering problems

1) Design of multistage catalytical convertor for highly exothermic reaction. Earlier two stage
converter is used but nowadays the design of three or four stages rather than conventional two stage
operation are developed.

2) To optimize space velocity in catalyst chamber because it deals with pumping cost or fixed
charges of reactor

3) Thin catalyst beds of 30-50cm height used to avoid above difficultties. Yield can drop due to
longitudinal mixing if the convective gas velocity through the bed is low

4) Removal of heat of absorption of SO3 in acid. Pipe coolers with water dripping over external
surface have been replaced by cast iron pipe with internal fins to promote better heat transfer.

5) Pressure drop must be low, so, 8cm stacked packing is often used.
Nitric acid (HNO3) or aqua fortis (strong water) packed in layers inside the tube. Contact time and of the gas passes downward in the catalyst zone
Nitric acid (HNO3), also known as aqua fortis (strong water) and spirit of niter, is a highly 2.5 X 10-4sec and are heated at 800oC.
corrosive strong mineral acid.
Product gases from the reactor which contain 10-12% NO, are sent through heat recovery units
Ostwald's process or Ammonia oxidation process consisting of heat recovery boiler, super heater and quenching unit for rapid cooling to remove
large fraction of product heat, and into the oxidizer-absorber system. Air is added to convert NO
Reaction - 4NH3 + 5O2 = 4NO + 6H2O; 2NO+O2 = 2NO2; 3NO2 + H2O = 2HNO3+ NO
to NO2 at the more favorable temperature (40-50oC) environment of the absorption system. The
Nitric acid is made by the oxidation of ammonia, using platinum or platinum- rhodium as catalyst, equipment in the absorption train may be series of packed or sieve tray vertical towers or a series
followed by the reaction of the resulting nitrogen oxides with water. The process involves four of horizontal cascade absorbers. The product from this water absorption system is 57-60% HNO3
steps. Catalytic oxidation of ammonia with atmospheric oxygen to yield nitrogen monoxide. solution. The towers contain large number of inert plates packed with inert granular materials
Oxidation of the nitrogen monoxide product to nitrogen dioxide or di-nitrogen tetroxide. designed to increase the contact between the gases and water. This reaction is exothermic and
Absorption of the nitrogen oxides to yield nitric acid. continuous cooling is needed. The conversion is favored by low temperatures and significant
reaction occurs until the gases leave the towers. Nitrogen dioxide gas is pumped at 5 to 10 atm
across the inert packing material, through which water is trickled from above. Reaction between
the water and the gas produces nitric acid, which then dissolves in the remaining water. Small
quantities of NO are also produced, which reacts with oxygen from the air in the tower to produce
2 NO which then reacts as before.

Concentration by H2SO4 - Rectification with 93% H2SO4 in silicon-iron or stoneware tower

produces concentrated nitric acid and 70% H2SO4 which can be re-evaporated to 93% H2SO4.

Concentration by Mg(NO3)2 - Magnesium nitrate solution containing 70-75% Mg (NO3)2 is fed

to dehydrating tray along with dilute HNO3 from the absorption tower. The salt solution acts as an
extractive distillation agent, removing water at 100oC or higher, thus allowing rectification with
azeotropic formation. The dilute Mg (NO3)2 solution re-concentrated by evaporation.

Advantages-Operating cost is half compare to H2SO4 process; Acid quality and yield improved.

Disadvantage - Increase in 70% capital expenditure.

Absorption of nitrogen oxides into water

Rate of absorption depends on concentration of NO2 in gas phase. In absorber where concentration
The ratio of air/ammonia must be carefully monitored and is maintain at between 9 and 12%. If
of NO2 is greater than 5%, the controlling reaction is solution of N2O4 accompanied by hydrolysis
the concentration of ammonia rises much beyond this, the mixture becomes explosive. The catalyst
used in this process is 90% platinum alloyed with 10% rhodium for increased strength. The catalyst of HNO3 and HNO2. Low temperature is beneficial for absorber operation efficiency. Increasing
consists of several woven or knitted gauzes formed from the alloy. The gauze mats are preheated pressure favors physical absorption rate and shift chemical equilibrium to produce higher acid
so that the gases are directly heated as they pass over the catalyst. The catalyst may become strength.
poisoned by air pollution and contamination from the ammonia which reduces its efficiency. The
cost of these catalysts are extremely high and need to be frequently replaced due to the wear and WASTES AND MANAGEMENT
tear they experience under such severe conditions. A cheaper alternative is yet to be developed.
Compressed air is mixed with anhydrous ammonia, fed to a shell and tube convertor designed so The Ostwald process is very energy efficient and produces little waste.
that the preheater and steam heat recovery boiler-super heater are within the same reactor shell. • The oxidation of ammonia is highly exothermic, generating sufficient heat energy to meet the
energy needs of the rest of the plant.
The convertor section consists of 10-30 sheets of Pt-Rh alloy in the form of 60-80 mesh wire gauge

• The main gaseous emissions from the Ostwald process include NO and NO2. Both gases Weak acid are used to digest crude phosphates.
contribute to photochemical smog, and therefore, careful attention must be paid to minimizing how As a nitrating agent in the preparation of explosives such as TNT, nitroglycerine, cellulose
much of these gases are emitted into the atmosphere. The gas mixture entering the converter is polynitrate, ammonium picrate
filtered to remove catalytic poisons, which increases the efficiency of the catalysts and hence
In manufacture of organic intermediates such as nitroalkanes and nitroaromatics.
decreasing the pressure (and energy) required to force the gas through the catalyst bed.
• Heat exchangers are employed to remove heat released by the reaction in the converter and then Used in the production of adipic acid.
using it to heat incoming gases or generate electricity. Used in fibers, plastics and dyestuffs industries
• At the high temperatures and pressures used in the converter, the catalyst slowly vaporizes and Used in metallurgy and in rocket fuel production
is lost. Gases leaving the converter are passed through a filter to recover the metals and minimize As the replacement of sulfuric acid in acidulation of phosphate rock.
the impact of these vapors on the environment.
HEALTH AND SAFETY
• Concentrated nitric acid is corrosive and causes severe burns to the skin and eyes. Its fumes
evolve nitrogen dioxide gas which at low concentrations may cause lung oedema (fluid in the
lungs) and fatal with excessive exposure.
• As a strong oxidant, nitric acid reacts readily with a range of organic materials and metals to
produce flammable and/or explosive products.
• x NO gases are significant greenhouse gases and some can react with water to form acid rain.
Safety Measures Employed:
• There is careful monitoring in nitric acid plants for leaks and spills and all employees are trained
to handle such if they do occur.
• Equipment must be carefully maintained to avoid corrosion.
• Acid spills are contained using materials such as earth, clay or sand, and then neutralized with a
base such as slaked lime [Ca(OH)2] or sodium carbonate.
• Full protective equipment and breathing apparatus is readily accessible across the plant.
• The ratio of ammonia to air in the gas entering the converter is continuously measured and
controlled to ensure it does not reach explosive conditions.
• Un-reacted gases are recycled where possible.
• Various methods are employed to limit x NO emissions, maximize conversion efficiency, and
minimize loss of energy.
PROPERTIES OF NITRIC ACID
Nitric acid:
• Is colorless in its pure form but may become orange or reddish in color if contaminated by
nitrogen oxides.
• Is highly corrosive.
• Is a poisonous liquid (freezing point -42°C, boiling point 83°C).
• Reacts with water or steam to produce heat and toxic, corrosive and flammable vapours.
• Can cause severe burns.
• Miscible in water at all concentrations.
• Has an acid dissociation constant (pKa) of −1.4. In aqueous solution, it almost completely (93%
at 0.1 mol/L).
• Will decompose at higher temperatures to form nitrogen oxides. Nitric acid is both a strong
monoprotic acid and a strong oxidant, particularly when hot and concentrated.
USES
As a starting material in the manufacture of nitrogen fertilizers such as ammonium nitrate,
ammonium phosphate and nitro-phosphate. Large amounts are reacted with ammonia to yield
ammonium nitrate.