INDUSTRIAL GASES

Chemical Process Industries

Carbon Dioxide
 Thiolier- produced solid CO2 in 1835 from liquid material
 Solid CO2 is for refrigerating and freezing ice cream, meat and other foods.
 Solid CO2 provides atmosphere reduces the meat and bacteria spoilage, source for carbonated
drinks occasionally.
 Chilling aluminum rivets and shrink-fitting machine parts
 Carbonated drinks- largest outlet of liquid CO2
 Fire extinguishing material
 Making of Salicylic acid makes use of gaseous CO2
Manufacturing:
1. Recovery from syn gas in ammonia production
2. Recovery as by-product in the production of SNG
3. Recovery from the production of ethanol by fermentation
4. Recovery from natural wells
 Absorption system- used for concentrating CO2 gas up to 99% purity.
Chemical reaction for concentrating CO2: Na2CO3+CO2+H2O=2NaHCO3
Oil, natural gas or coke- burned to give off 15% CO2 at 345C
Flue gas- cooled, purified and washed by passing through two water scrubbers
Ethanolamines- CO2 can be absorbed by this in a selective countercurrent absorption.
CO2-Ethanolamine mixture is pumped into a steam-heated reactivator
CO2 and steam leave at the top of the reactor passing through a cooler and condensing the steam and
fed back to the tower as reflux. CO2 is compressed, cooled and liquefied.
Liquid CO2 is draw off from CO2 receiver.
For dry ice, the liquid CO2 is reduced to atmospheric pressure with partial solidification. CO2 “snow” is
compressed to form cake. These Dry ice cakes are sawed to 25 cm with a 23-kg weight.
Fermentation industry- one of sources of CO2 as by product of alcohol production using yeast. From a 50
kg of starchy material produces 17L of 190-proof ethanol and 14kg of CO2.
Recovery: gas in fermenters are passed in scrubbers with stoneware spiral packing and on to the
gasometer.
1st scrubber- contains weak alcohol, removes alcohol carry-over
2nd and 3rd scrubber – deaerated with water to remove water-soluble impurities
From the gasometer, it is then fed to the scrubber having a K2Cr2O7 solution which oxidizes aldehydes
and alcohols. The next scrubber has sulfuric acid, oxidation is completed and the gas is dehydrated. The
entrained acid after this scrubber is passed thru a packed tower of Na2CO3. Before entering the
compressor, the stream is passed thru a scrubber with glycerin to remove oxidized products.
 INDUSTRIAL GASES
Chemical Process Industries

Hydrogen
 Sold as gas and liquid (more profitable)
 Metal hydrides as hydrogen sponges 2 MPa
 Hydrides used are usually alloys of Mg-Ni,Fe-Ti,La-Ni and misch metal-nickel
 Hydrogenating liquid oils in foods
 Chemical manufacturing of ammonia and methanol
 Hydrogenating nonedible oils for soaps, insulation, plastics, ointments and other specialty
chemicals
 Production of semiconductor circuits
 Power generation as a heat transfer medium to cool high-speed turbine generators

Manufacture:

 Electrolytic Method- consists of passing DC through an aqueous solution of alkali and

decomposing water
2H2O (l) = 2H2 (g)+O2 (g)
Theoretical decomposition voltage 1.23 V but usually 2 to 2.25V is used
Usually uses 15% NaOH solution and iron cathode and Ni-plated-iron anode, has an asbestos
diaphragm separating the electrode compartments. Produces gas of about 99.7% pure.

Other processes:
 Steam-hydrocarbon reforming process
 Partial Oxidation Process
 Coal Gasification Process
 Cracked Ammonia process

Purification processes:

 CO Removal- removal by conversion to hydrogen via water-shift-gas reaction

 CO2 and H2S removal
 Monoethanolamine or Girbotol process- MEA water solution reacted with CO2. The MEA
solution is heated to a reactivation column where MEA.CO2 complex Is dissociated by
stripping.
 Hot potassium carbonate process
 Physical solvent processes
 Adsorptive purification

Oxygen and Nitrogen

Oxygen

 A component in calibration gas mixtures for environmental monitoring systems and industrial
hygiene gas mixtures
 Instrumentation in the petrochemical industry
 First-aid treatment in cases of heart attack or suffocation
 Treating respiratory disorders
 INDUSTRIAL GASES
Chemical Process Industries

 Anesthetic
 Plasma etching
 A carrier gas in certain deposition or diffusion operations

Manufacture:

The most common method is to fractionally distill liquefied air into its various components,
with N2 distilling as a vapor while O2 is left as a liquid. Oxygen gas can also be produced
through electrolysis of water into molecular oxygen and hydrogen.

Nitrogen:

 A component in both controlled and modified atmosphere packaging applications

 A pure gas and a component gas in calibration gases
 A component in industrial gas mixtures
 Used in the petrochemical industry for instrumentation
 A component in laser gas mixtures

Manufacture:

Nitrogen gas is an industrial gas produced by the fractional distillation of liquid air, or by mechanical
means using gaseous air

In a chemical laboratory it is prepared by treating an aqueous solution of ammonium

chloride with sodium nitrite.

NH4Cl(aq) + NaNO2(aq) → N2(g) + NaCl(aq) + 2H2O (l)

Very pure nitrogen can be prepared by the thermal decomposition of barium azide or sodium azide.

2NaN3 → 2Na + 3N2

Sulfur Dioxide

 Sulfur Dioxide is a chemical compound with a chemical formula SO2. At standard atmosphere, it
is a toxic gas with a pungent, irritating and rotten smell. It is released naturally by volcanic
activity.
 Sulfur dioxide was used by the Romans in wine making when they discovered that burning sulfur
candles inside empty vessels kept them fresh and free from vinegar smell.
 It is found on Earth and exists in very small concentrations and in the atmosphere at about 1
ppb.

1.) Burning Sulfur or materials containing Sulfur.

S+O2=SO2

2.) Combustion of Hydrogen Sulfide/ Organosulfur compounds.

 INDUSTRIAL GASES
Chemical Process Industries

2H2S+3O2=2H2O+2SO2

Other Organosulfur compounds:

a. Pyrite

4FeS2+11O2=2Fe2O3 + 8SO2

b. Sphalerite

2ZnS+3O2=2ZnO+2SO2

c. Cinnabar

HgS+O2=Hg+SO2

3.) By product in the manufacture of Calcium Silicate Cement.

2CaSO4+2SiO2+C=2CaSiO3+2SO2+CO2

Acetylene

 Acetylene is a chemical compound with a chemical formula C2H2. It is a hydrocarbon and the
simplest alkyne called ethyne. This colorless gas is widely used as a fuel and a chemical building
block.
 It is unstable in pure form and thus is usually handled as a solution.
 Pure C2H2 is odorless, but commercial grades usually have a marked odor due to impurities
 Acetylene was discovered in 1836 by Emund Davy, who identified it as a new carburet of
hydrogen. It was rediscovered by French Chemist Marcellin Berthelot, who coined the name
acetylene.

Manufacture:

1.) By reaction of Calcium Carbide with water.

CaC2+2H2O=Ca(OH)2+C2H2

2.) By Paraffin hydrocarbons by Pyrolysis. ( Wulff process )

C4H10=C2H2+C2H4+CO+H2

3.) From Natural gas by Partial Oxidation. ( Sacchase process )

4.) From partial combustion of Methane.

These days Acetylene is mainly manufactured by the partial combustion of methane or appears as a
side product in the ethylene stream from high temperature cracking of hydrocarbons. Heat for the
cracking operation is developed by partial oxidation of the feed stock with oxygen. The heat evolved
cracks the excess hydrocarbon to acetylene.
 INDUSTRIAL GASES
Chemical Process Industries

CH4+2O2=CO2+H2O

2CH4=C2H2+3H2

Carbon Monoxide

 Chief constituent of syn gas

 Obtained in pure form thru cryogenic procedures with H2 as coproduct
 Important raw material in methanol production and other alcohols
 Used for making diisocyanate and ethyl acrylate by:
2CO+2Cl2=2COCl2 (phosgene) =toluene2,4-diamine=CH3C6H3(NCO)2+4HCl
CO+CH:CH+C2H5OH=Ni(CO)4 and HCl=Ethyl acrylate

Nitrous Oxide

 Generally prepared by heating very pure ammonium nitrate to 200C in aluminum retorts
N4NO3 (c)= N2O (g)+2H2O (g) Heat of reaction=-36.8Kj
 Purification involves caustic treatment to remove nitric acid and dichromate to remove
nitric oxide. Shipped in cylinders as liquid at pressure of 10MPa
 Used as anesthetic and usually mixed with oxygen