INDUSTRIAL GASES

CHEMICAL PROCESSING INDUSTRIES

SUBMITTED TO: SIR ANSAR GROUP MEMBERS: RAHEELA BIBI KIRAN ABDUL RAUF HAFSA ARIF FAIZA ILYAS VOHRA ANOSHIA ILYAS CH-002 CH-010 CH-011 CH-014 CH-031

OCTOBER 1, 2012

INDUSTRIAL GASES
INTRODUCTION:
Industrial gases is a group of gases that are commercially manufactured and sold for use in industrial processes, such as steelmaking, oil refining, medical applications, fertilizers, semiconductors, etc. They may be both organic and inorganic, are produced by extraction from the air by a process of separation or are produced by chemical synthesis, and will take various forms such as compressed, liquid, or solid.

COMMON INDUSTRIAL GASES:

This list shows the most common gases sold by industrial gas companies. Many gas mixtures are also sold.

AIR

NOBLE ELEMENTAL COMPOUND GASES GAESES GASES

Ammonia

HYDROCARBON GASES
Methane Acetylene Ethane Ethene Propane Propene Butane Butene

Nitrogen Oxygen Argon

Argon Neon Krypton Xenon

Carbon dioxide Carbon monoxide Sulfur dioxide Sulfur hexaflouride Nitrous oxide Nitrogen Tetraflouride Hyrogen Chlorine Flourine

IMPORTANT LIQUIFIED GASES:

Many gases are also sold in the liquid form like: Liquid oxygen Liquid nitrogen Liquefied petroleum gas Liquid hydrogen, etc.

APPLICATIONS:
These gases find vast applications in many diverse fields like: Chemical industry Cryogenics Cutting and welding Environmental protection Food processing Metrology & measurement Laboratory and instrumentation Gases for breathing Gases for safety and inerting Glass, ceramics, other minerals Medical gases Metallurgy paintball Rubber, plastics, paint Semiconductor industry Water treatment Welding Scuba diving

CARBONDIOXIDE (CO2)
INTRODUCTION:
Carbon dioxide (CO2), a chemical compound made up of two oxygen atoms covalently bonded to a single carbon atom, is a slightly toxic, odorless, colorless gas, used for various industrial purposes. CO2 is a gas at standard temperature and pressure. Its existence in Earth's atmosphere as a small but important constituent of air is in the form of a gas with a slightly pungent, acid taste. Being one of the most abundant gases in the atmosphere, CO2 plays a vital role in plant and animal process, like photosynthesis and respiration. Large quantities of carbon dioxide are produced and consumed at industrial sites making fertilizers, plastics and rubber.

SOURCES OF CARBONDIOXIDE:
Most gas plants produce CO2 from the following sources: Steam methane and naptha reformers High pressure wells Ammonia plants Heavy fuel burning facilities Hydrogen plants Commercial alcohol plants

MANUFACTURING PROCESS:
Cryogenic separation is a distillation process that demands cryogenic temperature, which means low temperatures close to -170 C, and high pressure, approximately 80 bar. Because CO2, CH4 and all other biogas contaminants liquefy at different temperature-pressure domains, it is possible to produce pure CH4 from biogas. This is done by cooling and compressing the

crude biogas to liquefy CO2 which is then easily separated from the remaining gas. The extracted CO2 can also be used as a solvent to remove impurities from the gas. In this process the crude biogas is compressed to approximately 80 bar. The Precooled compressed gas is dried to avoid freezing during the cooling following on the compression. The next step is the further cooling of the biogas in chillers and series of linear heat exchangers to 45 C. Condensed CO2 is removed in a separator. This CO2 is processed further to recover dissolved CH4 which is recycled to the gas inlet. The gas is cooled further to approximately -55 C by heat exchangers. The cold gas is expanded through a Joule-Thomson nozzle into an expansion vessel. The pressure in the vessel is 8-10 bar and the temperature is approximately 110C. In the expansion vessel a gas solid phase equilibrium is established. The solid phase is frozen CO2. The gas phase, which consists of more than 97% CH4, is heated before leaving the plant. The main advantages of cryogenic separation are: Cryogenics can produce large quantities with high purity of the products. Expansion or reduction of product quantity by cryogenics processes ,i.e. scaling up, does not need new equipments in the process. The process makes no use of chemicals. The main disadvantage of cryogenic separation is: Cryogenic processes require the use of numerous equipments and devices,namely: compressors, turbines, heat exchangers, insulators, and distillation columns. The need to maintain these equipment makes from this separation technique a process with large capital costs.

USES OF CARBONDIOXIDE:
Gas Plants produce Carbon dioxide in mainly two forms - Liquid and Solid. Solid CO2 is also known as "dry ice" and is used as refrigerants in food industry and for small shipments. CO 2 is widely utilized during the storage and shipping of ice cream and other frozen foods. Some of the CO2 applications are listed below:

Fire Extinguishers: CO2 extinguishes fires. Beverage: This gas is used to make carbonated soft drinks and soda water. Solvent: Liquid CO2 is considered as a good dissolving agent for many organic compounds. Here it can be used to remove caffeine from coffee. Plants: Plants require CO2 to execute photosynthesis, and greenhouses can promote plant growth with additional CO2. Pressured Gas: It is used as the cheapest noncombustible pressurized gas. Pressured CO2 are inside tins in life jackets. Compressed CO2 gas is used in paintball markers, airguns, for ballooning bicycle tires. Medicine: In medicine, up to 5% CO2 is added to pure oxygen. This helps in provoking breathing and to stabilize the O2/CO2 balance in blood. CO2 Laser: The CO2 laser, a common type of industrial gas laser uses CO2 as a medium. Welding: It also finds its use as an atmosphere for welding. Oil Wells: Carbon dioxide is commonly injected into or next to producing oil wells to draw lost traces of crude oil. Chemical Industry: It is used as a raw material in the chemical process industry, especially for urea and methanol production. Metals Industry: It is used in the manufacture of casting influences so as to enhance their hardness. Fumigation: Used as a fumigent to increase shelf life and remove infestations.

OXYGEN (O2)
INTRODUCTION:
Oxygen, or O2, which comprises 21 percent of the earth's atmosphere, supports life and makes combustion possible. The most abundant of all elements on earth, oxygen comprises 85 percent of its oceans and, as a component of most rocks and minerals, 46 percent of its solid crust. In addition, it constitutes 60 percent of the human body. Colorless, odorless and tasteless, oxygen has poor solubility in water. A specific gravity of 1.105 makes it slightly heavier than air. Although oxygen itself is nonflammable, it enhances combustion and enables all materials that are flammable in air to burn much more vigorously. These combustion-supporting properties account for its use in many industrial applications. Oxygen reacts with all elements, except inert gases, to form compounds called oxides.

PRODUCTION PROCESS:
Oxygen is the most common element in the earths crust and the second largest industrial gas. The purity of oxygen can only be generated by cryogenic air separation. This process was pioneered by Dr. Carl von Lindes in 1902. The cryogenic air separation achieves high purity oxygen of more than 99.5%. The resulting high purity product can be stored as a liquid and or filled into cylinders.

THE CRYOGENIC PROCESS:

A cryogenic oxygen plant comprises: 1. Warm End (W/E) Container Compressor Air receiver Chiller (Heat exchanger) Pre-filter Air purification unit (APU) 2. Coldbox Main heat exchanger Boiler Distillation column Expansion brake turbine 3. Storage Liquid oxygen tank Vapouriser Filling station

WARM END PROCESS:

Atmospheric air is roughly filtered and pressurised by a compressor. The Air Receiver collects condensate and minimizes pressure drop. The dry and compressed air leaves the air to refrigerant heat exchanger with about 10C. To clean the process air further, there are different stages of filtration. First of all, more condensate is removed, then a Coalescing filter acts as a gravity filter and finally an adsorber filled with activated carbon removes some hydrocarbons. The last unit process in the warm end container is the thermal swing adsorber (TSA). The Air purification unit cleans the compressed process air by removing any residual water vapour, carbon dioxide and hydrocarbons. It comprises two vessels.

COLDBOX PROCESS:
The process air enters the main heat exchanger in the Coldbox where it is cooled in counter flow with the waste gas stream. After leaving the main heat exchanger the process air has a temperature of about 112C and is partly liquefied. The complete liquefaction is achieved through evaporation of cooled liquid oxygen in the boiler. After passing a purity control valve process air enters on tip of the distillation column and flows down through the packing

material. The liquid air descending down the column loses nitrogen. It becomes richer in oxygen and collects at the base of the column as pure liquid oxygen. It flows out into the boiler. The rising oxygen vapour becomes rich in nitrogen and argon. It leaves the column and exits the cold box at ambient temperature through the main heat exchanger as a waste gas. Turbines located at the base of the cold box provide refrigeration for the process. A stream of highpressure gas from the main heat exchangers is cooled and expanded to low pressure in the turbine.

STORAGE AND VAPORIZING PROCESS:

Liquid from the tank is compressed to high pressure in a cryogenic liquid pump. It is then vaporised in an ambient air vaporiser to produce gaseous oxygen.

USES OF OXYGEN: Oxygen supplementation is used in medicine. A major use of oxygen is the production of steel in open hearth furnace. It is used in the preparation of many hydrocarbon oxides like ethylene oxide, methanol etc. Other uses include metalworking, underground gasification and fire flooding. It is also used for the disposal and conversion of refuse to usable by product. Animal respiration (breathing) Photosynthesis

HYDROGEN (H2)
INTRODUCTION:
Hydrogen gas is colorless, odorless, tasteless, flammable, and nontoxic . Hydrogen gas exists as a gas at ambient temperatures and atmospheric pressures. Hydrogen gas is the lightest gas known with a density approximately 0.07 that of air. The concentration of hydrogen gas in the atmosphere volume is 5.0 x 10-5 %. Hydrogen is principally shipped and used in gaseous form for refineries, petrochemical companies for hydro-treating, catalytic reforming and hydrocracking. Hydrogen is also used in heat treating, metal production, welding, lasers, plastics, food production, and semiconductors.

INDUSTRIAL PRODUCTION OF HYDROGEN:

Hydrogen gas may be produced by: Steam reforming of natural gas Electrolysis of water Chemical reactions using acid or alkali

STEAM REFORMING OF NATURAL GAS:

Economically the most important processes involve removal of hydrogen from hydrocarbons. Commercial bulk hydrogen is usually produced by the steam reforming of natural gas. At high temperatures (10001400 K, 20 MPa), steam (water vapor) reacts with methane to yield carbon monoxide and H2.

CH4 + H2O CO + 3 H2 ELECTROLYSIS OF WATER:

This reaction is conducted at 1.3V at room temperature using 15% NaOH solution with iron cathode and nickel plated iron anode has an asbestos diaphgram separating electrode compartments. H+ cations will accumulate at the anode and OH anions will accumulate at the cathode. This can be verified by adding a pH indicator to the water: the water near the anode is acidic while the water near the cathode is basic. The negative hydroxyl ions that approach the anode mostly combine with the positive hydronium ions (H3O+) to form water. The electrolytic process produces high purity hydrogen(99.7%) and consists in passing current through aqueous solution of alkali leading to decomposition of water into hydrogen and oxygen(at STP) Anode (oxidation): Cathode (reduction): Overall reaction: 2 H2O(l) O2(g) + 4 H+(aq) + 4e 2 H+(aq) + 2e H2(g) 2 H2O(l) 2 H2(g) + O2(g) (Eoox = -1.23 V) (Eored = 0.00 V)

CHEMICAL REACTIONS USING ACID OR ALKALI: Methods Using an Acid:

With Iron: If dilute sulphuric acid is brought into contact with iron, chemical action takes place, with the production of hydrogen and ferrous sulphate,

Fe + H2SO4 H2 + FeSO4
Theoretically, to produce 1000 cubic feet of hydrogen at 30 inches barometric pressure and 40 F. The hydrogen produced by this method varies considerable in purity. There are other metals which will yield hydrogen with sulphuric acid, such as cadmium and nickel, while many metals will yield hydrogen with hydrochloric acid, such as tin, nickel, and aluminium.

Methods Using an Alkali:

With Zinc:- If a solution of caustic soda in water is brought into contact with metallic zinc, chemical reaction takes place, with the production of sodium zincate and hydrogen

Zn + 2NaOH H2 + Na2ZnO2
Theoretically, to produce 1000 cubic feet of hydrogen at 30 inches barometric pressure and 40 F. The hydrogen produced by this process is generally very pure, but, depending on the purity of the zinc.

USES OF HYDROGEN:
1. Used to produce ammonia- used in common household cleaning products. 2. Hydrogen is used as a hydrogenating agent to produce methanol and convert unhealthy unsaturated fats and oils to saturated fats and oils. 3. The triple point of hydrogen can be used to calibrate some thermometers. 4. Tritium can be used to make hydrogen bombs 5. Used in the production of hydrochloric acid- used widely in chemical industries. 6. Hydrogen gas is used to reduce many metallic ores.

SULFURDIOXIDE (SO2)
INTRODUCTION:
Sulfur dioxide (also sulphur dioxide) is the chemical compound with the formula SO2. It is released by volcanoes and in various industrial processes. Sulfur dioxide is a heavy, colorless, poisonous gas with a pungent, irritating odor familiar to the smell of a just-struck match. It is soluble and can be easily liquefied under moderate pressures at room temperature.

SOURCES OF SULPHUR DIOXIDE:

Natural: Natural sources of sulfur dioxide include releases from volcanoes, oceans, biological decay and forest fires. Man-made sources: The most important man-made sources of sulfur dioxide are fossil fuel combustion, smelting, manufacture of sulfuric acid, conversion of wood pulp to paper, incineration of refuse and production of elemental sulfur . Coal burning is the single largest man-made source of sulfur dioxide accounting for about 50% of annual global emissions, with oil burning accounting for a further 25 to 30%.

INDUSTRIAL PRODUCTION:
Sulphur dioxide may be produced by: Burning of Sulphur Roasting of Metal sulphides such as Iron pyrite(FeS) Copper pyrite Zinc Blende Recovery from the waste gases of other industrial processes and reactions The most important raw materials for the production of gases containing SO 2 are elemental sulfur and pyrites (FeS2). Naturally occurring pyrite contains 4248 % sulfur. Other sulfide ores, such as copper pyrite, zinc blende and galena, are processed to produce metals. The sulfur dioxide inevitably obtained during roasting of these sulfides is used mainly for sulfuric acid production.

METHODS OF PRODUCTION:
There are several different processes for the production of liquid SO2: Compression and Condensing Partial Condensation Absorption and Acidification Sulphur trioxide and sulphur

Compression and Condensing:

At atmospheric pressure, pure SO2 will begin to condense at 10.1C (13.9F). If the gas is compressed to 388 kPa(g) (56.3 psig), SO2 will begin to condense at 32.2C (90F). This temperature is high enough that normal cooling water can be used to condense SO 2. When the concentration of SO2 is less than 100%, the gas must be compressed to higher pressures to obtain a high enough condensing temperature to use cooling water as the condensing medium. The tail gas leaving the system may be further cooled in a refrigeration unit to achieve nearly 100% or full condensation of the SO2.

Partial Condensation:
When the concentration of SO2 in the gas is low (typically 7-14%), it becomes impractical to attempt to fully condense all the SO2 contained in the gas. Extremely high pressures are required in order to use cooling water to condense SO2 from the gas. The alternative to full condensation is partial condensation of the SO2 is using refrigeration only. Refrigeration systems can achieve temperatures as low as 55C (-67F). Typically, only 50% of the SO2 can be condensed from the gas.

Absorption and Acidification:

The process is based on the absorption of sulphur dioxide in an aqueous solution of ammonium sulphite and the liberation of the absorbed sulphur dioxide by the addition of sulphur dioxide solution, forming ammonium sulphate as a by product. Gas containing low concentrations of SO2 (typically 1-2% vol) is scrubbed using an ammonia solution to form ammonium bisulphite according to the following reaction:

SO2(g) + NH4OH NH4HSO3

The ammonium bisulphite solution is reacted to sulphuric acid to form ammonium sulphate, water and SO2.

2 NH4HSO3 + H2SO4 (NH4)2SO4 + 2 H2O + 2 SO2(g)

The SO2 is stripped from the ammonium sulphate solution and is directed to liquid SO 2 production or to acid production plant directly. .

Sulphur Trioxide and Sulphur:

Molten sulphur is mixed with oleum on a reactor operating at a temperature of 110 degrees Celsius.The gas produced is passed through column of sulphur where any remaining sulphur trioxide is converted into sulphur dioxide. The pure sulfur dioxide is then condensed to liquid in a condenser circulating cooling water. Futhr development of this process involves feeding both oleum and liquid sulphur trioxide to the reactor at the same time.

HSO (l) HSO (l) + SO (g) 2SO + S 3S0 USES OF SULFUR DIOXIDE:
About 98 % of the SO2 employed industrially is used for sulfuric acid production (98%). Apart from production of sulfuric acid, sulfur dioxide is used in the following branches of industry: In the cellulose industry for the production of digestion solutions for sulfite cellulose, As a disinfectant In bleaching agent in textile and food industries As antichlor, for removing excess chlorine As a mold-preventer in the drying of fruits Controls fermentation in the making of wine As a reducing agent or liquid solvent in petroleum refining Paper pulp industry (Sulfite process)

HELIUM (He)
INTRODUCTION:
Helium, symbol He and atomic number 2, is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas that heads the noble gas group in the periodic table known for its low density and low chemical reactivity. It is probably best known as a non-flammable substitute for hydrogen to provide the lift in blimps and balloons. Its boiling and melting points are the lowest among the elements and it exists only as a gas except in extreme conditions.

Helium is the second lightest element and is the second most abundant element in the observable universe, being present at about 24% of the total elemental mass. Helium is named for the Greek God of the Sun, Helios. It was first detected as an unknown yellow spectral line signature in sunlight during a solar eclipse in 1868 by French astronomer Jules Janssen.

RAW MATERIALS:
Helium is generated underground by the radioactive decay of heavy elements, such as uranium and thorium, which consist of alpha particles i.e., helium nuclei Some of this helium escapes into the atmosphere the rest becomes trapped underground and mixes with the natural gases that form there. The amount of helium found in various natural gas deposits varies from almost zero to as high as 4% by volume. Helium can also be produced by liquefying air and separating the component gases. The production costs for this method are high, and the amount of helium contained in air is very low.

MANUFACTURING PROCESS:
Helium is usually produced as a byproduct of natural gas processing. Natural gas contains methane and other hydrocarbons, along with smaller quantities of nitrogen, water vapor, carbon dioxide, helium, and other non-combustible materials. These materials lower the potential heat energy of the gas hence must be removed in a process called upgrading. When the gas contains more than about 0.4% helium by volume, a cryogenic distillation method is often used in order to recover the helium content. Once the helium has been separated from the natural gas, it undergoes further refining to bring it to 99.99 +% purity for commercial use. Here is a typical sequence of operations for extracting and processing helium. Pretreating: The first step is that of Preheating and it involves the removal of impurities, such as water vapors, carbon dioxide and certain heavy hydro carbons, that might solidify during the cryogenic process. The natural gas, pressurized to about 800 psi, is flown into a scrubber where it is subjected to a spray of monoethanolamine, which absorbs the carbon dioxide and carries it away. The removal of water vapours is achieved by passing the gas through a sieve through which the big water particles are unable to pass. The gas is then passed though beds of activated carbon to remove the hydrocarbons.

Separating
Natural gas is then separated into its major components through a distillation process known as fractional distillation. In the fractional distillation process, the nitrogen and methane are separated in two stages, leaving a mixture of gases containing a high percentage of helium called crude helium. It contains about 50-70% helium, 1-3% unliquefied methane, small quantities of hydrogen and neon, and the balance nitrogen.

Purifying
Crude helium must be further purified to remove most of the other materials. Firstly it is cooled to about -193 C resulting in removal of nitrogen and methane. After this, air is passed to remove Hydrogen in the form of water vapors. The gas mixture is then passed through a porous material, which results in the removal of most of the remaining water vapor, nitrogen, and methane from the gas mixture. The helium is now about 99.99% pure.

USES OF HELIUM:
Helium is used for many purposes that require some of its unique properties:

Helium is used in Cryogenics to cool superconducting magnets in MRI scanners. As helium is lighter than air, airships and balloons can be filled with the gas to gain lift. Helium is used to condense hydrogen and oxygen to make rocket fuel. Helium can be added to oxygen tanks so that divers can breathe more easily. Used in helium-neon lasers. These lasers can be used to read barcodes. For materials easily contaminated by air, helium is used as a shielding gas in the arc welding process. Helium is used as a protective gas when growing silicon and germanium crystals and when producing titanium and zirconium. It is a fantastic protective gas as it is inert (unreactive).

ARGON (Ar)
INTRODUCTION:
Argon, symbol Ar and atomic number 18, belongs to the group of noble elements. It is the third most common gas in the Earth's atmosphere, at 0.93% (9,300 ppm). The name "argon" is derived from the Greek word meaning "lazy" or "the inactive one", a reference to the fact that the element undergoes almost no chemical reactions.

PRODUCTION:
Industrial: Argon is produced industrially by the fractional distillation of liquid air in a cryogenic air separation unit; a process that separates liquid nitrogen, which boils at 77.3 K, from argon, which boils at 87.3 K, and liquid oxygen, which boils at 90.2 K. 40 In radioactive decays: Ar, the most abundant isotope of argon, is produced by the decay of 40K with a half-life of 1.25109 years by electron capture or positron emission. Because of this, it is used in potassium-argon dating to determine the age of rocks.

MANUFACTURE PROCESS:
The production of argon involves connecting a "side arm" column, which receives a feed vapor from the low pressure column at a point near the maximum argon concentration.

USES:
Argon is used in the following applications:

Argon gas is used in graphite electric burners to prevent the graphite from burning. The graphite would burn in normal air with oxygen present. Crystals of silicon and germanium are grown in the presence of argon. Argon, in liquid form, is used by scientists to look for dark matter. Argon can be used to preserve paint, varnish and similar things for storage after opening. In the science laboratory, argon is often used as a carrier gas in gas chromatography. Blue argon lasers are used in surgery to weld arteries and correct eye problems. Lights are filled with argon to prevent the filament from reacting with air.

NEON (Ne)
INTRODUCTION:
Neon, symbol Ne and atomic number 10, belongs to the group of noble elements. Neon is a colorless, odorless monatomic gas. Its name is derived from Greek words meaning "new one." Neon is chemically inert and forms no uncharged chemical compounds.

PRODUCTION:
Neon is a rare gaseous element. It is present in the atmosphere to the extent of 1 part per 65,000 of air. Neon is obtained by liquefaction of air and separation using fractional distillation. It collects in the dome of main condenser as a non-condensable gas.

USES:
Neon has the following applications: As a filler gas for display lights and neon signs For high-energy research Deep-sea diving Liquid neon is used as a cryogenic refrigerant

KRYPTON (Kr) AND XENON (Xe)

Since Krypton and Xenon have high boiling points relative to oxygen, they normally accumulate in the liquid oxygen sump of the upper column of the main plant. The primary application of krypton is as a light bulb filler gas. Its thermal properties are more favourable than those of argon and lead to more effective light bulbs. Additionally, both Krypton and Xenon are used in instrumentation and research application.

RECOMMENDED QUESTIONS:
Q.1 Q.2 Q.3 Enlist the areas of applications of industrial gases? What are the various production methods of Hydrogen? Write a brief on cryogenic separation of air for production of oxygen?

REFERENCES:
Wikipedia Shreves Chemical Process Industries Google chrome