1 iv) Cryogenic Liquid Purification. An impure nywiven a arene . sndensed and separate iquid strean cooling to cryogenic temperature where the impurities will co Dee eat to SN This used for bulk separation of light hydrocarbons from hydrogen in a refinery of iow syng 3. CARBON DIOXIDE (CO2) a for! USES , Be ‘and foods in its solid form. Presence Largest use of CO> is for refrigeration, freezing ice cream, i } of CO; atmosphere reduces bacteria spoilage of food. It is also important for inert atmosphere, Largest 0b use is for carbonated beverages. It is also an important fire extinguisher. It has many applications in. fer shemical industry. It is ies and for pH control of waste water. The advantage of an chemical industry. It is used for neutralising alkalies and for PH Conon aca i using solid CO> as a refrigerant is attributed to its dryness, ely high refrigerating effect, its low temperature and the insulating and desiccating action of the gas evolved SOURCES Various reactions produce CO. Some of the reactions are given below : ; 1. From nature it is formed by burning of carbonaceous materials C + OQ; —+ CO, — (10 to 18% Pure) AH =~23.16 keals Carbon dioxide is produced by combustion of coal or hydrocarbons, the fermentation of liquids and the breathing of humans and animals. In addition, it is emitted from voleanoes, hot springs, geysers and other places where the earth crust is thin; and is freed from carbonate rocks by disslution. CO» is also found in lakes at depth under the sea, and mingled with oil and gas deposits. 2. In the production of Hy by steam in water gas shift reaction 16% pure CO) is obtained. CO + H,0 —> CO) + Hp water gas shift reaction 3. In manufacture of alcohol (ethanol) by the fermentation process. 99.9 % pure COp is obtained. 4. Incalcinations of CaCOs 40% CO, is obtained at 1000°C CaCO, —> Cad + CO, (40%) MANUFACTURE Although there are many sources of CO; the following four are the most important for commercial production, 1. Recovery from synthesis gas. The chemical composition of syngas varies based on the raw materials and the processes followed for the production. Syngas produced by coal gasification is ach f carbon dioxide and 0 to 5% methane. INDUSTRIAL GASES AND INORGANIC CHEMICALS jnixture of 30 to 60% carbon monoxide, 25 to 30% hydrogen, 5 to 15 it also contains lesser amount of other gases. When used as an intermediate in the large-scale, industrial synthesis of hydrogen it is also produced from natural gas (via the steam reforming reaction) as follows : CHy+H,O —» CO+3H) CO+H;O —> CO,+Hy In order to produce more hydrogen from this mixture, more steam is added and the water gas shift reaction is carried out. ‘The hydrogen must be separated from the CO) to be able to use it. This is primarily done by pressure swing adsorption (PSA), amine scrubbing, and membrane reactors. 2, Recovery as a by-product in the production of SNG. Natural gas that can be produced from coal or biomass is known as synthetic natural gas or substitute natural gas (SNG). CO is a by product of the coal to SNG process. (SNG) is an artificially produced version of natural gas. SNG can be produced from coal, biomass, petroleum coke, or solid waste. The carbon containing mass can be gasified, the resulting syngas can then be converter to methane, the major component of natural gas. There are several advantages for this. The biomass can be used along with coal to produce SNG. The use of biomass would reduce the ‘green house gas emissions as biomass is a carbon neutral fuel. In addition, the development of SNG technology would also boost the other gasification based technologies such as hydrogen generation. 3, Recovery from production of ethanol by fermentation. The yield of CO varies with the method of fermentation. For the recovery and purification of CO, from fermentation, temperature will not exceed 40°C ‘and CO, content is more than 99.5%. The purification involves the oxidation of the organic impurities and dehydration using chemicals. 4, Recovery from natural wells. Gases that commonly occur with the hydrocarbon gases in natural gases from wells are carbon dioxide, nitrogen, hydrogen and noble gases as helium and argon. Nitrogen and carbon dioxide are non combustible and found in substantial proportions. Nitrogen is inert, but, if present in significant amounts it must be removed, since it reduces the heating value of the mixture. Carbon dioxide is removed in order to raise heating value and to reduce volume. This CO can be recovered and used for different uses. Inall cases pure CO; is obtained by various chemical treatments to remove the minor impurities. One of the reversible reaction used for CO> concentration is NCO; + CO, + H,0s==* 2NaHCO, To increase the yield of CO, NazCOs solution is heated. Manufacture by the combustion of coke or fuel oll or natural gas Manufacture of carbon dioxide by the combustion of coke or fuel oil or natural gas is done in the following sequence. Raw materials. Coke or coal, natural gas or fuel oil, Reaction C + 0 —> CO; — (l0t018%Pure) AH =~23.16 kcals Coke, coal, fuel oil or natural gas is burned under a standard water-tube boiler for the production of steam, The flue gases containing 10-18% CO> are taken from the boiler at 345°C, cooled, purified and washed by passing through two water scrubbers. After passing through the scrubbing towers, the cooled flue gases pass through a booster blower and into the base of the absorption tower in which CO) is I¢ AND ENVIRONMENy io HEMICAL! ; Ine the gas stream. The Co, al Tcainen passing countet © ree stepped trom the mi bearing ethanolamine solution 1s pumped iy the reactivation tower bes ‘rom traces of HyS and amines in joy CO; and steam pass out through the f0P O° TS eg gut is purifies a condenses and returns to the tower: CO2 B® 4 permanganate scrubber and dried sua Lesson " _-—{Monoethanotsenin) €0p-Production Plant Flow Diagram water for washing POSES Syeln and reat Light Diese! or " NewaGe — CO:Generaoe and Reboiler Dual $ tothe process 7: IEA Lean SolMion Ding a Dosing 17 bar-23°C FX Winer cooling Tower Liquefied COs to Tank Fig. 1.5. Flow diagram for the manufacture of CO. Stage Liquefied CO> to Pleats If liquid or solid CO, is desired, it may be further purified for odour removal before compression. For dry ice liquid CO, is reduced to atmospheric pressure followed by partial solidification. CO. snow formed is compressed to form a cake. METHODS OF RECOVERY The processes most commonly used for recovery of carbon dioxide are, 1, Ethanolamine process 2. Sodium carbonate process 3. Potassium carbonate process. All the processes are in commercial use and choice of suitable conditions. In all the process CO, is recovered by absorption-d passed counter current to a solution that removes the CO, by heat in a separate piece of equipment, Due to relatively low process will depend on the individu! lesorption, First CO-bearing gas¢ absorption and retains it until desorbed © : ' water solubili Jone is 9 used as a absorption medium. Alkali carbonate and i lity of CO., water alone i sohblty of CO, with the absorbing median ns “anolamine solutions are used due to the Hi 1. Girbotol amine (Ethanolamine) process It was developed by the Girdler Corporation of Louisville, OS Ee Kentucky. The process uses #4! yeous nilINOUSTRIAL GASES AND INORGANIC CHEMICALS 13 Gitions of a mono-, di- oF triethanolamine as absorption medium. 20HC;HyNH3 + H;0 + CO) —» (OHC;H,NH3):CO3 above reaction, Forward reaction proceeds at rhe operation depends on the reversible nature of the on. Forw ction proc Jow temperatures (65°C) and absorbs CO, from the gas in the absorber. The amine solution, rich in CO low ts out of the bottom of the tower. Then solution passes counter current to a stream of CO> ani Pisin, which strips CO> out of the solution. As the solution reaches to bottom of the tower, it has been reactivated. This hot solution (140°C) passes out of the tower. ‘Advantages of the process are : . Complete removal of carbon dioxide Regeneration up to 100% with moderate steam consumption is possible 1 2 3. Higher absorption of CO; in the solution 4, Lower operating cost 2. Sodium carbonate process NaxCO; + H,O + CO, —> 2NaHCO; Recovery of pure carbon dioxide from gases containing other diluents, such as nitrogen and carbon monoxide, is based on the reversibility of the above reaction. This reaction proceeds to the right at low temperatures and takes place in the absorber where the CO» bearing gases are passed counter current to sodium carbonate solution. CO2 absorption rate depends up on temperature, pressure, partial pressure of CO; in the gas, and solution strength. Reverse reaction will proceed when heat is applied. CO, gas and water vapour released from the solution in the boiler pass through steam condenser where the water condenses out and returns to the system. The cool CO, proceeds to the gas holder and compressors. 3. Potassium carbonate process As potassium bicarbonate has more solubility than its corresponding sodium salt, it provides better absorption of CO; than other process. Operation and equipment layout of process are similar to sodium carbonate process. This process used for removing CO, from NH; synthesis gas mixtures, and from natural gas. These gas streams are treated at 250 psi, or higher pressure which increases the partial pressure of CO) so that the hot KzCO; solution (20-30%) will absorb substantial amount of CO, at 110°C. The solution sends to the CO; stripping tower operating at or near atmospheric pressure. Part of the absorbed COs flashes out of the solution as it enters the stripping tower, and the balance is stripped from the solution by steam. 4, RARE GASES OF THE ATMOSPHERE Air is the most important source for the noble gases, with the exception of helium (obtained from natural gas) and radon (obtained as a by product of the decay of radioactive elements). At sea level, dry air contains 0.93% argon, 0.0018% neon, 0.00052% helium, 0.0001 1% krypton and 0.0000087% xenon in addition to 78.08% nitrogen and 20.95% oxygen. Other components of dry air include carbon dioxide hydrogen, methane, nitric oxide and ozone. Smaller concentrations of rare gases are also occluded in igneous rocks, but the atmosphere is the principal commercial source of neon, argon, krypton and xenon, which are obtained as by-products of the liquefaction and separation of air. : 4.1. ARGON USES oxy, Primary application of argon is in metallurgical processes. It is used as a shielding gas from g in the welding of metals such as aluminium and stainless steel. It is also used in the refining of letals. such as zirconium, titanium, and many alloys. It is filled in incandescent light bulbs. For the Production of stainless steel by argon-oxygen decarburizing process large quantities of argon is required, este di MANUFACTURE of nitrogen and oxygen, using & separal ined during the cryogenic fy oxygen. Boiling point of Argon is obtained during the enegeni¢ ure) column used £0 a Roe ey ee nite — i tes jst above VEE Pr The feed is 8% argon is just below that of oxy imately 9 ‘Argon rich vapour is withdrawn from the upt n of approximale ae oxygen and 11% argon with only traces of nitrogen. It 96) argon, PUTE Liquid Argon (PLAR), is purity, known as industrial Argon. When very high grade (99.99: es eknown as the Argon Purification required, industrial grade argon is processed again in separate lee vith hydrogen and passing the Unit This plant removes remaining oxygen by mixing the gS SITET Tr is removed by passing mnixture over a catalyst, Oxygen combines with hydrogen and the Ware Ggenic temperatures through a molecular sieve. Residual nitrogen is then removed by furthe 4.2. NEON USES ee This used as a filler gas in display lights. Large quantity of the gas is Ut is also finding uses in instrumentation. It is a safe low temperature cryos Another use is in deep sea diving. in high energy research. It for speciality applications. MANUFACTURE cate be ‘Neon (boiling point 27 K) does not condense out at the temperatures used in air separation pI ES Hence it is withdrawn, with helium, and cooled to liquid nitrogen temperature. The helium is removed’ by adsorption on activated charcoal. 4.3. KRYPTON AND XENON Although traces of krypton are found in various minerals, the most important source of krypton is Earth’s atmosphere. Natural krypton is a mixture of six stable isotopes. Krypton-84, is the most stable one. The other stable isotopes of krypton are krypton-86, krypton-82, krypton-83 ; krypton-80 ; and krypton-78. Krypton can also exist as an unstable, radioactive isotope obtained from the fission of uranium, which occurs in nuclear power plants. Air contains only the stable isotopes of krypton. Uses Krypton is used with argon in fluorescent lamps to improve their brightness and with nitrogen in incandescent lights to extend their lifetime, It is also used in flash bulbs to produce a very bright light for a very short period of time, for use in high-speed photography. Radioactive krypton-85 can be used to locate small flaws in metal surfaces. The gas tends to collect in these flaws and its radioactivity can be detected. Both krypton and xenon are used in instrumentation and research applications. The very rare gases neon, krypton and xenon are marketed as speciality gases, rc 4 MANUFACTURE Neon, argon, krypton and xe ir i ; . ahaa non are obtained by the liquefaction of air. The following steps are Liquefaction of ai s act rea pie saree Particulate matter such as dust. The clean air is then passed to an alkali cooled by refrigeration, The ice: The clean, dry air is compressed under high pressure and then ofthe its allowed io expand int the chamber The sreoe ean empty chamber. A potion veal be rege Coe 'e chamber. The process of compression and expansion is repeated p dt transformed into liquids, ‘© a temperature of about 196°C, when most of the gases in the air areINDUSTRIAL GASES AND INORGANIC CHEMICALS 15 arating the gases : ee with very low boiling points are not liquefied and can be removed from the others directly. ‘These gases include helium, hydrogen, and neon, se Ts Various gases are then separated by fractional distillation of liquid air. The liquid air is allowed to arm slowly. As the temperature increases the component with the lowest boiling points eras gases tnd can be removed from the remaining liquid. Argon, oxygen and nitrogen are the fist transformed into fuses as the liquid air warms. Krypton and xenon have higher boiling points and remain in the liquid s when the other components of air have become gases. med into separating Krypton from Xenon “The liquid krypton and xenon are absorbed onto silica gel or onto activated charcoal. They are then subjected to fractional distillation. che liquid mixture is warmed slowly until the krypton is transformed into a gas. The xenon has a somewhat higher boiling point and remains behind as a liquid. The krypton is purified by passing it over hot titanium metal which can remove all elements except noble gases. ; Separating the isotopes of Krypton For most purposes, the krypton is now ready to be packaged. For some scientific purposes, however, only one of the six stable isotopes of krypton is desired. To separate these isotopes, a process known as thermal diffusion is used. This process depends on the fact that the isotopes have slightly different densities. The krypton gas is placed in a long vertical glass tube. A heated wire runs vertically through the centre of this tube. The hot wire sets up a convection current within the tube. This current of hot air tends to carry the lighter isotopes to the top of the tube, where they can be removed. 44, HELIUM Although helium is one of the most abundant elements in the universe, most of it exists outside of Earth's atmosphere. Helium was discovered in 1868, when French astronomer Pierre Janssen and English astronomer Sir Joseph Lockyer were independently studying an eclipse of the Sun. Using spectrometers, they both observed a band of yellow light that could not be identified with any known element. Lockyer suggested the name helium for the new element, derived from the Greek word helios for the sun. __ For the first time heliuni had been identified on Earth in 1905, During World War II, helium became a stitical war material. One of its more unusual uses was to inflate the tyres on long-range bomber aircraft. The lighter weight of helium allowed the plane to camry 154 Ib (70 kg) of extra fuel for an extended range. Helium is formed underground by the radioactive decay of heavy elements such i J und | as uranium and ee Part of the radiation from these elements consists of alpha particles, which form the nuclei of nn on is amount of helium found in various natural gas deposits varies from almost zero to as as volume. Only about one-tenth of the working natural gas fields hi i i Concentrations of helium greater than 0.4%, . pees Seo aan ane Helium can also be produced by liquefying air and sey osts for this method are high, hence the method is not ec: at is very low. Although this method is often used to pro Tarely used to produce helium. Because it is chemically inert, it is also used a: ield it B inert, i 's a gas shield in robotic are weldin; - ne ea meee Pane wes Gs Seal crystals used to make eaadoHie saaletiees s. Li i used to provide the extremel: ired ii i i ‘nd scientific applications, including superconduction retest eae ee etlID ENVIRONMENT ANI INDUSTRIAL CHEMICALS tains methane ing. Natural gas cont by product of natural £88 PTOPSSST ities of nitrogen, ior 1H as a by PI it contain -oduce natural gas wi ue Be von nate i ele materials. In order to a impurities upgrading and other hydrocarbons. Mos her non-combusti By removing the Vapour, carbon diode, helium, and other NOn-SOMN AT oved, By an acceptable level of heat energy, ee er oueray process is done to improve the level oy bale By 018 hen the natural gas contains more than 04% NEN f Once the helium has used to recover the helium content. Once the helium Wie further refining to bring it to 99.99+% purity for cor helium is given below : The steps involved for extracting and processing be solidified such as water vapour, carbon treating : In this step, all impurities that ean ret eas utilizing an extremely cold deed ce hydrocarbons. must be removed from the ee ek cryogenic section. Natural gas is pressurized to about 800 psi 1 inet oxide and can be removed. Then subjected toa spray of monoethanolamine, which absorbs the carbon diosiee Wk Tit TS ees or the gas steam passes through a molecular sieve, which holds the larger wate? WaPo’ MN ty eh steam while eng the sraller gas molecules pas. The water is back-fushed Oo rt A femoved, Any heavy hydrocarbons in the gas stream are collected on the surfaces OF 8 OY Na tmied carbon, The gas stream now contains mostly methane and nitrogen, and neon, : i an i agar avon ional distillation to (6) Separation ; Natural gas is separated into its major components by seat ates separate nitrogen and methane in two stages, leaving a mixture of gases containing high percatsns of helium, At each stage the level of concentration of each component is increased until P ic distil thod is cryogenic distil ion met nthe natural 20, it undergoes complete. Condensor }+ Cold crude helium Reflux subcooler i Activated yy: Loy pea cy Mae sete pcre =) aie Scrubber 2S Absorptor column column oe Water Heavy Expansior neter hydrocarbons | Valve 85 Monethalamine plus carbon dioxide Upgraded Natural gas Nitrogen Main heatexchanger Crude = subcooler +——_- Penetrating a ee efi Separating ed, Fig. 1.6. Flowchart for the manufacti i — f Helium, All impuriti ight soli oe : purities that ih soit and ce the cryogenic piping is removed from the natural gas in a process, am passes through one si methine nd eg ogenie section per or Si#© OF a late heat exchanger while very cold ‘ooled, while the methane and nitorerras: warb8ss through the other side. The incoming gas stream is7 Sxpansion cools the gas stream to the point gas, enters the base of the the internal baffles in the methane-rich mixture in the USTRIAL GASES AND INORGANIC CHEMICALS IND! — ite the pressure drops to about 145-360 psi. This rapid white the methane stars to liquefy. The gas stream, now Pal Figh-pressure fractionating column. As the gas works its ign, it ises additional heat. The methane continues to liquefy, forming & fottom of the column while most af the nitrogen and other gases flow to the toP- ‘The liquid methane mixture, called erude methane, is drawn out of the bottom of the high-pressure column and is cooled further in the crude sub cooler. Tt then passes through @ second expansion valve, “hich drops the pressure 10 about 22 psi before it enters the low-pressure fractionating column. As the jiquid methane works its way ‘down the column, most of the remaining nitrogeo is separated, leaving @ Tiguid that is not more than about {4% nitrogen and the balance methane. ‘This liquid is pumped off, ‘warmed, and evaporated to become upgraded natural gas. The gaseous nilropeh is piped off the top of the low-pressure column and is either ‘Vented or captured for further processing: ‘The gases from the top of the high-pressure column are ‘cooled in a condenser. Much of the nitrogen ‘condenses into a vapour and is fed into the top of the low-pressure column. ‘The remaining gas is crude helium. It contains about 50-70% helium, 1-3% unliquefied methane, small quantities of hydrogen and neon and the balance nitrogen. n : Crude helium is purified in a multi-stage process using several different separation d the intended application of the final product. e, most of the nitrogen and (c) Purificatio methods depending on the purity of the crude helium an ‘The crude helium is first cooled to about (193°C). At this temperatur: eee a Liquid and are drained off. The remaining gas mixture {s 90% pure helium. This is by passing over a catalyst, which causes most of the hydrogen in the mixture to react with the OxyBen in ake air to form water vapour. The gas is then cooled to modense water vapour which is drained off. The pas mixture enters a pressure swing adsorption (PSA) unit consisting of several adsorption vessels containing particles filled with tiny pores. As the gas inixture passes through these particles under pressure, venain gases are trapped within the particle pores: The pressure is then decreased and the flow of BAS oer to purge the trapped gases. This cycle is repeated after a few seconds or few minutes depending on the size of the vessels and the concentration Ofeases. This method removes most of the erring water vapor, nitrogen, and methane from the gas mmigture, The helium is now about 99.99% Pure Tre helium is to be liquefied, or if higher purity is required, the neon and any trace impurities are re: loved by passing the gas over a bed of activated carbon in a cryogenic adsorber operating at about (253°C), Purity levels of 99.99% or better can be achieved with this final step. (d Distribution : Heli low temperatures. Gaseous range of 900-6,000 psi. Bulk quantities of liquid up to about 56,000 litres. Large quantities of liquid helium are usually sl methane condet med with air and then warmed in a pre heater ‘um is distributed either as @ gas at normal temperatures or as a liquid at very helium is distributed in steel or aluminium alloy cylinders at pressures in the helium are distributed in insulated containers with capacities hipped in pressurized containers. 5, ACETYLENE USES ‘Acetylene mixed with oxygen to give a high welding temperature. It is used for the synthesis of chemicals such as acetic acid, viny! chloride, acrylo nitrile, poly vinyl pyrrolidone and tric hloro ethylene. Reactions of acetylene at high pressures in vinylation, ethynylation, and polymerisation are used for the synthesis of many industrial chemicals. MANUFACTURE 1. Acetylene can be made. by the reaction of calcium carbide with water Cac, + 24,0 —> CaOH) + Cathie)AND ENVIRONMENT AL CHEMICALS jnousTR! m carbide. lene from calcul : This takes pla eaction takes ylindrical water shell. Thy ace inac’ acetylene. Calcium, 18 jace producing, paration of acetyl ct process) bove F ds for Prel fo water pr neasure There are two metho. (@ Batch-carbide carbide is fed to water at 0 hydroxide is removed as SIU: oe (6) Continuous-dry process For large scale oi e «of ealeium carbide is used. Levee amount of Hea form, Continuous agitation 1S necessary to prevent 150°C. 2. Manufacture by pyrolys ‘The process involve partial -ocess(W' .d rate, The al romatic feed of Tkg of water water forming lime in ¢ erature should be kept at na continuous aut oduced vaporises ting since the temP' drocarbon and supply of electric arc at ble than other hydrocarbons, fast (milli seconds), ral gas or liquid hy thermal cracking ylene is more stal is of natui | oxidation using oxygen, 327°C and higher, ace high temperature. At temperature | ; but will ecompose into elements. Hence the conversio® should be done very 2CH, —> Git + 3th cH, — C + 2th the decomposition competes with 8°C. SO ne must be raised to 1327°C for fhane to elements starts at 57 degradation to acetylene at 1327°C. To prevent this decomposition metha ser aares and then the reaction must be quenched instantaneously: {natural gas is the method mostly used by many m The decomposition of met The partial combustion o janufacturers. This process can be done in the following steps oxygen and natural gases are pre heated separately to about 650°C using fuel gas. Two gases are mixed in a bumer in a molar ratio of 0.6 : 100 for oxygen-methane. ‘The furnace of this partial combustion of methane which is instantaneous consists of three parts: 1. Mixing chamber 2. Chemical conversion zone 3. A quench chamber with quench oil or water sprays ‘The overall reaction is 90-95%. Acetylene and i Ho! " ses i i 0 38°C. The composition of the product is given in the SAL: Beenie cae Caer Composition (%) Gases Composition (%) Acetylene x 8.5 Hydrogen Carbon monoxide Carbon dioxide Methane ae j Higher acetylenes Acetylene is removed ii dioxide is flushed an eee column wathg, » selectt id st ; elective solvent (di : ‘Acetylene is frecioasel aut cline Higher aceylene and water ae ee epee formamide), Gerocn f+ pure 30-36% yield fro inder reduced pressure. m natural gas, 6. SULFUR DIOXIDE