The Essential Chemical Industry - online search Oxygen, nitrogen and the rare gases Except for helium, which is mostly extracted from natural gas, oxygen, nitrogen and the other rare gases are extracted from the air that makes up Earth's atmosphere. Unlike the sources of some chemicals there are therefore no concerns Nig Og ‘about the depletion ofthis resource and if@ sample of airs used to produce one ofthe gases, there are no problems bout venting the Waste gases’ back into the atmosphere. The ready availabilty of oxygen and its reactivity with many other elements means tha it is used during the production ‘of many other chemicals, whereas some ofthe uses of nitrogen and the rare gases depend on their inertness. Uses Oxygen The largest ser of oxygen is tho steal (metasisoeI histo) industry. fs algo used inthe manufacture of ober ma, notably copper {imetaisicopperhnitcoppe’ and a (metasead nmiiea). t's more economic o use pure oxygen oF oxyger-enrihed a rather tan ai as this nereases the reacton rates and means that smatechemial plants canbe used. Furteritmekes casero ensure hat no gases such a5 slur dioxide ae lost and potte te atmosphere. ‘The gas is ako used in te manutacture of many chemicals incudng nie acs lcnemicasinie-aeé hm), hydrogen peroxide (chemiclsnyérogen-peoxte nm), epoxyethane chemicalslepoxyethane.hini) and chbroethene (polmersipalyehorethene.himipye) (ny chlor), the precursorto PVC. ‘Arvong i oer uses i the burning of of carbon deposited onthe fd catalst (processesichemicabreactors hmisfii_bed) used ine catalyi racking ofg98 oi A growing use for cxygen fin reat sewage and efuent tom dusty. Polluted vers and lakes can be cleaned by dissolving oxygen gas ioc nto the water to encourage a ater ecological balance ts used, or example, nf farming 0 provide bis balance. Ite algo use, wih sodum hydroxide, to bleach paper pulp as an atomatve to chlorine dioxide oF sodium enorto((sodkim hypachbtt). Nitrogen Nirogen is used to make ammonia (chemicals/ammoniaMimifammonia. tis also widely used to provide an inert atmosphere, @ process known as lanketng’, principally to exclude oxygen. For example, nirogen is used in his way in food packaging, glass making, and semiconductor manufacture itis also used fo purge out pes prior to weting (fr example, oll pias) to ensure that no flammable vapours are let behind. Liquid nitrogen ' being increasingly used to rerigerate food during transportation. Medical samples containing, for example blood, viruses for vaccinations and semen, can be stored fo lang perods if kept coolin quid nitrogen, >‘Figure 1 tankers ae purged with nitrogen to preven explosions during welding and other ‘maitanance. The photo iso the Omala moored in Retterdom, the Netartands yn pmo f Dy Canton Whe Con). Rare gases Ligue etiam, with very w boing pont of 4K has become veryimporantin cooing superconductor magnets, used for example, MRI scanners for madcal clagnosi. The magnets generate much heat and helum s the frat choles as thas the lowest boing poh of any Iquid. te ineress is undamental'o&s ater major uses, fr example, provide an net mosphere when Wein metab (o prevent metals reacting th at form oxides and rides), is also ust purge gas from tanks which have contained fuls such a qu hydrogen ako provides an nor aimesphere during the manufacture of high value malrials such as optical bras, Due to its low density, helium is used for weather baloons and airships. tis also used in combination wth oxygen to produce specialised breathing mixtures for divers. These mixtures are bottor than nitregen-oxygen maxures for prolonged diving as the blood wil absorb only Imitod amount of helum whereas wth nitagen, is concentration can Bull up to dangerous levels over a prolonged period, Helium is alo used in eximer lasers and helum-neon lasers that are used for bar code scanners. ‘Figure 2 Uses ofhllum in he United States ar 201m 0568 “The most common use for ngon'sin elec discharge lamps, ie. fMuorescent tubes. Like krypton and xenon, neon emis ight when an elctc currentis passed through the gas atlow pressures. Neon provides a red or orange colour, while diferent mitures ofneon, argon and hekum can be used to achieve white, mauve, yellow, blue and green. itis also used in lasers (nelium-neon lasers frlaser pointers) and in plasma display panels Alofthe major uses fr argon are related tothe production, processing and fabrication of metals. Argon s @ sgnifcant shaking gas used during arc welding processes, either on ts own or combined wih other gases. iis also used as the inert gasin lectc ight bulbs (whon mixed wil niogen), asa lew trermal conductivity medium within double-glazing window unis and for semiconductor manufacture, sro YopFigure 3 The closing ceremony of Otympics, August 12 2012. The Iuminated by mest halide Roosighs eat om the stat then provides he sible ght ‘Krypton snot only used in fuorescent lamps but also in incandescent lamps inchiding fash bulbs and halogen lamps which are used, for ‘example, in some cars, is aso found in some exime lasers and in plasma display panel, Xenonis, tke other rare gases, used in bubs including halogen lamps. Ithas a ight spectrum thats much wir than the other rare gases and ‘appears tothe human eye as daylght and sos used in ighing large areas such as sports stadiums, stage lighting and airor runways. Xenon, mixed with othe 92585 s used in eximer lasers for surgery (for example in eye surgery). "Maxed wi oxygen, iis used for GAT (Computer Aided Topography) scanning fr mapping blood flow, Xenon is aso being used as an anaesthote er Figure 4 An opthaimolosy surgeon athe US Nations! ations eye befor binning laser surgery Annual production About mon tones ofoxygen and nitogen (exuding ta! produced forthe manufacture of ammonia are produced annual inthe UK Im comparison, much smaller amounts ofthe rare gases are produced worldwide (Table 1). Ravegas | Abundance inthe World peryear hekom 52 28 0007 argon 9300 708 006? keypton 1 @ enon 008 owt Table 1 Rare gases: tir abundance inthe stmosphere and word production 3sas fo 1S Geta Se Se Manufacture ‘Ne contains nitrogen, oxygen and argon wth races of other gases, including water vapour, Although the presence of carbon dioxide in aris very Important environmental, ltaccounts for less than 0.04%. On average, the compostion af dy airs, by volume: on % nirogen 78 onaen 2 argon 0a Tbe 2 Composition of dy at Carbon dioxide, hatum, neon, krypton and xenon make up the balance. ‘There are several diferent methods for manufacturing niragen and oxygen 8) Dstlaton of igus a at cryogenic (very low) temperatures, This produces large volumes of very pure (up to 99.95%) oxygen, nltogen and the rare gases. Oxygen and nfrogen are often transported as iquids (by road tanker) and gases (by pipelne) to where they are tobe used on a large scale. Sometimes, however, the plants bull where the gases are being used (for example in the manufacture of see). b) Pressure swing adsorpton. This produces ether nirogen and oxygen, where its to be used (on ste), n smaller quantities and up o 95% purty, The main impurity is argon. 1) Vacuum swing adsorption, This is used o produce oxygen on ste, up to 95% purty. The main impuriy fs argon. 44) Membranes. These can alo produce nitogen on stein small amounts with purty of 95 to aver 99%, The choice of method depends onthe use ofthe gas and the amount needed. (a) Manufacture of nitrogen and oxygen by cryogenic separation of air “Tore are several diferent stages inthe process (Figure ), the three key ones being i) cleaning the a in iqueying he ai i station oft tau ie () Removing impurities from air In atypical plan, aris drawn in trough after to remove the dusl compressed fo about 6 alm and cooled to below ambient lemperature where much ofthe water vapour condenses. The aris then passed through a zeae (processesicatalss-n-ndustyhimiszeolte) molscular sieve to remove the resto he waler vapour and carbon dioxide. ee eee] sm thy nt motes ee nto Conattuens | Boling PoINIK at mosphere pressur| om 4 nitrogen 7 argon a7 nae | 80 Ss keypton 20 sell Topcarbon dixie 195 (sublines) Table The Bolling pont of the gases that mate up hy ar When a bicycle tye is pumped up, om atmospher toa higher pressure, heats produced. Conversely, fgas at high pressure is expanded io a lowor pressure, thers isa drop in temperature. Almost allmthads of producing low temperatures depend on this property bulls nota very efcient technique, Amore efcient way is expansion in a turbine, where mechanical work is extracted. Ar separation plans use ane or bath of those methods, in conjunction wih heat exchangers to achieve cooling ‘Te pure a, already compressed to 6 atm, s cooled wih the very cold product and the waste (nirogen IFoxygen is being made and oxygen, nivogen is being mace) in 8 series of heat exchangers (/processesichemical-eactors.nimltheat_exchangor) Eventually, his compressed airis cooled to about 100 K and then allowed to expand rapidly (the expansion turbine) which cools it further untl tis liquefied “The key othe whole proces is this use of he very cold nitagen, oxygen and argon to cao the incoming ar prior tothe expansion, (i) Distiation of liquid air ‘The liquié ai fs soparatod int its constiuent components by fractonal dislaton (processesicstilaion him). Ateach cstilation the vapour is Ficherin nirogen (the component wit the lower boling point}, while tre Iquid remaining contains more oxygen (Ihe component wih the higher boing point. ‘To produce pure oxygen the distillation system has two dilation columns, a'high’ ane a Tow column. Nitrogen plants often use a single column but some use two, trogen leaves the top ofthe column as a gas. Purty levels required by nitogen users are becoming increasingly stringent and itmay be lquefied again and resstiled. tis unusualfor the ntrogen to have an oxygen content of mare than 10 ppm and impurties contained in nivogen forthe elecitonics industry ae measured in parts per ion ‘Figure 6 An air separation lator te recovwy of ‘gen, nitogen and rare ‘tes In Leura naar Lapa, Germany. The estilaion ‘wo rectangular towers, known (th cold box. The lt hand ne ie ractionating a ‘obtain angen and nitrogen and te righthand one is covering argon. The ‘indors contin molecular sien ond bind them 8 Sioa i hated regenera ety. pin poison hinder ‘Tho tiqud containing oxygen and argon s further puried by disilaton Ina Sacond column. To obtain high purty oxygon further distlaton is needed and argon is removed, ‘Since air separation plans operate atlow temperatures, construction materials have to be chosen carefull. Aliinium alloys and stainless sts! are frequently used. They do not become bile at ow temperatures. Effeient plant insulation is nacessary to make techniques are commonly used (Faure 5). process economic and safe. Perlite (an expanded rock), class wool ané vacuum jacket (b) Manufacture of oxygen and nitrogen using pressure swing adsorption (PSA) Its sometimes more convenient for some industal plats to produce thelr own oxygen and nivogen on sie, provided a purty of 80% or s0 is accepiable. Pressure swing adsorption (chemicabletnanolnimiipsa) can provide this and produce upto about 100 tonnes a day To produce oxygen. a seam of clean aris passed through a bed of alumina to dry the gas and then through a bed of zeolite (orocessesicatalyss-n-ndusty.himltzeoke) molecular sieve. Nerogen i preferentaly retained (adsorbed) leaving an oxygen-enrcned saseous steam to passthrough (Figure 7}. When the zeolte becomes saturated with nirogen tis necessary to regenerate &. This can be Achieved simply by reducing the pressure, whereupon the nitrogen is released (desorbed) back ito the gaseous phase and rejected as waste. ‘The sieve s totally regenerated in ths way ands ready to repeat the cycle. ey “Two beds are usualy used in rotation. One is used to produce the oxygen while the other's being regenerated. Thefilleycle time caRw@mo Top between 2 and 8 minutes depending upon actual performance requirements.a Figure 7 Puritcton of oxygen using pressure swing adsorption Instoad of using a zeolte as inthe manufacture of oxygen, nitrogen is produced from ar using beds of carbon molecular seve (CMS). Clan, Ary, compressed ais passed through a bed of CMS (typically at 742 atm). Oxygen is adsorbed on the surface of te CMS and ntrogen passes through to storage. When oxygen saturation is reached a second bed is brought on-stream, retaining contnuly of supply and the fst vented to atmosphore to desorb the oxygon and hence regenerating the CMS prior tote next eyclo. Similar to te production of oxygen by PSA, te full cycle time for nirogen vares between 2 and 8 minutes. () Manufacture of oxygen by vacuum swing adsorption ‘Oxygen can be produced on ste by a process ver similar to pressure swing adsorption except that the sieve materilis regenerated by lacing itunder vacuum. This process is mare expensive to build butts more efficient to run. The sieve is more efectively regenerated and as a result, more oxygens obtained fom a given amount of a (a) Manufacture of nitrogen using membranes The pipe underlying tis method is that gases difuse a derentrates tough a polymer flm membrane, Oxygen and carbon doxde fuse more pial than nvogen and argon an this allows the remaining gas to become richerin nifogen and argon. Eventual, the ntrogen concentaton becomes over 95% “The polymer usd forthe membrane soften made of plymthy}entene) A atpressures of between 7 and 12 atm and heated to 290 o 310 i ispassed trough the membranes. The west gases permeate rough the membrane and ae vented tthe atmosphere (e) Manufacture of rare gases Argon oblained during te exyogenie manulacture ofnirogen and oxygen, using a Separate dstaloncokimn mounted alongside the second (ow pressure) column used to purty oxygen. [ALthis point nthe dstitaion process, the feed is typically 89% oxygen and 11% argon with only races of niogen ands e-datled to obtain argon of approximately 98% purty, known a8 Industial Argon. When very high grace (99.999%) argon, Pure Liquid Argon (PLA), needed, industial grade argon f processed ina separate plant the Argon Purficaton Unt. Ths plant removes residual oxygen by ming the gas steam with hydrogen and passing the mixture over a catalyst. Oxygen combines with hydrogen and the water formed s removed by passage through a molecular sieve. Residual nizogen i then removed by futher cstlaton at ryogenic temperatures. ‘Neon (boing point 27 K does not condense outa the temperatures used in air separation plants and fs wihdrawn, with Relium, and cooked to liquid nitrogen temperature. The helium is removed by adsorpfon on acvates charcoal -Reypton and xenon (bling points 120 and 185 Krespectvey accumulate inthe Iquid oxygen and are oblaines by further cision Holm s most obiained tom natural gas. Paticulay large amounts are found in the US, Qatar, Ageia, Russia (Sboia and Eastom Russi) ‘Australia and Canada, Some ofthe natural gas depos in tho US contain 16% helium, Natural gas is compressed (40 alm) and the condensed materials are removed. Hydrogen sulfide (chemicalsisuturhimitnysrogen_sude) is removed by washing wih 2-aminoethanol, asin he sulur exvacton provess and water vapour is removed by passing gas through specaly treated alumina. The gasis further purfled by a tree-stage cootng process, purr helium being remaved ater each stage and passed on othe next cooing step. Helum is avalabl in 9.95% and 99.995% purty grades. Date fast amended: 12th October 2016 (hppa shafts >Aninvitation Wie invite you to wite tous fyou have any specific comments about this ste, for example ‘errors that you have found, suggestions for new topics or for ading to the existing unis, suggestions for Inks to other ses and addons or alleratves to our examples. Please send these comments to: eci@essentatchemicalindusty.org(mailo:oci@essentalchemicalindustry org) ‘This we site is produced by the Centre for Industry Education Collaboration non-profit organization and an integral part ofthe Dep: CChemnistry, Univesity of York UK Copyright © 2016 University of York Cente for Industry Educate Cellabraten, York, UK. Al Rights Reserved, ment of > soln Top