The Essential Chemical Industry - online search Chlorine Chia, alons wins important by pedi, sodum heroes prodiced om he eal avalabe sang materal rock sat Cl (sou chore), itis wel known fo ts use in stesizingcrining water ann partclar swimming poo water. However, most Chlorine is usedin the chemical industry n the manfacure of eher products, Sometimes cherie iin the product molec bu on other ocasons its used o produce intermediates in the merece of procs tht co no onan chlorine ad he eemen is reojeted Uses of chlorine Thelargestusis in the manufacture of poh(chlorothere)(palmerspayeNereeene hin PYC. Obst major polymers produced using chloe neue se poirehanes(pehmerspoerebae nn), Aoughclrne das not appears he pohurthane molec, hia ex used o make the inlamaclae, he ocyanais. The onygenaes (Four) ae prepay eponypropane (propylene ode) and propane 2 ‘um to make polurehanes and poe inne Figure 1 The uses of chlorine. 1-Chioro-2.9-epoxypropane has many industial uses, the most important being in the manufacture ofthe epoxy resins (Imateias-and- appicatonsipaints ntmitepoxy).Among the uses of he chlorometnanes are the manufacture of slicones (polymersisiicones hm) and pobitetatuorosthene) (polymersipobietatuorosthene him), PTFE. ‘The solvents inching tichlooetnene) are used in dry cleaning, Chlorine s also used in the manufacture of many inorganic compounds, notably tanium dioxide chemicalttanium-dloxise.nml) and hydrogen chloride (chemicalsihydrogen-chioride him). Most chlorine is produced on the site on which tis going tobe used, for example, to make hydrochloric acid (/chemicalshydrogen-chlorde.Nim)) and the other compounds desorivec above.Figure 2 Atthough much rock salt Is pumped ote surface a brie, some fs ‘mined, 36s being done inthis large underground deposit in Cheshire Bykind pmb in However, some chlorne needs tobe transported for example, when fs tobe used to purly water For is, the chlorine is died by passing through concentrated sufurie acid ane then compressed and liquefied ito cylinders, ready for transportation. Annual production of chlorine wor 5 miton tonnes! us. _[1¥ mitlon tonnes? Europe | 10 millon tonnes? 1201 Boman of he an of hy Ane Cen Can Manufacture of chlorine Most chines manuacured by be olctayst of eum cre sears The oar main commer predete sdum hyéoxle {eheneaisodimsytoxd im, Te primary raw materia proces rock Godu che) avalole woe usualy te fom ofunderjound dapets chgh pity, tis pumped tre sutace wih Nigh peste wale as a oncenate auton, Thi soaten ohn cal one. Asolion fod ho conan Nag) and aa lone an, om he asodton of wae vor bw concenatan faq) and O98) fons. Duteg th ecb ah eahiton clone and hytogen gases ae produced © aro: 2Fan) —> Oh) 26% © Catode: W100) sm en) + OF frea sare fs hydrogen ons ae decharged more wale dsocesfoming moe hytrogen and hyroxd on. This resus a grado ule po the cncertatons ct hyéoxe ns sound he eae, bus producing esluon of sotum hose. The essential oquvenenti mmaia an facie and economic means cf spar he anode arcade reacions so ale produ, core ard cast sd, wl hottects fom sodum hypochbnie, Ths seperaonhas boon avd hsorealyby he meray omelyam and daphvegm processes However bese are bang pesed out and mostnew plants ssn xchange membranes, ic af e mst envformentaly and economcaly sone naan of ore roducton [@) Cation exchange membrane cal Te cation excnange membrane doesnot allow any 92s 0 negative ons to fow through it but allows Na ons to move between th bring and caustic compartments. (By Mercury amalgam eal In the flowing mercury cahoae process soaium ins are dschargedin tre form ofa mercury soe amalgam and chloride ions are converted ts clone. ‘The amalgam ws to totaly separate compartment the decomposer(denuder) mwah it 2 yl sodium hydroxide solution and hydrogen gas ce wih water (e Porcolating dlaphragm callA percottngaaphragm, usualy of asbestos, trough flow bin rom anode to eathodo It gration of OH ion rom he athode tothe anode it Prevented ay he veloty of gud ow agaist them the chlorine and hydrogen gas spaces. The Table 1 Th key fetes ofthe three electrolyte processes. (a) Cation exchange membrane cell The anodes are made of tanium coated win unenkim dloxde, Te cathodes ae nickel, ten wih a coathg te ec energy consumpton ‘The anode and cathode compartments are completely separated by an on-permeable membrane (Figure 3). The membrane is permeabye to cations, butnat anions: alows the passage of sadum ions but not chloride of hydroxide ons. Sodium ons pass though in hyated form (Naxts0) so some water's vansered, ut the membrane s permeable to fee water molecules. The sodum hydroxite soliton leaving he cells atca 30% (wl) concentration, I's concentrates by evaporation using steam, under pressure, unt he soliton i 6 50% (wy, the usu eoncentaton needed for ease of ransporaton and storage i AY al = ‘Figure 3 The membrane call ‘Tho membrane (0.15.0:3 mm thick) a co-polymer of tevatuorosthene (palymersipolyitafloroethene him) (and a similar Muornato ‘monomer with anionic (carboxylate and sutfonate) groups. ‘The plant shown in Figure 4 is using the new oxygen depolarized cathode, ODC, technology to produce chlorine, folowing atarge reswarch programme in Germany, le by Bayer. Figure 4 Chive Is bang produced inthis bank of ‘membrane cells, using he latest ecnnoogyinvelving ‘ngorepoarsed cathodes, (006. Tis photo shows fed pipes being checked a he ‘hema plant. ytd pemision of Ba When hydrogen fons migrate tothe cathode, hydrogen is berated. Howover, oxygen is pumped int this part of te col, the hydragen reacts to form water and the votage needed forthe electrolysis process is reduced by ated. This, n tum, reduces the power costs and thus the amount ‘of carbon dioxide formed inthe power station by atid, This ia great advantage as elecety accounts for about the lta cost of production, A lisadvantage s that the hydrogen s no longer avatable as an important and valuable by-produe, together wth oxygen being consumed as an additonal raw material. There have been technical ticles in applying this process {known as an oxygen-depolarised cathode, ODC) othe ‘electrolysis of brine and twas found easier appl to the electrolysis of aqueous hydrochloric acié inorder to generate chlorine. Large commercial plants have been constucied in China and Germany, using ODC technology. Now these dieu have been overcome and anew planthas been commissioned that uses brine asthe starting materi (b) The mercury cell “ypeal modem ga®-ight, rubber ined or PVC‘ned sel cel (Figure 4) are used, wich measure about 2 mx 15». They have a slghly sloping base over wich flows a hin layer of mercury, acing as a cathode, The anodes area series of anum pales coatd wih a precious metal oxide layer, and postoned about 2mm from te cathode, The calls Wpicaly opera nt setes of approxima 10Purifed, saturated brine (25% (win) sodium chioride solution) attypicaly 333 K fows through the celin te same direction as the mercury. This high sak concentation and te anode coating ensures the oxidation of chloride ions rather than that of water which would yield oxygen atthe tianlum anodes. © eng nary FL naan hon =e Porm) Beas ae = H9) Figur 5 The mercury cll and decompose. ‘The chlorine ied offas shown in Figura 5. [Attho mercury cathode, sodium fons are dlscharged in preference te hydrogen ions due tothe high overvotage of hydrogen. The sodium forms an amalgam with the mercury. ‘The amalgam contains approximately 0.9% (mtu) sodium. Irmaves on toa decomposer coll situated alongside the mercury cel ‘The ext brine, containing typically 15.20% (wiv) sodium chloride, eed of chlorine by blowing alr trough it or subjecting the sobition toa vacuum. The sokition Is resaturated wih sodium chiovide and retumed tothe cel, ‘Te decomposer cell Figure 5) # made of steel and contains graphite blocks ‘ed inthe fow ot amalgam. Aematvely, the decomposer's a ‘tower packed wih graphite spheres. The decomposer acts as a shor circuited cell At the anode ste, sodium is oxidized andthe ions pass into soluton. Atthe cathode ses, nydrogen is discharged. “The mercury is Jumadto the electrolysis cell and he hydragen passes out ofthe decomposer. A 50% (wi) soluton of sodium hydroxide ie produced inthe decomposar and most of tis sol! inthis frm. Some is concentrated by evaporation to 75% (wa) and then heat ad ta 750-860, to obtain sold sodium hydroxide, (0 The percolating diaphragm cell Inthe diaphragm cel (Fgure 8), the anodes are anium coated vit 8 precious metaloxde andthe cathodes ae stel. Ther porous asbestos daphragm to separate clone and hyerogen that re erated dung lectols “Te hydroxide ions formed in the cathode compariment ogeervth he sodium in, produce a sliion of adm hydroxide, The electohte levelis mainsines higher the anode comparment so tha the bine perolates through the dlaphragm nto the cate secton fom where t flows out ofthe cl wih the sod hydroxide soliton “| ‘Sate, TES» tmoen SU Te on 7 contanng sodhum tyrone Hom Ho T ‘Figur 6 The eaphragm call. ‘The chlorine formed onthe anodes rises ands led away.‘The cathode soliton contains about 10-12% (ww) sodum hydroxide and 15% (ww) sodium chloride, Ths is evaporated to one-ith of ts ‘orginal volume when the much les soluble sodum chloride erystalizes to leave a solution containing 50% (wi) sodium hydroxide and ess than 1% (wi) sodium chloride, ‘Comparison of mercury, diaphragm and membrane cells Factors such as captaand energy costs and envearmenta concerns alfavour the membrane process (Table 2)butits development was not possible uni work by Ou Pontin he USin the early 1960s, and more recent in Japan, resuted in the production ofthe membrane material discussed above. Ta Bapmam [waa [construction costs expensive retatvely cheap |Me*Per men * a mercury cell emery eva (ay om fevorctom [éapham [vemos tut |rpscres NaOH product high purty so | ee " ee oncwntaten eeremured | eperrton | concentration aa peony ho cn purty of brine [important important ve mean Throughout the world, the use ofthe mercury cells being phased out. For exampla, in Europe!, the proportion of chlosne made using the Morcury cellhas fall from 55% to 6% in 2017. In contast, the proportion af chlorine produced by a diaphragm cellhas risen from 20%. to 77% ‘verthe same period and the chlorine produced by a membrane cellhas dropped from 23% to 12% known a 2 Horton sphere Industry for liquid storage, for ‘example for he stilton products fom ol, such a pete! and naphtha. Thay are alzo used © stor quate gases propane and chlorine as wall 128 compressed gases such a8 Drydogen, oxygen and The chlorine-alkali balance For every tonne of chlorine, 2.25 tonnes of 50% sodium hydroxide and 340 m of hydragan (under normal conditions) ae also produced. is necessary, therefore, to ensure that all hes Date ast amended: 27th November 2018 products can be sold (hsputnpetomenaeiet shipingAninvitation We invite you to wite tous you have any specie comments about this ste, fr example ‘rrrs that you have found, suggestions for now topics of for adding tothe existing uns, suggestions for inks lo other ses and addtions or allematives to our examples. Ploase send these comments to: eci@essontatchemicaindusty.org (mailo:ec\@essentatchemicalindusty. org) ‘This website fs produced by the Cente for Industy Education Collaboration non-proft organization and an integral pat ofthe Department of Chemistry, Univesity of York UK. 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