The Essential Chemical Industry - online Cig ot Benzene and methylbenzenes xslenes), are manufactured from fractions obtained from the distillation of ll and are used as intermeciates inthe production of a very wide range of chemicals as well 8s in petrol, They are amongst the mast important organic oo" a. Benzene is the fundamental building block of aromatic compounds. It, and the methylbenzenes toluene and the CoHg Clty Imathitenare —12dnebybercene 1 2dnetnbersene ‘4dr benzene ‘aoe ‘ora ‘ovo ‘notre Uses of benzene and methylbenzenes Benzene ‘About haf ofthe benzene thats manufactured is used to produce ethylbenzene ([palymersipolyphenylethene.himifethylbenzene), which in tum 1s used to make poliphenylethene) palymersipolyphenylethene him) (polystyrene). (1-methylethy)benzene (cumene) accounts for another ‘quarter, wien is used to make phenol /chemicaliphenolhim) ang propanone (ichemicalsforopanone.him) (acetone) which are converted, for example, int a wide range of polymers. Another important use isto make cyclohexane, which is used, i tum, to make hexanedloic acd (adipic acid) and caprolactam, ental intermediates in the manufacture of polyamides (/polmers/polvamies him). Figure 1 Uses ofbenzane re Pi ne Usual Spy Dan enn Amare Chem Sy 23 osNtrobenzene (Figure 1) fs reduced to phenylamine (anne) used to make azo dyes (matevials-anc-applicationsicolorants:himi#azo_dyes) ‘methylene diphenyl disocyanate (MD used to make polyurethanes /polymersipolyurethane him) and itis ako used in the manufacture ofthe ‘analgesic, paracetamol. Another use of benzene isin the manufacture of akylbenzene sulfonates (materals-and- appicatonsisurtactants nmisakylbenzene), important surfactants ethylbenzene (Toluene) (Over 50% of the methybenzene(loivene) produced inthe refiner is converted into benzene by deaky/ation UUchemicalsbenzene hint#deakylaton) and isproportonaton (chemicabsrbenzene.himitdsproportonain). Methyloenzene is also used to make TOI toluene disocyanate or methybenzene disocyanats) one ofthe reagents used to make polyurethanes Upovmerspolyurethane himi#polyuretnanes}. tis also widely used as solvent, for example for alkyd polymers (materils-and. applcationsipaints nmalkyd_polymer) (resins) used n paints, Dimethylbenzenes (Xylenes) ‘The most widely used cimethylbenzene is 14-aimethybenzene (p-xylene). kis oxdied to benzene-t,4-icarboxyc acid Upalymersipolyesters hmibenzene-t.4-a 2 4 ‘Figure 2Benzane and the mathylbenzenes ae produced by 2 vary of ways, including cracking, reforming and lsomerisaton. This photo shows 2 plant wher these method are used and also how the aromatic rdocerbone oe puri. 1A reactor n which the C6-C8 stream Is Being dehydrogenated fo form aromatle hydrocarbons, Including ‘benzene andthe methybanzenes, an example of forming (iprocesseicrackingIsomersaon-and: -etorming hemtteaoring 2A rector in which somerleton (procerseierechngizomersaton.andreforming imiMizomerlation) ‘reactons ae taking place, for example to form branched cain alkanes rom naphtha. 1A rector in which erachng processeseracking-isomerisabomandvatorming hniferactng is king place long chain alkanes beng cracked o smaller alkanes and shones. 4 Separation of hydrogen and C1-C3 hydrocarbons hom higher hydrocarbons. | Removal of sulphurcontlning compounds. {64 esttaton column separating C86 rom C7.C9 hydrocarbons. 7A stack remove combustion ses om the mace Today, benzene and the methybenzenes are prmarly produced va: 2) steam cracking ofnaphthe and other liquid feeds b) catalytic reforming of naphtha Those two processes provide, in oqual shares, about 80% ofthe benzene produced. Inthe US, this is spt 30% and 50% rospectvaly but the proportion depends on many factors such as the use made ofthe other products ‘Smater amounts of benzene, in total about 20%, are produced from methybbenzene via ©) deakylaton 4) disproportonation In the US most ofthis benzene is produced by alsproporionation ©) An inereasing amount of benzene belng made tom blomass (a) Steam cracking of naphtha to produce benzene and dimethylbenzenes (xylenes) ‘This process i 9 major source of akenes (ethene and propene), key “uilding blocks for the chemical ndusty. A valuable co-poduet s RPS (raw pyroysis gas). buid rch n aromate hydrocarbons (benzene, methybenzene (oliene) andthe dimebiybenzenes (xylones)). This mixture of aromatic hydrocarbons is known as BTX. Steam cracking f alkanes such as propane and butane oblaines in the distilation ofa (rocessesitistiaton hint) abo yikds BTX To obtain these aromatic compounds, they are separated fom the non-aromatc compounds by solvent extraction (for example, using dethylne veo (3.oxa-pentane-t 5d) and ae then Factonalydisiled xo benzene, methybenzene andthe eimethybenzenes, ‘The relative proporton ofthe diferent aromatc hydrocarbons obtained ftom steam cracking depends on the condions employed. Atypical compositon i benzene ca 50%, methybenzene can vary between 3 and 30% and the dimethybenzenes are usualy ca 20% (b) Catalytic reforming of naphtha to produce benzene and dimethylbenzenes (xylenes) Reforming of napa produces pevl wih a high octane rating (fprocessesieacking‘somersaion-and-eforming himiactane_ rating) ts reformed using platinum or thenium, dispersed on alumina as the catalyst (processesieacking‘somerisaion-and-eforming himlireforming). The product contains BTX For example hexane is reformed fo benzene: werwoucoy—> CO) om 2‘Smiary, methybenzene and cimethybenzer 38 formed from heplane and octane respectvely: Hy Hortaino —» CJ +m monyoensre esto) HsC-(CHalo—CHs ee saa taser eores {As above, thoy are separate from the non aromatic compounds by solvent extracton for example, using dlathylone glycol (8-oxa-pontane- 4iot) and are thon Factionaly disied info benzene, methylbenzene and te dimothyBbenzones, Atypical composition of BTX obtained by reforming is benzene ca 15%, methylbenzene ca 40% and dmethylbenzenes c2-45%, Most countries use steam cracking and catalytic reforming to oblain benzene, the proporion of each process depending on whether the main aim sto produce aknes (othone, propane) o high grade potrel (which needs branched akanes, cyclbhexanes and the methylbenzenes) of specif aromatic hydrocarbons. However, a major disadvantage i that here ie not sufclnt demand forthe methylbenzene produced but ean be further treated to make the ‘more use‘ul benzene (see (¢) and (d) below), Figure 3 Thies partor BP's rene at Castlion near Valencia, In Spain. This ‘Photograph shows the ‘ata reforming unit in \nbich benzene and other ‘aromatl hydrocarbons are produced. Dying nomenon (0 The dealkylation of methylbenzene (toluene) to produce benzene On + Ovm (d) Disproportionation of ethylbenzene (toluene) to produce benzene and dimethylbenzenes (xylenesy=t= TorBenzene is he fundamental bulking block of aromate compounds. land the methybenzenes, are manufactured fom tractons obtained from the dstilaton of oil and are used as intermediates inthe production of avery wide range of chemicals a8 wl asin peta. They are amongst the ‘mostimporant organic chemicals. : So a Onn Hs ef tn pence on omy Gy In this process, methylbenzene and hydrogen are passed over a zeote catalyst at 16-25 alm and 700-750 K, Hydrogen is nottself consumed in this process, but suppresses undasirable side reactions and faciates the transfer ofthe methyl group. ‘Alas, the mature produces only contains about 25% 1 4-dimethylbenzene, the isomer thats most needed in industy, particulary fr the manufacture of the polyesters (polymersipalyesters htm). The others, 1.2- and 1.3-dimethylbenzenes, are only needed in comparatively small quantties. However, ithe zeolte (processesicatalysis-n-indusry himbfselectvey is washed with phosphoric aid and hested strongly, minute particles of hosphorus(V) oxide are deposted on the surface making the pores slighty smaller. This restricts the fusion ofthe 1,2-and 1,3somers and they ae held nthe pores unt hey are converted into the 1,4-somer and can escape (Fgure 4). “This romarkab lectvty enables the yielt of he 1 4-somer to be increased from 25% 10 97%. (@) From biomass ‘Thor is considerable interest in producing benzene and other aromate hydrocarbons from blamass, There are eeveral promising avenues: |. By heating nly clvided biomass, such as sawdust, which an act as alld as Itpasses over a heated zeolke(/processesistalysis-n industry himitzeotte catalyst in the absence of air to form a wide range of compounds from which aromatic hydrocarbons can be stile out. i. By gasifiation of biamass to form an ol, known as bo-ll(materials-and.applicationsfbofuels.Mnast pyrolysis) which is ich in aroatlc hydrocarbons. 1 By bioforming /materials-and-appliations/bioretineres hn, v1 A-Dimethylvenzene (para-aylene) can be produced (rom bie-based ethene Vmateras-and.-applications/biereinerieshimibe-sthene} Dats last amended: 18th October 2016 foe (http Ushtpuftnrmtac Aninvitation We invite you to wite fous fyou have any specific comments about ths ste, for example ‘errors that you have found, suggestions for new topics o for adding tothe existing uns, ‘suggestions for Inks to other stes and addons or altematves to our examples. Please send these comments to: ecl@essentalchemicalindusty.org (mato ecs@essentialchemicalindusty.or9) a