ria call Methanol Synthe: 93 troduction ‘he troduction by BASF in 1923 of the proces tosyntsie methane ftom carbon momowie and hysrogen at pressure mas the second Tirge-sale aplication of etsy ab higher technology f the Chemical edly. flowed some 10 year fer the itodacion of {cca ques of ammonia sed esoed fom te understanding ‘Of tne teimedynonie aid Kincte principles controling chemi feats winch fa come frm the mork of Oswall, Nernst, and fibers The process atthe OucOMC of extensive recarch of the Ayurogenton of carbon monoid, which Bad shown that, depending fn the cts wod an the process cations, carton monotde amd cogen oul be reacted at presoe of 1-50 bar ose prods Fanging fom mean to higher sles, other oxypenate eompounds Ind tpdmcatbons The work of Ficher and Tropse subsequent ed ie eabstnetithe 193 a he races forthe manufacture of ‘potite focs which Dears thir names Tike the ammonia procs, thanl synthesis was dependent onthe eyclopment of am ets catalyst, but unk the ammonia yathess ‘Stat he methunatlat ado be selective as well active It had fort pve seat smounte of methane or other Fcher-Tropch Products One saat, conning ine oxide and choi, was ound {ihich met these requremcnts well hat Compostion emsined ‘rally unchanged for 40 ears During hat ime several temps ner Ina prove the sts, bat without sacs, ut 96 when ICL vedced n coppenane oxdsumina extas with ch hpher {imiy, wha cnabed methine sje o be cried oot ‘rperaues, ts than SAC and which peraited operation at lower fut, 50-100 hr, The lw pressure proses 8 monet, ha 8 mcr cota cost ond cacaper tert than the eal Nigh-presare ‘loss, uh su chsnee, Aku other sew methan! proces Tm eatapats have been proposed i tosem yea. none has reached indestal practce and the iow presere proces remains the only Economy rut, Reteotadvanc in methuna production technology fine com fom inyrovements nets and procs design, Several “ - Satna oe “synthesis supplement his chapter. ik mi kz Thermodynamic $21 tome ‘The symthesis gas from which methanol is made used to be a - ‘manufactured by coke gasification, bat & wow almost invar et ! pel ten il a 3 bel ; OM EGION HO Sire mera ‘=a | sear a eee ee ‘Sian ee fw KAP Wate fa pit ot a Seance he a Khe Sma oe rp st non, By it na . 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Mae wp Gas Compton ta te catierpoc te makeup gn, wich wu roc by the poacaton of coke wh tum, conte! may ports, bu ach her py en pode ot “cube scam scoring oe bf se nese ae sro the come ac inceaing ality of etree at ha iy ‘tes ace tte for TC to ek pon he fcc Ie ‘rye whch lo the ntoacton oe wos it aces lrrgrom methane pce, ‘With metiane a he erm fede, a ethan mts wth an eee of Aydogen proce 8 need oe mn tes: HHO 00 aH CHON HH: 0) C12 2H,0-+C0, =H --CHHOH-+ H,0-“H UN ‘The cues ype canbe wed fr she by adag moe eben ese othe yt ani ave fam anshersoace, ssh 28 ‘ionisation Secloct ror tc tc rer aa et enoal of the coponets of pur aly pres ng ‘Sip: Inscnamnc rm hana beter acronis fs we the aes yee o mae more meth, Nap oF ‘Seomer hand wna higher OM rata spproninsingt CH, produ sian ey hinting Later nt ‘Bove he mporanefhetct nd cr 2m oe Shand yur "Ted netbeans tay sndcoddhne seu te oaneryean hve ne ict ee eae ne iecimenl ctr Ban tee tdci ay Ct ‘Sef somal te emperte ar tay, The salsa fie by respon oman schon eins, a Grom tien inte ce ped npg ‘roma pres th eat mya an 0 {eit acto Cx) prt xd en ath he han fe Ta roe ns ‘evel wh pretcoetonvads tmp acy, ee the ‘umn of COs toC20, nn to 20049) + 34a) C5040) + OD, mec I easemcy cathe Albough the be premre proces dom Aigo) te an smerny hen he pe ose en tear msl wis pe ious pe ee ae ‘etrme) se i_ Asides (Figure 9.3), cartons niger bol ate ‘ermadynanaly more slave meanest eel Ne formes {rom etn ids and bogs The ele to which theca inthe low presse proves Methanaionneod oe mnie. bth (cme om echo nd ns ply crtberme rato. ‘Ge cose temperate ramvays The hgh least copper stares tao mys Ath by pss fe fed pret, erp ecaome and mot by ay tntwe eto) te ‘Sts ean ect. mpncd aca orn aces me tho pes inproved ssc, Ths, be Soper cate re ‘eects tha sine ote cates ne the mene pone conor. eter inher See The ghosts tows he a ot wes ffs emt (eon) 39pm ae elie o ethan mies, Pecrne mo the Fart ‘aos have her ataton nes. oe ties ot Te intaccemahey oy any Inputs athe sat ether Lt in he ct ig ‘ungfatre of mtodced during se. The laine mprie an {eatin the rodcion hig ob and aio, ee some tes in atity. Smit npr (rename ‘hesapyort mitra) can edo he formation ot igh maa woh ‘encom aa which can couse ow of oti oc the tae pres. "The beaker sy found on The sre ot limin dct ot ve mast catoehe danraton 1 mth ee. Tese enol role read ind anuacin fects, ee eee eee — See Seater = — Sao arash" Nel nse —— Scere mar io co Sram Senertmee Iestermeee cattery Bh ess aay mee Hee Secenoet ere ‘he presnce of Group Vill meta sch as eo, pate dessa as hey ines bdogetation acy aod pone the ‘Stecaton ofcaton mona aa deed formation Inet rl of long parts andor wane by Packer ep fppe sesciom, histaaaion wus sive 's pobiem wih" the Aig pesure eas (Tate .2) andi hog a is ws ally ert Sens Peete Ne tt Clinics sto coc bee eon he cts otha mac tae (Getbecasa rer th nto th ed whch etre ns pd foe the sth od. Pasoning of Sst sat noma 2 fotiem cacpt m= 2 rsa of maperaton The ee eco ine comamnsnct and pone CWZOOPALO; sah el a = re teers en nen eens een ee Seer several reas a et Boece tooo eee eee eno VALOs i ath move complex ad mre wats tn the sapred met ais nih have fen Sted forma of te vats pone sian a onto of ‘Statin pode snd rncon cna 5A the atte of he cata ars with econ cons, the ‘uy isestetos one amie condom far removed om ‘mel prac of anc eleane 0te elce pxse 4 Antowgh pong ry rb i lan operant can ‘Gon ser tein teal le ting Ce Seon 13). ‘Sime iverson appear esl pecuions ‘Tere mud cotovers nthe aa of hace compote fhe lyn the econ tat abe plop hem, Chico ‘a eth dacuanon th sneer oe eo (6) metho ytheszed fom ata monoid oem de? (0) Wart sae fe copper na orig ets? (6) What aes are lye by he in one and in component ia (Mecommnercn cage? (4) Wat isthe mesh nd wh ontop ete-determining? (6) Mirae eer mein yen ZA Mach wo is i 1 be dane 1 somone remaining ambit, bat Ievertces» conse ptr cn be daw rm the sey 3 eta cto,ter ee ree ecm cota ee Pacis coe oowmttaeteees re sence Peete emt: Se elec ton "Co, mn ence en eo oe Seen fee acerca etre nn COKst) + Hs) COOL) wo) 2Hads) + HCOO(as) = CHLOKa) + Of) 7) ras) + CH,O(0) + CH.OH a WO=H, + (as) a 4a) +c0=00, eo Nat that ever f theses eatin hi eto chee ate Compost rencon, snd ah tt cnr esas essa ‘CO; ai pou Hy. and te csociation owt vue pws ‘on ares ony ‘menaremt Py sauming poste mechani iaag morn ‘acon of srfce spat an sesrpuon. aod Secopng {peo cach ecm an he ting Och ne st to he mee nts ne the al econ ath ‘Ths mprnch is truly worible, party becunestprinena ‘sal fen fe mare tha oe mola the exenion my he ol Aegan nied ran os, ym et 10h lloras pone. The completo of he once Stereo an a te vale tte he ct ret tay mechani sopetaon. “erates eh hve ben ealred™ "arf the pe te = pcan maiko) en wie piste paral prema, 0 py, ofthe nde eat pect. The ss“ kr mtb The ne tm onsaing the eli corsa fr fhe sates acto ‘eatpne ha the overall teat by te ae ofthe bask ‘eacon (nthe decomposition). nich nts suit rprachet IndeChapter 9. Methanol Synthesis novel supported copper catalysts with high activity for methanol synthesis have been reported. Raney copper, prepared by leaching ternary copper/zinc/aluminium alloys with strong aqueous sodium hydroxide, has activity comparable with industrial precipitated catalysts.°°* Both zinc and aluminium were removed, but not completely, from the alloys to give catalysts with maximum activity at about 98% copper. These results support the conclusions in Section 9.6.1 that copper metal is the catalytically-active phase. A more unusual route to supported-copper catalysts involves the careful oxidation of suitable intermetallic compounds. The thorium/copper compounds, ThCug, ThCuso, ThCu; and Th3Cu, all react directly with synthesis gas to give a form of copper supported on thoria which is extremely active for methanol synthesis.**”: *°' Carbon dioxide is not essential for these catalysts, so there is potential for a low-pressure process in which anhydrous methanol is made directly from a CO/H; feed. Since the discovery of the copper/thoria catalysts, similar copper catalysts made from non-radioactive rare-earth metals have been shown**” **5 to be surprisingly active in methanol synthesis, operating at temperatures as low as 70°C in gas mixtures that are essentially free of carbon dioxide. In contrast, catalysts based on the platinum group metals have generally shown poor selectivity for methanol (Section 9.5) because of the ease with which C-O bonds are broken. The discovery™ that palladium, on some supports and under certain conditions, could be selective in methanol synthesis has been followed by much work**>: 5% to identify the basis of the selectivity. So far there is no agreed interpretation. However, practical problems associated with the low rate of reaction, the high cost of palladium, and the relatively high reaction temperature leading to some methanation (Section 9.5), have discouraged any industrial applications, All-round, the conventional precipitated copper/zinc oxide/alumina catalyst remains the best available. A three-phase process, in which fine particles of a copper catalyst are suspended in a high-boiling hydrocarbon, has been designed by Chem Systems.**7 3° The liquid medium facilities heat transfer and methanol removal, but the added complexity of a liquid phase has so far Prevented its commercial exploitation. Future developments of the conventional process are likely to be mainly capital savings and improvements in energy efficiency. Catalysts of improved performance will doubtless enable process designers to circumvent chemical engineering constraints.