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atttrriittiion efffecttss [[589]].. IIndeed,, eiittherr abrrassiion orr ffrragmenttattiion coulld occurr.. Abrrassiion rremovess ffiine parrttiicllessofftthecattallyssttssurrfface,,ffrragmenttattiionsshuttterrtthessurrffaceiinsseverrallparrttss[[590]].. The prroductt yiielld,, tthe gass compossiittiion and tthe carrbon depossiittiion depend on operrattiing condiittiionss iinclludiing ttemperratturre,, prresssurre ((ssee Fiigurre 20)) and concenttrrattiion rrattiio bettween iinllett Energies 2020, 13, 420 46 of 96 rreacttanttss((H22//COxx))((sseeFiigurre21)).. Figure20...IInInflfflulueenencceceeofopffrpeprsreseussrsueurareendantnedmttpeememrpapteuerraettuournreethoencththeeme cichaeelmeqiicucaillibeerqiuimilliibcroriimumpocscoiotmimopnposfsiitatiiomonixotouffraea mwmiixtxhttuarnreeHwiit/thChOanraHti22o//CoOf 3rr.atRtiioeoporfifn3t..eRdeewpriritinhnttepededrwmwiittshsipopenerrmfmroiismssiio[o5n9f1frr]o.om[[591]].. 2 Temperature variation significantly affects the equilibrium composition of methane yield, both T Te em mp pe erra at tu urre e v va arri ia at ti io on n ssi ig gn ni if fi ic ca an nt tl ly y a af f f fe ec ct tss t th he e e eq qu ui il li ib brri iu um m c co om mp po ossi it ti io on n o of f m me et th ha an ne e y yi ie el ld d, , b bo ot th h in isothermal and adiabatic methanation. When temperature increases, the concentration of CO, H . i i n n i i s s o o t t h h e e r r m m a a l l a a n n d d a a d d i i a a b b a a t t i i c c m m e e t t h h a a n n a a t t i i o o n n . . W W h h e e n n t t e e m m p p e e r r a a t t u u r r e e i i n n c c r r e e a a s s e e s s , , t t h h e e c c o o n n c c e e n n t t r r a a t t i i o o n n o o f f C C O O , , H H 2 2 2. . CO andcarbondepositionareenhancedattheexpenseofmethane.Contrariwise,pressureincrease CO2andcarrbondepossiittiionarreenhancedattttheexpensseoffmetthane..Conttrrarriiwiisse,,prresssurreiincrreasse has a negligible impact on isothermal reaction, and only slightly increase the methane outcome in hassaneglliigiiblleiimpacttoniissottherrmallrreacttiion,,andonllysslliighttllyiincrreassetthemetthaneouttcomeiintthe the adiabatic process [592]. adiiabattiicprrocesss[[592]].. LargeH/CO concentrationratiooftheinletreactantsimprovesthemethaneyieldandreduces LarrgeH2//COxconcenttrrattiionrrattiiooffttheiinllettrreacttanttssiimprrovesstthemetthaneyiielldandrreducess carbon deposition. The increase in pressure reduces the minimum ratio required to avoid carbon carrbon depossiittiion.. The iincrreasse iin prresssurre rreducess tthe miiniimum rrattiio rrequiirred tto avoiid carrbon deposition. Indeed, the limiting boundary ratio, above which no carbon deposition is observed at any depossiittiion..IIndeed,,tthelliimiittiingboundarryrrattiio,,abovewhiichnocarrbondepossiittiioniissobsserrvedattany operating temperature, is placed at H /CO ratio of approximately 5 at standard pressure, whereas operrattiing ttemperratturre,, iiss pllaced att H2//COxx rrattiio off apprroxiimattelly 5 att ssttandarrd prresssurre,, wherreass the concentration ratio drop to 3 (stoichiometric ratio) with pressure higher than 10 atm [555,593]. ttheconcenttrrattiionrrattiiodrroptto3((ssttoiichiiomettrriicrrattiio))wiitthprresssurrehiigherrtthan10attm[[555,,593]].. Fiigurre 21.. Efffeecctt off H22//CO rrattiio on CH44 yiieelld ass a ffunccttiion off tteempeerratturree and prreesssurree:: ((a)) CO Figure 21. Effect of H2/CO ratio on CH4 yield as a function of temperature and pressure: (a) CO meetthanattiion;;((b))CO22meetthanattiion..Reeprroducceedwiitthpeerrmiisssiionffrrom[[594]].. methanation; (b) CO2 methanation. Reproduced with permission from [594]. Atsststatandaarrdrdpprperrsessussruer,ret,h,etthceoekceofkoeremffoaortrmimonattoiioconcnuorosccacutuarrssteamattpaerttaetmurpeearrbatotuvrere40a0bovCve,eb4u40t0w°i°CtCh,,inbcurtetawsinitthgh ◦ ipinrcecrsreseauassriein,gthperrecesassruburoren,,tdthepcoasrribtbiondisepsphosisfiitteiiodonaitissasshifgfttehededratteamahpiigeghrhaetrurtrtemrapnegrraeattu(u6rr5e0r–ra8n0g0ge(C(65)50[05–9850]0. °°C))[[595]].. Gaoettall.l..[5[[5959494]4]b]brborraodaldyllyiynivinevseteissgttiaigtgeatteheettheeffeecfftfeocfttoeomfftptemrapteueraeat,tuprre,,spspurreress,ssuHurre/,C,HOH22//CrCaOtixox,rratntiiodo,,tahanendedffttehcet eoeffeaecdttdoiftfiaoadndailitticionmalpl cocoumnpdposou(nHndsOs ((,HO22O,, OCOH22,, C, HC44,,HC22H)Ht44)h) taththattraearreceocmommonolnyllyiniinvnvovolovllvevedediniintththeeininlelett gas or 22424 added by recirculatiion off productts tto lliimiitt tthe ttemperratturreiincrreasseduettorreacttiioionexottherrmiiciciitityty.. Theaaditiititoiiononofosfftessattemeamamvoaivdvosoiitdhses ctthaherebocanarrdbeopnosdieteipoponossbiitutiiotonsnlibgbuhuttlyssldliigeghchrttellyaysdedemecreretehaasseneempereotthdhauanceteiopnrr.oWduhcettriioeoans.., WCWHhereacasisr,,cCuHlHa4t4irorenciidrrcocuelslanttioiotnmdodesisfynotohttempordoidiffyuyctththeceopmrropododusuicttitocnombmuptosslitgtiiohontnlybueuntthsslaliignghchettllytyhenchaharabnocenetdthepcocasrirbtbion 4 due to methane cracking reaction. C2H4, C2H6 and C2H2 reduce CH4 production because they compete with CO in the hydrogenase reaction. Carbon oxides commonly coexist in the syngas mixture, so the simultaneous conversion of both compounds was also investigated. The CO conversion rate is faster than that of CO2 since the CO ◦ 2xPDF Image | Green Synthetic Fuels
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