EATURE REPORT Heterogeneous catalysts lose some of their activity over time through poisoning, fouling, sintering or vapor transport. This article reviews the causes of deactivation, then shows how it can be avoided, slowed or reversed, and how to account for it in the design and operation of catalytic processes. Galvin Hi: Bartholomew, Brigham Young Unoriy — Dy Most fuels and chemicals are produced or refined {ing cali processes In petroleum refining, cali processes for cracking relorming, lation aed hydeo- treating have revotonized the ote and made pos ble grea improved yields of highctane gavline Ia ‘hemialsprocition, catalysts ae envental i aking Smmonia, methanol, Bydrogen and polyethslene aswel Ssinother shes oration liydfogenaton and poly fnerizaion Factions Catlyts sto play atl role in beeping the sir clean: Catal converters help control Auto emissions, and are finding more applicauons in ‘esning industrial exaust streams, TA caalyt i sometimes defined asa substance that aceleratera chem eatin and is eyliallyregener- ded inthe proces, The implication is thatthe call hot changed. However, tis a face of ie tha eats deactivate over time. A cracking catalyst may as onl few seconds, white an ammonsi-symest etalyt may las fr eat; butinevably lw deay—shough some ‘llega ther sgor temporary drag regeneration. "Een if deactivation ie nriable, some of is conve quences can be avoided or put off This arte wail view dhe causes of catalynt deactivation, then explore how deactivation may be slowed or prevented how Gepaate eatahste may he regeneraed, and how (0 Beef deactivation a ae dosga and opersion of GS precesaes The ale is necesarily limited to seid cats acy on ge Soe pa reactacrs. Nav. alook at how Causes and mechanisms ‘There ae four basic mechanisms of catalyst. decay poisoning, fouling, thermal degradation, and loss of {aalst material through formation and escape of ve- ors Poisoning and vapor transport ate basically chem £2 phenomena fouling is mechanical: eral desrad- tim is, naturally thermal eterogeneots catalysis basicaly nvoles adsorption fof reactants nthe catalyse surface, Followed by reac tion, and desorpdon of products, Fig illustrates the Tour deactivation mechani that slew or prevent the desiel atl reaction. Let us cover each som Poisoning Heerngentons cals ate ypicaly small ently | (cryalites) of metal metal oxide oF metal slide ae {ached t inert carters. Poisoning [12} i che song, ‘chemisorption of reactants, products oF inpiites 0 there ace caulyicused ates, A poison blocks the Sites, and may also induce changes in the srace oF Tesi in formation of compounds (2) This san operational definition, A certain species may bbeapeisonin some reactions, but notin thes, depend ing is adsorption stent relative to that of other species competing for catalsie sites For example ox dena reactant inthe partial oxiation of methane to ‘ethanol but a poon in ammonia syntes Catalyst potions ean be clasifed according to chemi cal species, types of reactions poisoned, and selectsfor ative ctl sites To begin with, chemical species 1 Group Valeg.N,P. As, Sb) and VIA eg.0.5,Se. ‘Te elements mersct with ely meal specs throu thei «and p eis The interaction depends on the poison's oxidation sate—ie. how many electron pairs Sreavaiable for bonding, and whether Mey ae hiided by ligands (1. For example, the order of decreasing Doty be ee eee Hs 204 50, Toxiceary metas andions fe Pb, Hg, i, SoZ, (64, Ga. Fe) aceupr done and may oem los ‘ata eta. Molecules having an unsaturated electron structure (6, CO, NO, HEN, benzene) may chemisr through supe bonds Table [st poisons for selected casts and reac tions Organic sea nd sami are poisons or ides tn caching and hydrocracking reactions ull ae af Senic compound are poisons for metals hye Hom delydeoenation an! steam reforming reactions ig. 2 lustats poisoning selectivig. On this ple of atl aetity eaction rate 3 faction of sna Feaction rte) poison concentration: 18 selective posoning process Is one that tll ep Posoning oF Patalyze ao-hyaogen comersion 2h. 1 Anonselective poisoning process one that reduces aulist acy in proportion to the amount of poison. The susceptibility to posing is shown bythe dope a ee 1 Ananlseletve poisoning process one that inital ty poisons the leastacive sites. An example isthe Po Potening of pstinam in CO oxidation [1 Sulfur poisoning Slur pioning merits separate dacusion because i ina dia problem in many largescale catlvic pro fetee—e-g, hydrogenation, methanation, eam forming Fischer-Tropsch sythess, and fuel-cell power production Early work onthe subject, reviewed i 2) ‘only deals i poaoning oF meal especaly NS) ‘aac by HS, Later works veviewed in D6 ‘Adsorption dis [5] indicate that H,S asrbe strongly and disodateson nickel surfaces. Big sows ‘he igh sabiy andl reversibly of adsorbed sor Sr plot of log Uiag/ ig) reciprocal temperature “Tas por represent ost ofthe preous equilriam, dara for nickel 3.0. Ti Fig. 8. the uppermost line coresponds «0 the ‘qin dn for fom of bulk Nis Baked on Ge Geccenery equation AG! = RT In (ha/Pi) AW ~ TAS. We slope of this Une i A2/R. Since adsorpion i exothermic, the slope is negative, The fnthalpy of nike! sulfide formation. Az is 75 V/mole, The poins for surfcecoverage fesons (8) Goen 05-00 fll between the nes coresponding £2 SH'~ ~ 125 and — 169 4)/mole, ‘Wiat des this plot show’ AU 795K (1000/7 = 1.88), ha coverage (0 5) occu a (Py,9/Py,) aos Tn other words hall he ick ‘toms on the suslace are covered wilt sulfa tom at fedauve HS concenratons beween T and 10 ppb thick area the lower limit of oar ayo measure HS [Ac the same temperature (725 K), almost complete overage (© ~ 09) occurs at eave iS concentrations ‘0.1 ppm epical ofthe H,S levels vemainng fer fst has heen tested to remove salir composi These dts are pial of slr adsorpaoe os sot saute metal Than ost processes cing such faust, we can expect hut HS and other sulfur mp Ses l iee l ‘ofthe catalystmetal uric ‘What happens once the fur i adsorbed? genera 1s presents the adsrpion and tus the reaction of other ‘molecules [5~ 7] For instance, H, adsorption on nickel [dclnes neal wath increasing male conerage Ia et. FH, adsorption an accurate measure of te unpossoned nickel surface in partlls poisoned catalys. CO adsorp- toms more complex [57] Adsorbed CO forms sever al lleren species on nice. and each affected ier. ‘rly by slr Te im reactions solving CO. sl poisoning ca fle reaction selec as well sate “The overall et of ilar ona metabeatat suxtce fs generally 3 substantial or complete los uf catahst, sci. Fot example Fig 4 shows tha jn methanasion the atsies of Co, eand Resales re reduced ”‘or 4 orders of magnitude by HS, oncenttions of 15-100 ppb, in ‘ther words, these catalysts have ‘xen ln tolerince for slr eis wot generaly practical to Fe ce sur Levels belo a few pats per billion. Bo, fortuna, exalts ‘an bemade more sulferesistant wi ‘dds, such as Mo. and 3B, that Selectively “adsorb salir and this rove the uals metal 5. cae ores SESS es on co Za Coking, carbon deposition se samie See See eon Fouling i a physical deposition of | ME) ayy sre ¥) species fom de Hud phe ont the ret Qs ‘als surface Ga rele in Block age reaction sites or pores Ext Sve hea Fouling say also resi disinegration of catalyst particles, and pinging of reactor wld spac, Depesiion of tabu or coke on pos outs catabsts 1 considered fonhng, bot species that act ae poisons my alo beimolved. “The dfinidons of erbon an coke are somevatarbitar, having to do withthe origin of the materia Carbon ia product of CO alsproportion: ation, while coke is produeed by decomportion or com Alemsation of Indrocarbons. Nevertheless, the forms of | formation om metals expsed to CO or hydrovarbons «coke range rom high-molecula-weighthydrocarbons to | The diferent kinds of carbon and coke formed, and ‘athons suc ae graphite ‘morphologies and reacuiis, alo are deserted. Fo ‘The mechanisms of carbon deposition and coke for- | example, CO dissociates on metal slow temperate to ‘mation on metal eaalysts have been detailed jn several | form Cyn atomic eathon that eas react to foro Cp. plumes casbonfilm. Achigh eemperatures,Uhesehighic |y reactive, amorphous forms of exrbon are concerted ‘overtime int les-rescive, graphite forms (10), ‘Some forms of carbon cause 4 decine in cate scvty and some donot For examples Low-temperature (aR SSIBO condensed pene o Gy a temperature (> 050°C) graphitic earbon, encaps lace the metal surfces of methanation and steate- {orming catayts (0), A375 650°C, however, carbon ‘laments giow. These raery metal parties say from the support sufice, but do not encapsulate the mets sutface iPenough His present. So this case, carbo Aeposition doesnot necessarily deacvate the ctalyt ‘As for oxide an slide cataists, couing here is a ‘emit of reactions that crack coke precursors these are ‘catalyzed by acid stes{23], The pathway to coke, satin Irom olefins or aromatics, may invate 3: 1. Polymerization of olefins An olin fg. propy ene) Feats witha Benne acid fe, 4 proton donot) form carbonium on, which ean condense wit ot cefin, den reat with a Brnsted base to for 3 Define. ned tspentene) ‘2 Cyclon fom oleline A large olein fog, ‘bse heptadiene) can react with a ised cd forma earbontum ion, then tse a drogen text wth Bred base (to oem 3 substituted iene ‘This ean rearrange into eyie molec (e 4 elon Ihoeadiene), whichafter eaction form carbonium