六铝酸盐LaMAl11O19-δ催化CO2重整甲烷制合成气

Vol 213 HE NS DE >"NSNS t2000A20ACHEMICAL JOURNAL OF CHINESE UNIVERSITIES298~300NEi40±AuAAeani LaMAlo19-8B3co, 0000v4x eOAEO 3EAoDi0A01 pla%A0cA÷2±0±A60ca1(1.A06N§。N和μ,2.A06NSAA0NNu,39130023)0如0 E AuAAEaNT lama1O12-aBA;xe;WN6。i400;9aEOD 14-0Aa A (643lAI×± eEAe ATAA±a9A0251-0790(2000)02-0298-03CO200k×e0?iE0BA“6啊20A900N0Ru,Rh,Pd,Pt9Ir16E61-4,0aDBAEa±036TBAB。-10,μ00a0n0y1E0aE0-,290AN61aA￡ac90}0A. Iyi HE50aAauaaeani'a0UB-Al2O2AHEA00a11E,C0EE%a1￥0A11啊。3EA心2ax“%a11sla113E.MA6μE00 Ni Duauaaean0AOUB,-CO200xe09TE0,·c0aN0%B0DA9AμAB*-DTE“D0.±4A0土 AEAuAAEani LaMa1O1=B》-A,d2AEa啊CO2000xfe0TaEa·^OHμ A B2 DOAU1印μNe2·01.1 AU aA ni lama1O1-aB”-AA0E±,°′n[La(NO3)3·6HO]:n[M(NO2)2·nHO]:n[Al(NO2)3·9HO]=1:1:11 Aa 3EEBEUC0,AAA°TAμ10μ900“4μA0土EE0090‰0EEc.p40a09,00353KE010E￥@0±0,OEOA°aa0D0413K9aE,№A￥,673K±9E02h96001523K±E05h两 Auv LaMA1O19=。B,-1AEaNN·A±0÷N·pA4saa114°±Ax"=0Uμ90XD-3 A DI XRD AEx OC?° VG ESCAMark I DI XPS REx OCEl le3E,00C,(EB=284.6eV) DE/41a°TA0.TPR印Neou1iE0c·“0E;0kD,·“0}10AU8mm,B。Ax°A0.4g.10-0110%H2/Aroi9TE0,A;EU30mL/min,0020K/minuAEy IAEUAEOEEO TAEy OA 1 373K, TCDvi2aRE .B, Amy ii Ai OA Perkin-Elmer TGA7 DiEE00-0100C2412aB-000·0D00U=N1q2A-BoA「E0c·}40BeE.·0}E;AU8mm,"B》-Ax°A0.2g,0- Al Ro xe SE V(CH1):V(CO2)=1:1,xA÷印30mL/min,·‘0A1053K.·0c°B-WA0A10%H2/ Ar i9IEoOU 1 173 K 210-1 h, fo laEEx-0U lB-0102ulTxe3E(Ar 00 FEo, Porapak-Q9I5A-0XOE TaEEx1i"la), TCD 14i2aE2%a00e0A02. 1 M Ei uAuAAEaNI LaMAlO19-oHA4s lava11 1v4 1(A)la ly E120 Eo Ae x0 M Ei uAuAAEaNl, 910EoN。 Ii LaMA1O1= HA XRD FEx I.0E41(A)E‰,用 a x ea iBnUea - a3ya,B9fafE00D2±a,用aN0Ea-aeyA°f10Au±Iaf,100÷a但35.9°,3,89131.9。.印 A: M Ei uauaaean而0DpAA1,DaEAE48 Tai-ACHE ha112Ns×6° EpAAuAAEani B2=A,0206003E00.·EuA,AAaB。1aa110,0A7.8中国煤化工2 AuAAEaNI LaMAl1O1g-GHA XPS-0I0 OE XPSCN MHGAal2Ey(1)l‰0M HAEi'uToauAAEaN± i laod la,Al?OwAμcxo‰aAUp00o0°Ti,,0YμcxOa° I AU%4Y座2aa0E0aEEU:1999-04-2605芳数据80(6093020AuEe:0ca(1932A36u),A,2E印μ}, EAnala'B*-NNo. 2Di0%A0正E: AuAaEant lamar1O-aB-CO200×e00299(B)_20304050608731073127328/()Fig 1 XRD(A)and TPR(B) profiles of hexaaluminate LaMAlO19-8 catalystsM: a. Fe: b. Co: c. Ni: d. Mn0±01L.a3+,A13+9O2-.BTA±E0E±1y0E60,00E”如01-E币 ETHA Al3+,2cE1 AuaAEaNT±300-00 HA ACIE4aa1151.OE土10Dcx0 a IAUEy%Y2ca? ITPR Va10EE0÷Ey框ME6N60±01Fe3+,Co2+,Ni2+,Mn2+9Cu2+Table 1 Binding energy and atomic percentage of surface elements and catal ytiactivities of hexaaluminate LaMAlOj-s catalyEB/evAtomic percentage(%) Distribution of products(%)Conversion(%)M Al O CH: CO H. CO CH COLaFeAlyO19835.5711.873.9530.99542.3655.1942.042.97.37.816.014.2LaCaL1O19-a835.4781.274.2531.20,391.1842.2956.1439.039.410.611.022,021.2LaNiAlo835.6856.274.1531.00.600.7741.7656.860.61.248.949.397.6LaMnAlO836.064274.5531.50.372.5841.4155.6344.644.95.05.510.810.2La CuAlyo934.774.1531.10.280.8139.2759.6±1AXPS016‰a10±A÷,La9yE6M0UB-A土AIaμAEA0 EyI la laxe 3E0D%2l2±,土Aa0LaMAμ0aa.阻a0,00Mn0土AaμAEA·0Eyx,B,M0 alate3E,N0U土 i Am laμAEA·0yxμ,61 a alaa"函1/5.AfIa,2-1y地EMEA山AEaN土Aa0B,n(M)/n(La)+ 21+.u o, 020e ia la xe 3E OD%2I,1-1, Ea OD oE oO n(Mn)/n(La)+Ex1 o, O% la ia lan(Mn)/n(La)土A7;n(Ni)/n(La)土xfBi,‰0 u lala1:1 HAxe3E.EμA÷2;l-yE6ME"90A心 AAEaNii fiala姬a,1y‰E6MLaaμAAaT》06201.1y框E6"y§币“ux÷0A,E1a±aC啊o^Ac}ED「 AuAaeani S laHA4S而0,}00,B·0Ec0EaμAAa》x"-,“0EA0土UAa,BTA0;16如bTA10xe0μAE0aB,ApA62.3ME“啊 Auaaeani lamar1O1-a10-D0uA0°n0EME“9函 a Amal1O=ATPR压xiv4 1(B)liEV0, LaFeAl,O,- OD A%, 02, A-DoHA10--a. XRD i XPS-01o0uA- Fe 2,a OUHU mTp003sI1E旺a10-1y31011面A773~1013K-1§A0Fe3+10-9Fe2+4°,BTA1173~1373K·sAFe2+2210-EFe°≠A1y3.TPREμN6°64-XRD·0160A÷0BFea0U. WaCoal1O13-a° LaNial1O19-a-93E“,‰0‰0143KE2AaE9610,10-a,c0T1373KE,10-a0 Ip lAV2uC-EA.EACo9Ni0UAAAEaNi 3s, n od oe ia au Ae x0oD%i ci HAvu; .,u%Y XPS i TPR-01o, EaiEAUv401--0to1a Co2+9iNi2+,co1373KE±00B20Co2+9Ni2±》10-. LaMna1O1-0873~1173KIA·q§0B0E610-a, OaiEAUoe Mn Ei uAuaaeani %s, nOD Mn HA lOEa361010-a,c0001273KE600。6x20,XRD9fT中国煤化工01143K比ECNH G96μAxRD.01mA0BC"aE,印uACu1-02 Ja UUUd'V1ie,xCu2+0TA框了143KEEEt》10-=ECu+,E翻xA·A0 DDI IA E14I Do Ey,B,Cu+1202±10-ECu2.4 AuAAEaNI LaMAlO19-aHABm 1D0i1421 *i 1 030HA LaMAluO19-8B> CO2 0000/ x le0FEI3EFo0(105数2h)AE小aE0,2nME“A山AEaN(B0200.xRD016土AEA30aAla‰a11,阻a》-Nx旺yE"yE6Ax0 +o la le E la l-.00E, AugEAn3 HE NS DE-NsNs±Vol 21LaMAlOg-auA'B21D00eEi u1yE10 Eo M AUCD1a10, EaoD00 La NiAl O19-oHA 1D0x1%A, 0U 1053K0}2h‘B,-AE±30 AEAYAuA'"B,-09fTET"D0,ylAa1.554%,T·ciB-wA,BTAE0aE§I. AaEu ly( Eo M(M=Fe, Co, Mn 91 Cu)Ei uAuAAEani LaMAlnO1g-a1D02 Ec LaNiAl O, HAA,“0}2h%AyaA-0±01a1.591%,0.970%,0,654%90.743%,10E6D0E301a> Fe>Mn>00E, Ni Ei uAuAAEani lanial1O19=aiEx÷lCO2000kx609I3E配0μ ADA B2 A0DEE6№14 IA x1 Rostrup-Nielsen J. R, Bak Hansen J. H. J. Catal. [J].1993,144:38-492 Bitter jJ.A..J.Cata.[J],1997,171:2792864 Ashcroft A. T, Cheetham A. K, Green M. L. H. et al.. Nature[J],1991, 352:225-2265 Iyi N, Takekawa S, Kimura S. J. Solid State Chem. [J],1989,83:8-156Min(wA), Bl Ying-Li(±I0±A6), ZHEN Kai-Ji(cia)etal.Chem.J. Chinese universities(,Bμ LENS DE。-NsN”)[J]7 Masato Machida, Koichi Eguchi, Hiromichi Arai. J. Catal. [J], 1990, 123:477--48:8 Cristiani C., Groppi G., Forzatti P. et aL.. 11th International Congress on Catalysis-4Oth Anniversary, Studies in Surface Sci-nce Catalysis[C],1996. 101:473-482Hexaaluminate Oxides LaMAlo19-8 Catalyzing CO2Reforming of Methane to Synthesis gasXU Zhan-Lin, CUI Xiang-Hao, BI Ying-Li, Zhen Kai-Ji(1. Department of chemistrInstitute of Theoritical Chemistry, ilin Univerisity, Changchun 130023, China)Abstract In this paper, a series of hexaaluminate oxides, LaMAl Oj9-(M=Fe, Co, Ni, Mn andCu), were prepared using transition metals M to substitute Al in the hexaaluminate lattices. XRDanalyses indicated that the series of hexaaluminates had almost the same magnetoplumbite crystalstructure, however, they exhibted different reducibility and catalytic activities for CO, reforming ofmethane to synthesis gas. Among the LaMAluO1g-a samples, LaNiAlnO1g-a showed the best catalyticactivity for the reaction at 1 053 K for 2 h, the conversion of CH, and CO2 was 98.8% and 97.6%,rectively, and the catalytic activities of rest M-substituted catalysts were extremely lower than thatof LaNiAlnO19-8. The sequence of affection on catalytic activity of transition metal M for the topic reaction was Ni>Co>>>cuKeywords Hexaaluminate LaMAlO19-a catalysts; Methane; CO2-reforming Synthesis gas(Ed:Y,X)中国煤化工CNMHG