第57卷第9期化工學(xué)報Vol. 57 No 92006年9月Journal of Chemical Industry and Engineering ChinaSeptember 2006研究論文 CoH-FBZ催化劑表征及選擇催化CH4還原No張金橋,劉于英,樊衛(wèi)斌,李瑞豐教育部煤科學(xué)與技術(shù)重點(diǎn)實(shí)驗(yàn)室,太原理工大學(xué)精細(xì)化工研究所,山西太原03004)摘要:一種具有FAU和BA雙微孔拓?fù)浣Y(jié)構(gòu)的分子篩催化劑CoH-FBZ用于富氧條件下CH4催化還原NOCH4SCR),應(yīng)用XRD、FTR、 DRS-UV-Vis、SEM、AS、H2-TPR和NH3TPD等技術(shù)對催化劑進(jìn)行表征.結(jié)果表明,CoH-FBZ為均勻單一物相,XRD和F-R譜圖中,FAU和BA拓?fù)浣Y(jié)構(gòu)特征峰明顯,NH3-TPD結(jié)果表明雙拓?fù)浣Y(jié)構(gòu)H-FBZ和 CoH-FBZ中產(chǎn)生了新的強(qiáng)酸位.CoH-FBZ較CoH-Beta與CoH-Y機(jī)械混合樣品的催化活性高;CoH-FBZ中FAU與BEA拓?fù)浣Y(jié)構(gòu)的相對含量FAU/BEA為(0.4:0.6)~(0.1:0.9)時,催化劑具有高的CH4-SCR催化活性強(qiáng)酸位與Co協(xié)同作用有利于提高催化劑的CH4-SCR催化活性關(guān)鍵詞:選擇催化還原;甲烷;一氧化氮;CoH-FBZ;雙微孔中圖分類號:TQ032.41文獻(xiàn)標(biāo)識碼:A文章編號:0438-1157(2006)09-2105-06Characterization of CoH-FBZ and selective catalyticreduction of no by chZHANG Jinqiao, LIU Yuying, FAN Weibin, LI RuifengKey Laboratory of Coal Science and Technology, Ministry of Education, Institute of Fine ChemicalsTaiyuan University of Technology Taiyuan 030024, Shanxi, ChinaAbstract: Selective catalytic reduction of no by CH C CH4-SCR in the presences of excess oxygen was studied overCoH-FBZ catalysts with FAU and BEA double micro-porous topology structure. The catalysts were characterized withXRD, FT-IR, SEM, DRS-UV-Vis, NH3-TPD and H2-TPR techniques. The results showed that uniform morphologywas observed over the SEM images of CoH-FBZ. Characteristic peaks attributed to FAU and BEA topology structurewere observed over the XRD patterns and the FT-IR spectra of the CoH-FBZ catalysts. New strong acidic sites wereformed over H-FBZ and Coh-FBZ based on the nh -tpd results. CoH-FBZ exhibited higher Ch -scr activity thanthe physical mixture of CoH-Y and CoH-Beta with comparable relative content of BEa topology structure. Over thephysical mixture catalysts of CoH-Y and CoH-Beta, the CH4-SCR activity decreased with increasing relative content ofCoh-Y. In contrasoH-FBZ in which the relative content of the fau to bea topology structure was(0.40.6)-(0. 1: 0.9) exhibited better CH4-SCR catalytic properties. The synergistic effect of the new strong acidicsites promoted the reduction of no by CH4Key words: selective catalytic reduction CHa NO: CoH-FBZ double micro-porous中國煤化工CNMHG2005-07-26收到初稿,2005-11-07收到修改稿聯(lián)系人:李瑞豐.第一作者:張金橋(1973-),男,博士研Received date: 2005-07-26究生,講師基金項(xiàng)目:國家自然科學(xué)基金項(xiàng)目(20206020Foundation item: supported by the National Natural Sciencedation of China( 20206020)2106化工學(xué)報第57卷微孔拓?fù)浣Y(jié)構(gòu)的Na-FBZ分子篩*],通過調(diào)節(jié)第二步晶化過程原始物料配比及晶化條件獲得不同的Na-FBZ樣品.Na-Y(FAU)采用常規(guī)水熱晶化法合NO(90%為NO)的排放造成了嚴(yán)重的環(huán)境污成;Na-Beta(SiAl=15)由南開大學(xué)催化劑廠購染,能導(dǎo)致酸雨和光化學(xué)霧等的形成1,并對大得.Na型分子篩用濃度為0.1mol·L的NH4NO氣臭氧層具有很大的破壞作用;No.對人類的健溶液交換3次,經(jīng)充分洗滌、110℃千燥、50℃焙康產(chǎn)生極大的影響甚至威脅人的生命.選擇催化燒后得H型分子篩.H型分子篩用乙酸鈷溶液交還原是一種降低NO排放的有效途徑,NH作還換,所得固體樣品經(jīng)清洗、過濾、110℃千燥12h原劑已經(jīng)成功地應(yīng)用于發(fā)電廠等行業(yè)NO.的脫除.在空氣氣流中以2℃·min由室溫升溫至550℃并由于氨氣運(yùn)輸、儲存、操作難度高、設(shè)備投資巨保持3h得催化劑樣品,CoNa-FBZ催化劑制備過程大,在反應(yīng)器出口容易形成(NH4)2SO4導(dǎo)致管道同上.交換條件及簡單物理性質(zhì)見表1.樣品經(jīng)壓堵塞等原因限制了該技術(shù)的廣泛應(yīng)用. Armor片、粉碎、篩分成0.21-0.35mm備用等2首先發(fā)現(xiàn)Co交換的ZSM5和FER分子篩能1.2催化劑評價催化甲烷還原NO,甲烷選擇催化還原NO(CH4SCR)的研究在世界范圍內(nèi)迅速展開31.所有催化劑活性評價在一臺微型固定床催化反應(yīng)裝置上進(jìn)行.0.5g催化劑裝填在內(nèi)徑為6mm的石英CH4-SCR催化劑中,以分子篩為載體負(fù)載金屬催化劑的相關(guān)研究最為活躍,提高催化活性及抗管反應(yīng)器內(nèi),在He氣氣流中以1℃·mmn從室溫H2O和SO2毒化性能是研究的熱點(diǎn)升溫至400℃并保持1h對催化劑進(jìn)行預(yù)處理,然本文研究了一種具有FAU和BEA雙微孔拓?fù)浜?降溫到250℃,通入組成為2180×10-6NO+結(jié)構(gòu)催化劑CoH-FBZ,顯示出良好的CH4SCR催化2054×106CH4+2%O2氦氣為平衡氣的反應(yīng)氣,活性,應(yīng)用XRD、FTF-IR、SEM、AAS、 DRS-UV并逐步升溫進(jìn)行反應(yīng).反應(yīng)氣流量75ml·minVis、NH12TPD、H2TPR等方法對催化劑進(jìn)行了用4套質(zhì)量流量控制器控制,出口氣體用裝有熱導(dǎo)表征檢測器(TCD)的GC9A氣相色譜儀在線分析,Po-rapa Q和5A分子篩填充柱分別用于分析N2O、1實(shí)驗(yàn)部分CO2和N2、CO、O2、CH4,以生成N2量評價催化劑活性.1.1催化劑的制備采用兩步水熱晶化法合成具有FAU和BEA雙Table 1 Catalyst preparation and compositionchanging conditionCo/ABET speciCatalystSi/Alntent/%/mol·mol-10.0115,000.0110.78800.0l0.315CoH-FBⅢ)中國煤化工CNMHGCoH-FBA V)14.741.89353CoNa-FBZ0.0l0.379mixture①(n=1-5, physical mixtures containing ratio of CoH-Y to CoH-Beta are 0. 51: 0. 49, 0. 31: 0. 69, 0.23: 0. 77, 0. 17: 0.83 and 0.09:0.91第9期張金橋等:CoH-FBZ催化劑表征及選擇催化CH4還原NO21071.3催化劑表征TPD和H2-TPR實(shí)驗(yàn)時,反應(yīng)器出口安裝冷阱以消x射線衍射(XRD)圖在 Rigaku d/mx2500除對TCD的影響粉末X射線衍射儀上測定,用CuK。射線,管電壓40kV,管電流100mA,掃描速度4(°)·min1,掃2實(shí)驗(yàn)結(jié)果描范圍5°~35°.樣品的晶型晶貌圖用S-5200掃描電子顯微鏡(SEM)拍攝得到;組成采用原子吸收1催化劑活性評價光譜(AAS)進(jìn)行分析;傅里葉變換紅外譜圖NO還原為N2及CH4的轉(zhuǎn)化率結(jié)果見表2(FTR)在PEFR1760型紅外光譜儀上測定;漫CHBe、mre1-5及Co-FBZ系列催化劑上,反射紫外可見( DRS-UV-Vis)譜圖在 Pe Lambda No還原為N2的轉(zhuǎn)化率隨溫度升高出現(xiàn)一極大值Bio40型漫反射紫外可見光譜儀上測定,掃描范圍CHY上,NO還原為N2的轉(zhuǎn)化率均很低;Col-200-800m,掃描速度240m·mn-.BET假設(shè)Be較 mixture1-5的催化活性高,而且,催化活比表面積在NOVA1200e比表面積測定儀上進(jìn)行性隨機(jī)械混合樣品中CoH-Y含量增大而降低,NON2為吸附介質(zhì).氨程序升溫脫附(NH1-TPD)和氫在 CoH-Beta上的最高轉(zhuǎn)化率為697%.與同等程序升溫還原反應(yīng)(H2TPR)在 CHEMBE300化BEA拓?fù)浣Y(jié)構(gòu)相對含量的機(jī)械混合樣品相比,CoH學(xué)比表面吸附儀上進(jìn)行.進(jìn)行NH1TPD實(shí)驗(yàn)時,FB系列催化劑的活性更高;在整個實(shí)驗(yàn)溫度范圍0.15g樣品置入U形石英反應(yīng)器,在高純氦(He,內(nèi), CoH-FBZ(N)和 CoH-FBZ(V)較 CoH-Bet90995氣氣流中以2℃.mn2的升溫速率從室NO的轉(zhuǎn)化率高隨FAU結(jié)構(gòu)相對含量增大,溫升溫至650℃并保持1h,然后降溫至100℃,通 CoH-FBZ系列催化劑上NO轉(zhuǎn)化率的極大值增大到入NH1/He(10%)至吸附飽和,用高純氦氣吹掃定程度后下降, CoH-FBZ(I)(Ⅱ(Ⅲ入30min,然后進(jìn)行TPD操作.80m·mn2高純He(Ⅳ)(V)上,NO的最大轉(zhuǎn)化率分別為71.2%流經(jīng)樣品,以10℃mn的升溫速率從100℃升(520℃,表未給出)86.1%、85.5%、80.3%和溫至650℃并保持30min,同時記錄數(shù)據(jù).進(jìn)行H278.4%.與機(jī)械混合樣品相比,CoH-FBZ系列催化劑TPR實(shí)驗(yàn)時,0.1g物料置入U形石英反應(yīng)器,氬上甲烷轉(zhuǎn)化率較低,結(jié)合Amor提出的甲烷選擇性表氣氣流中以2℃·min-的升溫速率從室溫升溫至達(dá)式可知甲烷的選擇性相對較高],表明甲烷被O2600℃并保持60min預(yù)處理,然后降溫至室溫,通直接燃燒的比例降低.CoH-FBZ中FAU與BEA拓?fù)淙?0mlmn-的H2/A(10%)混合氣吹掃,待檢結(jié)構(gòu)相對含量 FAUZBEA為(04:0.6)-(0.1測器基線水平后,以10℃·min-的升溫速率升溫至800℃并保持30min,同時記錄數(shù)據(jù).進(jìn)行MH20.9)時,催化劑顯示出較高的催化活性Table 2 Conversion ratio of NO to N, and CHaConversion ratio of NO to N,( CHa y%Sample450℃480℃℃650℃CoH-FBA D)2.1)3.4(3.1)15.810.2)38.4(25.8)56.1(41.8)67.1(55.4)67.x92.4)56.4100.0CoH-FBⅢ)3.1(2.0)6.I(4.7)20.315.9)46.x33.7)71.351.7)86.1(78.5)82.x94.9)60.3100.0)CoH-FBⅢ)4.6(2.1)6.49.8)24.6(18.1)60.x(41.0)82.671.0)85.5(93.2)65.x(100.0)55.x100.0)FBⅣ)2.30.5)10.x7.8)34.0(20.9)72.0(53.9)80.389.2)78.x97.2)60.3100.0)55.0(100.0CoH-FBZ V)3.6(1.2)9.(2.6)33.921.8)74.960.9)78.486.9)72.6%6.7)59.8100.0)56.l(100.0)CoNa-FBZ0.1(1.3)2.K3.8)15.1(13.5)45.0(47.8)65.X(70.2)68.0(83.2)55.(100.0)37.l100.0)CoH-Beta1.44.4)7.x(4.5)32.0(23.6)63.853.6)69.X95.7)52.l(100.0)38.9100.00.90.1)1.x(0.2)1.40.9)2.56.1)0.8(1.2)1.32.1)1l.l(8.1)35.727.4)47.x(45.2mixture20.x(0.8)1.6(3.8)22.(20.7)49.l(56.3)54.x(78.YH坐作mixture31.(0.7)1.x4.3)2.1(19.8)53.0(66.1)56.l(80.7)59.089.1)52.l(97.3)40.l100.0)mixture41.l(1.8)3.u4.3)34.x(23.9)56.l(69.0)59.x88.8)55.094.7)41.x(100.0)33.1(100.0)mixture 51.92.1)3.64.8)36.7(31.5)60.X78.4)62.x(89.6)55.x92.5)50.9100.0)40.5(100.0)Note: reaction conditions: NO 2180 x 10, CH4 2050 x 10, 0, 2% balanced by He GHSV 4500 h2108化工學(xué)報第57卷2.2催化劑表征催化劑樣品 CoH-FBZ(I)(Ⅱ)(Ⅲ)(Ⅳ入(V)的XRD圖見圖1(本文未發(fā)表的數(shù)據(jù)表明,CoH-FBZ為母體H-FBZ結(jié)晶度90%~95%,表明Co交換后分子篩骨架沒有被破壞)可以看出,CoH-FBZ催化劑具有FAU和BEA拓?fù)浣Y(jié)構(gòu)的l600140012001000800600400特征峰.應(yīng)用XRD對CoH-FBZ中FAU和BEA拓?fù)浣Y(jié)構(gòu)的相對含量進(jìn)行定量:制備相對含量為(1of catalysts CoH-YCoH-Beta,OoH-FBI),(Ⅱ),(Ⅲ),(Ⅳ),(V)9)~(9:1)的H-Y與H-Bete機(jī)械混合的9種樣-CoH-Y; b--CoH-Beta ;c-CoH-FBA I)品,測定其XRD圖,對歸屬于H-Y和H-Beta分子d-CoH-FBfⅢ);e-CoH-FBⅢ)篩特征峰的峰面積分別積分,將峰面積之比與H-Y、f--CoH-FBA I): g--CoH-FBZ( V)H-Beta相對含量關(guān)聯(lián)獲得標(biāo)準(zhǔn)曲線;測定H-FBZ系列樣品的XRD圖,對歸屬于FAU和BA拓?fù)浣Y(jié)構(gòu)特征峰的峰面積分別積分并得岀它們的比值,所得結(jié)果與標(biāo)準(zhǔn)曲線對比,即可獲得樣品中FAU和BEA拓?fù)浣Y(jié)構(gòu)的相對含量,催化劑CoH-FBZ(I)(Ⅱ)(Ⅲ)(Ⅳ)(V)的分子篩母體中FAU/BEA分別為0.51:0.49、0.31:0.69、0.23( a) SEM image of mixture0.77、0.17:0.83、0.09:0.91CoH-FBZACoH-FBz(n11)510152025303526()(b)SEM image of Co H-Y sampleig. 1 XRD patterns of catalysts CoH-FBZ( IⅡ),(Ⅲ),(Ⅳ),(V)催化劑FT-R圖譜見圖2.Y型分子篩主要的特征骨架振動峰51:四面體伸縮振動峰1005cm768cm-、700cm;骨架雙環(huán)振動峰569cm-;彎曲振動峰459cm-;Beta分子篩典型吸收峰為5I8cm-1,567cm-屬于雙五元環(huán)振動峰671,1220譜帶則屬于骨架四面體外部連接反對稱伸縮振(c) SEM image of CoH-Beta sample動.CoH-FBZ系列催化劑的FT-IR譜圖有FAU和BEA雙拓?fù)浣Y(jié)構(gòu)特征吸收峰,結(jié)合XRD結(jié)果可知CoH-FBZ具有FAU和BEA雙微孔拓?fù)浣Y(jié)構(gòu)CoH-Y、CoH-Beta、CoH-FBZ(Ⅲ)及 mixture2中國煤化工的SEM圖見圖3.CoH-Y呈光滑八面體形[圖3CNMHb)],CoH-Beta呈光滑的橢球形[圖3(c)],mixture2則可清晰地看出CoH-Y和CoH-Beta兩者之間的界面[圖3(a)]圖3(d)中CoH-FBZ(d) SEM image of CoH-FBA Il)sampleFig 3 SEM images of catalysts〔Ⅲ)呈均一不規(guī)則顆粒,表面粗糙,沒有可辨的第9期張金橋等:CoH-FBZ催化劑表征及選擇催化CH4還原NO2109八面體形或橢球形NH2-TPD曲線分別在低溫區(qū)和高溫區(qū)有兩個交疊催化劑在12500~25000cm-范圍內(nèi) DRS-UV-NH3脫附峰.與H型分子篩的NH3-TPD圖相比,Ⅴis圖譜見圖4,CoH-Beta在15200cm-、17000Co交換分子篩的NH3-TPD曲線強(qiáng)度有所提高,與m2和19800cm處存在明顯吸收, CoH-FBZ V) Resini等8的報道一致.高溫區(qū)脫附的NH3為分子與CoH-Beta的DRS-UⅤVis圖譜差別不明顯;CoH-篩表面的 Bronsted酸位與NH2作用,Co交換催化劑Y則至少在15500cm-、17300cm9300cm上仍然存在,但強(qiáng)度減弱;而且NH3脫附峰向高溫存在吸收峰.CoH-FBκⅡ)(〔Ⅲ)和(Ⅳ)催化方向移動,可能是由于離子交換使酸性增強(qiáng)或較弱劑的DRS-UV-Vis圖譜則存在明顯的區(qū)別,3種催化劑酸位首先被交換]的 DRS-UV-Vis圖譜在1580cm-、18000cm-1和E0252000cm-處存在吸收峰H-YCoH-YCoH-Y,CoH-Beta,CoH-FBZ(Ⅰ)(Ⅲ)和(Ⅳ)的H2-TPR結(jié)果見圖5.僅在750~770℃附近出現(xiàn)單一還原峰,說明處于交換位置的Co很難被8005還原.emperature/℃C a) NH3-TPD spectra of H-Y and CoH-YH-BetaCoH-Beta008121416182022242wavenumberX10-/cm-IFig 4 DRS-UV-Vis spectra of catalysts CoH-YCoH-Beta,CoH-FBI),(Ⅱ),(Ⅲ),(Ⅳ),(V)(b)NH3-TPD spectra of H-Beta and CoH-Beta6000.16HY+HBeta5000.040102030405060time×10-/s200300400500600g 5 H2-TPR spectra of catalysts CoHCoH- Beta and Coh-FBfI),(Ⅲ),(Ⅳ)(c)NH3-TPD curves of mixture 2 and its parent zeolite樣品表面的酸性采用NH3TPD測定,由于篇幅E0.16所限,圖6僅給出CoH-Y、CoH-Beta、 mixtureH-FBZ0.12CoH-FBZ(IInCoH-FBKⅢ)及其母體H型分子篩的NH3-TPD圖如圖6(a)所示,H-Y和CoH-Y的NH3TPD曲線008分別在225℃和265℃有2個相互交疊NH3脫附峰,中國煤化工H-Y在約360℃而CoH-Y在370℃存在1個交疊NH3CNMH00600700脫附峰.如圖6(b)所示,H-Beta和CoH-Beta的temperature℃NH3-TPD曲線約在240℃有一個NH3脫附峰,H-B(d)NH3-TPD curves of H-FBZ and CoH-FBZ(l)ta在約400℃而CoH-Beta在約440℃有1個可分辨Fig 6 NH3-TPD spectra of catalysts的NH3脫附峰.如圖6(c)所示, mixture2的and their parent zeolites2110化工學(xué)報第57卷如圖6(d)所示,H-FBZ的NH3-TPD曲線約FBZ及CoH-FBZ產(chǎn)生了單一結(jié)構(gòu)中不存在的強(qiáng)酸在240℃有一個NH3脫附峰,約在350℃中溫區(qū)存位,該強(qiáng)酸位對CH4選擇催化還原NO具有協(xié)同效在一交疊NH3脫附峰.與H-Y、 H-Beta及機(jī)械混合應(yīng),提高了催化劑的催化性能.CoH-FBZ催化劑顯樣品最大的區(qū)別在于HFBZ的NH3-TPD曲線在示出良好的CH4-SCR活性和甲烷選擇性,BEA與575℃岀現(xiàn)1個可分辨的NH3脫附峰,說明H- FBZ FAU拓?fù)浣Y(jié)構(gòu)的最優(yōu)相對含量FAU/BEA為(0.4上存在新強(qiáng)酸位.CoH-FB(Ⅲ)的NH3-TPD曲線0.6)~(0.1:0.9)在240℃存在可分辨的NH3脫附峰,在335℃和References410℃分別存在兩個交疊NH3脫附峰;在600℃存在個NH3脫附峰,表明進(jìn)行Co交換后,強(qiáng)酸位仍[1] Armor N. Catalytic reduction of nitrogen oxides with methane in然存在而且酸強(qiáng)度有所增強(qiáng);與其他催化劑類似,the presence of excess oxygen a review. Catal. Today, 1995CoH-FBZ較母體NH3-TPD曲線強(qiáng)度增強(qiáng)26(2):147-158[2] Li Y, Armor J N. Catalytic reduction of nitrogen oxides with2.3討論methane in the presence of excess oxygen. Appl. Catal. B, 1992FTIR、XRD、SEM結(jié)果表明,FBZ是一種具有FAU和BEA雙拓?fù)浣Y(jié)構(gòu)新型材料;根據(jù)NH3-TPD[3] Zhang tao(張濤), Ren lili(任麗麗), Lin liwu(林勵吾)結(jié)果,H-FBZ上產(chǎn)生了新的強(qiáng)酸位Chinese Journal of catalysis(催化學(xué)報),2004,25(1DRS-UV-Ⅴis圖譜表明,催化劑在可見區(qū)1250025000cm存在吸收,與 Kaucky等所報道的結(jié)[4] Li ruifeng(李瑞豐), Guo Qun(郭群), Li Zhifeng(李志果一致. Kaucky等將Co在ZSM-5、FER、MOR和峰). CN Appl.,200400123332BEA中的位置分為a、B和y位,并通過分析DRS[5]Ⅻ u Ruren(徐如人), Pang Wenqin(龐文琴), Yu jihe于吉紅), Huo Sisheng(霍啟升), Chen jiesheng(陳接UV-ⅵis譜帶,獲得了3種Co位相對含量,他們發(fā)). Chemistry- zeolites and Porous Materials(分子篩與多孔現(xiàn)在Co交換H-MOR和H-FER中處于直通主孔道a材料化學(xué)) Beijing: Science press,2004:171-173位的Co,在H-ZSM中處于Zigg交叉處的B位及61 Eapen M J, Reddy K S N, Shiralkzr V H. HydrothermH-Beta中β位Co為主要CH4SCR活性中心.本研rystallization of zeolite beta using tetraehtylammium. Zeolites94,14(4):295-302究中,CoH-FBZ與CoH-Y及CoH-Beta的 DRS-UV[7] Perez-Pariente J, Martens J A, Jacobs P A. CrystallizatiⅤis譜圖存在差別,并非二者簡單代數(shù)疊加,作者mechanism of zeolite beta from TEA ),0, Na,0 and K, 0認(rèn)為可能產(chǎn)生了新的Co位,但目前還沒有有效的ontaining aluminusilicate. App/. Catal. 1987, 31(1): 35-64檢測手段確定Co在高Si分子篩中的位置1,由于[8] Resini C, Montanari T, Nappi L, Bagnasco G, Turco M, Busca雙拓?fù)浣Y(jié)構(gòu)FBZ的復(fù)雜性,確定Co位顯得更加困G, Bregani F, Notaro M, Rocchini G. Selective catalyticreduction of No. by methane over Co-H-MFI and Co-H-FER難,以后將進(jìn)一步深入研究zeolite catalysts: characterization and catalytic activity. J. Catal.CoH-FBZ較CoNa-FBZ的催化活性高(表2),2003,214(2):179190表明分子篩表面的酸性對催化劑的CH4SCR活性具[9] Kaucky D, Vondrova A, Dedecek J, Wichterlova B. Activity of有協(xié)同效應(yīng).已有的研究表明,分子篩中的catalytic reduction of No with methane. J. Catal., 2000, 194Bronsted酸位能吸附碳?xì)浠衔锖蚇O,并對二者具(2):318-329有攏動作用,而且大小適當(dāng)?shù)奶細(xì)寤衔锓肿幽芨?0] Armaroli T, Trombetta m, Gutierrez Alejandre A, Ramirez Sol集在 Bronsted酸附近1.以上兩方面因素有利于兩Busca G. Ftir study of the interaction of some branched種反應(yīng)物活化,從而有利于CoH-FBZ的CH4SCRaliphatic molecules with the external and internal sites of H-ZSMPhys. Chem. Chem. Phy2000,2活性的提高.CoH-FBZ的催化活性與其拓?fù)浣Y(jié)構(gòu)的相對含量有關(guān),當(dāng)FAU/BEA為(0.4:0.6)~(0.1中國煤化工0.9)時,CoH-FBZ具有好的催化活性THCNMHG3結(jié)論綜上所述,具有FAU和BEA雙拓?fù)浣Y(jié)構(gòu)的