六组分甲烷氧化偶联催化剂酸碱性对其反应性能的影响研究
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摘要
甲烷氧化偶联催化反应自1982年Kelter和Bhasin报道以后，一直是近年来多相催化领域中十分活跃的热点之一。甲烷氧化偶联反应制乙烯不仅为有机化工提供最上游的产品，而且也为天然气有效利用提供了一种途径。这一课题的开发研究不仅对获得活性和选择性良好的催化剂，实现甲烷氧化偶联反应的工业化有重要意义，而且对小分子活化的基础研究也同样重要。近年来虽然这项工作取得了一定的进展，但是甲烷氧化偶联反应研究的还存在两个难点：①开发具有高活性和高选择性的催化剂；②甲烷氧化偶联反应催化剂的催化机理。
由于甲烷氧化偶联反应过程的复杂性，单组分或双组分催化剂很难胜任提高C_2收率的要求。因此，近年来出现一些多组分互配氧化物催化剂，其中浙江大学联合反应工程研究所黄凯利用人工神经元网络优化设计的六组分甲烷氧化偶联催化剂在1069K，CH_4:O_2=3:1，GHSV=33313 ml·g~(-1)·hr~(-1)条件下，甲烷转化率达到37.79％，C_2烃选择性达到73.50％(C_2烃收率为27.78％)。
由于在甲烷氧化偶联催化反应中甲烷的活化是关键，甲烷活化又涉及到催化剂的表面活性氧物种，而氧气的活化需要一定的酸碱性，因此，甲烷氧化偶联催化剂酸碱性的研究不仅对于酸碱性与催化性能之间的关系还是整个甲烷氧化偶联反应机理的认识都是很有帮助的，但关于甲烷氧化偶联催化剂的酸碱性，近年来尚未形成一个统一的认识。依据以上观点，本文着重针对自行开发的六组分甲烷氧化偶联催化剂，开展了其酸碱性对催化剂反应性能的影响规律的研究工作，主要有以下几方面的研究内容和结果。
(1)六组分过渡金属氧化物催化剂的表面酸碱性测定。实验中采用CO_2-TPD和NH_3-TPD方法，结果并未检测到明显的催化剂表面的酸碱中心。
(2)分别选用H_3PO_4、LiOH、BaO、MgO、CaO和Na_2CO_3等物质修饰一定组成的六组分催化剂的表面。实验结果表明NH_3-TPD未测试到H_3PO_4修饰的催化剂表面上存在酸性中心且修饰后的催化剂的CH_4转化率、C_2选择性、C_2收率是降低的；催化剂表面修饰被LiOH、Na_2CO_3修饰后，催化剂的催化性能也有所下降；催化剂jx-2表面修饰碱土金属氧化物MgO、BaO的催化剂的性能有所提高，并且通过CO_2-TPD检测到，修饰过的催化剂表面在620℃左右有一微峰出现，不过峰的
浙江大学硕士研究生论文
大小并不随修饰碱量的增加而增加，此现象也进一步说明催化剂表面的碱性不随修
饰碱量的增加而增加，但是催化剂表面弱碱性的修饰可以提高其催化反应性能。
臼）催化剂载体酸碱性对催化性能的影响。将jXI催化剂载体的pH值分别
调节至：1、3、5、7、9、12，实验发现催化剂载体为酸性或中性时，C。收率和选
择性都有所提高，特别是催化剂jX上吃一a4（载体接近中性），在 1073K，CH人 OZ二3：
l，GHSV－33313 ml4·卜1条件下，获得 46．ZI％的甲烷转化率，C。烃选择性达
53．ZI％广烃收率为24．59％h 但载体为偏碱性时，CZ收率有所降低。
u）综合利用了 SEM、XRD及 BET几种不同的表征手段考察催化剂微观性
质，通过对此类催化剂SEM和XRD表征得出：载体经微量的H3PO4的调节后，所
制得的催化剂的表面从致密的片状结构转变为比较疏松的结构，特别是中性载体的
jX上七一a4催化剂表面呈现网状交织的结构，并通过 XRD测试到该催化剂中的 SIOZ
载体以高度分散的a一方石英存在，且其比表面大约是原配方催化剂的1．9倍。
综上所述，载体为偏酸性或中性，表面为弱碱性是自行开发的六组分催化剂反
应性能良好的条件。
Since Kelter and Bhasin reported the reaction of oxidative coupling of methane (viz.OCM) in1982, it became one of hotspot topic in the realm of multi-phase catalysts.
The research of OCM helps not only to obtain the fundamental production--ethane,
but also provide a path to make use of natural gas. Moreover, this topic can provide better catalysts with high performance, realize its industrialization and make foundmental research for little molecule. Up to now, to obtain catalysts with high activity and high selectivity is still one of nudoses in the research of OCM.
For the complexities of OCM reaction process, unicomponent or dicompomponent can't meet with the require of high C2 yield. Therefore, multi-component catalyst was applied and showed better reaction performance in the reaction of OCM. For example, Huang kai in the Chemical Engineering Department in Zhejiang University had optimized a muli-component catalyst with artifical neural network aided-design. And the conversion of methane would be 37.79% and the total selectivity of ethane and ethylene would be 73.50% (C2 yield being 27.78%) when GHSV was 33313 ml g-1 hr-1, the proportion CH4 to O2 was 3 to 1 at 1069K.
In the reaction of oxidative coupling of methane, Whether basicity is favorable to the performance of catalyst is uncertain. Howerver, According to two acpects that activation of methane is the key of the reaction and activation of methane have a consanguineous relationship with acidity-basicity of OCM catalyst, the effects of acidity-basicity on the catalyst performance in the process of OCM were investigated. Here the catalysts prepared by our lab were multi-component transition metal catalysts. The results of exiperiments were described as following.
(1) The surface acidity or basicity of six-component transition metal catalyst was studied. After a series of experiment, acidity-basicity on the six-component catalysts surface weren't obvious by CO2-TPD and NH3-TPD.
(2)These six-component catalysts modified acid-basic compound such as H3PO4, LiOH, BaO, MgO, CaO Na2CO3 were investigated. The results showed that the differrent modifiers have distinct influencing on the performance of catalysts. For jx-2
catalyst, the reaction performance was increased a little with its surface modified with BaO and MgO, but decreased with CaO. However, the performance of catalyst whose surface was modified LiOH or Na2CO3 was decreased with the increasing of modifying amount.
(3) Acidity-basicity of catalyst support influencing on the performance of reaction were studied. The value of pH was adjusted to 1,3, 5, 7, 9 and 12. The experimental data showed that C2 yield and C2 selectivity were improved when the catalyst support was acid or neutral. In special, for catalyst jx-3-13, CH4 conversion would be 37.79% and C2 selectivity would be 73.50%(C2 yield being 27.78%) when GHSV was 33313 ml g-1 hr-1, the proportion CH4 to O2 was 3 to 1 at 1073K. However, the performance was some decreased when the catalyst support was basic.
(4) Some different methods are used to characterize catalyst micro-properties. When a few H3PO4 was added to the catalyst support, that surface structure was changed from dense to loose by SEM. And the catalyst jx-3-13 existed in interlaced reticulation and SiO2 was disperse extensively in the form of a -cristobalite by XRD. In addition, the BET surface of jx-3-13 was approximately 1.9 times than the original catalyst prescription. In a word, Addition of a few H3PO4 could improved the performance of catalysts comparing to original catalyst.
In conclusion, the six-component catalyst would be good reaction performance with acidity or neutral in support and weak basicity in surface.
由于甲烷氧化偶联反应过程的复杂性，单组分或双组分催化剂很难胜任提高C_2收率的要求。因此，近年来出现一些多组分互配氧化物催化剂，其中浙江大学联合反应工程研究所黄凯利用人工神经元网络优化设计的六组分甲烷氧化偶联催化剂在1069K，CH_4:O_2=3:1，GHSV=33313 ml·g~(-1)·hr~(-1)条件下，甲烷转化率达到37.79％，C_2烃选择性达到73.50％(C_2烃收率为27.78％)。
由于在甲烷氧化偶联催化反应中甲烷的活化是关键，甲烷活化又涉及到催化剂的表面活性氧物种，而氧气的活化需要一定的酸碱性，因此，甲烷氧化偶联催化剂酸碱性的研究不仅对于酸碱性与催化性能之间的关系还是整个甲烷氧化偶联反应机理的认识都是很有帮助的，但关于甲烷氧化偶联催化剂的酸碱性，近年来尚未形成一个统一的认识。依据以上观点，本文着重针对自行开发的六组分甲烷氧化偶联催化剂，开展了其酸碱性对催化剂反应性能的影响规律的研究工作，主要有以下几方面的研究内容和结果。
(1)六组分过渡金属氧化物催化剂的表面酸碱性测定。实验中采用CO_2-TPD和NH_3-TPD方法，结果并未检测到明显的催化剂表面的酸碱中心。
(2)分别选用H_3PO_4、LiOH、BaO、MgO、CaO和Na_2CO_3等物质修饰一定组成的六组分催化剂的表面。实验结果表明NH_3-TPD未测试到H_3PO_4修饰的催化剂表面上存在酸性中心且修饰后的催化剂的CH_4转化率、C_2选择性、C_2收率是降低的；催化剂表面修饰被LiOH、Na_2CO_3修饰后，催化剂的催化性能也有所下降；催化剂jx-2表面修饰碱土金属氧化物MgO、BaO的催化剂的性能有所提高，并且通过CO_2-TPD检测到，修饰过的催化剂表面在620℃左右有一微峰出现，不过峰的
浙江大学硕士研究生论文
大小并不随修饰碱量的增加而增加，此现象也进一步说明催化剂表面的碱性不随修
饰碱量的增加而增加，但是催化剂表面弱碱性的修饰可以提高其催化反应性能。
臼）催化剂载体酸碱性对催化性能的影响。将jXI催化剂载体的pH值分别
调节至：1、3、5、7、9、12，实验发现催化剂载体为酸性或中性时，C。收率和选
择性都有所提高，特别是催化剂jX上吃一a4（载体接近中性），在 1073K，CH人 OZ二3：
l，GHSV－33313 ml4·卜1条件下，获得 46．ZI％的甲烷转化率，C。烃选择性达
53．ZI％广烃收率为24．59％h 但载体为偏碱性时，CZ收率有所降低。
u）综合利用了 SEM、XRD及 BET几种不同的表征手段考察催化剂微观性
质，通过对此类催化剂SEM和XRD表征得出：载体经微量的H3PO4的调节后，所
制得的催化剂的表面从致密的片状结构转变为比较疏松的结构，特别是中性载体的
jX上七一a4催化剂表面呈现网状交织的结构，并通过 XRD测试到该催化剂中的 SIOZ
载体以高度分散的a一方石英存在，且其比表面大约是原配方催化剂的1．9倍。
综上所述，载体为偏酸性或中性，表面为弱碱性是自行开发的六组分催化剂反
应性能良好的条件。
Since Kelter and Bhasin reported the reaction of oxidative coupling of methane (viz.OCM) in1982, it became one of hotspot topic in the realm of multi-phase catalysts.
The research of OCM helps not only to obtain the fundamental production--ethane,
but also provide a path to make use of natural gas. Moreover, this topic can provide better catalysts with high performance, realize its industrialization and make foundmental research for little molecule. Up to now, to obtain catalysts with high activity and high selectivity is still one of nudoses in the research of OCM.
For the complexities of OCM reaction process, unicomponent or dicompomponent can't meet with the require of high C2 yield. Therefore, multi-component catalyst was applied and showed better reaction performance in the reaction of OCM. For example, Huang kai in the Chemical Engineering Department in Zhejiang University had optimized a muli-component catalyst with artifical neural network aided-design. And the conversion of methane would be 37.79% and the total selectivity of ethane and ethylene would be 73.50% (C2 yield being 27.78%) when GHSV was 33313 ml g-1 hr-1, the proportion CH4 to O2 was 3 to 1 at 1069K.
In the reaction of oxidative coupling of methane, Whether basicity is favorable to the performance of catalyst is uncertain. Howerver, According to two acpects that activation of methane is the key of the reaction and activation of methane have a consanguineous relationship with acidity-basicity of OCM catalyst, the effects of acidity-basicity on the catalyst performance in the process of OCM were investigated. Here the catalysts prepared by our lab were multi-component transition metal catalysts. The results of exiperiments were described as following.
(1) The surface acidity or basicity of six-component transition metal catalyst was studied. After a series of experiment, acidity-basicity on the six-component catalysts surface weren't obvious by CO2-TPD and NH3-TPD.
(2)These six-component catalysts modified acid-basic compound such as H3PO4, LiOH, BaO, MgO, CaO Na2CO3 were investigated. The results showed that the differrent modifiers have distinct influencing on the performance of catalysts. For jx-2
catalyst, the reaction performance was increased a little with its surface modified with BaO and MgO, but decreased with CaO. However, the performance of catalyst whose surface was modified LiOH or Na2CO3 was decreased with the increasing of modifying amount.
(3) Acidity-basicity of catalyst support influencing on the performance of reaction were studied. The value of pH was adjusted to 1,3, 5, 7, 9 and 12. The experimental data showed that C2 yield and C2 selectivity were improved when the catalyst support was acid or neutral. In special, for catalyst jx-3-13, CH4 conversion would be 37.79% and C2 selectivity would be 73.50%(C2 yield being 27.78%) when GHSV was 33313 ml g-1 hr-1, the proportion CH4 to O2 was 3 to 1 at 1073K. However, the performance was some decreased when the catalyst support was basic.
(4) Some different methods are used to characterize catalyst micro-properties. When a few H3PO4 was added to the catalyst support, that surface structure was changed from dense to loose by SEM. And the catalyst jx-3-13 existed in interlaced reticulation and SiO2 was disperse extensively in the form of a -cristobalite by XRD. In addition, the BET surface of jx-3-13 was approximately 1.9 times than the original catalyst prescription. In a word, Addition of a few H3PO4 could improved the performance of catalysts comparing to original catalyst.
In conclusion, the six-component catalyst would be good reaction performance with acidity or neutral in support and weak basicity in surface.
引文
[1] 张凌霄，化工技术经济，2002，20(4)，32-36
[2] Keller G E and Bhasin M M.J.Catal.,1982,73:9
[3] 赵修太，石油与天然气化工，1994，23(1)：23-
[4] 王海南 傅和清 曹舟华．石油与天然气化工,2000,29(6)，289-293
[5] 丘显清，彭永忠，朱起明，催化学报，1996,17(6)：507～
[6] 鲁灵江，谢卫国，丘发礼等．天然气化工，1996,21(1)：15-
[7] 黄部文，徐奕德，黄家生，催化学报，1993，14(4)：270～
[8] 刘福生，石油化工，1991,20(3)：150～
[9] 余林，徐奕德，黄家生等，催化学报，1993，14(1)：31-35
[10] 徐立进，丘发礼，吕绍洁等．天然气化工，1996,21(2)：19-
[11] 汤凤洁，甄开吉，毕颖丽，天然气化工，1991，16(1)：20～
[12] 刘宝生，黄仲涛，催化学报，1999,20(1)：12～16
[13] 刘勤，邵允，顾景贤等．催化学报，1988,9(2)：214～
[14] 远松月，赵震，刘宝春等．催化学报,1995，16(1)：15-
[15] 蒋宗轩，李灿，辛勤，燃烧化学学报，1992,20(1)：26～31
[16] 徐建晶，庞先桑，黄仲涛，天然气化工，1992,17(1)：7～
[17] Laconbe S,Ceantet C,Mirodatos C.J.Catal.1994,151:439～
[18] 徐竹生，张涛，吴金荣等．天然气化工，1995,20(1)：1～
[19] Lunsfored J H. Study. Surf.Sci.Catal.,1994,81:1～
[20] Lunsford J H.Hinson P G,Rosynek M P et al.J.,Catal.,1994,147:301
[21] Kham A Z and Kunckenstein E.Catal.Lett.,1992,13:95～
[22] Au C T, He H, Lai S Y et al.J.Catal,1996,159:280～
[23] Au C T, Zhang Y Q,He H et al.J Catal,1997,167:354～
[24] Au C T, Liu Y W and Ng C F. J.Catal,1997,171:231～
[25] Long Ruiqiang and Wan Huilin.J.Catal,1997,172:471～
[26] Au C T, Zhou X P, Liu Y W et al.J.Catal.,1998,174:153～
[27] Au C T, He H,Lai S Y et al. J.Catal,1996,163:399～
[28] Yamashita,H.,Machido,Y.and Tomita,A..Appl.Catal.,1991,79:203.
[29] Choudhary,V.R.,Chaudhari,S.T.,Rajput,A.M.et al.,J Chem.Soc.Chem.Commun.,
1989(9):555.
[30] Choudhary, V. R.,Chaudhari,S.T.,Rajput,A.M.et al.,J Chem.Soc.Chem.Commun.,1989(10):605.
[31] Choudhary, V. R., Uphade,B.S.and Mulla,S.A.R.,Ind.Eng.Chem.Res.1997,36:3594.
[32] Choudhary, V. R., Mulla, S.A.R.and Rane,V.H.,J Chem.Technol.Biotech.1998.
[33] Choudhary, V. R., Mulla, S. A. R. and Uphade,B.S.,Ind.Eng.Chem.Res.1997,37(6):2142.
[34] Filkova,D.,Wolf,D.,Gayko,G.,etal.,Appl.Catal.A.1997,159:33.
[35] Long, R.Q.,Wan,H.L.,Appl.Catal.A.1997,159:45.
[36] 余振强，沈师孔，李树本等，分子催化．1989，3(3)：181．
[37] 朴红，宿美平，毕颖丽等，高等学校化学学报．1998，19(2)：261．
[38] Au, C.T.,He, H.,Lai, S.Y.,et al.,Appl.Catal.A.1997,159:133.
[39] Yoon, K J,Seo,S W.Applied Catalysis A,1997,161:L5.
[40] 季生福，李树本等．分子催化，2000，14(2)：107．
[41] 陈宏善，牛建中等．高等学校化学学报，2001，22(5)：814．
[42] 吴金刚，李树本．分子催化，1994，8(2)：131．
[43] 方学平，李树本等．分子催化，1992，6(6)：427．
[44] 林景治，顾靖芳等．石油化工，1993，24(5)：293．
[45] 蒋致诚，方学平，于长江，李树本．分子催化，1992，6(6)：484．
[46] Ji,S.F.,Li,S.B.,et al.J Nat.Gas Chem.,1999,8(1):1.
[47] 陈宏善，牛建中等．物理化学学报，2000，16(6)：543．
[48] 季生福，李树本等，分子催化，2000，14(1)：1．
[49] 王恒秀．浙江大学博士论文[D]，1998．
[50] Choudharg V R and Rare V H.J Catal.,1991,130:411-422.
[51] Ross,I, Garrone,E.,Geobaldo,F.,et al.Appl.Catal.B.2001, 30:61.
[52] 黄凯，陈丰秋，吕德伟．浙江大学学报：工学版．2002，36(2)12，129-133．
[53] 黄凯，陈丰秋，吕德伟．天然气化工，2001，26(5)：1．
[54] Huang,K.,Chen,F.Q.,Lu,D.W.,Applied Catalysis A:General,2001,219:61
[55] 赵震，远松月，于作龙，催化学报，1995，16(1)：15～
[56] 徐立进，丘发礼，吕绍洁．天然气化工，1996,21(3)：26～
[57] Eraralanoglu Y, Onal 1,Dogn T and Senkan S.Appl.Catal.A,1996,145:15
[58] 蔡启瑞，彭少逸等．碳-化学中的催化作用．化学工业出版社，1995，45-126
[59] 沈鸿福，王新平，刘勤，催化学报，1990，11(1)：60～
[60] Lunsford,J.H.,in "New Frontiers In Catalysis"(L.Guczi rt al.,eds.)Series A,P.103.Elsevier,New Youd,1993.
[61] Amerebieta, V.T.,and Colussi,A.J.,J.Phys.Chem.92,4576(1988).
[62] Feng,Y.,Niiranen,J.,and Gutman,D.,J.Phys.Chem.95,6564(1991).
[63] Dricall D J,Mareir W and Lunsford J H.J Phys.Chem.,1985,(89):4415.
[64] Carreiro J A S P and Baerns M. J Catal,1989,117:258;396
[65] C.Y.Yu,W.Feng,A.Qi and Y.Chen.Stud.Surf.Sci. Catal.,75(1993)1119
[66] Dricall D.J.,Mareir W and Wang and Lunsford J.H.,J.Am.Chem.Soc.,107(1985)58
[67] S.Lacombe,C.Mirodatos.J.Catal.,151(1994)439.
[68] S.Lacombe,H.Zanthoff,C.Mirodatos.J.Catal.,155(1995)106
[69] C.Y.Yu~a,W.Z.Lia, G.A.Martin~b,C.Mirodatos~(b.~*),Appl.Catal.A,General 1997,158,201-214
[70] Daniel J.Driscoll, Wilson Martir,Ji-Xiang Wang,and Jack H.Lunsford~*.J.Am.Chem.Soc.1985,107,58-63.
[71] Sokolovskii V R and Aliev S M. et al.Catal Today,1989,(4):293
[72] O.V.Buyevskaya,M.Rothaemel,H.W.Zanthoffand M.Baerns,J.Catal.,1994,146,346.
[73] Spinicci R.and Tofanari A.. Catal.Today,1990,6:473.
[74] Lunsford J.H.,Yang X.and Knozinger H..J Phys.Chem.,1993,97:13810.
[75] 楼辉，郑洪元等．高等学校化学学报，1995，16(1)：107．
[76] 蒋致诚，于长江，方学平，李树本，分子催化，1992，6(6)，481-483．
[77] Ohtsuka Y.and Asamil K.et al.J.Chin.Inst.Chem.Eng.,1999,30(6):439.
[78] Dubois J.L., et al.Appl.Catal.,1990,67(1):49.
[79] Sikolovskii V D.Catal Today,1989,4:293
[80] Carreiro J.A.S.P.,Baerns M..React.Kinet.Caal.Lett.[J],1987,35:349-360
[81] Ohtsuka K.Chem Lett,1987,77.
[82] Tong Y.,Rosynek M.P.and Lunsford J.H..J Catal.,1989, 126:291.
[83] Bytyn W.,Beaern M. Appl.Catal.[J],1989,28:199-207
[84] O.V.Buyevskaya,A.I.Suleimanov,S.M.Aliev,and V.D.Sokolovskii,React.Kinet.Catal.
Lett.,33(1987)223
[85] V.D. Sokoiovskii,O.V. Buyevskaya,S.M.Aliev and A.A.Davydov,Catal.Today,4(1989)293
[86] V.P. Vislovskii,I.V.Baidikova,e.A.mamedov and R.G.Rizayev,React.Kinet.Catal.Lett.,47(1992) 193
[87] Buyevskaya O.V.,Suleimanov A.I.,Aliev S.M.et al..React.Kinet.Catal.Lett.[J],1987,33:223-227
[88] 蔚新运，徐奕德等．催化学报，1994，15(3)：184．
[89] Wang D.,Rosynek M.P.,Lunsford J.H..J.Catal.[J],1995,155:390-402
[90] Lunsford J. H.,Hinson P.G.,Rosynek M.P.et al..J.Catal.[J],1994,147:301-310
[91] V.R.Choudhary~*, V.H. Rane,S.T.Chaudhari,applied Catalysis A:General 158(1997) 121-136
[92] Choudhary V.R.,Mulla S.A.R..Fuel,1999,78:427.
[93] 谢卫国，丘发礼等．天然气化工，1994，19(4)：19．
[94] Wan H.L.,Zhou X.P.,et al.Catal.Today,1999,51:161.
[95] 翁维正，陈明树等．高等学校化学学报，2000，21(4)：575．
[96] A.J.Tenth,T.Lawson and J.F.J.Kibblewhite,J.chem..Soc.,Faraday Trans.1,68(1972)1169
[97] Z.L.Zhang and M.Baerns,J.Catal.,135(1992)317
[98] M.che and A.J.Teneh.Adv.Catal.,31(1982)77
[99] K.P.Peil,G.Marcelin and J.G.Goodwin,jr,in E.E.Wolf(Editor),Methane conversion by oxidative processes,Van Nostrand Reinhold,NewYork,1992,Ch.5
[100] C.Yu.W.Li,W.Feng,A.Qi and y.chen,Prep.,10th Int.Congr.Catal.,Budapest,1992,P.181
[101] Z. Kalenik and E.E.Wolf, Prep.,10th Int. Congr. Catal.,Budapest,1992,p.176
[102] Z. Kalenik and E.E.Wolf, Catal.Today,13(1992)255
[103] Baronetti,G.T.,Padro,C.L.,etal.Stud.Surf.Sci.Catal.,1998,119:337.
[104] Aritani, H., Yamada, H.,et al.J.Phys.Chem.B,2000,104(44):10133.
[105] Hong,J.H.,Yoon,K.J.Appl.Catal.:A. 2001,205:253.
[106] Murata,K.,Hayakawa,T.,Hamakawa,S.,et al.Catal.Today.1998, 45(1～4):41.
[107] Au,C.T.,Chen,K.D.,Ng,C.F.Appl.Catal.:A,1998,170:81.
[108] Kong,J.I.,Tung,T.S.,Choi,J.G.,et al.Appl.Catal.:A.2000,204: 241.
[109] Ozakan,U.S.,Kumthekar,M.W.,Karakas,G.Catal.Today,1998,40:3.
[110] Zeng,Y.and Lin,Y.S.J.Catal.,1999,182(1):30.
[111] 刘宝生，黄仲涛．催化学报，1999，20(1)：12．
[112] Lin, Y.,Liu, X.,et al.Appl.Catal: A.1998,168:139.
[113] Filho,J.G.A.,Pacheco, et al.Catal.Lett.,2000, 68(3～4):197.
[114] Xu,Y.D.,Guo,X.X..J.Nat.Gas Chem.,1999,8(1):18.
[115] 魏光，黄遵楠等．化学物理学报，1998，11(5)：471．
[116] Holgado, M.J.,Martin,C.et al.Catal.Lett.,1993, 49(1):139.
[117] Da,J.W.and Shen,S.K.J.Nat.Gas Chem.,2000, 9(3):231.
[118] 徐桂芬，王学林，石军雄等，天然气化工．1994，19(3)：4．
[119] Do,K T.,Edwards,H.and Tyler,R.J..Stud.Sur.Sci.Catal.1994,81,193.
[120] Pugsley,T.S.and Berruti,F.,Chem.Eng.Sci.1996,51:2751.
[121] Santos,A.,Santamaria,J.and Menendez,M..Ind.Eng.Chem.Res.1995,34:1581.
[122] Mleczko,L.,Rothaemel,M.,Andof,R.et al.,Fluidization Ⅶ,Potter,O.E.,and Nicklin,D.J.Eds.AIChE,New York.1992:487.
[123] Mleczko,L.,Pannek,U.,Rothaemel,M.,et al.,Can.J Chem.Eng.1996,74:279.
[124] Mleczko,L.,Pannek,U.,Gayko,G.,et al.,AIChE Symp.Ser.,1996 313:10.
[125] Pannek, U. and Mleczko,L.,Chem.Eng.Sci.1996,51:3575.
[126] Pannek, U. and Mleczko,L.,Chem.Eng.Sci.,1997,52:2429.
[127] Mleczko,L. and Marschall K.J.,Can.J Chem.Eng.1997,75:610.
[128] 王晓来，张嘉宁，杨得信等，石油化工，1997，26(6)：361．
[129] Garnier,O.,Shu,J.and Grandjean,B.P.A.,Ind.Eng.Chem.Res.1997,36:553.
[130] Nozaki,T.,Hashimoto,S.,Omata,K.,et al.,Ind.Eng.Chem.Res.1993,32:1174.
[131] Lafarga,D.,Santamaria,J.and Menendez,M.,Chem.Eng.Sci.1994,49(12):2005.
[132] Elshof J. E.,Bouwmeester,H.J.M.and Verweij,H.,Appl.Catal.A.1995,130:195.
[133] Coronas,J.,Menendez,M.and Santamaria,J.,Chem.Eng.Sci.1994,49(24A):4749.
[134] Langguth,J.,Dittmeyer, R.,Holfmann,H.,et al.,Appl.Catal.A.1997,158:287.
[135] Zeng, Y.and Lin,Y.S.,Appl.Catal.A.1997,159:101.
[136] 王保伟，许根慧，刘昌俊，陈洪钫．化工进展，2001，4：14．
[137] 国秀梅，陈洪钫．化工学报．1995，46(3)：304．
[138] 国秀梅，陈洪钫．化工学报．1995，46(3)：310．
[139] Guo,X M.,Hidajat,K.and Ching,C.B.,Ind.Eng.Chem.Res.1997,36:3576.
[140] Seimanides,S.and Stoukides,M.,.J Electrochem.Soc.1986,133:1535.
[141] White J.H.,Needlham,E.A.,Cook,R.L.et al.,Solid State Ionics.1992,53～56:149.
[142] Ohtsuka, K,Jinno, K.and Morikawa,A.,J Catal. 1986,100:358.
[143] Mazanec, T.J.,Cable,T.L.and Frye,T.G.,Solid State Ionics.1992,53～56:111.
[144] Steele,B.C.,Kelly,I., Middleton, H. et al.,Solid State Ionics. 1988,28～30: 1547.
[145] Kuchynka,D.J.,Cook,R.L.and Sammells,A.F.,J Electrochem.Soc.1991,138:1284.
[146] Ohtsuka,K.,Yokyama,S.and Morikawa,A.,Chem.Lett.1985(3):319.
[147] 江义，阎景旺，李文钊 等．天然气化工，1995，20(6):25
[148] Bader, R A.,Axelrod, M G;,US 4855111.
[149] Victor R, Christopher L B,et al.,US 5 012 028(1991).
[150] 樊汝栋。天然气化学，1992,3(4):1
[151] Gradassi Mj, green N W,Fuel proc.Technol.1995,42(2,3):65～83
[152] Carreiro, J.A.S.P.and Baerns,M.,J Catal.,1989,117:396
[153] J.I.jezl,g.O.Michaels,m.J.Spangler and M.L.winzenburg,US patent 4 814 539(1989)
[2] Keller G E and Bhasin M M.J.Catal.,1982,73:9
[3] 赵修太，石油与天然气化工，1994，23(1)：23-
[4] 王海南 傅和清 曹舟华．石油与天然气化工,2000,29(6)，289-293
[5] 丘显清，彭永忠，朱起明，催化学报，1996,17(6)：507～
[6] 鲁灵江，谢卫国，丘发礼等．天然气化工，1996,21(1)：15-
[7] 黄部文，徐奕德，黄家生，催化学报，1993，14(4)：270～
[8] 刘福生，石油化工，1991,20(3)：150～
[9] 余林，徐奕德，黄家生等，催化学报，1993，14(1)：31-35
[10] 徐立进，丘发礼，吕绍洁等．天然气化工，1996,21(2)：19-
[11] 汤凤洁，甄开吉，毕颖丽，天然气化工，1991，16(1)：20～
[12] 刘宝生，黄仲涛，催化学报，1999,20(1)：12～16
[13] 刘勤，邵允，顾景贤等．催化学报，1988,9(2)：214～
[14] 远松月，赵震，刘宝春等．催化学报,1995，16(1)：15-
[15] 蒋宗轩，李灿，辛勤，燃烧化学学报，1992,20(1)：26～31
[16] 徐建晶，庞先桑，黄仲涛，天然气化工，1992,17(1)：7～
[17] Laconbe S,Ceantet C,Mirodatos C.J.Catal.1994,151:439～
[18] 徐竹生，张涛，吴金荣等．天然气化工，1995,20(1)：1～
[19] Lunsfored J H. Study. Surf.Sci.Catal.,1994,81:1～
[20] Lunsford J H.Hinson P G,Rosynek M P et al.J.,Catal.,1994,147:301
[21] Kham A Z and Kunckenstein E.Catal.Lett.,1992,13:95～
[22] Au C T, He H, Lai S Y et al.J.Catal,1996,159:280～
[23] Au C T, Zhang Y Q,He H et al.J Catal,1997,167:354～
[24] Au C T, Liu Y W and Ng C F. J.Catal,1997,171:231～
[25] Long Ruiqiang and Wan Huilin.J.Catal,1997,172:471～
[26] Au C T, Zhou X P, Liu Y W et al.J.Catal.,1998,174:153～
[27] Au C T, He H,Lai S Y et al. J.Catal,1996,163:399～
[28] Yamashita,H.,Machido,Y.and Tomita,A..Appl.Catal.,1991,79:203.
[29] Choudhary,V.R.,Chaudhari,S.T.,Rajput,A.M.et al.,J Chem.Soc.Chem.Commun.,
1989(9):555.
[30] Choudhary, V. R.,Chaudhari,S.T.,Rajput,A.M.et al.,J Chem.Soc.Chem.Commun.,1989(10):605.
[31] Choudhary, V. R., Uphade,B.S.and Mulla,S.A.R.,Ind.Eng.Chem.Res.1997,36:3594.
[32] Choudhary, V. R., Mulla, S.A.R.and Rane,V.H.,J Chem.Technol.Biotech.1998.
[33] Choudhary, V. R., Mulla, S. A. R. and Uphade,B.S.,Ind.Eng.Chem.Res.1997,37(6):2142.
[34] Filkova,D.,Wolf,D.,Gayko,G.,etal.,Appl.Catal.A.1997,159:33.
[35] Long, R.Q.,Wan,H.L.,Appl.Catal.A.1997,159:45.
[36] 余振强，沈师孔，李树本等，分子催化．1989，3(3)：181．
[37] 朴红，宿美平，毕颖丽等，高等学校化学学报．1998，19(2)：261．
[38] Au, C.T.,He, H.,Lai, S.Y.,et al.,Appl.Catal.A.1997,159:133.
[39] Yoon, K J,Seo,S W.Applied Catalysis A,1997,161:L5.
[40] 季生福，李树本等．分子催化，2000，14(2)：107．
[41] 陈宏善，牛建中等．高等学校化学学报，2001，22(5)：814．
[42] 吴金刚，李树本．分子催化，1994，8(2)：131．
[43] 方学平，李树本等．分子催化，1992，6(6)：427．
[44] 林景治，顾靖芳等．石油化工，1993，24(5)：293．
[45] 蒋致诚，方学平，于长江，李树本．分子催化，1992，6(6)：484．
[46] Ji,S.F.,Li,S.B.,et al.J Nat.Gas Chem.,1999,8(1):1.
[47] 陈宏善，牛建中等．物理化学学报，2000，16(6)：543．
[48] 季生福，李树本等，分子催化，2000，14(1)：1．
[49] 王恒秀．浙江大学博士论文[D]，1998．
[50] Choudharg V R and Rare V H.J Catal.,1991,130:411-422.
[51] Ross,I, Garrone,E.,Geobaldo,F.,et al.Appl.Catal.B.2001, 30:61.
[52] 黄凯，陈丰秋，吕德伟．浙江大学学报：工学版．2002，36(2)12，129-133．
[53] 黄凯，陈丰秋，吕德伟．天然气化工，2001，26(5)：1．
[54] Huang,K.,Chen,F.Q.,Lu,D.W.,Applied Catalysis A:General,2001,219:61
[55] 赵震，远松月，于作龙，催化学报，1995，16(1)：15～
[56] 徐立进，丘发礼，吕绍洁．天然气化工，1996,21(3)：26～
[57] Eraralanoglu Y, Onal 1,Dogn T and Senkan S.Appl.Catal.A,1996,145:15
[58] 蔡启瑞，彭少逸等．碳-化学中的催化作用．化学工业出版社，1995，45-126
[59] 沈鸿福，王新平，刘勤，催化学报，1990，11(1)：60～
[60] Lunsford,J.H.,in "New Frontiers In Catalysis"(L.Guczi rt al.,eds.)Series A,P.103.Elsevier,New Youd,1993.
[61] Amerebieta, V.T.,and Colussi,A.J.,J.Phys.Chem.92,4576(1988).
[62] Feng,Y.,Niiranen,J.,and Gutman,D.,J.Phys.Chem.95,6564(1991).
[63] Dricall D J,Mareir W and Lunsford J H.J Phys.Chem.,1985,(89):4415.
[64] Carreiro J A S P and Baerns M. J Catal,1989,117:258;396
[65] C.Y.Yu,W.Feng,A.Qi and Y.Chen.Stud.Surf.Sci. Catal.,75(1993)1119
[66] Dricall D.J.,Mareir W and Wang and Lunsford J.H.,J.Am.Chem.Soc.,107(1985)58
[67] S.Lacombe,C.Mirodatos.J.Catal.,151(1994)439.
[68] S.Lacombe,H.Zanthoff,C.Mirodatos.J.Catal.,155(1995)106
[69] C.Y.Yu~a,W.Z.Lia, G.A.Martin~b,C.Mirodatos~(b.~*),Appl.Catal.A,General 1997,158,201-214
[70] Daniel J.Driscoll, Wilson Martir,Ji-Xiang Wang,and Jack H.Lunsford~*.J.Am.Chem.Soc.1985,107,58-63.
[71] Sokolovskii V R and Aliev S M. et al.Catal Today,1989,(4):293
[72] O.V.Buyevskaya,M.Rothaemel,H.W.Zanthoffand M.Baerns,J.Catal.,1994,146,346.
[73] Spinicci R.and Tofanari A.. Catal.Today,1990,6:473.
[74] Lunsford J.H.,Yang X.and Knozinger H..J Phys.Chem.,1993,97:13810.
[75] 楼辉，郑洪元等．高等学校化学学报，1995，16(1)：107．
[76] 蒋致诚，于长江，方学平，李树本，分子催化，1992，6(6)，481-483．
[77] Ohtsuka Y.and Asamil K.et al.J.Chin.Inst.Chem.Eng.,1999,30(6):439.
[78] Dubois J.L., et al.Appl.Catal.,1990,67(1):49.
[79] Sikolovskii V D.Catal Today,1989,4:293
[80] Carreiro J.A.S.P.,Baerns M..React.Kinet.Caal.Lett.[J],1987,35:349-360
[81] Ohtsuka K.Chem Lett,1987,77.
[82] Tong Y.,Rosynek M.P.and Lunsford J.H..J Catal.,1989, 126:291.
[83] Bytyn W.,Beaern M. Appl.Catal.[J],1989,28:199-207
[84] O.V.Buyevskaya,A.I.Suleimanov,S.M.Aliev,and V.D.Sokolovskii,React.Kinet.Catal.
Lett.,33(1987)223
[85] V.D. Sokoiovskii,O.V. Buyevskaya,S.M.Aliev and A.A.Davydov,Catal.Today,4(1989)293
[86] V.P. Vislovskii,I.V.Baidikova,e.A.mamedov and R.G.Rizayev,React.Kinet.Catal.Lett.,47(1992) 193
[87] Buyevskaya O.V.,Suleimanov A.I.,Aliev S.M.et al..React.Kinet.Catal.Lett.[J],1987,33:223-227
[88] 蔚新运，徐奕德等．催化学报，1994，15(3)：184．
[89] Wang D.,Rosynek M.P.,Lunsford J.H..J.Catal.[J],1995,155:390-402
[90] Lunsford J. H.,Hinson P.G.,Rosynek M.P.et al..J.Catal.[J],1994,147:301-310
[91] V.R.Choudhary~*, V.H. Rane,S.T.Chaudhari,applied Catalysis A:General 158(1997) 121-136
[92] Choudhary V.R.,Mulla S.A.R..Fuel,1999,78:427.
[93] 谢卫国，丘发礼等．天然气化工，1994，19(4)：19．
[94] Wan H.L.,Zhou X.P.,et al.Catal.Today,1999,51:161.
[95] 翁维正，陈明树等．高等学校化学学报，2000，21(4)：575．
[96] A.J.Tenth,T.Lawson and J.F.J.Kibblewhite,J.chem..Soc.,Faraday Trans.1,68(1972)1169
[97] Z.L.Zhang and M.Baerns,J.Catal.,135(1992)317
[98] M.che and A.J.Teneh.Adv.Catal.,31(1982)77
[99] K.P.Peil,G.Marcelin and J.G.Goodwin,jr,in E.E.Wolf(Editor),Methane conversion by oxidative processes,Van Nostrand Reinhold,NewYork,1992,Ch.5
[100] C.Yu.W.Li,W.Feng,A.Qi and y.chen,Prep.,10th Int.Congr.Catal.,Budapest,1992,P.181
[101] Z. Kalenik and E.E.Wolf, Prep.,10th Int. Congr. Catal.,Budapest,1992,p.176
[102] Z. Kalenik and E.E.Wolf, Catal.Today,13(1992)255
[103] Baronetti,G.T.,Padro,C.L.,etal.Stud.Surf.Sci.Catal.,1998,119:337.
[104] Aritani, H., Yamada, H.,et al.J.Phys.Chem.B,2000,104(44):10133.
[105] Hong,J.H.,Yoon,K.J.Appl.Catal.:A. 2001,205:253.
[106] Murata,K.,Hayakawa,T.,Hamakawa,S.,et al.Catal.Today.1998, 45(1～4):41.
[107] Au,C.T.,Chen,K.D.,Ng,C.F.Appl.Catal.:A,1998,170:81.
[108] Kong,J.I.,Tung,T.S.,Choi,J.G.,et al.Appl.Catal.:A.2000,204: 241.
[109] Ozakan,U.S.,Kumthekar,M.W.,Karakas,G.Catal.Today,1998,40:3.
[110] Zeng,Y.and Lin,Y.S.J.Catal.,1999,182(1):30.
[111] 刘宝生，黄仲涛．催化学报，1999，20(1)：12．
[112] Lin, Y.,Liu, X.,et al.Appl.Catal: A.1998,168:139.
[113] Filho,J.G.A.,Pacheco, et al.Catal.Lett.,2000, 68(3～4):197.
[114] Xu,Y.D.,Guo,X.X..J.Nat.Gas Chem.,1999,8(1):18.
[115] 魏光，黄遵楠等．化学物理学报，1998，11(5)：471．
[116] Holgado, M.J.,Martin,C.et al.Catal.Lett.,1993, 49(1):139.
[117] Da,J.W.and Shen,S.K.J.Nat.Gas Chem.,2000, 9(3):231.
[118] 徐桂芬，王学林，石军雄等，天然气化工．1994，19(3)：4．
[119] Do,K T.,Edwards,H.and Tyler,R.J..Stud.Sur.Sci.Catal.1994,81,193.
[120] Pugsley,T.S.and Berruti,F.,Chem.Eng.Sci.1996,51:2751.
[121] Santos,A.,Santamaria,J.and Menendez,M..Ind.Eng.Chem.Res.1995,34:1581.
[122] Mleczko,L.,Rothaemel,M.,Andof,R.et al.,Fluidization Ⅶ,Potter,O.E.,and Nicklin,D.J.Eds.AIChE,New York.1992:487.
[123] Mleczko,L.,Pannek,U.,Rothaemel,M.,et al.,Can.J Chem.Eng.1996,74:279.
[124] Mleczko,L.,Pannek,U.,Gayko,G.,et al.,AIChE Symp.Ser.,1996 313:10.
[125] Pannek, U. and Mleczko,L.,Chem.Eng.Sci.1996,51:3575.
[126] Pannek, U. and Mleczko,L.,Chem.Eng.Sci.,1997,52:2429.
[127] Mleczko,L. and Marschall K.J.,Can.J Chem.Eng.1997,75:610.
[128] 王晓来，张嘉宁，杨得信等，石油化工，1997，26(6)：361．
[129] Garnier,O.,Shu,J.and Grandjean,B.P.A.,Ind.Eng.Chem.Res.1997,36:553.
[130] Nozaki,T.,Hashimoto,S.,Omata,K.,et al.,Ind.Eng.Chem.Res.1993,32:1174.
[131] Lafarga,D.,Santamaria,J.and Menendez,M.,Chem.Eng.Sci.1994,49(12):2005.
[132] Elshof J. E.,Bouwmeester,H.J.M.and Verweij,H.,Appl.Catal.A.1995,130:195.
[133] Coronas,J.,Menendez,M.and Santamaria,J.,Chem.Eng.Sci.1994,49(24A):4749.
[134] Langguth,J.,Dittmeyer, R.,Holfmann,H.,et al.,Appl.Catal.A.1997,158:287.
[135] Zeng, Y.and Lin,Y.S.,Appl.Catal.A.1997,159:101.
[136] 王保伟，许根慧，刘昌俊，陈洪钫．化工进展，2001，4：14．
[137] 国秀梅，陈洪钫．化工学报．1995，46(3)：304．
[138] 国秀梅，陈洪钫．化工学报．1995，46(3)：310．
[139] Guo,X M.,Hidajat,K.and Ching,C.B.,Ind.Eng.Chem.Res.1997,36:3576.
[140] Seimanides,S.and Stoukides,M.,.J Electrochem.Soc.1986,133:1535.
[141] White J.H.,Needlham,E.A.,Cook,R.L.et al.,Solid State Ionics.1992,53～56:149.
[142] Ohtsuka, K,Jinno, K.and Morikawa,A.,J Catal. 1986,100:358.
[143] Mazanec, T.J.,Cable,T.L.and Frye,T.G.,Solid State Ionics.1992,53～56:111.
[144] Steele,B.C.,Kelly,I., Middleton, H. et al.,Solid State Ionics. 1988,28～30: 1547.
[145] Kuchynka,D.J.,Cook,R.L.and Sammells,A.F.,J Electrochem.Soc.1991,138:1284.
[146] Ohtsuka,K.,Yokyama,S.and Morikawa,A.,Chem.Lett.1985(3):319.
[147] 江义，阎景旺，李文钊 等．天然气化工，1995，20(6):25
[148] Bader, R A.,Axelrod, M G;,US 4855111.
[149] Victor R, Christopher L B,et al.,US 5 012 028(1991).
[150] 樊汝栋。天然气化学，1992,3(4):1
[151] Gradassi Mj, green N W,Fuel proc.Technol.1995,42(2,3):65～83
[152] Carreiro, J.A.S.P.and Baerns,M.,J Catal.,1989,117:396
[153] J.I.jezl,g.O.Michaels,m.J.Spangler and M.L.winzenburg,US patent 4 814 539(1989)