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采用等体积共浸渍法,制备了一批不同钾含量的KxMoP/Al2O3x表示K与Mo摩尔比,0≤x≤3)催化剂,考察其对高硫合成气制甲硫醇性能的影响,并采用X射线衍射分析(XRD)、程序升温还原法(TPR)和激光拉曼光谱(LRS)等技术手段对催化剂进行了表征。结果表明,氧化铝负载的磷钼氧化物前驱体在850℃经H2气还原制备出了MoP/Al2O3催化剂,少量添加钾催化剂有较高的甲烷选择性,大量添加钾助剂促进了催化剂表面活泼钼硫物种的生成,使得磷化钼基催化剂有较好的甲硫醇选择性,而过量添加钾又会阻碍了甲硫醇的生成。当n(K)/n(Mo)比在2~2.5之间时,磷化钼基催化剂对该反应有较好的催化活性。

A series of KxMoP/Al2O3(x is K/Mo molar ratio, 0≤x≤3) catalysts with different K/Mo molar ratios was prepared through co-impregnation and characterized using X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The effects of different potassium content of the catalysts for the synthesis of methyl mercaptan from high H2S-containing syngas were investigated. The results indicate that MoP/Al2O3 catalysts are formed by hydrogen reduction at 850℃ from phosphorus molybdenum oxide precursor. With a small amount of potassium, the catalysts show higher methane selectivity. Further increase of potassium content promotes the generation of activity molybdenum sulfur phase, showing good methyl mercaptan selectivity. Excessive potassium hinders the generation of methyl mercaptan. When K/Mo molar ratio is between 2 and 2.5, MoP-based catalysts shows good catalytic activity and selectivity.

参考文献

[1] Hao Y J,Zhang Y H,Chen A P,et al.Study on Methanethion Synthesis from H2S-Rich Syngas Over K2MoO4 Catalyst Supported on Electrolessly Ni-plated SiO2[J].Catal Lett,2009,129(3/4):486-492.
[2] Barrault J,Boulinguiez M,Forquy C,et al.Synthesis of Methanethiol from Carbon Oxides and H2S with Tungsten-Alumina Catalysts[J].Appl Catal,1987,33(2):309-330.
[3] WANG Qi,CHEN Aiping,XIE Chunfang,et al.Novel Mo-based Catalysts for Methanethiol Synthesis from High H2S-containing Syngas[J].Acta Chmi Sin,2004,62(23):2297-2302(in Chinese).
王琪,陈爱平,谢春芳,等.高硫化氢合成气制甲硫醇新型钼基催化剂研究[J].化学学报,2004,62(23):2297-2302.
[4] WANG Qi,YANG Yiquan,YUAN Youzhu,et al.The Study of the Promotion of Co to the Supported Catalyst K2MoO4 for the Synthese of Methanethiol from H2S-Containing Syngas[J].J Xiamen Univ(Nat Sci),2003,42(1):64-68(in Chinese).
王琪,杨意泉,袁友珠,等.钴对高硫合成气制甲硫醇负载型钼酸钾催化剂的促进作用[J].厦门大学学报(自然科学版),2003,42(1):64-68.
[5] WANG Qi,HAO Yingjuan,CHEN Aiping,et al.Effect on Thermal Treatment on Structure and Catalytic Performance of K2MoO4-NiO/SiO2 Catalyst for One-step Synthesis of Methanethiol from High H2S-Containing Syngas[J].Chinese J Catal,2010,31(2):242-247(in Chinese).
王琪,郝影娟,陈爱平,等.热处理对高硫化氢合成气一步法制甲硫醇K2MoO4-NiO/SiO2催化剂结构及性能的影响[J].催化学报,2010,31(2):242-247.
[6] Bai J,Li X,Wang A J,et al.Incorporation of Sulfur on the Bulk MoP During Hydrodesulfurization Reaction:Different Role of H2S and Dibenzothiophene[J].J Catal,2013,300(1):197-200.
[7] Oyama S T,Gott T,Zhao H,et al.Transition metal Phosphide Hydroprocessing Catalysts:A Review[J].Catal Today,2009,143(1/2):94-107.
[8] Sun F X,Wu W C,Wu Z L,et al.Dibenzothiophene Hydrodesulfurization Activity and Surface Sites of Silica-supported MoP,Ni2P and Ni-Mo-P Catalysts[J].J Catal,2004,228(2):298-310.
[9] ZHOU Guilin,WANG Puguang,JIANG Zongxuan,et al.Selective Hydrogenation of Acetylene over a MoP Catalyst[J].Chinese J Catal,2011,32(1):27-30(in Chinese).
周桂林,王普光,蒋宗轩,等.MoP催化剂上乙炔选择性加氢[J].催化学报,2011,32(1):27-30.
[10] YANG Yiquan,WANG Qi,DAI Shenjun,et al.Preparation of Mo-S-based Catalysts for Methanthiol Synthesis from High H2S-Containing Syngas[J].Chinese J Appl Chem,1999,16(4):47-51(in Chinese).
杨意泉,王琪,戴深峻,等.高硫合成气制甲硫醇钼硫基催化剂的制备[J].应用化学,1999,16(4):47-51.
[11] Clark P,Oyama S T.Alumina-supported Molybdenum Phosophide Hydroprocessing Catalysts[J].J Catal,2003,218(1):78-87.
[12] Damyanova S,Petrov L,Grange P.XPS Characterization of Zirconiumpromoted CoMo Hydrodesulfurization Catalysts[J].Appl Catal A:Gen,2003,239(1):241-252.
[13] Jeziorowski H,Knozinger H.Raman and Ultraviolet Spectroscopic Characterization of Molybdena on Alumina[J].J Phys Chem,1979,83(9):1166-1173.
[14] Stinner C,Prins R,Weber T.Formation,Structure,and HDN Activity of Unsupported Molybdenum Phosphide[J].J Catal,2000,191(2):438-444.
[15] Cheng C P,Schrader G L.Characterization of Supported Molybdate Catalysts During Preparation Using Laser Raman Spectroscopy[J].J Catal,1979,60(2):276-294.
[16] WANG Qi.Study on the Mo-S-based Catalysts Promoted by Nickel for Methanethiol Synthesis from High H2S-Containing Gas[D].Xiamen:Xiamen University,2007(in Chinese).
王琪.镍促进高硫合成气制甲硫醇钾钼基催化剂的研究[D].厦门:厦门大学,2007.
[17] CHEN Aiping.Study on the Synthesis of Methanethiol from H2S-rich Syngas over Mo-based Catalysts[D].Xiamen:Xiamen University,2008(in Chinese).
陈爱平.钼基催化剂上的高硫合成气制甲硫醇研究[D].厦门:厦门大学,2008.
[18] WANG Qi,HAO Yingjuan,CHEN Aiping,et al.XRD and TPR Studies on MoO3/SiO2 Catalysts Doped with Potassium[J].Chinese J Appl Chem,2007,24(5):561-564(in Chinese).
王琪,郝影娟,陈爱平,等.钾修饰的MoO3/SiO2催化剂的XRD和TPR表征[J].应用化学,2007,24(5):561-564.
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