Effect of calcination temperature on performance of K-Cu/Zn/La/ZrO2 for isobutanol synthesis
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摘要: 采用共沉淀法制备了Cu/Zn/La/ZrO2催化剂,并浸渍K对其进行改性.以合成气合成异丁醇为探针反应,考察了焙烧温度对K-Cu/Zn/La/ZrO2催化剂合成反应的影响.采用XRD、TG、BET、NH3-TPD、H2-TPR、Raman及XPS等手段表征了催化剂的结构和表面性质.结果表明,催化剂体相结构、比表面积与其催化活性没有直接关系;催化剂表面强酸中心的存在不利于异丁醇的生成;Cu-Zn-Zr活性组分间协同作用对催化剂活性影响很大,450 ℃焙烧温度下,Cu-Zn-Zr活性组分间协同作用最强,CuO最容易还原,催化活性最高,此时CO的转化率(物质的量)达到69.47%,醇中异丁醇的选择性(质量分数)为19.09%,甲醇+异丁醇的选择性(质量分数)为95.02%.Abstract: K-promoted Cu/Zn/La/ZrO2 catalyst were prepared by coprecipitation methods. Hydrogenation of CO was used as a probe reaction to investigate the catalytic performance. Structure and surface properties of K-Cu/Zn/La/ZrO2 catalysts were characterized by XRD,TG,BET, NH3-TPD, H2-TPR, Raman and XPS technics. The results indicated that structure and specific surface had no direct relationship with the catalyst activity. Strong acidic sites of catalyst surface were not good for the formation of isobutanol. Synergy among Cu-Zn-Zr has an important effect on the activity of K-Cu/Zn/La/ZrO2 catalysts. When the calcinations temperature was at 450 ℃, synergistic effect of Cu-Zn-Zr became strongest and CuO could be reduced easily. Under the optimum calcination temperature, conversion of CO reached 69.47% and selectivity of isobutanol approached 19.09%. Methanol and isobutanol were the primary products and occupied 95.02% in the alcohol products.
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Key words:
- syngas /
- isobutanol /
- calcination temperature /
- copper /
- zirconia
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EPLING W S, HOFLUND G B, MINAHAN D M. Reaction and surface characterization study of higher alcohol synthesis catalysts: I. K-promoted commercial Zn/Cr spinel[J]. J Catal, 1997, 169: 438. BERETTA A, SUN Q, HERMAN R G, KLIER K.Production of methanol and isobutyl alcohol mixtures overdouble-bed Cesium-promoted Cu/ZnO/Cr2O3 and ZnO/Cr2O3catalysts[J]. Ind Eng ChemRes, 1996, 35: 1534-1542. BURCHAM M M, HERMAN R G, KLIER K.Higher alcohol synthesis over double bed Cs-Cu/ZnO/Cr2O3catalysts: optimizing the yields of 2-Methyl-1-propanol (Isobutanol) [J]. Ind Eng Chem Res, 1998, 37: 4657-4668. 姜 涛,牛玉琴,钟炳.超临界相由合成气合成低碳醇的研究[J].催化学报, 2000, 21(3): 319-322. (JIANG Tao, NIU Yu-qin, ZHONG Bing.Study on synthesis of lower alcohols from syngas in supercritical fluids[J].Chinese Journal of Catalysis, 2000, 21(3): 319-322.) 谭猗生,牛玉琴,钟炳,彭少逸. ZrO2涂层催化剂用于合成甲醇、异丁醇的初步研究[J]. 燃料化学学报1996, 24(4): 368-371. (TAN Yi-sheng, NIU Yu-qin, ZHONG Bing, PENG Shao-yi. Conversion of synthesis gas to methanol and isobutanol over ZrO2 coated catalysts[J]. Journal of Fuel Chemistry and Technology, 1996, 24(4): 368-371.) 蔡亚宁,牛玉琴,陈正华,钟炳,彭少逸.锆系催化剂上合成气合成甲醇、异丁醇的研究[J]. 燃料化学学报, 1996, 24(1): 11-16. (CAI Ya-ning, NIU Yu-qin, CHEN Zheng-hua, ZHONG Bing, PENG Shao-yi. Synthesis of methanol and isobutanol from syngas over ZrO2-based catalysts[J]. Journal of Fuel Chemistry and Technology, 1996, 24(1): 11-16.) 赵宁,杨成,魏 伟,王太英,孙予罕,张静,谢亚宁,胡天斗.焙烧温度对合成低碳醇用Cu/ Mn/ Ni/ ZrO2催化剂性能的影响[J]. 催化学报, 2002, 23(6): 571-574. (ZHAO Ning, YANG Cheng, WEI Wei, WANG Tai-ying, SUN Yu-han, ZHANG Jing, XIE Ya-ning, HU Tian-dou. Effect of calcination temperature on Cu/ Mn/ Ni/ZrO2 catalystf or synthesis of higher alcohols[J]. Chinese Journal of Catalysis, 2002, 23(6): 571-574.) 何代平,丁云杰.Pd改性K/MnOx-ZrO2催化剂上CO加氢制甲醇和异丁醇[J]. 催化学报, 2005, 26(11): 961-964. (HE Dai-ping, DING Yun-jie. Synthesis of methanol and isobutanol by CO hydrogenation over Pd-modified K/MnOx-ZrO2 catalyst[J]. Chinese Journal of Catalysis, 2005, 26(11): 961-964.) 王军威,谭猗生,牛玉琴,钟炳,彭少逸. 燃料化学学报, 1998, 26(5): 390-394. (WANG Jun-wei, TAN Yi-sheng, NIU Yu-qin, ZHONG Bing, PENG Shao-yi. Relations between ZrO2 crystal structure and its catalytic activity to methanol and isobutanol[J]. Journal of Fuel Chemistry and Technology, 1998, 26(5): 390-394.) KEIM W, FALTER W. Isobutanol from synthesis gas[J].Catal Lett, 1989, 3: 59-64. NIX R M, RAYMENT T, LAMBERT R M, JENNINGS J R, OWEN G. An in situ X-ray diffraction study of the activation and performance of methanol synthesis catalysts derived from rare earth-copper alloys[J]. J Catal, 1987, 106: 216. 吴贵升,任杰,孙予罕. La与Cu/ ZrO2作用形式对合成醇催化剂性能的影响[J]. 燃料化学学报, 1999, 27(5): 472-475. (WU Gui-sheng, REN Jie, SUN Yu-han. Effect of La modified Cu/ZrO2 catalysts on alcohol synthesis[J]. Journal of Fuel Chemistry and Technology, 1999, 27(5): 472-475.) SHIMOKAWABE M, ASAKAWA H, TAKEZAWA N. Characterization of copper/zirconia catalysts prepared by an impregnation method[J]. Appl Catal, 1990, 59(1): 45. ZHOU R, YU T, JIANG X, CHEN F, ZHENG X. Temperature-programmed reduction and temperature-programmed desorption studiesof CuO/ZrO2 catalysts[J]. Appl Surf Sci, 1999, 148(3-4): 263. 吴贵升, 任杰, 孙予罕. 焙烧温度对Cu/ZrO2和Cu-La2O3/ZrO2催化性能的影响[J]. 物理化学学报, 1999, 15(6): 564-567. (WU Gui-sheng, REN Jie, SUN Yu-han. The effect of calcinations temperature on the performance of Cu/ZrO2 and Cu-La2O3/ ZrO2[J]. Acta Physico-Chimica Sinica, 1999, 15(6): 564-567.) BATYREV E D, VAN DEN HEUVEL J C, BECKERS J, JANSEN W P A, CASTRICUM H L. The effect of the reduction temperature on the structure of Cu/ZnO/SiO2 catalysts for methanol synthesis[J]. J Catal, 2005, 229(1): 136. LUO M-F, PING F, He M, XIE Y-L.In situ XRD, Raman, and TPR studies of CuO/Al2O3 catalysts for CO oxidation[J]. Journal of Molecular Catalysis A: Chemical, 2005, 239(1-2): 243-248. YU Q, YAO X-J, ZHANG H-L, GAO F, DONG L. Effect of ZrO2 addition method on the activity of Al2O3-supported CuO for NO reduction with CO: Impregnation vs. coprecipitation[J]. Applied Catalysis A: General, 2012, 423- 424: 42- 51. 段军红,刘智昂,江茫. ZnO纳米棒阵列的制备、微结构及光学性能研究[J].南昌航空大学学报(自然科学版) , 2012, 26(1): 41-46. (DUAN Jun-hong, Liu Zhi-ang, JIANG Mang. Research on preparation, microstructure and optical properties of ZnO nanorod arrays[J]. Journal of Nanchang Hangkong University(Natural Sciences), 2012, 26(1): 41-46.) 李忠,范辉,郑华艳,刘岩. 微波辐射对浆态床合成甲醇 Cu/ZnO/Al2O3催化剂前驱体微观结构及催化性能的影响[J]. 催化学报, 2010, 31(4): 471-478. (LI Zhong, FAN Hui, ZHENG Hua-yan, LIU Yan. Influence of Microwave Irradiation on Precursor Microstructure and Catalytic Performance of Cu/ZnO/Al2O3 for Slurry Methanol Synthesis[J]. Chinese Journal of Catalysis,2010, 31(4):471-478.) VELU S, SUZUKI K, GOPINATH C S, YOSHIDA H and HATTORI T. XPS, XANES and EXAFS investigations of CuO/ZnO/Al2O3/ZrO2mixed oxide catalysts[J]. Phys Chem Chem Phys, 2002, 4: 1990-1999. 庄会栋, 白绍芬, 刘欣梅,阎子峰. Cu/ZrO2 催化剂的结构及其CO2 加氢合成甲醇催化反应性能[J]. 燃料化学学报2010, 38(4): 462-467. (ZHUANG Hui-dong, BAI Shao-fen, LIU Xin-mei, YAN Zi-feng. Structure and performance of Cu/ZrO2 catalyst for the synthesis of methanol from CO2hydrogenation[J]. Journal of Fuel Chemistry and Technology, 2010, 38(4): 462-467.) FISHER I A, BELL A T. In-situ infrared study of methanol synthesis from H2/CO2 over Cu/SiO2 and Cu/ZrO2/SiO2[J]. J Catal, 1997, 172(1): 222. 马中义,杨成,周玮,张德胜,李正,魏伟,孙予罕. 载体表面性质对Cu/ZrO2催化剂Co加氢反应行为的影响[J]. 燃料化学学报, 2009, 37(2): 217-221. (MA Zhong-yi, YANG Cheng, ZHOU Wei, ZHANG De-sheng, LI Zheng, WEI Wei, SUN Yu-han. Effect of zirconia surface propertieson the catalytic performance of Cu/ZrO2 for CO hydrogenation[J]. Journal of Fuel Chemistry and Technology, 2009, 37(2): 217-221.) 何代平,丁云杰,尹红梅,朱何俊,熊健民,罗洪源. 碱金属助剂对MnO/ZrO2催化合成甲醇及异丁醇反应性能的影响[J]. 催化学报, 2003, 24(2): 111-114. (HE Dai-ping, DING Yun-jie, YIN Hong-mei, ZHU He-jun, XIONG Jian-min, LUO Hong-yuan. Effect of Alkali promoters on catalytic performance of MnO/ZrO2 for synthesis of methanol and isobutanol from syngas[J]. Chinese Journal of Catalysis, 2003, 24(2): 111-114.) JACKSON N B, EKERDT J G.The surface characteristics required for isosynthesis over zirconium dioxide and modified zirconium dioxide[J].J Catal, 1990, 126(1): 31-45. LI Y-W, HE D-H, YUAN Y-B CHENG Zh-X, ZHU Q-M. Influence of acidic and basic properties of ZrO2 based catalysts on isosynthesis[J]. Fuel, 2002, 81: 1611-1617.
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