Ni-M/SiO_2催化1,4-丁炔二醇加氢的金属助剂效应
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摘要
以SiO_2气凝胶为载体,采用等体积浸渍法制备了Ni/SiO_2及不同金属助剂改性的Ni-M/SiO_2(M=Fe、 Co、 Cu)催化剂,利用ICP、 BET、 XRD、 H_2-TPR、 H_2-TPD等手段对催化剂进行了表征,考察了不同第二金属对催化剂结构与1,4-丁炔二醇加氢性能的影响.结果表明,第二金属与Ni物种具有不同程度的双金属协同效应,其中Cu的加入不仅能够提高Ni活性物种的分散度,而且Ni-Cu双金属间的相互作用改善了NiO物种的还原性能及氢活化能力,有利于氢和1,4-丁炔二醇在活性位点的快速转化.在反应温度50℃,氢压1 MPa,反应时间3 h的加氢评价条件下, 15Ni5Cu/SiO_2催化剂不仅可以实现1,4-丁炔二醇的完全转化,而且能够有效降低难分离副产物2-羟基四氢呋喃的含量,具有最优的加氢活性和对1,4-丁烯二醇的选择性.
Ni/SiO_(2 )and 15 Ni5 M/SiO_(2 )(M = Fe, Co, Cu) catalysts modified by different metal promoters were prepared by incipient impregnation method using SiO_2 aerogel as supports. Different bimetallic catalyst structures were characterized by means of ICP, BET, XRD, H_2-TPR, H_2-TPD etc, and their promotion effect in the 1,4-butynediol hydrogenation performance were thoroughly investigated. It was found that different second metal element has various bimetallic synergy with the Ni species and the addition of appropriate amount of Cu into the Ni-based catalyst can not only improve the dispersibility of active Ni species, but also promote the metal reduction/overflow ability as well as the H_2 adsorption/activation capacity, which is benefit for the hydrogenation of 1,4-butynediol. The catalytic activity was test under a condition of 50 ℃, H_2 pressure 1 MPa with a reaction time of 3 h, the result showed that 15 Ni5 Cu/SiO_2 with a little amount of Cu modification can achieve 100% 1,4-butynediol conversion and possess the superior 1,4-butenediol selectivity with the lower byproduct which is hard to separate.
Ni/SiO_(2 )and 15 Ni5 M/SiO_(2 )(M = Fe, Co, Cu) catalysts modified by different metal promoters were prepared by incipient impregnation method using SiO_2 aerogel as supports. Different bimetallic catalyst structures were characterized by means of ICP, BET, XRD, H_2-TPR, H_2-TPD etc, and their promotion effect in the 1,4-butynediol hydrogenation performance were thoroughly investigated. It was found that different second metal element has various bimetallic synergy with the Ni species and the addition of appropriate amount of Cu into the Ni-based catalyst can not only improve the dispersibility of active Ni species, but also promote the metal reduction/overflow ability as well as the H_2 adsorption/activation capacity, which is benefit for the hydrogenation of 1,4-butynediol. The catalytic activity was test under a condition of 50 ℃, H_2 pressure 1 MPa with a reaction time of 3 h, the result showed that 15 Ni5 Cu/SiO_2 with a little amount of Cu modification can achieve 100% 1,4-butynediol conversion and possess the superior 1,4-butenediol selectivity with the lower byproduct which is hard to separate.
引文
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[14] Yang Yong-ning (杨永宁), Zhang Huai-ke(张怀科), Lv En-jing(吕恩静), et al. Effect of Fe, Mo promoters on acetic acid hydrodeoxygenation performance of niclel-based catalyst ( Fe、Mo助剂对Ni基催化剂加氢脱氧性能的影响 ) [J]. J Mol Catal (China) (分子催化), 2011, 25(1): 30-36.
[15] Hao Zhi-qiang (郝志强), Yu Zhi-hui (于智慧), Li Zhong (李忠) . Influence of Ni/Fe molar ratio on surface properties of Ni-Fe catalysts and hydrogenation performance of dinitrotoluene (Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响) [J]. Chin J Inorg Chem (China) (无机化学学报), 2015, 31(8): 1571-1580.
[16] YuZhi-hui (于智慧), Yan Ze (闫泽), Fan Hui (范辉), et al. Influence of addictives on Ni/SiO2 catalyst microstructure and the performance of dinitrotoluene hydrogenation (助剂对Ni/SiO2催化剂微观结构及二硝基甲苯催化加氢性能的影响) [J]. Chin J Inorg Chem (China) (无机化学学报), 2014, 30(6): 1317-1324.
[17] Ardiyanti A, Khromova S, Venderbosch R, et al. Catalytic hydrotreatment of fastpyrolysis oil using non-sulfided bimetallic Ni-Cu catalysts on a δ-Al2O3 support [J]. Appl Catal B-Environ, 2012, 117/118: 105-117.
[18] Robertson S,Mcnicol B, Baas J, et al. Determination of reducibility and identification of alloying in copper-nic- kel-on-silica catalysts by temperature-programmed reduction [J]. J Catal, 1975, 37(3): 424-431.
[19] Rogatis L, Montini T, Cognigni A. Methane partial oxidation on NiCu-based catalysts [J]. Catal Today, 2009, 145(1/2): 176-185.
[20] Zhao Y, Zhao X, Zhang M, et al. Preparation and composition analysis of catalysts supported by CuO CoOMnO/SiO2 nanocomposite aerogels [J]. Micro Mes Mater, 2018, 261: 220-226.
[21] Li F, Wang X,Zheng Y, et al. Influence of metallic promoters on the performance of Ni/SiO2 catalyst in the hydrodeoxygenation of anisole [J]. J Fuel Chem Technol, 2018, 46(1): 75-83.
[22] Xu Jing (许静), Xie Kai (谢凯), Chen Yi-min (陈一民), et al. Catalytic oxidation of CO on Cu/SiO2 aerogel catalysts (Cu/SiO2气凝胶催化剂上CO的催化氧化性能 ) [J]. J Mol Catal (China) (分子催化), 2010, 24(1): 71-73.
[23] Zhao Yong-xiang (赵永祥), Wu Zhi-gang (武志刚), Wang Yong-zhao (王永钊), et al. Study on the property of NiO/SiO2 aerogel catalysts (NiO/SiO2气凝胶催化剂性能研究) [J]. J Fuel Chem Technol (China) (燃料化学学报), 2001, 29(z1): 182-184.
[24] Changzhen Wang, Nannan Sun, Ning Zhao, et al. Template-free preparation of bimetallic mesoporous Ni-Co-CaO-ZrO2 catalysts and their synergetic effect in dry reforming of methane [J]. Catal Today, 2017, 281(Pt.2): 268-275.
[25] Surapas Sitthisa, Wei An, Daniel E. Resasco. Selective conversion of furfural to methylfuran over silica-supported Ni-Fe bimetallic catalysts [J]. J Catal, 2011, 284(1): 90-101.
[26] Wang X, Wang F, Chen M,et al. Studies on nickel-based bimetallic catalysts for hydrodeoxygenation [J]. J Fuel Chem Technol, 2005, 33(5): 612-616.
[27] Liu Y, Zhao J, Feng J, et al. Layered double hydroxide-derived Ni-Cu nanoalloy catalysts for semihydrogenation of alkynes: Improvement of selectivity and anti-coking ability via alloying of Ni and Cu [J] . J Catal, 2018, 359: 251-260.
[28] Yudi Chen, Changming Li, Junyao Zhou, et al. Metal phosphides derived from hydrotalcite precursors toward the selective hydrogenation of phenylacetylene [J]. ACS Catal, 2015, 5(10): 5756-5765.
[29] Tianbao Shi, Hui Li, Lianghong Yao, et al. Ni-Co-Cu supported on pseudoboehmite-derived Al2O3: Highly efficient catalysts for the hydrogenation of organic functional groups [J]. Appl Catal A: Gener, 2012, 425/426: 68-73.
[2] Liu Xiang (刘响), Liao Qi-jiang (廖启江), Zhang Min-qing (张敏卿). Research progress of 1,4-Butynediol hydrogenation process (1,4-丁炔二醇加氢过程研究进展) [J]. Chem Ind &Engineer Pro (China) (化工进展), 2017, 36(8): 2787-2797.
[3] Li C, Zhang M, Di X, et al. One-step synthesis of Pt@ZIF-8 catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol [J] . Chin J Catal, 2016, 37(9): 1555-1561.
[4] Zhuang Chang-jian (庄昌建), Ma Kong-jun (马空军), Lu Jiang-yin (陆江银), et al. Research on catalyst in second section of hydrogenation of 1,4-butynediol (1,4-丁炔二醇二段加氢催化剂的研究) [J]. Mod Chem Ind (China) (现代化工), 2017, 37(4): 59-62.
[5] Wetherill Franke. US [P] 3449445A (美国专利), 1969.
[6] Hort Eugene V, Graham David et al. US [P] 2967893A (美国专利), 1983.
[7] Eugene V H, WALDO R D. GB [P] 2104794A(英国专利), 1983.
[8] HADLEY ROBERTL. US [P] 2948687 (美国专利), 1960.
[9] Waldo R De Thomas, Parsippany, Eugene VHort, Wayne, N J. US [P] 4153578 (美国专利), 1979.
[10] Xiao Chen, Mingming Zhang, Kaixuan Yang, et al. Raney-Ni-Si catalysts for selective hydrogenation of highly concentrated 2-Butyne-1,4-diol to 2-Butene-1,4-diol [J]. Catal Lett, 2014, 144(7): 1118-1126.
[11] Fischer Rolf, Sigwart Christoph. US [P] 5977417A(美国专利), 1999.
[12] Juan M,Campelo, Rafael Guardefio, et al. Metal-support interaction effects in the liquid-phase selective hydrogenation of 1,4-butynediol with nickel catalysts supported on AlPO4, and on other conventional nonreducible compounds [J]. J Mol Catal (China) (分子催化), 1993, 7(3): 305-325.
[13] Liu Lin-li (刘琳丽), Li Hai-tao (李海涛), Wang Chang-zhen (王长真), et al. Effect of supports on the hydrogenation of 1,4-butynediol over supported Ni catalyst (负载Ni催化剂上1,4-丁炔二醇加氢反应的载体效应研究) [J]. J Mol Catal (China) (分子催化), 2018, 32(2): 100-106.
[14] Yang Yong-ning (杨永宁), Zhang Huai-ke(张怀科), Lv En-jing(吕恩静), et al. Effect of Fe, Mo promoters on acetic acid hydrodeoxygenation performance of niclel-based catalyst ( Fe、Mo助剂对Ni基催化剂加氢脱氧性能的影响 ) [J]. J Mol Catal (China) (分子催化), 2011, 25(1): 30-36.
[15] Hao Zhi-qiang (郝志强), Yu Zhi-hui (于智慧), Li Zhong (李忠) . Influence of Ni/Fe molar ratio on surface properties of Ni-Fe catalysts and hydrogenation performance of dinitrotoluene (Ni/Fe物质的量的比对Ni-Fe催化剂表面性质和二硝基甲苯加氢活性的影响) [J]. Chin J Inorg Chem (China) (无机化学学报), 2015, 31(8): 1571-1580.
[16] YuZhi-hui (于智慧), Yan Ze (闫泽), Fan Hui (范辉), et al. Influence of addictives on Ni/SiO2 catalyst microstructure and the performance of dinitrotoluene hydrogenation (助剂对Ni/SiO2催化剂微观结构及二硝基甲苯催化加氢性能的影响) [J]. Chin J Inorg Chem (China) (无机化学学报), 2014, 30(6): 1317-1324.
[17] Ardiyanti A, Khromova S, Venderbosch R, et al. Catalytic hydrotreatment of fastpyrolysis oil using non-sulfided bimetallic Ni-Cu catalysts on a δ-Al2O3 support [J]. Appl Catal B-Environ, 2012, 117/118: 105-117.
[18] Robertson S,Mcnicol B, Baas J, et al. Determination of reducibility and identification of alloying in copper-nic- kel-on-silica catalysts by temperature-programmed reduction [J]. J Catal, 1975, 37(3): 424-431.
[19] Rogatis L, Montini T, Cognigni A. Methane partial oxidation on NiCu-based catalysts [J]. Catal Today, 2009, 145(1/2): 176-185.
[20] Zhao Y, Zhao X, Zhang M, et al. Preparation and composition analysis of catalysts supported by CuO CoOMnO/SiO2 nanocomposite aerogels [J]. Micro Mes Mater, 2018, 261: 220-226.
[21] Li F, Wang X,Zheng Y, et al. Influence of metallic promoters on the performance of Ni/SiO2 catalyst in the hydrodeoxygenation of anisole [J]. J Fuel Chem Technol, 2018, 46(1): 75-83.
[22] Xu Jing (许静), Xie Kai (谢凯), Chen Yi-min (陈一民), et al. Catalytic oxidation of CO on Cu/SiO2 aerogel catalysts (Cu/SiO2气凝胶催化剂上CO的催化氧化性能 ) [J]. J Mol Catal (China) (分子催化), 2010, 24(1): 71-73.
[23] Zhao Yong-xiang (赵永祥), Wu Zhi-gang (武志刚), Wang Yong-zhao (王永钊), et al. Study on the property of NiO/SiO2 aerogel catalysts (NiO/SiO2气凝胶催化剂性能研究) [J]. J Fuel Chem Technol (China) (燃料化学学报), 2001, 29(z1): 182-184.
[24] Changzhen Wang, Nannan Sun, Ning Zhao, et al. Template-free preparation of bimetallic mesoporous Ni-Co-CaO-ZrO2 catalysts and their synergetic effect in dry reforming of methane [J]. Catal Today, 2017, 281(Pt.2): 268-275.
[25] Surapas Sitthisa, Wei An, Daniel E. Resasco. Selective conversion of furfural to methylfuran over silica-supported Ni-Fe bimetallic catalysts [J]. J Catal, 2011, 284(1): 90-101.
[26] Wang X, Wang F, Chen M,et al. Studies on nickel-based bimetallic catalysts for hydrodeoxygenation [J]. J Fuel Chem Technol, 2005, 33(5): 612-616.
[27] Liu Y, Zhao J, Feng J, et al. Layered double hydroxide-derived Ni-Cu nanoalloy catalysts for semihydrogenation of alkynes: Improvement of selectivity and anti-coking ability via alloying of Ni and Cu [J] . J Catal, 2018, 359: 251-260.
[28] Yudi Chen, Changming Li, Junyao Zhou, et al. Metal phosphides derived from hydrotalcite precursors toward the selective hydrogenation of phenylacetylene [J]. ACS Catal, 2015, 5(10): 5756-5765.
[29] Tianbao Shi, Hui Li, Lianghong Yao, et al. Ni-Co-Cu supported on pseudoboehmite-derived Al2O3: Highly efficient catalysts for the hydrogenation of organic functional groups [J]. Appl Catal A: Gener, 2012, 425/426: 68-73.