富含介孔Ni/W-USY/Al_2O_3催化剂的费托蜡加氢裂化性能
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摘要
制备了富含介孔的Ni/W-USY/Al_2O_3催化剂并开展费托合成蜡加氢裂化实验,从反应性能、产品特性以及催化剂性质变化三方面对该催化剂进行评价。312 h运行实验结果表明,催化剂初始活性较高,120 h后趋于稳定,无明显失活现象,重质蜡转化率为73.95%时,轻质油选择性达到98.46%,裂解气以C_(3,4)为主;石脑油、煤油、柴油为无色透明液体,以正构烷烃和甲基、多甲基取代的异构烷烃为主,异构烃含量分别达到63.98%、52.26%、48.90%;对反应前后催化剂分析发现,新鲜催化剂的金属分散性较好、介孔含量高,加氢活性中心以WS_2、NiWS为主,随着反应由高活性到稳定阶段过渡,WS_2部分迁移并与Ni形成更多Ni-S-W键,部分W-S键断裂释放出S后形成W-W键,使得稳定后催化剂的NiWS活性中心增加而WS_2活性中心降低,并引起L酸密度降低而B酸密度增加。
Ni/W-USY/Al_2O_3 with full mesoporous structure was prepared and used for hydrocracking of Fischer Fropsch wax. The catalyst was evaluated for its reaction performance, product characteristics and catalyst properties change. In a 312 h experiment, the result showed that the catalyst possessed high initial activity, and maintained stable after 120 h, and did not show obvious deactivation afterward. When the heavy wax conversion reached 73.95% at the stable stage, the fuel oil selectivity reached to 98.46% and C_(3,4) constituted the most cracked gas. Gasoline, kerosene and diesel, as the products, were transparent and composed of paraffins and iso-paraffins substituted by methyl-groups. The iso-paraffin contents in the three products were 63.98%, 52.26% and 48.90% respectively. The fresh catalyst contained two main active states of WS_2 and NiWS, had good metal dispersion and rich mesoporous structure. With transition from high activity to stable state of the catalyst property, part of W migrated and formed more Ni-S-W bonds with Ni, and some W-S bonds broke to form W-W bonds after releasing S, resulting in the increase of active states of NiWS and the decrease of WS_2, and forming more Brönsted acid sites and less Lewis acid sites.
Ni/W-USY/Al_2O_3 with full mesoporous structure was prepared and used for hydrocracking of Fischer Fropsch wax. The catalyst was evaluated for its reaction performance, product characteristics and catalyst properties change. In a 312 h experiment, the result showed that the catalyst possessed high initial activity, and maintained stable after 120 h, and did not show obvious deactivation afterward. When the heavy wax conversion reached 73.95% at the stable stage, the fuel oil selectivity reached to 98.46% and C_(3,4) constituted the most cracked gas. Gasoline, kerosene and diesel, as the products, were transparent and composed of paraffins and iso-paraffins substituted by methyl-groups. The iso-paraffin contents in the three products were 63.98%, 52.26% and 48.90% respectively. The fresh catalyst contained two main active states of WS_2 and NiWS, had good metal dispersion and rich mesoporous structure. With transition from high activity to stable state of the catalyst property, part of W migrated and formed more Ni-S-W bonds with Ni, and some W-S bonds broke to form W-W bonds after releasing S, resulting in the increase of active states of NiWS and the decrease of WS_2, and forming more Brönsted acid sites and less Lewis acid sites.
引文
[1] GREGOR H, ERIK R, MATTHIAS J. Design and evaluation of a Fischer-Tropsch process for the production of waxes from biogas[J]. Energy, 2017, 132(1): 370-381.
[2] 杨超, 蒋坚, 鲁丹. F-T合成蜡油加氢裂解反应过程研究进展[J]. 化工进展, 2013, 32(12): 2882-2890. (YANG Chao, JIANG Jian, LU Dan. Advances in Fischer-Tropsch wax hydrocracking process[J]. Chem Ind Eng Prog, 2013, 32(12): 2882-2890.)
[3] DIETER L. Hydrocracking of iron-catalyzed fischer-tropsch waxes[J]. Energy Fuels, 2005, 19(5): 1795-1803.
[4] JIANG J, YANG C, LU Z J, DING J, LI T, LU Y, CAO F H. Characterization and application of a Pt/ZSM-5/SSMF catalyst for hydrocracking of paraffin wax[J]. Catal Commun, 2015, 60(5): 1- 4.
[5] YAN P H, TAO Z C, HAO K, WANG Y D, YANG Y, LI Y W. Effect of impregnation methods on nickel-tungsten catalysts and its performance on hydrocracking Fischer-Tropsch wax[J]. J Fuel Chem Technol, 2013, 41(6): 691-697.
[6] HAAN-DE R, JOORST G, MOKOENA E, NICOLAIDES C P. Non-sulfided nickel supported on silicated alumina as catalyst for the hydrocracking of n-hexadecane and of iron-based Fischer-Tropsch wax[J]. Appl Catal A: Gen, 2007, 327(2): 247- 254.
[7] KAZAKOW M O, NADEINA K A, DANILOVA I G, DIK P P, KLIMOV O V, PEREYMA V Y. Hydrocracking of vacuum gas oil over NiMo/Y-Al2O3: Effect of mesoporosity introduced by zeolite Y recrystallization[J]. Catal Today, 2018, 305(1): 117-125.
[8] 李宇慧, 冯丽娟, 王景刚, 徐康文, 李春虎. MoO3/Al2O3介孔催化剂在柴油氧化脱硫中的应用[J]. 石油学报(石油加工), 2011, 27(6): 878-883.(LI Yu-hui, FENG Li-juan, WANG Jing-gang, XU Kang-wen, LI Chun-hu. Oxidative desulfurization of diesel oil by mesoporous catalyst MoO3/Al2O3[J]. Acta Pet Sin (Pet Process Sect), 2011, 27(6): 878-883.)
[9] ATAUSHI I, DAISUKE K, THANITA S, HIROYUKI N, TADANON H. Preparation and characterization of zeolite-containing silica-aluminas with three layered micro-meso-meso-structure and their reactivity for catalytic cracking of soybean oil using Curie point pyrolyzer[J]. Fuel Process Technol, 2017, 161(15): 8-16.
[10] 李涛, 车晓莉, 云一峰, 陶智超, 赵春利, 杨勇, 李永旺. 无定形硅铝载体的酸性对费托蜡加氢裂化反应中柴油选择性的影响[J]. 燃料化学学报, 2017, 45(5): 589-595. (LI Tao, CHE Xiao-li, YUN Yi-feng, TAO Zhi-chao, ZHAO Chun-li, YANG Yong, LI Yong-wang. Study of the relationship between the acidity of amorphous silica-alumina supports and diesel selectivity in Fischer-Tropsch wax hydrocracking[J]. J Fuel Chem Technol, 2017, 45(5): 589-595.)
[11] SIMONE G, LAURA A P, VINCENZO C, CHIARA G. Liquid fuels from Fischer-Tropsch wax hydrocracking: Isomer distribution[J]. Catal Today, 2010, 156(1/2): 58-64.
[12] VINCENZO C, CHIARA G, WALLACE O P, ROSA C, ROBERTO G, PIETRO S. Middle distillates from hydrocracking of FT waxes: Composition, characteristics and emission properties[J]. Catal Today, 2010, 149(1/2): 40-46.
[13] 杨平, 辛靖, 李明丰. 负载Mo、W氧化物对Y型分子筛结构及酸性的影响[J]. 石油学报(石油加工), 2011, 25(5): 668-673. (YANG Ping, XIN Jing, LI Ming-feng. Effects of Molybdenum/Tungsten Oxides Loading on Structure and Acidity of Y Zeolites[J]. Acta Pet Sin (Pet Proces Sect), 2011, 25(5): 668-673.)
[14] 覃正兴, 申宝剑. 水热处理过程中Y分子筛的骨架脱铝、补硅及二次孔的形成[J]. 化工学报, 2016, 67(8): 3160-3167. (TAN Zheng-xing, SHEN Bao-jian. Dealumination, silicon reinsertion, and secondary pore formation in steaming of zeolite Y[J]. J Chem Ind Eng, 2016, 67(8): 3160-3167.)
[15] JOHN W. Hydrocracking processes and catalysts[J]. Fuel Process Technol, 1993, 35(2): 55-85.
[16] GOLUBINA E V, LOKTEVA E S, EROKHIN A V, VELIGZHANIN A A, ZUBAVICHUS Y V, LIKHOLOBOV V A, LUNIN V V. The role of metal-support interaction in catalytic activity of nanodiamond-supported nickel in selective phenylacetylene hydrogenation[J]. J Catal, 2016, 344: 90-99.
[17] 左东华, 聂红, MICHEL Vrinat, 石亚华, MICHEL Lacroix, 李大东. 硫化态 NiW/Al2O3 催化剂加氢脱硫活性相的研究I. XPS 和 HREM表征[J]. 催化学报, 2004, 25(4): 309-314. (ZUO Dong-hua, NIE Hong, MICHEL Vrinat, SHI Ya-hua, MICHEL Lacroix, LI Da-dong. Study on the hydrodesulfurization active phase insulfided NiW/Al2O3 catalyst I .XPS and HREM characterizations[J]. Chin J Catal, 2004, 25(4): 309-314.)
[18] SANTOLALLA-VARGAS C E, SUAREZ T V A , REYES J A, CROMWELL D K, PAWELEC B, FIERRO J L G. Effects of pH and chelating agent on the NiWS phase formation in NiW/γ-Al2O3 HDS catalysts[J]. Mater Chem Phys, 2015, 166: 105-115.
[19] DIAZ-DE-LEON J N, PICQUART M, MASSIN L, VRINAT M, REYES-LOS-DE J A. Hydrodesulfurization of sulfur refractory compounds: Effect of gallium as an additive in NiWS/γ-Al2O3 catalysts[J]. J Mol Catal A: Chem, 2012, 363-364: 311-321.
[20] PARTHASARATHI B, SEENIVASAN H, RAJAM K S, WILLIAM G. XRD, FESEM and XPS studies on heat treated Co-W electrodeposits[J]. Mater Lett, 2012, 76: 103-105.
[21] LU S S, XIAO S, ZHANG L M, DONG B, GAO W K, DAI F N, LIU B, CHAI Y M, LIU C G. Heterostructured binary Ni-W sulfides nanosheets as pH-universal electrocatalyst for hydrogen evolution[J]. Appl Surf Sci, 2018, 455: 455-435.
[22] SZILAGYI I M, SAJIO I, KIRALY P, TARKANYI G, TOTH A L. Phase transformations of ammonium tungsten bronzes[J]. J Therm Anal Calorim, 2009, 98 (3): 707-716.
[23] 张军. 加氢裂化多产中间馏分油分子筛和催化剂的设计[D]. 青岛: 中国石油大学(华东), 2008: 91-95. (ZHANG Jun. Design of zeolites and hydrocracking catalyst for maximizing middle distillates[D]. Qingdao: China University of Petroleum, 2008: 91-95.)
[24] 闫鹏辉. 费托蜡合成蜡在Ni/W-HY-Al2O3催化剂上的加氢裂化性能基础研究[D]. 北京: 中国科学院大学, 2013: 37-42. (YAN Peng-hui. Fundermantal research of hydrocracking perfomance over Ni/W-HY/Al2O3 catalyst on fischer-tropsch wax[D]. Beijing: University of Chinese Academy of Sciences, 2013: 37-42.)
[25] 张健, 卢海龙, 孙建伟, 姚建东, 李全芝. 分子筛和γ-Al2O3混合载体上负载Ni和W的加氢裂解催化剂的EXAFS研究[J]. 高等学校化学学报. 2000, 21(10): 1459-1463. (ZHANG Jian, LU Hai-long, SUN Jian-wei, YAO Jian-dong, LI Quan-zhi. EXSFS study of Ni/W/zeolite/Al2O3 hydrocracking catalyst sulfurized with different modified zeolites[J]. Chem J Chin Univ, 2000, 21(10): 1459-1463.)Investigation of performance of Ni/W-USY/Al2O3 catalyst with full mesoporous in Fischer Tropsch wax hydrocrackingHAN Lei HUANG Chuan-feng LIU Shu-wei CHENG Qiu-xiang CHANG Fang-yuan富含介孔Ni/W-USY/Al2O3能提高费托蜡加氢裂化轻燃料油的选择性和性质,初始活性较高,120 h后趋于稳定且无明显失活现象。J Fuel Chem Technol, 2019, 47(3): 338-343氨基修饰的金属有机框架Cu3(BTC)2的制备及其CO2吸附性能研究*鲁雪婷蒲彦锋李磊赵宁王峰肖福魁
[2] 杨超, 蒋坚, 鲁丹. F-T合成蜡油加氢裂解反应过程研究进展[J]. 化工进展, 2013, 32(12): 2882-2890. (YANG Chao, JIANG Jian, LU Dan. Advances in Fischer-Tropsch wax hydrocracking process[J]. Chem Ind Eng Prog, 2013, 32(12): 2882-2890.)
[3] DIETER L. Hydrocracking of iron-catalyzed fischer-tropsch waxes[J]. Energy Fuels, 2005, 19(5): 1795-1803.
[4] JIANG J, YANG C, LU Z J, DING J, LI T, LU Y, CAO F H. Characterization and application of a Pt/ZSM-5/SSMF catalyst for hydrocracking of paraffin wax[J]. Catal Commun, 2015, 60(5): 1- 4.
[5] YAN P H, TAO Z C, HAO K, WANG Y D, YANG Y, LI Y W. Effect of impregnation methods on nickel-tungsten catalysts and its performance on hydrocracking Fischer-Tropsch wax[J]. J Fuel Chem Technol, 2013, 41(6): 691-697.
[6] HAAN-DE R, JOORST G, MOKOENA E, NICOLAIDES C P. Non-sulfided nickel supported on silicated alumina as catalyst for the hydrocracking of n-hexadecane and of iron-based Fischer-Tropsch wax[J]. Appl Catal A: Gen, 2007, 327(2): 247- 254.
[7] KAZAKOW M O, NADEINA K A, DANILOVA I G, DIK P P, KLIMOV O V, PEREYMA V Y. Hydrocracking of vacuum gas oil over NiMo/Y-Al2O3: Effect of mesoporosity introduced by zeolite Y recrystallization[J]. Catal Today, 2018, 305(1): 117-125.
[8] 李宇慧, 冯丽娟, 王景刚, 徐康文, 李春虎. MoO3/Al2O3介孔催化剂在柴油氧化脱硫中的应用[J]. 石油学报(石油加工), 2011, 27(6): 878-883.(LI Yu-hui, FENG Li-juan, WANG Jing-gang, XU Kang-wen, LI Chun-hu. Oxidative desulfurization of diesel oil by mesoporous catalyst MoO3/Al2O3[J]. Acta Pet Sin (Pet Process Sect), 2011, 27(6): 878-883.)
[9] ATAUSHI I, DAISUKE K, THANITA S, HIROYUKI N, TADANON H. Preparation and characterization of zeolite-containing silica-aluminas with three layered micro-meso-meso-structure and their reactivity for catalytic cracking of soybean oil using Curie point pyrolyzer[J]. Fuel Process Technol, 2017, 161(15): 8-16.
[10] 李涛, 车晓莉, 云一峰, 陶智超, 赵春利, 杨勇, 李永旺. 无定形硅铝载体的酸性对费托蜡加氢裂化反应中柴油选择性的影响[J]. 燃料化学学报, 2017, 45(5): 589-595. (LI Tao, CHE Xiao-li, YUN Yi-feng, TAO Zhi-chao, ZHAO Chun-li, YANG Yong, LI Yong-wang. Study of the relationship between the acidity of amorphous silica-alumina supports and diesel selectivity in Fischer-Tropsch wax hydrocracking[J]. J Fuel Chem Technol, 2017, 45(5): 589-595.)
[11] SIMONE G, LAURA A P, VINCENZO C, CHIARA G. Liquid fuels from Fischer-Tropsch wax hydrocracking: Isomer distribution[J]. Catal Today, 2010, 156(1/2): 58-64.
[12] VINCENZO C, CHIARA G, WALLACE O P, ROSA C, ROBERTO G, PIETRO S. Middle distillates from hydrocracking of FT waxes: Composition, characteristics and emission properties[J]. Catal Today, 2010, 149(1/2): 40-46.
[13] 杨平, 辛靖, 李明丰. 负载Mo、W氧化物对Y型分子筛结构及酸性的影响[J]. 石油学报(石油加工), 2011, 25(5): 668-673. (YANG Ping, XIN Jing, LI Ming-feng. Effects of Molybdenum/Tungsten Oxides Loading on Structure and Acidity of Y Zeolites[J]. Acta Pet Sin (Pet Proces Sect), 2011, 25(5): 668-673.)
[14] 覃正兴, 申宝剑. 水热处理过程中Y分子筛的骨架脱铝、补硅及二次孔的形成[J]. 化工学报, 2016, 67(8): 3160-3167. (TAN Zheng-xing, SHEN Bao-jian. Dealumination, silicon reinsertion, and secondary pore formation in steaming of zeolite Y[J]. J Chem Ind Eng, 2016, 67(8): 3160-3167.)
[15] JOHN W. Hydrocracking processes and catalysts[J]. Fuel Process Technol, 1993, 35(2): 55-85.
[16] GOLUBINA E V, LOKTEVA E S, EROKHIN A V, VELIGZHANIN A A, ZUBAVICHUS Y V, LIKHOLOBOV V A, LUNIN V V. The role of metal-support interaction in catalytic activity of nanodiamond-supported nickel in selective phenylacetylene hydrogenation[J]. J Catal, 2016, 344: 90-99.
[17] 左东华, 聂红, MICHEL Vrinat, 石亚华, MICHEL Lacroix, 李大东. 硫化态 NiW/Al2O3 催化剂加氢脱硫活性相的研究I. XPS 和 HREM表征[J]. 催化学报, 2004, 25(4): 309-314. (ZUO Dong-hua, NIE Hong, MICHEL Vrinat, SHI Ya-hua, MICHEL Lacroix, LI Da-dong. Study on the hydrodesulfurization active phase insulfided NiW/Al2O3 catalyst I .XPS and HREM characterizations[J]. Chin J Catal, 2004, 25(4): 309-314.)
[18] SANTOLALLA-VARGAS C E, SUAREZ T V A , REYES J A, CROMWELL D K, PAWELEC B, FIERRO J L G. Effects of pH and chelating agent on the NiWS phase formation in NiW/γ-Al2O3 HDS catalysts[J]. Mater Chem Phys, 2015, 166: 105-115.
[19] DIAZ-DE-LEON J N, PICQUART M, MASSIN L, VRINAT M, REYES-LOS-DE J A. Hydrodesulfurization of sulfur refractory compounds: Effect of gallium as an additive in NiWS/γ-Al2O3 catalysts[J]. J Mol Catal A: Chem, 2012, 363-364: 311-321.
[20] PARTHASARATHI B, SEENIVASAN H, RAJAM K S, WILLIAM G. XRD, FESEM and XPS studies on heat treated Co-W electrodeposits[J]. Mater Lett, 2012, 76: 103-105.
[21] LU S S, XIAO S, ZHANG L M, DONG B, GAO W K, DAI F N, LIU B, CHAI Y M, LIU C G. Heterostructured binary Ni-W sulfides nanosheets as pH-universal electrocatalyst for hydrogen evolution[J]. Appl Surf Sci, 2018, 455: 455-435.
[22] SZILAGYI I M, SAJIO I, KIRALY P, TARKANYI G, TOTH A L. Phase transformations of ammonium tungsten bronzes[J]. J Therm Anal Calorim, 2009, 98 (3): 707-716.
[23] 张军. 加氢裂化多产中间馏分油分子筛和催化剂的设计[D]. 青岛: 中国石油大学(华东), 2008: 91-95. (ZHANG Jun. Design of zeolites and hydrocracking catalyst for maximizing middle distillates[D]. Qingdao: China University of Petroleum, 2008: 91-95.)
[24] 闫鹏辉. 费托蜡合成蜡在Ni/W-HY-Al2O3催化剂上的加氢裂化性能基础研究[D]. 北京: 中国科学院大学, 2013: 37-42. (YAN Peng-hui. Fundermantal research of hydrocracking perfomance over Ni/W-HY/Al2O3 catalyst on fischer-tropsch wax[D]. Beijing: University of Chinese Academy of Sciences, 2013: 37-42.)
[25] 张健, 卢海龙, 孙建伟, 姚建东, 李全芝. 分子筛和γ-Al2O3混合载体上负载Ni和W的加氢裂解催化剂的EXAFS研究[J]. 高等学校化学学报. 2000, 21(10): 1459-1463. (ZHANG Jian, LU Hai-long, SUN Jian-wei, YAO Jian-dong, LI Quan-zhi. EXSFS study of Ni/W/zeolite/Al2O3 hydrocracking catalyst sulfurized with different modified zeolites[J]. Chem J Chin Univ, 2000, 21(10): 1459-1463.)Investigation of performance of Ni/W-USY/Al2O3 catalyst with full mesoporous in Fischer Tropsch wax hydrocrackingHAN Lei HUANG Chuan-feng LIU Shu-wei CHENG Qiu-xiang CHANG Fang-yuan富含介孔Ni/W-USY/Al2O3能提高费托蜡加氢裂化轻燃料油的选择性和性质,初始活性较高,120 h后趋于稳定且无明显失活现象。J Fuel Chem Technol, 2019, 47(3): 338-343氨基修饰的金属有机框架Cu3(BTC)2的制备及其CO2吸附性能研究*鲁雪婷蒲彦锋李磊赵宁王峰肖福魁