Investigation of performance of Ni/W-USY/Al2O3 catalyst with full mesoporous in Fischer Tropsch wax hydrocracking
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摘要: 制备了富含介孔的Ni/W-USY/Al2O3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C3，4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WS2、NiWS为主，随着反应由高活性到稳定阶段过渡，WS2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WS2活性中心降低，并引起L酸密度降低而B酸密度增加。Abstract: Ni/W-USY/Al2O3 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 C3, 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 WS2 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 WS2, and forming more Brönsted acid sites and less Lewis acid sites.
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Key words:
- Fischer Tropsch wax /
- hydrocracking /
- catalyst /
- fuel oil /
- iso-paraffin
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图 2 石脑油、煤油、柴油馏分段GC-MS分析质谱图
Figure 2 GC-MS analysis for the products of naphtha, kerosene and diesel
图 3 石脑油、煤油、柴油馏分段碳数分布图
— ■ —: normal; — ● —: isomer; — ▲ —: total
Figure 3 Carbon number distribution of naphtha, kerosene and diesel oil
图 5 样品的N2吸附-脱附曲线以及孔径分布图
Figure 5 N2-adsorption desorption curves and pore size distribution of the catalyst samples
图 8 硫化态催化剂空气条件下的TG-DTA曲线
Figure 8 TG-DTA curves of the sulfide catalyst under air condition
表 1 催化剂DH的部分物理性质
Table 1 Physical properties of DH
Shape d/mm Length/mm Bulk density ρ/(g·mL-1) Cylinder 1.50 3.00-5.00 0.772 
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表 2 费托蜡的元素组成及性质
Table 2 Elemental composition and properties of Fischer-Tropsch wax
Element Content w/% H/C(atomic ratio) tSP/℃ Density /(g·mL-1) C H N S O F-T wax 85.01 14.53 0 0 0.46 2.05 76 0.756 Boiling range distribution 10% 20% 30% 40% 50% 60% 70% 80% 90% 192.5 234.0 287.5 370.0 442.5 491.3 534.3 588.4 652.7
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表 3 产品的物化性质
Table 3 Physical and chemical properties of the products
Item Unit Naphtha Kerosene Diesel Chroma colorless/transparent colorless/transparent colorless/transparent Density ρ/(g·mL-1) 0.717 0.733 0.759 SP t/℃ - ＜-51 -26 Bromine w/(mg· (100 g)-1) 25.5 23.7 20.3 Sulfur w/% 0.0004 0.0006 0.0006 Calorific value Q/(MJ·kg-1) 47.17 47.03 47.48 Cetane number - - 71 Normal/isomerism m/m 36.02/63.98 47.74/52.26 51.10/48.90 Boiling range distribution 10% t/℃ 62 143 189 20% t/℃ 86 158 204 50% t/℃ 131 173 244 70% t/℃ 152 211 271 90% t/℃ 174 228 305 Final distillate t/℃ 199 241 348
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表 4 催化剂的元素组成(XRF)
Table 4 Elemental composition of the catalysts (XRF)
Sample Content w/% WO3 SiO2 NiO Al2O3 Na2O SO3 DH 27.16 8.65 8.28 53.30 0.27 0 DH-R 27.26 8.67 8.38 53.30 0.21 0.74
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表 5 DH催化剂的比表面积和孔结构
Table 5 Specific surface area and pore structure of samples
Sample Specific surface area A/(m2·g-1) Volume v/(cm3·g-1) dmeso/nm total micro meso total meso DH 208 74 134 0.307 0.261 31.1 DH-R 144 35 109 0.250 0.225 32.5
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表 6 硫态化催化剂表面金属化学态分布比例
Table 6 Percentage of the surface metal species of sulfide catalysts
Sample w/% W0 W4+S W6+O Ni2+S Ni2+WS Ni2+O DH-S 18.05 51.05 30.90 23.52 22.53 53.95 DH-RS 21.74 49.26 29.00 19.08 32.76 48.16
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表 7 DH-S和DH-RS的TG-DTA分析
Table 7 TG-DTA analyses of DH-R and DH-RS
Catalyst Lost weight w/% Ⅰ/(Ⅰ+Ⅱ)/% Exothermic Q/(kJ·g-1) Ⅰ/(Ⅰ+Ⅱ)/% Ⅰ Ⅱ Ⅰ Ⅱ Ⅰ+Ⅱ DH-S 11.10 10.51 51.37 0.81 2.13 2.94 27.55 DH-RS 2.01 7.08 22.10 1.24 1.32 2.56 48.43
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[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. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=c9472efb318bb46dee6106a4f13c696e [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. http://d.old.wanfangdata.com.cn/Periodical/hgjz201312016YANG Chao, JIANG Jian, LU Dan. Advances in Fischer-Tropsch wax hydrocracking process[J]. Chem Ind Eng Prog, 2013, 32(12):2882-2890. http://d.old.wanfangdata.com.cn/Periodical/hgjz201312016 [3] DIETER L. Hydrocracking of iron-catalyzed fischer-tropsch waxes[J]. Energy Fuels, 2005, 19(5):1795-1803. doi: 10.1021/ef050085v [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. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=8e54d7415c3ceb28f65ae30783c5ce03 [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. doi: 10.1016/S1872-5813(13)60032-8 [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. doi: 10.1016/j.apcata.2007.05.022 [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. doi: 10.3969/j.issn.1001-8719.2011.06.007LI 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. doi: 10.3969/j.issn.1001-8719.2011.06.007 [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. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=60f384911c66cf1470d70f259b737f24 [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. doi: 10.3969/j.issn.0253-2409.2017.05.010LI 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. doi: 10.3969/j.issn.0253-2409.2017.05.010 [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. http://d.old.wanfangdata.com.cn/NSTLQK/NSTL_QKJJ0217210601/ [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. http://www.sciencedirect.com/science/article/pii/S0920586109001771 [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. doi: 10.3969/j.issn.1001-8719.2011.05.002YANG 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. doi: 10.3969/j.issn.1001-8719.2011.05.002 [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. http://d.old.wanfangdata.com.cn/Periodical/hgxb201608004TAN 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. http://d.old.wanfangdata.com.cn/Periodical/hgxb201608004 [15] JOHN W. Hydrocracking processes and catalysts[J]. Fuel Process Technol, 1993, 35(2):55-85. http://d.old.wanfangdata.com.cn/Periodical/hljsyhg200704003 [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. doi: 10.1016/j.jcat.2016.08.017 [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. doi: 10.3321/j.issn:0253-9837.2004.04.014ZUO Dong-hua, NIE Hong, MICHEL Vrinat, SHI Ya-hua, MICHEL Lacroix, LI Da-dong. Study on the hydrodesulfurization active phase insulfided NiW/Al2O3catalyst I.XPS and HREM characterizations[J]. Chin J Catal, 2004, 25(4):309-314. doi: 10.3321/j.issn:0253-9837.2004.04.014 [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. doi: 10.1016/j.matchemphys.2015.09.033 [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-Al2O3catalysts[J]. J Mol Catal A:Chem, 2012, 363-364:311-321. doi: 10.1016/j.molcata.2012.07.006 [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. doi: 10.1016/j.matlet.2012.02.046 [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. doi: 10.1016/j.apsusc.2018.05.155 [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. doi: 10.1007/s10973-009-0287-x [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. doi: 10.3321/j.issn:0251-0790.2000.10.003ZHANG Jian, LU Hai-long, SUN Jian-wei, YAO Jian-dong, LI Quan-zhi. EXSFS study of Ni/W/zeolite/Al2O3hydrocracking catalyst sulfurized with different modified zeolites[J]. Chem J Chin Univ, 2000, 21(10):1459-1463. doi: 10.3321/j.issn:0251-0790.2000.10.003 -
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