拟薄水铝石老化pH对氧化铝载体及加氢催化剂脱硫性能的影响

摘要/Abstract

摘要： 研究了NaAlO₂-Al₂(SO₄)₃法分步连续中和制备拟薄水铝石工艺中老化pH的影响，并制备了相应的NiMoP/Al₂O₃催化剂，使用4,6-二甲基二苯并噻吩作为反应物对催化剂进行加氢脱硫性能评价。结果表明：老化pH对拟薄水铝石性质影响显著，老化pH为8.6时产品中硫酸根含量过高，老化pH为10.0时产品中三水氧化铝杂晶和Na₂O杂质含量过高，老化pH为9.0~9.5时可以得到杂质含量较低的拟薄水铝石；老化pH还影响不同晶面的生长速率，老化pH高有利于提高（020）晶面的生长速率；老化pH为9.0和9.5时载体的孔体积和比表面积较大，最可几孔径为9.1 nm；老化pH显著影响载体表面不同类型羟基的比例，从而影响不同载体负载的活性金属的低温还原峰温度和六配位二维钼多聚物所占比例。催化剂的加氢脱硫活性与载体上负载的活性金属的低温还原峰温度和六配位二维钼多聚物所占比例顺序一致。当拟薄水铝石老化pH为9.0时，最有利于制备高活性加氢脱硫催化剂载体。

关键词: 拟薄水铝石, 老化pH, 氧化铝, 孔结构, 加氢脱硫催化剂

Abstract: The effect of aging pH on the preparation of pseudo-boehmite by stepwise continuous neutralization with NaAlO₂-Al₂(SO₄)₃ method was investigated, the corresponding Ni-Mo-P/Al₂O₃ catalysts were prepared, and the hydrodesulfurization performance was evaluated by using 4,6-dimethyldibenzothiophene (4,6-DMDBT) as the reactant. The results showed that the aging pH had a significant effect on the properties of pseudo-boehmite. The content of sulfate in the product was too high at pH 8.6, and the mass fraction of alumina trihydrate and Na₂O in the product was too high at pH 10.0. The proposed pseudo-boehmite with lower content of impurities could be obtained at the aging pH of 9.0-9.5. The aging pH also affected the growth of different crystalline surfaces, and high aging pH was conducive to increasing the growth rate of (020) crystalline surfaces. The pore volume and specific surface area of Al2O3 support were larger at the aging pH of 9.0 and 9.5, and the most probable pore diameter was about 9.1 nm. The aging pH significantly affected the distribution ratio of different types of hydroxyl groups in the supports, thus, the reduction temperature at the low temperature reduction peaks of the active metals and the proportion of hexa-coordinated 2D polymers were affected. The order of hydrodesulfurization activity of the catalysts was consistent with the order of the low temperature reduction peak temperature of the active metal supported on the carries and the proportion of hexa-coordinated 2D polymers of molybdenum. The preparation of pseudo-boehmite for high activity hydrodesulfurization catalyst support was most favorable when the aging pH was 9.0.

Key words: pseudo-boehmite, aging pH, alumina, pore structure, hydrodesulfurization catalyst

郭锦春鲍俊桑小义温昌盛曾双亲. 拟薄水铝石老化pH对氧化铝载体及加氢催化剂脱硫性能的影响[J]. 石油炼制与化工, 2024, 55(10): 15-23.

参考文献

[1]杜艳泽，秦波，王会刚, 等.多级孔分子筛在重油加氢裂化催化剂的应用进展[J].化工进展, 2021, 40(4):1859-1867 [2]Babich I V, Moulijn J A.Science and technology of novel processes for deep desulfurization of oil refinery streams: a review☆[J].Fuel, 2003, 82(6):607-631 [3]Stanislaus A, Marafi A, Rana M S.Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production[J].Catalysis today, 2010, 153(1-2):1-68 [4]Hein J, Gutiérrez O Y, Albersberger S, et al.Towards Understanding Structure–Activity Relationships of Ni–Mo–W Sulfide Hydrotreating Catalysts[J].ChemCatChem, 2017, 9(4):629-641 [5]Li P, Chen Y, Zhang C, et al.Highly selective hydrodesulfurization of gasoline on unsupported Co-Mo sulfide catalysts: Effect of MoS2 morphology[J].Applied Catalysis A: General, 2017, 533:99-108 [6]辛靖, 宋宇, 吕艳艳, 等.孔结构优化对渣油加氢脱金属剂的影响研究[J].Inorganic Chemicals Industry, 2022, 54(6):125-133 [7]张哲民, 杨清河, 聂红, 等.法制备拟薄水铝石成胶机理的研究[J].石油化工, 2003, 32(7):552-554 [8]杨清河, 李大东, 庄福成, 等.法制备拟薄水铝石规律的研究[J].石油炼制与化工, 1999, 30(4):59-63 [9]Bejenaru N, Lancelot C, Blanchard P, et al.Synthesis,characterization,and catalytic performances of novel CoMo hydrodesulfurization catalysts supported on mesoporous aluminas[J].Chemistry of Materials, 2009, 21(3):522-533 [10]Hu Di, Li Huiping, Mei Jinlin, et al.The effect of chelating agent on hydrodesulfurization reaction of ordered mesoporous alumina supported NiMo catalysts[J].Petroleum Science, 2022, 19(1):321-328 [11]Yang L, Peng C, Fang X, et al.Hierarchically macro-mesoporous Ni-Mo/Al2O3 catalysts for hydrodesulfurization of dibenzothiophene[J].Catalysis Communications, 2019, 121:68-72 [12] 曾双亲.氧化铝载体表面化学性质对Ni-W/γ-Al2O3加氢催化剂活性影响的研究[D]. 北京：中国石化石油化工科学研究院, 2000 [13]马淑花, 王晓辉, 王月娇, 等.拟薄水铝石制备技术研究进展[J].材料科学, 2021, 11(09):1042-1051 [14]轩晓蝶, 刘锰钰, 郭静静, 等.拟薄水铝石合成及其性能研究进展[J].工业催化, 2022, 30(06):21-30 [15]杨晶铃, 燕溪溪, 刘震, 等.拟薄水铝石的制备最新进展及其应用[J].上海第二工业大学学报, 2021, 38(03):189-196 [16] 杨雨哲.铝醇盐法制备拟薄水铝石及相关设备设计[D]. 大连理工大学, 2021 [17]蔡卫权, 李会泉, 张懿.SB粉水热种分过饱和铝酸钠溶液制备拟薄水铝石[J].无机化学学报, 2006, (07):1303-1306 [18]张哲, 李殿卿, 白立光, 等.双铝法制拟薄水铝石的制备条件对胶溶性能的影响[J].化学推进剂与高分子材料, 2021, 19(1):48-51 [19]曾丰, 杨清河, 曾双亲.采用-连续中和法制备拟薄水铝石[J].石油学报石油加工, 2015, 31(05):1069-1074 [20]长岭炼油厂加氢催化剂会战组.硫酸铝-偏铝酸钠法制备γ-Al2O3的研究[J].石油炼制与化工, 1978, (Z1):51-57 [21]王康, 杨文建, 高秀娟, 等.制备条件对拟薄水铝石晶粒度与孔结构的影响[J].天津大学学报自然科学与工程技术版, 2013, 46(10):934-938 [22]罗铃, 李平, 黄凯, 等.硫酸法合成高质量拟薄水铝石[J].过程工程学报, 2022, 22(12):1710-1718 [23]李振华, 张孔远, 刘静怡, 等.老化条件对硫酸铝法制备拟薄水铝石性能的影响[J].工业催化, 2010, 18(05):26-28 [24]曾双亲, 杨清河, 刘滨, 等.拟薄水铝石工业生产中三水氧化铝含量的控制[J].石油学报石油加工, 2021, 37(04):719-727 [25]贾燕子, 赵新强, 邓中活, 等.双峰孔对渣油加氢降残炭催化剂性能的影响[J].石油炼制与化工, 2022, 53(03):9-15 [26]左东华, 谢玉萍, 聂红, 等.二甲基二苯并噻吩加氢脱硫反应机理的研究 Ⅰ体系催化剂的催化行为[J].催化学报, 2002, 23(3):271-275 [27]Liu Guihua, Li Zheng, Li Xiaobin, et al.Precipitation of spherical boehmite from concentrated sodium aluminate solution by adding gibbsite as seed[J].International Journal of Minerals, Metallurgy, and Materials, 2017, 24(8):954-963 [28]Morterra C, Magnacca G.A case study: surface chemistry and surface structure of catalytic aluminas,as studied by vibrational spectroscopy of adsorbed species[J].Catalysis Today, 1996, 27(3):497-532 [29]Li H, Chen J, Han S, et al.Electrochemiluminescence from tris(2,2′-bipyridyl)ruthenium(II)–graphene –Nafion modified electrode[J].Talanta, 2009, 79(2):165-170 [30]Kn?zinger H, Ratnasamy P.Catalytic aluminas: surface models and characterization of surface sites[J].Catalysis Reviews, 1978, 17(1):31-70 [31]Qu L, Zhang W, Kooyman P J, et al.MAS NMR,TPR,and TEM studies of the interaction of NiMo with alumina and silica–alumina supports[J].Journal of Catalysis, 2003, 215(1):7-13 [32]Ramírez J, Macías G, Cede?o L, et al.The role of titania in supported Mo,CoMo,NiMo,and NiW hydrodesulfurization catalysts: analysis of past and new evidences[J].Catalysis Today, 2004, 98(1):19-30 [33]张轩, 杨清河, 胡大为.载体水热处理时间对催化剂性质及加氢降残炭活性的影响[J].石油炼制与化工, 2015, 46(7):58-62 [34]袁蕙, 徐广通, 齐和日玛等.激光拉曼光谱在加氢脱硫催化剂-中的应用研究[J].光谱学与光谱分析, 2014, 34(02):435-438 [35]Payen E, Grimblot J, Kasztelan S.Study of oxidic and reduced alumina-supported molybdate and heptamolybdate species by in situ laser Raman spectroscopy[J].The Journal of Physical Chemistry, 1987, 91(27):6642-6648 [36]魏昭彬, 魏成栋, 辛勤.原位拉曼技术研究Mo催化剂的还原和硫化[J].物理化学学报, 1994, (05):402-408 [37]Arab M, Bougeard D, Aubry J M, et al.Structure and Raman spectra of transient species in the catalytic disproportionation of hydrogen peroxide by molybdate ions[J].Journal of Raman Spectroscopy, 2002, 33(5):390-396 [38]García-Martínez J C, Castillo-Araiza C O, De Los Reyes Heredia J A, et al.Kinetics of HDS and of the inhibitory effect of quinoline on HDS of 4, 6-DMDBT over a Ni–Mo–P/Al2O3 catalyst: Part I[J].Chemical Engineering Journal, 2012, (210):53-62 [39]Isoda T, Nagao S, Ma X, et al.Hydrodesulfurization of refractory sulfur species1. selective hydrodesulfurization of 4,6-dimethyldibenzothiophene in the major presence of naphthalene over CoMoAl2O3 and RuAl2O3 blend catalysts[J].Energy & Fuels, 1996, 10(2):482-486 [40]Kim J H, Ma X, Song C, et al.Kinetics of two pathways for 4,6-dimethyldibenzothiophene hydrodesulfurization over NiMo,CoMo sulfide,and nickel phosphide catalysts[J].Energy & fuels, 2005, 19(2):353-364 [41]Li X, Wang A, Egorova M, et al.Kinetics of the HDS of 4,6-dimethyldibenzothiophene and its hydrogenated intermediates over sulfided Mo and NiMo on γ- Al2O3[J].Journal of Catalysis, 2007, 250(2):283-293 [42]Bataille F, Lemberton J L, Michaud P, et al.Alkyldibenzothiophenes hydrodesulfurization-promoter effect,reactivity,and reaction mechanism[J].Journal of Catalysis, 2000, 191(2):409-422 [43]Kabe T, Ishihara A, Zhang Q.Deep desulfurization of light oilPart 2: hydrodesulfurization of dibenzothiophene,4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene[J].Applied Catalysis A: General, 1993, 97(1):L1-L9