有序介孔材料Al-FDU-12的合成及其加氢精制应用

doi:10.16085/j.issn.1000-6613.2020-0872

摘要/Abstract

摘要：

采用原位合成法合成了不同硅铝原子比（Si/Al=50、40、30、20、10）的Al-FDU-12介孔材料，进一步浸渍镍钼活性金属制备了催化剂。通过小角X射线衍射（XRD）、广角XRD、N₂吸附-脱附、扫描电镜（SEM）、透射电镜（TEM）和紫外等表征手段对材料及催化剂做了相应的表征，并且考察了不同硅铝比的NiMo/Al-FDU-12催化剂在催化裂化柴油中的加氢脱硫脱氮性能。结果表明，FDU-12介孔材料孔径、孔容以及比表面积大，活性金属分散度高。铝改性后的NiMo/Al-FDU-12催化剂加氢脱硫、脱氮活性得到显著提高。当反应条件为温度350℃、氢油体积比600、压力5.0MPa、质量空速（WHSV）1.0h^-1、硅铝比20时，催化剂的加氢脱硫脱氮活性最高，脱硫率可达98.9%，脱氮率可达95.3%。在相同反应条件下，工业催化剂催化柴油加氢脱硫、脱氮率低于NiMo/AF-20以及NiMo/AF-10催化剂。因此，铝改性后的FDU-12材料具有良好的工业应用前景。

关键词: 催化剂, 合成, 活性, 石油, 失活

Abstract:

Al-FDU-12 mesoporous materials with different silicon-to-aluminum atomic ratios (Si/Al=50, 40, 30, 20 and 10) were synthesized by in-situ synthesis, and the catalysts NiMo/Al-FDU-12 were prepared by further impregnating nickel and molybdenum active metals. The Al-FDU-12 and catalysts were characterized by means of small-angle XRD, wide-angle XRD, N₂ adsorption and desorption, SEM, TEM, UV and other characterization means. The hydrodesulfurization (HDS) performances of the NiMo/Al-FDU-12 with different Si and Al ratios were also evaluated. It showed that FDU-12 with high pore size, volume and surface area would lead to the high dispersion degree of active metals. The hydrodesulfurization and denitrification performances of NiMo/Al-FDU-12 catalyst were improved after Al modification. As the reaction conditions were: temperature of 350℃, hydrogen and oil volume ratio of 600, pressure of 5.0MPa, WHSV of 1.0h^-1, Si and Al atomic ratio of 20, the catalyst showed the highest hydrodesulfurization and denitrification activity. The desulfurization and denitrification rate could reach 98.9% and 95.3%, respectively. Under similar reaction conditions, the industrial catalyst presented lower hydrodesulfurization and denitrification activity than the NiMo/AF-20 and NiMo/AF-10 catalysts. Therefore, the FDU-12 materials after Al modification possessed good prospect of industrial application.

Key words: catalyst, synthesis, activity, petroleum, deactivation

中图分类号:

TQ028.8

曹正凯, 张霞, 段爱军. 有序介孔材料Al-FDU-12的合成及其加氢精制应用[J]. 化工进展, 2021, 40(3): 1449-1455.

CAO Zhengkai, ZHANG Xia, DUAN Aijun. Synthesis of well ordered Al-FDU-12 mesoporous materials and their application in hydrogenation[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1449-1455.

图/表 12

参考文献 32

9	林粤顺, 周红军, 周新华, 等. 介孔SBA-16负载毒死蜱载药微球的制备及其表征[J]. 化工新型材料, 2016, 44(12): 144-146.
	LIN Yueshun, ZHOU Hongjun, ZHOU Xinhua, et al. Preparation and characterization of chlorpyrifos loaded mesoporous SBA-16 microspheres[J]. New Chemical Material, 2016, 44(12): 144-146.
10	STEVENS W J J, LEBEAU K, MERTENS M, et al. Investigation of the morphology of the mesoporous SBA-16 and SBA-15 materials[J]. The Journal of Physical Chemistry B, 2006, 110(18): 9183-9187.
11	GOBIN O C, WAN Y, ZHAO D, et al. Mesostructured silica SBA-16 with tailored intrawall porosity Part 1: Synthesis and characterization[J]. The Journal of Physical Chemistry C, 2007, 111(7): 3053-3058.
12	WANG L, FAN J, TIAN B, et al. Synthesis and characterization of small pore thick-walled SBA-16 templated by oligomeric surfactant with ultra-long hydrophilic chains[J]. Microporous and Mesoporous Materials, 2004, 67(2/3): 135-141.
13	KIM T W, RYOO R, KRUK M, et al. Tailoring the pore structure of SBA-16 silica molecular sieve through the use of copolymer blends and control of synthesis temperature and time[J]. The Journal of Physical Chemistry B, 2004, 108(31): 11480-11489.
14	OLIVAS A, ZEPEDA T A. Impact of Al and Ti ions on the dispersion and performance of supported NiMo(W)/SBA-15 catalysts in the HDS and HYD reactions[J]. Catalysis Today, 2009, 143(1/2): 120-125.
15	MOULI K C, MOHANTY S, HU Y, et al. Effect of hetero atom on dispersion of NiMo phase on M-SBA-15 (M=Zr, Ti, Ti-Zr) [J]. Catalysis Today, 2013, 207: 133-144.
16	GUZMÁN M A, HUIRACHE-ACUÑA R, LORICERA C V, et al. Removal of refractory S-containing compounds from liquid fuels over P-loaded NiMoW/SBA-16 sulfide catalysts[J]. Fuel, 2013, 103: 321-333.
17	CALDERÓN-MAGDALENO M Á, MENDOZA-NIETO J A, KLIMOVA T E. Effect of the amount of citric acid used in the preparation of NiMo/SBA-15 catalysts on their performance in HDS of dibenzothiophene-type compounds[J]. Catalysis Today, 2014, 220: 78-88.
18	AMEZCUA J C, LIZAMA L, SALCEDO C, et al. NiMo catalysts supported on titania-modified SBA-16 for 4,6-dimethyldibenzothiophene hydrodesulfurization[J]. Catalysis Today, 2005, 107: 578-588.
19	HAO Y, CHONG Y, LI S, et al. Controlled synthesis of Au nanoparticles in the nanocages of SBA-16: improved activity and enhanced recyclability for the oxidative esterification of alcohols[J]. The Journal of Physical Chemistry C, 2012, 116(11): 6512-6519.
20	SHEN W, GU Y, XU H, et al. Alkylation of isobutane/1-butene on methyl-modified nafion/SBA-16 materials[J]. Industrial & Engineering Chemistry Research, 2010, 49(16): 7201-7209.
21	MA J, QIANG L, WANG J, et al. An easy route to synthesize novel mesostructured silicas Al/SBA-16 and its catalytic application[J]. Catalysis Letters, 2011, 141(2): 356-363.
22	ZHANG S, MURATSUGU S, ISHIGURO N, et al. Ceria-doped Ni/SBA-16 catalysts for dry reforming of methane[J]. ACS Catalysis, 2013, 3(8): 1855-1864.
23	KRUK M, HUI C M. Synthesis and characterization of large-pore FDU-12 silica[J]. Microporous and Mesoporous Materials, 2008, 114(1/2/3): 64-73.
24	FAN J, YU C, GAO F, et al. Cubic mesoporous silica with large controllable entrance sizes and advanced adsorption properties[J]. Angewandte Chemie: International Edition, 2003, 42(27): 3146-3150.
25	KUMAR A, SRINIVAS D. Aminolysis of epoxides catalyzed by three-dimensional, mesoporous titanosilicates, Ti-SBA-12 and Ti-SBA-16[J]. Journal of Catalysis, 2012, 293: 126-140.
26	YU J, JIMMY C Y, ZHAO X. The effect of SiO₂ addition on the grain size and photocatalytic activity of TiO₂ thin films[J]. Journal of Sol-Gel Science and Technology, 2002, 24(2): 95-103.
27	ZHAO L, YU J. Controlled synthesis of highly dispersed TiO₂ nanoparticles using SBA-15 as hard template[J]. Journal of Colloid and Interface Science, 2006, 304(1): 84-91.
1	CHEN Y, HSU W, LIN C, et al. Hydrodesulfurization reactions of residual oils over cobalt-molybdenum/alumina-aluminum phosphate catalysts in a trickle bed reactor[J]. Industrial & Engineering Chemistry Research, 1990, 29(9): 1830-1840.
2	DONGEN R VAN, BODE D, EIJK H VAN DER, et al. Hydrodemetallization of heavy residual oils in laboratory trickle-flow liquid recycle reactors[J]. Industrial & Engineering Chemistry Process Design and Development, 1980, 19(4): 630-635.
3	SONI K, RANA B S, SINHA A K, et al. 3-D ordered mesoporous KIT-6 support for effective hydrodesulfurization catalysts[J]. Applied Catalysis B: Environmental, 2009, 90(1/2): 55-63.
4	GAO D, DUAN A, ZHANG X, et al. Synthesis of NiMo catalysts supported on mesoporous Al-SBA-15 with different morphologies and their catalytic performance of DBT HDS[J]. Applied Catalysis B: Environmental, 2015, 165: 269-284.
5	HUIRACHE-ACUÑA R, PAWELEC B, RIVERA-MUÑOZ E, et al. Comparison of the morphology and HDS activity of ternary Co-Mo-W catalysts supported on P-modified SBA-15 and SBA-16 substrates[J]. Applied Catalysis B: Environmental, 2009, 92(1/2): 168-184.
6	ZHAO D, HUO Q, FENG J, et al. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures[J]. Journal of the American Chemical Society, 1998, 120(24): 6024-6036.
7	GALARNEAU A, CAMBON H, DI RENZO F, et al. True microporosity and surface area of mesoporous SBA-15 silicas as a function of synthesis temperature[J]. Langmuir, 2001, 17(26): 8328-8335.
8	金政伟, 汪晓东, 崔秀国. 弱酸性条件下SBA-16型二氧化硅介孔材料的合成与表征[J]. 化工学报, 2006, 57(6): 1487-1489.
	JING Zhengwei, WANG Xiaodong, CUI Xiuguo. Synthesis and characterization of SBA-16-type mesoporous silica under a moderately acidic condition[J]. CIESC Journal, 2006, 57(6):1487-1489.
28	CAO Z, ZHANG X, XU C, et al. The synthesis of Al-SBA-16 materials with a novel method and their catalytic application on hydrogenation for FCC Diesel[J]. Energy & Fuels, 2017, 31(1):805-814.
29	MENG Q, DU P, WANG B, et al. Synthesis of zirconium modified FDU-12 by different methods and its application in dibenzothiophene hydrodesulfurization[J]. RSC Advances, 2018, 8(48): 27565-27573.
30	LIU C, YUAN P, CUI C. The pore confinement effect of FDU-12 mesochannels on MoS₂ active phases and their hydrodesulfurization performance[J]. Journal of Nanomaterials, 2016, 9: 1-10.
31	CAO Z, DUAN A, ZHAO Z, et al. A simple two-step method to synthesize the well-ordered mesoporous composite Ti-FDU-12 and its application in the hydrodesulfurization of DBT and 4,6-DMDBT[J]. Journal of Materials Chemistry A, 2014, 2(46): 19738-19749.
32	WU Q, LI Y, HOU Z, et al. Synthesis and characterization of beta-FDU-12 and the hydrodesulfurization performance of FCC gasoline and diesel[J]. Fuel Processing Technology, 2018, 172: 55-64.

药品名称	化学式	等级	生产厂家
四水合钼酸铵	(NH₄)₆Mo₇O₂₄·4H₂O	分析纯	国药集团化学试剂公司
六水合硝酸镍	Ni(NO₃)₂·6H₂O	分析纯	国药集团化学试剂公司
正硅酸乙酯（TEOS）	CH₃CH₂OSi(OCH₂CH₃)₃	分析纯	国药集团化学试剂公司
正丁醇	C₄H₉OH	分析纯	国药集团化学试剂公司
盐酸	HCl	分析纯	北京化工厂
F127	EO₁₀₆PO₇₀EO₁₀₆	分析纯	Sigma-Alogrich公司
异丙醇铝	Al[(CH₃)₂CHO]₃	分析纯	北京化学试剂公司
1,3,5-三甲苯	C₆H₃(CH₃)₃	分析纯	天津市光复精细化工所
去离子水	H₂O		北京手表厂
石英砂	SiO₂	分析纯	天津石英钟厂
溴化钾	KBr	分析纯	北京益利精细化学品公司

药品名称	化学式	等级	生产厂家
四水合钼酸铵	(NH₄)₆Mo₇O₂₄·4H₂O	分析纯	国药集团化学试剂公司
六水合硝酸镍	Ni(NO₃)₂·6H₂O	分析纯	国药集团化学试剂公司
正硅酸乙酯（TEOS）	CH₃CH₂OSi(OCH₂CH₃)₃	分析纯	国药集团化学试剂公司
正丁醇	C₄H₉OH	分析纯	国药集团化学试剂公司
盐酸	HCl	分析纯	北京化工厂
F127	EO₁₀₆PO₇₀EO₁₀₆	分析纯	Sigma-Alogrich公司
异丙醇铝	Al[(CH₃)₂CHO]₃	分析纯	北京化学试剂公司
1,3,5-三甲苯	C₆H₃(CH₃)₃	分析纯	天津市光复精细化工所
去离子水	H₂O		北京手表厂
石英砂	SiO₂	分析纯	天津石英钟厂
溴化钾	KBr	分析纯	北京益利精细化学品公司

载体	孔径/nm	孔容/cm³·g^-1	比表面积/m²·g^-1
FDU-12	10.24	0.66	523
AF-50	10.14	0.71	620
AF-40	9.94	0.61	522
AF-30	9.28	0.55	507
AF-20	11.12	0.66	562
AF-10	9.18	0.56	510

载体	孔径/nm	孔容/cm³·g^-1	比表面积/m²·g^-1
FDU-12	10.24	0.66	523
AF-50	10.14	0.71	620
AF-40	9.94	0.61	522
AF-30	9.28	0.55	507
AF-20	11.12	0.66	562
AF-10	9.18	0.56	510

催化剂	硫含量 /mg·L^-1	脱硫率 /%	氮含量 /mg·L^-1	脱氮率 /%
NiMo/AF-50	120	88.2	95	85.2
NiMo/AF-40	92	90.9	74	88.4
NiMo/AF-30	65	93.6	55	91.4
NiMo/AF-20	11	98.9	30	95.3
NiMo/AF-10	36	96.5	38	94.1
NiMo/FDU-12	145	85.7	118	81.6
工业催化剂	40	96.0	45	93.0
再生后NiMo/AF-20	13	98.7	33	94.8