沉淀剂对NiW/TiO2-ASA催化剂加氢裂化性能的影响

doi:10.16085/j.issn.1000-6613.2022-0504

摘要/Abstract

摘要：

无定形硅铝的织构性质和酸性质对其加氢裂化性能有很大影响。本文以氨水、碳酸铵、氢氧化钠/尿素、氢氧化钠为沉淀剂，制备了4种含钛无定形硅铝（TiO₂-ASA），并以其为载体负载Ni-W加氢组分，制备了NiW/TiO₂-ASA加氢裂化催化剂，以十氢萘为模型化合物，考察NiW/TiO₂-ASA催化剂的加氢裂化性能，通过X射线衍射（XRD）、氮气吸附-脱附、氨气程序升温脱附（NH₃-TPD）、吸附吡啶原位红外（Py-IR）、扫描电镜（SEM）对TiO₂-ASA和NiW/TiO₂-ASA催化剂进行了表征。结果表明，沉淀剂对TiO₂-ASA的比表面积和孔容影响非常大，以碳酸铵为沉淀剂时，TiO₂-ASA具有高比表面积、窄孔分布的特点，沉淀剂为氢氧化钠时，则可制备出大孔容、宽孔分布的TiO₂-ASA。十氢萘的加氢裂化反应结果表明，以碳酸铵为沉淀剂制备的NiW/TiO₂-ASA催化剂，织构性质优良，且具有更多的中强酸量，十氢萘的转化率最高达52%，开环产物选择性达到了12%。

关键词: 沉淀剂, 二氧化钛, 无定形硅铝, 十氢萘, 加氢裂化

Abstract:

The texture and acid properties of amorphous silica-alumina have a great impact on its hydrocracking performance. Four kinds of TiO₂-ASA were prepared by using ammonia, ammonium carbonate, sodium hydroxide/urea and sodium hydroxide respectively as precipitants. Then NiW/TiO₂-ASA hydrocracking catalysts were prepared, and their hydrocracking performance was investigated using decalin as the model compound. The TiO₂-ASA and NiW/TiO₂-ASA catalysts were characterized by XRD, N₂ adsorption-desorption, NH₃-TPD, Py-IR, and SEM. The results showed that precipitant has a great influence on the specific surface area and pore volume of TiO₂-ASA. When ammonium carbonate was used as the precipitant, TiO₂-ASA has high specific surface area and narrow pore distribution. When the precipitant was sodium hydroxide, the TiO₂-ASA with large pore volume and wide pore distribution can be prepared. The results of decalin hydrocracking showed that the NiW/TiO₂-ASA catalyst prepared with ammonium carbonate had excellent texture properties and more moderate and strong acids, the conversion of decalin was up to 52%, and the ring-opening product selectivity reached 12%.

Key words: precipitation, titanium dioxide, amorphous silica-alumina, decahydronaphthalene, hydrocracking

中图分类号:

TQ032

孔倩, 孙巾超, 葛佳琪, 张鹏, 马艳龙, 刘百军. 沉淀剂对NiW/TiO₂-ASA催化剂加氢裂化性能的影响[J]. 化工进展, 2023, 42(1): 265-271.

KONG Qian, SUN Jinchao, GE Jiaqi, ZHANG Peng, MA Yanlong, LIU Baijun. Effect of precipitant on the hydrocracking performance of NiW/TiO₂-ASA catalyst[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 265-271.

图/表 10

参考文献 20

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样品	比表面积 /m²·g^-1	孔容/mL·g^-1			平均孔径 /nm
样品	比表面积 /m²·g^-1	总孔容	微孔孔容	介孔孔容	平均孔径 /nm
TiO₂-ASA-A	476	1.39	0.20	1.19	11.7
TiO₂-ASA-B	326	1.30	0.14	1.16	16.0
TiO₂-ASA-C	344	2.11	0.15	1.96	24.5
TiO₂-ASA-D	300	1.47	0.13	1.34	19.6

样品	比表面积 /m²·g^-1	孔容/mL·g^-1			平均孔径 /nm
样品	比表面积 /m²·g^-1	总孔容	微孔孔容	介孔孔容	平均孔径 /nm
TiO₂-ASA-A	476	1.39	0.20	1.19	11.7
TiO₂-ASA-B	326	1.30	0.14	1.16	16.0
TiO₂-ASA-C	344	2.11	0.15	1.96	24.5
TiO₂-ASA-D	300	1.47	0.13	1.34	19.6

样品	比表面积 /m²·g^-1	孔容/mL·g^-1			平均孔径 /nm
样品	比表面积 /m²·g^-1	总孔容	微孔孔容	介孔孔容	平均孔径 /nm
Cat-A	211	0.72	0.10	0.62	11.9
Cat-B	206	0.68	0.09	0.59	13.2
Cat-C	241	1.19	0.10	1.09	19.8
Cat-D	193	0.99	0.08	0.91	20.4

样品	比表面积 /m²·g^-1	孔容/mL·g^-1			平均孔径 /nm
样品	比表面积 /m²·g^-1	总孔容	微孔孔容	介孔孔容	平均孔径 /nm
Cat-A	211	0.72	0.10	0.62	11.9
Cat-B	206	0.68	0.09	0.59	13.2
Cat-C	241	1.19	0.10	1.09	19.8
Cat-D	193	0.99	0.08	0.91	20.4

样品	总酸酸量/μmol·g^-1				中强酸酸量/μmol·g^-1
样品	B酸酸量	L酸酸量	B+L	B/L	B酸酸量	L酸酸量	B+L	B/L
Cat-A	57.26	378.83	436.09	0.15	17.84	75.68	93.52	0.24
Cat-B	31.64	324.13	355.77	0.10	11.19	115.78	126.97	0.10
Cat-C	17.39	125.11	142.50	0.14	9.09	85.11	94.20	0.11
Cat-D	3.71	94.89	98.61	0.04	2.90	88.23	91.13	0.03

沉淀剂对NiW/TiO₂-ASA催化剂加氢裂化性能的影响

Effect of precipitant on the hydrocracking performance of NiW/TiO₂-ASA catalyst

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样品	转化率/%	开环产物选择性/%	开环产物收率/%
Cat-A	33.84	10.26	3.47
Cat-B	51.47	10.16	5.22
Cat-C	19.70	0.89	0.18
Cat-D	11.00	0.36	0.04

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