小晶粒ZSM-22的可控合成及其催化长链正构生物烷烃制航空煤油性能

doi:10.16085/j.issn.1000-6613.2021-0938

摘要/Abstract

摘要：

由生物脱氧油制生物航空煤油具有较大应用潜力和发展前景，为了提高生物航煤的收率，开发性能更好的加氢裂化/异构化催化剂是关键。本文采用水热合成法，在低温陈化、加入晶种、提高合成凝胶的碱度或加入有机碱条件下，合成了平均c轴尺寸在100~330nm的小晶粒ZSM-22分子筛，进行了XRD、SEM、N₂物理吸附、NH₃-TPD和吡啶红外表征，并以生物质油加氢脱氧得到的长链正构生物烷烃为原料，考察了不同晶粒尺寸 ZSM-22催化剂催化裂化和异构化制生物航空煤油的性能。结果表明，通过提高碱度合成的小晶粒H-ZSM-22 具有较强的酸中心，较多可及的强B酸中心数量，其长链正构烷烃转化率可达80%以上。在此基础上，制备的Pt/ZSM-22催化剂具有较高的Pt分散度，表现出很好的加氢裂化/异构化性能，其长链正构烷烃的转化率高达97.79%，生物航煤收率达50.25%，航煤产物异正比为7.55。

关键词: ZSM-22分子筛, 长链正构生物烷烃, 加氢裂化/异构化, 收率, 小晶粒

Abstract:

The production of bio-jet fuel from biological deoxygenated oil has great application potential and development prospects. To improve the yield of bio-jet fuel, it is essential to develop high-performance catalysts for the hydrocracking and hydroisomerization. After low-temperature aging, adding seeds or increasing the alkalinity of the initial gel and crystallization, small size ZSM-22 zeolites were obtained with the average c-axis size between 100—330nm. The samples were characterized by XRD, SEM, N₂ physical adsorption, NH₃-TPD and Py-IR. Catalysts prepared by ZSM-22 with different crystal sizes were evaluated on the cracking and isomerization of long-chain normal bio-paraffins from hydrodeoxygenated biomass oil to bio-jet fuel. The results indicated that, the small crystal size H-ZSM-22 synthesized by increasing alkalinity of gel had stronger acid centers and more accessible strong B acid centers. The conversion of long-chain normal bio-paraffins were more than 80%. Further, the Pt/ZSM-22 catalyst possessed high Pt dispersion and exhibited great hydrocracking and isomerization performance. The conversion reached 97.79%, and the yield of bio-jet fuel was as high as 50.25% with an iso/n-paraffin ratio of 7.55.

Key words: ZSM-22 zeolite, long-chain normal bio-paraffins, hydrocracking and hydroisomerization, yield, small crystal size

中图分类号:

S216

韩京京, 谭涓, 刘靖, 刘宇. 小晶粒ZSM-22的可控合成及其催化长链正构生物烷烃制航空煤油性能[J]. 化工进展, 2022, 41(4): 1916-1924.

HAN Jingjing, TAN Juan, LIU Jing, LIU Yu. Controllable synthesis of small size ZSM-22 zeolites and their performance in the production of bio-jet fuel by hydrocracking and hydroisomerization of long-chain normal bio-paraffins[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1916-1924.

图/表 12

参考文献 24

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样品	晶种量/μg·g^-1	陈化条件	n(K₂O/SiO₂)	添加剂	晶相组成	相对结晶度/%
A-1	0	—	0.13	—	ZSM-22+少量ZSM-5	76
A-2	0	50℃，6h	0.13	—	ZSM-22	100
A-3	1000	—	0.13	—	ZSM-22	89
A-4	1000	50℃，6h	0.13	—	ZSM-22	92
A-5	0	50℃，6h	0.16	—	ZSM-22	106
A-6	1000	50℃，6h	0.13	四乙基氢氧化铵	ZSM-22	94
A-7	1000	50℃，6h	0.13	尿素	ZSM-22	76

样品	晶种量/μg·g^-1	陈化条件	n(K₂O/SiO₂)	添加剂	晶相组成	相对结晶度/%
A-1	0	—	0.13	—	ZSM-22+少量ZSM-5	76
A-2	0	50℃，6h	0.13	—	ZSM-22	100
A-3	1000	—	0.13	—	ZSM-22	89
A-4	1000	50℃，6h	0.13	—	ZSM-22	92
A-5	0	50℃，6h	0.16	—	ZSM-22	106
A-6	1000	50℃，6h	0.13	四乙基氢氧化铵	ZSM-22	94
A-7	1000	50℃，6h	0.13	尿素	ZSM-22	76

样品	聚集体长度 /μm	晶粒c轴长度 /nm	晶粒直径 /nm	晶粒长径比
A-1	—	2600	170	15.3
A-2	1.1	170	60	2.8
A-3	0.9	230	50	4.6
A-4	1.1	330	50	6.6
A-5	0.9	140	50	2.8
A-6	0.6	108	40	2.7
A-7	0.3	190	50	3.8

样品	聚集体长度 /μm	晶粒c轴长度 /nm	晶粒直径 /nm	晶粒长径比
A-1	—	2600	170	15.3
A-2	1.1	170	60	2.8
A-3	0.9	230	50	4.6
A-4	1.1	330	50	6.6
A-5	0.9	140	50	2.8
A-6	0.6	108	40	2.7
A-7	0.3	190	50	3.8

样品	比表面积 /m²·g^-1	外比表面积 /m²·g^-1	微孔比表面积 /m²·g^-1	孔容 /cm³·g^-1	微孔孔容 /cm³·g^-1
A-1	222	39	183	0.25	0.07
A-2	273	48	225	0.35	0.09
A-3	259	44	215	0.39	0.08
A-4	279	33	246	0.44	0.09
A-5	260	40	220	0.26	0.09
A-6	249	55	194	0.55	0.08
A-7	223	84	139	0.48	0.06