分散型钼基催化剂在煤显微组分与催化裂化油浆共加氢反应中的应用

石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (9): 77-83.

分散型钼基催化剂在煤显微组分与催化裂化油浆共加氢反应中的应用

涂椿滟,秦鹏伟,刘昌伟,黄伟

太原理工大学化学工程与技术学院，省部共建煤基能源清洁高效利用国家重点实验室

收稿日期:2023-03-28 修回日期:2023-05-10 出版日期:2023-09-12 发布日期:2023-08-29
通讯作者: 涂椿滟 E-mail:tuchunyan@tyut.edu.cn
基金资助:
国家自然科学基金项目;国家重点研发计划

APPLICATION OF DISPERSED MOLYBDENUM-BASED CATALYSTS IN CO- HYDROPROCESSING OF COAL MACERALS AND FCC SLURRY

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Received:2023-03-28 Revised:2023-05-10 Online:2023-09-12 Published:2023-08-29

摘要/Abstract

摘要： 采用正辛基三甲基氯化铵与四硫代钼酸铵（MS）反应法合成了正辛基三甲基硫代钼酸铵（OT-MS）。由OT-MS催化剂前躯体形成的MoS2催化剂比表面积高且MoS2片晶长度集中在3～6 nm、堆叠层数主要为1～3层。以凉水井原煤（LSJR）及其惰质组富集物（LSJ-I）和镜质组富集物（LSJ-V）为原料煤，催化裂化（FCC）油浆为原料油，研究煤显微组分与重油共加氢的反应特性。结果表明，与MS相比，OT-MS在LSJR与FCC油浆共加氢反应中表现出更高的催化活性，干基无灰煤转化率提升至77.1%，固体残渣收率降低至8.3%；对于OT-MS催化的煤/油共加氢反应体系，随着原料煤中镜质组含量的增加，反应的转化效率和液体收率明显增大，液体产物中饱和分含量逐渐增加，胶质、沥青质含量减少；当采用LSJ-V与重油进行反应时干基无灰煤转化率达到90.3%，固体残渣收率低至3.4%，共加氢液体产物中沥青质含量最低，H/C原子比最高。

关键词: 煤/重油共加氢, 煤显微组分, MoS2, 四硫代钼酸铵, 正辛基三甲基硫代钼酸铵, 催化裂化油浆

Abstract: n-Octyltrimethylammonium thiomolybdates (OT-MS) was synthesized by the reaction of n-octyltrimethylammonium chloride with ammonium tetrathiomolybdate (MS). The specific surface area of MoS2 catalyst formed by the OT-MS precursor was high, the slab length of the MoS2 crystallites was concentrated in 3-6 nm, and the stacking number was mainly 1-3 layers. The characteristics of co-hydroprocessing reaction of coal macerals with fluid catalytic cracking (FCC) slurry were studied by using Liangshuijing raw coal (LSJR), its inertinite-rich fractions (LSJ-I) and vitrinite-rich fractions (LSJ-V),and FCC slurry as feedstock. Compared with MS, the OT-MS sample showed higher catalytic activity in the co-hydroprocessing reaction of LSJR and FCC slurry. The conversion of dry base ash-free coal increased to 77.1%, while the solid residue yield decreased to 8.3%. For the coal/oil co-hydroprocessing system catalyzed by OT-MS, with the increase of vitrinite content in raw coal, the conversion efficiency and liquid yield of the reaction increased obviously, and the content of saturates fraction in liquid product increased gradually, while the resin and asphaltene fractions decreased. When LSJ-V reacted with heavy oil, the coal conversion reached 90.3%, and the yield of solid residue was as low as 3.4%; the asphaltene content in the iquid product was the lowest, and the H/C atomic ratio was the highest.

Key words: coal/oil co-hydroprocessing, coal macerals, MoS2, ammonium tetrathiomolybdate, n-octyltrimethylammonium thiomolybdate, FCC slurry

涂椿滟秦鹏伟刘昌伟黄伟. 分散型钼基催化剂在煤显微组分与催化裂化油浆共加氢反应中的应用[J]. 石油炼制与化工, 2023, 54(9): 77-83.

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