Effect of ZSM-5/γ-Al2O3 mass ratio on isomerization/aromatization performance of FCC light gasoline

doi:10.16085/j.issn.1000-6613.2022-0734

Abstract

Abstract:

A series of FCC light gasoline isomerization/aromatization catalysts with different ZSM-5/γ-Al₂O₃ mass ratio were prepared by the incipient wetness method. The physico-chemical properties of the catalysts were characterized by XRD, N₂ adsorption desorption, SEM, NH₃-TPD, IR and pyridine FTIR. The isomerization/aromatization properties of the catalysts were evaluated using etherified C₅light gasoline in Urumqi Petrochemical Company with LPG as feedstocks. The results showed that the acidity and pore structure of the catalysts can be changed by adjusting the ZSM-5/γ-Al₂O₃ mass ratio. Under the ZnLa/ZSM-5/γ-Al₂O₃-1 catalyst at the reaction temperature 380℃, reaction pressure 1.0MPa, the space velocity 1.0h^-1, hydrogen/oil volume ratio 100 and LPG feed rate 4.4g/h by comparing the isomerization/aromatization products with feedstocks, the volume fraction of olefins decreased by 27.49%, the volume fraction of isoalkanes increased by 15.87%, the volume fraction of aromatics increased by 3.97%, the octane number reduced by 3.38 and the yield of the product was up to 89.90%. The goal of greatly reducing olefins with maintaining octane number by isomerization/aromatization was achieved.

Key words: ZSM-5, γ-Al₂O₃, mass ratio, light FCC gasoline, isomerization/aromatization

摘要：

通过调变ZSM-5分子筛与γ-Al₂O₃质量比，采用等体积浸渍法制备系列FCC轻汽油异构化/芳构化催化剂。本文采用X射线衍射（XRD）、N₂吸附脱附、扫描电子显微镜（SEM）、氨气程序升温脱附（NH₃-TPD）、红外光谱（IR）和吡啶红外光谱（Py-IR）等手段对其进行表征，并以乌鲁木齐石化醚后C₅掺杂液化石油气（LPG）为原料对催化剂异构化/芳构化性能进行评价。实验结果表明，ZSM-5分子筛与γ-Al₂O₃质量比的调变可以改变催化剂的酸性质及孔结构性质。在反应温度380℃、反应压力1.0MPa、反应空速1.0h^-1、氢/油体积比100、LPG进量4.4g/h的条件下，ZnLa/ZSM-5/γ-Al₂O₃-1异构化/芳构化产物与反应原料相比，烯烃体积分数降低27.49%、异构烷烃体积分数增加15.87%、芳烃体积分数增加3.97%，辛烷值损失3.38个单位，产品收率高达89.90%，实现了异构化/芳构化大幅降烯烃保辛烷值的目标。

关键词: ZSM-5, γ-Al₂O₃, 质量比, FCC轻汽油, 异构化/芳构化

CLC Number:

SONG Shaotong, LYU Zhongwu, JIANG Zengkun, LI Yang, WU Pei, ZHANG Yalin, ZHANG Ran, CHEN Jinyang, JU Yana. Effect of ZSM-5/γ-Al₂O₃ mass ratio on isomerization/aromatization performance of FCC light gasoline[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 229-238.

宋绍彤, 吕忠武, 姜增琨, 李阳, 吴培, 张雅琳, 张然, 陈金洋, 鞠雅娜. ZSM-5/γ-Al₂O₃质量比对FCC轻汽油异构化/芳构化性能影响[J]. 化工进展, 2022, 41(S1): 229-238.

Figures/Tables 15

References 20

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样品	比表面积^① /m²∙g^-1	微孔比表面积^② /m²∙g^-1	外比表面积^② /m²∙g^-1	孔容^③ /cm³∙g^-1	介孔孔容^④ /cm³∙g^-1	微孔孔容^② /cm³∙g^-1	孔径^⑤ /nm
γ-Al₂O₃	211.6	6.8	204.8	0.51	0.51	0	9.71
ZSM-5	311.3	277.4	33.9	0.24	0.11	0.13	3.12
ZnLa/ZSM-5/γ-Al₂O₃-1	221.3	19.9	201.4	0.42	0.41	0.01	7.61
ZnLa/ZSM-5/γ-Al₂O₃-2	244.6	79.3	165.4	0.35	0.32	0.03	5.80
ZnLa/ZSM-5/γ-Al₂O₃-3	256.8	96.4	160.4	0.36	0.32	0.04	5.61

样品	比表面积^① /m²∙g^-1	微孔比表面积^② /m²∙g^-1	外比表面积^② /m²∙g^-1	孔容^③ /cm³∙g^-1	介孔孔容^④ /cm³∙g^-1	微孔孔容^② /cm³∙g^-1	孔径^⑤ /nm
γ-Al₂O₃	211.6	6.8	204.8	0.51	0.51	0	9.71
ZSM-5	311.3	277.4	33.9	0.24	0.11	0.13	3.12
ZnLa/ZSM-5/γ-Al₂O₃-1	221.3	19.9	201.4	0.42	0.41	0.01	7.61
ZnLa/ZSM-5/γ-Al₂O₃-2	244.6	79.3	165.4	0.35	0.32	0.03	5.80
ZnLa/ZSM-5/γ-Al₂O₃-3	256.8	96.4	160.4	0.36	0.32	0.04	5.61

样品	酸量/μmol·g^-1
样品	弱酸	中强酸	强酸	总酸
ZnLa/ZSM-5/γ-Al₂O₃-1	204	363	113	680
ZnLa/ZSM-5/γ-Al₂O₃-2	215	377	114	706
ZnLa/ZSM-5/γ-Al₂O₃-3	229	373	145	747

样品	酸量/μmol·g^-1
样品	弱酸	中强酸	强酸	总酸
ZnLa/ZSM-5/γ-Al₂O₃-1	204	363	113	680
ZnLa/ZSM-5/γ-Al₂O₃-2	215	377	114	706
ZnLa/ZSM-5/γ-Al₂O₃-3	229	373	145	747

样品	酸量（200℃）/μmol·g^-1				酸量（350℃）/μmol·g^-1
样品	L	B	L+B	L/B	L	B	L+B	L/B
ZSM-5/γ-Al₂O₃-1	72.5	82.0	154.5	0.9	49.5	41.3	90.8	1.2
ZnLa/ZSM-5/γ-Al₂O₃-1	150.8	25.2	176.0	6.0	68.8	6.6	75.3	10.4
ZnLa/ZSM-5/γ-Al₂O₃-2	170.0	39.8	209.9	4.3	88.4	15.6	104.0	5.7
ZnLa/ZSM-5/γ-Al₂O₃-3	214.5	36.5	251.0	5.9	108.8	22.2	131.0	4.9

Effect of ZSM-5/γ-Al₂O₃ mass ratio on isomerization/aromatization performance of FCC light gasoline

ZSM-5/γ-Al₂O₃质量比对FCC轻汽油异构化/芳构化性能影响

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