Y型沸石在异丁醇齐聚反应中的催化性能

doi:10.16085/j.issn.1000-6613.2022-0736

摘要/Abstract

摘要：

异丁醇经脱水齐聚反应可生产无芳烃、无硫的清洁燃料油（C₈、C $8 +$ ），是一条不依赖化石能源生产动力燃料的有深远发展前景的工艺新路线。本文利用X射线衍射（XRD）、扫描电子显微镜（SEM）、NH₃-程序升温脱附（NH₃-TPD）、Py-傅里叶变换红外光谱（Py-FTIR）和N₂吸附-脱附等手段对具有不同酸性和孔结构的HY沸石进行了表征，并将其用于异丁醇齐聚反应，考察了沸石的酸性质、孔结构以及反应时间等因素对异丁醇转化率和C₈及C $8 +$ 产物选择性的影响。结果表明：硅铝比（SiO₂/Al₂O₃）为20.9的HY样品表现出最佳的催化性能，异丁醇转化率可达94%，C₈及C $8 +$ 选择性将近90%；HY中介孔的存在有利于三聚物的生成，在沸石织构性质相似的情况下，酸量增加有利于提高异丁醇的转化率。反应后的催化剂在空气中煅烧后可重新恢复原有的催化性能。另外，与Hβ沸石相比，HY沸石催化异丁醇齐聚有更高的C₈和C $8 +$ 产物选择性。

关键词: 异丁醇, Y沸石, 酸性, 齐聚, 选择性, 生物燃料

Abstract:

Isobutyl alcohol can be used to produce aromatics and sulfur free fuel oil (C₈, C $8 +$ ) through dehydration and oligomerization. It is a new non-fossil process for producing power fuel. In this work, HY zeolites with different acidity and pore structure were characterized by XRD, SEM, NH₃-TPD, Py-FTIR and N₂ adsorption desorption and were used in the dehydration oligomerization of isobutyl alcohol. The effects of acidity and pore structure of the zeolites, and reaction time on the isobutyl alcohol conversion and C₈, C $8 +$ product selectivity were investigated. HY zeolite with a SiO₂/Al₂O₃ of 20.9 showed the best catalytic performance, and the isobutyl alcohol conversion and the selectivity of C₈ and C $8 +$ reached 94% and nearly 90%, respectively. The mesoporous HY was beneficial to the formation of trimers, and for HY zeolites with similar textural properties, the increase of acid content was conducive to improve the conversion of isobutyl alcohol. The catalytic activity of deactivated catalyst could be recovered by calcination in air. In addition, compared with Hβ zeolite with similar Si/Al ratio and mesoporous properties, HY zeolite had a higher C₈ and C $8 +$ product selectivity for isobutyl alcohol oligomerization.

Key words: isobutyl alcohol, Y zeolite, acidity, oligomerization, selectivity, biofuel

中图分类号:

TQ032.4

陈昊, 张传浩, 于峰, 范彬彬, 李瑞丰. Y型沸石在异丁醇齐聚反应中的催化性能[J]. 化工进展, 2023, 42(2): 794-802.

CHEN Hao, ZHANG Chuanhao, YU Feng, FAN Binbin, LI Ruifeng. Catalytic performance of zeolite Y in oligomerization of isobutyl alcohol[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 794-802.

图/表 17

图1 不同HY-x沸石的XRD图

图2 不同HY-x样品的SEM图

图3 不同HY-x样品的N2吸附-脱附等温曲线

表1 Y沸石的孔结构参数

样品	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	外表面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	介孔体积/cm³·g^-1
HY-8.0	746	704	42	0.32	0.27	0.05
HY-13.0	750	630	120	0.44	0.24	0.20
HY-20.9	859	736	123	0.48	0.28	0.20
HY-28.0	906	768	138	0.52	0.30	0.22
HY-30.7	905	775	130	0.53	0.30	0.23

图4 不同HY-x样品的NH3-TPD图

表2 不同HY-x样品的NH3-TPD数据

样品	脱附峰温度/℃	峰面积	总酸量
HY-8.0	239	914	3265
	352	1403
	462	948
HY-13.0	139	414	2101
	195	1020
	423	667
HY-20.9	129	265	1178
	189	658
	392	255
HY-28.0	125	169	1124
	177	686
	388	269
HY-30.7	133	144	609
	187	297
	403	168

表3 不同HY-x样品的Py-IR数据

样品	温度/K	L酸量/µmol·g^-1	B酸量/µmol·g^-1	总酸量/µmol·g^-1	L酸/B酸
HY-8.0	423	710	360	1070	1.97
HY-8.0	623	640	330	970	1.94
HY-13.0	423	123	389	512	0.32
HY-13.0	623	65	316	381	0.21
HY-20.9	423	97	262	359	0.37
HY-20.9	623	47	217	264	0.21
HY-28.0	423	54	236	290	0.23
HY-28.0	623	36	186	222	0.19
HY-30.7	423	35	182	217	0.19
HY-30.7	623	24	144	168	0.16

图5 不同HY-x样品在异丁醇齐聚反应中的催化性能（10mL异丁醇；0.5g HY-x；1MPa N2；反应温度240℃；反应时间4h）

图6 不同L/B值对异丁醇齐聚产物选择性的影响（10mL异丁醇；0.5g HY-x；1MPa N2；反应温度240℃；反应时间4h）

图7 异丁醇齐聚反应中C4丁烯在不同HY-x样品上的选择性

图8 异丁醇齐聚反应C8产物在不同HY-x样品上的分布图

图9 反应时间对异丁醇齐聚反应的影响

图10 再生催化剂的催化性能（10mL异丁醇；0.5g HY-20.9；1MPa N2；反应温度240℃；反应时间4h）

图11 反应后催化剂的热重分析

图12 HY-20.9和Hβ-22.4样品的NH3-TPD曲线

表4 HY-20.9与Hβ-22.4的孔结构参数

样品	BET比表面积/m²·g^-1	微孔面积/m²·g^-1	外表面积/m²·g^-1	总孔体积/cm³·g^-1	介孔体积/cm³·g^-1	微孔体积/cm³·g^-1
HY-20.9	864	737	127	0.49	0.21	0.28
Hβ-22.4	582	471	111	0.38	0.20	0.18

图13 HY-20.9和Hβ-22.4样品异丁醇齐聚反应的催化性能（10mL异丁醇；0.5g催化剂；1MPa N2；反应温度240℃；反应时间4h）

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