硼掺杂Y分子筛的合成、改性及烯烃脱除性能研究

doi:10.19964/j.issn.1006-4990.2022-0119

摘要/Abstract

摘要：

采用水热合成法制备了硼掺杂Y分子筛（B-Y分子筛），并对其进行铵交换和水热处理，得到了改性B-Y分子筛（B-USY分子筛）。利用多种表征技术对B-Y分子筛及B-USY分子筛的组成、孔道结构、酸性质进行了表征，并将改性后的B-USY分子筛应用于重整生成油脱烯烃反应。结果表明：引入硼以后，Y分子筛的晶胞参数减小、相对结晶度降低、骨架稳定性下降；硼的引入促使改性过程中脱铝深度增加，并且形成连通介孔。相比于未掺杂硼的Y分子筛改性后的USY分子筛，B-USY分子筛具有丰富的连通介孔和良好的孔道扩散性能，并且保留了更多弱的B酸位点。以重整C₇⁺芳烃为原料，在反应温度为170 ℃、反应压力为1.2 MPa、空速（LHSV）为10 h^-1条件下，B-USY分子筛催化剂的单程寿命较USY分子筛催化剂提升30%。

关键词: 硼掺杂Y分子筛, 介孔, 扩散, 酸性质, 脱烯烃

Abstract:

Boron-doped Y zeolite（B-Y zeolite） was prepared by hydrothermal synthesis and then subjected to ammonium exchange and hydrothermal treatment to obtain modified B-Y zeolite（B-USY zeolite）.The composition，pore structure and acid property of B-Y zeolite and B-USY zeolite were characterized by a variety of characterization techniques，and the B-USY zeolite was used in the olefin removal reaction of reformate.The results showed that the unit cell parameters，relative crystallinity and framework stability of Y zeolite were decreased after the introduction of boron.Moreover，the introduction of boron promoted the increase of dealumination depth and the formation of connected mesopores during the modification process.Compared with USY zeolite modified by Y zeolite without boron doping，B-USY zeolite had abundant connected mesopores and good channel diffusion properties，and retained more weak Bronsted acid sites.Using reformed C₇⁺aromatics as raw material，the one-way life of B-USY zeolite catalyst was increased by 30% than that of USY zeolite under the conditions of reaction temperature of 170 ℃，pressure of 1.2 MPa and space velocity（LHSV） of 10 h^-1.

Key words: boron-doped Y zeolite, mesopores, diffusion, acid property, olefin removal

中图分类号:

O643

洪美花,臧甲忠,王凌涛,刘冠锋,宫毓鹏,彭晓伟. 硼掺杂Y分子筛的合成、改性及烯烃脱除性能研究[J]. 无机盐工业, 2022, 54(12): 139-147.

HONG Meihua,ZANG Jiazhong,WANG Lingtao,LIU Guanfeng,GONG Yupeng,PENG Xiaowei. Study on synthesis，modification and olefin removal performance of boron-doped Y zeolite[J]. Inorganic Chemicals Industry, 2022, 54(12): 139-147.

图/表 17

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分子筛	w（SiO₂）/ %	w（Al₂O₃）/ %	w（Na₂O）/ %	相对结晶度/%	晶胞参数/nm	n（Β）/ n（Al）
B-Y	64.4	21.2	11.4	95	2.463	0.016
Y	65.3	21.8	12.6	100	2.467	0.000
B-USY	85.6	12.3	0.47	75	2.442	—
USY	85.2	13.0	0.59	82	2.445	—

分子筛	I[Q⁴（3Al）]∶I[Q⁴（2Al）]∶I[Q⁴（1Al）]∶ I[Q⁴（0Al）]∶I[X]	Si含量最多	n（Si）/n（Al）	I[Al（Ⅳ）]∶I[Al（Ⅴ）]∶ I[Al（Ⅵ）]
B-Y	6.4%∶51.4%∶36.3%∶5.9%∶0%	Q⁴（2Al）	2.82	100%∶0%∶0%
B-USY	1.1%∶8.2%∶36.1%∶40.8%∶13.8%	Q⁴（0Al）	6.18	75.9%∶4.3%∶19.8%
Y	5.4%∶43.6%∶38.5%∶11.2%∶1.3%	Q⁴（2Al）	2.78	100%∶0%∶0%
USY	1.8%∶10.2%∶38.2%∶39.5%∶10.3%	Q⁴（0Al）	5.80	74.9%∶7.0%∶18.1%

分子筛	NH₃-TPD峰积分面积
分子筛	弱酸	强酸	总酸
B-HY	7.087	2.204	9.291
HY	6.824	1.838	8.662
B-USY	6.642	2.310	8.952
USY	6.138	1.890	8.028

分子筛	B酸量/（mmol?g^-1）			L酸量/（mmol?g^-1）			B酸量与L酸量之比
分子筛	200 ℃	300 ℃	450 ℃	200 ℃	300 ℃	450 ℃	200 ℃	300 ℃	450 ℃
B-HY	0.424	0.346	0.299	0.856	0.414 0.269		0.495	0.836	1.112
HY	0.118	0.124	0.157	0.581	0.286 0.163		0.203	0.434	0.965
B-USY	0.477	0.409	0.389	0.647	0.313 0.203		0.737	1.309	1.916
USY	0.122	0.182	0.216	0.439	0.216 0.123		0.278	0.843	1.750

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