乙酸处理脱铝对丝光沸石结构、酸性质及其催化性能的影响

doi:10.15541/jim20180220

无机材料学报 ›› 2019, Vol. 34 ›› Issue (2): 179-185.DOI: 10.15541/jim20180220

乙酸处理脱铝对丝光沸石结构、酸性质及其催化性能的影响

韩海波^1,2, 王有和¹, 李康², 雷杰², 刘丹禾², 阎子峰¹

1. 中国石油大学重质油国家重点实验室, 青岛 266580;
2. 中石化炼化工程集团洛阳技术研发中心, 洛阳 471003

收稿日期:2018-05-11 修回日期:2018-07-17 出版日期:2019-02-20 网络出版日期:2019-01-24
作者简介:韩海波(1976–), 男, 博士研究生. E-mail: hanhb.lpec@sinopec.com
基金资助:
中石化炼化工程(集团)股份有限公司支持项目(SER118020);国家自然科学基金(21776311);中央高校基本科研业务费专项资金(15CX05030A)

Acetic Acid Leaching on the Structure, Acidity and Performance of HMOR Catalyst

HAN Hai-Bo^1,2, WANG You-He¹, LI Kang², LEI Jie², LIU Dan-He², YAN Zi-Feng¹

1. State Key Laboratory for Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China;
2. Luoyang R&D Center of Technology of Sinopec Engineering (Group) CO., LTD., Luoyang 471003, China

Received:2018-05-11 Revised:2018-07-17 Published:2019-02-20 Online:2019-01-24
About author:HAN Hai-Bo. E-mail: hanhb.lpec@sinopec.com
Supported by:
Sinopec Engineering (Group) CO., LTD. Support Project (SER118020);National Natural Science Foundation of China (21776311);Fundamental Research Funds for the Central Universities (15CX05030A)

摘要/Abstract

摘要：

基于丝光沸石(HMOR)催化合成乙酸甲酯稳定性较差及八元环边袋结构酸性位专一性催化作用的特性, 提出了利用乙酸处理具有八元环-Na和十二元环-H的MOR以制备选择性脱铝及疏通八元环边袋结构技术。采用XRD、²⁷Al-NMR、NH₃-TPD、吡啶红外和N₂吸-脱附等手段对催化剂进行了表征, 分别考察了不同乙酸浓度处理条件对分子筛催化剂骨架结构、酸性质、微孔结构以及催化合成乙酸甲酯性能的影响。结果表明, 通过合适浓度乙酸溶液处理, HMOR分子筛的硅铝比、微孔体积、中值孔径都增大, BJH孔径分布未见明显变化, 乙酸溶液处理脱除了HMOR中十二元环的Al, 最大限度地保留了八元环边袋结构中的Al。改性后的HMOR催化剂二甲醚转化率平稳期由18 h延长至50 h, 催化剂的稳定性能得以改善, 催化剂转化率由45.6%降至43.8%, 催化剂活性略有降低。

关键词: DME羰基化, 酸处理, 脱铝, 孔分布

Abstract:

Acid sites located inside the 8-ring side-pockets of mordenite are highly active for DME carbonylation. However, mordenite deactivates very fast during the reaction because of non-selective reactions happening inside the 12-ring main channels of zeolites. In the present study, HMOR was treated by acid leaching using acetic acid of different concentration, with the purpose to selectively remove framework Al which is located inside 12-ring channels. Physicochemical characteristics of the parent and acid-treated mordenites were studied by complementary methods including: XRD, ²⁷Al-NMR, NH₃-TPD, pyridine IR, and N₂ adsorption-desorption. The results show that the acid treatment, if appropriately applied, increases both the Si/Al and micropore volume of the samples, without significantly changing the mesopore size distribution. Most of the framework Al species in the 12-membered ring channels of HMOR were removed, without impacting those located inside the 8-ring channels. The catalytic results show that the initial activity of catalyst decreased slightly from 45.6% to 43.8%. On the other hand, the activity stability improved substantially, with stabilization period prolonged obviously from 18 h to 50 h.

Key words: DME carbonylation, acid treatment, dealumination, pore size distribution

中图分类号:

O643

韩海波, 王有和, 李康, 雷杰, 刘丹禾, 阎子峰. 乙酸处理脱铝对丝光沸石结构、酸性质及其催化性能的影响[J]. 无机材料学报, 2019, 34(2): 179-185.

HAN Hai-Bo, WANG You-He, LI Kang, LEI Jie, LIU Dan-He, YAN Zi-Feng. Acetic Acid Leaching on the Structure, Acidity and Performance of HMOR Catalyst[J]. Journal of Inorganic Materials, 2019, 34(2): 179-185.

图/表 10

图1 不同浓度乙酸处理丝光沸石的XRD图谱

Fig. 1 XRD patterns of HMOR zeolites treated with different concentrations of acetic acid

表1 不同浓度乙酸处理丝光沸石的相对结晶度和硅铝比

Table 1 Relative crystallinity and Si/Al of HMOR zeolites treated with different concentrations of acetic acid

Sample	AC00	AC01	AC02	AC03
n(Si)/n(Al)	10.2	12.3	13.6	15.2
Crystallinity/%	100	99	97	95

图2 不同浓度乙酸处理丝光沸石的27Al-NMR图谱

Fig. 2 27Al-NMR spectra of HMOR zeolites treated with different concentrations of acetic acid

图3 不同浓度乙酸处理丝光沸石的酸性质

Fig. 3 Acidity properties of HMOR zeolites treated with different concentrations of acetic acid (a) NH3-TPD; (b) FT-IR

表2 不同浓度乙酸处理丝光沸石不同孔道B酸性质

Table 2 Properties of B acid sites in different channels of HMOR zeolites treated with different concentrations of acetic acid

Sample	B_framework /(μmol•g^-1)	B_12-MR /(μmol•g^-1)	B_8-MR /(μmol•g^-1)
AC00	898.1	436.3	461.8
AC01	780.2	322.5	457.7
AC02	668.8	225.3	443.5
AC03	591.6	170.4	421.2

图4 不同浓度乙酸处理丝光沸石的等温吸脱附曲线及孔径分布曲线

Fig. 4 N2 adsorption-desorption isotherms and pore diameter distribution of HMOR zeolites treated with different concentrations of acetic acid

表3 不同浓度乙酸处理分子筛催化剂的比表面积和孔性质

Table 3 Textural and structural properties of HMOR zeolites treated with different concentration of acetic acid

Samples	AC00	AC01	AC02	AC03
S_BET/(m²•g^-1)	477	476	455	449
S_mic/(m²•g^-1)	422	416	386	387
S_ext/(m²•g^-1)	55	60	69	62
V_total/(cm³•g^-1)	0.28	0.28	0.28	0.27
V_micro/(cm³•g^-1)	0.18	0.18	0.19	0.19
Median pore diameter/nm	0.59	0.60	0.61	0.62
Micropore distribution /(cm³•g^-1)
<0.6/nm	0.066	0.071	0.076	0.081
0.6-0.7/nm	0.029	0.027	0.021	0.020
0.7-1.2/nm	0.032	0.037	0.043	0.044

图5 不同浓度乙酸处理丝光沸石的H-K累积孔体积图

Fig. 5 H-K cumulative pore volume of HMOR zeolites treated with different concentrations of acetic acid

图6 不同浓度乙酸处理丝光沸石的H-K孔径分布图

Fig. 6 H-K differential pore volume of HMOR zeolites treated with different concentrations of acetic acid

图7 不同浓度乙酸处理丝光沸石失活曲线

Fig. 7 Inactivation curves of HMOR zeolites treated with different concentrations of acetic acid

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乙酸处理脱铝对丝光沸石结构、酸性质及其催化性能的影响

Acetic Acid Leaching on the Structure, Acidity and Performance of HMOR Catalyst

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