四乙基氢氧化铵改性对HMOR分子筛结构及二甲醚羰基化性能的影响

doi:10.11949/0438-1157.20210987

化工学报 ›› 2022, Vol. 73 ›› Issue (2): 712-721.DOI: 10.11949/0438-1157.20210987

• 催化、动力学与反应器 • 上一篇下一篇

四乙基氢氧化铵改性对HMOR分子筛结构及二甲醚羰基化性能的影响

苏畅^1,²(),冯晓博^1,²(),张立云^1,²,陈峰^1,²,赵小燕^1,²,曹景沛^1,²()

^1.中国矿业大学化工学院，江苏徐州 221116
^2.中国矿业大学江苏省碳资源精细化利用工程研究中心，江苏徐州 221116

收稿日期:2021-07-14 修回日期:2021-10-20 出版日期:2022-02-05 发布日期:2022-02-18
通讯作者: 冯晓博,曹景沛
作者简介:苏畅（1995—），男，硕士研究生，suchang9821@163.com.
基金资助:
中国博士后科学基金第2批特别资助项目(2020TQ0353);中国矿业大学大型仪器设备开放共享基金项目

Effect of tetraethylammonium hydroxide treatment on the structure of HMOR zeolite and its catalytic performance in the carbonylation of dimethyl ether

Chang SU^1,²(),Xiaobo FENG^1,²(),Liyun ZHANG^1,²,Feng CHEN^1,²,Xiaoyan ZHAO^1,²,Jingpei CAO^1,²()

^1.School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
^2.Jiangsu Province Engineering Research Center of Fine Utilization of Carbon Resources, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China

Received:2021-07-14 Revised:2021-10-20 Online:2022-02-05 Published:2022-02-18
Contact: Xiaobo FENG,Jingpei CAO

摘要/Abstract

摘要：

合成气经二甲醚（DME）羰基化合成乙酸甲酯（MA），MA进一步加氢制备乙醇是一种新型高效的煤基合成气制备乙醇路线。采用温和的后处理方法改性DME羰基化分子筛，进一步提高DME羰基化效率，对其工业应用具有重要意义。本研究利用四乙基氢氧化铵（TEAOH）对HMOR分子筛改性处理，探讨了有机碱改性处理对HMOR分子筛的结构和DME羰基化催化性能的影响。研究发现，TEAOH浓度为0.3 mol/L时，HMOR分子筛介孔孔容增大约26%，外比表面积增大约10%，DME的转化率增幅达68%。TEAOH水解产生的OH^-能够温和脱除HMOR分子筛中的骨架硅，获得介-微多级孔结构，提高DME羰基化反应过程中的传质速率。此外，水解的TEA⁺在分子筛表面富集，抑制了OH^-的过度脱硅，保护分子筛基本骨架结构不被更深层次破坏。

关键词: 乙醇, 二甲醚, 羰基化, 乙酸甲酯, 四乙基氢氧化铵后处理, HMOR分子筛

Abstract:

The synthesis gas is carbonylated with dimethyl ether (DME) to synthesize methyl acetate (MA). The further hydrogenation of MA to produce ethanol is a new and efficient route for the production of ethanol from coal-based synthesis gas. Modification of HMOR zeolite using mild post-treatment method to improve its catalytic efficiency of DME carbonylation is considered as an efficient strategy for the industrialization application. In this study, tetraethylammonium hydroxide (TEAOH) was used to modify HMOR zeolite. The effects of organic base modification on the structure and catalytic performance of DME carbonylation of HMOR zeolite were firstly discussed. It was found that when the concentration of TEAOH was 0.3 mol/L, the mesopore volume and external specific surface area of the HMOR zeolite are increased about 26% and 10%, respectively, and the conversion rate of DME is increased by 68%. The OH^- generated by the hydrolysis of TEAOH can gently remove the skeleton silicon in the HMOR zeolite and the hierarchical pore structure can be successfully obtained. The generated hierarchical pore structure is favorable to the mass transfer rate in the carbonylation reaction process of DME. In addition, the hydrolyzed TEA⁺ is enriched on the surface of HMOR zeolite, which inhibits the excessive desilication of OH^- and protects the basic skeleton structure of HMOR zeolite from further destruction.

Key words: ethanol, dimethyl ether, carbonylation, methyl acetate, post-treatment of TEAOH, HMOR zeolite

中图分类号:

O 643

苏畅, 冯晓博, 张立云, 陈峰, 赵小燕, 曹景沛. 四乙基氢氧化铵改性对HMOR分子筛结构及二甲醚羰基化性能的影响[J]. 化工学报, 2022, 73(2): 712-721.

Chang SU, Xiaobo FENG, Liyun ZHANG, Feng CHEN, Xiaoyan ZHAO, Jingpei CAO. Effect of tetraethylammonium hydroxide treatment on the structure of HMOR zeolite and its catalytic performance in the carbonylation of dimethyl ether[J]. CIESC Journal, 2022, 73(2): 712-721.

图/表 10

图1 不同TEAOH浓度溶液处理HMOR分子筛的XRD谱图

Fig.1 XRD patterns of HMOR zeolites treated by TEAOH solutions with different concentration

图2 不同HMOR分子筛的FE-SEM图像

Fig.2 FE-SEM images of different HMOR zeolites

图3 不同TEAOH浓度溶液处理HMOR分子筛的N2吸附-脱附曲线（a）和孔径分布曲线（b）

Fig.3 N2 adsorption-desorption isotherms (a) and pore distribution (b) of HMOR zeolites treated by TEAOH solutions with different concentration

表1 不同TEAOH浓度溶液处理HMOR分子筛的比表面积和孔结构

Table 1 Specific surface areas and pore properties of HMOR zeolites treated by TEAOH solutions with different concentration

HMOR zeolites	S_BET^①/(m²/g)	S_micro^②/(m²/g)	S_ext/(m²/g)	V_total^③/(cm³/g)	V_micro^②/(cm³/g)	V_meso^④/(cm³/g)
HMOR	506	449	57	0.308	0.181	0.127
HMOR-0.2TEA	516	456	60	0.357	0.183	0.174
HMOR-0.3TEA	548	484	64	0.351	0.191	0.160
HMOR-0.4TEA	533	474	59	0.331	0.190	0.141
HMOR-0.5TEA	524	467	56	0.335	0.188	0.147

图4 不同TEAOH浓度溶液处理HMOR分子筛的NH3-TPD谱图

Fig.4 NH3-TPD profiles of HMOR zeolites treated by TEAOH solutions with different concentration

图5 不同TEAOH浓度溶液处理HMOR分子筛的FT-IR谱图

Fig.5 FT-IR spectra of HMOR zeolites treated by TEAOH solutions with different concentration

表2 不同TEAOH浓度溶液处理HMOR分子筛的八元环B酸位点与十二元环B酸位点的比值

Table 2 B8-MR/B12-MR of HMOR zeolites treated by TEAOH solutions with different concentration

样品	(B_8-MR/B_12-MR)/%^①
HMOR	13.6
HMOR-0.2TEA	15.5
HMOR-0.3TEA	16.7
HMOR-0.4TEA	14.8
HMOR-0.5TEA	13.5

图6 不同浓度TEAOH溶液处理的HMOR分子筛催化DME羰基化反应结果

Fig.6 DME conversion over HMOR zeolite treated by TEAOH solutions with different concentration(reaction conditions: 220℃, 1.5 MPa, DME∶CO∶Ar=4.32∶5.06∶90.62 (vol.), 1600 h-1)

图7 吡啶预处理HMOR分子筛催化DME羰基化反应结果

Fig.7 DME conversion over HMOR zeolites by pyridine treatment(reaction conditions: 220℃, 1.5 MPa, DME∶CO∶Ar=4.32∶5.06∶90.62 (vol.), 1600 h-1)

图8 不同浓度TEAOH溶液处理HMOR分子筛DME羰基化反应评价后的TG曲线

Fig.8 TG curves of spent HMOR zeolites treated by TEAOH solutions with different concentration

参考文献 31

1	Li Y, Sun Q, Huang S Y, et al. Dimethyl ether carbonylation over pyridine-modified MOR: enhanced stability influenced by acidity[J]. Catalysis Today, 2018, 311: 81-88.
2	李振宇, 李顶杰, 黄格省, 等. 燃料乙醇发展现状及思考[J]. 化工进展, 2013, 32(7): 1457-1467.
	Li Z Y, Li D J, Huang G S, et al. Insights on current development of fuel ethanol[J]. Chemical Industry and Engineering Progress, 2013, 32(7): 1457-1467.
3	黄守莹, 熊雄, 贺培, 等. 二甲醚羰基化丝光沸石成型催化剂黏结剂的研究[J]. 化工学报, 2020, 71(10): 4642-4651.
	Huang S Y, Xiong X, He P, et al. Study on binder of extruded mordenite catalyst for dimethyl ether carbonylation[J]. CIESC Journal, 2020, 71(10): 4642-4651.
4	Farrell A E, Plevin R J, Turner B T, et al. Ethanol can contribute to energy and environmental goals[J]. Science, 2006, 311(5760): 506-508.
5	冯晓博, 刘天龙, 赵小燕, 等. 合成气与二甲醚为原料直接制乙醇催化反应研究进展[J]. 化工学报, 2021, 72(8): 3958-3967.
	Feng X B, Liu T L, Zhao X Y, et al. Advance in ethanol synthesis from syngas via carbonylation of dimethyl ether and hydrogenation of methyl acetate[J]. CIESC Journal, 2021, 72(8): 3958-3967.
6	Cleveland C J, Hall C A, Herendeen R A. Energy returns on ethanol production[J]. Science, 2006, 312(5781): 1746-1748.
7	王鹏, 王宪贵, 郭战英, 等. 合成气合成乙醇的研究进展[J]. 洁净煤技术, 2010(1): 55-58.
	Wang P, Wang X G, Guo Z Y, et al. Research progress in producer gas to ethanol technology [J]. Clean Coal Technology, 2010(1): 55-58.
8	Choi Y, Liu P. Mechanism of ethanol synthesis from syngas on Rh(111)[J]. Journal of the American Chemical Society, 2009, 131(36): 13054-13061.
9	Portillo C M A, Villanueva P A L, Vidal-Barrero F, et al. Effects of methanol co-feeding in ethanol synthesis from syngas using alkali-doped MoS₂ catalysts[J]. Fuel Processing Technology, 2015, 134: 270-274.
10	Mei D H, Rousseau R, Kathmann S M, et al. Ethanol synthesis from syngas over Rh-based/SiO₂ catalysts: a combined experimental and theoretical modeling study[J]. Journal of Catalysis, 2010, 271(2): 325-342.
11	Lopez L, Montes V, Kušar H, et al. Syngas conversion to ethanol over a mesoporous Cu/MCM-41 catalyst: effect of K and Fe promoters[J]. Applied Catalysis A: General, 2016, 526: 77-83.
12	赵娜, 牛君阳, 刘亚华, 等. 预处理条件及金属离子改性对H-MOR分子筛的DME羰基化性能影响[J]. 化工学报, 2015, 66(9): 3504-3510.
	Zhao N, Niu J Y, Liu Y H, et al. Influence of pretreatment and metal cation modification of H-MOR zeolite on performance of DME carbonylation[J]. CIESC Journal, 2015, 66(9): 3504-3510.
13	黄守莹, 王悦, 吕静, 等. 合成气经二甲醚/乙酸甲酯制无水乙醇的研究进展[J]. 化工学报, 2016, 67(1): 240-247.
	Huang S Y, Wang Y, Lü J, et al. Advances in indirect synthesis of ethanol from syngas via dimethyl ether/methyl acetate[J]. CIESC Journal, 2016, 67(1): 240-247.
14	Cheung P, Bhan A, Sunley G J, et al. Selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites[J]. Angewandte Chemie, 2006, 118(10): 1647-1650.
15	Boronat M, Martínez-Sánchez C, Law D, et al. Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO[J]. Journal of the American Chemical Society, 2008, 130(48): 16316-16323.
16	Wang X S, Li R J, Yu C C, et al. Enhanced activity and stability over hierarchical porous mordenite (MOR) for carbonylation of dimethyl ether: influence of mesopores[J]. Journal of Fuel Chemistry and Technology, 2020, 48(8): 960-969.
17	Sheng H B, Qian W X, Zhang H T, et al. Synthesis of hierarchical porous H-mordenite zeolite for carbonylation of dimethyl ether[J]. Microporous and Mesoporous Materials, 2020, 295: 109950.
18	Yuan Y Y, Wang L Y, Liu H C, et al. Facile preparation of nanocrystal-assembled hierarchical mordenite zeolites with remarkable catalytic performance[J]. Chinese Journal of Catalysis, 2015, 36(11): 1910-1919.
19	Wang X S, Li R J, Yu C C, et al. Enhancing the dimethyl ether carbonylation performance over mordenite catalysts by simple alkaline treatment[J]. Fuel, 2019, 239: 794-803.
20	韩海波, 王有和, 李康, 等. 超声波碱处理改性对丝光沸石结构、酸性质及其催化性能的影响[J]. 化工学报, 2018, 69(7): 3001-3008.
	Han H B, Wang Y H, Li K, et al. Effect of ultrasonic alkali treatment on structural, acidic properties and performance of MOR catalyst[J]. CIESC Journal, 2018, 69(7): 3001-3008.
21	李莎, 李玉平, 狄春雨, 等. TPAOH/NaOH混合碱体系对ZSM-5沸石的改性及其催化性能研究[J]. 燃料化学学报, 2012, 40(5): 583-588.
	Li S, Li Y P, Di C Y, et al. Modification and catalyst performance of ZSM-5 zeolite by treatment with TPAOH/NaOH mixed alkali[J]. Journal of Fuel Chemistry and Technology, 2012, 40(5): 583-588.
22	张云鹏, 李明罡, 王萍, 等. 四乙基氢氧化铵后晶化处理对ZSM-5分子筛结构及其甲醇制丙烯催化性能的影响[J]. 石油学报(石油加工), 2018, 34(4): 817-824.
	Zhang Y P, Li M G, Wang P, et al. Enhancing the catalytic performance of ZSM-5 zeolite in methanol to propene reaction via recrystallization in the presence of tetraethylammonium hydroxide[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2018, 34(4): 817-824.
23	Abelló S, Bonilla A, Pérez-Ramírez J. Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching[J]. Applied Catalysis A: General, 2009, 364(1/2): 191-198.
24	Ravishankar R, Kirschhock C, Schoeman B J, et al. Physicochemical characterization of silicalite-1 nanophase material[J]. The Journal of Physical Chemistry B, 1998, 102(15): 2633-2639.
25	Bagnasco G. Improving the selectivity of NH₃TPD measurements[J]. Journal of Catalysis, 1996, 159(1): 249-252.
26	Bai L Y, Xiong Z P, Zhan E S, et al. Piperazine as a versatile organic structure-directing agent for zeolite synthesis: effect of SiO₂/Al₂O₃ ratio on phase selectivity[J]. Journal of Materials Science, 2019, 54(10): 7589-7602.
27	Xue H F, Huang X M, Zhan E S, et al. Selective dealumination of mordenite for enhancing its stability in dimethyl ether carbonylation[J]. Catalysis Communications, 2013, 37: 75-79.
28	Li Y, Huang S Y, Cheng Z Z, et al. Promoting the activity of Ce-incorporated MOR in dimethyl ether carbonylation through tailoring the distribution of Brønsted acids[J]. Applied Catalysis B: Environmental, 2019, 256: 117777.
29	Zhao N, Tian Y, Zhang L F, et al. Spacial hindrance induced recovery of over-poisoned active acid sites in pyridine-modified H-mordenite for dimethyl ether carbonylation[J]. Chinese Journal of Catalysis, 2019, 40(6): 895-904.
30	王伟, 钱伟鑫, 马宏方, 等. 吡啶修饰H-MOR上二甲醚羰基化吸附-扩散理论研究[J]. 化工学报, 2021, 72(9): 4786-4795.
	Wang W, Qian W X, Ma H F, et al. A theoretical study on adsorption-diffusion of dimethyl ether carbonylation on pyridine-modified H-MOR[J]. CIESC Journal, 2021, 72(9): 4786-4795.
31	Xue H F, Huang X M, Ditzel E, et al. Coking on micrometer- and nanometer-sized mordenite during dimethyl ether carbonylation to methyl acetate[J]. Chinese Journal of Catalysis, 2013, 34(8): 1496-1503.

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四乙基氢氧化铵改性对HMOR分子筛结构及二甲醚羰基化性能的影响

Effect of tetraethylammonium hydroxide treatment on the structure of HMOR zeolite and its catalytic performance in the carbonylation of dimethyl ether

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