Vapor-phase synthesis of guaethol on amorphous Al-P-O catalyst

doi:10.16085/j.issn.1000-6613.2021-0825

Abstract

Abstract:

Amorphous mesoporous Al-xP-O catalysts with different P/Al molar ratios (x=1.00, 1.05, 1.10, 1.15, 1.20) were prepared by a one-pot precipitation-evaporation route. The Al-xP-O catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption method, ICP-AES, NH₃ temperature-programmed desorption (NH₃-TPD) and CO₂-TPD experiment. The relationship between P/Al molar ratio and surface acidic-basic properties of Al-xP-O catalysts were also studied. The results demonstrated that with the increase of the P/Al molar ratio in the range of 1.00~1.10, the amounts of weak acidic sites increased, the amounts of medium-strength basic sites decreased, the conversion to catechol increased, and the selectivity to guaethol increased significantly. As the reaction conditions were: temperature of 270℃, LHSV of 3.0mL/(g_cat·h) and P/Al molar ratio of 1.10, the catalyst exhibited the relative higher catalytic activity. In the reaction period of the 200h stability test, the selectivity to guaethol remained stable at 93.0%, and there was no obvious coke-deposition after reaction. The result indicated the catalyst has good industrial application prospects due to the properties of high stability for the vapor-phase selective synthesis of guaethol with catechol and ethanol.

Key words: Al-P-O catalyst, fixed-bed, desorption, deactivation

摘要：

通过一步沉淀-蒸发法制备了具有不同P/Al摩尔比（x=1.00、1.05、1.10、1.15、1.20）的无定形介孔Al-xP-O催化剂。通过X射线衍射（XRD）、N₂吸附-脱附、电感耦合等离子体原子发射光谱（ICP-AES）、NH₃程序升温脱附（NH₃-TPD）和CO₂程序升温脱附（CO₂-TPD）等手段对制备的Al-xP-O催化剂进行表征，考察了P/Al摩尔比对催化剂表面酸碱性及催化性能的影响。当P/Al摩尔比在1.00~1.10范围时，随P/Al摩尔比增加，催化剂弱酸性位点数量增加，中等强度碱性位点数量降低，邻苯二酚转化率提高，邻羟基苯乙醚选择性提高。当反应温度为270℃、空速为3.0mL/(g_cat·h)、P/Al摩尔比为1.10时，催化性能最佳。200h稳定性测试中，邻羟基苯乙醚选择性始终保持在93.0%左右，反应后催化剂无明显积炭，表明该催化剂对邻苯二酚与乙醇气相合成邻羟基苯乙醚反应具有较高的稳定性和工业应用价值。

关键词: Al-P-O催化剂, 固定床, 脱附, 失活

CLC Number:

TQ426.94

CHENG Gonglin, REN Xinfeng, XU Dongfei, WANG Xueguang, LU Xionggang, SHANG Xingfu. Vapor-phase synthesis of guaethol on amorphous Al-P-O catalyst[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1900-1907.

程功林, 任新峰, 徐冬菲, 汪学广, 鲁雄刚, 尚兴付. 无定形Al-P-O催化剂上气相合成邻羟基苯乙醚[J]. 化工进展, 2022, 41(4): 1900-1907.

Figures/Tables 11

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样品	P/Al摩尔比^①	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm	相对酸性位点密度^②	转化率/%	相对碱性位点密度^③	选择性/%
Al-1.00P-O	1.02	284	0.84	17.8	1.00	32.3	3.09	73.4
Al-1.05P-O	1.07	191	0.80	17.8	1.33	39.1	2.91	91.5
Al-1.10P-O	1.13	180	0.75	17.9	1.59	45.2	1.16	92.8
Al-1.15P-O	1.17	161	0.73	18.3	1.51	38.6	1.00	95.6
Al-1.20P-O	1.21	125	0.64	21.2	1.30	28.6	1.04	96.8
Al-1.10P-O （使用200h后）	1.09	147	0.43	10.9	—	—	—	—

样品	P/Al摩尔比^①	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm	相对酸性位点密度^②	转化率/%	相对碱性位点密度^③	选择性/%
Al-1.00P-O	1.02	284	0.84	17.8	1.00	32.3	3.09	73.4
Al-1.05P-O	1.07	191	0.80	17.8	1.33	39.1	2.91	91.5
Al-1.10P-O	1.13	180	0.75	17.9	1.59	45.2	1.16	92.8
Al-1.15P-O	1.17	161	0.73	18.3	1.51	38.6	1.00	95.6
Al-1.20P-O	1.21	125	0.64	21.2	1.30	28.6	1.04	96.8
Al-1.10P-O （使用200h后）	1.09	147	0.43	10.9	—	—	—	—

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