无定形Al-P-O催化剂上气相合成邻羟基苯乙醚

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

摘要/Abstract

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

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

中图分类号:

TQ426.94

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.

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.

图/表 11

图1 催化剂活性评价装置示意图1—氮气瓶；2—稳流阀；3—转子流量计；4—加热炉；5—程序升温温控仪；6—热电偶；7—反应管；8—收集瓶；9—催化剂床层；10—输液泵；11—反应物

图2 Al-xP-O材料的XRD图谱

图3 Al-xP-O材料的氮气吸附-脱附等温线和孔径分布图

表1 Al-xP-O材料的物化性质

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	—	—	—	—

图4 Al-xP-O材料的NH3-TPD和CO2-TPD谱图

图5 不同P/Al摩尔比对Al-xP-O催化性能的影响[n(邻苯二酚)∶n(乙醇)=1∶6，空速=3.0mL/(gcat·h)，反应温度270℃，反应时间2~3h。其他副产物主要有3-乙基邻苯二酚、4-乙基邻苯二酚、2-乙氧基-4-乙基苯酚等]

图6 不同反应温度对Al-1.10P-O催化性能的影响[n(邻苯二酚)∶n(乙醇)=1∶6，LHSV=3.0mL/(gcat·h)，反应时间2~3h]

图7 不同空速对Al-1.10P-O催化性能的影响[n(邻苯二酚)∶n(乙醇)=1∶6，反应温度270℃，反应时间2~3h]

图8 不同乙醇/邻苯二酚摩尔比对Al-1.10P-O催化性能的影响[反应温度270℃，LHSV=3.0mL/(gcat·h)，反应时间2~3h]

图9 Al-1.10P-O催化剂的稳定性[n(邻苯二酚)∶n(乙醇)=1∶6，LHSV=3.0mL/(gcat·h)，反应温度270℃]

图10 反应前以及反应后Al-1.10P-O催化剂的热重曲线

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