Molecular simulation of the effect of doping modification on the adsorption properties of calcium-aluminum-based composites ester exchange catalysts

doi:10.11949/0438-1157.20200357

Abstract

Abstract:

With the help of molecular simulations, the effect of zinc, lanthanum and magnesium doping modification on the transesterification catalyzed by calcium-aluminum composite catalyst was studied. The model for Al₂O₃(110) and CaO(100) surfaces were constructed and a series of derivative models doped by zinc, lanthanum, and magnesium were then obtained. Doping binding energy of various doped Al₂O₃(110) surfaces were calculated. The adsorption process of methanol and methyl acetate on CaO(100) and its derivative surfaces were analyzed. The adsorption process of methanol on Al₂O₃(110) and its derivative surfaces and the Mulliken charge density change were discussed. The results show that the calcium-aluminum composite catalysts doped with zinc, lanthanum, and magnesium can enhance the adsorption performance for methanol, which contribute a lot to catalyzing transesterification reaction.

Key words: biodiesel, calcium-aluminum binary composite catalyst, adsorption, doped modification, molecular simulation

摘要：

借助分子模拟手段，研究了锌、镧、镁掺杂改性对钙铝基复合型金属氧化物催化酯交换的影响。构建了Al₂O₃(110)、CaO(100)以及锌、镧、镁掺杂改性的衍生模型。计算了不同改性氧化铝表面的掺杂结合能，分析了甲醇和乙酸甲酯在氧化钙及其衍生物表面的吸附过程，讨论了甲醇在Al₂O₃(110)及其衍生物表面的吸附过程及其Mulliken电荷密度的变化。结果表明，采用锌、镧、镁掺杂改性能强化钙铝复合型金属氧化物催化剂对甲醇的吸附性能，有助于催化酯交换反应的进行。

关键词: 生物柴油, 钙铝二元复合物催化剂, 吸附, 掺杂改性, 分子模拟

CLC Number:

TK 6

Zhipeng LI, Shengli NIU, Kuihua HAN, Chunmei LU. Molecular simulation of the effect of doping modification on the adsorption properties of calcium-aluminum-based composites ester exchange catalysts[J]. CIESC Journal, 2020, 71(8): 3625-3632.

厉志鹏, 牛胜利, 韩奎华, 路春美. 掺杂改性对钙铝基复合物酯交换催化剂吸附性能影响的分子模拟[J]. 化工学报, 2020, 71(8): 3625-3632.

Figures/Tables 11

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分子	键	键长/ nm
分子	键	本文	文献^[4,20]
甲醇	O—H	0.097	0.096
	C—O	0.143	0.143
	C—H_1/2/3	0.109/0.110/0.110	0.110/0.110/0.110
乙酸甲酯	C—O_1/2	0.144/0.136	0.143/0.136
	C—C	0.150	0.150
	CO	0.122	0.122
	C—H_1/2/3	0.109/0.109/0.109	0.109/0.109/0.109
	C—H_4/5/6	0.109/0.110/0.110	0.109/0.109/0.109

分子	键	键长/ nm
分子	键	本文	文献^[4,20]
甲醇	O—H	0.097	0.096
	C—O	0.143	0.143
	C—H_1/2/3	0.109/0.110/0.110	0.110/0.110/0.110
乙酸甲酯	C—O_1/2	0.144/0.136	0.143/0.136
	C—C	0.150	0.150
	CO	0.122	0.122
	C—H_1/2/3	0.109/0.109/0.109	0.109/0.109/0.109
	C—H_4/5/6	0.109/0.110/0.110	0.109/0.109/0.109

掺杂方式	掺杂结合能（kJ/mol）
掺杂方式	Ca, M=0	Ca, M=Zn	Ca, M=La	Ca, M=Mg
Ca 取代 Al_3c-1, M 取代 Al_5c-1	215.03 215.03	969.33	151.23	652.17
Ca 取代 Al_3c-1, M 取代 Al_4c-1	215.03 215.03	982.20	284.34	688.67
Ca 取代 Al_4c-1, M 取代 Al_3c-1	294.06 294.06	1037.07	310.07	728.05
Ca 取代 Al_4c-1, M 取代 Al_5c-1	294.06 294.06	893.98	228.42	721.49
Ca 取代 Al_5c-1, M 取代 Al_4c-1	214.50 214.50	970.12	242.60	676.59
Ca 取代 Al_5c-1, M 取代 Al_3c-1	214.50 214.50	960.15	213.98	643.25

掺杂方式	掺杂结合能（kJ/mol）
掺杂方式	Ca, M=0	Ca, M=Zn	Ca, M=La	Ca, M=Mg
Ca 取代 Al_3c-1, M 取代 Al_5c-1	215.03 215.03	969.33	151.23	652.17
Ca 取代 Al_3c-1, M 取代 Al_4c-1	215.03 215.03	982.20	284.34	688.67
Ca 取代 Al_4c-1, M 取代 Al_3c-1	294.06 294.06	1037.07	310.07	728.05
Ca 取代 Al_4c-1, M 取代 Al_5c-1	294.06 294.06	893.98	228.42	721.49
Ca 取代 Al_5c-1, M 取代 Al_4c-1	214.50 214.50	970.12	242.60	676.59
Ca 取代 Al_5c-1, M 取代 Al_3c-1	214.50 214.50	960.15	213.98	643.25

吸附位置	H—O键长/nm	H—M键长/nm	吸附能/ (kJ/mol)
钙催化剂表面	0.140	0.107	-137.051
钙锌催化剂表面	0.151	0.103	-164.094
钙镧催化剂表面	0.149	0.104	-136.001
钙镁催化剂表面	0.148	0.105	-158.318