Zn(Al)O复合氧化物负载Au催化剂催化氧化甘油制备1,3-二羟基丙酮

doi:10.16085/j.issn.1000-6613.2020-1243

摘要/Abstract

摘要：

以尿素为沉淀剂，采用均匀沉积沉淀法制备了Zn(Al)O复合氧化物负载Au催化剂，并用于无碱条件下催化氧化甘油制备1,3-二羟基丙酮（DHA）反应，值得注意的是随着载体中Zn/Al摩尔比的不同，负载Au催化剂的催化活性和产物DHA的选择性呈现明显差距。结合X射线衍射（XRD）、X射线光电子能谱（XPS）、透射电镜（TEM）、CO吸附傅里叶变换红外光谱（CO吸附FTIR）等表征手段，发现载体Zn(Al)O复合氧化物中Zn/Al摩尔比会影响表面氧物种的含量并进一步会影响催化剂的催化活性和选择性。当Zn/Al摩尔比为7∶1、反应温度为80℃、氧气压力为10bar、反应2h时获得最佳的甘油转化率（58.5%）和DHA的选择性（95.3%）。同时，还考察了反应温度、反应时间、反应压力及载体的焙烧温度对催化性能的影响，并发现反应条件对催化剂的催化活性和选择性均有不同程度的影响。此外，以Au/Zn(Al)O-7∶1催化剂为基准考察了催化剂的稳定性，并通过表征手段分析了催化剂失活的主要原因。

关键词: 甘油, 1,3-二羟基丙酮, 催化, 氧化, 活性, 选择性, 催化剂载体, 负载Au催化剂

Abstract:

A series of Zn(Al)O composite oxides supported Au catalysts were prepared by deposition-precipitation with urea. Interestingly, the catalysts with varied Zn/Al molar ratios showed different catalytic performance for selective catalytic oxidation of glycerol to 1,3-dihydroxyacetone (DHA) without base. The physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), CO adsorbed Fourier transform infrared (FTIR) spectroscopy. The results showed that the molar ratio of Zn/Al in the Zn(Al)O composite metal oxide affected the content of the reactive oxygen species and in turn the catalytic activity of glycerol oxidation. When the molar ratio of Cu/Al reached 7∶1, the supported catalyst showed the best performance, i.e. the conversion of glycerol and product selectivity of DHA reached 58.5% and 95.3% respectively with the initial O₂ pressure of 10bar, at 80℃ for 2h. Then, the Au/Zn(Al)O-7∶1 catalyst was used to investigate the effects of reaction temperature, reaction time, reaction pressure and calcination temperature of supports on the catalytic oxidation of glycerol and the selectivity for DHA. Additionally, we also studied the stability of the Au/Zn(Al)O-7∶1 catalyst and discussed the deactivation reasons.

Key words: glycerol, 1,3-dihydroxyacetone, catalysis, oxidation, reactivity, selectivity, catalyst support, supported Au catalysts

中图分类号:

O643.36⁺1

柯义虎, 李景云, 刘春玲, 董文生, 刘海. Zn(Al)O复合氧化物负载Au催化剂催化氧化甘油制备1,3-二羟基丙酮[J]. 化工进展, 2021, 40(5): 2581-2592.

KE Yihu, LI Jingyun, LIU Chunling, DONG Wensheng, LIU Hai. Zn(Al)O composite oxides supported Au catalysts for selective oxidation of glycerol to 1, 3-dihydroxyacetone[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2581-2592.

图/表 18

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催化剂	Au负载量/%	Zn质量分数/%	Al质量分数/%	Au/Al原子比	Zn/Al原子比	S_BET /m²·g^-1	V_p/m³·g^-1	D_p/nm
Au/Zn(Al)O-1	1.37	33.4	12.8	0.015	1.08	113.8	0.16	7.7
Au/Zn(Al)O-2	1.21	41.1	7.6	0.022	2.23	66.2	0.21	13.6
Au/Zn(Al)O-3	1.15	46.5	5.6	0.028	3.45	37.7	0.20	22.3
Au/Zn(Al)O-4	1.33	54.0	3.6	0.051	6.23	34.9	0.21	25.0
Au/Zn(Al)O-5	1.43	60.2	2.6	0.075	9.58	30.7	0.17	22.5
Au/Zn(Al)O-6	1.14	64.9	2.2	0.071	12.25	28.9	0.17	22.9

催化剂	Au负载量/%	Zn质量分数/%	Al质量分数/%	Au/Al原子比	Zn/Al原子比	S_BET /m²·g^-1	V_p/m³·g^-1	D_p/nm
Au/Zn(Al)O-1	1.37	33.4	12.8	0.015	1.08	113.8	0.16	7.7
Au/Zn(Al)O-2	1.21	41.1	7.6	0.022	2.23	66.2	0.21	13.6
Au/Zn(Al)O-3	1.15	46.5	5.6	0.028	3.45	37.7	0.20	22.3
Au/Zn(Al)O-4	1.33	54.0	3.6	0.051	6.23	34.9	0.21	25.0
Au/Zn(Al)O-5	1.43	60.2	2.6	0.075	9.58	30.7	0.17	22.5
Au/Zn(Al)O-6	1.14	64.9	2.2	0.071	12.25	28.9	0.17	22.9

催化剂	Au 4f_7/2结合能/eV	Zn 2p_3/2结合能/eV	Al 2p_3/2结合能/eV	O 1s结合能/eV	Au/Al原子比	Zn/Al原子比
Au/Zn(Al)O-1	83.57	1021.86	74.01	530.61	0.023	0.148
Au/Zn(Al)O-2	83.48	1021.73	74.15	531.84	0.044	0.294
Au/Zn(Al)O-3	83.41	1021.73	74.19	530.13	0.087	0.583
Au/Zn(Al)O-4	83.43	1021.71	74.33	530.15	0.180	1.060
Au/Zn(Al)O-5	83.51	1021.83	74.55	530.25	1.431	9.73
Au/Zn(Al)O-6	83.54	1021.64	74.70	530.10	0.102	1.172

催化剂	Au 4f_7/2结合能/eV	Zn 2p_3/2结合能/eV	Al 2p_3/2结合能/eV	O 1s结合能/eV	Au/Al原子比	Zn/Al原子比
Au/Zn(Al)O-1	83.57	1021.86	74.01	530.61	0.023	0.148
Au/Zn(Al)O-2	83.48	1021.73	74.15	531.84	0.044	0.294
Au/Zn(Al)O-3	83.41	1021.73	74.19	530.13	0.087	0.583
Au/Zn(Al)O-4	83.43	1021.71	74.33	530.15	0.180	1.060
Au/Zn(Al)O-5	83.51	1021.83	74.55	530.25	1.431	9.73
Au/Zn(Al)O-6	83.54	1021.64	74.70	530.10	0.102	1.172

催化剂	转化率 /%	选择性/%				转换频率 /s^-1
催化剂	转化率 /%	草酸	甘油酸	乙醇酸	DHA	转换频率 /s^-1
Au/Zn(Al)O-1	28.9	1.8	2.4	2.4	93.4	0.0143
Au/Zn(Al)O-2	32.6	0.8	4.5	5.6	89.1	0.0339
Au/Zn(Al)O-3	48.2	0.6	2.0	5.8	91.6	0.0343
Au/Zn(Al)O-4	51.3	0.6	1.6	5.7	92.2	0.0302
Au/Zn(Al)O-5	58.5	0.4	0.9	3.4	95.3	0.0393
Au/Zn(Al)O-6	54.4	0.5	1.2	5.0	93.3	0.0459