CuO含量对Pd/Al2O3催化剂乙醇氧化性能的影响

doi:10.16085/j.issn.1000-6613.2018-1358

摘要/Abstract

摘要：

采用浸渍法制备了一系列具有不同CuO含量的Pd-CuO/Al₂O₃催化剂，并将其用于乙醇氧化反应，其结构与性质通过XRD、H₂-TPR和NH₃-TPD等手段进行分析。结果发现，催化剂的活性并不是随着CuO含量的增加而增强，Pd-1.0%CuO/Al₂O₃催化剂表现出最佳的活性，其点火温度和完全转化温度比Pd/Al₂O₃催化剂至少降低了50℃。与Pd/Al₂O₃催化剂相比，含CuO催化剂增强的衍射峰强度以及氢化钯分解峰的消失，说明Pd-Cu合金结构的形成有利于Pd、Cu物种之间的协同作用。对于Pd-1.0%CuO/Al₂O₃催化剂来说，还原峰向低温的移动以及还原峰面积的增大说明该催化剂上氧化性物质更易被还原且数量在增加，这对于氧化反应是十分有利的，新出现的还原峰表示Pd、Cu的相互作用生成了新物种。NH₃-TPD结果中更高含量的低温酸有利于高活性，而且新出现的脱附峰说明形成了新的酸性位点。

关键词: CuO含量, Pd-CuO/Al₂O₃, 醇, 氧化, Pd-Cu合金

Abstract:

A series of Pd/Al₂O₃-CuO catalysts with different CuO contents were prepared by impregnation method. The catalysts were then used in the ethanol oxidation reaction and their structures and properties were investigated by using XRD, H₂-TPR and NH₃-TPD techniques. The results showed that the reactivity was not always enhanced with the increase of CuO contents. The Pd-1.0%CuO/Al₂O₃ catalyst showed the best performance whose T ₅₀ and T ₉₀ decreased more than 50℃ in comparison with Pd/Al₂O₃. Compared to Pd/Al₂O₃ catalyst, catalysts with CuO showed an enhancement in diffraction peak intensity but no decomposition of palladium hydride, indicating that the Pd-Cu alloy structure was formed leading to the synergistic effect between Pd and Cu species. For Pd-1.0%CuO/Al₂O₃, the shift of reduction peak to low temperatures and the increase in area demonstrated the reduction of the oxidizing substances on the catalyst and the amount of them was increased which was beneficial to the oxidation reaction. The new reduction peak illustrated that the interaction between Pd and Cu had produced some new species. NH₃-TPD results showed the high content of low temperature acid was conducive to the high reactivity and the new desorption peak indicated that new acidic sites were formed on the Pd-1.0%CuO/Al₂O₃ catalyst.

Key words: CuO contents, Pd-CuO/Al₂O₃, alcohol, oxidation, Pd-Cu alloy

中图分类号:

O643.32

张申, 郭玉玉, 李星颖, 李哲. CuO含量对Pd/Al₂O₃催化剂乙醇氧化性能的影响[J]. 化工进展, 2019, 38(02): 885-891.

Shen ZHANG, Yuyu GUO, Xingying LI, Zhe LI. Effects of CuO content on the performance of Pd/Al₂O₃ catalysts in ethanol oxidation[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 885-891.

图/表 7

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催化剂	T1/℃	C1/%	T2/℃	C2/%	T3/℃	C3/%	T4/℃	C4/%	T5/℃	C5/%	T6/℃	C6/%
Pd/Al₂O₃	109	8.85	133	25.03	165	17.83	202	23.28	266	20.04	331	4.97
Pd-0.1%CuO/Al₂O₃	105	8.84	128	22.62	163	31.68	212	17.24	280	19.62	—	—
Pd-0.3%CuO/Al₂O₃	104	8.42	126	22.22	159	30.91	213	19.87	281	16.89	348	1.69
Pd-0.5%CuO/Al₂O₃	102	9.22	123	17.01	156	37.34	216	17.92	291	18.51	—	—
Pd-0.8%CuO/Al₂O₃	103	12.04	127	24.87	171	28.21	226	24.75	307	9.21	364	0.92
Pd-1.0%CuO/Al₂O₃	100	13.36	123	27.79	171	31.80	247	15.64	304	9.91	350	1.50
Pd-3.0%CuO/Al₂O₃	100	12.26	122	20.44	162	31.83	239	35.47	—	—	—	—

催化剂	T1/℃	C1/%	T2/℃	C2/%	T3/℃	C3/%	T4/℃	C4/%	T5/℃	C5/%	T6/℃	C6/%
Pd/Al₂O₃	109	8.85	133	25.03	165	17.83	202	23.28	266	20.04	331	4.97
Pd-0.1%CuO/Al₂O₃	105	8.84	128	22.62	163	31.68	212	17.24	280	19.62	—	—
Pd-0.3%CuO/Al₂O₃	104	8.42	126	22.22	159	30.91	213	19.87	281	16.89	348	1.69
Pd-0.5%CuO/Al₂O₃	102	9.22	123	17.01	156	37.34	216	17.92	291	18.51	—	—
Pd-0.8%CuO/Al₂O₃	103	12.04	127	24.87	171	28.21	226	24.75	307	9.21	364	0.92
Pd-1.0%CuO/Al₂O₃	100	13.36	123	27.79	171	31.80	247	15.64	304	9.91	350	1.50
Pd-3.0%CuO/Al₂O₃	100	12.26	122	20.44	162	31.83	239	35.47	—	—	—	—

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CuO含量对Pd/Al₂O₃催化剂乙醇氧化性能的影响

Effects of CuO content on the performance of Pd/Al₂O₃ catalysts in ethanol oxidation

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