镍/氧化铝加氢催化剂的制备及性能研究

doi:10.19964/j.issn.1006-4990.2022-0080

摘要/Abstract

摘要：

羟基新戊醛（HPA）的加氢多采用贵金属和铜系催化剂，为了更好地降低催化剂生产成本和操作成本，分别对比了共沉淀法和浸渍法制备的镍/氧化铝催化剂，并以HPA为原料，在固定床装置上考察了系列催化剂加氢合成新戊二醇（NPG）的催化性能。采用X射线衍射（XRD）、氮气物理吸附（BET）、一氧化碳脉冲吸附等方法进行表征，结果表明，浸渍法制备的20%镍/氧化铝催化剂，比表面积较大，金属分散性好，且催化剂中的镍物种易被还原，其反应性能良好。在相对较温和的反应条件下，即反应温度为103 ℃、反应压力为3 MPa、液时空速为1 h^-1、氢醛物质的量比为10时，HPA转化率为100%，NPG选择性为99.3%。在1 000 h的长周期评价过程中，该催化剂保持了较好的活性，具有更好的工业化前景。

关键词: 羟基新戊醛, 加氢, 镍催化剂, 新戊二醇

Abstract:

Noble metals and copper-based catalysts had been often used for the hydrogenation of hydroxypivaldehyde（HPA）.In order to better reduce the production cost and operation cost of catalysts，Ni/Al₂O₃ prepared by co-precipitation method and impregnation method were compared respectively，and the catalytic performance of a series of catalysts for the hydrogenation of HPA as raw materials to neopentyl glycol（NPG） was investigated in a fixed bed reactor.X-ray diffraction（XRD），N₂ physical adsorption（BET） and CO pulse adsorption were used for characterization.The results showed that 20%Ni/Al₂O₃ catalyst prepared by impregnation method had a good catalytic performance，which had a large specific surface area，good metal dispersion and the nickel species in the catalyst could be easily reduced，which had good reaction performance.Under relatively mild reaction conditions that reaction temperature of 103 ℃，reaction pressure of 3 MPa，liquid hourly space velocity of 1 h^-1 and the ratio of hydrogen to aldehyde of 10，the conversion of HPA was 100% and the selectivity of NPG was 99.3%.In the long-term evaluation process of 1 000 h，the catalyst maintained good activity and had better industrial prospect.

Key words: hydroxypivaldehyde, hydrogenation, nickel catalyst, neopentyl glycol

中图分类号:

TQ223.162

杨文龙,程鹏,卢雁飞,南芷钰,李宇航,李世松,王春雷,舒畅,张东升. 镍/氧化铝加氢催化剂的制备及性能研究[J]. 无机盐工业, 2022, 54(7): 141-148.

YANG Wenlong,CHENG Peng,LU Yanfei,NAN Zhiyu,LI Yuhang,LI Shisong,WANG Chunlei,SHU Chang,ZHANG Dongsheng. Study on preparation and performance of Ni/Al₂O₃ hydrogenation catalyst[J]. Inorganic Chemicals Industry, 2022, 54(7): 141-148.

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催化剂种类	理论值 w（NiO）/%	实测值
催化剂种类	理论值 w（NiO）/%	w（NiO）/%	w（Al₂O₃）/%	w（其他）/%
20%Ni/Al₂O₃^a	20.3	21.2	77.2	1.6
40%Ni/Al₂O₃^a	33.7	33.9	64.6	1.5
20%Ni/Al₂O₃^b	20.3	21.1	77.9	1.0
商用催化剂	—	78.7	20.2	1.1

催化剂种类	比表面积/（m²·g^-1）	孔容/ （cm³·g^-1）	孔径/ nm
20%Ni/Al₂O₃^a	211	0.370 5	9.4
40%Ni/Al₂O₃^a	189	0.495 7	7.4
20%Ni/Al₂O₃^b	200	0.523 9	15.2
商用催化剂	133	0.251 0	7.7

催化剂	累积吸附量/（cm³·g^-1）	金属分散度/%
20%Ni/Al₂O₃^a	0.960 7	1.258 2
40%Ni/Al₂O₃^a	0.668 7	0.437 9
20%Ni/Al₂O₃^b	1.270 6	1.664 1
商用催化剂	0.468 5	0.405 6

催化剂种类	反应后溶液中w（Ni²⁺）/10^-6	取反应液质量/g	稀释倍数
20%Ni/Al₂O₃^a	0.635 0	1.025 9	200
40%Ni/Al₂O₃^a	0.626 3	1.000 3	200
20%Ni/Al₂O₃^b	0.514 8	1.042 2	200
商用催化剂	0.786 5	0.999 8	200

催化剂	反应温度/℃	反应压力/MPa	HPA转化率/%	NPG选择性/%	NPG收率/%
20%Ni/Al₂O₃	103	3	100	99.3	99.3
雷尼镍^［21］	130	8	98	98	96
Cu-Zn-Al^［10］	130	3	100	97	97
Cu-Zn-Zr^［36］	100	3.5	97	99	96
BaMn/CuCrO₄^［22］	155	0.08	100	99	99
Pd/C^［18］	95	4	99.9	94.7	94.6
Ru/Al₂O₃^［20］	120	5.44	—	99	—

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