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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参考文献 36

1	ELIOT EDLING H， MONDSCHEIN R J， DAVIS M K，et al.Amorphous copolyesters based on bibenzoic acids and neopentyl gly-
	col［J］.Journal of Polymer Science Part A：Polymer Chemistry，2019，57（5）：579-587.
2	AZIZ N A M， YUNUS R， RASHID U，et al.Temperature effect on tribological properties of polyol ester-based environmentally adapt-
	ed lubricant［J］.Tribology International，2016，93：43-49.
3	SUZUKI H， KAIZUKA Y， TATSUTA M，et al.Neopentyl glycol as a scaffold to provide radiohalogenated theranostic pairs of high in vivo stability［J］.Journal of Medicinal Chemistry，2021，64（21）：15846-15857.
4	SERRANO A， DAUVERGNE J L， DOPPIU S，et al.Neopentyl glycol as active supporting media in shape-stabilized PCMs［J］.Materials，2019，12（19）.Doi：10.3390/ma12193169 . doi: 10.3390/ma12193169
5	BOUSCHER R F.Advancements in powder coating processing and in real-time film formation analysis of thermoset coatings［D］.Akron：The University of Akron，2021.
6	ZHOU R， MU J， SUN X，et al.Application of intumescent flame retardant containing aluminum diethyphosphinate，neopentyl glycol，and melamine for polyethylene［J］.Safety Science，2020，131.Doi：10.1016/j.ssci.2020.104849 . doi: 10.1016/j.ssci.2020.104849
7	RAOF N A， YUNUS R， RASHID U，et al.Palm-based neopentyl glycol diester：A potential green insulating oil［J］.Protein and Peptide Letters，2018，25（2）：171-179.
8	王帅.2021年中国新戊二醇五大数据关注点［EB/OL］.［2021-02-18］..
	WANG Shuai.Five data focus of China′ s neopentyl glycol in
	2021［EB/OL］.［2021-02-18］..
9	郑磊，岳金彩，王宁，等.2，2-二甲基-1，3-环氧丙烷水解制取新戊二醇工艺优化［J］.现代化工，2019，39（4）：221-224.
	ZHENG Lei， YUE Jincai， WANG Ning，et al.Process optimization for preparing neopentyl glycol by hydrolysis of 2，2-dimethyl-1，3-epoxypropane［J］.Modern Chemical Industry，2019，39（4）：221-224.
10	季维鹏.催化加氢制新戊二醇研究［D］.上海：华东理工大学，2012.
	JI Weipeng.The study of catalysis and hydrogenation to neopentyl glycol［D］.Shanghai：East China University of Science and Technology，2012.
11	郝庆亮.新戊二醇行业发展分析［J］.精细与专用化学品，2017，25（12）：5-8.
	HAO Qingliang.Development analysis of neopentyl glycol industry［J］.Fine and specialty Chemicals，2017，25（12）：5-8.
12	王建爽.羟基新戊醛加氢催化剂的制备及其反应性能研究［D］.青岛：青岛科技大学，2020.
	WANG Jianshuang.Preparation and reactivity of hydroxyl neopentaldehyde hydrogenation catalyst［D］.Qingdao：Qingdao University of Science and Technology，2020.
13	YANG A， YANG X， YUE J，et al.Facile and rapid synthesis of neopentyl glycol in a continuous-flow microreactor［J］.Chemical Engineering & Technology，2022，45（1）：6-14.
14	WEI X， WANG Y， YAN H，et al.A sustainable valorization of neopentyl glycol salt waste containing sodium formate via bipolar membrane electrodialysis［J］.Separation and Purification Technology，2021，254.Doi：10.1016/j.seppur.2020.117563 . doi: 10.1016/j.seppur.2020.117563
15	谢晓梅.新戊二醇生产污水预处理及深度处理工艺研究［D］.青岛：青岛科技大学，2016.
	XIE Xiaomei.Study on pretreatment and advanced treatment tech-
	nology of neopentyl glycol production wastewater［D］.Qingdao：Qingdao University of Science and Technology，2016.
16	刘丹.羟基新戊醛加氢制新戊二醇Ni/Al₂O₃催化剂的研究［D］.上海：华东理工大学，2015.
	LIU Dan.Study on Ni/Al₂O₃ catalyst for hydrogenation of hydroxypivalaldehyde to neopentyl glycol［D］.Shanghai：East China University of Science and Technology，2015.
17	王广建，王建爽，王芳，等.B助剂对Cu基催化剂羟基新戊醛加氢反应性能的影响［J］.当代化工，2021，50（1）：55-59.
	WANG Guangjian， WANG Jianshuang， WANG Fang，et al.Effect of B additive on the performance of Cu-based catalyst for hydrogenation of hydroxypivalaldehyde［J］.Contemporary Chemical Industry，2021，50（1）：55-59.
18	李吉明，庄怀鹏，刘亚楠.绿色加氢合成新戊二醇的一锅法合成［J］.当代化工，2020，49（6）：1031-1034.
	LI Jiming， ZHUANG Huaipeng， LIU Yanan.One-pot synthesis of neopentyl glycol by green hydrogenation process［J］.Contemporary Chemical Industry，2020，49（6）：1031-1034.
19	MONASTERSKA E， CHROBOK A， PANKALLA E，et al.Development of methods for the synthesis of neopentyl glycol by hydrogenation of hydroxypivaldehyde［J］.Molecules，2021，26（19）.Doi：10.3390/molecules 26195822 . doi: 10.3390/molecules 26195822
20	TIKE M A， GHARDE A M， MAHAJANI V V.Studies to aid process development for the manufacture of neopentyl glycol from isobutyraldehyde：Aldol condensation followed by hydrogenation［J］.Asia-Pacific Journal of Chemical Engineering，2008，3（3）：333-346
21	SCHALAPSKI K， KRETZ T， KREICKMANN T，et al.Method of
	producing neopentyl glycol：US，08394998［P］.2013-03-12.
22	EISENACHER M， SCHALAPSKI K， HEYMANNS P，et al.Continuous method for the production of neopentyl glycol：US，9133083［P］.2015-09-15.
23	吴文娟，孙卫中，戴成勇，等.甲醛和异丁醛缩合加氢合成新戊二醇的研究［J］.化学世界，2015，56（1）：42-46.
	WU Wenjuan， SUN Weizhong， DAI Chengyong，et al.Studies on the synthesis of neopentyl glycol via condensation and hydrogenation of formaldehyde and isobutyraldehyde［J］.Chemical World，2015，56（1）：42-46.
24	MICHALSKA K， KOWALIK P， PRÓCHNIAK W，et al.The effect of La₂O₃ on Ni/Al₂O₃ catalyst for methanation at very low CO _x /H₂ ratio［J］.Catalysis Letters，2018，148（3）：972-978.
25	HONGLOI N， PRAPAINAINAR P， SEUBSAI A，et al.Nickel catalyst with different supports for green diesel production［J］.Energy，2019，182：306-320.
26	YAO D， YANG H， CHEN H，et al.Co-precipitation，impregnation and sol-gel preparation of Ni catalysts for pyrolysis-catalytic steam reforming of waste plastics［J］.Applied Catalysis B：Environmental，2018，239：565-577.
27	PINTON N， VIDAL M V， SIGNORETTO M，et al.Ethanol steam reforming on nanostructured catalysts of Ni，Co and CeO₂：Influence of synthesis method on activity，deactivation and regenerability［J］.Catalysis Today，2017，296：135-143.
28	SRIDEVI A， KRISHNAMOHAN S， THAIRIYARAJA M，et al.Visible-light driven γ-Al₂O₃，CuO and γ-Al₂O₃/CuO nanocataly- doi: 10.1016/j.inoche
	sts：Synthesis and enhanced photocatalytic activity［J］.Inorganic Chemistry Communications，2022，138.Doi：10.1016/j.inoche . doi: 10.1016/j.inoche
	2022.109311. doi: 10.1016/j.inoche
29	PONGSIRIYAKUL K， KIATKITTIPONG W， ADHIKARI S，et al.Effective Cu/Re promoted Ni-supported γ-Al₂O₃ catalyst for upgrading algae bio-crude oil produced by hydrothermal liquefaction［J］.Fuel Processing Technology，2021，216.Doi：10.1016/j.fuproc.2020.106670 . doi: 10.1016/j.fuproc.2020.106670
30	SALHI N， PETIT C， KIENNEMANN A.Steam reforming of methane on nickel aluminate defined structures with high Al/Ni-
	ratio［J］.Studies in Surface Science and Catalysis，2008，174：1335-1338.
31	BAGABAS A， AL-FATESH A S， KASIM S O，et al.Optimizing MgO content for boosting γ-Al₂O₃-supported Ni catalyst in dry reforming of methane［J］.Catalysts，2021，11（10）.Doi：10.3390/catal 11101233 . doi: 10.3390/catal 11101233
32	蔡秀兰，林维明.掺杂助剂Ce和Zr的Ni/Al₂O₃催化剂的X光电子能谱分析［J］.分析测试学报，2013，32（2）：253-256.
	CAI Xiulan， LIN Weiming.Study on Ni/Al₂O₃ catalyst doped with Ce and Zr by XPS［J］.Journal of Instrumental Analysis，2013，32（2）：253-256.
33	GRAŽĖNAITĖ E.Inorganic green pigments：Investigation of historical and synthesis of novel pigments by sol-gel method［D］.Vilnius：Vilnius University，2018.
34	袁利静，孟现洁，冯军鹏，等.不同镍含量钨基碳化态催化剂对十氢萘加氢开环的影响［J］.石油炼制与化工，2019，50（5）：18-23.
	YUAN Lijing， MENG Xianjie， FENG Junpeng，et al.Effect of different nickel content on ring opening of decalin of tungsten-based carbide catalysts［J］.Petroleum Processing and Petrochemicals，2019，50（5）：18-23.
35	PENG H， ZHANG X， HAN X，et al.Catalysts in coronas：A surface spatial confinement strategy for high-performance catalysts in methane dry reforming［J］.ACS Catalysis，2019，9（10）：9072-9080.
36	YONEOKA M， WATABE K， MATSUDA G.Process for producing neopentyl glycol：US，5395989［P］.1995-03-07.

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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