Ni/WO<sub>3</sub>-ZrO<sub>2</sub>催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究

严亚韩; 吴潘; 何坚; 蒋炜; 刘长军; 梁斌

doi:10.12434/j.issn.2097-2547.20250117

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Ni/WO₃-ZrO₂催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究

低碳分子转化合成 | 更新时间：2026-02-02

- Ni/WO₃-ZrO₂催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究
- Study on hydroisomerization of 1,4-butenediol to 2-hydroxytetrahydrofuran catalyzed by Ni/WO₃-ZrO₂ and its reaction kinetics
- 低碳化学与化工 2026, 51(1): 63-72.
- 作者机构：
  
  1.四川大学化学工程学院，四川成都 610207
  2.四川大学新能源与低碳技术研究院，四川成都 610207
- 作者简介：
  
  严亚韩（2000—），硕士研究生，研究方向为多相催化，E-mail：yahanyan2020@163.com。
  刘长军（1979—），博士，副教授，研究方向为多相催化、化工新工艺，E-mail：liuchangjun@scu.edu.cn。
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250117
  中图分类号： TQ426;O643.3
- 收稿：2025-03-18，
  
  修回：2025-04-15，
  
  纸质出版：2026-01-25
- 稿件说明：
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严亚韩,吴潘,何坚等.Ni/WO₃-ZrO₂催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究[J].低碳化学与化工,2026,51(1):63-72.

YAN Yahan,WU Pan,HE Jian,et al.Study on hydroisomerization of 1,4-butenediol to 2-hydroxytetrahydrofuran catalyzed by Ni/WO₃-ZrO₂ and its reaction kinetics[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(1):63-72.
严亚韩,吴潘,何坚等.Ni/WO₃-ZrO₂催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究[J].低碳化学与化工,2026,51(1):63-72. DOI： 10.12434/j.issn.2097-2547.20250117.

YAN Yahan,WU Pan,HE Jian,et al.Study on hydroisomerization of 1,4-butenediol to 2-hydroxytetrahydrofuran catalyzed by Ni/WO₃-ZrO₂ and its reaction kinetics[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(1):63-72. DOI： 10.12434/j.issn.2097-2547.20250117.

摘要

2-羟基四氢呋喃（2-HTHF）是重要的精细化工原料，构建金属中心和酸中心强度可控的双功能催化剂是经顺-1

4-丁烯二

醇（

cis

-BED）临氢异构制2-HTHF的关键。采用等体积浸渍法制备了一系列Ni/WO

-ZrO

双功能催化剂，其结构经NH

-TPD、XPS和XRD等表征。分析了还原温度、还原时间、Ni和WO

负载量（质量分数）及Ni和WO

分散性等因素对催化剂结构和催化性能的影响，并研究了优选催化剂在设定条件下催化

cis

-BED临氢异构反应的动力学。结果表明，在催化剂用量为0.2 g、反应温度为200 ℃、H

压力为0.4 MPa和气时空速为37.8 L/(g·h)的条件下，600 ℃下还原2 h所得10%Ni/20%WO

-ZrO

-HT（Ni、WO

负载量分别为10%、20%）的催化性能最佳，其

cis

-BED转化率和2-HTHF选择性分别为67.9%和30.1%。建立的反应网络和反应动力学模型能够较好地描述10%Ni/20%WO

-ZrO

-HT催化的

cis

-BED临氢异构反应过程，即

cis

-BED异构化生成2-HTHF的主要路径是

cis

-BED先转化为反-1

4-丁烯二醇，再异构化为2-HTHF。

Abstract

2-hydroxytetrahydrofuran (2-HTHF) is an important fine chemical material. The key to 2-HTHF production via hydroisomerization of

cis

-1

4-butenediol (

cis

-BED) lies in constructing the bifunctional catalyst with controllable metal center and acid strength. A series of Ni/WO

-ZrO

bifunctional catalysts were prepared by incipient wetness impregnation method and their structures were characterized by NH

-TPD

XPS

XRD

etc. The effects of reduction temperatures

reduction time

loading amounts of Ni and WO

and dispersions of Ni and WO

on the structures and catalytic performances of catalysts were investigated. Additionally

the kinetics of the

cis

-BED hydroisomerization reaction over the optimal catalyst under specified conditions were studied. The results show that under the conditions of catalyst dosage of 0.2 g

reaction temperature of 200 ℃

pressure of 0.4 MPa and gas hourly space velocity of 37.8 L/(g·h)

10%Ni/20%WO

-ZrO

-HT (loading amounts of Ni and WO

are 10% and 20%

respectively) obtained by reducing at 600 ℃ for 2 h exhibits the best catalytic performance with

cis

-BED conversion rate of 67.9% and 2

-HTHF selectivity of 30.1%

respectively. The established reaction network and kinetic model can effectively describ the

cis

-BED hydroisomerization process catalyzed by 10%Ni/20%WO

-ZrO

-HT

revealing that the primary pathway for 2-HTHF formation involves the isomerization of

cis

-BED to

trans

-1

4-butenediol

follows by its further conversion to 2-HTHF.

关键词

Keywords

references

LEITE L , STONKUS V , EDOLFA K , et al . Active phases of supported cobalt catalysts for 2,3-dihydrofuran synthesis [J ] . Journal of Molecular Catalysis A: Chemical , 2004 , 215 ( 1/2 ): 95 - 101 .

LEBEDEV A , LEITE L , FLEISHER M , et al . Tautomerism and vapor-phase transformations of 2-hydroxytetrahydrofuran [J ] . Chemistry of Heterocyclic Compounds , 2000 , 36 ( 7 ): 775 - 778 .

MUSOLINO M G , APA G , DONATO A , et al . Supported palladium catalysts for the selective conversion of cis -2-butene-1,4-diol to 2-hydroxytetrahydrofuran: Effect of metal particle size and support [J ] . Applied Catalysis A: General , 2007 , 325 ( 1 ): 112 - 120 .

TAKESHI O . Preparation of 2 -hydroxytetrahydrofuran : JPS5425017B2 [P ] . 1974-04-27 .

LIN J , KNIFTON J F . Hydroformylation of allyl alcohol : EP0150943A2 [P ] . 1985-08-07 .

刘响 , 廖启江 , 张敏卿 . 1,4-丁炔二醇加氢过程研究进展 [J ] . 化工进展 , 2017 , 36 ( 8 ): 2787 - 2797 .

LIU X , LIAO Q J , ZHANG M Q . Research progress of 1,4-butynediol hydrogenation process [J ] . Chemical Industry and Engineering Progress , 2017 , 36 ( 8 ): 2787 - 2797 .

周港 , 谭平华 , 吴潘 , 等 . 1,4-丁炔二醇选择性加氢催化剂：Pd/ZrO 2 及其碱金属改性 [J ] . 精细化工 , 2024 , 41 ( 3 ): 640 - 648 .

ZHOU G , TAN H P , WU P , et al . Selective hydrogenation of 1,4-butynediol to 1,4-butenediol: Pd/ZrO 2 catalyst and alkali metals modification [J ] . Fine Chemicals , 2024 , 41 ( 3 ): 640 - 648 .

MUSOLINO M G , CAIA C V , MAURIELLO F , et al . Hydrogenation versus isomerization in the reaction of cis -2-butene-1,4-diol over supported catalysts: The role of group VIII transition metals in driving the products selectivity [J ] . Applied Catalysis A: General , 2010 , 390 ( 1/2 ): 141 - 147 .

TELKAR M M , RODE C V , JAGANATHAN R , et al . Platinum catalyzed hydrogenation of 2-butyne-1,4-diol [J ] . Journal of Molecular Catalysis A: Chemical , 2002 , 187 ( 1 ): 81 - 93 .

TANIELYAN S , SCHMIDT S , MARIN N , et al . Selective hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol over particulate Raney ® nickel catalysts [J ] . Topics in Catalysis , 2010 , 53 ( 15/16/17/18 ): 1145 - 1149 .

赵芳 . Ni/SiO 2 中Ni存在状态的调控及催化1,4-丁炔二醇加氢反应的研究 [D ] . 太原 : 山西大学 , 2019 .

ZHAO F . Study on the regulation of the presence of Ni in Ni/SiO 2 and catalytic hydrogenation of 1,4-butynediol [D ] . Taiyuan : Shanxi University , 2019 .

MUSOLINO M G , CUTRUPI C M S , DONATO A , et al . Liquid phase hydrogenation of 2-butyne-1,4-diol and 2-butene-1,4-diol isomers over Pd catalysts: Roles of solvent, support and proton on activity and products distribution [J ] . Journal of Molecular Catalysis A: Chemical , 2003 , 195 ( 1/2 ): 147 - 157 .

万晶晶 . 1,4-丁炔二醇可控加氢催化剂的研究 [D ] . 厦门 : 厦门大学 , 2020 .

WAN J J . Study on the controllable hydrogenation catalyst of 1,4-butynediol [D ] . Xiamen : Xiamen University , 2020 .

URZHUNTSEV G A , KODENEV E G , ECHEVSKII G V . Prospects for using Mo- and W-containing catalysts in hydroisomerization: A patent review. II: Catalysts based on molybdenum and tungsten carbides [J ] . 2016 , 8 ( 3 ): 224 - 230 .

BENADDA A , KATRIB A , SOBCZAK J W , et al . Hydroisomerization of n -heptane and dehydration of 2-propanol on bulk and supported WO 2 (H x ) ac on TiO 2 [J ] . Applied Catalysis A: General , 2004 , 260 ( 2 ): 175 - 183 .

LYU Y C , YU Z M , YANG Y , et al . Metal-acid balance in the in-situ solid synthesized Ni/SAPO-11 catalyst for n -hexane hydroisomerization [J ] . Fuel , 2019 , 243 : 398 - 405 .

GARCIA-PEREZ D , LOPEZ-GARCIA A , RENONES P , et al . Influence of nickel loading on the hydroisomerization of n -dodecane with nickel-tungsten oxide-alumina supported catalysts [J ] . Molecular Catalysis , 2022 , 529 : 112556 .

王菊霞 . Ni/SiO 2 催化剂上1,4-丁烯二醇加氢/异构反应性能 [D ] . 太原 : 山西大学 , 2020 .

WANG J X . Study on hydrogenation/isomerization of 1,4-butenediol over Ni/SiO 2 catalyst [D ] . Taiyuan : Shanxi University , 2020 .

KAIM J , SLIWA M , KUTERASINSKI L , et al . Gas-phase hydrogenation and decarbonylation of furfuryl aldehyde over catalysts containing Cu and Ni [J ] . Catalysis Today , 2024 , 441 : 114897 .

ORTEGA-DOMÍNGUEZ R A , VARGAS-VILLAGRÁN H , PEÑALOZA-ORTA C , et al . A facile method to increase metal dispersion and hydrogenation activity of Ni/SBA-15 catalysts [J ] . Fuel , 2017 , 198 : 110 - 122 .

MIYAZAKI S , LI Z , LI L , et al . Chemical looping dry reforming of methane over Ni-modified WO 3 /ZrO 2 : Cooperative work of dispersed tungstate species and Ni over the ZrO 2 surface [J ] . Energy & Fuels , 2023 , 37 ( 11 ): 7945 - 7957 .

SMOLIKOV M D , SHKURENOK V A , KIR’YANOV D I , et al . Active surface formation of tungstated zirconia catalysts for n -heptane isomerization [J ] . Catalysis Today , 2019 , 329 : 63 - 70 .

SCHEITHAUER M , GRASSELLI R K , KNOZINGER H . Genesis and structure of WO x /ZrO 2 solid acid catalysts [J ] . Langmuir , 1998 , 14 ( 11 ): 3019 - 3029 .

LIU C J , SUN J M , BROWN H M , et al . Aqueous phase hydrodeoxygenation of polyols over Pd/WO 3 -ZrO 2 : Role of Pd-WO 3 interaction and hydrodeoxygenation pathway [J ] . Catalysis Today , 2016 , 269 : 103 - 109 .

BARTON D G , SHTEIN M , WILSON R D , et al . Structure and electronic properties of solid acids based on tungsten oxide nanostructures [J ] . The Journal of Physical Chemistry B , 1999 , 103 ( 4 ): 630 - 640 .

ROSS-MEDGAARDEN E I , WACHS I E . Structural determination of bulk and surface tungsten oxides with UV-Vis diffuse reflectance spectroscopy and Raman spectroscopy [J ] . The Journal of Physical Chemistry C , 2007 , 111 ( 41 ): 15089 - 15099 .

BERGUERAND C , YURANOV I , CÁRDENAS-LIZANA F , et al . Size-controlled Pd nanoparticles in 2-butyne-1,4-diol hydrogenation: Support effect and kinetics study [J ] . The Journal of Physical Chemistry C , 2014 , 118 ( 23 ): 12250 - 12259 .

TANIELYAN S K , MORE S R , AUGUSTINE R L , et al . Continuous liquid-phase hydrogenation of 1,4-butynediol to high purity 1,4-butanediol over particulate raney nickel catalyst in a fixed bed reactor [J ] . Organic Process Research & Development , 2017 , 21 ( 3 ): 327 - 335 .

RODE C V , TAYADE P R , NADGERI J M , et al . Continuous hydrogenation of 2-butyne-1,4-diol to 2-butene- and butane-1,4-diols [J ] . Organic Process Research & Development , 2006 , 10 ( 2 ): 278 - 284 .

KIWI-MINSKER L , JOANNET E , RENKEN A . Solvent-free selective hydrogenation of 2-butyne-1,4-diol over structured palladium catalyst [J ] . Industrial & Engineering Chemistry Research , 2005 , 44 ( 16 ): 6148 - 6153 .

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Ni/WO3-ZrO2催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究

Study on hydroisomerization of 1,4-butenediol to 2-hydroxytetrahydrofuran catalyzed by Ni/WO3-ZrO2 and its reaction kinetics

DOI：10.12434/j.issn.2097-2547.20250117

摘要

Abstract

关键词

Keywords

references

Ni/WO₃-ZrO₂催化1,4-丁烯二醇临氢异构制2-羟基四氢呋喃及其反应动力学研究

Study on hydroisomerization of 1,4-butenediol to 2-hydroxytetrahydrofuran catalyzed by Ni/WO₃-ZrO₂ and its reaction kinetics