Study on preparation of Mg-doping Cu/SiO<sub>2</sub> catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol

WANG Wenyu; WANG Xinyi; WANG Kangjun; LIU Guoguo

doi:10.12434/j.issn.2097-2547.20240357

您当前的位置：

首页 >

文章列表页 >

Study on preparation of Mg-doping Cu/SiO₂ catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol

更新时间：2025-04-27

- Study on preparation of Mg-doping Cu/SiO₂ catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol
- Vol. 50, Issue 4, Pages: 38-45(2025)
- 作者机构：
  
  沈阳化工大学化学工程学院，辽宁沈阳 110142
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240357
  CLC： TQ426.8
- Received：28 August 2024，
  
  Revised：2024-09-22，
  
  Published：25 April 2025
- 稿件说明：
移动端阅览
王文玉,王馨艺,王康军等.Mg掺杂Cu/SiO₂催化剂制备及其甲醇和乙醇合成异丁醛催化性能研究[J].低碳化学与化工,2025,50(04):38-45.

WANG Wenyu,WANG Xinyi,WANG Kangjun,et al.Study on preparation of Mg-doping Cu/SiO₂ catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(04):38-45.
王文玉,王馨艺,王康军等.Mg掺杂Cu/SiO₂催化剂制备及其甲醇和乙醇合成异丁醛催化性能研究[J].低碳化学与化工,2025,50(04):38-45. DOI： 10.12434/j.issn.2097-2547.20240357.

WANG Wenyu,WANG Xinyi,WANG Kangjun,et al.Study on preparation of Mg-doping Cu/SiO₂ catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(04):38-45. DOI： 10.12434/j.issn.2097-2547.20240357.

摘要

异丁醛作为重要的有机化工原料，可由甲醇和乙醇一步合成。目前异丁醛合成催化剂还不能实现甲醇和乙醇高效转化，且催化剂异丁醛选择性偏低，严重限制了甲醇和乙醇一步合成异丁醛工业化的发展，亟需开发高效稳定的异丁醛合成催化剂。采用蒸氨法制备了Cu/SiO

和

CuMg/SiO

催化剂，通过N

吸/脱附、H

-TPR、CO

-TPD、XRD、XPS和TEM等对催化剂物化性质进行了表征，考察了不同Mg掺杂量对

CuMg/SiO

催化剂一步合成异丁醛催化性能的影响。结果表明，Mg的掺杂不仅增大了催化剂表面碱性位点及Cu颗粒活性位点数量，还提高了活性组分Cu颗粒分散度，进而提高了乙醇转化率和异丁醛选择性。在常压、还原温度为320 °C、反应温度为360 °C、液时空速为1.42 h

-1

和

(甲醇):

(乙醇)为10:1的条件下，1CuMg/SiO

催化剂性能较好，乙醇转化率可达97.26%，异丁醛选择性为89.03%，且连续反应200 h后未见明显失活，具有较高的稳定性。

Abstract

Isobutylaldehyde

as an important organic chemical raw material

can be synthesized in one-step from methanol and ethanol. Currently

the catalysts used for isobutyraldehyde synthesis are unable to achieve the highly efficient conversion of methanol and ethanol

and selectivity of isobutyraldehyde is relatively low. This has seriously hampered the development of the industrialization of the one-step synthesis of isobutyraldehyde from methanol and ethanol. Hence

there is an urgent need to develop highly efficient and stable catalysts for isobutyral

dehyde synthesis. The Cu/SiO

and

CuMg/SiO

catalysts were prepared using the ammonia evaporation method. The physicochemical properties of these catalysts were characterized by N

adsorption/desorption

-TPR

-TPD

XRD

XPS and TEM. The impact of different Mg-doping amounts on the performance of the

CuMg/SiO

catalysts in the one-step synthesis of isobutyraldehyde was investigated. The results show that the Mg-doping not only increases the basic sites on the catalyst surface and the active sites of Cu particles but also enhances the dispersion degree of the active component Cu particles. As a result

it increases the conversion rate of ethanol and the selectivity of isobutyraldehyde. Under the conditions of normal pressure

reduction temperature of 320 ℃

reaction temperature of 360 ℃

liquid hourly space velocity of 1.42 h

-1

and

(methanol):

(ethanol) of 10:1

the 1CuMg/SiO

catalyst exhibits better performance

with the ethanol conversion rate can reach 97.26% and selectivity of isobutyraldehyde is 89.03%. Furthermore

no obvious deactivation is observed after continuous reaction for 200 h

indicating the catalyst has high stability.

关键词

Keywords

references

张汉力 , 张娟 , 宋怀俊 . 甲醇、乙醇合成异丁醛催化剂的研究进展 [J ] . 河南化工 , 2014 , 31 ( 7 ): 17 - 20 .

ZHANG H L , ZHANG J , SONG H J . Research progress of catalysts for synthesis of isobutylaldehyde from methanol and ethanol by one-step method [J ] . Henan Chemical Industry , 2014 , 31 ( 7 ): 17 - 20 .

樊晶晶 , 王丽军 . 丙烯羰基化过程在催化剂失活下的长周期操作策略优化 [J ] . 化学反应工程与工艺 , 2016 , 32 ( 5 ): 415 - 422 .

FAN J J , WANG L J . Optimazation long period operational strategy of hydroformylation process under catalytic deactivation [J ] . Chemical Reaction Engineering and Technology , 2016 , 32 ( 5 ): 415 - 422 .

WANG F L . LEE W S. Catalytic synthesis of isobutyraldehyde from methanol and ethanol over titanium oxide-supported vanadium oxide catalysts [J ] . Chemical Communications , 1991 , 24 ( 24 ): 1760 - 1763 .

胡虹 , 陶文晟 , 施力 , 等 . V 2 O 5 催化剂上甲醇乙醇一步合成醛类化合物的研究 [J ] . 天然气化工—C1化学与化工 , 2006 , 31 ( 5 ): 1 - 4 .

HU H , TAO W S , SHI L , et al . Study on the one-step synthesis of aldehydes from methanol and ethanol over vanadium oxide catalyst [J ] . Natural Gas Chemical Industry , 2006 , 31 ( 5 ): 1 - 4 .

ZHANG J F , WU Y Q , LI L , et al . Ti-SBA-15 supported Cu-MgO catalyst for synthesis of isobutyraldehyde from methanol and ethanol [J ] . RSC Advances , 2016 , 6 ( 89 ): 85940 - 85950 .

ZHANG J , ZHANG M , WANG X , et al . Direct synthesis of isobutyraldehyde from methanol and ethanol on Cu-Mg/Ti-SBA-15 catalysts: The role of Ti [J ] . New Journal of Chemistry , 2017 , 41 ( 18 ): 9639 - 9648 .

刘翠改 , 吴静 , 王康军 , 等 . 甲醇乙醇合成异丁醛的Cu基催化剂的制备和性能研究 [J ] . 天然气化工—C1化学与化工 , 2011 , 36 ( 4 ): 21 - 24 .

LIU C G , WU J , WANG K J , et al . Preparation ant performances of Cu-based catalyst for synthesis of isobutyraldehyde from methanol and ethanol [J ] . Natural Gas Chemical Industry , 2011 , 36 ( 4 ): 21 - 24 .

王康军 , 左丹 , 吴静 , 等 . Fe修饰V 2 O 5 催化剂催化甲醇与乙醇一步合成异丁醛 [J ] . 石油化工 , 2012 , ( 7 ): 754 - 756 .

WANG K J , ZUO D , WU J , et al . One-step synthesis of isobutyraldehyde from methanol and ethanol over Fe modified V 2 O 5 catalyst [J ] . Petrochemical Technology , 2012 , ( 7 ): 754 - 756 .

SONG J S , SONG T Y , ZHNAG T T , et al . High performance V 2 O 5 /MgF 2 catalysts for gas-phase dehydrofluorination of 1,1,1,3,3-pentafluoropropane: Support-induced evolution of new active sites [J ] . Journal of Catalysis , 2018 , 364 : 271 - 281 .

NI K W , PENG Y W , WU X M , et al . Enhancement of SO 2 resistance on submonolayer V 2 O 5 -MnO 2 /CeO 2 catalyst by three-dimensional ordered mesoporous CeO 2 in low-temperature NH 3 -SCR [J ] . Energy & Fuels , 2022 , 36 ( 5 ): 2787 - 2798 .

YUAN B H , ZHANG L L , GE X H , et al . The study of zirconium vanadate as a cathode material for lithium ion batteries [J ] . RSC Advances , 2021 , 11 ( 38 ): 23533 - 23540 .

LI Y P , LIU G X , JIA D M , et al . Nanoporous FeVO 4 photoanodes modified with ultrathin C 3 N 4 for high photoelectrochemical water splitting performance [J ] . Catalysis Letters , 2019 , 149 ( 1 ): 19 - 24 .

王惠颖，吴静，张轶，等 . V 2 O 5 /TiO 2 -SiO 2 催化剂用于甲醇乙醇合成异丁醛的研究 [J ] . 沈阳化工学院学报 , 2008 , 22 ( 3 ): 200 - 202 .

WANG H Y , WU J , ZHANG Y , et al . V 2 O 5 /TiO 2 -SiO 2 catalysts for the synthesis of isobutyraldehyde from methanol and ethanol [J ] . Journal of Shenyang Institute of Chemical Technology , 2008 , 22 ( 3 ): 200 - 202 .

CAO X L . Preparation and catalytic performance of La-V/TiO 2 -SiO 2 catalyst for synthesis of isobutyraldehyde from methanol and ethanol [J ] . Industrial Catalysis , 2017 , 25 ( 6 ): 36 - 38 .

BING W W , WANG H M , ZHENG L , et al . A CaMnAl-hydrotalcite solid basic catalyst toward the aldol condensation reaction with a comparable level to liquid alkali catalysts [J ] . Green Chemistry , 2018 , 20 ( 13 ): 3071 - 3080 .

KAUR P , KHANNA A . Structural, electrical and luminescence properties of M 2 V 2 O 7 (M = Mg, Ca, Sr, Ba, Zn) [J ] . Journal of Materials Science: Materials in Electronics , 2021 , 32 ( 16 ): 21813 - 21823 .

SHAN Y L , ZHAO W T , ZHAO S L , et al . Effects of alumina phases on the structure and performance of VO x /Al 2 O 3 catalysts in non-oxidative propane dehydrogenation [J ] . Molecular Catalysis , 2021 , 504 : 111466 .

金方 . 草酸二甲酯催化加氢Cu/SiO 2 催化剂的研究 [D ] . 合肥 : 合肥工业大学 , 2014 .

JIN F . Study on Cu/SiO 2 catalyst of dimethyl oxalate hydrogenation [D ] . Hefei : Hefei University of Technology , 2014 .

程思番 , 任鹏超 , 田芸 , 等 . Cu/MgO催化剂中Cu与MgO协同作用对合成气加氢制甲醇性能的影响 [J ] . 天然气化工—C1化学与化工 , 2022 , 47 ( 1 ): 44 - 50+114 .

CHENG S F , REN P C , TIAN Y , et al . Effect of synergistic effect of Cu and MgO in Cu/MgO catalyst on performance of syngas hydrogenation to methanol [J ] . Natural Gas Chemical Industry , 2022 , 47 ( 1 ): 44 - 50+114 .

HUANG R Y , CHEN L , YU C G , et al . In-situ synthesis of well-dispersed Cu/Cu 2 O nanoparticles supported on petaloid SiO 2 for efficient degradation of high concentration tetracycline hydrochloride [J ] . Journal of Environmental Chemical Engineering , 2023 , 11 : 110326 .

景培 . 醇类化合物脱氢偶联反应催化剂的设计制备与性能研究 [D ] . 吉林 : 吉林大学 , 2023 .

JING P . Study on the fabrication and performance of catalysts for the dehydrogenation coupling of alcohol compounds [D ] . Jilin : Jilin University , 2023 .

LUO H Y , WAN Y , CAI Y H , et al . Ferrate(VI) activation with nanoconfined Cu-Mg sites for water treatment: Selective Cu(III) production via support-dependent redox catalysis [J ] . ACS ES&T Engineering , 2024 , 4 : 1712 - 1724 .

TOMASZ K , ONDREJ H , STANISLAV S , et al . Hollow@CuMgAl double layered hydrotalcites and mixed oxides with tunable textural and structural properties, and thus enhanced NH 3 -NO x -SCR activity [J ] . Nanoscale Advances , 2023 , 5 : 3063 .

张英政 . 氧化锌基复合纳米材料制备及电催化二氧化碳还原性能研究 [D ] . 青岛 : 青岛科技大学 , 2023 .

ZHANG Y Z . Preparation of zinc oxide based nanocomposites for electrocatalytic carbon dioxide reduction reaction [D ] . Qingdao : Qingdao University of Science and Technology , 2023 .

MAO W Z , LIU J H , YIN B Q , et al . Transfer hydrogenation of furfural catalyzed by multi-centers collaborative Ni-based catalyst and kinetic research [J ] . Applied Catalysis A: General , 2021 , 623 : 118247 .

ZHANG J , SHI K , AN Z , et al . Acid-base promoted dehydrogenation coupling of ethanol on supported Ag particles [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 ( 8 ): 3342 - 3350 .

ZHENG J W , ZHOU J F , LIN H Q , et al . CO-mediated deactivation mechanism of SiO 2 -supported copper catalysts during dimethyl oxalate hydrogenation to ethylene glycol [J ] . The Journal of Physical Chemistry C , 2015 , 119 ( 24 ): 13758 - 13766 .

薛婧 , 武朦朦 , 宋有为 , 等 . Ag改性层状硅酸铜催化剂的草酸二甲酯加氢合成乙醇酸甲酯性能研究 [J ] . 燃料化学学报 , 2022 , 50 ( 8 ): 1014 - 1022 .

XUE J , WU M M , SONG Y W , et al . Study on performance of Ag-modified layered copper silicate catalyst for hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Journal of Fuel Chemistry and Technology , 2022 , 50 ( 8 ): 1014 - 1022 .

YANG D L , LIN L , GUO R , et al . Bimetallic Cu-Ag/SiO 2 catalysts with tunable product selectivity and enhanced low-temperature stability in the dimethyl oxalate hydrogenation [J ] . Molecular Catalysis , 2022 , 528 : 112508 .

HAI Y H , GUAN T , FENG Y B , et al . Facile synthesis of Cu@Ag/SiO 2 catalysts for the selective hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Molecular Catalysis , 2024 , 294 : 120121 .

CHEN L F , GUO P J , QIAO M H , et al . Cu/SiO 2 catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Journal of Catalysis , 2008 , 257 : 172 - 180 .

CHENG F L , GUO H Q , CUI J L , et al . Coupling of methanol and ethanol over CuMgAlO x catalysts: The roles of copper species and alkalinity [J ] . Reaction Kinetics, Mechanisms and Catalysis , 2019 , 126 : 119 - 136 .

GOODARZNIA S , SMITH K J . Properties of alkali-promoted Cu-MgO catalysts and their activity for methanol decomposition and C 2 -oxygenate formation [J ] . Journal of Molecular Catalysis A: Chemical , 2010 , 320 ( 1 ): 1 - 13 .

Views

255

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Influence of Promoters on the Structure and Performance of the Catalysts for the Synthesis of Isobutyraldehyde from Methanol and Ethanol

Preparation ant performances of Cu-based catalyst for synthesis of isobutyraldehyde from methanol and ethanol

Synthesis of isobutyraldehyde from methanol and ethanol over Fe-modified V-La catalysts

Determination and correlation of phase equilibrium about methanol-ethanol at atmospheric pressure

Related Author

耿彩军

吴静

汪海滨

张轶

王惠颖

岳宏

刘翠改

吴静

Related Institution

沈阳化工学院化学工程学院

沈阳化工学院化学工程学院辽宁沈阳110142

沈阳化工大学化学工程学院

Innovation Center of Fine Chemical Industry

College of Chemistry and Environment Engineering, Baise University

Postal code：610225
Tel：028-85964717 Email：236764603@qq.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：408680 Visits Today：717

⁰

Study on preparation of Mg-doping Cu/SiO2 catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol

DOI：10.12434/j.issn.2097-2547.20240357

摘要

Abstract

关键词

Keywords

references

Study on preparation of Mg-doping Cu/SiO₂ catalyst and its catalytic synthesis performance of isobutyraldehyde from methanol and ethanol