Study on performances of glycerol to acrolein catalyzed by copper phosphates

ZHANG Yuanyuan; LI Shuangming; CHEN Feng; WANG Yiwen; YU Sansan

doi:10.12434/j.issn.2097-2547.20250188

您当前的位置：

首页 >

文章列表页 >

Study on performances of glycerol to acrolein catalyzed by copper phosphates

更新时间：2026-03-19

- Study on performances of glycerol to acrolein catalyzed by copper phosphates
- Vol. 51, Issue 3, Pages: 60-67(2026)
- 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.2097-2547.20250188
  CLC： TQ23
- Received：18 April 2025，
  
  Revised：2025-06-04，
  
  Published：25 March 2026
- 稿件说明：
移动端阅览
张媛媛,李双明,陈峰等.磷酸铜催化甘油制丙烯醛性能研究[J].低碳化学与化工,2026,51(3):60-67.

ZHANG Yuanyuan,LI Shuangming,CHEN Feng,et al.Study on performances of glycerol to acrolein catalyzed by copper phosphates[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(3):60-67.
张媛媛,李双明,陈峰等.磷酸铜催化甘油制丙烯醛性能研究[J].低碳化学与化工,2026,51(3):60-67. DOI： 10.12434/j.issn.2097-2547.20250188.

ZHANG Yuanyuan,LI Shuangming,CHEN Feng,et al.Study on performances of glycerol to acrolein catalyzed by copper phosphates[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(3):60-67. DOI： 10.12434/j.issn.2097-2547.20250188.

摘要

甘油转化为高附加值的丙烯醛是推动化工行业绿色低碳发展的有效途径之一。催化剂是影响甘油制丙烯醛路线产能的关键。采用旋转蒸发法制备了一系列磷酸铜催化剂，并通过XRD、SEM等对催化剂进行了表征。研究了不同

(Cu)/

(P)及Cu源对催化剂构效关系的影响。结果表明，增大

(Cu)/

(P)可增大催化剂的比表面积，进而提高催化剂的催化性能；不同Cu源可影响催化剂的表面形貌，进而影响其丙烯醛选择性。在反应温度为300 ℃、甘油溶液（质量分数为10%）进料流速为4 mL/h的条件下，

(Cu)/

(P) = 1.0、硝酸铜为Cu源制备的催化剂表现出相对最优的催化性能，其甘油转化率、丙烯醛选择性和丙烯醛产率分别为97%、80%和78%。

Abstract

Converting glycerol into high-value-added acrolein is one of the effective ways to promote green and low-carbon development of chemical industry. The catalyst is the key factor influencing the production capacity of the glycerol to acrolein route. A series of copper phosphate catalysts were prepared by rotary evaporation method

and the catalysts were

characterized by XRD

SEM and so on. Effects of different

(Cu)/

(P) and Cu sources on structure-activity relationships of catalysts were studied. The results show that increasing

(Cu)/

(P) can increase the specific surface area of catalyst

thereby improving the catalytic performance of the catalyst. Different Cu sources can affect the surface morphology of the catalyst

and thereby influence its acrolein selectivity. Under the conditions of reaction temperature of 300 ℃ and glycerol solution (mass fraction of 10%) feed flow rate of 4 mL/h

the catalyst prepared with

(Cu)/

(P) of 1.0 and copper nitrate as the Cu source exhibits relatively optimal catalytic performance

with glycerol conversion rate

acrolein selectivity and acrolein yield of 97%

80% and 78%

respectively.

关键词

Keywords

references

MUSA S D , TANG Z H , IBRAHIM A O , et al . China’s energy status: A critical look at fossils and renewable options [J ] . Renewable and Sustainable Energy Reviews , 2018 , 81 : 2281 - 2290 .

NADJI L . Gas phase dehydration of glycerol to acrolein over WO 3 -based catalysts prepared by non-hydrolytic sol-gel synthesis [J ] . RSC Advances , 2018 , 8 : 13344 - 13352 .

吕士忠 , 李天龙 , 房睿 , 等 . 磷酸钒钠正极材料的Zr 4+ 掺杂改性研究 [J ] . 石油化工高等学校学报 , 2024 , 37 ( 6 ): 44 - 51 .

LV S Z , LI T L , FANG R , et al . Modification of sodium vanadate cathode by Zr 4+ doping [J ] . Journal of Petrochemical Universities , 2024 , 37 ( 6 ): 44 - 51 .

VALTER M , SANTOS E C D , PETTERSSON L G M , et al . Selectivity of the first two glycerol dehydrogenation steps determined using scaling relationships [J ] . ACS Catalysis , 2021 , 11 ( 6 ): 3487 - 3497 .

KUMAR L R , YELLAPU S K , YAN S , et al . Elucidating the effect of impurities present in different crude glycerol sources on lipid and citric acid production by Yarrowia lipolytica SKY7 [J ] . Journal of Chemical Technology & Biotechnology , 2021 , 96 ( 1 ): 227 - 240 .

SOUZA JÚNIOR R L , ROSSI T M , DETONI C , et al . Glycerol carbonate production from transesterification of glycerol with diethyl carbonate catalyzed by Ca/Al-mixed oxides derived from hydrocalumite [J ] . Biomass Conversion and Biorefinery , 2023 , 13 ( 2 ): 661 - 673 .

DING J F , MA T L , CUI M Y , et al . Gas phase dehydration of glycerol to acrolein over Cs 2.5 H 0.5 PW 12 O 40 /Zr-MCM-41 catalysts prepared by supercritical impregnation [J ] . Molecular Catalysis , 2018 , 461 : 1 - 9 .

PALA-ROSAS I , CONTRERAS J L , SALMONES J , et al . Catalytic deactivation of HY zeolites in the dehydration of glycerol to acrolein [J ] . Catalysts , 2021 , 11 ( 3 ): 360 .

NITAYAVARDHANA S , KHANAL S K . Biodiesel-derived crude glycerol bioconversion to animal feed: A sustainable option for a biodiesel refinery [J ] . Bioresource Technology , 2011 , 102 ( 10 ): 5808 - 5814 .

SHEN L Q , YIN H X , YIN H B , et al . Conversion of glycerol to lactic acid catalyzed by different-sized Cu 2 O nanoparticles in NaOH aqueous solution [J ] . Journal of Nanoscience and Nanotechnology , 2017 , 17 : 780 - 787 .

CHOTCHUANG A , KUNSUK P , PHANPITAKKUL A , et al . Production of glycerol carbonate from glycerol over modified sodium-aluminate-doped calcium oxide catalysts [J ] . Catalysis Today , 2022 , 388/389 : 351 - 359 .

MISHRA N K , KUMAR P , SRIVASTAVA V C , et al . Synthesis of Cu-based catalysts for hydrogenolysis of glycerol to 1,2-propanediol with in-situ generated hydrogen [J ] . Journal of Environmental Chemical Engineering , 2021 , 9 ( 4 ): 105263 .

温英林 , 刘世钰 , 沈卫华 , 等 . Pt/WO x /Al 2 O 3 及其改性催化剂氢解甘油制备1,3-丙二醇 [J ] . 天然气化工—C1化学与化工 , 2021 , 46 ( 5 ): 68 - 73 .

WEN Y L , LIU S Y , SHEN W H , et al . Preparation of 1,3-propanediol by hydrogenolysis of glycerol over Pt/WO x /Al 2 O 3 and its modified catalysts [J ] . Natural Gas Chemical Industry , 2021 , 46 ( 5 ): 68 - 73 .

刘珂 , 张琪 , 王敏 , 等 . 生物基甘油气相脱水制丙烯醛的研究进展 [J ] . 天然气化工—C1化学与化工 , 2021 , 46 ( 3 ): 15 - 21 .

LIU K , ZHANG Q , WANG M , et al . Research progress in bioglycerol dehydration in vapor phase to acrolein [J ] . Natural Gas Chemical Industry , 2021 , 46 ( 3 ): 15 - 21

VÁZQUEZ E S , PLIEGO J A , PARIENTE J P , et al . Obtaining of value added chemicals from catalityc dehydration of glycerol [J ] . Catalysis Today , 2020 , 356 : 349 - 358 .

BUI L , CHAKRABARTI R , BHAN A . Mechanistic origins of unselective oxidation products in the conversion of propylene to acrolein on Bi 2 Mo 3 O 12 [J ] . ACS Catalysis , 2016 , 6 ( 10 ): 6567 - 6580 .

张业 , 周梅 , 魏文珑 , 等 . 丙烯醛合成工艺及催化剂研究进展 [J ] . 天然气化工—C1化学与化工 , 2008 , 33 ( 2 ): 54 - 59 .

ZHANG Y , ZHOU M , WEI W L , et al . Progress in synthesis of acrolein and the catalysts thereof [J ] . Natural Gas Chemical Industry , 2008 , 33 ( 2 ): 54 - 59 .

WANG F , DUBOIS J L , UEDA W . Catalytic performance of vanadium pyrophosphate oxides (VPO) in the oxidative dehydration of glycerol [J ] . Applied Catalysis A: General , 2010 , 376 ( 1/2 ): 25 - 32 .

ULGEN A , HOELDERICH W F . Conversion of glycerol to acrolein in the presence of WO 3 /TiO 2 catalysts [J ] . Applied Catalysis A: General , 2011 , 400 ( 1/2 ): 34 - 38 .

张跃 , 谢国红 , 刘建武 , 等 . H 3 PW 12 O 40 /SiO 2 催化甘油制备丙烯醛的研究 [J ] . 天然气化工—C1化学与化工 , 2008 , 33 ( 6 ): 24 - 26 .

ZHANG Y , XIE G H , LIU J W , et al . Preparation of acrolein from glycerol over H 3 PW 12 O 40 /SiO 2 catalys [J ] . Natural Gas Chemical Industry , 2008 , 33 ( 6 ): 24 - 26 .

ZHANG S Q , LI S M , SU T Y , et al . Polybasic organic acids controlled synthesis of Mo-V-O composite metal oxide for the catalytic conversion of glycerol [J ] . Carbon Resources Conversion , 2024 : 100247 .

ATIA H , ARMBRUSTER U , MARTIN A . Dehydration of glycerol in gas phase using heteropolyacid catalysts as active compounds [J ] . Journal of Catalysis , 2008 , 258 ( 1 ): 71 - 82 .

DELEPLANQUE J , DUBOIS J L , DEVAUX J F , et al . Production of acrolein and acrylic acid through dehydration and oxydehydration of glycerol with mixed oxide catalysts [J ] . Catalysis Today , 2010 , 157 ( 1/2/3/4 ): 351 - 358 .

MA T L , DING J F , LIU X L , et al . Gas-phase dehydration of glycerol to acrolein over different metal phosphate catalysts [J ] . Korean Journal of Chemical Engineering , 2020 , 37 ( 6 ): 955 - 960 .

WANG F , DUBOIS J L , UEDA W . Catalytic dehydration of glycerol over vanadium phosphate oxides in the presence of molecular oxygen [J ] . Journal of Catalysis , 2009 , 268 ( 2 ): 260 - 267 .

IN-NOI O , DAORATTANACHAI P , RUNGNIM C , et al . Insight into fructose de hydration over lewis acid α ‐Cu 2 P 2 O 7 catalyst [J ] . ChemNanoMat , 2021 , 7 ( 3 ): 292 - 298 .

于东北 , 李学 , 杨昕毓 , 等 . 沉淀剂对CuO/CeO 2 催化剂织构性质及CO催化氧化性能的影响 [J ] . 辽宁石油化工大学学报 , 2023 , 43 ( 6 ): 48 - 53 .

YU D B , LI B , YANG X Y , et al . The effect of precipitators on the texture properties and CO catalytic oxidation performance of CuO/CeO 2 catalysts [J ] . Journal of Liaoning Petrochemical University , 2023 , 43 ( 6 ): 48 - 53 .

邓建雄 . 焦磷酸铜的制备及催化降解苯酚的性能研究 [D ] . 成都 : 成都理工大学 , 2022 .

DENG J X . Preparation of copper pyrophosphate and performance study on its catalytic degradation of phenol [D ] . Chengdu : Chengdu University of Technology , 2022 .

RAHMAN MD M , MUTTAKIN M , PAL A , et al . A statistical approach to determine optimal models for IUPAC-classified adsorption isotherms [J ] . Energies , 2019 , 12 ( 23 ): 4565 .

SONG R R , SONG H H , CHEN X H , et al . Effects of copper nitrate addition on the pore property and lithium storage performance of hierarchical porous carbon nanosheets from phenolic resin [J ] . Electrochimica Acta , 2014 , 127 : 186 - 192 .

SANTRA C , SHAH S , MONDAL A , et al . Synthesis, characterization of VPO catalyst dispersed on mesoporous silica surface and catalytic activity for cyclohexane oxidation reaction [J ] . Microporous and Mesoporous Materials , 2016 , 223 : 121 - 128 .

HORVÁTH B , ŠUSTEK M , ŠKRINIAROVÁ J , et al . Gas phase hydroxylation of benzene with air-ammonia mixture over copper-based phosphate catalysts [J ] . Applied Catalysis A: General , 2014 , 481 : 71 - 78 .

MOREIRA A B F , BRUNO A M , SOUZA M M V M , et al . Continuous production of lactic acid from glycerol in alkaline medium using supported copper catalysts [J ] . Fuel Processing Technology , 2016 , 144 : 170 - 180 .

彭洁 , 于杨 , 王伟 , 等 . 老化时间对铜硅环己醇脱氢催化剂副产物苯酚选择性的影响 [J ] . 低碳化学与化工 , 2025 , 50 ( 4 ): 64 - 70 .

PENG J , YU Y , WANG W , et al . Effects of aging time on selectivity of by-product phenol in cyclohexanol dehydrogenation catalyzed by copper-silicon catalysts [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 4 ): 64 - 70 .

TANG C , LI S M , LI S Q , et al . The structure-activity relationship of CuO in the catalytic conversion reaction of glycerol to lactic acid [J ] . Catalysts , 2023 , 13 ( 8 ): 1218 .

杨昕毓 , 孙舒 , 石岩 , 等 . 水热时间对CuO/CeO 2 催化甲醇水蒸气重整制氢的影响 [J ] . 石油化工高等学校学报 , 2023 , 36 ( 2 ): 63 - 69 .

YANG X Y , SUN S , SHI Y , et al . Effects of hydrothermal reaction time on the performance of CuO/CeO 2 catalyst for hydrogen production from steam reforming methanol [J ] . Journal of Petrochemical Universities , 2023 , 36 ( 2 ): 63 - 69 .

TSUKUDA E , SATO S , TAKAHASHI R , et al . Production of acrolein from glycerol over silica-supported heteropoly acids [J ] . Catalysis Communications , 2007 , 8 ( 9 ): 1349 - 1353 .

王焕 , 熊晓云 , 郑云锋 , 等 . FCC催化剂传质性能与孔结构和酸性的关联性探究 [J ] . 石油化工高等学校学报 , 2024 , 37 ( 3 ): 58 - 65 .

WANG H , XIONG X Y , ZHENG Y F , et al . Study on the correlation between mass transfer performance and pore structure and acidity of FCC catalysts [J ] . Journal of Petrochemical Universities , 2024 , 37 ( 3 ): 58 - 65 .

XIE Q L , LI S S , GONG R C , et al . Microwave-assisted catalytic dehydration of glycerol for sustainable production of acrolein over a microwave absorbing catalyst [J ] . Applied Catalysis B: Environmental , 2019 , 243 : 455 - 462 .

GAN H M , ZHAO X G , SONG B N , et al . Gas phase dehydration of glycerol to acrolein catalyzed by zirconium phosphate [J ] . Chinese Journal of Catalysis , 2014 , 35 ( 7 ): 1148 - 1156 .

ZHANG H G , BAO F P , LIU Q W , et al . Combining structure design and surface modification of BPO 4 solid acid catalyst to boost the anti-coking performance in dehydration reaction of glycerol [J ] . Applied Catalysis A: General , 2024 , 670 : 119553 .

MA T L , DING J F , SHAO R , et al . Dehydration of glycerol to acrolein over Wells-Dawson and Keggin type phosphotungstic acids supported on MCM-41 catalysts [J ] . Chemical Engineering Journal , 2017 , 316 : 797 - 806 .

SU C X , ZHOU S Q , WU S Y , et al . Highly efficient dehydration of polyols: In-situ Brønsted acid from boron phosphate catalyst [J ] . Chemical Engineering Journal , 2024 , 483 : 149273 .

Views

126

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Performance evaluation of a H₃PW₁₂O₄₀/Al₂O₃ catalyst for preparation of acrolein by glycerol dehydration

Study on catalytic properties of H₃PW₁₂O₄₀/γ-Al₂O₃ catalysts modified with metal oxides for preparation of acrolein from glycerol

Research progress on Fe-based catalysts for CO₂ hydrogenation to high carbon α-olefins

Research progress in bioglycerol dehydration in vapor phase to acrolein

Related Author

CHEN Feng

WANG Yiwen

沈介发

严生虎

刘建武

丁海亮

张跃

严生虎

Related Institution

江苏工业学院精细化工研究所

常州大学精细化工研究所

School of Materials and New Energy, Ningxia University

State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University

Lanzhou Petrochemical Polytechnic

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：395733 Visits Today：219

⁰