Pd改性ZnCr氧化物催化合成气制异丁醇性能研究

王立言; 谭余杭; 杨晓军; 王志鹏

doi:10.12434/j.issn.2097-2547.20250333

您当前的位置：

首页 >

文章列表页 >

Pd改性ZnCr氧化物催化合成气制异丁醇性能研究

更新时间：2026-01-21

- Pd改性ZnCr氧化物催化合成气制异丁醇性能研究
- Study on catalytic performances of Pd-modified ZnCr oxides for syngas to isobutanol
- 低碳化学与化工 2026: 1-9.
- 作者机构：
  
  1.中北大学化学与化工学院，山西太原 030051
  2.潞安化工集团有限公司，山西长治 046000
- 作者简介：
  
  王立言（1992—），博士，讲师，研究方向为C1化学，E-mail：20220058@nuc.edu.cn。
  王志鹏（1988—），博士，讲师，研究方向为炔化催化剂，E-mail：20200004@nuc.edu.cn。
- 基金信息：
  
  国家自然科学基金青年基金(22202185);山西省基础研究计划(202203021222062;202203021212128)
- DOI：10.12434/j.issn.2097-2547.20250333
  中图分类号： TQ426
- 收稿：2025-07-30，
  
  修回：2025-12-27，
  
  网络出版：2026-01-21，
- 稿件说明：
移动端阅览
王立言,谭余杭,杨晓军等.Pd改性ZnCr氧化物催化合成气制异丁醇性能研究[J].低碳化学与化工,

WANG Liyan,TAN Yuhang,YANG Xiaojun,et al.Study on catalytic performances of Pd-modified ZnCr oxides for syngas to isobutanol[J].Low-Carbon Chemistry and Chemical Engineering,
王立言,谭余杭,杨晓军等.Pd改性ZnCr氧化物催化合成气制异丁醇性能研究[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20250333.

WANG Liyan,TAN Yuhang,YANG Xiaojun,et al.Study on catalytic performances of Pd-modified ZnCr oxides for syngas to isobutanol[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20250333.

摘要

合成气制异丁醇是实现碳资源高效利用的重要途径，然而现有催化剂存在产物收率低的问题。采用共沉淀-浸渍法制备了一系列Pd改性ZnCr催化剂并研究了其催化性能。结合XRD和XPS等表征方法研究了Pd质量分数对催化剂构效关系的影响，并分析了不同催化剂作用下的合成气制异丁醇反应路径。结果表明，Pd的引入可增大催化剂表面氧空位和活性羟基含量，进而促进CO的活化与转化；同时，Pd可通过优化中间体的稳定性，有效抑制烃类和甲醇等副产物的生成。在温度为400 ℃、压力为10 MPa、空速为3000 h

-1

和

(CO) = 2:1的条件下，Pd质量分数为0.5%的Pd-ZnCr催化剂具有较好的催化性能，其CO转化率为30.6%，总醇选择性为44.1%，异丁醇选择性为23.6%。

Abstract

Syngas to isobutanol is a crucial route for the efficient utilization of carbon resources. However

conventional catalysts suffer from limited product selectivity. A series of Pd-modified ZnCr catalysts were prepared via coprecipitation-impregnation method and the catal

ytic performances of catalysts were investigated. Effects of Pd mass fractions on structure-activity relationships of catalysts were characterized by XRD

XPS and so on

and the reaction pathways of syngas to isobutanol with different catalysts were analyzed. The results show that the introduction of Pd can increase the contents of surface oxygen vacancies and active hydroxyls

thereby promoting activation and conversion of CO. Meanwhile

Pd can optimize the stabilities of intermediates and effectively suppress the formation of by-products such as hydrocarbons and methanol. Under reaction conditions of temperature of 400 °C

pressure of 10 MPa

space velocity of 3000 h

-1

and

(CO) = 2:1

Pd-ZnCr catalyst with Pd mass fraction of 0.5% exhibits good catalytic performance

with CO conversion rate of 30.6%

total alcohol selectivity of 44.1% and isobutanol selectivity of 23.6%.

关键词

Keywords

references

OLSON A L , TUNER M , VERHELST S . A review of isobutanol as a fuel for internal combustion engines [J ] . Energies , 2023 , 16 ( 22 ): 7470 .

王慧君 , 武应全 , 田少鹏 , 等 . F-T组分改性KCuZrO 2 催化剂上CO加氢合成异丁醇的性能研究 [J ] . 燃料化学学报 , 2020 , 48 ( 3 ): 302 - 310 .

WANG H J , WU Y Q , TIAN S P , et al . Study on the performance of F-T component modified KCuZrO 2 catalyst for CO hydrogenation to isobutanol [J ] . Journal of Fuel Chemistry and Technology , 2020 , 48 ( 3 ): 302 - 310 .

王立言 . ZnCr催化剂上氧空位对合成气制异丁醇性能影响的研究 [D ] . 北京 : 中国科学院大学 , 2022 .

WANG L Y . The effect of surface oxygen vacancy on the catalytic performance of syngas to isobutanol over ZnCr catalysts [D ] . Beijing : University of Chinese Academy of Sciences , 2022 .

TIAN S P , TAN L , WU Y Q , et al . The role of different state ZnO over non-stoichiometric Zn-Cr spinel catalysts for isobutanol synthesis from syngas [J ] . Applied Catalysis A: General , 2017 , 536 : 57 - 66 .

WANG L Y , GAO X F , BAI Y X , et al . The synergistic effect between ZnO and ZnCr 2 O 4 on the catalytic performance for isobutanol synthesis from syngas [J ] . Fuel , 2019 , 253 : 1570 - 1577 .

葛浩 , 孙燕 , 孙启文 . Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响 [J ] . 低碳化学与化工 , 2025 , 50 ( 7 ): 10 - 19 .

GE H , SUN Y , SUN Q W . Effect of Al additive contents on structure of CoMn catalysts and their catalytic performance in synthesis of higher alcohols from syngas [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 7 ): 10 - 19 .

徐浩浩 , 穆晓亮 , 房克功 , 等 . 氧空穴ZrO 2 复合CuFe催化剂合成气制高级醇 [J ] . 低碳化学与化工 , 2024 , 49 ( 10 ): 11 - 19 .

XU H H , MU X L , FANG K G , et al . Study on reaction performances of oxygen-vacancies ZrO 2 composite CuFe catalysts for syngas to higher alcohols [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 10 ): 11 - 19 .

YAN G H , PRŠLJA P , CHEN G F , et al . Syngas conversion to higher alcohols via wood-framed Cu/Co-carbon catalyst [J ] . ACS Catalysis , 2025 , 15 ( 3 ): 2492 - 2503 .

LI Z S , FAN S Q , ZENG Z , et al . Co-Co 2 C catalysts supported on carbon-coated ordered mesoporous silica with promoted CO insertion and C—C coupling for higher alcohol synthesis from syngas [J ] . Journal of Materials Chemistry A , 2024 , 12 ( 22 ): 13127 - 13138 .

GUO S X , LI Z S , LI Y J , et al . CoMn catalysts derived from partial decomposed layered CoMn-MOF materials for higher alcohol synthesis from syngas [J ] . Chemical Engineering Journal , 2023 , 463 : 142359 .

ZAMAN S F , PASUPULETY N , AL-ZAHRANI A A , et al . Carbon monoxide hydrogenation on potassium promoted Mo 2 N catalysts [J ] . Applied Catalysis A: General , 2017 , 532 : 133 - 145 .

LIU C , VIRGINIE M , GRIBOVAL C A , et al . Impact of potassium content on the structure of molybdenum nanophases in alumina supported catalysts and their performance in carbon monoxide hydrogenation [J ] . Applied Catalysis A: General , 2015 , 504 : 565 - 575 .

XUE F , CHEN W M , SONG X G , et al . Promotional ef fects of Cr and Fe on Rh/SiO 2 catalyst for the preparation of ethanol from CO hydrogenation [J ] . RSC Advances , 2016 , 6 ( 42 ): 35348 - 35353 .

ZHOU W , DOCHERTY S R , LAM E , et al . Conversion of syngas to ethanol over a RhFe alloy catalyst [J ] . Journal of the American Chemical Society , 2025 , 147 ( 15 ): 12890 - 12896 .

GONG N N , ZHANG T , TAN M H , et al . Realizing and revealing complex isobutyl alcohol production over a simple Cu-ZrO 2 catalyst [J ] . ACS Catalysis , 2023 , 13 ( 6 ): 3563 - 3574 .

WANG L Y , WU Y Q , GONG N N , et al . Optimizing surface oxygen vacancy sites for CO hydrogenation to isobutanol over ZnCr catalyst [J ] . Fuel , 2022 , 315 .

FICHTL M B , SCHLERETH D , JACOBSEN N , et al . Kinetics of deactivation on Cu/ZnO/Al 2 O 3 methanol synthesis catalysts [J ] . Applied Catalysis A: General , 2015 , 502 : 262 - 270 .

程淑艳 , 寇佳伟 , 黄伟 . 钾助剂对CuZnAl催化剂合成气制异丁醇反应的影响 [J ] . 天然气化工—C1化学与化工 , 2018 , 43 ( 2 ): 14 - 18 .

CHENG S Y , KOU J W , HUANG W . Effect of potassium promoter on CuZnAl catalysts for isobutanol synthesis from syngas [J ] . Natural Gas Chemical Industry , 2018 , 43 ( 2 ): 14 - 18 .

MA E J , TIAN X , LIU J , et al . Modulation of electronic metal-support interaction on Cu/ZnO by metal oxides for iso-butanol synthesis from syngas [J ] . Fuel , 2025 , 386 : 134256 .

AIT EL FAKIR A , DU P F , WAN L , et al . Direct syngas-to-ethanol conversion over lithium-promoted Rh/MgO catalysts [J ] . ACS Catalysis , 2025 , 15 ( 3 ): 2033 - 2044 .

TIAN S P , WANG S C , WU Y Q , et al . The real active sites over Zn-Cr catalysts for direct synthesis of isobutanol from syngas: structure-activity relationship [J ] . RSC Advances , 2015 , 5 ( 108 ): 89273 - 89281 .

TIAN S P , WANG S C , WU Y Q , et al . Cation distribution in Zn-Cr spinel structure and its effects on synthesis of isobutanol from syngas: Structure-activity relationship [J ] . Journal of Molecular Catalysis A: Chemical , 2015 , 404/405 : 139 - 147 .

GAO X F , ZHANG T , WU Y Q , et al . Isobutanol synthesis from syngas on Zn-Cr based catalysts: New insights into the effect of morphology and facet of ZnO nanocrystal [J ] . Fuel , 2018 , 217 : 21 - 30 .

TIAN S P , WANG S C , WU Y Q , et al . The role of potassium promoter in isobutanol synthesis over Zn-Cr based catalysts [J ] . Catalysis Science & Technology , 2016 , 6 ( 12 ): 4105 - 4115 .

WANG L Y , ZHANG T , WU Y Q , et al . Promotion effect of La on oxygen vacancy formation over Zn-Cr based catalyst for isobutanol synthesis from syngas [J ] . Fuel , 2021 , 288 : 119633 .

WANG L Y , ZHANG T , YANG J Q , et al . Direct conversion syngas to isobutanol over Ce/ZC catalysts: Effect of Ce promoter on the catalytic performance [J ] . ChemCatChem , 2022 , 14 ( 10 ): e202101892 .

ZHANG T , ZENG C Y , WU Y Q , et al . Role of Ga 3+ promoter in the direct synthesis of iso-butanol via syngas over a K-ZnO/ZnCr 2 O 4 catalyst [J ] . Catalysis Science & Technology , 2021 , 11 ( 3 ): 1077 - 1088 .

WU Y Q , GONG N N , ZHANG M , et al . Insight into the branched alcohol formation mechanism on K-ZnCr catalysts from syngas [J ] . Catalysis Science & Technology , 2019 , 9 ( 10 ): 2592 - 2600 .

JIAO F , BAI B , LI G , et al . Disentangling the activity-selectivity trade-off in catalytic conversion of syngas to light olefins [J ] . Science , 2023 , 380 ( 6646 ): 727 - 730 .

WANG N , SHEN K , HUANG L H , et al . Facile route for synthesizing ordered mesoporous Ni-Ce-Al oxide materials and their catalytic performance for methane dry reforming to hydrogen and syngas [J ] . ACS Catalysis , 2013 , 3 ( 7 ): 1638 - 1651 .

ZHANG M , ZHANG J F , WU Y Q , et al . Insight into the effects of the oxygen species over Ni/ZrO 2 catalyst surface on methane reforming with carbon dioxide [J ] . Applied Catalysis B: Environmental , 2019 , 244 : 427 - 437 .

LI X , MA Y , WANG X N , et al . Regulating the oxidation state of Pd to enhance the selective hydrogenation for 5-hydroxymethylfurfural [J ] . Chinese Journal of Chemical Engineering , 2024 , 72 : 60 - 68 .

KONG X P , ZHANG X C , CHEN J G . Highly active and selective CoCu/ZnO catalysts prepared by mild oxalic acid co-precipitation method in dimethyl oxalate hydrogenation [J ] . Catalysis Communications , 2015 , 65 : 46 - 50 .

WEI Z X , WEI L , GONG L , et al . Combustion synthesis and effect of LaMnO 3 and La 0.8 Sr 0.2 MnO 3 on RDX thermal decomposition [J ] . Journal of Hazardous Materials , 2010 , 177 ( 1 ): 554 - 559 .

ZHANG T , WU Y Q , GAO X F , et al . Effects of surface hydroxyl groups induced by the co-precipitation temperature on the catalytic performance of direct synthesis of isobutanol from syngas [J ] . Fuel , 2019 , 237 : 1021 - 1028 .

浏览量

下载量

CNKI被引量

文章被引用时，请邮件提醒。

提交

工具集

关联资源

超临界相合成气制甲醇-异丁醇工艺条件的研究

煤/煤焦与天然气协同转化研究进展

Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响

甲烷干重整制合成气反应水滑石衍生Ni基催化剂的研究进展

氧空穴ZrO₂复合CuFe催化剂合成气制高级醇反应性能研究