Citation: WANG Hui-jun, WU Ying-quan, TIAN Shao-peng, WANG Li-yan, GONG Na-na, XIE Hong-juan, TAN Yi-sheng. Study on the performance of F-T component modified KCuZrO₂ catalyst for CO hydrogenation to isobutanol[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(3): 302-310. shu

Study on the performance of F-T component modified KCuZrO₂ catalyst for CO hydrogenation to isobutanol

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
School of Science Xijing University, Xi'an 710000, China

Corresponding author: WU Ying-quan, wvyq@sxicc.ac.cn TAN Yi-sheng, tan@sxicc.ac.cn
Received Date: 21 January 2020
Revised Date: 3 March 2020

Fund Project: The project was supported by the National Natural Science Foundation of China 21706218The project was supported by the National Natural Science Foundation of China (21573269, 21706218)The project was supported by the National Natural Science Foundation of China 21573269

Figures(6)

KCuZrO₂ catalysts modified with different F-T elements (Fe, Co, Ni) were prepared by co-precipitation method and then were tested for isobutanol synthesis from catalytic CO hydrogenation. The catalysts were characterized by N₂ adsorption and desorption experiments (BET), XRD, TEM, XPS, H₂-TPR, CO-TPD and in situ DRIFTS. The results showed that the addition of F-T components promoted the formation of ethanol and propanol, and had different effects on the selectivity of isobutanol. The characterization results showed that Fe promoted the dispersion of catalyst components, and enriched the active component Cu on the catalyst surface, which improved the active adsorption of H₂ and CO. In addition, more C₁ species were formed on the KFeCuZrO₂ catalyst surface, and these C₁ species could further react with ethanol and propanol to produce isobutanol. However, the catalysts modified by Co and Ni lacked sufficient C₁ species, so the selectivity of isobutanol did not increase significantly. The introduction of Co had little effect on the structure of catalyst and the dispersion of Cu, but the activity of catalyst decreased after Co addition, which might be due to the deactivation of catalyst. After adding Ni to the catalyst, the specific surface area decreased and the particle size increased, and the Cu/Zr molar ratio on the catalyst surface also decreased to 0.19. The interaction between Cu-Zr was weakened, and the isobutanol selectivity was also reduced.
- CO hydrogenation,
- F-T elements,
- Cu/ZrO₂,
- isobutanol
1. [1]
  LI Ming-yang. Study on the catalyst for isobutanol synthesis from syngas[D]. Shanghai: East China University of Science and Technology, 2015.
2. [2]
  SLATING T A, KESAN J P. Making regulator innovation keep pace with technological innovation[J]. Wis Law Rev, 2011:1109-1179.
3. [3]
  TIAN Yu, WANG Yi-qiang, WANG Qi-ye. Research progress of isobutanol biosynthesis[J]. Biotechnol Bull, 2013,1(5):40-44.
4. [4]
  KOU Yong-li, XIE Hong-juan, LIU Guang-bo, ZHANG Xin-yue, HAN Yi-zhuo, NORITATSU Tsubaki, TAN Yi-sheng. Effect of calcination temperature on the performance of ZnCr based catalyst in isobutanol synthesis[J]. J Fuel Chem Technol, 2013,41(6):703-709.
5. [5]
  GAO X F, WU Y Q, ZHANG T, WANG L Y, LI X L, TAN Y S. Binary ZnO/Zn-Cr nanospinel catalysts prepared by a hydrothermal method for isobutanol synthesis from syngas[J]. Cat Sci Technol, 2018,8:2975-2986.
6. [6]
  KOU J W, CHENG S Y, GAO Z H, CHENG F Q, HUANG W. Synergistic effects of potassium promoter and carbon fibers on direct synthesis of isobutanol from syngas over Cu/ZnO/Al₂O₃ catalysts obtained from hydrotalcite-like compounds[J]. Solid State Sci, 2019,87:138-145. doi: 10.1016/j.solidstatesciences.2018.11.007
7. [7]
  TAN Li, WU Ying-quan, ZHANG Tao, XIE Hong-juan, CHEN Jian-gang. Effect of precipitation temperature on the performance of K-CuLaZrO₂ catalyst for isobutanol synthesis from syngas[J]. J Fuel Chem Technol, 2019,47(9):1096-1102.
8. [8]
  HE Dai-ping. Higher alcohol and ketone synthesis study on ZrO₂-based catalysts[D]. Beijing: University of Chinese Academy of Science, 2004.
9. [9]
  ARTYUKH Y N, LUNEY N K, VERKHGRADSKII O P, ZELENKOV G A, OEVA L A, LIMOVICH E A. Effect of the introduction of certain additives to the CO+H₂ mixture and the scheme for the formation of alcohols higher than C₁[J]. Theor Exp Chem, 1990,26:476-479. doi: 10.1007/BF00530266
10. [10]
  BERETTA A, LIETTI L, TRONCONI E, FORZATTI P, PASQUON I. Development of a mechanistic kinetic model of the higher alcohol synthesis over a Cs-doped Zn/Cr/O catalyst 2. Analysis of chemical enrichment experiments[J]. Ind Eng Chem Res, 1996,35:2154-2160.
11. [11]
  WU Y Q, XIE H J, KOU Y L, NORITASTU T, HAN Y Z, TAN Y S. The mechanism of higher alcohol formation on ZrO₂-based catalyst from syngas[J]. Korean J Chem Eng, 2015,32:406-412.
12. [12]
  XU X, DOESBURG E B M, SCHOLTEN J J F. Synthesis of higher alcohols from syngas recent patented catalysts and tentative on the mechanism[J]. Catal Today, 1987,2:125-170. doi: 10.1016/0920-5861(87)80002-0
13. [13]
  AO M, PHAM G H, SUNARSO J, TADE M O, LIU S. Active centers of catalysts for higher alcohol synthesis from syngas:A review[J]. ACS Catal, 2018,8:7025-7050.
14. [14]
  LUK H T, MONDELI C, FERRE D C, STEWART J A, PEREZ-RAMIREZ J. Status and prospects in higher alcohols synthesis from syngas[J]. Chem Soc Rev, 2017,46:1358-1426.
15. [15]
  WANG P, CHEN S Y, BAI Y X, GAO X F, LI X L, SUN K, XIE H J, YANG G H, HAN Y Z, TAN Y S. Effect of the promoter and support on cobalt-based catalysts for higher alcohols synthesis through CO hydrogenation[J]. Fuel, 2017,195:69-81.
16. [16]
  SPIVEY J J, EGBEBI A. Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas[J]. Chem Soc Rev, 2007,36:1514-1528.
17. [17]
  XIAO K, BAO Z, QI X, WANG X, ZHONG L, FANG K, LIN M, SUN Y. Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J]. Chin J Catal, 2013,34:116-129.
18. [18]
  XIAO K, QI X, BAO Z, WANG X, ZHONG L, FANG K, LIN M, SUN Y. CuFe, CuCo and CuNi nanoparticles as catalysts for higher alcohol synthesis from syngas:a comparative study[J]. Catal Sci Technol, 2013,3:1591-1602.
19. [19]
  SUN X, YU Y, ZHANG M. Insight into the effect of promoter Co on C₂ oxygenate formation from syngas on CoCu(100) and Cu(100):a comparative DFT study[J]. Appl Surf Sci, 2018,434:28-39. doi: 10.1016/j.apsusc.2017.10.164
20. [20]
  AO M, PHAM G H, SAGE V, PAREEK V. Selectivity enhancement for higher alcohols synthesis product in Fischer-Tropsch synthesis over nickel-substituted La_0.9Sr_0.1CoO₃ perovskite catalysts[J]. Fuel, 2017,206:390-400.
21. [21]
  AO M, PHAM G H, SAGE V, PAREEK V, LIU S M. Perovskite-derived trimetallic Co-Ni-Cu catalyst for higher alcohol synthesis from syngas[J]. Fuel Process Technol, 2019,193:141-148.
22. [22]
  CHEN Xiao-ping. Study on F-T element modified Cu/Mn/ZrO₂ methanol catalysts for higher alcohol synthesis[D]. Beijing: University of Chinese Academy of Science, 1999.
23. [23]
  XU R, YANG C, WEI W, LI W H, SUN Y H, HU T D. Influence of promoter on catalytic properties of Cu-Mn-Fe/ZrO₂ catalysts for alcohols synthesis[J]. React Kinet Catal Lett, 2004,81:91-98.
24. [24]
  LI W Z, HUANG H, LI H J, ZHANG W, LIU H C. Facile synthesis of pure monoclinic and tetragonal zirconia nanoparticles and their phase effects on the behavior of supported molybdena catalysts for methanol-selective oxidation[J]. Langmuir, 2008,24:8358-8366.
25. [25]
  LI G R, LI W, ZHANG M H, TAO K Y. Characterization and catalytic application of homogeneous nano-composite oxides ZrO₂-Al₂O₃[J]. Catal Today, 2004,93(5):95-601. doi: 10.1016/j.cattod.2004.06.010
26. [26]
  SUN K, WU Y Q, TAN M H, WANG L Y, YANG G H, ZHANG M, ZHANG W, TAN YS. Ethanol and higher alcohols synthesis from syngas over CuCoM (M=Fe, Cr, Ga and Al) nanoplates derived from hydrotalcite-like precursors[J]. ChemCatChem, 2019,11:2695-2706. doi: 10.1002/cctc.201900096
27. [27]
  AVGOUROPOULOS G, IOANNIDES T, MATRALIS H. Influence of the preparation method on the performance of CuO-CeO₂ catalysts for the selective oxidation of CO[J]. Appl Catal B:Environ, 2005,56:87-93.
28. [28]
  WU Y Q, XIE H J, TIAN S P, NORITATSU T, HAN Y Z, TAN Y S. Isobutanol synthesis from syngas over K-Cu/ZrO₂-La₂O₃(x) catalysts:Effect of La-loading[J]. J Mol Catal A:Chem, 2015,396:254-260. doi: 10.1016/j.molcata.2014.10.003
29. [29]
  YU Q, YAO X J, ZHANG H L, GAO F, DONG L. Effect of ZrO₂ addition method on the activity of Al₂O₃-supported CuO for NO reduction with CO:Impregnation vs. co-precipitation[J]. Appl Catal A:Gen, 2012,423/424:42-51. doi: 10.1016/j.apcata.2012.02.017
30. [30]
  RIBEIRO N F P, SOUZA M M V M, SCHMAL M. Combustion synthesis of copper catalysts for selective CO oxidation[J]. J Power Sources, 2008,179:329-330. doi: 10.1016/j.jpowsour.2007.12.096
31. [31]
  WU Y Q, WANG S C, XIE H J, GAO J W, TIAN S P, HAN Y Z, TAN Y S. Influence of Cu on the K-LaZrO₂ Catalyst for Isobutanol Synthesis[J]. Acta Phys Chim Sin, 2015,31(1):166-172.
32. [32]
  JUNG K T, BELL A T. An in situ infrared study of dimethyl carbonate synthesis from carbon dioxide and methanol over zirconia[J]. J Catal, 2001,204:339-347.
33. [33]
  POKROVSKI K, JUNG K T, BELL A T. Investigation of CO and CO₂ adsorption on tetragonal and monoclinic zirconia[J]. Langmuir, 2001,17:4297-4300. doi: 10.1016/j.jpowsour.2007.12.096
34. [34]
  SANTOS V P, VANDER L B, CHOJECKI A, BUDRONI G, CORTHALS S, SHIBATA H, MEIMA G R, KAPTEIJIN F, MAKKEE M, GASCON J. Mechanistic insight into the synthesis of higher alcohols from syngas:The role of K promotion on MoS₂ catalysts[J]. ACS Catal, 2013,3:1634-1637. doi: 10.1021/cs4003518
35. [35]
  WU Y Q, GONG N N, ZHANG M, ZHANG W, ZHANG T, ZHANG J F, WANG L Y, XIE H J, TAN Y S. Insight into the branched alcohol formation mechanism on K-ZnCr catalysts from syngas[J]. Catal Sci Technol, 2019,9(10):2592-2600. doi: 10.1039/C9CY00542K
1. [1]
  Doudou Liu , Weiwei Guo , Guoliang Mei , Youpeng Dan , Rong Yang , Chao Huang , Yanling Zhai , Xiaoquan Lu . Application of catalyst Cu-t-ZrO₂ based on the electronic metal-support interaction in electrocatalytic nitrate reduction. Chinese Chemical Letters, 2025, 36(8): 110578-. doi: 10.1016/j.cclet.2024.110578
2. [2]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
3. [3]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-0. doi: 10.1016/j.actphy.2025.100054
4. [4]
  Xiaorui Chen , Xuan Luo , Tongming Su , Xinling Xie , Liuyun Chen , Yuejing Bin , Zuzeng Qin , Hongbing Ji . Ga-doped Cu/γ-Al₂O₃ bifunctional interface sites promote the direct hydrogenation of CO₂ to DME. Acta Physico-Chimica Sinica, 2025, 41(10): 100126-0. doi: 10.1016/j.actphy.2025.100126
5. [5]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
6. [6]
  Qinhui Guan , Yuhao Guo , Na Li , Jing Li , Tingjiang Yan . Molecular sieve-mediated indium oxide catalysts for enhancing photocatalytic CO₂ hydrogenation. Acta Physico-Chimica Sinica, 2025, 41(11): 100133-0. doi: 10.1016/j.actphy.2025.100133
7. [7]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
8. [8]
  Yongqing Xu , Yuyao Yang , Mengna Wu , Xiaoxiao Yang , Xuan Bie , Shiyu Zhang , Qinghai Li , Yanguo Zhang , Chenwei Zhang , Robert E. Przekop , Bogna Sztorch , Dariusz Brzakalski , Hui Zhou . Review on Using Molybdenum Carbides for the Thermal Catalysis of CO₂ Hydrogenation to Produce High-Value-Added Chemicals and Fuels. Acta Physico-Chimica Sinica, 2024, 40(4): 2304003-0. doi: 10.3866/PKU.WHXB202304003
9. [9]
  Zhipeng Bao , Yilin Wang , Yu Chen , Beirui Jia , Congcong Wang , Zean Xie , Xuehua Yu , Zhen Zhao . Digital and Intelligent Integration under the “Dual Carbon” Strategy: Plasma Reaction-Separation Coupling for CO₂ Hydrogenation to Methanol. University Chemistry, 2026, 41(1): 29-40. doi: 10.12461/PKU.DXHX202506009
10. [10]
  Beibei Gao , Lipeng Zhou , Dexin Yang . Integrating the “Dual Carbon” Concept into Teaching Reform of Physical Chemistry: A Case of CO₂ Hydrogenation to CH₃OH. University Chemistry, 2026, 41(3): 248-253. doi: 10.12461/PKU.DXHX202504011
11. [11]
  Dawei Han , Jing Xiong , Yitao Yang , Zhenpeng Wang , Qifeng Sun , Zhen Zhao , Yuechang Wei . Binary Ni-Ce active sites embedded on 3D ordered macro-mesoporous ZrO₂ for boosting coke-resistance dry reforming of methane. Chinese Chemical Letters, 2026, 37(11): 113210-. doi: 10.1016/j.cclet.2026.113210
12. [12]
  Yuanyuan Zeng , Xiaoti Chang , Jingru Li , Qilin Wang . 骨架编辑策略：异喹啉到2-氨基-1-萘甲醛的转化. University Chemistry, 2026, 41(10): 309-315. doi: 10.12461/PKU.DXHX202510028
13. [13]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
14. [14]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
15. [15]
  Mengyun Wu , Yuxin Deng , Wenhui Wang , Dongdong Xu , Langui Xie , Peipei Sun . 电化学合成4-氯-2-三异丙基硅基喹啉. University Chemistry, 2026, 41(5): 222-229. doi: 10.12461/PKU.DXHX202511044
16. [16]
  Yufei Jia , Fei Li , Ke Fan . Surface reconstruction of Cu-based bimetallic catalysts for electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100255-100255. doi: 10.1016/j.cjsc.2024.100255
17. [17]
  Zekun Zhang , Shiji Li , Qian Zhang , Shanshan Li , Liu Yang , Wei Yan , Hao Xu . Further study of CO₂ electrochemical reduction to gas products on Cu: Influence of the electrolyte. Chinese Chemical Letters, 2025, 36(9): 110742-. doi: 10.1016/j.cclet.2024.110742
18. [18]
  Yanping Qiu , Lei Ge . Low-coordination Cu3 motif for selective photocatalytic conversion of CO2 to ethanol. Chinese Journal of Structural Chemistry, 2025, 44(11): 100716-100716. doi: 10.1016/j.cjsc.2025.100716
19. [19]
  Wei Peng , Yao Shen , Xiaolin Yu , Chenghang Zheng , Xiao Zhang , Jingkai Zhao , Jiexu Ye , Shihan Zhang , Xiang Gao . Asymmetric coupling of atop-type and hollow-type adsorbed *CO to boost electrocatalytic CO₂-to-C₂ conversion on high-index Cu₂O crystal planes. Chinese Chemical Letters, 2026, 37(1): 111187-. doi: 10.1016/j.cclet.2025.111187
20. [20]
  Yuhan Zheng , Yunzhen Jia , Xuelei Lang , Dazhong Zhong , Jinping Li , Qiang Zhao . Stabilizing Cu²⁺ in perovskite via A-site modulation for efficient CO₂ electrocatalysis to CH₄. Chinese Chemical Letters, 2025, 36(8): 111193-. doi: 10.1016/j.cclet.2025.111193

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(1811)
HTML views(267)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Study on the performance of F-T component modified KCuZrO2 catalyst for CO hydrogenation to isobutanol

Metrics

通讯作者: 陈斌, bchen63@163.com

Study on the performance of F-T component modified KCuZrO₂ catalyst for CO hydrogenation to isobutanol