Citation: DENG Hao-yue, GAO Zhi-hua, HUANG Wei. Effect of heat treatment time on the performance of CuZnAl catalysts in the synthesis of higher alcohols from syngas[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(5): 532-539. shu

Effect of heat treatment time on the performance of CuZnAl catalysts in the synthesis of higher alcohols from syngas

Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China

Corresponding author: GAO Zhi-hua, gaozhihua@tyut.edu.cn
Received Date: 25 January 2019
Revised Date: 19 March 2019

Fund Project: Natural Science Foundation of Shanxi Province 201601D011021The project was supported by the National Natural Science Foundation of China (21336006) and Natural Science Foundation of Shanxi Province (201601D011021, 201601D202017)Natural Science Foundation of Shanxi Province 201601D202017the National Natural Science Foundation of China 21336006

Figures(6)

A series of CuZnAl catalysts were prepared by the complete liquid-phase method with different heat treatment times and characterized by XPS, XRD, H₂-TPR, NH₃-TPD-MS and N₂ adsorption-desorption; their catalytic performances in the synthesis of higher alcohols from syngas were investigated in a slurry bed reactor. The results indicate that an increase in the heat treatment time can enhance the interaction between the Cu and Al species and alter the amount of Cu⁺ species over the CuZnAl catalysts, influencing the synergistic effect of Cu⁺-Cu⁰ sites. In addition, with the increase of heat treatment time, the surface acidity of CuZnAl catalyst decreases, accompanying with an increase in the pore volume and pore size; small amount of surface weak acid sites, large pore volume and large pore size are beneficial to the formation of higher alcohols. The CuZnAl catalyst obtained by heat-treating for 7 h exhibits excellent performance in the synthesis of higher alcohols, with a CO conversion of 38.1% and a higher alcohols mass fraction of 65.9% in the total alcohols.
- complete liquid-phase method,
- CuZnAl catalyst,
- heat treatment time,
- higher alcohols,
- Cu⁺-Cu⁰
1. [1]
  SUBRAMANI V, GANGWAL S K. A review of recent literature to search for an efficient catalytic process for the conversion of syngas to ethanol[J]. Energy Fuels, 2008,22(2):117-136.
2. [2]
  GUPTA M, SMITH M L, SPIVEY J J. Heterogeneous catalytic conversion of dry syngas to ethanol and higher alcohols on cu-based catalysts[J]. Acs Catal, 2011,1(6):641-656. doi: 10.1021/cs2001048
3. [3]
  LUK H T, MONDELLI C, FERRE D C, STEWART J A, PEREZ R. Status and prospects in higher alcohols synthesis from syngas[J]. Chem Soc Rev, 2017,46(5):1358-1426. doi: 10.1039/C6CS00324A
4. [4]
  JAKOBSEN J G, JAKOBSEN M, CHORKENDORFF I, SEHESTED J. Methane steam reforming kinetics for a rhodium-based catalyst[J]. Catal Lett, 2010,140(3):90-97.
5. [5]
  BAEK S C, BAE J W, CHEON J Y, JUN K W, LEE K Y. Combined steam and carbon dioxide reforming of methane on Ni/MgAl₂O₄:Effect of CeO₂ promoter to catalytic performance[J]. Catal Lett, 2011,141(2):224-234.
6. [6]
  MEI D, ROUSSEAU R, KATHMANN S M. Ethanol synthesis from syngas over Rh-based/SiO₂ catalysts:A combined experimental and theoretical modeling study[J]. J Catal, 2010,271(2):325-342.
7. [7]
  YANG X M, WEI Y, SU Y L, ZHOU L P. Characterization of fused Fe-Cu based catalyst for higher alcohols synthesis and DRIFTS investigation of TPSR[J]. Fuel Process Technol, 2010,91(9):1168-1173. doi: 10.1016/j.fuproc.2010.03.032
8. [8]
  HERACLEOUS E, LIAKAKOU E T, LAPPAS A A, LEMONIDOU A A. Investigation of K-promoted Cu-Zn-Al, Cu-X-Al and Cu-Zn-X (X=Cr, Mn) catalysts for carbon monoxide hydrogenation to higher alcohols[J]. Appl Catal A:Gen, 2013,455(2):145-154.
9. [9]
  GAO Z H, HAO L F, HUANG W, XIE K C. A novel liquid-phase technology for the preparation of slurry catalysts[J]. Catal Lett, 2005,102(3/4):139-141.
10. [10]
  HUANG W, YU L M, LI W H, MA Z L. Synthesis of methanol and ethanol over CuZnAl slurry catalyst prepared by complete liquid-phase technology[J]. Front Chem Eng China, 2010,4(4):472-475.
11. [11]
  YU Shi-rui. Study on the preparation and performance of Cu-based catalyst for ethanol synthesis in slurry reactor[D]. Taiyuan: Taiyuan University of Technology, 2013.
12. [12]
  LIU Yong-jun. Study on the ethanol synthesis from syngas over CuZnAl catalysts[D]. Taiyuan: Taiyuan University of Technology, 2016.
13. [13]
  DONG Wei-bing. Effect of heat treatment conditions on catalytic performance of CuZnAl catalysts for higher alcohol synthesis[D]. Taiyuan: Taiyuan University of Technology, 2017.
14. [14]
  SCHULZ H. Short history and present trends of Fischer-Tropsch synthesis[J]. Appl Catal A:Gen, 1999,186(1/2):3-12.
15. [15]
  YE Tong-qi, ZHANG Zhao-xia, XU Yong, YAN Shi-zhi, ZHU Jiu-fang, LIU Yong, LI Quan-xin. Higher alcohol synthesis from bio-syngas over Na-promoted CuCoMn catalyst[J]. Acta Phys-Chim Sin, 2011,27(6):1493-1500. doi: 10.3866/PKU.WHXB20110610
16. [16]
  BOZ I. Higher alcohol synthesis over a K-promoted Co₂O₃/CuO/ZnO/Al₂O₃ catalyst[J]. Catal Lett, 2003,87(3/4):187-194. doi: 10.1023/A:1023499324647
17. [17]
  LI Z H, ZUO Z J, HUANG W, XIE K C. Research on Si-Al based catalysts prepared by complete liquid-phase method for DME synthesis in a slurry reactor[J]. Appl Surf Sci, 2011,257(6):2180-2183. doi: 10.1016/j.apsusc.2010.09.069
18. [18]
  SUH Y W, MOON S H, RHEE H K. Active sites in Cu/ZnO/ZrO₂ catalysts for methanol synthesis from CO/H₂[J]. Catal Today, 2000,63(2/4):447-452.
19. [19]
  GAO W, ZHAO Y F, LIU J M, HUANG Q W, HE S, LI C M, ZHAO J W, WEI M. Catalytic conversion of syngas to mixed alcohols over CuFe-based catalysts derived from layered double hydroxides[J]. Catal Sci Technol, 2013,3(5):1324-1332. doi: 10.1039/c3cy00025g
20. [20]
  FIGUEIREDO R T, MARTINEZ-ARIAS A, GRANADOS M L, FIERRO J L G. Spectroscopic evidence of Cu-Al interactions in Cu-Zn-Al mixed oxide catalysts used in CO hydrogenation[J]. J Catal, 1998,178(1):146-152.
21. [21]
  GAO Zhi-hua, HUANG Wei, LI Jun-fang, YIN Li-hua, XIE Ke-chang. Liquid-phase preparation of DME slurry catalysts using pseudo-boehmite as aluminum source[J]. Chem J Chin Univ, 2009,30(3):534-538. doi: 10.3321/j.issn:0251-0790.2009.03.020
22. [22]
  FANG De-ren, LIU Zhong-min, LIU De-chen, ZHANG Hui-min, MENG Shuang-he, WANG Li-gang. Influence of Al salt addition methods on performance of CuO/ZnO/Al₂O₃ catalysts[J]. Petrochem Technol, 2004,33(11):1041-1045. doi: 10.3321/j.issn:1000-8144.2004.11.008
23. [23]
  LIU Y J, ZUO Z J, LIU C B, LI C, DENG X, HUANG W. Higher alcohols synthesis via CO hydrogenation on Cu/Zn/Al/Zr catalysts without alkalis and F-T elements[J]. Fuel Process Technol, 2016,144:186-190. doi: 10.1016/j.fuproc.2016.01.005
24. [24]
  DONG Wei-bing, HAO Shu-hong, GAO Zhi-hua. Effect of preheating liquid paraffin on synthesis of higher alcohols by CuZnAl catalyst[J]. Nat Gas Chem Ind, 2017,42(5):27-33. doi: 10.3969/j.issn.1001-9219.2017.05.006
25. [25]
  MAO Dong-sen, GUO Qiang-sheng, YU Jun, HAN Lu-peng, LU Guan-zhong. Effect of cerium addition on the catalytic performance of Cu-Fe/SiO₂ for the synthesis of lower alcohols from syngas[J]. Acta Phys-Chim Sin, 2011,27(11):2639-2645. doi: 10.3866/PKU.WHXB20111125
26. [26]
  XU Hui-yuan, CHU Wei, SHI Li-min, ZHANG Hui, DENG Si-yu. Effect of glow discharge plasma on copper-cobalt-aluminum catalysts for higher alcohols synthesis[J]. J Fuel Chem Technol, 2009,37(2):212-216. doi: 10.3969/j.issn.0253-2409.2009.02.016
27. [27]
  CHU W, KIEFFER R, KIENNEMANN A, HINDERMANN J P. Conversion of syngas to C1-C6 alcohol mixtures on promoted CuLa₂Zr₂O₇ catalysts[J]. Appl Catal A:Gen, 1995,27(121):95-111.
28. [28]
  OKAMOTO Y, FUKINO K, IMANAKA T, TERANISHI S. Surface characterization of copper(Ⅱ) oxide-zinc oxide methanol-synthesis catalysts by x-ray photoelectron spectroscopy. 2. Reduced catalysts[J]. J Phys Chem, 1983,87(19):3740-3747. doi: 10.1021/j100242a034
29. [29]
  FAN Jin-chuan, YANG Rui-qing, ZHAO Jie, HUANG Wei. Chemical change of copper species in liquid paraffin[J]. Chin J Appl Chem, 2013,30(1):67-72.
30. [30]
  LV Xiao-dong. The study of preparation and synthesis of ethanol of Cu-Zn-Al catalyst by complete liquid-phase technology[D]. Taiyuan: Taiyuan University of Technology, 2015.
31. [31]
  SUN Kai, ZHANG Xiao-yu, ZHANG Lin, BIAN Zhong-kai, HUANG Wei, ZHAO Zhi-huan. Influence of acidic and alkaline silica sols on the performance of Cu/Zn/Al slurry catalysts[J]. J Fuel Chem Technol, 2015,43(10):1221-1229. doi: 10.3969/j.issn.0253-2409.2015.10.010
32. [32]
  MA Qiang, HUANG Wei, FAN Jin-chuan, ZHAO Jie, REN Jie. Study on the deactivation of Cu-Zn-Si-Al slurry catalyst prepared by complete liquid-phase for one-step dimethyl ether synthesis[J]. J Mol Catal(China), 2009,23(6):499-505.
33. [33]
  GAO Z H, LIU Y, LI L L, LI S S, HUANG W. CuZnAl catalysts prepared by precipitation-hydrothermal method for higher alcohols synthesis from syngas[J]. Energy Source Part A, 2017,39(6):1-7.
34. [34]
  LIU Jian-guo, DING Ming-yue, WANG Tie-jun, MA Long-long. Structure and performance of Cu-Fe bimodal support for higher alcohol syntheses[J]. Acta Phys-Chim Sin, 2012,28(8):1964-1970. doi: 10.3866/PKU.WHXB201205213
1. [1]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
2. [2]
  Lele Feng , Xueying Bai , Jifeng Pang , Hongchen Cao , Xiaoyan Liu , Wenhao Luo , Xiaofeng Yang , Pengfei Wu , Mingyuan Zheng . Single-atom Pd boosted Cu catalysts for ethanol dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(9): 100100-0. doi: 10.1016/j.actphy.2025.100100
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]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
5. [5]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Research on Cu-Based and Pt-Based Catalysts for Hydrogen Production through Methanol Steam Reforming. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-0. doi: 10.1016/j.actphy.2025.100049
6. [6]
  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
7. [7]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
8. [8]
  Xueting Feng , Ziang Shang , Rong Qin , Yunhu Han . Advances in Single-Atom Catalysts for Electrocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2305005-0. doi: 10.3866/PKU.WHXB202305005
9. [9]
  Haoyu Sun , Dun Li , Yuanyuan Min , Yingying Wang , Yanyun Ma , Yiqun Zheng , Hongwen Huang . Hierarchical Palladium-Copper-Silver Porous Nanoflowers as Efficient Electrocatalysts for CO₂ Reduction to C₂₊ Products. Acta Physico-Chimica Sinica, 2024, 40(6): 2307007-0. doi: 10.3866/PKU.WHXB202307007
10. [10]
  Wenhao Chen , Muxuan Wu , Han Chen , Lue Mo , Yirong Zhu . Cu₂Se@C thin film with three-dimensional braided structure as a cathode material for enhanced Cu²⁺ storage. Chinese Chemical Letters, 2024, 35(5): 108698-. doi: 10.1016/j.cclet.2023.108698
11. [11]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-0. doi: 10.3866/PKU.WHXB202404012
12. [12]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-0. doi: 10.3866/PKU.WHXB202406005
13. [13]
  Lu Zhuoran , Li Shengkai , Lu Yuxuan , Wang Shuangyin , Zou Yuqin . Cleavage of C―C Bonds for Biomass Upgrading on Transition Metal Electrocatalysts. Acta Physico-Chimica Sinica, 2024, 40(4): 2306003-0. doi: 10.3866/PKU.WHXB202306003
14. [14]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
15. [15]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
16. [16]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
17. [17]
  Xichen YAO , Shuxian WANG , Yun WANG , Cheng WANG , Chuang ZHANG . Oxygen reduction performance of self?supported Fe/N/C three-dimensional aerogel catalyst layers. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1387-1396. doi: 10.11862/CJIC.20240384
18. [18]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
19. [19]
  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
20. [20]
  Yanxue Wu , Xijun Xu , Shanshan Shi , Fangkun Li , Shaomin Ji , Jingwei Zhao , Jun Liu , Yanping Huo . Facile construction of Cu_2-xSe@C nanobelts as anode for superior sodium-ion storage. Chinese Chemical Letters, 2025, 36(6): 110062-. doi: 10.1016/j.cclet.2024.110062

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(855)
HTML views(62)

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