Abstract: A series of CuFeCrNi/ZnO catalysts with different Cu/Ni molar ratios (7/0.5,7/1.0,7/1.5,7/2.0) are prepared by stepwise precipitation method and their structures are characterized by nitrogen adsorption and XRD,etc.The catalytic performances of CuFeCrNi/ZnO catalysts in CO hydrogenation to make low-carbon alcohols are evaluated and the effects of reaction temperature and pressure on the catalytic properties of the catalysts are investigated by means of a continuous flow fixed bed micro-reactor.The results indicate that the addition of small amount of Ni auxiliary can help catalysts to expand BET surface area,facilitate the dispersion degree of oxide copper,promote the growth of carbon chain and increase the selectivity of C2+OH.Under a Cu/Ni ratio of 7/1.0,the prepared catalyst exhibits the highest BET surface area (85.09 m2·g-1),a higher selectivity of alcohols,the highest mass ratio of C2+OH to MeOH (0.67) and the maximum content of C2+OH in the liquid products.The conditions that are beneficial to the formation of C2+OH,especially propanol,in the synthesis of low-carbon alcohols over Cu7FeNi1.0/ZnO catalyst are as follows:reaction temperature is at 340℃,reaction pressure is 6 MPa,GHSV=5 000 h-1 and V(H2)/V(CO)=2.
段玉梅, 郑长征, 李亚斐, 丁羽佳, 张兴. Ni改性Cu-Fe基催化剂的制备及其在CO加氢制低碳醇中的性能研究[J]. 现代化工, 2018, 38(8): 139-142,144.
DUAN Yu-mei, ZHENG Chang-zheng, LI Ya-fei, DING Yu-jia, ZHANG Xing. Synthesis of Ni modified Cu-Fe based catalyst and its catalytic performance in production of low-carbon alcohols through CO hydrogenation. Modern Chemical Industry, 2018, 38(8): 139-142,144.
[1] 门秀杰,崔德春,于广欣,等.合成气制低碳醇技术在中国的研究进展及探讨[J].现代化工,2013,33(12):21-25. [2] 胡伟.合成气制低碳醇Cu-Fe催化剂的制备及改性机制研究[D].上海:华东理工大学,2017. [3] Jie S,Qiu X C,Yan W,et al.Promotional effects of cesium promoter on higher alcohol synthesis from syngas over cesium-promoted Cu/ZnO/Al2O3 catalysts[J].ACS Catal,2016,6:5771-5785. [4] Kararin M Walter,Martin Schubert,Wolfgang,et al.Effect of the addition of ethanol to synthesis gas on the production of higher alcohols over Cs and Ru modified Cu/ZnO catalysts[J].Ind Eng Chem Res,2015,54:1452-1463. [5] 张建国,宋昭峥,史德文.合成气合成低碳混合醇技术的研究[J].现代化工,2007,27:494-496. [6] Shi L M,Chu W,Deng S Y J.Studies on higher alcohols from syngas over the La promoted CuCo catalysts[J].Fuel Chem Technol,2012,40:436-440. [7] 韩涛,黄伟,王晓东,等.Ce-Cu-Co/CNTs催化剂催化合成气制低碳醇及乙醇的研究[J].物理化学学报,2014,30(11):2127-2133. [8] Guo H J,Zhang H R,Peng F,et al.Effects of Cu/Fe ratio on structure and performance of attapulgite supported CuFeCo-based catalyst for mixed alcohols synthesis from syngas[J].Applied Catalysis A:General,2015,503:51-61. [9] 郭强胜,毛东森,俞俊,等.不同载体对负载型Cu-Fe催化剂CO加氢反应性能的影响[J].燃料化学学报,2012,40(9):1103-1109. [10] 罗彩容,熊莲,郭海军.碱金属对CO加氢制备低碳醇Cu-Fe-Co基催化剂的影响[J].高校化学工程学报,2012,26(5):823-828. [11] Shi Xuemin,Yang Xuzhuang,Bai Fenghua,et al.Progress in additives of molybdenum based catalysts for higher alcohol synthesis from syngas[J].Chemical Industry and Engineering Process,2010,29(12):2291-2297. [12] Tang X B,Tsubaki N,Xie H J,et al.Effect of modifiers on the performance of Cu-ZnO-based catalysts for low-temperature methanol synthesis[J].Journal of Fuel Chemistry & Technology,2014,42(6):704-709. [13] Li D B,Qi H J,Li,et al.Surficial structure and charge effects of Ni promoted K2CO3/MoS2 catalysts for higher alcohols synthesis[J].Acta Physico-Chimica Sinica,2006,22(9):1132-1136. [14] Li D B,Yang C,Zhao N,et al.The performances of higher alcohol synthesis over nickel modified K2CO3/MOS2 catalyst[J].Fuel Processing Technology,2007,88(2):125-127. [15] Hu W,Li W,Shen R.CTAB-promoted MnCuFe/ZnO catalyst for the hydrogenation reaction of CO to low carbon alcohols[J].Energy Technology,2016,5(4):557-567. [16] 王宪贵.CO加氢合成低碳醇的研究[D].北京:中国矿业大学(北京),2013. [17] 姜涛,牛玉琴,钟炳.CO+H2合成醇体系的化学平衡分析[J].天然气化工,1999,(2):27-32.