Synthesis of 1,4-butynediol via ethynylation of formaldehyde over Cu/Bi/kieselguhr catalyst
CHEN Ke-xiang, LIN Ke-jing, ZHENG Ti-yan, WANG Peng, GAO Feng, YANG Gui-hua
Key Laboratory of Oil & Gas Fine Chemicals of Ministry of Education and Xinjiang Uyghur Autonomous Region, College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China
Abstract: Cu-Bi based catalysts loaded on kieselguhr are prepared by impregnation and solid grinding methods,respectively,and applied in the ethynylation of formaldehyde for synthesis of 1,4-butynediol.These catalyst samples are characterized by XRD,H2-TPR,SEM,TEM,N2 adsorption/desorption.It is found that Cu-Bi based catalyst prepared by solid grinding method exhibits the higher catalytic activity,over which the conversion of formaldehyde can reach 70% and the selectivity of 1,4-butynediol achieves 86% after the reaction has performed for 7 h under atmospheric pressure.The performance is equivalent to that of commercial catalyst.It is attributed to the catalysts with the bigger surface area,smaller CuO particles size and CuO well dispersed in kieselguhr,forming more active centers.
陈可祥, 林柯静, 郑体彦, 王鹏, 高峰, 杨桂花. 硅藻土铜铋基催化剂炔醛化反应合成1,4-丁炔二醇的研究[J]. 现代化工, 2021, 41(3): 130-133,139.
CHEN Ke-xiang, LIN Ke-jing, ZHENG Ti-yan, WANG Peng, GAO Feng, YANG Gui-hua. Synthesis of 1,4-butynediol via ethynylation of formaldehyde over Cu/Bi/kieselguhr catalyst. Modern Chemical Industry, 2021, 41(3): 130-133,139.
[1] Trotus I T,Zimmermann T,Schüth F.Catalytic reactions of acetylene:A feedstock for the chemical industry revisited[J].Chemical Reviews,2014,114:1761-82. [2] 伍小明.我国1,4-丁二醇的市场分析[J].精细与专用化学品,2018,26(11):13-15. [3] 陈海红.1,4-丁二醇生产工艺及其技术进展[J].精细石油化工进展,2014,15(1):46-58. [4] Reppe W,Keyssner E.Production of alkinols:US,2232867[P].1941-02-25. [5] Kirchner J R.Ethynylation catalyst,catalyst preparation,and process:US,3650985[P].1972-03-21. [6] 杨桂花,王吉德,徐世美,等.炔醛法合成1,4-丁炔二醇催化剂研究进展[J].材料导报,2014,28(19):68-74. [7] 杜建强,邓少亮,孙继光,等.合成1,4-丁炔二醇的孔雀石催化剂研究[J].辽宁化工,2016,45:677-678. [8] 郑艳,孙自瑾,王永钊,等.CuO-Bi2O3/SiO2-MgO催化剂的制备及炔化性能[J].分子催化,2012,(3):233-238. [9] 王志鹏,牛珠珠,班丽君,等.不同晶相TiO2负载Cu2O催化甲醛乙炔化反应[J].高等学校化学学报,40(2):334-341. [10] Li H T,Ban L J,Niu Z Z,et al.Application of CuxO-FeyOz Nanocatalysts in Ethynylation of Formaldehyde[J].Nanomaterials,2019,9:1301-1316. [11] Wang Z P,Ban L J,Meng P F,et al.Ethynylation of formaldehyde over CuO/SiO2 catalysts modified by Mg species:Effects of the existential states of Mg species[J].Nanomaterials,2019,9:1137-1158. [12] Yang G H,Yu Y M,Tahir M U,et al.Promotion effect of Bi species in Cu/Bi/MCM-41 catalysts for 1,4-butynediol synthesis by ethynylation of formaldehyde[J].Reaction Kinetics,Mechanisms and Catalysis,2019,127(1):42-436. [13] Liu P,He H P,Wei G L,et al.An efficient catalyst of manganese supported on diatomite for toluene oxidation:Manganese species,catalytic performance,and structureactivity relationship[J].Microporous and Mesoporous Materials,2017,239:101-110. [14] Toshtay K,Auezov A B.Hydrogenation of vegetable oils over a palladium catalyst supported on activated diatomite[J].Catalysis in Industry,2020,12:7-15. [15] Guo S F,Shi L.Synthesis of succinic anhydride from maleic anhydride on Ni/diatomite catalysts[J].Catalysis Today,2013,212:137-141. [16] Du X Q,Huang J W,Feng Y Y,et al.Flower-like 3D CuO microsphere acting as photocatalytic water oxidation catalyst[J].Chinese Journal of Catalysis,2016,37:123-134. [17] Wang Z P,Ban L J,Meng P F,et al.Ethynylation of formaldehyde over binary Cu-based catalysts:Study on synergistic effect between Cu+ species and acid/base sites[J].Nanomaterials,2019,9:1038-1054. [18] Sun Z M,Bai C H,Zheng S L,et al.A comparative study of different porous amorphous silica minerals supported TiO2 catalysts[J].Applied Catalysis A:General,2013,458:103-110. [19] Yue C J,Yao S S,Gu L P.Diatomite-entrapped hydrosulfate catalysts for the efficient nitration of toluene with nitric acid[J].Journal of Porous Material,2015,22:455-464. [20] Santos S C G,Machado S W M,Garrido Pedrosa A M,et al.Development of micro-mesoporous composite material of the ZSM-12/MCM-41 type for the CO2 adsorption[J].Journal of Porous Material,2015,22:1145-1151.