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载体H+含量对CuY甲醇氧化羰基化反应性能影响
引用本文:李梦云,付廷俊,王玉春,阎立飞,李忠.载体H+含量对CuY甲醇氧化羰基化反应性能影响[J].无机化学学报,2016,32(11):1951-1958.
作者姓名:李梦云  付廷俊  王玉春  阎立飞  李忠
作者单位:太原理工大学煤化工研究所, 煤科学与技术教育部和山西省重点实验室, 太原 030024,太原理工大学煤化工研究所, 煤科学与技术教育部和山西省重点实验室, 太原 030024,太原理工大学煤化工研究所, 煤科学与技术教育部和山西省重点实验室, 太原 030024,太原理工大学煤化工研究所, 煤科学与技术教育部和山西省重点实验室, 太原 030024,太原理工大学煤化工研究所, 煤科学与技术教育部和山西省重点实验室, 太原 030024
基金项目:国家自然科学基金(No.21276169,U151020023)资助项目。
摘    要:通过过量浸渍Cu(NO_3)_2溶液于Y分子筛载体上,制备出Cu负载量为6.4%的CuY催化剂,考察了甲醇氧化羰基化反应的催化性能,并采用X射线衍射(XRD)、H2程序升温还原(H2-TPR)、透射电子显微镜(TEM)和NH3程序升温脱附(NH3-TPD)等手段对催化剂表面微观结构进行了表征。研究表明,随Y分子筛载体H+含量的增加,可使更多Cu物种落位于分子筛微孔笼结构中,且高度分散,而笼内未交换的Na+能进一步促进铜物种更多落位于载体超笼结构中,形成更多甲醇氧化羰基化反应的Cu+活性中心。同时随铜物种引入,催化剂中产生了明显的中强酸,酸量随落位于载体笼结构中的Cu物种的增加而增加,催化剂总酸量随之增加,导致甲醇氧化羰基化产物分布发生改变,碳酸二甲酯(DMC)选择性明显降低。对比等体积浸渍法制备的92.3%的高DMC选择性CuY催化剂,以不含H+的NaY分子筛为载体,过量浸渍法制备的CuY催化剂酸量少、Cu物种活性中心多,在保持82.4%的高DMC选择性时,其DMC的时空收率(STY)也高达109.1mg·g~(-1)·h-1。

关 键 词:甲醇氧化羰基化  Y分子筛  铜催化剂  酸性  产物选择性
收稿时间:3/5/2016 12:00:00 AM
修稿时间:2016/8/30 0:00:00

Influence of H+ Contents of Support on CuY Catalyst for Catalytic Performances of Oxidative Carbonylation of Methanol
LI Meng-Yun,FU Ting-Jun,WANG Yu-Chun,YAN Li-Fei and LI Zhong.Influence of H+ Contents of Support on CuY Catalyst for Catalytic Performances of Oxidative Carbonylation of Methanol[J].Chinese Journal of Inorganic Chemistry,2016,32(11):1951-1958.
Authors:LI Meng-Yun  FU Ting-Jun  WANG Yu-Chun  YAN Li-Fei and LI Zhong
Affiliation:Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China,Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China,Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China,Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China and Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China
Abstract:A series of Y zeolite supported Cu catalysts (CuY) with Cu loading of 6.4% were prepared by wet impregnation method and investigated in oxidative carbonylation of methanol. The microstructure and surface properties of the catalysts were characterized by X-ray diffraction (XRD), H2-temperature program reduction (H2-TPR), NH3-temperature program desorption (NH3-TPD), transmission electron microscope(TEM) techniques. With the increase of H+ content, the Y zeolite supports were more conductive to the cation exchangment with Cu2+, leading to well dispersed Cu species in cages. Above all, the non-exchanged Na+ of Y zeolite resulted in more Cu species located in the super cages. After calcination, the copper species converted into Cu+, which enhanced the catalytic activity of oxidative carbonylation of methanol. The introduction of Cu species into Y zeolite produced moderate acid sites and the amount of acid was also increased with the increase of Cu species located in the cages, As a result, the reaction product distribution varied and the selectivity of DMC decreased with the increase of H+ content. The CuY catalyst prepared by incipient-wetness impregnation method gave 92.3% selectivity of DMC, whereas the Cu catalyst supported on NaY zeolite by wet impregnation method gave 82.4% selectivity of DMC and high space-time yield (STY) of DMC, 109.1 mg·g-1·h-1.
Keywords:methanol oxidative carbonylation  Y zeolite  copper catalyst  acidity  product selectivity
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