| 载体H+含量对CuY甲醇氧化羰基化反应性能影响 |
| Influence of H+ Contents of Support on CuY Catalyst for Catalytic Performances of Oxidative Carbonylation of Methanol |
| 作者 | 单位 | E-mail | | 李梦云 | 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 | | | 付廷俊 | 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 | | | 王玉春 | 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 | | | 阎立飞 | 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 | | | 李忠 | 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 | lizhong@tyut.edu.cn |
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| 摘要: 通过过量浸渍Cu（NO3）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109.1 mg·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 |
| 基金项目: 国家自然科学基金（No.21276169，U151020023）资助项目。 |
| 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 |
| 投稿时间：2016-03-05 修订日期：2016-08-30 |
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| 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. |
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