| 介孔调变对CuY催化剂甲醇氧化羰基化反应活性的影响 |
| Influence of Mesoporous Modulation on CuY Catalyst for Oxidative Carbonylation of Methanol |
| 作者 | 单位 | E-mail | | 阎立飞 | 太原理工大学, 煤科学与技术教育部和山西省重点实验室, 太原 030024 | | | 张国强 | 太原理工大学, 煤科学与技术教育部和山西省重点实验室, 太原 030024 | | | 李艳娇 | 太原理工大学, 煤科学与技术教育部和山西省重点实验室, 太原 030024 | | | 郑华艳 | 太原理工大学, 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: 碱溶液处理NaY分子筛形成的介孔有利于反应物及产物分子的扩散，调节碱溶液浓度可控制Y分子筛中的介孔结构，通过溶液离子交换法制备CuY催化剂，研究了NaY分子筛介孔结构调变对CuY催化剂催化甲醇氧化羰基化反应活性的影响。通过BET、29Si-NMR、XRD、NH3/CO-TPD、H2-TPR和TEM等表征及催化活性分析表明，在碱溶液处理过程中，NaY分子筛骨架中的Si（0Al）和Si（1Al）原子被优先脱除，且笼结构坍塌使得临近超笼连接，逐步形成直径为3.47~3.66 nm，孔容介于0.142~0.226 cm3·g-1的介孔，在提高反应物分子和产物分子扩散性能的同时，提高了活性物种的可接近性。随着碱液浓度的增加，CuY催化剂的催化活性先升高后降低。当碱液浓度为0.2 mol·L-1时，NaY分子筛介孔直径为3.47 nm，孔容达到最大（0.226 cm3·g-1），相应CuY催化剂DMC的时空收率、选择性和甲醇转化率分别达到204.0 mg·g-1·h-1、67.8%和14.0%，活性最佳。 |
| 关键词: NaY分子筛 CuY催化剂 介孔 氧化羰基化 |
| 基金项目: 国家自然科学基金（No.U1510203，No.21276169）和山西省青年科技研究基金（No.2015021030）资助项目。 |
| Abstract: The mesoporous generated from the alkali treatment was conducive to the diffusion of the reactant and product molecules. Adjust the alkali solution concentration could control the mesoporous structure in Y zeolite, CuY catalysts were prepared by liquid ion exchange method employing NaY as supports and the influence of mesoporous modulation of NaY on the catalytic performace of CuY for oxidative carbonylation of methanol was investigated. The results of characterization (N2 adsorption-desorption, 29Si-NMR, XRD, NH3/CO-TPD, H2-TPR, TEM) and catalytic activity indicate that Si(0Al) and Si(1Al) atoms were selectively removed from zeolite framework, resulting in the cross-linking of nearby supercage and the formation of mesopores with diameter ranging from 3.47~3.66 nm and pore volume ranging from 0.142~0.226 cm3·g-1,the generated mesoporous is conducive to the improvement of the diffusion of reactants and products as well as the accessibility of active copper species. CuY catalytic activity increases and then decreases with the increase of alkali concentration. As the concentration of alkali solution is 0.2 mol·L-1, the mesoporous diameter was 3.47 nm and the mesoporous volume of NaY had attained the maximum (0.226 cm3·g-1). The corresponding CuY catalyst shows the optimal catalytic performance, the conversion of methanol, selectivity and space-time yield of DMC are 14.0%, 67.8% and 204.0 mg·g-1·h-1, respectively. |
| Keywords: NaY zeolite CuY catalyst mesoporous oxidativecarbonylation |
| 投稿时间：2017-03-04 修订日期：2017-06-02 |
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| 阎立飞,张国强,李艳娇,郑华艳,李忠.介孔调变对CuY催化剂甲醇氧化羰基化反应活性的影响[J].无机化学学报,2017,33(8):1435-1442. |
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