草酸处理对丝光沸石催化二甲醚羰化反应性能的影响  

Effect of Oxalic Acid Treatment on Mordenite Structure and Catalytic Performance of Dimethyl Ether Carbonylation

作　　者：王晓胜[1] 刘少铎 杨韬 李然家[1] 余长春[1] 刘毓翔 谢正求 王永强 李晓娇 WANG Xiaosheng;LIU Shaoduo;YANG Tao;LI Ranjia;YU Changchun;LIU yuxiang;XIE Zhengqiu;WANG Yongqiang;LI Xiaojiao(College of New Energy and Materials,China University of Petroleun-Beijing,Beijing 102249,China;College ofChemical Engineering,Qingdao University of Science and Technology,Qingdao 266042,Shandong,China;Yueyang Jucheng Chemical Co,Ltd,Yueyang 414409,Hunan,China;Refining Department,China Petroleum and Chemical Corporation,Biing 100327,China;College of Economics and Management,China University of Petroleum Beiing,Beiing 102249,China)

机构地区：[1]中国石油大学(北京)新能源与材料学院,北京102249 [2]青岛科技大学化学工程学院,山东青岛266042 [3]岳阳聚成化工有限公司,湖南岳阳414009 [4]中国石油化工股份有限公司炼油事业部,北京100327 [5]中国石油大学(北京)经济管理学院,北京102249

出　　处：《硅酸盐学报》2022年第7期1955-1963,共9页Journal of The Chinese Ceramic Society

基　　金：国家自然科学基金(22008260);中国石油大学(北京)科研基金资助(2462021YJRC011);中国石油天然气集团有限公司-中国石油大学(北京)战略合作科技专项(ZLZX2020-04)。

摘　　要：丝光沸石是二甲醚羰基化反应的高活性催化剂,通过对其酸中心进行调控是进一步提高其催化性能的有效方法。采用不同浓度的草酸溶液对丝光沸石进行了酸处理,通过X射线粉末衍射、N2吸附-脱附、扫描电子显微镜、氨气-程序升温脱附、吡啶-红外等技术手段对草酸处理前后丝光沸石结构及酸中心的变化进行了表征。结果表明:草酸处理对丝光沸石的相对结晶度、晶型影响较小,但能够通过“蚀刻”或络合作用有效脱除部分酸中心,尤其是优先脱除十二元环孔道中的酸中心,同时能够在颗粒中制造出部分介孔、提升丝光沸石的介孔孔容。适当浓度的草酸处理能够有效提高丝光沸石的二甲醚羰基化反应活性,二甲醚转化率明显升高,乙酸甲酯选择性仅略有下降。草酸浓度过高时会脱除部分羰基化反应的活性中心,从而导致催化活性的降低。为丝光沸石的酸中心调控及其二甲醚羰基化反应活性的提高提供了简单有效的方法。Mordenite is highly active for the carbonylation of dimethyl ether reaction, and the regulation of its acid sites is an effective way to improve its catalytic performance. In this paper, a series of mordenite was subjected to the post-treatment of oxalic acid solution. The changes in the structure and acid sites were characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, NH3-temperature-programmed desorption and Py-infrared spectroscopy, respectively. The results show that the overall relative crystallinity and crystal phase of mordenite remain stable. However, the acid wash post-treatment can effectively remove parts of the acid sites through "etching" or complexation, especially those located in the twelve-membered ring channels.Meanwhile, it can create a certain amount of mesopores inside the particles, leading to an increase of the mesopore volume. The catalytic test results of dimethyl ether carbonylation reaction indicate that the sample treated with a suitable concentration of oxalic acid solution can effectively improve the dimethyl ether carbonylation activity. The dimethyl ether conversion significantly increases,despite the methyl acetate selectivity only slightly decreases. However, parts of the active sites responsible for the carbonylation reaction are removed when treated with high-concentration oxalic acid solution, resulting in a decrease in the catalytic activity. This research provides a simple and effective method for the regulation of the acid sites in mordenite and the improvement of its dimethyl ether carbonylation activity.

关 键 词：酸处理 丝光沸石 二甲醚 羰基化 

分 类 号：TE646[石油与天然气工程—油气加工工程]