李思洁,吴国星,郭益铜,柳婧,王吉垒,郭洪臣.酸、碱处理对HY沸石酸性和环己酮肟液相贝克曼重排反应的影响[J].分子催化编辑部,2021,35(3):201-214
酸、碱处理对HY沸石酸性和环己酮肟液相贝克曼重排反应的影响
Effect of Alkali and Acid Modification on HY Zeolite and Its Catalytic Performance in Liquid-phase Beckmann Rearrangement Reaction of Cyclohexanone Oxime
投稿时间:2020-11-08  修订日期:2021-01-13
DOI:10.16084/j.issn1001-3555.2021.03.001
中文关键词:  负Y沸石  碱-酸改性  酸性  环己酮肟  液相贝克曼重排反应
英文关键词:Y zeolite  alkali-acid modification  acidity  cyclohexanone oxime  liquid-phase Beckmann rearrangement
基金项目:
作者单位E-mail
李思洁 大连理工大学 催化化学与工程系, 精细化工国家重点实验室, 辽宁 大连 116024  
吴国星 大连理工大学 催化化学与工程系, 精细化工国家重点实验室, 辽宁 大连 116024  
郭益铜 大连理工大学 催化化学与工程系, 精细化工国家重点实验室, 辽宁 大连 116024  
柳婧 大连理工大学 催化化学与工程系, 精细化工国家重点实验室, 辽宁 大连 116024  
王吉垒 大连理工大学 催化化学与工程系, 精细化工国家重点实验室, 辽宁 大连 116024  
郭洪臣 大连理工大学 催化化学与工程系, 精细化工国家重点实验室, 辽宁 大连 116024 hongchenguo@dlut.edu.cn 
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中文摘要:
      采用FT-IR、NH3-TPD和27Al MAS NMR等催化剂表征手段和间歇反应方法,系统研究了NaOH溶液(0.2~0.4 mol/L)的碱改性和NaOH溶液与硝酸溶液(0.2 mol/L)的碱-酸组合改性对一种氢型Y沸石(Si/Al=7.5)的物化性质和环己酮肟液相贝克曼重排反应性能的影响.结果表明,碱改性具有脱硅作用,可使Y沸石的表面Bronsted酸中心和Lewis酸中心数量显著增加.酸处理具有脱铝作用,可以选择性地脱除Y沸石中的一部分非骨架铝,从而降低碱改性催化剂的Lewis酸性.用0.2 mol/L NaOH溶液和0.2 mol/L硝酸溶液通过碱-酸组合改性得到的催化剂DeSiAl-Y-0.2在环己酮肟液相重排反应中表现出较好性能.在以苯甲腈为溶剂、反应温度和时间分别为130℃和3 h的条件下,其环己酮肟转化率和己内酰胺选择性都达到了82.9%,分别比Y沸石母体提高了18%和1.5%.在DeSiAl-Y-0.2催化剂上初步开展了反应条件和溶剂效应的研究工作,从中可以看出研制用于环己酮肟液相重排反应的Y型沸石催化剂的关键在于提高其己内酰胺选择性.
英文摘要:
      The influences of an alkali modification with NaOH solution (0.2~0.4 mol/L) and a combinational alkali-acid modification with NaOH solution and nitric acid solution (0.2 mol/L) on the physicochemical properties of a HY zeolite (Si/Al=7.5) as well as its catalytic performancein the liquid-phase Beckmann rearrangement reaction of cyclohexanone oxime were systematically studied with multiple catalyst characterization methods such as FT-IR, NH3-TPD, and 27Al MAS NMR, and batch reaction method. Results show that alkali modification has a desiliconisation effect whichcan significantly increase the number of Bronsted acid and Lewis acid centers on the surface of Y zeolite. The acid treatment has a dealumination effect which can selectively remove part of the non-framework aluminum in the Y zeolite and consequently reduce the Lewis acidity of the alkali-modified catalyst. A catalyst DeSiAl-Y-0.2 obtained by the combinational alkali-acid modification with 0.2 mol/L NaOH solutionand 0.2 mol/L nitric acid solution, shows better performance in the liquid-phase Beckmann rearrangement reaction of cycloheanone oxime. When benzonitrile was used as solvent and the rearrangement reaction was carried out at 130 ℃ for 3 h, both the conversion of cyclohexanone oxime and selectivity of caprolactam of the catalyst reached 82.9%, increased by 18% and 1.5%, respectively, if the corresponding values of HY zeolite parent was compared with. Preliminary researches on reaction conditions and solvent effects were also carried out with DeSiAl-Y-0.2 catalyst. These researches show that the key to the preparation of a Y zeolite catalyst for the liquid-phase Beckmann rearrangement reaction of cyclohexanone oxime is to increase its caprolactam selectivity.
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