Zr-β分子筛催化合成柠檬酸三丁酯性能研究
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摘要
本文首先通过草酸对β分子筛进行脱铝,再用硝酸氧锆对其进行改性制备了Zr-β分子筛,考察了改性时间对Zr-β分子筛结构的影响。采用柠檬酸与正丁醇反应制备柠檬酸三丁酯的反应对改性分子筛的催化性能进行研究。结果表明:改性时间24h的催化剂酸性较好。当Zr-β分子筛占反应原料的质量分数为3. 6%时,反应4h柠檬酸的转化率为74. 1%,高于浓硫酸的71. 5%。另外,柠檬酸与正丁醇物质的量比为1∶4时有最高的柠檬酸转化率。因此,Zr-β分子筛可代替浓硫酸作为合成柠檬酸三丁酯的固体催化剂。
Zirconium modified beta( Zr-β) zeolite was prepared by modification with Zr O( NO3)2after dealumination with oxalic acid. The effect of modification time on the Zr-β and its catalytic performance of citric acid and n-butanol for the synthesis of Tri-n-butyl citrate was investigated. The results showed that the conversion of citric acid was 74. 1% after 4 hour,which was higher than 71. 5% of concentrated sulfuric acid. The catalyst accounted for 3. 6% of the raw material. The conversion of citric acid can be further improved by increasing the ratio of citric acid to n-butanol to 1 ∶ 4. Therefore,Zr-β zeolite can completely replace concentrated sulfuric acid as a solid catalyst for the preparation of tri-n-butyl citrate.
Zirconium modified beta( Zr-β) zeolite was prepared by modification with Zr O( NO3)2after dealumination with oxalic acid. The effect of modification time on the Zr-β and its catalytic performance of citric acid and n-butanol for the synthesis of Tri-n-butyl citrate was investigated. The results showed that the conversion of citric acid was 74. 1% after 4 hour,which was higher than 71. 5% of concentrated sulfuric acid. The catalyst accounted for 3. 6% of the raw material. The conversion of citric acid can be further improved by increasing the ratio of citric acid to n-butanol to 1 ∶ 4. Therefore,Zr-β zeolite can completely replace concentrated sulfuric acid as a solid catalyst for the preparation of tri-n-butyl citrate.
引文
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[3]周扬志,何伟,佘鹏伟,等.柠檬酸酯的催化工艺[J].工业催化,2012,20(2):58-62.
[4]于清跃,王监宗,于荟,等.Zr O2-Ti O2复合催化剂的制备及其催化合成柠檬酸三丁酯[J].过程工程学报,2016,16(5):876-881.
[5]李敢,曹飞,王德堂.NKC-9酸性树脂催化合成柠檬酸三丁酯[J].化学世界,2015,56(2):110-113.
[6]黄润均,陈东莲,黄增尉,等.Na2S2O8改性活性炭负载三聚磷酸二氢铝催化合成柠檬酸三丁酯[J].应用化工,2017,46(2):168-172.
[7]赵瑞兰,赵振华,李龙.用β沸石分子筛作催化剂液-固相合成丁酸戊酯的研究[J].合成化学,2003,11(6):540-543.
[8]杨雨.含铁SAPO-34分子筛催化剂的合成及NH3-SCR性能研究[D].重庆:重庆大学,2017.
[9]徐晨瑀,张海燕,马宇彤,等.分子筛改性研究综述.能源化工[J].2017,38(1):51-55.
[10]王小静,马晓轩,王军峰,等.固体酸催化合成1,6-己二醇二丙烯酸酯工艺条件的优化[J].化学工程,2017,45(5):62-67.