二氧化硅负载磷钨酸催化合成葸醌.pdf

石油化工
2011年第40卷第1期
PETROCHEMICAL TECHNOLOGY
69
二氧化硅负载磷钨酸催化合成蔥醌
王桂荣,栾艳勤,郝苏霞,赵新强,王延吉
(河北工业大学化工学院,天津300130)
摘要采用等体积浸渍法制备了负载型磷钨酸(HPW)催化剂,将其用于催化邻苯甲酰苯甲酸(BBA)脱水合成蒽醌;采用XRD,
FTR,TG-DTG等手段对SiO2负载的磷钨酸( HPW/Sio2)催化剂进行表征;考察了载体种类、焙烧温度、HPW负載量对其催化
性能的影响。实验结果表明,制备负载型HIPW催化剂的适宜条件为:以SiO2为载体、焙烧温度250℃、焙烧时间3b、IHPW负载
量为30%。HPW/SiO2催化剂催化合成蒽配的适宜反应条件为:催化剂与BBA的质量比为1.60、反应温度220℃、反应时同
2.0b,在此条件下,蔥能收率可达99.6%。 HPW/Sio2催化剂的稳定性较差,BET,UV-Vis,PyーR表征结果显示,积碳结焦使
催化剂B酸酸量减小是催化剂失活的原因。
[关键词]邻苯甲酰苯甲酸;脱水;蒽醌;磷钨酸催化剂;二氧化硅
「文章编号]1000-8144(201)01-0069-06[中图分类号了TQ426.91[文献标识码j」A
Synthesis of Anthraquinone over HPW/Sio, Catalyst
Wang Guirong, Luan Yanqin, Hao Suxia, Zhao Xinqiang, Wang Yanji
(School of Chemical Enginccring and Technology, Hebei University of Technology, Tianjin 300130, China
I Abstract] A series of the supported phosphotungstic acid(HPW) catalysts were prepared through an
isochoric impregnation method and were used in synthesis of anthraquinone(AQ)through dehydration
of o-benzoylbenzoic acid(BBA), with Sio activated carbon, bentonite or Y-A12 O, as supports. The
supported catalyst HPW/SIO, was characterized by mcans of TG-DTG, XRD and FTIR. Effects of the
support type, calcination temperature and HPW loading on the catalyst activity were investigated and
the catalytic performance of HPW/SIO, catalyst in the anthraquinone synthesis was evaluated. The
results indicated that under the optimal conditions for the catalyst preparation: SIO as support
calcination temperature 250 t, calcination time 3 h and HPW loading 30%(mass fraction) and the
optimal conditions for the synthesis: m(catalyst): m(BBA) 1.60, reaction temperature 220 C and
reaction time 2 h, the AQ yield could reach 99. 6%. But the HPW/Sio catalyst stability in the AQ
synthesis was not good. It was found by means of BET, Uv-vis and PY-IR that the catalyst
deactivation was due to decrease of the Bronsted acid sites, which was caused by coking on the catalyst
Surface
I Keywords] 0-benzoylbenzoic acid; dehydration; anthraquinone; phosphotungstic acid catalyst;
silicon dioxide
蔥配(AQ)是一种重要的化工中间体,广泛应绿色化。
用于染料、医药以及农药等领域。传统的苯酐法合
对于BBA脱水闭环生成AQ过程, Cundy等山
成AQ分为两步:(1)以AICI3为催化剂,邻苯二甲以高硅沸石分子筛及H-ZSM-5分子筛为催化剂
酸酊(PHA)和苯进行酰基化反应生成邻苯甲酰苯进行研究,但需要用二氯甲烷做溶剂;Bram等2以
甲酸(BBA);(2)以浓硫酸为催化剂,BBA脱水闭
环生成AQ。该方法以AIC14和浓硫酸为催化剂,存[收稿日期!2010-7-20:[修改稿日期】200-10-19
作者简介]王桂荣(1963-),女,河北省枣强县人,博士,教授,电
在腐蚀设备、污染环境等缺点。国内外研究人员对
话022-26564289,电邮wangguirong111126.com
苯酐法合成AQ投入了大量研究,以开发无污染、无[基金项目」河北省自然科学基金资助项目(B2000河北省
腐蚀的固体酸催化剂,实现苯酐法合成AQ工艺的教育厅博土基金资助项日(B20004)