Me-OL-1s催化叔丁基过氧化氢歧化分解制叔丁醇.pdf

石油化
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PETROCHEMICAL TECHNOLOGY
2014年第43卷第4期
MeOL-1s催化叔丁基过氧化氢歧化分解制叔丁醇
王丽丽,冯利利2,齐麟,卢书培,齐兴义
(1.北京航空航天大学化学与环境学院仿生智能界面科学与技术教育部重点实验室,北京100191
2.北京建筑大学城市南水系统与水环境教育部重点实验室,北京10004)
L摘要」采用静态水热法合成了水钠锰矿型层状氧化锰Me-OL-1ls(Me:K,Mg,Fe,Ni,Cu)催化剂,对所合成的催化剂进
行了XRD和ICP-AES表征,并将该系列催化剂用于叔丁基过氧化氯(TBHP)歧化分解制备叔丁醇的反应,考察了反应温度、
反应时间及催化剂用量对TBHP歧化分解反应的影响。实验结果表明,所合成的Me-OL-1s催化剂均为水钠锰矿型氧化锰;在
温和的反应条件(323~338K)下,Me-OL-1s催化剂均对TBHP歧化分解反应具有活性,其中Cu-OL-1催化剂的活性最高,
在65%(w)TBHP水溶液1mL、反应介质乙腩SmL、Cu-OL-1催化剂用量(基于TBHP水溶液和乙腈的总体积)1.67~8.33mg/
mL、338K下反应1h时,TBHP的转化率均达到96%以上,且叔丁醇的选择性均为100%。
[关键词』叔丁基过氧化氢;歧化分解;叔丁醇;水钠锰矿;Me-OL-1s催化剂
[文章编号]10008144(2014)04-0430-05
中图分类号]TQ223.1
文献标志码]A
Disproportionation Decomposition of tert-butyl Hydroperoxide to
tert-butyl Alcohol over ME-OL-IS Catalysts
Wang Lili, Feng Lili, Oi
Oi Xingyi
(1. Key Laboratory of Bio-inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry
and Environment, Beihang University, Beijing 100191, China; 2. Key Laboratory of Urban Stormwater System and Water
Environment of Ministry of Education, Beijing University of Civil Engineering and Architecture, Beijing 100
China
Abstract] Birnessite-type manganese oxides ME-OL-IS(Me: K, Mg, Fe, Ni and Cu)were
synthesized by static hydrothermal method and characterized by XRD and ICP-AES. The oxides were
used in the disproportionation decomposition of ter-butyl hydroperoxide(TBHP)to ter-butyl alcohol
The effects of reaction temperature, reaction time and catalyst dosage were investigated. The results
showed that all the Me- catalysts had the catalytic activity under mild reaction conditions(323-338
K and the activity of the CU-OL-1 catalyst was the highest. The conversion of TBHP and the selectivit
to tert-butyl alcohol reached more than 96% and 100% under the conditions of 65%(WTBHP aqueo
solution I ml, reaction medium acetonitrile 5 ml, the CU-OL-1 catalyst dosage(based on the total
volume of TBHP aqueous solution and acetonitrile)1.67-8.33 m/ml, 338K and 1 h
I Keywords J ter-butyl hydroperoxide; disproportionation decomposition; tert-butyl alcohol
birnessite; ME-OL-1S catalyst
叔丁醇是一-种重要的精细化工产品,可用作内艺步骤冗长、繁杂,致使多数采用该方法制备叔丁
燃机的燃料添加剂和抗爆剂,也可用作有机合成的醇的企业难以获得生产过程的最大经济效益。
中间体及生产叔丁基化合物的烷基化剂。叔丁醇的「收稿日期」203-11
修改稿日期]2013-12
传统制备方法主要有异丁烯硫酸水合法、异丁烯直『作者简介]王丽丽(199-),女,河南省许昌市人,硕土生,
接水合法和丙烯叔丁烷共氧化法(简称哈康法)リ,
电邮wangli20110101@126.com。联系人:冯利利,电话010
其中哈康法是目前叔丁醇的主要工业制备方法,由
6832124,电邮fenglili(@bucea.edu.cn;齐兴义,电话010
叔丁烷自氧化、丙烯催化环氧化和产物混合物(环
82317126,电邮giwy@のbua.ecdu.cn
基金项目]国家自然科学基金项目(51206009);北京市青年英
氧内烷十叔丁醇)纯化分离三步组成。因哈康法エ才项目(2127141311)