权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

TRANSITION METAL-CATALYZED FANCTIONALIZATION REACTION OF ALKANES IN SUPERCRITICAL FLUID

过渡金属催化超临界流体中烷烃的官能化反应

基本信息

批准号：
10650835
负责人：
TANIGUCHI Yuki
金额：
$ 2.24万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650835/
关键词：
ALKANE METHANE VANADIUM TRIFLUOROACETIC ACID ACETIC ACID CARBOXYLATION SUPERCRITICAL CO2 C-H結合活性化

项目摘要

(1) The new catalytic system has been examined for the partial oxidation of methane in liquid phase. It was found that the vanadium containing heteropolyacids/K2S2O8/(CF3CO)2O/CF3COOH catalyst system converts methane to methyl trifluoroacetate along with a trace amount of methyl acetate in a 95% yield based on methane. The activation energy of the reaction was estimated to be 27.9 kcal/mol.(2) The VO(acac)2(acac=2,4-pentanedionato) catalyst in the presence of K2S2O8 and CF3COOH has been found to efficiently transform methane and CO to acetic acid selectively. The reaction of Methane (5 atm) with CO (20 atm) at 80ィイD1゜ィエD1C for 20 h gives acetic acid in 93% yield based on methane. Other vanadium compounds such as V2O3, V2O5, and NaVO3 and various vanajium-containing heteropolyacids such as H5PV2Mo10O40, H4PVW11O40, and H5SiVW11O40 also work as catalysts.(3) As a catalyst of the above two reactions, VO(OCOCF3)3 complex was isolated. This new catalytic system has been examined for the carboxylation and oxidation of methane in supercritical carbon dioxide. It was found that this vanadium complex is insoluble to supercritical carbon dioxide and has no catalytic activity affording no product.(4) Cobalt (II) acetate (Co(OAc)2) has been found to be an efficient catalyst for the carboxylation reaction of saturated hydrocarbons with CO to yield the corresponding carboxylic acids in high yields in the presence of K2S2O8 and CF3COOH. About 89.55 conversion of propane is obtained in this reaction. The activation parameters of the reaction of propane have been determined by Arrhenius and Eyring plots.

(1)考察了该催化体系在甲烷液相部分氧化反应中的催化性能。结果表明，含钒杂多酸/K_2S_2O_8/（CF_3CO）_2O/CF_3COOH催化体系可将甲烷转化为三氟乙酸甲酯，其中沿着少量乙酸甲酯，产率为95%（以甲烷计）。反应的活化能为27.9 kcal/mol。(2)VO（acac）_2（acac= 2，4-戊二酮）催化剂在K_2S_2O_8和CF_3COOH存在下，可有效地将甲烷和CO选择性转化为乙酸。甲烷（5个大气压）与CO（20个大气压）在80 ℃下反应20小时，得到乙酸，以甲烷计产率为93%。其他钒化合物如V2 O3、V2 O 5和NaVO 3以及各种含钒杂多酸如H5 PV 2 Mo 10 O 40、H4 PVW 11 O 40和H5 SiVW 11 O 40也用作催化剂。(3)作为上述两个反应的催化剂，VO（OCOCF 3）3络合物被分离。在超临界二氧化碳中考察了该催化体系对甲烷羧化和氧化反应的催化性能。结果表明，该钒配合物不溶于超临界二氧化碳，没有催化活性，不生成产物。(4)乙酸钴（II）（Co（OAc）2）已被发现是饱和烃与CO在K2 S2 O 8和CF 3COOH存在下的羧化反应的有效催化剂，以高产率产生相应的羧酸。丙烷转化率可达89.55。用Arrhenius图和Eyring图确定了丙烷反应的活化参数。