Catalytic Properties of Heteropoly Compounds in 1,3-Butadiene Oxidation with Hydrogen Peroxide
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Translated
|
| Journal |
Kinetics and Catalysis
ISSN: 0023-1584
, E-ISSN: 1608-3210
|
| Output data |
Year: 2013,
Volume: 54,
Number: 4,
Pages: 420-430
Pages count
: 11
DOI:
10.1134/S0023158413040071
|
| Authors |
Kuznetsova L.I.
1
,
Kuznetsova N.I.
1
,
Maksimovskaya R.I.
1
,
Koshcheeva O.S.
2
,
Utkin V.A.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis SB RAS
|
| 2 |
Nikolaev Institute of Inorganic Chemistry SB RAS
|
|
The homogeneous oxidation of 1,3-butadiene (BD) in H2O2-HPC-CH3CN (HPC = heteropoly compound) solutions has been investigated. The route of the reaction depends on the nature of the metal capable of coordinating with active oxygen in the HPC. The products of radical BD oxidation (acrolein, 3-butene-1,2-diol, 2-butene-1,4-diol, furan) form in the presence of H3+n PMo12 − n V n O40 (n = 1, 2) acids. 3,4-Epoxy-1-butene (EB) and acrolein + furan, which form in equal amounts in the presence of the (n-Bu4N)5PW11O39Fe(OH) salt, result, respectively, from the electrophilic addition of hydrogen peroxide to BD and from radical BD oxidation on iron-oxygen complexes in the HPC composition. The reaction carried out in the presence of (n-Bu4N)3{PO4[WO(O2)2]4}, (n-Bu4N)5Na0.6H1.4PW11O39, or (EMIm)5NaHPW11O39 yields EB with high selectivity on the reacted BD basis (up to 97%) and H2O2 (about 100%). The formation and conversion of the phosphotungstate peroxo complexes PW n O m α−(n = 2, 3, 4) that are active in BD epoxidation have been investigated by 31PNMR spectroscopy. The role of the tetrabutylammonium and ethylmethylimidazolium cations in the formation of these complexes has been demonstrated.