No. 4094

I.
-4
ge-S2-'1:11 v
'
FISHERIES AND MARINE SERVICE
Translation Series No. 4094
Liquid-phase catalytic oxidation of n-decane with ozone
by A. A. Vikhorev and A. M. Syroyezhko
Original title: Zhidkofaznoye kataliticheskoye okisleniye n-dekana ozonom
From: Ref. Zh. Khim. p. 43-45, 1975
Translated by the Translation Bureau (NDe)
Multilingual Services Division
Department of the Secretary of State of Canada
Department of Fisheries and the Environment
Fisheries and Marine Service
• Halifax Laboratory
Halifax, N.S.
1977
4 pages typescript
F e
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DEPARTMENT OF THE SECRETARY OF STATE
SECRÉTARIAT D'ÉTAT
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MULTILINGUAL SERVICES
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TRANSLATED FROM — TRADUCTION DE
INTO - EN
:nglish
Russian
AUTHOR — AUTEUR
A. A.
Vikhorev, . 0 1 0 Zyroyezhko
TITLE IN ENGLISH — TITRE ANGLAIS
Liquid-phase catalytic oxidation of n-decane with ozone
TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS)
TITRE EN LANGUE ÉTRANGÉRE (TRANSCRIRE EN CARACTÉRES ROMAINS)
L'h.idkofaznoye k ,--ltalitichcskoye okisleniye n-dekana ozonom
REFERENCE IN FOREIGN LANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE , FOREIGN CHARACTERS.
RÉFÉRENCE EN LANGUE ÉTRANGÉRE (NOM DU LIVRE OU PUBLICATION), AU COMPLET, TRANSCRIRE EN CARACTÉRES ROMAINS.
Sb. Issled. v obl , khimii i tekhnol. produktov pererabotki
goryuchikh iskopayemykh
REFERENCE IN ENGLISH — RÉFÉRENCE EN ANGLAIS
Investigtions in the chemistry :nci technology of fuel derivatives
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DATE OF PUBLICATION
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NUMÉROS DES PAGES DANS
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41
-45
NUMBER OF TYPED PAGES
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DACTYLOGRAPHIÉES
USSR
1975
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V. sb. Issled. v obi. khimii i tekhnol. produktov pererabotki goryuankh te
C)
iskOpayemykh, 1975, pp. 43-45.
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Liquid-phase catalytic oxidation of n-decane with ozone at 1
/43/ *
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A.A. Vikhorev, A.M. Syroyezhko
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Interest in the utilization of ozone is continuously growing chiè to
the development of industrial methods for its electrosynthesis.
The high oxidative
potential and the lack of inert components in ozone make it possible to use it
as an oxidizing agent. The possibilities of utilizing ozone in organic synthesis
have not yet been sufficiently developed.
This paper discusses ozonized
oxidation of n-decane in the presence of the salts of intermediate metals which
are capable of serving as electron donors in the process of ozonization.
Ozonized oxidation of n-decane ([0 ] = 4 percent by volume) was carried
3
out in a bubbler-type glass reactor with a temperature range of 40-100 ° C.
The catalysts were manganese acetylacetonate (III),
cobalt stearate (II),
potassium permanganate, industrial manganic potassium (4 wt.% Mn and 0.39 wt.%
NaOH) and experimental catalysts (manganese salts of monocarboxylic acids
*
The numbers in the right-hand margin are the pages of the Russian
text. - Translator.
SEC 5-25T (6/76)
2
C
5
- C 9 ) in a concentration of 0.1 percent by weight.
The experimental and
industrial catalysts were obtained from the synthetic fatty acid shop of
*
the Shchebekinsky Chemical Works. We have found that these catalysts
accelerate the consumption of hydrocarbon, as compared with the experiments
in which they are not used, and take the following order as to catalytic
activity:
Mn(AcAc)
KM0
4
3
> industrial catalyst >
> experimental catalyst > CoSt
2
The products of ozonized oxidation of n-decane are hydroperoxides,
alcohols, ketones, acids and ester-type compounds.
Hydroperoxides, alcohols and ketones are the intermediate products
of oxidation.
The maximum yield of hydroperoxides (0.55 mole/litre) is attained
at 40 ° C in the absence of catalysts.
The free alcohols consist of isomeric decanols and primary alcohols
of normal structure C 2 - C
10 '
However, the yield of primary free alcohols
is insignificant (up to 0.05 mole/litre). The ratio of primary and
secondary free alcohols accumulating in the n-decane oxide varies depending
on the nature of the catalyst and the extent of oxidation, amounting to
19.0-0.58 (conversion to 25%).
mixture of isomeric decanols.
The ketones consist of an equimolecular
The ratio of free alcohols and ketones
varies within a broad range from 0.21 to 1.25 (conversion 10-25%).
The regulating role of the catalysts is seen in the yield ratio of
free acids and the sum of alcohols and ketones. We found that KMn0 4' industrial
and experimental catalysts manifested maximum selectivity for monocarboxylic
acids.
Transliterated from the Russian.
/44/
3
The free monocarboxylic acids consist of acids with a normal
structure C
1
- C .
9
Their ratio varies greatly depending on the nature
of the catalysts and the depth of the process. In the absence of catalysts
(conversion 10-15%) the ratio of free acids to esters is equal to 0.59-1.1;
with catalysts it is equal to 0.17-0.87. Mostly acids accumulate with an
increase in hydrocarbon conversion (25%) in the presence of catalysts, and
then this ratio is equal to 1.03-1.2.
The esters consist of true esters
and lactones, the homologs of y-butyrolactone. Esterification is preferably
carried out with acetic acid.
The non-volatile acids containing steam consist of y-ketovaleric,
y- and 8-ketocaproic, y-ketocaprylic and E-ketoenanthic acids.
The yield
of these compounds in the presence of an experimero- ?1 and industrial catalysts
is lower (7-15.4%) than when CoSt
2
and (MnAcAc), 3 are used (12.5-18.7%) with
the oxidation process lasting 2-6 hours respectively.
The selectivity of
the ozonization process depends on the rate of interaction of ozone with
the introduced catalysts and on the rate of ozonolysis of the initial
molecule of n-decane (at the onset) and of the intermediate products (in the
course of the reaction).
Since the constant of the rate of interaction of ozone with the
salts of intermediate metals varies from 1.6.10 3 to 3.7.10 2 and the constant
of the rate of interaction of ozone with the oxidizing compounds (hydrocarbons,
alcohols, ketones, hydroperoxides) is lower by several orders, the role of
the catalysts is confined to the generation of the active particles which
carry out the oxidation process [1]:
+3
+2 + + Me ,
0
3
•
+
0
+ H + HO - + HO' + 0
3
3
2.
0
3
+ Me
4
When the oxidizing potential of the cation Me+3 is high enough, it
participates in the following oxidation reactions:
RH + Me-I-3
R . + Me
2+
+
+ H
However, if the activation energy of the reaction of the initial
hydrocarbon and the cation Me
+3
is high, the more active radical *OH can begin
the reaction.
Reference
1. Yakobi V.A., Ponomaryov B.A., Tyupalo N.F., Galstyan G.A.,
Petrenko L.P., Tyutyunnik S.M., Karpukhin P.P.
IN: Teoriya i praktika
zhidkofaznogo okisleniya (The theory and practice of liquid-phase oxidation).
Moscow, "Nauka", p. 303.
/45/