RESEARCH OF ORGANIC COCATALYSTS IN THE PROCESS OF
OXIDATION OF CYCLOHEXANE
Sergiy Mudryy, Oleksandr Ivashchuk, Victor Reutskyy
National university „Lvivs’ka polytechnika”, Institute of chemistry and chemical technology, Department of
technology of organic products, Ukraine, Lviv, St. Bandery str. 12
Organic modifiers of different nature allows to refine engineering-and-economical
performance in the process of oxidation of cyclohexane [1]. As known, process of oxidation of
cyclohexane at application of industrial catalyst – cobalt naphthenate (CoNph) has a number of
the substantial failings, e.g. low conversion of cyclohexane (4-5%) and low selectivity of end
products – cyclohexanol (COL) and cyclohexanone (CON) (75-78%). Therefore, the matter of
creation of new more effective catalytic system or existing modification remains actual for
today.
Survey researches of catalytic influence of whole number of organic compounds – ethers,
esters, ammonium salts, CN-containing substances on the process of oxidation of cyclohexane
were conducted. Organic compounds were used as additives to the basic industrial catalyst of
process – cobalt naphthenate.
So, at the industrial values of conversion (X=4%), additives of tetraethyl ammonium
iodide (TEI), polyethyleneglycol succinate (PS), cyanoethyl ether (CE) and mixture of
polyoxyethyleneglycol ethers of higher fatty alcohols (DS-20) shown good results in comparison
with individual CoNph.
85,0
2,5
80,0
2,0
COL/CON
70,0
65,0
60,0
1,5
1,0
Picture 1. The selectivity of end products at
X=4% for different additives
CE
PS
0,0
DS-20
TEI
CE
PS
DS-20
CoNph
50,0
TEI
0,5
55,0
CoNph
S,%
75,0
Picture 2. Proportion of COL/CON at X=4%
for different additives
The best results for selectivity of end products received in the presence of TEI and CE
(pic.1). A value of selectivity is 79,6% and 80,2% at application of TEAY and CE accordingly,
at that time in the presence of CoNph it is 76,7%.
A composition of oxide mixture, notably proportion COL/CON is also very important.
Proportion of COL/CON is displaced in the side of cyclohexanol only in the presence of DS-20
as additive (pic.2). Values of ratio COL/CON are 2,3 for DS-20 and 2,1 for individual CoNph.
Waste products of oxidation of cyclohexane (mainly it is adipic acid (AdA)) is important
too. Content of AdA in oxide mixture without additives of cocatalysts is 15,8%. That is
considerably higher index in comparing to the test additives – 11,2% (PS) and 10,1% (TEI).
Thorough researches of these organic cocatalysts is perspective, in consideration of
positive results of experiments. Scientific investigation in this concept will enable to create more
effective and forecast catalytic system for a process homogeneously-catalytic oxidation of
cyclohexane.
[1] Ivashchuk O.S., Reutskyy V.V. Research of action mechanism of catalytic solutions in the oxidization
process of cyclohexane // Chemistry & Chemical Technology. – Vol.2. – Number 2. – Lviv. – 2008. –
P.85-90.