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94 CHEMICAL PROBLEMS 2021 no. 2 (19) ISSN 2221-8688
<3
UDC 547.2/4;547.917/.918;544.4
CATALYTIC OXIDATION OF OXYGEN CONTAINING ALIPHATIC HYDROCARBONS IN THE PRESENCE OF METALPOLYMER COMPLEXES
R.H. Suleymanova, N.А. Zeynalov, О.Т. Badalova, L.N. Qulubayova, А.R. Guliyeva, U.A. Mammadova
M.Nagiyev Institute of Catalysis and Inorganic Chemistry 113, H. Javidave., AZ 1143, Baku, Azerbaijan, e-mail: [email protected]
Received 02.04.2021 Accepted 20.07.2021
Abstract: The reactions of liquid-phase oxidation of aliphatic oxygen containing hydrocarbons, in particular, nonanol-4 and nonanon-4 in the presence of polyethylene-polyamine complexes (PEPA) with sorbated ions of metals with changeable valency (Co2+,Cu2+, Ni2+) were studied. It revealed that the oxidation of nonanole-4 and nonanone-4 in the presence of Cu2+ and Ni2+ ions in the analyzed system is less active while in the presence of Co2+ ions decarboxylation of acids it is practically absent and it leads mainly to formation of carbonic acids. It has been established that the character of oxidation reaction mostly depends on the properties of metals fixed on polymer matrix.
Keywords: liquid-phase, oxidation, metal-polymer complex, metal, nonanol-4, nonanon-4, carbonic acids. DOI: 10.32737/2221-8688-2021-2-94-100
Introduction
Aliphatic carbonic acids, as well as their salts and ethers are widely used in pharmaceutical, vitamin, cosmetic, food and automobile industries [1-4].
It is well-known that chemical methods of obtaining carbonic acids by means of oxidation of aliphatic alcohols are noted for some deficiencies which are due to the use of rather expensive and toxic chemical oxidants, such as potassium permanganate, chrome complexes and etc [5-7].
Chemically tied active forms of oxygen: ^O-O\ •OH , HO^ that are ecologically pure oxidizing reagents - can be the alternative to these oxidants.
In the previous studies we examined regularities of liquid-phase oxidation of aliphatic hydrocarbons in the presence of metal-polymer complexes. The results showed that in this observed system the reaction runs selectively, with predominant formation of one or two components. Besides, the direction of the process and the rate of products accumulation mainly depend on the quantity and properties of the initiating ion of metal [8-9].
Proceeding from the analysis [10-12] of the
regularities of liquid-phase oxidation of saturated hydrocarbons, it revealed that the primary products of the starting stage of oxidation are hydroperoxides, and their decomposition mostly leads to the formation of carbonyl complexes and alcohols. However, it should be emphasized that the latter ones, being in reaction zone under the influence of oxygen, are subjected to further oxidation to form carbonic acids, complicated ethers, carbon dioxide and the products of condensation.
Observation of the system of liquid-phase oxidation of individual, carbonyl complexes and alcohols in the presence of metalpolymer complexes will permit us to identify the regularities of the running processes. For this purpose, the aliphatic alcohol nonalol-4 and the aliphatic ketone nonanon-4 were chosen as a model reaction and an object of investigation. The choice of these compounds is due to the mechanism of attack of aliphatic hydrocarbons by oxygen atoms and the composition of the resulting products. According to references [1314], in the system of liquid-phase oxidation, the most subjected to oxygen atoms attack are methylene groups of hydrocarbon. Therefore,
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the formation of secondary oxygen-containing products is the most favorable.
Experimental part
The oxidation of nonanol-4 and nonanol-4 was carried out in a bubble type glass reactor with the participation of oxygen torrent, at a temperature of 1200C and the atmosphere pressure, in the presence of polyethylene-polyamine (PEPA) disposed to the sorption of ions Co2+, Cu2+ and Ni2+. In the course of the
experiment the selected tests were analyzed for containing hydroperoxides, carbonic acids, and in the exit gases we identified the quantity of carbon dioxide. The obtained hydroperoxides were determined iodometrically, and the acids through the use of reverse titration.
Discussion of results
The kinetic curves of accumulation of the products of oxidation of nonanol-4 in the presence of Co2+ ions are presented in Fig.1.
As seen from Fig. 1, an oxidation of alcohol leads to the formation of hydroperoxides, carbonyl compounds and carbonic acids. It is obvious that the obtained hydroperoxides and carbonyl compounds are intensively oxidized
into carbonic acids. For this reason, the accumulation of the latter grows rather fast, at a small accumulation of the first two products. Under similar conditions reactions were carried out in the presence of Cu2+, Ni2+ ions. It revealed that the activity of Cu2+ and Ni2+ ions is insignificant.
tttt
Fig. 1. Kinetic curves of the accumulation of nonanol-4 oxidation products. T-1200C, catalyst (PEPA) Co2+. 1- hydroperoxides, 2 - carbonic acids, 3 - carbonyl complexes
The kinetic curves of the accumulation of products of reaction following oxidation of the nonanon-4 in the presence of Co2+,Cu2+, Ni2+ ions are shown in Fig. 2,3,4. As is seen from the figures above, the nonanon-4 oxidation leads mainly to the formation of carbonic acids. The ion Co2+ is distinguished by high initiating
property. The activity of ions Cu2+ and Ni2+ is rather small, so the reaction runs rather weak. In Fig.5, there are kinetic curves of thermal oxidation of nonanon-4. With the absence of catalyst in the selected conditions, the rate of reaction is quite insignificant.
T, h
Fig. 2. Kinetic curves of the accumulation of nonanon-4 oxidation products. T-1200C, catalyst (PEPA) Co2+. 1- hydroperoxides, 2 - carbonic acids.
3 ■ 2 1 2
-•- —e— -©- -0 1
1 2 3 4 5 6 7
T, h
Fig. 3. Kinetic curves of the accumulation
of nonanon-4 oxidation products. T-1200C, catalyst (PEPA) Cu2+. 1- hydroperoxides 2 - carbonic acids.
Fig. 4. Kinetic curves of the accumulation of nonanon-4 oxidation products. T-1200C, catalyst (PEPA) Ni2+. 1- hydroperoxides, 2 - carbonic acids.
Fig. 5. Kinetic curves of the accumulation of nonanon-4 thermal oxidation products. 1- hydroperoxides, 2 - carbonic acids
As shown above, the oxidation of Oxidation of alcohol in the presence of PEPA aliphatic alcohol and ketone leads to the with sorbed cobalt ions can be represented as formation of mainly carbonic acids, the accumulation of which occurs most intensively in the presence of Co2 + ions in comparison with Cu2+ and Ni2+ ions, which indicates a higher activity of cobalt ions.
follows: when it enters into a reaction with nonanol-4, PEPA combined with sorbed cobalt ions o forme a complex with the atoms of oxygen.
CH3 - CH2- CH2 - CHO + CH3 - CH2- CH2 -CH2 - CHO + H20 The created two molecules of aldehyde are further oxidized into a carbonic acid.
2CH, - CH,- CH-, - CHO + Oo
2CH, - CH,- CH, -CHo - CHO + O
2CH, - CH,- CH, - COOH
2CH, - CH,- CH, - CHo - COOH
When the oxygen molecule joins the other created, which are also oxidized into a carbonic methylene group, both ketone and aldehyde are acid, namely:
2CH, -CHO + O
2CH, - COOH
Thus, as a result of oxidation from one In the presence of polyethylen-
molecule of aliphatic alcohol, nearly four polyamine with the sorbed ions Co2+, the molecules of carbonic acids are obtained. oxidation of nonanon-4 is as follows:
Thus, as a result of oxidation from one molecule of naonanon-4, one molecule of carbonic acid and one molecule of aldehyde are obtained which are also oxidized into a carbonic acid.
In case of the oxygen molecule joining another methylene group, the reaction can be presented as follows:
CH3 -CH2 - CH-> - C - CH2 - CH, - CH,-CH2 - CH3 + O, CH3 - CH2 - CH2 - C - CH2 - CH -CH2- CH2 - CH3 -►
CH3 - CH2 - CH2 - C - CH3 + CH3 - CH2 - CH2 - COOH
CH3 - CH2 - CH2 - C - CH3 + 02-►CHg - CH2 - CH - C - CH
2CH3 - CHO + 02 —--► 2CH3 - COOH
If the presented schemes of the oxidation of aliphatic alcohol and ketone are fair, then the observed high yield of carbonic acids becomes a logical consequence of existing reactions.
It should also be noted that in oxidation
reactions in the presence of complex [PEPA]Co2+decarbooxidation of carbonic acids is practically absent. Obtained results are presented in Table 1.
Table 1. The quantity of evolved carbon dioxide in different systems.
Compound Metal ions Quantity of CO2, mol
Nonanol-4 Co2+ 0.2
Nonanon-4 Co2+ 0
Nonanon-4 Cu2+ 2.15
Nonanon-4 Ni2+ 2.2
Nonanon-4 Therm 0
On the basis of the obtained experimental material we can conclude that the ions Co2+ sorbed on polymer matrix PEPA initiate the
process of oxidation of aliphatic alcohol and ketone and selectively lead the reaction towards the preferential formation of carbonic acids.
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METAL POLÍMER KOMPLEKSLdRÍN i§TÍRAKI iLd OKSÍGEN TdRKiBLi ALiFATiK KARBOHiDROGENLdRIN KATALiTiKOKSiDLd§MdSi
R.H. Süleymanova, N.A. Zeynalov, O.T. B9d9lova, L.N. Qulubdyova, A.R. Quliyeva, Ü.d. M9mmzdova
AMEA akademik M.Nagiyev adina Kataliz va Qeyri-üzvi Kimya institutu AZ1143 Baki §ah., H. Cavid pr. 113, e-mail:[email protected]
Dayi§kan valentli metal ionlari (Co2+, Cu2+, Ni2+) sorbsiya olunmu§ polietilenpoliamin komplekslarinin i§tiraki ila oksigen tarkibli alifatik karbohidrogenlarin, o cümladan nonanol-4 va nonanon-4-ün maye fazada oksidla§ma reaksiyasi oyranilmi§dir. Gostarilmi§dir ki, oyranilmi§ sistemda Cu2+ va Ni2+ ionlarinin i§tiraki ila nonanol-4 va nonanon-4-ün oksidla^masi zamani katalizatorlarin aktivliyi azalir, Co2+ ionlarinin i§tirakinda isa artir, bela ki, kobalt ionlarinin i§tiraki ila tur§ularin dekarboksilla§masi praktiki olaraq ba§ vermir, bu da asasan karbon tur§ularinin yaranmasina gatirib gixarir. Müayyan edilmi§dir ki, oksidla§ma reaksiyasinin xarakteri polimer matrisasina barkidilmi§ metal ionlarinin xassalarindan ahamiyyatli daracada asilidir.
Agar sozfor: maye faza, oksidla§ma, metal polimer komplekslar, nonanol-4, nonanon-4, karbon tur§ulari
КАТАЛИТИЧЕСКОЕ ОКИСЛЕНИЕ КИСЛОРОДСОДЕРЖАЩИХ АЛИФАТИЧЕСКИХ УГЛЕВОДОРОДОВ В ПРИСУТСТВИИ МЕТАЛЛОПОЛИМЕРНЫХ КОМПЛЕКСОВ
Р.Г. Сулейманова, Н.А. Зейналов, О. Т. Бадалова, Л.Н. Кулибекова, А.Р. Кулиева, У.А. Мамедова
Институт Катализа и Неорганической химии имени академика М.Нагиева Национальной АН Азербайджана AZ1143 Баку, пр. Г. Джавида,113, e-mail: [email protected]
Изучены реакции жидкофазного окисления алифатических кислородсодержащих углеводородов, в частности нонанола-4 и нонанона-4 в присутствии комплексов полиэтиленполиамина с ионами металлов переменной валентности (Со2+, Си2+, Ni2+). Показано, что при окислении нонанола-4 и нонанона-4 в присутствии ионов Си2+, Ni2+ в изученной системе активность катализаторов низкая, а в случае ионов Со2+ она увеличивается, т.к. практически отсутствует декарбоксилирование кислот, что приводит в основном к образованию карбоновых кислот. Установлено, что характер реакции окисления существенно зависит от свойств металлов, закрепленных на полимерной матрице.
Ключевые слова: жидкая фаза, окисление, металлополимерные комплексы, нонанол-4, нонанон-4, карбоновые кислоты.
