scholarly journals CATALYSTS OF OXIDATION REACTION OF BUTENE-1 TO METHYLETHYLKETONE

Author(s):  
Minira M. Agaguseynova ◽  
Gunel I. Amanullayeva ◽  
Zehra E. Bayramova

The available and simple metal complex systems of catalytic oxidation of unsaturated hydrocarbons were developed. It is shown that these systems catalyze the selective liquid-phase oxidation of butene-1 to methyl ethyl ketone by molecular oxygen at low temperature. The best results were revealed using Cu(I)Cl monovalent chloride. The catalyst for the production of methylethylketone is a binary system containing complexes of copper and palladium chloride at a molar ratio of 2:1. Hexamethylphosphoramide is used as the ligand and palladium chloride complex as an additional complex contains benzonitrile. A combined catalyst has been offered. It allows to carry out the oxidation reaction of butene to methyl ethyl ketone under mild conditions (low temperature, atmospheric pressure) with high selectivity and yield of the desired product. The proposed binary system is able to coordinate molecular oxygen and butene-1, and thus it becomes possible to conduct the oxidation reaction not directly between butene-1 and O2, and using a specific complex catalyst system allowing them to react with each other in an activated coordinated state. Absorption properties of catalysts synthesized on the bases of transition metals have been studied and activation of molecular oxygen and butane-1 has been determined. As a result of interaction of coordinated oxygen and butane-1 it is possible to carry out oxidation reaction to methylethylketone in mild condition. The specific feature of the offered binary catalyst is irreversible absorption of molecular oxygen. Mild conditions of the reaction proceeding decreases considerably amount of by-products and simplify obtaining and separation of the main product-methylethylketone. Due to the fact that the absorption of O2 is irreversible and it is possible to easily remove the excess amount of O2 after the formation of the oxygen complex. The developed method has the advantage from the point of view of safety.Forcitation:Agaguseynova M.M., Amanullayeva G.I., Bayramova Z.E. Catalysts of oxidation reaction of butene-1 to methylethylketone. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 2. P. 53-57

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3317
Author(s):  
Maria Carolina Pereira Gonçalves ◽  
Jéssica Cristina Amaral ◽  
Roberto Fernandez-Lafuente ◽  
Ruy de Sousa Junior ◽  
Paulo Waldir Tardioli

In this paper, we have performed the Lipozyme 435-catalyzed synthesis of xylose oleate in methyl ethyl ketone (MEK) from xylose and oleic acid. The effects of substrates’ molar ratios, reaction temperature, reaction time on esterification rates, and Lipozyme 435 reuse were studied. Results showed that an excess of oleic acid (xylose: oleic acid molar ratio of 1:5) significantly favored the reaction, yielding 98% of xylose conversion and 31% oleic acid conversion after 24 h-reaction (mainly to xylose mono- and dioleate, as confirmed by mass spectrometry). The highest Lipozyme 435 activities occurred between 55 and 70 °C. The predicted Ping Pong Bi Bi kinetic model fitted very well to the experimental data and there was no evidence of inhibitions in the range assessed. The reaction product was purified and presented an emulsion capacity close to that of a commercial sugar ester detergent. Finally, the repeated use of Lipozyme 435 showed a reduction in the reaction yields (by 48 and 19% in the xylose and oleic acid conversions, respectively), after ten 12 h-cycles.


Catalysts ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 622 ◽  
Author(s):  
Zahraa Al-Auda ◽  
Hayder Al-Atabi ◽  
Keith Hohn

Methyl ethyl ketone (MEK) was converted to heavier ketones in one step, using a multi-functional catalyst having both aldol condensation (aldolization and dehydration) and hydrogenation properties. 15% Cu supported zirconia (ZrO2) was investigated in the catalytic gas phase reaction of MEK in a fixed bed reactor. The results showed that the main product was 5-methyl-3-heptanone (C8 ketone), with side products including 5-methyl-3-heptanol, 2-butanol, and other heavy products (C12 and up). The effects of various reaction parameters, like temperature and molar ratio of reactants (H2/MEK), on the overall product selectivity were studied. It was found that with increasing the temperature of the reaction, the selectivity to the C8 ketone increased, while selectivity to the 2-butanol decreased. Also, hydrogen pressure played a significant role in the selectivity of the products. It was observed that with increasing the H2/MEK molar ratio, the 2-butanol selectivity increased because of the hydrogenation reaction, while decreasing this ratio led to increasing the aldol condensation products. In addition, it was noted that both the conversion and selectivity to the main product increased using a low loading percentage of copper, 1% Cu–ZrO2. The highest selectivity of 5-methyl-3-heptanone reached ~64%, and was obtained at a temperature of around 180 °C and a molar ratio of H2/MEK equal to 2. Other metals (Ni, Pd, and Pt) that were supported on ZrO2 also produced 5-methyl-3-heptanone as the main product, with slight differences in selectivity, suggesting that a hydrogenation catalyst is important for producing the C8 ketone, but that the exact identity of the metal is less important.


The kinetics of the reaction between oxygen and gaseous methyl ethyl ketone (butanone) have been investigated in the range 250 to 450° C. The anomalous temperature coefficient of the rate offers a good example of the transition from a low-temperature mode of oxidation to a high-temperature mode. Similar behaviour has been observed with hydrocarbons and is ascribable to the diminishing part played at higher temperatures by the peroxides, which at low temperatures play a key role in generating branching chains. In the low-temperature range the rate of oxidation varies steeply with the initial pressure of butanone and is a very unusual function of the oxygen pressure, passing through a sharp maximum at certain pressures above which the rate falls and then tends to become constant. The maximum tends to disappear as the temperature is raised. Increase of the surface / volume ratio causes a diminution in rate, while addition of inert gases has no appreciable influence. The various complex relationships are well accounted for in their general form by a modification of the theory previously applied to pentane and hexane. This theory postulates a series of reaction steps of maximum simplicity, permitting a slow branching of chains by fission of peroxides. It leads to a rate expression which according to circumstances may become infinite at certain critical concentrations or remain finite throughout. The critical limits may be related to explosions or cool flames. In the application to butanone oxidation the peculiar form of the dependence of rate on oxygen pressure may be accounted for and a general account given of the observed cool-flame limits. The agreement of the theory with a number of rather unusual facts is considered to be of greater significance than its lack of quantitative accuracy which is ascribed to the approximate nature of its basis.


1960 ◽  
Vol 38 (10) ◽  
pp. 2015-2023 ◽  
Author(s):  
Irwin Siegelman ◽  
C. H. Sorum

A complete investigation of the phase equilibrium relationships in the binary system of the partially miscible liquid pair methyl ethyl ketone–water is presented. The system shows a minimum azeotrope at 73.35 ± 0.05 °C with a composition of 88.45 ± 0.15 wt.% ketone. The azeotrope falls outside of the miscibility gap for this system. The liquid–vapor curves intersect the miscibility gap at the temperature of 73.60 ± 0.05 °C at which two conjugate solutions of compositions 18.10 ± 0.10 and 87.78 ± 0.15 wt.% ketone, respectively, are in equilibrium with a vapor phase of composition 88.00 ± 0.15 wt.% ketone. The partially miscible liquid pair shows an upper consolute temperature of 139 ± 0.5 °C at a composition of 44.9 ± 0.2 wt.% ketone. The liquid–liquid curves intersect the solid–liquid curves at a temperature of −6.0 ± 0.5° C at which two conjugate solutions of composition 40.0 ± 0.2 and 78.0 ± 0.2 wt.% ketone, respectively, are in equilibrium with ice. A binary eutectic exists at a temperature of −89.0 ± 0.5 °C with composition of the eutectic solid equal to 99.4 ± 0.4 wt.% ketone. The freezing point of pure, dry methyl ethyl ketone is determined to be −83.5 ± 0.5 °C.


2018 ◽  
Vol 8 (15) ◽  
pp. 3863-3875 ◽  
Author(s):  
Yanfei Jian ◽  
Mudi Ma ◽  
Changwei Chen ◽  
Chao Liu ◽  
Yanke Yu ◽  
...  

MnOx nanowires with highly exposed {101} facets of Mn3O4 possess excellent low-temperature activity and stability for methyl ethyl ketone destruction.


Author(s):  
Tat'yana Raskulova ◽  
Mihail Fereferov ◽  
Marina Kurbatova ◽  
Mariya Cherencova ◽  
Irina Polyak

The replace ability of traditional complex solvent (toluene – methyl ethyl ketone) for low temperature de-waxing with an individual methyl isobutyl ketone is considered.


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