The method of producing ethyl ketone

 

(57) Abstract:

The invention relates to a method for producing methyl ethyl ketone, which is widely used as a solvent perchlorovinyl, nitrocellulose lacquers and adhesives. The method consists in the interaction of butanol-2 with hydrogen peroxide, when 220-350oC and a molar ratio of reagents (1,0-5,0) : 1, respectively, at the time of contacting 3-8 c. The method provides increased output from 44 to 64% and waste is reduced. 2 C.p. f-crystals, 1 table.

The invention relates to chemical technology and can be used in the production of methyl ethyl ketone (MEK), which finds extensive use as a solvent perchlorovinyl, nitrocellulose, poly (acrylic varnishes and adhesives, for dewaxing oil fractions, as a component to remove paint.

Known for more than 10 methods of obtaining IEC, based on the catalytic oxidation of butylene, dehydrogenation or oxidation of butanol-2, with the joint receipt of phenol through Gidropress second-butylbenzoyl or acetic acid in the oxidation of butane. In industry the main mass of MEK is produced by dehydration of butanol-2 [1-7] or as a by-product in the e on the catalyst the Raney-Nickel or copper chromite, when 130-180oC. the Process is carried out in an inert solvent with high boiling paraffin and has a number of disadvantages (small removal of product per unit of catalyst to about 1.1 kg/(AU), short life of the catalyst is not more than 2 years, the need to use and regeneration of solvent). Obtaining IEC together with acetic acid is characterized by low productivity of the process, a large number of by-products, a complicated scheme of separation of the reaction mixture.

In Russia, the IEC was produced until 1996, through a process of catalytic oxidation of butanol-2 oxygen. The process is characterized by low selectivity and yield, low quality product, a large amount of waste.

The prototype of the present invention is a method of obtaining IEC through high temperature non-catalytic oxidation of butanol-2 hydrogen peroxide [8]. The process is carried out at 460-560oC and a volume ratio of butanol-2 and 25-35% hydrogen peroxide = 1:(1,7-3,5), or approximately at a molar ratio of 1: 3. The maximum yield of the process of 44.2%. According to the authors of this invention, the selectivity of the process depending on the temperature of IIA, since the conduction of the process when 460-560oC was observed ignition of the reaction mass in the reactor and the main products of the conversion of butanol-2 were carbon dioxide and water (exit IEC does not exceed 10%). It is doubtful, and the absolute absence of losses of the reaction products by separation of the reaction mixture with a total less than 1 year

For industrial process of obtaining IEC with high values of selectivity and yield, small number of waste high quality product and simplicity of instrumentation, we propose a method, characterized in that the oxidation of butanol-2 hydrogen peroxide is carried out at 220-350oC, molar ratio of butanol-2 and 50% hydrogen peroxide (1,0-5,0):1 and at time of contact 2-12 C.

Unlike the prototype, the process is carried out at significantly lower temperatures, in excess of butanol-2, with a higher concentration of hydrogen peroxide in the preliminary mixing of the reagents and feeding them into the reactor in the form of a single material flow. Essential time contacting the source reagent in the zone of elevated temperature, which depends on the dimensions of the reactor at a feed rate of it is: examples of the process in the laboratory reactor, made of quartz glass, heated, allowing to carry out the process at temperatures up to 600oC. the Reactor simulates industrial tubular apparatus. The volume of the reactor 0,078 DM3. The source reagents are pre-mixed in a desired ratio, and then served with a certain velocity in the reactor, maintained the required temperature. The feed rate of the reactants determines the time of their contact in the reactor. The reaction gases condense in the refrigerator, cooled cooled to a temperature of 5oC water. At the end of the experience condensate weighed and analyzed by gas chromatography. The table below shows examples of the process for different combinations of process parameters, whose values are the distinguishing features of the invention.

In conditions like elevated (examples 1-2) and low (example 12) of the temperature decrease of the output of the IEC, and, at high temperatures there is a high content of impurities and increased the amount of misalignment material balance (unbalance experience). These facts confirm the occurrence of adverse reactions and partly deep oxidation of butanol-2 (dioxide to ogleroot, apparently, insufficient.

With the increased excess butanol-2 (examples 3, 7) with increasing time of contact output IEC also reduced. Similar phenomenon is observed with increasing time of contact and increase the concentration of atomic oxygen (example 4), which, apparently, can be explained also by the processes further oxidation IEC. Output IEC decreases and decreasing the time of contact (examples 5, 9), which is associated with the presence of "breakthrough of unreacted components.

In examples 6, 8, 10, 11 achieved the best performance, especially when 250oC and time of contact 3,5-4,0 C.

The use of the present invention can effectively and reliably solve the problem of large-scale industrial production of IEC. The above production is characterized by high technical and economic parameters, determined by such factors as the absence of expensive catalysts, high selectivity, lack of auxiliary solvents, the use of the reactants in the ratio close to stoichiometry, high speed process, the absence of elevated pressure, etc.

Literature

1. Kire Otmer "

3. A. S. Sultanov and others Ed. the certificate of the USSR, 293790, 1971.

4. Patent Germany, 1965186, 1979.

5. U.S. patent 2829165, 1958.

6. Chem. Eng. 63, 1960.

7. U.S. patent, 2153582.

8. T. M. Nagiyev, etc. Ed. the certificate of the USSR 1074858, 1984.

1. The method of producing ethyl ketone, including the interaction of butanol-2 with hydrogen peroxide, wherein the process is carried out at 220-350oC, preferably at 250-280°C., at a molar ratio of butanol-2 and hydrogen peroxide (1,0-5,0):1, preferably at (1.5 to 2.5):1, and at the time of contact of the reactants in the reactor 2-12, preferably 3-8 c.

2. The method according to p. 1, characterized in that the source reagents are pre-mixed and in the form of solution fed into the reactor one material stream.

3. The method according to p. 1, characterized in that the peroxide is used in the form of an aqueous solution with a concentration of 30-50 wt.%.

 

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