Methyl ethyl ketone production process

FIELD: industrial organic synthesis.

SUBSTANCE: in presence of a process for production of methyl ethyl ketone widely applicable in petroleum processing and petrochemical industries at oil dewaxing and paraffin deoiling plants, in varnish-and-paint industry to produce polyurethane coatings, in wood processing industry to produce a variety of glues, in industrial rubber article industry, in perfumery, and in other areas. Process comprises 2-butanol/hydrogen peroxide reaction conducted at 20-100°C and butanol/peroxide molar ratio (1.0-13.0):1 on titanium silicate catalyst having MFI, MEL, or beta zeolite topology and containing 0.1 to 9.5% titanium, content of catalyst ranging from 0.01 to 20% based on the total weight of reaction medium. Thus formed methyl ethyl ketone is isolated from reaction medium via rectification in the form of azeotrope with water while unreacted 2-butanol with admixture of water is recycled to synthesis stage. Methyl ethyl ketone/water azeotrope is separated via extraction with organic solvent as extractant at extractant-to-azeotrope ratio (0.5-10):1 and number of extraction steps from 1 to 10. Extract is separated via rectification or distillation processes to recover commercial methyl ethyl ketone while returning extractant to separation stage.

EFFECT: increased yield of methyl ethyl ketone and reduced power consumption.

2 cl, 1 tbl

 

The invention relates to chemical technology, and in particular to methods of acquisition and allocation of methyl ethyl ketone (MEK).

Methyl ethyl ketone is used in the refining and petrochemical industry plants dewaxing oils and obezbalivaniya paraffins, in the paint industry as a component of the volatile part polyurethane coatings, wood industry for various adhesives, industrial rubber products, perfumery and other industries.

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, or as a by-product in the production of acetic acid by the oxidation of butane.

The dehydrogenation process is conducted in the liquid phase catalyst is Raney Nickel or copper chromite, when 130-180°C. 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/(kg-h), short life of the catalyst is not more than 2 years, the need to use and reg is the generation 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 (US 2829165, SS 49/10, 1958).

The prototype of the present invention is a method of obtaining IEC through high temperature non-catalytic oxidation of butanol-2 aqueous solution of hydrogen peroxide with a concentration of 30-50% when 220-350°and a molar ratio of reagents (1,0-5,0):1, respectively, at the time of contact 2-12 (EN 2169726, SS 49/10, SS 45/49, 2001).

However, a significant drawback of the described method is that the oxidation reaction is carried out at elevated temperature, which requires additional energy and special construction materials, in addition, produces by-products (e.g., acetic acid), complicating the extraction of saleable product and there is no stage of the selection commodity IEC.

The task of the invention is the development of efficient technologies for the synthesis and selection IEC.

The technical result from the use of the invention is to reduce the cost of obtaining, enhancing ecological production and increase output of the IEC.

The technical result is achieved in that in the method of producing methyl ethyl ketone (MEK), including collaboration is the development of butanol-2 and hydrogen peroxide, the process is carried out at from 20 to 100°With, at a molar ratio of butanol-2 and hydrogen peroxide (1,0-13,0):1, on the catalyst silicalite titanium with the topology of MFI, MEL or etazolate with titanium content ranging from 0.1%to 9.5% in the amount of from 0.01 to 20 wt%. of the total reaction mass obtained IEC removed from the reaction mass by distillation in the form of an azeotrope with water, and unreacted butanol-2 mixed with water return to the stage of synthesis, the azeotrope IEC-water divide extraction, using as a solvent an organic solvent, at a ratio of extractant - azeotrope IEC-water (0.5 to 10):1, and the number of stages of extraction from 1 to 10, and the extract obtained is divided by the methods of rectification or distillation emitting commodity IEC and the return of the extractant to the extraction. As the organic solvent used: toluene, isopropylbenzene, o-kisla, p-xylene, m-kisla, o-diisopropylbenzene, p-diisopropylbenzene, m-diisopropylbenzene, n-decane, n-pentane, ISO-pentane and/or mixtures thereof.

The invention is illustrated in the examples of the process in a glass reactor with jacket, equipped with a reflux condenser and a thermometer. Stirring of the reaction mixture with a magnetic stirrer.

Example

In the reactor download the necessary amount of butanol-2 and silicalite titanium include magni is strong stirrer and thermostatic to a predetermined temperature. After loading of hydrogen peroxide, record the start time of the experiment. After the experience of the reaction mass analyzed by gas chromatography. The process of allocating the IEC conducted in the following way. After completion of the oxidation reaction, the reaction mixture is subjected to separation. With this purpose by distillation from the reaction mass is distilled azeotrope IEC with water, and the cube is given butanol-2 with impurities in water which is sent to the stage of oxidation. Obtained in the distillate of the column azeotrope IEC with water treated with n-pentane and intensively stirred. After that, the mixture of n-pentane and IEC are sent to the delamination. Below are selected heavy aqueous phase. Top lightweight organic layer containing the IEC, is subjected to rectification or distillation for separation of a commercial product.

The table below shows examples of the process for different combinations of process parameters, whose values are the distinguishing features of the invention.

The table shows that the optimum temperature is about 30-60°providing the maximum yield of MEK at 20 and 100°output IEC below. With increasing molar ratio IEC - hydrogen peroxide 1:1 to 13:1 and increasing the concentration of catalyst increases output IEC. By increasing the concentration was pushing the congestion more than 20% of the mass. increase the output of the IEC is not detected, the amount of catalyst is less than 0.01% of the mass. almost not catalyzes an oxidation reaction.

As a solvent, addition of n-pentane, used toluene, isopropylbenzene, o-kisla, p-xylene, m-kisla, o-diisopropylbenzene, p-diisopropylbenzene, m-diisopropylbenzene, n-decane, ISO-pentane and/or their mixtures (20%-kisla, 60% m-kisla, 20% p-cyclol; 50% of n-pentane; 50% ISO-pentane). The test results are similar to those shown in the table.

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 side products, the absence of an auxiliary solvent, the absence of elevated pressure, etc.

# example
1234The placeholder
Temperature, °203251100220-350
The molar ratio of butanol-2: hydrogen peroxide11,112,37,04,01,0-5,0
The concentration of catalyst, % wt.0,5811,204,804,88-
The concentration of H2About2, % of the mass.34,7536,4534,7534,7530-50
The output of the IEC, % mass.45,5690,78to 97.9184,1722,1-66,1
Extraction rate IEC of the azeotrope IEC-water %99,699,599,899,5-
Note to table
1. The ratio of n-pentane azeotrope IEC-water of 0.5:1; the number of stages of extraction 1.

1. The method of producing methyl ethyl ketone (MEK), including the interaction of butanol-2 and hydrogen peroxide, wherein the process is carried out at from 20 to 100°With, at a molar ratio of butanol-2 and hydrogen peroxide (1,0-13,0):1, on the catalyst silicalite titanium with the topology of MFI, MEL or etazolate with titanium content ranging from 0.1%to 9.5% in the amount of from 0.01 to 20 wt.% of the total reaction mass obtained IEC removed from the reaction mass by distillation in the form of an azeotrope with water, and unreacted butanol-2 mixed with water return to the stage of synthesis, the azeotrope IEC-water divide extraction with the use of what Finance as a solvent of an organic solvent at a ratio of extractant-azeotrope IEC-water (0.5 to 10):1, and the number of stages of extraction from 1 to 10, and the extract obtained is divided by the methods of rectification or distillation emitting commodity IEC and the return of the extractant to the extraction.

2. The method according to claim 1, characterized in that the organic solvent used toluene, cumene, o-xylene, p-xylene, m-kisla, o-diisopropylbenzene, p-diisopropylbenzene, m-diisopropylbenzene, n-decane, n-pentane, ISO-pentane and/or mixtures thereof.



 

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