KR101762979B1

KR101762979B1 - Process for production of ketone

Info

Publication number: KR101762979B1
Application number: KR1020127007540A
Authority: KR
Inventors: 후미오 야마까와
Original assignee: 이데미쓰 고산 가부시키가이샤
Priority date: 2009-10-23
Filing date: 2010-10-15
Publication date: 2017-08-04
Also published as: JP5615834B2; MY165490A; JPWO2011048783A1; WO2011048783A1; CN102596876A; KR20120089656A

Abstract

The present invention provides a process for producing ketone which dehydrogenates aliphatic alcohols at a reaction pressure of 0.1 MPaG or lower using a copper catalyst.

Description

PROCESS FOR PRODUCTION OF KETONE [0002]

The present invention relates to a process for producing a ketone using a copper-based catalyst.

Ketones are useful materials for solvents and organic chemicals. In particular, methyl ethyl ketone (MEK, 2-butanone) is a colorless and transparent hygroscopic liquid having excellent dissolving ability and freely miscible with commonly used organic solvents. Particularly, it is widely used in the solvent field because of its high ability to dissolve in synthetic resins, oils, higher fatty acids, and the like. Recently, there is a demand for a high performance solvent in the electronic industry such as a magnetic tape binder.

The synthesis method of MEK includes dehydrogenation of sec-butanol (SBA, 2-butanol), oxidation of n-butene or n-butane, isomerization of butylene oxide, and the like, but industrially it is the mainstream by dehydrogenation reaction of SBA .

The dehydrogenation reaction of SBA is classified into a vapor phase method using a metal oxide such as Cu, Zn, Cr, etc., and a liquid phase method using a sponge Ni catalyst. The vapor phase method has the drawback that the SBA conversion rate is high (80% or more), the MEK selectivity is low (95% to 99%), and the catalyst life is short because the reaction temperature is high (generally 300 to 400 ° C). On the other hand, the liquid phase process has an advantage that the reaction temperature is low (130 to 200 ° C), the SBA conversion rate is low but the MEK selectivity is high (99.5% or more) and the catalyst life is long.

Patent Document 1 discloses a method of performing a reaction at 170 to 230 ° C using a catalyst in which a metal such as Cu, Ag, Au, Sn, Pb, Zn, Cd, In and Ge is added to sponge (Rainey) Document 2 discloses a method of reacting at 160 to 190 캜 and 2 to 8 atm using a sponge Ni catalyst.

Patent Document 3 discloses a process for producing ketones which dehydrogenate secondary alcohols using a spherical modified Raney copper catalyst in which a ternary alloy of copper, zinc and aluminum is developed. Patent Document 4 discloses a method for producing a carbonyl compound dehydrogenating a primary or secondary alcohol using a modified Raney copper catalyst in which copper, zinc and an iron alloy are developed.

Although these techniques can provide MEK having good purity to a certain degree, a very high purity exceeding 99.95% is required in the field of electronics industry and the like, and therefore, a technique for manufacturing high purity MEK has been required.

U.S. Patent No. 4380673 Japanese Patent Application Laid-Open No. 60-258135 Japanese Patent Application Laid-Open No. 7-53433 Japanese Patent Application Laid-Open No. 7-316089

It is an object of the present invention to provide a process for producing high purity ketones.

According to the present invention, the following process for producing ketones is provided.

1. A process for producing ketone by dehydrogenating an aliphatic alcohol at a reaction pressure of 0.1 MPaG or less using a copper catalyst.

2. The process for producing a ketone according to 1 above, wherein the copper-based catalyst is an oxide solid catalyst containing copper and chromium or zinc.

3. The method for producing a ketone according to 1 above, wherein the copper-based catalyst is a sponge-based catalyst.

4. The process for producing a ketone according to any one of 1 to 3 above, wherein the dehydrogenation is carried out by continuously blowing the aliphatic alcohol into a solvent in which the copper catalyst is suspended at a reaction temperature of 200 ° C or lower.

5. The process for producing a ketone according to any one of 1 to 4 above, wherein the aliphatic alcohol is 2-butanol.

6. The process for producing a ketone according to any one of 1 to 5 above, wherein the ketone is methyl ethyl ketone.

According to the present invention, a method for producing a high purity ketone is provided.

In the method for producing ketones of the present invention, aliphatic alcohols are dehydrogenated using a copper catalyst to produce ketones.

As the starting aliphatic alcohol, a secondary alcohol is preferred. As the secondary alcohol, 2-propanol and 2-butanol can be used, but 2-butanol is preferable.

The resulting ketone is acetone, methyl ethyl ketone and the like, in particular methyl ethyl ketone.

As the copper-based catalyst, it is preferable to use copper and chromium (Cr) or zinc (Zn) as a main component. To increase the durability of the catalyst, it can be added for the barium (Ba), calcium (Ca), manganese (Mn), alumina (Al ₂ O _3), silica (SiO ₂₎ or the like.

As the copper-based catalyst, a sponge-copper catalyst prepared by expanding an alloy such as copper and aluminum can be mentioned.

As the dehydrogenation reaction, there can be mentioned a liquid phase process in which catalyst particles are suspended in a high boiling point solvent by using a vapor-phase or stirred-tank reactor using a fixed-bed tubular flow reactor, and alcohol is continuously blown into the catalyst particles. .

The reaction temperature is preferably 130 ° C or more and 200 ° C or less. If it is less than 130 캜, the reaction efficiency may be lowered in terms of reaction rate and chemical equilibrium (equilibrium conversion rate). If it is higher than 200 DEG C, the side reaction tends to proceed and the selectivity (product purity) may be lowered. Further, the deterioration of the catalyst is also likely to proceed, and the frequency of regeneration or replacement of the catalyst is increased, thereby deteriorating the economical efficiency. More preferably from 135 deg. C to 170 deg. C, further preferably from 140 deg. C to less than 150 deg.

The reaction pressure of the dehydrogenation reaction is 0.1 MPaG or less. It is advantageous to have low pressure in terms of chemical equilibrium. Preferably 0.05 MPaG or less, and more preferably 0.03 MPaG or less. The lower limit may be normal pressure or may be greater than 0 MPaG.

The catalyst concentration in the solvent is not particularly limited, but is preferably 1 to 30% by weight in view of operability and efficiency.

The solvent is preferably a high boiling solvent. Saturated hydrocarbons having a low vapor pressure under the reaction conditions are preferably used, and paraffins having a carbon number of about 12 to 30 and a boiling point of about 200 to 400 캜 are preferred. If the solvent is too hard, it is likely to volatilize under the reaction conditions, which may increase the load of recovery and recycling of the solvent. On the other hand, if it is excessively heavy, the viscosity becomes high, so that there is a fear that the reaction efficiency is lowered in terms of stirring and mixing.

The supply amount of the raw material alcohol to the amount of the catalyst is usually 1 to 30 h ^-1 in terms of the space-time velocity (WHSV) for each weight by weight. If it is more than 30 h ^{-1, the} reaction rate may decrease and the yield (productivity) of the product may be deteriorated. If it is less than 1 h ^-1 , the economical efficiency and the productivity may be lowered.

In the method of the present invention, ketones having a high selectivity and a high purity can be produced by suppressing side reactions such as hydrogenolysis and suppressing the formation of by-products such as acetone and isopropyl alcohol. For example, the selectivity may be 99.95% or more. In addition, since the side reaction can be suppressed, impurities (methane, ethane, propane, butane, etc.) in the generated hydrogen gas are reduced, and hydrogen gas of high purity is also obtained.

[Example]

Example 1

24 g of a commercially available sponge copper catalyst (CDT-60 manufactured by Kawaken Fine Chemicals Co., Ltd., developed and Al: 1%) was introduced into a four-necked flask having an internal volume of 500 cc and charged with 2-butanol Several times. 165 cc of isoparaffin was added, and a stirrer, a raw material (SBA) supply line, and a cooling tube for extracting the product liquid were placed and replaced with nitrogen gas. The flask was heated with a mantle heater while stirring at 1000 rpm, and the SBA was supplied at a flow rate of 120 cc / h (96 g / h) to set the liquid temperature in the flask to 145 캜 and the reaction pressure to 0.01 MPaG. The resulting methyl ethyl ketone (MEK), unreacted SBA and byproducts (isopropyl alcohol, acetone, etc.) were condensed in a cooling tube and continuously extracted, and the generated hydrogen gas was discharged to the vent line. The WHSV was 4 h ^-1 .

After several days, the reaction solution was analyzed with a gas chromatograph (GC-FID) under stable activity, and the conversion and the selectivity were determined by the following equation (1). [Area] represents the amount quantified from the peak area of the chromatogram. The SBA conversion rate was 30% and the MEK selectivity was 99.99%. The results are shown in Table 1 below.

The analysis conditions are shown below.

Equipment used: Agilent Technologies 6850GC

Column: HP-Innoax (INNOWAX) (length 60 m, inner diameter 0.25 mm, film thickness 0.25 탆), He 2.0 ml / min.

Inlet: 250 DEG C, Split 1/250

Oven: The temperature was maintained at 60 캜 for 10 minutes, and the temperature was raised to 240 캜 at a rate of 15 캜 /

Detector: FID, 250 ° C

Example 2

Except that a commercially available copper chromium catalyst (N203S manufactured by Nikkiso Co., Ltd., chemical composition: 46% of CuO, 44% of Cr ₂ O ₃ , 4% of MnO ₂ ) was used instead of the catalyst used in Example 1 The reaction and analysis were carried out in the same manner as in Example 1. The MEK selectivity was 99.99%. The results are shown in Table 1.

Example 3

The reaction and analysis were carried out in the same manner as in Example 2 except that the reaction temperature was 165 캜. The conversion rate was increased but the MEK selectivity was not lowered to 99.99%. The results are shown in Table 1.

Example 4

Except that a commercially available copper zinc catalyst (E01X manufactured by Nikkiso Co., Ltd., chemical composition: 46% of CuO, 48% of ZnO, 6% of Al ₂ O ₃ ) was used instead of the catalyst used in Example 1 The reaction and analysis were carried out in the same manner as in Example 1. The MEK selectivity was 99.99%. The results are shown in Table 1.

Comparative Example 1

The reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst used in Example 1 was replaced with a commercially available sponge nickel catalyst (developed by Nikkorika Co., Ltd., developed and Al / Ni = 8% Respectively. The MEK selectivity was 99.90%. The results are shown in Table 1.

Compared with Comparative Example 1, in Examples 1 to 4, by using a copper-based catalyst, the by-product was further reduced to realize a high MEK selectivity and a highly pure MEK could be produced.

The ketone prepared by the method of the present invention can be preferably used as a raw material for a solvent or an organic compound.

Although the embodiments and / or examples of the invention have been described in some detail above, those skilled in the art will readily recognize that many changes to the illustrative embodiments and / or examples are possible without departing from the novel teachings and advantages of the invention It is easy. Accordingly, many of these modifications are within the scope of the present invention.

The entire contents of the document described in this specification are incorporated herein by reference.

Claims

A copper catalyst selected from a sponge copper catalyst (Cu, Al), a copper chromium catalyst (CuO, Cr ₂ O ₃ , MnO ₂ ) and a copper zinc catalyst (CuO, ZnO, Al ₂ O ₃ ) MPaG or less and a reaction temperature of not higher than 200 ° C, a secondary alcohol selected from 2-propanol and 2-butanol is continuously blown into a solvent in which the copper catalyst is suspended to dehydrogenate the secondary alcohol, &Lt; / RTI > ketone.

The process for producing a ketone according to claim 1, wherein the secondary alcohol is 2-butanol.

3. The method according to claim 1 or 2, wherein the ketone is methyl ethyl ketone.

The process for producing a ketone according to claim 1 or 2, wherein the supply amount of the secondary alcohol to the amount of the catalyst is 1 to 30 h ^-1 in terms of weight hourly space velocity (WHSV).

The process according to claim 1 or 2, wherein the solvent is a paraffin having 12 to 30 carbon atoms at a boiling point of 200 to 400 ° C.

The method of claim 1 or 2, wherein the selectivity of the ketone is 99.95% or more.