CA1256121A - Process for the production of methyl isobutyl ketone - Google Patents
Process for the production of methyl isobutyl ketoneInfo
- Publication number
- CA1256121A CA1256121A CA000498659A CA498659A CA1256121A CA 1256121 A CA1256121 A CA 1256121A CA 000498659 A CA000498659 A CA 000498659A CA 498659 A CA498659 A CA 498659A CA 1256121 A CA1256121 A CA 1256121A
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- Prior art keywords
- catalyst
- palladium
- reaction
- acetone
- mibk
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for production of methyl isobutyl ketone from acetone and hydrogen by a one-stage reaction is disclosed, comprising contacting acetone and hydrogen in the presence of a catalyst comprising niobic acid and palladium. The catalyst is excellent in activity, MIBK
selectivity, and service life. Thus the invention permits production of methyl isobutyl ketone in high yield for long periods of time.
A process for production of methyl isobutyl ketone from acetone and hydrogen by a one-stage reaction is disclosed, comprising contacting acetone and hydrogen in the presence of a catalyst comprising niobic acid and palladium. The catalyst is excellent in activity, MIBK
selectivity, and service life. Thus the invention permits production of methyl isobutyl ketone in high yield for long periods of time.
Description
~256~21 P~OCESS FOR PRODUCTION OF METHYL ISOBUTYL KETONE
FIELD OF THE INVENTION
The present invention relates to a process for production of methyl isobutyl ketone and more particularly to a process for producing methyl isobutyl ketone from acetone and hydrogen by a one-stage reaction.
BACKGROUND OF THE INVENTION
Methyl isobutyl ketone (hereinafter abbreviated to "MIBK") is useful as an organic solvent, or as a material for use in preparation of paints and chemical compounds such as stabilizers. MIBK is usually industrially produced from acetone and hydrogen by the following three-stage reaction.
A tone condensatin ~ Diacetone alcohol dehYdratin ~ Mesityl oxide hydroqenation) MIBK
First acetone is condensed by contacting with a solid alkaline catalyst such as barium hydroxide in a liquid phase under conditions of 10 to 20C and atmospheric pressure to prepare diacetone alcohol. Then the diacetone alcohol thus prepared is separated from unreacted acetone and dehydrated by heating at 100 to 120C in a liquid phase in the presence of an acid catalyst such as sulfuric acid and phosphoric acid to ~;-~2S6~21 1 prepare mesityl oxide. Subsequently this mesityl oxide is separated and purified, and then hydrogenatéd in the presence of, e.g., a Raney nickel catalyst to prepare MIBK .
5The above process has been widely used on a commercial scale, but has disadvantages in that the process is complicated because it needs three stages of condensation, dehydration and hydrogenation, and also separation and purification of intermediate products such as diacetone alcohol and mesityl oxide, and in that in the condensation of diacetone alcohol from acetone the conversion is as low as about 15% because the reaction is an equilibrium reaction.
For this reason it has been investigated to15 produce MIBK from acetone and hydrogen by a one-stage reaction. This one-stage process is very advantageous from a standpoint of equilibrium and permits to increase a one-pass conversion of the starting material, and thus is economically advantageous over the three-stage process.
Several methods of production of MIBK by a one-stage reaction have already been proposed. For example, German Patent No. 1,238,453 discloses a method of synthesizing MIBK by the use of an acid-type ion exchange resin and a palladium-carbon combination as a catalyst; Japanese 25Patent Publication No. 6994/74 discloses a method using a ~256~Z~
1 catalyst comprising zirconium phosphate having palladium deposited thereon; and Japanese Patent Publication No.
2643/71 discloses a method using a catalyst comprising an H-type zeolite having palladium deposited thereon.
These methodsl however, have disadvantages in that it is not possible to increase the reaction temperature because they use resins, preparation of the catalysts is complicated, and the MIBK yield is low. Thus they are unsatisfactory for commercial use.
SUMMARY OF THE INVENTION
The present invention is intended to overcome the above problems of the conventional one-stage processes for production of MIBK.
Therefore, an object of the present invention is to provide a process for the production of MIBK in high yield by a simplified procedure.
It has been found that MIBK can be produced in high yield by a one-stage reaction by contacting acetone and hydrogen in the presence of a catalyst comprising a niobic acid and palladium.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for producing methyl isobutyl ketone which comprises contacting acetone and hydrogen in the presence of a 25 catalyst comprising niobic acid and palladium.
~56~21 1 The catalyst that is used in the present invention comprises niobic acid and palladium. Niobic acid is a solid called hydrated niobium oxide, and its properties are described in "Third Solid Acid Process Conference Preprint", pp. 1-4, Nov. 11, 1983 (Catalysis Society of Japan). It is reported that niobic acid possesses acidic properties and has activities on hydration and esterification of ethylene, but its catalytic action on other reactions has not substantially been known. According to the present invention, MIBK can be produced in high yield by a one-stage reaction by using a catalyst comprising niobic acid and palladium.
The catalyst of the present invention can take various forms. For example, it can be used in the form that palladium is deposited on niobic acidr or in the form that niobic acid and various palladium catalysts such as palladium-carbon, palladium-alumina and palladium black are physically mixed. In addition, palladium may be deposited on a mixed carrier of niobic acid and alumina or silica. In the case where a catalyst comprising niobic acid having palladium deposited thereon is used, the amount of palladium deposited or mixing ratio of palladium is pre~erably 0.01 to 5.0 wt% and more preferably 0.02 to 1.0 wt%.
The process of the present invention can be ~256~
1 carried out in various manners such as a so-called fixed bed flow reaction in which a catalyst comprising niobic acid and palladium is packed in an adiabatic or isothermic reactor and acetone and hydrogen are passed therethrough and a suspension reaction in which a catalyst comprising niobic acid and palladium is suspended in acetone and hydrogen is blown therethrough. In the case of the fixed bed flow reaction, acetone and hydrogen may be reacted in either a liquid phase or a gas phase. In some cases, a reaction system such as trickle phase may be employed. In the case of the suspension reaction, the reaction may be carried out either batchwise or continuously. In the fixed bed flow reaction, it is preferred to use a catalyst comprising niobic acid having palladium deposited hereon, and in the suspension reaction, it is preferred to use a mixture of niobic acid and a palladium catalyst.
In the practice of the process of the present invention, the reaction temperature is usually 80 to 250C
and preferably 120 to 200C. If the reaction temperature is less than 80C, a rate of reaction is low. On the other hand, if it is more than 250C, the amounts of highly condensed products o~ acetone being formed are increased.
The reaction pressure is usually from atmospheric pressure to 50 a.ms. Although a preferred 1 reaction pressure varies with the reaction temperature employed, it is 10 to 30 atms.
The catalyst of the present invention is high in activity, good in selectivity, and high in stability.
Moreover, the catalyst has a long service life. Thus the present invention permits to produce MIBX in high yield and in a sta~le manner for a long period of time.
The present invention is described below in greater detail by reference to the following examples although it is not intended to be limited thereto.
EX~PLE 1 A 200-milliliter autoclave provided with a magnetic stirrer was charged with 100 ml of acetone, and then 2 g of niobic acid (a powder having a water content of 7 wt~, produced by CBMM Co.) and 1 g of palladium-alumina ~a powder having a palladium content of 0.1 wt~, produced by Sumitomo Aluminum Co., Ltd.) were introduced in the autoclave. The autoclave was heated to 160C and hydrogen was introduced in the autoclave, and the reaction was carried out while stirring in such a manner that the pressure in the autoclave was 20 kg/cm . Hydrogen was continuously supplemented for compensation of consumed hydrogen so that the total pressure was always maintained at 20 kg/cm2. After reacting for 2 hours, the autoclave was cooled, and the reaction mixture was taken out the ~5~
1 autoclave and separated from hydrogen and the catalyst.
The reaction ~ixture was analyzed by gas chromatography.
The results are as follows:
Acetone conversion: 49.3%
MIBK selectivity: 92.3 IPA (isopropanol) selectivity: 0.8~
DIBK (diisobutyl ketone~ selectivity: 3.8%
COMPARATIVE EXAMPLE
The same procedure as in Example 1 was repeated lQ with the exception that only the palladium-alumina was used in an amount of 3 g. The results are as follows:
Acetone conversion: 3.8 MIBK selectivity: 62.3%
IPA selectivity: 35.8~
DIBK selectivity: 0.6%
It can be seen from the above results that the palladium-alumina catalyst used in Example 1 has almost no activity in production of MIBK from acetone by a one-stage reaction.
The same procedure as in Example 1 was repeated with the exception that each of the catalysts shown in Table 2 was used. The results are shown in Table 1.
12561~1 Table 1 Example Acetone Selectivity (%~
No. CatalystConversion MIBK IPA DIBX
FIELD OF THE INVENTION
The present invention relates to a process for production of methyl isobutyl ketone and more particularly to a process for producing methyl isobutyl ketone from acetone and hydrogen by a one-stage reaction.
BACKGROUND OF THE INVENTION
Methyl isobutyl ketone (hereinafter abbreviated to "MIBK") is useful as an organic solvent, or as a material for use in preparation of paints and chemical compounds such as stabilizers. MIBK is usually industrially produced from acetone and hydrogen by the following three-stage reaction.
A tone condensatin ~ Diacetone alcohol dehYdratin ~ Mesityl oxide hydroqenation) MIBK
First acetone is condensed by contacting with a solid alkaline catalyst such as barium hydroxide in a liquid phase under conditions of 10 to 20C and atmospheric pressure to prepare diacetone alcohol. Then the diacetone alcohol thus prepared is separated from unreacted acetone and dehydrated by heating at 100 to 120C in a liquid phase in the presence of an acid catalyst such as sulfuric acid and phosphoric acid to ~;-~2S6~21 1 prepare mesityl oxide. Subsequently this mesityl oxide is separated and purified, and then hydrogenatéd in the presence of, e.g., a Raney nickel catalyst to prepare MIBK .
5The above process has been widely used on a commercial scale, but has disadvantages in that the process is complicated because it needs three stages of condensation, dehydration and hydrogenation, and also separation and purification of intermediate products such as diacetone alcohol and mesityl oxide, and in that in the condensation of diacetone alcohol from acetone the conversion is as low as about 15% because the reaction is an equilibrium reaction.
For this reason it has been investigated to15 produce MIBK from acetone and hydrogen by a one-stage reaction. This one-stage process is very advantageous from a standpoint of equilibrium and permits to increase a one-pass conversion of the starting material, and thus is economically advantageous over the three-stage process.
Several methods of production of MIBK by a one-stage reaction have already been proposed. For example, German Patent No. 1,238,453 discloses a method of synthesizing MIBK by the use of an acid-type ion exchange resin and a palladium-carbon combination as a catalyst; Japanese 25Patent Publication No. 6994/74 discloses a method using a ~256~Z~
1 catalyst comprising zirconium phosphate having palladium deposited thereon; and Japanese Patent Publication No.
2643/71 discloses a method using a catalyst comprising an H-type zeolite having palladium deposited thereon.
These methodsl however, have disadvantages in that it is not possible to increase the reaction temperature because they use resins, preparation of the catalysts is complicated, and the MIBK yield is low. Thus they are unsatisfactory for commercial use.
SUMMARY OF THE INVENTION
The present invention is intended to overcome the above problems of the conventional one-stage processes for production of MIBK.
Therefore, an object of the present invention is to provide a process for the production of MIBK in high yield by a simplified procedure.
It has been found that MIBK can be produced in high yield by a one-stage reaction by contacting acetone and hydrogen in the presence of a catalyst comprising a niobic acid and palladium.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for producing methyl isobutyl ketone which comprises contacting acetone and hydrogen in the presence of a 25 catalyst comprising niobic acid and palladium.
~56~21 1 The catalyst that is used in the present invention comprises niobic acid and palladium. Niobic acid is a solid called hydrated niobium oxide, and its properties are described in "Third Solid Acid Process Conference Preprint", pp. 1-4, Nov. 11, 1983 (Catalysis Society of Japan). It is reported that niobic acid possesses acidic properties and has activities on hydration and esterification of ethylene, but its catalytic action on other reactions has not substantially been known. According to the present invention, MIBK can be produced in high yield by a one-stage reaction by using a catalyst comprising niobic acid and palladium.
The catalyst of the present invention can take various forms. For example, it can be used in the form that palladium is deposited on niobic acidr or in the form that niobic acid and various palladium catalysts such as palladium-carbon, palladium-alumina and palladium black are physically mixed. In addition, palladium may be deposited on a mixed carrier of niobic acid and alumina or silica. In the case where a catalyst comprising niobic acid having palladium deposited thereon is used, the amount of palladium deposited or mixing ratio of palladium is pre~erably 0.01 to 5.0 wt% and more preferably 0.02 to 1.0 wt%.
The process of the present invention can be ~256~
1 carried out in various manners such as a so-called fixed bed flow reaction in which a catalyst comprising niobic acid and palladium is packed in an adiabatic or isothermic reactor and acetone and hydrogen are passed therethrough and a suspension reaction in which a catalyst comprising niobic acid and palladium is suspended in acetone and hydrogen is blown therethrough. In the case of the fixed bed flow reaction, acetone and hydrogen may be reacted in either a liquid phase or a gas phase. In some cases, a reaction system such as trickle phase may be employed. In the case of the suspension reaction, the reaction may be carried out either batchwise or continuously. In the fixed bed flow reaction, it is preferred to use a catalyst comprising niobic acid having palladium deposited hereon, and in the suspension reaction, it is preferred to use a mixture of niobic acid and a palladium catalyst.
In the practice of the process of the present invention, the reaction temperature is usually 80 to 250C
and preferably 120 to 200C. If the reaction temperature is less than 80C, a rate of reaction is low. On the other hand, if it is more than 250C, the amounts of highly condensed products o~ acetone being formed are increased.
The reaction pressure is usually from atmospheric pressure to 50 a.ms. Although a preferred 1 reaction pressure varies with the reaction temperature employed, it is 10 to 30 atms.
The catalyst of the present invention is high in activity, good in selectivity, and high in stability.
Moreover, the catalyst has a long service life. Thus the present invention permits to produce MIBX in high yield and in a sta~le manner for a long period of time.
The present invention is described below in greater detail by reference to the following examples although it is not intended to be limited thereto.
EX~PLE 1 A 200-milliliter autoclave provided with a magnetic stirrer was charged with 100 ml of acetone, and then 2 g of niobic acid (a powder having a water content of 7 wt~, produced by CBMM Co.) and 1 g of palladium-alumina ~a powder having a palladium content of 0.1 wt~, produced by Sumitomo Aluminum Co., Ltd.) were introduced in the autoclave. The autoclave was heated to 160C and hydrogen was introduced in the autoclave, and the reaction was carried out while stirring in such a manner that the pressure in the autoclave was 20 kg/cm . Hydrogen was continuously supplemented for compensation of consumed hydrogen so that the total pressure was always maintained at 20 kg/cm2. After reacting for 2 hours, the autoclave was cooled, and the reaction mixture was taken out the ~5~
1 autoclave and separated from hydrogen and the catalyst.
The reaction ~ixture was analyzed by gas chromatography.
The results are as follows:
Acetone conversion: 49.3%
MIBK selectivity: 92.3 IPA (isopropanol) selectivity: 0.8~
DIBK (diisobutyl ketone~ selectivity: 3.8%
COMPARATIVE EXAMPLE
The same procedure as in Example 1 was repeated lQ with the exception that only the palladium-alumina was used in an amount of 3 g. The results are as follows:
Acetone conversion: 3.8 MIBK selectivity: 62.3%
IPA selectivity: 35.8~
DIBK selectivity: 0.6%
It can be seen from the above results that the palladium-alumina catalyst used in Example 1 has almost no activity in production of MIBK from acetone by a one-stage reaction.
The same procedure as in Example 1 was repeated with the exception that each of the catalysts shown in Table 2 was used. The results are shown in Table 1.
12561~1 Table 1 Example Acetone Selectivity (%~
No. CatalystConversion MIBK IPA DIBX
2 Niobic acid: 2 g a 5~6 Pd-Carbon: 1 g 43.186.3 7. 2.1
3 Niobic acid with 0.1% 47 393 5 0 4 3 4 Pd deposited: 3 g The same procedure as in Example 1 was repeated with the exception that the reaction conditions were changed as shown in Table 2. The results are shown in Table 2.
Table 2 15Example Reaction Reaction Acetone Selectivity(%) No Temperature Pressure Convertion MIBK IPA DIBK
(C) (kg/cm ) (96)
Table 2 15Example Reaction Reaction Acetone Selectivity(%) No Temperature Pressure Convertion MIBK IPA DIBK
(C) (kg/cm ) (96)
4 140 2038.4 93.8 1.3 2.6 180 3056.2 91.3 1.1 4.3 6 160 3050.1 92.5 1.4 3.9 7 160 4051.2 91.8 2.1 3.7 Niobic acid (a cylindrical form having a water content of 7 wtg~, produced by CBMM Co.) was soaked in an aqueous solution of palladium chloride, reduced with hydrazine, and then calcined at 300C. The amount of palladium deposited was 0.1 wt~.
1~ ~ 6~ ~
1 Then 100 ml of the catalyst thus prepared was packed in a vertically aligned reactor having an inner diameter of 28 mm. Under conditions of temperature of 160C and pressure of 20 kg/cm2, acetone and hydrogen were introduced in the reactor at rates of 158 g/hr (LHSV=2) and 256 Nml/min, respectively, and reacted. The results are shown in Table 3.
Table 3 Reaction Selectivity (~) 10 TimeAcetone Conversion MIBK IPA DIBK
(hr) (%) 41.8 93.5 0.3 3.6 100 40.3 93.6 0.2 4.2 500 41.2 92.8 0.2 3.8 The same procedure as in Example 6 was repeated with the exception that the reaction pressure was changed to 10 kg/cm2 and that acetone was reacted in a gas phase.
The results (after 10 hours) are shown below.
Acetone conversion: 43.8 MIBK selectivity: 90.1%
IPA selectivity: 0.1%
DIBK selectivity: 5.8%
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various _ 9 _ l~5S~Zl changes and modif ications can be made therein without departing from the spirit and scope thereof.
-- 1 o --
1~ ~ 6~ ~
1 Then 100 ml of the catalyst thus prepared was packed in a vertically aligned reactor having an inner diameter of 28 mm. Under conditions of temperature of 160C and pressure of 20 kg/cm2, acetone and hydrogen were introduced in the reactor at rates of 158 g/hr (LHSV=2) and 256 Nml/min, respectively, and reacted. The results are shown in Table 3.
Table 3 Reaction Selectivity (~) 10 TimeAcetone Conversion MIBK IPA DIBK
(hr) (%) 41.8 93.5 0.3 3.6 100 40.3 93.6 0.2 4.2 500 41.2 92.8 0.2 3.8 The same procedure as in Example 6 was repeated with the exception that the reaction pressure was changed to 10 kg/cm2 and that acetone was reacted in a gas phase.
The results (after 10 hours) are shown below.
Acetone conversion: 43.8 MIBK selectivity: 90.1%
IPA selectivity: 0.1%
DIBK selectivity: 5.8%
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various _ 9 _ l~5S~Zl changes and modif ications can be made therein without departing from the spirit and scope thereof.
-- 1 o --
Claims (3)
1. A process for producing methyl isobutyl ketone which comprises contacting acetone and hydrogen in the presence of a catalyst comprising niobic acid and palladium.
2. A process as claimed in Claim 1, wherein the catalyst comprises niobic acid having palladium deposited thereon.
3. A process as claimed in Claim 1, wherein the catalyst is a mixture of niobic acid and a palladium catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000498659A CA1256121A (en) | 1985-12-27 | 1985-12-27 | Process for the production of methyl isobutyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000498659A CA1256121A (en) | 1985-12-27 | 1985-12-27 | Process for the production of methyl isobutyl ketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1256121A true CA1256121A (en) | 1989-06-20 |
Family
ID=4132183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000498659A Expired CA1256121A (en) | 1985-12-27 | 1985-12-27 | Process for the production of methyl isobutyl ketone |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1256121A (en) |
-
1985
- 1985-12-27 CA CA000498659A patent/CA1256121A/en not_active Expired
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