CA1157038A - Manganese catalyzed carbonylation of aliphatic alcohols - Google Patents
Manganese catalyzed carbonylation of aliphatic alcoholsInfo
- Publication number
- CA1157038A CA1157038A CA000364609A CA364609A CA1157038A CA 1157038 A CA1157038 A CA 1157038A CA 000364609 A CA000364609 A CA 000364609A CA 364609 A CA364609 A CA 364609A CA 1157038 A CA1157038 A CA 1157038A
- Authority
- CA
- Canada
- Prior art keywords
- manganese
- promoter
- carbon monoxide
- psi
- iodine
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Aliphatic alcohols are carbonylated with a promoted manganese catalyst to provide the corres-ponding carboxylic acids, esters and anhydrides.
Aliphatic alcohols are carbonylated with a promoted manganese catalyst to provide the corres-ponding carboxylic acids, esters and anhydrides.
Description
11~703~ 12,310 BACKGROUND OF THE INVENTION
This invention pertains to the carbonylationof aliphatic alcohols and in particular to promoted manganese catalysts therefor.
A variety of transition metal complexes are known to catalyze halide promoted carbonylation of methanol to acetic acid. These systems require severe reaction conditions and/or the use of expensive metal catalysts in order ~o provide commercially economical processes. For example, a process is des-cribed in U.S. 4,102,920 for the carbonylation of alcohols among other substrates in the presence of a catalyst system comprising a Group VIII metal component and a halogen component with a polydentate chelating phos-phorus or arsenic ligand.
It is an ob;ect of this invention to provide an inexpensive catalyst system which permits the carbony-lation of saturated aliphatic alcohols at low tempera-tures, that is, below about 200C. in order to minimize corrosion.
It is a further object of this invention to provide an inexpensive catalyst system for the carbony-lation of saturated aliphatic alcohols which can be operated at low pressures, that is, below about 2000 psia in order to min~ize equipment cost.
It is another object of this invention to provide a catalyst system which provides primarily aliphatic acids from the corresponding alcohols, but which also provides esters or anhydrides by controlling
This invention pertains to the carbonylationof aliphatic alcohols and in particular to promoted manganese catalysts therefor.
A variety of transition metal complexes are known to catalyze halide promoted carbonylation of methanol to acetic acid. These systems require severe reaction conditions and/or the use of expensive metal catalysts in order ~o provide commercially economical processes. For example, a process is des-cribed in U.S. 4,102,920 for the carbonylation of alcohols among other substrates in the presence of a catalyst system comprising a Group VIII metal component and a halogen component with a polydentate chelating phos-phorus or arsenic ligand.
It is an ob;ect of this invention to provide an inexpensive catalyst system which permits the carbony-lation of saturated aliphatic alcohols at low tempera-tures, that is, below about 200C. in order to minimize corrosion.
It is a further object of this invention to provide an inexpensive catalyst system for the carbony-lation of saturated aliphatic alcohols which can be operated at low pressures, that is, below about 2000 psia in order to min~ize equipment cost.
It is another object of this invention to provide a catalyst system which provides primarily aliphatic acids from the corresponding alcohols, but which also provides esters or anhydrides by controlling
2.
12,310 ~57V38 reaction conditions.
These snd other objects will become apparent to those skilled in the art upon a further reading of the specification.
SUMMARY OF THE INVENTION
A catalyst system for the carbonylation of saturated aliphatic alcohols has been found meeting the above objects which comprises a compound of manganesei which is soluble in the reaction mixture and a promoter selected from the group consisting of iodine and an alkyl iodide wherein the alkyl moieties of the iodide contain 1 to about 6 carbon atoms. This catalyst can be used withbest results at a temperature ~rom about 100C.
to about 180Co in a conventional carbonylation process wherein a saturated aliphatic alcohol having the formula ROH, where R is alkyl having values of 1 to about 18, is contacted with carbon monoxide or a mixture of carbon monoxide and hydrogen at supra atmospheric pressures below about 2000 psi.
A preferred pressure range is about 500 psi to about 2000 pæi.
A preferred temperature range is about 120C.
to about 150C.
DESCRIPTION OF THE INVENTION
A general procedure for utilizing the carbony-lation çatalyst of this invention is described below.
A 500 cc high-pressure reactor equipped with a glass liner is charged with a solution composed of a catalytic amount of manganese compound dissolved in a known amount acetic acid and/or methanol together with r 3 ~
~S7~38 12,310 a controlled amount of a halide promoter and optionally an inert diluent for use in subsequent analytical work as an internal standard. The system is purged and then placed under a prescribed pressure of carbon monoxide or a mixture of carbon monoxide and hydrogen, heated to the desired temperature and agitated by means of rocking. Upon completion of each experiment which may vary in time from about 15 minutes to about 12 hours, the system is cooled, vented, and the contents of the reactor isolated for spectral infrared or nuclear magnetic resonance analysis as well as for vapor phase chromatographic analysis.
The actual form of the manganese catalyst pre-cursor used in this invention is not critical since man-ganese in a variety of oxidation states provides the re-quired catalytic activity. Thus, for example, one may use manganese in the -1 valence state as, for example, in NaMn(C0)5, manganese in the zero valence state as found in compounds, such as, Mn2C010, manganese in the +1 valence state as found in compounds, such as, IMn(C0)5, or manganese in the +2 valence state as found in such compounds as Mn(OAc)2 . 4 ~ 0. These systems are extremely complicated and abstruse because of the various complexes which can form in reaction media. This is reflected in the speed with which reaction is initiated which appears to lie between the extremes of immediate gas uptake indicating immediate activity of the catalyst as soon as the proper reaction conditions of temperature and pressure have been reached and evidence of a delayed 4.
..
- 12,310 ~L~57~38 activity indicating an induction period in order to allow formation of certain reactive species or complexes.
While the ratio of manganese to promoter is not narrowly critical, a ratio of promoter:manganese catalyst of about 5 to about 7 is preferred.
The carbonylation react~on using this ca~alyst system can be practised either as a batch process or a continuous process.
While commercial interest center mainly in the use of this catalyst system for the carbonylation of methanol, it is equally applicable to higher alcohols ranging from ethanol to octadecanol Furthermore, by appropriate control of the composition of the reaction solvent, that is, by con-trolling the amount of water, methanol, acetic acid~
acetone, etc., one may selectively favor the formation from methanol in this carbonylation reaction of acetic acid, methyl acetate or acetic anhydride permitting the scope of the reaction to produce a variety of industrially important chemicals.
The form in which the iodine promoter i9 added to the mRnganese catalyst is not critical. Thus, for example, one may use elemental iodine, hydriodic acid, alkyl iodides wherein the alkyl group contains 1 to abo~t 6 carbon atoms as for example, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, and the likeO
The in~ention is further described in the examples which follow. All parts and percentages are by weight unless otherwise specified.
5.
~ 310 , . ~
7 ~ 3 Example 1 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(CO)10 1.6 g, CH3I 1.0 g, and C6H5CH3 1.0 g. The system was then purged with ca. 1000 psi of carbon monoxide ~nd then charged with 1500 psi of carbon monoxide.
The reactor was heated to 120C. at which time the solu-tion was agitated by mesns of rocking. Upon completion of the experiment, 5.5 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liqu~d contents isolated for analysis.
Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed w~th 10% SP-1200/1% H3P04 (low polarlty ester sold by Supelco Co. used as the stationary phase and contain~ng 1% H3P04) on 80tlOO
Chromo~or ~ W/AW (acid washed firebrick support sold ~y Johns Manv~lle).
Analy~is of the final reaction solution showed lt to contain CH30H 27.5 g ~0.86 mol) and CH3C02CH3 6.6 g (0.09 mol).
Example 2 A 500 cc high pressure reactor equipped with a glass l~ner was charged with the following: CH30H 32 g, (CO)lo 1.6 g, CH3I 1.0 g, 47% aq. HI 0.25 g and C6H5CH3 1.0 g. The syst~m was then purget with ca. 1000 p5i of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 120C. at which time the solution was agi~a~ed by means of roc~ing.
6.
~ j 12,310 ~57~38 Upon completion of the experiment, 5.7 hours, the rocking was stopped, the system cooled to 20-25C, the remaining gas was vented, and the liquid contents isolated for analysis. ~apor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x l/8"
stainless steel column packed with 10% SP-1200/1% H3P04 on 80/lO0 Chromosorb W/AW.
Analysis of the final reactor solution showed it to contain CH30H 23 . 7 g and CH3C02CH3 ll . l g.
Example 3 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2 (CO)lo 1.6 g~ 47% aq. HI 0.25 g, and C6H5CH3 1.0 g.
- The system was then purged with caO 1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heatet to 150C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 3.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1~00/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 31.0 g and CH3CO2CH3 l.0 g.
~1~L5703~ 12 9 310 Example 4 A ~00 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2 (C0)10 1.6 g, CH3I 0O5 g, 47% aq. HI 0.25 g, and C6H5CH3 1.0 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 150C.
at which time the solution was agitated by means of rock-ing. Upon completion of the experiment, 3.0 hours, the 10 rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was ob-tained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10%
SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final reaction solution was analyzed and found to contain CH30H 29.6 g and CH3C02CH3 5.5 g.
Example 5 A 500 cc high pressure reactor equipped with a 20 glass liner was charged with the following: CH30H 32 g, Mn2(C0)10 1.6 g, CH31 3.6 g, 47% aq. HI 0.25 g, and C6H5CH3 1.0 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 3.0 hours, the rocking was stopped, the systesll cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis.
Vapor phase chromatographic data was obtained on an HP-5830 r 8 ~
12,310 ~ 57 0 3~
gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10~/o SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 12.2 g and CH3C02CH3 24 g.
Exam~le 6 A 500 cc high press~re reactor equipped with a glass liner was charged with the following: CH30H 48 g, Mn2(CO)10 1.6 g, CH3I 5.4 g, 47/0 aq. HI 0.25 g, and C6H5CH3 1.5 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was obtainet on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 20.3 g and CH3C02CH3 31 g.
Example 7 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, CH3C02H 39.6 g, Mn2(CO)10 1.0 g, CH3I 5-8 g, 47% aq-HI 0.25 g, and C6H5CH3 3.0 g. The system was then purged with ca. 1000 psi of carbon monoxide and then ~ 12,310 charged with 2000 psi carbon monoxide. The reactor was heated to 155C. at which time the solution was agitated by means of rocking. Upon completion of the experiment,
12,310 ~57V38 reaction conditions.
These snd other objects will become apparent to those skilled in the art upon a further reading of the specification.
SUMMARY OF THE INVENTION
A catalyst system for the carbonylation of saturated aliphatic alcohols has been found meeting the above objects which comprises a compound of manganesei which is soluble in the reaction mixture and a promoter selected from the group consisting of iodine and an alkyl iodide wherein the alkyl moieties of the iodide contain 1 to about 6 carbon atoms. This catalyst can be used withbest results at a temperature ~rom about 100C.
to about 180Co in a conventional carbonylation process wherein a saturated aliphatic alcohol having the formula ROH, where R is alkyl having values of 1 to about 18, is contacted with carbon monoxide or a mixture of carbon monoxide and hydrogen at supra atmospheric pressures below about 2000 psi.
A preferred pressure range is about 500 psi to about 2000 pæi.
A preferred temperature range is about 120C.
to about 150C.
DESCRIPTION OF THE INVENTION
A general procedure for utilizing the carbony-lation çatalyst of this invention is described below.
A 500 cc high-pressure reactor equipped with a glass liner is charged with a solution composed of a catalytic amount of manganese compound dissolved in a known amount acetic acid and/or methanol together with r 3 ~
~S7~38 12,310 a controlled amount of a halide promoter and optionally an inert diluent for use in subsequent analytical work as an internal standard. The system is purged and then placed under a prescribed pressure of carbon monoxide or a mixture of carbon monoxide and hydrogen, heated to the desired temperature and agitated by means of rocking. Upon completion of each experiment which may vary in time from about 15 minutes to about 12 hours, the system is cooled, vented, and the contents of the reactor isolated for spectral infrared or nuclear magnetic resonance analysis as well as for vapor phase chromatographic analysis.
The actual form of the manganese catalyst pre-cursor used in this invention is not critical since man-ganese in a variety of oxidation states provides the re-quired catalytic activity. Thus, for example, one may use manganese in the -1 valence state as, for example, in NaMn(C0)5, manganese in the zero valence state as found in compounds, such as, Mn2C010, manganese in the +1 valence state as found in compounds, such as, IMn(C0)5, or manganese in the +2 valence state as found in such compounds as Mn(OAc)2 . 4 ~ 0. These systems are extremely complicated and abstruse because of the various complexes which can form in reaction media. This is reflected in the speed with which reaction is initiated which appears to lie between the extremes of immediate gas uptake indicating immediate activity of the catalyst as soon as the proper reaction conditions of temperature and pressure have been reached and evidence of a delayed 4.
..
- 12,310 ~L~57~38 activity indicating an induction period in order to allow formation of certain reactive species or complexes.
While the ratio of manganese to promoter is not narrowly critical, a ratio of promoter:manganese catalyst of about 5 to about 7 is preferred.
The carbonylation react~on using this ca~alyst system can be practised either as a batch process or a continuous process.
While commercial interest center mainly in the use of this catalyst system for the carbonylation of methanol, it is equally applicable to higher alcohols ranging from ethanol to octadecanol Furthermore, by appropriate control of the composition of the reaction solvent, that is, by con-trolling the amount of water, methanol, acetic acid~
acetone, etc., one may selectively favor the formation from methanol in this carbonylation reaction of acetic acid, methyl acetate or acetic anhydride permitting the scope of the reaction to produce a variety of industrially important chemicals.
The form in which the iodine promoter i9 added to the mRnganese catalyst is not critical. Thus, for example, one may use elemental iodine, hydriodic acid, alkyl iodides wherein the alkyl group contains 1 to abo~t 6 carbon atoms as for example, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, and the likeO
The in~ention is further described in the examples which follow. All parts and percentages are by weight unless otherwise specified.
5.
~ 310 , . ~
7 ~ 3 Example 1 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(CO)10 1.6 g, CH3I 1.0 g, and C6H5CH3 1.0 g. The system was then purged with ca. 1000 psi of carbon monoxide ~nd then charged with 1500 psi of carbon monoxide.
The reactor was heated to 120C. at which time the solu-tion was agitated by mesns of rocking. Upon completion of the experiment, 5.5 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liqu~d contents isolated for analysis.
Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed w~th 10% SP-1200/1% H3P04 (low polarlty ester sold by Supelco Co. used as the stationary phase and contain~ng 1% H3P04) on 80tlOO
Chromo~or ~ W/AW (acid washed firebrick support sold ~y Johns Manv~lle).
Analy~is of the final reaction solution showed lt to contain CH30H 27.5 g ~0.86 mol) and CH3C02CH3 6.6 g (0.09 mol).
Example 2 A 500 cc high pressure reactor equipped with a glass l~ner was charged with the following: CH30H 32 g, (CO)lo 1.6 g, CH3I 1.0 g, 47% aq. HI 0.25 g and C6H5CH3 1.0 g. The syst~m was then purget with ca. 1000 p5i of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 120C. at which time the solution was agi~a~ed by means of roc~ing.
6.
~ j 12,310 ~57~38 Upon completion of the experiment, 5.7 hours, the rocking was stopped, the system cooled to 20-25C, the remaining gas was vented, and the liquid contents isolated for analysis. ~apor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x l/8"
stainless steel column packed with 10% SP-1200/1% H3P04 on 80/lO0 Chromosorb W/AW.
Analysis of the final reactor solution showed it to contain CH30H 23 . 7 g and CH3C02CH3 ll . l g.
Example 3 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2 (CO)lo 1.6 g~ 47% aq. HI 0.25 g, and C6H5CH3 1.0 g.
- The system was then purged with caO 1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heatet to 150C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 3.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1~00/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 31.0 g and CH3CO2CH3 l.0 g.
~1~L5703~ 12 9 310 Example 4 A ~00 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2 (C0)10 1.6 g, CH3I 0O5 g, 47% aq. HI 0.25 g, and C6H5CH3 1.0 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 150C.
at which time the solution was agitated by means of rock-ing. Upon completion of the experiment, 3.0 hours, the 10 rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was ob-tained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10%
SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final reaction solution was analyzed and found to contain CH30H 29.6 g and CH3C02CH3 5.5 g.
Example 5 A 500 cc high pressure reactor equipped with a 20 glass liner was charged with the following: CH30H 32 g, Mn2(C0)10 1.6 g, CH31 3.6 g, 47% aq. HI 0.25 g, and C6H5CH3 1.0 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 3.0 hours, the rocking was stopped, the systesll cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis.
Vapor phase chromatographic data was obtained on an HP-5830 r 8 ~
12,310 ~ 57 0 3~
gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10~/o SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 12.2 g and CH3C02CH3 24 g.
Exam~le 6 A 500 cc high press~re reactor equipped with a glass liner was charged with the following: CH30H 48 g, Mn2(CO)10 1.6 g, CH3I 5.4 g, 47/0 aq. HI 0.25 g, and C6H5CH3 1.5 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was obtainet on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 20.3 g and CH3C02CH3 31 g.
Example 7 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, CH3C02H 39.6 g, Mn2(CO)10 1.0 g, CH3I 5-8 g, 47% aq-HI 0.25 g, and C6H5CH3 3.0 g. The system was then purged with ca. 1000 psi of carbon monoxide and then ~ 12,310 charged with 2000 psi carbon monoxide. The reactor was heated to 155C. at which time the solution was agitated by means of rocking. Upon completion of the experiment,
3.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromato-graphic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10% SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH3OH 5.6 g, CH3C02CH3 47.3 g and CH3C02H
14.8 g.
Example 8 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 41.6 g, Mn2(CO~10 0.9 g, CH3I 5.1 g, 47% aq. HI 0.1 g, and C6H5CH3 1.3 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rockiDg.
Upon completion of the experiment, 6.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1~ H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 1.6 g and CH3C02CH3 28.9 g.
10 .
~~ 12,310 5~ ~ 3 Example 9 A 500 cc high pressure reactor equipped with a glass liner was charged with the follow~ng: CH30H 56 g, Mn2(C0)10 1.2 g, CH3I 6.8 g, 47% aq. HI 0.12 g. and C6H5CH3 1.75 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 7.0 hours, the rocking was stoppèd, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was abtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1% H3P04 on 80/lO0 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 29.4 g, CH3C~2CH3 29.6 g and CH3C02H
The final solution was analyzed and found to contain CH3OH 5.6 g, CH3C02CH3 47.3 g and CH3C02H
14.8 g.
Example 8 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 41.6 g, Mn2(CO~10 0.9 g, CH3I 5.1 g, 47% aq. HI 0.1 g, and C6H5CH3 1.3 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rockiDg.
Upon completion of the experiment, 6.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1~ H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 1.6 g and CH3C02CH3 28.9 g.
10 .
~~ 12,310 5~ ~ 3 Example 9 A 500 cc high pressure reactor equipped with a glass liner was charged with the follow~ng: CH30H 56 g, Mn2(C0)10 1.2 g, CH3I 6.8 g, 47% aq. HI 0.12 g. and C6H5CH3 1.75 g. The system was then purged with ca.
1000 psi of carbon monoxide and then charged with 1500 psi of carbon monoxide. The reactor was heated to 150C. at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 7.0 hours, the rocking was stoppèd, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chromatographic data was abtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/1% H3P04 on 80/lO0 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 29.4 g, CH3C~2CH3 29.6 g and CH3C02H
4.8 g.
Example 10 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(CO)10 1.6 g, CH31 1.0 g, 47% aq. HI 0.l2 g, and C6H5CH3 1.0 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi of 1:1 carbon monoxide:hydrogen. The reactor was heated to 120C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated ~57~38 12,310 for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10%
SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 29.7 g and CH3C02CH3 5.1 g.
Example 11 A 50Q cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(C0)10 1.6 g, CH3I 2.0 g, 47% aq. HI 0.12 g, and C6H5CH3 1.0 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi 1:1 carbon monoxide:hydrogen. The reactor was heated to 120C.
at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid co~tents isolated for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/170 H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 20.5 g and CH3CO2CH3 13.0 g.
Example 12 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(CO)10 1.6 g, RhCl~CO)(PPh3)2 ?0 mg, CH3I 1.0 g, 47% aq. HI 0.12 g, and C6H5CH3 1.0 g. The system was 12.
.
12,310 ~S7~338 was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi 1:1 carbon monoxide:hydrogen.
The reactor was heated to 120C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chroma-tographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10% SP-1200/1% H3P04 on 80/100 Chromosorb ~/AW.
The final solution was analyzed and found to contain CH30H 24.7 g and CH3C02CH3 8.4 g.
It was demonstrated in the carbonylation of methanol that the rates of methanol carbonylation and catalyst deacti.vation are both dependent on the ratio of iodine to manganese. In a series of runs delineated in Table I, it was demonstrated that for a given level of manganese catalyst increasing the amount of iodide pro-moter will increase both carbonylation and deactivation until an iodine to manganese ratio of 8:1 is reached.
At this point an increase in the iodide promoter level preferentially accelerates deactivation of the catalyst.
13.
12, 310 ~3.57038 ~ I , . . . . o C~. . .
o I o o , u~ ~ ~ O O O O a~
o o o ~ o ~ ~
o ~ o o o o o o o o o o ~ a~ ;~
o o o o o o o o ~ o a ~ O ~
U ~ o ~ -~
C S O = O ~ O O O U O O
~o ~o oO
O 1` ~
O¢ ~ ~ =~ x~
o ~
~ a O o o O O o. o. , o.
~ ~ ~ o ~ ~ ~ ~ ~ ~o o o. o o o~ o.
I ~ I ., . ,.,.. ,., , o. o~ o ~ ~ .
i l , -:
o ~ o o o o o o o o o o c~
o o o o o o o u~ ~ o o o o o o _- o o ~ o O
e e J
14.
12,310 ~L~L$7038 Although the invention has been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure of the preferred forms has been made only by way of examples and that numerous changes may be resorted to without de-parting from the spirit and the scope of the invention.
Example 10 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(CO)10 1.6 g, CH31 1.0 g, 47% aq. HI 0.l2 g, and C6H5CH3 1.0 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi of 1:1 carbon monoxide:hydrogen. The reactor was heated to 120C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated ~57~38 12,310 for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10%
SP-1200/1% H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 29.7 g and CH3C02CH3 5.1 g.
Example 11 A 50Q cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(C0)10 1.6 g, CH3I 2.0 g, 47% aq. HI 0.12 g, and C6H5CH3 1.0 g. The system was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi 1:1 carbon monoxide:hydrogen. The reactor was heated to 120C.
at which time the solution was agitated by means of rocking.
Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid co~tents isolated for analysis. Vapor phase chromatographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8"
stainless steel column packed with 10% SP-1200/170 H3P04 on 80/100 Chromosorb W/AW.
The final solution was analyzed and found to contain CH30H 20.5 g and CH3CO2CH3 13.0 g.
Example 12 A 500 cc high pressure reactor equipped with a glass liner was charged with the following: CH30H 32 g, Mn2(CO)10 1.6 g, RhCl~CO)(PPh3)2 ?0 mg, CH3I 1.0 g, 47% aq. HI 0.12 g, and C6H5CH3 1.0 g. The system was 12.
.
12,310 ~S7~338 was then purged with ca. 1000 psi of carbon monoxide and then charged with 1500 psi 1:1 carbon monoxide:hydrogen.
The reactor was heated to 120C. at which time the solution was agitated by means of rocking. Upon completion of the experiment, 5.0 hours, the rocking was stopped, the system cooled to 20-25C., the remaining gas was vented, and the liquid contents isolated for analysis. Vapor phase chroma-tographic data was obtained on an HP-5830 gas chromatograph equipped with 6 ft x 1/8" stainless steel column packed with 10% SP-1200/1% H3P04 on 80/100 Chromosorb ~/AW.
The final solution was analyzed and found to contain CH30H 24.7 g and CH3C02CH3 8.4 g.
It was demonstrated in the carbonylation of methanol that the rates of methanol carbonylation and catalyst deacti.vation are both dependent on the ratio of iodine to manganese. In a series of runs delineated in Table I, it was demonstrated that for a given level of manganese catalyst increasing the amount of iodide pro-moter will increase both carbonylation and deactivation until an iodine to manganese ratio of 8:1 is reached.
At this point an increase in the iodide promoter level preferentially accelerates deactivation of the catalyst.
13.
12, 310 ~3.57038 ~ I , . . . . o C~. . .
o I o o , u~ ~ ~ O O O O a~
o o o ~ o ~ ~
o ~ o o o o o o o o o o ~ a~ ;~
o o o o o o o o ~ o a ~ O ~
U ~ o ~ -~
C S O = O ~ O O O U O O
~o ~o oO
O 1` ~
O¢ ~ ~ =~ x~
o ~
~ a O o o O O o. o. , o.
~ ~ ~ o ~ ~ ~ ~ ~ ~o o o. o o o~ o.
I ~ I ., . ,.,.. ,., , o. o~ o ~ ~ .
i l , -:
o ~ o o o o o o o o o o c~
o o o o o o o u~ ~ o o o o o o _- o o ~ o O
e e J
14.
12,310 ~L~L$7038 Although the invention has been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure of the preferred forms has been made only by way of examples and that numerous changes may be resorted to without de-parting from the spirit and the scope of the invention.
Claims (17)
1. In a carbonylation process which comprises contacting a saturated aliphatic alcohol with carbon monoxide or a carbon monoxide/hydrogen mixture at elevated temperatures and superatmospheric pressures in the presence of a catalyst, the improvement which comprises using a catalytic amount of a catalyst con-sisting essentially of a compound of manganese, which is soluble in reaction mixture, and a promoter containing iodine at a temperature of from about 100°C. to about 180°C.
2. Process claimed in claim 1 wherein the manganese compound is Mn2(CO)10.
3. Process claimed in claim 1 wherein the manganese compound is NaMn(CO)5.
4. Process claimed in claim 1 wherein the manganese compound is IMn(CO)5.
5. Process claimed in clsim 1 wherein the manganese compound is Mn(OCOCH3)2. 4 H2O.
6. Process claimed in claim 1 wherein the promoter is iodine.
7. Process claimed in claim 1 wherein the promoter is an alkyl iodide.
8. Process claimed in claim 7 wherein the alkyl iodide is methyl iodide.
16.
12,310
16.
12,310
9. Process claimed in claim 1 wherein the promoter is hydriodic acid.
10. Process claimed in claim 1 wherein the reaction temperature is about 120°C. to about 160°C.
11. Process claimed in claim 1 wherein the pressure is about 500 to about 2000 psi.
12. Process claimed in claim 1 wherein the alcohol is methanol.
13. Process claimed in claim 1 wherein the alcohol is ethanol.
14. Process claimed in claim 1 wherein the ratio of manganese compound to iodine promoter is about 1:5 to about 1:7.
15. Process claimed in claim 1 wherein the iodine promoter is selected from the class consisting of elemental iodine, hydriodic acid, or an alkyl iodide where the alkyl group contains 1 to about 6 carbon atoms.
16. Process claimed in claim 1 wherein the manganese compound is a manganese carbonyl complex.
17. Process claimed in claim 1 wherein the temperature is about 120°C. to about 150°C.
17.
17.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9442379A | 1979-11-15 | 1979-11-15 | |
| US094,423 | 1979-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1157038A true CA1157038A (en) | 1983-11-15 |
Family
ID=22245104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000364609A Expired CA1157038A (en) | 1979-11-15 | 1980-11-13 | Manganese catalyzed carbonylation of aliphatic alcohols |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS56135430A (en) |
| CA (1) | CA1157038A (en) |
| DE (1) | DE3043112C2 (en) |
| GB (1) | GB2063265B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482735A (en) * | 1983-09-29 | 1984-11-13 | Chevron Research Company | Process for preparation of methyl methoxyacetate |
| JPH086254Y2 (en) * | 1992-05-19 | 1996-02-21 | 株式会社マイゾックス | Push button device in box measure |
| US5760279A (en) * | 1995-06-19 | 1998-06-02 | Bp Chemicals Limited | Process for the carbonylation of alkyl alcohols |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2731962A1 (en) * | 1977-07-15 | 1979-02-01 | Imhausen Chemie Gmbh | METHOD FOR MANUFACTURING CARBONIC ETHYLESTER |
-
1980
- 1980-11-13 CA CA000364609A patent/CA1157038A/en not_active Expired
- 1980-11-14 GB GB8036637A patent/GB2063265B/en not_active Expired
- 1980-11-14 JP JP15964680A patent/JPS56135430A/en active Granted
- 1980-11-14 DE DE19803043112 patent/DE3043112C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3043112A1 (en) | 1981-06-11 |
| DE3043112C2 (en) | 1983-07-28 |
| GB2063265B (en) | 1983-10-19 |
| JPS6113688B2 (en) | 1986-04-15 |
| JPS56135430A (en) | 1981-10-22 |
| GB2063265A (en) | 1981-06-03 |
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