CA1238919A - Obtaining anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formate - Google Patents
Obtaining anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formateInfo
- Publication number
- CA1238919A CA1238919A CA000476766A CA476766A CA1238919A CA 1238919 A CA1238919 A CA 1238919A CA 000476766 A CA000476766 A CA 000476766A CA 476766 A CA476766 A CA 476766A CA 1238919 A CA1238919 A CA 1238919A
- Authority
- CA
- Canada
- Prior art keywords
- formic acid
- hydrolysis
- process according
- distillation column
- methyl formate
- 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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Anhydrous of substantially anhydrous formic acid is obtained by hydrolysis of methyl formate by a process in which, methyl formate is hydrolyzed in the presence of a carboxamide of the general formula (I):
Anhydrous of substantially anhydrous formic acid is obtained by hydrolysis of methyl formate by a process in which, methyl formate is hydrolyzed in the presence of a carboxamide of the general formula (I):
Description
389~L9 O.Z. 0050/37040 Obtain;ng anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formate The present invention relates to a process for obtaining anhydrous or substantially anhydrous formic 5 acid by hydrolysis of methyl formate. The production of anhydrous formic acid by hydrolysis of methyl formate has - been described in several publications in the patent literature, for example in German Laid-Open Applications DOS 2~744~313~o DOS 2,853,991 and DOS 2,914,671.
For example, German La;d-Open Application DOS
For example, German La;d-Open Application DOS
2,744,313 discloses that the hydrolysis of the methyl - formate can be carried out ;n the presence of an organic base, eg. 1-pentylimidazole, an adduct of formic acid with the particular base being formed. The remaining 15 reactants are first separated from the adduct and the formic acid is then separated from the base, these opera-tions being carried out in two separate distillation stages taking place in succession. The disadvantage of this process is that the cleavage of the formic acid from 20 the adduct requires severe distillation conditions, under which both the formic acid and the base begin to decompose.
This disadvantage is avoided by the processes des-cribed irk German Laid-Open Applications D0S 2,853,991 and DOS 2,914,671. In these processes, the components metha-25 nol and methyl formate are first distilled off, at the top, from the mixture of substances obtained in the hydro-lysis of the methyl formate, and the bottom product con-sisting of formic acid and water is fed to a liquid-liquid extraction with an extracting agent which mainly 30 takes up the formic acid. First the water and then the formic acid are subsequently distilled off from the extract phase in two separate steps, without significant decomposition reactions taking place, as are observèd in the procedure described in German Laid~Open Application 35 DOS 2,744,313. In contrast to this laid-open application, however, the processes described in German Laid-Open Applications DOS 2,853,991 and DOS 2,914~671 employ a ~3~
liquid-phase extraction in order to separate off the water.
I-t is an object of the present invention to provide an economical process for obtaining anhydrous or substantially anhydrous formic acid, the process being free of troublesome decomposition reactions and not requiring a liquid-liquid extraction for separating off the unLeacted water from the methyl formate hydrolysis.
We have found that this object is achieved, in accordance with the invention, by a process for obtaining anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formate wherein a) methyl formate is hydrolyzed in the presence of a carboxamide of the general formula (I):
Rl \ N-CO-R (I) R
where R1 is alkyl or hydrogen, R2 is alkyl, R3 is hydrogen or a Cl to C4 alkyl, and R1 and R2 may form part of a 5-membered or 6-membered ring, and the sum of the carbon atoms in the radicals R1, R2 and R3 is from 1 to 14, b) a mixture formed during the hydrolysis is separated into its individual components in a 1st distillation column which is divided into a feed part and a take-off part by separating means which are effective in the longitudinal direction, - the hydrolysis mixture being fed into the feed part, - methanol and unreacted methyl formate being taken off as a top product and as a side product, - formic acid and the carboxamide of the formula I, as an extracting agent, being taken off as an anhydrous or substantially anhydrous bottom product, and - water, preferably in liquid form, being removed from the take-off part, and c) the bottom product Erom the 1st distillation column is separated, in a 2nd distillation column, into formic acid and the extracting agent.
The carboxamide of the Eormula I may be a formamide which does not form an azeotropic mixture with formic acid. The carboxamides used may be N,N-di-n-propyl-formamide and/or N,N-di-n-butylformamide. When Rl and R2 form part of a five or six-membered ring, it is preferred that the ring be either piperidine or pyrolidine.
Carboxamides where the sum of the carbon atoms in Rl, R2 and R3 is from 1 to 6, are preferred.
To improve the separating power of the ls-t distil-lation column it was found to be advantageous if an aditional amount of the carboxamide was fed into the 1st distillation column, above the feed point for the hydrolysis mixture and below the take-off point for the water.
The feed part and the take-off part of the 1st distillation column may consist of 2 distillation columns arranged separately side by side. It is also possible for the take-off part to be in the form of a rectifying column or a stripping column.
The core of the present invention, and critical with regard to the cost-efficiency of the process, is the use of the 1st distillation column divided in the longitudinal direction, which makes it possible to remove the unreacted water from the methyl formate hydrolysis in liquid or vapor form, preferably in liquid form, and sub-stantially free of formic acid. fence the heat of con-densation of the water separated off is utilized for the ~3~39~
- 4 - O.Z. 0050/37040 separat;on of substances in the distillation column. Com-pared with the processes described in German Laid-Open ApPlications DOS 2~853,991 and DOS 2,914,671, the novel process has the advantage that the completely water 5 miscible carboxamides, too, can be used in the dehydra-tion of the formic acid by distillation, these carboxam-ides having a fairly low boiling point in some cases and hence permitting simpler and more economical separation of the formic acid from the extracting agent in the 2nd distillation column. Another advantage of the novel pro-cess ;s that the extracting agent is already present in the reacted mixture, and re-esterification in the course of the methanol/methyl formate separation is thus sub-stantially suppressed. An example of the invention is ~5 shown in the drawing and is described in detail below.
The drawing shows a floh diagram of the process according to the invention.
The experimental plant consisted of a reactor 1 for carrying out the hydrolysis and two distillation col-urns 2 and 3 for separating the hydrolysis mixture formedin the reaction into ;ts individual components. The reactor used was a stirred vessel having a reaction space of 0.8 l, the reaction being carried out at about 150C
and under about 10 bar. The reactor was charged with the fresh feeds 7, consisting of 180 g/h of methyl formate ~23~
- 5 - O.Z. 0050l37040 with an additional 5 g/h of methanol, and 55.5 gth of water. Furthermore, the top product 5 from the 1st dis-tillation column, consisting of 244 g/h of methyl formate and 13 g/h of methanol, the lower sidestream 6 from the 1st distillation column, consisting of 72~5 g/h of water, 4.5 g/h of formic acid, 1 g/h of di-n-butyLformamide and 6 g/h of methanol, and the bottom product 4 from the 2nd distillation column, consisting of 657 g/h of di-n-butyl-formamide and 1 g/h of formic acid were fed to the reactor. The residence time in the reactor was about 30 minutes. The hydrolysis mixture which was obtained as a liquid reaction product 8 and consisted of 25~t g/h of methyl formate, 115 g/h of methanol, 135~5 g/h of for-mic acid, 77 g/h of water and 65~ g/h of di-n-butylformam-ide was fed into the 1st distillation column at the middleof the feed part. In addition to the abovementioned amounts of top product and sidestream 6 from the 1st dis-tillation column, 125.5 g/h of formic acid, 657 g/h of di-n-butylformamide and 6.5 g/h of water were removed as Z0 a bottom product 9 from this distillation column and fed to the 2nd distillation column. 92 g/h of methanol and 17.5 g/h of methyl formate were taken off in liquid form, - as a further sidestream 1.0 from the 1st distillation col-umn. In addition to the abovementioned bottom product 4, the desired end product was obtained from the 2nd dis-tillation column as a top product 11 ;n an amount of 124.5 g/h of formic acid and 6.5 g/h of water, the di-n-butylformamide content being below S ppm The 1st distillation column was operated under atmospheric pressure, had an internal diameter of 50 mm and contained packing which was 4,000 mm high and con-sisted of glass Raschig rings having a diameter of 5 mm.
The height of the packing corresponded to 50 theoretical plates. between the 5th and the 20~h theoretical plates, the distillation column was divided, by means of a glass plate,into 2 sections, both having the same cross-section, so that cross-mixing of liquid streams and vapor streams ~2~
-6 - O.Z. 0050~37040 was prevented in this region of the distillation column.
The point at which the reaction mixture was fed into the distillation column was located in the middle of the feed part, to at the height of the ~3th theoretical plate, while the take-off point for the sidestream 6 was located exactly opposite at the same height, in the take-off part. The sidestream 10 was removed at the level of the 43rd theoretical plate. The temperature profile within the distillation column was as follows: 3ZC at the top, 53C at the 43rd theoretical plate, 9~C at the 13th theoret;cal plate in the take-off part, and 162C
at the bottom. The reflux ratio was 1Ø At the upper end of the longitudinal division, the liquid was divided between the take-off part and the feed part in a ratio of 7.3 : 1.
The 2nd distillation column was operated at a top pressure of 80 mbar and with a reflux ratio of 1.6, and the number of separating stages corresponded to 20 theore-tical plates. The temperature at the top of the distil-lation column was 37C, while that at the bottom was159C.
To improve the separating power of the 1st dis-tillation column, it was found to be advantageous if 100 g/h of di-n-butylformamide were fed in above the feed point (about 3 theoretical plates higher) and below the side take-off point tabout 3 theoretical plates lower) in the lbngitudinally divided sect;on of the d;stillation column. these amounts are not taken into account in the above balance of amounts.) In a further embod;ment of the apparatus for the novel Process instead of a distillation column which has in the middle section a separating means which is effec-tive in the longitudinal direction, a column system`is used in which the feed part and the ~ake-off part are in the form of distillation columns arranged side by side.
It is also possible for the take off part to be in the form of a rectifying column or a stripping column.
This disadvantage is avoided by the processes des-cribed irk German Laid-Open Applications D0S 2,853,991 and DOS 2,914,671. In these processes, the components metha-25 nol and methyl formate are first distilled off, at the top, from the mixture of substances obtained in the hydro-lysis of the methyl formate, and the bottom product con-sisting of formic acid and water is fed to a liquid-liquid extraction with an extracting agent which mainly 30 takes up the formic acid. First the water and then the formic acid are subsequently distilled off from the extract phase in two separate steps, without significant decomposition reactions taking place, as are observèd in the procedure described in German Laid~Open Application 35 DOS 2,744,313. In contrast to this laid-open application, however, the processes described in German Laid-Open Applications DOS 2,853,991 and DOS 2,914~671 employ a ~3~
liquid-phase extraction in order to separate off the water.
I-t is an object of the present invention to provide an economical process for obtaining anhydrous or substantially anhydrous formic acid, the process being free of troublesome decomposition reactions and not requiring a liquid-liquid extraction for separating off the unLeacted water from the methyl formate hydrolysis.
We have found that this object is achieved, in accordance with the invention, by a process for obtaining anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formate wherein a) methyl formate is hydrolyzed in the presence of a carboxamide of the general formula (I):
Rl \ N-CO-R (I) R
where R1 is alkyl or hydrogen, R2 is alkyl, R3 is hydrogen or a Cl to C4 alkyl, and R1 and R2 may form part of a 5-membered or 6-membered ring, and the sum of the carbon atoms in the radicals R1, R2 and R3 is from 1 to 14, b) a mixture formed during the hydrolysis is separated into its individual components in a 1st distillation column which is divided into a feed part and a take-off part by separating means which are effective in the longitudinal direction, - the hydrolysis mixture being fed into the feed part, - methanol and unreacted methyl formate being taken off as a top product and as a side product, - formic acid and the carboxamide of the formula I, as an extracting agent, being taken off as an anhydrous or substantially anhydrous bottom product, and - water, preferably in liquid form, being removed from the take-off part, and c) the bottom product Erom the 1st distillation column is separated, in a 2nd distillation column, into formic acid and the extracting agent.
The carboxamide of the Eormula I may be a formamide which does not form an azeotropic mixture with formic acid. The carboxamides used may be N,N-di-n-propyl-formamide and/or N,N-di-n-butylformamide. When Rl and R2 form part of a five or six-membered ring, it is preferred that the ring be either piperidine or pyrolidine.
Carboxamides where the sum of the carbon atoms in Rl, R2 and R3 is from 1 to 6, are preferred.
To improve the separating power of the ls-t distil-lation column it was found to be advantageous if an aditional amount of the carboxamide was fed into the 1st distillation column, above the feed point for the hydrolysis mixture and below the take-off point for the water.
The feed part and the take-off part of the 1st distillation column may consist of 2 distillation columns arranged separately side by side. It is also possible for the take-off part to be in the form of a rectifying column or a stripping column.
The core of the present invention, and critical with regard to the cost-efficiency of the process, is the use of the 1st distillation column divided in the longitudinal direction, which makes it possible to remove the unreacted water from the methyl formate hydrolysis in liquid or vapor form, preferably in liquid form, and sub-stantially free of formic acid. fence the heat of con-densation of the water separated off is utilized for the ~3~39~
- 4 - O.Z. 0050/37040 separat;on of substances in the distillation column. Com-pared with the processes described in German Laid-Open ApPlications DOS 2~853,991 and DOS 2,914,671, the novel process has the advantage that the completely water 5 miscible carboxamides, too, can be used in the dehydra-tion of the formic acid by distillation, these carboxam-ides having a fairly low boiling point in some cases and hence permitting simpler and more economical separation of the formic acid from the extracting agent in the 2nd distillation column. Another advantage of the novel pro-cess ;s that the extracting agent is already present in the reacted mixture, and re-esterification in the course of the methanol/methyl formate separation is thus sub-stantially suppressed. An example of the invention is ~5 shown in the drawing and is described in detail below.
The drawing shows a floh diagram of the process according to the invention.
The experimental plant consisted of a reactor 1 for carrying out the hydrolysis and two distillation col-urns 2 and 3 for separating the hydrolysis mixture formedin the reaction into ;ts individual components. The reactor used was a stirred vessel having a reaction space of 0.8 l, the reaction being carried out at about 150C
and under about 10 bar. The reactor was charged with the fresh feeds 7, consisting of 180 g/h of methyl formate ~23~
- 5 - O.Z. 0050l37040 with an additional 5 g/h of methanol, and 55.5 gth of water. Furthermore, the top product 5 from the 1st dis-tillation column, consisting of 244 g/h of methyl formate and 13 g/h of methanol, the lower sidestream 6 from the 1st distillation column, consisting of 72~5 g/h of water, 4.5 g/h of formic acid, 1 g/h of di-n-butyLformamide and 6 g/h of methanol, and the bottom product 4 from the 2nd distillation column, consisting of 657 g/h of di-n-butyl-formamide and 1 g/h of formic acid were fed to the reactor. The residence time in the reactor was about 30 minutes. The hydrolysis mixture which was obtained as a liquid reaction product 8 and consisted of 25~t g/h of methyl formate, 115 g/h of methanol, 135~5 g/h of for-mic acid, 77 g/h of water and 65~ g/h of di-n-butylformam-ide was fed into the 1st distillation column at the middleof the feed part. In addition to the abovementioned amounts of top product and sidestream 6 from the 1st dis-tillation column, 125.5 g/h of formic acid, 657 g/h of di-n-butylformamide and 6.5 g/h of water were removed as Z0 a bottom product 9 from this distillation column and fed to the 2nd distillation column. 92 g/h of methanol and 17.5 g/h of methyl formate were taken off in liquid form, - as a further sidestream 1.0 from the 1st distillation col-umn. In addition to the abovementioned bottom product 4, the desired end product was obtained from the 2nd dis-tillation column as a top product 11 ;n an amount of 124.5 g/h of formic acid and 6.5 g/h of water, the di-n-butylformamide content being below S ppm The 1st distillation column was operated under atmospheric pressure, had an internal diameter of 50 mm and contained packing which was 4,000 mm high and con-sisted of glass Raschig rings having a diameter of 5 mm.
The height of the packing corresponded to 50 theoretical plates. between the 5th and the 20~h theoretical plates, the distillation column was divided, by means of a glass plate,into 2 sections, both having the same cross-section, so that cross-mixing of liquid streams and vapor streams ~2~
-6 - O.Z. 0050~37040 was prevented in this region of the distillation column.
The point at which the reaction mixture was fed into the distillation column was located in the middle of the feed part, to at the height of the ~3th theoretical plate, while the take-off point for the sidestream 6 was located exactly opposite at the same height, in the take-off part. The sidestream 10 was removed at the level of the 43rd theoretical plate. The temperature profile within the distillation column was as follows: 3ZC at the top, 53C at the 43rd theoretical plate, 9~C at the 13th theoret;cal plate in the take-off part, and 162C
at the bottom. The reflux ratio was 1Ø At the upper end of the longitudinal division, the liquid was divided between the take-off part and the feed part in a ratio of 7.3 : 1.
The 2nd distillation column was operated at a top pressure of 80 mbar and with a reflux ratio of 1.6, and the number of separating stages corresponded to 20 theore-tical plates. The temperature at the top of the distil-lation column was 37C, while that at the bottom was159C.
To improve the separating power of the 1st dis-tillation column, it was found to be advantageous if 100 g/h of di-n-butylformamide were fed in above the feed point (about 3 theoretical plates higher) and below the side take-off point tabout 3 theoretical plates lower) in the lbngitudinally divided sect;on of the d;stillation column. these amounts are not taken into account in the above balance of amounts.) In a further embod;ment of the apparatus for the novel Process instead of a distillation column which has in the middle section a separating means which is effec-tive in the longitudinal direction, a column system`is used in which the feed part and the ~ake-off part are in the form of distillation columns arranged side by side.
It is also possible for the take off part to be in the form of a rectifying column or a stripping column.
Claims (10)
1. A process for obtaining anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formate, wherein a) methyl formate is hydrolyzed in the presence of a carboxamide of the general formula (I):
(I) where R1 is alkyl or hydrogen, R2 is alkyl, R3 is hydrogen or a C1 to C4 alkyl, and R1 and R2 may form part of a 5-membered or 6-membered ring, and the sum of the carbon atoms in the radicals R1, R2 and R3 is from 1 to 14, b) a mixture formed during the hydrolysis is separated into its individual components in a 1st distillation column which is divided into a feed part and a take-off part by separating means which are effective in the longitudinal direction, - the hydrolysis mixture being fed into the feed part, - methanol and unreacted methyl formate being taken off as a top product and as a side product, - formic acid and the carboxamide of the formula I, as an extracting agent, being taken off as an anhydrous or substantially anhydrous bottom product, and - water being removed from the take-off part, and c) the bottom product from the 1st distillation column is separated, in a 2nd distillation column, into formic acid and the extracting agent.
(I) where R1 is alkyl or hydrogen, R2 is alkyl, R3 is hydrogen or a C1 to C4 alkyl, and R1 and R2 may form part of a 5-membered or 6-membered ring, and the sum of the carbon atoms in the radicals R1, R2 and R3 is from 1 to 14, b) a mixture formed during the hydrolysis is separated into its individual components in a 1st distillation column which is divided into a feed part and a take-off part by separating means which are effective in the longitudinal direction, - the hydrolysis mixture being fed into the feed part, - methanol and unreacted methyl formate being taken off as a top product and as a side product, - formic acid and the carboxamide of the formula I, as an extracting agent, being taken off as an anhydrous or substantially anhydrous bottom product, and - water being removed from the take-off part, and c) the bottom product from the 1st distillation column is separated, in a 2nd distillation column, into formic acid and the extracting agent.
2. A process according to claim 1, wherein the water is removed in liquid form.
3. A process according to claim 1, wherein a formamide which does not form an azeotropic mixture with formic acid is used as the carboxamide of the formula I.
4. A process according to claim 1, wherein the carboxamides used are N,N-di-n-propylformamide and/or N,N-di-n-butylformamide.
5. A process according to claim 1, wherein an additional amount of the carboxamide is fed into the 1st distillation column, above the feed point for the hydrolysis mixture and below the take-off point for the water.
6. A process according to claim 1, wherein the feed part and the take-off part of the 1st distillation column consist of 2 distillation columns arranged separately side by side.
7. A process according to claim 6, wherein the separate take-off part consists only of a rectifying column at whose upper end the water to be recycled is condensed in a heat exchanger and removed in liquid form, and the heat of condensation evolved is used for vaporising liquid from the main column.
8. A process according to claim 6, wherein the separate take-off part consists only of a stripping column whose lower end is heated with vapors from the main column, and from which the water to be recycled is taken off as a bottom product in liquid form.
9. A process according to claim 1, wherein R1 and R2 together form part of a piperidine or pyrrolidine ring.
10. A process according to claim 1, wherein the sum of the carbon atoms in the radicals R1, R2 and R3 is from 1 to 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843411384 DE3411384A1 (en) | 1984-03-28 | 1984-03-28 | METHOD FOR THE EXTRACTION OF WATER-FREE OR MOSTLY WATER-FREE FORMIC ACID BY HYDROLYSIS OF METHYLFORMIAT |
| DEP3411384.3 | 1984-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1238919A true CA1238919A (en) | 1988-07-05 |
Family
ID=6231846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000476766A Expired CA1238919A (en) | 1984-03-28 | 1985-03-18 | Obtaining anhydrous or substantially anhydrous formic acid by hydrolysis of methyl formate |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0156309B1 (en) |
| JP (1) | JPS60218355A (en) |
| CA (1) | CA1238919A (en) |
| DE (2) | DE3411384A1 (en) |
| FI (1) | FI84259C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6695952B1 (en) | 1999-07-22 | 2004-02-24 | Consortium Fur Elektrochemische Industrie Gmbh | Method for the separation of and purification of an aqueous mixture consisting of the main components acetic acid and formic acid |
| US6793777B1 (en) | 1999-07-22 | 2004-09-21 | Consortium für elektrochemische Industrie GmbH | Method for separating and purifying an aqueous mixture that mainly consists of acetic acid and formic acid |
| US6838579B2 (en) | 2000-01-24 | 2005-01-04 | Basf Aktiengesellschaft | Utilization of an extracting agent as antifoaming agent in the production of anhydrous formic acid |
| WO2019027953A1 (en) * | 2017-08-02 | 2019-02-07 | Eastman Chemical Company | Process for making formic acid utilizing higher-boiling formate esters |
| US10266467B2 (en) | 2017-08-02 | 2019-04-23 | Eastman Chemical Company | Synthesis of glycols via transfer hydrogenation of alpha-functional esters with alcohols |
| US10266466B2 (en) | 2017-08-02 | 2019-04-23 | Eastman Chemical Company | Iron-catalyzed transfer hydrogenation of esters to alcohols |
| US10435349B2 (en) | 2017-08-02 | 2019-10-08 | Eastman Chemical Company | Iron-catalyzed cross-coupling of methanol with secondary or tertiary alcohols to produce formate esters |
| US10570081B2 (en) | 2017-08-02 | 2020-02-25 | Eastman Chemical Company | Process for making formic acid utilizing lower-boiling formate esters |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4735690A (en) * | 1986-03-10 | 1988-04-05 | Lloyd Berg | Dehydration of impure formic acid by extractive distillation |
| US4670105A (en) * | 1986-04-07 | 1987-06-02 | Lloyd Berg | Dehydration of propanoic acid by extractive distillation |
| DE4211141A1 (en) * | 1992-04-03 | 1993-10-07 | Basf Ag | Process for the preparation of formic acid by thermal cleavage of quaternary ammonium formates |
| DE10002790A1 (en) * | 2000-01-24 | 2001-07-26 | Basf Ag | Production of anhydrous formic acid involves hydrolysis of methyl formate followed by distillation, extraction with amide and further distillation stages, using the same extractant to wash useful products out of the off-gas |
| DE10002794A1 (en) * | 2000-01-24 | 2001-07-26 | Basf Ag | Production of anhydrous formic acid involves hydrolysis of methyl formate, steam distillation, extraction with amide and further distillations, with prior use of steam for stripping aqueous extraction residue |
| DE10002791A1 (en) * | 2000-01-24 | 2001-07-26 | Basf Ag | Production of anhydrous formic acid by hydrolyzing methyl formate comprises introducing methanol-containing methyl formate into distillation column used to distil hydrolysis mixture |
| WO2013030162A1 (en) | 2011-08-27 | 2013-03-07 | Taminco | Process of formic acid production by hydrolysis of methyl formate |
| TWI715627B (en) * | 2015-09-16 | 2021-01-11 | 德商羅伊姆公司 | Extractive workup of a sodium-salt-containing mma-methanol mixture |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2545658C2 (en) * | 1975-10-11 | 1985-12-19 | Basf Ag, 6700 Ludwigshafen | Process for the production of carboxylic acids from their aqueous solutions |
| DE2853991A1 (en) * | 1978-12-14 | 1980-07-03 | Basf Ag | METHOD FOR DETERMINING WATER-FREE OR MOSTLY WATER-FREE FORMIC ACID |
| DE2914671A1 (en) * | 1979-04-11 | 1980-10-23 | Basf Ag | METHOD FOR DETERMINING WATER-FREE OR MOSTLY WATER-FREE FORMIC ACID |
-
1984
- 1984-03-28 DE DE19843411384 patent/DE3411384A1/en not_active Withdrawn
-
1985
- 1985-03-13 FI FI851003A patent/FI84259C/en not_active IP Right Cessation
- 1985-03-18 CA CA000476766A patent/CA1238919A/en not_active Expired
- 1985-03-21 EP EP85103303A patent/EP0156309B1/en not_active Expired
- 1985-03-21 DE DE8585103303T patent/DE3571026D1/en not_active Expired
- 1985-03-27 JP JP60061049A patent/JPS60218355A/en active Pending
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|---|---|---|---|---|
| US6695952B1 (en) | 1999-07-22 | 2004-02-24 | Consortium Fur Elektrochemische Industrie Gmbh | Method for the separation of and purification of an aqueous mixture consisting of the main components acetic acid and formic acid |
| US6793777B1 (en) | 1999-07-22 | 2004-09-21 | Consortium für elektrochemische Industrie GmbH | Method for separating and purifying an aqueous mixture that mainly consists of acetic acid and formic acid |
| US6838579B2 (en) | 2000-01-24 | 2005-01-04 | Basf Aktiengesellschaft | Utilization of an extracting agent as antifoaming agent in the production of anhydrous formic acid |
| WO2019027953A1 (en) * | 2017-08-02 | 2019-02-07 | Eastman Chemical Company | Process for making formic acid utilizing higher-boiling formate esters |
| US10266467B2 (en) | 2017-08-02 | 2019-04-23 | Eastman Chemical Company | Synthesis of glycols via transfer hydrogenation of alpha-functional esters with alcohols |
| US10266466B2 (en) | 2017-08-02 | 2019-04-23 | Eastman Chemical Company | Iron-catalyzed transfer hydrogenation of esters to alcohols |
| US10435349B2 (en) | 2017-08-02 | 2019-10-08 | Eastman Chemical Company | Iron-catalyzed cross-coupling of methanol with secondary or tertiary alcohols to produce formate esters |
| US10544077B2 (en) | 2017-08-02 | 2020-01-28 | Eastman Chemical Company | Process for making formic acid utilizing higher-boiling formate esters |
| US10570081B2 (en) | 2017-08-02 | 2020-02-25 | Eastman Chemical Company | Process for making formic acid utilizing lower-boiling formate esters |
| CN110958999A (en) * | 2017-08-02 | 2020-04-03 | 伊士曼化工公司 | Method for producing formic acid using high-boiling formic acid ester |
| CN110997605A (en) * | 2017-08-02 | 2020-04-10 | 伊士曼化工公司 | Synthesis of diols by transfer hydrogenation of α -functionalized esters with alcohols |
| CN111032603A (en) * | 2017-08-02 | 2020-04-17 | 伊士曼化工公司 | Iron-catalyzed transfer hydrogenation of esters to alcohols |
| CN110958999B (en) * | 2017-08-02 | 2022-07-12 | 伊士曼化工公司 | Method for producing formic acid using high-boiling formic acid ester |
| CN111032603B (en) * | 2017-08-02 | 2023-07-25 | 伊士曼化工公司 | Iron-catalyzed transesterification hydrogenation of esters to alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0156309A3 (en) | 1987-04-29 |
| EP0156309B1 (en) | 1989-06-14 |
| DE3411384A1 (en) | 1985-10-10 |
| FI84259C (en) | 1991-11-11 |
| FI84259B (en) | 1991-07-31 |
| EP0156309A2 (en) | 1985-10-02 |
| DE3571026D1 (en) | 1989-07-20 |
| JPS60218355A (en) | 1985-11-01 |
| FI851003A0 (en) | 1985-03-13 |
| FI851003L (en) | 1985-09-29 |
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