CA2298545A1 - Process for producing metal-free querbet alcohols - Google Patents
Process for producing metal-free querbet alcohols Download PDFInfo
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- CA2298545A1 CA2298545A1 CA002298545A CA2298545A CA2298545A1 CA 2298545 A1 CA2298545 A1 CA 2298545A1 CA 002298545 A CA002298545 A CA 002298545A CA 2298545 A CA2298545 A CA 2298545A CA 2298545 A1 CA2298545 A1 CA 2298545A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a method for producing metal-free and soap-free Guerbet alcohols, whereby primary and/or secondary alcohols containing 2 to 30 carbon atoms are condensed in the presence of alkaline and/or heavy metal catalysts at a high temperature, while water is removed from the reaction, and whereby the product is then directly separated from the reaction by distillation, with no additional purification process.
Description
D-97009 PCT PCT text as amended during CH.II proceedings PROCESS FOR PRODUCING METAL-FREE GUERBET ALCOHOLS
The present invention relates to a process for producing high-purity Guerbet alco-hols by condensation of primary and/or secondary alcohols having 2 to 30 carbon atoms in the presence of one or more alkaline catalysts) and/or one or more heavy metal catalyst(s).
to Guerbet alcohols are known compounds used as base materials for a large number of applications, e. g. in the cosmetic, pharmaceutical, textile and lubricants indus-tries.
Guerbet alcohols can be produced by condensation of primary and secondary alco-hots in the presence of strong alkali bases according to the following reaction scheme:
The present invention relates to a process for producing high-purity Guerbet alco-hols by condensation of primary and/or secondary alcohols having 2 to 30 carbon atoms in the presence of one or more alkaline catalysts) and/or one or more heavy metal catalyst(s).
to Guerbet alcohols are known compounds used as base materials for a large number of applications, e. g. in the cosmetic, pharmaceutical, textile and lubricants indus-tries.
Guerbet alcohols can be produced by condensation of primary and secondary alco-hots in the presence of strong alkali bases according to the following reaction scheme:
2 R-CH2-CH2-OH -~ R-CH-CH2-OH + H20 There exist a large number of catalyst systems based on alkali/alkaline earth salts in the presence of heavy metals as co-catalysts.
Among alkaline catalysts, alkali metals, alkali metal hydroxides, alkali metal ox-ides and alkali metal alcoholates are known. Furthermore, there have been de-scribed combinations, such as KOH with ZnO. However, such combinations often have specific disadvantages (see e. g. Soap/Cosmetics/Chemical Specialties, pages 52 - 55 and 115, April 1987).
Among heavy metals as co-catalysts, there have been described ZnO, PbO, NiO, Pd, Ti and Zr compounds. A large number of useful co-catalysts have been de-scribed in German Patent Specification DE 24 00 326. According to German Patent Specification DE 26 34 676, insoluble salts of the group of lead silicates, lead ti-tanates, and lead zirconates(IV) in the presence of alkali bases can also be used as catalysts.
D-97009 PCT text as annexed to the CH.II report may have discretionary ratios of Pb0 to Si02, Ti02, or Zr02 resulting in different basicities of the co-catalysts.
Furthermore, it is known to use heterogeneous catalyst systems, e. g. those con-sisting of platinum supported on activated carbon having a large surface and potas-sium or sodium hydroxide.
to Although suitable catalyst systems can significantly increase rate and yield of the alcohol reaction providing Guerbet alcohols, the heavy metal salts used require careful separation and disposal because of their detrimental effect to the environ-ment.
There exists yet another problem, that is the crude product obtained by Guerbet reaction normally contains byproducts, such as aldehydes, unsaturated compounds and, especially, soaps in different quantities. It is particularly important that the soaps contained in the reaction 2o mixture which are soluble and insoluble at room temperature be separated after the reaction is complete. Said soaps are usually separated by washing with partially acidified aqueous solutions, e. g. 6 % sodium chloride solution (DE AI 26 34 676).
This treatment produces large quantities of waste water also containing the heavy metals. Subsequent precipitation and separation of said heavy metals used as cata-lysts or co-catalysts will involve considerable costs. Moreover, using aqueous so-lutions for this washing treatment has another disadvantage, that is waste water having a high content of organic materials will be obtained and, additionally, the Guerbet alcohols yield will decrease. A theoretical solution to this problem would be using a solid carrier, e. g. activated carbon, for the co-catalysts which can be so separated by filtration after the reaction is complete. In practice, however, the sup-ports were found to undergo mechanical and chemical decomposition during the reaction so that complete separation by simple filtration will not produce the de-sired result. Furthermore, the pro-2a duction of supported co-catalysts instead of employing the transition metal salts and oxides commonly used would result in considerably higher costs.
DE-A-40 14 736 discloses a process employing a cascade reactor with condenser wherein the educt is re-circulated and condensation water is separated. The conden-sation product received is metal and soap containing and must be purified -after to being removed from the cascade reactor - with conventional techniques.
In order to avoid the problems mentioned hereinabove, it has been suggested in DE
195 31 714 to eliminate the soaps which are difficultly soluble at room temperature by filtration, centrifugation and/or extraction and subsequent distillation.
However, the filter cake produced during filtration will increase the amount of waste and the extraction with water will produce waste water having a high content of heavy met-als.
Among alkaline catalysts, alkali metals, alkali metal hydroxides, alkali metal ox-ides and alkali metal alcoholates are known. Furthermore, there have been de-scribed combinations, such as KOH with ZnO. However, such combinations often have specific disadvantages (see e. g. Soap/Cosmetics/Chemical Specialties, pages 52 - 55 and 115, April 1987).
Among heavy metals as co-catalysts, there have been described ZnO, PbO, NiO, Pd, Ti and Zr compounds. A large number of useful co-catalysts have been de-scribed in German Patent Specification DE 24 00 326. According to German Patent Specification DE 26 34 676, insoluble salts of the group of lead silicates, lead ti-tanates, and lead zirconates(IV) in the presence of alkali bases can also be used as catalysts.
D-97009 PCT text as annexed to the CH.II report may have discretionary ratios of Pb0 to Si02, Ti02, or Zr02 resulting in different basicities of the co-catalysts.
Furthermore, it is known to use heterogeneous catalyst systems, e. g. those con-sisting of platinum supported on activated carbon having a large surface and potas-sium or sodium hydroxide.
to Although suitable catalyst systems can significantly increase rate and yield of the alcohol reaction providing Guerbet alcohols, the heavy metal salts used require careful separation and disposal because of their detrimental effect to the environ-ment.
There exists yet another problem, that is the crude product obtained by Guerbet reaction normally contains byproducts, such as aldehydes, unsaturated compounds and, especially, soaps in different quantities. It is particularly important that the soaps contained in the reaction 2o mixture which are soluble and insoluble at room temperature be separated after the reaction is complete. Said soaps are usually separated by washing with partially acidified aqueous solutions, e. g. 6 % sodium chloride solution (DE AI 26 34 676).
This treatment produces large quantities of waste water also containing the heavy metals. Subsequent precipitation and separation of said heavy metals used as cata-lysts or co-catalysts will involve considerable costs. Moreover, using aqueous so-lutions for this washing treatment has another disadvantage, that is waste water having a high content of organic materials will be obtained and, additionally, the Guerbet alcohols yield will decrease. A theoretical solution to this problem would be using a solid carrier, e. g. activated carbon, for the co-catalysts which can be so separated by filtration after the reaction is complete. In practice, however, the sup-ports were found to undergo mechanical and chemical decomposition during the reaction so that complete separation by simple filtration will not produce the de-sired result. Furthermore, the pro-2a duction of supported co-catalysts instead of employing the transition metal salts and oxides commonly used would result in considerably higher costs.
DE-A-40 14 736 discloses a process employing a cascade reactor with condenser wherein the educt is re-circulated and condensation water is separated. The conden-sation product received is metal and soap containing and must be purified -after to being removed from the cascade reactor - with conventional techniques.
In order to avoid the problems mentioned hereinabove, it has been suggested in DE
195 31 714 to eliminate the soaps which are difficultly soluble at room temperature by filtration, centrifugation and/or extraction and subsequent distillation.
However, the filter cake produced during filtration will increase the amount of waste and the extraction with water will produce waste water having a high content of heavy met-als.
~=~#83~1e~e~-r~s~ e~ployi~g a.ca~scad.~--~~r...w wherein the educt is re-circulated and condensation water is separated.
sation product received is metal and soap containing and m usx.~~re~"purified -after being removed from the cascade reactor - with conven ' al techniques.
In order to avoid the problems mention ereinabove, it has been suggested in DE
195 31 714 to eliminate the soa ich are difficultly soluble at room temperature by filtration, centrifu and/or extraction and subsequent distillation.
However, the filter cake uced during filtration will increase the amount of waste and the io extrac ' with water will produce waste water having a high content of heavy met-It was the object of the present invention to provide an economic process for pro-ducing Guerbet alcohols, wherein waste water usually obtained during conventional purification is completely avoided and which yields metal- and soap-free products.
The subject matter of the present invention is a process for producing high-purity Guerbet alcohols, particularly soap- and heavy metal-free Guerbet alcohols, by condensation of primary and/or secondary alcohols having 2 to 30 carbon atoms in 2 o the presence of one or more alkaline catalysts) and/or one or more heavy metal catalyst(s), wherein the reaction product is directly split up by distillation, i. e.
without any different intermediate purification steps, yielding product alcohol and educt alcohol (starting alcohol), if any, on the one hand and catalyst/catalyst mix-ture and higher-molecular products, if any, on the other hand, and in which the re-action product can be removed batchwise or continuously from the reaction space.
The reaction product is directly led to the distillation stage without any preceding washing, filtration, centrifugation, steam distillation or other purification steps. The bottoms produced during distillation are highly viscous at room temperature and 3o can readily be disposed o~
It was surprisingly found that according to the process of the invention it is possi-ble to free the reaction mixture obtained by Guerbet reaction from heavy metal ions and alkaline catalyst residues in a simple and economic way by distilling the crude reaction product. Thus, no waste water is produced and loading of waste water with heavy metal ions is prevented. The co-catalysts used are commercially available heavy metal salts. It is not necessary to use any supported compounds. Further-more, products not containing any heavy metals are obtained which is highly im-portant when said products are to be used in pharmaceuticals and cosmetics.
According to this invention, primary and/or secondary, linear or cyclic alkanols having 2 to 30 carbon atoms and alkanols having a methylene group in a-position to the carbon atom bearing the hydroxyl group are reacted to yield the desired Guerbet alcohols which are essentially free from higher-molecular condensation to products. Such alkanols used as educts can be represented by the general formula wherein the residues R' and R2 can be a hydrogen atom, an aryl residue or a straight-chain or branched alkyl group, and R' and R2 can be the same or different.
Favorable starting materials are those educts wherein Rl represents an alkyl group and R2 is a hydrogen atom, i.e. primary alkan-1-ols. Typical examples of said alka-2o nols each having a terminal OH function are ethanol, propanol, iso-propyl alcohol, butanol, pentanol, hexanol, octanol, decanol, undecanol, dodecanol, tridecanol, tet-radecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetraco-sanol, hexacosanol, octacosanol, and triacontanol, and, furthermore, secondary al-kanols, such as 4-methylpentan-2-ol, hexan-2-ol, octan-2-ol, cyclopentanol, cyclohexanol and the corresponding isomers of the primary alkanols mentioned hereinabove.
The educts mentioned hereinabove can be synthetic products, e. g. Ziegler alcohols or oxoalcohols, or natural products. Particularly preferred starting materials are straight-chain primary alkanols having 6 to 22 carbon atoms. Typical examples are caproic -, oenanthic -, capryl -, pelargonic -, caprinic -, lauryl -, myristyl -, cetyl -, stearyl -, arachidyl -, and behenyl alcohol.
Said starting materials can also be used as technical-grade mixtures with other al-cohols which is common practice in fats chemistry.
Suitable catalysts for the process of the invention are those known in the art.
Among alkaline catalysts, the oxides, hydroxides, and alcoholates of the alkali met-als lithium, sodium, potassium, and cesium are particularly suitable.
Potassium hy-droxide and/or cesium hydroxide are particularly preferred.
sation product received is metal and soap containing and m usx.~~re~"purified -after being removed from the cascade reactor - with conven ' al techniques.
In order to avoid the problems mention ereinabove, it has been suggested in DE
195 31 714 to eliminate the soa ich are difficultly soluble at room temperature by filtration, centrifu and/or extraction and subsequent distillation.
However, the filter cake uced during filtration will increase the amount of waste and the io extrac ' with water will produce waste water having a high content of heavy met-It was the object of the present invention to provide an economic process for pro-ducing Guerbet alcohols, wherein waste water usually obtained during conventional purification is completely avoided and which yields metal- and soap-free products.
The subject matter of the present invention is a process for producing high-purity Guerbet alcohols, particularly soap- and heavy metal-free Guerbet alcohols, by condensation of primary and/or secondary alcohols having 2 to 30 carbon atoms in 2 o the presence of one or more alkaline catalysts) and/or one or more heavy metal catalyst(s), wherein the reaction product is directly split up by distillation, i. e.
without any different intermediate purification steps, yielding product alcohol and educt alcohol (starting alcohol), if any, on the one hand and catalyst/catalyst mix-ture and higher-molecular products, if any, on the other hand, and in which the re-action product can be removed batchwise or continuously from the reaction space.
The reaction product is directly led to the distillation stage without any preceding washing, filtration, centrifugation, steam distillation or other purification steps. The bottoms produced during distillation are highly viscous at room temperature and 3o can readily be disposed o~
It was surprisingly found that according to the process of the invention it is possi-ble to free the reaction mixture obtained by Guerbet reaction from heavy metal ions and alkaline catalyst residues in a simple and economic way by distilling the crude reaction product. Thus, no waste water is produced and loading of waste water with heavy metal ions is prevented. The co-catalysts used are commercially available heavy metal salts. It is not necessary to use any supported compounds. Further-more, products not containing any heavy metals are obtained which is highly im-portant when said products are to be used in pharmaceuticals and cosmetics.
According to this invention, primary and/or secondary, linear or cyclic alkanols having 2 to 30 carbon atoms and alkanols having a methylene group in a-position to the carbon atom bearing the hydroxyl group are reacted to yield the desired Guerbet alcohols which are essentially free from higher-molecular condensation to products. Such alkanols used as educts can be represented by the general formula wherein the residues R' and R2 can be a hydrogen atom, an aryl residue or a straight-chain or branched alkyl group, and R' and R2 can be the same or different.
Favorable starting materials are those educts wherein Rl represents an alkyl group and R2 is a hydrogen atom, i.e. primary alkan-1-ols. Typical examples of said alka-2o nols each having a terminal OH function are ethanol, propanol, iso-propyl alcohol, butanol, pentanol, hexanol, octanol, decanol, undecanol, dodecanol, tridecanol, tet-radecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetraco-sanol, hexacosanol, octacosanol, and triacontanol, and, furthermore, secondary al-kanols, such as 4-methylpentan-2-ol, hexan-2-ol, octan-2-ol, cyclopentanol, cyclohexanol and the corresponding isomers of the primary alkanols mentioned hereinabove.
The educts mentioned hereinabove can be synthetic products, e. g. Ziegler alcohols or oxoalcohols, or natural products. Particularly preferred starting materials are straight-chain primary alkanols having 6 to 22 carbon atoms. Typical examples are caproic -, oenanthic -, capryl -, pelargonic -, caprinic -, lauryl -, myristyl -, cetyl -, stearyl -, arachidyl -, and behenyl alcohol.
Said starting materials can also be used as technical-grade mixtures with other al-cohols which is common practice in fats chemistry.
Suitable catalysts for the process of the invention are those known in the art.
Among alkaline catalysts, the oxides, hydroxides, and alcoholates of the alkali met-als lithium, sodium, potassium, and cesium are particularly suitable.
Potassium hy-droxide and/or cesium hydroxide are particularly preferred.
Suitable co-catalysts for the process of the invention are those known in the art which are listed for example in DE Al 24 00 326.
Said co-catalysts can be used in quantities of 0.05 to 3.0 grams per mol, referring to io the total amount of alcohol used.
According to this invention, soap and heavy metals are separated from the crude Guerbet alcohols without the washing treatment usually performed in the art or steam distillation (see US 2,457,866). The term 'washing treatment' means treating the crude Guerbet alcohols with an excess of aqueous solutions to eliminate by-products and soaps. Such treatment produces a large amount of waste water loaded with metals and organic solvents. Furthermore, according to the process of the in-vention, no filtration, extraction, or centrifugation is necessary.
The optimum temperature for producing Guerbet alcohols according to this inven-tion depends on the type of starting alcohol. Normally, the reaction will yield good results when it is conducted at the boiling temperature of the alcohol. Even tem-peratures of as low as approximately 180 °C will give satisfactory results, but the preferred temperature according to this invention is from 200 to 320 °C, particu-larly from 250 to 320 °C, occasionally up to 350 °C in order to eliminate the reac-tion water as rapidly as it is formed from the reaction equilibrium. High conver-sions and yields are thus achieved. The maximum allowable temperature is the temperature at which starting alcohol or reaction product start to decompose.
Usu-3o ally, the temperature limit is between about 350 °C and 400 °C. A reaction tem-perature of 250 to 320 °C in the reaction mixture is normally sufficient to give good results.
The reaction is usually carried out at atmospheric pressure. If, however, the boiling point of the starting alcohol is below the optimum reaction temperature, the reac-tion can also be performed in a closed system at pressures of up to 30 bar.
Prefera-bly, the pressure should be high enough to keep the reaction system liquid. When carrying out the reaction in a closed system at elevated pressure, it is important that all of the water formed dur-ing the reaction be immediately eliminated in order to ensure high yields.
When using longchain alcohols, e. g. tetradecanol, the reaction water must be removed under vacuum. The reaction time does not require special consideration and can be varied in a wide range, provided there is sufficient time to allow formation of di-mers. On the other hand, the reaction time should not be too long, thereby pre-venting formation of trimers as a result of continuing condensation. Normally, the io average residence time is from 0.5 to 4 hours, the preferred reaction time being between 1.5 and 3 hours at a given temperature, pressure, and catalyst concentra-tion.
The reaction mixture is purified by distillation. In contrast to prior art processes, i5 the bottoms stay liquid, thus being pumpable. Additionally, it is advantageous that the reboiler cannot get plugged with solids, thereby avoiding cleaning procedures.
The overall yields of valuable products, recyclable frontend alcohol, and Guerbet alcohol increase in each of the process steps. The distillation residue can readily be disposed o~
The distillation is carried out in at least two stages, wherein in the first stage pri-marily educt alcohol is separated by flash distillation, the reactor effluent thereby being preferably distilled essentially without any supply of thermal energy and at essentially unchanged temperature. In the second stage, primarily product alcohol and catalyst are separated from each other, preferably by thin-layer or molecular distillation.
The average holdup time of the reaction product in the distillation app~ratus(es) until the catalyst or catalyst mixture is separated is preferably 0.1 to 10 minutes, 3o most preferably less than 6 minutes. In addition, the distillation is preferably car-ried out in one of the distillation stages, most preferably in both stages, at a vacuum of 1 to 100 mbar, most preferably S to 50 mbar, and temperatures of 200 to 320 °C.
The distillation is preferably carried out such that the remaining catalyst bottoms are liquid and pumpable at temperatures of greater than 200 °C.
Said co-catalysts can be used in quantities of 0.05 to 3.0 grams per mol, referring to io the total amount of alcohol used.
According to this invention, soap and heavy metals are separated from the crude Guerbet alcohols without the washing treatment usually performed in the art or steam distillation (see US 2,457,866). The term 'washing treatment' means treating the crude Guerbet alcohols with an excess of aqueous solutions to eliminate by-products and soaps. Such treatment produces a large amount of waste water loaded with metals and organic solvents. Furthermore, according to the process of the in-vention, no filtration, extraction, or centrifugation is necessary.
The optimum temperature for producing Guerbet alcohols according to this inven-tion depends on the type of starting alcohol. Normally, the reaction will yield good results when it is conducted at the boiling temperature of the alcohol. Even tem-peratures of as low as approximately 180 °C will give satisfactory results, but the preferred temperature according to this invention is from 200 to 320 °C, particu-larly from 250 to 320 °C, occasionally up to 350 °C in order to eliminate the reac-tion water as rapidly as it is formed from the reaction equilibrium. High conver-sions and yields are thus achieved. The maximum allowable temperature is the temperature at which starting alcohol or reaction product start to decompose.
Usu-3o ally, the temperature limit is between about 350 °C and 400 °C. A reaction tem-perature of 250 to 320 °C in the reaction mixture is normally sufficient to give good results.
The reaction is usually carried out at atmospheric pressure. If, however, the boiling point of the starting alcohol is below the optimum reaction temperature, the reac-tion can also be performed in a closed system at pressures of up to 30 bar.
Prefera-bly, the pressure should be high enough to keep the reaction system liquid. When carrying out the reaction in a closed system at elevated pressure, it is important that all of the water formed dur-ing the reaction be immediately eliminated in order to ensure high yields.
When using longchain alcohols, e. g. tetradecanol, the reaction water must be removed under vacuum. The reaction time does not require special consideration and can be varied in a wide range, provided there is sufficient time to allow formation of di-mers. On the other hand, the reaction time should not be too long, thereby pre-venting formation of trimers as a result of continuing condensation. Normally, the io average residence time is from 0.5 to 4 hours, the preferred reaction time being between 1.5 and 3 hours at a given temperature, pressure, and catalyst concentra-tion.
The reaction mixture is purified by distillation. In contrast to prior art processes, i5 the bottoms stay liquid, thus being pumpable. Additionally, it is advantageous that the reboiler cannot get plugged with solids, thereby avoiding cleaning procedures.
The overall yields of valuable products, recyclable frontend alcohol, and Guerbet alcohol increase in each of the process steps. The distillation residue can readily be disposed o~
The distillation is carried out in at least two stages, wherein in the first stage pri-marily educt alcohol is separated by flash distillation, the reactor effluent thereby being preferably distilled essentially without any supply of thermal energy and at essentially unchanged temperature. In the second stage, primarily product alcohol and catalyst are separated from each other, preferably by thin-layer or molecular distillation.
The average holdup time of the reaction product in the distillation app~ratus(es) until the catalyst or catalyst mixture is separated is preferably 0.1 to 10 minutes, 3o most preferably less than 6 minutes. In addition, the distillation is preferably car-ried out in one of the distillation stages, most preferably in both stages, at a vacuum of 1 to 100 mbar, most preferably S to 50 mbar, and temperatures of 200 to 320 °C.
The distillation is preferably carried out such that the remaining catalyst bottoms are liquid and pumpable at temperatures of greater than 200 °C.
In order to prevent formation of byproducts, the reaction is discontinued by distill-ing off the organic compounds from the crude product within the shortest possible time which is technically feasible.
s In said distillation step the crude product leaving the reactor is preferably split up at first by flash distillation into a monomeric alcohol fraction (educt) and a dimeric alcohol fraction (product). During flash distillation the gaseous phase is withdrawn after the equilibrium between liquid phase and vapor phase has been established.
The vaporous monomer fraction (the educt alcohol which is unsubstituted in the io beta position) is condensed, slightly supercooled and directly returned to the reac-tor. The alkaline dimer fraction which stays liquid during flash distillation is dis-tilled in a thin-layer evaporator in order to separate alkaline by-products.
The term 'thin-layer distillation' used herein includes film distillation, falling-film distilla-tion, and molecular distillation (short-path or open-path distillation). In thin-layer 15 evaporation the liquid to be evaporated is mechanically distributed, e. g. by gravitation, centrifugal force, or mechanical wipers, thereby forming thin layers which are less than 0.3 mm, pref erably less than 0.2 mm thick and which are evaporated at reduced pressure.
The preferred residence time during flash distillation is 0.1 to 5 minutes, while the distillation temperature is preferably 200 to 320 °C at 5 to 100 mbar.
When utiliz-ing thin-layer or molecular distillation, the preferred residence time is 0.1 to 5 min-utes, while the distillation temperature is preferably 200 to 320 °C at 5 to 100 2 s mbar.
After leaving the thin-layer evaporator, the alkaline by-products which are essen-tially free from dimeric alcohol are cooled to ambient temperature and disposed of as highly viscous material.
After leaving the thin-layer evaporator, the dimeric fraction which is no longer al-kaline is condensed and, optionally, further purified by distillation, e. g.
by con-ventional fractional distillation, whereby a light intermediate fraction and higher organic compounds are obtained as by-products. The monomeric alcohol obtained as well is returned to the reaction stage.
s In said distillation step the crude product leaving the reactor is preferably split up at first by flash distillation into a monomeric alcohol fraction (educt) and a dimeric alcohol fraction (product). During flash distillation the gaseous phase is withdrawn after the equilibrium between liquid phase and vapor phase has been established.
The vaporous monomer fraction (the educt alcohol which is unsubstituted in the io beta position) is condensed, slightly supercooled and directly returned to the reac-tor. The alkaline dimer fraction which stays liquid during flash distillation is dis-tilled in a thin-layer evaporator in order to separate alkaline by-products.
The term 'thin-layer distillation' used herein includes film distillation, falling-film distilla-tion, and molecular distillation (short-path or open-path distillation). In thin-layer 15 evaporation the liquid to be evaporated is mechanically distributed, e. g. by gravitation, centrifugal force, or mechanical wipers, thereby forming thin layers which are less than 0.3 mm, pref erably less than 0.2 mm thick and which are evaporated at reduced pressure.
The preferred residence time during flash distillation is 0.1 to 5 minutes, while the distillation temperature is preferably 200 to 320 °C at 5 to 100 mbar.
When utiliz-ing thin-layer or molecular distillation, the preferred residence time is 0.1 to 5 min-utes, while the distillation temperature is preferably 200 to 320 °C at 5 to 100 2 s mbar.
After leaving the thin-layer evaporator, the alkaline by-products which are essen-tially free from dimeric alcohol are cooled to ambient temperature and disposed of as highly viscous material.
After leaving the thin-layer evaporator, the dimeric fraction which is no longer al-kaline is condensed and, optionally, further purified by distillation, e. g.
by con-ventional fractional distillation, whereby a light intermediate fraction and higher organic compounds are obtained as by-products. The monomeric alcohol obtained as well is returned to the reaction stage.
Ezamples 1. Production of 2-Butyloctanol from 1-Hexanol The process was conducted under the conditions described hereinabove yielding crude Guerbet alcohol. The product was continuously charged without cooling to a flash apparatus thereby reducing the pressure to 50 mbar. While the equilibrium temperature established in the flash apparatus, most of the hexan-1-of was removed overhead and returned to the reaction stage. The residence time in the flash appa-Zo ratus was set to less than 5 minutes.
The alkaline dimeric fraction containing the catalyst was directly charged to a thin-layer evaporator wherein at a pressure of 30 mbar and temperatures of 250 to °C the reaction product was liberated from the catalyst system, higher oligomers, i5 and metal soaps.
The bottoms thus obtained were free from 1-hexanol and 2-butyloctanol and, by employing the distillation conditions described hereinabove, they were obtained as a pumpable liquid which was discharged, cooled, and disposed of as a highly vis-2o cous material. 2-Butyloctanol was obtained in high yields as a metal- and alkali-free product of value.
2. Production of 2-Octyldodecanol from 1-Decanol The process was conducted under the conditions described hereinabove yielding crude Guerbet alcohol. The product was continuously charged without cooling to a flash apparatus thereby reducing the pressure to 50 mbar. While the equilibrium temperature established in the flash apparatus, most of the I-decanol was removed overhead and returned to the reaction stage. The residence time in the flash appa-ratus was set to less than 5 minutes.
The alkaline dimeric fraction containing the catalyst was directly charged to a thin-layer evaporator wherein at a pressure of 5 mbar and temperatures of 250 to 290 °C
the reaction product was liberated from the catalyst system, higher oligomers, and metal soaps.
The alkaline dimeric fraction containing the catalyst was directly charged to a thin-layer evaporator wherein at a pressure of 30 mbar and temperatures of 250 to °C the reaction product was liberated from the catalyst system, higher oligomers, i5 and metal soaps.
The bottoms thus obtained were free from 1-hexanol and 2-butyloctanol and, by employing the distillation conditions described hereinabove, they were obtained as a pumpable liquid which was discharged, cooled, and disposed of as a highly vis-2o cous material. 2-Butyloctanol was obtained in high yields as a metal- and alkali-free product of value.
2. Production of 2-Octyldodecanol from 1-Decanol The process was conducted under the conditions described hereinabove yielding crude Guerbet alcohol. The product was continuously charged without cooling to a flash apparatus thereby reducing the pressure to 50 mbar. While the equilibrium temperature established in the flash apparatus, most of the I-decanol was removed overhead and returned to the reaction stage. The residence time in the flash appa-ratus was set to less than 5 minutes.
The alkaline dimeric fraction containing the catalyst was directly charged to a thin-layer evaporator wherein at a pressure of 5 mbar and temperatures of 250 to 290 °C
the reaction product was liberated from the catalyst system, higher oligomers, and metal soaps.
The bottoms thus obtained were free from 1-decanol and 2-octyldodecanol and, by employing the distillation conditions described hereinabove, they were obtained as a pumpable liquid which was discharged, cooled, and disposed of as a highly vis-cous material. 2-Octyldodecanol was obtained in high yields as a metal- and alkali-s free product of value.
Claims (9)
- claim 1 1. Process for producing high-purity Guerbet alcohols by condensation of primary and/or secondary alcohols having 2 to 30 carbon atoms in the presence of one or more alkaline catalyst(s) and/or one or more heavy metal catalyst(s), characterised in that the reaction product after removal from the reaction space is immediately split up by a distillation conducted in at least two stages yielding product alcohol, optionally containing some educt alcohol, and catalyst/
catalyst mixture, optionally containing some higher-molecular products, the distillation in the first stage being a flash distillation induced by expansion.
Claims - 2. Process according to claim 1, characterised in that the average residence time of the reaction product until the catalyst/catalyst mixture is separated in the distillation apparatus(es) is 0.1 to 10 minutes, preferably 0.1 to 6 minutes.
- 3. Process according to any one of the preceding claims, characterised in that in the first distillation stage primarily educt alcohol is separated from the product alcohol/catalyst reaction mixture, while in the second stage mainly product alcohol is separated from the catalyst.
- 4. Process according to any one of the preceding claims, characterised in that the second distillation is a thin-layer or molecular distillation.
- 5. Process according to any one of the preceding claims, characterised in that a vacuum of 1 to 100 mbar, preferably 5 to 50 mbar, and temperatures of 200 to 320 °C are utilized in at least one of the distillation stages, preferably in both.
- 6. Process according to any one of the preceding claims, characterised in that the distillation is conducted such that the catalyst bottoms have temperatures of higher than 200 °C and are pumpable as a liquid.
- 7. Process according to any one of the preceding claims, characterised in that in a third distillation stage a catalyst-free product alcohol containing little educt is subjected to fractional distillation which is preferably conducted continuously.
- 8. Process according to any one of the preceding claims, characterised in that the reaction product to be purified is obtained by carrying out the reaction for producing Guerbet alcohols at temperatures of 200 °C to 320 °C, most preferably 250 °C to 320 °C, and pressures of 50 mbar to 30 bar.
- 9. Process according to any one of the preceding claims, characterised in that the reaction product to be purified is produced by condensing straight-chain, primary or cyclic alkanols having 6 to 22 carbon atoms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19734673.1 | 1997-08-11 | ||
| DE19734673A DE19734673A1 (en) | 1997-08-11 | 1997-08-11 | Process for the production of metal-free Guerbet alcohols |
| PCT/DE1998/002345 WO1999007661A1 (en) | 1997-08-11 | 1998-08-07 | Method for producing metal-free guerbet alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2298545A1 true CA2298545A1 (en) | 1999-02-18 |
Family
ID=7838583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002298545A Abandoned CA2298545A1 (en) | 1997-08-11 | 1998-08-07 | Process for producing metal-free querbet alcohols |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6419797B1 (en) |
| EP (1) | EP1003700B1 (en) |
| JP (1) | JP4168363B2 (en) |
| CN (1) | CN1105095C (en) |
| AT (1) | ATE219478T1 (en) |
| CA (1) | CA2298545A1 (en) |
| DE (2) | DE19734673A1 (en) |
| ID (1) | ID24898A (en) |
| MY (1) | MY116767A (en) |
| TW (1) | TW467885B (en) |
| WO (1) | WO1999007661A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011121087A1 (en) | 2011-12-14 | 2013-06-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for catalytic condensation or coupling |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19928112A1 (en) * | 1999-06-19 | 2000-12-21 | Cognis Deutschland Gmbh | Balanced mixtures of Guerbet alcohols, including new 2-hexyl-1-tetradecanol, useful as oil components of cosmetic and pharmaceutical compositions |
| DE10059208C5 (en) * | 2000-11-29 | 2013-01-10 | Cognis Ip Management Gmbh | Process for the preparation of lower iodine and carbonyl Guerbet alcohols |
| PT1181272E (en) * | 2000-12-28 | 2003-01-31 | Lundbeck & Co As H | PROCESS FOR THE PREPARATION OF PURE CITALOPRAM |
| JP2008303160A (en) * | 2007-06-06 | 2008-12-18 | Mitsubishi Chemicals Corp | Method for producing alcohol |
| US8137807B2 (en) * | 2010-03-26 | 2012-03-20 | 3M Innovative Properties Company | Pressure-sensitive adhesives derived from 2-alkyl alkanols |
| CN103119013B (en) * | 2010-09-15 | 2015-06-17 | 三仪股份有限公司 | Method for producing alcohol by guerbet reaction |
| EP2573150A1 (en) | 2011-09-26 | 2013-03-27 | 3M Innovative Properties Company | Multilayer pressure-sensitive adhesive films with pressure-sensitive adhesives comprising (meth)acrylate esters of 2-alkyl alkanols |
| EP2855409B1 (en) * | 2012-05-30 | 2016-07-13 | Basf Se | Method for processing mixtures |
| CN102766487A (en) * | 2012-08-07 | 2012-11-07 | 中国科学技术大学 | Liquid fuel and preparation method thereof |
| US8809594B2 (en) | 2012-09-21 | 2014-08-19 | Eastman Chemical Company | Dual catalyst system for the self-condensation of alcohols |
| CN104981528B (en) | 2013-02-01 | 2017-03-29 | 3M创新有限公司 | Contact adhesive composition and the adhesive article comprising the contact adhesive composition |
| CN104974015A (en) * | 2014-04-11 | 2015-10-14 | 中国石油大学(华东) | Synthesis method of alcohol |
| EP3218339B1 (en) | 2014-11-14 | 2022-01-05 | Abengoa Bioenergía Nuevas Tecnologías, S. A. | Process for the preparation of higher alcohols from ethanol and n-hexanol by guerbet condensation |
| JP6806338B2 (en) * | 2015-05-29 | 2021-01-06 | 国立研究開発法人産業技術総合研究所 | How to make branched alcohol |
| US10487043B2 (en) | 2015-07-15 | 2019-11-26 | Lanxess Solutions Us Inc. | Diaryl amine antioxidants prepared from branched olefins |
| US9834501B2 (en) | 2016-01-28 | 2017-12-05 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta—unsaturated aldehydes from methanol and an aldehyde |
| US9828322B2 (en) | 2016-01-28 | 2017-11-28 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta-unsaturated aldehydes over a regenerable anatase titania catalyst |
| CN111511848B (en) | 2017-12-20 | 2023-05-16 | 3M创新有限公司 | Low dielectric constant curable ink composition |
| KR20210097129A (en) | 2018-11-30 | 2021-08-06 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Low dielectric constant curable composition |
| US20220306789A1 (en) | 2019-05-03 | 2022-09-29 | 3M Innovative Properties Company | Low dielectric constant curable compositions |
| CN114853569B (en) * | 2022-05-26 | 2023-07-11 | 南京威尔药业科技有限公司 | Purification method of octyl dodecanol |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2400326C2 (en) | 1973-06-06 | 1983-10-27 | Conoco Inc., 74691 Ponca City, Okla. | Process for the production of higher alcohols |
| US4011273A (en) | 1975-08-04 | 1977-03-08 | Henkel Inc. | Method for the production of guerbet alcohols utilizing insoluble lead catalysts |
| DE2703746C2 (en) * | 1977-01-29 | 1985-08-29 | Henkel KGaA, 4000 Düsseldorf | Process for the production of isododecanol by condensation of n-hexanol |
| WO1991004242A1 (en) * | 1989-09-13 | 1991-04-04 | Henkel Research Corporation | Improved guerbet process |
| DE4014736A1 (en) * | 1990-05-08 | 1991-11-14 | Henkel Kgaa | Guerbet alcohol(s) prodn. - by condensn. of prim. linear alkanol(s) in presence of alkali and catalyst mixt. of iron-III sulphate, basic copper carbonate and nickel |
| DE19524245C1 (en) * | 1995-07-04 | 1996-12-05 | Henkel Kgaa | Guerbet alcohol prepn. in high yield and purity |
-
1997
- 1997-08-11 DE DE19734673A patent/DE19734673A1/en not_active Ceased
-
1998
- 1998-08-07 CN CN98807997A patent/CN1105095C/en not_active Expired - Lifetime
- 1998-08-07 DE DE59804527T patent/DE59804527D1/en not_active Expired - Lifetime
- 1998-08-07 ID IDW20000403A patent/ID24898A/en unknown
- 1998-08-07 JP JP2000507198A patent/JP4168363B2/en not_active Expired - Lifetime
- 1998-08-07 CA CA002298545A patent/CA2298545A1/en not_active Abandoned
- 1998-08-07 EP EP98947392A patent/EP1003700B1/en not_active Expired - Lifetime
- 1998-08-07 WO PCT/DE1998/002345 patent/WO1999007661A1/en active IP Right Grant
- 1998-08-07 AT AT98947392T patent/ATE219478T1/en not_active IP Right Cessation
- 1998-08-07 US US09/485,574 patent/US6419797B1/en not_active Expired - Lifetime
- 1998-08-11 MY MYPI98003661A patent/MY116767A/en unknown
- 1998-08-17 TW TW087113189A patent/TW467885B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011121087A1 (en) | 2011-12-14 | 2013-06-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for catalytic condensation or coupling |
| WO2013087211A1 (en) | 2011-12-14 | 2013-06-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for the purpose of a catalytic condensation or coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1266418A (en) | 2000-09-13 |
| US6419797B1 (en) | 2002-07-16 |
| WO1999007661A1 (en) | 1999-02-18 |
| EP1003700A1 (en) | 2000-05-31 |
| TW467885B (en) | 2001-12-11 |
| DE19734673A1 (en) | 1999-02-18 |
| MY116767A (en) | 2004-03-31 |
| EP1003700B1 (en) | 2002-06-19 |
| CN1105095C (en) | 2003-04-09 |
| JP4168363B2 (en) | 2008-10-22 |
| ATE219478T1 (en) | 2002-07-15 |
| DE59804527D1 (en) | 2002-07-25 |
| ID24898A (en) | 2000-08-31 |
| JP2001513521A (en) | 2001-09-04 |
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| FZDE | Discontinued |