CA1338237C - Process for the direct production of alkyl glycosides - Google Patents
Process for the direct production of alkyl glycosidesInfo
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- CA1338237C CA1338237C CA000614415A CA614415A CA1338237C CA 1338237 C CA1338237 C CA 1338237C CA 000614415 A CA000614415 A CA 000614415A CA 614415 A CA614415 A CA 614415A CA 1338237 C CA1338237 C CA 1338237C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
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- Detergent Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Surface-active alkyl glycosides, ie. the acetals of sugars and aliphatic alcohols, are produced by a direct acid-catalyzed reaction of the alcohol with the saccharide with elimination of water. Light coloured and alkali-stable akyl glucosides are produced by acetialization of higher aliphatic primary alcohols with glycoses, particularly glucose, in the presence of an acidic catalyst. The aliphatic alcohol is present in a molar acess in relation to the glycosis. Water of the reaction is rapidly removed under reduced pressure and elevated reaction temperatures. The catalystis neutralized with a base, excess alcohol is removed by distillation and conversion of the reaction product into an aqueous paste, and the paste is subsequently bleached.
Description
-A PROCESS FOR THE DIRECT PRODUCTION OF ALKYL GLYCOSIDES
Background of the Invention The invention is a process for the direct production of surface-active alkyl glycosides, i.e. the acetals of sugars and aliphatic alcohols, by direct acid-catalyzed reaction of the alcohol with the saccharide with elimination of water.
Field of the Invention The name alkyl glycosides as used herein refers to the reaction products of saccharides and aliphatic alcohols, the saccharide component being selected from any of the aldoses or ketoses in the broadest sense hereinafter referred to as glycoses, including for example glucose, fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose. The aldoses are preferably used by virtue of their better reactivity. Among the aldoses, glucose is particularly suitable because it is readily obtainable and available in industrial quantities.
The alkyl glycosides produced with particular preference by the process according to the invention are the alkyl glucosides. The term alkyl as used herein includes the residue of an aliphatic alcohol of any chain length, preferably a primary aliphatic alcohol and, more preferably, a fatty alcohol obtainable from natural fats.
-The term encompasses saturated and unsaturated residues and mixtures thereof, including those of different chain length in admixture. The names alkyl oligoglycoside, alkyl polyglycoside, alkyl oligosaccharide and alkyl polysaccharide apply to those alkylated glycoses in which an alkyl radical in the form of the acetyl, is attached to a residue comprising more than one glycose residue, i.e. to a poly- or oligosaccharide residue. These names are regarded as synonymous with one another. Accordingly, an alkyl monoglycoside is the acetal of a monosaccharide.
Since mixtures are generally obtained in the acid-catalyzed reaction of sugars and fatty alcohols, the name alkyl glycoside is used herein both for alkyl mono-glycosides and also for alkyl poly(oligo)glycosides and, in particular, mixtures thereof, including any secondary components, providing the structural differences are not critical.
Related Art The surface-active alkyl glycosides have been known for more than 50 years as ingredients of detergents. Thus, Austrian patent 135 333 describes the production of lauryl glucoside and acetyl glucoside from acetobromoglucose and the particular fatty alcohol in the presence of a base.
Direct synthesis from glucose and lauryl alcohol using hydrogen chloride as an acidic catalyst is also described therein. According to the teaching of German patent 611 055, alkyl glucosides are produced from pentaacetyl glucose and the fatty alcohol in the presence of anhydrous zinc chloride. The maltosides and lactosides of aliphatic alcohols containing more than 8 carbon atoms and their use as surfactants are known from German patent 593 422. For example, it is stated in this publication that cetyl maltoside improves the washing effect of soap, which at that time was the most important surfactant, which is explained by the effect of cetyl maltoside as a lime soap dispersant.
The 1960's and 1970's saw several proposals for the improved production of alkyl glycosides either by direct reaction of the glycose, generally glucose, with an excess of the alcohol in the presence of an acid catalyst.
Another process comprised reacting a lower alcohol or glycol as solvent and reactant in the presence of an acid catalyst to form a primary reaction product, from which the surface-active alkyl glycoside is obtained by transacetalization with the relatively long-chain alcohol.
U.S. Patent 3,450,690 (Gibbons et al) describes a process for the direct synthesis of alkyl glucosides, with C1-8 alkanols, secondary synthesis products or impurities which produced unwanted discoloration in the alkaline medium were removed from the crude product by treatment of the crude product in aqueous solution while heating with inorganic or organic bases such as, for example, sodium hydroxide, sodium methylate, calcium hydroxide, barium hydroxide, barium methylate or strongly basic amines. The acidic catalyst (for example sulfuric acid) not only is said to be neutralized, an alkaline pH value of at least 8 is actually provided. After heating to temperatures of 50 to 200C, the impurities precipitate. They are then filtered off and the alcohol excess is distilled off. The aqueous solution in this literature reference is understood to be the mixture of the excess of the alcoholic reactant and the water formed during the reaction. In some Examples, the excess alcohol (ethanol) is removed and partly replaced by water. After the insoluble precipitate has been filtered off, the filtrate is lightened by treatment with active carbon. Bleaching with hydrogen peroxide is also mentioned as an equivalent measure to the treatment with active carbon. Calcium hydroxide is preferably used as the base.
U.S. Patent 3,839,318 (Mansfield et al) describes a process for the direct glucosidation of long-chain alcohols 1 338~37 in which the reaction rate is controlled through the reaction temperature and the catalyst concentration in such a way that the water of reaction formed is quickly removed from the reaction mixture by azeotropic distillation. A
S hydrocarbon, for example hexane or heptane, is preferably added as solvent to facilitate the rapid azeotropic distillation of the water. The reaction mixture is then neutralized with an aqueous solution of sodium hydroxide (alkaline pH values may even be provided in this neutralization step). The excess alcohol is then removed in the usual way by distillation. Conversion of the reaction product into an aqueous paste and bleaching of this paste with sodium perborate are also described.
According to European patent application 132 046 (Procter & Gamble, Letton) the acidic catalyst in a direct synthesis process is neutralized with an organic base, a narrow pH range in the vicinity of the neutral point (pH
6.6 to 7 and preferably 6.7 to 6.8) being obtained. The organic base used is either an alkali (Na, K, Li) or alkaline earth (Ba, Ca) or aluminum salt of a weak low molecular weight acid, for example sodium acetate, or a corresponding alcoholate, for example sodium ethylate.
European patent application 96 917 (Procter & Gamble, Farris) describes an improved process for acid-catalyzed direct synthesis, in which a monosaccharide, preferably glucose, is added continuously or in portions to a mixture of fatty alcohol and catalyst at 80 to 150C so that never more than 10% unreacted monosaccharide is present in the reaction mixture.
According to European patent application 77 167 (Rohm & Haas, Arnaudis), the color quality of surface-active al~yl glycosides can be improved by using a typical acidic catalyst together with an acidic reducing agent from the group consisting of phosphorous acid, hypophosphorous acid, sulfurous acid, hyposulfurous acid, nitrous acid and/or hyponitrous acid or the corresponding salts in the produc-tion of the alkyl glycosides.
According to the teaching of European patent applica-tion 102 558 (BASF, Lorenz et al), light-colored C3 5 alkyl glucosides are obtained by production in the presence of an acidic catalyst and at least equivalent quantities of an alkali metal salt of a boric acid, preferably sodium perborate.
It is proposed in European patent application 165 721 (Staley, McDaniel et al) to treat an aqueous solution of a surface-active alkyl polyglucoside first with an oxidizing agent, preferably with a hydrogen peroxide solution, and then with a sulfur dioxide source, for example an aqueous solution of sodium bisulfite. The products thus obtained are said to be color-stable, even after prolonged storage.
In the production of surfactant raw materials, efforts have always been made to obtain substantially colorless products. Colored impurities or initially colorless products which discolor in storage are often classified as low-grade or unuseable unless aesthetically satisfactory mixtures can be obtained with them. Color stability in alkaline medium is a particularly important factor in the further processing of surfactant raw materials.
Although industrial surfactant raw materials can often be converted into light-colored products, which remain light-colored even in storage and in alkaline medium, by bleaching, for example with aqueous hydrogen peroxide solutions, this bleaching treatment has not been successfully applied to hitherto known surface-active alkyl glycosides. Even apparently lightened products reassume a dark-brown coloration when, after bleaching, they are treated with aqueous alkali at elevated temperature.
Known processes for the production of alkyl glycosides, which also seek to improve color quality and stability in storage, are attended by the disadvantage that either additional chemical agents have to be added during the production process or the reaction product itself has to be aftertreated with such chemical agents. The object of the present invention is to provide a new and improved process for the production of surface-active alkyl glycosides by direct synthesis in which a suitable choice and configuration of the process parameters ensures that the product bleached in the final step of the process retains its lightness during storage and further process-ing, even under alkaline conditions at elevated tempera-ture. Another object of the invention is to arrange the process steps in such a way that a minimum of chemical reactants and a minimum of process measures are required.
A final object of the invention is to select the process steps in such a way that the process can be carried out on an industrial scale without any scaling-up problems and is suitable for the production of surface-active alkyl glyco-sides in such quantities that the end product can be processed as a surfactant raw material in the detergent industry.
Brief Description of the Invention It has now been found that these and other objects can be achieved by a novel combination of known and new process steps into a new direct synthesis process.
Accordingly, the present invention is a process for the direct production of alkyl glycosides by acetalization of higher aliphatic primary alcohols with glycoses, particularly glucose, in the presence of an acidic catalyst, rapid removal of the water of reaction, neutralization of the catalyst with a base, removal of the alcohol excess by distillation and conversion of the reaction product into an aqueous paste and bleaching of the paste. The aliphatic alcohol is present in a molar excess in relation to the glycose and the formation and removal of the water of reaction is done under reduced pressure and reaction temperatures above 80 C are utilized.
The process comprises (a) preparing a mixture of aliphatic primary alcohol, glycose and acidic catalyst in a molar ratio of qlycose to primary alcohol of from 1:2 to 1:10 and preferably 1:3 to 1:6 at elevated temperature, by (1) mixing a portion of the alcohol with the catalyst, heating the mixture and admixing a heated suspension of the glycose in the remaining quantity of alcohol continuously or in portions to the alcohol/catalyst mixture;
Background of the Invention The invention is a process for the direct production of surface-active alkyl glycosides, i.e. the acetals of sugars and aliphatic alcohols, by direct acid-catalyzed reaction of the alcohol with the saccharide with elimination of water.
Field of the Invention The name alkyl glycosides as used herein refers to the reaction products of saccharides and aliphatic alcohols, the saccharide component being selected from any of the aldoses or ketoses in the broadest sense hereinafter referred to as glycoses, including for example glucose, fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose. The aldoses are preferably used by virtue of their better reactivity. Among the aldoses, glucose is particularly suitable because it is readily obtainable and available in industrial quantities.
The alkyl glycosides produced with particular preference by the process according to the invention are the alkyl glucosides. The term alkyl as used herein includes the residue of an aliphatic alcohol of any chain length, preferably a primary aliphatic alcohol and, more preferably, a fatty alcohol obtainable from natural fats.
-The term encompasses saturated and unsaturated residues and mixtures thereof, including those of different chain length in admixture. The names alkyl oligoglycoside, alkyl polyglycoside, alkyl oligosaccharide and alkyl polysaccharide apply to those alkylated glycoses in which an alkyl radical in the form of the acetyl, is attached to a residue comprising more than one glycose residue, i.e. to a poly- or oligosaccharide residue. These names are regarded as synonymous with one another. Accordingly, an alkyl monoglycoside is the acetal of a monosaccharide.
Since mixtures are generally obtained in the acid-catalyzed reaction of sugars and fatty alcohols, the name alkyl glycoside is used herein both for alkyl mono-glycosides and also for alkyl poly(oligo)glycosides and, in particular, mixtures thereof, including any secondary components, providing the structural differences are not critical.
Related Art The surface-active alkyl glycosides have been known for more than 50 years as ingredients of detergents. Thus, Austrian patent 135 333 describes the production of lauryl glucoside and acetyl glucoside from acetobromoglucose and the particular fatty alcohol in the presence of a base.
Direct synthesis from glucose and lauryl alcohol using hydrogen chloride as an acidic catalyst is also described therein. According to the teaching of German patent 611 055, alkyl glucosides are produced from pentaacetyl glucose and the fatty alcohol in the presence of anhydrous zinc chloride. The maltosides and lactosides of aliphatic alcohols containing more than 8 carbon atoms and their use as surfactants are known from German patent 593 422. For example, it is stated in this publication that cetyl maltoside improves the washing effect of soap, which at that time was the most important surfactant, which is explained by the effect of cetyl maltoside as a lime soap dispersant.
The 1960's and 1970's saw several proposals for the improved production of alkyl glycosides either by direct reaction of the glycose, generally glucose, with an excess of the alcohol in the presence of an acid catalyst.
Another process comprised reacting a lower alcohol or glycol as solvent and reactant in the presence of an acid catalyst to form a primary reaction product, from which the surface-active alkyl glycoside is obtained by transacetalization with the relatively long-chain alcohol.
U.S. Patent 3,450,690 (Gibbons et al) describes a process for the direct synthesis of alkyl glucosides, with C1-8 alkanols, secondary synthesis products or impurities which produced unwanted discoloration in the alkaline medium were removed from the crude product by treatment of the crude product in aqueous solution while heating with inorganic or organic bases such as, for example, sodium hydroxide, sodium methylate, calcium hydroxide, barium hydroxide, barium methylate or strongly basic amines. The acidic catalyst (for example sulfuric acid) not only is said to be neutralized, an alkaline pH value of at least 8 is actually provided. After heating to temperatures of 50 to 200C, the impurities precipitate. They are then filtered off and the alcohol excess is distilled off. The aqueous solution in this literature reference is understood to be the mixture of the excess of the alcoholic reactant and the water formed during the reaction. In some Examples, the excess alcohol (ethanol) is removed and partly replaced by water. After the insoluble precipitate has been filtered off, the filtrate is lightened by treatment with active carbon. Bleaching with hydrogen peroxide is also mentioned as an equivalent measure to the treatment with active carbon. Calcium hydroxide is preferably used as the base.
U.S. Patent 3,839,318 (Mansfield et al) describes a process for the direct glucosidation of long-chain alcohols 1 338~37 in which the reaction rate is controlled through the reaction temperature and the catalyst concentration in such a way that the water of reaction formed is quickly removed from the reaction mixture by azeotropic distillation. A
S hydrocarbon, for example hexane or heptane, is preferably added as solvent to facilitate the rapid azeotropic distillation of the water. The reaction mixture is then neutralized with an aqueous solution of sodium hydroxide (alkaline pH values may even be provided in this neutralization step). The excess alcohol is then removed in the usual way by distillation. Conversion of the reaction product into an aqueous paste and bleaching of this paste with sodium perborate are also described.
According to European patent application 132 046 (Procter & Gamble, Letton) the acidic catalyst in a direct synthesis process is neutralized with an organic base, a narrow pH range in the vicinity of the neutral point (pH
6.6 to 7 and preferably 6.7 to 6.8) being obtained. The organic base used is either an alkali (Na, K, Li) or alkaline earth (Ba, Ca) or aluminum salt of a weak low molecular weight acid, for example sodium acetate, or a corresponding alcoholate, for example sodium ethylate.
European patent application 96 917 (Procter & Gamble, Farris) describes an improved process for acid-catalyzed direct synthesis, in which a monosaccharide, preferably glucose, is added continuously or in portions to a mixture of fatty alcohol and catalyst at 80 to 150C so that never more than 10% unreacted monosaccharide is present in the reaction mixture.
According to European patent application 77 167 (Rohm & Haas, Arnaudis), the color quality of surface-active al~yl glycosides can be improved by using a typical acidic catalyst together with an acidic reducing agent from the group consisting of phosphorous acid, hypophosphorous acid, sulfurous acid, hyposulfurous acid, nitrous acid and/or hyponitrous acid or the corresponding salts in the produc-tion of the alkyl glycosides.
According to the teaching of European patent applica-tion 102 558 (BASF, Lorenz et al), light-colored C3 5 alkyl glucosides are obtained by production in the presence of an acidic catalyst and at least equivalent quantities of an alkali metal salt of a boric acid, preferably sodium perborate.
It is proposed in European patent application 165 721 (Staley, McDaniel et al) to treat an aqueous solution of a surface-active alkyl polyglucoside first with an oxidizing agent, preferably with a hydrogen peroxide solution, and then with a sulfur dioxide source, for example an aqueous solution of sodium bisulfite. The products thus obtained are said to be color-stable, even after prolonged storage.
In the production of surfactant raw materials, efforts have always been made to obtain substantially colorless products. Colored impurities or initially colorless products which discolor in storage are often classified as low-grade or unuseable unless aesthetically satisfactory mixtures can be obtained with them. Color stability in alkaline medium is a particularly important factor in the further processing of surfactant raw materials.
Although industrial surfactant raw materials can often be converted into light-colored products, which remain light-colored even in storage and in alkaline medium, by bleaching, for example with aqueous hydrogen peroxide solutions, this bleaching treatment has not been successfully applied to hitherto known surface-active alkyl glycosides. Even apparently lightened products reassume a dark-brown coloration when, after bleaching, they are treated with aqueous alkali at elevated temperature.
Known processes for the production of alkyl glycosides, which also seek to improve color quality and stability in storage, are attended by the disadvantage that either additional chemical agents have to be added during the production process or the reaction product itself has to be aftertreated with such chemical agents. The object of the present invention is to provide a new and improved process for the production of surface-active alkyl glycosides by direct synthesis in which a suitable choice and configuration of the process parameters ensures that the product bleached in the final step of the process retains its lightness during storage and further process-ing, even under alkaline conditions at elevated tempera-ture. Another object of the invention is to arrange the process steps in such a way that a minimum of chemical reactants and a minimum of process measures are required.
A final object of the invention is to select the process steps in such a way that the process can be carried out on an industrial scale without any scaling-up problems and is suitable for the production of surface-active alkyl glyco-sides in such quantities that the end product can be processed as a surfactant raw material in the detergent industry.
Brief Description of the Invention It has now been found that these and other objects can be achieved by a novel combination of known and new process steps into a new direct synthesis process.
Accordingly, the present invention is a process for the direct production of alkyl glycosides by acetalization of higher aliphatic primary alcohols with glycoses, particularly glucose, in the presence of an acidic catalyst, rapid removal of the water of reaction, neutralization of the catalyst with a base, removal of the alcohol excess by distillation and conversion of the reaction product into an aqueous paste and bleaching of the paste. The aliphatic alcohol is present in a molar excess in relation to the glycose and the formation and removal of the water of reaction is done under reduced pressure and reaction temperatures above 80 C are utilized.
The process comprises (a) preparing a mixture of aliphatic primary alcohol, glycose and acidic catalyst in a molar ratio of qlycose to primary alcohol of from 1:2 to 1:10 and preferably 1:3 to 1:6 at elevated temperature, by (1) mixing a portion of the alcohol with the catalyst, heating the mixture and admixing a heated suspension of the glycose in the remaining quantity of alcohol continuously or in portions to the alcohol/catalyst mixture;
(2) mixing the entire amount of alcohol and glycose, heating the mixture and adding the acidic catalyst to the heated mixture;
(b) reacting the mixture at an elevated temperature and under reduced pressure, preferably while mixing, whereby the water of reaction is removed, (c) cooling the reaction mixture to about 90CC;
(d) adding to the cooled reaction mixture a sufficient amount of an organic or inorganic basic alkali metal, alkaline-earth metal, aluminum or alkali/ aluminum compound to neutralize the acidic catalyst, and raise the pH
of the mixture to at least 8 and preferably in the range from 8 to 10 preferably normal pressure is established after the addition of basic material;
(e) separating the excess alcohol from the alkaline mixture under reduced pressure, preferably without preliminary filtration, to a value below 5% by weight of the reaction product by any of the methods which do not damage the reaction product; and (f) cooling the mixture to about 105 to 130C and adding a sufficient amount of water to produce a 30 to 70% paste and mixing the mixture for about 0.1 to 5 hours at approximately 80C, preferably an active oxygen compound, preferably hydrogen peroxide, is added to the mixture with the water to ensure that the pH of the mixture is maintained remains at 8 to 10 during the addition of bleach.
Detailed Description of the Invention The product of the process is obtained in the form of a colorless to yellowish aqueous paste. It has unexpectedly been discovered that the paste retains its original color quality substantially unchanged during storage and, particularly during further processing in an alkaline medium. The color stability of the product is determined by a simple test. A sample of the product is mixed with water to form an approximately 50% paste, after which concentrated sodium hydroxide is added at normal temperature to bring the pH to about 12 to 13. The paste is then heated for 30 minutes at 100C. The product of the process of this invention shows little or no color change after this treatment. The color values of the products produced by the process of the invention were determined by the KLETT method (5% solution in water/isopropyl alcohol 1:1, 1 cm cell, blue filter). Long-term storage tests of the paste-form product under typical storage conditions and further processing of the stored product into detergents and cleaning preparations under alkaline conditions which this involves, can be reliably simulated by this test method. The end products of the process preferably have Klett values of less than 35.
The glycose preferably used in the process of the invention is glucose. Commercially available glucose often 13,38237 contains 1 mol water of crystallization. The glucose containing water of crystallization may readily be used, although the water of crystallization present should be removed from the reaction medium by thermal measures, preferably before contact with the acid catalyst. However, since anhydrous glucose is also commercially available in large quantities, it is preferred to use anhydrous glucose in the form of a finely divided powder.
Suitable catalysts comprise acidic compounds, including the Lewis acids, which catalyze the acetalization reaction between the fatty alcohol and the sugar molecule.
Of these catalysts, sulfuric acid, phosphoric acid, aliphatic and/or aromatic sulfonic acids, preferably p-toluenesulfonic acid, and the sulfoacidic ion exchanger resins are particularly suitable. Preferred catalysts for the process according to the invention are sulfuric acid and p-toluenesulfonic acid which has a less corrosive effect on appliances and pipes of steel. Acidic ion exchange resins are also useful in the present process provided the catalyst is separated from the reaction mixture after acetalization of the glycose. In such a case, a suitable basic compound is preferably added after separation of the acidic ion exchange resin to adjust the mixture to a pH of 8 to 10.
The conditions under which the three components, aliphatic alcohol, glycose and catalyst, are mixed may be varied within wide limits. Thus, in one embodiment of the process of the invention, it is possible initially to introduce a mixture of the total quantities of all three components and to initiate the reaction by heating. In another embodiment, part of the alcohol is initially introduced with the catalyst and a heated suspension of the glycose in the remaining quantity of alcohol is gradually added. Addition in portions is preferred for laboratory-scale batches while continuous addition is preferred for 1 3382~
industrial batches. The time intervals at which the individual portions are added are preferably selected so that a substantially clear phase is always present, i.e.
the quantity of unreacted glycose in the reaction mixture is kept very small, i.e. no more than 10%. The mixing ratio of glycose to aliphatic alcohol may also be varied within wide limits. It is possible in this way to control the distribution between alkyl monoglycoside and alkyl oligoglycosides in the reaction product.
In the case of laboratory-scale batches and, particularly in the case of industrial-scale batches, it has been found that a dispersion of fine glycose particles in the alcohol, particularly the long-chain alcohol, has a substantial positive effect on the quality of the reaction product. A fine dispersion is achieved by intensively mixing a finely powdered glycose, preferably glucose, optionally after fine grinding, with the alcohol. For laboratory batches, it has proved to be suitable to use a high-speed standard laboratory stirrer or even ultrasonica-tion for this purpose. For industrial batches, inline mixers, for example a stator/rotor mixer, are preferably used to produce the fine dispersion. This fine-dispersion measure has the desired additional effect of heating the suspension.
A vacuum of approximately 10 to 50 mbar is applied during formation and removal of the water of reaction. The mixture is heated and preferably continuously mixed during the reaction which, in the case of laboratory-scale bat-ches, is done by simple stirring whereas, in the case of industrial-scale batches, the mixture is heated and mixed by pump circulation through an external liquid circuit incorporating a heat exchanger. During application of the heat required to maintain the reaction temperature, it is essential that there be only a slight temperature dif-ference between the wall of the reactor and the reaction mixture to avoid overheating. To establish this slight temperature difference, it is sufficient for laboratory-scale batches to use a standard oil bath with a thermostat and, at the same time, to vigorously stir the reaction mixture. In the case of industrial-scale batches, it has proved to be particularly useful to apply the heat through an external circuit preferably consisting of a pump and a heat exchanger. Preferably, part of the reaction mixture is continuously removed through a pipe, heated in the heat exchanger and returned to the reactor. In this way, it is possible to avoid high reactor wall temperatures, i.e.
above 125C, and hence to prevent the color values of the end product from being adversely affected by temperature.
The aliphatic primary alcohols reacted in accordance with the invention can basically have any chain lengths, i.e. from 1 to about 30 carbon atoms. To obtain surface-active reaction products which are useful as surfactant raw materials in detergents and cleaning preparations, it is preferred to use aliphatic primary alcohols containing from 8 to 20 carbon atoms and more preferred from 12 to 18 carbon atoms. These higher aliphatic alcohols are prefer-ably produced from industrial fatty compounds. However, synthetic primary alcohols, for example the oxoalcohols, may of course also be used in the process according to the 2S invention.
Where the portion variant of the process is used, 30 to 70% by weight of the alcohol is preferably initially mixed with the catalyst, the mixture is heated to 100 to 120C and the glycose is subsequently added, preferably continuously under a reduced pressure, in the form of a suspension in the heated remaining quantity of alcohol.
The water of reaction formed is continuously removed from the reaction mixture. The reaction is regarded as over when no more water of reaction is eliminated. To determine the quantity of water of reaction and thus to ascertain the 1 338~37 -end of the reaction, the water may be collected, for example, by freezing in a cold trap. Accordingly, with predetermined quantities of mixture and reaction conditions, the reaction time can be reliably determined without the water of reaction having to be collected and measured each time.
In an equally preferred variant where the total quantity of mixture is introduced, the mixture of alcohol and glycose is preferably initially introduced and then heated with stirring, i.e. to a sump temperature of approx-imately 80C, after which the acidic catalyst is added to the heated mixture. A vacuum is then applied and the mixture further heated to approximately 100 to 120C, the water of reaction formed being distilled off.
Since, as already mentioned, the alcohols may be used in a wide chain-length range in the process according to the invention, the vacuum is also adjusted so that the boiling point of the alcohol is reduced by at least 30C.
For the reaction of the long-chain C1218 fatty alcohols, the vacuum is preferably adjusted to a value of 10 to 50 mbar.
The higher aliphatic, primary C1218 alcohols particu-larly useful as the alcohol component are preferably saturated and, in particular, linear alcohols of the type obtainable on an industrial scale, by hydrogenation of native fatty acids. Typical representatives of the higher aliphatic alcohols which may be used in the process accord-ing to the invention are, for example, the compounds n-dodecyl alcohol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n-octyl alcohol, n-decyl alcohol, undecyl alcohol, tridecyl alcohol. Since the fatty alco-hols preferably emanate from natural fats, mixtures of technical fatty alcohols are also usually suitable as reactants. Besides the actual fatty alcohols, branched-chain primary alcohols, for example the so-called oxoal-cohols, are also suitable for the reaction. Typical oxoalcohols are, for example, the compounds C1213 alkanol with approximately 25% mainly 2-methyl branching (Dobanol 23) and the corresponding Cg11 alkanol (Dobanol 9l). How-ever, a major advantage of the process is that it can be used in the production of surfactants obtainable exclusive-ly from renewable raw materials.
Suitable basic alkali metal, alkaline earth metal, or aluminum or alkali/aluminum compounds, which may be organic or inorganic, are, for example, calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, the zeolites NaA or NaX, preferably in combination with calcium hydroxide, anhydrous sodium carbonate, potassium carbonate, magnesium and calcium carbonate, sodium methylate, sodium ethylate, magnesium methylate, magnesium ethylate, sodium or magnesium propylate or butylate, i.e. the alcoholates of low-boiling alcohols, preferably C14 alcohols. The particularly preferred inorganic basic compound is magnesium oxide while the particularly preferred organic base is a magnesium alcoholate, more particularly the ethanolate of magnesium. Both the magnesium oxide and the magnesium alcoholate may be partly replaced, i.e. up to half the molecular amount, by powdered sodium hydroxide in equivalent quantities.
One particular feature of the process is that the additions of the basic compounds are controlled in such a way that, over and above neutralization of the acidic catalyst, an excess of the basic compound is present so that the reaction mixture shows a distinctly basic reaction and, hence, preferably has a pH value in the range from 8 to 10. The pH value is measured in a 10% aqueous/alcoholic mixture of a sample using a standard pH meter.
The alcohol excess is distilled off without damaging the reaction product by a suitable vacuum distillation method. The distillation process is carried out under an absolute pressure of 0.0l to 1 mbar. Basically, the product-protecting distillation also includes the establishment of a low sump temperature, by which is meant the temperature of the boiling mixture. In the present case, however, it has surprisingly been found to be preferred to heat the reaction mixture to a sump temperature in the range from 160 to 180C and more especially in the range from 160 to 170C, and specifically independently of whether such a high value is actually necessary at the existing vacuum power for distilling off the excess alcohol. Such a high sump temperature leads directly to a crude product with initially poorer color quality. However, it was unexpectedly discovered that the products treated at the high sump temperature, after bleaching, had a lighter color and a better alkali stability, in the sense of the above-mentioned tests, than products which had been treated at lower sump temperatures and had a better color quality prior to bleaching. It is therefore another important feature of the process of the invention to bring the reaction mixture, during the process step of removing the alcohol excess under high vacuum, to a sump temperature of about 160 to 170C, even if this high a sump temperature would not be necessary for distilling off the alcohol excess, such as in the case of the shorter-chain fatty alcohols.
Generally known vacuum distillation devices can be used for removing the excess alcohol in the distillation of laboratory batches. In the case of production-scale industrial batches, the removal of the excess alcohol is preferably performed according to a 2-step process. If the fatty alcohol has a carbon chain length range of 12 to 20, preferably the reduction of the fatty alcohol fraction to values of from about 40 to about 20% is performed in a first step in a thin film evaporator or a falling-film evaporator. The first step also serves to degass the reaction mixture. In a second step, preferably using a _.
short-path evaporator, a further fatty alcohol reduction to the desired final value is carried out. The final content of fatty alcohol can be less than 0.5 wt% based on the final product if the product is to be practically free from the fatty alcohol. When a specific fatty alcohol content is desired in the final product, these fatty alcohol contents can be established at about 3 to about 5 wt%. It has been found that finished products with a fatty alcohol content of more than 2 wt%, preferably 3 to 5 wt%, based on the weight of the product have certain advantages in terms of application.
For gentle separation of temperature-sensitive mixtures, it may generally be said that falling film evaporators and, preferably, thin-film evaporators are particularly suitable for gentle evaporation under reduced pressure, since extremely short residence times at the relatively high temperatures necessary can be achieved in evaporators of this type. In the present case, thin-film evaporators are particularly useful for removing the excess C1018 fatty alcohol from the alkyl glycoside with particularly good surfactant properties.
Thin-film evaporators are evaporators in which a highly viscous mixture is applied to a heated wall and mechanically distributed thereon by rotating wiping elements. Thin liquid layers or liquid films are thus formed and the film surfaces are continually renewed. The vapors formed flow countercurrent to the product film and leave the evaporator through an externally arranged condenser. Thin-film evaporators are generally operated at pressures of only a few mbar and the residence time for the product is only a few seconds. In a two-stage evaporating method, of the type preferably used in the process of the invention, the first evaporator also acts as a preliminary degassing stage for the second stage evaporator. Gases dissolved in the viscous liquid are removed from the liquid 1 3387~7 during the removal of excess fatty alcohol from the reac-tion product in the first thin-film evaporator. The short-path evaporator which is preferably used as the second stage evaporator is, in principle, a wiped-film evaporator with a condenser built into the evaporator. These evapor-ators are suitable for the distillation of high-boiling, temperature-sensitive products in the range from 101 to 10 4 mbar. In short-path evaporators, as in thin-film evaporators, the liquid is mechanically distributed over the heating surface by wipers. According to the invention, the excess alcohol is removed to almost any residual con-tents, which may be below 1%, in the short-path evaporator or thin-film evaporator as the second stage. The two-stage arrangement of the evaporators provides for high through-puts in conjunction with the specific establishment of the desired residual content of fatty alcohol in the end product. For industrial purposes, thin-film and short-path evaporators can be dimensioned so that throughputs of up to 300 kg/m2 per hour are readily possible. In principle, the preferred embodiment of the process according to the invention with the two-stage fatty alcohol removal step can also be used in suitable dimensions for working up laboratory-scale mixtures.
The alkyl glycosides produced in accordance with the invention are mixtures consisting essentially of alkyl monoglycoside and the alkyl oligoglycosides, essentially confined here to di- and triglycosides, and small amounts of tetra- and pentaglycosides. The distribution between mono- and oligoglycosides in the end product gives a theoretical degree of oligomerization of from 1 to 5. The process is preferably carried out so that the degree of oligomerization is between about 1 and about 1.5, the quantity of alkyl monoglycoside, based on the total quantity, of alkyl monoglycoside and alkyl oligoglycoside generally exceeds about 70% by weight. (For a definition of the degree of oligomerization, see Paul J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaca, New York, 1953, pages 35 to 37). The total quantity of other secondary constituents is generally below 20% by weight. Of these secondary constituents the fatty alcohol component is variable because it depends upon the intensity of the fatty alcohol distillation process. The quantity of residual alcohol in the end products is adjusted to a preferred range of 0.2 to 5% by weight and more especially 0.5 to 2.5% by weight. The residues of unreacted glycose are below 1%. The contents of polymeric glucose in the end product is from about 2 to about 20% by weight and preferably from 5 to 20% by weight. The quantities of the neutralization products of acidic cata-lyst and basic compound and any excess of this basic com-pound in the end product are between 0.5 and 1.5% by weight.
These quantities are based on the reaction product as its exists immediately after removal of the fatty alcohol excess by distillation. The actual end product of the process is an aqueous paste containing 30 to 60% by weight water which is obtained from the reaction product by treat-ment with warm water and bleaching with active oxygen com-pounds, preferably hydrogen peroxide. The quantity of active oxygen compound is generally from 0.2 to 1.5% by weight, expressed as H202 and based on the quantity of product after the removal of alcohol. Since the pH value falls during the bleaching step, a base, for example sodium hydroxide, is added together with the per oxygen compound to maintain pH values in the range from 8 to 10. The resulting solution or paste preferably contains the salts emanating from neutralization of the catalyst and the bleaching process which have not been separated off. It has been found that there are many applications in which neither the type nor quantity of these residual salts in _ the aqueous alkyl glycoside paste is problematical. On the contrary, the compounds in question are in any event typical constituents of typical detergents and cleaning preparations.
The pH value of the paste-form end product of the process is generally left as its accumulates after the bleaching step, i.e. the paste has a pH value in the range from 8 to 10. For special applications, the pH may be reduced to about the neutral point by addition of an acidic compound which is preferably favorable, but at least not harmful, to the application envisaged. Suitable acidic materials are, for example, acidic salts, such as sodium or potassium hydrogen sulfate, inorganic acids, such as sulfuric acid, or organic acids, such as citric acid, or sulfonate or sulfate surfactants in the acid form.
For prolonged storage or prolonged transport of the paste-form reaction product, it is important to prevent microbial degradation processes. Accordingly, the paste-form reaction product prepared in accordance with the invention preferably contains an antimicrobial effective quantity of a antimicrobial agent which improves stability in storage. The antimicrobial additive comprises, for example, of 0.1 to 0.2% by weight glutardialdehyde.
One particularly preferred embodiment of the process for the production of light-colored and color-stable alkyl glycosides by the direct synthesis method is characterized by application of the following cumulative process steps:
1. The finely divided particulate glycose, particularly glucose, is dispersed in the alcohol by high-speed stirrers or by other high-performance industrial mixers.
2. The base used to neutralize the acid catalyst, preferably a sulfonic acid, consists completely or predominantly of magnesium oxide.
(b) reacting the mixture at an elevated temperature and under reduced pressure, preferably while mixing, whereby the water of reaction is removed, (c) cooling the reaction mixture to about 90CC;
(d) adding to the cooled reaction mixture a sufficient amount of an organic or inorganic basic alkali metal, alkaline-earth metal, aluminum or alkali/ aluminum compound to neutralize the acidic catalyst, and raise the pH
of the mixture to at least 8 and preferably in the range from 8 to 10 preferably normal pressure is established after the addition of basic material;
(e) separating the excess alcohol from the alkaline mixture under reduced pressure, preferably without preliminary filtration, to a value below 5% by weight of the reaction product by any of the methods which do not damage the reaction product; and (f) cooling the mixture to about 105 to 130C and adding a sufficient amount of water to produce a 30 to 70% paste and mixing the mixture for about 0.1 to 5 hours at approximately 80C, preferably an active oxygen compound, preferably hydrogen peroxide, is added to the mixture with the water to ensure that the pH of the mixture is maintained remains at 8 to 10 during the addition of bleach.
Detailed Description of the Invention The product of the process is obtained in the form of a colorless to yellowish aqueous paste. It has unexpectedly been discovered that the paste retains its original color quality substantially unchanged during storage and, particularly during further processing in an alkaline medium. The color stability of the product is determined by a simple test. A sample of the product is mixed with water to form an approximately 50% paste, after which concentrated sodium hydroxide is added at normal temperature to bring the pH to about 12 to 13. The paste is then heated for 30 minutes at 100C. The product of the process of this invention shows little or no color change after this treatment. The color values of the products produced by the process of the invention were determined by the KLETT method (5% solution in water/isopropyl alcohol 1:1, 1 cm cell, blue filter). Long-term storage tests of the paste-form product under typical storage conditions and further processing of the stored product into detergents and cleaning preparations under alkaline conditions which this involves, can be reliably simulated by this test method. The end products of the process preferably have Klett values of less than 35.
The glycose preferably used in the process of the invention is glucose. Commercially available glucose often 13,38237 contains 1 mol water of crystallization. The glucose containing water of crystallization may readily be used, although the water of crystallization present should be removed from the reaction medium by thermal measures, preferably before contact with the acid catalyst. However, since anhydrous glucose is also commercially available in large quantities, it is preferred to use anhydrous glucose in the form of a finely divided powder.
Suitable catalysts comprise acidic compounds, including the Lewis acids, which catalyze the acetalization reaction between the fatty alcohol and the sugar molecule.
Of these catalysts, sulfuric acid, phosphoric acid, aliphatic and/or aromatic sulfonic acids, preferably p-toluenesulfonic acid, and the sulfoacidic ion exchanger resins are particularly suitable. Preferred catalysts for the process according to the invention are sulfuric acid and p-toluenesulfonic acid which has a less corrosive effect on appliances and pipes of steel. Acidic ion exchange resins are also useful in the present process provided the catalyst is separated from the reaction mixture after acetalization of the glycose. In such a case, a suitable basic compound is preferably added after separation of the acidic ion exchange resin to adjust the mixture to a pH of 8 to 10.
The conditions under which the three components, aliphatic alcohol, glycose and catalyst, are mixed may be varied within wide limits. Thus, in one embodiment of the process of the invention, it is possible initially to introduce a mixture of the total quantities of all three components and to initiate the reaction by heating. In another embodiment, part of the alcohol is initially introduced with the catalyst and a heated suspension of the glycose in the remaining quantity of alcohol is gradually added. Addition in portions is preferred for laboratory-scale batches while continuous addition is preferred for 1 3382~
industrial batches. The time intervals at which the individual portions are added are preferably selected so that a substantially clear phase is always present, i.e.
the quantity of unreacted glycose in the reaction mixture is kept very small, i.e. no more than 10%. The mixing ratio of glycose to aliphatic alcohol may also be varied within wide limits. It is possible in this way to control the distribution between alkyl monoglycoside and alkyl oligoglycosides in the reaction product.
In the case of laboratory-scale batches and, particularly in the case of industrial-scale batches, it has been found that a dispersion of fine glycose particles in the alcohol, particularly the long-chain alcohol, has a substantial positive effect on the quality of the reaction product. A fine dispersion is achieved by intensively mixing a finely powdered glycose, preferably glucose, optionally after fine grinding, with the alcohol. For laboratory batches, it has proved to be suitable to use a high-speed standard laboratory stirrer or even ultrasonica-tion for this purpose. For industrial batches, inline mixers, for example a stator/rotor mixer, are preferably used to produce the fine dispersion. This fine-dispersion measure has the desired additional effect of heating the suspension.
A vacuum of approximately 10 to 50 mbar is applied during formation and removal of the water of reaction. The mixture is heated and preferably continuously mixed during the reaction which, in the case of laboratory-scale bat-ches, is done by simple stirring whereas, in the case of industrial-scale batches, the mixture is heated and mixed by pump circulation through an external liquid circuit incorporating a heat exchanger. During application of the heat required to maintain the reaction temperature, it is essential that there be only a slight temperature dif-ference between the wall of the reactor and the reaction mixture to avoid overheating. To establish this slight temperature difference, it is sufficient for laboratory-scale batches to use a standard oil bath with a thermostat and, at the same time, to vigorously stir the reaction mixture. In the case of industrial-scale batches, it has proved to be particularly useful to apply the heat through an external circuit preferably consisting of a pump and a heat exchanger. Preferably, part of the reaction mixture is continuously removed through a pipe, heated in the heat exchanger and returned to the reactor. In this way, it is possible to avoid high reactor wall temperatures, i.e.
above 125C, and hence to prevent the color values of the end product from being adversely affected by temperature.
The aliphatic primary alcohols reacted in accordance with the invention can basically have any chain lengths, i.e. from 1 to about 30 carbon atoms. To obtain surface-active reaction products which are useful as surfactant raw materials in detergents and cleaning preparations, it is preferred to use aliphatic primary alcohols containing from 8 to 20 carbon atoms and more preferred from 12 to 18 carbon atoms. These higher aliphatic alcohols are prefer-ably produced from industrial fatty compounds. However, synthetic primary alcohols, for example the oxoalcohols, may of course also be used in the process according to the 2S invention.
Where the portion variant of the process is used, 30 to 70% by weight of the alcohol is preferably initially mixed with the catalyst, the mixture is heated to 100 to 120C and the glycose is subsequently added, preferably continuously under a reduced pressure, in the form of a suspension in the heated remaining quantity of alcohol.
The water of reaction formed is continuously removed from the reaction mixture. The reaction is regarded as over when no more water of reaction is eliminated. To determine the quantity of water of reaction and thus to ascertain the 1 338~37 -end of the reaction, the water may be collected, for example, by freezing in a cold trap. Accordingly, with predetermined quantities of mixture and reaction conditions, the reaction time can be reliably determined without the water of reaction having to be collected and measured each time.
In an equally preferred variant where the total quantity of mixture is introduced, the mixture of alcohol and glycose is preferably initially introduced and then heated with stirring, i.e. to a sump temperature of approx-imately 80C, after which the acidic catalyst is added to the heated mixture. A vacuum is then applied and the mixture further heated to approximately 100 to 120C, the water of reaction formed being distilled off.
Since, as already mentioned, the alcohols may be used in a wide chain-length range in the process according to the invention, the vacuum is also adjusted so that the boiling point of the alcohol is reduced by at least 30C.
For the reaction of the long-chain C1218 fatty alcohols, the vacuum is preferably adjusted to a value of 10 to 50 mbar.
The higher aliphatic, primary C1218 alcohols particu-larly useful as the alcohol component are preferably saturated and, in particular, linear alcohols of the type obtainable on an industrial scale, by hydrogenation of native fatty acids. Typical representatives of the higher aliphatic alcohols which may be used in the process accord-ing to the invention are, for example, the compounds n-dodecyl alcohol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, n-octyl alcohol, n-decyl alcohol, undecyl alcohol, tridecyl alcohol. Since the fatty alco-hols preferably emanate from natural fats, mixtures of technical fatty alcohols are also usually suitable as reactants. Besides the actual fatty alcohols, branched-chain primary alcohols, for example the so-called oxoal-cohols, are also suitable for the reaction. Typical oxoalcohols are, for example, the compounds C1213 alkanol with approximately 25% mainly 2-methyl branching (Dobanol 23) and the corresponding Cg11 alkanol (Dobanol 9l). How-ever, a major advantage of the process is that it can be used in the production of surfactants obtainable exclusive-ly from renewable raw materials.
Suitable basic alkali metal, alkaline earth metal, or aluminum or alkali/aluminum compounds, which may be organic or inorganic, are, for example, calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, the zeolites NaA or NaX, preferably in combination with calcium hydroxide, anhydrous sodium carbonate, potassium carbonate, magnesium and calcium carbonate, sodium methylate, sodium ethylate, magnesium methylate, magnesium ethylate, sodium or magnesium propylate or butylate, i.e. the alcoholates of low-boiling alcohols, preferably C14 alcohols. The particularly preferred inorganic basic compound is magnesium oxide while the particularly preferred organic base is a magnesium alcoholate, more particularly the ethanolate of magnesium. Both the magnesium oxide and the magnesium alcoholate may be partly replaced, i.e. up to half the molecular amount, by powdered sodium hydroxide in equivalent quantities.
One particular feature of the process is that the additions of the basic compounds are controlled in such a way that, over and above neutralization of the acidic catalyst, an excess of the basic compound is present so that the reaction mixture shows a distinctly basic reaction and, hence, preferably has a pH value in the range from 8 to 10. The pH value is measured in a 10% aqueous/alcoholic mixture of a sample using a standard pH meter.
The alcohol excess is distilled off without damaging the reaction product by a suitable vacuum distillation method. The distillation process is carried out under an absolute pressure of 0.0l to 1 mbar. Basically, the product-protecting distillation also includes the establishment of a low sump temperature, by which is meant the temperature of the boiling mixture. In the present case, however, it has surprisingly been found to be preferred to heat the reaction mixture to a sump temperature in the range from 160 to 180C and more especially in the range from 160 to 170C, and specifically independently of whether such a high value is actually necessary at the existing vacuum power for distilling off the excess alcohol. Such a high sump temperature leads directly to a crude product with initially poorer color quality. However, it was unexpectedly discovered that the products treated at the high sump temperature, after bleaching, had a lighter color and a better alkali stability, in the sense of the above-mentioned tests, than products which had been treated at lower sump temperatures and had a better color quality prior to bleaching. It is therefore another important feature of the process of the invention to bring the reaction mixture, during the process step of removing the alcohol excess under high vacuum, to a sump temperature of about 160 to 170C, even if this high a sump temperature would not be necessary for distilling off the alcohol excess, such as in the case of the shorter-chain fatty alcohols.
Generally known vacuum distillation devices can be used for removing the excess alcohol in the distillation of laboratory batches. In the case of production-scale industrial batches, the removal of the excess alcohol is preferably performed according to a 2-step process. If the fatty alcohol has a carbon chain length range of 12 to 20, preferably the reduction of the fatty alcohol fraction to values of from about 40 to about 20% is performed in a first step in a thin film evaporator or a falling-film evaporator. The first step also serves to degass the reaction mixture. In a second step, preferably using a _.
short-path evaporator, a further fatty alcohol reduction to the desired final value is carried out. The final content of fatty alcohol can be less than 0.5 wt% based on the final product if the product is to be practically free from the fatty alcohol. When a specific fatty alcohol content is desired in the final product, these fatty alcohol contents can be established at about 3 to about 5 wt%. It has been found that finished products with a fatty alcohol content of more than 2 wt%, preferably 3 to 5 wt%, based on the weight of the product have certain advantages in terms of application.
For gentle separation of temperature-sensitive mixtures, it may generally be said that falling film evaporators and, preferably, thin-film evaporators are particularly suitable for gentle evaporation under reduced pressure, since extremely short residence times at the relatively high temperatures necessary can be achieved in evaporators of this type. In the present case, thin-film evaporators are particularly useful for removing the excess C1018 fatty alcohol from the alkyl glycoside with particularly good surfactant properties.
Thin-film evaporators are evaporators in which a highly viscous mixture is applied to a heated wall and mechanically distributed thereon by rotating wiping elements. Thin liquid layers or liquid films are thus formed and the film surfaces are continually renewed. The vapors formed flow countercurrent to the product film and leave the evaporator through an externally arranged condenser. Thin-film evaporators are generally operated at pressures of only a few mbar and the residence time for the product is only a few seconds. In a two-stage evaporating method, of the type preferably used in the process of the invention, the first evaporator also acts as a preliminary degassing stage for the second stage evaporator. Gases dissolved in the viscous liquid are removed from the liquid 1 3387~7 during the removal of excess fatty alcohol from the reac-tion product in the first thin-film evaporator. The short-path evaporator which is preferably used as the second stage evaporator is, in principle, a wiped-film evaporator with a condenser built into the evaporator. These evapor-ators are suitable for the distillation of high-boiling, temperature-sensitive products in the range from 101 to 10 4 mbar. In short-path evaporators, as in thin-film evaporators, the liquid is mechanically distributed over the heating surface by wipers. According to the invention, the excess alcohol is removed to almost any residual con-tents, which may be below 1%, in the short-path evaporator or thin-film evaporator as the second stage. The two-stage arrangement of the evaporators provides for high through-puts in conjunction with the specific establishment of the desired residual content of fatty alcohol in the end product. For industrial purposes, thin-film and short-path evaporators can be dimensioned so that throughputs of up to 300 kg/m2 per hour are readily possible. In principle, the preferred embodiment of the process according to the invention with the two-stage fatty alcohol removal step can also be used in suitable dimensions for working up laboratory-scale mixtures.
The alkyl glycosides produced in accordance with the invention are mixtures consisting essentially of alkyl monoglycoside and the alkyl oligoglycosides, essentially confined here to di- and triglycosides, and small amounts of tetra- and pentaglycosides. The distribution between mono- and oligoglycosides in the end product gives a theoretical degree of oligomerization of from 1 to 5. The process is preferably carried out so that the degree of oligomerization is between about 1 and about 1.5, the quantity of alkyl monoglycoside, based on the total quantity, of alkyl monoglycoside and alkyl oligoglycoside generally exceeds about 70% by weight. (For a definition of the degree of oligomerization, see Paul J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaca, New York, 1953, pages 35 to 37). The total quantity of other secondary constituents is generally below 20% by weight. Of these secondary constituents the fatty alcohol component is variable because it depends upon the intensity of the fatty alcohol distillation process. The quantity of residual alcohol in the end products is adjusted to a preferred range of 0.2 to 5% by weight and more especially 0.5 to 2.5% by weight. The residues of unreacted glycose are below 1%. The contents of polymeric glucose in the end product is from about 2 to about 20% by weight and preferably from 5 to 20% by weight. The quantities of the neutralization products of acidic cata-lyst and basic compound and any excess of this basic com-pound in the end product are between 0.5 and 1.5% by weight.
These quantities are based on the reaction product as its exists immediately after removal of the fatty alcohol excess by distillation. The actual end product of the process is an aqueous paste containing 30 to 60% by weight water which is obtained from the reaction product by treat-ment with warm water and bleaching with active oxygen com-pounds, preferably hydrogen peroxide. The quantity of active oxygen compound is generally from 0.2 to 1.5% by weight, expressed as H202 and based on the quantity of product after the removal of alcohol. Since the pH value falls during the bleaching step, a base, for example sodium hydroxide, is added together with the per oxygen compound to maintain pH values in the range from 8 to 10. The resulting solution or paste preferably contains the salts emanating from neutralization of the catalyst and the bleaching process which have not been separated off. It has been found that there are many applications in which neither the type nor quantity of these residual salts in _ the aqueous alkyl glycoside paste is problematical. On the contrary, the compounds in question are in any event typical constituents of typical detergents and cleaning preparations.
The pH value of the paste-form end product of the process is generally left as its accumulates after the bleaching step, i.e. the paste has a pH value in the range from 8 to 10. For special applications, the pH may be reduced to about the neutral point by addition of an acidic compound which is preferably favorable, but at least not harmful, to the application envisaged. Suitable acidic materials are, for example, acidic salts, such as sodium or potassium hydrogen sulfate, inorganic acids, such as sulfuric acid, or organic acids, such as citric acid, or sulfonate or sulfate surfactants in the acid form.
For prolonged storage or prolonged transport of the paste-form reaction product, it is important to prevent microbial degradation processes. Accordingly, the paste-form reaction product prepared in accordance with the invention preferably contains an antimicrobial effective quantity of a antimicrobial agent which improves stability in storage. The antimicrobial additive comprises, for example, of 0.1 to 0.2% by weight glutardialdehyde.
One particularly preferred embodiment of the process for the production of light-colored and color-stable alkyl glycosides by the direct synthesis method is characterized by application of the following cumulative process steps:
1. The finely divided particulate glycose, particularly glucose, is dispersed in the alcohol by high-speed stirrers or by other high-performance industrial mixers.
2. The base used to neutralize the acid catalyst, preferably a sulfonic acid, consists completely or predominantly of magnesium oxide.
3. The quantity of base is calculated so that, over and above the actual neutralization, a basically reacting mixture, preferably of pH 8 to 10, is obtained.
4. The reaction mixture is not filtered after the neutralization step.
5. Finally, during removal of the excess alcohol by distillation under reduced pressure, the reaction mixture is heated to a sump temperature of 160 to 180C or the heating temperature in the evaporator of the second stage is brought to about 170 to 180C.
The high quality of the end product after bleaching is attributable to the cumulative application of these process steps together with the other process steps. This combina-tion of process parameters may also be applied in the same way in other processes for the production of alkyl glyco-sides, for example in the transacetalization process with butanol or propylene glycol, or in processes where polygly-coses, particularly starch and starch degradation products, are used as starting materials.
EXAMPLES
The process according to the invention is illustrated by the following Examples.
This Example illustrates a process according to the invention for the direct synthesis of C12 alkyl glucoside on a laboratory scale, by the method where a glucose/fatty alcohol suspension is added in portions (slurry variant).
559 g (3 mol) n-dodecanol and 2.2 g (11.2 mmol) p-toluenesulfonic acid were introduced into and heated to between 110 and 114C in a 2-liter three-necked flask equipped with a stirrer, dropping funnel and water separa-tion column. A suspension of 180 g (1 mol) anhydrous -glucose (Puridex, a product of Cerestar Deutschland GmbH) in another 559 g (3 mol) n-dodecanol was then added in portions, more particularly in 10 portions, at intervals of 5 minutes. A reduced pressure varying from 10 to 15 mbar was applied before the first addition. The glucose/fatty alcohol suspension was also heated to about 110~C before the addition. The water of reaction was removed from the reaction medium through the distillation head and frozen and collected in a cold trap cooled with liquid nitrogen.
A total of 19 g water was recovered.
Thereafter, the reaction mixture was stirred for another 120 minutes at 110 to 115C. The reaction mixture was then cooled to 90C, after which 2.0 g (17.5 mmol) magnesium ethylate were added at normal pressure. The mixture was stirred for 30 minutes. The reaction mixture had a pH of 9 to 10. The excess alcohol was distilled off from the reaction flask under a vacuum of 0.1 to 0.01 mbar and at a sump temperature of 120 to 170C. The quantity of distillate was 976 g; the distillation residue, i.e. the actual product, accumulated in a quantity of 299.1 g.
Water and 4.5 g of a 35% H2O2 solution were added to the residue at a temperature of 90C. The residue was thus processed with stirring to a 60% by weight alkyl glucoside paste over a period of 120 minutes. The pH was monitored during the bleaching process and was maintained at pH 9 by addition of 50% NaOH.
Product characteristics: hydroxyl value 656; residual fatty alcohol 0.7%; dodecyl monoglucoside 67% by weight; dodecyl diglucoside 16% by weight; dodecyl triglucoside 5%; dodecyl tetraglucoside 2% by weight; dodecyl pentaglucoside 1% by weight; polyglucose 7% by weight; glucose below 1% by weight. Klett values: after bleaching: 20; after the color stability test: 25.
This Example illustrates the production of a C1214 alkyl glucoside from anhydrous glucose and a technical fatty alcohol (mixture of approximately 7S% by weight dodecanol and approximately 25% by weight tetradecanol) by the batch embodiment (mixture containing the total quantity of reaction components) on a pilot-plant scale.
25.0 kg (129 mol) of a dodecanol/tetradecanol mixture (Lorol S, Henkel KGaA) and 7.7 kg (43 mol) anhydrous glu-cose (Puridex) were introduced into a 150 liter stainless steel vessel and heated with stirring to approximately 80C. 53 g (0.28 mol) p-toluenesulfonic acid were than added to the mixture. The mixture was then heated to approximately 115C, a vacuum of approximately 20 mbar being applied at the same time. The reaction mixture was stirred for about 4 hours under these conditions and the water of reaction distilled Gff at the reduced pressure.
The resulting yellowish and cloudy reaction solution was cooled to 90C, after which 35 g (0.87 mol) magnesium oxide were added under normal pressure, followed by stirring for 30 minutes. A pH of approximately 10 was measured in the reaction mixture. The alcohol excess was then distilled off under a vacuum of 0.5 to 1 mbar, the sump temperature increased to 170C over a period of 3 hours. Approximately 20 kg of fatty alcohol were distilled off during the distillation process which lasted a total of 3 hours and was carried out in the reaction vessel. The distillation residue was an orange-red, clear melt which was cooled to approximately 105C and then mixed with deionized water at 70C to form an approximately 50% by weight alkyl glucoside paste. 100 ml 50% sodium hydroxide in one portion and 200 ml 35% hydrogen peroxide in five portions were then added over a period of 2.5 hours. The reaction mixture was then stirred for another 5 hours at 80C. 18.9 kg of a light yellow transparent paste (49.1% water, pH value 9 to 10) were thus obtained as the reaction product. Product characteristics: hydroxyl value 694; residual fatty alcohol 1.8%; monoglucoside 51% by weight; diglucoside 16% by weight; triglucoside 6% by weight; tetraglucoside 4% by weight; pentaglucoside 2% by weight; hexaglucoside below 1%
by weight; polyglucose approx. 17% by weight; salts below 2% by weight. Klett values: 20 after bleaching, 20 after the color stability test.
After storage of the product for 6 months, the color values and composition (as determined by gas chromato-graphy) were unchanged.
The color stability of a product produced in accord-ance with the prior art was determined for comparison.
This product had been produced in accordance with Example 6 of US-PS 3,839,318 (Mansfield~ using a mixture of dodec-anol and tetradecanol. However, the aqueous sodium hydrox-ide of Example 6 was not used to neutralize the acidic catalyst (sulfuric acid), instead sodium methylate was used as base in accordance with EP 132 046 Bl and the pH value adjusted to 7Ø The product thus obtained had a Klett value of 45 and a Klett value of 125 after treatment with alkali in the color stability test. After conversion into a 60% paste and bleaching with H202, the Klett values measured 25 (immediately after bleaching, pH value below 7) and 110 (after the color stability test). In a repetition of the experiment, the distillation residue was cooled to only 130C. The resulting end product had the same characteristics.
This Example illustrates the production of C1214 alkyl glucoside on an industrial scale.
Of the total quantity of 1860 kg C1zl4 fatty alcohol (distribution: dodecanol approx. 75% by weight, tetradecan-ol approx. 25% by weight), half was processed with 300 kg anhydrous glucose (Puridex) in a 2.5 m3 reactor to form a -suspension. The suspension was finely dispersed by means of a stator/rotor mixer, undergoing an increase in temper-ature to 75C in the process. In a second reactor (3.2 m3) with a distillation column and an external liquid circuit consistinq of a pump and a heat exchanger, the remaining fatty alcohol and 3.9 kg p-toluenesulfonic acid were heated to 115C. The reactor was then evacuated to a pressure of 20 to 30 mbar. The glucose/fatty alcohol suspension was then continuously added over a period of 1 hour. A total of 30 kg water was distilled off during this period and an after-reaction time of 2 hours. The heat required to remove the water and to maintain the reaction temperature was introduced into the reaction mixture through the external liquid circuit. The water of reaction was collec-ted in a cooled receiver and measured. On completion of the reaction, the mixture was cooled to 90C. 2.9 kg magnesium methylate in solid form was then taken in through the external liquid circuit to neutralize the acidic catalyst. Normal pressure was then established.
The reaction mixture was then introduced into a thin-film evaporator of the Sambay type (0.75 m2 evaporator surface, 8 mbar, approx. 170C) and the excess fatty alco-hol was removed to a concentration of approximately 32% by weight of the mixture. The product kept at 135C was low in viscosity and could readily be transferred to a short-path evaporator with a roller wiper of the Leybold KD 75 type. The short-path evaporator was operated under the following conditions: evaporator surface 0.75 m2; operating pressure 0.075 mbar, as measured in the evaporator; heating temperature 170C; sump temperature 162C. Alternatively, a thin-film evaporator was also used in the second depletion stage in a second batch. In a pressure vessel, approximately 88 kg water at room temperature were added to batches of the product (90 kg) in molten form at 150C to prepare an approximately 50% by weight of alkyl glucoside paste. 1.3 kg of a 35% H202 solution and 0.9 kg of a 50%
NaOH solution were added separately. After stirring for 3 hours at 9ooc, the product was cooled to 50C.
Product characteristics: pH 9.5; Klett value 23 (after bleaching) and 26 after the treatment with alkali and heating in the color stability test. Composition of the product (anhydrous): hydroxyl value 650: residual fatty alcohol 3% by weight; alkyl monoglucoside 62.8% by weight;
alkyl diglucoside 15.4% by weight; alkyl triglucoside 5.8%
by weight; alkyl tetraglucoside 2.5% by weight; alkyl pentaglucoside 1.1% by weight; alkyl hexaglucoside 0.2% by weight; polyglucose 6% by weight; glucose less than 1% by weight; salts less than 2% by weight.
The high quality of the end product after bleaching is attributable to the cumulative application of these process steps together with the other process steps. This combina-tion of process parameters may also be applied in the same way in other processes for the production of alkyl glyco-sides, for example in the transacetalization process with butanol or propylene glycol, or in processes where polygly-coses, particularly starch and starch degradation products, are used as starting materials.
EXAMPLES
The process according to the invention is illustrated by the following Examples.
This Example illustrates a process according to the invention for the direct synthesis of C12 alkyl glucoside on a laboratory scale, by the method where a glucose/fatty alcohol suspension is added in portions (slurry variant).
559 g (3 mol) n-dodecanol and 2.2 g (11.2 mmol) p-toluenesulfonic acid were introduced into and heated to between 110 and 114C in a 2-liter three-necked flask equipped with a stirrer, dropping funnel and water separa-tion column. A suspension of 180 g (1 mol) anhydrous -glucose (Puridex, a product of Cerestar Deutschland GmbH) in another 559 g (3 mol) n-dodecanol was then added in portions, more particularly in 10 portions, at intervals of 5 minutes. A reduced pressure varying from 10 to 15 mbar was applied before the first addition. The glucose/fatty alcohol suspension was also heated to about 110~C before the addition. The water of reaction was removed from the reaction medium through the distillation head and frozen and collected in a cold trap cooled with liquid nitrogen.
A total of 19 g water was recovered.
Thereafter, the reaction mixture was stirred for another 120 minutes at 110 to 115C. The reaction mixture was then cooled to 90C, after which 2.0 g (17.5 mmol) magnesium ethylate were added at normal pressure. The mixture was stirred for 30 minutes. The reaction mixture had a pH of 9 to 10. The excess alcohol was distilled off from the reaction flask under a vacuum of 0.1 to 0.01 mbar and at a sump temperature of 120 to 170C. The quantity of distillate was 976 g; the distillation residue, i.e. the actual product, accumulated in a quantity of 299.1 g.
Water and 4.5 g of a 35% H2O2 solution were added to the residue at a temperature of 90C. The residue was thus processed with stirring to a 60% by weight alkyl glucoside paste over a period of 120 minutes. The pH was monitored during the bleaching process and was maintained at pH 9 by addition of 50% NaOH.
Product characteristics: hydroxyl value 656; residual fatty alcohol 0.7%; dodecyl monoglucoside 67% by weight; dodecyl diglucoside 16% by weight; dodecyl triglucoside 5%; dodecyl tetraglucoside 2% by weight; dodecyl pentaglucoside 1% by weight; polyglucose 7% by weight; glucose below 1% by weight. Klett values: after bleaching: 20; after the color stability test: 25.
This Example illustrates the production of a C1214 alkyl glucoside from anhydrous glucose and a technical fatty alcohol (mixture of approximately 7S% by weight dodecanol and approximately 25% by weight tetradecanol) by the batch embodiment (mixture containing the total quantity of reaction components) on a pilot-plant scale.
25.0 kg (129 mol) of a dodecanol/tetradecanol mixture (Lorol S, Henkel KGaA) and 7.7 kg (43 mol) anhydrous glu-cose (Puridex) were introduced into a 150 liter stainless steel vessel and heated with stirring to approximately 80C. 53 g (0.28 mol) p-toluenesulfonic acid were than added to the mixture. The mixture was then heated to approximately 115C, a vacuum of approximately 20 mbar being applied at the same time. The reaction mixture was stirred for about 4 hours under these conditions and the water of reaction distilled Gff at the reduced pressure.
The resulting yellowish and cloudy reaction solution was cooled to 90C, after which 35 g (0.87 mol) magnesium oxide were added under normal pressure, followed by stirring for 30 minutes. A pH of approximately 10 was measured in the reaction mixture. The alcohol excess was then distilled off under a vacuum of 0.5 to 1 mbar, the sump temperature increased to 170C over a period of 3 hours. Approximately 20 kg of fatty alcohol were distilled off during the distillation process which lasted a total of 3 hours and was carried out in the reaction vessel. The distillation residue was an orange-red, clear melt which was cooled to approximately 105C and then mixed with deionized water at 70C to form an approximately 50% by weight alkyl glucoside paste. 100 ml 50% sodium hydroxide in one portion and 200 ml 35% hydrogen peroxide in five portions were then added over a period of 2.5 hours. The reaction mixture was then stirred for another 5 hours at 80C. 18.9 kg of a light yellow transparent paste (49.1% water, pH value 9 to 10) were thus obtained as the reaction product. Product characteristics: hydroxyl value 694; residual fatty alcohol 1.8%; monoglucoside 51% by weight; diglucoside 16% by weight; triglucoside 6% by weight; tetraglucoside 4% by weight; pentaglucoside 2% by weight; hexaglucoside below 1%
by weight; polyglucose approx. 17% by weight; salts below 2% by weight. Klett values: 20 after bleaching, 20 after the color stability test.
After storage of the product for 6 months, the color values and composition (as determined by gas chromato-graphy) were unchanged.
The color stability of a product produced in accord-ance with the prior art was determined for comparison.
This product had been produced in accordance with Example 6 of US-PS 3,839,318 (Mansfield~ using a mixture of dodec-anol and tetradecanol. However, the aqueous sodium hydrox-ide of Example 6 was not used to neutralize the acidic catalyst (sulfuric acid), instead sodium methylate was used as base in accordance with EP 132 046 Bl and the pH value adjusted to 7Ø The product thus obtained had a Klett value of 45 and a Klett value of 125 after treatment with alkali in the color stability test. After conversion into a 60% paste and bleaching with H202, the Klett values measured 25 (immediately after bleaching, pH value below 7) and 110 (after the color stability test). In a repetition of the experiment, the distillation residue was cooled to only 130C. The resulting end product had the same characteristics.
This Example illustrates the production of C1214 alkyl glucoside on an industrial scale.
Of the total quantity of 1860 kg C1zl4 fatty alcohol (distribution: dodecanol approx. 75% by weight, tetradecan-ol approx. 25% by weight), half was processed with 300 kg anhydrous glucose (Puridex) in a 2.5 m3 reactor to form a -suspension. The suspension was finely dispersed by means of a stator/rotor mixer, undergoing an increase in temper-ature to 75C in the process. In a second reactor (3.2 m3) with a distillation column and an external liquid circuit consistinq of a pump and a heat exchanger, the remaining fatty alcohol and 3.9 kg p-toluenesulfonic acid were heated to 115C. The reactor was then evacuated to a pressure of 20 to 30 mbar. The glucose/fatty alcohol suspension was then continuously added over a period of 1 hour. A total of 30 kg water was distilled off during this period and an after-reaction time of 2 hours. The heat required to remove the water and to maintain the reaction temperature was introduced into the reaction mixture through the external liquid circuit. The water of reaction was collec-ted in a cooled receiver and measured. On completion of the reaction, the mixture was cooled to 90C. 2.9 kg magnesium methylate in solid form was then taken in through the external liquid circuit to neutralize the acidic catalyst. Normal pressure was then established.
The reaction mixture was then introduced into a thin-film evaporator of the Sambay type (0.75 m2 evaporator surface, 8 mbar, approx. 170C) and the excess fatty alco-hol was removed to a concentration of approximately 32% by weight of the mixture. The product kept at 135C was low in viscosity and could readily be transferred to a short-path evaporator with a roller wiper of the Leybold KD 75 type. The short-path evaporator was operated under the following conditions: evaporator surface 0.75 m2; operating pressure 0.075 mbar, as measured in the evaporator; heating temperature 170C; sump temperature 162C. Alternatively, a thin-film evaporator was also used in the second depletion stage in a second batch. In a pressure vessel, approximately 88 kg water at room temperature were added to batches of the product (90 kg) in molten form at 150C to prepare an approximately 50% by weight of alkyl glucoside paste. 1.3 kg of a 35% H202 solution and 0.9 kg of a 50%
NaOH solution were added separately. After stirring for 3 hours at 9ooc, the product was cooled to 50C.
Product characteristics: pH 9.5; Klett value 23 (after bleaching) and 26 after the treatment with alkali and heating in the color stability test. Composition of the product (anhydrous): hydroxyl value 650: residual fatty alcohol 3% by weight; alkyl monoglucoside 62.8% by weight;
alkyl diglucoside 15.4% by weight; alkyl triglucoside 5.8%
by weight; alkyl tetraglucoside 2.5% by weight; alkyl pentaglucoside 1.1% by weight; alkyl hexaglucoside 0.2% by weight; polyglucose 6% by weight; glucose less than 1% by weight; salts less than 2% by weight.
Claims (23)
1. A process for the direct production of alkyl glyco-sides by acetalization of higher aliphatic primary alcohols with a glycose which comprises:
(a) preparing a mixture of aliphatic primary alcohol, glycose and acid catalyst in a molar ratio of glycose to alcohol of from about 1:2 to about 1:10 at an elevated temperature by (1) mixing a first portion of the alcohol with the catalyst, heating the mixture and admixing a heated suspension of the glycose in a second portion of alcohol, continuously or in portions; or (2) mixing the entire amount of alcohol and glycose, heating the mixture and adding the acidic catalyst to the heated mixture;
(b) reacting the mixture at an elevated temperature and under reduced pressure while mixing, whereby the water of reaction is removed, to form a reaction mixture;
(c) cooling the reaction mixture to about 90°C;
(d) admixing with the cooled reaction mixture a sufficient amount of a composition, the composition being an organic or inorganic basic alkali metal compound, alkaline earth metal compound, aluminum compound or alkali/aluminum compound to neutralize the acidic catalyst and to raise the pH of the cooled mixture to at least 8;
(e) separating the unreacted alcohol from the alkaline mixture under a reduced pressure and an elevated temperature of up to about 180°C to provide a product containing less than about 5%
by weight of free higher aliphatic alcohol;
(f) cooling the product to about 105 to about 130°C
and adding an amount of an aqueous material selected from the group consisting of water and peroxygen compound and water to the product with stirring to form an aqueous mixture containing from about 30% by weight to about 70% by weight of the alkyl glycoside while maintaining the pH
of the aqueous mixture in the range of from about 8 to about 10.
(a) preparing a mixture of aliphatic primary alcohol, glycose and acid catalyst in a molar ratio of glycose to alcohol of from about 1:2 to about 1:10 at an elevated temperature by (1) mixing a first portion of the alcohol with the catalyst, heating the mixture and admixing a heated suspension of the glycose in a second portion of alcohol, continuously or in portions; or (2) mixing the entire amount of alcohol and glycose, heating the mixture and adding the acidic catalyst to the heated mixture;
(b) reacting the mixture at an elevated temperature and under reduced pressure while mixing, whereby the water of reaction is removed, to form a reaction mixture;
(c) cooling the reaction mixture to about 90°C;
(d) admixing with the cooled reaction mixture a sufficient amount of a composition, the composition being an organic or inorganic basic alkali metal compound, alkaline earth metal compound, aluminum compound or alkali/aluminum compound to neutralize the acidic catalyst and to raise the pH of the cooled mixture to at least 8;
(e) separating the unreacted alcohol from the alkaline mixture under a reduced pressure and an elevated temperature of up to about 180°C to provide a product containing less than about 5%
by weight of free higher aliphatic alcohol;
(f) cooling the product to about 105 to about 130°C
and adding an amount of an aqueous material selected from the group consisting of water and peroxygen compound and water to the product with stirring to form an aqueous mixture containing from about 30% by weight to about 70% by weight of the alkyl glycoside while maintaining the pH
of the aqueous mixture in the range of from about 8 to about 10.
2. A process of claim 1, wherein the higher aliphatic primary alcohol contains from 8 to about 20 carbon atoms.
3. A process of claim 2 wherein the alcohol contains from about 12 to about 18 carbon atoms.
4. A process of claim 1, wherein the first portion of about 30 to 70% by weight of the alcohol is mixed with the catalyst, the mixture is heated to around 100 to 120°C and the glycose in the form of a heated suspension in the second portion of alcohol is added to the mixture of the first portion of alcohol and acid catalyst and the water of reaction formed is removed under a reduced pressure.
5. A process of claim 1, wherein a mixture of the entire quantity of alcohol and the glycose is heated, the acidic catalyst is added to the heated mixture, and the pressure is reduced, and the mixture is further heated to about 100 to about 120°C and the water of reaction is removed under reduced pressure.
6. A process of claim 1, wherein the glycose/alcohol suspension comprises a dispersion of fine glycose particles in the alcohol.
7. A process of claim 1, wherein the pressure is adjusted so that the boiling temperature of the alcohol is lowered by at least 30°C.
8. A process of claim 7 wherein the pressure is in the range of from about 10 to about 50 mbar.
9. A process of claim 1 wherein the higher aliphatic primary alcohols comprise saturated, linear, C12-18 alcohols.
10. A process of claim 1 wherein the acidic catalyst is used in an amount such that the catalyst salt after neutralization can remain in the product.
11. A process of claim 10 wherein the catalyst comprises at least one compound selected from the group consisting of sulfuric acid, phosphoric acid, aliphatic and/or aromatic sulfonic acids, in an amount of from about 0.005 to about 0.02 mol per mol of the glycose used.
12. A process of claim 1 wherein the composition utilized to neutralize the acid catalyst and to raise the pH
above about 8 comprises at least one composition selected from the group consisting of finely divided compounds selected from the group consisting of calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, zeolite NaA and zeolite NaX, alkali metal and alkaline earth metal alcoholates of low-boiling alcohols.
above about 8 comprises at least one composition selected from the group consisting of finely divided compounds selected from the group consisting of calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, zeolite NaA and zeolite NaX, alkali metal and alkaline earth metal alcoholates of low-boiling alcohols.
13. A process of claim 12 wherein the composition comprises at least one compound selected from the group consisting of magnesium oxide and magnesium alcoholate.
14. A process of claim 13 wherein the magnesium alcoholate is magnesium ethylate.
15. A process of claim 1 wherein after neutralization, the basic reaction mixture is heated under a reduced pressure to distill off the excess alcohol to a sump temperature of from 160 to 180°C.
16. A process of claim 1 wherein the glycose/alcohol suspension comprises a dispersion of fine glycose particles in the alcohol and wherein the finely divided glycose is dispersed in the alcohol by high-speed stirrers or high-performance industrial mixers; the base used to neutralize the acid catalyst, is comprised completely or predominantly of magnesium oxide; the quantity of base added is sufficient to raise the pH of the cooled mixture to a pH of 8 to 10; the reaction mixture is not filtered after the neutralization step; and during removal of the excess alcohol by distillation under reduced pressure the product is heated to a temperature of 160 to 180°C.
17. The process of claim 1 wherein the degree of oligomerization of the product produced by the process is in the range from 1 to 5.
18. The process of claim 17 wherein the degree of oligomerization of the product produced by the process is from about 1 to about 1.5.
19. The process of claim 17 wherein an amount of alkyl monoglycoside in the product by the process is greater than 70% by weight of the amount of alkyl monoglycoside and alkyl oligoglycoside.
20. The process of claim 19 wherein the product produced by the process contains from about 0.2 to about 5% by weight of the alcohol based on the anhydrous product.
21. The process of claim 20 wherein the amount of alcohol in the product produced by the process is between 0.5 and 2.5 percent by weight.
22. The process of claim 19 wherein the product produced by the process is in the form of an aqueous paste containing 30 to 60% by weight water, and the salts emanating from neutralization of the catalyst and the bleaching process.
23. The process of claim 19 wherein the product produced by the process is in the form of an aqueous paste and contains an antimicrobial additive in quantities of from 0.1 to 0.2% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3833780.0 | 1988-10-05 | ||
| DE3833780A DE3833780A1 (en) | 1988-10-05 | 1988-10-05 | METHOD FOR THE DIRECT PRODUCTION OF ALKYL GLYCOSIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338237C true CA1338237C (en) | 1996-04-09 |
Family
ID=6364381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000614415A Expired - Fee Related CA1338237C (en) | 1988-10-05 | 1989-09-29 | Process for the direct production of alkyl glycosides |
Country Status (11)
| Country | Link |
|---|---|
| EP (2) | EP0362671A1 (en) |
| JP (1) | JP3031933B2 (en) |
| KR (1) | KR0144673B1 (en) |
| CN (1) | CN1041599A (en) |
| AT (1) | ATE106085T1 (en) |
| BR (1) | BR8907696A (en) |
| CA (1) | CA1338237C (en) |
| DE (2) | DE3833780A1 (en) |
| ES (1) | ES2052973T3 (en) |
| MX (1) | MX170844B (en) |
| WO (1) | WO1990003977A1 (en) |
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| DE593422C (en) * | 1931-02-05 | 1934-02-26 | H Th Boehme A G | Use of high molecular weight synthetic glucosides as a saponin substitute, as an emulsifying, cleaning and wetting agent |
| AT135333B (en) * | 1931-08-06 | 1933-11-10 | H Th Boehme Ag | Method of increasing capillary activity. |
| DE611055C (en) * | 1933-06-04 | 1935-03-21 | H Th Boehme Akt Ges | Process for the preparation of glucosides of higher aliphatic alcohols |
| US3450690A (en) * | 1966-12-23 | 1969-06-17 | Corn Products Co | Preparation of alkali-stable alkyl glucosides |
| US3839318A (en) * | 1970-09-27 | 1974-10-01 | Rohm & Haas | Process for preparation of alkyl glucosides and alkyl oligosaccharides |
| EP0096917A1 (en) * | 1982-06-14 | 1983-12-28 | THE PROCTER & GAMBLE COMPANY | Process for preparation of alkyl glycosides |
| DE3232791A1 (en) * | 1982-09-03 | 1984-03-08 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING ALKYL GLUCOSIDES |
| EP0132046B1 (en) * | 1983-06-15 | 1988-04-20 | The Procter & Gamble Company | Improved process for preparing alkyl glycosides |
| US4557729A (en) * | 1984-05-24 | 1985-12-10 | A. E. Staley Manufacturing Company | Color stabilization of glycosides |
| DE3723826A1 (en) * | 1987-07-18 | 1989-01-26 | Henkel Kgaa | METHOD FOR PRODUCING ALKYL GLYCOSIDES |
-
1988
- 1988-10-05 DE DE3833780A patent/DE3833780A1/en not_active Ceased
-
1989
- 1989-09-26 BR BR898907696A patent/BR8907696A/en not_active IP Right Cessation
- 1989-09-26 AT AT89910858T patent/ATE106085T1/en not_active IP Right Cessation
- 1989-09-26 DE DE58907719T patent/DE58907719D1/en not_active Expired - Lifetime
- 1989-09-26 JP JP1510201A patent/JP3031933B2/en not_active Expired - Lifetime
- 1989-09-26 WO PCT/EP1989/001118 patent/WO1990003977A1/en active IP Right Grant
- 1989-09-26 EP EP89117745A patent/EP0362671A1/en active Pending
- 1989-09-26 ES ES89910858T patent/ES2052973T3/en not_active Expired - Lifetime
- 1989-09-26 EP EP89910858A patent/EP0437460B1/en not_active Expired - Lifetime
- 1989-09-29 CN CN89107548A patent/CN1041599A/en active Pending
- 1989-09-29 CA CA000614415A patent/CA1338237C/en not_active Expired - Fee Related
- 1989-10-02 MX MX017787A patent/MX170844B/en unknown
-
1990
- 1990-06-05 KR KR90701194A patent/KR0144673B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780416A (en) * | 1994-02-10 | 1998-07-14 | Henkel Kommanditgesellschaft Auf Aktien | Acidic hard surface cleaning formulations comprising APG and propoxylated-ethoxylated fatty alcohol ether |
| US10253058B2 (en) | 2014-06-23 | 2019-04-09 | Basf Se | Alkylglycoside sulfomethylsuccinate surfactants |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04500967A (en) | 1992-02-20 |
| DE3833780A1 (en) | 1990-04-12 |
| EP0362671A1 (en) | 1990-04-11 |
| ES2052973T3 (en) | 1994-07-16 |
| EP0437460B1 (en) | 1994-05-25 |
| MX170844B (en) | 1993-09-20 |
| DE58907719D1 (en) | 1994-06-30 |
| KR900701808A (en) | 1990-12-04 |
| BR8907696A (en) | 1991-07-30 |
| KR0144673B1 (en) | 1998-07-15 |
| CN1041599A (en) | 1990-04-25 |
| EP0437460A1 (en) | 1991-07-24 |
| ATE106085T1 (en) | 1994-06-15 |
| WO1990003977A1 (en) | 1990-04-19 |
| JP3031933B2 (en) | 2000-04-10 |
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| MKLA | Lapsed |