Process for preparing solubilization adjuvants from fusel...

Details Process for preparing solubilization adjuvants from fusel... Process for preparing solubilization adjuvants from fusel...

2001-11-13

2004-08-10

Wilson, James O. (Department: 1623)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Carbohydrate doai

C536S004100, C536S018500, C536S124000, C536S127000, C536S018600, C514S054000

Reexamination Certificate

active

06774113

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to processes for manufacturing solubilization adjuvants, to their uses and to their formulations.
BACKGROUND OF THE INVENTION
Fusel oils form colourless or yellowish liquids, which have a characteristic odour. They have a density of about 0.83. Their boiling point is far from constant, since they are complex mixtures of substances with a very variable boiling point: boiling commences at about 80° C. and rises to 130-134° C.
Fusel oils are fatal co-products of alcohol fermentation. These oils, which are produced by yeast in anaerobiosis from nitrogenous materials, are recovered after rectification or on the middle plates of a column for which the alcoholic liquids have a titre of 40-50°. They are insoluble in water and are usually washed with water and separated out by settling of the phases in order to reduce the amount of ethanol they contain by about 4% to 5%. In the present invention, all the percentages are expressed on a weight basis.
Fusel oils represent on average 2% to 5% of the ethanol manufactured. As the industrial production of ethanol in France is 3 million hectoliters, not including biofuels, the potential stock is thus about 900 tonnes.
Fusel oils, occasionally referred to as “amyl oils” or “fusels”, have compositions which vary depending on their origin (potato, beet, wheat, barley, etc. musts).
They are a mixture:
of 5% to 20% of water,
of 60% to 95% of alcohols mainly consisting of linear or branched alkanols containing from 2 to 5 carbon atoms,
of impurities (furfurols, ethers, fatty acids, etc.) which, in extreme cases, may be up to 15%.
The distribution of the main alkanols is as follows:
Alkanol
Content (%)
Formula
Ethanol
 5 to 40
CH
3
—CH
2
—OH
1-Propanol
1 to 8
CH
3
—(CH
2
)
2
—OH
2-Propanol
0 to 1
CH
3
—CH(OH)—CH
3
2-Methylpropanol
 5 to 15
CH
3
—CH(CH
3
)—CH
2
—OH
1-Butanol
0 to 1
CH
3
—(CH
2
)
3
—OH
2-Methylbutanol
10 to 30
CH
3
—CH
2
—CH(CH
3
)—CH
2
—OH
3-Methylbutanol
25 to 70
CH
3
—CH(CH
3
)—(CH
2
)
2
—OH
the combination of alkanols representing 100%.
It should be noted that fusel alcohols are natural alcohols directly produced via biotechnology in distilleries, without any intermediate chemical step.
DETAILED DESCRIPTION OF THE INVENTION
One subject of the invention is a process for preparing a solubilization adjuvant, which comprises placing fusel oils in contact with one or more reducing sugars in the presence of an acid catalyst, at a temperature of between 50° C. and 130° C. and while removing the water from the reaction medium until a solution of alkyl glycosides is obtained, and separating the glycosides from this solution.
The term “reducing sugar” means reducing saccharides chosen from aldoses such as threose, erythrose, xylose, lyxose, ribose, arabinose, glucose, galactose, mannose, idose, gulose, talose, allose or altrose; ketoses such as fructose, sorbose, erythrulose, etc.; disaccharides such as maltose, oligosaccharides and polysaccharides such as starch, dextrans, arabino-xylans, pentosans and xylans.
The term “reducing sugar” also means uronic acids such as galacturonic acid, glucuronic acid or mannuronic acid. The term “reducing sugar” furthermore means non-reducing disaccharides and oligosaccharides such as, for example, sucrose which, in the presence of an acid catalyst such as sulfuric acid, lead to reducing monosaccharides. Finally, the term “reducing sugar” means mixtures of these sugars mentioned above.
Each saccharide may be in &agr; or &bgr; isomeric form, in L or D form, and in furanose or pyranose form.
Pentoses are preferred and most particularly L-arabinose and D-xylose which are abundantly present in the hemicelluloses of many plants.
Hexoses of the D series are also used, especially D-glucose on account of its abundance on the sugar market.
Mixtures of reducing sugars mainly consisting of D-glucose and pentoses, especially D-xylose and L-arabinose, are most particularly appreciated. Preferably, use is made of mixtures of reducing sugars derived from hemicellulose-rich and/or starch-rich agricultural co-products such as, for example, wheat straw, raw or starch-freed wheat bran, starch factory co-products as defined in patent EP 0 699 472, agricultural co-products as defined in patent EP 0 880 538 and more particularly mixtures of reducing sugars containing from 25% to 98%, preferably 60% to 100% and more particularly 90% to 100%, of pentoses and 0% to 34%, and 2% to 75%, preferably 0% to 40% and more particularly 0% to 10%, of hexoses.
The reducing sugars or mixtures of reducing sugars may be crystallized or, preferably, used in the form of syrups.
The first stage of the process according to the invention, commonly known as glycosylation, consists in placing fusel oils in contact with sugars in the presence of an acid catalyst while removing the water from the reaction medium. However, before the placing in contact, it is preferred to purify the fusel oils. This step is advantageously performed by rectification. It allows the removal of the heavy residues from the fusel oils (mainly consisting of impurities) which have boiling points of greater than 140° C. In addition to the heavy fractions, it also allows the removal of light fractions with boiling points of less than 100° C. and which consist mainly of water, ethanol, propanol and 2-methylpropanol. In general, 1 to 20 molar equivalents of alkanols are used relative to the sugars, and preferably 1.5 to 6 equivalents.
During the placing in contact, the alkanols contained in the crude or purified fusel oils are grafted onto the anomeric carbons of sugars to manufacture alkyl glycosides.
The placing in contact is performed in the presence of an acid catalyst such as sulfuric acid, a sulfonic acid such as methanesulfonic acid, hydrochloric acid or hypophosphorous acid or any other acid catalyst for carrying out a glycosidation, and mixtures thereof. This acid catalysis may also be carried out with 0.05 to 6 equivalents by weight of a sulfonic resin in its H
+
form or an acidic resin.
The placing in contact is carried out at a temperature of between 50° C. and 130° C. and preferably between 90° C. and 110° C, for a period of from 15 minutes to 3 hours and preferably from 1 hour to 2 hours.
In order to obtain quantitative yields, it is preferable to remove, in the course of the glycosylation, the water initially present in the starting materials or released during the reaction. This operation is advantageously performed by azeotropic distillation using a rectification column. The condensed vapours are decanted in a static decanter; the water-rich lower phase is removed and the upper phase ensures the reflux of the rectification column.
It is preferred to carry out this glycosylation reaction in the total absence of solvents, but, where appropriate, it is possible to use a solvent such as an oxide ether such as tetrahydrofuran, diethyl ether, 1,4-dioxane, isopropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether or diglyme, a halogenated hydrocarbon such as methylene chloride, chloroform or 1,2-dichloroethane, a nitro solvent such as nitromethane or 2-nitropropane, a solvent of the amide of family such as N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, a nitrile such as acetonitrile, an alkane such as hexane, heptane or octane, or an aromatic solvent such as toluene or xylene.
The placing in contact can also be performed in the presence of microwaves.
To collect the mixture of alkyl glycosides, the process consists:
in removing the reaction solvent, if it is present,
in neutralizing the acid catalyst and then in filtering off the salt obtained. The neutralization is performed, for example, using an alkali metal or alkaline-earth metal carbonate or hydrogen carbonate, especially sodium hydrogen carbonate, an alkali metal or alkaline-earth metal hydroxide, especially sodium hydroxide, or an organic base such as triethanolamine,
in purifying the desired product:
either by evaporation of the excess alkanols under a vacuum of between 0.001 and 100 mbar at a t

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