Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/02—Refining fats or fatty oils by chemical reaction
  • C11B3/08—Refining fats or fatty oils by chemical reaction with oxidising agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

• the present invention relates to a process for treating fats with silica gel and hydrogen peroxide, the process having a lowering of the pH of the fatty substance, which process has the advantage that both undesirably high pH values of the fatty substances are lowered also that a bleaching effect can be achieved.
• Organic substances especially ingredients for cosmetics, cleaners or pharmaceutical products, should be as colorless as possible for the application, so that they can be incorporated into the respective formulations without contributing to a basic color. For this reason, organic substances, especially for the above applications, subjected to a so-called bleaching process.
• the color of the substance is lightened, preferably, the substance is colorless in the visible light.
• a bleaching agent z.
• Bleaching earths used which are natural magnesium aluminum silicates.
• activated carbons are used for decolorization. Further decolorization methods are, for example, the adsorption on polymeric absorber resins or the distillation.
• peroxo compounds and preferably hydrogen peroxide in aqueous solution is used for decolorization.
• the degree of decolorization is often insufficient in this application.
• hydrogen peroxide is critical in terms of safety, as it easily splits off oxygen.
• bleach boosters namely alkaline earth ions, zinc ions and / or alkali silicates.
• the DE 41 42 592 names a large number of surface-active compounds which can be bleached by means of peroxygen in the presence of the known bleach boosters, although suitable silicates are exclusively alkali metal silicates.
• DE 41 42 592 also the concomitant use of alkaline earth ions and in particular magnesium ions as suitable bleaching boosters for bleaching surface-active compounds.
• alkaline earth ions and in particular magnesium ions as suitable bleaching boosters for bleaching surface-active compounds.
• magnesium silicates are suitable compounds which can advantageously bleach surface-active compounds in the presence of peroxygen compounds.
• the organic substances mentioned in the previous paragraph contain alkaline impurities as a result of the preparation, and therefore have an undesirably high pH.
• fatty substances are defined more precisely in the present specification.
• these two problems occur with fatty substances which, as a result of the preparation, have an undesirably high pH value as crude product. This is especially the case with such fatty substances, in the preparation of bases such.
• bases such as B. hydroxides, such as. B. alkali hydroxides, such as. As NaOH or KOH, are used. These bases are z. B. used as catalysts.
• catalysts e.g. As the said hydroxides used.
• z. B. used to convert the starting material ethylene oxide or propylene oxide to said ethoxyl radicals or propoxyl radicals or Oligoethyoxyketten or Oligopropoxyketten.
• FR-A 1 216 645 discloses a process for bleaching a vegetable oil with a bleaching agent containing H2O2 and a magnesium silicate. The lowering of the pH of the oil is not disclosed.
• US 2006/094894 discloses a process for bleaching a hexalester with a bleaching agent containing H2O2 and a magnesium silicate. The lowering of the pH of the oil is not disclosed.
• H 2 O 2 It should preferably be bleached with H 2 O 2 , wherein the bleaching effect of H 2 O 2 should be enhanced.
• magnesium silicates can solve the problem outlined above.
• An object of the present technical teaching is therefore a method for lowering the pH and bleaching of fatty substances having at least 6 C atoms in the molecule, characterized in that the fatty substances with a H 2 O 2 -containing bleach and with a Brings magnesium silicate into contact until a discoloration has occurred, and then preferably removes the magnesium silicate, wherein in carrying out the process a lowering of the pH of the fatty substance, preferably by at least one unit, preferably by at least 0.5 and in particular by at least 0, 1 takes place.
• the fatty substance is preferably heated with stirring to temperatures above the melting point of the fatty substances before carrying out the process.
• the pH of the fat can be either immediate if the fat contains enough water. If this is not the case, the pH can be measured by adding a small amount of water.
• the heated surface-active compound is treated with the magnesium silicate and then this mixture is bleached with the H 2 O 2 -containing bleach.
• the magnesium silicate is removed, for example, by filtration or any other alternative method known to those skilled in the art.
• Another likewise suitable variant of the process consists in first heating the surface-active compound, wherein besides the H 2 O 2 the magnesium silicate is simultaneously contained. In both cases, excellently bleached substrates are obtained.
• the bleaching agents used are preferably aqueous, alkaline H 2 O 2 solutions. Typically, these contain up to 30% by weight of H 2 O 2 .
• Another object of the present invention is the use of a combination of a H 2 O 2 -containing bleaching agent and a magnesium silicate for lowering an undesirably high pH and for bleaching fatty substances, preferably in the process according to the invention or in one of its particular or preferred embodiments.
• Silicates are generally understood to mean the salts and esters (silicic acid esters) of orthosilicic acid [Si (OH) 4 ], and their condensation products. According to the degree of dispersion, the silicates can be classified into coarse-disperse (minerals and glasses), colloidal (eg clay minerals) and molecular disperse silicates (eg present in strongly alkaline solution). Special importance is attached to the technical silicates. For the present technical teaching, however, it is essential that magnesium silicates are used and preferably those silicates which are solid and insoluble in water. Magnesium silicates follow the general formula Mg 2 SiO 4 , but the concrete molar ratio MgO: SiO 2 can be in the range from 1: 4 to 1: 2.
• Such preferred silicates according to the invention are produced synthetically.
• a preferred range is from 1: 2.5 to 1: 3.8 and in particular to 1: 2.6.
• Such silicates are commercially available and are marketed under the brand Magnesol ® from. Dallas Group.
• the specific surface area (BET) is typically and preferably between 100 and 600 m 2 / g.
• the silicate is according to the invention preferably in amounts of 0.001 to 20 wt .-%, in particular from 0.01 to 2.0 wt .-% and most preferably in amounts of 0.1 to 1.0 wt .-%, respectively used on the fatty substances as bleaching amplifiers.
• the temperature at which the bleach booster is used is preferably increased from room temperature. It may be particularly preferred to carry out the reaction with the magnesium silicate at temperatures of 60 to 160 ° C and in particular from 80 to 140 ° C.
• Fatty substances in the context of the present technical teaching are all compounds which can be derived from fats and oils and which have at least 6 C atoms in the molecule.
• fatty substances are linear, branched, cyclic, saturated or unsaturated fatty alcohols, fatty ethers, fatty acid, fatty acid esters, preferably fatty acid esters of glycerol, alkyl (oligo) glycosides, fatty acid amides, fatty acid amines and / or their preferably alkoxylated derivatives.
• other derivatives are also included, for example sulfated, sulfonated or hydroxylated derivatives of the fatty substances described above.
• Preferred fatty substances are those which, owing to their production, have an undesirably high pH (for example due to alkaline impurities).
• Oligo is here to be interpreted broadly. Oligo can z. From 1 to 1000, in particular from 2 to 1000, to 500, to 100, to 50 or to 10 ethoxy units or propoxy units.
• fatty substances which have surface-active properties ie can act as surfactants.
• the fatty substances in the sense of the technical teaching described here are anionic, nonionic, cationic or amphoteric surfactants. These are listed by way of example in the following table (according to Römpp-Online, Version 2.10, 31.3.2006, keyword: "Surfactants”) : class typical representative anion.
• Surfactants Soap Alkylbenzenesulfonates, alkanesulfonates alkyl sulfates alkyl ether nonion.
• surfactants Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers (ethoxylated) sorbitan fatty acid esters, alkyl polyglucosides, fatty acid glucamides, fatty acid polyglycol esters, ethylene oxide-propylene oxide block polymers, polyglycerol fatty acid esters, fatty acid alkanolamides cation.
• surfactants quaternary ammonium compound with one or two hydrophobic groups, (eg cetyltrimethylammonium bromide and cetyltrimethylammonium chloride); Salts long-chain prim.
• fatty substances which have a melting point of more than 21 ° C. ie are solid at room temperature. Since the process described here preferably proceeds at elevated temperature, suitable fatty substances preferably remain stable in the range up to 120 ° C. and in particular up to 140 ° C. without changing chemically. Preference is therefore given to fatty substances which have melting points of greater than 21 ° C., preferably greater than 80 ° C. and particularly preferably greater than 120 ° C. and in particular greater than or equal to 140 ° C.
• the bleaching itself that is, the contacting of the fatty substances with the H 2 O 2 also takes place advantageously and therefore preferably at elevated temperatures.
• Particularly preferred is such a process procedure in which the fatty substances are treated with the bleaching agent at temperatures of 60 to 100 ° C and preferably at temperatures of 60 to 90 ° C.
• nonionic surfactants and fatty substances which are described in detail below:
• R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R 2 is -CH (OH) CH 2 , where R 2 is a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms.
• Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and especially 8 to 10 carbon atoms, where R 1 is a linear alkyl radical and x for 40 to 60.
• R 1 is a linear alkyl radical and x for 40 to 60.
• such compounds are of the general formula (I) in which the index x stands for a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50. M is then a hydrogen atom.
• hydroxy mixed ethers of the formula (I) where R 1 is an alkyl radical having 8 to 10 carbon atoms, in particular based on a native fatty alcohol, R 2 is an alkyl radical having 10 carbon atoms, in particular a linear alkyl radical and x is 40 to 60 stands.
• R 1 is an alkyl and / or alkenyl radical having 8 to 10 carbon atoms
• R 2 is an alkyl or alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50, wherein also here M stands for a hydrogen atom.
• R 1 is an alkyl or alkenyl radical having 8 to 10 carbon atoms
• R 2 is a radical having 8 to 12 carbon atoms
• M is a saturated alkyl radical having 1 to 6, preferably 1 to 4 carbon atoms.
• the latter compound contains no free hydroxyl groups - rather, the hydroxyl functions were alkylated with suitable reagents, for example alkyl halides.
• R 3 in the formula (II) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms
• R 4 is an alkyl radical having 10 to 12, preferably 10 carbon atoms
• y is a number of 15 to 35, preferably 20 to 30
• z is a number from 1 to 3, preferably 1 means.
• Preference is also given to mixtures which contain as surface-active compounds those of the general formula (II) in which R 3 is an alkyl and / or alkenyl radical having 11 to 18 carbon atoms and R 4 is an alkyl or alkenyl radical having 8 to 10 Carbon atoms and y is a number from 20 to 35.
• the compounds of type (II) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with Alkylepoxiden by ring opening in an alkaline medium.
• R 5 is linear or branched alkyl and / or alkenyl radicals having 8 to 22 carbon atoms and z is an integer from 1 to 20 and preferably from 1 to 15, and especially from 1 to 10.
• Typical examples are the adducts of on average 1 to 20 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and Brassidyl alcohol and their technical mixtures, for example, in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred.
• Particularly preferred fatty alcohol ethoxylates are based on tallow alcohols ethoxylated with 2 to 10 and preferably 2 to 5 moles of ethylene oxide per mole of alcohol.
• R 6 CO- (OC 2 H 4 ) m -OR 7 where R 6 is an alkyl and / or alkenyl radical having 7 to 21 carbon atoms and m is a number from 11 to 100, and R 7 represents a hydrogen atom or a radical CO-R 6 .
• R 6 R 7
• R 6 ⁇ R 7 unbalanced connections
• alky (oligo) glycosides These compounds are also known as alky (oligo) glycosides.
• Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula R 8 O- [G] p in which R 8 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p stands for numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
• the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
• the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
• alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
• the alkyl or alkenyl radical R 8 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
• Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes of Roelen's oxosynthesis.
• the alkyl or alkenyl radical R 8 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
• Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds.
• the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine.
• unsaturated carboxylic acids such as acrylic acid is possible.
• betaines are the carboxyalkylation products of secondary and in particular tertiary amines, which follow the formula: in the R I for alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R II is hydrogen or alkyl radicals having 1 to 4 carbon atoms, R III is alkyl radicals having 1 to 4 carbon atoms, n is from 1 to 6, and X is a Alkali and / or alkaline earth metal or ammonium.
• Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalkyldimethylamine, Myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C 16/18 tallowalkyldimethylamine and technical mixtures thereof.
• R IV CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
• m is a number from 1 to 3
• R II , R III , n and X have the meanings given above.
• Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
• the use of a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate
• suitable starting materials for the betaines to be used in the context of the invention are also imidazolines which follow this formula, in which R V is an alkyl radical having 5 to 21 carbon atoms, R 6 is a hydroxyl group, an OCOR V or NHCOR V radical and m is 2 or 3.
• R V is an alkyl radical having 5 to 21 carbon atoms
• R 6 is a hydroxyl group
• an OCOR V or NHCOR V radical an hydroxyl group
• m 2 or 3.
• AEEA aminoethylethanolamine
• the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
• Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on
• nonionic compounds which are also known, are prepared, for example, by reacting alkyl epoxides with ethylene glycol and then with further ethylene oxide. These are also commercially available substances. They follow the general formula (IV) in which R 9 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms and o is a number from 1 to 20 and the subscript p is zero or numbers from 1 to 20.
• R 10 CH (OR 11 ) CH 2 -OR 11 (V) in which R 10 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl radical having 8 to 16 carbon atoms, and R 11 each independently of one another symbolize a radical (CH 2 CH 2 O) r CH 2 CH (OH) R 12 , wherein r in each radical R 11 is independently zero or a number from 1 to 50 and R 12 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl radical having 8 to 16 carbon atoms.
• Compounds of type b8) are obtainable, for example, by ethoxylation of alkylamines or of triethanolamine and subsequent reaction with alkylene oxides with alkyl chains having 8 to 18 carbon atoms under conditions of alkaline catalysis.
• Fatty alcohols are primary aliphatic alcohols of the formula R 14 -OH in which R is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
• Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the like technical mixtures which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
• Preferred are technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel
• fatty acids are meant aliphatic carboxylic acids of the formula (VII) R 15 CO-OH (VII) in which R 15 CO is an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
• Typical examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof , which occur, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from the Roelen oxo synthesis or the dimerization of unsaturated fatty acids.
• Preference is given to technical fatty acids having 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty acid.
• hydroxy mixed ethers of the above description of the formulas (I) and (II) are particularly preferred substrates in the context of the present technical teaching.
• Examples 2 and 3 were carried out analogously to Example 1.
• the color numbers of the starting and end products were determined using a color number determination device from the company Dr. Ing. Lange, model Lico 200 intended.
• values were also measured for bleaching with H 2 O 2 but without added magnesium silicate.
• the results are shown in the following Table 1. ⁇ u> Table 1 ⁇ / u> attempt 1 2 3 Color number according to Hazen before bleaching 478 567 > 1000 after treatment with magnesium silicate 51 80 91 Bleaching without addition of magnesium silicate 472 213 143
• the surfactants treated in the example were not sales products but crude solutions obtained from the reaction to make the surfactants. Before they are for sale, they must be bleached and the pH must be lowered.

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• 2007
  • 2007-08-31 EP EP20070017060 patent/EP1897931A2/fr not_active Withdrawn

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