EP0603275A1 - Procede d'amelioration de la couleur de tensioactifs sulfates ou sulfones sans decoloration - Google Patents
Procede d'amelioration de la couleur de tensioactifs sulfates ou sulfones sans decolorationInfo
- Publication number
- EP0603275A1 EP0603275A1 EP92919449A EP92919449A EP0603275A1 EP 0603275 A1 EP0603275 A1 EP 0603275A1 EP 92919449 A EP92919449 A EP 92919449A EP 92919449 A EP92919449 A EP 92919449A EP 0603275 A1 EP0603275 A1 EP 0603275A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- ester sulfonate
- dark
- surfactant
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 41
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 title claims description 12
- 239000007844 bleaching agent Substances 0.000 title description 4
- 239000012535 impurity Substances 0.000 claims abstract description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- -1 Methyl ester sulfonates Chemical class 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000003463 adsorbent Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 150000002148 esters Chemical class 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 150000004702 methyl esters Chemical class 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 150000004703 alkoxides Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfate Natural products OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 19
- 239000000194 fatty acid Substances 0.000 abstract description 19
- 229930195729 fatty acid Natural products 0.000 abstract description 19
- 230000008020 evaporation Effects 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000004042 decolorization Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 238000006386 neutralization reaction Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 13
- 238000006277 sulfonation reaction Methods 0.000 description 13
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004061 bleaching Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000003039 volatile agent Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000159 acid neutralizing agent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 229910006127 SO3X Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940067592 ethyl palmitate Drugs 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- FTBUKOLPOATXGV-UHFFFAOYSA-N propyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCC FTBUKOLPOATXGV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
Definitions
- the invention is directed to improving the color of sulfonated or sulfated surfactant compositions, particularly alpha-sulfo fatty acid alkyl ester compositions, without the need for bleaching.
- ester sulfonates alkali metal salts of alpha-sulfo fatty acid alkyl esters
- ester sulfonic acids from which the ester sulfonates are derived, are obtained by sulfonation of fatty acid esters or, less preferably, by sulfonation and esterification of fatty acids.
- excess sulfonating agent in combination with greater processing times and/or temperatures is required. These conditions can result in undesirable side reactions including the formation of the dark-colored impurities. Examples of such sulfonation processes are described in U.S. .. i --
- the dark-colored ester sulfonate 5 compositions are not suitable for use directly in washing or cleansing agents and products. Therefore, the dark ester sulfonate products have heretofore been bleached in order to lighten their color.
- the dark products are treated with an aqueous bleaching agent, such as hydrogen peroxide or Q hypochlorite, before and/or after neutralization.
- an aqueous bleaching agent such as hydrogen peroxide or Q hypochlorite
- a method of improving the color of dark-colored ester sulfonate compositions without the need for bleaching has now been discovered. More specifically, it has been discovered that the dark-colored impurities can be separated by known separation methods from a solution comprising the ester sulfonate 0 substantially dissolved in a suitable solvent. Separation of the dark-colored impurities from the solution can be enhanced with an adsorbent material. After removal of the dark-colored impurities, the ester sulfonate can be recovered from the solvent to yield a product with improved, i.e. lighter, color. The process also provides a particulate ester sulfonate surfactant having improved physical properties', relative to that obtained by drying of the surfactant from aqueous pastes and improved surfactant odor. -- J --
- inventive process can also be applied to other sulf(on)ated surfactants whose preparation may result in the formation of dark-colored impurities during and/or after the sulfation or sulfonation reaction.
- surfactants include, but are not limited to, alkylbenzene sulfonates, linear alkane sulfonates, alpha-olefin sulfonates, fatty alcohol sulfates (i.e. alkyl sulfates), and alkyl ether sulfates.
- the present invention involves a novel process for improving the color of a sulfonated or sulfated (hereinafter sulf(on)ated) surfactant composition, said surfactant composition comprising:
- a sulf(on)ated surfactant preferably selected from the group consisting of alkylbenzene sulfonates, linear alkane sulfonates, alpha-olefin sulfonates, ester sulfonates, fatty alcohol sulfates, alkyl ether sulfates and mixtures thereof; and
- step (1) wherein the amount of water present in said solution in step (1) is sufficiently low to avoid interference with effective separation of the dark-colored impurities from said solution.
- the invention is particularly significant for improving the color of ester sulfonate compositions, since methods have been discovered for making the other sulf(on)ated surfactants with low levels of dark impurities.*
- the following disclosure is therefore
- R2 is a C1-C8 alkyl
- X is a water-soluble salt-forming cation.
- Particularly useful ester sulfonates are those wherein R2 is -CH3, i.e. methyl ester sulfonates, and more particularly methyl ester sulfonates wherein R-* is Cjo-Ci ⁇ -
- the cation X is obtained from the agent used to neutralize the ester sulfonic acid to form the ester sulfonate.
- Suitable X cations are monovalent cations, including alkali metals such as sodium, potassium, and lithium; substituted or unsubstituted ammonium; and cations derived from lower alkanolamines, for example monoethanola ine, diethanola ine, and triethanola ine; and mixtures thereof.
- Particularly suitable cations are sodium, potassium, lithium, and those derived from lower alkanolamines.
- the neutralization agent can also provide a cation having a valence number greater than one, for example, alkaline earth metals such as magnesium and calcium.
- the general formula (I) would be modified to reflect the greater number of moles of ester sulfonic acid associated with the cation in the salt (ester sulfonate) form, said number being equal to the cation valence number.
- the ester sulfonic acids from which the ester sulfonates are prepared, can be obtained by sulfonating and then esterifying natural or synthetic fatty acids, or by sulfonating synthetic fatty acid esters.
- the ester sulfonic acids are preferably prepared by sulfonating fatty acid esters.
- Suitable fatty acid esters include, but are not limited to, methyl laurate, ethyl laurate, propyl laurate, methyl pal itate, ethyl palmitate, methyl stearate, ethyl stearate, methyl hydrogenated tallow fatty acid ester, ethyl hydrogenated tallow fatty acid ester, methyl hydrogenated coco fatty acid ester, ethyl hydrogenated coco fatty acid ester, methyl hydrogenated palm fatty acid ester, and mixtures thereof.
- the fatty acid esters can be sulfonated to the sulfofatty acid esters by known processes, for example, by thin layer or batch sulfonation.
- Suitable sulfonating agents include anhydrous SO3, SO3 diluted with nitrogen or dry air, and the like.
- linear esters of C8-C20 carboxylic acids can be * sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
- the sulfonation of the fatty acids or fatty acid esters can result in the formation of dark-colored impurities in the ester sulfonic acid product.
- Neutralization of the ester sulfonic acid with an agent providing the water-soluble cation X results in ester sulfonate comprising dark-colored impurities.
- these dark-colored impurities can be separated from the ester sulfonate to provide a product having significantly lighter color.
- the process comprises the step of forming a solution of the dark ester sulfonate product in a suitable solvent.
- suitable solvents include any which are capable of substantially dissolving the ester sulfonate under appropriate temperatures and pressures. Mixtures of solvents can be used provided that the mixture is capable o * f substantially dissolving the ester sulfonate under appropriate process conditions.
- Particularly suitable solvents for processing ester sulfonates are Ci-Cs alcohols and lower esters thereof. Preferably C ⁇ -C8 alcohols are used; therefore, the process is further described in terms of lower alcohol solvents.
- any solvent as broadly defined above is usable in the process. More preferably methanol, ethanol and mixtures thereof are used, and most preferably methanol is used.
- the weight ratio of lower alcohol to ester sulfonate will generally be from 10:1 to 0.75:1 at temperatures of between about 10 ⁇ C to about 110 ⁇ C, more preferably from 5:1 to 0.75:1, even more preferably from 3:1 to 0.75:1, and most preferably from 2:1 to 1:1.
- Higher ratios of lower alcohol to ester sulfonate can be used, but are probably not any more effective.
- the amount of lower alcohol required to solubilize the ester sulfonate can be added at any or all of the points before, during and after neutralization of the ester sulfonic acid to form the ester sulfonate, further discussed herein.
- some or all of the lower alcohol is added during neutralization.
- Preferably substantially all of the lower alcohol is added during the neutralization step.
- the amount of water in the solution must be sufficiently low to avoid interference with effective separation of the dark-colored impurities from the solution. Without intending to limit the invention, it is theorized that too much water, in relation to the amount of lower alcohol and ester sulfonate present, can result in the formation of a separate ester sulfonate/water phase which can make it difficult to separate the dark-colored impurities from the lower alcohol solvent-containing phase. It is further theorized that in the presence of sufficient water, the ester sulfonate can act as a surfactant to effectively solubilize at least a portion of the dark-colored impurities.
- the dark-colored impurities are soluble or suspendable in the lower alcohol and/or the solution. It is believed that such soluble or suspendable impurities can be separated by adsorbents,- such as activated carbon. The other portion of the dark impurities, which are not soluble or suspendable in the lower alcohol and/or solution, can be separated from the solution by other separation methods as described herein.
- the selection of suitable ratios of lower alcohol to water relative to a given amount of ester sulfonate is considered to be within the experimental ability of one having ordinary skill in the art.
- the weight ratio of alcohol to water is at least 3:1, more preferably 10:1, and even more preferably 30:1.
- the solution is essentially free of water in order to achieve more effective separation of the dark-colored impurities.
- the neutralization process used to prepare the ester sulfonate minimize the amount of water in the ester sulfonate product.
- the alcohol: water ratios required for effective separation of the dark-colored impurities can be obtained without the -need for excessively large amounts of alcohol or the need for a separate dehydration step for the ester sulfonate, prior to dissolving with lower alcohol.
- neutralization is performed with substantially anhydrous solutions of the neutralization agent in a lower alcohol solvent.
- the selection of the particular alcohol solvent depends upon the desired ester, since transesterification may occur during neutralization. For example, where methyl ester sulfonates are desired, methanol is the preferred alcohol solvent.
- neutralization is performed by addition of the ester sulfonic acid to a solution of alkoxide in alcohol, said alkoxide having the formula R*-*0X, wherein R 3 is C -Cs alkyl and X is a water-soluble salt-forming cation as hereinbefore defined.
- the alkoxide in alcohol solution can be added to the ester sulfonic acid, or the two solutions can be mixed together simultaneously, as which occurs in an in-live mixer.
- the alkoxide solution can be prepared by known methods, for example, by dissolving an alkali- or alkaline earth- metal Ci-Cs alkoxide in the respective alcohol to directly provide an essentially anhydrous neutralization system.
- the alkoxide solution can also be formed by dissolving a solid alkali- or alkaline earth- metal hydroxide in the alcohol, although this method of forming the alkoxide solution is less preferred since one mole of water is formed for each mole of alkoxide generated. If this latter method is used, the water from alkoxide generation can optionally be removed by known methods to provide an essentially anhydrous neutralization system.
- An amount of lower alcohol sufficient to dissolve the resultant neutralized ester sulfonate can be used in the preferred substantially anhydrous neutralization.
- Additional solvent can be added after neutralization as required to dissolve the ester sulfonate prior to separating the dark-colored impurities.
- additional solvent can be any as defined above in forming the solution comprising the ester sulfonate surfactant and the lower alcohol solvent.
- ester sulfonate can also be prepared by neutralizing the ester sulfonic acid by well-known processes, including conventional neutralization processes involving aqueous 5-50% caustic solutions. Any residual water in the ester sulfonate product can then be removed as necessary by known methods, such as drying, before proceeding to separate the dark-colored impurities.
- At least a portion of the alcohol required to substantially dissolve the ester sulfonate is mixed with the ester sulfonic acid prior to neutralization.
- the ester sulfonic acid By premixing the ester sulfonic acid with alcohol, it has been shown in the art (See, for example, U.S. 4,404,143, Sekiguchi et al , September 13, 1983, incorporated herein by reference) that reduced levels of fatty acid disalts are formed during neutralization, relative to systems where no premixing with alcohol is performed. Additionally, premixing suppresses the formation of an ester sulfonate/water phase, thereby providing better mixing and improved neutralization.
- the process of the present invention further comprises the step of separating dark-colored impurities from the solution of the ester sulfonate product in alcohol. Separation can be achieved by conventional ' methods such as settling/clarification, centrifugation, filtration, adsorption, or a combination thereof. The particular separation method or methods employed will depend upon a number of factors, such as the amount and proportion of dark-colored impurities which are insoluble in the solvent, versus those that are soluble or suspendable in the solvent, and the amount and proportion of water relative to the amount of solvent and ester sulfonate surfactant.
- Clarification can be accomplished by simple gravitation; on an industrial scale the use of conventional equipment, such as revolving plows or rakes, can be used to aid separation. Centrifugation can be by either a batch method or a continuous method, involving decantation of the supernatant from the sedimented dark-colored impurities.
- Filtration can be performed through conventional filters.
- filtration through paper, diatomaceous earth, or adsorbent are suitable.
- suitable filtration equipment includes pressure filters of the piate-and-frame or shell-and-leaf construction, or of the rotating drum or disk type; vacuum or suction filters of the rotating drum or disk type; edge filters; clarification filters; etc.
- the solution is treated with an adsorbent material, such as activated carbon, activated alumina, or silica gel.
- adsorbent material such as activated carbon, activated alumina, or silica gel.
- activated carbon is used as the adsorbent.
- Adsorbent treatment occurs during filtration.
- Adsorbent treatment can alternatively occur either before or, preferably, after separation of dark impurities by a non-adsorbent method.
- the solution can be mixed with a suitable amount of adsorbent particulate, such that dark-colored impurities adsorb onto the particulate, followed by separating the adsorbent particulate by, for example, centrifugation and/or non-adsorbent filtration.
- Treatment can also, and most preferably, occur by passing the liquor obtained after an initial separation of dark-colored impurities by, for example, centrifugation and/or non-adsorbent filtration, through an adsorbent bed.
- the liquor can be mixed with fresh adsorbent particulate such that dark impurities adsorb onto the particulate, followed by separating the spent or used adsorbent particulate by any suitable method, such as those previously described.
- the temperature required to solubilize the ester sulfonate (in the step of forming the solvent solution of the ester sulfonate composition) is maintained throughout the separation and through to the final product recovery step. Additional lower alcohol can be added as needed to solubilize any ester sulfonate which may precipitate during the separation.
- ester sulfonate dissolving and impurity separation steps would preferably be conducted in suitable pressurized, enclosed equipment and equipment systems to avoid evaporating the solvent at the selected solvent temperature. Such evaporation can result in undesirable evaporation cooling, and loss of solvent vapors to the environment.
- the ester sulfonate product having improved color can be recovered from the solvent solution by known methods.
- recovery methods include, for example, precipitation of the ester sulfonate from the solution, evaporation of the lower alcohol solvent from the solution or a combination thereof.
- Precipitation of the ester sulfonate can be achieved by reducing the temperature of the solution, and thereby the solubility of the ester sulfonate in the lower alcohol.
- the precipitated ester sulfonate can then be recovered by known methods, for example, filtration followed by evaporation of essentially all of any residual solvent. Evaporation may occur under normal or reduced pressure and with or without heating to yield a solid or molten ester sulfonate that can be processed by known methods to any desired form, such as- powder, flake, chunk or granulate.
- the lower alcohol, and any water which may be present can be removed by heating the solution and flashing or evaporating the alcohol (and water, if present).
- This can be done by any suitable method, including conventional processes, such as spray drying, atmospheric flash drying, vacuum flash drying, drum drying, wiped film evaporation, or a combination thereof.
- Spray drying can be used to direct-ly yield an ester sulfonate product in powdered or granular form.
- the other methods yield ester sulfonate products in a chunk, noodle, or large particulate form, which can be further processed by known methods to any desired form, for example, milling to a granular form, or flaking and then chopping or milling to a granular form.
- the alcohol which is removed to recover the ester sulfonate is advantageously condensed, recovered and recycled for re-use in any of the alcohol addition steps described herein.
- the ester sulfonate is recovered by filtration of precipitated (re-crystallized) ester sulfonate
- the resultant liquor obtained from filtration which contains lower alcohol and some amount of dissolved ester sulfonate, can be recycled to any preceding step in the process, preferably back to the step where fresh, dark-colored ester sulfonate is dissolved in lower alcohol to form a solution.
- ester sulfonates of improved, i.e. lighter, color are obtained.
- the resultant product is near-white in color and can be used directly in cleansing and washing agents and products.
- the resultant product may also be converted into a light-colored paste by addition of water after separation of the dark impurities.
- Effective adsorbent treatment further results in improved surfactant odor.
- Improved particle physical properties are also achieved by the present process, relative to those obtained by drying of a conventional aqueous system.
- the amount of water relative to alcohol in the separated solution is believed to have an important effect on the physical properties of the resultant light-colored ester sulfonate product. As the ratio of water: alcohol increases, it becomes increasingly difficult to remove the solvent comprising alcohol and water. Therefore, where water is present in the solution, removal of the solvent with heating is preferred for improved physical properties.
- the process further allows for greater flexibility in the raw materials and process conditions of sulfonation.
- starting materials having* a greater degree of impurities themselves which can result in the formation of the dark-colored impurities, or processing conditions for obtaining greater rates of conversion to the ester sulfonate may be used without the concerns heretofore associated with the need for bleaching.
- Impurities which can result in the formation of dark-colored impurities are known in the art, and include glycerine, glyceride (mono-, di- or tri-) and unsaturated fatty acid ester.
- the process may also avoid the formation of sensitizers, such as those described in D. Connor et al . ; Identification of Certain Sultones as the Sensitizers in an Alkyl Ethoxy Sulfate. "Fette Seifen Anstrichstoff " 77, 25-29 (1975).
- ester sulfonates obtained by the method of the present invention are useful as an active ingredient for cleansing and washing agents and products, and which can be employed either independently or in admixture with other surfactants.
- suitable co-surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants or amphoteric surfactants.
- Other ingredients conventionally used in detergent formulations may also be used. Such ingredients include those generally used as builders, enzymes, bleaching agents and activators, soil release agents, chelating agents, soil -removal ana anti-redeposition agents, dispersing agents, brighteners, suds suppressors, etc.
- Ester sulfonic acid was produced by conventional sulfonation of palm stearin fatty acid methyl ester.
- the acid component of the methyl ester consisted essentially of saturated fatty acids with an Iodine Value of 0.28 and the following chainlength distribution (by weight percent):
- the sulfonation reaction was carried out at 80 ⁇ C to 95 ⁇ C in an annular falling film reactor using a mixture of sulfur trioxide and air (SO3 content: 3-4% by volume; SO3 excess: 15-30 mole percent).
- SO3 content 3-4% by volume; SO3 excess: 15-30 mole percent.
- the sulfonated methyl ester acid mix was then digested in a closed vessel for 35 to 40 minutes at a temperature of 80°C to 95*C. The degree of sulfonation after digestion was 95%.
- 2g of activated carbon decolorizing activated carbon, Aldrich Chemical Co., catalog #16,155-1
- This solution was vacuum filtered through 15cm-diameter Whatman #41 paper onto which was added an additional 2g -activated carbon.
- the filtered liquor was passed a second time through the same filtration assembly. The liquor was then air dried to a 10.4% volatiles content (Cenco) and ground to a powder.
- Sulfonated methyl ester acid mix was prepared from the same palm stearin fatty acid methyl ester stock used in Example 1, using substantially the same sulfonation conditions.
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Abstract
Procédé servant à améliorer des compositions de tensioactifs sulfatés ou sulfonés à coloration sombre et, particulièrement, des compositions d'alpha-sulfoester d'alkyle d'acide gras, sans qu'il soit nécessaire de les décolorer. Le procédé comprend les étapes suivantes: (1) constitution d'une solution d'un tensioactif sulfaté ou sulfoné contenant des impuretés à coloration sombre, dans un solvant approprié; (2) séparation des impuretés à coloration sombre de ladite solution. Les sulfonates d'esters de méthyle, ainsi que les solvants de méthanol sont les plus adaptés. Le traitement de la solution avec un adsorbant, de préférence, un carbone activé, améliore la séparation des impuretés à coloration sombre. On récupère ensuite le tensioactif de la solution au moyen de procédés connus, par exemple, de la précipitation du tensioactif et/ou de l'évaporation du solvant. Après avoir été soumis au traitement décrit par l'invention, le tensioactif sulfaté ou sulfoné présente une amélioration de la couleur ainsi que des caractéristiques physiques et olfactives.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US75449591A | 1991-09-03 | 1991-09-03 | |
US754495 | 1991-09-03 | ||
PCT/US1992/007332 WO1993005013A1 (fr) | 1991-09-03 | 1992-08-28 | Procede d'amelioration de la couleur de tensioactifs sulfates ou sulfones sans decoloration |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0603275A1 true EP0603275A1 (fr) | 1994-06-29 |
Family
ID=25035066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92919449A Withdrawn EP0603275A1 (fr) | 1991-09-03 | 1992-08-28 | Procede d'amelioration de la couleur de tensioactifs sulfates ou sulfones sans decoloration |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0603275A1 (fr) |
JP (1) | JPH06510300A (fr) |
CN (1) | CN1073937A (fr) |
AU (1) | AU2559192A (fr) |
CA (1) | CA2116666A1 (fr) |
HU (1) | HUT67490A (fr) |
MA (1) | MA22641A1 (fr) |
MX (1) | MX9205029A (fr) |
WO (1) | WO1993005013A1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5429773A (en) * | 1993-02-05 | 1995-07-04 | The Procter & Gamble Company | Process to improve alkyl ester sulfonate surfactant compositions |
ATE210600T1 (de) * | 1995-10-17 | 2001-12-15 | Forschungszentrum Juelich Gmbh | Verfahren zur rückgewinnung gereinigter tenside aus waschlösungen, insbesondere zur wäsche kontaminierten erdbodens |
CN1615169A (zh) * | 2002-01-18 | 2005-05-11 | 先进菲涛尼克斯有限公司 | 使用非水溶剂纯化不纯材料的方法 |
MY187405A (en) * | 2014-09-29 | 2021-09-22 | Malaysian Palm Oil Board | Powder form of methyl ester sulphonates (mes) and process for producing the same |
JP6123864B2 (ja) * | 2015-10-19 | 2017-05-10 | ダイキン工業株式会社 | 炭素数2〜7の含フッ素有機酸および不純物を含む組成物の処理方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2502619A (en) * | 1947-10-23 | 1950-04-04 | Standard Oil Co | Purifying salts of sulfonic acids |
US3666795A (en) * | 1967-11-09 | 1972-05-30 | Phillips Petroleum Co | Metal petroleum sulfonate recovery |
JPS58157763A (ja) * | 1982-03-15 | 1983-09-19 | Lion Corp | αスルホ脂肪酸エステルの製造方法 |
-
1992
- 1992-08-28 JP JP5505333A patent/JPH06510300A/ja active Pending
- 1992-08-28 HU HU9400628A patent/HUT67490A/hu unknown
- 1992-08-28 AU AU25591/92A patent/AU2559192A/en not_active Abandoned
- 1992-08-28 EP EP92919449A patent/EP0603275A1/fr not_active Withdrawn
- 1992-08-28 WO PCT/US1992/007332 patent/WO1993005013A1/fr not_active Application Discontinuation
- 1992-08-28 CA CA 2116666 patent/CA2116666A1/fr not_active Abandoned
- 1992-09-02 MX MX9205029A patent/MX9205029A/es unknown
- 1992-09-02 MA MA22931A patent/MA22641A1/fr unknown
- 1992-09-03 CN CN 92111074 patent/CN1073937A/zh active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9305013A1 * |
Also Published As
Publication number | Publication date |
---|---|
HUT67490A (en) | 1995-04-28 |
WO1993005013A1 (fr) | 1993-03-18 |
CN1073937A (zh) | 1993-07-07 |
CA2116666A1 (fr) | 1993-03-18 |
MA22641A1 (fr) | 1993-04-01 |
MX9205029A (es) | 1993-04-01 |
AU2559192A (en) | 1993-04-05 |
JPH06510300A (ja) | 1994-11-17 |
HU9400628D0 (en) | 1994-06-28 |
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