EP1756256B1 - Targeted granulation achieved by neutralisation in a compomix-type machine - Google Patents
Targeted granulation achieved by neutralisation in a compomix-type machine Download PDFInfo
- Publication number
- EP1756256B1 EP1756256B1 EP04739932A EP04739932A EP1756256B1 EP 1756256 B1 EP1756256 B1 EP 1756256B1 EP 04739932 A EP04739932 A EP 04739932A EP 04739932 A EP04739932 A EP 04739932A EP 1756256 B1 EP1756256 B1 EP 1756256B1
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- EP
- European Patent Office
- Prior art keywords
- weight
- acid
- acids
- anionic surfactant
- mixer
- 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.)
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- 150000001299 aldehydes Chemical class 0.000 description 1
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- 125000005263 alkylenediamine group Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 239000013011 aqueous formulation Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
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- 239000013065 commercial product Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- HABLENUWIZGESP-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O.CCCCCCCCCC(O)=O HABLENUWIZGESP-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- AGDANEVFLMAYGL-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCC(O)=O AGDANEVFLMAYGL-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- JLRBNGCMXSGALP-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O.CCCCCCC(O)=O JLRBNGCMXSGALP-UHFFFAOYSA-N 0.000 description 1
- TUFOVEWZORBKNG-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O TUFOVEWZORBKNG-UHFFFAOYSA-N 0.000 description 1
- KYYWBEYKBLQSFW-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCC(O)=O KYYWBEYKBLQSFW-UHFFFAOYSA-N 0.000 description 1
- ZILMEHNWSRQIEH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O.CCCCCC(O)=O ZILMEHNWSRQIEH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000008297 liquid dosage form Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- BMQNWLUEXNQIGL-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O.CCCCCCCCC(O)=O BMQNWLUEXNQIGL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CNVZJPUDSLNTQU-OUKQBFOZSA-N petroselaidic acid Chemical compound CCCCCCCCCCC\C=C\CCCCC(O)=O CNVZJPUDSLNTQU-OUKQBFOZSA-N 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
Definitions
- the present invention relates to a process for the preparation of surfactant granules. It relates in particular to a process which makes it possible to adjust the bulk density of the surfactant granules and the distribution of grain sizes in a targeted manner.
- Surfactant granules are used for the preparation of solid detergents or cleaners which are e.g. as powder or Kompaktate, needed.
- the preparation of surfactant granules is carried out, for example, by reaction of anionic surfactant acids with neutralizing agents. This neutralization can be carried out both with solutions of alkali metal hydroxides, as well as within a dry neutralization with solid alkaline substances, in particular sodium carbonate.
- the surfactant salts are obtained in the form of aqueous formulations, wherein water contents in the range of about 10 to 80 wt .-% and in particular in the range of about 35 to 60 wt .-% are adjustable.
- products of this type have paste-like to cuttable properties, the flowability and pumpability of such pastes being already limited or even lost in the range of about 50% by weight of active substance, so that in the further processing of such pastes, in particular during their incorporation in Solid mixtures, for example, in solid detergents and cleaning agents, considerable problems arise. It is accordingly an old need to be able to provide anionic detergent surfactants in a dry, in particular free-flowing form.
- the European patent application EP-A-0 438 320 discloses a batch process for the preparation of surfactant granules having bulk densities above 650 g / l.
- a solution of an alkaline inorganic substance in water with the possible addition of other solids, is mixed with the anionic surfactant acid and granulated in a high-speed mixer / granulator with a liquid binder.
- neutralization and granulation occur in the same apparatus, but in separate process steps, so that the process can only be operated batchwise.
- EP-A-0 402 112 discloses a continuous neutralization / granulation process for the production of FAS and / or ABS granules from the acid in which the ABS acid is neutralized with at least 62% NaOH and then with the addition of adjuvants, for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000 is granulated.
- adjuvants for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000 is granulated.
- EP-A-0 508 543 (Procter & Gamble) refers to a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40 wt% surfactant paste, which is subsequently conditioned and granulated, with direct cooling with dry ice or liquid nitrogen.
- surfactant mixtures which are subsequently sprayed onto solid absorbents and provide detergent compositions or components therefor are also disclosed in U.S. Pat EP 265,203 (Unilever).
- the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and at most 10% by weight of water.
- the surfactant mixtures to be sprayed contain between 40 and 92% by weight of a surfactant mixture and more than 8 to at most 60% by weight of water.
- the surfactant mixture is in turn at least 50% of polyalkoxylated nonionic surfactants and ionic surfactants.
- a process for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in US Pat EP 507 402 (Unilever).
- the surfactant blends disclosed herein, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.
- German patent application DE-A-42 32 874 discloses a process for preparing washing and cleaning-active Anionentensidgranulate by neutralization of anionic surfactants in their acid form.
- a neutralizing agent solid powdery substances, in particular sodium carbonate, disclosed here, which reacts with the anionic surfactant to anionic surfactant, carbon dioxide and water.
- the granules obtained have surfactant contents of about 30% by weight and bulk densities of less than 550 g / l.
- EP 642 576 (Henkel KGaA) describes a two-stage granulation in two successive mixers / granulators, wherein in a first, low-speed granulator 40-100 wt .-%, based on the total amount of used Ingredients, pre-granulated solid and liquid ingredients and in a second, high-speed granulator, the pregranules are optionally mixed with the remaining ingredients and transferred into a granule.
- German patent application DE-A-43 14 885 discloses a process for preparing washing and cleaning-active anionic surfactant granules by neutralizing the acid form of anionic surfactants with a basic compound, wherein the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant is reacted with the neutralizing agent without releasing water.
- the neutralizing agent used is sodium carbonate, which reacts in this process to form sodium bicarbonate.
- Further processes for the preparation of anionic surfactant granules are WO 92/06170 . DE 19858599 and US 5576285 known.
- the bulk densities of the granules to be produced should be selectively adjustable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray-drying products by means of a non-tower process. Furthermore, it should be possible to influence the grain size distribution of the granules by varying suitable factors. Targeted process management should make it possible, in particular, for the end products to be superior to products that can be produced by prior art processes.
- the end products should have a high solubility, which is precisely when used in the form of Kompakteten a condition for the rapid and complete dissolution of the detergent or cleaning agent portion.
- the granules are expected to optimize shelf life. There should be no longer a sticking together of the individual granules, or an inhomogeneous distribution of the different granule sizes in a granulate quantity due to a broad grain size distribution with a longer storage life. Particular attention was paid to optimizing the cost of the process according to the invention in comparison to the process described in the prior art. So should process steps such as the energy-consuming evaporation of water or the use of energy-consuming high-speed mixer or high shear mixer are largely avoided.
- the present invention is a process for the preparation of surfactant granules having a bulk density of 300 to 800 g / l by neutralization of anionic surfactant acids and optionally other acidic components with solid neutralizing agents, in which the anionic surfactant (s) and the solid (s) neutralizing agent agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 5 and 24 wt .-%.
- anionic surfactant acids are reacted with solid neutralizing agents.
- Suitable anionic surfactant acids for this process are in principle all anionic surfactant acids known to the person skilled in the art.
- one or more substances from the group of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids, in particular from the group is / are used as the anionic surfactant acid (s) the C 8-16 -, in particular the C 9-13 -alkylbenzenesulfonic acids used.
- the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
- the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
- Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. For example, cleavage in an autoclave or the continuous high-pressure fission.
- hexanoic acid caproic acid
- heptanoic acid enanthic acid
- octanoic acid caprylic acid
- nonanoic acid pelargonic acid
- decanoic acid capric acid
- undecanoic acid etc.
- fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-oct
- Such mixtures are, for example, coconut oil fatty acid (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (ca.
- % C 16 ' 1% by weight C 17 , 2% by weight C 18 , 70% by weight C 18' , 10% by weight C 18 " , 0.5% by weight C 18 ''' ), technical palmitic / stearic acid (about 1 wt .-% C 12 , 2 wt .-% C 14 , 45 wt .-% C 16 , 2 wt .-% C 17 , 47 wt .-% C 18 , 1 wt .-% C 18 ' ) and soybean oil fatty acid (about 2 wt .-% C 14 , 15 G % by wt. C 16 , 5 wt.% C 18 , 25 wt.% C 18 ' , 45 wt.% C 18 " , 7 wt.% C 18'” ).
- Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention.
- Their alkali metal salts, in particular sodium salts the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
- the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
- the quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
- alkyl ether sulfuric acids which can be used in the process according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, are characterized by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
- Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
- Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
- Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
- Another process for producing alkanesulfonic acids is sulfoxidation in which n- paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
- This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
- the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical.
- the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
- this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
- Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
- alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
- Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
- petroleum fractions are separated on a large scale with molecular sieves in the n- paraffins of the desired purity and dehydrogenated to the n- olefins, resulting in both ⁇ - and i- olefins.
- the product as a 97 Wt .-% alkylbenzenesulfonic acid (ABSS) provide, which can be used in the context of the present invention as anionic surfactant acid.
- alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -benzenesulfonic acids used have a content of 2-phenyl-isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
- anionic surfactants in their acid form may be used alone or in admixture with each other in the process of the present invention.
- the anionic surfactant in acid form before addition to the solid neutralizing agent (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing mixture, are admixed.
- Suitable acid reactants in the context of the present invention are also the fatty acids, phosphonic acids, polymer acids or partially neutralized fatty acids mentioned Polymeric acids and "Builderklaren” and “complex builder” acids alone and in any mixtures.
- ingredients of detergents and cleaners that can be added to the anionic surfactant especially acid detergent and cleaning agent ingredients, so for example phosphonic acids, which are in neutralized form (phosphonates) as incrustation inhibitors part of many detergents and cleansers.
- the use of (partially neutralized) polymer acids such as polyacrylic acids, is possible.
- acid-stable ingredients with the anionic surfactant acid.
- offer so-called small components which would otherwise have to be added in elaborate further steps, so for example, optical brighteners, dyes, etc., in which case the acid stability is to be checked.
- the anionic surfactant in acid form nonionic surfactants in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing Mixture, mixed.
- This addition can improve the physical properties of the anionic surfactant-containing mixture and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent superfluous.
- the different representatives from the group of nonionic surfactants are described below.
- the anionic surfactant acids reacted in the process according to the invention have a water content between 5 and 24% by weight.
- anionic surfactant acids containing from 5 to 24% by weight of water are used in the process described.
- less than 5% by weight of water, based on the neutralizing agent is preferably introduced into the mixer by the neutralizing agent in this process.
- Particularly preferred is a water content of less than 4 wt .-%, in particular less than 3 wt .-% in the neutralizing agent.
- the neutralizing agent contains 1-2% by weight of water.
- the anionic surfactant acid contains 5-17% by weight of water.
- Water contents of the acid which are between 6 and 16% by weight, particularly preferably between 7 and 15% by weight and in particular between 8 and 14% by weight, are preferred for this embodiment.
- Very particular preference is given to a form of the process in which the water content of the anionic surfactant acid is between 9 and 13% by weight and in particular between 10 and 12% by weight.
- the bulk densities are preferably 300-600 g / l, particularly preferably 400-600 g / l, in particular 500-600 g / l.
- the proportion of the surfactant granules which have a particle size between 100 and 800 ⁇ m before the preparation in this preferred embodiment of the method, at least 40 wt .-%, preferably at least 47 wt .-%, particularly preferably at least 55 wt .-%, very particularly preferably at least 60% by weight and in particular at least 70% by weight.
- the proportion of coarse-grained granules with grain sizes between 800 and 1600 microns before the preparation is preferably more than 20 wt .-%, more preferably more than 25 wt .-%, in particular more than 30 wt .-%.
- the proportion of fine-grained granules with particle sizes between 100 and 200 .mu.m is preferably less than 17 wt .-%, more preferably less than 14 wt .-%, in particular between 1 and 12 wt .-%.
- Preferred subject matter of the invention is a process for the preparation of surfactant granules having a bulk density of 300 to 600 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 5 and 17 wt .-%.
- the anionic surfactant acid contains 10-24% by weight of water. Water contents are preferred for this embodiment the acid, which are between 11 and 23 wt .-%, more preferably between 12 and 22 wt .-% and in particular between 13 and 21 wt .-%. Very particular preference is given to a form of the process according to the invention in which the water content of the anionic surfactant acid is between 14 and 20% by weight and in particular between 15 and 19% by weight. If the water content of the anionic surfactant is selected from the range described in the previous section between 10 and 24 wt .-%, granules with average bulk densities are obtained after neutralization / granulation.
- the bulk densities are preferably 500-800 g / l, particularly preferably 500-700 g / l, in particular 500-600 g / l.
- the proportion of the surfactant granules which have a particle size between 100 and 800 ⁇ m before the preparation, in this preferred embodiment of the process at least 52 wt .-%, preferably at least 62 wt .-%, particularly preferably at least 70 wt .-%, most preferably at least 76 wt .-% and in particular at least 80 wt .-%.
- the proportion of coarse-grained granules having particle sizes between 800 and 1600 ⁇ m before preparation is less than 20% by weight, more preferably less than 15% by weight, in particular between 1 and 10% by weight.
- the proportion of fine-grained granules with particle sizes between 100 and 200 .mu.m is preferably greater than 17 wt .-%, more preferably greater than 23 wt .-%, in particular greater than 27 wt .-%.
- the preferred subject matter of the invention is a process for the preparation of surfactant granules having a bulk density of 500 to 800 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 10 and 24 wt .-%.
- the neutralized form of the anionic surfactant acids in short the anionic surfactants, may be present in varying amounts in the compositions made by the process of the present invention.
- Preferred processes according to the invention are characterized in that the content of neutralized anionic surfactant acid in the process products is not more than 80% by weight, preferably from 8 to 72% by weight, more preferably from 10 to 65% by weight and in particular from 15 to 55% by weight. is.
- the process according to the invention is suitable for producing surfactant-rich granules having a surfactant content of greater than 40% by weight, as well as for producing comparatively low-surfactant granules.
- the surfactant-rich process products preferably contain neutralized anionic surfactant acids in proportions by weight of 40 to 80 wt .-%, preferably from 45 to 75 wt .-%, particularly preferably from 50 to 72 wt .-% and in particular from 60 to 70 wt .-%. These process products are preferably used in detergent concentrates.
- surfactant-poor process products are obtained in which neutralized anionic surfactant acids in proportions by weight of not more than 50% by weight, preferably between 8 and 42% by weight, more preferably between 10 and 35% by weight and in particular between 20 and 30 wt .-% are included.
- These process products are preferably used in the production of high-volume standard washing and cleaning agents.
- Suitable solid neutralizing agents are in principle all neutralizing agents known to the person skilled in the art for this process.
- one or more substances of the compounds sodium carbonate, sodium hydroxide, sodium sesquicarbonate, potassium hydroxide and / or potassium carbonate are used as neutralizing agents.
- components which do not take part in the reaction may also be added to the neutralizing agent. These should then have sufficient stability against the added acids to avoid local decomposition and thus unwanted discoloration or other loading of the product.
- further solids from the groups of silicates, aluminum silicates, sulfates, citrates and / or phosphates are used.
- sodium sulfate which is still present today in some countries up to 45 wt .-% in the detergents, the / the solid neutralizing agent (s) is admixed.
- the weight ratio of the solid neutralizing agent (s) used in the process according to the invention can vary within wide limits.
- weight ratio of the solid neutralizing agent (s) used in the process according to the invention to the anionic surfactant acid (s) used and optionally other acidic components is between 100: 1 and 1: 5, preferably between 80: 1 and 1: 4, preferably between 60: 1 and 1: 3, very particularly preferably between 40: 1 and 1: 2 and in particular between 20: 1 and 1: 1.
- the neutralizing agent to be used preferably contains less than 5% by weight of free water. Particularly preferred is a water content of less than 4 wt .-%, in particular less than 3 wt .-%. In a particularly preferred embodiment of the process, the neutralizing agent contains less than 2% by weight of free water. Particular preference is given to using neutralizing agents which have a content of free, i. not present in the form of water of hydration and / or water of constitution below 1 wt .-%, preferably below 0.5 wt .-% and in particular no free water.
- the neutralizing agent described in the above section is mixed in the free-fall mixer with anionic surfactant acid containing 5 to 24 wt .-% of water.
- the choice of the weight ratio between neutralizing agent and water influences the storability and the dissolution behavior as well as the bulk density of the granules and the distribution of the particle sizes.
- the weight ratio of the solid neutralizing agent used to the water introduced with the anionic surfactant acid is between 800: 1 and 2: 3.
- the ratio of the proportionate weights of neutralizing agent and water is between 19: 1 and 19: 6.
- the water content of the process end products is preferably less than 26% by weight, preferably 1-15% by weight, more preferably 1-10% by weight and in particular 4-5% by weight.
- the neutralization reaction naturally produces water.
- a process procedure should be chosen in which, instead of water and CO 2, mainly sodium bicarbonate is formed. This procedure will be described below.
- Characteristic of the process according to the invention is the use of free-fall mixers for carrying out the neutralization of anionic surfactant acids with solid neutralizing agents.
- the free-fall mixers can be operated continuously or discontinuously.
- such a mixer is referred to as a free-fall mixer in which the mix is taken up by wall friction and subsequently falls freely through the mixing space due to its own gravity.
- Such free-fall mixers have a movable or rotating reactor housing or a moving mixing vessel.
- Suitable containers are those with simple geometric shapes (cylinder, single or double cone, cube, etc.).
- preferred mixing containers have as far as possible obtuse-angled inner corners, since this facilitates both the free movement of the mixed material and the emptying and cleaning of the container after the end of the process. The movement of the container must be transferred to the mix in the interior, so that the most irregular possible confusion and loosening of the reaction mixture takes place.
- the solid neutralizing agent moving in the tumbling mixer forms a falling powder curtain onto which the anionic surfactant acids are sprayed.
- the types of movement for the free-fall mixer are, in particular, rotation about a container axis (drum or rotary tube mixer) or about axes that do not coincide with geometric axes of the container or perpendicular to its symmetry planes (tumble mixer), or vibrate, preferably with high amplitude and low frequency and changing directions of the rashes, so that irregular shaking or tumbling movements occur.
- a directed component of motion must occur to ensure the continuous mass transfer and thus to allow a continuous process.
- a discontinuous process wherein a directional component of motion is not desired.
- Particularly suitable for continuous operation are those free-fall mixers which rotate about their horizontal, preferably about their little inclined axis. Due to the inclination of the axis of rotation, the mixture due to its own gravity on a directed movement, which allows a continuous discharge of the mix from the mixer. Such a directed movement can except by the inclination of the axis of rotation of course also be generated by a continuous input of anionic surfactant acids and solid neutralizing agent.
- the angle of inclination of the axis of rotation of a preferably used rotatable container with a certain number of revolutions correlates.
- the rotatable container of the tumbler mixer has an inclination angle ⁇ of 0 to 20 °, in particular from 0 to 15 °, most preferably from 1 to 15 ° and the movement of the rotatable container of the tumbler over the drive is set simultaneously to 20 to 70 revolutions per minute and in particular to 30 to 60 revolutions per minute.
- Free-fall mixers preferred in the context of the present invention are drum mixers, tumble mixers, cone mixers, double-cone mixers or V mixers.
- the free-fall mixers used in accordance with the invention provide, in the case of rotating or tumbling movements, walls alternately upraised and falling back inside, and thus diversion, widening or narrowing of the space, displacement and division of the material flow.
- Such reactors may further comprise static and / or mobile mixing and / or cutting tools.
- double-cone mixers with rotatable containers without mixing tools are used as free-fall mixers, wherein the continuously operated double-cone mixers are subdivided into a mixing zone and a post-mixing zone and have a knock-off strip which is fastened to an end plate and from there the entire mixing zone passes through and if necessary extends into the post-mixing zone.
- the ratio of the length of the mixing zone to the length of the post-mixing zone is preferably at least 1: 1.
- the tee bar may have a width of 50 to 150 mm, preferably from 75 to 130 mm.
- the top edge of the stripper has a distance from the internal mixer wall which is preferably at most 10% of the drum diameter of the narrowest point of the rotatable container, preferably at most 5% of the narrowest point of the rotatable container and more preferably less than 2.5% of the narrowest point of the rotatable container container accounts.
- the distance to the nearest inner mixer wall may well be greater than in the mixing zone; Values between 100 and 300 mm are quite common.
- the residence time of the reaction mixture in the free-fall mixer in preferred embodiments of the present inventive method is preferably less than 20 minutes, preferably between 1 and 600 seconds, more preferably between 1 and 300 seconds and in particular between 1 and 120 seconds.
- the temperature of the mixture to be applied as low as possible is.
- liquid, acidic component refers to the anionic surfactant acid, which comprises water and optionally further acidic components.
- the reaction between anionic surfactant (s) and sodium carbonate is conducted so that the reaction Na 2 CO 3 + 2 anionic surfactant H ⁇ 2 anionic surfactant Na + CO 2 + H 2 O is largely suppressed and in their place the reaction Na 2 CO 3 + anionic surfactant H ⁇ anionic surfactant Na + NaHCO 3 entry,
- the sodium carbonate is in this case used in excess, so that unreacted sodium carbonate remains in the product, while sodium bicarbonate in the reaction arises.
- the amount of sodium carbonate on average (based on the agent, without consideration of any water of hydration present) is related to the amount of sodium bicarbonate on average (based on the agent, without consideration of any water of hydration present).
- the mass ratio of sodium carbonate to sodium bicarbonate is within narrow limits, and in preferred processes according to the invention the weight ratio of sodium carbonate to sodium bicarbonate in the process end products is 50: 1 to 5: 1, preferably 40: 1 to 5.1: 1, particularly preferably 35: 1 to 5.2: 1 and in particular 30: 1 to 5.25: 1.
- Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or the coordination of the amounts of the reactants.
- the content of the process end products can vary with respect to sodium bicarbonate.
- the content of the process end products of sodium hydrogencarbonate is from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight and in particular from 1 to 10% by weight. -%, in each case based on the total weight of the process end products.
- the content of the process end products of sodium bicarbonate is between 2 and 10% by weight, preferably between 2.5 and 10% by weight, more preferably between 3 and 10% by weight and in particular between 4 and 10% by weight.
- the granules can be aftertreated if necessary.
- the surfactant granules after passing through the post-mixing zone, are either discharged directly via the discharge or transported on via a conveying device.
- the aftertreatment of the surfactant granules continuously or discontinuously perform. It is particularly preferred to connect to a batchwise operated mixing a likewise batchwise aftertreatment, which allows the whereabouts of the surfactant granules in the original reactor.
- aftertreatment in the context of the present application, in particular the spray granulation, that is, the further addition of liquid binder, the encapsulation, the powdering with surface modifiers, the application of nonionic surfactants, drying or spray drying, cooling, and the separation of coarse and / or fines is summarized.
- a powdering agent or surface modifier As a powdering agent or surface modifier, all known, finely divided representatives of this group can be added via a solids feed.
- Amorphous and / or crystalline aluminosilicates such as zeolite A, X and / or P, various types of silicas, calcium stearate, carbonates, sulfates, but also finely divided compounds, for example of amorphous silicates and carbonates, are preferred here.
- nonionic surfactants are preferably alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, alkyl glycosides of the general formula RO (G) x , alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, amine oxides and polyhydroxy fatty acid amides used.
- For drying hot air is preferably used.
- the cooling is preferably carried out by cold air or dry ice. Separated coarse and / or fines are preferably recycled to the process, preferably the coarse fraction being ground before being returned to the tumble mixer.
- the aftertreatment comprises a spray granulation and / or an encapsulation and / or a powdering with heatmodiflzierern and / or an exposure to nonionic surfactants and / or drying and / or spray drying on inert bodies and / or cooling and / or a separation of coarse and / or fines.
- the aftertreatment of the process products after discharge from the free-fall mixer on a reaction section is a characteristic of particularly preferred embodiments of the present inventive method, again such method variants are particularly preferred in which it is in the reaction section to a pneumatic fluidized bed and / or a conveyor belt and / or is a mixer. If this conveying and metering screw leads into the post-mixing zone (a direct connection of the conveying device to the discharge unit is also possible), then it is preferred that the screw only projects maximally into the second length half of the post-mixing zone and thus not into the part of the post-mixing zone that still includes the tee bar.
- the residence time in the post-mixing zone is preferably between 1 and 19 minutes, preferably between 2 and 17 minutes, very particularly preferably between 3 and 14 minutes, in particular between 3 and 10 minutes.
- the agents prepared by the process according to the invention may have different bulk densities depending on the content of the individual ingredients, in particular of the water, and other Aidsparametem. Preference is given to embodiments of the process according to the invention in which the bulk density of the process end products is from 300 to 800 g / l, preferably from 350 to 700 g / l, more preferably from 400 to 650 g / l and in particular from 500 to 600 g / l.
- the granules obtained have an increased solubility in water / aqueous solutions and an increased shelf life compared to the granules described in the prior art. Both the sticking of individual granules and the segregation of a quantity of granules after movement (tilting / shaking) of the storage container were not observed.
- These process products furthermore have a particle size distribution with an average particle size d 50 below 5000 ⁇ m, preferably between 20 and 3000 ⁇ m, more preferably between 40 and 2000 ⁇ m and in particular between 50 and 1600 ⁇ m.
- the surfactant granules having a particle size between 100 and 1600 ⁇ m preferably have a weight fraction of at least 80% by weight, preferably at least 82% by weight, particularly preferably at least 85% by weight, very particularly preferably at least 90% by weight. % and in particular at least 95 wt .-% on. It will be Surfactant granules which have a particle size between 100 and 800 microns prior to the preparation, in the inventive method in proportions by weight of at least 52 wt .-%, preferably at least 62 wt .-%, more preferably at least 70 wt .-%, most preferably at least 76 wt .-% and in particular at least 80 wt .-%.
- the surfactant granules prepared by the process according to the invention are particularly suitable for the production of detergents or cleaners, in particular solid detergents or cleaners, for example by further agglomeration, by extrusion or compaction.
- Such washing or cleaning agents contain in addition to the previously mentioned ingredients such as the anionic surfactants other ingredients, especially from the group of builders, co-builders, bleach, bleach activators, dyes and fragrances, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for the sake of completeness.
- Builders are used in detergents or cleaners especially for binding calcium and magnesium.
- Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent which also contains the process end products of the process according to the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
- trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal isilicates.
- polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
- the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
- a substance class with cobuilder properties are the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
- Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
- the builder used here is preferably HEDP from the class of phosphonates.
- the Aminoalkanphosphonate also have a pronounced Schwerrnetallbindeabmögen. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
- Suitable silicate builders are the crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is an integer from 1.9 to 4 and y is a number from 0 to 20 and preferred Values for x are 2, 3 or 4.
- Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
- zeolite P zeolite MAP ® commercial product from Crosfield
- zeolite X and mixtures of A, X and / or P are also suitable.
- acidifying agents especially acidifying agents, chelating agents or coating-inhibiting polymers are further preferred ingredients of detergents or cleaners.
- Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
- chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- Bleach activators aid the action of the bleaching agents.
- Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
- TAED tetraacetylethylenediamine
- N-acylimides in particular N-nonanoylsuccinimide (NOS
- bleach catalysts can also be present in the secondary products of the process according to the invention.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
- Detergents or cleaning agents may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Preferred agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
- BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
- biuret method biuret method.
- Detergents or detergents may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
- the enzymes can be encapsulated for both the solid and liquid dosage forms.
- Dyes and fragrances can be added to detergents or cleaners to improve the aesthetic appearance of the resulting products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance.
- perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
- the fragrances can be incorporated directly into the compositions, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and by a slower release of fragrance for long-lasting fragrance of the textiles to care.
- carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
- dyes In order to improve the aesthetic impression of the washing or cleaning agents, it (or parts thereof) can be dyed with suitable dyes.
- Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
- Detergents or cleaning agents may contain as optical brighteners derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
- the process end products of the process according to the invention can not only be mixed with particulate detergents or cleaners, but can also be used in detergent tablets. Surprisingly, the solubility of such tablets improved by the use of the process end products of the method according to the invention in comparison to the same hard and identically composed tablets, which do not include end products of the method according to the invention.
- Another object of the present invention is therefore the use of the process end products of the process according to the invention for the production of detergents, in particular detergent tablets.
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Tensidgranulaten. Sie betrifft insbesondere ein Verfahren, welches es gestattet, das Schüttgewicht der Tensidgranulate und die Verteilung der Korngrößen gezielt einzustellen.The present invention relates to a process for the preparation of surfactant granules. It relates in particular to a process which makes it possible to adjust the bulk density of the surfactant granules and the distribution of grain sizes in a targeted manner.
Tensidgranulate werden für die Herstellung von festen Wasch- oder Reinigungsmitteln, welche z.B. als Pulver oder Kompaktate vorliegen, benötigt. Die Herstellung von Tensidgranulaten erfolgt beispielsweise durch Umsetzung von Aniontensidsäuren mit Neutralisationsmitteln. Diese Neutralisation kann sowohl mit Lösungen von Alkalimetallhydroxiden, als auch innerhalb einer Trockenneutralisation mit festen alkalischen Substanzen, insbesondere Natriumcarbonat, durchgeführt werden.Surfactant granules are used for the preparation of solid detergents or cleaners which are e.g. as powder or Kompaktate, needed. The preparation of surfactant granules is carried out, for example, by reaction of anionic surfactant acids with neutralizing agents. This neutralization can be carried out both with solutions of alkali metal hydroxides, as well as within a dry neutralization with solid alkaline substances, in particular sodium carbonate.
Bei der Neutralisation mit wässrigen Alkalien fallen die Tensidsalze in Form wässriger Zubereitungsformen an, wobei Wassergehalte im Bereich von etwa 10 bis 80 Gew.-% und insbesondere im Bereich von etwa 35 bis 60 Gew.-% einstellbar sind. Produkte dieser Art haben bei Raumtemperatur pastenförmige bis schneidfähige Beschaffenheit, wobei die Fließ- und Pumpfähigkeit solcher Pasten schon im Bereich von etwa 50 Gew.-% Aktivsubstanz eingeschränkt ist oder gar verloren geht, so dass bei der Weiterverarbeitung solcher Pasten, insbesondere bei ihrer Einarbeitung in Feststoffmischungen, beispielsweise in feste Wasch- und Reinigungsmittel, beträchtliche Probleme entstehen. Es ist dementsprechend ein altes Bedürfnis, anionische Waschmitteltenside in trockener, insbesondere rieselfähiger Form zur Verfügung stellen zu können. Tatsächlich gelingt es auch, nach herkömmlicher Trocknungstechnik, zum Beispiel im Sprühturm, rieselfähige Aniontensidpulver oder -granulate, insbesondere solche von Fettalkoholsulfaten (FAS) zu gewinnen. Hier zeigen sich jedoch gravierende Einschränkungen, da die erhaltenen Zubereitungen oft hygroskopisch sind, unter Wasseraufnahme aus der Luft bei der Lagerung verklumpen und auch im Waschmittel-Fertigprodukt zur Verklumpung neigen. Aufgrund des notwendigerweise hohen Wassergehaltes der im Sprühturm verarbeiteten Pasten ist der Energieeinsatz bei derartigen Sprühverfahren vergleichsweise hoch.In the case of neutralization with aqueous alkalis, the surfactant salts are obtained in the form of aqueous formulations, wherein water contents in the range of about 10 to 80 wt .-% and in particular in the range of about 35 to 60 wt .-% are adjustable. At room temperature, products of this type have paste-like to cuttable properties, the flowability and pumpability of such pastes being already limited or even lost in the range of about 50% by weight of active substance, so that in the further processing of such pastes, in particular during their incorporation in Solid mixtures, for example, in solid detergents and cleaning agents, considerable problems arise. It is accordingly an old need to be able to provide anionic detergent surfactants in a dry, in particular free-flowing form. In fact, it is also possible, according to conventional drying technology, for example in the spray tower, to obtain free-flowing anionic surfactant powders or granules, in particular those of fatty alcohol sulfates (FAS). However, here are serious limitations, since the preparations obtained are often hygroscopic, clump together under water uptake from the air during storage and also tend to clump in the detergent finished product. Due to the necessarily high water content of the pastes processed in the spray tower, the energy input in such spraying is comparatively high.
Eine Alternative zur Sprühtrocknung tensidischer Pasten stellt die Granulierung dar. Auch in der Patentliteratur existiert ein breiter Stand der Technik zur Non-Tower-Herstellung von Wasch- und Reinigungsmitteln.
So beschreibt die europäische Patentanmeldung
This is how the European patent application describes
Die europäische Patentanmeldung
Aus der europäischen Patentanmeldung
Die europäischen Patentanmeldung
Trockenneutralisationsverfahren, in denen Sulfonsäuren neutralisiert und granuliert werden, sind in der
Ein ähnliches Verfahren, das ebenfalls in einem Hochgeschwindigkeitsmischer durchgeführt wird und bei dem auf 2 bis 20 µm vermahlenes Natriumcarbonat als Neutralisationsmittel dient, wird in der
Tensidmischungen, die nachfolgend auf feste Absorbentien aufgesprüht werden und Waschmittelzusammensetzungen bzw. Komponenten hierfür liefern, werden auch in der
Ähnliche Tensidmischungen werden auch in der älteren
Ein Verfahren zur Herstellung einer flüssigen Tensidmischung aus den drei Bestandteilen Aniontensid, Niotensid und Wasser wird in der
Die deutsche Offenlegungsschrift
Die europäische Offenlegungsschrift
Die deutsche Offenlegungsschrift
Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein kontinuierliches oder diskontinuierliches Verfahren zur Herstellung von Tensidgranulaten durch Neutralisation von Anionentensidsäuren und festen Neutralisationsmitteln bereitzustellen. Die Schüttgewichte der herzustellenden Granulate sollten dabei in breiten Grenzen gezielt einstellbar sein, wobei es ein besonderes Ziel der vorliegenden Erfindung war, auch mit Hilfe eines Non-Tower-Verfahrens die niedrigen Schüttgewichte herkömmlicher Sprühtrocknungsprodukte erreichen zu können. Desweiteren sollte eine Beeinflussung der Korngrößeverteilung der Granulate durch die Variation geeigneter Faktoren möglich werden. Durch eine gezielte Verfahrensführung sollte es insbesondere ermöglicht werden, dass die Endprodukte den nach Verfahren aus dem Stand der Technik herstellbaren Produkten überlegen sind. So sollten die Endprodukte eine hohe Löslichkeit aufweisen, was gerade beim Einsatz in Form von Kompakteten eine Bedingung für das zügige und vollständige Auflösen der Wasch- oder Reinigungsmittelportion ist. Desweiteren wird von den Granulaten eine Optimierung der Lagerfähigkeit erwartet. Es sollte bei längerer Lagerdauer weder ein Zusammenkleben der einzelnen Granulate, noch eine inhomogene Verteilung der unterschiedlichen Granulatgrößen in einer Granulatmenge aufgrund einer breiten Korngrößeverteilung auftreten.
Ein besonderes Augenmerk lag auf einer Kostenoptimierung des erfindungsgemäßen Verfahrens im Vergleich zum im Stand der Technik beschriebenen Verfahren. So sollten Verfahrensschritte wie die energieaufwendige Wasserverdampfung bzw. die Nutzung energieaufwendiger Hochgeschwindigkeitsmischer oder Hochschermischer weitestgehend vermeiden werden.It is an object of the present invention to provide a continuous or batch process for the preparation of surfactant granules by neutralization of anionic surfactant acids and solid neutralizing agents. The bulk densities of the granules to be produced should be selectively adjustable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray-drying products by means of a non-tower process. Furthermore, it should be possible to influence the grain size distribution of the granules by varying suitable factors. Targeted process management should make it possible, in particular, for the end products to be superior to products that can be produced by prior art processes. Thus, the end products should have a high solubility, which is precisely when used in the form of Kompakteten a condition for the rapid and complete dissolution of the detergent or cleaning agent portion. Furthermore, the granules are expected to optimize shelf life. There should be no longer a sticking together of the individual granules, or an inhomogeneous distribution of the different granule sizes in a granulate quantity due to a broad grain size distribution with a longer storage life.
Particular attention was paid to optimizing the cost of the process according to the invention in comparison to the process described in the prior art. So should process steps such as the energy-consuming evaporation of water or the use of energy-consuming high-speed mixer or high shear mixer are largely avoided.
Es wurde nun gefunden, dass sich Tensidgranulate mit steuerbarem Schüttgewicht und steuerbarer Korngrößeverteilung der Granulate herstellen lassen, wenn in einem Freifallmischer die Umsetzung der festen Neutralisationsmittel mit Aniontensidsäuren erfolgt, welche einen Wassergehalt von 5 bis 24 Gew.-% aufweisen.It has now been found that it is possible to prepare surfactant granules with controllable bulk density and controllable particle size distribution of the granules, if the reaction of the solid neutralizing agents with anionic surfactant acids having a water content of 5 to 24% by weight takes place in a free-fall mixer.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Tensidgranulaten mit einem Schüttgewicht von 300 bis 800 g/l durch Neutralisation von Aniontensidsäuren sowie gegebenenfalls weiteren sauren Komponenten mit festen Neutralisationsmitteln, bei welchem die Aniontensidsäure(n) und das/die feste(n) Neutralisationsmittel in einem Freifallmischer agglomeriert, und gegebenenfalls nachträglich aufbereitet werden, dadurch gekennzeichnet, dass die Aniontensidsäure einen Wassergehalt zwischen 5 und 24 Gew.-% aufweist.The present invention is a process for the preparation of surfactant granules having a bulk density of 300 to 800 g / l by neutralization of anionic surfactant acids and optionally other acidic components with solid neutralizing agents, in which the anionic surfactant (s) and the solid (s) neutralizing agent agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 5 and 24 wt .-%.
In dem erfindungsgemäßen Neutralisationsverfahren werden Aniontensidsäuren mit festen Neutralisationsmitteln umgesetzt. Als Aniontensidsäuren eignen sich für dieses Verfahren dabei grundsätzlich alle dem Fachmann bekannten Aniontensidsäuren. In bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens wird/werden als Aniontensidsäure(n) eine oder mehrere Substanz(en) aus der Gruppe der Carbonsäuren, der Schwefelsäurehalbester und der Sulfonsäuren, vorzugsweise aus der Gruppe der Fettsäuren, der Fettalkylschwefelsäuren und der Alkylarylsulfonsäuren, insbesondere aus der Gruppe der C8-16-, insbesondere der C9-13-Alkylbenzolsulfonsäuren, eingesetzt. Diese werden nachstehend beschrieben.In the neutralization process of the invention, anionic surfactant acids are reacted with solid neutralizing agents. Suitable anionic surfactant acids for this process are in principle all anionic surfactant acids known to the person skilled in the art. In preferred embodiments of the process according to the invention, one or more substances from the group of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids, in particular from the group, is / are used as the anionic surfactant acid (s) the C 8-16 -, in particular the C 9-13 -alkylbenzenesulfonic acids used. These are described below.
Um ausreichende oberflächenaktive Eigenschaften aufzuweisen, sollten die genannten Verbindungen dabei über längerkettige Kohlenwasserstoffreste verfügen, also im Alkyl- oder Alkenylrest mindestens 6 C-Atome aufweisen. Üblicherweise liegen die C-Kettenverteilungen der Aniontenside im Bereich von 6 bis 40, vorzugsweise 8 bis 30 und insbesondere 12 bis 22 Kohlenstoffatome.In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical. Usually, the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
Carbonsäuren, die in Form ihrer Alkalimetallsalze als Seifen in Wasch- und Reinigungsmitteln Verwendung finden, werden technisch größtenteils aus nativen Fetten und Ölen durch Hydrolyse gewonnen. Während die bereits im vergangenen Jahrhundert durchgeführte alkalische Verseifung direkt zu den Alkalisalzen (Seifen) führte, wird heute großtechnisch zur Spaltung nur Wasser eingesetzt, das die Fette in Glycerin und die freien Fettsäuren spaltet. Großtechnisch angewendete Verfahren sind beispielsweise die Spaltung im Autoklaven oder die kontinuierliche Hochdruckspaltung. Im Rahmen der vorliegenden Erfindung als Aniontensid in Säureform einsetzbare Carbonsäuren sind beispielsweise Hexansäure (Capronsäure), Heptansäure (Önanthsäure), Octansäure (Caprylsäure), Nonansäure (Pelargonsäure), Decansäure (Caprinsäure), Undecansäure usw.. Bevorzugt ist im Rahmen der vorliegenden Verbindung der Einsatz von Fettsäuren wie Dodecansäure (Laurinsäure), Tetradecansäure (Myristinsäure), Hexadecansäure (Palmitinsäure), Octadecansäure (Stearinsäure), Eicosansäure (Arachinsäure), Docosansäure (Behensäure), Tetracosansäure (Lignocerinsäure), Hexacosansäure (Cerotinsäure), Triacotansäure (Melissinsäure) sowie der ungesättigten Spezies 9c-Hexadecensäure (Palmitoleinsäure), 6c-Octadecensäure (Petroselinsäure), 6t-Octadecensäure (Petroselaidinsäure), 9c-Octadecensäure (Ölsäure), 9t-Octadecensäure ((Elaidinsäure), 9c,12c-Octadecadiensäure (Linolsäure), 9t,12t-Octadecadiensäure (Linolaidinsäure) und 9c,12c,15c-Octadecatreinsäure (Linolensäure). Aus Kostengründen ist es bevorzugt, nicht die reinen Spezies einzusetzen, sondern technische Gemische der einzelnen Säuren, wie sie aus der Fettspaltung zugänglich sind. Solche Gemische sind beispielsweise Kokosölfettsäure (ca. 6 Gew.-% C8, 6 Gew.-% C10, 48 Gew.-% C12, 18 Gew.-% C14, 10 Gew.-% C16, 2 Gew.-% C18, 8 Gew.-% C18', 1 Gew.-% C18"), Palmkernölfettsäure (ca. 4 Gew.-% C8, 5 Gew.-% C10, 50 Gew.-% C12, 15 Gew.-% C14, 7 Gew.-% C16, 2 Gew.-% C18, 15 Gew.-% C18', 1 Gew.-% C18"), Talgfettsäure (ca. 3 Gew.-% C14, 26 Gew.-% C16, 2 Gew.-% C16', 2 Gew.-% C17, 17 Gew.-% C18, 44 Gew.-% C18', 3 Gew.-% C18", 1 Gew.-% C18'''), gehärtete Talgfettsäure (ca. 2 Gew.-% C14, 28 Gew.-% C16, 2 Gew.-% C17, 63 Gew.-% C18, 1 Gew.-% C18'), technische Ölsäure (ca. 1 Gew.-% C12, 3 Gew.-% C14, 5 Gew.-% C16, 6 Gew.-% C16', 1 Gew.-% C17, 2 Gew.-% C18, 70 Gew.-% C18', 10 Gew.-% C18", 0,5 Gew.-% C18'''), technische Palmitin/Stearinsäure (ca. 1 Gew.-% C12, 2 Gew.-% C14, 45 Gew.-% C16, 2 Gew.-% C17, 47 Gew.-% C18, 1 Gew.-% C18') sowie Sojabohnenölfettsäure (ca. 2 Gew.-% C14, 15 Gew.-% C16, 5 Gew.-% C18, 25 Gew.-% C18', 45 Gew.-% C18", 7 Gew.-% C18''').Carboxylic acids, which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. For example, cleavage in an autoclave or the continuous high-pressure fission. For example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. are preferred in the context of the present invention Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid For reasons of cost, it is preferable not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipid cleavage. Such mixtures are, for example, coconut oil fatty acid (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (ca. 3% by weight C 14 , 26% by weight C 16 , 2% by weight C 16 ' , 2% by weight C 17 , 17% by weight C 18 , 44% by weight C 18' , 3% by weight C 18 " , 1% by weight C 18 '" ), hardened tallow fatty acid (about 2% by weight C 14 , 28% by weight C 16 , 2% by weight C 17 , 63 wt .-% C 18 , 1 wt .-% C 18 ' ), technical oleic acid (about 1 wt .-% C 12 , 3 wt .-% C 14 , 5 wt .-% C 16 , 6 wt. % C 16 ' , 1% by weight C 17 , 2% by weight C 18 , 70% by weight C 18' , 10% by weight C 18 " , 0.5% by weight C 18 ''' ), technical palmitic / stearic acid (about 1 wt .-% C 12 , 2 wt .-% C 14 , 45 wt .-% C 16 , 2 wt .-% C 17 , 47 wt .-% C 18 , 1 wt .-% C 18 ' ) and soybean oil fatty acid (about 2 wt .-% C 14 , 15 G % by wt. C 16 , 5 wt.% C 18 , 25 wt.% C 18 ' , 45 wt.% C 18 " , 7 wt.% C 18'" ).
Schwefelsäurehalbester längerkettiger Alkohole sind ebenfalls Aniontenside in ihrer Säureform und im Rahmen des erfindungsgemäßen Verfahrens einsetzbar. Ihre Alkalimetall-, insbesondere Natriumsalze, die Fettalkoholsulfate, sind großtechnisch aus Fettalkoholen zugänglich, welche mit Schwefelsäure, Chlorsulfonsäure, Amidosulfonsäure oder Schwefeltrioxid zu den betreffenden Alkylschwefelsäuren umgesetzt und nachfolgend neutralisiert werden. Die Fettalkohole werden dabei aus den betreffenden Fettsäuren bzw. Fettsäuregemischen durch Hochdruckhydrierung der Fettsäuremethylester gewonnen. Der mengenmäßig bedeutendste industrielle Prozess zur Herstellung von Fettalkylschwefelsäuren ist die Sulfierung der Alkohole mit SO3/Luft-Gemischen in speziellen Kaskaden-, Fallfilm- oder Röhrenbündelreaktoren.Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention. Their alkali metal salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters. The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
Eine weitere Klasse von Aniontensidsäuren, die im erfindungsgemäßen Verfahren eingesetzt werden kann, sind die Alkyletherschwefelsäuren, deren Salze, die Alkylethersulfate, sich im Vergleich zu den Alkylsulfaten durch eine höhere Wasserlöslichkeit und geringere Empfindlichkeit gegen Wasserhärte (Löslichkeit der Ca-Salze) auszeichnen. Alkyletherschwefelsäuren werden wie die Alkylschwefelsäuren aus Fettalkoholen synthetisiert, welche mit Ethylenoxid zu den betreffenden Fettalkoholethoxylaten umgesetzt werden. Anstelle von Ethylenoxid kann auch Propylenoxid eingesetzt werden. Die nachfolgende Sulfonierung mit gasförmigem Schwefeltrioxid in Kurzzeit-Sulfierreaktoren liefert Ausbeuten über 98% an den betreffenden Alkyletherschwefelsäuren.Another class of anionic surfactant acids which can be used in the process according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, are characterized by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates. Alkyl ether sulfuric acids, like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
Auch Alkansulfonsäuren und Olefinsulfonsäuren sind im Rahmen der vorliegenden Erfindung als Aniontenside in Säureform einsetzbar. Alkansulfonsäuren können die Sulfonsäuregruppe terminal gebunden (primäre Alkansulfonsäuren) oder entlang der C-Kette enthalten (sekundäre Alkansulfonsäuren), wobei lediglich die sekundären Alkansulfonsäuren kommerzielle Bedeutung besitzen. Diese werden durch Sulfochlorierung oder Sulfoxidation linearer Kohlenwasserstoffe hergestellt. Bei der Sulfochlorierung nach Reed werden n-Paraffine mit Schwefeldioxid und Chlor unter Bestrahlung mit UV-Licht zu den entsprechenden Sulfochloriden umgesetzt, die bei Hydrolyse mit Alkalien direkt die Alkansulfonate, bei Umsetzung mit Wasser die Alkansulfonsäuren, liefern. Da bei der Sulfochlorierung Di- und Polysulfochloride sowie Chlorkohlenwasserstoffe als Nebenprodukte der radikalischen Reaktion auftreten können, wird die Reaktion üblicherweise nur bis zu Umsetzungsgraden von 30% durchgeführt und danach abgebrochen.Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form. Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons. In the sulfochlorination according to Reed n paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to the corresponding sulfochlorides, which on hydrolysis with alkalis directly the alkanesulfonates, upon reaction with water, the alkanesulfonic provide. Since di- and Polysulfochloride and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.
Ein anderer Prozess zur Herstellung von Alkansulfonsäuren ist die Sulfoxidation, bei der n-Paraffine unter Bestrahlung mit UV-Licht mit Schwefeldioxid und Sauerstoff umgesetzt werden. Bei dieser Radikalreaktion entstehen sukzessive Alkylsulfonylradikale, die mit Sauerstoff zu den Alkylpersulfonylradikalen weiter reagieren. Die Reaktion mit unumgesetztem Paraffin liefert ein Alkylradikal und die Alkylpersulfonsäure, welche in ein Alkylperoxysulfonylradikal und ein Hydroxylradikal zerfällt. Die Reaktion der beiden Radikale mit unumgesetztem Paraffin liefert die Alkylsulfonsäuren bzw. Wasser, welches mit Alkylpersulfonsäure und Schwefeldioxid zu Schwefelsäure reagiert. Um die Ausbeute an den beiden Endprodukten Alkylsulfonsäure und Schwefelsäure möglichst hoch zu halten und Nebenreaktionen zu unterdrücken, wird diese Reaktion üblicherweise nur bis zu Umsetzungsgraden von 1% durchgeführt und danach abgebrochen.Another process for producing alkanesulfonic acids is sulfoxidation in which n- paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation. This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals. The reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid. In order to keep the yield of the two end products alkyl sulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
Olefinsulfonate werden technisch durch Reaktion von α-Olefinen mit Schwefeltrioxid hergestellt. Hierbei bilden sich intermediär Zwitterionen, welche sich zu sogenannten Sultonen zyklisieren. Unter geeigneten Bedingungen (alkalische oder saure Hydrolyse) reagieren diese Sultone zu Hydroxylalkansulfonsäuren bzw. Alkensulfonsäuren, welche beide ebenfalls als Aniontensidsäuren eingesetzt werden können.Olefinsulfonates are produced industrially by reaction of α-olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
Alkylbenzolsulfonate als leistungsstarke anionische Tenside sind seit den dreißiger Jahren unseres Jahrhunderts bekannt. Damals wurden durch Monochlorierung von Kogasin-Fraktionen und subsequente Friedel-Crafts-Alkylierung Alkylbenzole hergestellt, die mit Oleum sulfoniert und mit Natronlauge neutralisiert wurden. Anfang der fünfziger Jahre wurde zur Herstellung von Alkylbenzolsulfonaten Propylen zu verzweigtem α-Dodecylen tetramerisiert und das Produkt über eine Friedel-Crafts-Reaktion unter Verwendung von Aluminiumtrichlorid oder Fluorwasserstoff zum Tetrapropylenbenzol umgesetzt, das nachfolgend sulfoniert und neutralisiert wurde. Diese ökonomische Möglichkeit der Herstellung von Tetrapropylenbenzolsulfonaten (TPS) führte zum Durchbruch dieser Tensidklasse, die nachfolgend die Seifen als Haupttensid in Wasch- und Reinigungsmitteln verdrängte.Alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950's propylene was tetramerized into branched α-dodecylene to produce alkylbenzenesulfonates and the product was reacted via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride to tetrapropylenebenzene, which was subsequently sulfonated and neutralized. This economic possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced soaps as the major surfactant in detergents and cleaners.
Aufgrund der mangelnden biologischen Abbaubarkeit von TPS bestand die Notwendigkeit, neue Alkylbenzolsulfonate darzustellen, die sich durch ein verbessertes ökologische Verhalten auszeichnen. Diese Erfordernisse werden von linearen Alkylbenzolsulfonaten erfüllt, welche heute die fast ausschließlich hergestellten Alkylbenzolsulfonate sind und mit dem Kurzzeichen ABS belegt werden.Due to the lack of biodegradability of TPS, there was a need to present new alkylbenzenesulfonates that are characterized by improved environmental performance. These requirements are met by linear alkylbenzenesulfonates, which are today almost exclusively produced alkylbenzenesulfonates and are referred to by the abbreviation ABS.
Lineare Alkylbenzolsulfonate werden aus linearen Alkylbenzolen hergestellt, welche wiederum aus linearen Olefinen zugänglich sind. Hierzu werden großtechnisch Petroleumfraktionen mit Molekularsieben in die n-Paraffine der gewünschten Reinheit aufgetrennt und zu den n-Olefinen dehydriert, wobei sowohl α- als auch i-Olefine resultieren. Die entstandenen Olefine werden dann in Gegenwart saurer Katalysatoren mit Benzol zu den Alkylbenzolen umgesetzt, wobei die Wahl des Friedel-Crafts-Katalysators einen Einfluß auf die Isomerenverteilung der entstehenden linearen Alkylbenzole hat: Bei Verwendung von Aluminiumtrichlorid liegt der Gehalt der 2-Phenyl-Isomere in der Mischung mit den 3-, 4-, 5- und anderen Isomeren bei ca. 30 Gew.-%, wird hingegen Fluorwasserstoff als Katalysator eingesetzt, lässt sich der Gehalt an 2-Phenyl-Isomer auf ca. 20 Gew.-% senken. Die Sulfonierung der linearen Alkylbenzole schließlich gelingt heute großtechnisch mit Oleum, Schwefelsäure oder gasförmigem Schwefeltrioxid, wobei letzteres die weitaus größte Bedeutung hat. Zur Sulfonierung werden spezielle Film- oder Rohrbündelreaktoren eingesetzt, die als Produkt eine 97 Gew.-%ige Alkylbenzolsulfonsäure (ABSS) liefern, die im Rahmen der vorliegenden Erfindung als Aniontensidsäure einsetzbar ist.Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions are separated on a large scale with molecular sieves in the n- paraffins of the desired purity and dehydrogenated to the n- olefins, resulting in both α- and i- olefins. The resulting olefins are then reacted in the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of the Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear alkylbenzenes: When using aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt .-%, however, hydrogen fluoride is used as the catalyst, the content of 2-phenyl isomer can be reduced to about 20 wt .-% , The sulfonation of linear alkylbenzenes finally succeeds today industrially with oleum, sulfuric acid or gaseous sulfur trioxide, the latter having by far the greatest importance. For the sulfonation special film or tube bundle reactors are used, the product as a 97 Wt .-% alkylbenzenesulfonic acid (ABSS) provide, which can be used in the context of the present invention as anionic surfactant acid.
Durch Wahl des Neutralisationsmittels lassen sich aus den ABSS die unterschiedlichsten Salze, d.h. Alkylbenzolsulfonate, gewinnen. Aus Gründen der Ökonomie ist es hierbei bevorzugt, die Alkalimetallsalze und unter diesen bevorzugt die Natriumsalze der ABSS herzustellen und einzusetzen. Diese lassen sich durch die allgemeine Formel I beschreiben:
in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäße Verfahren, in denen als Aniontensid in Säureform C8-16-, vorzugsweise C9-13-Alkylbenzolsulfonsäuren eingesetzt werden, sind bevorzugt. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C8-16-, vorzugsweise C9-13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so dass die eingesetzten C8-16-, vorzugsweise C9-13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.in which the sum of x and y is usually between 5 and 13. Processes according to the invention in which C 8-16 -, preferably C 9-13 -alkylbenzenesulfonic acids are used as the anionic surfactant in acid form are preferred. It is further preferred in the context of the present invention to use C 8-16 , preferably C 9-13- alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -benzenesulfonic acids used have a content of 2-phenyl-isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
Die vorstehend genannten Aniontenside in ihrer Säureform können alleine oder in Mischung miteinander im erfindungsgemäßen Verfahren eingesetzt werden. Es ist aber auch möglich und bevorzugt, dass dem Aniontensid in Säureform vor der Zugabe zu dem/den festen Neutralisationsmittel(n) weitere, vorzugsweise saure, Inhaltsstoffe von Wasch- und Reinigungsmitteln in Mengen von 0,1 bis 40 Gew.-%, vorzugsweise von 1 bis 15 Gew.-% und insbesondere von 2 bis 10 Gew.-%, jeweils bezogen auf das Gewicht der Aniontensidsäure-haltigen Mischung, zugemischt werden.The above-mentioned anionic surfactants in their acid form may be used alone or in admixture with each other in the process of the present invention. However, it is also possible and preferred that the anionic surfactant in acid form before addition to the solid neutralizing agent (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing mixture, are admixed.
Als saure Reaktionspartner eignen sich im Rahmen der vorliegenden Erfindung neben den "Tensidsäuren" auch die genannten Fettsäuren, Phosphonsäuren, Polymersäuren oder teilneutralisierte Polymersäuren sowie "Buildersäuren" und "Komplexbuildersäuren" alleine sowie in beliebigen Mischungen. Als Inhaltsstoffe von Wasch- und Reinigungsmitteln, die der Aniontensidsäure zugemischt werden können, bieten sich vor allem saure Wasch- und Reinigungsmittel-Inhaltsstoffe an, also beispielsweise Phosphonsäuren, welche in neutralisierter Form (Phosphonate) als Inkrustationsinhibitoren Bestandteil vieler Wasch- und Reinigungsmittel sind. Auch der Einsatz von (teilneutralisierten) Polymersäuren wie beispielsweise Polyacrylsäuren, ist möglich. Es ist aber auch möglich, säurestabile Inhaltsstoffe mit der Aniontensidsäure zu vermischen. Hier bieten sich beispielsweise sogenannte Kleinkomponenten an, welche sonst in aufwendigen weiteren Schritten zugegeben werden müssten, also beispielsweise optische Aufheller, Farbstoffe usw., wobei im Einzelfall die Säurestabilität zu prüfen ist.Suitable acid reactants in the context of the present invention, besides the "surfactant acids", are also the fatty acids, phosphonic acids, polymer acids or partially neutralized fatty acids mentioned Polymeric acids and "Buildersäuren" and "complex builder" acids alone and in any mixtures. As ingredients of detergents and cleaners that can be added to the anionic surfactant, especially acid detergent and cleaning agent ingredients, so for example phosphonic acids, which are in neutralized form (phosphonates) as incrustation inhibitors part of many detergents and cleansers. The use of (partially neutralized) polymer acids such as polyacrylic acids, is possible. But it is also possible to mix acid-stable ingredients with the anionic surfactant acid. Here, for example, offer so-called small components, which would otherwise have to be added in elaborate further steps, so for example, optical brighteners, dyes, etc., in which case the acid stability is to be checked.
Bevorzugt werden dem Aniontensid in Säureform nichtionische Tenside in Mengen von 0,1 bis 40 Gew.-%, vorzugsweise von 1 bis 15 Gew.-% und insbesondere von 2 bis 10 Gew.-%, jeweils bezogen auf das Gewicht der Aniontensidsäure-haltigen Mischung, zugemischt. Dieser Zusatz kann die physikalischen Eigenschaften der Aniontensidsäure-haltigen Mischung verbessern und eine spätere Einarbeitung nichtionischer Tenside in das Tensidgranulat oder das gesamte Wasch- und Reinigungsmittel überflüssig machen. Die unterschiedlichen Vertreter aus der Gruppe der nichtionischen Tenside werden weiter unten beschrieben.Preferably, the anionic surfactant in acid form nonionic surfactants in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing Mixture, mixed. This addition can improve the physical properties of the anionic surfactant-containing mixture and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent superfluous. The different representatives from the group of nonionic surfactants are described below.
Die in den erfindungsgemäßen Verfahren umgesetzten Aniontensidsäuren weisen einen Wassergehalt zwischen 5 und 24 Gew.-% auf. Ein Wassergehalt von 6 bis 22 Gew.-% insbesondere zwischen 7 und 20 Gew.-% wird besonders bevorzugt.The anionic surfactant acids reacted in the process according to the invention have a water content between 5 and 24% by weight. A water content of 6 to 22 wt .-%, in particular between 7 and 20 wt .-% is particularly preferred.
Erfindungsgemäß werden im beschriebenen Verfahren Aniontensidsäuren eingesetzt, die 5 bis 24 Gew.-% Wasser enthalten. Hingegen wird bevorzugt in diesem Verfahren durch das Neutralisationsmittel weniger als 5 Gew.-% Wasser, bezogen auf das Neutralisationsmittel, in den Mischer eingebracht. Besonders bevorzugt ist ein Wasseranteil von weniger als 4 Gew.-%, insbesondere weniger als 3 Gew.-% im Neutralisationsmittel. In einer besonders bevorzugten Ausführungsform des Verfahrens enthält das Neutralisationsmittel 1-2 Gew.-% Wasser.
Ein solches Verfahren unterscheidet sich von typischen Verfahren des Standes der Technik, bei denen durch den Einsatz wasserhaltiger Neutralisationsmittel, wie wässrige Neutralisationsmittelpasten oder wässrige Lösungen von Neutratisationsmitteln, Wasser ins Reaktionsgemisch gelangt. Bei den Verfahren ist der Eintrag von Wasser in den Mischer durch den Einsatz der Aniontensidsäuren nicht beabsichtigt. Er kann jedoch nicht vollständig verhindert werden, da Aniontensidsäuren technisch bedingt bis zu 3 Gew.-% Wasser enthalten.According to the invention, anionic surfactant acids containing from 5 to 24% by weight of water are used in the process described. On the other hand, less than 5% by weight of water, based on the neutralizing agent, is preferably introduced into the mixer by the neutralizing agent in this process. Particularly preferred is a water content of less than 4 wt .-%, in particular less than 3 wt .-% in the neutralizing agent. In a particularly preferred embodiment of the process, the neutralizing agent contains 1-2% by weight of water.
Such a process differs from typical prior art processes in which water enters the reaction mixture through the use of water-containing neutralizing agents, such as aqueous neutralizing agent pastes or aqueous solutions of neutralizing agents. In the process, the entry of water into the mixer by the Use of anionic surfactant acids not intended. However, it can not be completely prevented since anionic surfactant acids contain up to 3% by weight of water for technical reasons.
Wie eingangs ausgeführt, lassen sich durch das erfindungsgemäße Verfahren sowohl Schüttgewichte, als auch die Korngrößenverteilung der Verfahrensprodukte gezielt einstellen.
In einer bevorzugten Ausführung des erfindungsgemäßen Verfahrens enthält die Aniontensidsäure 5 - 17 Gew.-% Wasser. Zu dieser Ausführung bevorzugt sind Wassergehalte der Säure, die zwischen 6 und 16 Gew.-%, besonders bevorzugt zwischen 7 und 15 Gew.-% und insbesondere zwischen 8 und 14 Gew.-% liegen. Ganz besonders bevorzugt ist eine Form des Verfahrens, in dem der Wassergehalt der Aniontensidsäure zwischen 9 und 13 Gew.-% und insbesondere zwischen 10 und 12 Gew.-% beträgt.
Wird der Wasseranteil der Aniontensidsäure aus dem im vorherigen Abschnitt beschriebenen Bereich zwischen 5 und 17 Gew.-% gewählt, werden nach der Neutralisation/Granulation Granulate mit niedrigen Schüttgewichten erhalten. Die Schüttgewichte liegen bevorzugt bei 300 - 600 g/l, besonders bevorzugt bei 400 - 600 g/l, insbesondere bei 500 - 600 g/l. Dabei beträgt der Anteil der Tensidgranulate, die vor der Aufbereitung eine Korngröße zwischen 100 und 800 µm aufweisen, in dieser bevorzugten Ausführung des Verfahrens mindestens 40 Gew.-%, vorzugsweise mindestens 47 Gew.-%, besonders bevorzugt mindestens 55 Gew.-%, ganz besonders bevorzugt mindestens 60 Gew.-% und insbesondere mindestens 70 Gew.-%.
Der Anteil der grobkörnigen Granulate mit Körngrößen zwischen 800 und 1600 µm beträgt vor der Aufbereitung bevorzugt mehr als 20 Gew.-%, besonders bevorzugt mehr als 25 Gew.-%, insbesondere mehr als 30 Gew.-%. Hingegen ist der Anteil an feinkörnigen Granulaten mit Korngrößen zwischen 100 und 200 µm bevorzugt kleiner als 17 Gew.-%, besonders bevorzugt kleiner als 14 Gew.-%, insbesondere zwischen 1 und 12 Gew.-%.
Bevorzugter Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Tensidgranulaten mit einem Schüttgewicht von 300 bis 600 g/l durch Neutralisation von Aniontensidsäuren sowie gegebenenfalls weiteren sauren Komponenten mit festen Neutralisationsmitteln, bei welchem die Aniontensidsäure(n) und das/die feste(n) Neutralisationsmittel in einem Freifallmischer agglomeriert, und gegebenenfalls nachträglich aufbereitet werden, dadurch gekennzeichnet, dass die Aniontensidsäure einen Wassergehalt zwischen 5 und 17 Gew.-% aufweist.As stated at the outset, bulk densities as well as the particle size distribution of the process products can be adjusted in a targeted manner by the process according to the invention.
In a preferred embodiment of the process according to the invention, the anionic surfactant acid contains 5-17% by weight of water. Water contents of the acid which are between 6 and 16% by weight, particularly preferably between 7 and 15% by weight and in particular between 8 and 14% by weight, are preferred for this embodiment. Very particular preference is given to a form of the process in which the water content of the anionic surfactant acid is between 9 and 13% by weight and in particular between 10 and 12% by weight.
If the water content of the anionic surfactant is selected from the range described in the previous section between 5 and 17 wt .-%, granules with low bulk densities are obtained after neutralization / granulation. The bulk densities are preferably 300-600 g / l, particularly preferably 400-600 g / l, in particular 500-600 g / l. In this case, the proportion of the surfactant granules which have a particle size between 100 and 800 μm before the preparation, in this preferred embodiment of the method, at least 40 wt .-%, preferably at least 47 wt .-%, particularly preferably at least 55 wt .-%, very particularly preferably at least 60% by weight and in particular at least 70% by weight.
The proportion of coarse-grained granules with grain sizes between 800 and 1600 microns before the preparation is preferably more than 20 wt .-%, more preferably more than 25 wt .-%, in particular more than 30 wt .-%. By contrast, the proportion of fine-grained granules with particle sizes between 100 and 200 .mu.m is preferably less than 17 wt .-%, more preferably less than 14 wt .-%, in particular between 1 and 12 wt .-%.
Preferred subject matter of the invention is a process for the preparation of surfactant granules having a bulk density of 300 to 600 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 5 and 17 wt .-%.
In einer weiteren bevorzugten Ausführung des erfindungsgemäßen Verfahrens enthält die Aniontensidsäure 10 - 24 Gew.-% Wasser. Zu dieser Ausführung bevorzugt sind Wassergehalte der Säure, die zwischen 11 und 23 Gew.-%, besonders bevorzugt zwischen 12 und 22 Gew.-% und insbesondere zwischen 13 und 21 Gew.-% liegen. Ganz besonders bevorzugt ist eine Form des erfindungsgemäßen Verfahrens, in dem der Wassergehalt der Aniontensidsäure zwischen 14 und 20 Gew.-% und insbesondere zwischen 15 und 19 Gew.-% beträgt.
Wird der Wasseranteil der Aniontensidsäure aus dem im vorherigen Abschnitt beschriebenen Bereich zwischen 10 und 24 Gew.-% gewählt, werden nach der Neutralisation/Granulation Granulate mit mittleren Schüttgewichten erhalten. Die Schüttgewichte liegen bevorzugt bei 500 - 800 g/l, besonders bevorzugt bei 500 - 700 g/l, insbesondere bei 500 - 600 g/l. Dabei beträgt der Anteil der Tensidgranulate, die vor der Aufbereitung eine Korngröße zwischen 100 und 800 µm aufweisen, in dieser bevorzugten Ausführung des Verfahrens mindestens 52 Gew.-%, vorzugsweise mindestens 62 Gew.-%, besonders bevorzugt mindestens 70 Gew.-%, ganz besonders bevorzugt mindestens 76 Gew.-% und insbesondere mindestens 80 Gew.-%.
In diesem bevorzugten Verfahren beträgt der Anteil der grobkörnigen Granulate mit Kömgrößen zwischen 800 und 1600 µm vor der Aufbereitung weniger als 20 Gew.-%, besonders bevorzugt weniger als 15 Gew.-%, insbesondere zwischen 1 und 10 Gew.-%. Hingegen ist der Anteil an feinkörnigen Granulaten mit Korngrößen zwischen 100 und 200 µm bevorzugt größer als 17 Gew.-%, besonders bevorzugt größer als 23 Gew.-%, insbesondere größer als 27 Gew.-%.
Bevorzugter Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Tensidgranulaten mit einem Schüttgewicht von 500 bis 800 g/l durch Neutralisation von Aniontensidsäuren sowie gegebenenfalls weiteren sauren Komponenten mit festen Neutralisationsmitteln, bei welchem die Aniontensidsäure(n) und das/die feste(n) Neutralisationsmittel in einem Freifallmischer agglomeriert, und gegebenenfalls nachträglich aufbereitet werden, dadurch gekennzeichnet, dass die Aniontensidsäure einen Wassergehalt zwischen 10 und 24 Gew.-% aufweist.In a further preferred embodiment of the method according to the invention, the anionic surfactant acid contains 10-24% by weight of water. Water contents are preferred for this embodiment the acid, which are between 11 and 23 wt .-%, more preferably between 12 and 22 wt .-% and in particular between 13 and 21 wt .-%. Very particular preference is given to a form of the process according to the invention in which the water content of the anionic surfactant acid is between 14 and 20% by weight and in particular between 15 and 19% by weight.
If the water content of the anionic surfactant is selected from the range described in the previous section between 10 and 24 wt .-%, granules with average bulk densities are obtained after neutralization / granulation. The bulk densities are preferably 500-800 g / l, particularly preferably 500-700 g / l, in particular 500-600 g / l. In this case, the proportion of the surfactant granules which have a particle size between 100 and 800 μm before the preparation, in this preferred embodiment of the process, at least 52 wt .-%, preferably at least 62 wt .-%, particularly preferably at least 70 wt .-%, most preferably at least 76 wt .-% and in particular at least 80 wt .-%.
In this preferred process, the proportion of coarse-grained granules having particle sizes between 800 and 1600 μm before preparation is less than 20% by weight, more preferably less than 15% by weight, in particular between 1 and 10% by weight. By contrast, the proportion of fine-grained granules with particle sizes between 100 and 200 .mu.m is preferably greater than 17 wt .-%, more preferably greater than 23 wt .-%, in particular greater than 27 wt .-%.
The preferred subject matter of the invention is a process for the preparation of surfactant granules having a bulk density of 500 to 800 g / l by neutralization of anionic surfactant acids and optionally further acidic components with solid neutralizing agents, in which the anionic surfactant acid (s) and the solid neutralizing agent (s) agglomerated in a free-fall mixer, and optionally subsequently processed, characterized in that the anionic surfactant acid has a water content between 10 and 24 wt .-%.
Die neutralisierte Form der Aniontensidsäuren, kurz die Aniontenside, können in variierenden Mengen in den nach dem erfindungsgemäßen Verfahren hergestellten Mitteln enthalten sein. Bevorzugte erfindungsgemäße Verfahren zeichnen sich dadurch aus, dass der Gehalt der Verfahrensprodukte an neutralisierten Aniontensidsäuren maximal 80 Gew.-%, vorzugsweise 8 bis 72 Gew.-%, besonders bevorzugt 10 bis 65 Gew.-% und insbesondere 15 bis 55 Gew.-% beträgt.The neutralized form of the anionic surfactant acids, in short the anionic surfactants, may be present in varying amounts in the compositions made by the process of the present invention. Preferred processes according to the invention are characterized in that the content of neutralized anionic surfactant acid in the process products is not more than 80% by weight, preferably from 8 to 72% by weight, more preferably from 10 to 65% by weight and in particular from 15 to 55% by weight. is.
Das erfindungsgemäße Verfahren eignet sich demnach zur Herstellung tensidreicher Granulate mit einem Tensidgehalt größer 40 Gew.-% ebenso wie zur Herstellung von vergleichsweise tensidarmen Granulaten.
Die tensidreichen Verfahrensprodukte enthalten bevorzugt neutralisierte Aniontensidsäuren in Gewichtsanteilen von 40 bis 80 Gew.-%, bevorzugt von 45 bis 75 Gew.-%, besonders bevorzugt von 50 bis 72 Gew.-% und insbesondere von 60 bis 70 Gew.-%. Diese Verfahrenprodukte werden bevorzugt in Wasch- und Reinigungsmittel-Konzentraten eingesetzt.
In einer weiteren bevorzugten Ausführung des erfindungsgemäßen Verfahrens werden tensidarme Verfahrensprodukte erhalten, in denen neutralisierte Aniontensidsäuren in Gewichtsanteilen von maximal 50 Gew.-%, bevorzugt zwischen 8 und 42 Gew.-%, besonders bevorzugt zwischen 10 und 35 Gew.-% und insbesondere zwischen 20 und 30 Gew.-% enthalten sind. Diese Verfahrenprodukte kommen vozugsweise bei der Herstellung von hochvolumigen Standardwasch- und reinigungsmitteln zum Einsatz.Accordingly, the process according to the invention is suitable for producing surfactant-rich granules having a surfactant content of greater than 40% by weight, as well as for producing comparatively low-surfactant granules.
The surfactant-rich process products preferably contain neutralized anionic surfactant acids in proportions by weight of 40 to 80 wt .-%, preferably from 45 to 75 wt .-%, particularly preferably from 50 to 72 wt .-% and in particular from 60 to 70 wt .-%. These process products are preferably used in detergent concentrates.
In a further preferred embodiment of the process according to the invention, surfactant-poor process products are obtained in which neutralized anionic surfactant acids in proportions by weight of not more than 50% by weight, preferably between 8 and 42% by weight, more preferably between 10 and 35% by weight and in particular between 20 and 30 wt .-% are included. These process products are preferably used in the production of high-volume standard washing and cleaning agents.
Als feste Neutralisationsmittel kommen für dieses Verfahren grundsätzlich alle dem Fachmann bekannten Neutralisationsmittel in Betracht. In bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens kommen als Neutralisationsmittel eine oder mehrere Substanzen der Verbindungen Natriumcarbonat, Natriumhydroxid, Natriumsesquicarbonat, Kaliumhydroxid und/oder Kaliumcarbonat zum Einsatz.Suitable solid neutralizing agents are in principle all neutralizing agents known to the person skilled in the art for this process. In preferred embodiments of the process according to the invention, one or more substances of the compounds sodium carbonate, sodium hydroxide, sodium sesquicarbonate, potassium hydroxide and / or potassium carbonate are used as neutralizing agents.
Alternativ oder in Ergänzung zur Kombination unterschiedlicher fester Neutralisationsmittel können dem Neutralisationsmittel auch an der Reaktion nicht teilnehmende Komponenten, insbesondere Trägermaterialien, zugesetzt werden. Diese sollten dann eine hinreichende Stabilität gegenüber den zugesetzten Säuren aufweisen, um lokale Zersetzung und damit unerwünschte Verfärbung oder anderweitige Belastung des Produkts zu vermeiden. Hier sind Verfahren bevorzugt, bei denen weitere Feststoffe aus den Gruppen der Silikate, Aluminiumsilikate, Sulfate, Citrate und/oder Phosphate eingesetzt werden. Insbesondere ist es bevorzugt, dass Natriumsulfat, das auch heute noch in einigen Ländern bis zu 45 Gew.-% in den Waschmitteln enthalten ist, dem/den festen Neutralisationsmittel(n) beigemischt wird.Alternatively or in addition to the combination of different solid neutralizing agents, components which do not take part in the reaction, in particular support materials, may also be added to the neutralizing agent. These should then have sufficient stability against the added acids to avoid local decomposition and thus unwanted discoloration or other loading of the product. Here are preferred processes in which further solids from the groups of silicates, aluminum silicates, sulfates, citrates and / or phosphates are used. In particular, it is preferred that sodium sulfate, which is still present today in some countries up to 45 wt .-% in the detergents, the / the solid neutralizing agent (s) is admixed.
Das Gewichtsverhältnis des/der in dem erfindungsgemäßen Verfahren eingesetzten festen Neutralisationsmittels/n einschließlich möglicher Zusätze zu der/den eingesetzten Aniontensidsäure(n) sowie gegebenenfalls weiteren sauren Komponenten kann in weiten Grenzen variieren.The weight ratio of the solid neutralizing agent (s) used in the process according to the invention, including possible additions to the anionic surfactant acid (s) used and optionally further acidic components, can vary within wide limits.
Bevorzugt werden hier erfindungsgemäße Verfahren, bei denen das Gewichtsverhältnis des/der in dem erfindungsgemäßen Verfahren eingesetzten festen Neutralisationsmittels/n zu der/den eingesetzten Aniontensidsäure(n) sowie gegebenenfalls weiteren sauren Komponenten zwischen 100:1 und 1:5, vorzugsweise zwischen 80:1 und 1:4, bevorzugt zwischen 60:1 und 1:3, ganz besonders bevorzugt zwischen 40:1 und 1:2 und insbesondere zwischen 20:1 und 1:1 beträgt.Preference is given here to processes according to the invention in which the weight ratio of the solid neutralizing agent (s) used in the process according to the invention to the anionic surfactant acid (s) used and optionally other acidic components is between 100: 1 and 1: 5, preferably between 80: 1 and 1: 4, preferably between 60: 1 and 1: 3, very particularly preferably between 40: 1 and 1: 2 and in particular between 20: 1 and 1: 1.
Das einzusetzende Neutralisationsmittel enthält bevorzugt weniger als 5 Gew.-% freies Wasser. Besonders bevorzugt ist ein Wasseranteil von weniger als 4 Gew.-%, insbesondere weniger als 3 Gew.-%. In einer besonders bevorzugten Ausführungsform des Verfahrens enthält das Neutralisationsmittel weniger als 2 Gew.-% freies Wasser. Mit besonderem Vorzug werden Neutralisationsmittel eingesetzt, die einen Gehalt an freiem, d.h. nicht in Form von Hydratwasser und/oder Konstitutionswasser vorliegendem Wasser unterhalb 1 Gew.-%, vorzugsweise unterhalb 0,5 Gew.-% und insbesondere kein freies Wasser aufweisen.The neutralizing agent to be used preferably contains less than 5% by weight of free water. Particularly preferred is a water content of less than 4 wt .-%, in particular less than 3 wt .-%. In a particularly preferred embodiment of the process, the neutralizing agent contains less than 2% by weight of free water. Particular preference is given to using neutralizing agents which have a content of free, i. not present in the form of water of hydration and / or water of constitution below 1 wt .-%, preferably below 0.5 wt .-% and in particular no free water.
Das im obigen Abschnitt beschriebene Neutralisationsmittel wird im Freifallmischer mit Aniontensidsäure enthaltend 5 bis 24 Gew.-% Wasser vermischt. Durch die Wahl des Gewichtsverhältnisses zwischen Neutralisationsmittel und Wasser wird die Lagerfähigkeit und das Lösungsverhalten sowie das Schüttgewicht der Granulate und die Verteilung der Korngrößen beeinflusst. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens beträgt das Gewichtsverhältnis des eingesetzten festen Neutralisationsmittels zu dem mit der Aniontensidsäure eingetragenem Wasser zwischen 800:1 und 2:3. Bevorzugt wird ein Verhältnis der anteiligen Gewichte zwischen 199:1 und 1:1, insbesondere zwischen 99:1 und 15:7. In einer besonders bevorzugten Ausführung des Verfahrens beträgt das Verhältnis der anteiligen Gewichte von Neutralisationsmittel und Wasser zwischen 19:1 und 19:6.The neutralizing agent described in the above section is mixed in the free-fall mixer with anionic surfactant acid containing 5 to 24 wt .-% of water. The choice of the weight ratio between neutralizing agent and water influences the storability and the dissolution behavior as well as the bulk density of the granules and the distribution of the particle sizes. In a preferred embodiment of the process according to the invention, the weight ratio of the solid neutralizing agent used to the water introduced with the anionic surfactant acid is between 800: 1 and 2: 3. Preference is given to a ratio of the proportionate weights between 199: 1 and 1: 1, in particular between 99: 1 and 15: 7. In a particularly preferred embodiment of the method, the ratio of the proportionate weights of neutralizing agent and water is between 19: 1 and 19: 6.
Der Wassergehalt der Verfahrensendprodukte, bestimmt durch Trocknungsverlust bei 120°C, beträgt vorzugsweise kleiner 26 Gew.-%, bevorzugt 1 - 15 Gew.-%, besonders bevorzugt 1 - 10 Gew.-% und insbesondere 4 - 5 Gew.-%.
Bei der Neutralisationsreaktion entsteht naturgemäß Wasser. Um Verfahrensprodukte mit einem Gesamtwassergehalt kleiner 26 Gew.-% zu gewährleisten sollte eine Verfahrensführung gewählt werden, bei der statt Wasser und CO2 hauptsächlich Natriumhydrogencarbonat gebildet wird. Diese Verfahrensführung wird weiter unten beschrieben.The water content of the process end products, determined by drying loss at 120 ° C., is preferably less than 26% by weight, preferably 1-15% by weight, more preferably 1-10% by weight and in particular 4-5% by weight.
The neutralization reaction naturally produces water. In order to ensure process products having a total water content of less than 26% by weight, a process procedure should be chosen in which, instead of water and CO 2, mainly sodium bicarbonate is formed. This procedure will be described below.
Kennzeichnend für das erfindungsgemäße Verfahren ist der Einsatz von Freifallmischern zur Durchführung der Neutralisation von Aniontensidsäuren mit festen Neutralisationsmitteln. Dabei können die Freifallmischer kontinuierlich oder diskontinuierlich betrieben werden.Characteristic of the process according to the invention is the use of free-fall mixers for carrying out the neutralization of anionic surfactant acids with solid neutralizing agents. The free-fall mixers can be operated continuously or discontinuously.
Als Freifallmischer werden im Rahmen der vorliegenden Erfindung solche Mischer bezeichnet, in welchen das Mischgut durch Wandreibung hochgenommen wird und anschließend aufgrund der eigenen Schwerkraft frei durch den Mischerraum fällt. Derartige Freifallmischer weisen ein bewegliches bzw. rotierendes Reaktorgehäuse, bzw. einen bewegten Mischbehälter auf. Als Behälter eignen sich solche mit einfachen geometrischen Formen (Zylinder, Einfach- oder Doppelkonus, Würfel u.ä.). Bevorzugte Mischbehälter weisen zudem möglichst stumpfwinkelige innere Ecken auf, da hierdurch sowohl die freie Bewegung des Mischguts als auch die Entleerung und Reinigung des Behälters nach Beendigung des Verfahrens erleichtert wird. Die Bewegung des Behälters muss sich so auf das Mischgut im Inneren übertragen, so dass ein möglichst unregelmäßiges Durcheinanderwerfen und Auflockern der Reaktionsmischung erfolgt.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens bildet das in dem Freifallmischer bewegte feste Neutralisationsmittel einen fallenden Pulvervorhang, auf welchen die Aniontensidsäuren aufgesprüht werden.In the context of the present invention, such a mixer is referred to as a free-fall mixer in which the mix is taken up by wall friction and subsequently falls freely through the mixing space due to its own gravity. Such free-fall mixers have a movable or rotating reactor housing or a moving mixing vessel. Suitable containers are those with simple geometric shapes (cylinder, single or double cone, cube, etc.). In addition, preferred mixing containers have as far as possible obtuse-angled inner corners, since this facilitates both the free movement of the mixed material and the emptying and cleaning of the container after the end of the process. The movement of the container must be transferred to the mix in the interior, so that the most irregular possible confusion and loosening of the reaction mixture takes place.
In a preferred embodiment of the method according to the invention, the solid neutralizing agent moving in the tumbling mixer forms a falling powder curtain onto which the anionic surfactant acids are sprayed.
Als Bewegungsarten für den Freifallmischer eignet sich insbesondere das Rotieren um eine Behälterachse (Trommel- oder Drehrohr-Mischer) bzw. um Achsen, die nicht mit geometrischen Achsen des Behälters übereinstimmen oder zu dessen Symetrieebenen senkrecht sind (Taumelmischer), oder das Vibrieren, vorzugsweise mit hoher Amplitude und geringer Frequenz sowie wechselnden Richtungen der Ausschläge, so dass unregelmäßig schüttelnde oder taumelnde Bewegungen auftreten.
In einem bevorzugten Verfahren muss eine gerichtete Bewegungskomponente auftreten um den kontinuierlichen Stofftransport zu gewährleisten und um so ein kontinuierliches Verfahren zu ermöglichen. In gleichem Maße bevorzugt ist ein diskontinuierliches Verfahren, wobei eine gerichtete Bewegungskomponente nicht gewünscht ist.The types of movement for the free-fall mixer are, in particular, rotation about a container axis (drum or rotary tube mixer) or about axes that do not coincide with geometric axes of the container or perpendicular to its symmetry planes (tumble mixer), or vibrate, preferably with high amplitude and low frequency and changing directions of the rashes, so that irregular shaking or tumbling movements occur.
In a preferred method, a directed component of motion must occur to ensure the continuous mass transfer and thus to allow a continuous process. Equally preferred is a discontinuous process wherein a directional component of motion is not desired.
Für den kontinuierlichen Betrieb sind insbesondere solche Freifallmischer besonders geeignet, die um ihre horizontale, vorzugsweise um ihre wenig geneigte Achse rotieren. Durch die Neigung der Rotationsachse weist das Mischgut aufgrund der eigenen Schwerkraft eine gerichtete Bewegung auf, welche eine kontinuierlichen Austrag des Mischguts aus dem Mischer ermöglicht. Eine solche gerichtete Bewegung kann außer durch die Neigung der Rotationsachse selbstverständlich auch durch einen kontinuierlichen Eintrag von Aniontensidsäuren und festem Neutralisationsmittel erzeugt werden. Für die Produkteigenschaften, insbesondere für die Einstellung des Schüttgewichts und der Löslichkeit der Reaktionsprodukte hat es sich als vorteilhaft erwiesen, wenn der Neigungswinkel der Rotationsachse eines bevorzugt eingesetzten drehbaren Behälters mit einer bestimmten Umdrehungszahl korreliert. Es werden daher solche erfindungsgemäße Verfahren besonders bevorzugt, in welchen der drehbare Behälter des Freifallmischers einen Neigungswinkel α von 0 bis 20 °, insbesondere von 0 bis 15 °, ganz besonders bevorzugt von 1 bis 15° aufweist und die Bewegung des drehbaren Behälters des Freifallmischers über den Antrieb gleichzeitig auf 20 bis 70 Umdrehungen pro Minute und insbesondere auf 30 bis 60 Umdrehungen pro Minute eingestellt wird.Particularly suitable for continuous operation are those free-fall mixers which rotate about their horizontal, preferably about their little inclined axis. Due to the inclination of the axis of rotation, the mixture due to its own gravity on a directed movement, which allows a continuous discharge of the mix from the mixer. Such a directed movement can except by the inclination of the axis of rotation of course also be generated by a continuous input of anionic surfactant acids and solid neutralizing agent. For the product properties, in particular for the adjustment of the bulk density and the solubility of the reaction products, it has proven to be advantageous if the angle of inclination of the axis of rotation of a preferably used rotatable container with a certain number of revolutions correlates. Therefore, such inventive method are particularly preferred in which the rotatable container of the tumbler mixer has an inclination angle α of 0 to 20 °, in particular from 0 to 15 °, most preferably from 1 to 15 ° and the movement of the rotatable container of the tumbler over the drive is set simultaneously to 20 to 70 revolutions per minute and in particular to 30 to 60 revolutions per minute.
Im Rahmen der vorliegenden Erfindung bevorzugte Freifallmischer sind Trommelmischer, Taumelmischer, Konusmischer, Doppelkonusmischer oder V-Mischer. Die erfindungsgemäß eingesetzten Freifallmischer bieten bei rotierenden oder taumelnden Bewegungen dem in Inneren hochgetragenen und wieder herabfallenden Gut wechselnd geneigte Wände und damit Umlenkung, Erweiterung oder Verengung des Raums, Verschiebung und Teilung des Gutstroms. Derartige Reaktoren können weiterhin statische und/oder bewegliche Misch-und/oder Schneidwerkzeuge aufweisen. Bevorzugt werden jedoch rotierende Reaktoren, in welchen das Mischgut durch Wandreibung hochgenommen wird und anschließend aufgrund der eigenen Schwerkraft frei durch den Mischerraum fällt.Free-fall mixers preferred in the context of the present invention are drum mixers, tumble mixers, cone mixers, double-cone mixers or V mixers. The free-fall mixers used in accordance with the invention provide, in the case of rotating or tumbling movements, walls alternately upraised and falling back inside, and thus diversion, widening or narrowing of the space, displacement and division of the material flow. Such reactors may further comprise static and / or mobile mixing and / or cutting tools. However, preference is given to rotating reactors in which the mix is taken up by wall friction and then falls freely through the mixer chamber due to its own gravity.
Besonders bevorzugt werden erfindungsgemäße Verfahren, in welchen als Freifallmischer Doppelkonusmischer mit drehbaren Behälter ohne Mischwerkzeuge eingesetzt werden, wobei die kontinuierlich betriebenen Doppelkonusmischer in eine Mischzone und eine Nachmischzone unterteilt sind und eine Abschlagleiste aufweisen, die an einer Stirnplatte befestigt ist und von dort aus die gesamte Mischzone durchquert und gegebenenfalls in die Nachmischzone hineinreicht. Bei den besonders bevorzugt eingesetzten Doppelkonusmischem beträgt das Verhältnis der Länge der Mischzone zur Länge der Nachmischzone vorzugsweise mindestens 1:1.Particular preference is given to processes according to the invention in which double-cone mixers with rotatable containers without mixing tools are used as free-fall mixers, wherein the continuously operated double-cone mixers are subdivided into a mixing zone and a post-mixing zone and have a knock-off strip which is fastened to an end plate and from there the entire mixing zone passes through and if necessary extends into the post-mixing zone. In the case of the double-cone mixers used with particular preference, the ratio of the length of the mixing zone to the length of the post-mixing zone is preferably at least 1: 1.
Die Abschlagleiste kann eine Breite von 50 bis 150 mm, vorzugsweise von 75 bis 130 mm aufweisen. Die obere Kante der Abschlagleiste weist eine Entfernung zur inneren Mischerwand auf, welche vorzugsweise maximal 10% des Trommeldurchmessers der engsten Stelle des drehbaren Behälters, vorzugsweise maximal 5% der engsten Stelle des drehbaren Behälters und insbesondere weniger als 2,5% der engsten Stelle des drehbaren Behälters ausmacht. In der Nachmischzone kann der Abstand zur nächstliegenden inneren Mischerwand durchaus größer sein als in der Mischzone; Werte zwischen 100 und 300 mm sind durchaus üblich.The tee bar may have a width of 50 to 150 mm, preferably from 75 to 130 mm. The top edge of the stripper has a distance from the internal mixer wall which is preferably at most 10% of the drum diameter of the narrowest point of the rotatable container, preferably at most 5% of the narrowest point of the rotatable container and more preferably less than 2.5% of the narrowest point of the rotatable container container accounts. In the post-mixing zone, the distance to the nearest inner mixer wall may well be greater than in the mixing zone; Values between 100 and 300 mm are quite common.
Die Verweilzeit des Reaktionsgemischs im Freifallmischer beträgt in bevorzugten Ausführungsformen des vorliegenden erfindungsgemäßen Verfahrens vorzugsweise weniger als 20 Minuten, bevorzugt zwischen 1 und 600 Sekunden, besonders bevorzugt zwischen 1 und 300 Sekunden und insbesondere zwischen 1 und 120 Sekunden.The residence time of the reaction mixture in the free-fall mixer in preferred embodiments of the present inventive method is preferably less than 20 minutes, preferably between 1 and 600 seconds, more preferably between 1 and 300 seconds and in particular between 1 and 120 seconds.
Unabhängig davon, ob eine einzige Aniontensidsäure oder mehrere Aniontensidsäuren - gegebenenfalls in Mischung mit weiteren sauren oder säurestabilen Inhaltsstoffen - auf das feste Neutralisationsmittel bzw. die Mischung aus mehreren Feststoffen gegeben wird bzw. werden, ist es bevorzugt, dass die Temperatur der aufzugebenden Mischung möglichst niedrig ist. Hier sind erfindungsgemäße Verfahren bevorzugt, bei denen die flüssige, saure Komponente beim Eintrag in den Freifallmischer eine Temperatur von 20 bis 60 °C, vorzugsweise von 30 bis 55 °C und insbesondere von 40 bis 50 °C aufweist.Regardless of whether a single anionic surfactant acid or more anionic surfactant acids - optionally mixed with other acid or acid-stable ingredients - is given to the solid neutralizing agent or the mixture of several solids, it is preferred that the temperature of the mixture to be applied as low as possible is. In this case, preference is given to processes according to the invention in which the liquid, acidic component has a temperature of from 20 to 60.degree. C., preferably from 30 to 55.degree. C. and in particular from 40 to 50.degree. C., when introduced into the free-fall mixer.
Wird in einem bevorzugten Verfahren Natriumcarbonat als Neutralisationsmittel eingesetzt, so ist es durch die Einhaltung dieser Temperaturvorgaben bei einem gegebenen Verhältnis von Aniontensidsäure zu Natriumcarbonat insbesondere möglich, den Anteil der Verfahrensprodukte an Natriumhydrogencarbonat zu kontrollieren. Als "flüssige, saure Komponente" wird dabei die Aniontensidsäure, welche Wasser und gegebenenfalls weitere saure Komponenten umfasst, bezeichnet.If sodium carbonate is used as the neutralizing agent in a preferred process, it is possible, in particular, to control the proportion of the sodium hydrogencarbonate in the process by maintaining these temperature specifications given a ratio of anionic surfactant acid to sodium carbonate. The term "liquid, acidic component" refers to the anionic surfactant acid, which comprises water and optionally further acidic components.
Bei der Durchführung eines bevorzugten erfindungsgemäßen Verfahrens wird die Reaktion zwischen Aniontensidsäure(n) und Natriumcarbonat so geführt, dass die Reaktion
Na2CO3 + 2 Aniontensid-H → 2 Aniontensid-Na + CO2 + H2O
weitgehend unterdrückt wird und an ihrer Stelle die Reaktion
Na2CO3 + Aniontensid-H → Aniontensid-Na + NaHCO3
eintritt,
Das Natriumcarbonat wird hierbei im Überschuss eingesetzt, so dass unumgesetztes Natriumcarbonat im Produkt verbleibt, während bei der Reaktion zusätzlich Natriumhydrogencarbonat entsteht. Die Menge an Natriumcarbonat im Mittel (bezogen auf das Mittel, ohne Berücksichtigung gegebenenfalls vorhandener Hydratwassergehalte) wird zur Menge an Natriumhydrogencarbonat im Mittel (bezogen auf das Mittel, ohne Berücksichtigung gegebenenfalls vorhandener Hydratwassergehalte) in Relation gesetzt.
In bevorzugten Ausführungsformen der vorliegenden Erfindung liegt das Massenverhältnis von Natriumcarbonat zu Natriumhydrogencarbonat innerhalb engerer Grenzen, wobei bei erfindungsgemäß bevorzugten Verfahren das Gewichtsverhältnis von Natriumcarbonat zu Natriumhydrogencarbonat in den Verfahrensendprodukten 50:1 bis 5:1, vorzugsweise 40:1 bis 5,1:1, besonders bevorzugt 35:1 bis 5,2:1 und insbesondere 30:1 bis 5,25:1, beträgt.In carrying out a preferred process according to the invention, the reaction between anionic surfactant (s) and sodium carbonate is conducted so that the reaction
Na 2 CO 3 + 2 anionic surfactant H → 2 anionic surfactant Na + CO 2 + H 2 O
is largely suppressed and in their place the reaction
Na 2 CO 3 + anionic surfactant H → anionic surfactant Na + NaHCO 3
entry,
The sodium carbonate is in this case used in excess, so that unreacted sodium carbonate remains in the product, while sodium bicarbonate in the reaction arises. The amount of sodium carbonate on average (based on the agent, without consideration of any water of hydration present) is related to the amount of sodium bicarbonate on average (based on the agent, without consideration of any water of hydration present).
In preferred embodiments of the present invention, the mass ratio of sodium carbonate to sodium bicarbonate is within narrow limits, and in preferred processes according to the invention the weight ratio of sodium carbonate to sodium bicarbonate in the process end products is 50: 1 to 5: 1, preferably 40: 1 to 5.1: 1, particularly preferably 35: 1 to 5.2: 1 and in particular 30: 1 to 5.25: 1.
Eine weitere Möglichkeit, die Bildung von Natriumhydrogencarbonat zu begünstigen und die Bildung von Kohlendioxid und Wasser zu vermeiden, besteht in der Einhaltung möglichst niedriger Temperaturen. Dies kann beispielsweise durch Kühlung, aber auch durch eine geeignete Verfahrensführung oder die Abstimmung der Mengen der Reaktanden erreicht werden. Hier sind erfindungsgemäße Verfahren bevorzugt, bei denen die Temperatur während des Verfahrens unterhalb von 100°C, vorzugsweise unterhalb von 80°C, besonders bevorzugt unterhalb von 60°C und insbesondere unterhalb von 50°C, gehalten wird.Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or the coordination of the amounts of the reactants. Here, preference is given to processes according to the invention in which the temperature during the process is kept below 100 ° C., preferably below 80 ° C., more preferably below 60 ° C. and in particular below 50 ° C.
In Abhängigkeit von den eingesetzten Mengen an Natriumcarbonat und Aniontensidsäure(n) kann der Gehalt der Verfahrensendprodukte an Natriumhydrogencarbonat variieren. Bei bevorzugten erfindungsgemäße Verfahren beträgt der Gehalt der Verfahrensendprodukte an Natriumhydrogencarbonat 0,01 bis 20 Gew.-%, vorzugsweise 0,1 bis 15 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-% und insbesondere 1 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Verfahrensendprodukte. In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens beträgt der Gehalt der Verfahrensendprodukte an Natriumhydrogencarbonat zwischen 2 und 10 Gew.-%, vorzugsweise zwischen 2,5 und 10 Gew.-%, besonders bevorzugt zwischen 3 und 10 Gew.-% und insbesondere zwischen 4 und 10 Gew.-%.Depending on the amounts of sodium carbonate and anionic surfactant acid (s) used, the content of the process end products can vary with respect to sodium bicarbonate. In the preferred process according to the invention, the content of the process end products of sodium hydrogencarbonate is from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight and in particular from 1 to 10% by weight. -%, in each case based on the total weight of the process end products. In a particularly preferred embodiment of the process according to the invention, the content of the process end products of sodium bicarbonate is between 2 and 10% by weight, preferably between 2.5 and 10% by weight, more preferably between 3 and 10% by weight and in particular between 4 and 10% by weight.
Nach Beendigung des Mischvorgangs kann das Granulat bei Bedarf nachbehandelt werden. Dazu wird im Falle eines kontinuierlichen Verfahrens das Tensidgranulat nach dem Durchlaufen der Nachmischzone entweder direkt über den Austrag ausgetragen oder über eine Fördervorrichtung weitertransportiert.
Wie im Falle eines kontinuierlichen Mischvorgangs ist es bei Nutzung eines Chargenverfahrens möglich, die Nachbehandlung des Tensidgranulates kontinuierlich oder diskontinuierlich durchzuführen. Dabei ist es besonders bevorzugt, an ein chargenweise betriebenes Mischverfahren eine ebenfalls chargenweise Nachbehandlung anzuschließen, die den Verbleib der Tensidgranulate in dem ursprünglichen Reaktor ermöglicht.After completion of the mixing process, the granules can be aftertreated if necessary. For this purpose, in the case of a continuous process, the surfactant granules, after passing through the post-mixing zone, are either discharged directly via the discharge or transported on via a conveying device.
As in the case of a continuous mixing process, it is possible when using a batch process, the aftertreatment of the surfactant granules continuously or discontinuously perform. It is particularly preferred to connect to a batchwise operated mixing a likewise batchwise aftertreatment, which allows the whereabouts of the surfactant granules in the original reactor.
Unter der Bezeichnung "Nachbehandlung" werden im Rahmen der vorliegenden Anmeldung dabei insbesondere die Sprühgranulation, das heißt, der weitere Zusatz flüssiger Bindemittel, die Verkapselung, die Abpuderung mit Oberflächenmodifizierern, die Beaufschlagung mit nichtionischen Tensiden, die Trocknung oder die Sprühtrocknung, die Kühlung, sowie die Abtrennung von Grob- und/oder Feinanteilen zusammengefasst.The term "aftertreatment" in the context of the present application, in particular the spray granulation, that is, the further addition of liquid binder, the encapsulation, the powdering with surface modifiers, the application of nonionic surfactants, drying or spray drying, cooling, and the separation of coarse and / or fines is summarized.
Als Abpuderungsmittel oder Oberflächenmodifizierer können alle bekannten, feinteiligen Vertreter dieser Gruppe über eine Feststoffzuführung zugegeben werden. Bevorzugt werden hierbei amorphe und/oder kristalline Aluminosilikate, wie Zeolith A, X und/oder P, verschiedene Arten von Kieselsäuren, Calciumstearat, Carbonate, Sulfate, aber auch feinteilige Compounds, beispielsweise aus amorphen Silikaten und Carbonaten.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid pro Mol Alkohol, Alkylglykoside der allgemeinen Formel RO(G)x, alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, Aminoxide und Polyhydroxyfettsäureamide eingesetzt.
Zur Trocknung wird bevorzugt Heißluft eingesetzt. Die Kühlung erfolgt vorzugsweise durch Kaltluft oder Trockeneis.
Abgetrennte Grob- und/oder Feinanteile werden bevorzugt in den Prozess zurückgeführt, wobei vorzugsweise der Grobanteil vor der Rückführung in den Freifallmischer vermahlen wird.As a powdering agent or surface modifier, all known, finely divided representatives of this group can be added via a solids feed. Amorphous and / or crystalline aluminosilicates, such as zeolite A, X and / or P, various types of silicas, calcium stearate, carbonates, sulfates, but also finely divided compounds, for example of amorphous silicates and carbonates, are preferred here.
As nonionic surfactants are preferably alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, alkyl glycosides of the general formula RO (G) x , alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, amine oxides and polyhydroxy fatty acid amides used.
For drying hot air is preferably used. The cooling is preferably carried out by cold air or dry ice.
Separated coarse and / or fines are preferably recycled to the process, preferably the coarse fraction being ground before being returned to the tumble mixer.
Zur Nachbehandlung zählt aber selbstverständlich wiederum auch die "Nachreifung" eines Produktes, also beispielsweise die Beendigung der chemischen Reaktion bei der Durchführung von Neutralisationsreaktionen. In einer bevorzugten Variante des erfindungsgemäßen Verfahrens umfasst die Nachbehandlung eine Sprühgranulation und/oder eine Verkapselung und/oder eine Abpuderung mit Oberflächenmodiflzierern und/oder eine Beaufschlagung mit nichtionischen Tensiden und/oder eine Trocknung und/oder eine Sprühtrocknung auf Inertkörper und/oder eine Kühlung und/oder eine Abtrennung von Grob- und/oder Feinanteilen.For the aftertreatment, however, it goes without saying that the "post-maturation" of a product, that is, for example, the termination of the chemical reaction when carrying out neutralization reactions, also counts. In a preferred variant of the method according to the invention, the aftertreatment comprises a spray granulation and / or an encapsulation and / or a powdering with Oberflächenmodiflzierern and / or an exposure to nonionic surfactants and / or drying and / or spray drying on inert bodies and / or cooling and / or a separation of coarse and / or fines.
Die Nachbehandlung der Verfahrensprodukte nach dem Austrag aus dem Freifallmischer auf einer Reaktionsstrecke ist ein Kennzeichen besonders bevorzugter Ausführungsformen des vorliegenden erfindungsgemäßen Verfahrens, wobei wiederum solche Verfahrensvarianten ganz besonders bevorzugt werden, bei denen es sich bei der Reaktionsstrecke um eine pneumatische Wirbelschicht und/oder ein Transportband und /oder um einen Mischer handelt. Führt diese Förder- und Dosierschnecke bis in die Nachmischzone hinein (möglich ist auch ein direkter Anschluss der Fördervorrichtung an die Austragseinheit), so ist es bevorzugt, dass die Schnecke nur maximal in die zweite Längenhälfte der Nachmischzone und damit nicht in den Teil der Nachmischzone hineinragt, der noch die Abschlagleiste beinhaltet.The aftertreatment of the process products after discharge from the free-fall mixer on a reaction section is a characteristic of particularly preferred embodiments of the present inventive method, again such method variants are particularly preferred in which it is in the reaction section to a pneumatic fluidized bed and / or a conveyor belt and / or is a mixer. If this conveying and metering screw leads into the post-mixing zone (a direct connection of the conveying device to the discharge unit is also possible), then it is preferred that the screw only projects maximally into the second length half of the post-mixing zone and thus not into the part of the post-mixing zone that still includes the tee bar.
Die Verweilzeit in der Nachmischzone beträgt vorzugsweise zwischen 1 und 19 Minuten, bevorzugt zwischen 2 und 17 Minuten, ganz besonders bevorzugt zwischen 3 und 14 Minuten, insbesondere zwischen 3 und 10 Minuten.The residence time in the post-mixing zone is preferably between 1 and 19 minutes, preferably between 2 and 17 minutes, very particularly preferably between 3 and 14 minutes, in particular between 3 and 10 minutes.
Die nach dem erfindungsgemäßen Verfahren hergestellten Mittel können in Abhängigkeit von dem Gehalt der einzelnen Inhaltsstoffe, insbesondere des Wassers, und anderen Verfahrensparametem unterschiedliche Schüttgewichte aufweisen. Bevorzugt sind Ausführungen des erfindungsgemäßen Verfahren, bei denen das Schüttgewicht der Verfahrensendprodukte 300 bis 800 g/l, bevorzugt 350 bis 700 g/l, besonders bevorzugt 400 bis 650 g/l und insbesondere 500 bis 600 g/l beträgt.The agents prepared by the process according to the invention may have different bulk densities depending on the content of the individual ingredients, in particular of the water, and other Verfahrensparametem. Preference is given to embodiments of the process according to the invention in which the bulk density of the process end products is from 300 to 800 g / l, preferably from 350 to 700 g / l, more preferably from 400 to 650 g / l and in particular from 500 to 600 g / l.
Die erhaltenen Granulate weisen im Vergleich zum im Stand der Technik beschriebenen Granulaten eine erhöhte Löslichkeit in Wasser/wässrigen Lösungen sowie eine erhöhte Lagerfähigkeit auf. Sowohl das Verkleben von einzelnen Granulaten als auch die Entmischung einer Granulatmenge nach Bewegung (Kippen/Schütteln) des Vorratsbehälters wurden nicht beobachtet.The granules obtained have an increased solubility in water / aqueous solutions and an increased shelf life compared to the granules described in the prior art. Both the sticking of individual granules and the segregation of a quantity of granules after movement (tilting / shaking) of the storage container were not observed.
Diese Verfahrensprodukte weisen weiterhin eine Korngrößenverteilung mit einer mittleren Korngröße d50 unterhalb 5000 µm, bevorzugt zwischen 20 und 3000 µm, besonders bevorzugt zwischen 40 und 2000 µm und insbesondere zwischen 50 und 1600 µm auf.These process products furthermore have a particle size distribution with an average particle size d 50 below 5000 μm, preferably between 20 and 3000 μm, more preferably between 40 and 2000 μm and in particular between 50 and 1600 μm.
Vorzugsweise weisen die Tensidgranulate mit einer Korngröße zwischen 100 und 1600 µm vor der Aufbereitung einen Gewichtsanteil von mindestens 80 Gew.-%, vorzugsweise mindestens 82 Gew.-%, besonders bevorzugt mindestens 85 Gew.-%, ganz besonders bevorzugt mindestens 90 Gew.-% und insbesondere mindestens 95 Gew.-% auf. Dabei werden Tensidgranulate, die vor der Aufbereitung eine Korngröße zwischen 100 und 800 µm aufweisen, in den erfindungsgemäßen Verfahren in Gewichtsanteilen von mindestens 52 Gew.-%, vorzugsweise mindestens 62 Gew.-%, besonders bevorzugt mindestens 70 Gew.-%, ganz besonders bevorzugt mindestens 76 Gew.-% und insbesondere mindestens 80 Gew.-% erhalten.The surfactant granules having a particle size between 100 and 1600 μm preferably have a weight fraction of at least 80% by weight, preferably at least 82% by weight, particularly preferably at least 85% by weight, very particularly preferably at least 90% by weight. % and in particular at least 95 wt .-% on. It will be Surfactant granules which have a particle size between 100 and 800 microns prior to the preparation, in the inventive method in proportions by weight of at least 52 wt .-%, preferably at least 62 wt .-%, more preferably at least 70 wt .-%, most preferably at least 76 wt .-% and in particular at least 80 wt .-%.
Die nach dem erfindungsgemäßen Verfahren hergestellten Tensidgranulate eignen sich in besonderer Weise zur Herstellung von Wasch- oder Reinigungsmitteln, insbesondere fester Wasch- oder Reinigungsmittel, beispielsweise durch weitergehende Agglomeration, durch Extrusion oder Kompaktierung. Derartige Wasch- oder Reinigungsmittel enthalten neben den bisher genannten Inhaltsstoffen wie den Aniontensidsäuren weitere Bestandteile, insbesondere aus der Gruppe der Builder, Cobuilder, Bleichmittel, Bleichaktivatoren, Farb- und Duftstoffe, optischen Aufheller, Enzyme, soil-release-Polymere usw.. Diese Stoffe werden nachstehend der Vollständigkeit halber beschrieben.The surfactant granules prepared by the process according to the invention are particularly suitable for the production of detergents or cleaners, in particular solid detergents or cleaners, for example by further agglomeration, by extrusion or compaction. Such washing or cleaning agents contain in addition to the previously mentioned ingredients such as the anionic surfactants other ingredients, especially from the group of builders, co-builders, bleach, bleach activators, dyes and fragrances, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for the sake of completeness.
Gerüststoffe werden in Wasch- oder Reinigungsmitteln vor allem zum Binden von Calcium und Magnesium eingesetzt. Übliche Builder, die im Rahmen der Erfindung bevorzugt in Mengen von 22,5 bis 45 Gew.-%, vorzugsweise von 25 bis 40 Gew.-% und insbesondere von 27,5 bis 35 Gew.-%, jeweils bezogen auf das gesamte Mittel, welches auch die Verfahrensendprodukte des erfindungsgemäßen Verfahrens enthält, zugegen sind, sind die niedermolekularen Polycarbonsäuren und ihre Salze, die homopolymeren und copolymeren Polycarbonsäuren und ihre Salze, die Carbonate, Phosphate und Natrium- und Kaliumsilikate. Für Wasch- oder Reinigungsmittel werden bevorzugt Trinatriumcitrat und/oder Pentanatriumtripolyphosphat und silikatische Builder aus der Klasse der Alkalidisilikate eingesetzt.Builders are used in detergents or cleaners especially for binding calcium and magnesium. Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent which also contains the process end products of the process according to the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. For washing or cleaning agents it is preferred to use trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal isilicates.
Als Builder bzw. Belagsinhibitor sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol.As a builder or coating inhibitor further polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wässrige Lösung eingesetzt werden. Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 3 bis 10 Gew.-%.The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
Eine Substanzklasse mit Cobuildereigenschaften stellen die Phosphonate dar. Dabei handelt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwerrnetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden.A substance class with cobuilder properties are the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The Aminoalkanphosphonate also have a pronounced Schwerrnetallbindeabmögen. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
Geeignete silikatische Builder sind die kristallinen, schichtförmigen Natriumsilikate der allgemeinen Formel NaMSixO2x+1 ·H2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5 ·yH2O bevorzugt.Suitable silicate builders are the crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is an integer from 1.9 to 4 and y is a number from 0 to 20 and preferred Values for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/ Verdichtung oder durch Übertrocknung hervorgerufen worden sein.It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
Der einsetzbare feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith A und/oder P. Als Zeolith P wird Zeolith MAP® (Handelsprodukt der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und/oder P.The usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable.
Neben den Gerüststoffen sind insbesondere Acidifizierungsmittel, Chelatkomplexbildner oder belags inhibierende Polymere weitere bevorzugte Inhaltsstoffe von Wasch- oder Reinigungsmitteln.In addition to the builders, especially acidifying agents, chelating agents or coating-inhibiting polymers are further preferred ingredients of detergents or cleaners.
Eine weitere mögliche Gruppe von Inhaltsstoffen stellen die Chelatkomplexbildner dar. Chelatkomplexbildner sind Stoffe, die mit Metallionen zyklische Verbindungen bilden, wobei ein einzelner Ligand mehr als eine Koordinationsstelle an einem Zentralatom besetzt, d. h. mind. "zweizähnig" ist. In diesem Falle werden also normalerweise gestreckte Verbindungen durch Komplexbildung über ein Ion zu Ringen geschlossen. Die Zahl der gebundenen Liganden hängt von der Koordinationszahl des zentralen Ions ab.Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
Gebräuchliche und im Rahmen der vorliegenden Erfindung bevorzugte Chelatkomplexbilder sind beispielsweise Polyoxycarbonsäuren, Polyamine, Ethylendiamintetraessigsäure (EDTA) und Nitrilotriessigsäure (NTA).Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
Besonders bevorzugt sind im Rahmen der vorliegenden Erfindung Wasch- oder Reinigungsmittel, die ein oder mehrere Chelatkomplexbildner aus den Gruppen der
- (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
- (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
- (iii) geminalen Diphosphonsäuren,
- (iv) Aminophosphonsäuren,
- (v) Phosphonopolycarbonsäuren,
- (vi) Cyclodextrine
- (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
- (ii) nitrogen-containing mono- or polycarboxylic acids,
- (iii) geminal diphosphonic acids,
- (iv) aminophosphonic acids,
- (v) phosphonopolycarboxylic acids,
- (vi) cyclodextrins
in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Wasch- oder Reinigungsmittels, enthalten.in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of Washing or cleaning agent, included.
Im Rahmen der vorliegenden Erfindung können alle Komplexbildner des Standes der Technik eingesetzt werden. Diese können unterschiedlichen chemischen Gruppen angehören. Vorzugsweise werden einzeln oder im Gemisch miteinander eingesetzt.In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used singly or in admixture with each other.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure.Among the compounds serving as bleaches in water H 2 O 2 , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
Bleichaktivatoren unterstützen die Wirkung der Bleichmittel. Bekannte Bleichaktivatoren sind Verbindungen, die eine oder mehrere N- bzw. O-Acylgruppen enthalten, wie Substanzen aus der Klasse der Anhydride, der Ester, der Imide und der acylierten Imidazole oder Oxime. Beispiele sind Tetraacetylethylendiamin TAED, Tetraacetylmethylendiamin TAMD und Tetraacetylhexylendiamin TAHD, aber auch Pentaacetylglucose PAG, 1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5-triazin DADHT und Isatosäureanhydrid ISA.Bleach activators aid the action of the bleaching agents. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen.As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
Bevorzugt werden Bleichaktivatoren aus der Gruppe der mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), n-Methyl-Morpholinium-Acetonitril-Methylsulfat (MMA), vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-% bezogen auf das gesamte Mittel, eingesetzt.Bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch sogenannte Bleichkatalysatoren in den Folgeprodukten des erfindungsgemäßen Verfahrens enthalten sein. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -Carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar. In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be present in the secondary products of the process according to the invention. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
Wasch- oder Reinigungsmittel können zur Steigerung der Wasch-, beziehungsweise Reinigungsleistung Enzyme enthalten, wobei prinzipiell alle im Stand der Technik für diese Zwecke etablierten Enzyme einsetzbar sind. Hierzu gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- und Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Bevorzugte Mittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 bis 5 Gewichts-Prozent bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren (Bicinchoninsäure; 2,2'-Bichinolyl-4,4'-dicarbonsäure) oder dem Biuret-Verfahren bestimmt werden.Detergents or cleaning agents may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Preferred agents preferably contain enzymes in total amounts of 1 × 10 -6 to 5 percent by weight based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
Wasch- oder Reinigungsmitteln können die Enzyme in jeder nach dem Stand der Technik etablierten Form zugesetzt werden. Hierzu gehören beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren versetzt.Detergents or detergents may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden.Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms.
Farb- und Duftstoffe können Wasch- oder Reinigungsmitteln zugesetzt werden, um den ästhetischen Eindruck der entstehenden Produkte zu verbessern und dem Verbraucher neben der Leistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden.Dyes and fragrances can be added to detergents or cleaners to improve the aesthetic appearance of the resulting products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
Die Duftstoffe können direkt in die Mittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.The fragrances can be incorporated directly into the compositions, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and by a slower release of fragrance for long-lasting fragrance of the textiles to care. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
Um den ästhetischen Eindruck der Wasch- oder Reinigungsmittel zu verbessern, kann es (oder Teile davon) mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber den mit den Mitteln zu behandelnden Substraten wie Glas, Keramik oder Kunststoffgeschirr, um diese nicht anzufärben.In order to improve the aesthetic impression of the washing or cleaning agents, it (or parts thereof) can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
Wasch- oder Reinigungsmittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.Detergents or cleaning agents may contain as optical brighteners derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brightener can be used.
Die Verfahrensendprodukte des erfindungsgemäßen Verfahrens können nicht nur teilchenförmigen Wasch- oder Reinigungsmitteln zugemischt werden, sondern können auch in Wasch- oder Reinigungsmitteltabletten Verwendung finden. Überraschenderweise verbessert sich die Löslichkeit solcher Tabletten durch den Einsatz der Verfahrensendprodukte des erfindungsgemäßen Verfahrens im Vergleich zu gleich harten und identisch zusammengesetzten Tabletten, welche keine Endprodukte des erfindungsgemäßen Verfahrens beinhalten. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher die Verwendung der Verfahrensendprodukte des erfindungsgemäßen Verfahrens zur Herstellung von Waschmitteln, insbesondere von Waschmitteltabletten.The process end products of the process according to the invention can not only be mixed with particulate detergents or cleaners, but can also be used in detergent tablets. Surprisingly, the solubility of such tablets improved by the use of the process end products of the method according to the invention in comparison to the same hard and identically composed tablets, which do not include end products of the method according to the invention. Another object of the present invention is therefore the use of the process end products of the process according to the invention for the production of detergents, in particular detergent tablets.
Claims (13)
- A method for preparing surfactant granules with an apparent density from 300 to 800 g/L by neutralization of anionic surfactant acids as well as optionally other acid components with solid neutralization agents, wherein the anionic surfactant acid(s) and the solid neutralization agent(s) are agglomerated in a freefall mixer, and optionally processed subsequently, characterized in that the anionic surfactant acid has a water content between 5 and 24% by weight.
- The method according to claim 1, characterized in that the anionic surfactant acid has a water content between 6 and 22, preferably between 7 and 20% by weight.
- The method according to any of claims 1 or 2, characterized in that one or more substances from the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, of fatty alkylsulfuric acids, and alkylaryl-sulfonic acids, in particular from the group of C8-16 in particular C9-13 alkylbenzene-sulfonic acids, are applied as anionic surfactant acid(s).
- The method according to any of claims 1 to 3, characterized in that the content of neutralized anionic surfactant acids in the method products is at most 50% by weight, preferably from 8 to 42% by weight, more preferably from 10 to 35% by weight, and in particular from 15 to 25% by weight.
- The method according to any of claims 1 to 4, characterized in that the liquid acid component upon introduction into the freefall mixer has a temperature from 20 to 60°C, preferably from 30 to 55°C and in particular from 40 to 50°C.
- The method according to any of claims 1 to 5, characterized in that the apparent density of the surfactant granules is from 350 to 700 g/L, more preferably from 400 to 650 g/L, and in particular from 500 to 600 g/L.
- The method according to any of claims 1 to 6, characterized in that the surfactant granules have a grain size distribution with an average grain size d50 below 5,000 µm, preferably between 20 and 3,000 µm, more preferably between 40 and 2,000 µm and in particular between 50 and 1,600 µm.
- The method according to any of claims 1 to 7, characterized in that the weight proportion of the surfactant granules with a grain size between 100 and 1,600 µm before the processing is at least 80% by weight, preferably at least 82% by weight, more preferably at least 85% by weight, most preferably at least 90% by weight, and in particular at least 95% by weight.
- The method according to any of claims 1 to 8, characterized in that the weight proportion of the surfactant granules with a grain size between 100 and 800 µm before the processing is at least 52% by weight, preferably at least 62% by weight, more preferably at least 70% by weight, most preferably at least 76% by weight, and in particular at least 80% by weight.
- The method according to any of claims 1 to 9, characterized in that, as for the freefall mixer, this is a drum mixer, tumbler mixer, cone mixer, double cone mixer, or V-mixer.
- The method according to any of claims 1 to 10, characterized in that the residence time of the reaction mixture in the rotatable container is less than 20 minutes, preferably between 1 and 600 seconds, more preferably between 1 and 300 seconds, and in particular between 1 and 120 seconds.
- The method according to any of claims 1 to 11, characterized in that the method products are subject to post-treatment on a reaction section after exiting the freefall mixer.
- The method according to claim 12, characterized in that, as for the reaction section, this is a pneumatic fluidized bed and/or a conveyer belt and/or a mixer.
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PCT/EP2004/006464 WO2005123893A1 (en) | 2004-06-16 | 2004-06-16 | Targeted granulation achieved by neutralisation in a compomix-type machine |
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EP1756256A1 EP1756256A1 (en) | 2007-02-28 |
EP1756256B1 true EP1756256B1 (en) | 2009-11-11 |
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US (1) | US20080261857A1 (en) |
EP (1) | EP1756256B1 (en) |
JP (1) | JP2008502746A (en) |
AT (1) | ATE448289T1 (en) |
DE (1) | DE502004010375D1 (en) |
WO (1) | WO2005123893A1 (en) |
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DE102005038070A1 (en) * | 2005-08-10 | 2007-03-15 | Henkel Kgaa | Detergents and cleaners with well soluble capsules |
DE102012217877A1 (en) * | 2012-10-01 | 2013-08-14 | Henkel Ag & Co. Kgaa | Producing detergent composition, comprises dry neutralizing anionic surfactant and optionally other acidic components with solid neutralizing agent in free-fall mixer, and mixing product with additional particulate and/or liquid components |
CN111542605A (en) * | 2017-12-27 | 2020-08-14 | 东丽株式会社 | Method for recovering nucleic acid |
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US4587029A (en) * | 1983-06-27 | 1986-05-06 | The Chemithon Corporation | Intermediate product for use in producing a detergent bar |
CA2027518A1 (en) * | 1990-10-03 | 1992-04-04 | Richard L. Tadsen | Process for preparing high density detergent compositions containing particulate ph sensitive surfactant |
DE4216774A1 (en) * | 1992-05-21 | 1993-11-25 | Henkel Kgaa | Process for the continuous production of a granular washing and / or cleaning agent |
US5576285A (en) * | 1995-10-04 | 1996-11-19 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
WO1997017422A1 (en) * | 1995-11-06 | 1997-05-15 | Kao Corporation | Method for producing crystalline alkali metal silicate granules and granular high density detergent |
GB9526097D0 (en) * | 1995-12-20 | 1996-02-21 | Unilever Plc | Process |
JPH09241698A (en) * | 1996-03-13 | 1997-09-16 | Lion Corp | Production of high-bulk density granular detergent composition |
GB9712583D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
DE19858859A1 (en) * | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Production of storage-stable, homogeneous detergent optionally containing heavy components by agglomeration in a rotatable mixer with anionic surfactant introduced in acid form |
GB0119708D0 (en) * | 2001-08-13 | 2001-10-03 | Unilever Plc | Process for the production of detergent granules |
DE10258011A1 (en) * | 2002-12-12 | 2004-07-08 | Henkel Kgaa | Dry neutralization process |
-
2004
- 2004-06-16 JP JP2007515786A patent/JP2008502746A/en not_active Withdrawn
- 2004-06-16 WO PCT/EP2004/006464 patent/WO2005123893A1/en active Application Filing
- 2004-06-16 EP EP04739932A patent/EP1756256B1/en not_active Revoked
- 2004-06-16 AT AT04739932T patent/ATE448289T1/en not_active IP Right Cessation
- 2004-06-16 US US11/629,598 patent/US20080261857A1/en not_active Abandoned
- 2004-06-16 DE DE502004010375T patent/DE502004010375D1/en not_active Expired - Fee Related
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JP2008502746A (en) | 2008-01-31 |
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WO2005123893A1 (en) | 2005-12-29 |
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