EP0541608A1 - Verfahren zur herstellung wasch- und reinigungsaktiver granulate. - Google Patents
Verfahren zur herstellung wasch- und reinigungsaktiver granulate.Info
- Publication number
- EP0541608A1 EP0541608A1 EP91913378A EP91913378A EP0541608A1 EP 0541608 A1 EP0541608 A1 EP 0541608A1 EP 91913378 A EP91913378 A EP 91913378A EP 91913378 A EP91913378 A EP 91913378A EP 0541608 A1 EP0541608 A1 EP 0541608A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- granules
- surfactant
- water
- weight
- surfactants
- 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.)
- Granted
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 111
- 238000005406 washing Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000004140 cleaning Methods 0.000 title description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 103
- 239000000203 mixture Substances 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 47
- 238000005469 granulation Methods 0.000 claims abstract description 28
- 230000003179 granulation Effects 0.000 claims abstract description 28
- 239000012459 cleaning agent Substances 0.000 claims abstract description 25
- -1 fatty-alcohol sulphates Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 3
- 239000003599 detergent Substances 0.000 claims description 50
- 230000008569 process Effects 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 31
- 239000003945 anionic surfactant Substances 0.000 claims description 28
- 239000002736 nonionic surfactant Substances 0.000 claims description 23
- 150000002191 fatty alcohols Chemical class 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000004753 textile Substances 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229930182470 glycoside Natural products 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 239000003082 abrasive agent Substances 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims 1
- 229960001545 hydrotalcite Drugs 0.000 claims 1
- 229910001701 hydrotalcite Inorganic materials 0.000 claims 1
- 239000011435 rock Substances 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 37
- 239000003760 tallow Substances 0.000 abstract description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 239000013065 commercial product Substances 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000009969 flowable effect Effects 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000013042 solid detergent Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 239000004165 Methyl ester of fatty acids Substances 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- KHLCTMQBMINUNT-UHFFFAOYSA-N octadecane-1,12-diol Chemical compound CCCCCCC(O)CCCCCCCCCCCO KHLCTMQBMINUNT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000010518 undesired secondary reaction Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000002888 zwitterionic surfactant 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
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
Definitions
- the invention relates to a process for converting aqueous preparation forms of washable and cleaning-active surfactant compounds into storage-stable surfactant granules and into storage-stable washing and cleaning agents in granular form.
- oleochemical surfactant compounds in washing and cleaning agents is of great and rapidly increasing importance.
- the considerations in the foreground are based, on the one hand, on the fact that surfactant compounds of this type are obtained from renewable vegetable and / or animal raw materials, but, on the other hand, it is in particular the high ecological compatibility of selected components of this type which is of crucial importance.
- Examples of such a class of oleochemical surfactant compounds are the known fatty alcohol sulfates, which are produced by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular the corresponding alkali metal salts.
- fatty alcohol sulfates which are based on at least predominantly straight-chain fatty alcohols or corresponding fatty alcohol mixtures with about 12 to 18 carbon atoms in the fatty alcohol molecule, are of particular practical importance.
- Tallow alcohol sulfates (TAS) with predominantly saturated Ciö-Cis- es in fatty alcohol are already of considerable importance for the production of textile detergents, especially in solid form, but fatty alcohol sulfates (FAS) with a further range in the C chain number are also important attributable to washing properties.
- fatty alcohol sulfates of the Ci2-Ci8 range with a high proportion of the lower fatty alcohols in this range can be important anionic surfactants for use in detergents and cleaning agents.
- anionic surfactants for use in detergents and cleaning agents.
- European patent application 342 917 also describes detergents in which the anionic surfactants consist predominantly of Ci2-Ci8-alkyl sulfates. The economic synthesis of light-colored anionic surfactants based on FAS is now a state of the art.
- the corresponding surfactant salts are obtained in aqueous preparation forms, water contents being adjustable in the range from about 20 to 80% and in particular in the range from about 35 to 60%.
- products of this type have a paste-like or cutable quality, the flowability and pumpability of such pastes being restricted or even being lost in the region of about 35% by weight of active substance, so that in the processing of such pastes, Considerable problems arise in particular when they are incorporated into solid mixtures, for example in solid detergents and cleaning agents.
- the conventional drying technology in particular in the spray tower, enables free-flowing FAS powders to be obtained.
- there are serious restrictions which in particular jeopardize the economic viability of the large-scale use of such FAS surfactants.
- TAS powder dried over the tower shows a very low bulk density, so that unprofitable conditions occur in the packaging and distribution of this detergent raw material.
- safety concerns can make such a restrictive manner of tower drying necessary that practical difficulties arise.
- safety-related studies on tower powder based on TAS or FAS with 20% or higher active substance contents indicate that the atomization drying of such formulations is only possible to a very limited extent and, for example, requires tower inlet temperatures below 200 ° C.
- sulfofatty acid methyl esters fatty acid methyl ester sulfonates, MES
- anion-active oleochemical surfactant compounds which by o-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty acid molecule and the following Neutralization to water-soluble mono-salts, in particular the corresponding alkali salts, can be prepared.
- ester splitting arise from the corresponding ⁇ -sulfofatty acids or their di-salts, which, like mixtures of di-salts and sulfofatty acid ethyl ester mono-salts, have important washing and cleaning properties inherent in the substance. Comparable problems also occur in other surfactant classes when trying to manufacture the corresponding surfactant raw materials in solid or granular form. Reference is made to washing and cleaning-active alkyl glycoside compounds. In order to obtain light-colored reaction products, a final bleaching, for example with aqueous hydrogen peroxide, is generally required in their synthesis, so that here too, today's technology leads to the aqueous paste form of the surfactant.
- APG pastes aqueous alkyl glycoside pastes
- ABS pastes alkylbenzenesulfonates
- paste viscosity of such aqueous substance mixtures is also strongly temperature-dependent, so that pastes of the type mentioned are practically not free from interference in the region of room temperature can work, the use of elevated temperatures of, for example, 50 to 70 ° C is required.
- EP 116 905 (Henkel) describes the use of alcohols with 8 to 40 carbon atoms which are substituted with 1 to 5 hydroxyl groups and / or to which up to 15 moles of ethylene oxide and / or propylene oxide are added per mole of alcohol are, as a viscosity regulator for highly viscous technical surfactant concentrates of the synthetic anionic surfactant type.
- Corresponding aqueous pastes of alkyl sulfates, alkylaryl sulfates and ⁇ -sulfofatty acid esters with a surfactant content of at least 30% by weight are mentioned in detail.
- viscosity regulators in amounts of 1 to 15% by weight, based on the amount of surfactant, leads, according to this teaching, to viscosities of the respective surfactant concentrate of at most 10,000 Pas at 70 ° C. (Höppler falling ball viscometer). Mixtures of saturated and unsaturated fatty alcohols with up to 8 mol E0 and / or PO units are particularly preferred as viscosity regulators.
- the viscosity behavior of aqueous pastes of mixed surfactants and in particular the unusual increase in viscosity when mixing aqueous ABS and TAS pastes is not addressed in this document.
- the invention is based on the object of demonstrating a simple alternative processing option for the aqueous, in particular pasty, surfactant preparations to form dry, in particular free-flowing and concentrated surfactant granules.
- the invention is based on the knowledge gained from the European patent application EP 116 905, but extends the principles described there beyond the knowledge known to date.
- the invention relates to a process for producing granules which are active in washing and cleaning by granulating a mixture of an aqueous surfactant preparation form and one or more water-soluble and / or water-insoluble solids, so that free-flowing granules are formed.
- the concentrated surfactant preparation forms contain, as viscosity regulators, alkoxylates of mono- and / or polyhydric alcohols with 8 to 40 carbon atoms, which have up to 20 ethylene oxide and / or propylene oxide groups.
- the free-flowing granules are preferably at least partially freed of their water content by drying.
- the process according to the invention is particularly suitable for the granulation of surfactant pastes, the surfactant components of which are solids in the range up to at least about 40 ° C. and which have a high viscosity per se, the viscosity being reduced according to the invention through the use of the viscosity regulator. At the same time, this results in the possibility of lowering the processing temperature and / or increasing the surfactant solids content in the aqueous paste material.
- the new process can be particularly suitable for the use of anionic surfactant pastes based on alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, ⁇ -sulfofatty acid esters, oc-sulfofatty acid disalts and / or soaps. It has surprisingly been found, in particular, that mixed pastes of the type mentioned here, which contain, for example, any desired quantity of mixtures of surfactant compounds based on ABS and TAS, can be converted into comparatively free-flowing and pumpable pastes by adding comparatively limited quantities of fatty alcohol alkoxylates .
- Suitable viscosity regulators in the context of the teaching according to the invention are, in particular, those alkoxylates of fatty alcohols synthetic and / or of natural origin, as they are common in today's technology of detergents and cleaning agents - especially textile detergents - as so-called nonionic surfactant components and are usually used here in a mixture with anionic surfactants of the type described above.
- the process according to the invention is also suitable for the use of aqueous pastes of wash-active alkyl glycoside compounds.
- the invention thus enables the economical production of virtually any mixtures of, for example, anionic surfactants and selected nonionic surfactants in dry form, which can be controlled and optimized in terms of their composition and type and / or amount by the intended use.
- the invention relates to a process for the production of highly concentrated surfactant granules using the granulation process described above, which can be used as a surfactant-rich compound for the production of detergents and cleaning agents.
- the invention relates to a process for the production of storage-stable and free-flowing detergents and cleaning agents, in particular textile detergents, which can also be used for subsequent Mixture with particularly temperature-sensitive components of the detergents and cleaning agents are suitable.
- the compounds preferred according to the invention as viscosity regulators are derived from monohydric alcohols in the C number range mentioned, it being possible for these alcohols to be of natural or synthetic origin. Aliphatic alcohols of this type are known to be derived from natural fats and oils and are obtained, for example, by reducing the corresponding fatty acid esters. These so-called fatty alcohols are straight-chain and can be saturated or unsaturated. Viscosity regulators based on alkoxylated fatty alcohol mixtures, such as those used in the production of detergents and cleaning agents as nonionic surfactant components, are particularly suitable for the purposes of the inventive action.
- Suitable viscosity regulators are therefore, in particular, ethoxylates of straight-chain and / or branched monofunctional fatty alcohols having about 10 to 20 carbon atoms, the range from 12 to 18 carbon atoms in the alcohol residues being of particular importance in the fatty alcohol or fatty alcohol mixture.
- these fatty alcohols are alkoxylated with an average of about 2 to 10 EO groups, the range of about 3 to 8 EO groups being particularly important here.
- a commercially available nonionic surfactant component of this type is, for example, the product sold by the applicant under the name "Dehydol LST 80:20", which is a mixture of 80 parts by weight of Ci2-i8 _rT ett alcohols and on average 5 EO units and 20 parts by weight of a Ci2 / 14 _fretta l ' ( ohols with 3 EO units.
- This nonionic surfactant used in numerous textile detergents is a very useful viscosity regulator in the sense of the action according to the invention.
- aliphatic alcohols or addition products suitable as viscosity regulators can also be alcohol components with a branched carbon chain
- alcohols with a branched carbon chain are oxo alcohols and Guerbet alcohols, ie alcohols obtained by the oxo synthesis or by the so-called Guerbet reaction and each branched in the 2-position.
- Light alcohols or their alkoxylates are based on di e teaching of EP 0 116905 referenced. For example, there are mentioned as basic alcohol Component compounds such as 12-hydroxystearyl alcohol, 9,10-dihydroxystearyl alcohol or their ethylene oxide products.
- aqueous anionic surfactant pastes can be achieved not only with selected individual anionic surfactants or their aqueous pastes, but even with small amounts of the nonionic surfactant component in the sense of the teaching of EP 0 116905 also added a few percent of the niotene surfactant to a completely solidified ABS / TAS paste, which ensures the desired flow and pumpability.
- the viscosity regulators in amounts of at least about 2% by weight, preferably in amounts of at least about 5% by weight, the weight given here being based on the solids weight of the mostly anionic surfactants Mixture component in the aqueous preparation relates. Amounts of the nonionic viscosity regulators in the range up to about 15% by weight can be particularly suitable, so that the range from about 5 to 15% by weight can be of particular importance.
- the invention is described in detail below using the example of converting aqueous FAS pastes into free-flowing granules.
- the measures and process parameters described in detail here can also be used broadly for other aqueous, in particular pasty, surfactant preparations of the type concerned, taking into account the general chemical specialist knowledge.
- the aqueous FAS mixtures used in the flowable and pumpable surfactant preparation forms are the reaction products from the sulfation and the subsequent aqueous-alkaline neutralization of the particular fatty alcohol used. As a rule, these are mixtures of corresponding FAS types of different chain lengths with a preferably straight-chain fatty alcohol residue within the specified range of Ci2-Ci8.
- the water content of these FAS mixtures is preferably in the range from about 20 to 80% by weight. -% and in particular in the range of about 30 to 50 wt .-%.
- the working temperature temperature of the surfactant paste
- the working temperature is room temperature or moderately elevated temperatures, for example between 40 and 60 ° C, preferred.
- the granulation process is as follows:
- a suitable mixing and granulating device for example in appropriate systems of the type of an Eirich mixer, a Lödige mixer, for example a ploughshare mixer from the Lödige company, or a mixer from the Schugi company, at peripheral speeds of the mixing elements, preferably between 2 and 7 m / s (ploughshare mixer) or 5 to 50 m / s (Eirich, Schugi), in particular between 15 and 40 m / s, the aqueous FAS / nonionic surfactant mixture on the one hand and on the other hand water-soluble and / or water-insoluble solids in such proportions and mixed so intensively that a free-flowing granulate is formed.
- a Lödige mixer for example a ploughshare mixer from the Lödige company, or a mixer from the Schugi company
- peripheral speeds of the mixing elements preferably between 2 and 7 m / s (ploughshare mixer) or 5 to 50 m / s (Eirich, Schugi), in
- a predeterminable grain size of the granules can be set in a manner known per se.
- the mixing process takes only a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) to homogenize the mixture with formation of the free-flowing granulate.
- a residence time of 0.5 to 10 seconds is usually sufficient to obtain a free-flowing granulate.
- the mixing ratios of the components and in particular the proportions of the solid added are to be matched to the water content introduced via the FAS mixture in such a way that the homogenized mixture of aqueous surfactant preparation form and added solid can form the free-flowing granules.
- the still moist granulate is preferably transferred to the drying stage, which in the preferred embodiment is designed as a fluidized bed drying, immediately after the granulation. In principle, however, no subsequent drying step is required to produce the free-flowing granules.
- Drying is, however, advantageous and therefore preferred, since this leads to surfactant granules with an increased surfactant content.
- low-concentration surfactant mixtures which contain, for example, more than 50% by weight and in particular more than 60% by weight of water, it may be necessary to remove the primarily AO standing granules to dry in order to obtain the preferred minimum content of 2 wt .-% surfactant in the granules.
- the drying process can be continued until the desired final value of unbound or bound water in the granulate.
- non-dried granules are mixed with partially or completely dried granules in any ratio.
- “Completely dried” is understood to mean the state in which the unbound water and possibly portions of the bound water have been removed from the granules.
- Fluidized bed drying is a preferred type of drying, since rapid drying of the outer surface of the granules occurs with simultaneous intensive agitation and mixing of the granules, so that undesired caking of the still moist granules is counteracted in this way.
- the invention provides for the granules which are still moist to be powdered - expediently immediately after the granules have been produced - with a dusty or pulverulent auxiliary and for the granules stabilized in this way to be added to the drying stage.
- the state of the free-flowing granulate is then quickly reached there even under comparatively mild drying conditions.
- the drying in particular the fluidized bed drying, is preferably carried out at temperatures of the gas phase below 200 ° C. and in particular at temperatures in the range from approximately 70 to 160 ° C., for example in the range from approximately 90 to 150 ° C. These temperatures relate primarily to the gas phase; the resulting final temperature of the granulate is kept in a preferred embodiment at comparatively low temperatures and here, for example, does not exceed 80 to 90 ° C, preferably it is not higher than 75 ° C. ⁇ A -
- the solids used in the granulation for the partial drying of the aqueous surfactant preparation form can be corresponding ingredients from customary formulations of detergents and / or cleaning agents, but they can also be foreign substances as long as they have the intended application of Surfactants are compatible. It will generally be preferred to use ingredients from washing and / or cleaning agents here. It is a particular advantage of the method according to the invention that there is a great deal of freedom in the selection of these solid mixture components. The reason for this is the fact that the granulation process according to the invention, with the preferably connected drying, provides such comparatively mild working conditions that undesired secondary reactions in the granulation and / or drying step are only to be feared in exceptional cases. General technical knowledge applies here.
- temperature-sensitive mixture components for example textile detergents, such as those used as bleaching agents of the perborate type
- textile detergents such as those used as bleaching agents of the perborate type
- water-soluble and / or water-insoluble solids which can be mixed with the water-containing surfactant preparation forms without hesitation under the working conditions, granulated and then dried under the stated working conditions.
- suitable water-soluble solids are inorganic salts, for example soda, alkali silicates, in particular water glass powder, sodium sulfate and / or phosphate salts such as sodium pyrophosphate and sodium tripolyphosphate.
- the teaching of the invention also provides for the use of corresponding insoluble, preferably finely divided materials.
- the grain size of the preferred solids is less than 1 mm and in particular less than 100 ⁇ m, for example not more than 30 ⁇ m.
- Typical examples from the field of detergents and / or cleaning agents are additives which are used as so-called powder substances to bind the alkaline earth metal ions and thus to remove the water hardness.
- Examples include finely divided crystalline zeolites, in particular sodium zeolite NaA in detergent quality, which preferably consists of at least 80% of particles of a size of less than 10 ⁇ m (volume distribution; ⁇ Coulter Counter).
- Other examples of preferably used solids are hydrotalcites, water-insoluble and crystalline layered silicas, abrasives such as stone powder and the like.
- a special feature of the invention is the use of preferably dried and again finely divided granules from ongoing production as a solid component of the mixture for working up further amounts of the aqueous surfactant preparation forms.
- this embodiment provides for a complete or partial cycle of the granules produced by the process according to the invention, in particular the dried granules, in the process cycle. Details of this particular embodiment are described below.
- the mixing ratios of the surfactants to be used in the mixing and granulating stage on the one hand and on the other hand of the solids it may be expedient to adapt these mixture components to the corresponding requirements of the components in the washing and / or cleaning agents which are ultimately to be created.
- the ratio of anionic surfactants to the finely divided solids used, for example, in textile detergents can provide clues for the composition of the mixture to be granulated. Such considerations may lead to the need to use various solid detergent components - expediently likewise in coordinated quantitative ratios.
- the water glass content of textile detergents in the overall formulation is comparatively low, for example it can be in the range from 2 to 5% by weight of the total formulation.
- a different A3 equally water-rich FAS surfactant mixture used so if water glass powder alone is used as a solid, much larger amounts of water glass would have to be mixed in in order to adjust the state of the free-flowing powder in the mixing and granulation stage than in the formulation of the finished agent are desired. It will therefore be advisable to use other dry detergent ingredients, such as soda and / or sodium sulfate.
- the desired percentage composition of the granules according to the invention can be combined with the proportional mixture prescribed by the full detergent formulation.
- Typical examples of this are mixtures of the water-containing surfactant pastes with sodium zeolite, soda and / or sodium sulfate.
- a particularly important embodiment of the invention provides for the already mentioned partial or complete circulation of the granules, preferably the dried granules, back into the mixing and granulating stage.
- the process in particular continuous, can be carried out in such a way that the entire solid phase added in the mixing and granulating stage is formed from a recycled material of this type, which consists of already dried granulate and thus already has considerable proportions, namely preferred ⁇ as more than 25 wt .-%, based on this dry granulate used as a solid, contains anionic surfactant.
- the dried granulate used as a solid in the mixing and granulating stage is first crushed, for example under the action of the mixing tools or a conventional mill.
- FAS contents in the granulate of at least 30% by weight and preferably of at least 35% by weight can be set easily. It is possible according to the invention to raise the corresponding surfactant content to at least 45% by weight or even to at least 50% by weight. In particular, a tensidge content between 30 and 75% by weight, based on the dried granules, is aimed for. The higher the surfactant content in the granules, the greater the tendency of the mixture to soften under the conditions of fluidized bed drying. In particular, the above-mentioned powdering with solid dry mixture components, for example with dried zeolite NaA in detergent quality, can become significant.
- the grain size range of the resulting granulate and the average grain size are adjusted in a manner known per se by adapting the working conditions in the granulation stage.
- granules with a grain size of approximately 0.01 to 3 mm (sieve analysis) and in particular those with a size of approximately 0.05 to 2 mm can be produced.
- An important embodiment of the invention provides for the classification of the dried granulate by separating undesired fine-grain and coarse-grain fractions in a manner known per se. In an important embodiment of the invention, these separated parts can even be returned to the mixing and granulating stage and used as a solid, if no recycling of the granulated and dried granules is otherwise provided.
- the physical properties of the granules can also be largely predetermined in other ways.
- the hardness of the granulate and in particular its abrasion hardness can be modified and, for example, increased by using suitable auxiliary substances.
- suitable auxiliary substances This is possible by using small amounts of polymer compounds, which are usually used in detergents and cleaning agents.
- Al Examples include the polyacrylates and polyacrylate copolymers known as builder substances, which can be used, for example, with relative molecular weights in the range from 30,000 to 100,000.
- Auxiliaries of this type can already be added to the mixture in the mixing and granulating stage, but it is also possible to apply them subsequently to the preformed granules before or during the drying process.
- the process according to the invention can also be modified in a completely different form and used to facilitate the production of granules of the type described.
- This modification is understandable in the following example:
- zeolite NaA is produced as an aqueous suspension (asterbatch) which can contain over 50% by weight of water and is usually worked up in the spray tower to give a powdery solid.
- the zeolite can be introduced into the mixing and granulating stage at least in part in the form of this suspension or as a not completely dried product, in order then to be dried up in the granulate in the mixture with the surfactant and the added dry solids.
- Such an embodiment can be of particular interest if the dried granules are circulated and the portion required as a solid is introduced into the mixing and granulating stage via the desired end product.
- Zeolite materials of the last-mentioned type but also other typical auxiliaries of detergents and cleaning agents, are in turn capable of partially binding water.
- auxiliaries of this type are anhydrous soda and anhydrous sodium sulfate, which can bind considerable amounts of water in the form of water of crystallization.
- One embodiment of the invention uses this ability of internal water binding for additional drying (internal drying) of the granules formed in the process according to the invention.
- the water content in the drying step is reduced to such an extent that the bound water present as crystal water is at least partially discharged.
- the water contents of the dried granules preferred according to the invention are accordingly comparatively low.
- the proportion of unbound water is preferably below 8% by weight, in particular below 5% by weight, based on the dried granules.
- Water bound in crystal form or bound into the molecular structure can be present in the substance mixture in limited amounts, but the storage stability of the granules becomes higher, in particular the lower the proportion of crystal water in the end product is reduced. It is understandable that this embodiment is of less importance if it is intended to further process the surfactant granules. If these granules are to be used as a form of trading in raw materials trading, the considerations discussed last should be given greater importance.
- nonionic surfactant component as a viscosity regulator of 2 to 15% by weight, based on the amount of solids of the mostly anionic surfactant in the surfactant paste, are used in the production of the free-flowing granules, then mixing ratios of anionic surfactant lie in the finished granulate to non-ionic surfactants, which - compared to conventional formulations of detergents and cleaning agents - are comparatively low in non-ionic surfactants. This can be insignificant for the teaching according to the invention of the improved production of the surfactant granules concerned here, but this must then be taken into account when mixing these granules into the finished detergent or cleaning agent.
- nonionic surfactant can even be a A ir preferred embodiment of the action according to the invention.
- this is the case if the processing conditions chosen for the granulation and preferably subsequent drying of the granules, on the one hand, and the volatility of the nonionic surfactants used as viscosity regulators, on the other hand, are suitable for triggering procedural concerns in the sense of so-called pluming, as is the case for spray drying of nonionic surfactant-containing active ingredient mixtures during drying in the tower is known.
- the invention opens up new work possibilities for the granulation process and in particular the subsequent drying stage: due to the effective reduction in viscosity in the sense of the action according to the invention, processing temperatures so low for the granulation stage - for example, working temperatures in the range from 20 to 40 ° C - accessible that concerns about a potential volatility of the non-surfactant mixture component become irrelevant.
- the preferably subsequent drying step can also be adapted to such a low or at least a comparably low temperature level. This is made possible by the use of underpressures in the drying stage, it being possible for the working pressures to be used individually to be adapted to the respectively selected process parameters in a manner known per se.
- the mixing ratio of anionic surfactants to the nonionic surfactants which is ultimately used is set in the preliminary stage of the granulation.
- the total amount of nonionic surfactant required in the finished textile detergent is entered into the granules together with the anionic surfactants as a viscosity regulator.
- the nonionic surfactant content for example to an amount of at most about 80% by weight and in particular to less than 50% by weight, based on the total amount of nonionic surfactants in the textile detergent.
- nonionic surfactant quantity as viscosity regulator in the last illustrated embodiments, which exceeds the range from E 116905 - and thus about 15% by weight (based on anionic surfactant).
- amount of niotes to be selected in each case will also be determined by the aim aimed at, either to produce anionic surfactant granules containing high surfactants or to use the process according to the invention for producing the detergents in their entirety.
- the teaching according to the invention enables the granulation with pastes to be carried out with a very limited water content even at very low temperatures, for example in the range from about 20 to 40 ° C.
- temperature-sensitive materials such as sodium perborate or enzymes or preparations containing enzymes can now be used as granulation aids in the solid phase. Due to the granulation at such low temperatures, certain temperature-dependent modifications of solid mixture components that bind water of crystallization can be used to facilitate the process. For example, it is known that soda in the temperature range up to about 32 ° C forms the decahydrate, which then converts with the release of water into the heptahydrate, which is stable up to about 35 ° C and finally passes into the monohydra with further temperature increase.
- Granules are released without their damage.
- the lower surfactant viscosity produces finer droplets when the surfactant pastes are sprayed into the mixing and granulation device. This results in a more even distribution of the flowable phase.
- a fluidized product zone is built up in the mixing area, into which the surfactant paste is injected. The high shear forces result in a very fine distribution of the more flowable aqueous surfactant.
- the granules according to the invention can have an increased bulk density, in particular in comparison with corresponding spray-dried materials.
- Typical granules within the meaning of the invention normally have a bulk density of at least about 350 g / l, preferably of at least about 500 g / l. Bulk weights between 600 and 800 g / l are particularly preferred.
- the process according to the invention can be used in a wide range with regard to the aqueous surfactant mixtures.
- mixtures of surfactants which are present in the region of the room temperature as sufficiently dimensionally stable solids and which are present in particular in the course of their preparation and / or workup as aqueous pastes which contain the surfactants dispersed in the aqueous phase.
- An important example of such surfactants are the ⁇ -sulfofatty acid ethyl ester mono salts and / or the so-called di-salts.
- the mono-salts of the sulfofatty acid ethyl ester are obtained even in their large-scale production as a mixture with limited amounts of di-salts, which are known to result from partial ester cleavage with the formation of the corresponding ⁇ -sulfo-fatty acids or their di-salts .
- the di-salt content of such MES-based surfactants is usually below 50 mol% of the anion surfactant, for example in the range up to about 30 mol%.
- the teaching according to the invention is suitable for its application on such before MES-based surfactant mixtures as well as corresponding blends with higher di-salt contents up to the pure di-salts.
- a preferred aqueous MES use is the comparatively strongly water-containing reaction products from the sulfonation and the subsequent aqueous-alkaline neutralization of the respective fatty acid methyl ester.
- these are mixtures of corresponding MES types of different chain lengths with preferably straight-chain fatty acid residues within the specified range of C 1-5.
- the water content of these MES raw products can be in the range from about 20 to 80% by weight. % and in particular in the range from about 30 to 60% by weight.
- Surfactant compounds based on alkyl glycosides and their production, in particular in the form of water-containing bleached pastes, are described in detail, for example, in international patent application WO 90/03977.
- Surfactant reaction products of this type are a further example of the applicability of the process according to the invention for the production of dry granules based on surfactants. It is very general that the method according to the invention can be used for the preparation of aqueous preparation forms of surfactant compounds from the class of anionic, nonionic, zwitterionic and / or cationic surfactants which are at least largely solid at room temperature, the selection of corresponding surfactant compounds having high ecological compatibility being preferred.
- a surfactant mixture of 95% by weight of Texin ES 68 (commercial product of the applicant, containing 53% by weight of sodium mono salt of the oc-su1fötalg fatty acid methyl ester and 11% by weight of disodium salt of sulfotalg fatty acid and 29% by weight of water) and 5% by weight of a Ci2 "Ci8 fatty alcohol with 5 ethylene oxide groups (EO) (Dehydol LT5, commercial product of the applicant) were mixed with 1.5 kg of soda for 3 minutes in a 10 liter Eirich mixer at a peripheral speed of 24 m / s, corresponding to 2500 revolutions per minute (rpm) (Sternwirbier), the granules were then dried in a fluidized bed (aeromatics) for 60 minutes at an air inlet temperature of 70 ° C.
- EO ethylene oxide groups
- the wash active substance content (WAS, anion surfactant content titrable according to Epton, here: methyl sulphide tallow and disaline content; accuracy i 2% by weight) was 34% by weight, the disaline content being 5.5% by weight.
- 1.5 kg of the surfactant mixture mentioned in Example 1 were granulated at 25 ° C. with 750 g of soda for about 1 minute in an Eirich mixer (10 liters, Sternwirbier, 2500 rpm, 24 m / s). The granules were then dried in a fluidized bed (aeromatics) for 60 minutes at 50 ° C. air inlet temperature. A free-flowing granulate with about 7% by weight of water and a bulk density of 590 g / l was obtained. The WAS content of the granules was 49% by weight.
- 150 kg of the surfactant mixture mentioned in Example 1 were granulated with 150 kg of soda for 2 minutes in a 300 liter Eirich mixer (Sternwirbier, 700 rpm, 18 m / s). The granules were then in a fluidized bed (Heinen) at an air inlet temperature of 100 ° C and a residence time of 20 according to
- Example 4 1.5 kg of the surfactant mixture mentioned in Example 4 were granulated with 1.5 kg of dried sodium zeolite A as in Example 1 and dried for 60 minutes at an air inlet temperature of 90 ° C.
- the product had a water content of less than 1% by weight and a bulk density which (depending on the proportion of fine and coarse grains) was between 600 and 700 g / l.
- 1.5 kg of the surfactant mixture mentioned in Example 4 were granulated with 1.5 kg of sodium perborate monohydrate as described in Example 1.
- the granules were dried in a fluidized bed at an air inlet temperature of 70 ° C. for 60 minutes.
- the granules had a water content of less than 5% by weight and a bulk density of 680 g / l.
- Example 4 2.5 kg of the surfactant mixture mentioned in Example 4 were mixed with 1.5 kg of a porous and absorbent detergent additive [containing 71% by weight of zeolite NaA, 4% by weight of a copolymeric polyacrylate (Sokalan CP5, commercial product from BASF), in each case based on anhydrous Substance, and 20 wt .-% water] as described in Example 6 granulated and dried. A further 500 g of the surfactant mixture were then applied and the new, more surfactant-rich granules were dried again. This resulted in a WAS content of 49% by weight with a water content of less than 1% by weight. The bulk density was 630 g / 1.
- composition of the "surfactant-free" detergent (in% by weight):
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4024657 | 1990-08-03 | ||
DE4024657A DE4024657A1 (de) | 1990-08-03 | 1990-08-03 | Verfahren zur trocknung und granulierung waessriger pasten waschaktiver wirkstoffgemische |
PCT/EP1991/001395 WO1992002609A1 (de) | 1990-08-03 | 1991-07-25 | Verfahren zur herstellung wasch- und reinigungsaktiver granulate |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0541608A1 true EP0541608A1 (de) | 1993-05-19 |
EP0541608B1 EP0541608B1 (de) | 1995-06-28 |
Family
ID=6411582
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91913378A Expired - Lifetime EP0541608B1 (de) | 1990-08-03 | 1991-07-25 | Verfahren zur herstellung wasch- und reinigungsaktiver granulate |
Country Status (8)
Country | Link |
---|---|
US (1) | US5397507A (de) |
EP (1) | EP0541608B1 (de) |
JP (1) | JPH05509120A (de) |
CN (1) | CN1058609A (de) |
AT (1) | ATE124446T1 (de) |
DE (2) | DE4024657A1 (de) |
ES (1) | ES2073764T3 (de) |
WO (1) | WO1992002609A1 (de) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR0170424B1 (ko) * | 1990-07-05 | 1999-01-15 | 호르스트 헤를레,요한 글라슬 | 세제 및 청정제용 표면 활성제 과립의 제조방법 |
US5663136A (en) * | 1992-06-15 | 1997-09-02 | The Procter & Gamble Company | Process for making compact detergent compositions |
DE4243704A1 (de) * | 1992-12-23 | 1994-06-30 | Henkel Kgaa | Granulare Wasch- und/oder Reinigungsmittel |
IL108500A (en) * | 1994-01-31 | 1998-06-15 | Zohar Detergent Factory | Fatty alcohol sulphates in granular form and process for their preparation |
DE4406592A1 (de) * | 1994-03-01 | 1995-09-07 | Henkel Kgaa | Verbesserte Mehrstoffgemische auf Basis wasserlöslicher Alkalisilikatverbindungen und ihre Verwendung, insbesondere zum Einsatz als Builder in Wasch- und Reinigungsmitteln |
WO1996025482A1 (en) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
GB9513327D0 (en) * | 1995-06-30 | 1995-09-06 | Uniliver Plc | Process for the production of a detergent composition |
DE19524464C2 (de) * | 1995-07-10 | 2000-08-24 | Cognis Deutschland Gmbh | Verfahren zur Herstellung von Zuckertensidgranulaten |
GB9604022D0 (en) * | 1996-02-26 | 1996-04-24 | Unilever Plc | Anionic detergent particles |
GB9604000D0 (en) * | 1996-02-26 | 1996-04-24 | Unilever Plc | Production of anionic detergent particles |
US6296936B1 (en) | 1996-09-04 | 2001-10-02 | Kimberly-Clark Worldwide, Inc. | Coform material having improved fluid handling and method for producing |
US6204208B1 (en) | 1996-09-04 | 2001-03-20 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability and skin wellness |
US6017832A (en) * | 1996-09-04 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability |
US6028016A (en) * | 1996-09-04 | 2000-02-22 | Kimberly-Clark Worldwide, Inc. | Nonwoven Fabric Substrates Having a Durable Treatment |
DE19641275C1 (de) * | 1996-10-07 | 1998-03-12 | Henkel Kgaa | Verfahren zur Herstellung wasser- und staubfreier Aniontensidgranulate |
US5914308A (en) * | 1996-10-23 | 1999-06-22 | Henkel Corporation | Process for agglomerating detergent powders |
GB9711356D0 (en) † | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
DE19911040A1 (de) * | 1999-03-12 | 2000-09-21 | Cognis Deutschland Gmbh | Tensidgranulate |
DE10118270A1 (de) * | 2001-04-12 | 2002-10-17 | Cognis Deutschland Gmbh | Wasch- und Reinigungsmittelformittelkörper mit verbesserten Zerfallseigenschaften |
CN1970084B (zh) * | 2006-12-04 | 2010-08-25 | 山东大学 | 一种类水滑石-囊泡复合体及其制备方法 |
EP2614841B1 (de) | 2012-01-12 | 2014-09-10 | Evonik Industries AG | Verfahren zur kontinuierlichen Herstellung von wasserabsorbierenden Polymeren |
CN103487310B (zh) * | 2013-09-10 | 2015-08-05 | 付茜 | 一种沉积岩中干酪根分离前岩石样品的处理方法 |
DE102014010875A1 (de) * | 2014-07-25 | 2016-01-28 | Basf Se | Transparente Textilpflegemittel |
GB201714024D0 (en) * | 2017-09-01 | 2017-10-18 | Syngenta Participations Ag | Adjuvants |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA995092A (en) * | 1972-07-03 | 1976-08-17 | Rodney M. Wise | Sulfated alkyl ethoxylate-containing detergent composition |
DE3066054D1 (en) * | 1979-09-01 | 1984-02-09 | Henkel Kgaa | Watery tenside concentrates and process for the improvement of the flowing property of difficultly movable watery tenside concentrates |
DE3151679A1 (de) * | 1981-12-28 | 1983-07-07 | Henkel KGaA, 4000 Düsseldorf | "verwendung von viskositaetsreglern fuer tensidkonzentrate" |
DE3305430A1 (de) * | 1983-02-17 | 1984-08-23 | Henkel KGaA, 4000 Düsseldorf | Verwendung von alkoholen und deren derivaten als viskositaetsregler fuer hochviskose technische tensid-konzentrate |
DE3504896A1 (de) * | 1985-02-13 | 1986-08-14 | Basf Ag, 6700 Ludwigshafen | Zusaetze fuer wasch- und reinigungsmittel |
DE3621536A1 (de) * | 1986-06-27 | 1988-01-07 | Henkel Kgaa | Fluessiges waschmittel und verfahren zu seiner herstellung |
DE3630533A1 (de) * | 1986-09-08 | 1988-03-10 | Henkel Kgaa | Neue tensidgemische und ihre verwendung |
GB8811672D0 (en) * | 1988-05-17 | 1988-06-22 | Unilever Plc | Detergent composition |
US4898585A (en) * | 1988-05-18 | 1990-02-06 | Baxter Healthcare Corporation | Implantable patient-activated fluid delivery device with bolus injection port |
US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
DE3833780A1 (de) * | 1988-10-05 | 1990-04-12 | Henkel Kgaa | Verfahren zur direkten herstellung von alkylglykosiden |
-
1990
- 1990-08-03 DE DE4024657A patent/DE4024657A1/de not_active Withdrawn
-
1991
- 1991-07-25 US US07/978,701 patent/US5397507A/en not_active Expired - Lifetime
- 1991-07-25 DE DE59105890T patent/DE59105890D1/de not_active Expired - Lifetime
- 1991-07-25 WO PCT/EP1991/001395 patent/WO1992002609A1/de active IP Right Grant
- 1991-07-25 EP EP91913378A patent/EP0541608B1/de not_active Expired - Lifetime
- 1991-07-25 ES ES91913378T patent/ES2073764T3/es not_active Expired - Lifetime
- 1991-07-25 AT AT91913378T patent/ATE124446T1/de not_active IP Right Cessation
- 1991-07-25 CN CN91105045A patent/CN1058609A/zh active Pending
- 1991-07-25 JP JP3512532A patent/JPH05509120A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9202609A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1992002609A1 (de) | 1992-02-20 |
EP0541608B1 (de) | 1995-06-28 |
DE59105890D1 (de) | 1995-08-03 |
DE4024657A1 (de) | 1992-02-06 |
ATE124446T1 (de) | 1995-07-15 |
US5397507A (en) | 1995-03-14 |
CN1058609A (zh) | 1992-02-12 |
JPH05509120A (ja) | 1993-12-16 |
ES2073764T3 (es) | 1995-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0541608B1 (de) | Verfahren zur herstellung wasch- und reinigungsaktiver granulate | |
EP0603207B1 (de) | Verfahren zur herstellung von tensidgranulaten | |
DE68912983T2 (de) | Waschmittelzusammensetzungen und Verfahren zu deren Herstellung. | |
EP0777721B1 (de) | Verfahren zur herstellung von wasch- oder reinigungsmitteltabletten | |
EP0538294B1 (de) | Verfahren zur herstellung wasch- und reinigungsaktiver tensidgranulate | |
DE69216191T2 (de) | Waschmittelpulver und Verfahren zu deren Herstellung | |
WO1995022592A1 (de) | Waschmittel mit amorphen silikatischen buildersubstanzen | |
WO1990004629A2 (de) | Verfahren zur herstellung von tensidhaltigen granulaten | |
WO1993015180A1 (de) | Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schüttgewicht und verbesserter lösegeschwindigkeit | |
EP0772674B1 (de) | Verfahren zur herstellung von tensidgranulaten | |
DE69826492T2 (de) | Synthetische waschmittelformulierungen | |
WO1995008616A1 (de) | Detergensgemische und wasch- oder reinigungsmittel mit verbesserten löseeigenschaften | |
DE60213399T2 (de) | Körnige zusammensetzung | |
DE60023470T2 (de) | Waschpulver | |
DE68924373T2 (de) | Verfahren zur Herstellung konzentrierter Granulatkörner von oberflächenaktiven Mitteln. | |
EP0560802B2 (de) | Verfahren zur herstellung von zeolith-granulaten | |
DE2361876A1 (de) | Verfahren zur herstellung von pulverfoermigen waschmitteln und ihre verwendung in vollwaschmitteln | |
EP0623593A2 (de) | Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel | |
EP0839178B1 (de) | Amorphes alkalisilicat-compound | |
WO1994014946A1 (de) | Granulare wasch- und/oder reinigungsmittel | |
EP0874684B1 (de) | Verfahren zur herstellung eines granularen additivs | |
DE19531690A1 (de) | Figurenhaft ausgestaltete feste und verdichtete Mehrkomponentengemische aus dem Bereich der Wasch- und Reinigungsmittel sowie Verfahren zu ihrer Herstellung | |
DE69632549T2 (de) | Verfahren zur herstellung kompakter waschmittelgranulate | |
EP0836641B1 (de) | Von staub- und feinanteilen freie granulare wasch- und reinigungsmittel hoher schüttdichte | |
DE69122730T2 (de) | Waschpulver |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19930125 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19931202 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19950628 Ref country code: DK Effective date: 19950628 |
|
REF | Corresponds to: |
Ref document number: 124446 Country of ref document: AT Date of ref document: 19950715 Kind code of ref document: T |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19950731 |
|
REF | Corresponds to: |
Ref document number: 59105890 Country of ref document: DE Date of ref document: 19950803 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2073764 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19951108 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20010704 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20010711 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20010730 Year of fee payment: 11 Ref country code: NL Payment date: 20010730 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20010918 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020726 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 |
|
BERE | Be: lapsed |
Owner name: *HENKEL K.G.A.A. Effective date: 20020731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030201 |
|
EUG | Se: european patent has lapsed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030201 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20090514 AND 20090520 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20100813 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20100721 Year of fee payment: 20 Ref country code: FR Payment date: 20100805 Year of fee payment: 20 Ref country code: DE Payment date: 20100721 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20100721 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59105890 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59105890 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20110724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110724 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20120110 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110726 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110726 |