EP0626004B1 - Procede de stabilisation de suspensions aqueuses de zeolites - Google Patents
Procede de stabilisation de suspensions aqueuses de zeolites Download PDFInfo
- Publication number
- EP0626004B1 EP0626004B1 EP93909530A EP93909530A EP0626004B1 EP 0626004 B1 EP0626004 B1 EP 0626004B1 EP 93909530 A EP93909530 A EP 93909530A EP 93909530 A EP93909530 A EP 93909530A EP 0626004 B1 EP0626004 B1 EP 0626004B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- suspensions
- fatty alcohol
- polyethylene glycol
- zeolite
- glycol ethers
- 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.)
- Expired - Lifetime
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 27
- 239000000725 suspension Substances 0.000 title claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 22
- 150000002170 ethers Chemical class 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 2
- -1 poly(ethylene glycol) Polymers 0.000 abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000013049 sediment Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 238000007046 ethoxylation reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 244000090125 Solidago odora Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
Definitions
- the invention relates to a method for stabilizing aqueous zeolite suspensions by adding selected fatty alcohol polyethylene glycol ethers.
- Zeolites in particular of the zeolite A type, are of particular importance as building blocks of modern detergents and have largely replaced the polyphosphates that have been used for decades. Their advantages lie not only in their high calcium binding capacity, but also in their high ecotoxicological compatibility [Tens.surf. Det., 24 , 322 (1987)] .
- the zeolites are obtained in the form of aqueous suspensions, which can either be stored as such and placed on the market, or can be subjected to spray drying.
- Zeolites have an extremely low solubility in water, so that suspensions of these substances are easy sediment. In the most favorable case, this leads to a phase separation, but usually considerable amounts of the solid separate out on the bottom of the vessels during storage, harden and then have to be separated, comminuted and resuspended with great technical effort. In other cases, the viscosity of the suspension increases so much that decanting or pumping over becomes difficult, if not impossible, and in any case is associated with considerable product losses.
- German patent application DE 33 30 220 A1 proposes adding 0.5 to 5% by weight of a mixture of fatty alcohol ethoxylates and fatty alcohol sulfates or fatty alcohol ether sulfates to the suspensions.
- German patent application DE 34 08 040 A1 describes a process for stabilizing 65% by weight zeolite A suspensions with the aid of 0.01 to 0.25% by weight xanthan gum and carboxyl- or hydroxyl-containing polymers.
- zeolite suspensions can also be stabilized at pH 9 to 10 by adding polyglycol ethers, fatty alcohol ether sulfates, fatty acid alkanolamides or fatty acid monoglycerides.
- EP-A 0 294 574 discloses methods for stabilizing aqueous mixtures of zeolites by adding nonionic surfactants, these are EO adducts of oxo alcohols which, for production reasons, contain up to 25% branched species.
- the literature also discloses the use of numerous other stabilizers, for example polycarboxylates with molecular weights above 1500, phosphonic acids, phosphoric acid esters, alkylbenzenesulfonates, layered silicates [ DE-OS 27 388 ], alkylphenol polyglycol ethers [ DE 34 01 861 A1 ], isotridecyl polyglycol ethers [ DE 34 44 311 A1 ] and addition products of ethylene oxide to oxo alcohols [ DE 37 19 042 A1 ].
- stabilizers for example polycarboxylates with molecular weights above 1500, phosphonic acids, phosphoric acid esters, alkylbenzenesulfonates, layered silicates [ DE-OS 27 388 ], alkylphenol polyglycol ethers [ DE 34 01 861 A1 ], isotridecyl polyglycol ethers [ DE 34 44 311 A1 ] and addition products of ethylene oxide to ox
- the object of the invention was therefore to develop an improved method for stabilizing aqueous zeolite suspensions which is free from the disadvantages described.
- the use of the selected fatty alcohol polyethylene glycol ethers or mixtures thereof with one another can reliably stabilize suspensions of zeolites over a wide temperature range, in particular from 10 to 60 ° C.
- the suspensions have a high storage stability even over a longer period of time, can be conveyed through pipelines and can be easily poured out with only minor product losses.
- Zeolites are optionally to be understood as meaning water-containing alkali metal or alkaline earth metal aluminosilicates of the general formula (V) M 2 / z O * Al2O3 * x SiO2 * y H2O (V) where M stands for an alkali or alkaline earth metal of valence z, x for numbers from 1.8 to 12 and y for numbers from 0 to 8 [Chem.iuZt., 20 , 117 (1986)] .
- Typical examples of zeolites whose aqueous dispersions can be stabilized in the process according to the invention are the naturally occurring minerals Clinoptilolite, erionite or chabazite.
- synthetic zeolites are preferred, for example Zeolite X Na86 [(AlO2) 86 (SiO2) 106] * 264 H2O Zeolite Y Na56 [(AlO2) 56 (SiO2) 136] * 325 H2O Zeolite L K9 [(AlO2) 9 (SiO2) 27] * 22 H2O Mordenite Na 8.7 [(AlO2) 8.7 (SiO2) 39.3 ] * 24 H2O and particularly Zeolite A Na12 [(AlO2) 12 (SiO2) 12] * 27 H2O.
- the aqueous suspensions can contain the zeolites in amounts of 20 to 60, preferably 25 to 50% by weight.
- Fatty alcohol polyethylene glycol ethers are known nonionic surfactants which are produced on an industrial scale by the process of ethoxylation known per se.
- addition products of an average of 4.2 to 4.8 mol of ethylene oxide onto technically strictly linear aliphatic fatty alcohols having 12 to 14 carbon atoms and 0 double bond are suitable as stabilizers.
- Typical examples are ethylene oxide adducts with lauryl alcohol and myristyl alcohol.
- Fatty alcohol polyglycol ethers of the formula (I) are preferred, in which R1 represents a strictly linear aliphatic alkyl radical having 12 to 14 carbon atoms and n represents numbers from 4.2 to 4.8.
- the fatty alcohol polyethylene glycol ethers can have both a conventional and a narrow homolog distribution, as is obtained, for example, when the ethoxylation of the fatty alcohols is carried out in the presence of hydrotalcite catalysts.
- fatty alcohol polyethylene glycol ethers can also be used, which are not derived from pure alcohols but from technical cuts, such as those obtained in the selective hydrogenation of fatty acid methyl ester fractions based on vegetable or animal raw materials.
- Fatty alcohol polyethylene glycol ethers based on coconut fatty alcohols are preferably used.
- Particularly preferred is an adduct of an average of 4.4 moles of ethylene oxide with a technical C 12/14 fatty alcohol with an iodine number in the range from 5 to 95, preferably 10 to 55.
- the fatty alcohol polyethylene glycol ethers can be used individually or as a mixture.
- mixtures of fatty alcohol polyethylene glycol ethers of a higher and / or lower average degree of ethoxylation can also be used or used if the average degree of ethoxylation of the resulting ones Mixture is within the range of 4.2 to 4.8 according to the invention.
- the introduction of the fatty alcohol polyethylene glycol ether into the suspension is not critical and can e.g. B. mechanically by stirring, optionally at elevated temperatures of 50 ° C. There is no chemical reaction.
- the stabilizers can be added to the suspensions in amounts of 0.1 to 5, preferably 1 to 3% by weight, based on the suspension.
- the zeolite suspensions obtainable by the process according to the invention are stable in temperature and storage. They are suitable, for example, for the production of washing and cleaning agent concentrates.
- Stabilizers A1 to A3 are according to the invention, stabilizers B1 to B3 are used for comparison.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Des suspensions aqueuses de zéolites sont stabilisées en ajoutant à celles-ci un polyéthylèneglycoléther d'alcool gras ayant la formule (I): R1O-(CH2CH2O)nH dans laquelle R1 désigne un reste alkyle ou alcényle aliphatique de 12 à 18 atomes de carbone, et n est un nombre compris entre 4 et 7.
Claims (3)
- Procédé pour la stabilisation de suspensions aqueuses de zéolithes par addition d'agents tensioactifs, caractérisé en ce qu'on ajoute aux suspensions exclusivement des éthers d'alcools gras-polyéthylèneglycol de formule (I)
R¹-O-(CH₂CH₂O)nH (I)
dans laquelle R¹ représente un radical alkyle aliphatique rigoureusement linéaire contenant de 12 à 14 atomes de carbone et n représente des nombres de 4,2 à 4,8. - Procédé selon la revendication 1, caractérisé en ce qu'on ajoute les éthers d'alcools gras-polyéthylèneglycol à des suspensions aqueuses de zéolithes A, qui présentent des zéolithes dans des quantités de 20 à 60% en poids.
- Procédé selon les revendications 1 et 2, caractérisé en ce qu'on ajoute aux suspensions les éthers d'alcools gras-polyéthylèneglycol dans des quantités de 0,1 à 5% en poids - rapportées à la suspension - .
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4203789A DE4203789A1 (de) | 1992-02-10 | 1992-02-10 | Verfahren zur stabilisierung von waessrigen zeolith-suspensionen |
| DE4203789 | 1992-02-10 | ||
| PCT/EP1993/000227 WO1993016159A1 (fr) | 1992-02-10 | 1993-02-01 | Procede de stabilisation de suspensions aqueuses de zeolites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0626004A1 EP0626004A1 (fr) | 1994-11-30 |
| EP0626004B1 true EP0626004B1 (fr) | 1996-05-15 |
Family
ID=6451311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93909530A Expired - Lifetime EP0626004B1 (fr) | 1992-02-10 | 1993-02-01 | Procede de stabilisation de suspensions aqueuses de zeolites |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5501817A (fr) |
| EP (1) | EP0626004B1 (fr) |
| JP (1) | JPH07503493A (fr) |
| KR (1) | KR950700398A (fr) |
| DE (2) | DE4203789A1 (fr) |
| ES (1) | ES2086940T3 (fr) |
| WO (1) | WO1993016159A1 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2872152B1 (fr) * | 2004-06-24 | 2006-08-11 | Inst Francais Du Petrole | Materiau a porosite hierarchisee comprenant du silicium |
| FR2920758B1 (fr) * | 2007-09-07 | 2009-11-13 | Inst Francais Du Petrole | Materiau cristallise a porosite hierarchisee et comprenant du silicium |
| EP3636691B1 (fr) | 2015-10-07 | 2021-03-03 | Elementis Specialties, Inc. | Agent mouillant et antimousse |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4083793A (en) * | 1973-05-23 | 1978-04-11 | Henkel Kommanditgesellschaft Auf Aktien | Washing compositions containing aluminosilicates and nonionics and method of washing textiles |
| US4169075A (en) * | 1974-10-10 | 1979-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of powdery washing agents by spray-drying |
| AT335035B (de) * | 1974-10-10 | 1977-02-25 | Henkel & Cie Gmbh | Stabile suspensionen wasserunloslicher, zum binden von calciumionen befahigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln |
| AT362481B (de) * | 1976-02-06 | 1981-05-25 | Henkel Kgaa | Stabile, pumpfaehige, als vorratssuspension geeignete waesserige suspension von wasserun- loeslichen, zum binden von calcium befaehigten silikaten |
| BE874420A (fr) * | 1978-03-02 | 1979-08-23 | Unilever Nv | Procede de production de compositions detergentes |
| GB2015488B (en) * | 1978-03-02 | 1982-09-22 | Unilever Ltd | Stabilised sodium aluminosilicate suspensions |
| JPS6022644B2 (ja) * | 1980-09-30 | 1985-06-03 | ライオン株式会社 | 水性ゼオライト懸濁液 |
| JPS5761616A (en) * | 1980-09-30 | 1982-04-14 | Lion Corp | Preparation of zeolite suspension |
| US4405483A (en) * | 1982-04-27 | 1983-09-20 | The Procter & Gamble Company | Stable liquid detergents containing aluminosilicate ion exchange material |
| US4483012A (en) * | 1983-04-18 | 1984-11-13 | At&T Information Systems | Differentially convolutional channel coding with expanded set of signalling alphabets |
| DE3423351A1 (de) * | 1984-06-25 | 1986-01-02 | Henkel KGaA, 4000 Düsseldorf | Stabilisierte, waessrige zeolith-suspension |
| ATE32328T1 (de) * | 1983-08-22 | 1988-02-15 | Henkel Kgaa | Stabilisierte, waessrige zeolith-suspension. |
| DE3330220A1 (de) * | 1983-08-22 | 1985-03-07 | Henkel KGaA, 4000 Düsseldorf | Stabilisierte, waessrige zeolith-suspension |
| DE3401861A1 (de) * | 1983-09-06 | 1985-03-21 | Degussa Ag, 6000 Frankfurt | Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate, deren verwendung zur herstellung von phosphatsubstituten fuer wasch- und reinigungsmittel und phosphatsubstitute |
| DE3408040A1 (de) * | 1984-03-05 | 1985-09-12 | Henkel KGaA, 4000 Düsseldorf | Stabilisierte, waessrige zeolith-suspension |
| DE3444311A1 (de) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln |
| DE3504451A1 (de) * | 1985-02-09 | 1986-08-14 | Degussa Ag, 6000 Frankfurt | Waschmittelbuilder |
| EP0294574A3 (fr) * | 1987-06-06 | 1989-04-26 | Degussa Aktiengesellschaft | Suspensions de silicates aqueuses stables, insolubles dans l'eau capables de fixer des ions de calcium et leur utilisation pour la production d'agents de lavage et de nettoyage |
| US5174918A (en) * | 1987-06-06 | 1992-12-29 | Degussa Ag | Stable aqueous suspensions of detergent zeolites and four oxo-alcohol ethoxylates |
| DE3835918A1 (de) * | 1988-10-21 | 1990-04-26 | Henkel Kgaa | Verfahren zur herstellung von tensidhaltigen granulaten |
| DE3929591A1 (de) * | 1989-09-06 | 1991-03-07 | Henkel Kgaa | Zeolithhaltiges fluessigwaschmittel |
| DE4109501A1 (de) * | 1991-03-22 | 1992-09-24 | Degussa | Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln |
| IT1250437B (it) * | 1991-07-01 | 1995-04-07 | Paolo Colombo | Sospensioni acquose stabili e facilmente pompabili di zeolite |
| DE4124247A1 (de) * | 1991-07-22 | 1993-01-28 | Henkel Kgaa | Verfahren zur stabilisierung von waessrigen zeolith-suspensionen |
-
1992
- 1992-02-10 DE DE4203789A patent/DE4203789A1/de not_active Withdrawn
-
1993
- 1993-02-01 KR KR1019940702702A patent/KR950700398A/ko not_active Withdrawn
- 1993-02-01 DE DE59302613T patent/DE59302613D1/de not_active Expired - Fee Related
- 1993-02-01 US US08/284,594 patent/US5501817A/en not_active Expired - Fee Related
- 1993-02-01 JP JP5513730A patent/JPH07503493A/ja active Pending
- 1993-02-01 ES ES93909530T patent/ES2086940T3/es not_active Expired - Lifetime
- 1993-02-01 EP EP93909530A patent/EP0626004B1/fr not_active Expired - Lifetime
- 1993-02-01 WO PCT/EP1993/000227 patent/WO1993016159A1/fr active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993016159A1 (fr) | 1993-08-19 |
| ES2086940T3 (es) | 1996-07-01 |
| DE59302613D1 (de) | 1996-06-20 |
| KR950700398A (ko) | 1995-01-16 |
| EP0626004A1 (fr) | 1994-11-30 |
| DE4203789A1 (de) | 1993-08-12 |
| US5501817A (en) | 1996-03-26 |
| JPH07503493A (ja) | 1995-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0161537A2 (fr) | Alcoxylates d'alcool gras ayant des groupes terminaux pour les procédés industriels de nettoyage spécialement pour le lavage de bouteilles et pour le nettoyage du métal | |
| EP0111135A2 (fr) | Utilisation d'acides alkylmonophosphoniques comme substances germicides dans les solutions acides | |
| EP0613457B1 (fr) | Esters d'acides gras avec polyols ethoxyles | |
| EP0185660B1 (fr) | Suspension aqueuse, stabilisee a base de zeolithe | |
| EP0231890A2 (fr) | Méthode pour la purification d'alkylglycosides, les produits ainsi obtenus et leur utilisation | |
| DE1280455B (de) | Hochalkalische, lagerstabile und schaumarme Flaschenreinigungsmittel | |
| CH667669A5 (de) | Im wesentlichen wasserfreies, fluessiges grobwaschmittel. | |
| DE2643699B2 (de) | Granulierte oder pulvrige Reinigungsmittelmischung | |
| DE4218050A1 (de) | Verfahren zur Entwässerung von feinteiligen Feststoffsuspensionen | |
| EP0626004B1 (fr) | Procede de stabilisation de suspensions aqueuses de zeolites | |
| EP0652932B1 (fr) | Procede de fabrication d'agents tensioactifs non ioniques stables au stockage | |
| DE4121147A1 (de) | Antischaummittel | |
| EP0324339A2 (fr) | Agent antimousse pour détergents contenant du chlore actif | |
| EP0573448B1 (fr) | Procede de production de pates de sulfate d'alkyle et/ou d'alcenyle a fluidite amelioree | |
| EP0295384B1 (fr) | Procédé pour diminuer la tendance à l'agglomération de composés oxygénés actifs sous forme de particules | |
| AT395169B (de) | Fluessiges nicht-waesseriges grobwaschmittel | |
| EP0647215B1 (fr) | Procede de fabrication de melanges d'oligoglycerine a teneur elevee en diglycerine | |
| EP0595919B1 (fr) | Procede de stabilisation de suspensions aqueuses de zeolites | |
| EP0040343B1 (fr) | Composés tensio-actifs non-ioniques à couleur stabilisée et leur utilisation comme substances actives dans des compositions de lavage et de nettoyage | |
| EP0652799B1 (fr) | Agents antimousse fermes au niveau du groupe terminal | |
| DE4342214C1 (de) | Nichtionische Detergensgemische | |
| DE2421924C2 (de) | Verfahren zum Herstellen von kugelförmigen Natriumperboratkörnern | |
| DE3837947A1 (de) | Neue fettalkoholgemische und ihre ethoxylate mit verbessertem kaelteverhalten | |
| EP0069332B2 (fr) | Composés solides, très alcalins et contenant du chlore actif | |
| CH684933A5 (de) | Schaumarme oberflächenaktive Verbindungen. |
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: 19940729 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES GB IT NL |
|
| 17Q | First examination report despatched |
Effective date: 19950513 |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES GB IT NL |
|
| REF | Corresponds to: |
Ref document number: 59302613 Country of ref document: DE Date of ref document: 19960620 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2086940 Country of ref document: ES Kind code of ref document: T3 |
|
| ITF | It: translation for a ep patent filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19960806 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19970228 |
|
| 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 | ||
| BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 19970228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19970901 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19970901 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20020717 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020827 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20020829 Year of fee payment: 10 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20030201 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20030203 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20030902 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030203 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050201 |