[go: up one dir, main page]

EP0185660A1 - Suspension aqueuse, stabilisee a base de zeolithe. - Google Patents

Suspension aqueuse, stabilisee a base de zeolithe.

Info

Publication number
EP0185660A1
EP0185660A1 EP84903064A EP84903064A EP0185660A1 EP 0185660 A1 EP0185660 A1 EP 0185660A1 EP 84903064 A EP84903064 A EP 84903064A EP 84903064 A EP84903064 A EP 84903064A EP 0185660 A1 EP0185660 A1 EP 0185660A1
Authority
EP
European Patent Office
Prior art keywords
suspension
zeolite
water
suspensions
acid
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
Application number
EP84903064A
Other languages
German (de)
English (en)
Other versions
EP0185660B1 (fr
Inventor
Elmar Wilms
Karl-Dieter Herold
Rainer Salz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19833330220 external-priority patent/DE3330220A1/de
Priority claimed from DE19843423351 external-priority patent/DE3423351A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT84903064T priority Critical patent/ATE32328T1/de
Publication of EP0185660A1 publication Critical patent/EP0185660A1/fr
Application granted granted Critical
Publication of EP0185660B1 publication Critical patent/EP0185660B1/fr
Expired legal-status Critical Current

Links

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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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 stabilized, aqueous suspension of synthetically produced zeolite of type A, a process for the production of this suspension on an industrial scale and the use of the suspension for the production of low-phosphate and phosphate-free powder detergents.
  • the stabilizers of DE-OS 2527 388 are used together with a stabilizing aid from the group of non-surfactant organic and inorganic water-soluble salts with molecular weights below 1,000, for example sodium sulfate, sodium citrate, sodium tripolyphosphate, sodium carbonate, etc.; this gives greater flexibility in adapting the viscosity of the suspensions to the storage and processing conditions.
  • German Offenlegungsschrift 30 21 295 recommends the use of nitrilotriacetate sodium salt; on the other hand, water glass solutions, gel-like aluminum oxides or silicon oxides, soaps of the chain length C 5 -C 22 , or sodium salts of the type of washing alkalis, including sodium hydroxide, are described in Japanese laid-open publications 54 064 504, 55 127 499, 57 034017, 57 061 615 and 57 067 697 suggested.
  • the requirements for the properties of the zeolite suspensions depend to a certain extent on the type of washing and cleaning agents for which they are to be used; However, it has been found that the zeolite suspensions, in order to be usable on an industrial scale, should have the following individual properties: stability in the widest possible temperature range, which ranges from room temperature or below to at least 70 ° C .; a sediment, if it arises after prolonged storage, must be able to be stirred up again using technical stirrers; the viscosity should remain low even in the lower temperature range, ie
  • the stabilized aqueous zeolite suspension that of industrially produced A-type zeolite, water and a stabilizer system with water-insoluble nonionic surfactant as suspension stabilizer and an additional stabilizing agent, can be significantly improved in its properties if the stabilizing agent consists of an anionic sulfate surfactant from the group
  • the proportions of the stabilizer system consisting of the suspension stabilizer and the stabilizing aid in the suspension according to the invention are preferably in the range from 0.5 to 5% by weight. Amounts of 1 to 3% by weight and in particular those of 1.5 to 2.5% by weight, based in each case on the stabilized aqueous zeolite suspension, are particularly preferred. Within these quantitative ranges, the ratio of the nonionic surfactant to the anionic sulfate surfactant is in the range from 5: 1 to 1: 5, and preferably in the range from 3: 1 to 1: 1.
  • the suspension according to the invention is low-viscosity over the entire temperature range from room temperature to 80 ° C. and can be stirred and pumped without problems.
  • Room temperature is understood here to mean the temperatures in the storage and processing rooms which fluctuate in the range from 15 to 25 C, depending on the season. Even after storage for several days in this temperature range, especially at elevated temperatures of 50 to 70 ° C, only a small amount of soft sediment is formed, which can be easily stirred up again.
  • the suspension according to the invention also shows excellent rheological properties, which are characterized above all by a narrow viscosity range and by perfect flow behavior.
  • the zeolite suspension In some technical processing equipment for zeolite suspensions for the production of powdered detergents, the zeolite suspension must be warmed, ie. above room temperature. It is then crucial for usability that the suspension remains stable over a longer period of time at elevated temperature and does not disintegrate.
  • the pH value of the aqueous zeolite suspension which is at pH 11 to 14, is not changed significantly by the stabilizer system according to the invention comprising nonionic surfactant and anionic sulfate surfactant.
  • the pH fluctuations caused by the free alkali present in industrial production have a significantly reduced influence on the stability of the suspension when the stabilizer system according to the invention is used.
  • a further reduction in viscosity is achieved by a targeted lowering of the pH by adjusting the suspensions to a pH of less than 12, in particular from 9 to 1 1, and adjusting this pH by adding an acidic salt.
  • the addition of acidic salt is generally in the range from 0.2 to 3% by weight, based on the finished suspension in which this salt is then present as a neutral salt.
  • the stabilizer system according to the invention has no negative influence on the calcium binding capacity of the zeolite.
  • the stabilizer system according to the invention consists of a mixture of detergent substances known per se; the zeolite suspension thus stabilized is therefore not only useful for the production of a large number of detergents and cleaning agents, but these detergent active substances which enter the finished detergents and cleaning agents via the zeolite suspension make a contribution to the washing and cleaning success of the finished product.
  • the neutral salts formed from the acidic salts are also generally used as components of detergents and cleaning agents.
  • Aqueous zeolite suspensions with an addition of dispersants from the group of water-soluble nonionic surfactants and synthetic organic surfactants of the sulfonate type are known from US Pat. No. 3,254,034 (Dwyer et al). These known zeolite suspensions are used to exchange the sodium cations for the rare earth cations and then to work up the exchanged zeolites into catalysts. In these known suspensions, which are constantly moved, special storage stability is not important; It is important, however, that only readily soluble compounds which can easily be separated off again after the cation exchange by filtration can be considered as organic additives.
  • the nonionic surfactant defined above is generally in amounts of 0.2 to 3% by weight and the stabilizing aid according to a) and / or b) according to the above definition in amounts of 0.2 to 3% by weight is present, the total amount of nonionic surfactant and stabilizing aid being in the range 0.5 to 5% by weight, based on the stabilized zeolite suspension.
  • the maximum amounts mentioned in order to achieve the improved viscosity and storage properties rather, total amounts of up to 2.5% by weight are sufficient for most further processing purposes.
  • the pH of aqueous zeolite suspensions which do not contain a stabilizer or a stabilizer which does not influence the pH is from pH 11 to pH 14, i.e. there is an excess of alkali. This alkali excess is often welcomed for further processing into detergents and cleaning agents because it is included in the final detergent product as an alkali reserve. If the pH value is lowered by the further addition of the acid salt, the corresponding neutral salts are formed, which, when the acid salts are selected appropriately, are also considered to be typical washing and cleaning agent components because they impart advantageous properties to the finished product.
  • German Offenlegungsschrift 26 52 409 recommends adding acid or an acid salt to the freshly prepared zeolite suspension to such an extent that the pH does not drop below 9.0. This measure improves the buffering capacity of the zeolite.
  • the references mentioned also explain that special precautions must be taken when admixing the acid, so that there is no local over-concentration of acid and the acid-sensitive zeolite structure is not destroyed.
  • German Offenlegungsschrift 26 15 698 describes the addition of a non-surfactant, organic or inorganic low molecular weight salt as a stabilizing aid to a stabilized zeolite suspension
  • European Offenlegungsschrift 870 describes the improvement of the rheological properties of zeolite suspensions by adding sodium sulfate -Neutral salt is known, but this prior art, neither as a single document nor when considered together, suggests adding an acidic salt for targeted pH adjustment to an aqueous zeolite suspension already stabilized by a stabilizer system comprising a nonionic and a sulfate surfactant, and thus to the desired narrow range of low viscosity, which is not temperature-dependent.
  • the anionic salt for targeted pH adjustment to an aqueous zeolite suspension already stabilized by a stabilizer system comprising a nonionic and a sulfate surfactant, and thus to the desired narrow range of low viscosity, which is not temperature-dependent.
  • Sulfate surfactants according to a) preferably the sulfuric acid monoester of a primary C 12 -C 18 alkanol in the form of the water-soluble salt, and as
  • Sulfate surfactant according to b) preferably the sulfuric acid monoester of a primary C 12 -C 18 alkanol reacted with ethylene oxide, likewise in the form of the water-soluble salt.
  • the degree of ethoxylation of the sulfate surfactants according to b) is generally on average 1 to 15 moles of ethylene oxide per mole of the alkanol, preferably 1 to 4 moles of ethylene oxide.
  • the C 12 -C 18 fatty alcohols which can be prepared from natural fats are particularly preferred. Such derivatives combine the particularly good stabilizing properties with those of perfect biodegradability and good accessibility from natural renewable raw materials.
  • Typical representatives of the sulfate surfactants used according to the invention are, for example, the products tallow alcohol sulfate (TAS) (where "tallow alcohol” stands for the hydrogenated tallow fatty alcohol mixture of the chain length range C 14 -C 18 ); Lauryl alcohol sulfate; Coconut alcohol sulfate (KOAS) (where "coconut alcohol” stands for the C 12 / C 18 cut from natural coconut fatty alcohol); Lauryl alcohol ether sulfate (LAES) (made from a C 12 / C 14 fatty alcohol reacted with 2 to 3 moles of ethylene oxide); coconut / tallow alcohol sulfate (made from coconut and tallow alcohol in a 1: 1 ratio); Cetyl / stearyl alcohol sulfate (Applicant's Lanette E product); Tallow alcohol 2EO sulfate.
  • TAS tallow alcohol sulfate
  • tallow alcohol stands for the hydrogenated tallow fatty alcohol mixture
  • Sulfate surfactants are present as sodium salts or as ethanolamine salts or triethanolamine salts.
  • the practically water-insoluble nonionic surfactants used as suspension stabilizers are those compounds whose cloud point, if determined by the method DIN 53917 in aqueous butyl diglycol solution, is 90 ° C and below, preferably 85 ° C and below. These nonionic surfactants are described in detail in German Offenlegungsschaben 25 27 388 and 26 15 698.
  • Typical examples of these practically water-insoluble nonionic surfactants are, for example, the verbin fertilize tallow alcohol polyglycol ether with 5 moles of ethylene oxide (TA 5E0); coconut alcohol (C 12 -C 18 cut ) polyglycol ether with 4 moles of ethylene oxide; Oleyl alcohol polyglycol ether with 5 moles of ethylene oxide; Oleyl / cetyl alcohol polyglycol ether with 7 moles of EO (made from an alcohol mixture with an iodine number of 50 to 55); C 14 -C 15 oxo alcohol polyglycol ether with 4 moles of EO; Nonylphenolp ⁇ lyglykolether with 5 moles of ethylene oxide.
  • T 5E0 the verbin fertilize tallow alcohol polyglycol ether with 5 moles of ethylene oxide
  • the amount of the acid salt is generally in the range from 0.2 to 3% by weight, based on the finished suspension. In individual cases, the additional quantities can also be above or below these range limits. In any case, the amount of acid salt added depends on the pH of the moist zeolite filter cake or the zeolite suspension at the end of the zeolite production process. The pH value is therefore not only dependent on the choice of the zeolite production process, but also on the degree of washing out of the zeolite with water.
  • the acidic salt is added in solid form or in the form of a concentrated aqueous solution in small portions with stirring.
  • the acid salts which can be used according to the invention are primarily inorganic acid salts, in particular the acid salts of sulfuric acid, carbonic acid, phosphoric acid and polyphosphoric acids, boric acid and silica.
  • the acid salts of polyvalent organic acids such as, for example, citric acid, diglycolic acid, gluconic acid, polyacrylic acid, nitrilotriacetic acid, hydroxyethane diphosphonic acid and analogous hydroxyalkane or aminoalkane polyphosphonic acids, can be used, although less preferred.
  • the acid salts of other inorganic and organic acids are also suitable; however, those acidic salts are considered preferred which are present after the partial neutralization as neutral salts which play an advantageous role in building up the detergent and cleaning agent or during the washing or cleaning process.
  • Acid salts are accordingly the salts of polyvalent acids which have at least one alkali or asmonium cation and react with the alkali in the aqueous zeolite suspension with partial neutralization.
  • the zeolite A used according to the invention can be prepared by numerous known processes by hydrothermal synthesis from sodium silicate and sodium aluminate solutions or from destructured kaolin and sodium hydroxide.
  • zeolite A is generally obtained as a moist filter cake with about 50 to 60% water content. Because of its thixotropic properties, this filter cake can be easily stirred immediately after production and mixed directly with the suspension stabilizer.
  • the suspensions according to the invention can be prepared by simply mixing the components.
  • the aqueous suspension of the zeolite which is still moist and undried from its production is preferably used by converting the moist filter cake obtained after separating the mother liquor and washing with water into a flowable suspension by stirring. A further addition of water is generally not necessary.
  • the stabilizing agents are used in the case of the nonionic surfactants in undiluted form and in the case of the anionic sulfate surfactants in the form of the commercially available technical aqueous concentrates of the sodium salts or as granules, flakes or pasta.
  • the acidic salts are mostly added in powder form.
  • the amount of water additionally introduced with paste-like concentrates is small in terms of quantity, so that it does not significantly influence the zeolite concentration in the stabilized suspension.
  • the suspensions according to the invention can be prepared with zeolite concentrations of at least 20% by weight; however, for economic reasons, ie in order to save transport and energy costs, for example Set the water content in the suspensions as low as possible. For example, efforts will be made to adjust the zeolite content to values above 40% by weight and, if possible, to values around 50% by weight.
  • the suspensions according to the invention are generally prepared at elevated temperatures, ie at about 50 ° C., which speeds up the mixing process.
  • an already dried zeolite powder can also be used for the production of the suspensions according to the invention if the zeolite filter cake that is still moist from the production is not available.
  • the stabilized zeolite suspensions are used as liquid raw materials according to the usual manufacturing processes for such agents.
  • the stabilized zeolite suspensions for the production of powdered detergents by the method of hot spray drying, the so-called slurry batch being prepared with the zeolite suspension and then converted into a detergent powder in spray towers in the usual way.
  • the suspension according to the invention can also be converted into a spray-dried powder as such or after the addition of further detergent substances.
  • the resulting powder product can be stirred again with water to a stable suspension, which increases the practical application possibilities for the suspension according to the invention.
  • Stabilizer system consisting of nonionic surfactant and anionic sulfate surfactant
  • a moist filter cake of zeolite NaA with the following properties was used to prepare the stabilized suspensions: Zeolite NaA content, based on the anhydrous substance (residue on ignition after heating to 800 ° C. for one hour): 47.0%;
  • the stabilized suspension had the following composition:
  • TA 5 EO 0.8% by weight of tallow fatty alcohol sulfate (TAS), 46.0% by weight of zeolite NaA, 0.35% by weight of sodium oxide, the rest being water.
  • TAS tallow fatty alcohol sulfate
  • the Brookfield viscosity was determined: 20 revolutions per
  • the viscosity behavior of the suspension according to the invention extends practically over the entire temperature range.
  • Example 1 describe bench tests of three suspensions according to the invention in comparison to a known suspension (see Example 1).
  • the stored suspensions are classified according to the criteria of sedimentation, i.e. Sediment formation and consistency assessment.
  • B W + low sediment formation, soft, easy to stir
  • B W sediment formation with a soft consistency, easy to stir
  • B M sediment formation with medium consistency, difficult to stir
  • B H sediment formation with hard consistency, cannot be stirred.
  • the storage tests were carried out at room temperature, 35 ° C, 50 ° C and 70 ° C, respectively. The viscosity of the suspensions was also measured at these temperatures before storage; No change in viscosity was observed during the storage period in the case of the completely homogeneous suspensions and in the case of the again stirred suspensions with a soft sediment consistency.
  • TA 5 EO and TAS have the meanings given in Example 1.
  • KOAS coconut fatty alcohol sulfate sodium salt (C 14 -C 18 cut ).
  • LAES lauryl alcohol (C 12 / C 14 ) ether sulfate sodium salt (with approx. 2 mol EO).
  • Stabilizer system composed of nonionic surfactant and anionic sulfate surfactant and with the addition of an acidic salt
  • the zeolite A filter cake used had the following properties:
  • Zeolite A content 46%; Calcium binding capacity: 160 mg CaO / g;
  • Particle size 100% smaller than 25 ⁇ ; 95% less than 10 ⁇ ; 71% less than 5 ⁇ ; 18% less than 3 ⁇ ; average particle diameter: 4.0 ⁇ ; Alkali content: 0.35% by weight.
  • the stabilized suspension had the following composition:
  • TAS tallow fatty alcohol sulfate
  • the Brookfield viscosity was determined: 20 revolutions per minute; Spindle depending on the viscosity range.
  • Example 6 the acidic salt NaHSO 4 is replaced by NaH 2 PO 4 , or the stabilizer TA 5 is reacted with a mixture of oleyl / cetyl alcohol with an iodine value of 50 to 55 in the same quantity, reacted with 4 mol or 6 mol ethylene oxide in a ratio of 1 : 1, replaced, then similar viscosity and stability properties are also observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Saccharide Compounds (AREA)

Abstract

Le système de stabilisation pour les suspensions préparées à partir de zéolithe A et d'eau présente la composition suivante: d'une part, un surfactif non-ionique, insoluble dans l'eau, tel que des polyéthers à base de glycol et d'alcool de la série grasse, et d'autre part, un surfactif anionique de la série sulfate, en particulier des mono-esters de l'acide sulfurique et soit d'alcools primaires en C12 à C18 respectivement d'alcools secondaires en C10 à C20, sous la forme de sels aqua-solubles, ou alors, des produits de réaction à base d'alcools sulfatés ayant réagi avec 1 à 4 mol-équivalent(s) d'oxyde d'éthylène, ou alors, d'alcanol-amides sulfatés de la série d'acides gras respectivement de mono-glycérides sulfatés de la série d'acides gras; et ceci, sous la forme de sels aqua-solubles ou de leurs mélanges comme moyens auxiliaires de stabilisation. La relation pondérale du surfactif non-ionique au surfactif anionique se situe entre 5:1 et 1:5. Quantité engagée: 0,5 à 5% en poids. Préférentiellement, le pH de la suspension est ajusté, par l'adjonction d'un sel acide, à une valeur inférieur à 12, en particulier à un pH se situant entre 9 et 11. Les suspensions utilisées pour la préparation de détergents et de produits de lessive seulement faiblement phosphatés ou alors même exempts de phosphates ne présentent qu'une faible viscosité, lors d'entreposage et utilisation dans le domaine de température se situant entre la température ambiante et 80oC, elles ont des propriétés irréprochables de ruissellement et ne produisent pas du tout ou alors que faiblement des produits résiduaires se déposant au fond.
EP84903064A 1983-08-22 1984-08-13 Suspension aqueuse, stabilisee a base de zeolithe Expired EP0185660B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84903064T ATE32328T1 (de) 1983-08-22 1984-08-13 Stabilisierte, waessrige zeolith-suspension.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19833330220 DE3330220A1 (de) 1983-08-22 1983-08-22 Stabilisierte, waessrige zeolith-suspension
DE3330220 1983-08-22
DE3423351 1984-06-25
DE19843423351 DE3423351A1 (de) 1984-06-25 1984-06-25 Stabilisierte, waessrige zeolith-suspension

Publications (2)

Publication Number Publication Date
EP0185660A1 true EP0185660A1 (fr) 1986-07-02
EP0185660B1 EP0185660B1 (fr) 1988-02-03

Family

ID=25813382

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84903064A Expired EP0185660B1 (fr) 1983-08-22 1984-08-13 Suspension aqueuse, stabilisee a base de zeolithe

Country Status (10)

Country Link
US (1) US4529541A (fr)
EP (1) EP0185660B1 (fr)
KR (1) KR850001800A (fr)
AT (1) ATE32328T1 (fr)
AU (1) AU3215784A (fr)
DE (1) DE3469159D1 (fr)
ES (1) ES535309A0 (fr)
FI (1) FI853339L (fr)
IT (1) IT1176619B (fr)
WO (1) WO1985001039A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1180819B (it) * 1984-09-12 1987-09-23 Mira Lanza Spa Metodo di neutralizzazione della zeolite a mediante trattamento con a cidi forti del panello di filtrazione addizionato con un fludificante
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
US4769168A (en) * 1985-08-05 1988-09-06 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
US4690771A (en) * 1985-08-05 1987-09-01 Colgate-Palmolive Company Phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
DE3832643A1 (de) * 1988-09-26 1990-03-29 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Verfahren zur herstellung einer reflexionsbeschichtung bei hochdruckentladungslampen
US5443812A (en) * 1989-04-24 1995-08-22 Kanebo Ltd. Stabilized synthetic zeolite and a process for the preparation thereof
FR2652819B1 (fr) * 1989-10-09 1994-01-07 Rhone Poulenc Chimie Suspension de zeolite comprenant un siliconate.
US5476610A (en) * 1991-07-22 1995-12-19 Henkel Kommanditgesellschaft Auf Aktien Process for stabilizing aqueous zeolite suspensions
DE4124247A1 (de) * 1991-07-22 1993-01-28 Henkel Kgaa Verfahren zur stabilisierung von waessrigen zeolith-suspensionen
DE4203789A1 (de) * 1992-02-10 1993-08-12 Henkel Kgaa Verfahren zur stabilisierung von waessrigen zeolith-suspensionen
CN1036782C (zh) * 1992-12-15 1997-12-24 国际壳牌研究有限公司 包含仲烷基硫酸脂/沸石的表面活性剂组合物
DE4303297A1 (de) * 1993-02-05 1994-08-11 Degussa Verfahren zur Verbesserung des Fließverhaltens von Zeolithpulvern
EP0693549A1 (fr) 1994-07-19 1996-01-24 The Procter & Gamble Company Compositions d'activateurs de blanchiment solides
GB2296919A (en) * 1995-01-12 1996-07-17 Procter & Gamble Detergent composition
AU5964296A (en) * 1995-05-26 1996-12-11 W.R. Grace & Co.-Conn. High-loading adsorbent/organic matrix composites
US5935891A (en) * 1995-05-26 1999-08-10 W. R. Grace & Co.-Conn. High-loading adsorbent/organic matrix composites
US5879764A (en) * 1996-11-06 1999-03-09 W. R. Grace & Co.-Conn. Desiccation using polymer-bound desiccant beads
EP2384432B1 (fr) 2007-06-21 2016-12-28 Gen-Probe Incorporated Instruments et réceptacles pour effectuer des procédés

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4409136A (en) * 1977-01-31 1983-10-11 Colgate Palmolive Company Molecular sieve zeolite-built detergent paste
GB2015488B (en) * 1978-03-02 1982-09-22 Unilever Ltd Stabilised sodium aluminosilicate suspensions
US4264466A (en) * 1980-02-14 1981-04-28 The Procter & Gamble Company Mulls containing chain structure clay suspension aids
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US4545919A (en) * 1982-08-31 1985-10-08 Ciba-Geigy Corporation Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8501039A1 *

Also Published As

Publication number Publication date
US4529541A (en) 1985-07-16
IT8422372A0 (it) 1984-08-21
FI853339A0 (fi) 1985-08-30
FI853339A7 (fi) 1985-08-30
FI853339L (fi) 1985-08-30
IT1176619B (it) 1987-08-18
ATE32328T1 (de) 1988-02-15
WO1985001039A1 (fr) 1985-03-14
DE3469159D1 (en) 1988-03-10
AU3215784A (en) 1985-03-29
EP0185660B1 (fr) 1988-02-03
KR850001800A (ko) 1985-04-01
ES8505550A1 (es) 1985-06-01
ES535309A0 (es) 1985-06-01

Similar Documents

Publication Publication Date Title
EP0185660B1 (fr) Suspension aqueuse, stabilisee a base de zeolithe
DE3300243A1 (de) Geschirrwaschmittel auf waessriger basis fuer automatische spuelmaschinen
DE3818829A1 (de) Koerniges adsorptionsmittel mit verbessertem einspuelverhalten
DE2264302A1 (de) Detergensmittel
DE2507926B2 (fr)
DE2204568C3 (de) Detergensmittel
DE2907791A1 (de) Reinigungsmittel und verfahren zu ihrer herstellung
DE2545190B2 (de) Pulverförmige Wasch- und Reinigungsmittel mit einem Gehalt an wasserunlöslichen Silikaten, sowie Verfahren zu deren Herstellung
DE69723607T2 (de) Tensid-Mischungen, Verfahren zu ihrer Herstellung und diese enthaltende teilchenförmige Reinigungsmittelzusammensetzungen
DE2843390A1 (de) Waschmittelzusammensetzung
CH667669A5 (de) Im wesentlichen wasserfreies, fluessiges grobwaschmittel.
DE2701664A1 (de) Waschmittel und verfahren zu ihrer herstellung
EP0283791B1 (fr) Suspensions de blanchiment aqueuses contenant un acide peroxycarboxylique, leur procédé de préparation et leur application
DE2448502C2 (de) Verfahren zur Herstellung eines homogenen, körnigen Wasch- und Reinigungsmittels
CH667668A5 (de) Fluessige vollwaschmittelzusammensetzung.
EP0183945B1 (fr) Suspensions aqueuses stables de silicates insolubles dans l'eau, capables de fixer les ions calcium, et leur utilisation pour la production d'agents de lavage et de nettoyage
EP0490912B1 (fr) Detergents liquides a teneur en zeolite
EP0623593A2 (fr) Procédé de neutralisation de la forme acide de tensioactifs anioniques, agglomérets et détergent ainsi obenus
DE3209631C2 (fr)
DE3330220A1 (de) Stabilisierte, waessrige zeolith-suspension
EP0848746B1 (fr) Nettoyant aqueux
DE3715052C2 (fr)
EP0000870A1 (fr) Procédé d'amélioration des propriétés des pâtes et poudres d'aluminosilicate de sodium
CH635614A5 (en) Liquid detergent and process for its preparation
DE2539071B2 (fr)

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: 19860418

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE FR LI

17Q First examination report despatched

Effective date: 19870410

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE FR LI

REF Corresponds to:

Ref document number: 32328

Country of ref document: AT

Date of ref document: 19880215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3469159

Country of ref document: DE

Date of ref document: 19880310

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: UNILEVER PLC / UNILEVER N.V.

Effective date: 19881027

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19890714

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19890718

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19890721

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890808

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19900813

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19900831

Ref country code: CH

Effective date: 19900831

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 19900723

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19910501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO