EP0572288B1 - Verwendung von amorphen Siliko-Aluminaten als Wirtsgitter von Kalcium-enthaltenden Niederschlägen - Google Patents

Verwendung von amorphen Siliko-Aluminaten als Wirtsgitter von Kalcium-enthaltenden Niederschlägen Download PDF

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Publication number
EP0572288B1
EP0572288B1 EP93400976A EP93400976A EP0572288B1 EP 0572288 B1 EP0572288 B1 EP 0572288B1 EP 93400976 A EP93400976 A EP 93400976A EP 93400976 A EP93400976 A EP 93400976A EP 0572288 B1 EP0572288 B1 EP 0572288B1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
calcium
carbonate
silicoaluminate
weight
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
Application number
EP93400976A
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English (en)
French (fr)
Other versions
EP0572288A1 (de
Inventor
Patrick Boittiaux
Virginie Couvret
Daniel Joubert
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.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP0572288A1 publication Critical patent/EP0572288A1/de
Application granted granted Critical
Publication of EP0572288B1 publication Critical patent/EP0572288B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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

Definitions

  • the subject of the present invention is a detergent composition
  • a detergent composition comprising at least one amorphous alkali metal silico-aluminate, as sensors for calcium precipitates, alkali metal carbonate and at least one inhibitor of crystal growth of calcium carbonate, the alkali metal carbonate being the main agent for removing ionic calcium.
  • This detergent composition can be used in particular in powder detergents for washing machines or for dishwashers.
  • a detergent composition must have a so-called "softening" effect. water used for washing. It must therefore eliminate calcium and magnesium which are present in water in the form of soluble salts and in the soils of linen in more or less soluble complex forms. The elimination of calcium and magnesium can be made either by complexation in the form of species soluble, either by ion exchange or by precipitation. When it comes to precipitation, this must be controlled to avoid encrustations on the laundry or on dishes or on washing machines.
  • amorphous silico-aluminates are used in an amount of 10 to 60%; optionally an alkali metal carbonate may be present (EP-A-0 150 613).
  • the present invention relates to a detergent composition without phosphate or zeolite, comprising at least one amorphous silico-aluminate of alkali metal, alkali metal carbonate, preferably the alkali metal is sodium, and at least one inhibitor of the crystal growth of carbonate of calcium, characterized in that the amorphous alkali metal silico-aluminate has the general formula (1): x M 2 O, y Al 2 O 3 , z SiO 2 , w H 2 O, formula in which M represents a metal alkaline, preferably sodium, x is between 0.8 and 1.2, y is equal to 1, z is between 8 and 15 and w is between 0.3 and 9, and in that it comprises from 2 to 10% of amorphous alkali metal silico-aluminate as sensor for calcium precipitates, from 10 to 30% of alkali metal carbonate as main agent for the elimination of ionic calcium, and from 3 to 15% of inhibitor of the crystal growth of calcium carbonate.
  • M represents
  • calcium precipitates is meant the calcium precipitates which are obtained by precipitation of calcium with the alkali metal carbonate, preferably the sodium carbonate, present in the detergent composition.
  • the amorphous alkali metal silico-aluminate capable of being used in as calcium precipitate sensors, according to the invention, is a good product known per se and can be obtained by the general process which consists in mixing, preferably with stirring, an alkali metal silicate solution and a solution of alkali metal aluminate or aluminum sulfate, hydroxide alkali metal can optionally be added, this mixture gels or precipitates, it is then filtered, washed and dried by any means known per se.
  • the amorphous silico-aluminate used according to the invention has a calcium exchange capacity greater than or equal to 50 mg of CaCO 3 / g of anhydrous silico-aluminate and / or has an absorbent capacity greater than 100 ml / 100 g , preferably more than 150 ml / 100g ("DOP" socket, ISO 787/5 standard).
  • the alkali metal carbonate is present in the detergent composition according to the invention, as the main calcium elimination agent ionic.
  • the minimum quantity of alkali metal carbonate present in the detergent composition corresponds to the amount necessary to precipitate ionic calcium.
  • detergent bath means the aqueous detergent solution (composition detergent) present in the washing machine during washing cycles.
  • inhibitors of crystal growth of calcium carbonate are meant products which therefore make it possible to stop the crystal growth of nuclei of calcium carbonate, without however preventing nucleation thereof. Indeed, without wishing to link the invention to any scientific theory, the presence of these inhibitors results in the rapid disappearance of the ionic calcium, without visible precipitation when alkali metal carbonate is added in hard water.
  • These inhibitors are, in general, water-soluble polymers, possibly biodegradable. However, citric, tartaric and phosphonic acids (such as Dequest® marketed by Monsanto) and their salts are also suitable.
  • polyacrylic acids preferably of molecular weights between 2000 and 10,000, and their salts
  • acrylic-maleic or vinylic copolymer acids preferably of molecular weights between 50,000 and 70,000, and their salts
  • polyaspartic acids and their salts the polyimide biopolymers described in European patent application No. 0511037 in the name of the Applicant.
  • These biopolymers have a COO charge density - which can range from 0 to 5.10 -4 mole / g of polymer and capable of acquiring, by hydrolysis in the detergent bath, a COO charge density - at least equal to 10 -3 mole / g of polymer.
  • These inhibitors can be used alone or as a mixture.
  • the detergent composition according to the invention preferably comprises: from 2 to 10% of amorphous alkali metal silico-aluminate, from 15 to 25% of alkali metal carbonate and from 3 to 6% of inhibitors of crystal growth of calcium carbonate.
  • the detergent composition can be prepared by any known means. She can in particular be prepared by the conventional method which consists in introducing the constituents in an aqueous suspension (slurry), this solution being then spray dried.
  • the detergent composition according to the invention advantageously comprises alkali metal silicate, preferably sodium silicate.
  • This silicate can be introduced into the aqueous solution containing the other constituents of the detergent to be then co-atomized.
  • the alkali metal carbonate and the alkali metal silicate are in the form of cogranules.
  • the composition detergent includes the amorphous alkali metal silico-aluminate, the inhibitor of crystal growth of calcium carbonate and spherical cogranules at base of hydrated alkali metal silicate and alkali metal carbonate.
  • cogranules are in particular characterized by their process of preparation which consists in: (a) spraying an aqueous solution based on alkali metal silicate or based on a mixture of silicate and carbonate alkali metal on a moving bed of particles based on alkali metal carbonate or based on the identical silicate-carbonate mixture cited above scrolling in a rotary granulating device, the speed of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle transforms into a plastic co-granule upon contact with others particles, (b) possibly drying said co-granules obtained in (a), these steps being implemented so that the water weight ratio associated silicate / silicate expressed as dry remains greater than or equal to 33/100, of preferably 36/100.
  • the co-granules are subjected to a densification operation.
  • the cogranules are added to the detergent composition in post-addition.
  • the cogranules are used in detergent compositions according to the invention for dishwashers at 3 to 90% by weight, preferably from 3 to 70% by weight, of said compositions; the quantities used in the detergent compositions according to the invention for washing machines are of the order of 3 to 60%, preferably of the order of 10 to 50%, of the weight of said compositions (these quantities are expressed by weight of dry silicate relative to the weight of the composition).
  • At least one surfactant in amount which can range from 8 to 30%, preferably of the order of 10 to 15%, of the weight of said composition.
  • Free calcium is measured in a 100 ml bath of water using a specific ionic calcium electrode (Orion ®).
  • Water has a Ca ++ concentration of 3 moles / liter.
  • the average residence time of a particle in the plate is approximately 10 to 15 minutes.
  • the temperature of the particles leaving the plate is the temperature ambient.
  • the granules exhibit excellent storage behavior.
  • compositions are listed in Table II.
  • compositions are tested in a MIELE® household dishwasher whose water softener is not regenerated; therefore it delivers hard water with a total hardness of 30 ° TH French.
  • the plates are then subjected to a photometric measurement using of a GARDNER device.
  • these cogranules are those described in examples 4 and 5 and are introduced by mixing dry additives to obtain the compositions for washing machine.
  • test pieces which have been washed 25 times are dried: they are weighed and calcined at 900 ° C.

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  • 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)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Removal Of Specific Substances (AREA)
  • Catalysts (AREA)
  • Silicon Compounds (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Claims (7)

  1. Detergens -Zusammensetzung, sowohl ohne Phosphat als auch ohne Zeolith, umfassend mindestens ein amorphes Silico-Aluminat eines Alkalimetalls, Alkalimetallcarbonat, wobei das Alkalimetall vorzugsweise Natrium ist, und mindestens einen Inhibitor für das kristalline Wachstum des Calciumcarbonats, dadurch gekennzeichnet, daß das amorphe Silico-Aluminat eines Alkalimetalls die allgemeine Formel (1) x M2O, y Al2O3, z SiO2, w H2O besitzt, worin M ein Alkalimetall ist, vorzugsweise Natrium, x zwischen 0,8 und 1,2 liegt, y gleich 1 ist, z zwischen 8 und 15 und w zwischen 0,3 und 9 liegen, und dadurch, daß sie 2 Gew.-% bis 10 Gew.-% amorphes Silico-Aluminat eines Alkalimetalls als Aufnehmer für die calciumhaltigen Niederschläge, 10 Gew.-% bis 30 Gew.-% Alkalimetallcarbonat als hauptsächliches Mittel zur Entfernung des ionischen Calciums und 3 Gew.-% bis 15 Gew.-% eines Inhibitors für das kristalline Wachstum des Calciumcarbonats umfaßt.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß sie 2 Gew.-% bis 10 Gew.-% amorphes Silico-Aluminat eines Alkalimetalls, 15 Gew.-% bis 25 Gew.-% Alkalimetallcarbonat und 3 Gew.-% bis 6 Gew.-% eines Inhibitors für das kristalline Wachstum des Calciumcarbonats umfaßt.
  3. Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das amorphe Silico-Aluminat des Alkalimetalls eine Austauschkapazität für Calcium von höher oder gleich 50 mg CaCO3/g wasserfreies Silico-Aluminat und/oder eine Absorptionsfähigkeit von höher als 100 ml/100 g, vorzugsweise höher als 150 ml/100 g besitzt.
  4. Zusammensetzung nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Inhibitor für das kristalline Wachstum des Calciumcarbonats unter Citronensäure, Weinsäure und Phosphonsäure und ihren Salzen, Polyacrylsäuren, vorzugsweise mit Molekulargewichten zwischen 2000 und 10000, und ihren Salzen, den acrylisch-maleinischen oder -vinylischen Copolymer-Säuren, vorzugsweise mit Molekulargewichten zwischen 50000 und 70000, und ihren Salzen, den Polyasparaginsäuren und ihren Salzen und den Polyimid-Biopolymeren mit einer Ladedichte COO- von 0 bis 5.10-4 Mol/g Polymer, die fähig sind, durch Hydrolyse im Waschbad eine Ladedichte COO- von mindestens gleich 10-3 Mol/g Polymer allein oder in Mischung anzunehmen, ausgewählt wird.
  5. Zusammensetzung nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie Alkalimetallsilicat, vorzugsweise Natriumsilicat umfaßt.
  6. Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß das Alkalimetallcarbonat und das Alkalimetallsilicat in Form von sphärischen Co-Granulaten auf der Basis von hydratisiertem Alkalimetallsilicat und Alkalimetallcarbonat vorliegen.
  7. Zusammensetzung nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß sie ebenfalls mindestens ein oberflächenaktives Mittel in einer Menge von 8 Gew.-% bis 30 Gew.-% umfaßt.
EP93400976A 1992-05-26 1993-04-14 Verwendung von amorphen Siliko-Aluminaten als Wirtsgitter von Kalcium-enthaltenden Niederschlägen Expired - Lifetime EP0572288B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9206419A FR2691715A1 (fr) 1992-05-26 1992-05-26 Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques.
FR9206419 1992-05-26

Publications (2)

Publication Number Publication Date
EP0572288A1 EP0572288A1 (de) 1993-12-01
EP0572288B1 true EP0572288B1 (de) 1998-07-15

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EP93400976A Expired - Lifetime EP0572288B1 (de) 1992-05-26 1993-04-14 Verwendung von amorphen Siliko-Aluminaten als Wirtsgitter von Kalcium-enthaltenden Niederschlägen

Country Status (24)

Country Link
US (1) US5700294A (de)
EP (1) EP0572288B1 (de)
JP (1) JPH0649485A (de)
KR (1) KR960001012B1 (de)
CN (1) CN1079251A (de)
AT (1) ATE168410T1 (de)
BG (1) BG97766A (de)
BR (1) BR9302020A (de)
CA (1) CA2096909A1 (de)
CZ (1) CZ98493A3 (de)
DE (1) DE69319664T2 (de)
DK (1) DK0572288T3 (de)
EE (1) EE9400075A (de)
FI (1) FI932375A (de)
FR (1) FR2691715A1 (de)
HU (1) HUT66731A (de)
LT (1) LT3599B (de)
LV (1) LV10300B (de)
NO (1) NO931871L (de)
PL (1) PL299048A1 (de)
RO (1) RO114631B1 (de)
SK (1) SK51993A3 (de)
TW (1) TW251317B (de)
YU (1) YU35293A (de)

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US7135448B2 (en) * 2003-07-02 2006-11-14 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US7196044B2 (en) * 2003-07-02 2007-03-27 Ecolab, Inc. Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor
WO2005106100A1 (en) * 2004-05-05 2005-11-10 Unilever N.V. Cleaning method
US20060174883A1 (en) * 2005-02-09 2006-08-10 Acoba, Llc Method and system of leak detection in application of positive airway pressure
US7759299B2 (en) * 2006-07-24 2010-07-20 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines

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Publication number Publication date
NO931871L (no) 1993-11-29
CA2096909A1 (fr) 1993-11-27
FI932375A0 (fi) 1993-05-25
BG97766A (en) 1994-05-27
HU9301530D0 (en) 1993-09-28
LT3599B (en) 1995-12-27
DE69319664D1 (de) 1998-08-20
CZ98493A3 (en) 1994-04-13
BR9302020A (pt) 1993-11-30
DK0572288T3 (da) 1998-10-26
HUT66731A (en) 1994-12-28
PL299048A1 (en) 1994-02-21
RO114631B1 (ro) 1999-06-30
KR930023449A (ko) 1993-12-18
LV10300B (en) 1995-04-20
LV10300A (lv) 1994-10-20
JPH0649485A (ja) 1994-02-22
LTIP573A (en) 1995-02-27
SK51993A3 (en) 1994-01-12
ATE168410T1 (de) 1998-08-15
DE69319664T2 (de) 1999-01-28
EE9400075A (et) 1995-12-15
NO931871D0 (no) 1993-05-24
YU35293A (sh) 1996-02-19
US5700294A (en) 1997-12-23
FI932375A (fi) 1993-11-27
KR960001012B1 (ko) 1996-01-17
FR2691715A1 (fr) 1993-12-03
TW251317B (de) 1995-07-11
EP0572288A1 (de) 1993-12-01
CN1079251A (zh) 1993-12-08

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