EP0422998B1 - Wässerige Zeolithsuspension, die ein Silikonat enthält - Google Patents

Wässerige Zeolithsuspension, die ein Silikonat enthält Download PDF

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Publication number
EP0422998B1
EP0422998B1 EP90402759A EP90402759A EP0422998B1 EP 0422998 B1 EP0422998 B1 EP 0422998B1 EP 90402759 A EP90402759 A EP 90402759A EP 90402759 A EP90402759 A EP 90402759A EP 0422998 B1 EP0422998 B1 EP 0422998B1
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EP
European Patent Office
Prior art keywords
suspension
siliconate
stabilizer
weight
zeolite
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
EP90402759A
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English (en)
French (fr)
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EP0422998A1 (de
Inventor
Daniel Joubert
Marc Malassis
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Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
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Publication of EP0422998A1 publication Critical patent/EP0422998A1/de
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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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • 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 present invention relates to aqueous zeolite suspensions.
  • aqueous suspensions of zeolites present many industrial handling difficulties due to their very particular rheological behavior.
  • the main object of the invention is therefore a system for obtaining aqueous suspensions of low viscosity zeolite, in particular pumpable.
  • Another object of the invention is a system which also makes it possible to obtain a stable aqueous suspension.
  • siliconates or derivatives has the effect of considerably lowering the viscosity of the zeolite suspensions. It also makes it possible to obtain manipulable suspensions with a higher dry extract, for example of at least 55%. Finally, it has been noted that the siliconates do not influence the exchange capacity of the zeolites.
  • the zeolites used in the context of the present invention include crystalline, amorphous and mixed crystalline-amorphous, natural or synthetic zeolites.
  • finely divided zeolites are used having an average diameter of primary particles of between 0.1 and 10 ⁇ m and, advantageously, between 0.5 and 5 ⁇ m, as well as a theoretical cation exchange power greater than 100 mg of CaCO 3 / g of anhydrous product and preferably greater than 200 mg.
  • Use is also more particularly made of zeolites of type A, X or Y and in particular 4A and 13X.
  • zeolites obtained by the processes described in the French patent applications in the name of the Applicant No. 2,376,074, 2,384,716, 2,392,932, 2,528,722.
  • the last reference cited refers in particular to zeolites having a speed constant, related to the surface of the zeolites per liter of solution greater than 0.15 s -1 .lm -2 , preferably greater than 0.25 and advantageously between 0.4 and 4 s -1 .lm -2 .
  • These zeolites have particularly interesting qualities in the use in detergency.
  • Application FR-A-2 392 932 in particular mentions zeolites obtained by a process consisting in injecting a sodium silicate solution in the axis of a venturi while a sodium aluminate solution is injected coaxially at the same venturi with recycling of the mixture obtained.
  • the suspensions can have a variable zeolite concentration depending on the application. This concentration is between 40 and 51% by weight.
  • the pH of the suspensions is also a function of their use. In the detergency application, this pH expressed at 1% by weight of dry zeolite is approximately 11.
  • a siliconate of formula (1) and / or a siliconate derivative is used.
  • Siliconates are well known products, they are salts of siliconic acid or its derivatives.
  • R can be an alkyl radical such as for example methyl, ethyl, propyl, butyl, isobutyl.
  • M mention may more particularly be made of sodium or potassium. Particularly sodium or potassium methylsiliconates are used.
  • alkaline siliconates are products, most of which are commercially available.
  • silanes having 3 hydrolyzable groups such as halogen atoms, alkoxy radicals, followed by dissolution of the product obtained in a solution of a strong inorganic base in proportions such that there is at least one equivalent in base per atom of silicon (see for example US-A-2,441,422, US-A-2,441,423 ).
  • the dispersant can also be chosen from siliconate derivatives.
  • derivative product is meant here the condensation products of the products corresponding to formula (1) described above, or those resulting from the at least partial polymerization into silicone compounds or polymers.
  • alkali metal alkylsiliconates can be transformed into polyalkylsiloxanes, in particular by the action of carbon dioxide or other acidifying agent.
  • the siliconates are used in the form of aqueous solutions.
  • siliconates has the effect of making the zeolite suspensions pumpable and manipulable due to their low viscosity.
  • suspensions which are stable that is to say which do not settle or little.
  • these suspensions can be transported or stored without difficulty.
  • the suspensions comprise, in addition to the siliconate, a stabilizer.
  • magnesium is preferably used.
  • the cation can, moreover, be provided in the form of a halide, in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.
  • a halide in particular a chloride, more particularly magnesium chloride, for example magnesium chloride hexahydrate, is used.
  • the amount of cation used generally varies between 0.002 and 0.5% relative to the weight of the final suspension.
  • stabilizers which can be used according to the invention, mention may be made of natural polysaccharides of animal origin such as chitosame and chitin; of plant origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.
  • animal origin such as chitosame and chitin
  • plant origin such as carragenanes, alginates, gum arabic, guar, carob, tara, cassia, konjak mannan, and finally those of bacterial or biogum origin.
  • Biogums are polysaccharides of high molecular weight, generally greater than a million, obtained by fermentation of a carbohydrate under the action of a microorganism.
  • biogum which can be used in the suspension which is the subject of the present invention there may be mentioned more particularly, xanthan gum, that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xanthomonas such as Xanthomonas begoniae, Xanthomonas campestris, Xanthomonas carotae, Xanthomonas hederae, Xanthomonas incanae, Xanthomonas malvacearum, Xanthomonas papavericola, Xanthomonas phaseoli, Xanthomonas pisi, Xanthomonas vasculorum, Xanthomonas vesicatoria, Xanthomonas vitians, Xanthomonas pelargonii.
  • Xanthan gum that is to say that obtained by fermentation under the action of bacteria or fungi belonging to the genus Xant
  • Xanthan gums are commonly found commercially.
  • gellan gum obtained from Pseudomonas Elodea, Rhamsan and Welan gums obtained from Alcaligenes.
  • cellulose and starch or their derivatives. Mention may be made, for example, of carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, cyanoethylated starch, carboxymethylated starch.
  • polysaccharides are used in solid form, in powder, or in aqueous solution.
  • carboxylic acids and their salts and in particular acetic, formic, oxalic, malic, citric and tartaric acids.
  • alkaline salts such as NaHCO 3 , NaCl, Na 2 CO 3 , Na 2 SO 4 and sodium pyrophosphate or tripolyphosphate.
  • water-soluble polymers of acrylic acid crosslinked with a polyallylether of sucrose for example in a proportion of approximately 1% and having an average of approximately 5.8 allyl groups for each molecule of sucrose.
  • polymers with a molecular weight greater than 1,000,000 polymers of this type can be found in the CARBOPOL® series for example CARBOPOL ® 934, 940 and 941.
  • the quantities used in percentage by weight relative to the final suspension vary between 0.001 and 2%.
  • the preparation of the aqueous zeolite suspensions according to the invention is carried out, as indicated above, by linking the following steps: the desired amount of siliconate of formula (1) and / or of siliconate derivative is introduced, and optionally at least one stabilizer, in an aqueous suspension of zeolite, and the whole is mixed.
  • the pH of the suspensions can be adjusted to the desired value in a known manner by the addition of any suitable neutralizing agent.
  • Suspensions comprising zeolites and stabilized by the systems which have just been described can be used in numerous applications.
  • They can be used in the form of suspensions based essentially on zeolites and the stabilizing additives mentioned above. In this case they can be used in any field other than detergency for which zeolites are used for example in stationery.
  • the present invention also relates to detergent compositions, in particular for liquid detergents, comprising, in addition to the suspensions based on zeolite and stabilizers of the invention, all the other additives known in detergency such as bleaching agents, foam control agents, anti-redeposition agents, perfumes, dyes, enzymes, optical agents.
  • the dry extract of the suspension is given in percentage by weight in% of anhydrous zeolite determined by a measurement of loss on ignition at 850 ° C. for one hour.
  • the pH indicated is given for an aqueous dispersion containing 1% of dry zeolite and it is measured using a high alkalite pH electrode.
  • the exchange capacity is given by the amount of calcium (expressed in mg of CaCO 3 ) exchanged with 1 g of anhydrous zeolite at 25 ° C.
  • the measurement is carried out as follows: 0.4 g of zeolite (expressed as anhydrous) is introduced into a solution of 5.10 -3 mole / l CaCl 2 . The mixture is kept stirring for 15 minutes. After filtration, the excess calcium is dosed at pH 10 in return by EDTA in the presence of a colored indicator, the black of eriochrome T.
  • the RHEOMAT® 30 equipped with the centered measurement system B is used as rheometer.
  • the measurement consists in performing a cycle in speed gradient (ascent plus descent).
  • the range of speed gradient explored is between 0.0215 and 157.9 s -1 , which corresponds to rotational speeds of the mobile from 0.0476 to 350 revolutions per minute.
  • the viscosities reported in the examples correspond to measurements obtained during the descent in speed gradient.
  • the sedimentation is determined by introducing the zeolite suspension into graduated cylinders of 50 or 100 cc. The volumes of supernatant and decantate are measured every five days. The test pieces are left at room temperature (20 ° C) or placed in a thermostatically controlled enclosure.
  • the zeolite used is a 4A zeolite with an average diameter of primary particles of 3.5 ⁇ m.
  • Table 1 Example 1 comparison 2 comparison 3 according to the invention 4 according to the invention Suspension% anhydrous zeolite 47.3 47.5 47.2 47.6 Exchange capacity 303 303 303 303 Siliconate% suspension 0 0 0.17 0.08 pH 10.88 11.07 10.87 11.06 Viscosity (in mPa.s) at 5 s -1 1250 2740 17 650
  • the siliconate used is the product sold under the name RHODORSIL® SILICONATE 51T by the Applicant with the formula CH 3 Si (OK) 3 .
  • Examples 8 to 9 describe the use of xanthan gum as a stabilizer. We always use the same siliconate. The results are given in Table 3. The amount of xanthan gum used is 0.12% and 0.1% by weight relative to the suspension for Examples 8 and 9 respectively.
  • Example 10 relates to the use of oxalic acid as a stabilizer. This is used at 1% by weight relative to the suspension.
  • the siliconate is the same as in Examples 8 and 9.
  • Example 11 relates to the use of Carbopol® 941 as a stabilizer at 0.1% by weight relative to the suspension.
  • Table 3 Examples 8 9 10 11 Suspension% anhydrous zeolite 47.5 49.3 49.3 49.7 Exchange capacity 288 288 288 Siliconate (% suspension) 0.17 0.2 0.1 0.1 pH 10.86 11.46 11.03 10.66 Viscosity in mPa.s at 5 s -1 1020 1020 650 310 Supernatant (% volume) 5 days 3 1.5 2 2 10 days 4 2 7 Decantate% 5 days ⁇ 0.5 ⁇ 1 0 1 10 days 0.5 1 ⁇ 1
  • a suspension of the same zeolite as the preceding examples is used at a concentration of 49.7% and without any additive.
  • the pH is 11.57.
  • a 5s -1 viscosity of 5900 mPa.s is then observed. After 5 days, there is 3.5% of supernatant and 60% of decantate.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)

Claims (15)

  1. Wäßrige Suspension auf der Basis eines Zeolithes, gekennzeichnet durch die folgenden Punkte:
    • sie umfaßt außerdem ein Siliconat der Formel

            R-Si-(OM)m(OH)3-m     (1)

    und/oder sein Kondensationsprodukt, wobei in der Formel (1) R einen Alkylrest mit 1 bis 6 Kohlenstoffatomen darstellt, m eine ganze oder gebrochene Zahl von 0,1 bis 3 ist und M ein Alkalimetall bedeutet;
    • der Zeolith stellt 40 bis 51 Gew.-% der genannten Suspension dar und das Siliconat und/oder das Siliconat-Derivat, ausgedrückt in Gewicht der Lösung des Siliconates und/oder des Siliconat-Derivates zu 50 Gew.-% in Wasser, stellen 0,01 bis 2 % des Gewichtes der genannten Suspension dar;
    • sie wird hergestellt unter Aneinanderreihung der folgenden Stufen: man trägt das Siliconat und/oder das Siliconat-Derivat in eine wäßrige Suspension des Zeolithes ein und vermischt das Ganze.
  2. Suspension nach Anspruch 1, dadurch gekennzeichnet, daß das Siliconat und/oder das Siliconat-Derivat, ausgedrückt in Gewicht der Lösung des Siliconates und/oder des Siliconat-Derivates zu 50 Gew.-% in Wasser, 0,05 bis 0,3 % des Gewichtes der genannten Suspension darstellt.
  3. Suspension nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie außerdem mindestens einen Stabilisator umfaßt.
  4. Suspension nach Anspruch 3, dadurch gekennzeichnet, daß der Stabilisator ein Kation aus der Gruppe der Erdalkalien ist.
  5. Suspension nach Anspruch 3, dadurch gekennzeichnet, daß der Stabilisator aus der die Polysaccharide pflanzlichen und tierischen Ursprungs und die Biogummi umfassenden Gruppe gewählt wird.
  6. Suspension nach Anspruch 5, dadurch gekennzeichnet, daß der Biogummi ein Xanthangummi ist.
  7. Suspension nach Anspruch 3, dadurch gekennzeichnet, daß der Stabilisator aus der die makromolekularen Polyholoside, insbesondere die Cellulose und die Stärke und ihre Derivate umfassenden Gruppe gewählt wird.
  8. Suspension nach Anspruch 3, dadurch gekennzeichnet, daß der Stabilisator aus der die Carbonsäuren und die Alkalisalze umfassenden Gruppe gewählt wird.
  9. Suspension nach Anspruch 3, dadurch gekennzeichnet, daß der Stabilisator ein Polymer der Acrylsäure ist, vernetzt mit einem Polyallylether der Sucrose.
  10. Verfahren zur Herstellung einer wäßrigen Suspension nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß man die gewünschte Menge an Siliconat und/oder Siliconat-Derivat, und gegebenenfalls mindestens einen Stabilisator in eine wäßrige Suspension des Zeolithes einträgt und vermischt.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß in dem Fall, wo man einen Stabilisator verwendet, der aus einem Kation der Gruppe der Erdalkalien besteht, die Menge zwischen 0,002 % und 0,5 % variiert, bezogen auf das Gewicht der Endsuspension.
  12. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß in dem Fall, wo man einen Stabilisator aus der die Polysaccharide pflanzlichen und tierischen Ursprungs und die Biogummi sowie die makromolekularen Polyholoside umfassenden Gruppe verwendet, die Menge zwischen 0,001 % und 2 % variiert, bezogen auf das Gewicht der Endsuspension.
  13. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß in dem Fall, wo man einen Stabilisator aus der die Carbonsäuren und die Alkalisalze umfassenden Gruppe verwendet, die Menge zwischen 0,05 % und 10 % variiert, bezogen auf das Gewicht der Endsuspension.
  14. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß in dem Fall, wo man einen Stabilisator verwendet, der aus einem Polymer der Acrylsäure besteht, vernetzt mit einem Polyallylether der Sucrose, die Menge zwischen 0,001 % und 2 % variiert, bezogen auf das Gewicht der Endsuspension.
  15. Waschmittel-Zusammensetzung, dadurch gekennzeichnet, daß sie eine Suspension nach irgendeinem der Ansprüche 1 bis 9 umfaßt.
EP90402759A 1989-10-09 1990-10-05 Wässerige Zeolithsuspension, die ein Silikonat enthält Expired - Lifetime EP0422998B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8913138 1989-10-09
FR8913138A FR2652819B1 (fr) 1989-10-09 1989-10-09 Suspension de zeolite comprenant un siliconate.

Publications (2)

Publication Number Publication Date
EP0422998A1 EP0422998A1 (de) 1991-04-17
EP0422998B1 true EP0422998B1 (de) 1996-06-19

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EP90402759A Expired - Lifetime EP0422998B1 (de) 1989-10-09 1990-10-05 Wässerige Zeolithsuspension, die ein Silikonat enthält

Country Status (17)

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US (2) US5401432A (de)
EP (1) EP0422998B1 (de)
JP (1) JPH0633408B2 (de)
KR (1) KR910008123A (de)
AT (1) ATE139560T1 (de)
BR (1) BR9005013A (de)
CA (1) CA2027012A1 (de)
DE (1) DE69027504T2 (de)
DK (1) DK0422998T3 (de)
ES (1) ES2087898T3 (de)
FI (1) FI904947A7 (de)
FR (1) FR2652819B1 (de)
GR (1) GR3020637T3 (de)
IE (1) IE903593A1 (de)
NO (1) NO177064C (de)
PT (1) PT95533B (de)
YU (1) YU47377B (de)

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GB2299097A (en) * 1995-03-24 1996-09-25 Procter & Gamble Detergent composition
US5780412A (en) * 1995-08-09 1998-07-14 The Sherwin-Williams Company Alkaline-stable hard surface cleaning compounds combined with alkali-metal organosiliconates
SE9601134D0 (sv) * 1996-03-25 1996-03-25 Eka Nobel Ab Zeolite dispersion
US5800603A (en) * 1996-03-25 1998-09-01 Eka Chemicals Ab Zeolite dispersion
DE60034592T2 (de) * 1999-10-21 2007-12-27 Daiso Co., Ltd. Vernetzungsmittel auf basis einer polyallyletherverbindung
DE102010031624A1 (de) * 2010-07-21 2012-01-26 Wacker Chemie Ag Wasserlösliche Organosiliconatpulver
US9744114B2 (en) * 2011-02-03 2017-08-29 Akzo Nobel Chemicals International B.V. Modified starches for use in personal care applications
BR112013024090A2 (pt) * 2011-04-12 2016-12-06 Basf Corp mistura estável, processos para produzir uma partícula superficialmente modificada e para tratar das partículas modificadas, e, uso de partículas modificads superficialmente

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FR2568790B1 (fr) * 1984-08-10 1990-01-12 Rhone Poulenc Chim Base Procede d'obtention d'une suspension aqueuse stable et pompable de zeolite et suspension ainsi obtenue
US4548733A (en) * 1984-10-05 1985-10-22 Dow Corning Corporation Anionic siliconates of silylorganocarboxylates, sulfonates and phosphonates to reduce viscosities of particulate slurries
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FR2652818B1 (fr) * 1989-10-09 1994-04-01 Rhone Poulenc Chimie Suspension de zeolite comprenant une resine silicone.

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Publication number Publication date
JPH03188196A (ja) 1991-08-16
FI904947A0 (fi) 1990-10-08
BR9005013A (pt) 1991-09-10
NO177064B (no) 1995-04-03
NO904359L (no) 1991-04-10
FR2652819B1 (fr) 1994-01-07
PT95533A (pt) 1991-08-14
NO177064C (no) 1995-07-12
US5401432A (en) 1995-03-28
YU188590A (sh) 1993-10-20
IE903593A1 (en) 1991-05-08
FI904947A7 (fi) 1991-04-10
ES2087898T3 (es) 1996-08-01
ATE139560T1 (de) 1996-07-15
NO904359D0 (no) 1990-10-08
DE69027504T2 (de) 1996-12-12
KR910008123A (ko) 1991-05-30
EP0422998A1 (de) 1991-04-17
FR2652819A1 (fr) 1991-04-12
GR3020637T3 (en) 1996-10-31
CA2027012A1 (fr) 1991-04-10
YU47377B (sh) 1995-01-31
DE69027504D1 (de) 1996-07-25
JPH0633408B2 (ja) 1994-05-02
US5618874A (en) 1997-04-08
DK0422998T3 (da) 1996-07-15
PT95533B (pt) 1997-07-31

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