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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • 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 stable aqueous suspensions of inorganic silica-based materials insoluble in water, in a finely subdivided form.
• the silica-based materials insoluble in water used in the present invention, are the silicalites and the compounds corresponding to the formula: (Cat 2/n O) x Me2O3(SiO2) y (H2O) w (III) wherein: Cat represents a cation of valency n, exchangeable with CA; x is a number between 0.7 and 1.5; Me represents boron or aluminium, y is a number between 0.8 and 200, but preferably between 1.3 and 4 and w is a number from 0 to 10.
• Cation Cat is sodium, although also other cations such as lithium, potassium, magnesium and so on may be used as well.
• inorganic materials used in the present invention are: silicalites, boro-silicates and alumino-­silicates, both in a crystalline as well as in an amorphous form.
• the present description will in particular concern the sodium alumino-silicates with a molar ratio SiO2/Na2O around 2:1, generally known as zeolites of the type '4A', but all indication concerning use, preparation and properties of such alumino-silicates may be applied to the totality of said insoluble inorganic materials of formula (III).
• the alumino-silicates and more particularly the zeolites of the type 4A, corresponding to global formula NA2O.Al2O3.2SiO2.4,5H2O, are in general used in detergents and detersives.
• 4A zeolites are produced in the form of a finely subdivided powder, showing a granulometry (particle size) between 0.5 and 10 micrometers.
• the 4A zeolites are suspended in water, and this operation is preferably carried out directly during the preparation of the zeolites, after the filtering and washing operations.
• French Patent 2.287.504 is describing suspensions of alumino-silicates or of boro-silicates insoluble in water and stabilized with a dispersing agent, in particular polymeric organic compounds with a molecular weight greater than 1500, containing carboxylic and/or hydroxylic groups, more in particular those derived from natural products such as for instance the polysaccharides.
• French Patent 2.512.690 describes 4A zeolites stabilized with a non-ionic surfactant agent consisting of a macromolecular polymeric organic compound containing hydroxylic groups and with an alkali metal hydroxide.
• Italian Patent 1173485 is suggesting to stabilize the aqueous zeolite suspensions by the addition of a hydrosoluble resin selected from Xanthan Gum, GUAR gum and their mixtures.
• acqueous suspensions stabilized by means of the above reported stabilizing agents are suited for being pumped through the standard pipes of industrial pumps and for withstanding vibrations during transport; but on the other side they show the drawback of not being storable for a long period without stirring, lest they suffer the phenomenon of decanting (settling). Moreover, when the aqueous suspensions are stabilized by the above mentioned agents, the decanted (settled) material proves of hard consistency and difficult to be removed.
• aqueous suspensions of isoluble inorganic silica-based materials in a finely subdivided form, and stabilized with at least one organic macromolecular polymeric compund od a molecular weoght reater than 1500 and containing hydroxylic groups, may be improved as far as their storage time is concerned, if to these suspensions small quantities of a cationic surfacting product are added, said product being consisting of an ammonium or phosphonium quaternary compound.
• One object of the present invention are aqueous suspensions of insoluble silica-based materials in a finely subdivided form stabilized with: - from 0.01 % to 5 % by weight of at least one organic polymeric compound having a molecular weight greater than 1500 and containing hydroxylic groups; and - from 0.001 % to 0.5 % by weight of an ammonium or phosphonium quaternary compound selected from: wherein: - B is nitrogen or phosphorus; - A ⁇ is a mono- or polyvalent anion, selected from halogen ions, ions of other inorganic acids and hydroxyl ions; - A′ ⁇ may be -SO3 ⁇ or -COO ⁇ ; - m is an integer equal to the valency of anion A; - R1, R2, R3 and R4, equal to or different from each other, are: an alkyl radical containing from 1 to 20 C atoms; an aryl radical containing from 1 to 4 C atoms; a phen
• the inorganic material amount, based on silica in the aqueous suspensions according to this invention is between 30% and 70% by weight.
• Examples of mono- or polyvalent anions 'A' are: chloride ions, bromide ions, iodide ions, fluoride ions, sulphate ions, bisulphate ions, nitrate ions, nitrite ions, sulphite ions, phosphate ions, phosphite ions, perchlorate ions, acetate ions, benzoate ions, benzene-sulphonate ions, p-toluene-sulphonate ions, stearate ions, sebacate ions and so on.
• At least one, but preferably two, of the radicals R1, R2, R3 and R4 are polyoxyalkylene radicals H(-O-R6) p
• at least one of said radicals is an alkyl radical containing from 8 to 20 C atoms or a phenyl-­alkylene radical containing from 1 to 4 C atoms in the alkylene chain and anion A ⁇ is a halogen.
• aqueous suspensions of silica-based inorganic materials of formula (III), stabilized with 0.05 - 1 % by weight of at least one polymeric organic compound containing hydroxylic groups and with from 0.02 to 0.15 % b.w. of an ammonium or phosphonium quaternary compound of formula (I) or (II) are practically preferred suspensions.
• the silica-based hydro-insoluble inorganic materials, used for producing these suspensions are in the form of particles having a size from 0.1 micrometer to 1 mm but preferably from 1 to 10 micrometers.
• these particles are of the primary type, namely they are formed by precipitation and optionally crystallization, whereas the secondary particles, that is those formed by agglomeration of the primary ones, are in general absent.
• the alumino-silicates may be produced as amorphous compounds, as crystals or in the form of mixtures thereof and may come from a natural or synthetic source; these latters are the preferred ones.
• the production of these compounds, and in particular of 4A zeolites, is quite known and is described for instance by French Patent 2.447.349.
• the preferred alumino-silicates are those falling within the composition: 0.7 -1.1 Na2O ⁇ Al2O3 1.3-3.3 siO2 ⁇ 4.5H2O.
• the alumino-­silicates appear as a wet filtration cake with a water content from about 40% to 60% by weight.
• Said cake may preferably be used directly for the preparation of a suspension or it may undergo a preliminary drying.
• the organic polymeric compound with a molecular weight greater than 1500 and containing hydroxylic groups, may come form a natural source or may be produced by synthesis.
• GUAR gum consisting prevailingly of polycarbohydrates (polysaccharides) based on galactose and mannose units
• Amigel 12014 which is a native amide of grass, traded by the "lich des Produits du Mais”.
• the XANTHAN gum which is a polysaccharide of high molecular weight and which is obtained from various trypes of 'Xanthomonas', such as for instance from 'Xanthomonas Campestris', showing the following formula:
• compositions used for stabilizing the new aqueous suspensions contain at least one organic polymer compound with a molecular weight greater thatn 1500 and containing hydroxilic groups.
• said organic polymeric compounds be at least two and be preferably different as to the origin, because at equal concentration they allow to obtain better results; the ratio between the two organic polymeric compounds may be varied at will, such as between 99:1 and 1:99.
• the suspensions of the present invention may be prepared by simply mixing together the components. Practically, it is preferred to use the aqueous suspension of the still wet, and thus not yet dried, zeolite for the suspension preparation, coverting, by vigorous stirring, the wet filtration cake, obtained after separation of the mother liquor and after rinsing with water, into a fluid suspension. To this purpose, in general, no further addition of water is required.
• the suspensions according to this invention may contain even up to 70% by weight of pure zeolite 4A of formula Na2O ⁇ Al2O3 ⁇ 2Sio2 ⁇ 4,5H2O, which corresponds to 56% by weight of anhydrous zeolite (that is, without the 4.5 mols of crystallization water); in general the viscosities of the suspensions are between 150 and 3500 mPas and the tank transportation does not cause any problem, without any formation of hardly removable settlings.
• the suspensions according to this invention may be pumped and stirred without any problem even after 30-40 days of storage, as they maintain a low viscosity both at room temperature as well as at temperatures up to 50 C. Even after an unlimited storage at room temperature, there forms only just a slight gelly-like sludge, which can easily be restirred.
• the suspensions according to the invention show excellent rheological properties even at higher temperatures, that is from 50 to 80 C.
• the stabilized zeolite suspensions are used as a liquid raw material according to the usual manufacturing operations.
• the stabilized zeolitic suspensions may also be transformed, by usual drying operations, for instance by spray- drying, into a powder that can easly be re-dispersed in water.
• spray- drying In the preparation of powdery detersives, by using the suspensions according to this invention, in particular according to the spray- drying method, there are obtained products extremely poor in dust and of excellent quality.
• suspensions according to the invention are also very suited for the preparation of dish-washing powders.
• ammonium- or phosphonium-­quaternary compounds are identified by the above reported numbers.
• the viscosity of the suspension was dermined at 20 and at 50 C by means of a "Brookfield" viscometer rotating at 20 r.p.m. Moreover, the suspension was evalueted according to the formation and consistency of the residual bottom.
• the fully filled container was then kept at rest for a certain time indicated as “storage period”.
• storage period At the end the level of the zone of the "clear” liquid above the suspension was measured and the settling behavior of the suspension was expressed as "% of suspension". Consequently 100% of suspension was meaning that no clear liquid phase did ever form.

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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)
• Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Molecular Biology (AREA)
• Emergency Medicine (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)

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Citations (8)

• 1988
  • 1988-07-29 EP EP88112299A patent/EP0352358A1/fr not_active Ceased

Patent Citations (8)

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