EP0758372B1 - Procede de production de granules d'adjuvants semblables a des silicates de densite apparente elevee - Google Patents

Procede de production de granules d'adjuvants semblables a des silicates de densite apparente elevee Download PDF

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Publication number
EP0758372B1
EP0758372B1 EP95918597A EP95918597A EP0758372B1 EP 0758372 B1 EP0758372 B1 EP 0758372B1 EP 95918597 A EP95918597 A EP 95918597A EP 95918597 A EP95918597 A EP 95918597A EP 0758372 B1 EP0758372 B1 EP 0758372B1
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Prior art keywords
silicates
silicate
weight
compaction
granules
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German (de)
English (en)
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EP0758372A1 (fr
Inventor
Hans-Friedrich Kruse
Beatrix Kottwitz
Volker Bauer
Berthold Schreck
Jörg Poethkow
Wolfgang Breuer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/08—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates

Definitions

  • the invention relates to a method for producing silicate or silicate-containing builder granules with bulk densities of at least 600 g / l, which have improved application properties, and Detergents or cleaning agents which contain such granules.
  • amorphous sodium silicate compounds are known as builder substances, which by spray drying aqueous water glass, whereby light silicates are obtained, followed by grinding and subsequent Compacting and rounding with additional dehydration of the ground material be, cf. see, for example, FIG. 3 of US 3,912,649.
  • the water content of the products used is around 18 to 20 % By weight at bulk densities well above 500 g / l.
  • EP-A-0 444 415 are amorphous low-water Sodium disilicates with a water content of 0.3 to 6 wt .-% known.
  • These highly dewatered amorphous disilicates are produced in one Multi-stage process, which initially involves the production of a powder Amorphous sodium silicate with a water content of 15 to 23 wt .-% provides.
  • This material is in a rotary kiln with flue gas at temperatures treated from 250 to 500 ° C in countercurrent. That from the rotary kiln escaping amorphous sodium silicate is using a mechanical crusher crushed to grain sizes from 0.1 to 12 mm and then with a Grind the mill to grain sizes from 2 to 400 ⁇ m.
  • European patent EP-B-0 374 017 describes conventional water-containing silicates in granular form with high density, the 1 to 10 wt .-% cellulose derivatives included, which reduces the rate of dissolution of the compressed Granules is improved. Statements about the secondary washing ability and in particular about incrustation inhibition are not discussed in this document met.
  • a sodium silicate containing water of crystallization can be prepared in that a 40 to 60 wt .-% aqueous solution of sodium silicate in one with striking tools equipped turbo dryer is treated with hot air.
  • the drying product passes through a pseudoplastic state a free water content of 5 to 12 wt .-%, based on the mass of is used to form a product in granular form.
  • the drying up these granules are carried out under working conditions that embrittlement of the outer shell of the granules and the associated breakage excludes the granular structure. That way it will be - while avoiding it the so-called "popcorn effect" - possible, water-soluble sodium silicates with specific weights in the range between 0.5 and 1.2 are characterized by complete solubility in water at ambient temperature.
  • the older European patent application EP-A-0 738 237 (priority date: 03.01.94; application date: 27.12.94; publication date: 23.10.96) describes sodium silicates in the module range (molar ratio SiO 2 / Na 2 O) from 1.3 to 4 inches in the form of a finely divided solid in a cullet structure, these silicates being X-ray amorphous and having an absolute water content of at most 15% by weight (over-dried silicates) and bulk densities below 500 g / l. These X-ray amorphous silicates are characterized in particular by the presence of microcrystalline solid areas, which can be determined via electron diffraction, but not via X-ray diffraction.
  • these silicates Due to their body structure, these silicates have a very high specific BET surface area.
  • the particle sizes are preferably in a range from 10 to 200 ⁇ m. From an application point of view, those silicates which have a bulk density below 400 g / l and in particular in the range from 100 to 350 g / l are particularly advantageous.
  • roller compaction of detergents or cleaning agents or individual ones Components of detergents or cleaning agents is the safe state of the technical knowledge.
  • EP-A-0 253 323 is known to builders such as zeolite and / or phosphate Roller compaction in granules with high bulk density and very good application properties can be transferred.
  • the current state of the art in print describes the conditions in detail. under which roller compaction is usually carried out becomes. It is stated that the pressure in the nip and the dwell time of the material in the area of the pressing pressure are to be set so that a well-formed, high-density cuff band is produced.
  • the task was to develop silicate or silicate-containing builders for the Use in modern laundry detergents or cleaning products that despite their compression still very good secondary washing performance in particular in the field of incrustation inhibition.
  • the invention relates in a first embodiment to a process for the preparation of silicate or silicate-containing builder granules by compacting light silicates with bulk densities of less than 500 g / l, sodium silicates in the module range (molar ratio SiO 2 / Na 2 O) from 1.3 to 4 are used, which are in the form of a finely divided solid in a cullet structure, are X-ray amorphous and have an absolute water content of at most 15% by weight, and bulk densities of at least 600 g / l are set by compression.
  • the granules according to the invention result from compacting, all of them known methods for compacting are available. Particularly preferred However, the roller compaction of silicates is preferred Modules between 1.5 and 3.3, in particular between 1.7 and 3.0, for example by 2.0, according to the older German patent application P 44 00 024.3. It is possible that the compression partially or entirely by a Roll compacting takes place.
  • the light starting silicates are in one preferred embodiment of the invention in a turbo dryer / granulator produced. In particular, those silicates are preferred which are characterized by a single or multiple, repeated drying step Water contents from 0 to a maximum of 15% by weight, preferably from 3 to 15% in particular from 6 to 13% by weight and in particular bulk weights below 400 g / l.
  • turbo dryer can be bulk weights obtained between 40 g / l and approx. 400 g / l, i.e. especially at high
  • the turbo dryer works not only as a dryer, but also also as a mill.
  • higher ones are required
  • a Increasing the liter weights of very light products can also be done in Turbo dryer, for example, also in a downstream mill or other Intermediate compacting stages take place.
  • the bulk density of the granules compacted according to the invention is then preferably even 700 g / l to 1100 g / l and in particular even 800 to 1000 g / l.
  • a Bulk weight of the compacted silicates set preferably at least is twice and in particular at least three times as high as that Bulk weight of light starting silicates.
  • the water content of the compacted Silicates is 0 to a maximum of 15% by weight. Preferred water levels However, as with the light starting silicates, they are 3 to 15% by weight and especially 6 to 13% by weight.
  • these compacted silicates don't just show the same thing good, but even an improved ability to inhibit incrustation than the relatively light parent silicates, although the surface of the compacted granules is less than that of the starting silicates, which in Cullet structure.
  • the "information" is the incrustation inhibition, the light and finely divided silicates shard structure, not only not destroyed, but transferred and preferably even reinforced.
  • the builder granules produced according to the invention can be made entirely of the possibly water-containing compacted silicates, they However, other components can also be used, in particular those that are conventional Ingredients of detergents or cleaning agents are known.
  • a preferred embodiment of the invention provides that silicate or silicate-containing builder granules are produced, wherein optionally water-containing silicates at 10 to 100 wt .-%, preferably at 30 to 100 wt .-% and in particular at least 45 wt .-% are used.
  • silicate starting materials which is produced according to the older German patent application P 44 00 024.3 and then compacted, these additional components already contain or whether initially mixtures of the individual components and the relative light starting silicates can be produced and compacted.
  • these additional components already contain or whether initially mixtures of the individual components and the relative light starting silicates can be produced and compacted.
  • mixtures of silicates and carbonates used in a weight ratio of 9: 1 to 1: 9.
  • washing or cleaning agents especially anionic and nonionic surfactants, but also other inorganic ones and organic builders, as well as bleaches and bleach activators, inorganic salts, enzymes and enzyme stabilizers and foam inhibitors, Graying inhibitors and color transfer inhibitors into consideration.
  • Suitable surfactants of the sulfonate type are preferably the known C 9 -C 13 alkylbenzenesulfonates, ⁇ -olefin sulfonates and alkanesulfonates. Esters of ⁇ -sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • Particularly suitable alkyl sulfates are the sulfuric acid monoesters of the C 12 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which also contain proportions of unsaturated alcohols, for example Oleyl alcohol can contain.
  • soaps are particularly suitable.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, Myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and Behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts in front.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants used is either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated fatty alcohols are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as they are described, for example, in Japanese patent application JP 58/217598 are or preferably according to that in the international patent application Methods described in WO-A-90/13533.
  • nonionic surfactants of the amine oxide type for example N-cocoalkylN, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Zeolite NaA is primarily suitable, but also zeolite P and mixtures of A, X and / or P.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • they contain according to the invention produced granules but at most 50 wt .-%, based on the Sum of zeolite, X-ray amorphous and crystalline layered silicates, on zeolite and crystalline layered silicates.
  • Useful organic builders are, for example, those preferred in Form of their sodium salts used polycarboxylic acids, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of Polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymers Polycarboxylates are especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • acrylic acid with maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to 90% by weight acrylic acid and 50 to 10% by weight maleic acid contain.
  • Their relative molecular mass, based on free acids is in generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymers are also particularly preferred, for example those as monomers salts of acrylic acid and maleic acid as well Vinyl alcohol or vinyl alcohol derivatives (DE 43 00 772) or as monomers Salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives (DE 42 21 381) included.
  • Suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts as they described for example in the international patent application WO-A-93/08251 be or their production, for example, in the international Patent application WO-A-93/16110 or the older German patent application P 43 30 393.0 is described.
  • components can also be used in the process, which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled previously several times with a detergent according to the invention, this contains oil and fat-dissolving component, is washed.
  • Oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and especially methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
  • nonionic cellulose ethers such as methyl cellulose and especially methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as those
  • constituents which: the solubility of the compacted and easily soluble granules continue to improve.
  • Such components are used, for example, in the international Patent application WO-A-93/02176 and the German patent application DE 42 03 031.
  • the preferred ingredients include in particular fatty alcohols with 10 to 80 moles of ethylene oxide per mole Fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, as well as polyethylene glycols with a relative molecular mass between 200 and 2000.
  • Suitable ingredients of the granules produced according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates, common amorphous silicates or mixtures of these.
  • water-soluble inorganic salts such as bicarbonates, carbonates, common amorphous silicates or mixtures of these.
  • P 43 19 578.4 can also by alkali carbonates sulfur-free, 2 to 11 carbon atoms and optionally one more Amino acids and / or salts thereof having carboxyl and / or amino groups be replaced.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can, if desired, also be incorporated into the granules.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, also carboxylic anhydrides and esters of polyols, such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors, for example those made from silicone or paraffins, are also used with advantages.
  • foam inhibitors in particular silicone or paraffin-containing foam inhibitors
  • silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • silicate-containing granules not produced according to the invention do not contain these foam inhibitors, but if appropriate they are already contained in the washing or cleaning agents in which the granules according to the invention are preferably used.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably are proteases of the subtilisin type and in particular proteases which are made up of Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing Mixtures of special interest.
  • Peroxidases or Oxidases have been found to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the percentage of enzymes Enzyme mixtures or enzyme granules can, for example, be about 0.1 to 5 % By weight, preferably 0.1 to about 2% by weight.
  • the stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • Ethylenediaminetetramethylenephosphonic acid into consideration.
  • Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the granules produced according to the invention can be used as optical brighteners
  • Derivatives of diaminostilbenedisulfonic acid or their alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group, an anilino group or a 2-methoxyethylamino group carry.
  • Brighteners of the substituted diphenylstyryl type can also be used be present, e.g.
  • heavy silicate or silicate-containing builder granules are produced, which have a bulk density of at least 850 g / l.
  • builder granules which may consist of 100% by weight hydrated silicates with a modulus of 1.7 to 3.0, whereby Water contents of 3 to 15% by weight and in particular of 6 to 13% by weight are preferred are exist.
  • the setting of the bulk weights can be done by one or more compaction steps take place, with - as indicated above - a first compression step can also be done by crushing.
  • a first compression step can also be done by crushing.
  • bulk weights of 800 g / l and above, starting of silicates in broken glass structure with bulk densities below 200 g / l can be set by 2 or 3 compression steps.
  • they are relative light starting silicates without a prior compression first Roll pressing fed.
  • the pair of rollers can be in any Spatial direction, in particular thus arranged vertically or horizontally to one another be.
  • the mixture to be compacted or the sole relative lightweight silicate feedstock is then either gravity filled or by means of a suitable device, for example one Darning screw, fed to the nip.
  • the good to be compacted becomes then under pressure through the gap of a pair of two with approximately the same Rotational speed of oppositely running rollers and led to one plate-shaped or band-shaped pressed material, which is also referred to as a sling band is compressed.
  • the pressing force is generally between 7 and 30 kN / cm roll length and in particular between 10 and 25 kN / cm roll length.
  • the silicate starting materials used according to the invention can or the silicate-containing starting materials or mixtures, in particular when the silicates have a water content of at least 6% by weight on the silicates, roller compacted in dry form. Only in the case of silicates free of water of hydration, if necessary - depending on the nature of the other raw materials - a small amount of water added will. However, roller compacting is preferred without adding water.
  • roller compaction carried out according to the invention not only can be carried out without problems at higher temperatures, but also that this improvement, in particular, is an improvement the dissolving behavior of the roller-compacted builder granules is achieved, if, in addition to amorphous or X-ray amorphous silicates, they are also crystalline contain layered silicates.
  • the roller temperatures come to 35 up to 120 ° C, with temperatures of 40 and 100 ° C and in particular between 45 to 90 ° C are particularly preferred.
  • the shoulder strap is then subjected to a comminution process.
  • This crushing or grinding can, for example, in one Mill done. This creates what are known as chip granules can be ground finer.
  • the comminuted material is expediently then subjected to a screening process using coarse material separated and returned to the shredder while being fine material with further raw materials again compacting in Roll nip is fed.
  • the wrist strap is thereby usual grinding in granules with a grain size range from 0.05 mm to about 2 mm, preferably with a grain spectrum that consists of at least 70 wt .-% Granules with a particle diameter between 0.1 and 1.6 mm, set, while fine-grain fractions with grain diameters below 0.05 mm fed back into the compacting and coarse fractions with granule diameters be returned to the grinding above 2 mm.
  • the roller-compacted granules can also have a total of one or several further compression steps that are not exclusively in a new roller compaction must exist, but also by others Known compaction measures can be carried out will. However, it is preferred that further compacting steps are also carried out be carried out by means of a roller.
  • the silicate-containing builder granules produced according to the invention which preferably up to 90% by weight of other usual ingredients of washing or Detergents can already be used as detergents or cleaning agents be used.
  • the silicate or silicate-containing produced according to the invention Builder granules can, however, also be added as an admixing component serve all modern washing or cleaning agents. These funds are also Subject of this application. Here are particularly granular ones Washing or cleaning agents preferred, which have bulk densities of at least 600 g / l, preferably at least 700 g / l and in particular of have at least 750 g / l.
  • the agents preferably contain biological degradable surfactants, for example fatty alkyl sulfates and / or ethoxylated Fatty alcohols and / or soaps and / or alkyl polyglycosides, and optionally as a cobuilder biodegradable polymers.
  • biological degradable surfactants for example fatty alkyl sulfates and / or ethoxylated Fatty alcohols and / or soaps and / or alkyl polyglycosides, and optionally as a cobuilder biodegradable polymers.
  • a 50 wt .-% aqueous sodium silicate solution with a weight ratio Na 2 O: SiO 2 of 1: 2.0 was in a turbo dryer / granulator from Vomm, Italy, at a wall temperature of 170 ° C with hot air of 220 ° C in dried two stages.
  • the silicate product of the first drying stage had a residual water content of 17% by weight and a bulk density of 850 g / l, after passing through the second drying stage a residual water content of 9% by weight was achieved with a bulk weight of 130 g / l.
  • the silicate was in X-ray amorphous form and had the typical body structure described in the older German patent application P 44 00 024.3.
  • the silicate was compacted in three stages at a pressing force of 17 kN / cm. The resulting slugs were each crushed through a 2 mm sieve.
  • the bulk density of the silicate was 900 g / l.
  • the heating element was switched off removed from the container and first to remove the precipitates in aqueous Citric acid heated to 80 ° C. The separation of the precipitates was then after alkalizing the solution with sodium hydroxide and additive of nitrilotriacetic acid sodium salt completed within 30 minutes.
  • the CaO content in the solution was determined directly by means of optical emission spectrometry (ICP-OC) determined. The liquid sample was in one vaporized and excited by high frequency ionized gas.
  • For Tap water was used to prepare the silicate solution and to rinse the containers used by adding calcium and magnesium chloride a content of 30 ° d with a calcium: magnesium ratio of 5: 1 had been discontinued.
  • the calcium deposits on the heating element were for the light starting silicate 322 mg CaO and for the silicate according to the invention 56 mg CaO.
  • Portil (R) A (spray-dried sodium water glass of module 2 and loss on ignition (800 ° C) approx. 18%; commercial product of the applicant, Germany) showed calcium deposits on the heating rod of 280 mg CaO in this test.
  • SKS-6 (R) (crystalline layered sodium disilicate; commercial product of Hoechst AG, Germany) obtained 92 mg CaO under these conditions.

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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)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Silicon Compounds (AREA)

Claims (13)

  1. Procédé de fabrication de granulés adjuvants silicatés ou contenant du silicate lourd par densification de silicates légers ayant des densités apparentes inférieures à 500 g/litre, dans lequel on utilise des silicates de sodium d'un intervalle de module (rapport molaire SiO2/Na2O) de 1,3 à 4, qui se présentent sous la forme d'un solide fin ayant une structure de petits morceaux, sont amorphes vis-à-vis des rayons X et présentent des teneurs en eau absolues de 15 % en poids au maximum, et que l'on règle par la densification à des densités apparentes d'au moins 600 g/litre.
  2. Procédé selon la revendication 1,
    caractérise en ce qu'
    on règle des densités apparentes ayant des valeurs voisines de 700 à 1100 g/litre, de préférence voisines de 800 à 1000 g/litre.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce que
    la densification s'effectue partiellement ou entièrement par compactage au cylindre.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    on procède tout d'abord à un concassage avec simultanément une prédensification avant de réaliser un compactage au cylindre.
  5. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    on utilise comme silicates de départ des solides fins ayant une structure de petits morceaux avec des densités apparentes libres inférieures à 400 g/litre, la teneur en eau ainsi aussi bien des silicates de départ que des silicates compactés s'élevant à 3 à 15 % en poids, de préférence de 6 à 13 % en poids.
  6. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    on utilise des silicates contenant éventuellement de l'eau à raison de 10 à 100 % en poids, de préférence à 30 à 100 % en poids, et en particulier à au moins 45 % en poids, toujours par rapport au granulat compacté, et où l'on ne doit envisager comme autre composant en particulier les constituants habituels des produits de lavage ou de nettoyage.
  7. Procédé selon l'une des revendications 1 à 6,
    caractérisé en ce qu'
    on règle une densité apparente des granulés compactés qui est au moins double, de préférence au moins triple de la densité apparente des silicates de départ.
  8. Procédé selon l'une des revendications 1 à 5 ou 7, caractérisé en ce qu'
    on fabrique des granulés d'adjuvants silicatés lourds qui présentent une densité apparente d'au moins 850 g/litre et se composent de 100 % en poids de silicates contenant éventuellement de l'eau avec un module de 1,7 à 3,0.
  9. Procédé selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    on règle des densités apparentes de 800 g/litre et plus, en partant de silicates ayant une structure de petits morceaux avec des densités apparentes inférieures à 200 g/litre, par deux ou trois étapes de densification.
  10. Procédé selon la revendication 3, ainsi que l'une des revendications 4 à 9,
    caractérisé en ce qu'
    on procède au compactage au cylindre à des températures élevées de 35 à 120°C, de préférence de 40 à 100°C et en particulier comprises entre 45 et 90°C.
  11. Procédé selon la revendication 3 ainsi que l'une des revendications 4 à 10,
    caractérisé en ce qu'
    on procède au compactage au cylindre sans addition d'eau.
  12. Procédé selon la revendication 3 ainsi que selon l'une des revendications 4 à 11,
    caractérisé en ce qu'
    on introduit le ruban de gales de fonte obtenu par un compactage au cylindre dans un procédé de concassage, de préférence dans un broyeur.
  13. Produit de lavage ou de nettoyage contenant des granulés d'adjuvants silicatés ou contenant des silicates fabriqués selon l'une des revendications 1 à 12.
EP95918597A 1994-05-02 1995-04-24 Procede de production de granules d'adjuvants semblables a des silicates de densite apparente elevee Expired - Lifetime EP0758372B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4415362A DE4415362A1 (de) 1994-05-02 1994-05-02 Verfahren zur Herstellung silikatischer Buildergranulate mit erhöhtem Schüttgewicht
DE4415362 1994-05-02
PCT/EP1995/001543 WO1995029978A1 (fr) 1994-05-02 1995-04-24 Procede de production de granules d'adjuvants semblables a des silicates de densite apparente elevee

Publications (2)

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EP0758372A1 EP0758372A1 (fr) 1997-02-19
EP0758372B1 true EP0758372B1 (fr) 1998-07-01

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US (1) US5807529A (fr)
EP (1) EP0758372B1 (fr)
JP (1) JPH09512574A (fr)
KR (1) KR970702357A (fr)
CN (1) CN1145633A (fr)
AT (1) ATE167894T1 (fr)
AU (1) AU2447995A (fr)
DE (2) DE4415362A1 (fr)
ES (1) ES2118600T3 (fr)
HU (1) HU220543B1 (fr)
RU (1) RU2144063C1 (fr)
WO (1) WO1995029978A1 (fr)

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DE19709411A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
EP0972822B1 (fr) * 1998-07-08 2007-02-21 Clariant Produkte (Deutschland) GmbH Compose granuléde tenside
US6387869B2 (en) * 1998-07-08 2002-05-14 Clariant Gmbh Granular surfactant composition of improved flowability compromising sodium silicate and linear alkylbenzenesulfonates
GB2339203A (en) * 1998-07-08 2000-01-19 Procter & Gamble A method of dipensing
GB9814819D0 (en) * 1998-07-08 1998-09-09 Unilever Plc Dye-transfer-inhibiting compositions and particulate detergent compositions containing them
DE19834382A1 (de) * 1998-07-30 2000-02-03 Henkel Kgaa Alkylpolyglycoside als Cobuilder
AU2110500A (en) * 1999-02-05 2000-08-25 Unilever Plc Dish washing process and compositions relating thereto
US6723693B1 (en) 1999-07-08 2004-04-20 The Procter & Gamble Company Method for dispensing a detergent comprising an amionic/silicate agglomerate

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WO1995029978A1 (fr) 1995-11-09
US5807529A (en) 1998-09-15
KR970702357A (ko) 1997-05-13
HU9603015D0 (en) 1997-01-28
ES2118600T3 (es) 1998-09-16
HU220543B1 (hu) 2002-03-28
DE59502692D1 (de) 1998-08-06
AU2447995A (en) 1995-11-29
HUT77828A (hu) 1998-08-28
JPH09512574A (ja) 1997-12-16
ATE167894T1 (de) 1998-07-15
DE4415362A1 (de) 1995-11-09
RU2144063C1 (ru) 2000-01-10
EP0758372A1 (fr) 1997-02-19
CN1145633A (zh) 1997-03-19

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