EP1891191B1 - Schnell zerfallende bentonitgranulate - Google Patents

Schnell zerfallende bentonitgranulate Download PDF

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Publication number
EP1891191B1
EP1891191B1 EP06742901A EP06742901A EP1891191B1 EP 1891191 B1 EP1891191 B1 EP 1891191B1 EP 06742901 A EP06742901 A EP 06742901A EP 06742901 A EP06742901 A EP 06742901A EP 1891191 B1 EP1891191 B1 EP 1891191B1
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EP
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Prior art keywords
bentonite
water
alkali metal
sodium
granulate
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German (de)
English (en)
French (fr)
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EP1891191A1 (de
Inventor
Ulrich Sohling
Andreas Werner
Olivier Mortaigne
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Sued Chemie AG
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Sued Chemie AG
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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
    • 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
    • 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
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • 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 process for the production of rapidly disintegrating bentonite granules and bentonite granules which can be obtained by this process.
  • Detergent formulations use bentonites to create a built-in soft-grip effect. These bentonites have a high swelling capacity, especially when activated as sodium bentonite. In the application, however, difficulties arise because rapidly forms a gel layer on the surface of the bentonite particles in contact with water, which hinders the further access of water. After a rapid initial formation of the gel layer, therefore, the decay of the bentonite granules slows down in the water, because the core of the particles remains stable for a long time and is only very slowly swollen by the penetrating water and thus decays.
  • This paste is then extruded through a 4 to 10 mm diameter orifice and the extrudate is dried to a moisture content of 10 to 14% by weight. After drying, the extrudates are calcined at 120 to 250 ° C until they have an ignition loss of less than 4% at 190 ° C.
  • the bentonite extrudates are then comminuted again. For the preparation of this bentonite with a low swelling capacity a bentonite is already used as starting material, which even after activation with sodium ions in contact with water only in proportion swells small extent or shows only a slight tendency to form a gel.
  • Bentonite agglomerates are described, which are prepared by spraying finely divided bentonite with sodium silicate as a binder.
  • the agglomerates contain 1 to 5% binder. Although they have a different bulk density, the agglomerates do not separate from the other detergent ingredients after incorporation into detergent powder because they have an irregular surface.
  • the agglomerates have an increased stability, so that they do not disintegrate in the further production steps of the detergent production. Nevertheless, they dissolve easily on contact with water.
  • a clay is used which has large proportions of montmorillonite. Particular preference is given to using a sodium bentonite.
  • the Na 2 O content of the agglomerates should be at least 0.5%, preferably at least 1%, particularly preferably at least 2%.
  • a water glass with a modulus Na 2 O: SiO 2 of 1: 1.6 to 1: 3.2, preferably 1: 2 to 1: 2.8 or 1: 3.0 is used for binding the bentonite agglomerates.
  • the bentonite agglomerates are prepared by spraying an aqueous solution of the binder onto finely divided bentonite while it is being agitated.
  • the binder used is a water glass solution having a solids content of 7% and a Na 2 O: SiO 2 module of about 1: 2.4. Furthermore, it is described that when using water glass solutions with another module Na 2 O: SiO 2 , which is chosen within a range of 1: 2 to 1: 3, a good agglomeration can be achieved, non-dusting agglomerates are obtained.
  • Similar bentonite agglomerates are used in the US 4,767,546 .
  • US 4,851,137 such as US 4,488,972 described, wherein the examples are each selected identically.
  • the bentonite agglomerates contain 1 to 5% sodium silicate as binder.
  • a water glass solution having a solids content of from 2 to 4% by weight and a modulus of Na 2 O: SiO 2 of from 1: 2 to 1: 3 is used in each case.
  • the content of sodium oxide in the bentonite can be selected in the range of 0.5 to 10 wt .-%.
  • detailed data is not executed in the examples.
  • commercially available sodium bentonites are used.
  • exact details of the degree of activation are missing.
  • the DE 33 11 568 C2 describes a particulate and softening laundry detergent for textiles, which contains, inter alia, sodium bentonite.
  • the sodium bentonite is present as an agglomerate of smaller particles of ground sodium bentonite from which the attendant Grus has been removed after milling and before agglomeration.
  • the bentonite agglomerates are coated with a silicate or partially coated to prevent the bentonite agglomerates from sticking to surfaces. The agglomeration of the bentonite takes place with the addition of dilute sodium silicate solution.
  • bentonite particles which consist of 82.3 parts by weight of anhydrous bentonite, 16.1 parts by weight of water, 1.5 parts by weight of sodium silicate and 0.06 parts by weight of a blue dye, based on the Surface of the particles is applied, exist.
  • the bentonite used is a sodium carbonate-treated bentonite which, after the sodium carbonate treatment, is freed from its Grus contents by centrifugation.
  • bentonite sodium bentonite is preferably used, wherein both a natural sodium bentonite as well as a Na 2 CO 3 activated calcium bentonite can be used.
  • the bentonite has a content of Na 2 O of 0.8 to 2.8%.
  • Example 1 an agglomerate of finely divided sodium bentonite and sodium sulfate is prepared using water as the binder. If the resulting agglomerates are compared in their softening properties with agglomerates obtained by agglomeration of the same bentonite with dilute sodium silicate solution, the agglomerates described first have much better properties.
  • the detergent additive contains (A) 30 to 90% by weight of a layered silicate, (B) 1 to 40% by weight of fine crystalline synthetic Zeolite NaA, (C) 0 to 30% by weight of water-soluble salts from the class of sulphates, carbonates, silicates and phosphates of sodium or potassium, and (D) the remainder to 100% by weight of water.
  • the detergent additives are free of phosphates and alkali silicates.
  • Preferred components of group (C) are sodium sulfate and sodium carbonate, both of which are used as anhydrous salts individually or in admixture. The components are dry blended, then mixed with an aqueous component containing a portion of the zeolite. Granulate formation thus takes place without the addition of water glass.
  • the softener mixture contains discrete softening particles containing at least about 75% by weight of a smectite-type clay and less than about 5% by weight of anionic, nonionic, ampholytic and zwitterionic surfactants.
  • the plasticizer particles are prepared by spraying the smectite clay with a solution containing a quaternary ammonium compound. Since there is no exchange reaction with the clay, as long as the ammonium compound is adsorbed only on the surface of the clay, the amount of the ammonium compound can be remarkably reduced.
  • the clays used are preferably sodium bentonites.
  • the plasticizer particles may optionally contain, in addition to the smectite-type clay, substances which soften the desired fabric or do not adversely affect washing, examples of suitable materials being binder or agglomerating agents, e.g. For example sodium silicate.
  • a suitable sodium silicate has a modulus Na 2 P: SiO 2 of, for example, 1: 2.4.
  • a detergent additive for producing a soft handle effect is described, which contains a natural hectorite of certain composition. The agglomeration of the natural hectorite is carried out in Example 1 with water as the agglomerating agent. The wet agglomerates are dried and sieved to the desired particle size.
  • a process is described for the preparation of sorbents which are used, for example, as animal litter.
  • a weakly swelling bentonite preferably a calcium bentonite, with a Montmorrilonitgehalt of about 40 to 65 wt .-% with a basic reacting alkali metal compound homogenized by intimate kneading and transferred under ion exchange in a swellable bentonite.
  • the alkali metal compound preferably the corresponding sodium compound, is used in an amount of from 0.1 to 1.5% by weight, preferably from 0.25 to 1.5% by weight, based on the dried crude bentonite.
  • the alkali metal compound among others, a water glass solution is used.
  • the added amounts correspond to a Na 2 O content of 0.5%, 1.0% and 1.5%.
  • the crude calcium bentonite is not first activated with an alkali metal compound, and then the activated bentonite is granulated.
  • the CH 656 394 A5 describes a particulate, bleaching and softening laundry detergent.
  • the detergent contains 5 to 25 wt .-% of an agglomerated bentonite.
  • the starting material used is a swellable bentonite. This can also be provided by treating calcium or magnesium bentonite with alkali carbonate so that 5 to 100% or 10 to 90% or 15 to 50% of the exchangeable calcium and / or magnesium is replaced by sodium or potassium, respectively becomes.
  • the bentonite particles can be agglomerated using water glass.
  • water glass as a binder for the production of bentonite agglomerates, as are customary in detergent additives, has been known for some time.
  • water glasses with a modulus of Na 2 O: SiO 2 of about 2.4 are used.
  • the water glasses must be strongly alkaline to prevent premature polymerization of the water glass. This would lead to a solidification of the granules and thus to a poor disintegration in the wash liquor.
  • the bentonite granules become detergent compositions further processed, for which the bentonite granules must first be packaged after production and then, for example, transported to the detergent producer. In the process, workers come into contact with the bentonite granules or the dust they produce. Because of the highly alkaline properties of the water glass, especially when used in higher amounts, the bentonite granules are irritating, ie when handling the bentonite granules appropriate safety precautions must be taken.
  • the invention was based on the object to provide a process for the production of bentonite granules are available, which are obtained with which bentonite granules that can be handled without major safety precautions.
  • the granules should be able to be stored for a long time and show rapid disintegration in the wash liquor.
  • alkali metal ion overactivated bentonite which is overactivated with at least 110% of its cation exchange capacity with alkali metal ions
  • the over-activated with alkali metal ions bentonite is granulated with a water glass solution.
  • a bentonite overactivated with alkali metal ions is meant a bentonite which has been reacted with a larger amount of an alkali metal compound, for example soda or potassium oxalate, than corresponds to its cation exchange capacity.
  • the cation exchange capacity is determined on the starting material, ie the non-activated bentonite, by first exchanging the exchangeable cations for ammonium ions and then the nitrogen content of the washed and dried bentonite is determined by elemental analysis. From the found amount of exchangeable cations then the amount of alkali metal compounds to be used can be calculated.
  • the molar excess of the amount of alkali metal ion used is at least 110%, preferably at least 120%, particularly preferably at least 140%, based on the cation exchange capacity of the bentonite.
  • the excess is selected in the range of 140% to 200%, more preferably in the range of 150% to 180% of the cation exchange capacity.
  • the activation of the bentonite used as starting material takes place in a manner known per se.
  • the wet bentonite which usually has a water content of 20 to 40 wt .-%, is kneaded with a suitable alkali metal compound, for example. Soda or potassium oxalate, and then dried.
  • a suitable alkali metal compound for example. Soda or potassium oxalate
  • the obtained with alkaline metal ions overactivated bentonite may optionally be ground again.
  • the bentonite overactivated with alkali metal ions before granulation has a dry sieve residue on a sieve with a mesh size of 75 ⁇ m, preferably less than 15% of the weighed amount.
  • the activation can also be carried out by first slurrying the bentonite used as starting material in water and then activating it by adding a solid or dissolved in water alkali metal compound.
  • concentration of the reaction components is chosen so that an activated with alkali metal ions bentonite is obtained, which has the required overactivation.
  • a water glass solution which has a modulus SiO 2 : Na 2 O of more than 3.2.
  • the waterglass solution preferably has a modulus SiO 2 : Na 2 O of more than 3.3, particularly preferably a modulus in the range of 3.3 to 4.0.
  • a water glass with a modulus SiO 2 : Na 2 O of more than 3.2 When using a water glass with a modulus SiO 2 : Na 2 O of more than 3.2, the irritant effect of the granules decreases significantly, which is why the granules are easier to transport and handle. For example, the granules no longer have to be classified as "irritating".
  • a potassium water glass solution or a sodium / potassium water glass solution having the above-mentioned modulus can be used in the same manner.
  • the modulus here is based on potassium oxide or the mixture of potassium oxide and sodium oxide, but has the abovementioned range of values.
  • the granulation preferably uses a water glass solution which has a solids content of at least 10% by weight, preferably at least 15% by weight, particularly preferably at least 30% by weight, particularly preferably at least 40% by weight, particularly preferably at least 50 % By weight.
  • the water glass solution is added in such an amount to the over-activated sodium bentonite that the bentonite granules at a water content of 8 wt .-% of alkali metal silicate, preferably sodium silicate, of less than 4.0 wt .-%, preferably less than 3, 5 wt .-%, particularly preferably less than 3.0 wt .-%, preferably less than 2.6 wt .-%, in particular less than 2.0 wt .-%.
  • alkali metal silicate preferably sodium silicate
  • the bentonite overactivated with alkali metal ions is prepared from a bentonite having a pH of more than 7, preferably a pH of more than 8, more preferably a pH of more than 9 in an aqueous slurry containing 2% by weight of bentonite , in particular has a pH in the range of 8-10.
  • the over-activated with alkali metal ions bentonite has a swelling capacity in water of at least 15 ml / 2 g. Due to the high swelling capacity of the rapid disintegration of the granules is supported. In spite of the high swelling capacity of the bentonite overactivated with alkali metal ions, no delay in the disintegration of the granules due to gelation on the bentonite grains is observed.
  • the over-activated alkali metal ion bentonite is preferably prepared by activation of a calcium bentonite.
  • a calcium bentonite Common calcium bentonites can be used.
  • Such calcium bentonites usually have cation exchange capacities in the range of 50 meq / 100 g to 120 meq / 100 g.
  • the alkali metal ions with which the bentonite is overactivated are preferably selected from the group of sodium ions and Selected potassium ions, with sodium ions being particularly preferred.
  • the bentonite used as starting material is activated preferably with a compound from the group of sodium carbonate, sodium bicarbonate, sodium phosphate, sodium oxalate and sodium citrate. Suitable sodium phosphates are, for example, trisodium monophosphate and trisodium polyphosphate.
  • the potassium compound is preferably selected from the group of potassium carbonate, potassium hydrogencarbonate, potassium phosphate, potassium citrate and potassium oxalate.
  • the activation of the bentonite, in particular calcium bentonite is carried out in a conventional manner.
  • the bentonite which may have a moisture in the range of 20 to 40 wt .-%, is kneaded with the calculated amount of the alkali metal compound. Subsequently, the over-activated with alkali metal ions bentonite can be dried, ground and optionally sifted to adjust the desired grain size.
  • the granulation of the over-activated with alkali metal bentonite takes place per se by conventional methods.
  • the waterglass solution can be sprayed onto the agitated bentonite which has been overactivated with alkali metal ions.
  • free-fall mixers can be used, in which a curtain of falling particles of the overactivated bentonite is formed, on which the water glass solution is then sprayed.
  • the water content of the granules can be lowered, for example, by introducing heated air to the desired value.
  • the water content of the finished bentonite granules is 6 to 14 wt .-%, preferably 7 to 12 wt .-%, particularly preferably 8 to 10 wt .-%.
  • the granulation of the over-activated alkali metal ion bentonite, in particular sodium bentonite but in such a way that the overactivated bentonite is placed in a high-speed mixer and the water glass is added within a short period of time in its entirety.
  • the granulation can be carried out both in a batch process and in a continuous process.
  • a so-called Eirich mixer and for continuous granulation for example, a continuously operating ploughshare mixer, as offered for example by the company Lödige, or a ring layer mixer, such as a Lödige CB mixer, can be used.
  • Another object of the invention is a bentonite granules, as it can be obtained, for example, with the method described above.
  • Bentonitgranulat is characterized by the fact that it dissolves very quickly in water or disintegrates very quickly.
  • the bentonite granules preferably have a decomposition in water after 90 seconds of at least 90%, particularly preferably of at least 95% and especially preferably of at least 99%.
  • the granulated overactivated bentonite preferably has a pH of more than 10 in an aqueous slurry containing 2% by weight of granules.
  • Nessler's reagent (Merck, item No. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0.1 N hydrochloric acid; NaCl solution, 0.1%; KCl solution, 0.1%.
  • Detection of the ionic freedom of the wash water is performed on NH 4 + ions with the sensitive Nessler's reagent.
  • the washing time can vary between 30 minutes and 3 days, depending on the key.
  • the leached NH 4 + clay is removed from the filter, dried at 110 ° C for 2 h, ground, sieved (63 micron sieve) and dried again at 110 ° C for 2 h. Thereafter, the NH 4 + content of the clay is determined by elemental analysis.
  • the CEC (cation exchange capacity) of the clay is conventionally determined by the NH 4 + content of the NH 4 + clay, which was determined by elemental analysis of the N content.
  • the device Vario EL 3 of the company Elementar-Heraeus, Hanau, DE was used according to the manufacturer's instructions. The data are given in mval / 100 g clay (meq / 100g).
  • the water content of the products at 105 ° C is determined using the method DIN / ISO-787/2.
  • the dissolution rate of the granules is investigated by a method as described in US Pat WO 99/32591 is described.
  • the granules are first screened with a sieve of mesh size 200 microns. 8 g of the sieved material are placed in one liter of water, which is heated to 30 ° C and 21 ° German hardness. With a paddle stirrer is for 90 sec. At 800 revolutions / min. touched. The remaining residue of the granules is sieved with a sieve of mesh size 0.2 mm and then dried to constant weight at 40 ° C. The residue is weighed and the solubility determined as the difference to the weighed-in amount of granules.
  • 105 to 115 g of the granules are placed on a sieve of mesh size 0.15 mm and sieved finely divided portions of the granules.
  • a graduated 100 ml graduated cylinder is filled with 100 ml of distilled water or an aqueous solution of 1% soda and 2% trisodium polyphosphate.
  • 2 g of bentonite are added slowly and in portions, each about 0.1 to 0.2 g, with a spatula on the surface of the water. After a drop of added portion, the next portion is added. After the 2 g of bentonite have been added and dropped to the bottom of the graduated cylinder, the cylinder is allowed to stand for one hour at room temperature. Then the height of the swollen substance in ml / 2g is read on the graduation of the measuring cylinder.
  • the X-ray images are taken on a Philips high-resolution powder diffractometer (X'-Pert-MPD (PW3040)) equipped with a CO anode.
  • the bentonite used was a natural Ca bentonite which has the following properties: ⁇ u> Table 1: Properties of the bentonite ⁇ / u> property value Montmorillonite content via methylene blue adsorption 75% Minor mineral content via X-ray measurements quartz ⁇ 1% by weight cristobalite ⁇ 5% by weight feldspar ⁇ 12% by weight Cation exchange capacity via the NH 4 method 75 meq / 100g
  • the granules were examined for their dispersion rate in the manner described above.
  • the data obtained are summarized in Table 4 for a granulation with a water glass with a modulus SiO 2 : Na 2 O of 2.65 and in Table 5 for a granulation with a water glass with a modulus SiO 2 : Na 2 O of 3.2 ,
  • the swelling volumes of the granules obtained and the pH during dissolution of the granules in water are also included in Tables 4 and 5.
  • the swelling volume of the unactivated bentonite is 12 ml / 2 mg, increases in stoichiometrically activated bentonite to 20 ml / 2 g, and then the overactivated bentonite back to 15 ml / 2 g to fall off.
  • the overactivated bentonite 3 is already at a water glass content of 1.2% after 30 s achieved a complete resolution, while the stoichiometrically activated bentonite 2 a much higher water glass content of 7.3% is required within 30 s to achieve a complete dissolution of the granules.

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
  • Disintegrating Or Milling (AREA)
  • Glanulating (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP06742901A 2005-05-12 2006-05-12 Schnell zerfallende bentonitgranulate Active EP1891191B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06742901T PL1891191T3 (pl) 2005-05-12 2006-05-12 Granulaty bentonitowe ulegające szybkiemu rozkładowi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005022075A DE102005022075A1 (de) 2005-05-12 2005-05-12 Schnell zerfallende Betonitgranulate
PCT/EP2006/004489 WO2006120011A1 (de) 2005-05-12 2006-05-12 Schnell zerfallende bentonitgranulate

Publications (2)

Publication Number Publication Date
EP1891191A1 EP1891191A1 (de) 2008-02-27
EP1891191B1 true EP1891191B1 (de) 2010-12-22

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EP (1) EP1891191B1 (zh)
JP (1) JP4971310B2 (zh)
CN (1) CN101175844B (zh)
AT (1) ATE492622T1 (zh)
BR (1) BRPI0608600A2 (zh)
DE (2) DE102005022075A1 (zh)
ES (1) ES2358212T3 (zh)
MX (1) MX2007013874A (zh)
PL (1) PL1891191T3 (zh)
WO (1) WO2006120011A1 (zh)
ZA (1) ZA200709019B (zh)

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JP2008290923A (ja) * 2007-05-28 2008-12-04 Kurosaki Hakudo Kogyo Kk 水分散性強化型改質ベントナイト及びその製造方法
KR101348134B1 (ko) 2012-09-28 2014-01-07 한국에너지기술연구원 그래뉼화 된 벤토나이트 성형체의 제조방법 및 이에 따라 제조된 그래뉼화 된 벤토나이트 성형체의 제조방법
WO2014051278A1 (ko) * 2012-09-28 2014-04-03 한국에너지기술연구원 그래뉼화 된 벤토나이트 성형체의 제조방법 및 이에 따라 제조된 그래뉼화 된 벤토나이트 성형체
CN108004054B (zh) * 2017-12-20 2020-04-14 苏州国建慧投矿物新材料有限公司 一种用于洗衣粉的柔顺功能粒子及其制备方法
CN111024884B (zh) * 2019-12-02 2022-04-22 武汉科技大学 一种用于冶金球团粘结剂的膨润土质量检测评价方法
NL2032305B1 (nl) * 2022-06-28 2024-01-16 Trisoplast Int B V Geconsolideerd droog mengsel dat granulair materiaal en bentoniet

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58117294A (ja) * 1981-12-30 1983-07-12 ライオン株式会社 芳香性洗剤組成物
DE3362488D1 (en) * 1982-02-19 1986-04-17 Laporte Industries Ltd A process for the manufacture of absorbent materials
US4746445A (en) * 1982-04-08 1988-05-24 Colgate-Palmolive Company Process for manufacturing bentonite agglomerates
DE3311368A1 (de) * 1982-04-08 1983-10-27 Colgate-Palmolive Co., 10022 New York, N.Y. Teilchenfoermiges, bleichendes und weichmachendes textilwaschmittel
DE3311568C2 (de) * 1982-04-08 1994-10-20 Colgate Palmolive Co Teilchenförmiges und weichmachendes Grobwaschmittel, Verfahren zu dessen Herstellung und als Zusatz für Grobwaschmittel geeignetes Bentonit-Agglomerat
US4767546A (en) * 1982-04-08 1988-08-30 Colgate-Palmolive Co. Fabric softening bentonite agglomerates for use in laundry detergents
US4536316A (en) * 1983-06-01 1985-08-20 Colgate-Palmolive Co. Fabric softening composition containing surface modified clay
US4609473A (en) * 1984-11-26 1986-09-02 Colgate Palmolive Company Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it
JPS63150390A (ja) * 1986-12-15 1988-06-23 株式会社豊田中央研究所 洗剤組成物
US4997695A (en) * 1988-11-21 1991-03-05 James Clem Corporation Clay mixture having contamination resistance
DE3908628A1 (de) * 1989-03-16 1990-09-20 Manfred Dr Ing Braun Brikettierung von tonmehlgemengen mit zusaetzen auf walzenpressen mit formmulden und verarbeitung dieser briketts zur errichtung von wasserdichten sperrschichten
DE4243389A1 (de) * 1992-12-21 1994-06-23 Sued Chemie Ag Verfahren zur Herstellung von Sorptionsmitteln zur Aufnahme von Flüssigkeiten
CN1061946C (zh) * 1997-03-31 2001-02-14 孙忠 一种用钙基膨润土生产钠基膨润土的方法
DE19943551A1 (de) * 1999-09-11 2001-03-15 Clariant Gmbh Schwerlösliches Alkalisilikat
DE10121051A1 (de) * 2001-04-28 2002-10-31 Clariant Gmbh Builder-Zusammensetzung
CN1155515C (zh) * 2002-04-16 2004-06-30 张兴华 颗粒膨润土的生产方法
JP2004073053A (ja) * 2002-08-14 2004-03-11 Kurosaki Hakudo Kogyo Kk ペット用トイレ砂

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JP4971310B2 (ja) 2012-07-11
EP1891191A1 (de) 2008-02-27
ZA200709019B (en) 2009-02-25
DE102005022075A1 (de) 2006-11-16
DE502006008561D1 (de) 2011-02-03
CN101175844B (zh) 2010-06-09
PL1891191T3 (pl) 2011-07-29
CN101175844A (zh) 2008-05-07
BRPI0608600A2 (pt) 2010-01-19
ATE492622T1 (de) 2011-01-15
WO2006120011A1 (de) 2006-11-16
ES2358212T3 (es) 2011-05-06
JP2008540749A (ja) 2008-11-20
MX2007013874A (es) 2008-01-28

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