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
  • C11D3/12—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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
  • B01J2/28—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using special binding agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/12—Naturally occurring clays or bleaching earth
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume

Definitions

• the invention relates to a process for the production of granules and granules containing a clay material.
• liquid raw materials must be converted into a solid form for special applications.
• the liquids are applied to suitable carrier materials.
• suitable carrier materials such as liquid detergent raw materials, such as nonionic surfactants, are granulated with carrier materials, so that they can be added to solid detergent formulations, such as detergent powders or detergent tablets.
• the carrier is simultaneously compounded to a specific particle size during the uptake of the detergent raw material.
• a large number of other areas exist in which liquid starting materials must be converted into a solid form, in order then to be further processed in a mixture with other solid raw materials.
• a large number of liquid raw materials are used, which are also applied to carriers, in order to then turn into solid livestock.
• liquid raw material is added directly to the animal feed, clumping generally occurs. The food can then no longer handle well. This concerns, for example, the production of fish feed pellets in which fats are applied to carriers.
• Other uses include the feeding of choline chloride in a 75% aqueous solution which is applied to precipitated silica.
• Other applications in which liquid raw materials must be converted into a solid form are, for example, plant extracts for pharmaceutical applications or pesticides, which are applied in solid form, for example. In a field.
• the resulting powder When transferring liquid raw materials into a solid form, it is essential that the resulting powder retains a free-flowing consistency so that, for example, it can be metered without problems. Also, the liquid raw material may not be released from the carrier during storage. Furthermore, the carrier should have the highest possible absorption capacity, since the carrier material is usually inert even for the intended application of the liquid raw material. If the absorption capacity is too low, the weight as well as the volume of the solid powder increases for a given amount of the liquid raw material. As a result, for example, also increase the transport or storage costs.
• synthetic silicic acids For the absorption of liquid raw materials in particular synthetic silicic acids have been used because of their high absorption capacity.
• These synthetic silicas are prepared by wet route from alkali silicate solutions, preferably soda water glass. By adding acid, amorphous silica is precipitated, which has a very high specific surface area and a very high absorption capacity. After filtration, washing and drying, the precipitated product consists of 86 to 88% SiO 2 and 10 to 12% water. The water is physically present both in the molecular structure and on the surface of the silica. quay-bound. Furthermore, the silicic acid still contains residues of the salts formed in the reaction and small amounts of metal oxide.
• Silica acids in the range of specific surface areas of about 25 to 700 m 2 / g can be provided.
• the silica suspension obtained in the precipitation is transferred to filter presses, wherein the solids content of the filter cake is between about 15 and 20%.
• the drying takes place by different methods, which are often followed by grinding and visual steps. Both hydrophilic and hydrophobic silicic acids can be used, it being possible for hydrophobic silicic acids to simultaneously serve as defoamers.
• the silicas mainly used as support materials preferably have an average particle diameter of about 1 to 100 ⁇ m.
• precipitated silicas with a high specific surface area and a high adsorption capacity, which is characterized by the oil number or the dibutylphthalate number (DBP number) according to DIN 5360 I, are preferred.
• Such precipitated silicas can take up about 50-75% by weight of liquid raw materials and allow them to be supplied in concentrated solid form to their respective applications.
• WO 99/32591 describes a particulate detergent and cleaner which comprises 40 to 80% by weight of zeolite and 20 to 60% by weight of one or more alkoxylated C 8 -C 18 -alcohols and alkyl polyglycosides contains. Based on the amount of zeolite, this contains at least 25 wt .-% of one or more zeolites of the faujasite type. Clay materials are used only in exceptional cases for the production of granules, which serve as a carrier for a valuable material. An essential field of application of clay materials has hitherto been used as bleaching earth for lightening fats and oils.
• the bleaching earths used it is desirable for the bleaching earths used to have the lowest possible absorption capacity for the fats and oils to be bleached, in order thus to suppress losses caused by oil or fat residues remaining in the bleaching earth after bleaching. Furthermore, these bleaching earths have a relatively high acidity, ie a suspension of such materials in water has a pH which is clearly in the acidic, ie at values below about pH 3. These bleaching earths are prepared either by natural clay materials with strong Acids are extracted or by natural clay materials are covered with an acid.
• DE 19 49 590 C2 describes cleaning and / or refining agents for oily substances which are obtained by extraction of an at least 50% by weight of montmorillonite-containing clay with acid.
• the clay and the acid are mixed in a ratio of 1 part by weight of clay to 0.3 to 2.5 parts by weight of acid. From this mixture small solid particles are formed, which in turn are extracted at elevated temperature with aqueous acid.
• the product has a particle diameter of 0.1 to 5 mm, a specific surface area of at least 120 m 2 / g and a pore volume of at least 0.7 ml / g.
• the pore volume corresponds to the difference between the reciprocal apparent density and the reciprocal true density of the acid-treated product.
• the total pore volume is preferably formed by small pores having a diameter of 0.02 to 10 microns.
• the acid-extracted clay material preferably has a proportion of the pore volume formed by small pores in the total pore volume in the region of 35 up to 75%. A high proportion of small pores is characteristic of clay materials extracted with strong acid.
• the precipitated silicas described above have a very high purity and a very high degree of whiteness. However, they are very expensive because of the special manufacturing process. For many applications, therefore, there is a need for inexpensive carrier materials with a high liquid absorption capacity.
• the object of the invention is therefore to provide a process for the production of granules available, with which inexpensive granules can be produced, which can accommodate large amounts of liquid recyclables.
• the absorption capacity for liquids can amount to up to 61% by weight and thus almost reaches the values of precipitated silica.
• the clay material can be obtained from natural sources and in the simplest case would only have to be freed of hard admixtures, such as quartz or feldspar, and possibly milled. The clay material can therefore be provided inexpensively.
• the absorption capacity of clay minerals for liquids, as used, for example, for bleaching oils, is usually about 40% by weight at most. By selecting special clay materials, however, a significantly higher absorption capacity for liquids can be achieved.
• the inventors believe that the high liquid absorption capacity of the clay materials used in the process according to the invention is based on the specific pore size. based on distribution.
• the use of special clay materials thus represents a cost-effective alternative to the synthetic precipitated silicas, especially for applications in which a high degree of whiteness is not important.
• inventive method for the production of granules is carried out in such a way that
• a solid granulation mixture which contains at least a portion of a clay material which
• the solid granulation is applied with a liquid granulating agent
• the mixture of the solid granulation and the liquid granulating agent is formed into a granulate.
• the specific surface of the clay material is preferably more than 180 m 2 / g, in particular more than 200 m 2 / g.
• the pore volume is measured by the BJH method and corresponds to the cumulative pore volume for pores having a diameter between 1.7 and 300 nm.
• the clay material has a pore volume of more than 0.5 ml / g.
• the cation exchange capacity of the clay material used in the process according to the invention is preferably more than 25 meq / 100 g, more preferably more than 40 meq / 100 g.
• the solid granulation mixture contains as its essential ingredient a clay material having the physical parameters given above.
• the solid granulation mixture can only consist of the clay material. However, it is also possible for the granulation mixture to contain other solid constituents in addition to the clay material.
• Such ingredients include, for example, precipitated silica, silica gels, aluminum silicates, e.g. Zeolites, powdered sodium silicates or other clay minerals, such as e.g. Bentonite or kaolin.
• the solid granulation mixture is in powder form, the average particle size (DT 50), determined by laser granulometry, preferably being in the range from 2 to 100 ⁇ m, preferably from 5 to 80 ⁇ m.
• the granulation mixture is preferably provided in the form of a fine powder.
• the average particle size (DT 50) is preferably less than 70 ⁇ m, preferably less than 50 ⁇ m, particularly preferably less than 30 ⁇ m.
• the granulation mixture preferably has a dry sieve residue on a sieve with a mesh width of 63 ⁇ m of at most 4%, preferably at most 2%.
• a suspension of the clay material in water has a neutral to slightly alkaline pH.
• the acidity of the clay material is preferably in a range from 6.5 to 9.5, preferably from pH 7 to 9.0, particularly preferably in a range from 7.5 to 8.5.
• a method for determining the acidity is given in the examples.
• the solid granulation mixture is charged with a liquid granulating agent.
• a liquid granulating agent can be water in the simplest case. However, any liquids can be used per se, as long as they can solidify the solid granulation mixture into a granulate.
• the mixture of the solid granulating mixture and the liquid granulating agent is formed into granules.
• the granulation is carried out in conventional granulation. All known granulation processes can be used per se.
• the solid granulation mixture can be agitated in a drum and the liquid granulation agent sprayed as a fine mist.
• the finished granules can then be dried to adjust the moisture content to a desired value.
• the granules can be comminuted and / or sieved in order to set a desired particle size.
• the size of the particles of the granules is not limited in itself and is selected according to the intended application.
• granules are preferably used which have a particle size in the range of 0.2 to 2 mm.
• animal feed additives mostly used particle sizes which form fine powders or micrograins.
• clay materials which, based on the anhydrous clay material (atro), have an SiO 2 content of more than 65% by weight. Furthermore, clay materials are preferred whose aluminum content, based on the anhydrous clay material and calculated as Al 2 O 3 , less than 11 wt .-% is.
• the clay material preferably has a water content of less than 15% by weight, preferably less than 5% by weight, particularly preferably 2-4% by weight.
• the clay materials most preferably used in the process of the invention may be described as a type of mixture of amorphous silica, such as the naturally occurring Opal A phase, with a layered silicate, such as a dioctaestris smectite.
• a layered silicate such as a dioctaestris smectite.
• dioctahedral smectite for example, a montmorillonite, a nontronite or a hectorite can be incorporated.
• the smectite layers are firmly embedded in the porous amorphous silica structure, whereby they are present mainly in the form of very thin platelets and possibly even completely delaminated.
• the clay materials preferably used in the process are essentially X-ray amorphous. Reflections typical of phyllosilicates, such as a hump at 20 to 30 ° and the 060 indifference are only weakly pronounced in these clay materials.
• the weakness of the 00L reflexes indicates, in particular, that the platelets of the layered silicate are almost completely delaminated in the porous structure. On average, the layered silicate is present as a layer stack of only a few fins. Due to the incorporated layered silicate these porous structures still have a significant cation exchange capacity, which is typical only for pure smectites.
• the clay materials used in the process according to the invention are preferably obtained from natural sources. However, it is also possible to use synthetically produced clay materials which have the properties described above. Such clay materials can be produced, for example, from water glass and bentonite. Preferably, the clay materials used in the process according to the invention are not obtained by acid leaching of clay minerals.
• Particularly preferred clay materials are used, which have only a low crystallinity, so are not assigned to the class of layer silicates per se.
• the low crystallinity can be determined, for example, by X-ray diffractometry.
• the particularly preferred clay materials are largely X-ray amorphous, i. In X-ray diffraction, they show essentially no sharp signals or only very small amounts of sharp signals. They therefore preferably do not belong to the class of attapulgites or smectites.
• the clay material used in the process according to the invention preferably shows virtually no swelling capacity in water.
• the sediment volume is determined essentially by the sediment density in water. There is little or no swelling. As a result, the sediment volume remains practically constant as a function of time. In addition, it is significantly lower than that of layered minerals.
• the swelling volume of calcium bentonites is typically about 10 ml / 2g, that of sodium bentonites up to 60 ml / 2g.
• the clay material preferably has a sediment volume in water of less than 15 ml / 2 g, preferably less than 10 ml / 2 g, particularly preferably less than 8 ml / 2 g. Even after prolonged storage in water or other liquids, no significant or no change in the sedi- ment volume observed.
• the sediment volume when the clay material is left in water at room temperature for three days is less than 15 ml / 2 g, preferably less than 10 ml / 2 g, particularly preferably less than 8 ml / 2 g.
• Room temperature is understood to mean a temperature in the range of about 15 to 25 ° C., in particular about 20 ° C.
• Sodium bentonites or potassium bentonites in contrast to the clay materials used in the process according to the invention, have a very high volume of swelling in water.
• the clay material used in the method according to the invention preferably has a certain pore radius distribution.
• the pore volume is essentially formed by pores having a diameter of more than 14 nm.
• the clay materials used in the process according to the invention particularly preferably have a pore radius distribution such that at least 40% of the total pore volume (determined according to the BJH method, see below) is formed by pores having a pore diameter of more than 14 nm.
• more than 50%, and more preferably more than 60%, of the total pore volume is formed by pores having a diameter of more than 14 nm.
• the total pore volume of these clay materials is, as already explained, more than 0.45 ml / g.
• the pore radius distribution or the total pore volume is determined by nitrogen porosimetry (DIN 66131) and evaluation of the adsorption isotherms according to the BJH method (see below).
• the granulation mixture may contain, in addition to the clay material described above, further constituents, for example further support materials or granulation aids.
• the proportion of the clay material in the solid granulation mixture is preferably at least 10% by weight, preferably at least 20% by weight, preferably at least 40% by weight, particularly preferably at least 60% by weight. Since that in the inventive Method used clay material can be provided relatively inexpensively, resulting in a high proportion of the clay material in the granulation cost advantages.
• naturally occurring clay minerals are usually not pure white, but may contain admixtures, for example. Metal oxides, which lead to a slight browning of the clay mineral.
• the solid granulation mixture may also contain a proportion of silica.
• Silica is pure white, especially when synthesized, and therefore contributes to the whitening of the granules.
• synthetic silica has a high liquid-carrying capacity, so that the receiving capacity of the produced granules is not deteriorated.
• the proportion of silica can be chosen arbitrarily. If an almost white appearance of the granules is required, the proportion of, preferably synthetic, silica is preferably at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 50% by weight. For economic reasons, the proportion of silica is preferably at most 90 wt .-%.
• water can be used as a liquid granulating agent.
• the granulating agent preferably contains a valuable substance.
• a valuable substance is understood as meaning a liquid substance which is to be converted into a solid, giant-shaped form by the process according to the invention.
• recyclables There are no limits in the selection of recyclables.
• the process according to the invention is suitable for solidifying virtually all liquid raw materials or valuable substances.
• valuable substances may be, for example, formic acid, fat concentrates, rubber auxiliaries, plant extracts, such as, for example, hops extract, molasses, perfume oils or fragrance substances, Pesticides, liquid vitamins, such as, for example, vitamin E acetate or a variety of other liquid recyclables.
• the proportion of the valuable substance which is contained in the liquid granulating agent is therefore preferably selected such that it corresponds to at least 40% by weight, preferably at least 50% by weight, of the solid granulating mixture.
• the liquid granulating agent can still contain an evaporable liquid as an auxiliary, for example water or alcohol, in order to be able to suitably adjust the viscosity of the liquid granulating agent, for example.
• the liquid used as auxiliaries can be evaporated during granulation, for example by blowing in heated air.
• the valuable substance is preferably a surfactant. It can be used, all surfactants that are common in the detergent production. For example, anionic surfactants may be used, as may cationic or nonionic surfactants, such as ethoxylated fatty alcohols. Since these granules are used in detergent compositions, the size of the granule particles is preferably selected in a range of 0.1 to 5 mm, preferably 0.2 to 2 mm.
• the particle size of the granules is therefore chosen to be somewhat lower than with detergent granules.
• the granules When used as feed, the granules preferably have a particle size in the range of less than 0.5 mm, preferably 0.1 to 0.4 mm.
• the size of the granulate particles can be adjusted, for example, by targeted process control during the application of water or the liquid granulating agent. Likewise, the particle size can be adjusted by screening. Preferably, however, the granulation process is performed so that the desired particle size is already obtained during granulation.
• the granules are produced by a mixing process. Depending on the desired properties of the granules different mixers are used. The granulation can be carried out both continuously and batchwise. The hardness of the granules can be adjusted by the intensity of the shear forces, which acts in the mixing process on the mixture of solid granulation and liquid granulating agent. For the production of soft powders, so-called drum mixers, V-blenders or tumblers are used. Harder granules are obtained by using cone mixers, plowshare mixers or spiral mixers. Examples of plowshare mixers are Lödige ® FKM mixers and Drais Turbo-Mix TM mixers.
• spiral mixer An example of a spiral mixer is the Nauta ⁇ mixer from Hokosawa, Japan. Hard granules are obtained for example. With Lödige CB mixers, Drais Corimix "K-TT mixers, Ballestra * Kettemix ® devices and Schugi 18 granulators. These mixers are preferably used for the preparation of granules for detergent applications.
• the granules can also be produced by extrusion and roll contacting with subsequent comminution.
• the granules obtained by the process according to the invention have a high content of liquid valuable material and a at the same time low proportion of adsorbent or clay material.
• the subject of the invention is therefore also a granulate containing at least one clay material which:
• - has a cation exchange capacity of more than 15 meq / 100 g.
• the specific surface of the clay material is preferably more than 180 m 2 / g, particularly preferably more than 200 m 2 / g.
• the pore volume is preferably more than 50 ml / g.
• the cation exchange capacity of the clay material is preferably more than 25 meq / 100 g, more preferably more than 40 meq / 100 g.
• the granules of the invention can be produced inexpensively and is particularly suitable for applications that do not require a high degree of whiteness.
• the proportion of the clay material in the granules is preferably more than 20% by weight, preferably more than 30% by weight.
• the granules preferably contain at least one valuable substance.
• Exemplary recyclables have already been described above. As such, the selection of recyclables is not limited. It can be contained in the granules per se any recyclables and are thus made available in a solid, free-flowing form.
• the proportion of valuable material in the granules is preferably at least 40 wt .-%, particularly preferably at least 50 wt .-%. In particularly preferred embodiments, the proportion of valuable material is up to 61 wt .-%.
• the granulate is particularly suitable as a component in laundry detergents or for use in animal feed. The valuable material is then selected accordingly from the group of surfactants or feed additives. Suitable feed additives are, for example, fats, choline, and vitamins.
• the granules are to have a high degree of whiteness, this preferably contains a proportion of silica.
• the proportion of silica on the granules is preferably at least 10 wt .-%, particularly preferably at least 20 wt .-%.
• they can finally be powdered with the clay material described above. If a particularly high degree of whiteness of the granules is required, a final powdering with, for example, precipitated silica can also be carried out.
• the clay material described above may also be used for other applications for powdering unless high whiteness is required. It can replace precipitated silica or zeolites as powdering agents in these processes.
• Another aspect of the invention is the use of the granules described above for the absorption of valuable material.
• the specific surface area was determined on a fully automatic nitrogen porosimeter from the company Micromeretix, type ASAP 2010, in accordance with DIN 66131.
• the pore volume was determined using the DJH method (E.P. Barrett, L.G. Joyner, P.P. Haienda, J. Am. Chem. Soc. 73 (1951) 373). Pore volumes of specific pore size ranges are determined by summing up incremental pore volumes, which are obtained from the evaluation of the adsorption isotherms according to BJH.
• the total pore volume according to the BJH method refers to pores with a diameter of 2 to 130 nm.
• the water content of the products at 105 0 C was determined using the method DIN / ISO-787/2.
• This analysis is based on the total digestion of the raw clay or the corresponding product. After dissolution of the solids, the individual components are separated by conventional specific analysis methods, e.g. ICB, analyzed and quantified.
• sample digestion finely ground about 10 g of the sample to be examined and dried in a drying oven at 105 ° C. for 2 to 3 hours to constant weight. Approximately 1.4 g of Dried sample is placed in a platinum crucible and the sample weight is determined to an accuracy of 0.001 g. Thereafter, the sample is mixed in the platinum crucible with 4 to 6 times the weight of a mixture of sodium carbonate and potassium carbonate (1: 1). The mixture is provided with the platinum crucible into a Simon-Müller furnace and 2 - melted 850 C 0 - 3 hours at 800th The platinum crucible with the melt is removed from the oven with a platinum plunger and left to cool.
• the cooled melt is rinsed with a little distilled water in a casserole and carefully mixed with concentrated hydrochloric acid. After completion of the evolution of gas, the solution is evaporated to dryness. The residue is again concentrated in 20 ml. Hydrochloric acid and evaporated again to dryness. The evaporation with hydrochloric acid is repeated again.
• the residue is moistened with about 5 - 10 ml of hydrochloric acid (12%), with about 100 ml of dist. Water is added and heated. Insoluble SiO 2 is filtered off, the residue is washed three times with hot hydrochloric acid (12%) and then washed with hot water (dist.) Until the filtrate water is chloride-free.
• the SiO 2 is ashed with the filter and weighed.
• the filter cake is dried for two hours at 110 0 C and the NH 4 content in the clay material by Kjeldahl nitrogen determination (CHN analyzer from. Leco) determined according to the manufacturer's instructions.
• the cation exchange capacity is calculated from the amount of NH 4 taken up in the clay material and determined.
• the proportion and type of exchanged metal ions is determined in the filtrate by ECP spectroscopy.
• the X-ray images were taken on a Philips high-resolution powder diffractometer (X'-Pert-MPD (PW3040) equipped with a CO anode.
• a graduated 100 ml measuring cylinder is filled with 100 ml of distilled water or an aqueous solution of 1% soda and 2% trisodium polyphosphate. 2 g of the substance to be measured 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 substance have been added and dropped to the bottom of the measuring 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. To determine the sediment volume after standing for three days, the batch is sealed with Para film 9 and allowed to stand for 3 days vibration-free at room temperature. The sediment volume is then read on the graduation of the measuring cylinder. Determination of dry residue
• the dissolution rate of. Granules are analyzed by a method as described in WO 99/32591.
• 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 0 C and 21 ° German hardness. With a paddle stirrer for 90 sec. At 800 revolutions / min, stirred. The remaining residue of the granules is sieved with a sieve of mesh size 0.2 mm and then dried at 40 0 C to constant weight. The residue is weighed and the solubility determined as the difference to the weighed-in amount of granules.
• the reference quantity for the whiteness measurement is the remission to BaSO 4 .
• the measurement of the reflection factor R 457 at a center-of-mass wavelength of 457 mm is performed by means of a Datacolor Elrepho 2000 instrument. With the help of a suitable additional program, the Hunter color coordinates L, a and b are determined, where L is the degree of whiteness expressed.
• the cooled powder is either measured directly or compressed in a Zeiss tablet press and immediately measured on the Elrepho device (Datacolor Elrepho 2000, program R 457, possibly Hunter color plate).
• the methylene blue value is a measure of the inner surface of the clay materials.
• the test of the clay material is carried out in the same way as for the test bentonite. From the used amount of methylene blue solution, the inner surface of the clay material can be calculated.
• a 5% strength by weight suspension of the clay material to be examined is prepared in distilled water.
• the pH value is determined at room temperature (20.0 0 C) using a calibrated glass electrode.
• Example 2 Carrying out the granulation
• an Eirich Intensive Mixer R02E was used to prepare the granules described in the following examples.
• the low setting (level 1) for the speed of rotation of the plate and the maximum speed of rotation for the whirl was chosen.
• the granulation parameters were each selected below such that more than 50% of the granules te in a particle size range of 0.4 to 1.6 mm.
• the mean particle size can be modified by varying the granulation parameters.
• the agglomerates were optionally coated with lime or zeolite.
• the granules were transferred to a plastic bag, the inorganic powder added and the contents of the bag shaken for about 2 minutes.
• the granules were coated in the Eirich mixer.
• the inorganic powder was added and the granules were mixed for 20 to 30 seconds at 50% of the maximum swirling revolution number.
• Example 1 400 g of the clay material A characterized in Example 1 were granulated in the manner described in Example 2 with Dehydol LT 7 (Cognis AG, Dusseldorf, DE).
• the granules were each coated with 10% zeolite A (Zeolon P4A, MAL alumina, Hungary) and the granules size fraction 0.4-1.6 mm separated by screening.
• Example 2 In the manner indicated in Example 2, 235 g of choline chloride were granulated as a 70% aqueous solution with 300 g of the clay material A characterized in Table 1. The granulation was stopped as soon as finely divided granules were obtained.
• the precipitated silica absorbs about 66% choline chloride solution.
• a common sodium bentonite absorbs only 29% by weight of the choline chloride solution.
• the clay material A characterized in Table 1 absorbs 43.9% by weight of choline chloride. The clay material A thus absorbs significantly higher amounts of liquid compared to an ordinary bentonite.
• the methylene blue value was determined for the clay material A characterized in Example 1 and for further bentonites. The results are given in Table 4 together with other parameters.
• Table 6 shows typical nonionic surfactant contents of granules made with various carrier materials.
• Table 5 Nonionic surfactant contents
• Example 7 Granulation of Vitamin E.
• vitamin E acetate vitamin E acetate oily feed BASF AG, Ludwigshafen, Germany
• carrier materials listed in Table 6.
• precipitated silica Sipernat * 22, Degussa AG
• 3 1 mixture of silica and the clay material A characterized in Example 1 were carried out.
• the maximum liquid carrying capacity of the individual powders is listed in Table 6 below: Table 6: Carrying capacity for vitamin E acetate
• the clay material A characterized in Example 1 has a very high carrying capacity for vitamin E.
• the clay material may also be used in admixture with precipitated silica.
• a powder mixture in which 25% of the precipitated silica has been replaced by the clay material shows almost the same fluid carrying capacity for vitamin E acetate as precipitated silica.
• Example 2 For the determination of the whiteness, a tablet was pressed from the clay material A characterized in Example 1 and these were measured. For comparison with precipitated silica, the unpressed material was used in each case since precipitated silica can not be pressed into tablets.
• Both the clay material A characterized in example 1 as well as hybrids of the clay material with precipitated silica have a high liquid-carrying capacity as well as a high degree of whiteness.
• the surfactant Texaco pon ® N70 (Cognis AG, Dusseldorf, Germany) was used. This contains 70% ether sulfate and 30% water.
• Example 1 A 800 g of the clay material characterized in Example 1 A were granulated with 945 g each Texapon ® N70. This corresponds to a content of 52% ether sulfate in the finished granules. Granules are obtained with a bulk density of 740 g / l, which is very soluble in water (solubility 98%).
• soybean lecithin was granulated as an example of a feed application with various carrier materials.
• a carrier material characterized in the Example 1
• a clay material and precipitated silica (Sipernat ® 22, Degussa AG) was used.
• the granulation parameters were adjusted so that a fine granules were obtained with a maximum Sojalecitingehalt which is free-flowing and in its consistency comparable to corresponding marketable granules Bergafit 50 and Bergafit ® 60 from the same manufacturer is that 50 or 60% LE cithin contain ,
• the carrying capacities are given in Table 8.
• Example 11 Granule production with pre-dried clay material
• the data show a very low metal leaching of the clay material.
• the clay material contains only very small amounts of leachable heavy metals.
• Example 14 Granulation of choline chloride solution
• Example 4 the clay material B characterized in Table 10 was granulated with choline chloride solution (75% solution in water). The clay material B shows a capacity of 49% for the aqueous choline chloride solution.

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