Classifications

• • 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
  • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3081—Treatment with organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/10—Solid density
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/11—Powder tap density
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/14—Pore volume

Definitions

• the present invention relates to the use of granules of pyrogenic silica as carriers.
• the granules can have the function of a carrier for foodstuffs additives, such as dyestuffs, antioxidants, preservatives, emulsifiers, gelling agents, thickeners and binders, stabilizers, alkalis, acids, salts, antilumping agents, flavour intensifiers, sweeteners, aromas, feedstuffs additives, chemical intermediates and plant protection agents, such as, for example, herbicides, insecticides, fungicides and others.
• foodstuffs additives such as dyestuffs, antioxidants, preservatives, emulsifiers, gelling agents, thickeners and binders, stabilizers, alkalis, acids, salts, antilumping agents, flavour intensifiers, sweeteners, aromas, feedstuffs additives, chemical intermediates and plant protection agents, such as, for example, herbicides, insecticides,
• silicon dioxide particles which are employed as carriers are their high water content, their too low purity and the poor flow properties of the loaded substance.
• Silicic acid esters, silica sols or silicates are employed as starting compounds, and then often lead to products of which the purity is not adequate for the desired intended uses because of considerable amounts of salts, so that an expensive washing is necessary.
• the invention is therefore based on the object of providing spherical silicon dioxide particles for use as carriers which do not have the disadvantages mentioned and moreover meet the high demands of uses in respect of purity, product safety and flow properties.
• the invention provides the use of granules based on pyrogenically prepared silicon dioxide as a carrier for substances chosen from the group consisting of foodstuffs additives, such as dyestuffs, antioxidants, preservatives, emulsifiers, gelling agents, thickeners and binders, stabilizers, alkalis, acids, salts, antilumping agents, flavour intensifiers, sweeteners, aromas, feedstuffs additives, chemical intermediates and plant protection agents, such as herbicides, insecticides, fungicides and others.
• foodstuffs additives such as dyestuffs, antioxidants, preservatives, emulsifiers, gelling agents, thickeners and binders, stabilizers, alkalis, acids, salts, antilumping agents, flavour
• the invention also provides an adsorbate of granules based on pyrogenically prepared silicon dioxide and at least one substance chosen from the group consisting of foodstuffs additives, such as dyestuffs, antioxidants, preservatives, emulsifiers, gelling agents, thickeners and binders, stabilizers, alkalis, acids, salts, antilumping agents, flavour intensifiers, sweeteners, aromas, feedstuffs additives, chemical intermediates and plant protection agents, such as herbicides, insecticides and fungicides.
• foodstuffs additives such as dyestuffs, antioxidants, preservatives, emulsifiers, gelling agents, thickeners and binders, stabilizers, alkalis, acids, salts, antilumping agents, flavour intensifiers, sweeteners, aromas, feedstuffs additives, chemical intermediates and plant protection agents, such as herbicides, insecticides and fungicides.
• the granules based on pyrogenically prepared silicon dioxide preferably have an average particle diameter of 10 to 120 ⁇ m and a BET surface area of 40 to 400 m 2 /g (determination in accordance with DIN 66 131 with nitrogen) .
• the silicon dioxide granules furthermore preferably have the following physico-chemical characteristic data, which are determined as described in EP PS 0 725 037:
• Pore volume 0.5 to 2.5 ml/g
• Pore size distribution less than 5% of the total pore volume has a pore diameter of less than 5 nm, remainder meso- and macropores
• Tamped density 220 to 700 g/1.
• Granules which are suitable for the use according to the invention and the preparation thereof are described, for example, in EP OS 0 727 037.
• the granules can preferably have meso- and macropores, the volume of the mesopores making up 10 to 80% of the total volume.
• the particle size distribution of the granules is preferably 80 vol.% larger than 8 ⁇ m and 80 vol.% smaller than 96 ⁇ m.
• the content of pores smaller than 5 ⁇ m is not more than 5%, based on the total pore volume.
• the granules employed according to the invention can be prepared, for example, by dispersing pyrogenically prepared silicon dioxide, preferably silicon dioxide prepared from silicon tetrachloride by means. of flame hydrolysis, in water, spray drying the dispersion and optionally then heat-treating the resulting granules at a temperature of 150 to 1,100 2 C for a period of 1 to 8 h.
• the dispersion in water preferably has a concentration of silicon dioxide of 5 to 25 wt.%, more preferably 5 to about 19.9 wt.%.
• the spray drying can be carried out at a temperature of 200 to 600 S C, and disc atomizers or nozzle atomizers can be employed in this context.
• the heat treatment of the granules can be carried out either in a static bed, such as, for example, in chamber ovens, or in an agitated bed, such as, for example, rotary tubular dryers .
• the pyrogenic silicon dioxide serving as the starting compound is prepared by a process in which a volatile silicon compound is injected into an oxyhydrogen gas flame of hydrogen and air. Silicon tetrachloride is used in most cases. This substance hydrolyses to silicon dioxide and hydrochloric acid under the influence of the water formed during the oxyhydrogen gas reaction. After leaving the flame the silicon dioxide enters into a so-called coagulation zone, in which the silicon dioxide primary particles and primary aggregates agglomerate. The product present as a type of aerosol in this stage is separated from the gaseous concomitant substances in cyclones and then after-treated with damp hot air. The residual hydrochloric acid content can be lowered to below 0.025% by this process .
• the granules based on pyrogenically prepared silicon dioxide can be silanized.
• the carbon content of the granules is then preferably 0.3 to 15.0 wt.%.
• Halogenosilanes, alkoxysilanes, silazanes and/or siloxanes can be employed for the silanization.
• R alkyl
• the silane Si 108 [ (CH3O) 3-Si-CgHi7_ trimethoxyoctylsilane can preferably be employed as the silanizing agent.
• Cyclic polysiloxanes of the type D 3, D 4, D 5, e.g. octamethylcyclotetrasiloxane D 4
• R alkyl, aryl, (CH2) n - NH2
• H R' alkyl, aryl, (CH ) n - NH 2
• H R" alkyl, aryl, (CH 2 ) n - H2
• H R'" alkyl, aryl, (CH2) - H2
• H Y CH3, H, C n H2 +l
• the silanization can be carried out by a procedure in which the granules are sprayed with the silanizing agent, which can optionally be dissolved in an organic solvent, such as, for example, ethanol, and the mixture is then heat-treated at a temperature of 105 to 400 a C over a period of 1 to 6 h.
• an organic solvent such as, for example, ethanol
• An alternative method of the silanization of the granules can be carried out by a procedure in which the granules are treated with the silanizing agent in vapour form and the mixture is then heat-treated at a temperature of 200 to 800 S C over a period of 0.5 to 6 h.
• the heat treatment can be carried out under an inert gas, such as, for example, nitrogen.
• the silanization can be carried out continuously or batchwise in heatable mixers and dryers with spray devices. Suitable devices can be, for example: plough share mixers or plate, fluidized bed or flow-bed dryers.
• Suitable devices can be, for example: plough share mixers or plate, fluidized bed or flow-bed dryers.
• the invention also provides :
• Antioxidant comprising granules based on pyrogenically prepared silicon dioxide.
• Preservative comprising granules based on pyrogenically prepared silicon dioxide.
• Emulsifier comprising granules based on pyrogenically prepared silicon dioxide.
• Binder comprising granules based on pyrogenically prepared silicon dioxide.
• Antilumping agent comprising granules based on pyrogenically prepared silicon dioxide.
• Feedstuffs additives comprising granules based on pyrogenically prepared silicon dioxide.
• Herbicides comprising granules based on pyrogenically prepared silicon dioxide.
• Insecticides comprising granules based on pyrogenically prepared silicon dioxide.
• Foodstuffs additives can be:
• Dyestuffs such as, for example:
• Antioxidants can be:
• E220 Sulfurous acid, sulfur dioxide E221 Sodium sulfite E222 Sodium hydrogen sulfite E223 Sodium disulfite E224 Potassium disulfite E300 Ascorbic acid E301 Sodium ascorbate E302 Calcium ascorbate E304 Ascorbyl palmitate ⁇ 306 Tocopherol-containing extracts of natural origin E307 alpha-Tocopherol E308 gamma-Tocopherol E309 delta-Tocopherol E310 Propyl gallate E311 Octyl gallate E312 Dodecyl gallate E320 Butylhydroxyanisole (BHA) E321 Butylhydroxytoluene (BHT) E330 Citric acid E331 Sodium citrate E332 Potassium citrate E333 Calcium citrate E472c Citric acid esters Ethoxiquin Preservatives can be:
• Emulsifiers can be:
• Gelling agents, thickeners and binders and stabilizers can be:
• Alkalis, acids and salts can be:
• Flavour intensifiers can be:
• Sweeteners can be:
• Isoamyl acetate G Isoamyl acetate nat.
• Sandel 80 Sandel extra Sandel Forte Sandel H&R Sandel H&R ECO Sandel H&R super Sandel SP Sandel type East Ind. Sandalwood type East Ind. Sandolene H&R
• Cinnamaldehyde Cinnamaldehyde nat. Cinnamyl alcohol Cinnamon leaf Identoil Cinnamon bark Identoil Feedstuffs additives can be:
• Chemical intermediates can be:
• Resinol acids Resinols Resinotannols Resenes Terpenes Diterpenes Triterpenes Sesquiterpenes Resin esters Resin soaps Alcohols Phenol derivatives Hydroguinone derivatives Quinoline derivatives Naturally occurring resins:
• Anionic surfactants Polyethylene ethers Polypropylene glycol ethers Pluronic ® Mixed ethers Inorg. peroxides:
• Di-tert-butyl peroxide Dibenzoyl peroxide Per-acids Per-acid esters Ketone peroxides Epidioxides Ascaridol Ergosterol peroxide
• Camphor Trimellitic acid Phosphoric acid esters Azelaic acid esters Sebacic acid esters Chioroparaffins Dioctyl phthalate Bis- (2-ethylhexyl) phthalate Diisononyl phthalate Diisodocecyl phthalate Phthalic acid esters Dibutyl phthalate Diisobutyl phthalate
• Wetting agents can be:
• Dimethyloctylphosphine oxide Dimethylnonylphosphine oxide Dimethyldecylphosphine oxide Dimethylundecylphosphine oxide Dimethyldodecylphoshine oxide N,N, -bis (3-D-gluconamidopropyl) cholamide N,N-Bis (3-D-gluconamidopropyl) deoxycholamide
• Plant protection agents can be:
• the silicon dioxide granules -employed according to the invention function as a carrier.
• the present invention therefore also relates to an adsorbate of the silicon dioxide granules described above and at least one of these substances.
• adsorbate as used herein includes the adsorption of a substance not only on to the surface -of the silicon dioxide, but also into the pores, as well as the “intercalation” into the intergrain volumes.
• Adsorbate can also mean that silicon dioxide granules or fragments thereof envelop solid particles or liquid droplets of the substance. In the latter case the forces of attraction between the particles or droplets are reduced and, for example, the flow properties are improved or the merging of droplets is impeded.
• the ratio of amounts of substance to silicon dioxide granules in the adsorbate can be chosen as desired as a function of the properties of the substance and the requirements for the end product. Preferably, however, 0.001 to 200 g of substance are employed per 100 g of silicon dioxide granules, particularly preferably 10 to 150 g.
• granules based on pyrogenically prepared silicon dioxide of average particle diameter from 10 to 120 ⁇ m and BET surface area from 40 to 400 m 2 /g can be used as the silicon dioxide granules .
• the silicon dioxide granules furthermore preferably have the following physico-chemical characteristic data, which are determined as described in EP PS 0 725 037:
• Pore volume 0.5 to 2.5 ml/g Pore size volume: less than 5% of the total pore volume has a pore diameter of less than 5 n , remainder meso- and macropores pH: 3.6 to 8.5 Tamped density: 220 to 700 g/1.
• Granules which are suitable for the use according to the invention and the preparation thereof are described, for example, in EP OS 0 727 037.
• An example of a process for the preparation of the adsorbate according to the invention comprises:
• step (a) mixing of the granules based on pyrogenically prepared silicon dioxide with the mixture from step (a) ; and where appropriate removal of the solvent.
• “Solvent” also includes mixtures of several different solvents. It goes without saying, furthermore, that substances which are already liquid at room temperature can be subjected to the mixing in step (b) without prior processing, since in this case the "melting operation" has already taken place.
• Mixing step (b) can be carried out either by adding the mixture from step (a) to the silicon dioxide granules, for example by spraying on, or vice versa. In both cases, the addition can be made in one amount or in portions.
• the duration of the mixing in step (b) depends here above all on the adsorption properties of the substance to be adsorbed on the silica surface. If a solvent is present, step (a) and (b) are carried out at a temperature which lies between the freezing and boiling point of the solvent. The solvent, where appropriate in excess, is preferably removed in step (c) at elevated temperature and/or under reduced pressure.
• step (c) The removal of the solvent in step (c) can also -be carried out by spray drying or fluidized bed drying, shaping taking place at the same time.
• the shaping process can accordingly be an extrusion.
• the adsorbates according to the invention can be used for the preparation of powders, liquids, foams, sprays, gels, creams, ointments, pastes, sticks and tablets.
• the adsorbates according to the invention can additionally be shaped. They can be processed, for example, to pellets, larger granules, extrudates etc.
• the advantage of the adsorbates according to the invention lies in their excellent flow properties, the low water content and the high purity of the starting granules. They offer a very good possibility for dispersing substances which are difficult to meter, and are easy to handle.
• the hazard potential to the administering person during use on toxic substances can be reduced significantly.
• the pyrogenically prepared silicon dioxide AEROSIL 300 commercially obtainable from Degussa AG, is used as the starting compound.
• the pyrogenically prepared silicon dioxide is dispersed in completely demineralized water.
• a dispersing unit which operates by the rotor/stator principle is used here.
• the suspension formed is spray dried.
• the finished product is separated off via a filter or cyclone.
• the heat treatment of the spray granules is carried out in a muffle oven.
• Vitamin E acetate silicone oil, paraffin oil and eucalyptus oil are used as model liquids for the fields of use according to the invention, vitamin E acetate is used, for example, in the nutrition of animals and humans, and eucalyptus oil as an aromatic or aroma substance.
• Granulated pyrogenic silica (AEROPERL ® 300/30) has a significantly lower water content (loss on drying and ignition) and a higher silicon dioxide content than the silicas used in the comparison examples. Furthermore, it is free from sulfates, typical impurities of precipitated silica and silica gels, and has the best flowability (the lowest slope angle) .
• Procedure: 50 g of carrier silica are initially introduced into a 2 litre three-necked flask equipped with a blade stirrer. 50 g of the model liquids from examples 1-4 are added dropwise from a dropping funnel in the course of 60 minutes, while stirring at a stirrer speed of 100 revolutions / minute.
• Comparison examples 1-3 are carried out with eucalyptus oil.
• the liquid-silica adsorbates are then sieved manually three times through a 0.8 mm sieve and left to stand overnight in a closed screw-cap glass bottle. The following day, the liquid-silica adsorbates are characterized by the following methods:
• liquid-silica adsorbates prepared with granulated pyrogenic silica are distinguished by a good flowability (flow rating 2, slope angle ⁇ 40 a C) .
• the liquid-silica adsorbates from comparison examples 1 to 3 show a significantly lower flowability. The latter moreover have significantly lower bulk densities.
• Liquid-silica adsorbates with a good flowability and high 0 bulk volume are advantageous for carrier uses.
• carrier silicas should have the lowest possible water content and should be very pure, in order to avoid decomposition of the adsorbed liquids under the (catalytic) influence of water or impurities, such as, for example, sulfates.
• impurities such as, for example, sulfates.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Analytical Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Cosmetics (AREA)
• Medicinal Preparation (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Silicon Compounds (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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• 2003
  • 2003-08-13 DE DE10337198A patent/DE10337198A1/de not_active Ceased
• 2004
  • 2004-06-22 KR KR1020067002992A patent/KR100863453B1/ko not_active Expired - Fee Related
  • 2004-06-22 JP JP2006522904A patent/JP2007501762A/ja active Pending
  • 2004-06-22 CN CNB2004800230417A patent/CN100384727C/zh not_active Expired - Fee Related
  • 2004-06-22 WO PCT/EP2004/006719 patent/WO2005016823A1/en not_active Ceased
  • 2004-06-22 US US10/568,012 patent/US20060229210A1/en not_active Abandoned
  • 2004-06-22 EP EP04740149A patent/EP1654197A1/en not_active Ceased

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