EP1521720A1 - Guanidincarbonat-haltiges kieselsol - Google Patents
Guanidincarbonat-haltiges kieselsolInfo
- Publication number
- EP1521720A1 EP1521720A1 EP03763721A EP03763721A EP1521720A1 EP 1521720 A1 EP1521720 A1 EP 1521720A1 EP 03763721 A EP03763721 A EP 03763721A EP 03763721 A EP03763721 A EP 03763721A EP 1521720 A1 EP1521720 A1 EP 1521720A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silica sol
- sol
- reaction
- guanidine carbonate
- fresh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 87
- 229910002027 silica gel Inorganic materials 0.000 title abstract description 4
- 239000000741 silica gel Substances 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- -1 guanidinium ions Chemical class 0.000 claims abstract description 12
- 230000014759 maintenance of location Effects 0.000 claims abstract description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 74
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 8
- 229910018557 Si O Inorganic materials 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims 1
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims 1
- 229910052913 potassium silicate Inorganic materials 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 44
- 239000000377 silicon dioxide Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229920006317 cationic polymer Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005495 investment casting Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BNEIONMRSYCOPM-UHFFFAOYSA-N carbamimidoyl(oxido)azanium Chemical compound NC(=N)[NH2+][O-] BNEIONMRSYCOPM-UHFFFAOYSA-N 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005100 correlation spectroscopy Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- ISNICOKBNZOJQG-UHFFFAOYSA-O guanidinium ion Chemical compound C[NH+]=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-O 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/148—Concentration; Drying; Dehydration; Stabilisation; Purification
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the present invention relates to silica sol containing guanidinium ions, a process for its production and concentration and its use, for example in paper retention.
- Silica sols are sedimentation-stable, colloidal solutions made of amorphous SiO 2 in water or alcohols and other polar solvents. They are mostly water-liquid, and some of the commercial products available today have high ones
- Silica sols are used in a variety of ways. For example, they are used as binders for investment casting, for fibers in the refractory sector and in the manufacture of catalysts, as coating agents for foils (antiblocking) or silicon steel sheets, in the textile sector for sliding resistant equipment, in the construction sector as additives for shotcrete or as binders for fire - and heat protection applications, as a polishing agent for electronics or in the paper sector, for example in the
- silica sols are milky cloudy, opalescent to colorless clear, depending on the particle size of the silicon dioxide particles.
- the particles of the silica sol have diameters of 3 nm to 250 nm, preferably 5 nm to 150 nm.
- the particles are generally spherical, spatially limited and preferably electrically negatively charged.
- SiOH groups are often arranged on the surface.
- Stable silica sols with specific surfaces of approximately 30 to 1200 m 2 / g are preferred for various applications.
- the stability of silica sols is of great importance.
- silica sols that contain very fine SiO 2 particles, ie silica sols with a high specific surface area tend to gel, so that stabilization is often necessary.
- Common methods for stabilizing silica sols are treatment with alkali hydroxides or modification of the surface with
- US Pat. No. 5,643,414 describes a colloidal, finely divided silica sol with a high BET surface area of greater than 500 m 2 / g, which is stabilized by treating the surface with aluminum ions.
- US-A-5 603 805 also describes one
- Aluminum-stabilized silica sol which, however, has a surface area of less than 700 m 2 / g.
- US Pat. No. 6,310,104 B1 describes a finely divided, colloidal borosilicate. According to US Pat. No. 6,310,104 B1, such a colloidal borosilicate is colloidal silica sol in the
- silica sols which have so-called structured or partially agglomerated particles.
- structured particles consist of small particles which are combined to form chain-like or spatial structures, so that the particles have an elongated structure.
- the individual particles are each arranged in one plane, so that two-dimensional
- US-A-3 630 954 describes, among other things, a guanidine silicate as a raw material for the
- the first step is to Implementation of Guamdmhydroxid and silica sol made a solution of amorphous guanidine silicate. This is then deionized using a dimethylamine sulfonic acid cation exchanger. In this step, the majority of the guanidinium ions are removed and a silica sol containing dimethylamine is formed, the molar ratio of SiO 2 to guanidine oxide being 7.5: 1 and that
- Dimethylamine amount is 1 mol.
- the surface, determined using Sears base titration, is 1500 m 2 / g. Due to the manufacturing process, the sol contains large amounts of dimethylamine.
- a fresh sol is generally first produced. This is an alkali-free SiO 2 solution, which is generated, for example, by removing the alkali cations from a water glass.
- the fresh sol obtained is very unstable and is therefore stabilized immediately by renewed alkalization and by growth on existing silica sol particles and by simultaneous, intermediate or subsequent thermal treatment.
- a process for concentrating the aqueous solution can follow. The concentration can take place, for example, thermally by evaporation or by ultrafiltration over membranes. Ceramic membranes are suitable for this.
- the silica sol is often stabilized by alkalizing the solution to an SiO 2 : Na 2 O molar ratio of 40 to 130: 1, heating part of the solution to increase the particle size to 60 to 100 ° C, and then continuously mixing the remaining fresh sol solution admits and grows on the already existing particles. Simultaneously or subsequently, a concentration of the solution can be made to the 'desired concentration by evaporation.
- a finely divided silica sol which is only alkalized via inorganic bases has the disadvantage that the BET surface area does not remain stable.
- Such silica sols are therefore generally stabilized with aluminum ions (KK Her, The Chemistry of Silica, Wiley & Sons, New York, 1979, pages 407-410).
- the stability towards irreversible gelation to silica gel decreases with increasing silicon dioxide content, increasing electrolyte contamination and decreasing particle size.
- finely divided silica sols for example those with particle sizes smaller than 6 nm, can only be set to lower solid concentrations of, for example, ⁇ 20% by weight than coarse-particle silica sols with particle sizes greater than 50 nm, in which solids contents of up to 60% by weight. -% can be achieved.
- An increase in the stability of finely divided silica sols is achieved by carrying out a surface modification with aluminum ions, as described in “The Chemistry of Silica by
- the object of the present invention is to provide silica sols, in particular those with a high specific surface area, which are notable for high stability without modification with aluminum ions and which can be used in particular in paper retention.
- the invention therefore relates to a method for producing a silica sol, a fresh sol being reacted with guanide carbonate.
- a desired BET surface can be set in the product by precise reaction control, pH control, temperature control or by specifically setting the dwell times.
- the process enables the production of a stabilized silica sol with a BET surface area of 100 to 1200 m 2 / g and a solids concentration of, for example, 0.05 to 15% by weight.
- Fresh sol is used in the implementation of the invention.
- This is an alkali-free SiO 2 solution, which is generated, for example, by removing the alkali cations from a water glass.
- the most common method of dealkalization is to treat the dilute water glass solutions with cation exchange resins in the H + form. Suitable ion exchange resins are, for example Lewatit ® grades from. Bayer AG. Water glass solutions with a silicon dioxide content of less than 10% by weight are preferably passed over exchange columns with the acidic ion exchangers. Short residence times in the exchange zone, in which the pH of the solutions is preferably 5 to 7, are important in order to avoid gelation of the solutions and silicification of the exchange resin.
- the fresh sol to be used according to the invention is preferably an aqueous system with a SiO 2 content of 4 to 8% by weight, preferably 5 to 7% by weight.
- Fresh brines are generally used which contain SiO 2 particles with an average particle diameter, determined by means of an ultracentrifuge, of ⁇ 5 nm.
- the fresh brines used preferably have a pH of 2 to
- the stated pH values are to be understood as pH values which are determined at 25 ° C.
- the fresh sol is reacted with guanide carbonate.
- the guanide carbonate is preferably used in the form of an aqueous solution.
- the guanide carbonate concentration of the aqueous solution is preferably 5 to 30% by weight.
- Fresh sol and guanide carbonate are preferably reacted with one another in amounts such that the weight ratio of SiO 2 to guanide carbonate is from 150 to 0.2, particularly preferably from 60 to 15.
- the reaction is preferably carried out at a pH of 8 to 12, measured at the reaction temperature.
- the pH in the reaction is particularly preferably from 8 to 10, measured at the reaction temperature, very particularly preferably from 8.5 to 9.5, measured at the reaction temperature.
- the reaction is carried out, for example, at a temperature from 25 ° C. to 100 ° C., preferably from 50 ° C. to 100 ° C., particularly preferably from 80 ° C. to 100 ° C.
- the reaction of fresh sol with guanide carbonate according to the invention can be carried out in the presence of a further base. This ensures that a defined pH value is maintained and that gelation is avoided.
- Potassium water glass, sodium water glass, potassium hydroxide and / or sodium hydroxide can be used as the base.
- Sodium water glass is preferably used as the base.
- Commercial sodium water glass has a composition of Na 2 O 3.34 SiO 2 and is usually produced by melting quartz sand with soda or a mixture of sodium sulfate and coal, whereby a transparent, colorless glass is obtained, so-called piece glass.
- This ground glass reacts in the ground form with water at elevated temperature and pressure to form colloidal, strongly alkaline solutions, which are then subjected to cleaning.
- Methods are also known in which finely divided quartz or others suitable SiO 2 raw materials can be digested with alkalis directly into aqueous water glasses under hydrothermal conditions.
- the base is preferably added in a molar ratio of SiO 2 to Na 2 O of from 80 to 20, particularly preferably from 60 to 30.
- the base can, for example, be metered into the reactor in the form of an aqueous solution in which the reaction of fresh sol and guanide carbonate is carried out. It is also possible to add some or all of the base directly to a solution of guanidine carbonate and then to bring this mixture to reaction with the fresh sol. The second approach is preferred.
- the process according to the invention can be carried out continuously or in batches.
- a continuous driving style is preferred.
- the procedure is preferably such that the fresh sol and an aqueous solution of guanidine carbonate are fed continuously to a reactor, with a pH of 8 to 12, measured at the reaction temperature, and a temperature between 25 ° C. and 100 ° C. are set and the average residence time is chosen so that the silica sol produced has a BET surface area of> 100 m 2 / g.
- Specific surfaces can be prepared either using the BET method (S. Brunauer, PH Emmet and E. Teller, J. Am. Soc., 1938, 60, p. 309) on dried SiO 2 powder or directly in solution by titration according to GW Sears (Analytical Chemistry, Vol.
- the reaction is preferably carried out at a temperature of 50 ° C. to 100 ° C., particularly preferably at 80 ° C. to 100 ° C.
- the residence time is essentially determined by the reaction volume and the inflow and outflow. From 1.0 to 6.5 l / h of fresh sol and from 0.1 to 0.5 l / h of an aqueous solution of guanidine carbonate or an aqueous alkaline guanidine carbonate solution are preferably a reactor with a reaction volume of 0.5 to 1.0 liters added.
- the outflow can be influenced in particular by evaporating a certain amount of water during the reaction, the amount of water evaporated being adjusted by the choice of the temperature.
- the process according to the invention is preferably carried out in a multi-stage reactor cascade, in particular in a reactor cascade comprising three reaction vessels connected in series.
- All of the starting materials are preferably fed to the first reaction vessel. However, it is also conceivable to introduce partial streams of the starting materials into the second or another reaction vessel. It is important, however, that at least part of the silica sol and also the guanidine carbonate is fed to the first reaction vessel.
- the reaction in a multi-stage reactor cascade allows the creation of spatially separated, stationary conditions with regard to pH value, temperature, average particle diameter, Na 2 O content and SiO 2 concentrations, and residence time.
- the residence time in those reactors in which fresh sol is added is of particular importance, since there the growth process to larger particles takes place preferentially.
- the mean residence time is preferably controlled by an amount of water evaporated or to be evaporated and by the addition of fresh brine to the respective reactors, with the evaporation of water simultaneously resulting in a concentration.
- the BET surface area of the silica sol obtained is essentially determined by the temperature and the residence time in the reaction vessel into which the starting materials are introduced.
- the apparatus which is used in the process according to the invention preferably consists of a plurality of at least 2 overflow reactors which are arranged one behind the other and are connected to one another. The contents of each reaction vessel are mixed. Appropriate heat sources are used to define the reactors
- the feedstocks fresh sol, guanidine carbonate and optionally base are added to the reactors using metering devices, at least in the first reactor which is in the direction of the material flow.
- concentration a temperature of approximately the boiling point of the solvent used, preferably water, is set in one or more of the reaction vessels, solvent will evaporate. In this way, the concentration of SiO 2 in the product can be increased. This process is called concentration.
- the stationary conditions described above and characteristic of the invention must be set with regard to pH, temperature and mean residence time. To start up, it is not necessary to fill all reactors of the multi-stage apparatus with suitable templates. It is sufficient to have or generate the appropriate template in the first reactor.
- an aqueous, alkaline colloidal silica sol solution with a pH> 8 an aqueous, alkaline colloidal silica sol solution which contains 0.1 to 10% by weight guanidine carbonate with a pH> 8 or an aqueous, alkaline guanidine carbonate solution containing 0.1 to 10% by weight
- guanidine carbonate Contains guanidine carbonate.
- continuous process control is preferred, batch process control is also possible.
- at least a portion of the fresh sol and an aqueous solution of guanidine carbonate are placed in a reactor and the rest of the fresh sol and the aqueous solution of
- Guanidine carbonate is metered into the reaction mixture, the temperature being adjusted so that an amount of solvent evaporates which corresponds to the amount of fresh sol and aqueous solution of guanide carbonate metered in.
- the concentration of SiO 2 can already during the
- Production can be increased by evaporating part of the solvent.
- the actual manufacturing process can also be followed by a separate process for concentrating.
- the concentration can again be carried out, for example, thermally by evaporation or by ultrafiltration over membranes. Ceramic membranes, for example, are suitable for this.
- the invention furthermore relates to a silica sol which can be obtained by the process according to the invention.
- the invention also relates to a silica sol with a BET surface area of 100 to 1200 m 2 / g, the silica sol containing 0.05 to 15% by weight of guanidinium ions, based on the total weight of the silica sol.
- the silica sol of the present invention has a negligibly low aluminum content, preferably less than 50 ppm. Nevertheless, it is characterized by high stability with a high BET surface area, and solids contents of the silica sol of up to 15% by weight of SiO 2 can be set.
- the concentration of SiO 2 in the silica sol according to the invention is preferably from 3 to 15% by weight, based on the total weight of the silica sol.
- the silica sol preferably contains 0.1 to 15% by weight of guanidinium ions, particularly preferably 0.5 to 10% by weight.
- the silica sol preferably has a BET surface area of 300 ' to 1200 m 2 / g, particularly preferably from 500 to 1000 m / g, very particularly preferably from 700 to 1000 m 2 / g.
- the silica sol has a BET surface area of 400 to 650 m 2 / g.
- the SiO 2 particles of the silica sols according to the invention preferably have particle sizes with a broad size distribution of 3 to 300 nm.
- other different methods are also suitable for measuring the particle sizes in the nanometer range, such as laser correlation spectroscopy, photon correlation spectroscopy, ultrasound measurements or
- Measurement of a fractionation of the dispersion is carried out according to the particle size.
- the large particles sediment faster in a homogeneous dispersion than the existing medium-sized and small particles.
- the particle sizes of the SiO 2 particles of the silica sols according to the invention are therefore determined using an ultracentrifuge.
- the average diameter of the SiO 2 particles of the silica sols according to the invention is preferably from 3 to 30 nm, this value likewise being determined using a commercially available ultracentrifuge.
- the silica sol according to the invention preferably has a pH of 2 to 12, particularly preferably the pH is between 8 and 11.
- the range between pH 5 and pH 6 is less preferred, since silica sols have only a low stability in this range.
- peptization and dissolution of the particles then increasingly occur with the formation of alkali silicate solution.
- the finely divided silica sols according to the invention are generally part-aggregated, ie individual spherical SiO 2 particles are stacked together and form irregular structures, the spherical SiO 2 particles being able to be arranged in a chain as well as spatially.
- the silica sols according to the invention are free of amines.
- Fig.l shows an electron microscopic transmission recording of a silica sol according to the invention.
- the magnification is 200000: 1.
- the silica sols according to the invention usually have a viscosity of less than 10 mPas with a solids content of 10% by weight.
- the stated viscosity is determined using a Höppler viscometer at a temperature of 20 ° C.
- the viscosity is preferably from 1.8 to 2.2 mPas with a solids content of 10% by weight.
- the viscosity of the silica sol depends in particular on the silicon dioxide content, the particle size of the silicon dioxide particles, the degree of crosslinking of the particles and the content of electrolytes.
- the silica sol according to the invention has a molar SiO 2 / N ratio of 2 to 20, preferably 4 to 12. The SiO 2 / N ratio is determined using a conventional elementary analysis.
- the zeta potential is an important and useful indicator of the surface charge, which can be used to predict and control the stability of a colloidal suspension or emulsion ("Zeta Potential A New Approach" by BB Weiner, WW Tscharnuter and D. Fairhurst, company publication Brookhaven Instruments The greater the zeta potential, the greater the zeta potential
- the zeta potential can thus be used to control the stability of a colloidal suspension.
- Colloidal suspensions with good stability have a zeta potential between -30 and -60 mV.
- Colloidal suspensions with very good to extreme stabilities have zeta potentials from -60 to -100 mV.
- the sol is unstable at zeta potentials below - 15 mV.
- the silica sol according to the invention has a
- Zeta potential from -20 to -80 mV, preferably from -30 to -60 mV.
- the Zeta potential was determined using a Brookhaven ZetaPALS.
- the silica sol according to the invention therefore has a band position of the Si-O stretching vibration at a wave number of 1113 cm “1 to 1080 cm “ 1 , preferably from 1113 cm “1 to 1100 cm “ 1 , particularly preferably from 1112 cm “1 up to 1104 cm “1 .
- the silica sol according to the invention has due to the guanidinium ion content, an NH
- Deformational vibration band (5 N - H ) at a wave number in the range from 1750 to 1640 cm "1.
- the LR spectra are measured with a Fourier transform infrared spectrometer Digilab FTS 4000. Sufficiently precise band positions and band shapes are among the following
- spectral resolution 1 cm "1
- apodization box car
- zerofilling factor at least 2
- number of scans 32.
- the measurements are carried out six times, preferably a relative standard deviation of less than 0 , 1% should be reached.
- the samples are prepared as KBr pellets. It should be noted that the spectra do not have an increasing baseline (Christianian effect due to scattering on small particles) but highest extinctions in the range of 0.7 and 1.3 A.
- the wavenumber is based on the maximum of the band concerned (absorption maximum).
- the IR band position of the silica sols according to the invention differs from silica sols not according to the invention on the one hand by the
- Silica sols are generally unstable to electrolyte addition, such as. B. Addition of sodium chloride, ammonium chloride and potassium fluoride. The silica sols according to the invention therefore preferably do not contain any electrolyte additive.
- silica sols according to the invention are suitable for a number of applications.
- the silica sols according to the invention can be used particularly advantageously in paper retention.
- the silica sols are usually in one
- Cationic polymers which can be used are all polymers which are usually used in paper production as retention and / or wet strength agents. Both natural polymers, for example based on carbohydrates, and artificial polymers are suitable. Examples include cationic starch and cationic starch
- Polyacrylamides Polyethyleneimines, polyamidoamines and poly (diallyldimethylammonium chloride) called.
- Preferred cationic polymers are cationic starch and cationic polyacrylamides.
- Papermaking used can vary widely and depend, among other things, on the type of paper stock, the presence of fillers and other conditions.
- the amount of silica sol used should generally be at least 0.01 kg
- Silica sol calculated as SiO, per ton of dry fibers and fillers if necessary.
- 0.1 to 2 kg of silica sol, calculated as SiO 2 are used per ton of dry fibers and optionally fillers.
- silica sol and the cationic polymer in papermaking is carried out according to the usual procedure and is described, for example, in US Pat. No. 5,643,414.
- An apparatus which consists of three glass overflow reactors arranged one behind the other and connected to one another.
- each reaction vessel is mixed with a propeller stirrer.
- the reactor contents are heated indirectly with steam.
- heating coils through which steam flows are attached inside the reaction vessels.
- the vapors are passed over a water cooler, condensed and then the volume of the condensate measured.
- an aqueous solution of fresh acidic sol prepared in accordance with US Pat. No. 2,244,325 was added using an addition device.
- the addition device was selected so that the addition could also take place in individual, selected reactors. That was also via a dosing device
- the alkaline guanidine carbonate solution was not cooled, it was used at ambient temperature. Guanidine carbonate from Agrolinz was used.
- a steady state was set in the three reaction vessels with an average residence time of 14 min in the 1st reaction vessel, 16 min in the 2nd reaction vessel and 20 min in the 3rd reaction vessel.
- 3200 ml of fresh sol with 5.6% by weight SiO 2 per hour were added to the first reaction vessel and 260 ml of alkaline guanidine carbonate solution per hour were also added to the first reaction vessel and 1160 ml of water were evaporated in the following reaction vessels.
- the alkaline guanidine carbonate solution contained 47.7 g guanidine carbonate and 9.3 g aqueous NaOH solution (45% by weight) in 945 ml water.
- a finely divided, partially structured silica sol was obtained which had a density of
- the alkaline guanidine carbonate solution contained 45.7 g guanidine carbonate and 8.4 g KOH in 945 ml water.
- the reaction was carried out in the apparatus described in Example 1.
- a steady state was set with an average residence time of 14 min in the 1st reaction vessel, 16 min in the 2nd reaction vessel and 20 min in the 3rd reaction vessel.
- 1600 ml of fresh sol with 5.6% by weight of SiO 2 per hour and 128 ml of aqueous guanidine carbonate solution per hour were added to the first reaction vessel and 1160 ml of water were evaporated in the following reaction vessels.
- the aqueous guanidine carbonate solution contained 50 g guanidine carbonate per 950 g water.
- a finely divided, partially structured silica sol was obtained which had a density of 1.031 g / ml, a pH of 8.46 and a BET surface area of 558 m 2 / g.
- the silica sol obtained had an SiO 2 content of 5.7% by weight, a BET surface area of 541 m 2 / g and a pH of 8.7.
- This example shows that the silica sol according to the invention can be produced in a batch process.
- the silica sol not according to the invention was produced as follows:
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- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10230982A DE10230982A1 (de) | 2002-07-10 | 2002-07-10 | Guanidincarbonat-haltiges Kieselsol |
DE10230982 | 2002-07-10 | ||
PCT/EP2003/007235 WO2004007367A1 (de) | 2002-07-10 | 2003-07-07 | Guanidincarbonat-haltiges kieselsol |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1521720A1 true EP1521720A1 (de) | 2005-04-13 |
Family
ID=29761807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03763721A Withdrawn EP1521720A1 (de) | 2002-07-10 | 2003-07-07 | Guanidincarbonat-haltiges kieselsol |
Country Status (15)
Country | Link |
---|---|
US (2) | US8299131B2 (de) |
EP (1) | EP1521720A1 (de) |
JP (1) | JP4471838B2 (de) |
KR (1) | KR101005418B1 (de) |
CN (1) | CN100358804C (de) |
AU (1) | AU2003250894A1 (de) |
BR (1) | BR0305433A (de) |
CA (1) | CA2492094C (de) |
DE (1) | DE10230982A1 (de) |
HK (1) | HK1084092A1 (de) |
NO (1) | NO20050500L (de) |
PL (1) | PL202798B1 (de) |
RU (1) | RU2343113C2 (de) |
TW (1) | TWI323722B (de) |
WO (1) | WO2004007367A1 (de) |
Families Citing this family (4)
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CN104785276B (zh) * | 2015-03-16 | 2017-05-17 | 中科合成油技术有限公司 | 一种以复合溶胶为硅源制备的费托合成催化剂及其制备方法与应用 |
PL423320A1 (pl) * | 2017-10-31 | 2019-05-06 | Politechnika Slaska Im Wincent | Sposób otrzymywania porowatych monolitów zol-żelowych o zwiększonych wymiarach geometrycznych przy zachowaniu hierarchicznej struktury porów |
IL296730A (en) * | 2020-04-06 | 2022-11-01 | Aspen Aerogels Inc | Improved airgel compositions and methods |
EP3988595A1 (de) | 2020-10-26 | 2022-04-27 | Covestro Deutschland AG | Einsatz von frischsol in formulierungen auf basis von polyurethandispersionen |
Family Cites Families (22)
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US2224325A (en) * | 1939-09-25 | 1940-12-10 | Charles E Wagner | Steam generator |
US3012973A (en) * | 1959-03-18 | 1961-12-12 | Du Pont | Concentrated silica aquasols of low viscosity and their preparation |
US3468813A (en) * | 1965-09-13 | 1969-09-23 | Nalco Chemical Co | Method of producing acid silica sols |
US3475375A (en) * | 1967-06-23 | 1969-10-28 | Du Pont | Novel amorphous guanidine silicates,and compositions thereof with synthetic resins |
US3597248A (en) * | 1967-06-23 | 1971-08-03 | Du Pont | Novel guanidine silicates,compositions and uses |
US3630954A (en) * | 1969-05-08 | 1971-12-28 | Du Pont | Organic amine-strong base stabilized high surface area silica sols and method for preparing same |
US3655578A (en) * | 1969-05-08 | 1972-04-11 | Du Pont | High surface area stabilized silica sols and process for preparing same |
US3894572A (en) * | 1971-06-01 | 1975-07-15 | Du Pont | Process for forming a refractory laminate based on positive sols and refractory materials containing chemical setting agents |
JPS58110417A (ja) | 1981-12-18 | 1983-07-01 | Asahi Denka Kogyo Kk | シリカゾルの製造法 |
US5221497A (en) * | 1988-03-16 | 1993-06-22 | Nissan Chemical Industries, Ltd. | Elongated-shaped silica sol and method for preparing the same |
SE500387C2 (sv) * | 1989-11-09 | 1994-06-13 | Eka Nobel Ab | Silikasoler, förfarande för framställning av silikasoler samt användning av solerna i pappersframställning |
ES2066158T3 (es) | 1990-07-02 | 1995-03-01 | Nalco Chemical Co | Preparacion de soles de silice. |
JP2843655B2 (ja) | 1990-07-09 | 1999-01-06 | イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー | コロイダルシリカの製造方法 |
US5192351A (en) * | 1991-12-17 | 1993-03-09 | Alfred University | Production of dehydroxylated glass |
DE4218306C2 (de) * | 1992-06-03 | 1995-06-22 | Bayer Ag | Verfahren zur kontinuierlichen Herstellung großpartikulärer Kieselsole |
SE501214C2 (sv) | 1992-08-31 | 1994-12-12 | Eka Nobel Ab | Silikasol samt förfarande för framställning av papper under användande av solen |
RU2072195C1 (ru) | 1994-12-09 | 1997-01-20 | Фирма "Арантур" | Бумажная масса для изготовления бумаги-основы облицовочных материалов |
JPH1036843A (ja) | 1996-07-24 | 1998-02-10 | Mitsui Petrochem Ind Ltd | 低温下での溶液安定性に優れる土質注入改良剤 |
ATE366844T1 (de) * | 1997-09-30 | 2007-08-15 | Nalco Chemical Co | Herstellung von papier mit kolloidalen borosilikaten |
CZ299031B6 (cs) | 1999-12-20 | 2008-04-09 | Akzo Nobel N.V. | Vodný sol na bázi oxidu kremicitého, zpusob jeho výroby a použití a zpusob výroby papíru |
JP2002145609A (ja) | 2000-11-02 | 2002-05-22 | Oji Paper Co Ltd | シリカ微粒子分散液の製造方法 |
DE10164262A1 (de) | 2001-12-27 | 2003-07-17 | Bayer Ag | Zusammensetzung für das chemisch-mechanische Polieren von Metall- und Metall/Dielektrikastrukturen |
-
2002
- 2002-07-10 DE DE10230982A patent/DE10230982A1/de not_active Withdrawn
-
2003
- 2003-07-07 BR BR0305433-0A patent/BR0305433A/pt not_active Application Discontinuation
- 2003-07-07 EP EP03763721A patent/EP1521720A1/de not_active Withdrawn
- 2003-07-07 US US10/520,574 patent/US8299131B2/en not_active Expired - Fee Related
- 2003-07-07 CN CNB038215225A patent/CN100358804C/zh not_active Expired - Fee Related
- 2003-07-07 CA CA2492094A patent/CA2492094C/en not_active Expired - Fee Related
- 2003-07-07 JP JP2004520498A patent/JP4471838B2/ja not_active Expired - Fee Related
- 2003-07-07 PL PL373105A patent/PL202798B1/pl not_active IP Right Cessation
- 2003-07-07 RU RU2005103599/15A patent/RU2343113C2/ru not_active IP Right Cessation
- 2003-07-07 WO PCT/EP2003/007235 patent/WO2004007367A1/de active Application Filing
- 2003-07-07 KR KR1020057000297A patent/KR101005418B1/ko not_active IP Right Cessation
- 2003-07-07 AU AU2003250894A patent/AU2003250894A1/en not_active Abandoned
- 2003-07-09 TW TW092118660A patent/TWI323722B/zh not_active IP Right Cessation
-
2005
- 2005-01-28 NO NO20050500A patent/NO20050500L/no not_active Application Discontinuation
-
2006
- 2006-04-10 HK HK06104318A patent/HK1084092A1/xx not_active IP Right Cessation
-
2012
- 2012-09-14 US US13/617,807 patent/US20130068139A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2004007367A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2005532249A (ja) | 2005-10-27 |
DE10230982A1 (de) | 2004-01-22 |
US20060013754A1 (en) | 2006-01-19 |
US8299131B2 (en) | 2012-10-30 |
WO2004007367A1 (de) | 2004-01-22 |
KR20050025598A (ko) | 2005-03-14 |
RU2343113C2 (ru) | 2009-01-10 |
CA2492094C (en) | 2011-12-20 |
RU2005103599A (ru) | 2005-08-27 |
TWI323722B (en) | 2010-04-21 |
PL373105A1 (en) | 2005-08-08 |
CA2492094A1 (en) | 2004-01-22 |
CN1681738A (zh) | 2005-10-12 |
AU2003250894A1 (en) | 2004-02-02 |
KR101005418B1 (ko) | 2010-12-30 |
US20130068139A1 (en) | 2013-03-21 |
JP4471838B2 (ja) | 2010-06-02 |
CN100358804C (zh) | 2008-01-02 |
NO20050500L (no) | 2005-01-28 |
BR0305433A (pt) | 2004-09-28 |
PL202798B1 (pl) | 2009-07-31 |
TW200413252A (en) | 2004-08-01 |
HK1084092A1 (en) | 2006-07-21 |
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