WO2004007367A1 - Guanidincarbonat-haltiges kieselsol - Google Patents
Guanidincarbonat-haltiges kieselsol Download PDFInfo
- Publication number
- WO2004007367A1 WO2004007367A1 PCT/EP2003/007235 EP0307235W WO2004007367A1 WO 2004007367 A1 WO2004007367 A1 WO 2004007367A1 EP 0307235 W EP0307235 W EP 0307235W WO 2004007367 A1 WO2004007367 A1 WO 2004007367A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica sol
- sol
- reaction
- guanidine carbonate
- fresh
- Prior art date
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- 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 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 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.
- 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 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 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.
- 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.
- 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 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 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 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 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 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.
- 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
- 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.
- the amount of silica sol used should generally be at least 0.01 kg
- 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 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.
- This example shows that the silica sol according to the invention can be produced in a batch process.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Compounds (AREA)
- Paper (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2492094A CA2492094C (en) | 2002-07-10 | 2003-07-07 | Guanidine carbonate-containing silica sol |
EP03763721A EP1521720A1 (de) | 2002-07-10 | 2003-07-07 | Guanidincarbonat-haltiges kieselsol |
JP2004520498A JP4471838B2 (ja) | 2002-07-10 | 2003-07-07 | 炭酸グアニジン含有シリカゾル |
AU2003250894A AU2003250894A1 (en) | 2002-07-10 | 2003-07-07 | Silica gel comprising guanidine carbonate |
BR0305433-0A BR0305433A (pt) | 2002-07-10 | 2003-07-07 | Sol de sìlica contendo carbonato de guanidina |
US10/520,574 US8299131B2 (en) | 2002-07-10 | 2003-07-07 | Silica gel comprising guanidine carbonate |
NO20050500A NO20050500L (no) | 2002-07-10 | 2005-01-28 | Guanidinkarbonatholdig kiselsol |
HK06104318A HK1084092A1 (en) | 2002-07-10 | 2006-04-10 | Silica gel comprising guanidine carbonate |
US13/617,807 US20130068139A1 (en) | 2002-07-10 | 2012-09-14 | Silica gel comprising guanidine carbonate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10230982A DE10230982A1 (de) | 2002-07-10 | 2002-07-10 | Guanidincarbonat-haltiges Kieselsol |
DE10230982.5 | 2002-07-10 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/617,807 Continuation US20130068139A1 (en) | 2002-07-10 | 2012-09-14 | Silica gel comprising guanidine carbonate |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004007367A1 true WO2004007367A1 (de) | 2004-01-22 |
Family
ID=29761807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/007235 WO2004007367A1 (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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3988595A1 (de) | 2020-10-26 | 2022-04-27 | Covestro Deutschland AG | Einsatz von frischsol in formulierungen auf basis von polyurethandispersionen |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US11912579B2 (en) * | 2020-04-06 | 2024-02-27 | Aspen Aerogels, Inc. | Aerogel compositions and methods |
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US3012973A (en) * | 1959-03-18 | 1961-12-12 | Du Pont | Concentrated silica aquasols of low viscosity and their preparation |
GB1202303A (en) * | 1967-06-23 | 1970-08-12 | Du Pont | Improvements relating to silicates |
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 |
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US2224325A (en) | 1939-09-25 | 1940-12-10 | Charles E Wagner | Steam generator |
US3468813A (en) | 1965-09-13 | 1969-09-23 | Nalco Chemical Co | Method of producing acid silica sols |
US3597248A (en) * | 1967-06-23 | 1971-08-03 | Du Pont | Novel guanidine silicates,compositions and uses |
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 |
EP0464289B1 (de) | 1990-07-02 | 1994-11-09 | Nalco Chemical Company | Herstellung von Kieselsäuresolen |
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 |
WO1999016708A1 (en) * | 1997-09-30 | 1999-04-08 | Nalco Chemical Company | Colloidal borosilicates and their use in the production of paper |
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 CA CA2492094A patent/CA2492094C/en not_active Expired - Fee Related
- 2003-07-07 KR KR1020057000297A patent/KR101005418B1/ko not_active IP Right Cessation
- 2003-07-07 JP JP2004520498A patent/JP4471838B2/ja not_active Expired - Fee Related
- 2003-07-07 US US10/520,574 patent/US8299131B2/en not_active Expired - Fee Related
- 2003-07-07 EP EP03763721A patent/EP1521720A1/de not_active Withdrawn
- 2003-07-07 AU AU2003250894A patent/AU2003250894A1/en not_active Abandoned
- 2003-07-07 PL PL373105A patent/PL202798B1/pl not_active IP Right Cessation
- 2003-07-07 CN CNB038215225A patent/CN100358804C/zh not_active Expired - Fee Related
- 2003-07-07 BR BR0305433-0A patent/BR0305433A/pt not_active Application Discontinuation
- 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
- 2003-07-09 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
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US3012973A (en) * | 1959-03-18 | 1961-12-12 | Du Pont | Concentrated silica aquasols of low viscosity and their preparation |
GB1202303A (en) * | 1967-06-23 | 1970-08-12 | Du Pont | Improvements relating to silicates |
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 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3988595A1 (de) | 2020-10-26 | 2022-04-27 | Covestro Deutschland AG | Einsatz von frischsol in formulierungen auf basis von polyurethandispersionen |
WO2022090066A1 (de) | 2020-10-26 | 2022-05-05 | Covestro Deutschland Ag | Einsatz von frischsol in formulierungen auf basis von polyurethandispersionen |
Also Published As
Publication number | Publication date |
---|---|
DE10230982A1 (de) | 2004-01-22 |
KR101005418B1 (ko) | 2010-12-30 |
CA2492094C (en) | 2011-12-20 |
US8299131B2 (en) | 2012-10-30 |
JP2005532249A (ja) | 2005-10-27 |
CN1681738A (zh) | 2005-10-12 |
JP4471838B2 (ja) | 2010-06-02 |
HK1084092A1 (en) | 2006-07-21 |
US20130068139A1 (en) | 2013-03-21 |
BR0305433A (pt) | 2004-09-28 |
TWI323722B (en) | 2010-04-21 |
PL373105A1 (en) | 2005-08-08 |
TW200413252A (en) | 2004-08-01 |
AU2003250894A1 (en) | 2004-02-02 |
PL202798B1 (pl) | 2009-07-31 |
EP1521720A1 (de) | 2005-04-13 |
RU2005103599A (ru) | 2005-08-27 |
KR20050025598A (ko) | 2005-03-14 |
RU2343113C2 (ru) | 2009-01-10 |
NO20050500L (no) | 2005-01-28 |
US20060013754A1 (en) | 2006-01-19 |
CA2492094A1 (en) | 2004-01-22 |
CN100358804C (zh) | 2008-01-02 |
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