WO2010100329A1 - Silicon compound, method for forming same, and use of same - Google Patents

Silicon compound, method for forming same, and use of same Download PDF

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Publication number
WO2010100329A1
WO2010100329A1 PCT/FI2010/050147 FI2010050147W WO2010100329A1 WO 2010100329 A1 WO2010100329 A1 WO 2010100329A1 FI 2010050147 W FI2010050147 W FI 2010050147W WO 2010100329 A1 WO2010100329 A1 WO 2010100329A1
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Prior art keywords
silicon
oxygen compound
compound
group
starting material
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PCT/FI2010/050147
Other languages
French (fr)
Inventor
Ali Harlin
Karita Kinnunen
Original Assignee
Oy Keskuslaboratorio - Centrallaboratorium Ab
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Publication of WO2010100329A1 publication Critical patent/WO2010100329A1/en

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    • 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
    • C01B33/126—Preparation of silica of undetermined type
    • C01B33/128—Preparation of silica of undetermined type by acidic treatment of aqueous silicate solutions
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • 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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—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
    • 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
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention relates to the method for forming a silicon-oxygen compound as defined in the preamble of claim 1, to the silicon-oxygen compound as defined in the preamble of claim 17, and to the use of the silicon-oxygen compound as defined in the preamble of claim 18.
  • silicate-based products by ion exchange technique.
  • salt that has been formed is removed.
  • silicate- based products may be manufactured by a more complicated and expensive process in which salt is not formed in connection with the manufacture of the product.
  • Salt in connection with silicate particles is problematic because it accelerates agglomeration of the particles during transportation and in storage. Agglomeration of silicate products during storage can be reduced by additives, which increases the costs. Removal of salt complicates the process and increases the process costs.
  • the objective of the invention is to eliminate the drawbacks referred to above.
  • a further objective of the invention is to disclose a new method for manufacturing a silicon- oxygen compound.
  • the invention is based on a method for forming a silicon-oxygen compound.
  • the silicon-oxygen compound is manufactured from silicon-based starting material so that reactivity of the silicon-based starting material in the reaction mixture is raised by a treatment selected from the group of heat treatment, dissolution, addition of water, mixing, acid treatment and their combinations, and acid compound selected from the group of acids, acid gases and their combinations is added to the formed reaction mixture to precipitate the silicon- oxygen compound.
  • an average particle size of the starting material of less than 37 ⁇ m, preferably 5 to 37 ⁇ m, is provided e.g. by grinding.
  • the silicon-based starting material is selected from the group of silicates, silanes, oxysilanes, silicones, silox- anes, silicate minerals and other suitable silicon compounds and their derivatives and their mixtures.
  • the silicon-based starting material is selected from the group of sodium, magnesium and cal- cium silicate compounds, e.g. the corresponding minerals such as olivite, serpentinite and wollastonite.
  • the starting material may contain additives such as surface-active agents.
  • the silicon-based starting material may be in the form of a solution, suspension or dispersion which may be formed in water or suitable solvent.
  • the formed silicon-oxygen compound is in the solid, solution, suspension or dispersion form.
  • the silicon-based starting material is dissolved in water or other suit- able solvent in the manufacture of the silicon-oxygen compound in connection with raising the reactivity of the silicon-based starting material.
  • the silicon-oxygen compound is selected from the group of sili- cates, siloxanes, silicic acids and equivalent silicon- oxygen compounds and their derivatives and their mixtures .
  • the silicon-oxygen compound is silicon oxide or its derivative.
  • the silicon oxide is silicon dioxide, SiO2, or its derivative.
  • the silicon oxide compound is formed from a compound or compounds containing silicon and oxygen.
  • SiO2 produced in the reaction forms, as it pre- cipitates, nanoparticles, the surface properties of which are changeable.
  • the silicon-oxygen compound may contain different additives and fillers.
  • the sili- con-oxygen compound is manufactured substantially in one step.
  • the silicon-oxygen compound is manufactured substantially in at least two steps, so that reactivity of the silicon-based starting material is raised in the first step.
  • nanoparticles of the silicon-oxygen compound are formed by precipitating the si- licon-based starting material with an acid compound.
  • the silicon-oxygen compound consists mainly of nanopar- ticles .
  • the acid compound is se- lected from the group of: different acids such as sulfuric acid, and acid gases such as carbon dioxide, or their derivatives. In one embodiment, the acid compound is carbon dioxide.
  • the following chemical re- actions take place in the precipitation in using gaseous carbon dioxide.
  • manufacture of the silicon-oxygen compound and preferably also properties of the product that is being formed are adjusted by the reaction conditions selected from the group of temperature, pressure, mixing and their combinations .
  • the sili- con-oxygen compound is formed by precipitation at a temperature of 140 to 185°C. In one embodiment, the silicon-oxygen compound may be formed at temperatures of below 350 0 C.
  • the sili- con-oxygen compound is formed by precipitation at a pressure of 10 to 40 bars. In one embodiment, the sili- con-oxygen compound may be formed at a pressure of less than 200 bars.
  • the acid compound is fed gradually in the formation of the silicon-oxygen compound. In one embodiment, substantially slow feed of the acid compound is used.
  • high mixing intensity is used in connection with the formation of the silicon- oxygen compound.
  • a mixture containing sili- con and oxygen is stirred with high intensity to control agglomeration in connection with the manufacture of the silicon-oxygen compound.
  • short dwell time in used in the reaction of forming the silicon-oxygen com- pound is not limited.
  • acidity of the reaction environment is adjusted so that the pH is between 7.5 and 8.2, preferably between 7.7 and 8.0, to control the formation of the silicon-oxygen com- pound.
  • Acidity can be adjusted by adding sodium bicarbonate, sodium nitrate and/or potassium nitrate to the reaction mixture.
  • the silicon-oxygen compound is precipitated from buffered solution formed by gradu- ally dissolving the silicon-based starting material in water and adjusting acidity of the solution.
  • the following chemical reactions take place in the precipitation when sodium bicarbonate is added to the reaction mixture of water and magnesium silicate such as olivine. Acidity of the reaction mixture is buffered to the level of pH 7.7 to 8.0, in which case the reaction mechanism changes and it is possible to shorten the reaction time.
  • the basic residue of the added salt tends to form a complex with metals dissolved from silicate.
  • the effect may be utilized in controlling the sedimentation.
  • rate of the reaction may be raised by treating the silicate mineral with acids, in which case dissolution is no longer a limiting step in the reaction.
  • Acid oxides such as free sulfur dioxide of combustion gases may be used as the acid.
  • surface properties of the silicon-oxygen compound particles may be modified.
  • surface of the silicon-oxygen compound particles is treated e.g. by absorbing suitable ions on the surface of the particles to modify the properties.
  • the silicon-oxygen compound product is formed in more than one reactor.
  • Al- ternatively, the silicon-oxygen compound product is formed in one reactor.
  • the product is formed in sequential reactors connected in series.
  • the product is formed in a multicompartment reactor in which individual sequential steps are integrated inside one case. Any reactor suitable for the purpose of use, e.g. a batch stirred reactor, precipitation reactor or the like, may be used as the reactor.
  • a combined stirred and spray reactor in which the starting mate- rials are mixed and the formed product is sprayed into the application, e.g. a carrier material, is used as the reactor.
  • dispersing means are included in the reactor or substantially in connection with it to disintegrate, i.e. disperse, aggregates which are possibly formed.
  • Different grinding devices, mills, e.g. a bead mill, or the like may be used as the dispersing means.
  • means to prevent or reduce agglomeration are included in the reactor or substantially in connection with it.
  • the produced nanoparticles may be kept in the reactor in which the particle size distribution is kept predetermined by high shear forces, ultrasound or the like until the product is used.
  • the invention relates to a silicon-oxygen compound formed by any of the above- described manners.
  • the produced silicon-oxygen compound is provided on the surface of a carrier mate- rial, e.g. the carrier material is coated with the silicon-oxygen compound, or as a filler or additive in the carrier material.
  • Properties or surface properties of the carrier material can preferably be modified by the silicon-oxygen compound that is being formed and by its composition.
  • the carrier material is selected from the group of a web, fibrous carrier material, platy base, rubber, paint and their combinations .
  • a web any fi- ber-based paper, board or fibrous web or an equivalent web or a sheet cut from a web or the like.
  • the web may be formed from chemical pulp, mechanical pulp, chemi- mechanical pulp, recycled pulp or other pulp. Any suitable fibers, e.g. softwood fibers, hardwood fi- bers, cotton fibers or equivalent fibers may be used as fibers in the manufacture of the web.
  • the silicon-oxygen compound is formed substantially close to the surface of the carrier material or on the surface of the carrier mate- rial. In one embodiment, the silicon-oxygen compound is formed substantially in connection with the manufacture of the carrier material. In one embodiment, the silicon-oxygen compound is formed in its own separate process.
  • the formed silicon-oxygen com- pound is used, i.e. provided in connection with the carrier material, substantially within short time from the formation of the silicon-oxygen compound and thus before agglomeration takes place to a harmful extent, preferably during less than 24 hours, more preferably less than 4 hours and most preferably less than 1 hour.
  • any possibly formed salt need not be separated from the product before use of the product .
  • the invention provides a new method for adjusting the properties of a carrier material, such as paper, by nanoscale silicon compound particles.
  • the method according to the invention is suited for use directly in connection with the manufacture of the carrier material, such as paper.
  • the reaction of forming the silicon compound particles and properties of the particles that are being formed can be easily controlled by the reaction conditions.
  • Properties of the particles may be modified according to the purpose of use depending on the kinds of properties that are selected.
  • colloidal silicate products which are manufactured by complicated ion exchange process may be replaced in papermaking with the product manufactured by the method according to the invention. These products may be used in papermaking at the wet end e.g. as retention and drainage aids, and in the fin- ishing of paper as spraying applications to add fric- tion to paper and ameliorate printing properties of paper.
  • Tailored silicon compound nanoparticles may be produced by the method according to the invention from inexpensive starting materials.
  • the method enables flexible finishing of paper and control of the proper- ties of paper. Finishing of paper by the silicon compound nanoparticles enables total or partial replacement of internal sizes (AKD, ASA) used at the wet end, which has an effect on the runnability and production efficiency of the paper machine.
  • the tailored silicon compound nanoparticles enable development of new paper and fiber products.
  • unit operations related to desalination are not needed in connection with the method according to the invention. Furthermore, thanks to the method according to the invention, costs related to treatment of spent solutions and spent ion- exchange resin may be reduced.
  • the method according to the invention is suited for use in connection with the manufacture of paper and fibrous webs and the manufacture of e.g. rubber, varnishes and paints.
  • Example 1 Activated magnesium silicate was manufactured from olivite, ground to a particle size of 37 ⁇ m, in contact with sulfur dioxide and sulfurous acid. Next, the activated magnesium silicate was suspended in wa- ter which was buffered by sodium bicarbonate to a pH value of 7.7.
  • the particles were formed by precipitation with carbon dioxide according to reaction equations (1) and (2) presented below.
  • the formed particles were provided on the surface of paper.
  • the tests to form the silicon compound were carried out by an apparatus comprising a 3dm 3 pressure reactor provided with stirring. lOOg of ground olivite damped with sulfurous acid was added to the reactor and dried for 6 hours at a temperature of 85°C, stirring the bed slowly at the same time with a stirrer at 2 to 5rpm. After this, the treated magnesium silicate was suspended in sodium bicarbonate containing water. Carbon dioxide was added to the reactor tank by pressurizing an overpressure of 18 bars in the gas space above the solution which filled the reactor and at 150 0 C. The solution in the reactor was agitated for an hour by an anchor agitator at a rate of lOOrpm so that it remained constantly well mixed. This way, a solution containing silicon dioxide particles of 10 to 60nm was achieved.
  • Nanoscale particles of silicon dioxide were manufactured from olivite in a manner corresponding to that of example 1.
  • the particles were formed by precipitation with carbon dioxide from a solution buff- ered with sodium bicarbonate.
  • the formed particles were provided on the surface of paper by injecting the obtained solution.
  • the method according to the invention to form a silicon-oxygen compound is suited in different applications to be used for the manufacture of most different silicon-oxygen products.

Abstract

The invention relates to a method for forming a silicon-oxygen compound. According to the invention, the silicon-oxygen compound is manufactured from silicon-based starting material so that reactivity of the silicon-based starting material is raised by a treatment selected from the group of heat treatment, dissolution, addition of water, mixing, acid treatment and their combinations, and acid compound selected from the group of acids, acid gases and their combinations is added to precipitate the silicon-oxygen compound. In addition, the invention relates to the corresponding silicon-oxygen compound and to its use.

Description

SILICON COMPOUND, METHOD FOR FORMING SAME, AND USE OF SAME
FIELD OF THE INVENTION The invention relates to the method for forming a silicon-oxygen compound as defined in the preamble of claim 1, to the silicon-oxygen compound as defined in the preamble of claim 17, and to the use of the silicon-oxygen compound as defined in the preamble of claim 18.
BACKGROUND OF THE INVENTION
Known from the prior art are different silicon-based and silicate-based compounds and methods for manufacturing them, e.g. in the field of papermaking. Especially known in the field of papermaking is the use of water glass, kaolin and talc as fillers in paper and in the coating of paper. These materials are added to the paper pulp or spread as a coating on the surface of paper by applicable methods.
Known is the manufacture of silicate-based products by ion exchange technique. In connection with the manufacture of silicate-based products, salt that has been formed is removed. Alternatively, silicate- based products may be manufactured by a more complicated and expensive process in which salt is not formed in connection with the manufacture of the product. Salt in connection with silicate particles is problematic because it accelerates agglomeration of the particles during transportation and in storage. Agglomeration of silicate products during storage can be reduced by additives, which increases the costs. Removal of salt complicates the process and increases the process costs. OBJECTIVE OF THE INVENTION
The objective of the invention is to eliminate the drawbacks referred to above.
A further objective of the invention is to disclose a new method for manufacturing a silicon- oxygen compound.
SUMMARY OF THE INVENTION
The method for manufacturing a silicon-oxygen compound according to the invention is characterized by what has been presented in the claims.
The invention is based on a method for forming a silicon-oxygen compound. According to the invention, the silicon-oxygen compound is manufactured from silicon-based starting material so that reactivity of the silicon-based starting material in the reaction mixture is raised by a treatment selected from the group of heat treatment, dissolution, addition of water, mixing, acid treatment and their combinations, and acid compound selected from the group of acids, acid gases and their combinations is added to the formed reaction mixture to precipitate the silicon- oxygen compound.
In one embodiment of the invention, an average particle size of the starting material of less than 37μm, preferably 5 to 37μm, is provided e.g. by grinding.
In one embodiment of the invention, the silicon-based starting material is selected from the group of silicates, silanes, oxysilanes, silicones, silox- anes, silicate minerals and other suitable silicon compounds and their derivatives and their mixtures. In one embodiment, the silicon-based starting material is selected from the group of sodium, magnesium and cal- cium silicate compounds, e.g. the corresponding minerals such as olivite, serpentinite and wollastonite. The starting material may contain additives such as surface-active agents.
In one embodiment, the silicon-based starting material may be in the form of a solution, suspension or dispersion which may be formed in water or suitable solvent. In one embodiment, the formed silicon-oxygen compound is in the solid, solution, suspension or dispersion form. In one embodiment, the silicon-based starting material is dissolved in water or other suit- able solvent in the manufacture of the silicon-oxygen compound in connection with raising the reactivity of the silicon-based starting material.
In one embodiment of the invention, the silicon-oxygen compound is selected from the group of sili- cates, siloxanes, silicic acids and equivalent silicon- oxygen compounds and their derivatives and their mixtures .
In one embodiment of the invention, the silicon-oxygen compound is silicon oxide or its derivative. In one preferred embodiment, the silicon oxide is silicon dioxide, SiO2, or its derivative. The silicon oxide compound is formed from a compound or compounds containing silicon and oxygen. In one preferred embodiment, SiO2 produced in the reaction forms, as it pre- cipitates, nanoparticles, the surface properties of which are changeable.
The silicon-oxygen compound may contain different additives and fillers.
In one embodiment of the invention, the sili- con-oxygen compound is manufactured substantially in one step. In one embodiment, the silicon-oxygen compound is manufactured substantially in at least two steps, so that reactivity of the silicon-based starting material is raised in the first step. In one embodiment, nanoparticles of the silicon-oxygen compound are formed by precipitating the si- licon-based starting material with an acid compound. The silicon-oxygen compound consists mainly of nanopar- ticles .
In one embodiment, the acid compound is se- lected from the group of: different acids such as sulfuric acid, and acid gases such as carbon dioxide, or their derivatives. In one embodiment, the acid compound is carbon dioxide.
In one embodiment, the following chemical re- actions take place in the precipitation in using gaseous carbon dioxide.
In a one-step process:
Mg/Ca-silicate + CO2 → Mg/Ca -CO3 + SiO2
In a two-step process in which the first step comprises dissolution in water and carbon dioxide forms a mildly acid HCO3 ":
Mg/Ca-silicate + 2H+ -> (Mg/Ca) 2+ + SiO2
(Mg/Ca) 2+ + HCO3 " -> (Mg/Ca) -CO3 + 2H+
In one embodiment of the invention, manufacture of the silicon-oxygen compound and preferably also properties of the product that is being formed are adjusted by the reaction conditions selected from the group of temperature, pressure, mixing and their combinations .
In one embodiment of the invention, the sili- con-oxygen compound is formed by precipitation at a temperature of 140 to 185°C. In one embodiment, the silicon-oxygen compound may be formed at temperatures of below 3500C.
In one embodiment of the invention, the sili- con-oxygen compound is formed by precipitation at a pressure of 10 to 40 bars. In one embodiment, the sili- con-oxygen compound may be formed at a pressure of less than 200 bars.
In one embodiment of the invention, the acid compound is fed gradually in the formation of the silicon-oxygen compound. In one embodiment, substantially slow feed of the acid compound is used.
In one embodiment, high mixing intensity is used in connection with the formation of the silicon- oxygen compound. Preferably, a mixture containing sili- con and oxygen is stirred with high intensity to control agglomeration in connection with the manufacture of the silicon-oxygen compound.
In one embodiment, short dwell time in used in the reaction of forming the silicon-oxygen com- pound.
In one embodiment of the invention, acidity of the reaction environment is adjusted so that the pH is between 7.5 and 8.2, preferably between 7.7 and 8.0, to control the formation of the silicon-oxygen com- pound. Acidity can be adjusted by adding sodium bicarbonate, sodium nitrate and/or potassium nitrate to the reaction mixture.
In one embodiment, the silicon-oxygen compound is precipitated from buffered solution formed by gradu- ally dissolving the silicon-based starting material in water and adjusting acidity of the solution.
In one embodiment, the following chemical reactions take place in the precipitation when sodium bicarbonate is added to the reaction mixture of water and magnesium silicate such as olivine. Acidity of the reaction mixture is buffered to the level of pH 7.7 to 8.0, in which case the reaction mechanism changes and it is possible to shorten the reaction time.
MgSiO4 (solid) + 2HCO3 " (solution) -> 2MgCO3 (solid) + SiO2 (solid) + 2OH" OH" (solution) + CO2 (gas) -> HCO3 (solution)
In one embodiment, the basic residue of the added salt tends to form a complex with metals dissolved from silicate. The effect may be utilized in controlling the sedimentation.
In one embodiment, rate of the reaction may be raised by treating the silicate mineral with acids, in which case dissolution is no longer a limiting step in the reaction. Acid oxides such as free sulfur dioxide of combustion gases may be used as the acid.
In one embodiment, surface properties of the silicon-oxygen compound particles may be modified. In one embodiment, surface of the silicon-oxygen compound particles is treated e.g. by absorbing suitable ions on the surface of the particles to modify the properties.
In one embodiment, the silicon-oxygen compound product is formed in more than one reactor. Al- ternatively, the silicon-oxygen compound product is formed in one reactor. In one embodiment, the product is formed in sequential reactors connected in series. In one embodiment, the product is formed in a multicompartment reactor in which individual sequential steps are integrated inside one case. Any reactor suitable for the purpose of use, e.g. a batch stirred reactor, precipitation reactor or the like, may be used as the reactor. In one embodiment, a combined stirred and spray reactor in which the starting mate- rials are mixed and the formed product is sprayed into the application, e.g. a carrier material, is used as the reactor.
In one embodiment, dispersing means are included in the reactor or substantially in connection with it to disintegrate, i.e. disperse, aggregates which are possibly formed. Different grinding devices, mills, e.g. a bead mill, or the like may be used as the dispersing means. In one embodiment, means to prevent or reduce agglomeration are included in the reactor or substantially in connection with it. In one embodiment, the produced nanoparticles may be kept in the reactor in which the particle size distribution is kept predetermined by high shear forces, ultrasound or the like until the product is used. In addition, the invention relates to a silicon-oxygen compound formed by any of the above- described manners.
Preferably, the produced silicon-oxygen compound is provided on the surface of a carrier mate- rial, e.g. the carrier material is coated with the silicon-oxygen compound, or as a filler or additive in the carrier material. Properties or surface properties of the carrier material can preferably be modified by the silicon-oxygen compound that is being formed and by its composition. In one embodiment, the carrier material is selected from the group of a web, fibrous carrier material, platy base, rubber, paint and their combinations .
In this connection, by a web is meant any fi- ber-based paper, board or fibrous web or an equivalent web or a sheet cut from a web or the like. The web may be formed from chemical pulp, mechanical pulp, chemi- mechanical pulp, recycled pulp or other pulp. Any suitable fibers, e.g. softwood fibers, hardwood fi- bers, cotton fibers or equivalent fibers may be used as fibers in the manufacture of the web.
In one embodiment, the silicon-oxygen compound is formed substantially close to the surface of the carrier material or on the surface of the carrier mate- rial. In one embodiment, the silicon-oxygen compound is formed substantially in connection with the manufacture of the carrier material. In one embodiment, the silicon-oxygen compound is formed in its own separate process.
Preferably, the formed silicon-oxygen com- pound is used, i.e. provided in connection with the carrier material, substantially within short time from the formation of the silicon-oxygen compound and thus before agglomeration takes place to a harmful extent, preferably during less than 24 hours, more preferably less than 4 hours and most preferably less than 1 hour. In this case, any possibly formed salt need not be separated from the product before use of the product .
Important advantages are achieved by the in- vention compared with the prior art.
The invention provides a new method for adjusting the properties of a carrier material, such as paper, by nanoscale silicon compound particles. The method according to the invention is suited for use directly in connection with the manufacture of the carrier material, such as paper.
In the method according to the invention, the reaction of forming the silicon compound particles and properties of the particles that are being formed can be easily controlled by the reaction conditions. Properties of the particles may be modified according to the purpose of use depending on the kinds of properties that are selected.
E.g. colloidal silicate products which are manufactured by complicated ion exchange process may be replaced in papermaking with the product manufactured by the method according to the invention. These products may be used in papermaking at the wet end e.g. as retention and drainage aids, and in the fin- ishing of paper as spraying applications to add fric- tion to paper and ameliorate printing properties of paper.
An industrially applicable easy method of good quality to form a silicon-based compound e.g. in connection with papermaking is achieved by the invention. Tailored silicon compound nanoparticles may be produced by the method according to the invention from inexpensive starting materials. The method enables flexible finishing of paper and control of the proper- ties of paper. Finishing of paper by the silicon compound nanoparticles enables total or partial replacement of internal sizes (AKD, ASA) used at the wet end, which has an effect on the runnability and production efficiency of the paper machine. In addition, the tailored silicon compound nanoparticles enable development of new paper and fiber products.
In addition, unit operations related to desalination are not needed in connection with the method according to the invention. Furthermore, thanks to the method according to the invention, costs related to treatment of spent solutions and spent ion- exchange resin may be reduced.
The method according to the invention is suited for use in connection with the manufacture of paper and fibrous webs and the manufacture of e.g. rubber, varnishes and paints.
DETAILED DESCRIPTION OF THE INVENTION
In the following, the invention will be described according to detailed examples of its embodiments .
Example 1 Activated magnesium silicate was manufactured from olivite, ground to a particle size of 37μm, in contact with sulfur dioxide and sulfurous acid. Next, the activated magnesium silicate was suspended in wa- ter which was buffered by sodium bicarbonate to a pH value of 7.7.
The particles were formed by precipitation with carbon dioxide according to reaction equations (1) and (2) presented below. The formed particles were provided on the surface of paper.
Mg SiO4 (solid) + 2H CO3 " (solution) -> 2Mg CO3 (solid) + SiO2 (solid) + 2OH" (1)
OH" (solution) + CO2 (gas) ->
HCO3 " (solution) (2)
The tests to form the silicon compound were carried out by an apparatus comprising a 3dm3 pressure reactor provided with stirring. lOOg of ground olivite damped with sulfurous acid was added to the reactor and dried for 6 hours at a temperature of 85°C, stirring the bed slowly at the same time with a stirrer at 2 to 5rpm. After this, the treated magnesium silicate was suspended in sodium bicarbonate containing water. Carbon dioxide was added to the reactor tank by pressurizing an overpressure of 18 bars in the gas space above the solution which filled the reactor and at 1500C. The solution in the reactor was agitated for an hour by an anchor agitator at a rate of lOOrpm so that it remained constantly well mixed. This way, a solution containing silicon dioxide particles of 10 to 60nm was achieved.
Example 2 Nanoscale particles of silicon dioxide were manufactured from olivite in a manner corresponding to that of example 1. The particles were formed by precipitation with carbon dioxide from a solution buff- ered with sodium bicarbonate. The formed particles were provided on the surface of paper by injecting the obtained solution.
The method according to the invention to form a silicon-oxygen compound is suited in different applications to be used for the manufacture of most different silicon-oxygen products.
The invention is not limited merely to the examples referred to above; instead, many variations are possible within the scope of the inventive idea defined by the claims.

Claims

1. A method for forming a silicon- oxygen compound, c h a r a c t e r i z e d in that the silicon-oxygen compound is manufactured from silicon- based starting material so that reactivity of the silicon-based starting material is raised by a treatment selected from the group of heat treatment, dissolution, addition of water, mixing, acid treatment and their combinations, and acid compound selected from the group of acids, acid gases and their combinations is added to precipitate the silicon-oxygen compound.
2. The method according to claim 1, c h a r a c t e r i z e d in that an average particle size of the starting material of less than 37μm is pro- vided.
3. The method according to claim 1 or 2, c h a r a c t e r i z e d in that the silicon-based starting material is selected from the group of silicates, silanes, oxysilanes, silicones, siloxanes, silicate minerals, their derivatives and their mixtures .
4. The method according to claim 3, c h a r a c t e r i z e d in that the silicon-based starting material is selected from the group of sodium, magnesium and calcium silicate compounds.
5. The method according to any one of claims 1 to 4, c h a r a c t e r i z e d in that the silicon-oxygen compound is selected from the group of silicon oxides, silicates, siloxanes, silicic acids, their derivatives and their mixtures.
6. The method according to claim 5, c h a r a c t e r i z e d in that the silicon-oxygen compound is silicon oxide or its derivative.
7. The method according to any one of claims 1 to 6, c h a r a c t e r i z e d in that the sili- con-oxygen compound is manufactured substantially in one step.
8. The method according to any one of claims 1 to 7, c h a r a c t e r i z e d in that the sili- con-oxygen compound is manufactured substantially in at least two steps.
9. The method according to any one of claims 1 to 8, c h a r a c t e r i z e d in that the acid compound is carbon dioxide.
10. The method according the any one of claims 1 to 9, c h a r a c t e r i z e d in that manufacture of the silicon-oxygen compound and preferably also properties of the product that is being formed are adjusted by the reaction conditions selected from the group of temperature, pressure, mixing and their combinations .
11. The method according to any one of claims 1 to 10, c h a r a c t e r i z e d in that the silicon-oxygen compound is manufactured by precipita- tion at a temperature of 140 to 185°C.
12. The method according to any one of claims 1 to 11, c h a r a c t e r i z e d in that the silicon-oxygen compound is manufactured by precipitation at a pressure of 10 to 40 bars.
13. The method according to any one of claims 1 to 12, c h a r a c t e r i z e d in that the acid compound is gradually fed in the formation of the silicon-oxygen compound.
14. The method according to any one of claims 1 to 13, c h a r a c t e r i z e d in that high mixing intensity is used in connection with the formation of the silicon-oxygen compound.
15. The method according to any one of claims 1 to 14, c h a r a c t e r i z e d in that forma- tion of the silicon-oxygen compound is controlled by acidity of the reaction environment by adjusting the pH between 7.5 and 8.2.
16. The method according to any one of claims 1 to 15, c h a r a c t e r i z e d in that nanoparticles of the silicon-oxygen compound are formed.
17. A silicon-oxygen compound, c h a r a c t e r i z e d in that it is formed by the method according to any one of claims 1 to 16.
18. Use of the silicon-oxygen compound according to claim 17, c h a r a c t e r i z e d in that the silicon-oxygen compound is provided in connection with a carrier material selected from the group of a web, fibrous carrier material, platy base, rubber, paint and their combinations.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017222396A1 (en) * 2016-06-24 2017-12-28 The University Of Canterbury Magnesium containing compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2940830A (en) * 1955-08-23 1960-06-14 Columbia Southern Chem Corp Method of preparing silica pigments
US3928540A (en) * 1971-07-26 1975-12-23 Ppg Industries Inc Process for preparing silica pigment
WO2004098740A2 (en) * 2003-05-02 2004-11-18 The Penn State Research Foundation Process for sequestering carbon dioxide and sulfur dioxide
WO2008004888A1 (en) * 2006-07-03 2008-01-10 Norut Teknologi As Production of silica from olivine
WO2008142025A2 (en) * 2007-05-21 2008-11-27 Shell Internationale Research Maatschappij B.V. A process for preparing an activated mineral

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2940830A (en) * 1955-08-23 1960-06-14 Columbia Southern Chem Corp Method of preparing silica pigments
US3928540A (en) * 1971-07-26 1975-12-23 Ppg Industries Inc Process for preparing silica pigment
WO2004098740A2 (en) * 2003-05-02 2004-11-18 The Penn State Research Foundation Process for sequestering carbon dioxide and sulfur dioxide
WO2008004888A1 (en) * 2006-07-03 2008-01-10 Norut Teknologi As Production of silica from olivine
WO2008142025A2 (en) * 2007-05-21 2008-11-27 Shell Internationale Research Maatschappij B.V. A process for preparing an activated mineral

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAROTO-VALER, M.M. ET AL.: "Activation of magnesium rich minerais as carbonation feedstock materials for C02 sequestration.", FUEL PROCESSING TECHNOLOGY, vol. 86, 2005, pages 1627 - 1645 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017222396A1 (en) * 2016-06-24 2017-12-28 The University Of Canterbury Magnesium containing compositions

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