CN103140446A - Magnesium hydroxide microparticles, magnexium oxide microparticles, and method for producing each - Google Patents
Magnesium hydroxide microparticles, magnexium oxide microparticles, and method for producing each Download PDFInfo
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- CN103140446A CN103140446A CN2011800470868A CN201180047086A CN103140446A CN 103140446 A CN103140446 A CN 103140446A CN 2011800470868 A CN2011800470868 A CN 2011800470868A CN 201180047086 A CN201180047086 A CN 201180047086A CN 103140446 A CN103140446 A CN 103140446A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/08—Magnesia by thermal decomposition of magnesium compounds by calcining magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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Abstract
Highly pure magnesium hydroxide microparticles and highly pure magnesium oxide microparticles that are even and have a small particle size are provided. Regarding the magnesium hydroxide microparticles, the BET specific surface area is at least 5 m2/g, the volume-based cumulative 50% particle diameter (D50) resulting from laser diffraction scattering measurement of the particle size distribution is 0.1-0.5 [mu]m, the ratio D90/D10 between the volume-based cumulative 90% particle diameter (D90) and the volume-based cumulative 10% particle diameter (D10) resulting from laser diffraction scattering measurement of the particle size distribution is no greater than 10, and the purity is at least 99.5 mass%. Regarding the magnesium oxide microparticles, the BET specific surface area is at least 5 m2/g, the volume-based cumulative 50% particle diameter (D50) resulting from laser diffraction scattering measurement of the particle size distribution is 0.1-0.5 [mu]m, the ratio D90/D10 between the volume-based cumulative 90% particle diameter (D90) and the volume-based cumulative 10% particle diameter (D10) resulting from laser diffraction scattering measurement of the particle size distribution is no greater than 10, and the purity is at least 99.5 mass%.
Description
Technical field
The present invention relates to particle diameter little and uniform high purity magnesium hydrate fine particle and high purity magnesium oxide fine particle and their manufacture method.
Background technology
Magnesium hydroxide and magnesium oxide are the inorganic materials of using in various fields, as the former purposes, can list additive, resin extender, high functionality material and catalyzer etc., as the latter's purposes, can list refractory materials, additive, resin extender, high functionality material, electro-magnetic steel plate material and catalyzer etc.Comprise these purposes, mostly require magnesium hydroxide and magnesian purity is high, particle diameter is little and for uniform fine particle state.
As the method for making the little and uniform magnesium hydroxide of particle diameter, proposition has by adding alkaloid substance in the aqueous solution that contains magnesium hydroxide, then adding tensio-active agent, prepares the fine grain method of magnesium hydroxide (with reference to patent documentation 1) of 10nm～1000nm.But in concrete example, how the alkali addition just has the problem of sneaking into impurity from autoclave vessel stripping impurity.
In addition, in the method that makes magnesium chloride and alkaloid substance hydro-thermal reaction manufacturing magnesium hydroxide in aqueous medium, also proposing has boric acid, silicic acid or their water-soluble salt of interpolation, can control arbitrarily the method (with reference to patent documentation 2) of the length-to-diameter ratio of resulting magnesium hydroxide.But, in the method, be difficult to control particle diameter, the fine grain problem that can not obtain uniform grading is arranged.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-62214 communique
Patent documentation 2: TOHKEMY 2005-200300 communique
Summary of the invention
The problem that invention will solve
The object of the invention is to address the above problem, provide particle diameter little and uniform high purity magnesium hydrate fine particle and high purity magnesium oxide fine particle and their manufacture method.
For the scheme of dealing with problems
The present invention relates to a kind of magnesium hydroxide fine particle, its purity is more than 99.5 quality %, and the BET specific surface area is 5m
2More than/g, the accumulation 50% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
50) be 0.1～0.5 μ m, the accumulation 10% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
10) with based on the accumulation 90% particle diameter (D of volume
90) ratio D
90/ D
10Be below 10.
In addition, the present invention relates to a kind of magnesium oxide fine particle, its purity is more than 99.5 quality %, and the BET specific surface area is 5m
2More than/g, the accumulation 50% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
50) be 0.1～0.5 μ m, the accumulation 10% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
10) with based on the accumulation 90% particle diameter (D of volume
90) ratio D
90/ D
10Be below 10.
In addition, the present invention relates to the fine grain manufacture method of a kind of magnesium hydroxide, it comprises
Operation (A): prepare magnesium chloride brine;
Operation (B): make the alkali aqueous solution of magnesium chloride brine and 1～18N with transformation efficiency 101～210mol% reaction, obtain magnesium hydroxide slurry;
Operation (C): the limit is stirred the magnesium hydroxide slurry limit and is kept with the temperature of 101～200 ℃, obtain hydrothermal treatment consists magnesium hydroxide slurry; And
Operation (D): with hydrothermal treatment consists magnesium hydroxide slurry filter, washing and dry, obtain the magnesium hydroxide fine particle.
In addition, the present invention relates to the fine grain manufacture method of a kind of magnesium oxide, it comprises operation (E): carry out roasting with 500～1500 ℃ with above-mentioned magnesium hydroxide fine particle or with the magnesium hydroxide fine particle that above-mentioned manufacture method obtains in air atmosphere.
The effect of invention
Magnesium hydroxide fine particle of the present invention and magnesium oxide fine particle are high purity, and its particle diameter is little and even, and operability is high in various fields.In addition, manufacturing method according to the invention can easily prepare fine particle as described above, and convenience is high.
Embodiment
About magnesium hydroxide fine particle of the present invention, its BET specific surface area is 5m
2More than/g, the accumulation 50% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
50) be 0.1～0.5 μ m, the accumulation 10% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
10) with based on the accumulation 90% particle diameter (D of volume
90) ratio D
90/ D
10Be below 10.This magnesium hydroxide fine particle is little due to particle shape, reactive excellent, is applicable to additive, resin extender and catalyzer etc.; In addition, little due to particle shape, the granularity deviation is few, excellent dispersion, also is suitable for high functionality material etc.The fine grain BET specific surface area of magnesium hydroxide of the present invention is preferably 10m
2More than/g, D
50Be preferably 0.2～0.5 μ m, D
90/ D
10Be preferably below 5.
The fine grain purity of magnesium hydroxide of the present invention is more than 99.5 quality %.As long as in this scope, just the extremely stripping of inhibition of impurities, be suitable for the high functionality material.More than the fine grain purity of magnesium hydroxide of the present invention is preferably 99.9 quality %.
In this manual, purity is the content of the impurity element (Ag, Al, B, Ba, Bi, Cd, Cl, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti and Zr) in the determination object fine particle and deducts with 100 quality % the value that their total content obtains.In this manual, high purity refers to that the purity of calculating as described above is more than 99.5 quality %.
Be to use ICP emmission spectrometric analysis device with sample dissolution quality measurement and value of obtaining after acid as the impurity element (Ag, Al, B, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti and Zr) of determination object, the amount of Cl is to use spectrophotometer with sample dissolution quality measurement and value of obtaining after acid.
The total content of the preferred Fe of magnesium hydroxide fine particle of the present invention, Ti, Ni, Cr, Mo and Mn is below 500 quality ppm.Their total content is 500 quality ppm when following, can extremely suppress the stripping of metallic impurity, is suitable for additive, resin extender, high functionality material.Amount to content more preferably below 450 quality ppm.
The content of the preferred chlorine of magnesium hydroxide fine particle of the present invention is below 500 quality ppm.This content is 500 quality ppm when following, and in the time of can extremely suppressing to obtain the magnesium oxide fine particle by roasting, particle is grown up, and can access small magnesium oxide powder.Content is more preferably below 450 quality ppm.
The median size (Dv) that magnesium hydroxide fine particle of the present invention is preferably based on volume is 1～10 with ratio Dv/Dn based on the median size (Dn) of number.This Dv/Dn is 1～10 o'clock, the black fixation performance when being used for black fixing salt purposes, thermotolerance, flame retardant resistance, flexibility function and catalysis excellence when resin etc. adds, and acid resistance, wet fastness improve.Dv/Dn more preferably 1～8.
About magnesium oxide fine particle of the present invention, its BET specific surface area is 5m
2More than/g, the accumulation 50% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
50) be 0.1～0.5 μ m, the accumulation 10% particle diameter (D based on volume that obtains by laser diffraction and scattering formula particle size distribution
10) with based on the accumulation 90% particle diameter (D of volume
90) ratio D
90/ D
10Be below 10.This magnesium oxide fine particle is little due to particle shape, reactive excellent, is applicable to refractory materials, additive, resin extender, electro-magnetic steel plate material and catalyzer etc.; In addition, little due to particle shape, the granularity deviation is few, excellent dispersion, also is suitable for high functionality material etc.
The fine grain BET specific surface area of magnesium oxide of the present invention is preferably 20m
2More than/g, 40m more preferably
2More than/g, D
50Be preferably 0.2～0.4 μ m, D
90/ D
10Be preferably below 5.
The fine grain purity of magnesium oxide of the present invention is more than 99.5 quality %.As long as in this scope, just the extremely stripping of inhibition of impurities, be suitable for the high functionality material.More than the fine grain purity of magnesium oxide of the present invention is preferably 99.9 quality %.
The total content of the preferred Fe of magnesium oxide fine particle of the present invention, Ti, Ni, Cr, Mo and Mn is below 500 quality ppm.Their total content is 500 quality ppm when following, can extremely suppress the stripping of metallic impurity, is suitable for additive, resin extender, high functionality material.Amount to content more preferably below 450 quality ppm.
The content of the preferred chlorine of magnesium oxide fine particle of the present invention is below 500 quality ppm.This content is 500 quality ppm when following, can extremely suppress the stripping of chlorine, is suitable for additive, resin extender, high functionality material.Content is more preferably below 450 quality ppm.
The median size (Dv) that magnesium oxide fine particle of the present invention is preferably based on volume is 1～10 with ratio Dv/Dn based on the median size (Dn) of number.This Dv/Dn is 1～10 o'clock, black fixation performance when being used for black fixing salt purposes, the thermotolerance when the interpolations such as resin, flame retardant resistance, flexibility function, light diffusion effect and catalytic effect excellence, and acid resistance, wet fastness improve, more preferably 1～8.
Magnesium oxide fine particle optimization citric acid activity degree of the present invention (final transformation efficiency 40%, 20.0 ℃) is 20～2000 seconds.When this citric acid activity degree is 20～2000 seconds, with the reactive excellence of iron, is suitable for electro-magnetic steel plate as the electro-magnetic steel plate material and uses the insulating coating material with insulating material and compressed-core (dust core).The citric acid activity degree is preferably 20～500 seconds.
Magnesium hydroxide fine particle of the present invention obtains by the following method, and the method comprises
Operation (A): prepare magnesium chloride brine;
Operation (B): make the alkali aqueous solution of magnesium chloride brine and 1～18N with transformation efficiency 101～210mol% reaction, obtain magnesium hydroxide slurry;
Operation (C): the limit is stirred the magnesium hydroxide slurry limit and is kept with the temperature of 101～200 ℃, obtain hydrothermal treatment consists magnesium hydroxide slurry; And
Operation (D): with hydrothermal treatment consists magnesium hydroxide slurry filter, washing and dry, obtain the magnesium hydroxide fine particle.
Operation (A) is for preparing the operation of magnesium chloride brine.The magnesium chloride brine preferred concentration is 0.1～10mol/L.Concentration is during less than 0.1mol/L, the production efficiency variation.In addition, concentration is during higher than 10mol/L, and the viscosity of magnesium hydroxide slurry uprises, the treatability variation.The concentration of magnesium chloride brine is preferably 0.5～5mol/L.
Operation (A) can for example comprise
Operation (A-1): prepare thick magnesium chloride brine;
Operation (A-2): make the alkali aqueous solution of thick magnesium chloride brine and 1～18N with transformation efficiency 1～30mol% reaction, obtain thick magnesium hydroxide slurry; And
Operation (A-3): add flocculation agent in thick magnesium hydroxide slurry after, filter magnesium hydroxide, obtain magnesium chloride solution as filtrate; Perhaps add flocculation agent in thick magnesium hydroxide slurry, make the magnesium hydroxide flocculation sediment, obtain magnesium chloride brine as supernatant liquor.
Operation (A-1) is for preparing the operation of thick magnesium chloride solution.For example, by to magnesium chloride (as magnesium chloride, can use magnesium chloride hexahydrate or Magnesium Chloride Anhydrous or seawater, salt solution or bittern) in add pure water (passing through, is the following water of 0.1 μ S/cm thereby be refined to specific conductivity) make thick magnesium chloride brine in ion exchange resin.The concentration of thick magnesium chloride brine can be 0.5～10mol/L, is preferably 1～5mol/L, more preferably 2～4mol/L.
The mode that operation (A-2) is 1～30mol% for the alkali aqueous solution that makes thick magnesium chloride brine and 1～18N according to transformation efficiency is reacted the operation that obtains thick magnesium hydroxide slurry.Transformation efficiency refers to and will make magnesium chloride become all that the required alkali number of magnesium hydroxide is made as 100mol% and the value calculated.For example 200mol% means to count with equivalent the alkali number of 2 times.
As alkali aqueous solution, can use aqueous sodium hydroxide solution, concentration can be 1～18mol/L, is preferably 5～18mol/L, more preferably 10～18mol/L.
Operation (A-3) is after the interpolation flocculation agent, to filter magnesium hydroxide in thick magnesium hydroxide slurry, obtains magnesium chloride solution as filtrate; Perhaps add flocculation agent in thick magnesium hydroxide slurry, make the magnesium hydroxide flocculation sediment, obtain the operation of magnesium chloride brine as supernatant liquor.
As flocculation agent, can suitable choice for use with the flocculation agent as main component such as acrylamide sodium acrylate copolymer, acrylamide acrylamide-2-methyl propane sulfonic acid sodium multipolymer, polyacrylamide, aminomethyl alkyl acrylate QAS polymer, ammonia acrylic acid alkyl ester quat acrylamide copolymer, poly-amidine hydrochloride, preferred acrylamide sodium acrylate copolymer.The addition of flocculation agent can be 100～1000 quality ppm with respect to the dry hydrogen magnesium oxide amount in thick magnesium hydroxide slurry.
Adjust the concentration of the magnesium chloride brine that obtains like this, can be made into the magnesium chloride brine of concentration 0.1～10.0mol/L.
Operation (B) obtains the operation of magnesium hydroxide slurry for the alkali aqueous solution that makes magnesium chloride brine and 1～18N with transformation efficiency 101～210mol% reaction.Transformation efficiency is during less than 101mol%, and crystal is excessively grown up in the hydrothermal treatment consists of magnesium hydroxide slurry, and it is excessive that particle diameter becomes.In addition, transformation efficiency is during higher than 210mol%, and element-specific (Fe, Ti, Ni, Cr, Mo and Mn) is easily sneaked into impurity from the autoclave vessel stripping.Transformation efficiency is preferably 103～200mol%, more preferably 105～180mol%.
The aqueous sodium hydroxide solution of alkali aqueous solution preferred concentration 1～18mol/L.The concentration of aqueous sodium hydroxide solution is during less than 1mol/L, the production efficiency variation.In addition, concentration is during higher than 18mol/L, and the viscosity of magnesium hydroxide slurry uprises, the treatability variation.The concentration of aqueous sodium hydroxide solution is preferably 4～16mol/L.
Operation (C) is that the limit stirs the magnesium hydroxide slurry limit and keep with the temperature of 101～200 ℃, obtain hydrothermal treatment consists the operation of magnesium hydroxide slurry.
Hydrothermal treatment consists can keep carrying out by for example stirring below the magnesium hydroxide slurry limit with autoclave at 101 ℃～200 ℃.The hydrothermal treatment consists temperature is during lower than 101 ℃, and crystal is not grown up, and generates the flocculation particle, disperses variation.In addition, the hydrothermal treatment consists temperature is during higher than 200 ℃, and crystal is excessively grown up, the tendency that exists particle diameter to become excessive.The hydrothermal treatment consists temperature is preferably 105 ℃～150 ℃.The hydrothermal treatment consists time can be 0.5～3 hour.The hydrothermal treatment consists time can be controlled at suitable scope with crystal growth and particle diameter when this scope.The hydrothermal treatment consists time is preferably 1～2 hour.
For obtain having uniform particle diameter, stable fine particle, as required, also can drop into pure water will be 30g/L～150g/L for the concentration adjustment in the magnesium hydroxide slurry of hydrothermal treatment consists.
Operation (D) for hydrothermal treatment consists magnesium hydroxide slurry filtration, washing and drying obtain the fine grain operation of magnesium hydroxide.
Operation (D) can for example comprise
Operation (D-1): with hydrothermal treatment consists magnesium hydroxide slurry filter, washing, obtain the first magnesium hydroxide filter cake;
Operation (D-2): adding in the first magnesium hydroxide filter cake with respect to dry hydrogen magnesium oxide quality datum quantity is that the pure water of 5～100 times stirs, and then filters, washes, and obtains the second magnesium hydroxide filter cake;
Operation (D-3): replace the first magnesium hydroxide filter cake, the second magnesium hydroxide filter cake is repeated 1～20 operation (D-2), obtain the high purity magnesium hydrate filter cake; And
Operation (D-4): dry high purity magnesium hydrate filter cake obtains the magnesium hydroxide fine particle.
Operation (D-1) for by with hydrothermal treatment consists the operation that magnesium hydroxide slurry filters, washing obtains the first magnesium hydroxide filter cake.Washing can by drop into afterwards in filtration with respect to dry hydrogen magnesium oxide with quality criteria count 5～100 times, the pure water that is preferably 20～50 times carries out.
Operation (D-2) is that the pure water of 5～100 times stirs for adding in the first magnesium hydroxide filter cake with respect to dry hydrogen magnesium oxide quality datum quantity, then filters, washes, and obtains the operation of the second magnesium hydroxide filter cake, and it is again the operation of pulping and washing.In this operation, for example drop in the dry hydrogen magnesium oxide of the first magnesium hydroxide filter cake and count the pure water of 5～100 times with quality criteria, obtain the second magnesium hydroxide slurry, this second magnesium hydroxide slurry is stirred, then filter, wash, thereby can obtain the second magnesium hydroxide filter cake.For example stir can 10～50 ℃, carried out 0.5～5 hour with the rotating speed of 100～800rpm.After stir finishing, can use filter paper etc. to filter, washing can be counted the pure water of 5～100 times with quality criteria and carries out by dropping in dry hydrogen magnesium oxide.
Operation (D-3) is for replacing the first magnesium hydroxide filter cake, to the second magnesium hydroxide filter cake, as 1 time and it is repeated 1～20 time, obtains the operation of high purity magnesium hydrate filter cake with the pulping and washing again of operation (D-2).
Operation (D-4) is dry high purity magnesium hydrate filter cake, obtains the fine grain operation of magnesium hydroxide.
Operation, can obtain magnesium hydroxide particle of the present invention like this.
Magnesium oxide fine particle of the present invention can be by supplying that magnesium hydroxide fine particle of the present invention obtain in the operation (E) with 500～1200 ℃ of roastings in air atmosphere.
In this operation, for example can be by the magnesium hydroxide fine particle (be preferably 3～10 ℃/minute with 1～20 ℃/minute of temperature rise rate in air atmosphere, more preferably 6 ℃/minute) be warming up to 500 ℃～1200 ℃, preferred 600～800 ℃, carry out roasting 0.1～5 hour with 500 ℃～1200 ℃, preferred 600～800 ℃ after heating up, obtain magnesium oxide fine particle of the present invention.In addition, also can make the high purity magnesium hydrate filtration cakes torrefaction that obtains in operation (D-3), after rubbing out gently, supply in above-mentioned calcination process.
Operation, can easily prepare high purity, particle diameter is little and uniform magnesium hydroxide fine particle and magnesium oxide fine particle like this.
Magnesium hydroxide fine particle of the present invention and magnesium oxide fine particle operability in various fields is high.For example, as the fine grain purposes of magnesium hydroxide, can list the black fixing salt of ink-jet printing paper etc. as additive; Can list raw material, the fire retardant of the barrier film refractory layer that secondary cell uses, the properties-correcting agent (improving thermotolerance, flexibility) of thin-film sheet etc. as resin extender; Can list fuel cell with the raw material used of raw material, phosphor raw material, superconducting thin film substrate of pottery, the tunnel barrier raw material of tunnel magnetoresistance element (TMR element) use etc. as the high functionality material; Can list draining processing and exhaust-gas disposal etc. as catalyzer.In addition, as the fine grain purposes of magnesium oxide, can list high functionality material and catalyzer etc.In addition, for the magnesium oxide fine particle, make its active height activation, be suitable for ceramic post sintering auxiliary agent etc. as refractory materials; Be suitable for the black fixing salt of ink-jet printing paper etc. as additive; Be suitable for the raw material of the barrier film refractory layer that secondary cell uses, the properties-correcting agent of thin-film sheet (improving thermotolerance, flexibility) etc. as resin extender; Be suitable for the raw material that the specific refractory power adjusting agent, light diffusing agent, fuel cell of LED sealing resin use with raw material, phosphor raw material, the superconducting thin film substrate of pottery, the tunnel barrier raw material of tunnel magnetoresistance element (TMR element) use etc. as the high functionality material; Be suitable for the electro-magnetic steel plate raw material of insulating material, compressed-core insulating coating material etc. as the electro-magnetic steel plate material; Be suitable for as catalyzer in the purposes such as draining processing and exhaust-gas disposal.
Embodiment
Below, by embodiment, the present invention is described in further detail.But the present invention is not limited to these embodiment.
Measure magnesium hydroxide fine particle and the fine grain particle diameter of magnesium oxide, specific surface area, purity and the activity degree that obtains according to following method.
(1) laser diffraction and scattering formula particle size distribution
Use laser diffraction and scattering formula particle size distribution device (Ltd. makes for trade(brand)name: MT3300, NIKKISO Co.) to measure the accumulation 10% particle diameter (D based on volume
10), based on the accumulation 50% particle diameter (D of volume
50) and based on the accumulation 90% particle diameter (D of volume
90).Use similarly said apparatus to measure based on the median size (Dv) of volume with based on the median size (Dn) of number.
(2) BET specific area measuring method
Use specific area measuring device (Ltd. makes for trade(brand)name: Macsorb1210, Mountech Co.) by the BET method measurement the specific area of gas adsorption method.
(3) the quality determination method of magnesium hydroxide and magnesium oxide impurity element
For the impurity element (Ag, Al, B, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti and Zr) as determination object, use ICP emmission spectrometric analysis device (trade(brand)name: SPS-5100, Seiko Instruments Inc. makes), with sample dissolution quality measurement after acid.
For the Cl amount, use spectrophotometer (trade(brand)name: UV-2550, Shimadzu Seisakusho Ltd. makes), with sample dissolution quality measurement after acid.
(4) purity testing method
For magnesium hydroxide and the fine grain purity of magnesium oxide, the form of the value that obtains with the total that deducts the quality that adopts the impurity element that above-mentioned " magnesium hydroxide and magnesium oxide impurity level assay method " determine from 100 quality % is calculated.
(5) measuring method of citric acid activity degree (40%)
According to making 0.4N aqueous citric acid solution 100ml be equivalent to 40% mode of magnesian dosis neutralisata, weighing magnesium oxide fine particle 2.02g, add this magnesium oxide fine particle in this aqueous citric acid solution that is stirring under 30.0 ℃, measure time till citric acid all reacts with magnesium oxide, be that pH surpasses the time till 7.
[embodiment 1]
As thick magnesium chloride brine, preparing purity is that 90 quality % are above, concentration is the magnesium chloride brine of 3.5mol/L.Adjust concentration by add pure water (passing through, is the following water of 0.1 μ S/cm thereby be refined to specific conductivity) in ion exchange resin in this magnesium chloride brine, become the thick magnesium chloride brine of concentration 2.0mol/L.
Then, in the thick magnesium chloride brine of concentration 2.0mol/L, the mode that the aqueous sodium hydroxide solution of interpolation concentration 17.84mol/L makes them be 20mol% according to transformation efficiency is reacted, add again the acrylamide sodium acrylate copolymer as flocculation agent of 500 quality ppm with respect to the magnesium hydroxide that generates, make the magnesium hydroxide flocculation sediment, get supernatant liquor, obtain thus magnesium chloride brine.
Adjust the concentration of resulting magnesium chloride brine, make the magnesium chloride brine of concentration 2.0mol/L.Making this magnesium chloride brine is the mode of 200mol% and the aqueous sodium hydroxide solution reaction of concentration 17.84mol/L according to transformation efficiency, the magnesium hydroxide slurry of preparation concentration 100g/L.
Use autoclave to stir below resulting magnesium hydroxide slurry at 150 ℃, the limit kept 1 hour, carried out hydrothermal treatment consists (heated and stirred processing).With hydrothermal treatment consists the first magnesium hydroxide slurry filter, washing, obtain thus the first magnesium hydroxide filter cake.Washing can be counted the pure water of 40 times with respect to dry hydrogen magnesium oxide with quality criteria and carries out by dropping into afterwards in filtration.
Then, resulting the first magnesium hydroxide filter cake is carried out pulping and washing again.With regard to pulping and washing again, at first drop in the dry hydrogen magnesium oxide of the first magnesium hydroxide filter cake and count the pure water of 40 times with quality criteria, obtain the second magnesium hydroxide slurry.Then, use whipping appts to stir this second magnesium hydroxide slurry 1 hour with the rotating speed of 500rpm at normal temperatures, re-use the second magnesium hydroxide slurry after filter paper filtering stirs end, drop in the magnesium hydroxide of drying after filtration and count the pure water of 20 times with quality criteria, wash, obtain thus the second magnesium hydroxide filter cake.As 1 time, and then repeat pulping and washing again 10 times with above-mentioned pulping and washing again, obtain thus the high purity magnesium hydrate filter cake.With the high purity magnesium hydrate filtration cakes torrefaction, thereby obtain the high purity magnesium hydrate fine particle.
[embodiment 2]
In the reaction of magnesium chloride brine and aqueous sodium hydroxide solution, transformation efficiency is made as 120mol%, the hydrothermal treatment consists time is made as 0.5 hour, in addition, carry out similarly to Example 1.
[embodiment 3]
In the reaction of magnesium chloride brine and aqueous sodium hydroxide solution, transformation efficiency is made as 105mol%, the hydrothermal treatment consists time is made as 3 hours, in addition, carry out similarly to Example 1.
[embodiment 4]
The hydrothermal treatment consists temperature is made as 130 ℃, is 8.92mol/L with aqueous sodium hydroxide solution with the pure water dilution, in addition, carries out similarly to Example 1.
[embodiment 5]
The hydrothermal treatment consists temperature is made as 105 ℃, will be made as 130g/L for the magnesium hydroxide slurry in hydrothermal treatment consists, in addition, carry out similarly to Example 1.
[embodiment 6]
Be 4.96mol/L with aqueous sodium hydroxide solution with the pure water dilution, in addition, carry out similarly to Example 1.
[embodiment 7]
To be 50g/L for the magnesium hydroxide slurry pure water dilution in hydrothermal treatment consists, in addition, carry out similarly to Example 1.
[comparative example 1]
In the reaction of magnesium chloride brine and aqueous sodium hydroxide solution, transformation efficiency is made as 250mol%, in addition, carries out similarly to Example 1.
[comparative example 2]
In the reaction of magnesium chloride brine and aqueous sodium hydroxide solution, transformation efficiency is made as 90mol%, in addition, carries out similarly to Example 1.
[comparative example 3]
In the reaction of magnesium chloride brine and aqueous sodium hydroxide solution, transformation efficiency is made as 105mol%, does not carry out hydrothermal treatment consists, in addition, carry out similarly to Example 1.
[comparative example 4]
Be 21mol/L with aqueous sodium hydroxide solution with the pure water dilution, in addition, carry out similarly to Example 1.
[embodiment 8]
By the magnesium hydroxide fine particle that will make in embodiment 1 in air atmosphere with 1000 ℃ of roastings 1 hour, obtain the magnesium oxide fine particle.
[embodiment 9]
By the magnesium hydroxide fine particle that will make in embodiment 3 in air atmosphere with 600 ℃ of roastings 1 hour, obtain the magnesium oxide fine particle.
[comparative example 5]
By the magnesium hydroxide fine particle that will make in embodiment 1 in air atmosphere with 1400 ℃ of roastings 1 hour, obtain the magnesium oxide fine particle.
To be shown in Table 1 about the fine grain measurement result of the magnesium hydroxide that obtains by above-described embodiment and comparative example, will be shown in Table 2 about the fine grain measurement result of magnesium oxide.
More than magnesium hydroxide fine particle in embodiment and magnesium oxide fine particle were purity 99.9 quality %, particle diameter was little and even.
Table 1
Table 2
Utilizability on industry
Magnesium hydroxide fine particle of the present invention and magnesium oxide fine particle are high purity, and particle diameter is little and even, good dispersity (because size-grade distribution is sharp), and therefore operability is high in various fields.In addition, manufacturing method according to the invention can easily be made fine particle as described above, and convenience is high.For example, as the fine grain purposes of magnesium hydroxide, can list additive, resin extender, high functionality material and catalyzer etc.
Particularly, the black fixing salt etc. that can be used for ink-jet printing paper as additive; Can be used for raw material, the fire retardant of the barrier film refractory layer that secondary cell uses, the properties-correcting agent (improving thermotolerance, flexibility) of thin-film sheet etc. as resin extender; Can be used for fuel cell with the raw material used of raw material, phosphor raw material, superconducting thin film substrate of pottery, the tunnel barrier raw material of tunnel magnetoresistance element (TMR element) use etc. as the high functionality material; Can be used for the purposes such as draining processing and exhaust-gas disposal as catalyzer.
In addition, as the fine grain purposes of magnesium oxide, can list refractory materials, additive, resin extender, high functionality material, electro-magnetic steel plate material and catalyzer etc.
Particularly, can be used for ceramic post sintering auxiliary agent etc. as refractory materials; Can be used for the black fixing salt of ink-jet printing paper etc. as additive; Can be used for the raw material of the barrier film refractory layer that secondary cell uses, the properties-correcting agent of thin-film sheet (improving thermotolerance, flexibility) etc. as resin extender; Can be used for the raw material that the specific refractory power adjusting agent, light diffusing agent, fuel cell of LED sealing resin use with raw material, phosphor raw material, the superconducting thin film substrate of pottery, the tunnel barrier raw material of tunnel magnetoresistance element (TMR element) use etc. as the high functionality material; Can be used for the electro-magnetic steel plate raw material of insulating material, compressed-core insulation coating material etc. as the electro-magnetic steel plate material; Can be used for the purposes such as draining processing and exhaust-gas disposal as catalyzer.
Claims (15)
1. magnesium hydroxide fine particle, its purity is more than 99.5 quality %, the BET specific surface area is 5m
2More than/g, the accumulation 50% particle diameter D based on volume that obtains by laser diffraction and scattering formula particle size distribution
50Be 0.1～0.5 μ m, the accumulation 10% particle diameter D based on volume that obtains by laser diffraction and scattering formula particle size distribution
10With the accumulation 90% particle diameter D based on volume
90Ratio D
90/ D
10Be below 10.
2. magnesium hydroxide fine particle according to claim 1, its purity is more than 99.9 quality %.
3. magnesium hydroxide fine particle according to claim 1 and 2, wherein, the total content of Fe, Ti, Ni, Cr, Mo and Mn is below 500 quality ppm.
4. the described magnesium hydroxide fine particle of any one according to claim 1～3, wherein, cl content is below 500 quality ppm.
5. the described magnesium hydroxide fine particle of any one according to claim 1～4, it is 1～10 based on the median size Dv of volume with ratio Dv/Dn based on the median size Dn of number.
6. magnesium oxide fine particle, its purity is more than 99.5 quality %, the BET specific surface area is 5m
2More than/g, the accumulation 50% particle diameter D based on volume that obtains by laser diffraction and scattering formula particle size distribution
50Be 0.1～0.5 μ m, the accumulation 10% particle diameter D based on volume that obtains by laser diffraction and scattering formula particle size distribution
10With the accumulation 90% particle diameter D based on volume
90Ratio D
90/ D
10Be below 10.
7. magnesium oxide fine particle according to claim 6, its purity is more than 99.9 quality %.
8. according to claim 6 or 7 described magnesium oxide fine particles, wherein, the total content of Fe, Ti, Ni, Cr, Mo and Mn is below 500 quality ppm.
9. the described magnesium oxide fine particle of any one according to claim 6～8, wherein, cl content is below 500 quality ppm.
10. the described magnesium oxide fine particle of any one according to claim 6～9, wherein, citric acid activity degree (40%) is 20～2000 seconds.
11. the described magnesium oxide fine particle of any one according to claim 6～10, it is 1～10 based on the median size Dv of volume with ratio Dv/Dn based on the median size Dn of number.
12. the fine grain manufacture method of magnesium hydroxide, it comprises
Operation (A): prepare magnesium chloride brine;
Operation (B): make the alkali aqueous solution of magnesium chloride brine and 1～18N with transformation efficiency 101～210mol% reaction, obtain magnesium hydroxide slurry;
Operation (C): the limit is stirred the magnesium hydroxide slurry limit and is kept with the temperature of 101～200 ℃, obtain hydrothermal treatment consists magnesium hydroxide slurry; And
Operation (D): with hydrothermal treatment consists magnesium hydroxide slurry filter, washing and dry, obtain the magnesium hydroxide fine particle.
13. the fine grain manufacture method of magnesium hydroxide according to claim 12, wherein, operation (D) comprises
Operation (D-1): with hydrothermal treatment consists magnesium hydroxide slurry filter, washing, obtain the first magnesium hydroxide filter cake;
Operation (D-2): adding in the first magnesium hydroxide filter cake with respect to dry hydrogen magnesium oxide quality datum quantity is that the pure water of 5～100 times stirs, and then filters, washes, and obtains the second magnesium hydroxide filter cake;
Operation (D-3): replace the first magnesium hydroxide filter cake, the second magnesium hydroxide filter cake is repeated 1～20 operation (D-2), obtain the high purity magnesium hydrate filter cake; And
Operation (D-4): dry high purity magnesium hydrate filter cake obtains the magnesium hydroxide fine particle.
14. the according to claim 12 or 13 fine grain manufacture method of described magnesium hydroxide, wherein, operation (A) comprises
Operation (A-1): prepare thick magnesium chloride brine;
Operation (A-2): make the alkali aqueous solution of thick magnesium chloride and 1～18N with transformation efficiency 1～30mol% reaction, obtain thick magnesium hydroxide slurry; And
Operation (A-3): add flocculation agent in thick magnesium hydroxide slurry after, filter magnesium hydroxide, obtain magnesium chloride solution as filtrate; Perhaps add flocculation agent in thick magnesium hydroxide slurry, make the magnesium hydroxide flocculation sediment, obtain magnesium chloride brine as supernatant liquor.
15. the fine grain manufacture method of magnesium oxide, it comprises operation (E): the described magnesium hydroxide fine particle of any one in claim 1～5 or the magnesium hydroxide fine particle that obtains with the described method of any one in claim 12～14 are carried out roasting with 500～1500 ℃ in air atmosphere.
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| JP2010217166A JP5686563B2 (en) | 2010-09-28 | 2010-09-28 | Magnesium hydroxide fine particles and magnesium oxide fine particles, and methods for producing them |
| JP2010-217166 | 2010-09-28 | ||
| PCT/JP2011/072083 WO2012043564A1 (en) | 2010-09-28 | 2011-09-27 | Magnesium hydroxide microparticles, magnexium oxide microparticles, and method for producing each |
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| KR (1) | KR101495777B1 (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332116A (en) * | 2001-08-20 | 2002-01-23 | 杜以波 | Homogeneous fluid process of preparing nanometer magnesium hydroxide |
| JP2009007215A (en) * | 2007-06-29 | 2009-01-15 | Sakai Chem Ind Co Ltd | Spherical magnesium oxide particles and method for producing the same |
| CN101475197A (en) * | 2009-01-09 | 2009-07-08 | 中国科学院青海盐湖研究所 | Method for preparing ultra-fine high dispersing magnesium hydrate flame retardant from saline lake bittern or bischofite |
| CN101687659A (en) * | 2007-06-27 | 2010-03-31 | 达泰豪化学工业株式会社 | Magnesium oxide particle aggregate, and method for production thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2320133C (en) * | 1998-12-14 | 2007-05-22 | Kyowa Chemical Industry Co., Ltd. | Magnesium hydroxide particles, method of the production thereof, and resin composition containing the same |
| JP3965270B2 (en) * | 2000-04-19 | 2007-08-29 | 宇部マテリアルズ株式会社 | Highly dispersible high purity magnesium hydroxide powder, method for producing the same, and magnesium hydroxide slurry |
| JP4849807B2 (en) * | 2005-02-21 | 2012-01-11 | 宇部マテリアルズ株式会社 | Magnesium oxide fine particle dispersion |
| JP4698448B2 (en) * | 2006-03-13 | 2011-06-08 | 新日本製鐵株式会社 | MgO for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet with excellent magnetic properties and glass coating properties using the same |
| JP5128882B2 (en) * | 2007-09-05 | 2013-01-23 | 関東電化工業株式会社 | Magnesium hydroxide fine particles and method for producing the same |
-
2010
- 2010-09-28 JP JP2010217166A patent/JP5686563B2/en active Active
-
2011
- 2011-09-27 KR KR1020137010610A patent/KR101495777B1/en active IP Right Grant
- 2011-09-27 WO PCT/JP2011/072083 patent/WO2012043564A1/en active Application Filing
- 2011-09-27 CN CN2011800470868A patent/CN103140446A/en active Pending
- 2011-09-28 TW TW100134937A patent/TWI529133B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332116A (en) * | 2001-08-20 | 2002-01-23 | 杜以波 | Homogeneous fluid process of preparing nanometer magnesium hydroxide |
| CN101687659A (en) * | 2007-06-27 | 2010-03-31 | 达泰豪化学工业株式会社 | Magnesium oxide particle aggregate, and method for production thereof |
| JP2009007215A (en) * | 2007-06-29 | 2009-01-15 | Sakai Chem Ind Co Ltd | Spherical magnesium oxide particles and method for producing the same |
| CN101475197A (en) * | 2009-01-09 | 2009-07-08 | 中国科学院青海盐湖研究所 | Method for preparing ultra-fine high dispersing magnesium hydrate flame retardant from saline lake bittern or bischofite |
Non-Patent Citations (1)
| Title |
|---|
| 吴会军等: "高分散氢氧化镁粉体的制备及其影响因素", 《无机材料学报》 * |
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| TWI529133B (en) | 2016-04-11 |
| WO2012043564A1 (en) | 2012-04-05 |
| TW201219307A (en) | 2012-05-16 |
| JP5686563B2 (en) | 2015-03-18 |
| JP2012072004A (en) | 2012-04-12 |
| KR20130081293A (en) | 2013-07-16 |
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