CN101033068A - Method of preparing high-purity ultra-fine sphere silicon micro-powder - Google Patents

Method of preparing high-purity ultra-fine sphere silicon micro-powder Download PDF

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Publication number
CN101033068A
CN101033068A CNA2007100344269A CN200710034426A CN101033068A CN 101033068 A CN101033068 A CN 101033068A CN A2007100344269 A CNA2007100344269 A CN A2007100344269A CN 200710034426 A CN200710034426 A CN 200710034426A CN 101033068 A CN101033068 A CN 101033068A
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powder
silicon micro
breeze
purity ultra
fine sphere
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CN100413782C (en
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袁茂豪
袁超
袁君
罗招梅
袁茂清
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袁茂豪
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Priority to PCT/CN2008/000235 priority patent/WO2008098470A1/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
    • 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
    • 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
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

This invention discloses a method for preparing purified super-fine spherical Si micro-powder, which first of all selects natural quartz breeze roughly, cleans it and adds an aging agent to be aged in an alkali condition and filtered, then dehydrates and dries the filtered matter and processes it to powder or blocks by adding a binder to be burnt under 1280-1680deg.C in a high temperature furnace for 1-10h to be cooled and dispersed to be grinded to powder spheres and graded by magnetic selection and wind selection to get purified super-fine spherical silicon micro-powder.

Description

A kind of preparation method of high-purity ultra-fine sphere silicon micro-powder
Technical field
The present invention relates to a kind of preparation method of silica powder, especially relate to a kind of preparation method of high-purity ultra-fine sphere silicon micro-powder.
Background technology
Continuous development along with science and technology, the silicon powder that is applied to new high-tech industries such as high-grade paint, senior filler, insulating material, electronic package material and aerospace not only requires it to have that good flowability, dispersiveness, thermal conductivity are little, electric conductivity is low and corrosion resistance nature, and require its silicon powder nodularization rate, whiteness and the high quality standard of purity, the demand of the ball-shaped silicon micro powder that simultaneously above-mentioned industry is used is big, and the world market demand has the market of 30,000,000,000 Renminbi at least.At present, the method for preparing high-purity ultra-fine sphere silicon micro-powder both at home and abroad probably has chemical preparation process and mechanical-physical preparation methods such as chemical gas-phase method, chemical precipitation method, high frequency plasma method, high-temperature melting method and sol-gel method, but existing above-mentioned chemical preparation process all has investment greatly, yield poorly, the cost height, problems such as the problem that the input-output rate is little, existing machinery physical preparation method exist the nodularization rate not high again, and whiteness is low.Therefore, existing above-mentioned ball-shaped silicon micro powder preparation method can't satisfy the big and high requirement of quality of ball-shaped silicon micro powder output simultaneously.
Summary of the invention
In above-mentioned prior art, the problem that exists among the ball-shaped silicon micro powder preparation method the present invention proposes a kind of not only output height, invests for a short time, and production cost is low, and silicon powder nodularization rate height, whiteness are good, the preparation method of the high-purity ultra-fine sphere silicon micro-powder that purity is high.
The preparation method of high-purity ultra-fine sphere silicon micro-powder of the present invention is: the natural powdery quartz breeze is by roughly selecting, obtain high-quality natural powdery quartz breeze, with high-quality natural powdery quartz breeze by the washing after, add accelerant, make its high-quality natural powdery quartz breeze under alkaline condition, carry out ageing, the ageing after-filtration, after will filtering the thing dewatered drying, decentralized system powdering or adding binding agent are made block or cellular, again with powdery, block or cellular high-quality natural powdery quartz breeze is incubated 1-10 hour and fires in 1280-1680 ℃ of High Temperature Furnaces Heating Apparatus, carry out the dispersion mill sphere of powderization after the cooling again, magnetic separation and selection by winnowing classification obtain high-purity ultra-fine sphere silicon micro-powder.
Described accelerant is a water glass, and add-on is the 2-10% of powder quartz ore grain weight amount, can be other accelerant also, as yellow soda ash; Its moisture content is not more than 1% behind the described high-quality natural powdery quartz breeze dewatered drying.
At present, China's quartz mine mainly contains natural blout ore deposit and natural powdery quartz mine, natural blout is pulverized by calcination and is obtained cristobalite, the cristobalite silicon crystal mostly is six prismatics, the four directions crystalline phase, and in the natural flint except that containing six prismatic silicon crystal, also contain more spherical silicon crystal.The natural powdery quartz breeze has very big storage capacity in the whole nation, as in Jiangxi Province's Pingxiang City, maximum natural powdery quartz ore deposit, the whole nation is just arranged, this natural powdery quartz breeze shows by scanning electronic microscope amplification 200 and shows, its natural powdery quartz powder is by after washing dewatered drying, physique structure is compared with the blout ore deposit, removes to contain few part six prismatic powder, outside a small amount of convex concave powder, also contain the spherical powder about 50%, roughly select by mineral resources, remove six prismatic powder, obtain high-quality natural powdery quartz breeze.
The present invention is a raw material with the high-quality natural powdery quartz breeze after roughly selecting, be prepared into ball-shaped silicon micro powder by washing, ageing and high-temperature calcination, not only nodularization rate of its silicon powder height, other elements such as whiteness is good, silicon content is high, iron content, aluminium are few, pH value is neutral slant acidity, flowability, good dispersity, and the coefficient of expansion is little, thermal conductivity is little, electric conductivity is low, corrosion-resistant, ultrapure, ultra-fine; And less investment, production cost is low, output is big, input-output can reach 1/5～1/8, be a kind of broad-spectrum inorganic materials, can be widely used in new and high technology industries such as high-grade paint, senior filler, insulating material, precision casting, electronic package material and aerospace.
Every technical indicator of high-purity ultra-fine sphere silicon micro-powder of the present invention is:
Silicon crystal is mainly the cristobalite peak, and the quartzy peak of carbamate additives for low phosphorus, nodularization rate are 75-95%, whiteness 85-95, granularity less than the ball-shaped silicon micro powder content of 10um be more than 50%, pH value 5-7, SiO 2Content is at 99-99.95%, Al 2O 3Content is below 0.06%, Fe 2O 3Content is below 0.03%.
Embodiment
Embodiment 1: by roughly selecting, remove six big prismatic powder of hardness with the natural powdery quartz breeze, obtain nodularization than high and the high high-quality natural powdery quartz breeze of purity.With the high-quality natural powdery quartz breeze after roughly selecting by after adding water washing, make its interior impurity and mud be suspended in the surface, remove after sieving, wash with pure water again, the water glass that then adds high-quality natural powdery quartz breeze weight 3% stirs, the pH value of regulating its aged high-quality natural powdery quartz breeze is in 9 ± 0.5, make it carry out ageing, digestion time is 10 hours, dewatered drying dispersion treatment after the ageing, make the flint breeze, or the sodium silicate binder dispersed with stirring of adding an amount of (content when making the konilite breeze after stirring, be the consistence state), (water glass forms nano level silicon powder by high temperature, wherein sodium oxide distils in the time of 1275 ℃), moisture content is controlled at 0.8%, make brick or blout breeze such as cellular, be convenient to loading of kiln, then by intermittently kiln insulation calcination in 8 hours under 1480 ℃, wherein, the flint breeze also can be directly with blowing and torch firing, after the cooling, through disperseing, the abrasive dust nodularization, magnetic separation is got classification and is gone out ball-shaped silicon micro powder, and this kind preparation method ratio is more suitable for high-grade paint, industries such as senior filler and insulating material.Amplify 200 times through X-ray diffraction and scanning electron microscope, its whiteness, granularity, pH value and Chemical Composition are: be mainly the cristobalite peak, and the quartzy peak of carbamate additives for low phosphorus, nodularization rate 79%, whiteness is 92, granularity less than the ball-shaped silicon micro powder content of 10um be 61%, pH value 6.5, SiO 2Content is 99.82%, Al 2O 3Content is 0.051%, Fe 2O 3Content is 0.027%.
Embodiment 2: remove six big prismatic powder of hardness with the natural powdery quartz breeze by roughly selecting, obtain nodularization than high and the high high-quality natural powdery quartz breeze of purity.With the high-quality natural powdery quartz breeze after roughly selecting by pickling after alkali cleaning neutralization again, removal of impurities, sieve, bleaching, remove impurity with the pure water washing and filtering again, the water glass that adds high-quality natural powdery quartz breeze weight 8% again stirs, the pH value of regulating aged high-quality natural powdery quartz breeze is in 10 ± 0.5, make its ageing 10 hours, its SiO2 content is 99.6%, dewatered drying disperses, moisture content is controlled at 0.65%, make the flint breeze, or the sodium silicate binder that adds an amount of (content when making quartzy breeze be the consistence state after stirring) stirs, (water glass forms nano level silicon powder by high temperature, sodium oxide is distilled) in the time of 1275 ℃, control moisture content is below 1%, make brick or blout breeze such as cellular, be convenient to loading of kiln, wherein, the flint breeze also can be directly with blowing and torch firing, carried out calcination by continuous kiln in 3 hours 1550 ℃ of calcining insulations then, the cooling back disperses polishing to disperse spheroidizing by sand mill, again by the magnetic separation removal of impurities, the selection by winnowing classification prepares ball-shaped silicon micro powder, and this kind method relatively is fit to Electronic Packaging and aerospace material industry.The amplification that process X-ray diffraction and scanning electronic microscope are 200 times, its whiteness, granularity, pH value and Chemical Composition analysis, be mainly the cristobalite peak, the quartzy peak of carbamate additives for low phosphorus, whiteness is 95, granularity is 65% less than the ball-shaped silicon micro powder content of 10um, the nodularization rate is 92%, and pH value is 5.8, SiO 2Content is 99.9%,, Al 2O 3Content is 0.046%, Fe 2O 3Content is 0.023%.

Claims (5)

1, a kind of preparation method of high-purity ultra-fine sphere silicon micro-powder, it is characterized in that: the natural powdery quartz breeze is by roughly selecting, obtain high-quality natural powdery quartz breeze, with high-quality natural powdery quartz breeze by the washing after, add accelerant, make its high-quality natural powdery quartz breeze under alkaline condition, carry out ageing, the ageing after-filtration, to filter the thing dewatered drying disperses, making powdery or adding binding agent makes block or cellular, again with powdery, block or cellular high-quality natural powdery quartz breeze is incubated 1-10 hour and fires in 1280-1680 ℃ of High Temperature Furnaces Heating Apparatus, carry out the dispersion mill sphere of powderization after the cooling again, magnetic separation, the selection by winnowing classification obtains high-purity ultra-fine sphere silicon micro-powder.
2, the preparation method of a kind of high-purity ultra-fine sphere silicon micro-powder according to claim 1, it is characterized in that: described high-purity ultra-fine sphere silicon micro-powder, through X-ray diffraction, scanning electronic microscope is amplified 200 times, and its ball-shaped silicon micro powder is mainly the cristobalite peak, the quartzy peak of a spot of phosphorus, 75%-95% is a spherical powder, and pH value is 5-7, and whiteness is 85-95, granularity is more than 50% less than the ball-shaped silicon micro powder content of 10um, SiO 2Content 99%-99.95%, Al 2O 3Content is below 0.06%, Fe 2O 3Content is below 0.04%.
3, the preparation method of a kind of high-purity ultra-fine sphere silicon micro-powder according to claim 1 is characterized in that: described washing is washing.
4, the preparation method of a kind of high-purity ultra-fine sphere silicon micro-powder according to claim 1 is characterized in that: described washing is alkali cleaning again after the pickling.
5, the preparation method of a kind of high-purity ultra-fine sphere silicon micro-powder according to claim 1 is characterized in that: described accelerant is a water glass.
CNB2007100344269A 2007-02-13 2007-02-13 Method of preparing high-purity ultra-fine sphere silicon micro-powder Expired - Fee Related CN100413782C (en)

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Cited By (9)

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WO2008098470A1 (en) * 2007-02-13 2008-08-21 Maohao Yuan A method for preparing high purity and ultrafine spherical silica micropowder
CN101817533A (en) * 2010-04-27 2010-09-01 中国地质大学（武汉） Preparation method of electronic-level crystalline silicon powder
CN102757052A (en) * 2012-07-31 2012-10-31 合肥工业大学 Method for separating and extracting silica micro powders from discarded quartz tailings
CN103043668A (en) * 2011-10-13 2013-04-17 沈阳黎明航空发动机(集团)有限责任公司 Preparation method of core additive
CN105036546A (en) * 2015-07-31 2015-11-11 四川南联矿业有限责任公司 Pelleting production method for superfine quartz sand
CN107033633A (en) * 2017-03-16 2017-08-11 湖南金马新材料科技有限公司 A kind of natural powdery quartz is brightened, shaping, the technology of modified integration
CN110803860A (en) * 2019-11-19 2020-02-18 新沂北美高科耐火材料有限公司 Preparation method of electronic-grade spherical fused quartz refractory material
CN113680462A (en) * 2021-10-27 2021-11-23 苏州锦艺新材料科技有限公司 Production process of spherical silicon micropowder
CN114308851A (en) * 2021-12-10 2022-04-12 连云港锐智新材料有限公司 Production method of high-purity silicon micro powder for electronic instrument

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CN114273075B (en) * 2022-01-10 2024-10-01 澳创万合(深圳)科技有限公司 Beneficiation method for extracting high-purity silicon micropowder from quartz tail mud
CN114620733B (en) * 2022-03-08 2023-05-16 北京科技大学 Low-carbon green SiO of superconducting high-strength magnetic coupling quartz ore 2 Fine purification method
CN117326563B (en) * 2023-09-28 2024-03-22 吉安豫顺新材料有限公司 Preparation method and system of low-impurity silicon micro powder for vehicle-mounted copper-clad plate

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CN101100391A (en) * 2007-03-29 2008-01-09 袁茂豪 Method for preparing cristobalite powder by using natural konilite

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008098470A1 (en) * 2007-02-13 2008-08-21 Maohao Yuan A method for preparing high purity and ultrafine spherical silica micropowder
CN101817533A (en) * 2010-04-27 2010-09-01 中国地质大学（武汉） Preparation method of electronic-level crystalline silicon powder
CN103043668A (en) * 2011-10-13 2013-04-17 沈阳黎明航空发动机(集团)有限责任公司 Preparation method of core additive
CN103043668B (en) * 2011-10-13 2014-11-19 沈阳黎明航空发动机(集团)有限责任公司 Preparation method of core additive
CN102757052A (en) * 2012-07-31 2012-10-31 合肥工业大学 Method for separating and extracting silica micro powders from discarded quartz tailings
CN102757052B (en) * 2012-07-31 2014-04-30 合肥工业大学 Method for separating and extracting silica micro powders from discarded quartz tailings
CN105036546A (en) * 2015-07-31 2015-11-11 四川南联矿业有限责任公司 Pelleting production method for superfine quartz sand
CN107033633A (en) * 2017-03-16 2017-08-11 湖南金马新材料科技有限公司 A kind of natural powdery quartz is brightened, shaping, the technology of modified integration
CN110803860A (en) * 2019-11-19 2020-02-18 新沂北美高科耐火材料有限公司 Preparation method of electronic-grade spherical fused quartz refractory material
CN113680462A (en) * 2021-10-27 2021-11-23 苏州锦艺新材料科技有限公司 Production process of spherical silicon micropowder
CN113680462B (en) * 2021-10-27 2021-12-31 苏州锦艺新材料科技有限公司 Production process of spherical silicon micropowder
CN114308851A (en) * 2021-12-10 2022-04-12 连云港锐智新材料有限公司 Production method of high-purity silicon micro powder for electronic instrument

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