[go: up one dir, main page]

WO2012060285A1 - Corps granulé de sable siliceux et son procédé de fabrication - Google Patents

Corps granulé de sable siliceux et son procédé de fabrication Download PDF

Info

Publication number
WO2012060285A1
WO2012060285A1 PCT/JP2011/074898 JP2011074898W WO2012060285A1 WO 2012060285 A1 WO2012060285 A1 WO 2012060285A1 JP 2011074898 W JP2011074898 W JP 2011074898W WO 2012060285 A1 WO2012060285 A1 WO 2012060285A1
Authority
WO
WIPO (PCT)
Prior art keywords
silica sand
silica
alkaline earth
earth metal
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/074898
Other languages
English (en)
Japanese (ja)
Inventor
誠司 今澄
福山　良樹
藤波　恭一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokuyama Corp
Original Assignee
Tokuyama Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokuyama Corp filed Critical Tokuyama Corp
Priority to CN201180052701.4A priority Critical patent/CN103201220B/zh
Priority to JP2012541829A priority patent/JP5875523B2/ja
Publication of WO2012060285A1 publication Critical patent/WO2012060285A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
    • 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
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • C01B33/025—Preparation by reduction of silica or free silica-containing material with carbon or a solid carbonaceous material, i.e. carbo-thermal process
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C04B2235/5472—Bimodal, multi-modal or multi-fraction
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Definitions

  • the present invention relates to a novel silica sand granule. More specifically, the present invention provides a silica sand granule that has properties that can be handled in the same way as silica stone that is normally used as a raw material when manufacturing metal silicon, and that can replace silica in the manufacture of metal silicon, and a method for manufacturing the same. To do.
  • metallic silicon is obtained by reducing silica at about 2000 ° C. in an arc furnace using silica, which is a silicon source, and charcoal, coke, coal, wood chips, etc. as a reducing material.
  • silica which is a silicon source
  • charcoal, coke, coal, wood chips, etc. as a reducing material.
  • the silica stone is usually 5 mm to 200 mm in size. This is to ensure air permeability in the furnace. That is, in the arc furnace, carbon monoxide (CO) gas and silicon monoxide (SiO) gas are generated as a gas phase in the process of the reduction reaction of the silica, so that all or a part of them is used as the raw material layer. Need to escape through.
  • CO carbon monoxide
  • SiO silicon monoxide
  • SiO 2 silicon dioxide
  • the reaction is complicated and is decomposed into the following elementary reactions, and these elementary reactions are considered to occur in parallel.
  • the condensed phase in the arc furnace temperature range is SiO 2 , C, SiC, Si, and the gas phase is CO, SiO.
  • SiO gas is generated from the high temperature portion near the tip of the in-furnace electrode by the reaction of formula (2). In the upper part of the raw material layer, when the SiO gas or CO gas that generated the gap between the layers rises and is discharged, precipitates adhere to the wall surface of the gap that is the passage by the following reaction.
  • quartz sand has abundant resources compared to quartz stone, and in addition, it is easy to mine, so it can be a great advantage to replace quartz stone as a raw material for metallic silicon.
  • the number of voids is smaller than that of silica stone, and when deposits are deposited due to the reactions of the above-described formulas (10) and (11), the voids are significantly reduced compared with the above-mentioned silica stone. It is feared that it is difficult to escape the gas of CO and SiO generated in the reaction. Further, as can be seen from the formulas (2) to (8), if the CO stays, the progress of the reaction is hindered. That is, SiC is deposited on the bottom of the furnace and causes operational troubles.
  • silica sand as a raw material for metallic silicon to be supplied to the arc furnace to have a size and strength equivalent to that of silica stone.
  • Patent Document 1 silica sand is mixed with a non-sintered carbon carrier such as petroleum coke and a pitch-containing binder and hardened to obtain green pellets, which are cured and heat-treated to give an arc furnace. It is described to form a charge pellet.
  • a non-sintered carbon carrier such as petroleum coke and a pitch-containing binder
  • the present invention replaces the silica usually used as a raw material in the production of metal silicon, and has a silica sand granule having a size and strength that can be handled in the same manner as silica. It aims at providing the method for manufacturing efficiently.
  • the present inventors have achieved this object according to the silica sand granule having a specific average particle diameter and crushing strength, If an inorganic substance having reactivity with SiO 2 is interposed between silica sand particles in the granule structure, the strength can be increased even by heat treatment at a relatively low temperature, and the problem of strength reduction at a high temperature can be solved.
  • an alkaline earth metal compound typically a calcium compound or a magnesium compound as the inorganic substance
  • the above object is achieved, and the use of the alkaline earth metal compound When this was used as the raw material for silicon production, it was found that the purity of the metal silicon obtained can be remarkably improved, and the present invention has been completed.
  • the silica sand granule of the present invention is formed from silica sand and has an average particle diameter of 5 mm to 200 mm and a crushing strength of 200 N to 100,000 N.
  • the silica sand granule is preferably molded using an alkaline earth metal compound as a binder.
  • an alkaline earth metal compound a calcium compound, a magnesium compound or a mixture thereof is preferable.
  • the ratio of the alkaline earth metal atom to the Si atom is 0.001 to 0.04. It is preferable in order to increase the purity of the silica sand granule itself while maintaining the high strength.
  • the ratio of calcium atoms to Si atoms is 0.001 to 0.04 to maintain the high strength of the silica sand granule.
  • SiO 2 content of silica sand constituting the silica sand granule is preferably at least 97% by weight.
  • the said silica sand can use a thing with a particle size in the range below 1400 micrometers suitably.
  • the use of silica sand having a relative particle amount (weight) of 25% to 70% within a particle size range of less than 75 ⁇ m is due to the action of the binder and a high-strength granule by heat treatment at a low temperature. Is particularly preferable.
  • the relative particle amount is in the range of 150 ⁇ m or more and less than 1400 ⁇ m and the relative particle amount is 10% to 50%
  • some silica sand is used as raw material silica sand by unpulverized or mild pulverization. Can be economical.
  • the relative particle amount in the range of less than 1400 ⁇ m is 100%.
  • the ratio of alkali metal atoms to Si atoms (M1 / Si) contained in the silica sand granule is preferably less than 0.01.
  • the silica sand granule can be produced by granulating silica sand to have an average particle diameter of 5 mm to 200 mm and a crushing strength of 200 N to 100,000 N.
  • the above-mentioned silica sand granule can be preferably produced by bringing an alkaline earth metal compound such as a calcium compound into contact with the surface of the silica sand for granulation.
  • the silica sand is obtained by granulating by contacting the silica sand with an alkaline earth metal compound such as a calcium compound in the presence of water, and then heating the granulated body to a temperature of 100 ° C. to 1600 ° C. This is preferable for further improving the strength of the granulated body.
  • alkaline earth metal compound calcium compounds such as calcium hydroxide, calcium carbonate, calcium oxide and calcium sulfate, magnesium compounds such as magnesium hydroxide, magnesium carbonate, magnesium oxide and magnesium sulfate, or a mixture thereof are suitable. Used for.
  • an alkaline earth metal compound such as a calcium compound is 0.1 to 5 parts by weight with respect to 100 parts by weight of silica sand.
  • silica sand used in the present invention can be adjusted to an average particle diameter of 1 ⁇ m to 200 ⁇ m by pulverization.
  • the silica sand granule of the present invention is suitably used as a silicon source in the production of metallic silicon, ferrosilicon or silicon carbide.
  • a method for producing metal silicon a method in which the silica sand granule of the present invention is supplied to an arc furnace as at least a part of a silicon source and a reduction reaction is suitably employed.
  • a step of forming silica sand to form a silica sand granule having an average particle size of 5 mm to 200 mm and a crushing strength of 200 N to 100,000 N, and the silica sand granule examples thereof include a method including a step of performing a reduction reaction by supplying at least part of a silicon source to an arc furnace.
  • the silica sand granule of the present invention achieves a crushing strength of 200 N or more, and when loaded into the raw material layer in the arc furnace with such strength, it does not collapse due to the load from the top even if handled in the same manner as silica stone, It is possible to ensure the voids in the layer. In addition, even at high temperatures, the strength is not significantly reduced, and the reaction can be performed stably.
  • the strength of the above-mentioned silica sand granule is increased by granulating using an alkaline earth metal compound such as a calcium compound or a magnesium compound as a binder, so that the alkaline earth metal is present on the surface of the silica sand particle. It is presumed that calcium silicate which is a reaction product reacts with the SiO 2 component and strongly binds the silica sand particles.
  • the silica sand granule obtained in the present invention is used as a raw material for metallic silicon
  • the metallic silicon reduced and melted in the arc furnace is easily separated when discharged from the furnace and solidifies, and has high purity.
  • Metallic silicon can be produced.
  • an alkaline earth metal compound typically a calcium compound or a magnesium compound
  • metallic silicon reduced and melted in the arc furnace is more easily separated when discharged from the furnace and solidifies.
  • higher purity metal silicon can be produced.
  • the purification mechanism is such that metal silicon obtained by reducing and melting the alkaline earth metal compound in an arc furnace is removed from the furnace. Since it is easily separated when discharged and solidified, the purity of the metal silicon is suppressed, and advantageously, the calcium compound acts as a scavenger to capture and remove phosphorus and boron in the metal silicon. It is estimated that the impurity concentration of phosphorus and boron can be reduced.
  • the effect of removing phosphorus, boron and the like is, for example, applied to semiconductors, solar cells, etc. in which impurities such as phosphorus and boron adversely affect the obtained metal silicon (for example, polycrystalline silicon obtained by further refining the silicon). It is effective when used for applications.
  • the silica sand granule having the above-mentioned excellent characteristics can be efficiently produced with low energy by a simple method.
  • the silica sand granule of the present invention is formed from silica sand and has an average particle diameter of 5 mm to 200 mm and a crushing strength of 200 N to 100,000 N.
  • the silica sand granule of the present invention has a crushing strength of 200 N or more while mainly containing silica sand.
  • the crushing strength is less than 200 N, the strength as a substitute for silica is insufficient, and, for example, in a raw material layer of an arc furnace in metal silicon production, there is a risk of collapsing due to a load from the top due to the deposition of the raw material. I can't.
  • the range of the crushing strength is preferably 500 N to 50,000 N, more preferably 1,000 N to 50,000 N, and preferably 1,000 N to 10,000 N. Also good.
  • the average particle size of the silica sand granule of the present invention is 5 mm to 200 mm. If the average particle size is less than 5 mm, a sufficient space for the gas to pass through the raw material layer in the arc furnace cannot be secured. It is disadvantageous in terms of cost and productivity to produce a granulated product.
  • the average particle diameter is preferably 5 mm to 150 mm, more preferably 30 mm to 150 mm, and still more preferably 50 mm to 150 mm.
  • the average particle size may be preferably 5 mm to 100 mm, more preferably 10 mm to 70 mm, and still more preferably 15 mm to 50 mm.
  • the average particle size of the granulated material of the present invention is a number average particle size obtained by sampling 50 randomly extracted granulated materials and calculating the arithmetic average of the particle sizes.
  • the SiO 2 content is preferably 90% by weight to 99.9% by weight. That is, when the SiO 2 content is less than 90% by weight, an excess of an alkaline earth metal component, for example, a calcium component or a magnesium component, which acts as a binder used as necessary, as described later, and other impurities. For example, when used as a raw material for producing metal silicon, there is a concern that the purity of the obtained metal silicon may be reduced.
  • an alkaline earth metal component for example, a calcium component or a magnesium component
  • organic components such as a resin added as a binder component also remain as impurities. There is. Such an organic component impurity is also considered to be a problem when used as a raw material for producing metal silicon, for example, so it is desirable to consider it as the above-mentioned impurity.
  • an alkaline earth metal compound as described later typically a calcium compound or a magnesium compound
  • the SiO 2 content is preferably 90% by weight or more and 99.9% by weight or less. . A more preferable range of the SiO 2 content is 94% by weight to 99.5% by weight.
  • the silica sand granule of the present invention contains alkali metal atoms derived from impurities contained in the raw material to some extent, cristobaliteization progresses during the heat treatment described later, resulting from a density difference.
  • the granulated body itself tends to self-destruct due to expansion. Therefore, the ratio of alkali metal atoms to Si atoms (M 1 / Si) contained in the silica sand granule is preferably less than 0.01.
  • the method for producing a silica sand granule according to the present invention is characterized in that silica sand is molded and granulated.
  • the silica sand used in the above production method of the present invention is not particularly limited as long as the silica sand can be molded. However, considering that the silica sand granule obtained by the present invention can typically be used as a raw material for metal silicon, the silica sand
  • the SiO 2 content is preferably 97% by weight or more, particularly preferably 98% or more, more preferably 99% by weight or more, and further preferably 99.5% by weight or more.
  • the average particle size of the silica sand is preferably 1000 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 150 ⁇ m or less.
  • the average particle size of the silica sand is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 50 ⁇ m or more.
  • the average particle size of the silica sand is particularly preferably adjusted by pulverization or the like so as to be preferably 1 ⁇ m to 200 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m.
  • silica sand particle size is reduced, silanol groups on the particle surface increase, and the interparticle bonding force in the granulated body structure tends to increase accordingly.
  • the smaller the average particle size the more energy is required for grinding.
  • the said silica sand can use what has a particle size in the range below 1400 micrometers from a viewpoint of improving granulation property.
  • the use of silica sand having a relative particle amount (weight) of 25% to 70% within a particle size range of less than 75 ⁇ m is due to the action of the binder and a high-strength granule by heat treatment at a low temperature. Is particularly preferable.
  • the particle size of the silica sand combined with the above-mentioned small particle size particles is not particularly limited, but as a raw material silica sand, from the viewpoint of being able to use uncrushed or lightly crushed silica sand, A particle having a relative particle amount in the range of 150 ⁇ m or more and less than 1400 ⁇ m is preferably 10% to 50%.
  • the total relative particle amount of the fine silica sand and the silica sands having a particle size of 150 ⁇ m or more and less than 1400 ⁇ m is more preferably 60% or more, particularly 70% or more.
  • the silica sand whose average particle diameter is adjusted to 200 ⁇ m or less, more preferably 150 ⁇ m or less by pulverization can also exhibit high strength.
  • the average particle diameter of silica sand is a median diameter determined on a volume basis determined by laser diffraction / scattering particle size analysis measurement.
  • the relative particle amount and the particle size distribution of the silica sand were determined with a sieve as shown in the examples.
  • the pulverization of the silica sand can be carried out using a known pulverizer.
  • the pulverizer include a screw mill described in Tables 1 and 10 on pages 503 to 505 of the powder engineering manual (edited by the Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun).
  • Powder layer striking crushers such as stamp mills, high speed rotary impact crushers such as disc mills, pin mills, screen mills, hammer mills, centrifugal classification mills, roll rolling crushers such as roller mills, ball mills, vibrations Ball mills such as ball mills and planetary pulverizers; tower pulverizers, stirred tank pulverizers, flow-tube pulverizers, annular pulverizers and other medium agitation pulverizers, and jet pulverizers.
  • a pulverizer that requires less energy for pulverization and contains fewer impurities during pulverization is preferable.
  • Examples of such a pulverizer include a medium agitating pulverizer, a ball ball mill such as a vibration ball mill, a rotary ball mill, and a planetary pulverizer, and a roll rolling pulverizer such as a roller mill.
  • the ball medium mill can be finely pulverized and is suitable for mass processing, and the roll-rolling pulverizer has little contamination and a large processing capacity. Therefore, each pulverizer may be used in accordance with the intended pulverized product.
  • the silica sand is preferably molded using an alkaline earth metal compound as a binder.
  • a silica sand granule using such an alkaline earth metal compound as a binder can be produced by bringing an alkaline earth metal compound such as a calcium compound or a magnesium compound into contact with the surface of the silica sand for granulation.
  • Silica sand granule obtained using an alkaline earth metal compound, for example, calcium compound or magnesium compound as a binder is mainly composed of silica sand, and the alkaline earth metal compound is bound by a reaction product of the binder between them. It is a thing.
  • a reaction product is presumed to be an alkaline earth metal silicate, such as calcium silicate, produced by reacting an alkaline earth metal compound with the SiO 2 component on the surface of the silica sand particles.
  • alkaline earth metal compounds calcium compounds, magnesium compounds, and mixtures thereof are preferable in that they are more easily available than other alkaline earth metal compounds in consideration of industrial applications.
  • Examples of the calcium compound include calcium hydroxide, calcium carbonate, calcium oxide, calcium sulfate, and mixtures thereof. These calcium compounds are suitable for increasing the strength of the granulated product obtained by the present invention. Among these, calcium hydroxide, calcium carbonate or a mixture thereof is preferably used. These exhibit alkalinity upon contact with water, increase the reactivity with SiO 2, and contribute to increasing the strength of the granulated body.
  • magnesium compound examples include magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium sulfate, and mixtures thereof.
  • magnesium hydroxide, magnesium carbonate or a mixture thereof is preferably used. These are suitable for increasing the strength of the granulated product obtained by the present invention by exhibiting alkalinity upon contact with water and increasing the reactivity with SiO 2 .
  • the particle size of the alkaline earth metal compound such as calcium compound or magnesium compound is preferably 0.001 ⁇ m to 20 ⁇ m, more preferably 0.001 ⁇ m to 10 ⁇ m.
  • the particle size of the alkaline earth metal compound such as calcium compound or magnesium compound is particularly preferably 0.1 ⁇ m to 20 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m.
  • alkaline earth metal compound particles, typically calcium compound particles or magnesium compound particles are agglomerated, a part or all of the agglomerates can be released in the mixing process described later, so that they can be used without problems. it can.
  • the addition ratio of the alkaline earth metal compound is preferably 0.1 to 5 parts by weight, and 0.5 to 3 parts by weight with respect to 100 parts by weight of silica sand. It is more preferable.
  • Alkaline earth metal compounds, typically calcium compounds or magnesium compounds need only be added in an amount sufficient to cover the surface of the silica sand, and the use of higher amounts may increase the amount of impurities. Moreover, even if the amount of the alkaline earth metal compound used is increased, even if a silica sand granule having a crushing strength exceeding 100,000 N is obtained, not only the quality is excessive, but a great deal of energy is required in the production. It is not industrial because it requires it.
  • silica sand is mainly used.
  • the ratio of alkaline earth metal atoms to Si atoms (M 2 / Si ) Is preferably 0.001 to 0.04, more preferably 0.004 to 0.03.
  • silica sand is mainly used.
  • the ratio of calcium atoms to Si atoms (Ca / Si) is 0. 0.001 to 0.04 is preferable, and 0.004 to 0.03 is preferable.
  • the ratio of the alkaline earth metal atom (for example, calcium atom) to the Si atom is within the above range, the purity of the silica sand granule itself can be increased while maintaining the high strength of the silica sand granule.
  • the means for bringing an alkaline earth metal compound, typically a calcium compound or a magnesium compound, into contact with the surface of the silica sand in the production method of the present invention is not particularly limited, but the alkaline earth metal compound is brought into more uniform contact with the silica sand surface.
  • an alkaline earth metal compound typically a calcium compound or a magnesium compound
  • the above mixing and granulation can be performed at room temperature, and heat treatment can be performed in a dryer or a kiln described below.
  • heat treatment can be performed in a dryer or a kiln described below.
  • granulation and heat treatment can be performed simultaneously.
  • a binder may be added to a mixture of silica sand and an alkaline earth metal compound, typically a calcium compound or magnesium compound, and water in order to improve granulation properties.
  • the binder is preferably a water-soluble organic substance.
  • water-soluble organic substances include, for example, carboxymethyl cellulose (CMC) described in Tables 1, 3, and 4 of the Granulation Handbook (edited by the Japan Powder Industry Association, published on May 30, 1975, Ohmsha).
  • CMC carboxymethyl cellulose
  • PVA Polyvinyl alcohol
  • sugar, dextrose, corn syrup and the like can be mentioned.
  • binders composed of organic substances that can be used include other starches such as dextrin, corn starch, and rice cake; proteins such as glue, casein and soybean protein; natural rubbers such as gum arabic; pitch, Tars such as processed tar and paving tar; asphalts such as straight asphalt and blown asphalt; other thermoplastic resins such as acrylic polymers, polyamide, polyethylene, and other cellulose; urea resin, melamine resin, phenol resin, furan resin And thermosetting resins such as epoxy resin, thermosetting polyester, and thermosetting polyurethane; and elastomers such as neoprene, nitrile rubber, styrene butadiene rubber, butyl rubber, and silicone rubber.
  • starches such as dextrin, corn starch, and rice cake
  • proteins such as glue, casein and soybean protein
  • natural rubbers such as gum arabic
  • pitch Tars such as processed tar and paving tar
  • asphalts such as straight asphalt and blown asphalt
  • other thermoplastic resins
  • usable inorganic binders include cements such as Portland cement, blast furnace cement, silica cement, alumina cement, fly ash, white cement, jet cement; sodium silicate 1 and sodium silicate 2 , Sodium silicate No. 3, sodium silicate No. 4, water glass such as metasilicic acid, and minerals such as clay and bentonite.
  • Granulation of a mixture of silica sand and an alkaline earth metal compound, typically a calcium compound or a magnesium compound, and water is carried out by a known method, for example, granulation manual (edited by the Japan Powder Industry Association, 1975 5). Of the methods classified in Part 1, Sections 1 and 4 (issued on May 30, Ohm), the general methods of rolling molds, compression molds and extrusion molds can be suitably employed. Since each method has a different granulation process, the best mode of each method will be described below.
  • each component of the silica sand, alkaline earth metal compound, typically calcium compound or magnesium compound, water, and optionally added binder is a.
  • each powder of silica sand, alkaline earth metal compound, and binder to be added as necessary can be generally performed using a known mixer.
  • powder engineering handbook powder engineering society, issued on February 28, 1986, Nikkan Kogyo Shimbun
  • horizontal cylindrical mixer shown in Fig. 9.1 on page 610 (with internal blades) , V-type mixers (with stirring blades), double-cone mixers and other container rotating mixers; ribbon mixers, conical screw mixers, high-speed fluid mixers, rotating disk mixers, airflow mixers
  • Examples thereof include a container-fixed mixer such as a mixer and a non-stirring mixer; and a composite mixer such as a stirring mixer (with a vibrator).
  • a kneading machine such as a powder engineering manual (edited by the Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun) 644 Various kneaders listed in Table 13.6 on page can also be used.
  • Rolling type granulation is, for example, drum type granulation described in Part II, Sections 2 and 6 of Granulation Handbook (edited by Japan Powder Industry Association, published on May 30, 1975, Ohmsha). It can be carried out by adopting a machine or a dish type granulator.
  • the dish-type granulator is preferable because the control of the granulation process is easy.
  • the dish shape of the dish-type granulator includes ordinary dish type (basket type), multi-stage dish type, spherical dish type, truncated cone type, etc., but multi-stage dish type, spherical dish type, truncated cone type, etc. Since the granulator automatically classifies the granulated material according to the difference in centrifugal force because the radius of rotation differs along the rotation axis, the granulated material having a uniform particle size is grown from the outer peripheral side of the rotating dish. Suitable for selective removal.
  • the supply of the mixed powder to the granulator is classified, for example, in Table 5.1 on page 567 of Powder Engineering Handbook (Edited by Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun). However, it is preferable to use a vibration feeder, a shaking feeder, a screw feeder, a belt conveyor or the like in terms of easy control of the supply amount. In addition, the supply of the mixed powder may be performed continuously or intermittently.
  • the amount of water is a solid / liquid / gas system classified in Table 8/3 on page 599 of the Powder Engineering Handbook (Edited by the Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun). It is preferable to add so that it becomes a policy area in the structure (hereinafter referred to as a filling area). This is because when the filling area is in the policy area, water intervenes between the particles and acts as a crosslinking liquid. The filling area is affected not only by the ratio of water added to the silica sand but also by the particle size of the silica sand.
  • the average particle diameter is within the above range, 10 to 30 parts by weight of water can be added to 100 parts by weight of the silica sand. It can function as a crosslinking liquid.
  • an alkaline earth metal compound such as a calcium compound or a magnesium compound or a binder is added, the addition amount is preferably 5 to 20 parts by weight with respect to 100 parts by weight of silica sand.
  • the proportion of the intermediate granule having a particle size of 20 mm or more present in the first-stage rolling granulator is preferably 30% by weight or less, more preferably 20% by weight or less, and further preferably 15% by weight. It is preferable to grow the grains so that
  • the first-stage rolling granulator By performing granulation so that the ratio of the intermediate granule of 20 mm or more existing in the first-stage rolling granulator is in the above range, it is supplied to the first-stage rolling granulator. Generation of new nuclei and grain growth occur from the mixture composed of silica sand and binder, and the number of granules can be reliably increased. In order to make the ratio of the granulated body having a particle size of 20 mm or more present in the first stage rolling granulator within the above range, the particles grown from the rolling granulator are selectively and continuously grown. You can take it out.
  • the granulated material that has undergone grain growth is present on the outer peripheral portion of a rotating dish, and therefore, an intermediate granule having a predetermined size existing on the outer peripheral portion may be taken out.
  • the intermediate granule is taken out from the first-stage rolling granulator so that the proportion of the granulated body having a particle size of 20 mm or more present in the rolling granulator becomes lower. It is desirable to do this.
  • the particle size of the granulated body existing in the first stage granulator is taken out in an excessively small state, the granulated grains are grown when further grain growth is performed in the next stage rolling granulator.
  • the intermediate granulated body may be destroyed by the body, and the production efficiency per unit granulator may be reduced.
  • an intermediate granule having an average particle diameter of 10 mm or more, more preferably 15 mm or more, and further preferably 20 mm or more from the first stage rolling granulator it is desirable to take out an intermediate granule having an average particle diameter of 10 mm or more, more preferably 15 mm or more, and further preferably 20 mm or more from the first stage rolling granulator.
  • the particle size of the intermediate granule taken out from the first-stage rolling granulator is too large, the ratio of the granulated body of 20 mm or more in the granulator tends to exceed the above range.
  • the condition for taking out the granulated body of the specific size from the first stage rolling granulator is that the ratio of the granulated body of 20 mm or more is within the above range, preferably the average particle size of the intermediate granulated body is the above What is necessary is just to set beforehand extraction conditions, for example, the inclination of a cone of a rolling granulator, a rotation speed, etc. so that it may become a range by experiment.
  • the intermediate granule taken out from the first-stage rolling granulator is supplied to the subsequent-stage rolling granulator, and further, silica sand and a binder are added to promote grain growth.
  • a quartz sand granule having a desired average particle diameter for example, an average particle diameter of 20 mm or more, preferably 30 mm to 200 mm, more preferably 30 mm to 100 mm can be obtained.
  • the handling property tends to be further improved, and there is a sufficient gap for the gas to pass through the raw material layer made of this silica sand granule in the arc furnace. It tends to be secured.
  • the average particle size of the silica sand granule is 200 mm or less, it is more advantageous in terms of cost and productivity to produce the granule.
  • the amount of water is the moisture absorption area in the filling area classified in Table 8.3 on page 599 of the Powder Engineering Handbook (Edited by the Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun). It is preferable to add so that it becomes. If the average particle size is within the above-mentioned range, it is preferable to add 1 to 20 parts by weight of water to 100 parts by weight of silica sand because the strength after molding is increased. In addition, when the binder is added, the addition amount is preferably 5 to 20 parts by weight with respect to 100 parts by weight of silica sand.
  • silica sand, alkaline earth metal compound, typically calcium or magnesium compound, water, and optionally added binder is the same as in the case of the rolling granulation described above. (The Society of Physical Engineering, published on February 28, 1986, Nikkan Kogyo Shimbun)) It can be carried out using the mixer shown in FIG. 9.1 on page 610.
  • a cylinder is filled with powder, tableting compressed by a piston, and briquetting compressing powder between two rotating rolls.
  • a granulated body can be produced using any of these methods.
  • a granulator a single tableting machine described in Part II, 4/5 of Granulation Handbook (Edited by Japan Powder Industry Association, published on May 30, 1975, Ohmsha); 1 point Examples of the rotary tableting machine include a compression type machine, a multipoint compression type machine, a multistage compression type machine, and an inclined roll type machine, and the briquette machine described in Sections 4 and 6 above.
  • the mixed powder can be supplied using a vibration feeder, a shaking feeder, a screw feeder, or the like as in the case of the rolling granulation.
  • Extrusion mold granulation Since extrusion pressure is applied in extrusion mold granulation, the amount of water is classified in Table 8.3 on page 599 of Powder Engineering Handbook (Edited by the Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun). It is preferable to add so as to be a suspended region in the filled region. If the average particle size is within the above-mentioned range, it is preferable to add 5 to 25 parts by weight of water to 100 parts by weight of silica sand since the strength after molding increases. In addition, when the binder is added, the addition amount is preferably 3 to 15 parts by weight with respect to 100 parts by weight of silica sand.
  • Extrusion mold granulation is an extruding granulator classified into, for example, Part II of the Granulation Handbook (edited by the Japan Powder Industry Association, published on May 30, 1975, Ohmsha), Tables 2.3.1. Can be implemented. Specifically, screw type extrusion granulators such as pre-extrusion type and vacuum extrusion type; cylindrical die horizontal granulator, cylindrical die vertical granulator, disc type die horizontal granulator, etc.
  • Examples thereof include a roll-type extrusion granulator; a blade-type extrusion granulator such as an oscillating granulator; a self-molding extrusion granulator such as a gear-type granulator; a ram-type extrusion granulator.
  • the mixed powder can be supplied using a vibration feeder, a shaking feeder, a screw feeder, or the like as in the case of the rolling granulation.
  • the granulated body obtained by the above granulation method is preferably subjected to a heat treatment in order to further increase the strength.
  • the heat treatment temperature is preferably a temperature at which the silica sand granule is not less than the temperature at which the desired strength is exhibited and the silica sand does not melt.
  • the said heat processing temperature is 700 degreeC or more, for example, Preferably it is 1000 degreeC or more.
  • the heat treatment temperature is preferably 1600 ° C. or lower, more preferably 1300 ° C. or lower, and a temperature higher than that is economically disadvantageous.
  • this heat processing temperature can be lowered more.
  • the heat treatment temperature when the alkaline earth metal compound is used in combination may be, for example, 50 ° C. or higher. However, when water is further used in the production of the granulated body, the temperature is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of efficiently removing water. Therefore, the heat treatment temperature may be appropriately determined in the range of 50 to 1600 ° C. according to the composition of the granulated body obtained by the granulation method.
  • Examples of the apparatus used for the heat treatment include a kiln described in Section 5.1 of the ceramics operation (Ceramics Reading Variety Committee, issued September 20, 1973, Ceramics Association). Specifically, as such a kiln, a flame flame corner kiln, a flame flame type round kiln, a shuttle kiln, a bell kiln discontinuous kiln; a ring kiln, a continuous chamber kiln, a continuous kiln of a tunnel kiln; a rotary kiln; An electric furnace such as a resistance furnace may be mentioned.
  • a suitable apparatus used for drying for example, a box-type dryer, a rotating machine, which is classified in 591 page of Powder Engineering Handbook (Edited by Powder Engineering Society, published on February 28, 1986, Nikkan Kogyo Shimbun) Examples include dryers.
  • the atmosphere for the heat treatment and drying may be an inert gas such as nitrogen, but may be air.
  • a known drying device or the like can be used as the heat treatment device. In this case, drying and heat treatment can be performed simultaneously.
  • the silica sand granule obtained by the production method of the present invention can be used for production of metal silicon, ferrosilicon, and silicon carbide, and is particularly suitably used for production of metal silicon by an arc furnace.
  • a silica sand granule which is a silicon source
  • silica stone which is a silicon source
  • charcoal, coke, coal, wood chips, etc. are mixed as a reducing material in an arc furnace.
  • a method of reducing and melting is mentioned.
  • the arc furnace is thoroughly mixed so as not to segregate, and the required amount is charged.
  • the tip of the electrode reaches the highest temperature due to arc discharge, and the silicon source is reduced by energization so that the ultimate temperature is 1900 ° C. to 2000 ° C., and the metal silicon melt accumulates at the bottom of the furnace.
  • the metal silicon melt collected at the bottom of the arc furnace is extracted into a ladle by opening the spout with oxygen gas or the like.
  • impurities such as calcium compounds are separated as slag by the difference in specific gravity.
  • a metallic silicon mass is obtained.
  • the method for producing the metal silicon includes a step of forming silica sand to produce a silica sand granule having an average particle diameter of 5 mm to 200 mm and a crushing strength of 200 N to 100,000 N, and the silica sand granule. Also preferred is an aspect in which the step of supplying the arc furnace as at least a part of the silicon source to perform the reduction reaction is integrated.
  • the former requires adding a predetermined amount of iron source so as to have a desired composition.
  • the reducing material is made of carbon. A large amount is added so that the molar equivalent is 3 times or more that of silica.
  • the heating temperature also needs to be adjusted according to the object.
  • the crushing strength (N) was measured with an electric universal compression tester (MIS-225-1-16, manufactured by MARUI) having a maximum pressurization weight of 100 kN. A columnar granule was erected and placed in a compressor, and loaded in the vertical direction. The load was set to a speed at which 1% of compressive strain was generated per minute.
  • MIS-225-1-16 electric universal compression tester
  • the weight of the particles passed through the 75 ⁇ m sieve and the weight of the particles passing through the 150 ⁇ m sieve and not passing through the 75 ⁇ m sieve was measured, and the weight was measured as a ratio (% by weight) when the whole was 100% by weight.
  • Example 1 Silica sand (average particle size: 245 ⁇ m, SiO 2 content: 99.4 wt%, Na 2 O content: 0.0 wt%) was pulverized to an average particle size of 130 ⁇ m with a planetary ball mill. To 100 parts by weight of this silica sand, 1.0 part by weight of calcium hydroxide (special grade of Wako Pure Chemicals) and 16.7 parts by weight of water were added and mixed well in a mortar. This mixture was transferred to a mold having an inner diameter of 20 mm and granulated under pressure at a pressure of about 6 MPa. The columnar granule taken out from the mold was dried at 150 ° C. in a blower dryer.
  • calcium hydroxide special grade of Wako Pure Chemicals
  • the weight of the obtained cylindrical granule was weighed, and the diameter and height were measured. And the average particle diameter and apparent density of the granulated body were calculated from these values. Furthermore, after measuring the SiO 2 content by elemental analysis, the crushing strength was evaluated. The results are summarized in Table 1.
  • Example 2-5 In addition to the 150 ° C. heat treatment of Example 1, a granulated body was obtained in exactly the same manner as in Example 1 except that the heat treatment was carried out in air in an electric furnace at the temperature shown in Table 1. The obtained granule was subjected to the same measurement as in Example 1. The results of various measurements are summarized in Table 1.
  • Example 6 and 7 A granulated material was obtained in exactly the same manner as in Example 3 except that the addition ratio of calcium hydroxide was changed as shown in Table 1. The results of various measurements are summarized in Table 1.
  • Example 8 Pressure granulation was performed in the same manner as in Example 1 using silica sand ground to an average particle size of 7 ⁇ m with a planetary ball mill. This cylindrical granule was subjected to various measurements similar to those in Example 1 by heat treatment only at 150 ° C. in a blower dryer. The results are summarized in Table 1.
  • Example 9-12 In addition to the heat treatment at 150 ° C. in Example 8, a granulated product was obtained in exactly the same manner as in Example 8, except that the heat treatment was performed in air in an electric furnace at the temperature shown in Table 1. The results of various measurements are summarized in Table 1.
  • Example 13 A granulated product was obtained in exactly the same manner as in Example 9, except that the addition ratio of calcium hydroxide was changed to 0.1 parts by weight as shown in Table 1. The results of various measurements are summarized in Table 1.
  • Comparative Example 4 A granulated body was obtained in the same manner as in Example 9 except that the calcium compound was not added. The results of various measurements are summarized in Table 1.
  • Example 14 Granules that were not pulverized by a planetary ball mill, that is, heat treated at 1500 ° C. in exactly the same manner as in Example 5 except that silica sand (average particle size 245 ⁇ m, SiO 2 content 99.4 wt%) was used. Got. The results of various measurements are summarized in Table 1.
  • Example 15 A granulated product was obtained in exactly the same manner as in Example 14, except that the addition ratio of calcium hydroxide was changed to 5.0 parts by weight as shown in Table 1. The results of various measurements are summarized in Table 1.
  • Comparative Example 5 A granulated body was obtained in the same manner as in Example 14 except that the calcium compound was not added. The results of various measurements are summarized in Table 1.
  • Example 16 Silica sand (average particle size 245 ⁇ m, SiO 2 content 99.4 wt%, Na 2 O content 0.0 wt%) was pulverized to an average particle size of 138 ⁇ m with a planetary ball mill. To 100 parts by weight of this silica sand, 1.4 parts by weight of calcium carbonate (special grade of Wako Pure Chemicals) and 20.8 parts by weight of water were added and mixed well in a mortar. This mixture was transferred to a mold having an inner diameter of 20 mm and granulated under pressure at a pressure of about 6 MPa. The columnar granule taken out from the mold was dried at 150 ° C. in a blower dryer, and subsequently heat-treated at 1100 ° C.
  • calcium carbonate special grade of Wako Pure Chemicals
  • Example 17 Granules were obtained in exactly the same manner as in Example 17 except that the heat treatment temperature was changed to 1300 ° C. as shown in Table 1. The results of various measurements are summarized in Table 1.
  • Example 18 Evaluation was performed in the same manner as in Example 3 except that the binder was 1.8 parts by weight of calcium sulfate. The results are summarized in Table 2.
  • Example 19 Evaluation was performed in the same manner as in Example 4 except that the binder was changed to 1.8 parts by weight of calcium sulfate. The results are summarized in Table 2.
  • Example 20 Evaluation was performed in the same manner as in Example 3 except that the binder was changed to 0.8 parts by weight of magnesium hydroxide. The results are summarized in Table 2.
  • Example 21 Evaluation was performed in the same manner as in Example 4 except that 0.8 parts by weight of magnesium hydroxide was used as the binder. The results are summarized in Table 2.
  • Example 24 Evaluation was performed in the same manner as in Example 3 except that the silica sand used was silica sand (average particle size 252 ⁇ m, SiO 2 content 98.2 wt%, Na 2 O content 1.5 wt%). The results are summarized in Table 3.
  • Examples 25-33 Silica sand (average particle size 245 ⁇ m, SiO 2 content 99.4 wt%, Na 2 O content 0.0 wt%) was pulverized to an average particle size of 18 ⁇ m with a planetary ball mill. It was mixed with unground crushed silica sand at a predetermined ratio and evaluated. The results are shown in Table 4.
  • Example 34 The silica sand granulate produced in Example 4 and calcined coke having an average particle diameter of 5 mm were mixed at a weight ratio of 2: 1, and a total of 30 kg of raw materials were used in an ER type arc furnace (manufactured by Ando Kogyosho). Heat treatment was performed. The internal temperature during operation was measured with a radiation thermometer and operated at 2000 ° C. for 6 hours. After completion of heating, cooling was performed for 16 hours, and a sample was taken out. 5 kg of high-purity metallic silicon lump was obtained at the bottom of the sample.
  • silica sand granule of the present invention can be effectively used for the production of metallic silicon, silicon alloys such as ferrosilicon, and silicon carbide as an alternative to silica stone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un corps granulé de sable siliceux qui présente une taille et une résistance suffisante pour être traité de la même manière qu'une pierre siliceuse, et un procédé efficace de fabrication du corps granulé, ledit corps granulé permettant de remplacer la pierre siliceuse qui est généralement utilisée en tant que matériau lorsque du silicium métallurgique est fabriqué. Le corps granulé de sable siliceux est caractérisé en ce que le sable siliceux est façonné en utilisant un composé de calcium en tant qu'agent de liaison, et le corps granulé a un diamètre de particule moyen de 5 à 100 mm et une résistance à l'écrasement de 200 à 100 000 N. Le corps granulé de sable siliceux peut être obtenu par mise en contact du composé de calcium avec la surface du sable siliceux pour la granulation.
PCT/JP2011/074898 2010-11-02 2011-10-28 Corps granulé de sable siliceux et son procédé de fabrication Ceased WO2012060285A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180052701.4A CN103201220B (zh) 2010-11-02 2011-10-28 硅砂造粒体及其制造方法
JP2012541829A JP5875523B2 (ja) 2010-11-02 2011-10-28 珪砂造粒体およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-246570 2010-11-02
JP2010246570 2010-11-02

Publications (1)

Publication Number Publication Date
WO2012060285A1 true WO2012060285A1 (fr) 2012-05-10

Family

ID=46024399

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/074898 Ceased WO2012060285A1 (fr) 2010-11-02 2011-10-28 Corps granulé de sable siliceux et son procédé de fabrication

Country Status (4)

Country Link
JP (1) JP5875523B2 (fr)
CN (1) CN103201220B (fr)
MY (1) MY161350A (fr)
WO (1) WO2012060285A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015098429A (ja) * 2013-10-16 2015-05-28 株式会社トクヤマ 珪砂造粒体の製造方法
WO2018145953A1 (fr) * 2017-02-13 2018-08-16 Sibelco Nederland N.V. Grains comprenant de la silice et méthodes de formation de grains comprenant de la silice
WO2021228371A1 (fr) * 2020-05-12 2021-11-18 Wacker Chemie Ag Procédé de production d'agglomérats contenant du dioxyde de silicium
WO2021228370A1 (fr) * 2020-05-12 2021-11-18 Wacker Chemie Ag Procédé de production de silicium technique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111268685B (zh) * 2020-03-09 2022-10-28 邓咏兰 一种气相二氧化硅的合成工艺
CN113231192B (zh) * 2021-06-16 2022-05-27 江西省矿产资源保障服务中心 一种植硅体矿中二氧化硅的选矿方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1095607A (ja) * 1996-09-18 1998-04-14 Denki Kagaku Kogyo Kk シリカ質フィラー及びその製法
JPH10297915A (ja) * 1997-04-28 1998-11-10 Asahi Glass Co Ltd シリカ系微小球状無孔質体及びその製造方法
JPH11343385A (ja) * 1998-05-29 1999-12-14 Kyocera Corp 耐トラッキング性フェノール樹脂組成物およびこれを用いた安全機器部品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06170206A (ja) * 1992-12-02 1994-06-21 Tosoh Corp 球状造粒方法
JP5399017B2 (ja) * 2008-07-24 2014-01-29 学校法人 龍谷大学 中空無機粒子とその製造方法、着色剤および塗料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1095607A (ja) * 1996-09-18 1998-04-14 Denki Kagaku Kogyo Kk シリカ質フィラー及びその製法
JPH10297915A (ja) * 1997-04-28 1998-11-10 Asahi Glass Co Ltd シリカ系微小球状無孔質体及びその製造方法
JPH11343385A (ja) * 1998-05-29 1999-12-14 Kyocera Corp 耐トラッキング性フェノール樹脂組成物およびこれを用いた安全機器部品

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015098429A (ja) * 2013-10-16 2015-05-28 株式会社トクヤマ 珪砂造粒体の製造方法
WO2018145953A1 (fr) * 2017-02-13 2018-08-16 Sibelco Nederland N.V. Grains comprenant de la silice et méthodes de formation de grains comprenant de la silice
WO2021228371A1 (fr) * 2020-05-12 2021-11-18 Wacker Chemie Ag Procédé de production d'agglomérats contenant du dioxyde de silicium
WO2021228370A1 (fr) * 2020-05-12 2021-11-18 Wacker Chemie Ag Procédé de production de silicium technique

Also Published As

Publication number Publication date
MY161350A (en) 2017-04-14
CN103201220A (zh) 2013-07-10
CN103201220B (zh) 2015-11-25
JP5875523B2 (ja) 2016-03-02
JPWO2012060285A1 (ja) 2014-05-12

Similar Documents

Publication Publication Date Title
JP5875523B2 (ja) 珪砂造粒体およびその製造方法
JP2013082588A (ja) 金属ケイ素の製造方法
CN101725206B (zh) 一种铁矿尾砂墙体蒸压砖及其制备方法
CN103502160A (zh) 用于制备玄武岩纤维的初始材料的预处理
JP5644955B2 (ja) 焼結原料の造粒方法
CN101194028A (zh) 一种处理冶金炉渣的方法
CN117813271A (zh) 加速碳酸化处理及其在再生混凝土废物和工业废气的处理中的实施
EA030463B1 (ru) Способ переработки отходов оптических волокон
CN1034148A (zh) 把垃圾转变成一种颗粒形状材料的方法
JP5877755B2 (ja) 珪砂造粒体およびその製造方法
CN100427429C (zh) 尖晶石系复合氧化物烧制体及其制造方法
JP7252454B2 (ja) 高炉用非焼成塊成鉱の製造方法
EP2980232B1 (fr) Procédé permettant de recycler des sous-produits contenant du fer rejetés par un procédé de fabrication de fer à base de charbon, système utilisé pour ce dernier et système d'agglomération de fer spongieux
CN104080550B (zh) 从包含有机物的废弃材料中获取能量的方法
JPS6081294A (ja) 製鋼炉用コークス団鉱の製造方法
JP2006255609A (ja) 焼結物の製造方法及び焼結物
JP4362494B2 (ja) 粉状スラグの造粒方法
JP6198272B2 (ja) 珪砂造粒体の製造方法
JP2013224234A (ja) 珪砂造粒体およびその製造方法
CN112384474B (zh) 用于生产含硅金属团块的方法
JPH11106821A (ja) 製鋼用塊成原料の製造方法
KR20090125511A (ko) 바인더 및 그 제조방법
JP2018002563A (ja) 水硬性石灰及びその製造方法
JP2013006711A (ja) 珪砂造粒体の製造方法
KR100416474B1 (ko) 암석미분 슬러지를 이용한 역청 포장용 채움재 및 그 제조방법과 이를 이용하여 제조되는 시멘트몰탈의 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11837935

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012541829

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11837935

Country of ref document: EP

Kind code of ref document: A1