[go: up one dir, main page]

EP2334597A1 - Procédé de fabrication de carbure de silicium de haute pureté à partir d'hydrates de carbone et d'oxyde de silicium par calcination - Google Patents

Procédé de fabrication de carbure de silicium de haute pureté à partir d'hydrates de carbone et d'oxyde de silicium par calcination

Info

Publication number
EP2334597A1
EP2334597A1 EP09736162A EP09736162A EP2334597A1 EP 2334597 A1 EP2334597 A1 EP 2334597A1 EP 09736162 A EP09736162 A EP 09736162A EP 09736162 A EP09736162 A EP 09736162A EP 2334597 A1 EP2334597 A1 EP 2334597A1
Authority
EP
European Patent Office
Prior art keywords
silicon carbide
silica
ppm
silicon
carbon
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.)
Withdrawn
Application number
EP09736162A
Other languages
German (de)
English (en)
Inventor
Jürgen Erwin LANG
Hartwig Rauleder
Ekkehard MÜH
Alfons Karl
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2334597A1 publication Critical patent/EP2334597A1/fr
Withdrawn legal-status Critical Current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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C01B32/963—Preparation from compounds containing silicon
    • C01B32/97—Preparation from SiO or SiO2
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/573—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a method for producing silicon carbide and / or silicon carbide-graphite particles by reacting silica and a
  • Carbon source comprising a carbohydrate, in particular of carbohydrates, at elevated temperature, in particular a technical process for the preparation of
  • Silicon carbide or for the preparation of compositions containing silicon carbide and the isolation of the reaction products. Furthermore, the invention relates to a high-purity silicon carbide, compositions containing it, the use as a catalyst and in the production of electrodes and other articles.
  • Silicon carbide or in other spellings silicon carbide or silicon carbide, has the common name carborundum.
  • Silicon carbide is a chemical compound of silicon and carbon belonging to the group of carbides and having the chemical formula SiC. Due to its hardness and high melting point, silicon carbide is used as an abrasive (carborundum) and as a component for refractories. Large quantities of less pure SiC are used as metallurgical SiC for alloying cast iron with silicon and carbon. It also finds application as an insulator of fuel elements in high-temperature nuclear reactors or in heat tiles in space technology. Likewise, it is used in admixture with other materials as a hard-concrete aggregate to make industrial flooring resistant to abrasion. Rings on high quality fishing rods are also made of SiC. In engineering ceramics, SiC is one of the most commonly used materials because of its many properties - especially its hardness.
  • silicon carbide powder is obtained by gas phase deposition of methylsilane with argon as the carrier gas at 1000 to 1800 0 C AlSb et a-silicon carbide powder.
  • the purity of metallurgical impurities, among other impurities, should be below 1000 ppm (process for the preparation of silicon carbide powders from the gas phase, W. Böcker et al., Ber. Dt., Keram., Ges., 55 (1978), no. 4, 233-237).
  • DE 25 18 950 teaches the production of silicon carbide by vapor phase reaction of a mixture of silicon halide, a boron halide and a hydrocarbon, such as toluene, in a plasma jet reaction zone.
  • the obtained ⁇ -silicon carbide has a content of 0.2 to 1 wt .-% boron.
  • a disadvantage of the prior art processes are the high raw material costs and / or the complicated handling of the hydrolysis-sensitive and / or self-destructive raw materials for producing pure silicon carbide.
  • Object of the present invention was to produce high-purity silicon carbide from significantly cheaper raw materials, and overcome the listed process disadvantages.
  • a high-purity silicon carbide in a carbon matrix and / or silicon carbide in a silica matrix and / or a silicon carbide silicon carbide and / or silicon dioxide in a composition can be produced inexpensively.
  • the silicon carbide is produced in a carbon matrix.
  • a silicon carbide particle having an outer carbon matrix, preferably having a graphite matrix on the inner and / or outer surface of the particles can be obtained. Thereafter, it can be easily recovered by passive oxidation with air in pure form, especially by removing the carbon by oxidation.
  • the silicon carbide may be further purified and / or precipitated by sublimation at high temperatures and optionally under high vacuum. Silicon carbide can be sublimated at temperatures around 2800 0 C.
  • the object is achieved by the method for producing silicon carbide by reacting silica, in particular silica and / or silica, and a carbon source comprising a carbohydrate at elevated temperature, in particular by pyrolysis and calcination.
  • a technical and industrial process for the production of silicon carbide is provided.
  • the reaction can be carried out at temperatures from 150 ° C., preferably from 400 to 3000 ° C., in a first pyrolysis step
  • the pyrolysis and calcination can be carried out successively in one process or in two separate steps.
  • the pyrolysis process product may be packaged as a composition and later used by a processor for the production of silicon carbide or silicon.
  • the reaction of silica and the carbon source comprising a carbohydrate can begin with a low temperature range, for example from 150 0 C, preferably at 400 0 C and increased continuously or stepwise, for example up to 1800 0 C or higher, in particular 1900 0 C.
  • This procedure can be favorable for removing the process gases formed.
  • the reaction can be carried out directly at high temperatures, in particular at temperatures above 1400 0 C to 3000 0 C, preferably between 1400 0 C and 1800 0 C, more preferably between 1450 and below about 1600 0 C.
  • the reaction is preferably conducted at temperatures below the decomposition temperature, in particular below 1800 0 C, preferably u nder 1600 0 C du RChG EFÜ h rt.
  • the invented insulated process product is high purity silicon carbide as defined below.
  • the recovery of silicon carbide in pure form can be carried out by post-treatment of the silicon carbide in a carbon matrix by passive oxidation with oxygen, air and / or NO x * H 2 O, for example at temperatures around 800 0 C.
  • oxygen air and / or NO x * H 2 O
  • carbon or the Carbon-containing matrix are oxidized and removed as a process gas from the system, for example as carbon monoxide.
  • the purified silicon carbide then optionally also comprises one or more silicon oxide matrices or optionally small amounts of silicon.
  • the silicon carbide itself is relatively resistant to oxidation at temperatures above 800 ° C. against oxygen. In direct contact with oxygen, it forms a passivating layer of silicon dioxide (SiO 2 , "passive oxidation") at temperatures above about 1600 ° C. and simultaneous oxygen deficiency (partial pressure below about 50 mbar). does not form the glassy SiO 2, but the gaseous SiO 2; a protective effect is then no longer present, and the SiC is rapidly burned ("active oxidation"). This active oxidation takes place when the free oxygen in the system is used up.
  • a C-based reaction product obtained according to the invention or a reaction product with a carbon matrix, in particular a pyrolysis product contains carbon, in particular in the form of coke and / or carbon black, and silica and optionally also other carbon forms, such as graphite, and is particularly poor Impurities, such as the elements boron, phosphorus, arsenic, iron and aluminum and their compounds.
  • the pyrolysis and / or calcination product of the present invention can be advantageously used as a reducing agent in the production of silicon carbide from sugar coke and silicic acid at high temperature.
  • the carbon- or graphite-containing pyrolysis and / or calcination product according to the invention can be used on account of its conductivity properties for the production of electrodes, for example in an arc reactor, or as a catalyst and raw material for silicon production, in particular for solar sicilium production.
  • the high-purity silicon carbide can be used as an energy source and / or as an additive for the production of high-purity steels.
  • the present invention therefore provides a process for producing silicon carbide by reacting silica, in particular silicon dioxide, and a carbon source comprising at least one carbohydrate at elevated temperature and, in particular, the isolation of the silicon carbide.
  • the invention also provides a silicon carbide or a composition containing silicon carbide obtainable by this process as well as the pyrolysis and / or calcination product obtainable by the process according to the invention, and in particular their isolation.
  • According to the invention is a technical, preferably a large-scale process for industrial implementation or industrial pyrolysis and / or calcination of a carbohydrate or Carbohydrate mixture at elevated temperature with the addition of silica and their conversion.
  • a silicon carbide is optionally isolated with a carbon matrix and / or silica matrix or a matrix comprising carbon and / or silicon oxide, in particular it is isolated as a product, optionally containing silicon.
  • the isolated silicon carbide can have any crystalline phase, for example an ⁇ or ⁇ silicon carbide phase or mixtures of these or further silicon carbide phases.
  • more than 150 polytype phases are known of silicon carbide.
  • the silicon carbide obtained via the process according to the invention preferably contains no or only a small amount of silicon or is infiltrated only to a small extent with silicon, in particular in the range of 0.001 and 60% by weight, preferably between 0.01 and 50% by weight.
  • the silicon carbide contains said matrices and optionally silicon.
  • no silicon is formed in the calcining or high-temperature reaction according to the invention because there is no agglomeration of the particles and, as a rule, no formation of a melt. Silicon would form only with the formation of a melt.
  • the further silicon content can be controlled by silicon infiltration.
  • a high-purity silicon carbide is preferably a corresponding silicon carbide with a Passivation layer comprising silicon dioxide.
  • high purity silicon carbide is considered to be a high purity composition containing or consisting of silicon carbide, carbon, silicon oxide and optionally small amounts of silicon, the high purity silicon carbide or high purity composition having in particular an impurity profile of boron and phosphorus below 100 ppm boron.
  • the impurity profile of the high-purity silicon carbide with boron, phosphorus, arsenic, aluminum, iron, sodium, potassium, nickel, chromium is preferably below 5 ppm to 0.01 ppt (wt) for each element, in particular below 2.5 ppm to 0, 1 ppt.
  • the silicon carbide obtained by the process according to the invention if appropriate with carbon and / or SiyO z matrices, particularly preferably has the following content: Boron below 100 ppm, preferably between 10 ppm and 0.001 ppt, particularly preferably from 5 ppm to 0.001 ppt or below 0.5 ppm to 0.001 ppt and / or phosphorus below 200 ppm, preferably between 20 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or from below 0.5 ppm to 0.001 ppt and / or sodium below 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt, or from less than 1 ppm to 0.001 ppt and / or
  • Aluminum below 100 ppm preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or from below 1 ppm to 0.001 ppt and / or iron below 100 ppm, preferably between 10 ppm and 0.001 ppt, particularly preferably of 5 ppm to 0.001 ppt or from below 0.5 ppm to 0.001 ppt and / or chromium below 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or from below 0.5 ppm to 0.001 ppt and / or Nickel below 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or from below 0.5 ppm to 0.001 ppt and / or potassium below 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably from 5 pp
  • Zirconia below 100 ppm preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or from below 0.5 ppm to 0.001 ppt and / or titanium below 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or less than 0.5 ppm to 0.001 ppt and / or calcium less than 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably from 5 ppm to 0.001 ppt or less than 0.5 ppm to 0.001 ppt and in particular magnesium with less than 100 ppm, preferably between 10 ppm to 0.001 ppt, more preferably between 1 1 ppm and 0.001 ppt and / or copper below 100 ppm, preferably between 10 ppm and 0.001 ppt, more preferably between 2 ppm and 0.001 ppt, and
  • Composition contains or consists of silicon carbide, carbon, silica and optionally small amounts of silicon, the high purity
  • Silicon carbide or the high purity composition in particular Impurity profile of boron, phosphorus, arsenic, aluminum, iron, sodium, potassium, nickel, chromium, sulfur, barium, zirconium, zinc, titanium, calcium, magnesium, copper, chromium, cobalt, zinc, vanadium, manganese and / or lead of below 100 ppm, preferably from below 20 ppm to 0.001 ppt, more preferably between 10 ppm and 0.001 ppt relative to the high purity total composition or the high purity silicon carbide.
  • high-purity silicon carbides or high-purity compositions can be obtained by the reactants, the carbohydrate-containing carbon source and the silicium oxide used, as well as the reactors, reactor components, feed lines, storage containers of the reactants, the reactor lining, casing and optionally added reaction gases or inert gases be used for a necessary purity in the process according to the invention.
  • the high-purity silicon carbide or the high-purity composition as defined above, in particular comprising a content of carbon; for example in the form of coke, carbon black, graphite; and / or silicon oxide, in particular in the form of SiO 2, has an impurity profile with boron and / or phosphorus or with boron and / or phosphorus-containing compounds, which is preferably less than 100 ppm for the element boron, in particular between 10 ppm and 0.001 ppt , and for phosphorus below 200 ppm, in particular between 20 ppm and 0.001 ppt.
  • the content of boron in a silicon carbide is preferably between 7 ppm and 1 ppt, preferably between 6 ppm and 1 ppt, particularly preferably between 5 ppm and 1 ppt or below, or for example between 0.001 ppm and 0.001 ppt, preferably in the range of the analytical detection limit .
  • the content of phosphorus of a silicon carbide should preferably be between 18 ppm and 1 ppt, preferably between 15 ppm and 1 ppt, more preferably between 10 ppm and 1 ppt or below.
  • the content of phosphorus is preferably in the range of the analytical detection limit.
  • the data ppm, ppb and / or ppt are throughout as shares of Weights, in particular in mg / kg, ⁇ g / kg ng / kg or in mg / g, ⁇ g / g or ng / g etc.
  • the actual pyrolysis usually takes place at temperatures below about 800 0 C.
  • the pyrolysis depending on the desired product at atmospheric pressure, in a vacuum or under high pressure are performed. If work is carried out under reduced pressure or low pressure, the process gases can be well removed and usually highly porous, particulate structures are obtained after pyrolysis. Under conditions in the range of normal pressure, the porous, particulate structures are usually more agglomerated.
  • the volatile reaction products may condense on the silica particles and, if appropriate, react with themselves or with reactive groups of the silica.
  • formed decomposition products of carbohydrates such as ketones, aldehydes or alcohols can react with free hydroxyl groups of the silica particles. This significantly reduces the burden on the environment with process gases.
  • the resulting porous pyrolysis products are slightly more agglomerated in this case.
  • pressure and temperature which are freely selectable depending on the desired pyrolysis within wide limits and the exact coordination to each other in the art is known, can also pyrolysis of the carbon source containing at least one carbohydrate in the presence of moisture, in particular residual moisture of the starting materials, or by adding moisture, in the form of condensed water, water vapor or hydrated components, such as SiO 2 * nH 2 O, or other hydrates familiar to those skilled in the art.
  • the presence of moisture in particular has the effect that the carbohydrate is more easily pyrolyzed and that expensive pre-drying of the starting materials can be omitted.
  • the process for the production of silicon carbide by reacting silicon oxide and a carbon source comprising at least one carbohydrate at elevated temperature, in particular at the beginning of the pyrolysis in the presence of moisture, is particularly preferably carried out; if appropriate, moisture is also present during the pyrolysis or is metered in.
  • the calcination step (high temperature step) usually follows pyrolysis directly, but it may be done at a later time, for example, when the pyrolysis product is resold.
  • the temperature ranges of the pyrolysis and calcination step may optionally overlap slightly.
  • the calcination at 1400 to 2000 0 C preferably carried out between 1400 to 1800 0 C. If the pyrolysis is carried out at temperatures below 800 0 C, the calcination step may extend to a temperature range of 800 0 C to about 1800 0 C.
  • high-purity silica spheres in particular quartz glass spheres and / or silicon carbide spheres or generally quartz glass and / or silicon carbide particles can be used in the process.
  • These heat exchangers are preferably used in rotary kilns or in microwave ovens. In microwave ovens, the microwaves can couple into the quartz glass particles and / or silicon carbide particles, so that the particles heat up.
  • the spheres and / or particles are well distributed in the reaction system to allow uniform heat transfer.
  • the impurities in the respective reactants and process products are determined by means of sample digestion methods known to the person skilled in the art, for example by detection in ICP-MS (analytics for the determination of the trace impurity).
  • carbohydrates or saccharides As carbon source comprising at least one carbohydrate, according to the invention carbohydrates or saccharides; or mixtures of carbohydrates or suitable derivatives of carbohydrates used in the process according to the invention.
  • the naturally occurring carbohydrates, anomers of these, invert sugars as well as synthetic carbohydrates can be used.
  • carbohydrates which have been obtained biotechnologically, for example by fermentation can be used.
  • the carbohydrate or derivative is selected from a monosaccharide, disaccharide, oligosaccharide or polysaccharide or a mixture of at least two of said saccharides.
  • the following carbohydrates are particularly preferably used in the process, these are mono-, that is to say aldoses or ketoses, such as trioses, tetroses, Pentoses, hexoses, heptoses, especially glucose and fructose, but corresponding oligomeric and polysaccharides based on said monomers, such as lactose, maltose, sucrose, raffinose - to name but a few, also derivatives of said carbohydrates can be used, as long as they to purity, including cellulose, cellulose derivatives, starch, including amylose and amylopectin, glycogen, glycosans and fructosans, to name but a few polysaccharides.
  • aldoses or ketoses such as trioses, tetroses, Pentoses, hexoses, heptoses, especially glucose and fructose, but corresponding oligomeric and polysaccharides based on said monomers, such as lactose, maltose, sucrose,
  • carbohydrate or carbohydrate component it is also possible to use a mixture of at least two of the abovementioned carbohydrates as carbohydrate or carbohydrate component in the process according to the invention.
  • all carbohydrates, derivatives of carbohydrates and carbohydrate mixtures can be used in the process according to the invention, wherein they preferably have a sufficient purity, in particular with respect to the elements boron, phosphorus and / or aluminum.
  • the said elements as impurity in total should be below 100 ⁇ g / g, in particular below 100 ⁇ g / g to 0.0001 ⁇ g / g, preferably below 10 ⁇ g / g to 0.001 ⁇ g / g, more preferably below 5 ⁇ g / g to 0.01 ⁇ g / g in carbohydrate or mixture.
  • the carbohydrates to be used according to the invention consist of the elements carbon, hydrogen, oxygen and optionally have the said impurity profile.
  • carbohydrates consisting of the elements carbon, hydrogen, oxygen and nitrogen, if appropriate with the aforementioned impurity profile, in the process, if a doped silicon carbide or a silicon carbide with proportions of silicon nitride is to be produced.
  • carbide with amounts of silicon nitride in which case the silicon nitride is not regarded as an impurity in this case, it is also expedient to use chitin in the process.
  • crystalline sugar which is available in economic quantities, a sugar which can be obtained, for example, by crystallization of a solution or from a juice of sugar cane or beets in a manner known per se, ie commercial crystalline sugar, in particular crystalline sugar in food quality.
  • the sugar or carbohydrate can, of course, if the impurity profile is suitable for the process, also generally liquid, as a syrup, in a solid phase, including amorphous, are used in the process. If appropriate, a formulation and / or drying step is then carried out in advance.
  • the sugar may also have been pre-purified in the liquid phase, if appropriate in demineralized water or another suitable solvent or mixture, via ion exchangers in order, if appropriate, to remove special impurities which are less readily separable via crystallization.
  • Suitable ion exchangers are strongly acidic, weakly acidic, amphoteric, neutral or basic ion exchangers. The choice of the correct ion exchanger is familiar to the person skilled in the art as a function of the impurities to be separated off.
  • the sugar can be crystallized, centrifuged and / or dried, or mixed with silica and dried.
  • the crystallization can be carried out by cooling or adding an anti-solvent or other methods known in the art.
  • the separation of the crystalline fractions can be carried out by means of filtration and / or centrifuging.
  • the carbon source containing at least one carbohydrate or the carbohydrate mixture has the following impurity profile: boron below 2 [ ⁇ g / g], phosphorus below 0.5 [ ⁇ g / g] and aluminum below 2 [ ⁇ g / g], preferably less than or equal to 1 [ ⁇ g / g], in particular iron below 60 [ ⁇ g / g], the iron content is preferably below 10 [ ⁇ g / g], more preferably below 5 [ ⁇ g / g].
  • the invention seeks to use carbohydrates, in which the content of impurities such as boron, phosphorus, aluminum and / or arsenic, etc., are below the respective technically possible detection limit.
  • the carbohydrate source comprising at least one carbohydrate, according to the invention, the carbohydrate or carbohydrate mixture, the following impurity profile of boron, phosphorus and aluminum and optionally iron, sodium, potassium, nickel and / or chromium.
  • the contamination with boron (B) is in particular between 5 to 0.000001 ⁇ g / g, preferably 3 to 0.00001 ⁇ g / g, more preferably 2 to 0.00001 ⁇ g / g, according to the invention below 2 to 0.00001 ⁇ g / g
  • the contamination with phosphorus (P) is in particular between 5 to 0.000001 ⁇ g / g, preferably 3 to 0.00001 ⁇ g / g, more preferably below 1 to 0.00001 ⁇ g / g, according to the invention below 0.5 to 0.00001 ug / g.
  • the contamination with iron (Fe) is between 100 to 0.000001 ⁇ g / g, in particular between 55 to 0.00001 ⁇ g / g, preferably 2 to 0.00001 ⁇ g / g, particularly preferred below 1 to 0.00001 ⁇ g / g , According to the invention below 0.5 to 0.00001 ug / g.
  • the contamination with sodium (Na) is in particular between 20 to 0.000001 ⁇ g / g, preferably 15 to 0.00001 ⁇ g / g, more preferably below 12 to 0.00001 ⁇ g / g, according to the invention below 10 to 0.00001 ⁇ g / G.
  • the contamination with potassium (K) is in particular between 30 to 0.000001 ⁇ g / g, preferably 25 to 0.00001 ⁇ g / g, more preferably below 20 to 0.00001 ⁇ g / g, according to the invention below 16 to 0.00001 ⁇ g / G.
  • the contamination with aluminum (AI) is in particular between 4 to 0.000001 ⁇ g / g, preferably 3 to 0.00001 ⁇ g / g, more preferably below 2 to 0.00001 ⁇ g / g, according to the invention under 1, 5 to 0.00001 ug / g.
  • the contamination with nickel (Ni) is in particular between 4 to 0.000001 ⁇ g / g, preferably 3 to 0.00001 ⁇ g / g, more preferably below 2 to 0.00001 ⁇ g / g, according to the invention under 1, 5 to 0.00001 ug / g.
  • the contamination with chromium (Cr) is in particular between 4 to 0.000001 ⁇ g / g, preferably 3 to 0.00001 ⁇ g / g, more preferably below 2 to 0.00001 ⁇ g / g, according to the invention below 1 to 0.00001 ⁇ g / G.
  • a crystalline sugar for example refined sugar
  • a crystalline sugar is mixed with a water-containing silica or a silica sol, dried and used in particulate form in the process.
  • any carbohydrate, especially sugar, invert sugar or syrup may be mixed with a dry, hydrous or aqueous Silica, silica, a silica with a water content or a silica sol or the below-mentioned silica components, optionally be subjected to drying and used as particles, preferably having a particle size of 1 nm to 10 mm in the process.
  • sugar with an average particle size of 1 nm to 10 cm, in particular 10 .mu.m to 1 cm, preferably 100 .mu.m to 0.5 cm is used.
  • sugar can be used with a mean particle size in the micrometer to millimeter range, preferably in the range of 1 micron to 1 mm, more preferably 10 microns to 100 microns.
  • the determination of the particle size can i.a. using sieve analysis, TEM (Transelectron Microscopy), SEM (Atomic Force Electron Microscopy) or Light Microscopy. It can also be a dissolved carbohydrate used as a liquid, syrup, paste, wherein the high-purity solvent evaporates before the pyrolysis. Alternatively, a drying step may be used to recover the solvent.
  • Preferred raw materials as a carbon source are far away from all organic compounds known to the person skilled in the art comprising at least one carbohydrate which meets the purity requirements, for example solutions of carbohydrates.
  • the carbohydrate solution used can also be an aqueous-alcoholic solution or a solution containing tetraethoxysilane (Dynasylan® TEOS) or a tetraalkoxysilane, the solution being evaporated and / or pyrolyzed before the actual pyrolysis.
  • the particle sizes of the individual components are matched to each other.
  • a sol is a colloidal solution in which the solid or liquid substance is dispersed in the finest distribution in a solid, liquid or gaseous medium (see also Römpp Chemie Lexikon).
  • the particle size of the carbon source comprising a carbohydrate and the particle size of the silicon oxide are particularly matched to one another in order to allow a good homogenization of the components and to prevent segregation before or during the process.
  • a porous silica in particular with an inner surface of 0.1 to 800 nrvVg, preferably from 10 to 500 m 2 / g or from 100 to 200 m 2 / g, and in particular with an average particle size of 1 nm and greater or also from 10 nm to 10 mm, in particular silicic acid with high (99.9%) to highest (99.9999%) purity, the content of impurities, such as B, P, As and Al compounds, in sum, advantageously less than 10 ppm by weight with respect to the total composition.
  • the purity is determined by the sample digestion known to the person skilled in the art, for example by detection in ICP-MS (analytics for the determination of trace contamination). Particularly sensitive detection is possible by electron-spin spectrometry.
  • the inner surfaces can be made, for example, using the BET method (DIN ISO 9277, 1995).
  • a preferred mean particle size of the silicon oxide is between 10 nm and 1 mm, in particular between 1 and 500 ⁇ m.
  • the determination of the particle size can ia. by means of TEM (Transelectron Microscopy), SEM (scanning electron microscopy) or light microscopy.
  • silicon oxides are generally all, a silicon oxide-containing compounds and / or minerals into consideration, provided that one for the process and thus have suitable purity for the process product and enter no interfering elements and / or compounds in the process or not burn residue.
  • pure or high purity silica-containing compounds or materials are used in the process.
  • the agglomeration during the pyrolysis may vary depending on the pH of the particle surface.
  • increased agglomeration of the particles is observed by the pyrolysis.
  • silica comprises a silica, in particular a fumed or precipitated silica, preferably a fumed or precipitated silica of high or very high purity.
  • highest purity is understood to mean a silicon oxide, in particular a silicon dioxide, in which the contamination of the silicon oxide with boron and / or phosphorus or boron and / or phosphorus-containing compounds should be below 10 ppm, in particular between 10 ppm and 0.001 ppt, and for phosphorus should be below 20 ppm, in particular between 20 ppm and 0.001 ppt.
  • the content of boron is preferably between 7 ppm and 1 ppt, preferably between 6 ppm and 1 ppt, more preferably between 5 ppm and 1 ppt or below, or for example between 0.001 ppm and 0.001 ppt, preferably in the range of the analytical detection limit.
  • the content of phosphorus of the silicon oxides should preferably be between 18 ppm and 1 ppt, preferably between 15 ppm and 1 ppt, more preferably between 10 ppm and 1 ppt or below.
  • the content of phosphorus is preferably in the range of the analytical detection limit.
  • silicas such as quartz, quartzite and / or silicas prepared by conventional means. These can be those in crystalline modifications occurring silicas, such as moganite (chalcedony), ⁇ -quartz (deep quartz), ß-quartz (high quartz), tridymite, cristobalite, coesite, stishovite or amorphous SiO 2 , in particular, if they meet the purity requirements mentioned. Furthermore, preference is given to using silicic acids, in particular precipitated silicas or silica gels, pyrogenic SiO 2, fumed silica or silica, in the process and / or the composition.
  • Conventional fumed silicas are amorphous SiO 2 powders on average from 5 to 50 nm in diameter and with a specific surface area of 50 to 600 m 2 / g.
  • the abovementioned list is not exhaustive, it is clear to the person skilled in the art that it can also use other sources of silica suitable for the process in the process if the source of silica has a corresponding purity or after its purification.
  • the silicon oxide in particular SiO 2
  • SiO 2 can be pulverulent, granular, porous, foamed, extruded, pressed and / or as a porous glass body optionally together with other additives, in particular together with the carbon source comprising at least one carbohydrate and optionally a binder and / or shaping assistant, submitted and / or used.
  • a powdery, porous silica is used as a shaped body, in particular as extrudate or pressing, particularly preferably together with the carbon source comprising a carbohydrate in an extrudate or pressing, for example in a pellet or briquette.
  • all solid reactants, such as silica, and optionally the carbon source comprising at least one carbohydrate in a form should be used in the process or be in a composition that provides the greatest possible surface area for the reaction to proceed.
  • this particulate mixture is present as a composition or as a kit, in particular packaged.
  • the amounts of starting material as well as the respective ratios of silicon oxide, in particular silicon dioxide and the carbon source comprising at least one carbohydrate, depend on the conditions or requirements known to the person skilled in the art, for example in a subsequent process for silicon production, sintering processes, processes for producing electrode materials or electrodes.
  • the carbohydrate may be used in a weight ratio of carbohydrate to silica, especially silica, in a weight ratio of 1,000 to 0.1 to 1 to 1,000 in terms of total weight.
  • the carbohydrate or the carbohydrate mixture in a weight ratio to the silica, in particular of the silica, from 100: 1 to 1: 100, more preferably from 50: 1 to 1: 5, most preferably from 20: 1 to 1: 2, with Preferred ranges of 2: 1 to 1: 1 used.
  • carbon over the carbohydrate is used in excess in relation to the silicon to be reacted in the silica in the process. If the silicon oxide is used in an expedient embodiment in excess, care must be taken when choosing the ratio that the formation of silicon carbide is not suppressed.
  • the preferred range of moles of carbon, via the carbon source comprising a carbohydrate, to moles of silicon introduced via the silica compound ranges from 100 moles to 1 mole to 1 mole to 100 moles (C to Si) in the educts), particularly preferably C to Si in a ratio of 50: 1 to 1:50, very particularly preferably from 20: 1 to 1:20, according to the invention in the range of 3: 1 to 2: 1 or to 1: 1 in front.
  • the procedure is usually more than one course.
  • the pyrolysis and / or calcination can be carried out in a reactor successively or separately from each other in different reactors.
  • the pyrolysis takes place in a first reactor and the subsequent calcination, for example in a microwave with fluidized bed.
  • the person skilled in the art is familiar with the fact that the reactor assemblies, containers, feeds and / or drains, and / or waste liquors may not contribute to co-precipitation of the process products.
  • the process is generally carried out so that the silica and the carbon source comprising at least one carbohydrate are intimately mixed, dispersed, homogenized or fed in a formulation to a first reactor for pyrolysis. This can be done continuously or discontinuously.
  • the feedstocks are dried before being fed into the actual reactor, preferably adhering water or a residual moisture can remain in the system.
  • the entire process is divided into a first phase in which the pyrolysis takes place and in another phase in which the calcination takes place.
  • the pyrolysis is carried out in the rule, especially in the at least one first reactor, in the low-temperature method to 700 0 C, usually between 200 0 C and 1600 0 C, more preferably between 300 0 C and 1500 0 C, in particular at 400 to 1400 0 C, wherein preferably a graphite-containing pyrolysis product is obtained.
  • the pyrolysis temperature is preferably the internal temperature of the reactants.
  • the pyrolysis product is preferably obtained at temperatures around 1300 to 1500 0 C.
  • the process is usually operated in the low pressure range and / or under an inert gas atmosphere. Argon or helium are preferred as the inert gas. Nitrogen may also be useful, or if silicon nitride is to form in addition to silicon carbide or n-doped silicon carbide in the calcining step, which may be desirable depending on the process. In order to produce n-doped silicon carbide in the calcination step, it is possible to add nitrogen in the pyrolysis and / or calcination step, if appropriate also via the carbohydrates, such as chitin, to the process. Equally expedient may be the production of specially p-doped silicon carbide, in this particular exception, for example, the aluminum content may be higher.
  • the doping can be carried out by means of aluminum-containing substances, for example via thmethylalumin
  • pyrolysis products or compositions of varying degrees of agglomeration and of different thickness can be produced in this process step.
  • vacuum less agglomerated pyrolysis products having an increased porosity are generally obtained than under normal pressure or elevated pressure.
  • the pyrolysis time can be between 1 minute and usually 48 hours, in particular between 15 minutes and 18 hours, preferably between 30 minutes and about 12 hours at the stated pyrolysis temperatures.
  • the heating up to the pyrolysis temperature is usually added here.
  • the pressure range is usually 1 mbar to 50 bar, in particular 1 mbar to 10 bar, preferably 1 mbar to 5 bar.
  • the pyrolysis step can also take place in a pressure range from 1 to 50 bar, preferably at 2 to 50 bar, more preferably at 5 to 50 bar.
  • the expert knows that the pressure to be selected is a compromise between gas removal, agglomeration and reduction of the process gases containing carbon.
  • the calcination or the high-temperature range of the process usually takes place in the pressure range from 1 mbar to 50 bar, in particular between 1 mbar and 1 bar (ambient pressure), in particular at 1 to 250 mbar, preferably at 1 to 10 mbar.
  • the calcination time depends on the temperature and the reactants used. In general, it is between 1 minute and can usually be 48 hours, in particular between 15 minutes and 18 hours, preferably between 30 minutes and about 12 hours at the above calcination temperatures.
  • the heating up to the calcination temperature is usually added here.
  • the implementation of silicon carbide at elevated temperature is preferably carried out at a temperature of 400 to 3000 0 C, preferably the calcination in the high temperature range between 1400 to 3000 0 C, preferably at 1400 0 C to 1800 0 C, particularly preferably between 1450 to 1500 and 1700 ° C.
  • the temperature ranges should not be limited to those disclosed, since the temperatures reached also depend on the reactors used.
  • the temperatures are based on measurements with stationary high temperature temperature sensors, for example encapsulated (PtRhPt element) or alternatively on the color temperature by optical comparison with an incandescent filament.
  • a calcination is understood to mean a process section in which the reactants essentially react to form high-purity silicon carbide, optionally containing a carbon matrix and / or a silicon oxide matrix and / or mixtures thereof.
  • the reaction of silicon oxide and the carbon source containing a carbohydrate can also be carried out directly in the high temperature range, wherein the gaseous reactants or process gases must be able to outgas well from the reaction zone. This can be ensured by a loose bed or a bed of moldings of silicon oxide and / or the carbon source or preferably with moldings comprising silicon dioxide and the carbon source (carbohydrate).
  • water vapor, carbon monoxide and secondary products can be formed as gaseous reaction products or process gases. At high temperatures, especially in the high temperature range, carbon monoxide predominantly forms.
  • Suitable reactors for use in the process according to the invention are all reactors known to the person skilled in the art for pyrolysis and / or calcination. Therefore, for the pyrolysis and subsequent calcination for SiC formation and optionally graphitization all known in the art laboratory reactors, reactors of a pilot plant or preferably large-scale reactors such as rotary tube reactor or a microwave reactor, as it is known for sintering of ceramics, can be used ,
  • the microwave reactors can be operated in the high frequency range RF range, in the context of the present invention by high frequency range 100 MHz to 100 GHz is understood, in particular between 100 MHz and 50 GHz or 100 MHz to 40 GHz. Preferred frequency ranges are approximately between 1 MHz to 100 GHz, with 10 MHz to 50 GHz being particularly preferred.
  • the reactors can be operated in parallel. Particular preference is given to using magnetrons with 2.4 MHz for the method.
  • the high temperature reaction can also be carried out in conventional melting furnaces for the production of steel or silicon, such as metallurgical silicon, or other suitable melting furnaces, for example induction furnaces.
  • suitable melting furnaces for example induction furnaces.
  • Melting furnaces particularly preferably electric ovens, which as an energy source a use electric arc, the skilled person is well known and is not part of this application.
  • DC furnaces they have a melting electrode and a bottom electrode or, as an AC furnace, usually three melting electrodes.
  • the arc length is controlled by means of an electrode regulator.
  • the arc furnaces are usually based on a reaction space of refractory material.
  • the raw materials are added, in particular the pyrolyzed carbohydrate on silica / SiO 2, in the upper region in which the graphite electrodes are arranged to generate the arc.
  • Operate these ovens usually at temperatures ranging around 1800 0 C. It is also known in the art that the furnace structures themselves must not contribute to contamination of the silicon carbide produced.
  • the invention also provides a composition comprising silicon carbide optionally with a carbon matrix and / or silicon oxide matrix or a matrix comprising silicon carbide, carbon and / or silicon oxide and optionally silicon obtainable by the process according to the invention, in particular by the calcination step, and in particular is isolated.
  • Isolation means that after the process has been carried out, the composition and / or the high-purity silicon carbide are obtained and isolated, in particular as a product.
  • the silicon carbide may be provided with a passivation layer, for example containing SiO 2.
  • This product can then serve as a reactant, catalyst, material for the production of articles, for example filters, moldings or green bodies, and can be used in other applications known to the person skilled in the art.
  • Another important application is the use of the composition comprising silicon carbide as reaction initiator and / or reactant and / or in the production of electrode material or in the production of silicon carbide with sugar coke and silica.
  • the invention also relates to the pyrolysis and optionally calcination product, in particular a composition obtainable according to the process according to the invention and in particular the pyrolysis and / or calcination product isolated from the process, having a content of carbon to silicon oxide, in particular of silicon dioxide, of 400 to 0.1 to 0.4 to 1000.
  • the aim is for the particular silicon carbide process product, a low conductivity, which correlates directly with the purity of the process product.
  • the pyroxylating and / or calcination product has a graphite content of from 0 to 50% by weight, preferably from 25 to 50% by weight, relative to the total composition.
  • the composition or the pyrolysis and / or calcination product has a content of silicon carbide of from 25 to 100% by weight, in particular from 30 to 50% by weight. in relation to the overall composition.
  • the invention also provides a silicon carbide having a carbon matrix comprising coke and / or carbon black and / or graphite or mixtures thereof and / or with a silicon oxide matrix comprising silicon dioxide, silica and / or mixtures thereof or with a mixture of the abovementioned components, obtainable by the process according to the invention, in particular according to one of claims 1 to 10.
  • the SiC is isolated and reused as set forth below.
  • the content of the elements boron, phosphorus, arsenic and / or aluminum is generally less than 10 ppm by weight in the silicon carbide according to the definition of the invention.
  • the invention also provides a silicon carbide optionally with carbon fractions and / or silicon oxide fractions or mixtures comprising silicon carbide, Carbon and / or silicon oxide, in particular silicon dioxide, containing in total less than 100 ppm by weight of the elements boron, phosphorus, arsenic and / or aluminum in the silicon carbide.
  • the impurity profile of the high-purity silicon carbide with boron, phosphorus, arsenic, aluminum, iron, sodium, potassium, nickel, chromium is preferably less than 5 ppm to 0.01 ppt (wt), in particular less than 2.5 ppm to 0.1 ppt.
  • the silicon carbide obtained by the process according to the invention if appropriate with carbon and / or Si y O z matrices, has an impurity profile as defined above with the elements B, P, Na, S, Ba, Zr, Zn, Al, Fe, Ti, Ca, K, Mg, Cu, Cr, Co, Zn, Ni, V, Mn and / or Pb and mixtures of these elements.
  • the available silicon carbide has an overall content of carbon to silicon oxide, in particular of silicon dioxide, of 400 to 0.1 to 0.4 to 1000, preferably, it has, in particular the composition, a graphite content of 0 to 50 wt .-% on , particularly preferably from 25 to 50 wt .-%.
  • the proportion of silicon carbide is in particular between 25 to 100 wt .-%, preferably 30 to 50 wt .-% in the silicon carbide (total) as defined above.
  • the subject of the invention is the use of silicon carbide Si or a composition or a pyrolysis and / or
  • the invention is in particular the
  • Silica preferably a fumed, precipitated or ion exchanger-cleaned silica or SiO 2, at high temperatures, as an abrasive, insulator, as a refractory material, such as a heat tile, or in the manufacture of articles or in the manufacture of electrodes.
  • the invention also provides the use of silicon carbide or a composition or a pyrolysis and / or calcination product obtainable by the process according to the invention, in particular according to one of claims 1 to 13, as a catalyst, in particular in the production of silicon, in particular in the preparation of Solar silicon, in particular in the production of solar silicon by reduction of silica at high temperatures.
  • silicon carbide for semiconductor applications or for use as a catalyst in the production of ultrapure silicon carbide for example by sublimation, or as a reactant in the production of silicon or in the production of silicon carbide, especially coke, preferably from sugar coke, and Silica, preferably with silicic acid, at high temperatures, or for use as a material of articles or as an electrode material, in particular for electrodes of electric arc furnaces.
  • Use as a material of articles, especially electrodes involves the use of the material as a material for the articles or also the use of further processed material for the manufacture of the articles, for example of sintered material or of abrasives.
  • Another object of the invention is the use of at least one carbohydrate in the production of silicon carbide, in particular as a product isolable silicon carbide, or a composition containing silicon carbide or a pyrolysis and / or calcination product containing silicon carbide, especially in the presence of silica, preferably in the presence of silica and / or silica.
  • a selection from at least one carbohydrate and a silicic oxide, in particular a silicon dioxide, in particular without further components, is used for producing silicon carbide, the silicon carbide comprising a composition comprising silicon carbide or a pyrolysis and / or calcining product Reaction product is isolated.
  • the invention also provides a composition, in particular a formulation, or a kit comprising at least one carbohydrate and silicon oxide, in particular for use in the method according to the invention or for the use according to the invention, in particular according to one of claims 1 to 10 or for use according to claim 16 the invention also relates to a kit containing separated formulations, in particular in separate containers, such as vessels, bags and / or cans, in particular in the form of an extrudate and / or powder of silica, in particular silica, optionally together with pyrolysis products of carbohydrates on SiO 2 and or the carbon source comprising at least one carbohydrate, in particular for use as described above.
  • a kit containing separated formulations in particular in separate containers, such as vessels, bags and / or cans, in particular in the form of an extrudate and / or powder of silica, in particular silica, optionally together with pyrolysis products of carbohydrates on SiO 2 and or the carbon source comprising at least one carbohydrate, in particular for use as described above.
  • the silicon oxide is present directly with the carbon source comprising a carbohydrate, for example impregnated therewith or the carbohydrate supported on SiO 2 etc. in the form of tablets, as granules, extrudate, in particular as pellet, in a container in the kit and optionally further carbohydrate and / or silica as a powder in a second container.
  • the carbon source comprising a carbohydrate, for example impregnated therewith or the carbohydrate supported on SiO 2 etc. in the form of tablets, as granules, extrudate, in particular as pellet, in a container in the kit and optionally further carbohydrate and / or silica as a powder in a second container.
  • a further subject of the invention is an article, in particular a green body, shaped body, sintered body, electrode, heat-resistant component comprising a silicon carbide according to the invention or a composition according to the invention containing silicon carbide, in particular according to one of claims 1 to 13 and optionally further customary additives, additives, Auxiliaries, pigments or binders.
  • the invention thus relates to an article comprising a silicon carbide according to the invention or which is prepared using the silicon carbide according to the invention, in particular according to one of claims 1 to 13.
  • Comparative Example 1 Commercially available refined sugar was melted in a quartz glass and then heated to about 1600 0 C. The reaction mixture foams up on heating and partially exits the quartz glass. At the same time a caramel formation is observed. The pyrolysis product formed adheres to the wall of the reaction vessel ( Figure 1a).
  • FIGS. 3 and 4 are micrographs of two samples of the calcination product. The formation of silicon carbide could be detected by XPS spectra and determination of the binding energies. Furthermore, Si-O structures could be detected. On the formation of graphite was closed by the metallic shimmer under a light microscope.
  • Example 2 In a rotary kiln with SiO 2 balls for the heat distribution, a fine particulate formulation of sugar, grown on SiO 2 particles, reacted at elevated temperature. For example, prepared by dissolving sugar in an aqueous silica solution with subsequent drying and, if necessary, homogenization. A residual moisture was still contained in the system. About 1 kg of the formulation was used.
  • the residence time in the rotary kiln depends on the water content of the fine particulate formulation.
  • the rotary kiln was equipped with a preheating zone for drying the formulation, then the formulation went through a pyrolysis and calcination zone with temperatures of 400 0 C to 1 800 0 C.
  • the residence time comprising the drying step, pyrolysis and calcining step was about 17 hours. Throughout the process, the generated process gases, such as water vapor and CO, could be easily removed from the rotary kiln.
  • the SiO 2 used had a boron content of less than 0.1 ppm, phosphorus of less than 0.1 ppm and an iron content of less than about 0.2 ppm.
  • the iron content of the sugar was determined to be less than 0.5 ppm before formulation.
  • Example 2 was repeated using laboratory rotary kilns previously with high purity
  • Silicon carbide was coated. This was reacted with SiO 2 balls for the heat distribution and a fine particulate formulation containing sugar, grown on SiO 2 particles, at elevated temperature.
  • a fine particulate formulation containing sugar, grown on SiO 2 particles, at elevated temperature.
  • a fine particulate formulation containing sugar, grown on SiO 2 particles, at elevated temperature.
  • the residence time in the rotary kiln depends on the water content of the fine particulate formulation.
  • the rotary kiln was equipped with a preheating zone for drying the Formu l ation, app l uid Highness ief t he formulation a pyrolysis and calcination at temperatures of 400 0 C to 1800 0 C.
  • the residence time comprising the drying step, pyrolysis and calcining step was about 17 hours. Throughout the process, the generated process gases, such as water vapor and CO, could be easily removed from the rotary kiln.
  • the SiO 2 used had a boron content of less than 0.1 ppm, phosphorus of less than 0.1 ppm and an iron content of less than about 0.2 ppm.
  • the iron content of the sugar was determined to be less than 0.5 ppm before formulation.
  • a fine particulate formulation of pyrolyzed sugar is reacted on SiO 2 particles at elevated temperature.
  • the formulation of pyrolyzed sugar was previously prepared by pyrolysis in a rotary kiln at about 800 0 C. About 1 kg of the fine particulate pyrolyzed formulation was used.
  • the formed process gas CO can easily escape via the intermediate spaces, which are formed by the particulate structure of the SiO 2 particles, and can be withdrawn from the reaction space.
  • electrodes were High-purity graphite electrodes and the lining of the reactor floor also high-purity graphite was used.
  • the electric arc furnace was operated with 1 to 12 kW. After the reaction, high-purity silicon carbide was obtained with proportions of graphite, ie in a carbon matrix.
  • the SiO 2 used had a boron content of less than 0.17 ppm, phosphorus of less than 0.15 ppm and an iron content of less than about 0.2 ppm.
  • the iron content of the sugar was determined to be less than 0.7 ppm before formulation.
  • the contents in the silicon carbide were again determined, the content of boron and phosphorus remaining below 0.17 ppm and below 0.15 ppm, respectively, and the iron content remaining below 0.7 ppm.
  • a corresponding reaction of a pyrolyzed formulation according to Example 3 was carried out in a microwave reactor.
  • about 0.1 kg of a dry, fine particulate formulation of pyrolyzed sugar on SiO 2 particles at frequencies above 1 gigawatt were converted to silicon carbide in a carbon matrix.
  • the reaction time depends directly on the input power and the reactants.
  • reaction times are correspondingly longer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention porte sur un procédé de fabrication de carbure de silicium par réaction d'oxyde de silicium et d'une source de carbone comprenant un hydrate de carbone à haute température, en particulier un procédé technique de fabrication de carbure de silicium ou de fabrication de compositions contenant du carbure de silicium. L'invention porte en outre sur un carbure de silicium de haute pureté, sur des compositions le contenant, sur leur utilisation en tant que catalyseur, ainsi que lors de la préparation d'électrodes et d'autres articles.
EP09736162A 2008-09-30 2009-09-28 Procédé de fabrication de carbure de silicium de haute pureté à partir d'hydrates de carbone et d'oxyde de silicium par calcination Withdrawn EP2334597A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102008042499A DE102008042499A1 (de) 2008-09-30 2008-09-30 Verfahren zur Herstellung von hochreinem Siliciumcarbid aus Kohlenhydraten und Siliciumoxid durch Kalzinierung
DE102008064642A DE102008064642A1 (de) 2008-09-30 2008-09-30 Zusammensetzung oder Kit für ein Verfahren zur Herstellung von hochreinem Siliciumcarbid aus Kohlenhydraten und Siliciumoxid sowie darauf basierende Artikel
PCT/EP2009/062482 WO2010037692A1 (fr) 2008-09-30 2009-09-28 Procédé de fabrication de carbure de silicium de haute pureté à partir d'hydrates de carbone et d'oxyde de silicium par calcination

Publications (1)

Publication Number Publication Date
EP2334597A1 true EP2334597A1 (fr) 2011-06-22

Family

ID=41354079

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09736162A Withdrawn EP2334597A1 (fr) 2008-09-30 2009-09-28 Procédé de fabrication de carbure de silicium de haute pureté à partir d'hydrates de carbone et d'oxyde de silicium par calcination

Country Status (14)

Country Link
US (1) US20110175024A1 (fr)
EP (1) EP2334597A1 (fr)
JP (1) JP2012504099A (fr)
KR (1) KR20110063497A (fr)
CN (1) CN102164852A (fr)
AU (1) AU2009299904A1 (fr)
BR (1) BRPI0920818A2 (fr)
CA (1) CA2739026A1 (fr)
DE (2) DE102008042499A1 (fr)
EA (1) EA201100568A1 (fr)
NZ (1) NZ591238A (fr)
TW (1) TW201026604A (fr)
WO (1) WO2010037692A1 (fr)
ZA (1) ZA201102322B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025210052A1 (fr) 2024-04-02 2025-10-09 The Yellow SiC Holding GmbH Procédé de fabrication d'une composition précurseur pour la fabrication d'un matériau contenant du carbure de silicium, composition précurseur et matériau contenant du carbure de silicium
WO2025210051A1 (fr) 2024-04-02 2025-10-09 The Yellow SiC Holding GmbH Procédé de production d'une composition précurseur pour la production d'un matériau contenant du carbure de silicium, composition précurseur et matériau contenant du carbure de silicium

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9663374B2 (en) * 2011-04-21 2017-05-30 The United States Of America, As Represented By The Secretary Of The Navy Situ grown SiC coatings on carbon materials
JP5618302B2 (ja) * 2011-05-26 2014-11-05 独立行政法人産業技術総合研究所 炭化ケイ素微粉末の製造方法及びその製造装置
EP2730541B1 (fr) * 2011-07-04 2018-02-28 Taiheiyo Cement Corporation Procédé de fabrication d'un mélange de silice et de carbone
FR2977578B1 (fr) 2011-07-06 2013-07-05 Produits Refractaires Procede de fabrication de carbure de silicium
EP2749531B1 (fr) 2011-08-24 2023-08-23 Taiheiyo Cement Corporation Poudre de carbure de silicium et procédé pour produire celle-ci
JP5797086B2 (ja) * 2011-11-01 2015-10-21 太平洋セメント株式会社 高純度炭化珪素粉末の製造方法
DE102012202586A1 (de) * 2012-02-21 2013-08-22 Evonik Degussa Gmbh Verfahren zur Herstellung von Silizium über carbothermische Reduktion von Siliciumoxid mit Kohlenstoff in einem Schmelzofen
WO2013156406A1 (fr) 2012-04-17 2013-10-24 Evonik Degussa Gmbh Procédé de traitement électrochimique d'une solution aqueuse concentrée de glucides et appareil pour la mise en œuvre du procédé
US9919972B2 (en) * 2013-05-02 2018-03-20 Melior Innovations, Inc. Pressed and self sintered polymer derived SiC materials, applications and devices
US9657409B2 (en) * 2013-05-02 2017-05-23 Melior Innovations, Inc. High purity SiOC and SiC, methods compositions and applications
US11091370B2 (en) 2013-05-02 2021-08-17 Pallidus, Inc. Polysilocarb based silicon carbide materials, applications and devices
US10322936B2 (en) 2013-05-02 2019-06-18 Pallidus, Inc. High purity polysilocarb materials, applications and processes
JP6297812B2 (ja) * 2013-10-30 2018-03-20 太平洋セメント株式会社 炭化珪素の製造方法
FI3878552T3 (fi) 2014-04-29 2023-04-25 Archer Daniels Midland Co Prosessi aldoosin selektiivistä hapettumista varten
US11253839B2 (en) 2014-04-29 2022-02-22 Archer-Daniels-Midland Company Shaped porous carbon products
DE102014009554A1 (de) * 2014-06-12 2015-12-17 Daimler Ag Elektrodenmaterial für einen elektrochemischen Speicher, Verfahren zur Herstellung eines Elektrodenmaterials sowie elektrochemischer Energiespeicher
TWI555720B (zh) * 2014-08-29 2016-11-01 國立成功大學 奈米陶瓷材料的製造方法
CN105481366A (zh) * 2014-09-15 2016-04-13 中国科学院上海硅酸盐研究所 一种碳化物陶瓷纳米粉体的制备方法
KR102355080B1 (ko) * 2015-01-16 2022-01-25 (주)에스테크 탄화규소 분말
US10722867B2 (en) 2015-10-28 2020-07-28 Archer-Daniels-Midland Company Porous shaped carbon products
US10464048B2 (en) 2015-10-28 2019-11-05 Archer-Daniels-Midland Company Porous shaped metal-carbon products
RU2642660C2 (ru) * 2016-03-21 2018-01-25 ООО НПО "КвинтТех" Способ получения карбида кремния
US10759664B2 (en) * 2016-12-27 2020-09-01 Korea Institute Of Energy Research Manufacturing method of silicon carbide and silicon carbide manufactured using the same
CN106938934B (zh) * 2017-02-28 2019-10-15 中国科学院上海硅酸盐研究所 一种超高温陶瓷基气凝胶材料及其制备方法
KR20190135504A (ko) 2017-03-29 2019-12-06 팔리두스, 인크. SiC 용적측정 형태 및 보올을 형성하는 방법
CN107473227A (zh) * 2017-08-11 2017-12-15 苏州吉云新材料技术有限公司 一种使金属硅熔化的微波加热方法
KR101942815B1 (ko) * 2017-11-13 2019-01-30 한국과학기술연구원 친환경적인 다공성 탄화규소 구조체의 제조방법
TWI640473B (zh) 2017-12-07 2018-11-11 財團法人工業技術研究院 除硼方法與除硼裝置
CN110273183B (zh) * 2018-03-17 2021-06-08 南京航空航天大学 一种碳化硅纳米晶须的制备方法
DE102020117478A1 (de) 2020-07-02 2022-01-05 Lhoist Recherche Et Développement S.A. Verfahren zur thermischen Behandlung von mineralischen Rohstoffen
DE102020005129B4 (de) 2020-08-21 2024-05-16 Technische Universität Bergakademie Freiberg, Körperschaft des öffentlichen Rechts Kohlenstoffärmere und kohlenstofffreie Elektroden für den Einsatz in der Stahlmetallurgie
DE102021131748B3 (de) 2021-12-02 2023-02-23 Nippon Kornmeyer Carbon Group Gmbh Verfahren zum Herstellen von hochreinem Siliziumkarbid-Pulver
CN116948601A (zh) * 2023-07-28 2023-10-27 北京晶格领域半导体有限公司 一种碳化硅磨料及其制备方法
DE102024110950A1 (de) * 2024-04-18 2025-10-23 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verfahren zur Herstellung von Siliciumcarbid

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0948605A (ja) * 1995-05-31 1997-02-18 Bridgestone Corp 炭化ケイ素単結晶製造用高純度炭化ケイ素粉体の製造方法及び単結晶

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085863A (en) * 1960-11-01 1963-04-16 Gen Electric Method of making silicon carbide
DE2518950A1 (de) 1974-05-20 1975-12-04 Gen Electric Gesintertes siliziumkarbidpulver und verfahren zu dessen herstellung
JPS5788019A (en) * 1980-11-13 1982-06-01 Asahi Chem Ind Co Ltd Manufacture of silicon carbide
JPS60235706A (ja) * 1984-05-09 1985-11-22 Central Glass Co Ltd シリコン系セラミツクス粉末の連続製造方法
US5244639A (en) * 1985-05-29 1993-09-14 Kawasaki Steel Corporation Method and apparatus for preparing high-purity metallic silicon
US5759508A (en) * 1996-06-28 1998-06-02 E. I. Du Pont De Nemours And Company Process for producing oxochlorides of sulfur
US6251353B1 (en) * 1996-08-26 2001-06-26 Bridgestone Corporation Production method of silicon carbide particles
JP4234800B2 (ja) * 1996-08-26 2009-03-04 株式会社ブリヂストン 炭化ケイ素粉体の製造方法
JP2001019552A (ja) * 1999-07-09 2001-01-23 Bridgestone Corp 炭化ケイ素焼結体及びその製造方法
JP4589491B2 (ja) * 1999-08-24 2010-12-01 株式会社ブリヂストン 炭化ケイ素粉末、グリーン体の製造方法、及び炭化ケイ素焼結体の製造方法
JP3864696B2 (ja) 2000-11-10 2007-01-10 株式会社デンソー 炭化珪素単結晶の製造方法及び製造装置
JP4480349B2 (ja) * 2003-05-30 2010-06-16 株式会社ブリヂストン 炭化ケイ素単結晶の製造方法及び製造装置
US7638108B2 (en) * 2004-04-13 2009-12-29 Si Options, Llc High purity silicon-containing products

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0948605A (ja) * 1995-05-31 1997-02-18 Bridgestone Corp 炭化ケイ素単結晶製造用高純度炭化ケイ素粉体の製造方法及び単結晶

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2010037692A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025210052A1 (fr) 2024-04-02 2025-10-09 The Yellow SiC Holding GmbH Procédé de fabrication d'une composition précurseur pour la fabrication d'un matériau contenant du carbure de silicium, composition précurseur et matériau contenant du carbure de silicium
WO2025210051A1 (fr) 2024-04-02 2025-10-09 The Yellow SiC Holding GmbH Procédé de production d'une composition précurseur pour la production d'un matériau contenant du carbure de silicium, composition précurseur et matériau contenant du carbure de silicium

Also Published As

Publication number Publication date
DE102008042499A1 (de) 2010-04-01
EA201100568A1 (ru) 2011-10-31
CN102164852A (zh) 2011-08-24
AU2009299904A1 (en) 2010-04-08
WO2010037692A1 (fr) 2010-04-08
NZ591238A (en) 2013-03-28
ZA201102322B (en) 2011-12-28
BRPI0920818A2 (pt) 2015-12-22
CA2739026A1 (fr) 2010-04-08
KR20110063497A (ko) 2011-06-10
DE102008064642A1 (de) 2010-04-01
JP2012504099A (ja) 2012-02-16
TW201026604A (en) 2010-07-16
US20110175024A1 (en) 2011-07-21

Similar Documents

Publication Publication Date Title
EP2334597A1 (fr) Procédé de fabrication de carbure de silicium de haute pureté à partir d'hydrates de carbone et d'oxyde de silicium par calcination
EP2331462A2 (fr) Production de silicium solaire à partir d'oxyde de silicium
EP2334598A2 (fr) Production de silicium solaire à partir d'oxyde de silicium
EP3490954B1 (fr) Procédé de fabrication d'un materiau isolant qui contient de la silice pyrogène hydrophobe
EP2376375B1 (fr) Procédé de fabrication de nitrure de silicium hautement pur
WO2010037699A2 (fr) Procédé de pyrolyse de glucides
EP2322474A1 (fr) Procédé de pyrolyse d'hydrates de carbone
EP2318312A2 (fr) Fabrication de silicium par réaction d'oxyde de silicium avec du carbure de silicium éventuellement en présence d'une seconde source de carbone
DE69019339T2 (de) Verfahren zum herstellen von siliciumkarbid.
US20130015175A1 (en) Method for producing silicon
Sugahara et al. The preparation of magaditepolyacrylonitrite intercalation compound and its conversion to silicon carbide
CA2753932A1 (fr) Fabrication et utilisation de composites de carbure et de nitrure modifies
KR101978938B1 (ko) 실리콘 카바이드 제조방법 및 이를 이용하여 제조된 실리콘 카바이드
EP4440984A1 (fr) Procédé de production d'une poudre de carbure de silicium de haute pureté
HK1158610A (en) Production of solar-grade silicon from silicon dioxide
WO2013124167A1 (fr) Procédé de production de silicium par réduction carbothermique d'oxyde de silicium avec du carbone dans un four de fusion

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110322

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20120611

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140124