Classifications

• • 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
  • C01B33/08—Compounds containing halogen
  • C01B33/107—Halogenated silanes
  • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
• • 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
  • C01B33/08—Compounds containing halogen
  • C01B33/107—Halogenated silanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/20—Carbon compounds
  • B01J27/22—Carbides
  • B01J27/224—Silicon carbide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/24—Nitrogen compounds
• • 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
  • C01B33/08—Compounds containing halogen
  • C01B33/107—Halogenated silanes
  • C01B33/10773—Halogenated silanes obtained by disproportionation and molecular rearrangement of halogenated silanes
• • 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
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
• • 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
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• • 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
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
• • 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
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
  • C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
• • 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
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers

Definitions

• the invention relates to a process for the preparation of trichlorosilane, characterized in that hydrogen and at least one organic chlorosilane are reacted in a pressure-operated reactor comprising one or more reactor tubes consisting of gas-tight ceramic material.
• TCS Trichlorosilane
• the separation of hyperpure silicon from TCS is carried out in a Chemical Vapor Deposition (CVD) process according to the Siemens method.
• CVD Chemical Vapor Deposition
• STC silicon tetrachloride
• the TCS used is usually prepared by a chlorosilane process, i. H. Conversion of crude silicon with HCl at temperatures around 300 ° C in a fluidized bed reactor or recovered at 1000 ° C in a fixed bed reactor, the separation of other than coupling products formed chlorosilanes such.
• B. STC is carried out by downstream distillation.
• Organic impurities also result in the above processes in the formation of organic chlorosilanes as further by-products. In large quantities, organic chlorosilanes, such as. B.
• Methyltrichlorosilane (MTCS), methyldichlorosilane (MHDCS) or propyltrichlorosilane (PTCS), in addition by Müller-Rochow synthesis of silicon and
• Alkyl chlorides are produced.
• economies of processes for the production of hyperpure silicon therefore require processes that allow an efficient transfer of silicon tetrachloride and organochlorosilanes in TCS, so that the coupling products from the Siemens process and the chlorosilane process and streams of Müller-Rochow synthesis for the production of Pure silicon can be harnessed.
• Various methods for hydrodechlorination of STC to TCS are known. According to the technical standard, a thermally controlled process is used in which the STC is passed together with hydrogen in a graphite-lined reactor, the so-called "Siemens furnace". The in the reactor
• Process improvements include, in particular, the use of carbon-based engineering materials with a chemically inert
• DE 102005046703 A1 describes a process for the dehydrohalogenation of a chlorosilane in which a graphitic heating element and the surface of the reaction chamber, which come into contact with the chlorosilane, in one of the Dehydrohalogenation upstream step in-situ with a protective SiC layer by reaction of graphite with organosilanes be coated at temperatures above the reaction temperature of dehydrohalogenation.
• the arrangement of the heating element inside the reaction chamber increases the efficiency of the energy input of the electrical resistance heating.
• Form reaction temperature also require regular cleaning of the reactor.
• the metallic pressure reactor has to be laboriously cooled on the one hand from the outside and be covered from the inside by a high temperature heat insulation, the cladding must simultaneously provide protection against corrosive attack.
• WO 2005/102927 A1 and WO 2005/102928 A1 describe the use of Ca, Sr, Ba or their chlorides or of a metallic heating element, in particular of Nb, Ta, W or their alloys as
• a pressure-operated reactor comprising one or more reactor tubes, which consist of gas-tight ceramic material.
• the pipe inner walls are preferably with a catalyst, the coated at least one active component selected from the metals Ti, Zr, Hf, Ni, Pd, Pt, Mo, W, Nb, Ta, Ba, Sr, Ca, Mg, Ru, Rh, Ir or combinations thereof or their silicide compounds wherein the tubes can optionally be filled with a fixed bed of analogously catalytically coated packing of the same ceramic material.
• the conversion to TCS takes place with almost
• reaction temperatures can advantageously be generated by arranging the reactor tubes in a combustion chamber which is heated by combustion of natural gas.
• Chlorosilanes in particular of STC.
• organic chlorosilanes as by-products from the Siemens process or the chlorosilane process or, in particular, as products of a Müller-Rochow synthesis, it would be very desirable for the utilization of these sources for the
• transition metals or their silicides are, as it were, suitable as catalysts for the dehydrohalogenation of STC and for the hydrogenation of organochlorine compounds.
• the proposed method uses full contacts. This means a relatively high material consumption and incomplete utilization of the catalytically active component.
• the execution in a flow reactor under atmospheric pressure also requires a
• Object of the present invention was therefore to provide an efficient and
• Wall coating provided and / or can be equipped with a fixed bed catalyst.
• the reaction in the reactor is catalyzed by a reaction catalyzing the inner coating of the one or more reactor tubes.
• the reaction in the reactor can additionally be catalyzed by a conversion-catalyzing coating of a fixed bed arranged in the reactor or in the one or more reactor tubes.
• Chlorosilane compounds are possible to TCS.
• suitable adjustment of the reaction parameters such as pressure, residence time and molar ratios of the educts, a process can be represented in which high space-time yields of TCS with a high selectivity are obtained.
• Hydrogen additionally contain STC as a further educt. It has been discovered that reactor tubes of certain hermetic ceramic materials specified below are useful for the hydrogenation of
• Chlorosilanes in particular organochlorosilanes can be used, since they are sufficiently inert even at the necessary reaction temperatures of about 700 ° C and able to ensure the pressure resistance of the reactor.
• Resistance heaters may have local overheating, because the electrical resistance can not be maintained uniformly enough by geometric deviations of the resistance-heated components or by wear, resulting in local deposits and expensive shutdowns associated with cleaning the result. Finally, in comparison with graphite-based hydrohalogenation reactors, there is no need for a metallic outer wall to be cooled, which must be protected against corrosion.
• the invention relates to a process for the preparation of trichlorosilane, characterized in that hydrogen and at least one organic
• Chlorosilane in a pressure-operated reactor comprising one or more reactor tubes, which are made of gas-tight ceramic material reacted.
• a specific embodiment of the process according to the invention in admixture with the at least one organic chlorosilane additionally
• Silicon tetrachloride reacted with hydrogen to trichlorosilane.
• methyltrichlorosilane can be used as the only organic chlorosilane.
• sole organic chlorosilane here means that the cumulative amount of other organic chlorosilanes contained in the reaction mixture is less than 3 mol%, based on the molar amount of methyltrichlorosilane.
• a hydrogen-containing feed gas and a feed gas containing at least one organic chlorosilane and, optionally, a silicon tetrachloride-containing feedstock may be used in the reaction
• Feedstock gas are reacted in a reactor by supplying heat to form a trichlorosilane-containing product gas, wherein the
• Organochlorosilane-containing reactant gas and / or the hydrogen-containing educt gas and / or the silicon tetrachloride-containing educt gas are passed as pressurized streams into the pressure-operated reactor and the product gas is taken out as a pressurized stream from the reactor.
• the product stream in addition to trichlorosilane and organic compounds which by
• the product stream generally also contains unreacted starting materials, ie the at least one organic chlorosilane, hydrogen and optionally silicon tetrachloride.
• the organochlorosilane-containing educt gas and the hydrogen-containing educt gas and, if present, the silicon tetrachloride-containing educt gas can also be conducted as a common stream into the pressure-operated reactor.
• the organochlorosilane-containing educt gas preferably contains organotrichlorosilanes of the formula RSlCl 3 where R is an alkyl group, in particular a linear or branched alkyl group having 1 to 8 C atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl, a phenyl group or an aralkyl group, thereby enabling high yields of the desired product TCS.
• R is an alkyl group, in particular a linear or branched alkyl group having 1 to 8 C atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl, a phenyl group or an aralkyl group, thereby enabling high yields of the desired product TCS.
• Particularly preferred may in
• Methyltrichlorosilane (MTCS), ethyltrichlorosilane (ETCS) and / or n-propyltrichlorosilane (PTCS) can be used as organochlorosilane according to the invention.
• These organic chlorosilanes can be taken individually or as a mixture, in particular as side streams, a chlorosilane process, the production of hyperpure silicon by the Siemens process and / or a Muller-Rochow synthesis after appropriate product gas treatment.
• a silicon tetrachloride-containing educt gas is used in the process according to the invention in addition to the educt gas containing organochlorosilane. It can also be an organochlorosilane and
• silicon tetrachloride-containing educt gas can be used.
• the reaction with hydrogen takes place in the reactor by parallel sequence of the hydrogenation of the at least one organochlorosilane and the hydrodehalogenation of SiCl 4 .
• Silicon tetrachloride-containing educt gas can be obtained in particular from secondary streams of a chlorosilane process and / or the hyperpure silicon production by the Siemens process after appropriate product gas treatment.
• the product mixture will only have a relatively low proportion of TCS.
• chlorosilanes with a higher hydrogen content or Si-Si bonds are included.
• Reactor tubes of the reactor are preferably selected from SiC or Si3N 4 , or mixed systems (SiCN) thereof. Pipes made of these materials are sufficiently inert, corrosion-resistant and pressure-stable, even at the high reaction temperatures of more than 700 ° C., so that the TCS synthesis can be operated from organic chlorosilanes and optionally STC at several bar overpressure.
• gastight materials are to be used as the reactor tube material. This also includes a possible use of suitable non-ceramic materials such. For example, a quartz glass.
• Especially reactors with SiC-containing reactor tubes are preferred because this material has a particularly good thermal conductivity and thus allows a uniform heat distribution and a good heat input for the reaction.
• these may in particular be gas-tight reactor tubes made of Si-infiltrated SiC (SiSiC) or non-pressure sintered SiC (SSiC), without herewith
• the corrosion resistance of the materials mentioned can additionally be increased by a SiO 2 layer with layer thicknesses in the range from 1 to 100 ⁇ m.
• reactor tubes made of SiC, S13N4 or SiCN with a corresponding Si0 2 layer are used as a coating.
• At least one reactor tube can be filled with random packings, which consist of the same gastight ceramic material as the tube.
• This inert bulk material can be used to optimize the flow dynamics. Bulk materials such as rings, spheres, rods or other suitable packing can be used as the bulk material.
• Methods are the inner walls of at least one reactor tube and / or at least a portion of the packing with at least one material that the
• the tubes can be used with or without catalyst, wherein the catalytically coated tubes represent a preferred embodiment, since suitable catalysts lead to an increase in the reaction rate and thus to an increase in the space-time yield.
• suitable catalysts lead to an increase in the reaction rate and thus to an increase in the space-time yield.
• Coated may optionally affect the catalytically active
• Catalyst systems eg., By fixed bed
• Reactor tubes and / or a fixed bed optionally used preferably consist of a composition comprising at least one active component selected from the metals Ti, Zr, Hf, Ni, Pd, Pt, Mo, W, Nb, Ta, Ba, Sr, Ca, Mg, Ru, Rh, Ir or combinations thereof or their silicide compounds, if any exist.
• active components are Pt, Pt / Pd, Pt / Rh and Pt / Ir.
• the application of the catalytically active coating to the inner walls of the reactor tubes and / or the optionally used fixed bed may comprise the following steps:
• the tempered fillers may then be in the one or more
• Reactor tubes are filled.
• the tempering and optionally also the previous drying can also be done with already filled in packing.
• suspending agent according to component b) of the suspension according to the invention in particular suspending agent with binding character, advantageously thermoplastic polymeric acrylate resins, as described, for. B. also used in the paint and coatings industry can be used. These include, for example, compositions based on polymethyl acrylate, polyethyl acrylate,
• Polypropylmethacrylat and / or Polybutylacrylat It is commercially available systems as they are available, for example under the brand name Degalan ® from Evonik Industries.
• auxiliary components are used.
• auxiliary component c) solvents or diluents Preferably, organic solvents, in particular aromatic Liere standing. Diluents, such as toluene, xylenes, as well as ketones, aldehydes, esters, alcohols or mixtures of at least two of the aforementioned solvents or diluents.
• organic solvents in particular aromatic Liere standing. Diluents, such as toluene, xylenes, as well as ketones, aldehydes, esters, alcohols or mixtures of at least two of the aforementioned solvents or diluents.
• inorganic or organic rheological additives include, for example, kieselguhr, bentonites, smectites and attapulgites, synthetic
• organic rheology additives or auxiliary components c) preferably include castor oil and its derivatives, such as polyamide-modified castor oil, polyolefin or polyolefin-modified polyamide, as well as polyamide and derivatives thereof, such as those sold under the brand name Luvotix®, and mixed systems of inorganic and organic rheology.
• castor oil and its derivatives such as polyamide-modified castor oil, polyolefin or polyolefin-modified polyamide, as well as polyamide and derivatives thereof, such as those sold under the brand name Luvotix®, and mixed systems of inorganic and organic rheology.
• auxiliary component c) for improving the adhesion of the suspension to the surface to be coated suitable adhesion promoters from the group of silanes or siloxanes can be used. These include, for example, but not limited to, dimethyl, diethyl, dipropyl, dibutyl, diphenylpolysiloxane or mixed systems thereof, such as phenylethyl or phenylbutylsiloxanes or other mixed systems, and mixtures thereof.
• the suspension according to the invention can be obtained in a comparatively simple and economical manner, for example by mixing, stirring or kneading the starting materials, ie components a), b) and optionally c), in suitable apparatuses known to the person skilled in the art.
• the reaction in the process according to the invention is typically carried out at a temperature in the range from 700 ° C. to 1000 ° C., preferably from 850 ° C. to 950 ° C. and / or a pressure in the range from 1 to 10 bar, preferably from 3 to 8 bar, particularly preferably carried out from 4 to 6 bar and / or a gas stream.
• the molar ratio of hydrogen to the sum of organochlorosilane (s) and silicon tetrachloride is advantageously set to be in a range of from 1 to 8: 1, preferably from 2: 1 to 6: 1, particularly preferably from 3: 1 to 5: 1, in particular 4: 1, is located.
• the dimensioning of the reactor tube and the design of the complete reactor are determined by the availability of the tube geometry, as well as by the requirements regarding the introduction of the required for the reaction
• Flow tubes here is the possibility of direct or indirect heating by means of natural gas burners, which provide much more economically the necessary energy input as electric power.
• the heat input for the reaction in the reactor can in principle by electrical resistance heating or combustion of a fuel gas such.
• An advantage of using fuel gas heated systems is the uniform temperature control. electrical
• Wderstandsloomtec can have local overheating, because the electrical resistance can not be maintained evenly enough by geometric deviations of the resistance-heated components or by wear, so that it comes to deposits and expensive shutdowns associated with cleaning the Consequence are.
• the burners In order to avoid local temperature peaks on the reactor tubes during heating by means of fuel gas, the burners should not be directed directly at the tubes. For example, they can be distributed and aligned over the heating chamber so that they point into the free space between parallel reactor tubes.
• the mechanical stability of the tubes made of ceramic materials described above is high enough to set pressure levels of several bar, preferably in the range of 1 -10 bar, more preferably in the range of 3- 8 bar, more preferably 4-6 bar.
• the need for a metallic wall to be cooled, which must be protected against corrosion, is in contrast to
• the reactor system can be connected to a
• Heat exchanger tube may be at least partially coated with the above-described catalytically active material.
• Aerosil R 974 6.0% by weight of phenylethylpolysiloxane, 16.8% by weight of aluminum pigment Reflaxal, 10.7% by weight of Degalan solution LP 62/03 and 12.2% by weight of tungsten silicide mixed intensively.
• Example 2 Aerosil R 974, 6.0% by weight of phenylethylpolysiloxane, 16.8% by weight of aluminum pigment Reflaxal, 10.7% by weight of Degalan solution LP 62/03 and 12.2% by weight of tungsten silicide mixed intensively.
• a silicon carbide (SSiC) ceramic tube was coated by the recipe described in Example 1 by placing the catalyst mixture in the
• the reactor tube was mounted in an electrically heatable tube furnace.
• the tube furnace with the respective tube was brought to 900 ° C, with nitrogen at 3 bar was passed through the reaction tube absolute. After two hours, the nitrogen was replaced by hydrogen. After another hour in a stream of hydrogen, also below 3.6 bar absolute, were
• the temperature in the tube furnace had already been set to 900 ° C as was changed from nitrogen to educt.
• the hydrogen stream was adjusted to a molar excess of 4 to 1.
• the reactor effluent was analyzed by online gas chromatography and from it the amounts of trichlorosilane, silicon tetrachloride, dichlorosilane and Calculated methyldichlorosilane. The calibration of the gas chromatograph was carried out with the pure substances.
• TCS trichlorosilane

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• Chemical & Material Sciences (AREA)
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• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Structural Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Silicon Compounds (AREA)

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• 2011
  • 2011-01-04 DE DE102011002436A patent/DE102011002436A1/de not_active Withdrawn
  • 2011-12-20 WO PCT/EP2011/073346 patent/WO2012093029A1/de active Application Filing
  • 2011-12-20 CN CN201180063997.XA patent/CN103269976B/zh not_active Expired - Fee Related
  • 2011-12-20 KR KR1020137017392A patent/KR20130133805A/ko not_active Application Discontinuation
  • 2011-12-20 US US13/977,984 patent/US20140178283A1/en not_active Abandoned
  • 2011-12-20 EP EP11805007.9A patent/EP2661415A1/de not_active Withdrawn
  • 2011-12-20 CA CA2823662A patent/CA2823662A1/en not_active Abandoned
  • 2011-12-20 JP JP2013547832A patent/JP5933592B2/ja not_active Expired - Fee Related
• 2012
  • 2012-01-03 TW TW101100179A patent/TW201245044A/zh unknown

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