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
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
  • B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
• • 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
  • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
• • 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
  • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
  • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
  • B01J19/2425—Tubular reactors in parallel
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
• • 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
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
  • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00504—Controlling the temperature by means of a burner
• • 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
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00513—Controlling the temperature using inert heat absorbing solids in the bed
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00157—Controlling the temperature by means of a burner
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/02—Apparatus characterised by their chemically-resistant properties
  • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
  • B01J2219/0263—Ceramic

Definitions

• the invention relates to an improved method for the implementation of
• the invention further relates to a catalytic system for such a hydrodechlorination reactor.
• SiCI 4 and HS1CI3 are formed together. It is therefore necessary to merge these two products into each other and thus meet the respective demand for one of the products.
• high-purity HS1CI3 is an important feedstock in the production of solar silicon.
• Reactor wall which can lead to silicon deposits, as possible to
• the current technology does not allow operation under pressure to achieve a higher space / time yield, thus reducing, for example, the number of reactors.
• EP 0 658 359 describes a process for the catalytic hydrodehalogenation of halogen-containing compounds in which transition metal silicides are obtained by reacting the salts of the metals with silicon and hydrogen and a halogen-containing silicon compound or by reacting and forming finely dispersed metal with a halogen-containing silicon compound with hydrogen becomes.
• transition metal silicides are obtained by reacting the salts of the metals with silicon and hydrogen and a halogen-containing silicon compound or by reacting and forming finely dispersed metal with a halogen-containing silicon compound with hydrogen becomes.
• a full contact is described, the high
• a microporous material is claimed for the claimed catalyst, preferably consisting of S1O2 / Al2O3, for example
• EP 0 255 877 describes a supported catalyst in which the support preferably undergoes a surface treatment. To a coating of
• Hydrogen is passed through a tubular reactor provided with a catalytic wall coating. It has also been found that the reactor can be operated simultaneously under pressure. The combination of the use of a catalyst to improve the reaction kinetics and
• reaction catalyzing inner wall coating of the reactor is a peculiarity of the method, since even at comparatively low temperatures of well below 1 .000 ° C, preferably below 950 ° C produces sufficiently high amounts of TCS can be incurred without significant losses due to the thermal decomposition would have to be accepted.
• gas-tightness and Inertness can be achieved by high temperature resistant ceramics, which are specified below.
• the reactor tube can be filled as an additional measure with an inert bulk material to the
• the bulk material can consist of the same material as the reactor material. Bulk materials such as rings, spheres, rods or other suitable packing can be used as the bulk material. In a particular embodiment, the fillers may additionally be coated with a catalytically active coating.
• 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 specifications regarding the introduction of the heat required for the reaction.
• both a single reaction tube with the associated periphery can be used as well as a combination of many reactor tubes.
• the arrangement of many reactor tubes in a heated chamber may be useful, in which the amount of heat is introduced, for example by natural gas burners.
• the burners should not be aimed directly at the tubes. They can, for example, be oriented indirectly from above into the reactor space and distributed over the reactor space, as shown by way of example in FIG.
• the reactor system can be connected to a heat recovery system.
• the suspension (hereinafter also referred to as lacquer or paste) contains catalytically active metals or metal compounds and during the heating phase forms a solid layer with the reactor tube or the carrier material (the bulk material of the fixed bed).
• the suspension usually has a flowable at room temperature, ie paint-like character;
• the suspension may also be pasty.
• a special feature of the suspension is that the surface of the reactor tube or the carrier need not be porous and also requires no pretreatment to increase the roughness. The suspension is described in more detail below. The suspension is applied after application z. B.
• Temperatures are set which are approximately at the level of the subsequent reaction or higher, ie at least 600 ° C, preferably 800 ° C, particularly preferably 900 ° C.
• the tempering can take place after installation of the tubes and the packing in the reactor space.
• the invention relates to a process for the reaction of silicon tetrachloride with hydrogen to trichlorosilane in a Hydrodechlon mecanicsreaktor, wherein the reaction is catalyzed in the Hydrodechlon mecanicsreaktor by a reaction catalyzing the coating of the reactor inner wall.
• the process according to the invention is a process in which, in the reaction, a reactant gas containing silicon tetrachloride and a hydrogen-containing educt gas are reacted in the hydrodechlorination reactor by the addition of heat to form a trichlorosilane-containing and HCl-containing
• product gas If desired, by-products such as dichlorosilane, monochlorosilane and / or silane may also be present in the product stream.
• by-products such as dichlorosilane, monochlorosilane and / or silane may also be present in the product stream.
• unreacted starting materials ie silicon tetrachloride and
• the equilibrium reaction in the hydrodechlorination reactor is typically at 700 ° C to 1, 000 ° C, preferably 850 ° C to 950 ° C and at a pressure in the range between 1 and 10 bar, preferably between 3 and 8 bar, more preferably carried out between 4 and 6 bar.
• the silicon tetrachloride-containing feed gas and the hydrogen-containing feed gas can also be conducted as a common stream into the hydrodechlorination reactor.
• the Hydrodechlor istsreaktor comprises one or more of ceramic material existing reactor tubes, which are provided on the inner wall with a conversion catalyzing the coating.
• the ceramic material of which the one or more reactor tubes can be made is preferably selected from Al 2 O 3, AlN, Si 3 N, SiCN or SiC, more preferably selected from Si-infiltrated SiC, isostatically pressed SiC, hot isostatically pressed SiC or non-pressure sintered SiC (SSiC ).
• the one or more reactor tubes consist of non-pressure-sintered SiC (SSiC).
• the educt gas containing silicon tetrachloride and / or the hydrogen-containing educt gas preferably with a pressure in
• Range of 1 to 10 bar preferably in the range of 3 to 8 bar, more preferably in the range of 4 to 6 bar, and having a temperature in the range of 150 ° C to 900 ° C, preferably in the range of 300 ° C to 800 ° C, more preferably in the range of 500 ° C to 700 ° C, is conducted into the Hydrodechlor mecanicsreaktor.
• Inner coating of one or more reactor tubes is catalyzed.
• the reaction in the hydrodechlorination 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. In this way, the catalytically useful surface can be maximized.
• 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 contains.
• 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 contains.
• Particularly preferred metals are Pt, Pd, Rh and Ir and their mixtures or
• a further subject of the invention is a catalytic system for a reactor for the conversion of silicon tetrachloride to trichlorosilane, the reactor comprising one or more reactor tubes, characterized in that the system catalyzes the conversion of silicon tetrachloride to trichlorosilane
• Inner wall coating comprises at least one of the reactor tubes.
• Implementation of silicon tetrachloride to trichlorosilane catalyzing coating may comprise a arranged in the at least one reactor tube fixed bed.
• the catalytic system comprises reactor tubes in addition to the catalyzing inner wall coating a ceramic material.
• the ceramic material is selected from Al 2 O 3, AlN, Si 3 N 4 , SiCN or SiC, more preferably the ceramic material is selected from Si-infiltrated SiC, isostatically pressed SiC, hot isostatically pressed SiC or pressureless sintered SiC (SSiC).
• the catalytic system comprising one or more reactor tubes and a catalyzing the implementation of silicon tetrachloride to trichlorosilane
• Inner wall coating can be made as follows:
• a suspension i. H. of a paint or paste containing a) 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, b) at least one suspending agent, and optionally c) at least one auxiliary component, in particular for stabilizing the suspension, for improving the storage stability of the suspension, for
• Suspension on the surface of random packings of the optionally provided fixed bed by drying the applied suspension; and by annealing the coated and dried suspension at a temperature in the range of 500 ° C to 1, 500 ° C under inert gas or hydrogen.
• the tempered fillers can then be filled into the one or more reactor tubes.
• the tempering and optionally also the previous drying can also be done with already filled in packing.
• thermoplastic polymeric acrylate resins such as those used in the paint and coatings industry. These include, for example, polymethyl acrylate,
• Polyethylacrylate, polypropylmethacrylate or polybutylacrylate It is a matter of commercially available systems, for example those available under the brand name Degalan® from Evonik Industries.
• auxiliaries or auxiliary components are used.
• auxiliary component c) optional solvent or diluent optional solvent or diluent.
• organic solvents in particular aromatic solvents or diluents, such as toluene, xylenes, and ketones, aldehydes, esters, alcohols or mixtures of at least two of the aforementioned solvents or diluents are suitable.
• 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.
• adhesion promoters from the group of silanes or siloxanes can also be used as auxiliary components c).
• auxiliary components c for example, but not limited to, dimethyl, diethyl, dipropyl, dibutyl, diphenylpolysiloxane or mixed systems thereof, such as
• phenylethyl or phenylbutylsiloxanes or other mixing systems, as well as mixtures thereof.
• the lacquer or paste according to the invention can be produced in a comparatively simple and economical manner, for example by mixing, stirring or kneading the starting materials, cf. Components a), b) and optionally c), in corresponding, the Professional known per se, common apparatuses are obtained. Furthermore, reference is made to the present inventive examples.
• FIG. 1 shows, by way of example and schematically, a hydrodechlorination reactor which can be used in accordance with the invention for reacting silicon tetrachloride with hydrogen to form trichlorosilane, provided it is equipped with a corresponding catalytically active coating (not shown).
• the Hydrodechlon mecanicsreaktor shown in Figure 1 comprises a plurality of arranged in a combustion chamber 15 reactor tubes 3a, 3b, 3c, a common reactant gas 1, 2, which is guided into the plurality of reactor tubes 3a, 3b, 3c and one of the plurality of reactor tubes 3a, 3b, 3c led out line 4 for a product stream.
• the reactor shown further comprises a combustion chamber 15 and a conduit for fuel gas 18 and a line for combustion air 19, which lead to the four burners of the combustion chamber 15 shown. Shown is finally still out of the combustion chamber 15 leading pipe for flue 20.
• a varnish-containing paste containing the catalyst was prepared by mixing together the following components:
• the recipe was prepared as in Example 1, but instead of the platinum black, the same amount of tungsten silicide (Sigma-Aldrich) was used.
• the SSiC tube was used without the use of a catalytically active paste.
• the recipe was prepared as in Example 1, but instead of the platinum black, the same amount of nickel powder was used.
• Silicon tetrachloride pumped into the reaction tube.
• the hydrogen flow was adjusted to a molar excess of 4.2 to 1.
• the reactor effluent was analyzed by online gas chromatography and from this the silicon tetrachloride conversion and the molar selectivity to trichlorosilane were calculated.
• TCS trichlorosilane

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Silicon Compounds (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2010
  • 2010-01-18 DE DE102010000980A patent/DE102010000980A1/de not_active Withdrawn
  • 2010-12-16 KR KR1020127018695A patent/KR20120127412A/ko not_active Application Discontinuation
  • 2010-12-16 CN CN2010800617637A patent/CN102725059A/zh active Pending
  • 2010-12-16 US US13/522,514 patent/US20130216464A1/en not_active Abandoned
  • 2010-12-16 CA CA2786667A patent/CA2786667A1/en not_active Abandoned
  • 2010-12-16 JP JP2012549272A patent/JP2013517209A/ja not_active Ceased
  • 2010-12-16 WO PCT/EP2010/069920 patent/WO2011085900A1/de active Application Filing
  • 2010-12-16 EP EP10798059A patent/EP2525904A1/de not_active Withdrawn
• 2011
  • 2011-01-13 TW TW100101286A patent/TW201139274A/zh unknown

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