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WO2014116341A1 - Procédé de préparation de trihalosilane - Google Patents

Procédé de préparation de trihalosilane Download PDF

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Publication number
WO2014116341A1
WO2014116341A1 PCT/US2013/069522 US2013069522W WO2014116341A1 WO 2014116341 A1 WO2014116341 A1 WO 2014116341A1 US 2013069522 W US2013069522 W US 2013069522W WO 2014116341 A1 WO2014116341 A1 WO 2014116341A1
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Prior art keywords
copper catalyst
trihalosilane
reactor
supported copper
catalyst
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English (en)
Inventor
Aaron COPPERNOLL
Catharine HORNER
Krishna Janmanchi
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Dow Silicones Corp
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Dow Corning Corp
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • 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
    • C01B33/10705—Tetrafluoride
    • 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
    • C01B33/10768—Tetrabromide; Tetraiodide

Definitions

  • a number of methods of producing trihalosilane have been disclosed. For example, the reaction of HCI with zero-valent silicon has been described.
  • trichlorosilane has been produced by passing silicon tetrachloride (SiCl4), H2, and HCI over zero-valent silicon (Si 0 ) at 600 °C.
  • trichlorosilane (HSiCl3) has been produced by passing H2 and S1CI4 over silicon particles in a first stage, adding HCI to the effluent from the first stage, and then passing the effluent and HCI over more silicon particles optionally containing a catalyst (i.e., CuCI) in a second stage.
  • HSiCl3 has been produced by passing H2, S1CI4, and HCI over Si 0 containing homogeneously distributed copper silicide.
  • the method includes the separate and consecutive steps of (i) contacting a copper catalyst with hydrogen gas and a silicon tetrahalide at a temperature of from 500 to 1400 °C to form a silicon-containing copper catalyst comprising at least 0.1 % (w/w) of silicon; and (ii) contacting the silicon-containing copper catalyst with a hydrogen halide at a temperature from 100 to 600 °C to form the trihalosilane.
  • a method of preparing a reaction product comprising a trihalosilane comprises:
  • the method of preparing the reaction product comprising the trihalosilane may comprise:
  • the trihalosilane is formed by the method without a separate step of adding a hydrogen halide, from a source outside the reactor, after contacting the supported copper catalyst with the silicon tetrahalide.
  • the method described herein produces the reaction product comprising the trihalosilane.
  • This method uses silicon tetrahalide as a reactant to form the trihalosilane.
  • Silicon tetrahalide is a byproduct of industrial processes and may be produced using less energy than the energy required to produce Si 0 .
  • the method described herein may be more economical than prior processes for producing trihalosilane.
  • the method may generate a hydrogen halide in situ, thereby eliminating the need for a separate step of adding a hydrogen halide from outside the reactor after contacting the supported copper catalyst with the silicon tetrahalide. Therefore, the method described herein may be simpler than prior processes for producing trihalosilane.
  • the trihalosilane produced by the method of the invention can be used as a reactant (e.g., raw material) to make high purity polycrystalline silicon such as solar grade polycrystalline silicon, which is used in solar cells or semiconductor grade polycrystalline silicon, which is used in electronic chips.
  • the trihalosilane can be used as a reactant (e.g., raw material) in hydrolysis processes to produce polysiloxane resins, which find use in many industries and applications.
  • the trihalosilane can be used as a reactant (e.g., raw material) to make organosilanes.
  • the supported copper catalyst used in the method comprises Cu.
  • Cu may be used as the only metal on the support.
  • the supported copper catalyst may comprise a combination comprising Cu and at least one element selected from Au and Mg.
  • the combination may include all three of Cu, Au, and Mg.
  • the combination typically comprises 0.1 % to less than 100%, alternatively from 50% to less than 100%, alternatively, 70% to less than 100%, alternatively, from 80% to 99.9%, of Cu, based on the total weight of the combination, with the balance of the combination being at least one of Au and Mg.
  • the supported copper catalyst further comprises a support.
  • supports include, but are not limited to, oxides of aluminum, titanium, zirconium, and silicon; activated carbon; carbon nanotubes; fullerenes; graphene and other allotropic forms of carbon.
  • the support is activated carbon.
  • the supported copper catalyst may be free of carbon, for example, when alumina or silica is used as the support. "Free of carbon" means that the support is not activated carbon, e.g., the support may be a metal oxide such as alumina, silica, titania, or zirconia.
  • a supported copper catalyst that is free of carbon may be beneficial to reduce potential for contamination of the reaction product with carbonaceous compounds that could be detrimental to a particular use of the trihalosilane, for example, when the trihalosilane will be used as a raw material to prepare polycrystalline silicon, particularly semiconductor grade polycrystalline silicon.
  • the supported copper catalyst typically comprises 0.1 % to less than 100%, alternatively 0.1 % to 65%, alternatively 0.1 % to 55%, and alternatively 0.1 % to 35%, of the metal, based on the combined weight of the support and the metal; with the balance being the support.
  • the metal is copper
  • the supported copper catalyst is copper and the support.
  • the metal is a combination of copper and one or more of Au and Mg; and the supported copper catalyst is the combination and the support.
  • the term "metal” refers to zero-valent metal, a metal compound, or a combination of zero-valent metal and a metal compound.
  • the oxidation number of the metal can vary, for example, from 0 to an oxidation number equal to the metal's group number in the Periodic Table of Elements; alternatively the oxidation number is from 0 to 2, alternatively the oxidation number is 0 for Cu and Au, and the oxidation number 2 for Mg.
  • Periodic Table of the Elements refers to the lUPAC periodic table of the elements dated June 2012, and available at
  • the supported copper catalyst may be prepared by, for example, dissolving a copper salt, such as cupric chloride or cupric nitrate, in a solvent, such as water or acid, applying this copper salt solution to a support, and reducing the copper salt on the surface of the support.
  • a copper salt such as cupric chloride or cupric nitrate
  • a solvent such as water or acid
  • CuC _ can be dissolved in water or hydrochloric acid and mixed with activated carbon. Excess CuC _ solution can then be removed, and the activated carbon-CuCl2 mixture dried. The CuC _ can then be reduced on the activated carbon with hydrogen at high temperature, typically 500 °C, to give the supported copper catalyst.
  • the order of addition and reduction and multistep addition of salts and subsequent reduction can also be carried out to prepare the supported copper catalyst.
  • the supported copper catalyst may be prepared by separately reducing separate metals on separate supports and then mixing the separately supported metals to form the supported copper catalyst.
  • the supported copper catalyst may be prepared by a process comprising impregnating or depositing-adsorbing a metal halide such as a metal chloride
  • metal nitrate e.g., 0 ⁇ ( ⁇ 3 ) 2
  • hydrate thereof e.g., CuCI-H 2 0
  • at least two different metals at least one co-metal chloride or nitrate (e.g., CUCI3 and Mg(N03) 2 ) on a support such as carbon to give an impregnated or deposited-adsorbed material; and activatingly reducing the metal and, if present the additional metal(s), of the impregnated or deposited-adsorbed material so as to produce the supported copper catalyst, which may be finely divided.
  • the activatingly reducing means adding electrons or hydrogen (e.g., via H 2 (g) or a hydride reagent such as NaBH 4 ) so as to produce a functional catalyst.
  • the "depositing-adsorbing" means accumulating material onto a surface of a support when the material is slurried in an aqueous solution. The resulting deposited-adsorbed material would be retained by the support even after washing the carrier with deionized or distilled water.
  • Example 3 of WO 201 1 /106194 An illustrative example of the depositing-adsorbing technique may be found in Example 3 of WO 201 1 /106194.
  • the "impregnating” means permeating with a wetted, melted, or molten substance substantially throughout a support (e.g. , via an incipient wetness technique), preferably to a point where essentially all of a liquid phase substance is adsorbed, producing a liquid-saturated but unagglomerated solid.
  • An illustrative example of the impregnating technique may be found in Example 1 of WO 201 1 /106194.
  • the support may be activated carbon or a metal oxide, as described above.
  • the supported copper catalyst may be dried, e.g., at 120 °C under vacuum (e.g., ⁇ 20 kPa) for 4 hours under a bleed of an inert gas (e.g., nitrogen, helium, or argon gas).
  • an inert gas e.g., nitrogen, helium, or argon gas
  • the silicon tetrahalide used in the method has the formula S1X4, where each X is independently halo; alternatively X is Br, CI, F, or I; alternatively Br, CI, or I; and alternatively CI.
  • Examples of the silicon tetrahalide include, SiBr4, S1CI4, S1F4, and S1I4.
  • the silicon tetrahalide is S1CI4.
  • the method can be performed in any reactor suitable for the contacting of gases and solids.
  • the reactor configuration can be a packed bed, stirred bed, vibrating bed, moving bed, re-circulating bed, or a fluidized bed (FBR).
  • the reactor may be a FBR.
  • the reactor may have means to control the temperature of the reaction zone, i.e., the portion of the reactor in which H2 and S1X4 contact the supported copper catalyst.
  • the H2 and S1X4 may be fed to the reactor simultaneously; however, other methods of combining, such as by separate pulses, are also envisioned.
  • the H2 and S1X4 may be mixed together before feeding to the reactor; alternatively, the H2 and S1X4 may be fed into the reactor as separate streams.
  • the temperature of the reactor in which H2 and S1X4 are contacted with the supported copper catalyst is at least 300 °C.
  • the temperature may be 300 °C to 950 °C; alternatively 450 °C to 950 °C; alternatively 500 °C to 950 °C, and alternatively 750 °C to 950 °C.
  • the pressure at which H2 and S1X4 are contacted with the supported copper catalyst can be sub-atmospheric, atmospheric, or super-atmospheric.
  • the pressure is typically atmospheric pressure (0 kilopascals gauge) to 5,000 kilopascals gauge (kPag); alternatively 0 kPag to 415 kPag.
  • the mole ratio of H2 to silicon tetrahalide (H2/SiX4) contacted with the supported copper catalyst may be 15:1 to 1 :1 , alternatively 1 1 :1 to 1 :1 , alternatively 10:1 to 1 :1 , alternatively 5:1 to 1 :1 , alternatively 4:1 to 1 :1 , alternatively 3:1 to 1 :1 , alternatively 2:1 to 1 :1 , and alternatively 4:1 to 2:1 .
  • One benefit of the method described herein is that a relatively low H2/S1X4 ratio may be used with good conversion and selectivity, thereby reducing the amount of H2 required.
  • the relatively low H2/S1X4 molar ratio may be 4:1 to 1 :1 , alternatively 3:1 to 1 :1 , alternatively 2:1 to 1 :1 , and alternatively 4:1 to 2:1 .
  • the residence time for the H2 and S1X4 in the reactor is sufficient for the H2 and
  • a sufficient residence time for the H2 and S1X4 is typically at least 0.01 seconds (s) ; alternatively at least 0.1 s; alternatively from 0.1 s to 10 minutes (min) ; alternatively from 0.1 s to 1 min; alternatively from 1 s to 10 s.
  • "residence time” means the time which a material takes to pass through a reactor system in a continuous process, or the time a material spends in a reactor in a batch process.
  • residence time may refer to the time for one reactor volume of reactant gases to pass through a reactor charged with catalyst. (E.g., the time for one reactor volume of H2 and S1X4 to pass through a reactor charged with supported copper catalyst.)
  • the supported copper catalyst is used in a sufficient amount.
  • a sufficient amount of supported copper catalyst is enough supported copper catalyst to form the trihalosilane, when the H2 and S1X4 are contacted with the supported copper catalyst.
  • the exact amount of supported copper catalyst depends upon various factors including the type of reactor used (e.g., batch or continuous), the residence time, temperature, the H2/SiX4 molar ratio, and the particular silicon tetrahalide used.
  • a sufficient amount of supported copper catalyst may be at least 0.01 milligram catalyst per cubic centimeter (mg catalyst/cm 3 ) of reactor volume; alternatively at least 0.5 mg catalyst/cm 3 of reactor volume, and alternatively 1 mg catalyst/cm 3 of reactor volume to the maximum bulk density of the metal oxide supported copper catalyst, alternatively 1 mg to 5,000 mg catalyst/cm 3 of reactor volume, alternatively 1 mg to 1 ,000 mg catalyst/cm 3 of reactor volume, and alternatively 1 mg to 900 mg catalyst/cm 3 of reactor volume.
  • mg catalyst/cm 3 milligram catalyst per cubic centimeter
  • step (ii) of the method may be conducted for at least 0.1 s, alternatively 1 s to 30 hours (h), alternatively 1 s to 5 h, alternatively 1 min to 30 h, alternatively 3 h to 30 h, alternatively 3 h to 8 h, and alternatively 3 h to 5 h.
  • the method described herein may also comprise purging the reactor before the contacting of the supported copper catalyst with the H2 and S1X4.
  • purging the reactor before the contacting of the supported copper catalyst with the H2 and S1X4.
  • Purging means to introduce a gas stream to the reactor containing the supported copper catalyst to remove unwanted materials. Unwanted materials are, for example, air, O2 and/or H2O. Purging may be accomplished with a gas such as Ar, He, H2, and/or N2; alternatively H2; alternatively an inert gas such as Ar, He, and/or N2. Alternatively, the purge gas may be S1X4, where X is as defined above.
  • the method may further comprise pre-heating and vaporizing the S1X4, such as by known methods, before contacting with the supported copper catalyst.
  • the method may further comprise bubbling the H2 through the S1X4 to vaporize the S1X4 before contacting the vaporous S1X4 with the supported copper catalyst.
  • the method may further comprise recovering the reaction product, for example, to purify the trihalosilane produced.
  • the trihalosilane may be recovered by, for example, removing gaseous trihalosilane and any other vapors from the reaction product followed by condensation of the vapors and/or isolation of the trihalosilane from any other compounds in the reaction product by distillation.
  • the trihalosilane produced by the method described and exemplified herein has the formula HS1X3, wherein X is as defined and exemplified for the silicon tetrahalide.
  • trihalosilanes prepared according to the present process include, but are not limited to, HS1CI3, HSiBrCl2, HSiB ⁇ , and HS1I3; alternatively, the trihalosilane produced may be HS1CI3.
  • Activated carbon, CuCI 2 -2H 2 0, AUCI3, and MgCI 2 -6H 2 0 and other reagents used in the examples were purchased from Sigma Aldrich (Milwaukee, Wl).
  • a method of producing a supported copper catalyst comprising copper, gold, and magnesium was performed by dissolving CuCI 2 -2H 2 0 (99+%, 1 .0526 g), 0.0192 g AuCI 3 (99%), and
  • the reaction apparatus comprised a 4.8 mm inner diameter quartz glass tube in a flow reactor.
  • the reactor tube was heated using a Lindberg/Blue Minimite 2.54 cm tube furnace. Brook 5850E mass flow controllers were used to control gas flow rates.
  • a stainless steel SiCl4 bubbler was used to introduce S1CI4 into the H 2 gas stream. The amount of SiCl4 in the H 2 gas stream was adjusted by changing the temperature of the
  • a copper catalyst (0.6085 g) comprising an activated carbon supported mixture of 22.3% Cu, 0.71 % Au, and 0.24% Mg was prepared as described above.
  • the copper catalyst was then treated with H2 and SiCl4 at a mole ratio of H2 to SiCl4 of 16:1 for 30 min by bubbling H2 (100 seem) through a stainless steel bubbler containing liquid SiCl4 at 0 °C and into a flow reactor containing the copper catalyst at 750 °C to form a silicon- containing copper catalyst comprising 4% Si.
  • H2 100 seem
  • a stainless steel bubbler containing liquid SiCl4 at 0 °C and into a flow reactor containing the copper catalyst at 750 °C to form a silicon- containing copper catalyst comprising 4% Si.
  • the S1CI4 flow was ceased, and the hydrogen flow was maintained for 1 h while cooling the reactor contents to 300 °C.
  • the reactor containing the silicon-containing copper catalyst was then purged with a 50 seem argon flow for 15 min. After the purging, HCI was fed through the reactor at a flow rate of 5 seem. The reaction effluent was periodically analyzed by GC to determine the HS1CI3 selectivity. After the silane production rate declined, the HCI feed was ceased, and the silicon-containing copper catalyst was contacted again with H2 and S1CI4 for 30 min at 750 °C to reform the silicon-containing copper catalyst. The reformed silicon- containing copper catalyst was then purged with argon and contacted again with HCI as described above.
  • a catalyst comprising 16.5% Cu, 0.7% Au, and 0.2% Mg on activated carbon was prepared and treated as described in Comparative Example 1 , except the stainless steel bubbler was at 23 °C to give a mole ratio of H2 to S1CI4 of 10:1 and the time was varied as indicated in Table 3, to form a silicon-containing copper catalyst comprising 4% Si.
  • the silicon-containing copper catalyst was reacted in step 2 as in Comparative Example 1 but with the parameters listed in Table 3 and at 300 °C in every cycle. Comparative Example 2 shows that HSiCl3 can be produced with good selectivity, the benefits of adding hydrogen with the hydrogen halide, and that the silicon-containing copper catalyst can be regenerated repeatedly.
  • a catalyst comprising 16.3% (w/w) Cu, 0.7% (w/w) Au, and 0.2% (w/w) Mg on activated carbon was prepared and treated as described in Comparative Example 1 , except the stainless steel bubbler was at 22 °C to give a mole ratio of H2 to S1CI4 of 10:1 and the time was varied as indicated in Table 4, to form a silicon-containing copper catalyst comprising 4% Si.
  • the silicon-containing copper catalyst was reacted in step 2 as in Comparative Example 1 but with the parameters listed in Table 4 and at 300 °C in every cycle. Table 4. Production of HS1CI3 at various temperatures and pressures with catalyst comprising Cu, Au, and Mg on activated carbon (16.3% (w/w) Cu, 0.7% (w/w) Au, 0.2%
  • a catalyst comprising 17.3% (w/w) Cu, 0.7% (w/w) Au, and 0.2% (w/w) Mg on activated carbon was prepared and treated as described in Comparative Example 1 , except the stainless steel bubbler was at 23 °C to give a mole ratio of H2 to S1CI4 of 10:1 and the time was varied as indicated in Table 5, to form a silicon-containing copper catalyst comprising 4% Si.
  • the silicon-containing copper catalyst was reacted in step 2 as in Comparative Example 1 but with the parameters listed in Table 5 and at 300 °C in every cycle.
  • a copper catalyst (0.5 grams) comprising an activated carbon supported mixture of copper, gold and magnesium, prepared by incipient wetness impregnation, was treated with H 2 /SiCl4 for 30 min at 750 °C - 950 °C by bubbling H 2 through a stainless steel S1CI4 bubbler.
  • the total flow of H2 and S1CI4 was varied from 1 10 seem to 150 seem and the mole ratio of H2 to S1CI4 was 5:1 to 1 1 :1 .
  • the S1CI4 flow was controlled by H2 flow by varying the bubbler temperature from 1 1 °C to -3.6 °C.
  • trichlorosilane was produced by the method described herein under the conditions in this example.
  • a copper catalyst (0.5 grams) comprising an activated carbon supported mixture of copper, gold and magnesium, prepared by incipient wetness impregnation, was treated with H 2 /SiCl4 for 30 min at 750 °C to 950 °C by bubbling H 2 through a stainless steel S1CI4 bubbler.
  • the total flow of H2 and S1CI4 was 150 seem and the mole ratio of H2 to S1CI4 was 1 to 4.
  • the S1CI4 flow was controlled by H2 flow by varying the bubbler temperature from 14.6°C to 37.2 °C.
  • the gas and vapor leaving the bubbler is fed into the glass tube of a flow reactor containing the supported copper catalyst at atmospheric pressure for 30 min.
  • Example 2 demonstrates that trichlorosilane was produced by the method described herein and tetrachlorosilane conversion to trichlorosilane was increased with increase in reaction temperature and decreases with decreasing H2 to
  • the gas and vapor leaving the bubbler was fed into the glass tube of a flow reactor containing the supported copper catalyst at atmospheric pressure for 30 min.
  • the reaction was periodically sampled and analyzed by GC to determine the weight percent HS1CI3, based on the total mass leaving the reactor. The results are shown in
  • An activated carbon supported copper catalyst was prepared as described above, and 0.5 grams of this catalyst ((22.3wt% Cu-0.71wt% Au-0.24wt% Mg)/C) was treated with H2/S1CI4 for 3h continuously at 950 °C by bubbling H2 through a stainless steel SiCl4 bubbler.
  • the total flow of H2 and S1CI4 was 150 seem and the mole ratio of H2 to SiCl4 was 4.
  • the SiCl4 flow was controlled by H2 flow by keeping the bubbler temperature at
  • SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was varied from 1 to 4.
  • the S1CI4 flow was controlled by H2 flow by varying the bubbler temperature from 14.6°C to 37.2 °C.
  • Example 5 demonstrated that trichlorosilane was produced by the method with the conditions in this example.
  • Table 9 Production of Trichlorosilane Using Alumina Supported Copper Catalyst
  • Example 6 demonstrated that trichlorosilane production increased with an increase in reaction temperature under the conditions in this example.
  • a spray dried 65wt% CuO/SiC>2 catalyst obtained from Sud Chemie was tested for the hydrodechlorination of tetrachlorosilane to trichlorosilane. An amount of 1 gram of this catalyst was reduced under H2 at 500 °C with 100 seem for 3h to 4h then treated with
  • H2/S1CI4 for 30 min at 750 °C to 950 °C by bubbling H2 through a stainless steel S1CI4 bubbler.
  • the total flow of H2 and SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was varied from 1 to 4.
  • the S1CI4 flow was controlled by H2 flow by varying the bubbler temperature from 14.6°C to 37.2 °C.
  • the gas and vapor leaving the bubbler was fed into the glass tube of a flow reactor containing the copper catalyst at atmospheric pressure for 30 min.
  • the reactor effluent was periodically sampled and analyzed by GC to determine the weight percent HS1CI3, based on the total mass leaving the reactor. The results are shown in Table 1 1 .
  • Table 1 1 Production of Trichlorosilane Using Silica 65wt% CuO/Silica (spray dried catalyst)
  • Comparative Example 5 demonstrated that unsupported copper catalyst built up pressure within the reactor, and upon removal, was shown to be sintered together. The results are shown in Table 12.
  • the method described herein may provide one or more benefits over previously disclosed processes for making trihalosilanes.
  • a lower amount of H2 relative to S1X4 may be used with good yield as compared to previous processes.
  • Example 1 The method described herein may also be simpler and allow for a longer run time without drop in selectivity necessitating the need to regenerate the catalyst, as shown in Example 4. Furthermore, for example, in Example 1 and Comparative Example 1 , it can be seen that a yield of trichlorosilane may be maintained for a longer period of time using the method described herein as compared to a previous method.
  • the method described herein may be suitable for making HS1CI3 for semiconductor grade polycrystalline silicon production, particularly when a carbon free supported copper catalyst (such as a silica or alumina supported copper catalyst) is used, thereby minimizing potential for carbon contamination of trihalosilane in the reaction product because carbon contamination is undesirable in the raw materials used for polycrystalline silicon production, particularly semiconductor grade polycrystalline silicon.
  • a carbon free supported copper catalyst such as a silica or alumina supported copper catalyst
  • any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of 300 to 950" may be further delineated into a lower third, i.e., from 300 to 516, a middle third, i.e., from 517 to 733, and an upper third, i.e., from 734 to 950, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range such as "at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of "at least 0.1 %" inherently includes a subrange from 0.1 % to 65%, a subrange from 10% to 25%, a subrange from 23% to 50%, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range of “4:1 to 1 :1” includes various individual members, such as 3:1 , as well as individual numbers including a decimal point (or fraction), such as 2.1 :1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Compounds (AREA)
  • Catalysts (AREA)

Abstract

Cette invention concerne un procédé de préparation d'un produit réactionnel contenant un trihalosilane, ledit procédé comprenant la mise en contact d'un catalyseur de cuivre supporté avec H2 et un tétrahalogénure de silicium à une température d'au moins 300°C pour former le produit réactionnel. Le catalyseur de cuivre supporté contient du Cu et éventuellement un ou plusieurs éléments parmi Au et Mg. Le procédé est mis en œuvre sans étape séparée d'ajout d'un halogénure d'hydrogène après mise en contact du catalyseur de cuivre supporté avec le tétrahalogénure de silicium.
PCT/US2013/069522 2013-01-25 2013-11-12 Procédé de préparation de trihalosilane Ceased WO2014116341A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN112203972A (zh) * 2018-05-02 2021-01-08 氢试实验室有限公司 制备和再生氢载体化合物的方法
CN117401685A (zh) * 2023-12-13 2024-01-16 唐山三孚硅业股份有限公司 一种同时生产高纯度三氯氢硅和四氯化硅的方法
WO2024251705A1 (fr) 2023-06-05 2024-12-12 Totalenergies Onetech Catalyseurs métalliques pour une hydrogénation de co2 en co

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WO2011106194A2 (fr) 2010-02-23 2011-09-01 Dow Global Technologies Llc Procédé de fabrication d'éthers de polyol
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112203972A (zh) * 2018-05-02 2021-01-08 氢试实验室有限公司 制备和再生氢载体化合物的方法
CN112203972B (zh) * 2018-05-02 2024-02-06 氢试实验室有限公司 制备和再生氢载体化合物的方法
WO2024251705A1 (fr) 2023-06-05 2024-12-12 Totalenergies Onetech Catalyseurs métalliques pour une hydrogénation de co2 en co
CN117401685A (zh) * 2023-12-13 2024-01-16 唐山三孚硅业股份有限公司 一种同时生产高纯度三氯氢硅和四氯化硅的方法
CN117401685B (zh) * 2023-12-13 2024-02-20 唐山三孚硅业股份有限公司 一种同时生产高纯度三氯氢硅和四氯化硅的方法

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