WO2006098722A1 - Process for the production of hydrochlorosilanes - Google Patents
Process for the production of hydrochlorosilanes Download PDFInfo
- Publication number
- WO2006098722A1 WO2006098722A1 PCT/US2005/008204 US2005008204W WO2006098722A1 WO 2006098722 A1 WO2006098722 A1 WO 2006098722A1 US 2005008204 W US2005008204 W US 2005008204W WO 2006098722 A1 WO2006098722 A1 WO 2006098722A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicon
- hydrogen
- metal
- hydrochlorosilanes
- promoter metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 109
- 239000010703 silicon Substances 0.000 claims abstract description 109
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 22
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 104
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 42
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 35
- 239000005052 trichlorosilane Substances 0.000 claims description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 19
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 19
- 229940045803 cuprous chloride Drugs 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 17
- 230000001737 promoting effect Effects 0.000 claims description 14
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000011856 silicon-based particle Substances 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 6
- 239000001301 oxygen Substances 0.000 claims 6
- 229910052760 oxygen Inorganic materials 0.000 claims 6
- 238000000151 deposition Methods 0.000 claims 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005046 Chlorosilane Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004721 HSiCl3 Inorganic materials 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- 229910003910 SiCl4 Inorganic materials 0.000 description 3
- -1 copper Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010010144 Completed suicide Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910021471 metal-silicon alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- 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
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
Definitions
- This invention concerns a process for the production of hydrogen-containing chlorosilanes, particularly trichlorosilane and dichlorosilane from silicon.
- trichlorosilane can be prepared by the reaction of hydrogen chloride and silicon without a catalyst as represented by:
- Wakamatsu (DE 19654154) teaches that trichlorosilane may be produced using a copper suicide catalyst.
- Margaria, et al. (US 6057469) describe copper deposited on the surface of silicon grains.
- Bulan, et al. (US Pat. Application 2004/0022713Al) indicate that to be effective copper must be in a granular form 30 to 100 times finer than the silicon particle.
- copper can be incorporated into the bulk of the silicon by adding copper in the form of elemental copper metal or as a copper compound to the silicon during metallurgical processing.
- such bulk incorporation must be at a much higher copper concentration in order to achieve the same catalytic effect than if the copper were applied only to the surface of the silicon.
- the higher concentrations of copper required by bulk addition poses challenges for effective disposal of the spent silicon containing the additional copper.
- a native oxide on the silicon metal retards the effective bonding of copper to the silicon surface, which in turn, reduces the effective incorporation of the catalyst or delays the benefit of the catalyst until the native oxide can be removed by other chemical action within the process.
- the native oxide may be somewhat removed by extreme milling. But once the oxide is removed, the silicon must be maintained in an oxygen-free condition, a difficult and expensive process in practical commercial endeavors.
- hydrochlorosilanes can be produced from the reaction of silicon and hydrogen along with a chlorine source.
- the chlorine source may be hydrogen chloride, silicon tetrachloride or a combination of the two.
- the ratio of dichlorosilane and trichlorosilane may be altered by adjusting the hydrogenxhloride ratio, gas residence time, and the reaction temperature and pressure when using the effective catalyst.
- the resulting silicon surface is then substantially free of oxide if maintained in an oxygen-free environment.
- Cuprous chloride is a reducible substance that rapidly reduces with hydrogen at elevated temperatures:
- reaction (5) occurs autogenously at temperatures above about 275°C in a hydrogen atmosphere.
- metallurgical grade or refined grade silicon is used as a starting material in the production of trichlorosilane by reaction (1) or (2).
- Such silicon inherently has a native oxide present on the silicon surface.
- the silicon is milled and screened to provide a particle size suited to the particular requirements of the chosen process design.
- a particle size of about 200 microns is suitable in many processes, but size is of no issue so long as the particles are small enough to operate in a mixing environment, such as in a fluidized bed or stirred bed reactor, wherein gases readily can be brought into contact with the silicon particles.
- silicon is added into a vessel, such as a fluidized or mechanically stirred bed reactor, and the reactor is brought to normal operating conditions of 275 0 C - 550 0 C with a feed of gaseous hydrogen and a chlorine source.
- the chlorine source can be hydrogen chloride, silicon tetrachloride, or a combination thereof.
- HCl aggressively attacks the silicon at any temperature above 275 0 C by reaction (2).
- reaction (2) The combination of reactions (2) and (6) results in reaction (1).
- the effect of the silicon is to remove HCl from the reaction environment and shift the equilibrium concentration of reaction (1) to the right, increasing the overall yield of hydrochlorosilanes.
- Reactions (6) and (7) are operated with an excess amount OfH 2 . Together, reactions (6) and (7) combine to remove any oxides or moisture from at least a portion of the surface of the silicon. The resulting substantially oxide-free silicon surface is then able to effectively accept and bond with an active copper metal.
- Copper most effectively in form of cuprous chloride (CuCl), is then added to the reactor and the reduction with excess hydrogen at 275°C to 550 0 C occurs to form copper metal and additional HCl, by reaction (5).
- the copper produced on an atomic basis, is deposited upon at least a portion of the substantially oxide-free surface of the silicon by chemical vapor deposition to form a copper-silicon alloy.
- particles of CuCl are reduced in situ in close proximity with the oxide-free silicon to form the effective alloy catalyst.
- the copper deposit may consist of randomly arranged "islands" of copper on the surface of the silicon.
- the copper-silicon surface alloy is a very effective catalyst for reactions (1), (2) and (3). Very effective results are obtained at copper levels of less than 1.0%.
- reducible copper compounds may be employed in addition to or as a substitute for copper chloride. Copper oxide or mixtures of copper oxide and copper metal may be used. But when these are used, the extra moisture that is formed by the hydrogen reduction of the copper oxide results in a loss of chlorosilane by hydrolysis of the chlorosilanes to siloxanes, high boiling impurities that pose a difficult problem in disposal.
- Another suitable reducible material is chloroplatinic acid.
- silicon tetrachloride is the chlorine source
- the promoter metal should be chosen to be capable of promoting the hydrochlorination reaction in the presence of silicon tetrachloride and hydrogen.
- the promoter metal should be a metal capable of promoting hydrochlorination of silicon in the presence of hydrogen chloride and hydrogen.
- a material such as a promoter metal
- a promoter metal is not associated with the silicon surface, it is ineffective in catalyzing reaction (1).
- a promoter metal is present on an otherwise non-reactive surface, such as silica or carbon, no promotional effect is noted.
- the promoter metal must be present at the surface of the silicon. The rapid consumption of silicon occurs only in the region immediately adjacent to the location of the promoter metal on the oxide-free silicon surface.
- the promoter metal-silicon alloy need not be uniformly distributed on the surface of the silicon. It merely needs be present in an adequate amount. And the removal of the native oxide on silicon need not be complete or uniform, just sufficient to accommodate the amount of promoter metal to be deposited.
- An elevated temperature is maintained to achieve the production of the one or more desired hydrochlorosilanes.
- the temperature inside the reactor is best maintained at 400 0 C to 500 0 C.
- the temperature inside the reactor is best maintained at 275°C to 350 0 C.
- the reactor should be of a type that facilitates mixing of the de-oxidized silicon with the reducible substance that includes the promoter metal so that the decomposing reducible substance is transported to the surface of the silicon onto which the promoter metal is to be deposited.
- Particularly suitable reactors include fluidized bed reactors wherein moving gas provides the mixing force, mechanically agitated bed reactors such as rotary kiln and stirred bed reactors, and tower reactors wherein the silicon and copper chloride particles can fall by gravity against an upwardly rising stream of hydrogen rich gas.
- the hydrogenation reaction can also be carried out in a dilute phase (few solid particles relative to the reactor volume).
- fresh silicon is required to be added to the hydrochlorination reactor to maintain a substantially constant inventory as the silicon is consumed by reaction (1), (2) or (3) and hydrochlorosilanes are removed from the reactor.
- the granulated silicon can be fed either continuously or intermittently in small increments.
- cuprous chloride powder co-feeding cuprous chloride powder with the granulated silicon, a single, simplified system can be used.
- the cuprous chloride is thus preferably added directly to the reaction zone where it decomposes to copper and deposits onto the substantially oxide-free surface of the silicon already present in the reaction zone.
- the fresh silicon co-fed with the cuprous chloride enjoys a brief period of conditioning in the reaction zone to lose its native oxide and is thus prepared for reaction with the cuprous chloride being added at the next opportunity.
- This procedure one need not make any special arrangements to precondition either the silicon or the copper-containing substance and the overall effect is for a beneficially high rate of production of hydrochlorosilanes at normal temperature and pressure.
- promoter materials which can act to promote the hydrochlorination or to form proportionately higher yields of the more hydrogenated chlorosilanes can be added in a similar manner.
- Such materials include the oxides, carbonates, and chlorides of zinc and tin and the chlorides and carbonates of ruthenium, rhenium, platinum, silver, osmium, and nickel. The following non-limiting examples demonstrate the implementation of this process:
- a fluidized bed reactor 122 cm diameter was charged with 13,000 kg of metallurgical grade silicon ground to an average particle size of 200 micron.
- the reactor was started up by flowing 3350 m 3 /hr of hydrogen at a temperature of 500 0 C and a pressure of 3 Mpa.
- silicon tetrachloride vapor at a flow of 3350 m 3 /hr was started at a temperature of 500 0 C and a pressure of 3 Mpa.
- a reactor product containing 20 mole % trichlorosilane on a hydrogen-free basis was obtained.
- the reactor level decreased by 150 kg, by consumption of silicon via reaction (1), periodic addition of metallurgical grade silicon was commenced and the process continued in that manner for several days.
- a blend of metallurgical grade silicon and cuprous chloride was prepared by adding 4.5 kg of cuprous chloride to a bulk bag containing 1363 kg of silicon. Using a pneumatic conveyor to transport the copper/silicon blend to a lock hopper atop the fluidized bed reactor, the copper/silicon blend was substituted for the normal metallurgical grade silicon feed to the reactor. Shortly after the addition of the cuprous chloride/silicon mix, the hydrogen consumption was noted to have significantly increased. The reactor product, on a hydrogen-free basis, increased to 25 mole % trichlorosilane.
- This example shows that adding a reducible substance that contains a promoter metal directly to the reaction zone where oxide-free silicon is already present results in higher conversion to trichlorosilane. It also shows that the copper chloride had become intimately associated with the silicon and that the yield of trichlorosilane was directly related to the concentration of copper in the reaction mass.
- Example 2 Using the same apparatus as in Example 2, 49 g metallurgical grade silicon was placed into the reactor tube and heated to 525°C in a hydrogen atmosphere. After the silicon had been exposed to the hot hydrogen, 0.39 g of cuprous chloride were added to the reactor, while the hydrogen continued to flow. Then the hydrogen flow was routed through the thermostated reservoir of silicon tetrachloride and the effluent sampled. The concentration of trichlorosilane on a hydrogen free basis was 6.14%.
- Example 2 Using the same apparatus as in Example 2, the reactor was charged with a mixture of 49.9 g of metallurgical grade silicon and 0.1 gram of 5% Platinum on silica gel. The result was a trichlorosilane concentration, on a hydrogen-free basis of 4.28%.
- the reactor tube was filled with 49 g of white quartz and 0.1 gram of 5% platinum on activated carbon. Under the same standard conditions as used in Example 2, the trichlorosilane concentration in the effluent was ⁇ 0.1%.
- the reactor can be charged with 50 grams of metallurgical grade silicon and heated to 300 0 C under a stream of 12 cc/min hydrogen and 6 cc/min hydrogen chloride. After the silicon is exposed to the hot hydrogen and hydrogen chloride mixture for several hours, 0.4 gram of cuprous chloride is added to the reactor, while the hydrogen/hydrogen chloride flow continues.
- the effluent contains trichlorosilane and several percent dichlorosilane. Without the copper-silicon alloy catalyst, the level of dichlorosilane would be only a trace.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800497460A CN101189245B (en) | 2005-03-09 | 2005-03-09 | Process for the production of hydrochlorosilanes |
EP05725398A EP1861408A4 (en) | 2005-03-09 | 2005-03-09 | Process for the production of hydrochlorosilanes |
KR1020077023115A KR101176088B1 (en) | 2005-03-09 | 2005-03-09 | Process for the production of hydrochlorosilanes |
PCT/US2005/008204 WO2006098722A1 (en) | 2005-03-09 | 2005-03-09 | Process for the production of hydrochlorosilanes |
JP2008500692A JP4813545B2 (en) | 2005-03-09 | 2005-03-09 | Method for producing hydrochlorosilane |
DE112005003497T DE112005003497T5 (en) | 2005-03-09 | 2005-03-09 | Process for the preparation of hydrochlorosilanes |
TW095107967A TWI454424B (en) | 2005-03-09 | 2006-03-09 | Process for the production of hydrochlorosilanes |
NO20076030A NO20076030L (en) | 2005-03-09 | 2007-11-23 | Process for the preparation of hydrochlorosilanes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2005/008204 WO2006098722A1 (en) | 2005-03-09 | 2005-03-09 | Process for the production of hydrochlorosilanes |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006098722A1 true WO2006098722A1 (en) | 2006-09-21 |
Family
ID=36991997
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/008204 WO2006098722A1 (en) | 2005-03-09 | 2005-03-09 | Process for the production of hydrochlorosilanes |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1861408A4 (en) |
JP (1) | JP4813545B2 (en) |
KR (1) | KR101176088B1 (en) |
CN (1) | CN101189245B (en) |
DE (1) | DE112005003497T5 (en) |
NO (1) | NO20076030L (en) |
TW (1) | TWI454424B (en) |
WO (1) | WO2006098722A1 (en) |
Cited By (7)
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US20150329367A1 (en) * | 2013-03-07 | 2015-11-19 | Hanwha Chemical Corporation | Method for preparing trichlorosilane |
US20160101983A1 (en) * | 2013-06-19 | 2016-04-14 | Hanwha Chemical Corporation | Method of preparing trichlorosilane |
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Cited By (13)
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WO2009153090A1 (en) * | 2008-06-19 | 2009-12-23 | Evonik Degussa Gmbh | Method for removing boron-containing impurities from halogen silanes and apparatus for performing said method |
US9463982B2 (en) | 2011-10-20 | 2016-10-11 | Rec Silicon Inc | Fouling reduction in hydrochlorosilane production |
CN104080738A (en) * | 2011-10-20 | 2014-10-01 | 瑞科硅公司 | Fouling reduction in hydrochlorosilane production |
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WO2014172102A1 (en) * | 2013-04-19 | 2014-10-23 | Rec Silicon Inc | Corrosion and fouling reduction in hydrochlorosilane production |
US20160101983A1 (en) * | 2013-06-19 | 2016-04-14 | Hanwha Chemical Corporation | Method of preparing trichlorosilane |
CN106536409A (en) * | 2014-07-22 | 2017-03-22 | 韩华化学株式会社 | Trichlorosilane preparation method |
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WO2016100429A1 (en) * | 2014-12-18 | 2016-06-23 | Hemlock Semiconductor Corporation | Methods of hydrogenating a halosilane |
Also Published As
Publication number | Publication date |
---|---|
NO20076030L (en) | 2007-12-07 |
KR101176088B1 (en) | 2012-08-22 |
EP1861408A4 (en) | 2011-08-03 |
JP4813545B2 (en) | 2011-11-09 |
TW200704589A (en) | 2007-02-01 |
KR20080008323A (en) | 2008-01-23 |
CN101189245B (en) | 2012-06-13 |
TWI454424B (en) | 2014-10-01 |
CN101189245A (en) | 2008-05-28 |
DE112005003497T5 (en) | 2008-01-24 |
EP1861408A1 (en) | 2007-12-05 |
JP2008532907A (en) | 2008-08-21 |
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