CN103945932A - Method and apparatus to reduce contamination of particles in a fluidized bed reactor - Google Patents

Method and apparatus to reduce contamination of particles in a fluidized bed reactor Download PDF

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Publication number
CN103945932A
CN103945932A CN201380003733.4A CN201380003733A CN103945932A CN 103945932 A CN103945932 A CN 103945932A CN 201380003733 A CN201380003733 A CN 201380003733A CN 103945932 A CN103945932 A CN 103945932A
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China
Prior art keywords
protective layer
fluidized
bed reactor
tce
coated
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CN201380003733.4A
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Chinese (zh)
Inventor
马修·J·米勒
迈克尔·V·斯潘格勒
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Rec Silicon Inc
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Rec Silicon Inc
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Priority claimed from US13/670,200 external-priority patent/US9587993B2/en
Priority claimed from US13/939,067 external-priority patent/US9212421B2/en
Application filed by Rec Silicon Inc filed Critical Rec Silicon Inc
Priority to CN201811452397.2A priority Critical patent/CN109453729A/en
Publication of CN103945932A publication Critical patent/CN103945932A/en
Pending legal-status Critical Current

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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
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1809—Controlling processes
    • 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
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
    • 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
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • 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
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0236—Metal based

Abstract

A method and fluidized bed reactor for reducing or eliminating contamination of silicon-coated particles are disclosed. The metal surface of one or more fluidized bed reactor components is at least partially coated with a hard protective layer comprising a material having an ultimate tensile strength of at least 700 MPa at 650 DEG C.

Description

Reduce the method and apparatus that fluidized-bed reactor endoparticle pollutes
The cross reference of related application
The present invention is the U. S. application 13/670 of submitting on November 6th, 2012, the part continuation application of No. 200, and on July 10th, 2013 No. 13/939,067, U. S. application submitting to part continuation application, above-mentioned two U. S. applications are all by reference to being incorporated herein in full.
Technical field
The disclosure relates to for fluidized-bed reactor, is coated with especially the hard protective layer of the fluidized-bed reactor of silicon grain for silicon-containing gas cracking with manufacture.
Background technology
In fluid bed, cracking silicon-containing gas, due to excellent mass transfer and heat transfer, the deposition surface of increase and continuous production, is therefore the technique of a kind of attractive manufacture photoelectricity and semicon industry polysilicon.Compared with Siemens reactors, fluidized-bed reactor provides the productivity ratio greatly improving with sub-fraction energy consumption.Fluidized-bed reactor can be increasingly automated significantly to reduce labour cost.
Relate in fluidized-bed reactor cracking silicon-containing material as silane by chemical vapour deposition technique, disilane or halosilanes are fabricated to that those skilled in the art know and by as illustrated in many announcements as the particulate polysilicon of trichlorosilane or tetrachloro silicane, comprise following patent and announcement: US8, 075, 692, US7, 029, 632, US5, 810, 934, US5, 798, 137, US5, 139, 762, US5, 077, 028, US4, 883, 687, US4, 868, 013, US4, 820, 587, US4, 416, 913, US4, 314, 525, US3, 012, 862, US3, 012, 861, US2010/0215562, US2010/0068116, US2010/0047136, US2010/0044342, US2009/0324479, US2008/0299291, US2009/0004090, US2008/0241046, US2008/0056979, US2008/0220166, US2008/0159942, US2002/0102850, US2002/0086530 and US2002/0081250.
Decomposition by being selected from following silicon-containing gas in reactor by siliceous deposits on particle: silane (SiH 4), disilane (Si 2h 6), high order silanes (Si nh 2n+ 2), dichlorosilane (SiH 2cl 2), trichlorosilane (SiHCl 3), silicon tetrachloride (SiCl 4), two bromo-silicane (SiH 2br 2), tribromosilane (SiHBr 3), silicon bromide (SiBr 4), diiodo-silane (SiH 2i 2), triiodo silane (SiHI 3), silicon tetraiodide (SiI 4), with and composition thereof.Halogen-containing to silicon-containing gas and one or more gas can be mixed, described halogen-containing gas is defined as following any person: chlorine (Cl 2), hydrogen chloride (HCl), bromine (Br 2), hydrogen bromide (HBr), iodine (I 2), hydrogen iodide (HI), with and composition thereof.Also can be by silicon-containing gas and one or more other gas as hydrogen (H 2) and/or one or more be selected from nitrogen (N 2), the inert gas of helium (He), argon gas (Ar) and neon (Ne) mixes.In detailed description of the invention, silicon-containing gas is silane, and silane mixes with hydrogen.Silicon-containing gas is introduced to thermal decomposition in fluidized-bed reactor and in reactor together with any hydrogen of following, halogen-containing gas and/or inert gas, to produce silicon, to be made in the seed particles of described siliceous deposits in reactor.
Common problem is the material contamination that is coated with silicon grain in fluid bed and is used to construct reactor and its assembly under high operating temperature in fluidized-bed reactor.For example, shown that nickel is diffused in silicon layer and (is for example being coated with silicon grain) from the base metal of some nickel alloys for constructing reactor part.Produce similar problem in the cracking being fabricated for germanic gas to manufacture in the fluidized-bed reactor that is coated with germanium particle.
Summary of the invention
The disclosure relate to reduce or eliminate be coated with silicon grain because contacting with the metal surface in fluidized-bed reactor the pollution causing.The reactor assemblies with this metal surface includes but not limited to inject jet pipe, fluidizing gas inlet tube, crystal seed inlet tube, product extraction outlet, liner, probe assembly, sample jet pipe, pressure jet pipe, thermocouple, internal heater and defoamer.
At least one fluidized-bed reactor assembly has and comprises the metallic surface that is coated with at least in part protective layer, and when described protective layer comprises 650 DEG C, ultimate tensile strength is the material of 700MPa at least.In some embodiments, at least 95% of described surface be coated with protective layer.Protective layer can have at least average thickness of 0.1mm, as the average thickness of 0.1mm to 1mm.The thickness of protective layer can be across face width and/or length and changing surfacewise.In one embodiment, a part for fluidized-bed reactor assembly is completely by the chemical composition material structure identical in fact with protective layer.
Metal and protective layer have thermal coefficient of expansion (TCE) separately.In some embodiments, TCE differ each other≤30%.Can between metal and protective layer, inter coat be set, between the TCE and the TCE of protective layer of the TCE of wherein said inter coat in metal.
Exemplary protective layer comprises cobalt-base alloys, nickel-base alloy or its combination.In one embodiment, protective layer is cobalt-base alloys, comprises: 25-35%Cr ,≤10%W ,≤10%Ni ,≤5%Mo ,≤3%Fe ,≤2%Si ,≤2%C ,≤1.5%Mn ,≤1%B ,≤0.05%P ,≤0.05%S and 30.5-75% cobalt.In another embodiment; protective layer is nickel based super alloy, comprises: 4-30%Mo, 5-25%Cr, 2-15%Co ,≤3.5%Ti ,≤2%Fe ,≤2%Al ,≤1%Mn ,≤1%Si ,≤0.5%Cu ,≤0.1%C ,≤0.1%Zr ,≤0.01%B and 23.4-89% nickel.
Comprise the reactor that defines reative cell for the manufacture of the fluidized-bed reactor unit of polysilicon, and one or more surperficial reactor assemblies having towards reative cell, described surface comprises and is coated with at least in part the metal of protective layer as disclosed herein.
The embodiment of manufacturing the method for granular polycrystalline silicon particle comprises that silicon-containing gas is flowed through contains the fluidized-bed reactor of seed particles at the reative cell being defined by fluidized-bed reactor; to realize the cracking of silicon-containing gas and the deposition of polysilicon layer in seed particles to form the particle that is coated with polysilicon; wherein said fluidized-bed reactor comprises one or more surperficial reactor assemblies that have towards reative cell, and described surface comprises and is coated with at least in part the metal of protective layer as disclosed herein.Protective layer can reduce or eliminate and be coated with the particle of polysilicon and contacting of metal, and reduces or eliminates the metallic pollution of polycrysalline silcon.
According to following detailed description, it is more obvious that Characteristics and advantages of the present invention will become, and below describe in detail and carry out with reference to accompanying drawing.
Brief description of the drawings
Fig. 1 is the schematic cross-sectional elevation of fluidized-bed reactor.
Fig. 2 is the schematic cross-sectional elevation that is coated with the inlet tube of middle combination or gluing promotion coating and external protection.
Fig. 3 is the schematic cross-sectional elevation of inlet tube, and described inlet tube comprises the top being made up of protective layer material and is coated with the bottom of protective layer material.
Detailed description of the invention
The method of pollution and the embodiment of fluidized-bed reactor that are coated with silicon grain for reducing or eliminating are disclosed.The metal surface of one or more fluidized-bed reactor assemblies is coated with hard protective layer at least in part.As used herein, term " reactor assemblies " refers to that having of fluidized-bed reactor can be coated with any assembly on the surface (for example comprising metallic surface) of silicon grain in the contact of reactor operating period.
Unless context obviously specifies in addition, otherwise " comprising " used herein refers to that " comprising " and singulative " one (kind) " or " described " comprise a plurality of things of mentioning.Unless context obviously specifies in addition, otherwise term "or" refers to the combination of the single key element of described substituting key element or more than two key element.
Unless explain in addition, otherwise the implication of all technical terms used herein and scientific terminology is all identical with common the understood implication of disclosure those of ordinary skill in the field.Although can be used for practice or the test disclosure with those similar or equivalent methods as herein described and material, below describe suitable method and material.Material, method and embodiment only have illustrative and are not intended to have restricted.According to following detailed description and claims, further feature of the present disclosure is obvious.
Unless otherwise prescribed, otherwise will about composition all percentages all be understood as percentage by weight, i.e. % (w/w).For example, the composition that comprises 20% cobalt comprises 20g cobalt in every 100g composition.
Fig. 1 is the rough schematic view for the manufacture of the fluidized-bed reactor 10 of painting silicon grain.Reactor 10 vertically extends, has the outer wall 20, the central shaft A that define reative cell 30 conventionally 1, and there is different cross sectional dimensions at differing heights.It is I-V that reactor shown in Fig. 1 has five regions, and it highly has different cross sectional dimensions at each.Reative cell can be defined by the wall with varying cross-section size, and it can make gas upwards flow through reactor at differing heights with friction speed.
Grow by making silicon-containing gas in the interior cracking of reative cell 30 and silicon is deposited in fluid bed to make to be coated with silicon grain on particle.Provide one or more inlet tube 40 for example, to enter in reative cell 30 with the mixture of allowing for example silicon-containing gas of main gas or silicon-containing gas, hydrogen and/or inert gas (helium, argon gas).Reactor 10 further comprises one or more fluidizing gas inlet tube 50.Additional hydrogen and/or inert gas can be delivered in reactor so that enough air-flows to be provided by fluidisation inlet tube 50 so that grain fluidized in reaction bed.In the time starting to manufacture and in the normal operation period, seed particles is introduced in reactor 10 by crystal seed inlet tube 60.Remove painting silicon grain by one or more products export pipe 70 from reactor 10 and collect painting silicon grain.Liner 80 can vertically extend through reactor 10.In some are arranged, liner 80 is concentric with reactor wall 20.Illustrated liner 80 has drum conventionally.In some embodiments, probe assembly 90 extends in reative cell 30.Reactor 10 further comprises one or more heaters 100.In some embodiments, reactor is included in heater 100 annular arrays around reative cell 30 concentric locatings between liner 80 and outer wall 20.In some systems, multiple pharoids 100 are used with heater 100, equi-spaced apart is opened each other.
Temperature in reactor is different in the various piece of reactor.For example, in the time operating using silane as the silicon-containing compound that discharges silicon in the time manufacturing polycrysalline silcon, I region is that the temperature in base area is environment temperature to 100 DEG C (Fig. 1).Be in cooling zone in II region, temperature is typically in scope 50-700 DEG C.Be in mesozone in III region, temperature is identical with IV region in fact.IV region being reacted with the core of splash zone and maintained 620-760 DEG C, and advantageously maintain 660-690 DEG C, is that near the wall of radiation area, temperature is increased to 700-900 DEG C in IV region.V region is that the temperature on the top of quench region is 400-450 DEG C.
The surface contacting with painting silicon grain in reative cell 30 can be the source of contamination of products.Soft metal is for example easy to because contacting and denude with fluidized silicon particle.Term " abrasion " refers to that material between the metal surface of direct contact weares and teares and shifts because of relative motion.The metallic pollution that silicon grain may be transferred.Abrasion also causes metal assembly abrasion, thereby induces reaction the device downtime, because will replace, assembly maybe will grind or processing metal is surperficial so that its recovery re-uses condition.Therefore, need to be by the reactor surface that tolerance response device condition, minimizing contamination of products or both processes are improved better.
The embodiment that is applicable to tolerance response device condition and/or reduces the protective layer of contamination of products is disclosed.Disclosed protective layer can be coated to one or more reactor assemblies that will be exposed in reactor operating period the metal surface (having in the metal surface of reactor operating period towards painting silicon grain) that is coated with silicon grain that have.The reactor assemblies that can accept protective layer includes but not limited to inject jet pipe or inlet tube 40, fluidizing gas inlet tube 50, crystal seed inlet tube 60, product extraction outlet 70, liner 80, probe assembly 90, sample jet pipe (not shown), pressure jet pipe (not shown), thermocouple (not shown), internal heater (not shown) and froth breaker (not shown).Be coated with at least a portion on the exposing metal surface of reactor assemblies with the embodiment of disclosed protective layer.In some embodiments, be coated with protective layer the metal surface exposing completely or in fact completely.For example, the metal surface of at least 95%, at least 97% or at least 99% exposure can be coated with protective layer.Therefore, in reactor operating period towards reative cell and/or be exposed to and be coated with the surface of silicon grain and comprise the metal that is coated with at least in part protective layer.
May be difficult to measure hardness at high temperature under as the operating temperature in fluidized-bed reactor.But, between hardness and ultimate tensile strength, there is positive correlation.Therefore, ultimate tensile strength can be worth as the agency of hardness under high temperature.In some embodiments, when 650 DEG C of protective layer, ultimate tensile strength is 700MPa at least, and 650 DEG C time, ultimate tensile strength is advantageously 800MPa at least, at least 900MPa or 1000MPa at least.Can use cupping machine (for example State of Massachusetts, US Nuo Wude's ) determination limit hot strength (the maximum engineering stress that material tolerates during tension test, for example peak value in the stress/strain curves of material).The method that is applicable to test metal ultimate tensile strength comprises ASTM (U.S.'s test and materialogy meeting) E8 and ASTMA370.
Because the assembly in fluidized-bed reactor experiences large variations in temperature, the thermal coefficient of expansion (TCE-1) of following lining material be similar to the thermal coefficient of expansion (TCE-2) of protective layer.In some embodiments, TCE-2 and TCE-1 differ≤30%, advantageously differ≤20% or≤10%.Instantly lining material is 304H steel (TCE=18.6 × 10 -6/ K) or 800H steel (TCE=16.9 × 10 -6/ K) time, for example, the TCE of protective layer can be 11.8 × 10 -6/ K (being TCE-1 × 0.7) is to 24.2 × 10 -6/ K (being TCE-1 ÷ 0.7), TCE is advantageously 13.5 × 10 -6/ K to 22.3 × 10 -6/ K.Conventionally the TCE that, hardness is enough to the protective layer of tolerance response device condition is less than or equal to the TCE of lower lining material.
In some embodiments, centre combination or gluing promotion coating are coated to reactor assemblies, be coated with subsequently protective layer.For example, as shown in Figure 2, combination or gluing promotion coating 210 and external protection 220 in the middle of inlet tube 200 can be coated with.Advantageously, the thermal coefficient of expansion of inter coat (TCE-3) is between TCE-1 and TCE-2.Inter coat can be by reducing or preventing that protective layer and lower lining reactor assemblies from improving the durability of protective layer in fluidized-bed reactor operating period layering.In one embodiment, inter coat is nichrome.
In some embodiments, protective layer has at least minimum average thickness of 0.1mm, and/or 0.1mm to 1mm, as 0.1mm to 0.7mm, or the average thickness of 0.25mm to 0.5mm.In some embodiments, coating layer thickness is across assembly surface and/or in the scope of length component and change.For example, if a part for probe, jet pipe or liner is typically in the larger corrosion of fluidized-bed reactor operating period experience, thicker protective layer can be coated so to that part of probe, jet pipe or liner.
In some embodiments, a part for reactor assemblies can have the composition identical with protective layer material.The remainder of reactor assemblies can be coated with protective layer.For example, as shown in Figure 3, the top 310 of inlet tube 300 (for example, towards upper injection jet pipe or fluidizing gas inlet tube) can be made up of protective layer material completely, and the bottom 320 of inlet tube 300 is coated with the protective layer 330 of protective layer material.
Suitable protective layer material comprise some cobalt-based and Ni-based alloy and superalloy, carborundum, tungsten carbide (WC), silicon nitride with and combination.Term used herein " superalloy " refers to the Ni-based or cobalt-base alloys of (Butterworth field) structure that has face-centered cubic.In some embodiments, suitable protective layer is cobalt-base alloys or superalloy, nickel-base alloy or superalloy or its any combination.
Desirably, under the operating condition of fluidized-bed reactor, protective layer can not discharge the metal that (for example, by corroding or spreading) in a large number can polluted product particle.Be coated with when silicon grain when manufacturing, cause that the contamination of products level of some thousandths of (for example) is undesirably by electron donor and/or electron acceptor as aluminium, arsenic, boron or phosphorus.In some embodiments, under reactor operating condition, protective layer has enough hardness and/or corrosion resistance discharges aluminium, arsenic, boron or phosphorus to minimize or to prevent from protective layer.In some embodiments, protective layer material does not comprise aluminium, arsenic, boron or phosphorus, or, do not comprise (for example≤2% or≤1%) aluminium, arsenic, boron or the phosphorus that exceed trace.
In some embodiments; protective layer material is cobalt-base alloys; its comprise 25-35%Cr ,≤10%W ,≤10%Ni ,≤5%Mo ,≤3%Fe ,≤2%Si ,≤2%C ,≤1.5%Mn ,≤1%B ,≤0.05%P and≤0.05%S, all the other (30.5-75%) are cobalts.In some embodiments; protective layer material is nickel-base alloy; its have comprise following composition: 4-30%Mo, 5-25%Cr, 2-15%Co ,≤2%Fe ,≤3.5%Ti ,≤2%Al ,≤1%Mn ,≤1%Si ,≤0.5%Cu ,≤0.1%C ,≤0.1%Zr and≤0.01%B, all the other (23.4-89%) are nickel.
In one embodiment; protective layer material is cobalt alloy; its have comprise following composition: 26-33%Cr, 7-9.5%W ,≤7%Ni ,≤2.5%Fe ,≤2%Si, 1.1-1.9%C, 0.5-1.5%Mn, 0.1-1.5%Mo ,≤1%B ,≤0.03%P and≤0.03%S, all the other (approximately 60%) be cobalt (for example 12 alloys, can be available from the Ken Nasitaili of Indiana, USA dagger-axe Shen).In another embodiment, protective layer material is cobalt superalloy, and it has and comprises following composition: 26%Cr, 9%Ni, 5%Mo, 3%Fe and 2%W, all the other (approximately 55%) be cobalt (for example alloy, can be available from the Ha Shi international corporation of Indiana, USA section Como).
In one embodiment; protective layer material is nickel based super alloy; its have comprise following composition: 20%Cr, 10%Co, 8.5%Mo, 2.1%Ti, 1.5%Al ,≤1.5%Fe ,≤0.3%Mn ,≤0.15%Si ,≤0.06%C and≤0.005%B, all the other (approximately 57%) be nickel (for example alloy, can be available from the Ha Shi international corporation of Indiana, USA section Como).In another embodiment; protective layer material is nickel based super alloy; its have comprise following composition: 24-26%Mo, 7-9%Cr, 2.5%Co ,≤0.8%Mn ,≤0.8%Si ,≤0.5%Al ,≤0.5%Cu ,≤0.03%C and≤0.006%B, all the other (approximately 65%) be nickel (for example alloy, can be available from the Ha Shi international corporation of Indiana, USA section Como).In another embodiment; protective layer material is nickel based super alloy; its have comprise following composition: 18-21%Cr, 12-15%Co, 3.5-5%Mo, 2.75-3.25%Ti, 1.2-1.6%Al, 0.03-0.1%C, 0.02-0.08%Zr, 0.003-0.01%B ,≤2%Fe ,≤0.15%Si ,≤0.1%Cu ,≤0.1%Mn ,≤0.015%P and≤0.015%S, all the other be nickel (for example waspaloy alloy, can be available from the Ha Shi international corporation of Indiana, USA section Como).
When in fluidized-bed reactor for the manufacture of being coated with when silicon grain, the embodiment of disclosed protective layer can reduce the metallic pollution being coated with in silicon grain.In some embodiments; compared with the painting silicon grain of preparing, be reduced by least 70%, at least 80%, at least 90% or at least 95% by the metallic pollution that the metal surface of the embodiment coating exposure of disclosed protective layer makes to be coated with in silicon grain in the uncoated reactor in metal surface exposing.In an example, with the Particle Phase ratio of preparing in the reactor that comprises uncoated 304H stainless steel probe assembly, be coated with 304H stainless steel probe assembly with cobalt-base superalloy metallic pollution is reduced more than 90%.In addition, after using 50 days, do not show wearing and tearing through the probe assembly of coating.
In some embodiments; protective layer material is powder as powdery alloy or to be enough to form the mixture of the non-alloy powder that the ratio of the alloy of expecting provides; and by any suitable method; comprise and topple over, cast, flood, spray or rotate, then carry out heat and melt described powder coated in the surface of expecting.Described powder can melt before being applied to surface.
In other embodiments, for example, as spraying (high-speed flame sprinkling) or pass through plasma transferred arc-welding, flame is coated with protective layer by thermology method.In the time using thermology method coating protective layer; protective layer material can be following form: powder dress alloy, silk alloy, electrode are maybe combined to form and expect that two or more of alloy have the material (for example powder, silk or electrode) of different chemical composition in the time coating surface.
Embodiment
To by plasma transferred 12 alloy protecting layers are coated the top probe assembly that comprises 304H stainless steel base.The average thickness of protective layer is 0.020 " (0.5mm).The probe of being made up of 304H can use in approximately 90 days worn out in the fluidized-bed reactor of manufacturing painting silicon granule.Except protective layer, reactor material is not containing cobalt.
To be put in fluidized-bed reactor and during twice test run and move approximately 50 days through the assembly of coating.On probe or protective layer, have no wearing and tearing.The analysis of granular silicon product is presented to the stable state cobalt level of about 1.5ppbw (by weight, 1.5/1000000000ths) during test run for the first time.At run duration for the second time, cobalt level drops to about 0.5ppbw.Cobalt analysis before using probe shows about 0.3ppbw.Estimate that the corrosion meeting of naked 304H probe exceedes total metal of 25ppbw to pelletized product pollution contribution.By contrast, 12 protective layers provide minimum pollution.
In test run for the second time, follow the trail of tungsten and observe the stable state lower than detectable limit 0.1ppbw.Chromium detected with lower individual digit ppbw, but believe that this carrys out the stainless steel surfaces of other exposure in autoreactor.
Reduce or eliminate be coated with silicon grain because of with fluidized-bed reactor in the method for the pollution that causes of Surface Contact comprise that (i) provides on fluidized-bed reactor operating period surface towards the fluidized-bed reactor assembly that is coated with silicon grain in fluidized-bed reactor, wherein said surface comprises that to be coated with at least in part while comprising 650 DEG C ultimate tensile strength be the metal of the protective layer of the material of 700MPa at least; And (ii) operate described fluidized-bed reactor with manufacture be coated with silicon grain.In some embodiments, at least 95% surface-coated matcoveredn.
In any or all above-mentioned embodiment, metal all has thermal coefficient of expansion TCE-1 and protective layer all has thermal coefficient of expansion TCE-2, wherein TCE-2 and TCE-1 may differ≤30%.In some embodiments, the inter coat of thermal coefficient of expansion TCE-3 between TCE-1 and TCE-2 is being set between metal and protective layer.
In any or all above-mentioned embodiment, protective layer can have the minimum average thickness of 0.1mm.In some embodiments, protective layer has across face width and/or length and the thickness that changes surfacewise.
In any or all above-mentioned embodiment, a part for fluidized-bed reactor assembly can be completely by the chemical composition material structure identical in fact with protective layer.
In any or all above-mentioned embodiment, fluidized-bed reactor assembly is injection jet pipe, fluidizing gas inlet tube, crystal seed inlet tube, product extraction outlet, liner, probe assembly, sample jet pipe, pressure jet pipe, thermocouple, internal heater or froth breaker.
In any or all above-mentioned embodiment, protective layer can comprise cobalt-base alloys, nickel-base alloy or its combination.In some embodiments, protective layer is cobalt-base alloys, comprises: 25-35%Cr ,≤10%W ,≤10%Ni ,≤5%Mo ,≤3%Fe ,≤2%Si ,≤2%C ,≤1.5%Mn ,≤1%B ,≤0.05%P ,≤0.05%S and 30.5-75% cobalt.In some embodiments; protective layer is nickel based super alloy, comprises: 4-30%Mo, 5-25%Cr, 2-15%Co ,≤3.5%Ti ,≤2%Fe ,≤2%Al ,≤1%Mn ,≤1%Si ,≤0.5%Cu ,≤0.1%C ,≤0.1%Zr ,≤0.01%B and 23.4-89% nickel.
Comprise the reactor that defines reative cell for the manufacture of the fluidized-bed reactor unit of polysilicon; and one or more surperficial reactor assemblies that have towards reative cell, it is the metal of the protective layer of 700MPa at least that described surface comprises while being coated with at least in part 650 DEG C ultimate tensile strength.In some embodiments, a part for reactor assemblies is completely by the chemical composition material structure identical in fact with protective layer.
In any or all above-mentioned embodiment, metal all has the first thermal coefficient of expansion (TCE-1) and protective layer all has the second thermal coefficient of expansion (TCE-2), and described TCE-2 and TCE-1 differ≤and 30%.In some embodiments, reactor assemblies further comprises the inter coat of thermal coefficient of expansion TCE-3 between TCE-1 and TCE-2, and wherein said intermediate layer is between metal and protective layer.
In any or all above-mentioned embodiment, protective layer can have the average thickness of 0.1mm to 1mm.In some embodiments, protective layer has across face width and/or length and the thickness that changes surfacewise.
In any or all above-mentioned embodiment, protective layer can comprise cobalt-base alloys, nickel-base alloy or its combination.
The method of manufacturing granular polycrystalline silicon particle comprises that silicon-containing gas is flowed through contains the fluidized-bed reactor of seed particles at the reative cell being defined by fluidized-bed reactor; to realize the cracking of silicon-containing gas and the deposition of polysilicon layer in seed particles to form the particle that is coated with polysilicon; wherein said fluidized-bed reactor comprises and one or morely has the surperficial reactor assemblies towards reative cell in reactor operating period, and it is the metal of the protective layer of 700MPa at least that described surface comprises while being coated with at least in part 650 DEG C ultimate tensile strength.In some embodiments, at least 95% surface-coated matcoveredn, is coated with the particle of polysilicon and contacting of metal thereby reduce or eliminate, and reduces or eliminates the metallic pollution of polycrysalline silcon.
In view of the many possible embodiment that the principle of disclosed invention may be suitable for, it should be understood that illustrated embodiment is only the preferred embodiments of the present invention and should not be regarded as and limits the scope of the invention.In fact, scope of the present invention is to be defined by claims.

Claims (20)

1. reduce or eliminate be coated with silicon grain because of with fluidized-bed reactor in the method for the pollution that causes of Surface Contact, described method comprises:
Fluidized-bed reactor assembly is provided in fluidized-bed reactor, this fluidized-bed reactor assembly has in described fluidized-bed reactor operating period towards the surface that is coated with silicon grain, wherein said surface comprises the metal that is coated with at least in part protective layer, and when this protective layer comprises 650 DEG C, ultimate tensile strength is the material of 700MPa at least; And
Operate described fluidized-bed reactor and be coated with silicon grain to manufacture.
2. the method for claim 1, at least 95% of wherein said surface is coated with described protective layer.
3. the method for claim 1, wherein said metal has thermal coefficient of expansion TCE-1, and described protective layer has thermal coefficient of expansion TCE-2, wherein TCE-2 and TCE-1 differ≤30%.
4. method as claimed in claim 3 wherein arranges the inter coat with thermal coefficient of expansion TCE-3 between described metal and described protective layer, and TCE-3 is between TCE-1 and TCE-2.
5. the method for claim 1, wherein said protective layer has the minimum average thickness of 0.1mm.
6. method as claimed in claim 5, wherein said protective layer has the thickness changing across the width on described surface and/or along the length direction on described surface.
7. the method for claim 1, a part for wherein said fluidized-bed reactor assembly is completely by the chemical composition material structure identical in fact with described protective layer.
8. the method for claim 1, wherein said fluidized-bed reactor assembly is injection jet pipe, fluidizing gas inlet tube, crystal seed inlet tube, product extraction outlet, liner, probe assembly, sample jet pipe, pressure jet pipe, thermocouple, internal heater or froth breaker.
9. the method as described in any one in claim 1 to 8, wherein said protective layer comprises cobalt-base alloys, nickel-base alloy or its combination.
10. method as claimed in claim 9, wherein said protective layer is the cobalt-base alloys that comprises 25-35%Cr ,≤10%W ,≤10%Ni ,≤5%Mo ,≤3%Fe ,≤2%Si ,≤2%C ,≤1.5%Mn ,≤1%B ,≤0.05%P ,≤0.05%S and 30.5-75% cobalt.
11. methods as claimed in claim 9, wherein said protective layer is the nickel based super alloy that comprises 4-30%Mo, 5-25%Cr, 2-15%Co ,≤3.5%Ti ,≤2%Fe ,≤2%Al ,≤1%Mn ,≤1%Si ,≤0.5%Cu ,≤0.1%C ,≤0.1%Zr ,≤0.01%B and 23.4-89% nickel.
12. 1 kinds of fluidized-bed reactor unit for the manufacture of polysilicon, described unit comprises:
Define the reactor of reative cell; And
One or more reactor assemblies, it has the surface towards described reative cell, and described surface comprises the metal that is coated with at least in part protective layer, and described protective layer is at least the ultimate tensile strength of 700MPa while having 650 DEG C.
13. fluidized-bed reactor unit as claimed in claim 12; wherein said metal has the first thermal coefficient of expansion (TCE-1) and described protective layer has the second thermal coefficient of expansion (TCE-2), and described TCE-2 and TCE-1 differ≤and 30%.
14. fluidized-bed reactor unit as claimed in claim 13; wherein said reactor assemblies further comprises the inter coat with thermal coefficient of expansion TCE-3; described TCE-3 is between TCE-1 and TCE-2, and wherein said inter coat is between described metal and described protective layer.
15. fluidized-bed reactor unit as claimed in claim 12, wherein said protective layer has the average thickness of 0.1mm to 1mm.
16. fluidized-bed reactor unit as claimed in claim 15, wherein said protective layer has the thickness changing across the width on described surface and/or along the length direction on described surface.
17. fluidized-bed reactor unit as claimed in claim 12, a part for wherein said reactor assemblies is completely by the chemical composition material structure identical in fact with described protective layer.
18. fluidized-bed reactor unit as described in any one in claim 12 to 17, wherein said protective layer comprises cobalt-base alloys, nickel-base alloy or its combination.
Manufacture the method for granular polycrystalline silicon particle for 19. 1 kinds, described method comprises that silicon-containing gas is flowed through contains the described fluidized-bed reactor of seed particles at the reative cell being defined by fluidized-bed reactor, to realize the cracking of described silicon-containing gas and the deposition of polysilicon layer in described seed particles to form the particle that is coated with polysilicon, wherein said fluidized-bed reactor comprises one or more reactor assemblies, described reactor assemblies has on the surface of reactor operating period towards described reative cell, described surface comprises the metal that is coated with at least in part protective layer, described protective layer is at least the ultimate tensile strength of 700MPa while having 650 DEG C.
20. methods as claimed in claim 19, at least 95% of wherein said surface is coated with described protective layer, thereby described in reducing or eliminating, is coated with the particle of polysilicon and contacting of described metal, and reduces or eliminates the metallic pollution of described polycrysalline silcon.
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CN105463405A (en) * 2014-08-15 2016-04-06 瑞科硅公司 High-purity silicon to form silicon carbide for use in fluidized bed reactor
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CN108699683A (en) * 2016-02-26 2018-10-23 瓦克化学股份公司 In-situ TEM is deposited to the method in the heat carrying and chemical load bearing component of the fluidized-bed reactor for producing high-purity polycrystalline silicon

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