CN109453729A - The method and apparatus for reducing the pollution of fluidized-bed reactor endoparticle - Google Patents
The method and apparatus for reducing the pollution of fluidized-bed reactor endoparticle Download PDFInfo
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- CN109453729A CN109453729A CN201811452397.2A CN201811452397A CN109453729A CN 109453729 A CN109453729 A CN 109453729A CN 201811452397 A CN201811452397 A CN 201811452397A CN 109453729 A CN109453729 A CN 109453729A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses the method and apparatus for reducing the pollution of fluidized-bed reactor endoparticle.The described method includes: providing fluidized-bed reaction device assembly in fluidized-bed reactor, the fluidized-bed reaction device assembly has during fluidized-bed reactor operation towards the surface for applying silicon particle, wherein the surface includes the metal for being at least partly coated with matcoveredn, the protective layer is comprising 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, the nickel based super alloy of≤0.01%B and 23.4-89% nickel, and the average thickness with 0.1mm to 1mm；And the operation fluidized-bed reactor is to manufacture painting silicon particle.
Description
The application is that International Application Serial No. PCT/US2013/068487 enters National Phase in China, application on April 30th, 2014
Number for 201380003733.4, the division Shen of entitled " method and apparatus for reducing the pollution of fluidized-bed reactor endoparticle "
Please.
Cross reference to related applications
The present invention is U. S. application 13/670, the 200 part continuation applications submitted on November 6th, 2012, and
The part continuation application of the U. S. application submitted on July 10th, 2013 13/939,067, above-mentioned two U. S. application all pass through
It is herein with reference to being incorporated by.
Technical field
This disclosure relates to be used for fluidized-bed reactor, silicon-containing gas cracking is particularly used for manufacture the fluidisation for applying silicon particle
The hard protective layer of bed reactor.
Background technique
Cracking silicon-containing gas is due to excellent mass transfer and heat transfer, the deposition surface of increase and continuous life in a fluidized bed
It produces, therefore is the technique of a kind of attractive manufacture photoelectricity and semicon industry polysilicon.With Siemens reactors
It compares, fluidized-bed reactor provides the productivity greatly improved with sub-fraction energy consumption.Fluidized-bed reactor can be highly automated
Change to significantly reduce labour cost.
It is related to cracking silicon-containing material such as silane, disilane or the halogen in fluidized-bed reactor by chemical vapour deposition technique
The particle polysilicon of silane such as trichlorosilane or tetrachloro silicane is fabricated to known to those skilled in the art and by many announcement institutes
Illustrate, including following patent and announcement: US 8,075,692, US 7,029,632, US 5,810,934, US 5,798,137,
US 5,139,762、US 5,077,028、US 4,883,687、US 4,868,013、US 4,820,587、US 4,416,
913、US 4,314,525、US 3,012,862、US 3,012,861、US2010/0215562、US2010/0068116、
US2010/0047136、US2010/0044342、US2009/0324479、US2008/0299291、US2009/0004090、
US2008/0241046、US2008/0056979、US2008/0220166、US 2008/0159942、US2002/0102850、
US2002/0086530 and US2002/0081250.
In the reactor by the decomposition of silicon-containing gas selected from the following by siliceous deposits on particle: silane (SiH4), second
Silane (Si2H6), high order silanes (SinH2n+2), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), silicon tetrachloride
(SiCl4), two bromo-silicane (SiH2Br2), tribromosilane (SiHBr3), silicon bromide (SiBr4), diiodo- silane (SiH2I2), three
Iodine silane (SiHI3), silicon tetraiodide (SiI4) and its mixture.It can be by silicon-containing gas and one or more halogen-containing gas
Body mixing, the halogen-containing gas be defined as it is following any one: chlorine (Cl2), hydrogen chloride (HCl), bromine (Br2), hydrogen bromide
(HBr), iodine (I2), hydrogen iodide (HI) and its mixture.It can also be by silicon-containing gas and one or more other gases such as hydrogen
Gas (H2) and/or it is one or more selected from nitrogen (N2), the inert gas mixing of helium (He), argon gas (Ar) and neon (Ne).?
In specific embodiment, silicon-containing gas is silane, and silane is mixed with hydrogen.By silicon-containing gas together with any adjoint
Hydrogen, halogen-containing gas and/or inert gas are concomitantly introduced into fluidized-bed reactor and thermally decompose in reactor to produce
Raw silicon, makes the siliceous deposits in the seed particles in reactor.
It is used to construct under high operation temperature common issue is that applying silicon particle in fluidized bed in fluidized-bed reactor
The material contamination of reactor and its component.For example, having shown that nickel from some nickel alloys for constructing reactor part
Base metal is diffused into silicon layer (such as on applying silicon particle).Germanium is applied in the cracking for being constructed to germanic gas to manufacture
It is led to the problem of in the fluidized-bed reactor of grain similar.
Summary of the invention
This disclosure relates to caused by reducing or eliminating painting silicon particle due to contacting with the metal surface in fluidized-bed reactor
Pollution.Reactor assemblies with this metal surface include but is not limited to inject jet pipe, fluidisation gas inlet pipe, crystal seed entrance
Pipe, product extract outlet, liner, probe assembly, sample jet pipe, pressure nozzle, thermocouple, internal heater and defoaming agent.
At least one fluidized-bed reaction device assembly has the metallic surface comprising being at least partly coated with matcoveredn, institute
Stating ultimate tensile strength when protective layer includes 650 DEG C is at least material of 700MPa.In some embodiments, the surface
At least 95% coating matcoveredn.Protective layer can have at least average thickness of 0.1mm, such as the average thickness of 0.1mm to 1mm
Degree.The thickness of protective layer can change across face width and/or along length surface.In one embodiment, it fluidizes
A part of bed reactor assemblies is constructed by substantially the same material of chemical composition and protective layer completely.
Metal and protective layer respectively have thermal expansion coefficient (TCE).In some embodiments, TCE differ each other≤
30%.Inter coat can be set between metal and protective layer, wherein the TCE of the inter coat be in metal TCE and
Between the TCE of protective layer.
Illustrative protective layer includes cobalt-base alloys, nickel-base alloy or combinations thereof.In one embodiment, protective layer is cobalt
Based alloy includes: 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 Ni-based super conjunction
Gold includes: 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.
Fluidized-bed reactor unit for manufacturing polysilicon includes to define the reactor of reaction chamber, and one or more
Reactor assemblies with the surface towards reaction chamber, the surface include at least partly to be coated with guarantor as disclosed herein
The metal of sheath.
The embodiment for manufacturing the method for granular polycrystalline silicon particle includes flowing through silicon-containing gas by fluidized-bed reactor
Fluidized-bed reactor containing seed particles in the reaction chamber that defines, with realize silicon-containing gas cracking and polysilicon layer in crystal seed
Deposition on particle is to form the particle for being coated with polysilicon, wherein the fluidized-bed reactor includes one or more with face
To the reactor assemblies on the surface of reaction chamber, the surface includes at least partly to be coated with protective layer as disclosed herein
Metal.Protective layer can reduce or eliminate the contact of the particle with metal that are coated with polysilicon, and reduce or eliminate polysilicon
The metallic pollution of grain.
It will become apparent according to feature and advantage described in detail below, of the invention, described in detail below is with reference to attached
What figure carried out.
Detailed description of the invention
Fig. 1 is the schematic cross-sectional elevation of fluidized-bed reactor.
Fig. 2 is to be coated with intermediate combine or gluing promotes the schematic cross-section of the inlet tube of coating and external protection to face
Figure.
Fig. 3 is the schematic cross-sectional elevation of inlet tube, and the inlet tube includes the top being made of protective layer material
With the lower part for being coated with protective layer material.
Specific embodiment
It discloses for reducing or eliminating the method for the pollution for applying silicon particle and the embodiment of fluidized-bed reactor.One
Or the metal surface of multiple fluidized-bed reaction device assemblies is at least partly coated with hard protective layer.As used herein, term " reaction
Device assembly " refers to that having for fluidized-bed reactor contact can apply the surface of silicon particle (such as comprising gold during reactor operates
The surface of category) any component.
Unless in addition context obviously provides, otherwise "comprising" used herein refers to " comprising " and singular " one
A (kind) " or " described " include a plurality of referring to object.Unless in addition context obviously provides, otherwise term "or" refers to described replace
The combination of single element or more than two elements for property element.
Unless in addition explaining, otherwise the meaning of all technical terms and scientific terms used herein is all and belonging to the disclosure
The meaning that the those of ordinary skill in field is generally understood is identical.Although with those described herein similar or equivalent method and
Material can be used for practicing or testing the disclosure, but suitable method and material is described below.Material, method and embodiment only have
It being described property and is not intended to restrictive.According to described in detail below and claims, the other feature of the disclosure is
Significantly.
Unless otherwise defined, all percentages about composition are all understood as weight percent, i.e. % (w/w).
For example, the composition comprising 20% cobalt includes 20g cobalt in every 100g composition.
Fig. 1 is the rough schematic view for manufacturing the fluidized-bed reactor 10 for applying silicon particle.Reactor 10 usually vertically prolongs
It stretches, with outer wall 20, the central axis A for defining reaction chamber 301, and there is different cross sectional dimensions in different height.In Fig. 1
Shown in reaction utensil there are five region, that is, I-V, there is different cross sectional dimensions in each height.Reaction chamber can be by having
There is the wall of varying cross-section size to define, gas can be made to flow through reactor upwards in different height with friction speed.
Make to apply silicon and cracking silicon-containing gas in reaction chamber 30 and depositing to silicon in fluidized bed on particle
Grain growth.One or more inlet tube 40 is provided to allow predominant gas such as silicon-containing gas or silicon-containing gas, hydrogen and/or lazy
The mixture of property gas (such as helium, argon gas) enters in reaction chamber 30.Reactor 10 further includes one or more fluidisation
Gas inlet pipe 50.Additional hydrogen and/or inert gas can be delivered in reactor by fluidizing inlet tube 50 to mention
It is for enough air-flows so that grain fluidized in reaction bed.When starting manufacture and in the normal operation period, by seed particles
It is introduced into reactor 10 by crystal seed inlet tube 60.It is removed by one or more products export pipe 70 from reactor 10 and applies silicon
Grain collects painting silicon particle.Liner 80 can extend vertically through reactor 10.In some arrangements, liner 80 and reactor
Wall 20 is concentric.Illustrated liner 80 usually has cylindrical shape.In some embodiments, probe assembly 90 extends to reaction
In room 30.Reactor 10 further includes one or more heaters 100.In some embodiments, reactor is included
100 annular array of heater of 30 concentric locating of reaction chamber is surrounded between lining 80 and outer wall 20.In some systems, by multiple spokes
It penetrates heater 100 and heater 100 uses, it is equally spaced apart from one another.
Temperature in reactor is different in the various pieces of reactor.For example, when using silane as in manufacture polycrystalline
The silicon-containing compound of silicon is discharged when silicon particle when being operated, the temperature in the area Ji Di of the region I is environment temperature to 100 DEG C of (figures
1).In the region II, that is, cooling zone, temperature is typically in 50-700 DEG C of range.In the region III, that is, middle area, temperature essence
It is upper identical as the region IV.It is to react to maintain 620-760 DEG C with the central part of splash zone, and advantageously maintain by the region IV
At 660-690 DEG C, near the region IV, that is, radiation area wall, temperature is improved to 700-900 DEG C.The region V is the top for being quenched area
Temperature be 400-450 DEG C.
The surface contacted in reaction chamber 30 with painting silicon particle can be the source of contamination of products.Soft metal be for example easy to because with
Fluidisation silicon particle is contacted and is denuded.Term " abrasion " refers to that the material between the metal surface directly contacted is ground because of relative motion
Damage and transfer.The metallic pollution that silicon particle may be transferred.Abrasion also results in metal assembly abrasion, so as to cause reactor down-time
Phase, because to replace component or to grind or process metal surface so that its recovery reuses condition.Therefore, it is necessary to will preferably
Tolerance response device condition, reduction contamination of products or both pass through improved reactor surface.
Disclose the embodiment suitable for tolerance response device condition and/or the protective layer for reducing contamination of products.Can by institute
Disclosed protective layer is coated on one or more metal surfaces having painting silicon particle is exposed to during reactor operates (i.e.
With during reactor operates towards apply silicon particle metal surface) reactor assemblies.It can receive the reaction of protective layer
Device assembly includes but is not limited to that injection jet pipe or inlet tube 40, fluidisation gas inlet pipe 50, crystal seed inlet tube 60, product extract
It is mouthful pipe 70, liner 80, probe assembly 90, sample jet pipe (not shown), pressure nozzle (not shown), thermocouple (not shown), interior
Heater (not shown) and froth breaker (not shown).With the exposure of the embodiment coating reactor assemblies of disclosed protective layer
At least part of metal surface.In some embodiments, it is totally coated with exposed metal completely or substantially with protective layer
Surface.For example, the metal surface of at least 95%, at least 97% or at least 99% exposure can be coated with matcoveredn.Therefore, exist
Reactor towards reaction chamber and/or is exposed to that apply the surface of silicon particle include at least partly to be coated with matcoveredn during operating
Metal.
It is likely difficult to measure hardness under the operation temperature in high temperature such as fluidized-bed reactor.However, in hardness and the limit
Exist between tensile strength and is positively correlated.Therefore, ultimate tensile strength can be used as to agency's value of hardness under high temperature.In some implementations
In mode, ultimate tensile strength is at least 700MPa at 650 DEG C of protective layer, at 650 DEG C ultimate tensile strength be advantageously to
Few 800MPa, at least 900MPa or at least 1000MPa.Cupping machine (such as State of Massachusetts, US promise Wood can be used) determination limit tensile strength (the maximum engineering stress that material is resistant to during tension test, such as answering in material
Peak value on power/strain curve).Method suitable for testing metal ultimate tensile strength includes ASTM (U.S.'s test and material
Association) E8 and ASTMA370.
Because the component in fluidized-bed reactor undergoes big temperature change, following lining material thermal expansion coefficient
(TCE-1) it is similar to the thermal expansion coefficient (TCE-2) of protective layer.In some embodiments, TCE-2 and TCE-1 difference≤
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) when, for example, the TCE of protective layer can be 11.8 × 10-6/ K (i.e. TCE-1 × 0.7) to 24.2 × 10-6/ K (i.e. TCE-1 ÷ 0.7), TCE is advantageously 13.5 × 10-6/ K to 22.3 × 10-6/K.In general, hardness is sufficient to resist reaction
The TCE of the protective layer of device condition is less than or equal to the TCE of lower lining material.
In some embodiments, centre is combined or gluing promotes coating to be coated on reactor assemblies, then coating is protected
Sheath.For example, as shown in Figure 2, inlet tube 200 can be coated with intermediate combination or gluing promotes coating 210 and external protection
220.Advantageously, the thermal expansion coefficient (TCE-3) of inter coat is between TCE-1 and TCE-2.Inter coat can be by subtracting
Less or protective layer and lower lining reactor assemblies is prevented to be layered and improve the durability of protective layer during fluidized-bed reactor operation.
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, such as
The average thickness of 0.1mm to 0.7mm or 0.25mm to 0.5mm.In some embodiments, coating layer thickness is across component table
Face and/or change along in the range of length component.For example, if a part of probe, jet pipe or liner is typically flowing
Fluidized bed reactor undergoes biggish corrosion during operating, then probe, jet pipe or liner can be coated on thicker protective layer
That part.
In some embodiments, a part of reactor assemblies can have composition identical with protective layer material.Instead
Matcoveredn can be coated with by answering the rest part of device assembly.For example, as shown in Figure 3, inlet tube 300 (such as injection upwardly
Jet pipe or fluidisation gas inlet pipe) top 310 can be made of completely protective layer material, and inlet tube 300 lower part 320 apply
It is furnished with the protective layer 330 of protective layer material.
Suitable protective layer material includes certain cobalt-baseds and Ni-based alloy and superalloy, silicon carbide, tungsten carbide (WC), nitrogen
SiClx with and combinations thereof.The term as used herein " superalloy " refers to the Ni-based or cobalt-based with face-centered cubic (Butterworth field) structure
Alloy.In some embodiments, suitable protective layer is cobalt-base alloys or superalloy, nickel-base alloy or superalloy or its is any
Combination.
Desirably, under the operating condition of fluidized-bed reactor, protective layer will not discharge (such as by corroding or spreading)
Largely it is capable of the metal of polluted product particle.When manufacture applies silicon particle, by electron donor and/or electron acceptor such as aluminium, arsenic, boron
Or phosphorus causes contamination of products (such as level in some thousandths of) to be undesirably.In some embodiments, in reactor
Under operating condition, protective layer has enough hardness and/or corrosion resistance to minimize or prevent to discharge aluminium, arsenic, boron from protective layer
Or phosphorus.In some embodiments, protective layer material do not include aluminium, arsenic, boron or phosphorus, alternatively, be not comprise more than trace (such as
≤ 2% or≤1%) aluminium, arsenic, boron or phosphorus.
In some embodiments, protective layer material is cobalt-base alloys, it includes 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, remaining
(30.5-75%) is cobalt.In some embodiments, protective layer material is nickel-base alloy, has and includes composition below: 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, remaining (23.4-89%) is nickel.
In one embodiment, protective layer material is cobalt alloy, has and includes composition below: 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, remaining (about 60%) be cobalt (such as12 alloys, available from Indiana, USA dagger-axe
The Ken Nasitaili of Shen).In another embodiment, protective layer material is cobalt superalloy, has and includes composition below:
26%Cr, 9%Ni, 5%Mo, 3%Fe and 2%W, remaining (about 55%) be cobalt (such asAlloy is printed available from the U.S.
The Kazakhstan international corporation of the state An Na section Como).
In one embodiment, protective layer material is nickel based super alloy, has and includes composition below: 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, remaining (about 57%) be nickel (such asAlloy, available from Indiana, USA section Como
Kazakhstan international corporation).In another embodiment, protective layer material is nickel based super alloy, has and includes composition below:
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, remaining (about 65%) be nickel (such as Alloy, available from Indiana, USA section Como
Kazakhstan international corporation).In yet another embodiment, protective layer material is nickel based super alloy, has and includes below group
At: 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, remaining be nickel (such asWaspaloy alloy, available from the Kazakhstan state of Indiana, USA section Como
Border company).
When applying silicon particle for manufacturing in fluidized-bed reactor, the embodiment of disclosed protective layer can reduce painting
Metallic pollution in silicon particle.In some embodiments, with prepare in the uncoated reactor in exposed metal surface
It applies silicon particle to compare, the metal for making to apply in silicon particle with the metal surface of the embodiment coating exposure of disclosed protective layer is dirty
Dye reduces at least 70%, at least 80%, at least 90% or at least 95%.In an example, with including uncoated 304H
The particle prepared in the reactor of stainless steel probe assembly is compared, and makes gold with cobalt-base superalloy coating 304H stainless steel probe assembly
Belong to pollution and reduces 90% or more.In addition, the probe assembly by coating does not show abrasion after using 50 days.
In some embodiments, protective layer material is powder such as powdery alloy or to form the ratio of desired alloy to be enough
The mixture for the non-alloyed powder that rate provides, and by any suitable method, including topple over, cast, impregnate, spray or revolve
Turn, then carrying out heat, melt will be described powder coated in desired surface.The powder can melt before being applied to surface.
In other embodiments, by thermology method such as flame spraying (such as high-speed flame sprinkling) or pass through plasma
Body shifts arc-welding coat protective layer.When using thermology method coat protective layer, protective layer material can be in the form of the following: powder dress
Alloy, silk alloy, electrode, or combine when being coated on surface to be formed desired alloy two or more with different chemical groups
At material (such as powder, silk or electrode).
Embodiment
It will by plasma transferred12 alloy protecting layers are coated on the top comprising 304H stainless steel base
Probe assembly.The average thickness of protective layer is 0.020 " (0.5mm).The probe made of 304H can be in the stream of manufacture painting silicon granule
Using worn out in about 90 days in fluidized bed reactor.In addition to protective layer, reactor material is free of cobalt.
It will be put into fluidized-bed reactor and run during test run twice about 50 days by the component of coating.?
Abrasion is had no on probe or protective layer.To granular silicon product analysis shows that during first time test run about 1.5ppbw (with
Poidometer, 1.5/1000000000ths) stable state cobalt is horizontal.During second runs, cobalt descends horizontally into about 0.5ppbw.It is using
Cobalt before probe is analysis shows that about 0.3ppbw.Estimating the corrosion of naked 304H probe can be more than to pelletized product pollution contribution
Total metal of 25ppbw.In contrast,12 protective layers provide the smallest pollution.
In second of test run, tracks tungsten and observe the stable state lower than detectable limit 0.1ppbw.With lower
Individual digit ppbw detects chromium, it is believed that this carrys out the stainless steel surface of other exposures in autoreactor.
Reducing or eliminating the method for pollution caused by applying silicon particle due to contacting with the surface in fluidized-bed reactor includes
(i) fluidized-bed reactor group of the surface towards painting silicon particle during fluidized-bed reactor operation is provided in fluidized-bed reactor
Part, wherein the surface includes that be at least partly coated with comprising ultimate tensile strength at 650 DEG C be at least material of 700MPa
Protective layer metal；And (ii) operates the fluidized-bed reactor to manufacture painting silicon particle.In some embodiments, until
Few 95% surface is coated with matcoveredn.
In any or all above embodiment, metal all has thermal expansion coefficient TCE-1 and protective layer all has
Thermal expansion coefficient TCE-2, wherein TCE-2 and TCE-1 may differ by≤30%.In some embodiments, in metal and protection
Setting thermal expansion coefficient TCE-3 is in the inter coat between TCE-1 and TCE-2 between layer.
In any or all above embodiment, protective layer may have the minimum average thickness of 0.1mm.Some
In embodiment, protective layer has across face width and/or the thickness changed along length surface.
In any or all above embodiment, a part of fluidized-bed reaction device assembly can be completely by chemical group
It is constructed at substantially the same material of protective layer.
In any or all above embodiment, fluidized-bed reaction device assembly be injection jet pipe, fluidisation gas inlet pipe,
Crystal seed inlet tube, product extract outlet, liner, probe assembly, sample jet pipe, pressure nozzle, thermocouple, internal heater or disappear
Bubbler.
In any or all above embodiment, protective layer may include cobalt-base alloys, nickel-base alloy or combinations thereof.?
In some embodiments, protective layer is cobalt-base alloys, includes: 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 realities
Apply in mode, protective layer is nickel based super alloy, include: 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.
Fluidized-bed reactor unit for manufacturing polysilicon includes to define the reactor of reaction chamber, and one or more
Reactor assemblies with the surface towards reaction chamber, the surface include ultimate elongation when being at least partly coated with 650 DEG C
Intensity is the metal of at least protective layer of 700MPa.In some embodiments, a part of reactor assemblies is completely by chemistry
Composition is constructed with substantially the same material of protective layer.
In any or all above embodiment, metal all has the first thermal expansion coefficient (TCE-1) and protective layer
All there is the second thermal expansion coefficient (TCE-2), the TCE-2 differs≤30% with TCE-1.In some embodiments, it reacts
Device assembly further includes the inter coat that thermal expansion coefficient TCE-3 is between TCE-1 and TCE-2, wherein the middle layer
Between metal and protective layer.
In any or all above embodiment, protective layer may have the average thickness of 0.1mm to 1mm.One
In a little embodiments, protective layer has across face width and/or the thickness changed along length surface.
In any or all above embodiment, protective layer can include cobalt-base alloys, nickel-base alloy or combinations thereof.
The method for manufacturing granular polycrystalline silicon particle includes flowing through silicon-containing gas in the reaction defined by fluidized-bed reactor
Fluidized-bed reactor of the interior containing seed particles, cracking and the polysilicon layer to realize silicon-containing gas are heavy in seed particles
Product is to form the particle for being coated with polysilicon, wherein the fluidized-bed reactor includes one or more during reactor operation
Reactor assemblies with the surface towards reaction chamber, the surface include ultimate elongation when being at least partly coated with 650 DEG C
Intensity is the metal of at least protective layer of 700MPa.In some embodiments, at least 95% surface is coated with matcoveredn, from
And the contact of the particle with metal that are coated with polysilicon is reduced or eliminated, and the metal for reducing or eliminating polycrysalline silcon is dirty
Dye.
The many possible embodiments that may be applicable in view of the principle of disclosed invention, it is recognized that illustrated
Embodiment is only the preferred embodiment of the present invention and should not be considered as limiting the scope of the present invention.In fact, of the invention
Range be to be defined by tbe claims.
Claims (14)
1. it is a kind of reduce or eliminate apply silicon particle because in fluidized-bed reactor surface contact due to caused by pollution method, institute
The method of stating includes:
Fluidized-bed reaction device assembly is provided in fluidized-bed reactor, which has anti-in the fluidized bed
Towards the surface for applying silicon particle during answering device to operate, wherein the surface includes the metal for being at least partly coated with matcoveredn,
The protective layer be comprising 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 nickel based super alloy, and have
The average thickness of 0.1mm to 1mm；And
The fluidized-bed reactor is operated to manufacture painting silicon particle.
2. the method as described in claim 1, wherein at least the 95% of the surface is coated with the protective layer.
3. the method as described in claim 1, wherein the metal has thermal expansion coefficient TCE-1, and the protective layer has
There is thermal expansion coefficient TCE-2, wherein TCE-2 and TCE-1 difference≤30%.
4. method as claimed in claim 3, wherein setting has thermal expansion coefficient between the metal and the protective layer
The inter coat of TCE-3, TCE-3 are between TCE-1 and TCE-2.
5. the method as described in claim 1, wherein the protective layer has across the width on the surface and/or along described
The thickness of the length direction variation on surface.
6. the method as described in claim 1, wherein a part of the fluidized-bed reactor component completely by chemical composition with
Substantially the same material construction of the protective layer.
7. the method as described in claim 1, wherein the fluidized-bed reactor component is injection jet pipe, fluidisation gas inlet
Pipe, crystal seed inlet tube, product extract outlet, liner, probe assembly, sample jet pipe, pressure nozzle, thermocouple, internal heater
Or froth breaker.
8. a kind of for manufacturing the fluidized-bed reactor unit of polysilicon, the unit includes:
Define the reactor of reaction chamber；And
One or more reactor assemblies, have the surface towards the reaction chamber, and the surface includes at least partly to apply
The metal of cloth matcoveredn, the protective layer be comprising 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%
The nickel based super alloy of nickel, and the average thickness with 0.1mm to 1mm.
9. fluidized-bed reactor unit as claimed in claim 8, wherein the metal has the first thermal expansion coefficient (TCE-1)
And the protective layer has the second thermal expansion coefficient (TCE-2), and the TCE-2 differs≤30% with TCE-1.
10. fluidized-bed reactor unit as claimed in claim 9 has heat swollen wherein the reactor assemblies further include
The inter coat of swollen coefficient T CE-3, the TCE-3 are between TCE-1 and TCE-2, wherein the inter coat is positioned at described
Between metal and the protective layer.
11. fluidized-bed reactor unit as claimed in claim 8, wherein the protective layer has the width across the surface
And/or the thickness of the length direction variation along the surface.
12. fluidized-bed reactor unit as claimed in claim 8, wherein a part of the reactor assemblies is completely by chemistry
Composition is constructed with substantially the same material of the protective layer.
13. a kind of method for manufacturing granular polycrystalline silicon particle, the method includes flowing through silicon-containing gas by fluidized-bed reaction
The fluidized-bed reactor containing seed particles in the reaction chamber that device defines, to realize cracking and the polycrystalline of the silicon-containing gas
Deposition of the silicon layer in the seed particles is to form the particle for being coated with polysilicon, wherein the fluidized-bed reactor includes one
A or multiple reactor assemblies, the reactor assemblies have the surface towards the reaction chamber during reactor operation, institute
Stating surface includes the metal for being at least partly coated with matcoveredn, and the protective layer is comprising 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%
The nickel based super alloy of Zr ,≤0.01%B and 23.4-89% nickel, and the average thickness with 0.1mm to 1mm.
14. method as claimed in claim 13, wherein at least the 95% of the surface is coated with the protective layer, to reduce
Or the particle of polysilicon and the contact of the metal are coated with described in eliminating, and reduce or eliminate the gold of the polycrysalline silcon
Belong to pollution.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/670,200 US9587993B2 (en) | 2012-11-06 | 2012-11-06 | Probe assembly for a fluid bed reactor |
| US13/670,200 | 2012-11-06 | ||
| US13/939,067 US9212421B2 (en) | 2013-07-10 | 2013-07-10 | Method and apparatus to reduce contamination of particles in a fluidized bed reactor |
| US13/939,067 | 2013-07-10 | ||
| CN201380003733.4A CN103945932A (en) | 2012-11-06 | 2013-11-05 | Method and apparatus to reduce contamination of particles in a fluidized bed reactor |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380003733.4A Division CN103945932A (en) | 2012-11-06 | 2013-11-05 | Method and apparatus to reduce contamination of particles in a fluidized bed reactor |
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| CN109453729A true CN109453729A (en) | 2019-03-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380003733.4A Pending CN103945932A (en) | 2012-11-06 | 2013-11-05 | Method and apparatus to reduce contamination of particles in a fluidized bed reactor |
| CN201811452397.2A Pending CN109453729A (en) | 2012-11-06 | 2013-11-05 | The method and apparatus for reducing the pollution of fluidized-bed reactor endoparticle |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380003733.4A Pending CN103945932A (en) | 2012-11-06 | 2013-11-05 | Method and apparatus to reduce contamination of particles in a fluidized bed reactor |
Country Status (7)
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|---|---|
| JP (1) | JP2016503377A (en) |
| KR (1) | KR20150082349A (en) |
| CN (2) | CN103945932A (en) |
| DE (1) | DE112013005298T5 (en) |
| SA (1) | SA515360365B1 (en) |
| TW (1) | TWI623420B (en) |
| WO (1) | WO2014074510A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9238211B1 (en) | 2014-08-15 | 2016-01-19 | Rec Silicon Inc | Segmented silicon carbide liner |
| US9662628B2 (en) | 2014-08-15 | 2017-05-30 | Rec Silicon Inc | Non-contaminating bonding material for segmented silicon carbide liner in a fluidized bed reactor |
| US9446367B2 (en) | 2014-08-15 | 2016-09-20 | Rec Silicon Inc | Joint design for segmented silicon carbide liner in a fluidized bed reactor |
| US20160045881A1 (en) * | 2014-08-15 | 2016-02-18 | Rec Silicon Inc | High-purity silicon to form silicon carbide for use in a fluidized bed reactor |
| US9404177B2 (en) * | 2014-08-18 | 2016-08-02 | Rec Silicon Inc | Obstructing member for a fluidized bed reactor |
| DE102014221928A1 (en) * | 2014-10-28 | 2016-04-28 | Wacker Chemie Ag | Fluidized bed reactor and process for producing polycrystalline silicon granules |
| CN105568254B (en) * | 2016-02-24 | 2018-10-30 | 清华大学 | A kind of gas inlet device for fluidized-bed chemical vapor deposition reactor |
| DE102016203082A1 (en) * | 2016-02-26 | 2017-08-31 | Wacker Chemie Ag | Process for depositing an in-situ coating on thermally and chemically stressed components of a fluidized bed reactor for producing high-purity polysilicon |
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| EP0896952A1 (en) * | 1997-08-14 | 1999-02-17 | Wacker-Chemie GmbH | Process for preparing high-purity silicium granules |
| CN101378989A (en) * | 2006-02-07 | 2009-03-04 | 韩国化学研究院 | High-pressure fluidized bed reactor for preparing granular polycrystalline silicon |
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| JPH06127916A (en) * | 1992-10-16 | 1994-05-10 | Tonen Chem Corp | Production of spherical high-purity polycrystalline silicon |
| US8168123B2 (en) * | 2009-02-26 | 2012-05-01 | Siliken Chemicals, S.L. | Fluidized bed reactor for production of high purity silicon |
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2013
- 2013-11-05 KR KR1020157013800A patent/KR20150082349A/en not_active Application Discontinuation
- 2013-11-05 CN CN201380003733.4A patent/CN103945932A/en active Pending
- 2013-11-05 JP JP2015540861A patent/JP2016503377A/en active Pending
- 2013-11-05 DE DE112013005298.9T patent/DE112013005298T5/en not_active Withdrawn
- 2013-11-05 TW TW102140019A patent/TWI623420B/en active
- 2013-11-05 CN CN201811452397.2A patent/CN109453729A/en active Pending
- 2013-11-05 WO PCT/US2013/068487 patent/WO2014074510A1/en active Application Filing
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2015
- 2015-04-30 SA SA515360365A patent/SA515360365B1/en unknown
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| EP0896952A1 (en) * | 1997-08-14 | 1999-02-17 | Wacker-Chemie GmbH | Process for preparing high-purity silicium granules |
| CN101378989A (en) * | 2006-02-07 | 2009-03-04 | 韩国化学研究院 | High-pressure fluidized bed reactor for preparing granular polycrystalline silicon |
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Also Published As
| Publication number | Publication date |
|---|---|
| SA515360365B1 (en) | 2017-10-31 |
| JP2016503377A (en) | 2016-02-04 |
| WO2014074510A1 (en) | 2014-05-15 |
| CN103945932A (en) | 2014-07-23 |
| DE112013005298T5 (en) | 2015-07-23 |
| KR20150082349A (en) | 2015-07-15 |
| TW201434618A (en) | 2014-09-16 |
| WO2014074510A8 (en) | 2015-05-14 |
| TWI623420B (en) | 2018-05-11 |
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