CN103055863B - Iron catalyst and preparation method and application thereof - Google Patents
Iron catalyst and preparation method and application thereof Download PDFInfo
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- CN103055863B CN103055863B CN201110321966.1A CN201110321966A CN103055863B CN 103055863 B CN103055863 B CN 103055863B CN 201110321966 A CN201110321966 A CN 201110321966A CN 103055863 B CN103055863 B CN 103055863B
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Abstract
The invention discloses an iron catalyst. The iron catalyst contains 20-95wt% of iron and 0.5-70wt% of silicon. A preparation method of the catalyst is characterized by heating iron, silicon and a transition metal M until the components are molten, quickly curing the melt at a cooling rate more than 1000 DEG C/S and carrying out extraction treatment on the alloy obtained after curing with an alkali-acid solution to extract part of silicon, thus obtaining the catalyst. The catalyst has higher activity and selectivity than conventional catalysts and has good stability when used in the silicon tetrachloride hydrogenation reaction.
Description
Technical field
The invention relates to a kind of iron catalyst, preparation method and application thereof, is more specifically about a kind of iron catalyst for silicon tetrachloride hydrogenation production trichlorosilane, preparation method and the application in hydrogenation of silicon tetrachloride thereof.
Background technology
In recent years, along with worldwide traditional energy is exhausted and oil price continues the continuous aggravation that rises, the whole world just utilizes regenerative resource at active development.Solar energy as reproducible clear energy sources, because it is clean, safety, aboundresources are developed rapidly.Thus, the demand as the high purity polycrystalline silicon of solar cell raw material constantly increases.
Silicon tetrachloride and about 1 ~ 5 ton of hydrogen chloride that 1 ton of polysilicon can produce more than 10 tons is produced in production of polysilicon.Due to also do not have extensive, high efficiency and safely digestion process produce the SiCl produced in polysilicon process
4method, a large amount of high-load chlorine compounds can only be hoarded, and brings great hidden danger to Environmental security.In order to reduce production of polysilicon material consumption, reduce production cost, avoid environmental pollution, hydrogenation of silicon tetrachloride is converted into trichlorosilane by the most effective, the most most economical method exactly, trichlorosilane is sent back to polysilicon system again as raw material and produces polysilicon, thus form " closed loop " production.
SiCl disclosed in CN85107465A
4new process for hydrogenation is mixed by a certain percentage with silica flour by Powdered nickel accelerant, loads in reactor, after carrying out 4 hours activation process, can pass into SiCl in nitrogen atmosphere and at 430 DEG C of temperature to it
4and H
2mist, carries out hydrogenation, and reaction temperature is 400-500 DEG C, pressure 10-20kg/cm
2, in the life-span term of validity of catalyst, hydrogenation can carry out continuously.
In the method for a kind of producing trichloro hydrosilicon by hydrogenation of silicon tetrachloride disclosed in CN 1436725A, be by after powdery nickel accelerant and silica flour by a certain percentage Homogeneous phase mixing, at H
2atmosphere and by activation process under 20 DEG C to final temperature 420 DEG C of continually varying temperature conditions: H according to a certain ratio
2, SiCl
4namely mist realizes SiCl by the catalyst after activation process and the silica flour bed of material
4hydrogenation.The mass ratio of Powdered nickel accelerant and silica flour is 1-10%, H
2with SiCl
4mol ratio is 1-10, reaction temperature 400-500 DEG C, reaction pressure 1.2-1.5Mpa, and hydrogenation carries out continuously, and compound consumes continuous supplementation with reaction.
At present, industrially mainly through two kinds of methods, silicon tetrachloride is carried out hydroconverted.
A kind of technology path is SiCl
4hot hydrogenation, by SiCl
4and H
2siHCl is converted under the high temperature of 1200-1500 DEG C and 0.6MPa pressure
3.The method reaction temperature is high, and energy consumption is large, and a low conversion rate, is up to 18%.
Another kind of technology path is SiCl
4cold hydrogenation, namely under the effect of metallic catalyst, under certain temperature, pressure, makes H
2with SiCl
4mist and silica flour contact the process of carrying out hydrogenation in reactor with fluidized state, the catalyst that this process uses is mainly with diatomite, active carbon, Al
2o
3for granular nickel salt, the mantoquita even load type catalyst of carrier.Except catalytic performance is poor, because the fusing point of copper is lower, often there is catalyst melting blocking pipeline in this kind of nickel salt, copper salt catalyst, not only causes unnecessary parking loss, and cause loss of material in application process.And the aluminium chloride that alumina support generates in hydrogenation process and water, be constantly brought in follow-up system as a vapor under the condition of 450-500 DEG C, reduce the purity of product trichlorosilane, for the purification of product brings adverse effect.
Therefore, the Ni-based and copper-based catalysts of tradition, has following shortcoming: (1) is active low, loss of active component; (2) active component caking; (3) follow-up system is entered as impurity; (4) catalyst needs to carry out activation process at higher than the temperature of 400 DEG C before using; (5) cost is higher.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, a kind of lower-cost iron catalyst is provided, this catalyst has good polishing machine, two of object is to provide the preparation method of this catalyst, and three of object provides this catalyst to produce the application in trichlorosilane process at silicon tetrachloride hydrogenation.
Therefore, iron catalyst provided by the invention, is characterized in that this catalyst contains 20-95 % by weight iron and 0.5-70 % by weight silicon.
Present invention also offers the preparation method of above-mentioned iron catalyst, it is characterized in that will by iron, silicon, with or discord at least one be selected from the periodic table of elements I B, II B, III B, IV B, VI B, the fused mass of the alloy that the transition metal in VII B or VIII race forms is to be greater than the cooldown rate rapid curing of 1000 DEG C/S, cured product under agitation adds that to be heated to extraction temperature be in the alkali lye of 10-100 DEG C, silicon in alloy and alkali are fully reacted, then decantation liquid, solid sample is washed with distilled water to after pH is less than 10, join again in the acid solution of 10-100 DEG C and oxidative deactivation is carried out to catalyst surface, sample after pickling is washed with distilled water to pH and obtains catalyst after 6-7, the concentration of said alkali lye is 2-40 % by weight, the weight ratio of alloy and alkali is 1: 1-10, the concentration of said acid solution is 2-40 % by weight, and alloy is 1: 1-10 with the weight ratio of acid.
The present invention still further provides the application of above-mentioned iron catalyst, described iron catalyst is used for silicon tetrachloride Hydrogenation and reacts for trichlorosilane.For catalyst of the present invention, reaction temperature is at 350 ~ 500 DEG C, and reaction pressure 0.5-4.0MPa, H2/SiCl4 all can realize than the process conditions for 0.5-10, air speed 500-100000h-1.In described application, reactor types can adopt fixed bed reactors, fluidized-bed reactor or other forms of suspended-bed reactor.
Compared with the current conventional Raney nickel adopted or loaded catalyst compare, FeSi alloy catalyst has the following advantages: (1), compared with conventional Raney nickel, Fe catalyst cost is low nearly 10 times; (2) FeSi alloy does not have carrier, can not as loaded catalyst as active carbon, Al
2o
3follow-up system can be brought in carrier, affect polysilicon purity, especially for this reaction very high to purity requirement of polysilicon, significantly can reduce the purifying process of product; (3) in alloy Si add the activity not only increasing catalyst, and due to its participate in reaction, effectively can reduce the addition of Si powder, simplify structure of reactor.
Detailed description of the invention
Iron catalyst provided by the invention, containing 20-95 % by weight iron and 0.5-70 % by weight silicon, can also be selected from the transition metal of the periodic table of elements I B, II B, III B, IV B, VI B, VII B and VIII race containing at least one of ≯ 40 % by weight, the transition metal of said VII B race is not manganese.The preferred transition metal by the iron of 50-90 % by weight, the silicon of 0.5-30% and 0.5-20 % by weight of catalyst forms; More preferably be made up of the transition metal of the iron of 60-80 % by weight, the silicon of 5-20% and 2-20 % by weight.
In iron catalyst provided by the invention, said transition metal can be selected from one or more in nickel, copper, cobalt, molybdenum, tungsten, cerium, titanium, zirconium, chromium, platinum, ruthenium and palladium.Preferably be selected from one or more in nickel, copper, cobalt, molybdenum and platinum.
The preparation method of iron catalyst provided by the invention is by iron, silicon, and or discord transition metal be heated to melting, by fused mass cooling curing, with alkali-acid solution, the alloy after solidification is carried out to extracting process and obtains catalyst with extraction section silicon.When this catalyst is used for hydrogenation of silicon tetrachloride reaction, there is the activity and selectivity higher than conventional catalyst, and there is good stability.More particularly this preparation method will by iron, silicon, with or discord at least one be selected from the periodic table of elements I B, II B, III B, IV B, VI B, the fused mass of the alloy that the transition metal in VII B or VIII race forms is to be greater than the cooldown rate rapid curing of 1000 DEG C/S, cured product under agitation adds that to be heated to extraction temperature be in the alkali lye of 10-100 DEG C, silicon in alloy and alkali are fully reacted, then decantation liquid, solid sample is washed with distilled water to after pH is less than 10, join in the acid solution of 10-100 DEG C the sodium metasilicate that removes and not easily wash again and oxidative deactivation is carried out to catalyst surface, sample after pickling is washed with distilled water to pH and obtains catalyst after 6-7, the concentration of said alkali lye is 2-40 % by weight, the weight ratio of alloy and alkali is 1: 1-10, the concentration of said acid solution is 2-40 % by weight, and alloy is 1: 1-10 with the weight ratio of acid.
In preparation method provided by the invention, atwirl single roller or two roller cooling molten metal can be adopted, also can adopt the quick cool metal of the mode of spray atomization and deposition more than 1300 DEG C.
In preparation method provided by the invention, described alkali density process is: under agitation add through quick-setting quick cooling alloy and be heated in the alkali lye of extraction temperature, silicon in alloy and alkali lye are fully reacted, obtain black solid catalyst, extraction temperature is 10-100 DEG C, preferred 40-90 DEG C, alkali concn is 2-40 % by weight, preferably 10-20 % by weight, extraction times is 5-600min, preferably 30-120min, alloying pellet size is 8-400 order, preferably 80-200 order, is 1: 1-10, preferably 1: 1.5-4 in iron in alloy, with the weight ratio of alkali.After alkali density, catalyst sample is washed with distilled water to after pH is less than 10, join in the acid solution of 10-100 DEG C the sodium metasilicate that removes and not easily wash again and oxidative deactivation is carried out to catalyst surface, reaction temperature is 10-90 DEG C, preferred 40-90 DEG C, acid concentration is 2-40 % by weight, preferably 10-20 % by weight, reaction time is 5-600min, preferably 30-120min, and alloy is 1: 1-10, preferably 1: 2-4 with the weight ratio of acid.Wash with ethanol after sample after pickling is washed with distilled water to neutrality and preserve in ethanol, preferably preserving under the condition having indifferent gas or hydrogen shield.
In method provided by the invention, described alkali is solubility highly basic, as the hydroxide of alkali and alkaline earth metal ions, can be NaOH, KOH, Ba (OH)
2in one, wherein preferred NaOH or KOH.
Said acid is preferably HNO
3or perchloric acid.
Iron catalyst provided by the invention be applied to silicon tetrachloride Hydrogenation for trichlorosilane reaction in time, the ratio of reaction pressure, reaction temperature and silicon tetrachloride and hydrogen, prior art instruction scope in all can realize.For novel iron catalyst of the present invention, in reaction temperature 350 ~ 500 DEG C, reaction pressure 0.5-4.0MPa, H
2/ SiCl
4than being 0.5-10, air speed 500-100000h
-1process conditions be relatively suitable for; In the preferred embodiment of the present invention, said reaction temperature is 400 ~ 450 DEG C, reaction pressure 1.0-2.0MPa, H
2/ SiCl
4than being 1.5-5, air speed 1000-30000h
-1; And in the most preferred embodiment, said reaction temperature is 450 DEG C.In described application, reactor types can adopt fixed bed reactors, fluidized-bed reactor or other forms of suspended-bed reactor.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
In embodiment, in catalyst, each constituent content adopts plasma emission spectrum (ICP) to measure.
Embodiment 1 ~ 8 illustrates and is used for catalyst of the present invention and preparation process thereof.
Embodiment 1
1.5kg iron, 1.5kg silicon are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 600 turns ~ 1000/ point, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity of 1000 DEG C/more than s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 100 DEG C washing to pH value.Obtained catalyst is numbered catalyst-1, and the composition of catalyst-1 is in table 1.
Embodiment 2
1.5kg iron, 1.0kg silicon and 0.5kg nickel are joined in graphite crucible, it is heated to melting in coreless induction furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 900 revs/min, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity of 1000 DEG C/more than s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-2, and the composition of catalyst-2 is in table 1.
Embodiment 3
Join in graphite crucible by 1.5kg iron, 1.0kg silicon and 0.1kg cobalt, it is heated to melting in coreless induction furnace, it is on the copper roller of 900 revs/min that this fused solution is sprayed onto a rotating speed from crucible nozzle, and logical cooling water in copper roller, aluminium alloy is with 10
5dEG C/cooling velocity of s is got rid of in water along copper roller tangent line after cooling fast, and form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-3, and the composition of catalyst-3 is in table 1.
Embodiment 4
1.5kg iron, 1.0kg silicon and 0.5kg copper are joined in graphite crucible, it is heated to melting in coreless induction furnace, it is on the copper roller of 900 revs/min that this fused solution is sprayed onto a rotating speed from crucible nozzle, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity of 1000 DEG C/s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-4, and the composition of catalyst-4 is in table 1.
Embodiment 5
1.5kg iron, 1.0kg silicon and 0.1kg molybdenum are joined in graphite crucible, it is heated to melting in coreless induction furnace, it is on the copper roller of 900 revs/min that this fused solution is sprayed onto a rotating speed from crucible nozzle, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-5, and the composition of catalyst-5 is in table 1.
Embodiment 6
1.5kg iron, 1.0kg silicon and 0.01kg platinum are joined in graphite crucible, it is heated to melting in coreless induction furnace, it is on the copper roller of 900 revs/min that this fused solution is sprayed onto a rotating speed from crucible nozzle, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-6, and the composition of catalyst-6 is in table 1.
Embodiment 7
1.5kg iron, 1.0kg silicon and 0.2kg nickel are joined in graphite crucible, it is heated to melting in coreless induction furnace, it is on the copper roller of 900 revs/min that this fused solution is sprayed onto a rotating speed from crucible nozzle, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity of 1000 DEG C/more than s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-7, and the composition of catalyst-7 is in table 1.
Embodiment 8
1.5kg iron, 1.0kg silicon and 0.2kg cobalt are joined in graphite crucible, it is heated to melting in coreless induction furnace, it is on the copper roller of 900 revs/min that this fused solution is sprayed onto a rotating speed from crucible nozzle, logical cooling water in copper roller, get rid of in water along copper roller tangent line after aluminium alloy cools fast with the cooling velocity being greater than 1000 DEG C/s, form flakey band, flakey band is less than 500 microns through being ground to particle diameter, obtains foundry alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% sodium hydrate aqueous solutions by 50g foundry alloy, controlling its temperature is that 60 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, decantation liquid, adds distilled water washing and is less than 10 to pH value; And then joining in the salpeter solution of 100 grams of 20wt%, control temperature 80 DEG C also constant temperature stirs 1 hour.Be 7 with the distilled water of 80 DEG C washing to pH value.Obtained catalyst is numbered catalyst-8, and the composition of catalyst-8 is in table 1.
Table 1
Embodiment 9 ~ 16
The present embodiment illustrates and adopts iron catalyst provided by the invention to produce SiHCl in fixed bed reactors
3.
At Catalyst packing 0.3g, reaction temperature 450 DEG C or 400 DEG C, reaction pressure 1.2MPa, H
2/ SiCl
4=2, air speed 24000h
-1condition under, reaction result is in table 2.
Table 2
Claims (5)
1. the preparation method of iron catalyst, it is characterized in that will by iron, silicon, with or discord at least one be selected from periodic table of elements IB, IIB, IIIB, IVB, VIB, the fused mass of the alloy that the transition metal in VIIB or VIII forms is to be greater than the cooldown rate rapid curing of 1000 DEG C/S, cured product under agitation adds that to be heated to extraction temperature be in the alkali lye of 10-100 DEG C, silicon in alloy and alkali are fully reacted, then decantation liquid, be washed with distilled water to after pH is less than 10, join again in the acid solution of 10-100 DEG C and oxidative deactivation is carried out to catalyst surface, sample after pickling is washed with distilled water to pH and obtains catalyst after 6-7, said alkali is solubility highly basic, the concentration of said alkali lye is 2-40 % by weight, the weight ratio of alloy and alkali is 1: 1-10, said acid is HNO
3or perchloric acid, the concentration of said acid solution is 2-40 % by weight, and alloy is 1: 1-10 with the weight ratio of acid, and the transition metal of said VIIB race is not manganese.
2. according to the preparation method of claim 1, wherein, said rapid curing adopts atwirl single roller or two roller cooling molten metal.
3. want the preparation method of 1 according to right, wherein, said rapid curing is the mode cooling molten metal adopting spray atomization and deposition more than 1300 DEG C.
4. according to the preparation method of claim 1, wherein, said solubility highly basic is selected from the hydroxide of alkali-metal hydroxide or alkaline-earth metal.
5. according to the preparation method of claim 1, wherein, said solubility highly basic is NaOH or KOH.
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| CN105817178B (en) * | 2016-03-22 | 2018-01-19 | 湖州慧金材料科技有限公司 | A kind of atomized molten system and using activity spherical cuprous chloride catalyst made from the system and preparation method thereof |
| CN107774281B (en) * | 2016-08-30 | 2020-10-27 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, preparation method thereof and method for preparing low-carbon olefin by carbon monoxide hydrogenation |
Citations (3)
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|---|---|---|---|---|
| US5250716A (en) * | 1992-05-28 | 1993-10-05 | Mui Jeffrey Y P | Method for making a silicon/copper contact mass suitable for direct reaction |
| CN101190412A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Fe catalyst for preparing hydrocarbons with synthesis gas and preparation method thereof |
| CN101816946A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Preparation method and application of catalyst used in hydrogenation of silicon tetrachloride |
-
2011
- 2011-10-21 CN CN201110321966.1A patent/CN103055863B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250716A (en) * | 1992-05-28 | 1993-10-05 | Mui Jeffrey Y P | Method for making a silicon/copper contact mass suitable for direct reaction |
| CN101190412A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Fe catalyst for preparing hydrocarbons with synthesis gas and preparation method thereof |
| CN101816946A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Preparation method and application of catalyst used in hydrogenation of silicon tetrachloride |
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