CN105399101A - Method for preparing trichlorosilane through cold hydrogenation - Google Patents
Method for preparing trichlorosilane through cold hydrogenation Download PDFInfo
- Publication number
- CN105399101A CN105399101A CN201510936653.5A CN201510936653A CN105399101A CN 105399101 A CN105399101 A CN 105399101A CN 201510936653 A CN201510936653 A CN 201510936653A CN 105399101 A CN105399101 A CN 105399101A
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- China
- Prior art keywords
- cuprous chloride
- silica flour
- trichlorosilane
- silicon tetrachloride
- silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
Abstract
The invention relates to a method for preparing trichlorosilane through cold hydrogenation; molten-state cuprous chloride is subjected to spray atomization to a heated and dried silica fume surface, the silica fume having the surface uniformly sprayed with cuprous chloride enters a reactor and is reduced by hydrogen, the obtained copper/silicon particles rapidly undergo a reaction with hydrogen and silicon tetrachloride, and the trichlorosilane product is generated. A catalyst preparation step and a catalyst mixing step are avoided, so that the utilization rate of cuprous chloride is greatly improved compared with the utilization rate when cuprous chloride is made into a catalyst.
Description
Technical field
The field of the present invention relates to is silicon purification field, is specifically related to a kind of cold hydrogenation process route, silicon tetrachloride Hydrogenation of adopting for the processing method of trichlorosilane.
Background technology
Coal in fossil energy, oil are the important energy sourceses in current countries in the world.The exhausted problem of fossil energy perplexs the energy industry of countries in the world always.Oil in 2015, coal price depression does not represent the excessive increase of its allowable exploitation.Sun power because it is clean, pollute the incomparable advantage of other fossil class energy such as little, renewable, obtain the attention of various countries.Polysilicon is the main raw material preparing solar cell, and the improvement of polycrystalline silicon preparing process becomes study hotspot.
At present, domestic improved Siemens occupies the main flow of production of polysilicon, the method operating severity is relatively low, but often producing 1 ton of polysilicon just can by-product more than 10 tons silicon tetrachloride, for reducing production of polysilicon unit consumption, reducing production cost, avoiding environmental hazard, converting silicon tetrachloride is trichlorosilane by most effective means exactly, and the latter is used for production of polysilicon as raw material, can reach pollution-free closed production completely theoretically.
Converting silicon tetrachloride is in trichlorosilane technological process by cold hydrogenation technology, usually needs to add catalyzer in order to accelerate this reaction process.Domesticly carry out large quantifier elimination in catalyst field, roughly can divide precious metal, nickel, copper catalyst according to active composition.CN102838120, CN102909006 disclose and adopt precious metal as the active ingredient of hydrogenation of silicon tetrachloride catalyzer, and precious metal is used for this process and has that price is high, precious metal is difficult to the problems such as recovery.CN1436725 discloses a kind of method of producing trichloro hydrosilicon by hydrogenation of silicon tetrachloride, and described nickel accelerant is Powdered hydrogenation nickel accelerant.CN102626630, CN102627283, CN102626630 disclose a kind of Catalysts and its preparation method and application, described catalyst preparation process is: the soluble salt compound of soluble nickel salt, metal M, can provide the silicon source of silicon-dioxide and can the precipitation agent of coprecipitated nickel hydroxide and/or metal M ion contact in a solvent, and products therefrom filters, dry, roasting.CN101816946 discloses a kind of preparation method and application thereof of the catalyzer for hydrogenation of silicon tetrachloride, will mix, and heat under hydrogen shield through pretreated cuprous chloride and silica flour in agitated bed reactor.Described pre-treatment refers to and cuprous chloride is joined stirring heating in silicon tetrachloride, dry under protection gas after filtration.CN101941702 discloses a kind of tetrachloro hydrogen silicon and transforms the method for producing trichlorosilane, described copper based supported catalyst comprises carrier and the activeconstituents of load on carrier, described carrier is silicon-dioxide, described activeconstituents is one or more in elemental copper, cupric chloride and cuprous chloride, vector contg 30%-70%, active component content 30%-70%.CN102350351 discloses a kind of hydrogenation catalyst and preparation method thereof, and described catalyst active component is cupro silicon, Corson alloy, copper silicon rare earth alloy or copper nisiloy rare earth alloy.Preparation process comprises melting, atomization, reduction drying, screening.Above-mentioned hydrogenation catalyst preparation process is complicated.Field polysilicon is increasingly competitive, and strict all the more to the control of production cost, as hydrogenation catalyst requisite in production process, falling price becomes trend, and therefore, it is inevitable that developing low-cost, highly active hydrogenation process become this area development.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, provide a kind of method that trichlorosilane is prepared in cold hydrogenation, solve speed of reaction and the dissatisfactory problem of transformation efficiency in prior art.
Technical scheme of the present invention comprises the steps:
Cuprous chloride is heated to 450-650 DEG C of molten state, after pump pressurizing atomizing, be sprayed in the silica flour of temperature 400 ~ 500 DEG C, nitrogen-sealed, stirring, the mass ratio of cuprous chloride and silica flour is 1:(75 ~ 250), the silica flour of spraying cuprous chloride enters into reactor and reacts.The mol ratio of silicon tetrachloride, hydrogen, silica flour is 1:(2 ~ 6): (700 ~ 900), temperature of reaction 400-500 DEG C, pressure 2.0MPa, duration of contact 15-30s, obtain trichlorosilane and silicon tetrachloride mixture, calculate converting silicon tetrachloride rate.
Described cuprous chloride purity 98%, cuprous chloride is containing elemental copper 62.9%.
The preferred molar ratio of described silicon tetrachloride, hydrogen, silica flour is 1:4:800.
Advantageous effect of the present invention is as follows:
A kind of technological process of cold hydrogenation trichlorosilane, this process by molten state cuprous chloride through jet atomization to the silicon powder surface of heat drying, the silica flour of surface uniform spraying cuprous chloride enters into reactor, with through hydrogen reducing, the silicon obtained/copper particle and hydrogen and silicon tetrachloride react rapidly, generate trichlorosilicane product.
In the inventive method, form new cuprous chloride/silicon powder particles by silica flour and the cuprous chloride spraying to silicon powder surface, obtain copper/silicon powder particle through hydrogen reducing, then react.Concrete advantage is as follows;
(1) catalyst preparing link and catalyst mix link is avoided.
(2) cuprous chloride sprays to silicon powder surface, makes cuprous chloride relative to utilization ratio when being prepared into catalyzer greatly to improve.
(3) active sites that copper/silicon grain surface exists, i.e. copper-Siliciumatom point of contact increases greatly compared to silica flour-catalyst system, and in the mutual collision process of copper/silicon grain, copper atom can contact with the Siliciumatom on other copper/silicon grains, there is katalysis equally to the Siliciumatom of this point of contact, therefore speed of reaction of the present invention and transformation efficiency obviously increase.
The present invention is under the prerequisite of same system copper content, and transformation efficiency comparatively comparative example improves 5 percentage points, and processing method provided by the invention effectively can improve transformation efficiency.And when reducing reactive system copper content, transformation efficiency declines slowly, shows that whole reaction system is still in the operating mode of high conversion under the prerequisite of lower cuprous chloride add-on.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
The following examples will be further described with regard to method provided by the invention and set forth, but not limit the present invention.
Embodiment 1
Containing cuprous chloride (purity 98%) 100g of elemental copper 62.9%, be heated to 450 DEG C of molten states, after pump pressurizing atomizing, be sprayed in the silica flour of temperature 400 DEG C, nitrogen-sealed, stirring, the mass ratio of cuprous chloride and silica flour is 1:75 (copper: silicon=1:120), and the silica flour of spraying cuprous chloride enters into reactor.The mol ratio of silicon tetrachloride, hydrogen, silica flour is 1:4:800, temperature of reaction 450 DEG C, pressure 2.0MPa, duration of contact 20s.Obtain trichlorosilane and silicon tetrachloride mixture, calculate converting silicon tetrachloride rate, the results are shown in table 1.Comparative example 1
By cuprous chloride (purity 98%) 100g containing elemental copper 62.9%, be impregnated into SiO
2on, the weight ratio of copper and silicon-dioxide is 50:50, and the catalyzer of preparation reacts according to the processing condition of embodiment 1, calculates converting silicon tetrachloride rate, the results are shown in table 1.
Embodiment 2
Other are with embodiment 1, and difference is that the cuprous chloride of silicon/cuprous chloride particle of preparation and the mass ratio of silica flour are 1:150 (copper: silicon=1:238).
Embodiment 3
Other are with embodiment 1, and difference is that the cuprous chloride of silicon/cuprous chloride particle of preparation and the mass ratio of silica flour are 1:200 (copper: silicon=1:318).
Embodiment 4
Other are with embodiment 1, and difference is that the cuprous chloride of silicon/cuprous chloride particle of preparation and the mass ratio of silica flour are 1:250 (copper: silicon=1:397).
Embodiment 5
Cuprous chloride is heated to 450 DEG C of molten states, after pump pressurizing atomizing, be sprayed in the silica flour of temperature 400 DEG C, nitrogen-sealed, stirring, the mass ratio of cuprous chloride and silica flour is 1:75, and the silica flour of spraying cuprous chloride enters into reactor, the mol ratio of silicon tetrachloride, hydrogen, silica flour is 1:2:700, temperature of reaction 400 DEG C, pressure 2.0MPa, duration of contact 15s, obtain trichlorosilane and silicon tetrachloride mixture, calculate converting silicon tetrachloride rate.
Embodiment 6
Cuprous chloride is heated to 650 DEG C of molten states, after pump pressurizing atomizing, be sprayed in the silica flour of temperature 500 DEG C, nitrogen-sealed, stirring, the mass ratio of cuprous chloride and silica flour is 1:250, and the silica flour of spraying cuprous chloride enters into reactor, the mol ratio of silicon tetrachloride, hydrogen, silica flour is 1:6:900, temperature of reaction 500 DEG C, pressure 2.0MPa, duration of contact 30s, obtain trichlorosilane and silicon tetrachloride mixture, calculate converting silicon tetrachloride rate.
Concrete evaluating data sees the following form.
The evaluating data of the different embodiment of table 1
Claims (3)
1. the method for trichlorosilane is prepared in a cold hydrogenation, it is characterized in that comprising the steps: cuprous chloride to be heated to 450-650 DEG C of molten state, after pump pressurizing atomizing, be sprayed into temperature 400-500 DEG C, nitrogen-sealed, in the silica flour stirred, the mass ratio of cuprous chloride and silica flour is 1:75-250, the silica flour of spraying cuprous chloride enters into reactor, silicon tetrachloride, hydrogen, the mol ratio of silica flour is 1:(2 ~ 6): (700 ~ 900), temperature of reaction 400-500 DEG C, pressure 2.0MPa, duration of contact 15-30s, obtain trichlorosilane and silicon tetrachloride mixture, calculate converting silicon tetrachloride rate.
2. the method for trichlorosilane is prepared in a kind of cold hydrogenation according to claim 1, it is characterized in that described cuprous chloride purity 98%, and cuprous chloride is containing elemental copper 62.9%.
3. the method for trichlorosilane is prepared in a kind of cold hydrogenation according to claim 1, it is characterized in that the preferred molar ratio of described silicon tetrachloride, hydrogen, silica flour is 1:4:800.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936653.5A CN105399101A (en) | 2015-12-14 | 2015-12-14 | Method for preparing trichlorosilane through cold hydrogenation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510936653.5A CN105399101A (en) | 2015-12-14 | 2015-12-14 | Method for preparing trichlorosilane through cold hydrogenation |
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| CN105399101A true CN105399101A (en) | 2016-03-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108069428A (en) * | 2016-11-18 | 2018-05-25 | 江苏中能硅业科技发展有限公司 | For handling the device and technique of polysilicon by-product slurry |
| CN114505084A (en) * | 2022-01-18 | 2022-05-17 | 石河子大学 | Pretreatment method of cuprous chloride catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157259A (en) * | 1995-12-25 | 1997-08-20 | 德山株式会社 | Trichlorosilane production process |
| CN1437562A (en) * | 2000-04-20 | 2003-08-20 | 通用电气公司 | Method for preparing a contact mass |
| 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 |
| WO2014137096A1 (en) * | 2013-03-07 | 2014-09-12 | Hanwha Chemical Corporation | A method for preparing trichlorosilane |
| WO2014204207A1 (en) * | 2013-06-19 | 2014-12-24 | Hanwha Chemical Corporation | Method of preparing trichlorosilane |
-
2015
- 2015-12-14 CN CN201510936653.5A patent/CN105399101A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157259A (en) * | 1995-12-25 | 1997-08-20 | 德山株式会社 | Trichlorosilane production process |
| CN1437562A (en) * | 2000-04-20 | 2003-08-20 | 通用电气公司 | Method for preparing a contact mass |
| 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 |
| WO2014137096A1 (en) * | 2013-03-07 | 2014-09-12 | Hanwha Chemical Corporation | A method for preparing trichlorosilane |
| WO2014204207A1 (en) * | 2013-06-19 | 2014-12-24 | Hanwha Chemical Corporation | Method of preparing trichlorosilane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108069428A (en) * | 2016-11-18 | 2018-05-25 | 江苏中能硅业科技发展有限公司 | For handling the device and technique of polysilicon by-product slurry |
| CN108069428B (en) * | 2016-11-18 | 2023-10-10 | 江苏中能硅业科技发展有限公司 | Device and process for treating polysilicon byproduct slag slurry |
| CN114505084A (en) * | 2022-01-18 | 2022-05-17 | 石河子大学 | Pretreatment method of cuprous chloride catalyst |
| CN114505084B (en) * | 2022-01-18 | 2023-09-12 | 石河子大学 | Pretreatment method of cuprous chloride catalyst |
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