CN102350362A - Nanometer catalyst for silicon tetrachloride hydrogenation reaction and preparation method thereof - Google Patents
Nanometer catalyst for silicon tetrachloride hydrogenation reaction and preparation method thereof Download PDFInfo
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- CN102350362A CN102350362A CN2011102254418A CN201110225441A CN102350362A CN 102350362 A CN102350362 A CN 102350362A CN 2011102254418 A CN2011102254418 A CN 2011102254418A CN 201110225441 A CN201110225441 A CN 201110225441A CN 102350362 A CN102350362 A CN 102350362A
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Abstract
The invention relates to the field of catalysts, and discloses a nanometer catalyst for silicon tetrachloride 'cold hydrogenation' reaction. The nanometer catalyst comprises the following components in percentage by weight: 0 to 99 percent of copper element and 0 to 99 percent of nickel element which serve as active ingredients and the balance of cocatalyst metal, wherein the components are loaded on the surface of silicon powder in a form of nanometer granules. A preparation process comprises the following steps of: dissolving the active ingredients and loading the dissolved active ingredients on the surface of the silicon powder in a form of nanometer granules by an immersion method or preparing nanometer granules from the active ingredients in a hydrothermal method, and mixing the nanometer granules and the silicon powder, so that the catalyst fully contacts the silicon powder to prepare a mixture of the catalyst and the silicon powder; and activating the mixture in advance at high temperature under the atmosphere of hydrogen, and guiding into a reactor to perform reaction. The nanometer catalyst prepared by the method is small in granules and high in utilization rate, can contact the silicon powder fully, and has the characteristics of high dispersity, high activity and the like when used for the silicon tetrachloride cold hydrogenation reaction.
Description
Technical field
The invention belongs to catalyst and technology of preparing thereof, particularly a kind of nanocatalyst that is used for the hydrogenation of silicon tetrachloride reaction and preparation method thereof.
Background technology
Polysilicon is widely used in semiconductor and photovoltaic industry.Particularly in recent years, an urgent demand that free of contamination new forms of energy become social development is sought in the enhancing of energy crisis and people's environmental consciousness.Solar energy is because its cleaning, safety and aboundresources, and receives much concern.Silica-based solar cell utilizes the mainstream technology of solar energy now, makes many demands to high-purity crystal silicon improve greatly.
High purity polycrystalline silicon is mainly through also original production of trichlorosilane, and this method is Germany (siemens) invention in 1954, and be otherwise known as " west door method " occupied the market share more than 80%, and its main chemical reactions equation is:
Use above-mentioned west door method in the trichlorosilane reduction process except generating silicon, also can produce a large amount of generation silicon tetrachlorides, one kilogram of silicon generates about 20 kilograms of silicon tetrachlorides.Silicon tetrachloride generates trichlorosilane in improved " Siemens Method " behind the hydrogen hydrogenation, has realized closed loop cycle, reduces because the environmental pollution that the silicon tetrachloride discharging brings.The hydrogenation of silicon tetrachloride technology mainly contains two kinds, hot hydrogenation technology and cold hydrogenation technology.Hot hydrogenation technology is under 1000-1200 ℃ of high temperature, and silicon tetrachloride and hydrogen are sent out and should be generated trichlorosilane, and conversion ratio is about 20%, and its shortcoming is that energy consumption is high, and per kilogram trichlorosilane power consumption is at the 3-5 degree, and its chemical equation is:
" cold hydrogenation " technology is meant that silicon tetrachloride, silica flour and hydrogen react the generation trichlorosilane under 400-600 ℃ temperature, and its advantage is that energy consumption is low, and per kilogram trichlorosilane power consumption is lower than 0.8 degree, and does not have HCl in the product, and subsequent separation process is simple.After some difficult points that solved on " cold hydrogenation " equipment, it becomes the technology that pursued by most polysilicon enterprise rapidly, and its main chemical reactions equation is:
Commonly used to pulverous copper base and nickel-base catalyst in " cold hydrogenation " technology, can improve conversion ratio 2-3%.In course of reaction, relate to admittedly reaction, catalyst granules and silicon powder particle are bigger, and contacting efficiency is lower, influences the result of use of catalyst, and catalyst taken out of by air-flow in fluid bed easily, lose catalytic effect.
Based on above-mentioned background, proposed the nanocatalyst of the cold hydrogenation of silicon tetrachloride and, specifically, related to the Catalysts and its preparation method that is used for silicon tetrachloride " cold hydrogenation " preparation trichlorosilane in the preparation method.For example; Open day is 2011.02.16; The Chinese patent document of publication number position CN101972657A; A kind of catalyst technology of hydrogenation of silicon tetrachloride system trichlorosilane is disclosed; Belong to chemical technology field; Catalyst is active component with nickel; Silica is as carrier; Also can contain rare-earth additive; Carry out according to the following step successively: precipitate joining in the silicon source after the nickel source dissolving, treat to join in the alkali lye after deposition is accomplished, will more than the nickel deposition fully; To be deposited under 100～150 ℃ of temperature dry 5-10 hour, get final product at 400～500 ℃ of following roasting 5-10 hours then.The active metal component major part is carried on inert carrier SiO in this technical scheme
2In the endoporus, be unfavorable for that the reactant silica flour contacts with active component, has reduced the catalytic efficiency of catalyst.
Summary of the invention
It is bigger to the present invention is directed in the cold hydrogenation of silicon tetrachloride catalyst granules; The characteristics that utilization rate is not high; Provide a kind of nanocatalyst that is used for silicon tetrachloride " cold hydrogenation " reaction and and preparation method thereof; This catalyst is used for the course of reaction of the cold hydrogenation of silicon tetrachloride; Have active high; Characteristics such as good dispersion are suitable for fluidized-bed reactor more.
Technical scheme of the present invention is following:
A kind of nanocatalyst that is used for silicon tetrachloride " cold hydrogenation " reaction; It is characterized in that: comprise copper and nickel element as active component; Wherein, It is 0 ~ 99wt% that copper accounts for weight ratio; It is 0-99 wt % that nickel element accounts for weight ratio; All the other are for helping catalyst component, and above component loads to silicon powder surface with the form of nano particle;
The preparation method of the said nanocatalyst of preparation claim 1; It is characterized in that: at first the starting compound of copper and/or nickel is dissolved in deionized water or hydrochloric acid or the nitric acid and forms solution; The compound that will contain aiding catalytic component again is dissolved in the material solution that makes; Adding silica flour then floods; At the following dipping of 0 ~ 50 ℃ of temperature; Then in 50 ~ 150 ℃ of oven dry; Under 200 ~ 800 ℃ temperature, in hydrogen atmosphere, carry out roasting reduction again; The nanocatalyst that makes is the nano particle in the 1-100nm scope; The nanocatalyst of gained directly loads on the surface of silica flour, can directly be used for cold hydrogenation.
Said catalyst also can prepare through " hydro-thermal method " method: the starting compound of copper and/or nickel is dissolved in deionized water or hydrochloric acid or the nitric acid forms solution; Aiding catalytic component is dissolved in the material solution that makes again; Regulate between pH value to 7 ~ 10; In temperature is 100 ~ 300 ℃; Pressure is to react 3 ~ 30 hours in the water heating kettle of 0.1 ~ 1Mpa; Make the particle that nanoparticle catalyst is 2-100 nm; After 90 ~ 135 ℃ of oven dry; Carry out mechanical mixture with silica flour, after in hydrogen atmosphere, carrying out roasting reduction under 200 ~ 800 ℃ the temperature, be used for cold hydrogenation.
Said starting compound as copper or nickel composition is one or more in copper nitrate, metallic copper, cupric phosphate, permolybdic acid copper, cupric oxide, copper chloride, copper sulphate, protochloride nickel, nickel nitrate, nickelous carbonate, nickelous sulfate, permolybdic acid nickel, nickel phosphate, nickel protoxide, the metallic nickel.
Said catalyst helps catalyst component can be one or more metallic elements in chromium, molybdenum, tungsten, manganese, ruthenium, iridium, palladium, platinum, silver, gold, zinc, cadmium, indium, tin, lead, lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, scandium, yttrium, the lanthanum.
Beneficial effect of the present invention is following:
Nanocatalyst particle of the present invention is little, and utilization rate is high, is used for the course of reaction of the cold hydrogenation of silicon tetrachloride, has characteristics such as active height, good dispersion, is suitable for fluidized-bed reactor more than traditional catalyst; Through the reactant silica flour directly is carrier, and the catalyst of preparation is that nano-scale particle is distributed to silicon powder surface uniformly, has improved the contacting efficiency of silica flour and catalyst greatly, has improved the conversion ratio of reaction; Preparation method of the present invention is simple, owing to there is not extra carrier, has avoided the introducing of other impurity, can access high-quality product.
The specific embodiment
Followingly describe the present invention in detail, but the present invention is confined to this never in any form according to embodiment and Comparative Examples.The material quantity that the composition ratio homophase of the respective element in the gained catalyst should constitute element calculates.Same a kind of formation element of supposing to be included in the initiation material that is used for Preparation of Catalyst gets into this catalyst same as before.
Embodiment 1:
It is in 10% the hydrochloric acid solution that 1g copper chloride, 0.05g palladium bichloride are dissolved in the 100g mass content, and stirs, and treats that solid is all after the dissolving.The 200g silica flour is added in the solution make, leave standstill 5h after, earlier at 100 ℃ of oven dry 5h down, 450 ℃ of following roasting 8h in hydrogen atmosphere then, nitrogen atmosphere is preserved subsequent use down.
Embodiment 2:
It is in 10% the hydrochloric acid solution that 0.1g copper chloride, 1.0 g nickel chlorides, 0.05g manganese chloride, 0.2g cesium chloride are dissolved in the 100g mass content, and stirs, and treats that solid is all after the dissolving.200 g silica flours are added in the solution make, leave standstill 5h after, earlier at 50 ℃ of oven dry 5h down, 700 ℃ of following roasting 8h in hydrogen atmosphere then, nitrogen atmosphere is preserved subsequent use down.
Embodiment 3:
It is in 10% the hydrochloric acid solution that 0.3g cuprous oxide, 1.0 g nickel chlorides, 0.1g potassium chloride are dissolved in 100 g mass content, and stirs, and treats that solid is all after the dissolving.Place water heating kettle, under 200 ℃, 1.3Mpa, carry out hydro-thermal reaction, make nano particle less than 100nm, isolated by filtration, then in hydrogen atmosphere at 800 ℃ of following roasting 8h, nitrogen atmosphere is preserved subsequent use down.
Embodiment 4:
It is in 10% the hydrochloric acid solution that 0.5g copper nitrate, 1g nickel nitrate, 0.4g barium nitrate are dissolved in the 100g mass content, and stirs, and solid is all dissolved.In above-mentioned solution, added silica flour 200 g dipping 4 hours, 80 ℃ dry 8 hours down, then in hydrogen atmosphere at 240 ℃ of following roasting 5h, nitrogen atmosphere is preserved subsequent use down.
Embodiment 5:
It is in 10% the aqueous hydrochloric acid solution that 1g copper chloride, 0.1g six water nickel chlorides, 0.1g sodium chloride are dissolved in the 100g mass content, and stirs, and solid is all dissolved.Insert in the water heating kettle, under 150 ℃, 0.5MPa, carry out hydro-thermal reaction, obtain the nano particle of little 100 nm, add 300 g silica flour mechanical mixture, then in hydrogen atmosphere at 600 ℃ of following roasting 8h, nitrogen atmosphere is preserved subsequent use down
| Catalyst | Temperature (℃) | Pressure (MPa) | Hydrogen and silicon tetrachloride mol ratio | Silicon tetrachloride conversion ratio (%) |
| The 1# catalyst | 460 | 2．8 | 4 | 37 |
| The 2# catalyst | 460 | 1．5 | 3 | 23 |
| The 3# catalyst | 460 | 3．0 | 7 | 28 |
| The 4# catalyst | 460 | 1．2 | 2 | 30 |
| The 5# catalyst | 460 | 1．2 | 3 | 25 |
| Industrial catalyst | 500 | 2．8 | 3．5 | 23 |
Claims (6)
1. one kind is used for the nanocatalyst that hydrogenation of silicon tetrachloride reacts; It is characterized in that: comprise copper and nickel element as active component; Wherein, It is 0 ~ 99wt% that copper accounts for weight ratio; It is 0-99 wt % that nickel element accounts for weight ratio; All the other are the content that helps the catalyst component metal, and above component loads to silicon powder surface with the form of nano particle.
2. nanocatalyst according to claim 1 is characterized in that: the said catalyst component metal that helps is the oxide or the salt of one or more metallic elements in alkali metal, alkaline-earth metal, the transition metal.
3. the preparation method who prepares the said nanocatalyst of claim 1; It is characterized in that: at first the starting compound of copper and/or nickel is dissolved in deionized water or hydrochloric acid or the nitric acid and forms solution; The compound that will contain aiding catalytic component again is dissolved in the material solution that makes; Adding silica flour then floods; Under 0 ~ 50 ℃ of temperature, flood; Then in 50 ~ 150 ℃ of oven dry; Under 200 ~ 800 ℃ temperature, in hydrogen atmosphere, carry out roasting reduction again; The nanocatalyst that makes is the nano particle in the 1-100nm scope; The nanocatalyst of gained directly loads on the surface of silica flour, directly is used for cold hydrogenation.
4. the preparation method who prepares the said nanocatalyst of claim 1; It is characterized in that: the starting compound of copper and/or nickel is dissolved in deionized water or hydrochloric acid or the nitric acid forms solution; Aiding catalytic component is dissolved in the material solution that makes again; Regulate between pH value to 7 ~ 10; In temperature is that 100 ~ 300 ℃, pressure are to react 3 ~ 60 hours in the water heating kettle of 0.1 ~ 1Mpa; Make the particle that nanoparticle catalyst is 2-100nm; After 90 ~ 135 ℃ of oven dry; Carry out mechanical mixture with silica flour, after in hydrogen atmosphere, carrying out roasting reduction under 200 ~ 800 ℃ the temperature, be used for cold hydrogenation.
5. prepare any described preparation method in the claim 3 ~ 4, it is characterized in that: it is the oxide or the salt of one or more metallic elements in alkali metal, alkaline-earth metal, the transition metal that said catalyst helps catalyst component.
6. prepare any described preparation method in the claim 3 ~ 4, it is characterized in that: said starting compound as copper or nickel composition is one or more in copper nitrate, metallic copper, cupric phosphate, permolybdic acid copper, cupric oxide, copper chloride, copper sulphate, protochloride nickel, nickel nitrate, nickelous carbonate, nickelous sulfate, permolybdic acid nickel, nickel phosphate, nickel protoxide, the metallic nickel.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838120A (en) * | 2012-09-18 | 2012-12-26 | 特变电工新疆硅业有限公司 | Method for catalyzing and hydrogenating silicon tetrachloride by using nano platinum |
| CN104399479A (en) * | 2014-11-25 | 2015-03-11 | 山西潞安矿业(集团)有限责任公司 | Catalyst for hydrogenation reaction of silicon tetrachloride, and preparation method of catalyst |
| CN108283925A (en) * | 2018-01-10 | 2018-07-17 | 辽宁石油化工大学 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
| CN109732096A (en) * | 2019-02-01 | 2019-05-10 | 东南大学 | A kind of preparation method of metal nanoparticle |
| CN113996298A (en) * | 2021-11-30 | 2022-02-01 | 新特能源股份有限公司 | Supported catalyst and preparation method thereof |
| CN114054035A (en) * | 2021-11-30 | 2022-02-18 | 新特能源股份有限公司 | Catalyst for catalyzing silicon tetrachloride conversion and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972657A (en) * | 2010-11-19 | 2011-02-16 | 山东齐鲁科力化工研究院有限公司 | Catalyst for hydrogenating silicon tetrachloride for preparing trichlorosilane and preparation method thereof |
| CN102114426A (en) * | 2010-12-23 | 2011-07-06 | 内蒙古工业大学 | Special catalyst for cold hydrogenation of silicon tetrachloride and preparation method thereof |
-
2011
- 2011-08-08 CN CN2011102254418A patent/CN102350362A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972657A (en) * | 2010-11-19 | 2011-02-16 | 山东齐鲁科力化工研究院有限公司 | Catalyst for hydrogenating silicon tetrachloride for preparing trichlorosilane and preparation method thereof |
| CN102114426A (en) * | 2010-12-23 | 2011-07-06 | 内蒙古工业大学 | Special catalyst for cold hydrogenation of silicon tetrachloride and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838120A (en) * | 2012-09-18 | 2012-12-26 | 特变电工新疆硅业有限公司 | Method for catalyzing and hydrogenating silicon tetrachloride by using nano platinum |
| CN102838120B (en) * | 2012-09-18 | 2014-09-03 | 新特能源股份有限公司 | Method for catalyzing and hydrogenating silicon tetrachloride by using nano platinum |
| CN104399479A (en) * | 2014-11-25 | 2015-03-11 | 山西潞安矿业(集团)有限责任公司 | Catalyst for hydrogenation reaction of silicon tetrachloride, and preparation method of catalyst |
| CN108283925A (en) * | 2018-01-10 | 2018-07-17 | 辽宁石油化工大学 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
| CN108283925B (en) * | 2018-01-10 | 2020-07-21 | 辽宁石油化工大学 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
| CN109732096A (en) * | 2019-02-01 | 2019-05-10 | 东南大学 | A kind of preparation method of metal nanoparticle |
| CN109732096B (en) * | 2019-02-01 | 2022-01-28 | 东南大学 | Preparation method of metal nanoparticles |
| CN113996298A (en) * | 2021-11-30 | 2022-02-01 | 新特能源股份有限公司 | Supported catalyst and preparation method thereof |
| CN114054035A (en) * | 2021-11-30 | 2022-02-18 | 新特能源股份有限公司 | Catalyst for catalyzing silicon tetrachloride conversion and preparation method thereof |
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Application publication date: 20120215 |