CN105536789A - Method for preparing trichlorosilane catalyst through hydrogenation dechlorination of silicon tetrachloride - Google Patents
Method for preparing trichlorosilane catalyst through hydrogenation dechlorination of silicon tetrachloride Download PDFInfo
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- CN105536789A CN105536789A CN201510920901.7A CN201510920901A CN105536789A CN 105536789 A CN105536789 A CN 105536789A CN 201510920901 A CN201510920901 A CN 201510920901A CN 105536789 A CN105536789 A CN 105536789A
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- catalyst
- amorphous silicon
- silicon tetrachloride
- trichlorosilane
- stannous chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to a method for preparing a trichlorosilane catalyst through hydrogenation dechlorination of silicon tetrachloride; cuprous chloride is used as an active component, and amorphous silicon aluminum is used as a catalyst carrier. An amorphous silicon aluminum powder after calcination is mixed with a certain amount of cuprous chloride, the mixture is treated at high temperature and in an inert atmosphere, and the product is cooled to obtain the finished product catalyst. The method has the advantages of simple preparation process, and no wastewater, waste gas and waste residue pollution. The catalyst is evaluated to indicate that under process conditions of the reaction temperature of 450 DEG C, the pressure of 1.2 MPa, the H2/SiCl4 molar ratio of 25 and the airspeed of 1000 h<-1>, the conversion rate can reach more than or equal to 30%, and the requirement of industrialized production can be met.
Description
Technical field
The present invention relates to silicon purification field, be specifically related to a kind of for the preparation method of silicon tetrachloride Hydrogenation for the catalyst of trichlorosilane.
Background technology
The exhausted problem of following fossil energy annoyings the energy industry of countries in the world always, the direction that alternative energy source is especially pollution-free, low cost alternative energy source is various countries' develop actively.Solar energy obtains the attention of various countries as regenerative resource, naturally becomes study hotspot as the polysilicon of solar cell primary raw material and preparation process amelioration thereof.
At present, domestic improved Siemens occupies the main flow of production of polysilicon, the severity of the method operating condition 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 method exactly, and the latter, as the raw material reuse of producing polysilicon, can reach pollution-free closed production theoretically completely.
Adopt cold hydrogenation technology, be in trichlorosilane process by converting silicon tetrachloride, hydrogenation catalyst plays and promotes reaction, improves the effect of reaction conversion ratio, has domesticly carried out large quantifier elimination in catalyst field, roughly can divide noble metal, nickel, copper according to active composition.CN102838120, CN102909006 disclose the active component adopting noble metal as hydrogenation of silicon tetrachloride catalyst.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 silica and can the precipitating reagent 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 catalyst for hydrogenation of silicon tetrachloride, will mix, and heat under hydrogen shield through pretreated stannous chloride and silica flour in agitated bed reactor.Described pretreatment refers to and stannous chloride is joined agitating 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 active component of load on carrier, described carrier is silica, described active component is one or more in elemental copper, copper chloride and stannous 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 relative complex, or operating process requires harsh, must bring catalyst preparing cost up.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 catalyst 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 silicon tetrachloride hydrogenation-dechlorination prepares the catalyst of trichlorosilane, the catalyst preparation process solving trichlorosilane in prior art is complicated, the problem that cost is high.
Catalyst preparation process provided by the invention comprises the steps:
(1) amorphous silicon aluminium after roasting, specific surface 150 ~ 500m
2/ g, pore volume 0.5 ~ 1.5mL/g, silica content 1wt% ~ 90wt%, granularity 40 μm ~ 4000 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=2.5 ~ 6:1.
(2) under inert gas shielding, said mixture heats, and programming rate 30 DEG C/h ~ 300 DEG C/h, sintering temperature 450 DEG C ~ 900 DEG C, constant temperature time 1min ~ 300min, constant temperature terminates rear Temperature fall.
In described step (1), the amorphous silicon aluminium of roasting is commercial goods, and residual >=95% of its burning, burns residual condition: 550 DEG C of constant temperature 3h.
In described step (1), specific surface is 300 ~ 400m preferably
2/ g; Described pore volume preferably 0.7 ~ 1.1mL/g; Described silica content is preferably 5wt% ~ 85wt%; Described granularity is preferably 80 μm ~ 2000 μm.
In described step (1), stannous chloride: amorphous silicon aluminium preferred mass ratio is 2.8 ~ 5.5:1.
In described step (2), sintering temperature preferably 500 ~ 800 DEG C, the preferred 10min ~ 60min of constant temperature time.The advantage that the present invention is compared with prior art had and effect:
In the inventive method, by amorphous silicon aluminium and stannous chloride mixing, roasting Kaolinite Preparation of Catalyst, tool has the following advantages:
(1) utilize stannous chloride at high temperature to melt, by the method for motlten metal salt direct impregnation, effectively prevent water and make solvent and carry out in dipping process, there is the low problem of amount of metal on single.
(2) utilize stannous chloride at high temperature to melt, by the method for motlten metal salt direct impregnation, effectively prevent water and make solvent and carry out the problems such as dipping process energy consumption is high, step is numerous and diverse.
(3) utilize stannous chloride at high temperature to melt, by the method for motlten metal salt direct impregnation, effectively prevent water when making solvent, the Cl formed when stannous chloride is water-soluble
-1to the equipment corrosion problem of dipping, stirring, drying, each section of roasting.
(4) stannous chloride is utilized at high temperature to melt, by the method for motlten metal salt direct impregnation, effectively prevent the emission problem of the furnace zone chloride ion-containing waste gas existed when water makees solvent, decrease relevant pollution treatment instrument and operating cost, also solve the storage of dipping waste liquid, emission problem.
(5) catalyst prepared of this method, due to the existence of carrier, effectively can avoid catalytic active component agglomeration in hydrogenation-dechlorination process.
Method for preparing catalyst disclosed by the invention, through evaluating, evaluation result shows, catalyst of the present invention is used for preparing trichlorosilane from silicon tetrachloride through hydrogenation and has higher activity.
Detailed description of the invention
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
(1) amorphous silicon aluminium after roasting, specific surface 150m
2/ g, pore volume 0.7mL/g, silica content 5wt%, granularity 125 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=2.8:1.
(2) under inert gas shielding, said mixture heats, programming rate 50 DEG C/h, sintering temperature 450 DEG C, constant temperature time 30min, and after constant temperature terminates, Temperature fall, obtains finished catalyst.
Embodiment 2
Other are with embodiment 1, and difference is that, in step (2), during roasting, temperature is 600 degrees Celsius, constant temperature 30min.
Embodiment 3
(1) amorphous silicon aluminium after roasting, specific surface 500m
2/ g, pore volume 1.0mL/g, silica content 50wt%, granularity 200 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=4.0:1.
(2) under inert gas shielding, said mixture heats, programming rate 100 DEG C/h, sintering temperature 600 DEG C, constant temperature time 60min, and after constant temperature terminates, Temperature fall, obtains finished catalyst.
Embodiment 4
(1) amorphous silicon aluminium after roasting, specific surface 410m
2/ g, pore volume 1.5mL/g, silica content 30wt%, granularity 300 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=5.6:1.
(2) under inert gas shielding, said mixture heats, programming rate 100 DEG C/h, sintering temperature 800 DEG C, constant temperature time 30min, and after constant temperature terminates, Temperature fall, obtains finished catalyst.
Embodiment 5
(1) amorphous silicon aluminium after roasting, specific surface 150m
2/ g, pore volume 0.5mL/g, silica content 1wt%, granularity 40 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=2.5:1.
(2) under inert gas shielding, said mixture heats, programming rate 30 DEG C/h, sintering temperature 450 DEG C, constant temperature time 300min, and after constant temperature terminates, Temperature fall, obtains finished catalyst.
Embodiment 6
(1) amorphous silicon aluminium after roasting, specific surface>=150m
2/ g, pore volume>=0.5mL/g, silica content 90wt%, granularity 4000 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=6:1.
(2) under inert gas shielding, said mixture heats, programming rate 300 DEG C/h, sintering temperature 900 DEG C, constant temperature time 1min, and after constant temperature terminates, Temperature fall, obtains finished catalyst.
Embodiment 7
In described step (1), the amorphous silicon aluminium of roasting is commercial goods, and it burns residual 95%, burns residual condition: 550 DEG C of constant temperature 3h; Specific surface 300m
2/ g; Pore volume 0.7mL/g; Silica content is 5wt%; Granularity is 80 μm; Stannous chloride: amorphous silicon aluminium mass ratio is 2.8:1.Under inert gas shielding, said mixture heats, sintering temperature 500 DEG C, constant temperature time 10min.Other step is with embodiment 1.
Embodiment 8
In described step (1), the amorphous silicon aluminium of roasting is commercial goods, and residual>=95% of its burning, burns residual condition: 550 DEG C of constant temperature 3h; Specific surface 300m
2/ g; Pore volume 0.7mL/g; Silica content is 85wt%; Granularity is 2000 μm; Stannous chloride: amorphous silicon aluminium mass ratio is 5.5:1.Under inert gas shielding, said mixture heats, sintering temperature 800 DEG C, constant temperature time 60min.Other step is with embodiment 1.
Embodiment 9
The catalyst adopting above-described embodiment 1 ~ 8 to prepare is evaluated, and evaluates process conditions: adopt fixed bed reactors, in certain reaction temperature, and pressure 1.2MPa, H
2/ SiCl
4(mol)=25, air speed 1000h
-1process conditions under, product during assaying reaction 20h, calculate the conversion ratio of silicon tetrachloride, described in the present embodiment, converting silicon tetrachloride rate is defined as:
The invention provides the Catalysts and its preparation method that a kind of silicon tetrahydride hydrogenation-dechlorination prepares trichlorosilane, the method preparation process is simple, pollute without waste water,waste gas and industrial residue.This catalyst adopts stannous chloride to form as activity, and amorphous silicon aluminium is as catalyst carrier.Amorphous silicon aluminium powder after roasting mixes with a certain amount of stannous chloride, high-temperature process under inert atmosphere, after product cooling, is finished catalyst.Show through evaluating catalyst, reaction temperature 450 DEG C, pressure 1.2MPa, H
2/ SiCl
4(mol)=25, air speed 1000h
-1process conditions under, conversion ratio can reach 30%, can meet industrialization production requirements.
The evaluating data of the different embodiment of table 1
Claims (5)
1. silicon tetrachloride hydrogenation-dechlorination prepares a method for the catalyst of trichlorosilane, it is characterized in that comprising the steps:
(1) amorphous silicon aluminium after roasting, specific surface 150 ~ 500m
2/ g, pore volume 0.5 ~ 1.5mL/g, silica content 1wt% ~ 90wt%, granularity 40 μm ~ 4000 μm, mixes with stannous chloride, and mixing quality is than being stannous chloride: amorphous silicon aluminium=2.5 ~ 6:1.
(2) under inert gas shielding, said mixture heats, and programming rate 30 DEG C/h ~ 300 DEG C/h, sintering temperature 450 DEG C ~ 900 DEG C, constant temperature time 1min ~ 300min, constant temperature terminates rear Temperature fall.
2. a kind of silicon tetrachloride hydrogenation-dechlorination according to claim 1 prepares the method for the catalyst of trichlorosilane, and it is characterized in that, in described step (1), the amorphous silicon aluminium of roasting is commercial goods, residual >=95% of its burning, burns residual condition: 550 DEG C, 3h.
3. a kind of silicon tetrachloride hydrogenation-dechlorination according to claim 1 prepares the method for the catalyst of trichlorosilane, it is characterized in that in described step (1), specific surface is 300 ~ 400m preferably
2/ g; Described pore volume preferably 0.7 ~ 1.1mL/g; Described silica content is preferably 5wt% ~ 85wt%; Described granularity is preferably 80 μm ~ 2000 μm.
4. a kind of silicon tetrachloride hydrogenation-dechlorination according to claim 1 prepares the method for the catalyst of trichlorosilane, it is characterized in that in described step (1), stannous chloride: amorphous silicon aluminium preferred mass ratio is 2.8 ~ 5.5:1.
5. a kind of silicon tetrachloride hydrogenation-dechlorination according to claim 1 prepares the method for the catalyst of trichlorosilane, it is characterized in that in described step (2), sintering temperature preferably 500 ~ 800 DEG C, the preferred 10min ~ 60min of constant temperature time.
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Cited By (1)
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| CN112456500A (en) * | 2021-01-29 | 2021-03-09 | 中国科学院过程工程研究所 | Preparation method of trichlorosilane |
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