CN102626630B - Catalyst as well as preparation method and application thereof - Google Patents
Catalyst as well as preparation method and application thereof Download PDFInfo
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- CN102626630B CN102626630B CN 201210103164 CN201210103164A CN102626630B CN 102626630 B CN102626630 B CN 102626630B CN 201210103164 CN201210103164 CN 201210103164 CN 201210103164 A CN201210103164 A CN 201210103164A CN 102626630 B CN102626630 B CN 102626630B
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Abstract
The invention discloses a catalyst as well as a preparation method thereof. The preparation method comprises the steps of: contacting a soluble nickel salt, a soluble salt compound of metal M, a silicon source capable of providing silicon dioxide and a precipitating agent capable of precipitating nickel and/or metal M ions, filtering a product obtained through contact, and drying and roasting obtained solids in sequence, wherein M is selected from one or some of IB, IIB, IIA and VIIIth groups of metal besides Ni. The catalyst prepared according to the preparation method disclosed by the invention is applied to preparation of trichlorosilane from silicon tetrachloride through hydrogenation. Compared with the conventional aluminum-based catalyst, the catalyst prepared according to the preparation method disclosed by the invention has the following advantages that: a SiO2 carrier is stable in a reaction atmosphere for preparing the trichlorosilane from the silicon tetrachloride through hydrogenation, a catalyst skeleton is not easily damaged as a carrier in the traditional hydrogenation catalyst and has longer service life, and the catalyst is increased in activity compared with nickel salt and copper salt catalysts which are commonly used in the prior art.
Description
Technical field
The present invention relates to a kind of preparation method and a kind of catalyst that is prepared by the method for catalyst, and the application in preparing trichlorosilane from silicon tetrachloride through hydrogenation.
Background technology
In recent years, the exhausted and lasting soaring continuous aggravation of oil price along with worldwide traditional energy, the whole world just utilizes regenerative resource at active development.Solar energy is as reproducible clear energy sources, because its cleaning, safety, aboundresources have obtained fast development.Thereby, constantly increase as the demand of the high purity polycrystalline silicon of solar cell raw material.
In production of polysilicon technique, produce 1 ton of polysilicon and can produce silicon tetrachloride and the about hydrogen chloride of 1-5 ton more than 10 tons., high efficiency extensive owing to also not having and safely digestion process produce the SiCl that produces in the polysilicon process
4Method, a large amount of high-load chlorine compounds can only be hoarded, and have brought great hidden danger to Environmental security.In order to reduce the production of polysilicon material consumption, to reduce production costs, avoid environmental pollution, the most effective, the most most economical method is converted into trichlorosilane with hydrogenation of silicon tetrachloride exactly, trichlorosilane is sent back to polysilicon system again as raw material produce polysilicon, produces thereby form " closed loop ".
At present, industrially mainly by two kinds of methods, silicon tetrachloride is carried out hydrogenation and transform.A kind of technology path is SiCl
4Hot hydrogenation is about to SiCl
4And H
2Be converted into SiHCl under the high temperature of 1200-1500 ℃ and 0.6MPa pressure
3, its chemical equation is: SiCl
4+ H
2→ SiHCl
3+ HCl.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 contacts the process of carrying out hydrogenation with fluidized state with silica flour in reactor, the catalyst that this process is used is mainly metallic nickel, copper even load type catalyst, and carrier is generally alundum (Al2O3).
For example, CN1436725A discloses a kind of cold method for hydrogenation of producing trichloro hydrosilicon by hydrogenation of silicon tetrachloride, wherein silica flour, SiCl
4And H
2Trichlorosilane is produced in reaction in the fluidized bed reactor of inner bag heating.Wherein catalyst is the Ni catalyst (being commonly referred to as nickel accelerant) of alumina load, due to Al
2O
3The carrier of base forms aluminium chloride and water and runs off in course of reaction, so this catalyst life is shorter.And due to AlCl
3Follow-up system is easily brought in distillation into, makes for polysilicon thisly to the exigent reaction of product purity, has increased the difficulty of product purifying.
CN101972657A discloses a kind of catalyst of preparing trichlorosilane from silicon tetrachloride through hydrogenation, this catalyst with nickel as active component, with silica as carrier, concrete preparation method is as follows: precipitate joining after nickel source dissolving in the silicon source, after completing, precipitation joins in alkali lye, with unnecessary nickel precipitation fully, will be deposited at 100-150 ℃ of temperature dry 5-10 hour, then at 400-500 ℃ of lower roasting 5-10 hour.The catalyst that the method prepares has effectively improved the activity of catalyst, but the catalyst that the method prepares still exists Active components distribution inhomogeneous, and catalyst is oxidation state, and in industrial use procedure, reduction moisture is brought SiCl into
4Hydrogenation system, thus cause device to stop up the defective of stopping.
This shows, existing preparing trichlorosilane from silicon tetrachloride through hydrogenation is used for the hydrogenation of silicon tetrachloride process with catalyst, there is following shortcoming: the less stable of catalyst, thereby cause active component easily run off and easily lump, and enter follow-up system as impurity after running off, affect the economy of integrated artistic.Therefore, the hydrogenation of silicon tetrachloride catalyst of exploitation high conversion, high stability is necessary.
Summary of the invention
For above technological deficiency, the invention provides a kind of new Catalysts and its preparation method that is applicable to fluid bed or fixed bed hydrogenation of silicon tetrachloride.
By background technology as can be known, the general prior art loading type nickel-based catalyst commonly used that adopts carries out hydrogenation of silicon tetrachloride at present, still there is no the special-purpose catalyst for hydrogenation of silicon tetrachloride, and the loading type nickel-based catalyst commonly used of prior art exists catalyst stability relatively poor for the hydrogenation of silicon tetrachloride process, thereby causes the easily problems such as loss and easy caking of active component.the present inventor infers it is to have than big difference due to hydrogenation of silicon tetrachloride and traditional hydrogenation reaction, thereby cause adopting the preparation method according to prior art (generally to adopt soluble-salt to load on carrier, dry, roasting obtains) hydrogenation catalyst for preparing is used for the hydrogenation of silicon tetrachloride process and easily has foregoing problems, based on this, the present inventor attempts to imagine the preparation method that whether can develop a kind of new hydrogenation catalyst and makes the catalyst for preparing can be more applicable for the hydrogenation of silicon tetrachloride reaction, thereby in the future can be as the special-purpose catalyst of hydrogenation of silicon tetrachloride reaction.Therefore, the present inventor's thinking of breaking the normal procedure is found, (being generally and adopting soluble-salt to load to loading process on carrier) in the loading process of traditional preparation hydrogenation catalyst adds precipitating reagent to carry out load, and introduce metal M as active component, can no longer exist the poor stability of aforementioned existence to cause the problem of activity decreased so that the catalyst for preparing according to method of the present invention is used for the reaction of preparing trichlorosilane from silicon tetrachloride through hydrogenation, based on this discovery, completed the present invention.
The invention provides a kind of preparation method of catalyst, wherein, the method comprises: with the soluble-salt compound of soluble nickel salt, metal M, silica can be provided the silicon source with can coprecipitated nickel hydroxide and/or the precipitating reagent of metal M ion contact in solvent, to contact products therefrom filters, and the gained solid is carried out drying and roasting successively, wherein, described M is selected from one or more in IB, IIB, IIA and the group VIII metal except Ni.
The invention provides the catalyst that a kind of preparation in accordance with the present invention prepares.
The invention provides the application of catalyst in preparing trichlorosilane from silicon tetrachloride through hydrogenation that a kind of preparation in accordance with the present invention prepares.
Compare with conventional aluminium-based catalyst according to the catalyst that preparation method of the present invention prepares, have the following advantages:
(1) catalyst that adopts preparation method of the present invention to prepare, the SiO in catalyst
2Carrier can be as the carrier in traditional hydrogenation catalyst the easy follow-up system of bringing into, especially for this reaction very high to purity requirement of polysilicon, purifying process that can the decrease subsequent product;
(2) catalyst that adopts preparation method of the present invention to prepare, SiO under the reaction atmosphere of preparing trichlorosilane from silicon tetrachloride through hydrogenation
2Carrier is stable, catalyst backbone can be as the carrier in traditional hydrogenation catalyst easy destruction, therefore have longer service life, thereby can effectively improve the ratio of reinforced middle silica flour and catalyst;
(3) catalyst activity of the present invention is compared in prior art nickel salt commonly used, copper salt catalyst is active improves.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of catalyst, wherein, the method comprises: with the soluble-salt compound of soluble nickel salt, metal M, silica can be provided the silicon source with can coprecipitated nickel hydroxide and/or the precipitating reagent of metal M ion contact in solvent, to contact products therefrom filters, and the gained solid is carried out drying and roasting successively, wherein, described M is selected from one or more in I B, II B, II A and the group VIII metal except Ni.
In the present invention, optional wider range of consumption of the soluble-salt compound of described soluble nickel salt, silicon source and metal M, specifically can decide according to the amount of each component in the catalyst of required acquisition, for the present invention, the consumption of the soluble-salt compound of preferred described soluble nickel salt, silicon source and metal M makes in the catalyst for preparing, take the gross weight of catalyst as benchmark, in oxide, the content of nickel is that the content of 30-65 % by weight, metal component M is that the content of 0.5-40 % by weight, silicon is the 30-60 % by weight.
In the present invention, optional wider range of the condition of described contact, in order to make the catalyst activity for preparing according to preparation method of the present invention further improve, for the present invention, the condition of preferred described contact comprises: the temperature of contact is 20-90 ℃, is preferably 50-80 ℃, and pH is 4-8, be preferably 5-7, be particularly preferably 7.
In the present invention, the time of described contact can decide according to concrete condition, and for the present invention, the time of preferred described contact is 0.1-10h, is preferably 0.5-5h.
In the present invention, optional wider range of the kind of described soluble nickel salt, soluble nickel salt that can be water-soluble all can be used for the present invention, for the present invention, preferred described nickel salt is one or more in nickel nitrate, nickel acetate, nickel chloride and nickelous sulfate, more preferably nickel nitrate.
In the present invention, described metal M is preferably one or more in cobalt, iron, copper, magnesium, platinum, ruthenium and palladium, is particularly preferably one or more in cobalt, iron, copper and magnesium, so can further improve the active and stable of catalyst of the present invention.For the present invention, more preferably the soluble-salt compound of described metal M is one or more in the sulfate of the chlorate of nitrate, metal M of metal M and metal M, is particularly preferably the nitrate of metal M.
In the present invention, the described silicon source that silica can be provided can be the material that can produce silica after silica or roasting, its optional wider range.In order further to improve the active and stable of the catalyst for preparing according to preparation method of the present invention, for the present invention, preferred described silicon source is liquid form, be for example colloidal sol, gel or solution form, one or more in Ludox, silicon gel, esters of silicon acis and waterglass more preferably.In the present invention, more preferably SiO in described Ludox and/or waterglass
2Concentration 10-40 % by weight.
In the present invention, optional wider range of the kind of described precipitating reagent, the reagent that can precipitate metal M ion and/or nickel ion all can be realized the object of the invention, preferred described precipitating reagent can precipitate described metal M ion and nickel ion, for the present invention, more preferably described precipitating reagent is one or more in soluble carbonate salt, solubility hydroxide and urea, is particularly preferably one or more in sodium carbonate, potash, ammonium carbonate, urea, ammoniacal liquor, NaOH and potassium hydroxide.
In the present invention, the selection of the kind of described solvent can be carried out with reference to prior art, is generally water, for the present invention, contain at least water in preferred described solvent or be all water, and suitably in situation, can add the solvent of other kind according to needs, for example can add organic solvent.
in the present invention, realization is with soluble nickel salt, the silicon source that silica can be provided with can coprecipitated nickel hydroxide and/or the mode that contacts in solvent of the precipitating reagent of metal M ion have multiple, for example can with soluble nickel salt with can coprecipitated nickel hydroxide and/or the precipitating reagent of metal M ion be mixed with the solution of certain concentration after being dissolved in respectively in described solvent, then separately with the solution form with realize described the contact after mix in described silicon source, wherein, the concentration 5-100g/L of the soluble nickel salting liquid that preferred preparation obtains, be preferably 10-50g/L, the concentration of precipitant solution is 0.5-5mol/L.
Preparation in accordance with the present invention, all can realize purpose of the present invention according to aforementioned techniques scheme of the present invention, described with soluble nickel salt, silica can be provided the silicon source with can coprecipitated nickel hydroxide and/or the mode that contacts in solvent of the precipitating reagent of metal M ion have multiple, for example soluble nickel salt can be carried out first with described precipitating reagent in solvent contacts, the first contact products therefrom is filtered, obtain solid material, then described solid material and described silicon source are carried out second and contact.
in order further to improve the active and stable of the catalyst for preparing according to preparation method of the present invention, the present inventor finds under study for action, described contact is conducive to further improve the active and stable of the catalyst for preparing as follows, be that the present invention is preferred: with soluble nickel salt, the soluble-salt compound of metal M, the silicon source that silica can be provided with can coprecipitated nickel hydroxide and/or the mode that contacts in solvent of the precipitating reagent of metal M ion be: will contain soluble nickel salt, the soluble-salt compound of metal M, can provide the silicon source of silica to contact with described precipitating reagent or precipitant solution with the slurries of solvent, and the described soluble nickel salt that contains, the soluble-salt compound of metal M, it is 3-8 that the pH of the slurries of the silicon source of silica and solvent can be provided, be preferably 5-7.
The pH value of described slurries can adopt the various pH adjusting agents of prior art to regulate, and for example can be one or more in hydrochloric acid, nitric acid, aqueous solution of nitric acid, NaOH, sodium hydrate aqueous solution, potassium hydroxide, potassium hydroxide aqueous solution and ammoniacal liquor.
In the present invention, as previously mentioned, the described soluble-salt compound that contains soluble nickel salt, metal, the slurries of silicon source and solvent that silica can be provided can obtain by the soluble-salt compound solution of soluble nickel salting liquid, metal is contacted with the silicon source that silica can be provided.
In the present invention, the method for described filtration, drying, roasting all can be carried out with reference to prior art, the present invention to this without specific (special) requirements, and the condition of dry and roasting all can be the condition of this area routine, for the present invention, preferred sintering temperature is 250-550 ℃, more preferably 300-500 ℃; Roasting time is 0.5-20h, is preferably 2-8h.Equally, in the present invention, preferred dry temperature is 100-120 ℃.
According to of the present invention preferred embodiment a kind of, the present invention adopts following method Kaolinite Preparation of Catalyst:
1) the soluble-salt compound with soluble nickel salt, metal M is mixed with respectively the aqueous solution, the soluble-salt compound water solution of soluble nickel saline solution and metal M is mixed to get mixed solution, can provide the silicon source of silica to join in described mixed solution and obtain slurries, regulate the pH value of slurries;
2) then add precipitant solution to contact, filtration afterwards, dry, roasting.
In the present invention, comparatively abundant in order to make contact, described contact is all carried out under stirring condition, and the mixing of various materials is all carried out under stirring condition with contacting also in an embodiment of the present invention, no longer specifically emphasizes afterwards.
The invention provides the catalyst for preparing according to preparation method of the present invention.
Generally speaking, the average grain diameter of the catalyst for preparing according to preparation method of the present invention is 150-300 μ m, and specific area is 40-400m
2/ g, pore volume are 0.1-0.7mL/g.
The invention provides the application of catalyst in preparing trichlorosilane from silicon tetrachloride through hydrogenation for preparing according to preparation method of the present invention.
The catalyst for preparing according to preparation method of the present invention shows the advantages such as high stability, high activity and high selectivity in the reaction of preparing trichlorosilane from silicon tetrachloride through hydrogenation.
The present invention is described in detail below by embodiment, but not thereby limiting the invention.
In this specification, conversion ratio (%) refers to the SiHCl of actual generation
3The SiHCl that generates of molal quantity/theory
3Molal quantity, wherein, the described theoretical SiHCl that generates
3Molal quantity refer to all transform according to the minimum raw material of stoichiometry addition the SiHCl that generate
3Molal quantity.
In actual production, in order to make SiCl
4All be converted into SiHCl
3, be used for the hydrogen of reaction and silica flour with respect to SiCl
4Greatly excessive, therefore, this area is usually with SiCl
4Be converted into SiHCl
3The conversion ratio of meter represents, i.e. the SiHCl of conversion ratio (%)=generation
3Molal quantity/SiCl
4The total mole number of raw material, the conversion ratio in this specification namely use the method to calculate.
In the present invention, gas hourly space velocity refers to the volume space velocity of hydrogen and the relative catalyst of silicon tetrachloride gaseous mixture.
In embodiment, in catalyst, each constituent content adopts x-ray fluorescence spectrometry.
Embodiment 1
(1) the six water nickel nitrates of 56.5 kilograms and the nine water ferric nitrates of 25 kilograms are dissolved in deionized water, be mixed with 500 liters of solution, adding concentration in the above-mentioned mixing salt solution is 320 kilograms of the sodium silicate aqueous solutions of 10 % by weight, mix and obtain slurries, the pH value that is the sodium hydrate aqueous solution adjusting slurries of 5 % by weight with concentration is 6; Go deionized water dissolving to obtain aqueous sodium carbonate with 400 liters 43 kilograms of natrium carbonicum calcinatums;
(2) above-mentioned aqueous sodium carbonate and slurries are joined in the reactor of 2000 liters and contact, regulating pH with the concentration sodium hydrate aqueous solution that is 5 % by weight, to make the pH value of contact be 7, the temperature of contact is 80 ℃, after contact 4h, filtration obtains solid, with after the gained solid drying in muffle furnace in 500 ℃ of lower roastings 6 hours, obtain catalyst A.
Comparative Examples 1
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is, does not add ferric nitrate in preparation process, and concrete preparation method is as follows:
(1) the six water nickel nitrates of 62.5 kilograms are dissolved in deionized water, be mixed with 500 liters of solution, adding concentration in the mentioned solution is 320 kilograms of the sodium silicate aqueous solutions of 10 % by weight, mix and obtain slurries, the pH value that is the sodium hydrate aqueous solution adjusting slurries of 5 % by weight with concentration is 5; 40 kilograms of natrium carbonicum calcinatums are obtained aqueous sodium carbonate with 400 liters of deionized water dissolvings;
(2) above-mentioned aqueous sodium carbonate and slurries are joined in the reactor of 2000 liters and contact, regulating pH with the concentration sodium hydrate aqueous solution that is 5 % by weight, to make the pH value of contact be 7, the temperature of contact is 80 ℃, after contact 4h, filtration obtains solid, with after the gained solid drying in muffle furnace in 500 ℃ of lower roastings 6 hours, obtain catalyst D1.
Comparative Examples 2
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different is, in preparation process, ferric nitrate is replaced by the rare earth compound lanthanum nitrate, and concrete preparation method is as follows:
(1) the six water nickel nitrates of 56.5 kilograms and the lanthanum nitrate hexahydrate of 12.5 kilograms are dissolved in deionized water, be mixed with 500 liters of solution, adding concentration in the above-mentioned mixed solution is 320 kilograms of the sodium silicate aqueous solutions of 10 % by weight, mix and obtain slurries, the pH value that is the sodium hydrate aqueous solution adjusting slurries of 5 % by weight with concentration is 5; Go deionized water dissolving to obtain aqueous sodium carbonate with 400 liters 43 kilograms of natrium carbonicum calcinatums;
(2) above-mentioned aqueous sodium carbonate and slurries are joined in the reactor of 2000 liters and contact, regulating pH with the concentration sodium hydrate aqueous solution that is 5 % by weight, to make the pH value of contact be 7, the temperature of contact is 80 ℃, after contact 4h, filtration obtains solid, with after the gained solid drying in muffle furnace in 500 ℃ of lower roastings 6 hours, obtain catalyst D2.
Embodiment 2
(1) with the nitrate trihydrate copper dissolution of the six water nickel chlorides of 42.5 kilograms and 18 kilograms in deionized water, be mixed with 500 liters of solution, adding solid content in the above-mentioned mixing salt solution is 80 kilograms of the Ludox of 20 % by weight, mix and obtain slurries, the pH value that is the sodium hydrate aqueous solution adjusting slurries of 5 % by weight with concentration is 5; 40 kilograms of ammonium carbonates are obtained ammonium carbonate solution with 400 liters of deionized water dissolvings;
(2) above-mentioned slurries and ammonium carbonate solution are joined in the reactor of 2000 liters and contact, regulating pH with the concentration sodium hydrate aqueous solution that is 5 % by weight, to make the pH value of contact be 7, the temperature of contact is 80 ℃, after contact 4h, filtration obtains solid, with after the gained solid drying in muffle furnace in 500 ℃ of lower roastings 6 hours, obtain catalyst B.
Embodiment 3
(1) the six water nickel nitrates of 44 kilograms and the cobalt nitrate hexahydrate of 18 kilograms are dissolved in deionized water, be mixed with 500 liters of solution, add 65 kilograms of tetraethyl orthosilicates in above-mentioned mixing salt solution, mix and obtain slurries, the pH value that is the sodium hydrate aqueous solution adjusting slurries of 5 % by weight with concentration is 5; 48 kilograms of natrium carbonicum calcinatums are obtained aqueous sodium carbonate with 400 liters of deionized water dissolvings;
(2) above-mentioned slurries and aqueous sodium carbonate are joined in the reactor of 2000 liters and contact, regulating pH with the concentration sodium hydrate aqueous solution that is 5 % by weight, to make the pH value of contact be 7, the temperature of contact is 80 ℃, after contact 4h, filtration obtains solid, with after the gained solid drying in muffle furnace in 500 ℃ of lower roastings 6 hours, obtain catalyst C.
Embodiment 4
(1) the six water nickel nitrates of 56.5 kilograms and the magnesium nitrate hexahydrate of 10 kilograms are dissolved in deionized water, be mixed with 500 liters of solution, adding concentration in the above-mentioned mixing salt solution is 320 kilograms of the waterglass of 10 % by weight, mix and obtain slurries, the pH value that is the sodium hydrate aqueous solution adjusting slurries of 5 % by weight with concentration is 7; 50 kilograms of natrium carbonicum calcinatums are obtained aqueous sodium carbonate with 500 liters of deionized water dissolvings;
(2) above-mentioned slurries and aqueous sodium carbonate are joined in the reactor of 2000 liters and contact, regulating pH with the concentration sodium hydrate aqueous solution that is 5 % by weight, to make the pH value of contact be 7, the temperature of contact is 80 ℃, after contact 4h, filtration obtains solid, with after the gained solid drying in muffle furnace in 500 ℃ of lower roastings 6 hours, obtain catalyst D.
Embodiment 5
According to the method Kaolinite Preparation of Catalyst of embodiment 4, different is, in step (1), the pH value of regulating slurries with the concentration aqueous solution of nitric acid that is 5 % by weight is 2, and all the other conditions are all identical, obtain catalyst E.
Embodiment 6
According to the method Kaolinite Preparation of Catalyst of embodiment 4, the waterglass that different is in step (1) is replaced by the silica gel of 16 kilograms, obtains catalyst F.
Embodiment 7
According to the method Kaolinite Preparation of Catalyst of embodiment 4, the magnesium nitrate hexahydrate that different is in step (1) is replaced by four water-calcium nitrate, obtains catalyst G.
Comparative Examples 3
According to the method Kaolinite Preparation of Catalyst of embodiment 4, the waterglass that different is in step (1) is replaced by aluminum sulfate, obtains catalyst D3.
EXPERIMENTAL EXAMPLE
EXPERIMENTAL EXAMPLE is used for explanation and adopts catalyst provided by the invention, adopts SiCl in fixed bed reactors
4Produce SiHCl
3Situation.
The catalyst that embodiment 1-7 is prepared obtains micro-spherical catalyst with granulator granulation, and the microsphere particle size is 200 μ m.
In fixed bed reactors, under micro-spherical catalyst exists, make silicon tetrachloride gas, hydrogen gas stream contacts with silica flour, wherein, and Catalyst packing 0.3g, the temperature of contact is 450 ℃ or 400 ℃, the pressure of contact is 1.2MPa, H
2/ SiCl
4(mol ratio)=20, silica flour/SiCl
4(mol ratio)=10, gas hourly space velocity are 24000h
-1, the results are shown in Table 1.
The experiment Comparative Examples
Method according to EXPERIMENTAL EXAMPLE is produced SiHCl
3, different is that catalyst is respectively 50CuO/50SiO
2 (The commercial goods of Luoyang brilliant brightness new forms of energy Science and Technology Ltd., its implication is that the weight ratio of cupric oxide and silica is 50: 50, all the other identical expressions are also anticipated for this reason), Al
2O
3Supported Nickel Catalyst (50.3NiO/49.7Al for carrier
2O
3, the female catalyst plant of producer Nanjing sky, trade mark NCL0505), the catalyst D1-D3 for preparing of Comparative Examples 1-3, the results are shown in Table 1.
Table 1
Can be found out by data in table, the catalyst for preparing according to preparation method of the present invention is used for having higher activity when preparing trichlorosilane from silicon tetrachloride through hydrogenation reacts, and after reaction is long-time, activity has no decline, this shows, also better according to the catalyst stability that preparation method of the present invention prepares.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove that in addition each the concrete technical characterictic described in the above-mentioned specific embodiment in reconcilable situation, can make up by any suitable mode.
In addition, also can carry out any combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. a preparing trichlorosilane from silicon tetrachloride through hydrogenation is with the preparation method of catalyst, wherein, the method comprises: with the soluble-salt compound of soluble nickel salt, metal M, silica can be provided the silicon source with can coprecipitated nickel hydroxide and/or the precipitating reagent of metal M ion contact in solvent, to contact products therefrom filters, and the gained solid is carried out drying and roasting successively, wherein, described metal M is one or more in cobalt, iron, copper, magnesium, platinum, ruthenium and palladium, the condition of described contact comprises: the temperature of contact is 20-90 ℃, and pH is 4-8.
2. preparation method according to claim 1, wherein, the consumption of the soluble-salt compound of described soluble nickel salt, silicon source and metal M makes in the catalyst for preparing, take the gross weight of catalyst as benchmark, in oxide, the content of nickel is that the content of 30-65 % by weight, metal component M is that the content of 0.5-40 % by weight, silicon is the 30-60 % by weight.
3. preparation method according to claim 1, wherein, with the soluble-salt compound of soluble nickel salt, metal M, silica can be provided the silicon source with can coprecipitated nickel hydroxide and/or the mode that contacts in solvent of the precipitating reagent of metal M ion be: will contain soluble nickel salt, metal M the soluble-salt compound, can provide the silicon source of silica to contact with described precipitating reagent or precipitant solution with the slurries of solvent, and the described pH that contains the slurries of the soluble-salt compound of soluble nickel salt, metal M, the silicon source that silica can be provided and solvent is 3-8.
4. preparation method according to claim 3, wherein, the described pH that contains the slurries of the soluble-salt compound of soluble nickel salt, metal M, the silicon source that silica can be provided and solvent is 5-7.
5. preparation method according to claim 1, wherein, the temperature of contact is 50-80 ℃, pH is 5-7.
6. the described preparation method of any one according to claim 1-4, wherein, the soluble-salt compound of described metal M is one or more in the sulfate of the chlorate of the nitrate of metal M, metal M and metal M.
7. preparation method according to claim 6, wherein, the soluble-salt compound of described metal M is the nitrate of metal M.
8. the described preparation method of any one according to claim 1-4, wherein, described soluble nickel salt is one or more in nickel nitrate, nickel acetate, nickel chloride and nickelous sulfate.
9. preparation method according to claim 8, wherein, described soluble nickel salt is nickel nitrate.
10. the described preparation method of any one according to claim 1-4, wherein, described silicon source is one or more in Ludox, silicon gel, esters of silicon acis and waterglass; Described precipitating reagent is one or more in soluble carbonate salt, solubility hydroxide and urea; Contain water in described solvent.
11. preparation method according to claim 10, wherein, described precipitating reagent is one or more in sodium carbonate, potash, ammonium carbonate, urea, ammoniacal liquor, NaOH and potassium hydroxide.
12. the catalyst that in claim 1-11, the described preparation method of any one prepares.
13. the application of the described catalyst of claim 12 in preparing trichlorosilane from silicon tetrachloride through hydrogenation.
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| 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 |
| CN103861596B (en) * | 2012-12-10 | 2016-12-21 | 正大能源材料(大连)有限公司 | A kind of preparation method of nickel-base hydrogenation catalyst |
| CN109835910B (en) * | 2017-11-28 | 2020-11-06 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
| 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 |
| CN108405881A (en) * | 2018-02-02 | 2018-08-17 | 贵研铂业股份有限公司 | A kind of preparation method of high pure spherical ruthenium powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102350351A (en) * | 2011-08-31 | 2012-02-15 | 郭屹宾 | Hydrogenation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102350351A (en) * | 2011-08-31 | 2012-02-15 | 郭屹宾 | Hydrogenation catalyst and preparation method thereof |
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