CN102658147A - Catalyst, preparation method thereof and application thereof - Google Patents
Catalyst, preparation method thereof and application thereof Download PDFInfo
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- CN102658147A CN102658147A CN2012101048969A CN201210104896A CN102658147A CN 102658147 A CN102658147 A CN 102658147A CN 2012101048969 A CN2012101048969 A CN 2012101048969A CN 201210104896 A CN201210104896 A CN 201210104896A CN 102658147 A CN102658147 A CN 102658147A
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Abstract
A catalyst and a preparation thereof are disclosed. The preparation method comprises the following steps: allowing a soluble nickel salt to contact with a silicon source which can provide silica and a precipitating agent which precipitates nickel irons in a solvent; and filtering products obtained after contact, drying the resulting solid, roasting, carrying out temperature programming reduction, and passivating. An application of the catalyst of the invention in the preparation of trichlorosilane from silicon tetrachloride through hydrogenation is also disclosed. According to the catalyst prepared through the preparation method of the invention, an SiO2 carrier in an atmosphere of a reaction that trichlorosilane is prepared from silicon tetrachloride through hydrogenation is stable, and the skeleton of the catalyst, which does not like that of traditional hydrogenation catalysts easy to destroy, is difficult to destroy, so the service life of the catalyst is long; and the catalyst of the invention has a higher activity than nickel salt and copper salt catalysts used in the prior art.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method and a kind of catalyst for preparing by this method, and prepare the application in the trichlorosilane at hydrogenation of silicon tetrachloride.
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 of 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 the production of polysilicon technology, produce the hydrogen chloride that 1 ton of polysilicon can produce silicon tetrachloride and about 1-5 ton more than 10 tons.Because the SiCl that also not have extensive, high efficiency and produced in the digestion process production polysilicon process safely
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, sends trichlorosilane back to the polysilicon system again as raw material and produces polysilicon, produces thereby form " closed loop ".
At present, mainly through two kinds of methods silicon tetrachloride being carried out hydrogenation in the industry transforms.A kind of technology path is SiCl
4Hot hydrogenation is about to SiCl
4And H
2Under 1200-1500 ℃ high temperature and 0.6MPa pressure, be converted into SiHCl
3, its chemical equation is: SiCl
4+ H
2→ SiHCl
3+ HCl.This method reaction temperature is high, and energy consumption is big, and one time conversion ratio is low, is up to 18%.Another kind of technology path is SiCl
4Cold hydrogenation promptly 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 (Al.
For example, CN1436725A discloses the cold method for hydrogenation that a kind of hydrogenation of silicon tetrachloride is produced trichlorosilane, wherein silica flour, SiCl
4And H
2Reacted trichlorosilane 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, because 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 because AlCl
3Follow-up system is brought in distillation easily into, and is feasible this to the exigent reaction of product purity for polysilicon, increased the difficulty of product purifying.
CN101972657A discloses the catalyst that a kind of hydrogenation of silicon tetrachloride prepares trichlorosilane; As active component, as carrier, concrete preparation method is following with silica with nickel for this catalyst: precipitate joining in the silicon source after the dissolving of nickel source; Treat to join in the alkali lye after deposition is accomplished; With unnecessary nickel deposition fully, will be deposited under the 100-150 ℃ of temperature dry 5-10 hour, then at 400-500 ℃ of following roasting 5-10 hour.The catalyst that this method prepares has effectively improved activity of such catalysts, but still there is the active component skewness in the catalyst that this method prepares, and catalyst is oxidation state, in the industry in the use reduction moisture bring SiCl into
4Hydrogenation system, thus cause device to stop up the defective of stopping.
This shows; Existing hydrogenation of silicon tetrachloride prepares trichlorosilane and is used for the hydrogenation of silicon tetrachloride process with catalyst; There is following shortcoming: the less stable of catalyst; Thereby cause active component to be prone to loss and to be prone to lump, and the back of running off influence the economy of integrated artistic as impurity entering follow-up system.Therefore, the hydrogenation of silicon tetrachloride catalyst of exploitation high conversion, high stability is necessary.
Summary of the invention
To above technological deficiency, the present invention provides a kind of new Catalysts and its preparation method that is applicable to fluid bed or fixed bed hydrogenation of silicon tetrachloride.
Can know by background technology; The loading type nickel-based catalyst of general at present employing prior art carries out hydrogenation of silicon tetrachloride; Research to the special-purpose catalyst of hydrogenation of silicon tetrachloride is less; And the loading type nickel-based catalyst commonly used of prior art is used for the hydrogenation of silicon tetrachloride process and has still that catalyst stability is relatively poor, active component is prone to run off and be prone to problem such as caking; Inventor of the present invention infers it is because hydrogenation of silicon tetrachloride and traditional hydrogenation reaction have than big difference; Thereby the hydrogenation catalyst that causes adopting the preparation method's (generally adopt soluble-salt to load on the carrier, dry, roasting obtains) according to prior art to prepare is used for the hydrogenation of silicon tetrachloride process and has foregoing problems easily, based on this; Inventor of the present invention attempts to imagine and whether can develop a kind of new hydrogenization catalyst preparation method and make the catalyst for preparing can be applicable to the hydrogenation of silicon tetrachloride reaction more, thereby in the future can be as the special-purpose catalyst of hydrogenation of silicon tetrachloride reaction.Inventor of the present invention finds through overtesting; In traditional preparation hydrogenation catalyst process, (be generally and adopt soluble-salt to load to the loading process on the carrier); Add precipitating reagent and carry out the dry afterwards and roasting of load; Further with the solid that obtains after the roasting reduce, passivation can no longer exist the poor stability of aforementioned existence to cause the active problem that reduces so that the catalyst for preparing is used for the reaction of hydrogenation of silicon tetrachloride, based on this discovery, accomplish the present invention.
The invention provides a kind of Preparation of catalysts method, wherein, this method comprises: soluble nickel salt and the silicon source that silica can be provided and precipitating reagent that can the coprecipitated nickel hydroxide ion are contacted in solvent; To contact products therefrom and filter, and the gained solid will be carried out drying, roasting, temperature programmed reduction and passivation successively.
The invention provides the catalyst that a kind of preparation in accordance with the present invention prepares.
The invention provides the catalyst that a kind of preparation in accordance with the present invention prepares and prepare the application in the trichlorosilane at hydrogenation of silicon tetrachloride.
Catalyst according to preparation method of the present invention prepares is compared with prior art catalyst commonly used, has the following advantages:
(1) catalyst that adopts preparation method of the present invention to prepare, the SiO in the 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 of polysilicon, can reduce the purifying process of subsequent product significantly to purity requirement;
(2) catalyst that adopts preparation method of the present invention to prepare prepares SiO under the reaction atmosphere of trichlorosilane at hydrogenation of silicon tetrachloride
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 than active raising of nickel salt, copper salt catalyst of prior art use.
Other features and advantages of the present invention will partly specify in the specific embodiment subsequently.
Description of drawings
Accompanying drawing is to be used to provide further understanding of the present invention, and constitutes the part of specification, is used to explain the present invention with the following specific embodiment, but is not construed as limiting the invention.In the accompanying drawings:
The TPR of the catalyst A that Fig. 1 prepares for the embodiment of the invention 1 is virgin curve also;
Fig. 2 is the TPR virgin curve also of commercially available NCL0505 catalyst.
The specific embodiment
Following specific embodiments of the invention is elaborated.Should be understood that the specific embodiment described herein only is used for explanation and explains the present invention, is not limited to the present invention.
The invention provides a kind of Preparation of catalysts method, wherein, this method comprises: soluble nickel salt and the silicon source that silica can be provided and precipitating reagent that can the coprecipitated nickel hydroxide ion are contacted in solvent; To contact products therefrom and filter, and the gained solid will be carried out drying, roasting, temperature programmed reduction and passivation successively.
Among the present invention; The optional wider range of the consumption in said soluble nickel salt and silicon source specifically can be decided according to the amount of each component in the catalyst of required acquisition, to the present invention; The consumption in preferred said soluble nickel salt and silicon source makes in the catalyst for preparing; Gross weight with catalyst is a benchmark, and in oxide, the content of nickel is that the content of 30-75 weight %, silicon is 25-70 weight %.
Among the present invention; Optional wider range of the condition of said contact is in order to make the catalyst activity for preparing according to preparation method of the present invention further improve, to the present invention; The condition of preferred said contact comprises: the temperature of contact is 20-90 ℃, more preferably 50-80 ℃; PH is 4-8, and more preferably 5-7 is preferably 7 especially.
Among the present invention, the time of said contact can decide according to concrete condition, and to the present invention, the time of preferred said contact is 0.1-10h, more preferably 0.5-5h.
Among the present invention; Optional wider range of the kind of said soluble nickel salt, soluble nickel salt that can be water-soluble all can be used for the present invention, to the present invention; Preferred said nickel salt is one or more in nickel nitrate, nickel acetate, nickel chloride and the nickelous sulfate, more preferably nickel nitrate.
Among the present invention, said the silicon source of silica can be provided can be the material that can produce silica after silica or the roasting, its optional wider range.In order further to improve activity of such catalysts and the stability for preparing according to preparation method of the present invention; To the present invention; Preferred said silicon source is a liquid form; For example be colloidal sol, gel or solution form, one or more in Ludox, silicon gel, esters of silicon acis and the waterglass more preferably.Among the present invention, SiO in more preferably said Ludox and/or the waterglass
2Concentration 10-40 weight %.
Among the present invention; Optional wider range of the kind of said precipitating reagent; Reagent that can the coprecipitated nickel hydroxide ion all can be realized the object of the invention; To the present invention, preferred said precipitating reagent is one or more in soluble carbon hydrochlorate, solubility hydroxide and the urea, more preferably one or more in sodium carbonate, potash, ammonium carbonate, urea, ammoniacal liquor, NaOH and the potassium hydroxide.
Among the present invention, the selection of said solvent types can be carried out with reference to prior art, is generally water; To the present invention, containing water in the preferred said solvent at least all is water perhaps, and under the suitable situation; The solvent of other kind can be added according to needs, for example organic solvent can be added.
Among the present invention, optional wider range of the condition of said temperature programmed reduction, in order further to improve activity of such catalysts of the present invention and stability, preferred said temperature programmed reduction carries out as follows:
In the presence of hydrogen, under reducing condition, at first the heating rate with 20-60 ℃/h is warming up to 100-120 ℃ from room temperature (being generally 10-40 ℃), under this temperature, keeps 1-4h then with the solid after the roasting;
Then the heating rate with 20-60 ℃/h is warming up to 280-300 ℃, under this temperature, keeps 1-4h then;
Then the heating rate with 20-60 ℃/h is warming up to 430-450 ℃, under this temperature, keeps 1-4h then;
Then the heating rate with 20-60 ℃/h is warming up to 480-500 ℃, under this temperature, keeps 1-10h then.
Among the present invention; Optional wider range of said reducing condition specifically can be selected according to prior art, in order further to improve activity of such catalysts of the present invention and stability; Preferred said reducing condition comprises: Hydrogen Vapor Pressure be normal pressure to 0.5MPa, hydrogen gas space velocity is 100-2000h
-1Among the present invention, hydrogen gas space velocity refers to the volume space velocity of hydrogen.The present invention does not have specific (special) requirements to the concentration of hydrogen in the reduction process, is generally more than the 90 volume %, is preferably 99.99 volume %, and to this, those skilled in the art all can know, the density of hydrogen that is 99.99 volume % that the present invention uses in concrete embodiment.
Among the present invention, the method for said passivation can be carried out with reference to prior art, and to the present invention, preferred said passivation is carried out as follows:
Solid after the reduction in the presence of inert gas, is cooled to below 100 ℃, is preferably 60-80 ℃; Be in the presence of the mist of inert gas and oxygen-containing gas of 1-10 volume % in oxygen-containing gas concentration then, be cooled to below 60 ℃, be preferably 30-50 ℃.
Among the present invention, said inert gas can be the various inert gases that this area is commonly used, for example can be in nitrogen, helium and the argon gas one or more.And inventor of the present invention finds in research process unexpectedly; Prepare catalyst according to method of the present invention,, can improve activity of such catalysts and stability greatly when the gas that uses in the said passivating process during as argon gas; Therefore, preferred said inert gas of the present invention is an argon gas.
Among the present invention; Realization has the mode that soluble nickel salt and the silicon source that silica can be provided and precipitating reagent that can the coprecipitated nickel hydroxide ion contact in solvent multiple; Be mixed with the solution of certain concentration after for example can being dissolved in soluble nickel salt and said precipitating reagent in the said solvent respectively; Mix the back with solution form and said silicon source separately then and realize said the contact, wherein, the concentration of the soluble nickel salting liquid that preferred preparation obtains is 5-100g/L; Be preferably 10-50g/L, the concentration of precipitant solution is 0.5-5mol/L.And for example can soluble nickel salt and said precipitating reagent be carried out first in solvent and contact, the first contact products therefrom is filtered, obtain solid material, then said solid material carried out second with said silicon source and contact.
In order further to improve activity of such catalysts and the stability for preparing according to preparation method of the present invention; Inventor of the present invention finds under study for action; Said contact helps further improving activity of such catalysts and the stability for preparing as follows; Be that the present invention is preferred: the mode that soluble nickel salt and the silicon source that silica can be provided and precipitating reagent that can the coprecipitated nickel hydroxide ion are contacted in solvent is: the silicon source that will contain soluble nickel salt, silica can be provided and the slurries of solvent and precipitating reagent that can the coprecipitated nickel hydroxide ion or precipitant solution that can the coprecipitated nickel hydroxide ion contact; And saidly containing soluble nickel salt, the pH of slurries of silicon source and the solvent of silica can be provided is 3-8, is preferably 5-7.
The pH value of said slurries can adopt the various pH conditioning agents of prior art to regulate, and for example can be in hydrochloric acid, nitric acid, aqueous solution of nitric acid, NaOH, sodium hydrate aqueous solution, potassium hydroxide, potassium hydroxide aqueous solution and the ammoniacal liquor one or more.
Among the present invention, as previously mentioned, saidly contain soluble nickel salt, can provide the silicon source of silica can obtain through the soluble nickel salting liquid is contacted with the silicon source that silica can be provided with the slurries of solvent.
Among the present invention, the method for said filtration, drying, roasting all can be carried out with reference to prior art, and the present invention does not have specific (special) requirements to this; And the condition of dry and roasting all can be the conventional condition in this area; To the present invention, preferred sintering temperature is 250-550 ℃, more preferably 300-500 ℃; Roasting time is 0.5-20h, is preferably 2-8h.Equally, preferred dry temperature is 100-120 ℃ among the present invention.
According to of the present invention preferred embodiment a kind of, the present invention adopts following method to prepare catalyst:
1) soluble nickel salt is mixed with the aqueous solution, obtains slurries in the aqueous solution that can provide the silicon source of silica to join said soluble nickel salt, regulate the pH value of slurries;
2) add then can the coprecipitated nickel hydroxide ion precipitant solution contact, filter afterwards, will filter then that the gained solid carries out drying, roasting obtains the solid after the roasting;
3) solid after the roasting is carried out temperature programmed reduction and passivation obtains catalyst.
Among the present invention, in order to make contact comparatively abundant, said 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, and is no longer specifically emphasical afterwards.
The invention provides the catalyst for preparing according to preparation method of the present invention.
The reduction temperature of the catalyst for preparing according to preparation method of the present invention is below 200 ℃; And conventional catalyst must could reduce more than 600 ℃ fully; This shows that catalyst reduction temperature of the present invention is low, this has guaranteed that further catalyst of the present invention has the following advantages: (1) catalyst activity is higher; (2) catalyst stability is better; And because catalyst can reduce at a lower temperature fully, under the silicon tetrachloride hydroconversion condition, can not generate water and bring subsequent separation system into, thereby cause device to stop up the defective of stopping, otherwise the water that gets into follow-up system can generate HCl and SiO with the silicon tetrachloride reaction
2, not only etching apparatus, and meeting blocking pipe causes device to stop.
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 catalyst for preparing according to preparation method of the present invention and prepare the application in the trichlorosilane at hydrogenation of silicon tetrachloride.
The catalyst for preparing according to preparation method of the present invention shows advantages such as high stability, high activity and high selectivity in hydrogenation of silicon tetrachloride prepares the reaction of trichlorosilane.
Through embodiment the present invention is elaborated below, but does not therefore limit the present 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 said theoretical SiHCl that generates
3Molal quantity be meant according to the reaction metering raw material minimum and all transform the SiHCl that generated than addition
3Molal quantity.
In actual production, in order to make SiCl
4All be converted into SiHCl
3, hydrogen that is used to react and silica flour are with respect to SiCl
4Excessive greatly, therefore, this area is usually with SiCl
4Be converted into SiHCl
3The conversion ratio of meter is represented, i.e. the SiHCl of conversion ratio (%)=generation
3Molal quantity/SiCl
4The total mole number of raw material, the conversion ratio in this specification promptly use the method to calculate.
Among the present invention, the TPR test method is: adopt U.S. Mai Ke company 2920 type temperature programming testers to measure catalyst reduction curve, (10%H
2+ 90%Ar) gaseous mixture is as the TPR medium, and initial temperature is 313K, and heating rate is 10K/min, adopts TCD detector recording TPR indicatrix.
Gas hourly space velocity refers to the volume space velocity of hydrogen and the relative catalyst of silicon tetrachloride gaseous mixture among the present invention.
Among the embodiment, each constituent content adopts x-ray fluorescence spectrometry in the catalyst.
Embodiment 1
(1) 62.5 kilograms six water nickel nitrates is dissolved in the deionized water; Be mixed with 500 liters of solution; In above-mentioned solution, add concentration and be 320 kilograms of the sodium silicate aqueous solutions of 10 weight %, mix and obtain slurries, using concentration is that the pH value that the sodium hydrate aqueous solution of 10 weight % is regulated slurries is 6; 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 2000 liters the reactor and contact; The temperature of contact is 80 ℃; Regulate pH with the sodium hydrate aqueous solution of 10 weight % and make that the pH value of contact is 7; Behind the contact 4h, filter and to obtain solid, with after the gained solid drying in muffle furnace the solid after 500 ℃ of following roastings obtained roasting in 6 hours;
(3) solid after the roasting is carried out temperature programmed reduction; Wherein, the temperature programmed reduction condition is seen table 1, and the solid after will reducing then is at first under argon gas atmosphere; Under normal pressure, be cooled to 60 ℃; Continuing in oxygen concentration then is under the atmosphere of gaseous mixture of argon gas and oxygen of 5 volume %, under normal pressure, is cooled to 40 ℃ and obtains catalyst A, and its TPR also virgin curve sees Fig. 1.
The TPR of comparison diagram 1 and Fig. 2 also virgin curve can find out; Catalyst of the present invention has lower reduction temperature; Can reduce fully being lower than 200 ℃; And conventional catalyst must could reduce more than 600 ℃ fully, and this has guaranteed that further catalyst of the present invention has the following advantages: (1) catalyst activity is higher; (2) catalyst stability is better; And because catalyst can reduce at a lower temperature fully, under the silicon tetrachloride hydroconversion condition, can not generate water and bring subsequent separation system into, thereby cause device to stop up the defective of stopping, otherwise the water that gets into follow-up system can generate HCl and SiO with the silicon tetrachloride reaction
2, not only etching apparatus, and meeting blocking pipe causes device to stop.
Embodiment 2
(1) 52.0 kilograms six water nickel chlorides is dissolved in the deionized water; Be mixed with 500 liters of solution; In above-mentioned solution, add concentration and be 320 kilograms of the waterglass of 10 weight %, mix and obtain slurries, using concentration is that the pH value that the sodium hydrate aqueous solution of 10 weight % is regulated slurries is 5; 30 kilograms of natrium carbonicum calcinatums are obtained aqueous sodium carbonate with 300 liters of deionized water dissolvings;
(2) above-mentioned aqueous sodium carbonate and slurries are joined in 2000 liters the reactor and contact; The temperature of contact is 80 ℃; With concentration is that the sodium hydrate aqueous solution of 10 weight % is regulated pH and made that the pH value of contact is 7; Behind the contact 4h, filter and to obtain solid, with after the gained solid drying in muffle furnace the solid after 500 ℃ of following roastings obtained roasting in 6 hours;
(3) solid after the roasting is carried out temperature programmed reduction, wherein, the temperature programmed reduction condition is seen table 1; Solid after will reducing then is at first under argon gas atmosphere; Under normal pressure, be cooled to 60 ℃, continuing in oxygen concentration then is under the atmosphere of gaseous mixture of argon gas and oxygen of 5 volume %, under normal pressure, is cooled to 40 ℃ and obtains catalyst B; Its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 3
(1) 62.5 kilograms six water nickel nitrates is dissolved in the deionized water; Be mixed with 500 liters of solution; In above-mentioned solution, add solid content and be 80 kilograms of the alkaline silica sols of 20 weight %, mix and obtain slurries, using concentration is that the pH value that the ammoniacal liquor of 10 weight % is regulated slurries is 5; 25 kg urea are obtained aqueous solution of urea with 250 liters of deionized water dissolvings;
(2) above-mentioned slurries and aqueous solution of urea are joined in 2000 liters the reactor and contact; The temperature of contact is 80 ℃; With concentration is that the ammoniacal liquor of 10 weight % is regulated pH and made that the pH value of contact is 7; Behind the contact 4h, filter and to obtain solid, with after the gained solid drying in muffle furnace the solid after 500 ℃ of following roastings obtained roasting in 6 hours;
(3) solid after the roasting is carried out temperature programmed reduction, wherein, the temperature programmed reduction condition is seen table 1; Solid after will reducing then is at first under argon gas atmosphere; Under normal pressure, be cooled to 60 ℃, continuing in oxygen concentration then is under the atmosphere of gaseous mixture of argon gas and oxygen of 5 volume %, under normal pressure, is cooled to 40 ℃ and obtains catalyst C; Its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 4
(1) 56.5 kilograms nickel sulfate hexahydrate is dissolved in the deionized water; Be mixed with 500 liters of solution; In above-mentioned solution, add 65 kilograms of positive tetraethyl orthosilicates, mix and obtain slurries, use concentration is that the pH value of the sodium hydrate aqueous solution adjusting slurries of 10 weight % 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 2000 liters the reactor and contact; The temperature of contact is 80 ℃; With concentration is that the ammoniacal liquor of 10 weight % is regulated pH and made that the pH value of contact is 7; Behind the contact 4h, filter and to obtain solid, with after the gained solid drying in muffle furnace the solid after 500 ℃ of following roastings obtained roasting in 6 hours;
(3) solid after the roasting is carried out temperature programmed reduction, wherein, the temperature programmed reduction condition is seen table 1; Solid after will reducing then is at first under argon gas atmosphere; Under normal pressure, be cooled to 60 ℃, continuing in oxygen concentration then is under the atmosphere of gaseous mixture of argon gas and oxygen of 5 volume %, under normal pressure, is cooled to 40 ℃ and obtains catalyst D; Its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 5
(1) 62.5 kilograms six water nickel nitrates is dissolved in the deionized water; Be mixed with 500 liters of solution; In above-mentioned solution, add concentration and be 250 kilograms of the waterglass of 10 weight %, mix and obtain slurries, using concentration is that the pH value that the sodium hydrate aqueous solution of 10 weight % is regulated slurries is 5; 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 2000 liters the reactor and contact; The temperature of contact is 80 ℃; With concentration is that the sodium hydrate aqueous solution of 10 weight % is regulated pH and made that the pH value of contact is 7; Behind the contact 4h, filter and to obtain solid, with after the gained solid drying in muffle furnace the solid after 500 ℃ of following roastings obtained roasting in 6 hours;
(3) solid after the roasting is carried out temperature programmed reduction, wherein, the temperature programmed reduction condition is seen table 1; Solid after will reducing then is at first under argon gas atmosphere; Under normal pressure, be cooled to 60 ℃, continuing in oxygen concentration then is under the atmosphere of gaseous mixture of argon gas and oxygen of 5 volume %, under normal pressure, is cooled to 40 ℃ and obtains catalyst E; Its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 6
Method according to embodiment 5 prepares catalyst, and different is, in the step (1); Use concentration is that the pH value of the aqueous solution of nitric acid adjusting slurries of 10 weight % is 2, and all the other conditions are all identical, obtain catalyst F; Its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 7
Method according to embodiment 5 prepares catalyst, and the waterglass that different is in the step (1) is replaced by 15 kilograms silica gel, obtains catalyst G, and its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 8
Method according to embodiment 5 prepares catalyst, and different is that the condition of temperature programmed reduction is as shown in table 1 in the step (3), obtains catalyst H, and its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Embodiment 9
Method according to embodiment 5 prepares catalyst, and the argon gas that different is in the step (3) is replaced by nitrogen, obtains catalyst I, and its TPR also virgin curve is consistent with catalyst A, and promptly reduction temperature is lower than 200 ℃.
Comparative Examples 1
Method according to embodiment 5 prepares catalyst, and the waterglass that different is in the step (1) is replaced by aluminum sulfate, obtains catalyst D1.
Comparative Examples 2
Method according to embodiment 5 prepares catalyst, and different is not have step (3), and promptly the solid after the roasting is directly as catalyst D2.
EXPERIMENTAL EXAMPLE
EXPERIMENTAL EXAMPLE is used for explanation and adopts catalyst provided by the invention, in fixed bed reactors, adopts SiCl
4Produce SiHCl
3Situation.
The catalyst that embodiment 1-9 is prepared obtains micro-spherical catalyst with the comminutor granulation, and the microsphere particle size is 200 μ m.
In fixed bed reactors, in the presence of micro-spherical catalyst, make silicon tetrachloride gas, hydrogen gas stream contacts with silica flour, wherein, and catalyst filling 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 result sees table 2.
The experiment Comparative Examples
Method according to EXPERIMENTAL EXAMPLE is produced SiHCl
3, different is that catalyst is respectively 50CuO/50SiO
2(commercial goods of the brilliant brightness new forms of energy in Luoyang 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
3Ni-based loaded catalyst (50.3NiO/49.7Al for carrier
2O
3, the female catalyst plant of producer Nanjing sky, trade mark NCL0505, its TPR also virgin curve sees Fig. 2), the catalyst D2 for preparing of the catalyst D1 for preparing of Comparative Examples 1 and Comparative Examples 2, the result sees table 2.
Table 1
Table 2
Can find out by data in the table; The catalyst for preparing according to preparation method of the present invention is used for having higher activity when hydrogenation of silicon tetrachloride prepares the trichlorosilane reaction; And after reaction is long-time; Activity is not fallen as follows, this shows, and is better according to the catalyst stability that preparation method of the present invention prepares yet.
More than describe preferred implementation of the present invention in detail; But the present invention is not limited to the detail in the 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 under reconcilable situation, can make up through any suitable manner.
In addition, also can carry out combination in any between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be regarded as the disclosed content of the present invention equally.
Claims (11)
1. Preparation of catalysts method, wherein, this method comprises: soluble nickel salt and the silicon source that silica can be provided and precipitating reagent that can the coprecipitated nickel hydroxide ion are contacted in solvent; To contact products therefrom and filter, and the gained solid will be carried out drying, roasting, temperature programmed reduction and passivation successively.
2. preparation method according to claim 1; Wherein, the consumption in said soluble nickel salt and silicon source makes in the catalyst prepare, is benchmark with the gross weight of catalyst; In oxide, the content of nickel is that the content of 30-75 weight %, silicon is 25-70 weight %.
3. preparation method according to claim 1; Wherein, The mode that soluble nickel salt and the silicon source that silica can be provided and precipitating reagent that can the coprecipitated nickel hydroxide ion are contacted in solvent is: the silicon source that will contain soluble nickel salt, silica can be provided and the slurries of solvent and precipitating reagent that can the coprecipitated nickel hydroxide ion or precipitant solution that can the coprecipitated nickel hydroxide ion contact; And saidly containing soluble nickel salt, the pH of slurries of silicon source and the solvent of silica can be provided is 3-8, is preferably 5-7.
4. according to any described preparation method among the claim 1-3, wherein, the condition of said contact comprises: the temperature of contact is 20-90 ℃, is preferably 50-80 ℃; PH is 4-8, is preferably 5-7.
5. according to any described preparation method among the claim 1-3, wherein, said soluble nickel salt is one or more in nickel nitrate, nickel acetate, nickel chloride and the nickelous sulfate, is preferably nickel nitrate; Said silicon source is one or more in Ludox, silicon gel, esters of silicon acis and the waterglass; Said precipitating reagent is one or more in soluble carbon hydrochlorate, solubility hydroxide and the urea, is preferably in sodium carbonate, potash, ammonium carbonate, urea, ammoniacal liquor, NaOH and the potassium hydroxide one or more; Contain water in the said solvent.
6. according to any described preparation method among the claim 1-3, wherein, said temperature programmed reduction carries out as follows:
In the presence of hydrogen, under reducing condition, at first the heating rate with 20-60 ℃/h is warming up to 100-120 ℃ from room temperature, under this temperature, keeps 1-4h then with the solid after the roasting;
Then the heating rate with 20-60 ℃/h is warming up to 280-300 ℃, under this temperature, keeps 1-4h then;
Then the heating rate with 20-60 ℃/h is warming up to 430-450 ℃, under this temperature, keeps 1-4h then;
Then the heating rate with 20-60 ℃/h is warming up to 480-500 ℃, under this temperature, keeps 1-10h then.
7. preparation method according to claim 6, wherein, said reducing condition comprises: Hydrogen Vapor Pressure be normal pressure to 0.5MPa, hydrogen gas space velocity is 100-2000h
-1
8. according to any described preparation method among the claim 1-3, wherein, said passivation is carried out as follows:
Solid after the reduction in the presence of inert gas, is cooled to below 100 ℃, is preferably 60-80 ℃; Be in the presence of the mist of inert gas and oxygen-containing gas of 1-10 volume % in oxygen-containing gas concentration then, be cooled to below 60 ℃, be preferably 30-50 ℃; More preferably said inert gas is an argon gas.
9. any catalyst that described preparation method prepares among the claim 1-8.
10. catalyst according to claim 9, wherein, the reduction temperature of said catalyst is below 200 ℃.
11. claim 9 or 10 described catalyst prepare the application in the trichlorosilane at hydrogenation of silicon tetrachloride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396592A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method for antiwear microspherical NiO/SiO2 catalyst |
| CN105670028A (en) * | 2016-04-06 | 2016-06-15 | 常州市好利莱光电科技有限公司 | Preparation method of conducting foam |
| CN113385176A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Hydrogenation saturation catalyst and preparation method and application thereof |
| CN114073990A (en) * | 2020-08-18 | 2022-02-22 | 中石化南京化工研究院有限公司 | Preparation method of copper-based hydrogenation catalyst without roasting |
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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 |
| 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 |
| CN102350351A (en) * | 2011-08-31 | 2012-02-15 | 郭屹宾 | Hydrogenation catalyst and preparation method thereof |
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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 |
| 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 |
| CN102350351A (en) * | 2011-08-31 | 2012-02-15 | 郭屹宾 | Hydrogenation catalyst and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105396592A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method for antiwear microspherical NiO/SiO2 catalyst |
| CN105670028A (en) * | 2016-04-06 | 2016-06-15 | 常州市好利莱光电科技有限公司 | Preparation method of conducting foam |
| CN113385176A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Hydrogenation saturation catalyst and preparation method and application thereof |
| CN113385176B (en) * | 2020-03-13 | 2023-09-05 | 中国石油化工股份有限公司 | Hydrogenation saturation catalyst and preparation method and application thereof |
| CN114073990A (en) * | 2020-08-18 | 2022-02-22 | 中石化南京化工研究院有限公司 | Preparation method of copper-based hydrogenation catalyst without roasting |
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