CN103285863B - Catalyst for preparing dichlorosilane, preparation method of catalyst and preparation method of dichlorosilane - Google Patents
Catalyst for preparing dichlorosilane, preparation method of catalyst and preparation method of dichlorosilane Download PDFInfo
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Abstract
The invention provides a preparation method of a catalyst for preparing dichlorosilane. The preparation method comprises the following steps of: step one, soaking active carbon in an aqueous solution of citric acid, taking out and drying the active carbon after the soaking is completed; step two, soaking the active carbon through soaking in an aqueous solution of cobalt salt, taking out and drying the active carbon after the soaking is completed, and then performing baking; and step three, performing a reduction reaction on the active carbon through baking so as to obtain the catalyst. The invention further provides the catalyst prepared and obtained through the preparation method and a preparation method of dichlorosilane adopting the catalyst. According to the preparation methods disclosed by the invention, the catalytic activity of the catalyst can be effectively improved, so that the catalytic efficiency of the catalyst is high; and the dichlorosilane is prepared by adopting the catalyst, so that the yield of the dichlorosilane can achieve more than 12%.
Description
Technical field
The present invention relates to the preparation field of dichloro hydrogen silicon, be specifically related to the preparation method of a kind of Catalysts and its preparation method for the preparation of dichloro hydrogen silicon and a kind of dichloro hydrogen silicon.
Background technology
Dichloro hydrogen silicon generally as the silicon source gas in semiconductor epitaxial and chemical vapor deposition method, for the preparation of silane.Dichloro hydrogen silicon obtains by various ways, such as: by preparing dichlorosilane by trichlorosilane disproportionation and silicon tetrachloride, then therefrom obtains required dichloro hydrogen silicon.The disproportionated reaction of trichlorosilane, carries out under suitable catalyst existent condition.
In recent years; along with the continuous aggravation of energy crisis; worldwide solar photovoltaic industry obtains swift and violent development; the demand of the main raw material(s) polysilicon to solar cell is caused sharply to increase; but under-supply its price that makes of polysilicon raw materials constantly goes up, become the Main Bottleneck of restriction theCourse of PV Industry.If the conversion ratio that trichlorosilane reaction generates dichloro hydrogen silicon can be improved, the production cost of polysilicon will be effectively reduced.
The catalyst that the production of current dichloro hydrogen silicon adopts Union Carbide Corporation to develop more; Described catalyst is mostly weak-base anion-exchange resin, and commercial disignation is respectively: Amberlyst A-21 and Dowex MWA-1.Due to resin type catalyst have easily aging, degrade, run off, stain the shortcomings such as product; in recent years; Japanese Scientists has researched and developed new catalyst; i.e. noble-metal-supported activated-carbon catalyst; this catalyst high temperature high voltage resistant, not easily degradation with aging, selective conversion rate is all relatively good; but can be applied in the production of dichloro hydrogen silicon of scale, there is not been reported.
The preparation method of existing noble-metal-supported activated-carbon catalyst is varied, topmost method is infusion process, active carbon needs to carry out pre-treatment before carried metal, mainly use the oxidizing process such as nitric acid, hydrogen peroxide, ozone, activated carbon surface is made to generate surface functional group, and then anchoring metallic particles, such as: Au, Pt, Ag etc.; But, adopt above oxidizing active carbon consuming time longer, and metallic particles adsorption effect is on the activated carbon not good enough, easily comes off, and causes the catalytic efficiency of catalyst low further.
Summary of the invention
The present invention in order to solve the existing catalyst for the preparation of dichloro hydrogen silicon preparation method obtained by the metallic particles adsorption effect on the activated carbon of noble-metal-supported activated-carbon catalyst not good enough, easily come off, the technical problem that the catalytic efficiency of catalyst is low.
Accordingly, the invention provides a kind of preparation method of the catalyst for the preparation of dichloro hydrogen silicon, comprise the steps:
Step 1: be soaked in by active carbon in lemon aqueous acid, has soaked rear taking-up and drying;
Step 2: impregnated in the aqueous solution of cobalt salt by the active carbon through soaking, has flooded rear taking-up and drying, has then carried out roasting;
Step 3: the active carbon through roasting is carried out reduction reaction in reducing atmosphere, obtains described catalyst.
Preferably, in step 1, employing concentration is the aqueous solution soaking active carbon 2-12h of the citric acid of 0.2-1.5mol/L.
Preferably, in step 2, CoCl is adopted
26H
2the aqueous impregnation active carbon of O, dip time is 0.5-48h, CoCl
26H
2coCl in the aqueous solution of O
26H
2the concentration of O is 0.01-1mol/L, and each gram of active carbon needs the CoCl of 0.1-2.5mmol
26H
2o.
Preferably, in step 2, the atmosphere of described roasting is nitrogen atmosphere, and sintering temperature is 280-350 DEG C, and roasting time is 8-16h.
Preferably, in step 3, described reduction reaction is carried out in the catalytic bed of the reactor for the preparation of dichloro hydrogen silicon.
Preferably, in step 3, the atmosphere of described reduction reaction is mixed-gas atmosphere, and air pressure is 2-12bar; Described mist comprises reducing gas CO, H
2and inert gas N
2, wherein, reducing gas CO, H
2with inert gas N
2volume ratio be that 1:3-5, CO account for reducing gas CO, H
2the 1-5% of cumulative volume.
Preferably, the temperature of described reduction reaction is 240-270 DEG C, and described reduction reaction adopts the method for segmented heating and heat preservation, from room temperature temperature programming to the temperature of reduction reaction, heating rate controls at 0.5-5 DEG C/min, after temperature from ambient rises to 150 DEG C, and insulation 3-6h; After rising to 250 DEG C by 150 DEG C, insulation 6-8h; After rising to 270 DEG C by 250 DEG C, insulation 0.5-72h.
Preferably, in step 1, before being soaked in by active carbon in lemon aqueous acid, first pre-treatment is carried out to active carbon, described pre-treatment comprises first employing deionized water and cleans active carbon, ultrasonic wave is adopted to carry out ultrasonic cleaning to active carbon again, and then adopt deionized water to clean active carbon, finally carry out drying.
Present invention also offers a kind of catalyst for the preparation of dichloro hydrogen silicon, described catalyst adopts method as above to prepare, and comprises active carbon and the cobalt metal being scattered in described activated carbon surface.
Invention further provides a kind of preparation method of dichloro hydrogen silicon, trichlorosilane and catalyst are joined in reactor and reacts, after reaction terminates, obtain dichloro hydrogen silicon; Described catalyst is obtained by preparation method as above.
The preparation method of catalyst of the present invention first adopts lemon aqueous acid process active carbon before the aqueous impregnation active carbon adopting cobalt salt, the oxygen-containing functional group of activated carbon surface is increased, add the application point between active carbon and cobalt metallic particles, anchoring metallic cobalt position on the activated carbon, add the decentralization of metallic cobalt at activated carbon surface, effectively reduce cobalt metallic particles granularity on the activated carbon, effectively can improve the catalytic activity of catalyst, make the catalytic efficiency of catalyst high; Adopt this catalyst preparing dichloro hydrogen silicon, the productive rate of dichloro hydrogen silicon can be made to reach more than 12%.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of preparation method of the catalyst for the preparation of dichloro hydrogen silicon, comprise the steps: step 1: be soaked in by active carbon in lemon aqueous acid, soak rear taking-up and drying.
In this step, active carbon is being soaked in citric acid (2-hydroxyl-1,2,3-tri-carboxyl propane) the aqueous solution in before first pre-treatment is carried out to active carbon, described pre-treatment comprises and takes a certain amount of active carbon, first adopts deionized water to carry out repeated washing for several times to active carbon, ultrasonic wave is adopted to carry out ultrasonic cleaning 5-10 minute to active carbon again, again adopt washed with de-ionized water active carbon for several times, until the clarification of water after cleaning, obtain clean active carbon.Then carry out drying, described drying can adopt nature dry or adopt oven for drying, and such as: the active carbon cleaned up is placed in convection oven, dry 5-8h with 80-120 DEG C, after dry, the active carbon of gained is labeled as active carbon CA-0.
In the prior art, active carbon usually adopts the oxidants such as nitric acid, hydrogen peroxide, ozone to carry out oxidation processes to active carbon before carried metal, activated carbon surface is made to generate surface functional group, so that follow-up anchoring metallic particles, but adopt above-mentioned oxidizing active carbon, and required effect be reached, consuming time longer, and metallic particles adsorption effect is on the activated carbon not good enough, easily comes off.
In the present invention, get above-mentioned active carbon CA-0, adopt the aqueous solution soaking active carbon of appropriate certain density citric acid, preferably, employing 180-300ml concentration is the aqueous solution soaking active carbon of the citric acid of 0.2-1.5mol/L, soak time is 2-12 hour, after immersion terminates, remove unnecessary citric acid, then drying is carried out, described drying can adopt nature dry or adopt oven for drying, such as: can first active carbon be dried naturally, and then be placed in convection oven 80-120 DEG C of baking 5-12h, after dry, the active carbon of gained is labeled as active carbon CA-1, this active carbon CA-1 is the active carbon that surface has oxygen-containing functional group.
Although adopt existing oxidant, such as: the object of the process active carbon such as nitric acid, hydrogen peroxide and citric acid treatment active carbon is all make activated carbon surface generate surface functional group, the position of metal nucleation is provided, but compared to existing oxidant, citric acid is adopted to process active carbon, activated carbon surface just can be made functionalized in short time, and citric acid treatment can make activated carbon surface produce more functional group, is more conducive to absorption and the anchoring of metal.
The preparation method of catalyst of the present invention first adopts lemon aqueous acid process active carbon before the aqueous impregnation active carbon adopting cobalt salt, the oxygen-containing functional group of activated carbon surface is increased, add the application point between active carbon and cobalt metallic particles, can in follow-up anchoring metallic cobalt position on the activated carbon, increase the decentralization of metallic cobalt particle at activated carbon surface, reduce cobalt metallic particles granularity on the activated carbon, effectively improve the catalytic activity of catalyst.
Step 2: impregnated in the aqueous solution of cobalt salt by the active carbon through soaking, has flooded rear taking-up and drying, has then carried out roasting.
In this step, adopt infusion process to be impregnated on active carbon by cobalt salt, the dipping of cobalt salt adopts the method for wet impregnation, and described wet impregnation method has been conventionally known to one of skill in the art.In the present invention, adopt wet impregnation cobalt salt, described cobalt salt can adopt cobalt chloride CoCl
26H
2o, cobalt nitrate Co (NO
3)
26H
2o, cobalt acetate C
4h
6o
4co4H
2one in O, by the aqueous solution of water-soluble for cobalt salt formation cobalt salt, in the aqueous solution of cobalt salt, the concentration of cobalt salt is 0.01-1mol/L.Active carbon CA-1 be impregnated in the aqueous solution of cobalt salt, take out after the dipping regular hour and drying, obtain the active carbon that surface distributed has cobalt salt.In the preferred case, described cobalt salt adopts cobalt chloride CoCl
26H
2o, gets appropriate active carbon CA-1 and CoCl
26H
2the aqueous solution of O, impregnated in CoCl by active carbon CA-1
26H
2in the aqueous solution of O, preferred compound concentration is the CoCl of 0.01-1mol/L
26H
2the aqueous solution of O, and ensure CoCl
26H
2the ratio of O and active carbon CA-1 meets 0.1-2.5mmol CoCl
26H
2o:1g active carbon, dip time is 0.5-48h, after dipping terminates, remove unnecessary maceration extract, then carry out drying, described drying can adopt nature dry or adopt oven for drying, such as: can first active carbon be dried naturally, and then be placed in convection oven 50-120 DEG C of baking 5-12h, after dry, the active carbon of gained is labeled as active carbon CA-2, and this active carbon CA-2 is the active carbon that surface distributed has cobalt chloride.
In the present invention, active carbon CA-2 is carried out roasting, the roasting apparatus that described roasting can adopt this area common, such as: stove, fixed bed, fluid bed, rotary kiln or mica calcining furnace.In order to ensure the purity of subsequent catalyst finished product, sintering temperature will be strict controlled in more than 275 DEG C, and namely sintering temperature is more than the decomposition temperature of citric acid, most of citric acid is decomposed, reduces the pollution to finished catalyst.Simultaneously in order to the possibility that the sintering reducing catalyst is rotten, sintering temperature also can not be too high, and in the preferred case, sintering temperature controls between 280-350 DEG C, and roasting time is 8-16h.Calcination atmosphere selects nitrogen atmosphere; in a nitrogen atmosphere; citric acid decomposes about 150 DEG C time; even if but decompose to citric acid major part when 250 DEG C. temperature crosses 600 DEG C; citric acid still can not decompose in a nitrogen atmosphere completely, and still have an appointment the residue (carbon deposit that heating citric acid does not decompose completely and produces) after decomposition 2wt%; And in air atmosphere, the carbon deposit complete oxidation combustion gas produced after about 460 DEG C citric acids decompose, does not have solid residue.Thus the present invention selects nitrogen atmosphere to carry out roasting, under such atmosphere, appropriate citric acid and residue (carbon distribution) thereof are containing more surface functional group, be conducive to cobalt metal in the dispersion of activated carbon surface and anchoring, roasting makes the cobalt chloride of activated carbon surface be oxidized to cobalt oxide, after roasting, the active carbon of gained is labeled as active carbon CA-3, and this active carbon CA-3 is the active carbon that surface distributed has cobalt oxide.
Step 3: the active carbon through roasting is carried out reduction reaction in reducing atmosphere, obtains described catalyst.
Skilled in the art will recognize that, one in the preparation method of noble-metal-supported activated-carbon catalyst important step is exactly last reduction activation step, reduction activation is generally carried out in special reduction furnace, because reducing atmosphere generally adopts hydrogen, and the aerial explosive range of hydrogen is large, LEL is less, therefore higher to the manufacture requirements of reduction furnace, this adds increased the manufacturing cost of catalyst, namely add the cost of equipment that dichloro hydrogen silicon is produced; And because the catalyst under reducing condition can spontaneously react with the oxygen in air, therefore also there is certain requirement to the unloading atmosphere of the catalyst after reduction, add the trouble in catalyst preparation process.
In the present invention, described reduction activation step is carried out in the catalytic bed of the reactor (or claiming the pyrolysis furnace of preparing dichlorosilane by trichlorosilane disproportionation) for the preparation of dichloro hydrogen silicon.Active carbon through roasting is placed in the catalytic bed of reactor by described reduction reaction, in mixed-gas atmosphere, carry out reduction reaction, and described mist comprises reducing gas CO, H
2and inert gas N
2, described mist meets following condition: (CO+H
2): N
2=1:3-5, this is because the shared volume ratio of inert gas is larger, the reduction of catalyst is more difficult, in order to reduction generates cobalt metal within the suitable time, control the addition of inert nitrogen gas; Meanwhile, because pure reducibility gas is easily blasted, consider security, also will control the addition of reducing gas well.And CO accounts for CO+H
2the 1-5% of cumulative volume, preferred CO accounts for CO+H
2during the 2-4% of cumulative volume, reduction effect is best, reducibility gas CO and H
2volume ratio to control well because CO is too much, deposited carbon effect can occur, the interpolation of hydrogen can effectively reduce this deposited carbon effect, and experiment shows that the volume ratio of mist meets above-mentioned condition, and the reduction activation effect of catalyst is better.
In the present invention, the temperature of reduction reaction is 240-270 DEG C, this is because critical reduction temperature is at 220-250 DEG C, test confirms, it is better that reduction temperature controls about 20 DEG C reduction effects more than critical reduction temperature, and namely reduction temperature is at 240-270 DEG C.Further, reduction reaction of the present invention adopts the method for segmented heating and heat preservation, and from room temperature temperature programming to critical reduction temperature, heating rate controls at 0.5-5 DEG C/min, after temperature from ambient rises to 150 DEG C, and insulation 3-6h; After rising to 250 DEG C by 150 DEG C, insulation 6-8h; After rising to 270 DEG C by 250 DEG C, insulation 0.5-72h.In addition, in reduction process, high pressure is more conducive to the carrying out of reduction reaction, therefore, controls the pressure of mist in pyrolysis furnace at 2-12bar in reduction process.The temperature and pressure of above reduction activation reaction all meets operating temperature and the operating pressure of trichlorosilane pyrolysis furnace, and thus reduction reaction of the present invention can be carried out in the catalytic bed of the pyrolysis furnace of preparing dichlorosilane by trichlorosilane disproportionation.Catalyst CA of the present invention is obtained through above-mentioned reduction reaction, described catalyst CA is the active carbon that area load has metallic cobalt simple substance, the catalyst obtained results from the catalytic bed of trichlorosilane pyrolysis furnace, can be directly used in preparing dichlorosilane by trichlorosilane disproportionation.
As from the foregoing, reduction activation reactions steps Kaolinite Preparation of Catalyst of the present invention directly carries out in catalytic bed, saves the expense of reduction apparatus, and reduction activation reaction adopts CO, H
2and N
2mist, CO adds, and improves the reducing power of metallic cobalt, decreases by H
2the CH generated during reducing activity charcoal
4to the possibility of contamination of products, adding of inert gas, suitably can reduce the reduction rate of catalyst, suitably improve pressure during reduction, thus effectively can improve the ability of reduction; Secondly, the temperature of priming reaction adopts the method for syllogic heating and heat preservation, reduces the possibility of the too early too fast reduction of catalyst; In addition, directly reduce in the preparation facilities of dichloro hydrogen silicon, save equipment cost, reduce the unloading of catalyst and the number of times of loading, avoid the spontaneous oxidation of cobalt metal after unloading from reduction furnace, be conducive to large-scale production and the application of catalyst.
Present invention also offers a kind of catalyst adopting above-mentioned preparation method to prepare, comprise active carbon and the cobalt metal being formed at described activated carbon surface.Load is firm on the activated carbon, granularity is little and be evenly distributed for the cobalt metallic particles of catalyst of the present invention, has higher catalytic activity.
Present invention also offers the preparation method of dichloro hydrogen silicon, trichlorosilane and catalyst are joined the disproportionated reaction of carrying out trichlorosilane in reactor, after reaction terminates, obtain dichloro hydrogen silicon; Described catalyst is obtained by preparation method of the present invention.
The preparation of dichloro hydrogen silicon adopts trichlorosilane disproportionated reaction to prepare, and reaction principle is as follows:
2SiHCl
3 SiH
2Cl
2+ SiCl
4
Disproportionated reaction is carried out under the catalysis of catalyst, as mentioned above, the catalyst obtained by preparation method of the present invention has been present in the catalytic bed of reactor, can directly use, reduce the unloading of catalyst and the step of loading, avoid the spontaneous oxidation of cobalt metal after unloading from reduction furnace.Further, the present invention adopts metallic cobalt load type active carbon, effectively can improve reaction temperature and the pressure of preparing dichlorosilane by trichlorosilane disproportionation, and can improve reaction temperature to 150-200 DEG C, pressure is increased to 0.6-0.8MPa.Skilled in the art will recognize that according to resin as catalyst, reaction temperature is up to 80 DEG C, and reaction pressure is up to 0.4MPa, because reaction temperature or hypertonia can make resin inactivation.And adopting catalyst of the present invention, reaction temperature can be increased to 150-200 DEG C, and reaction pressure more can be increased to 0.6-0.8MPa, makes the production rate of dichloro hydrogen silicon to reach more than 12%.
Below in conjunction with specific embodiment 1-5, the invention will be further elaborated.
embodiment 1
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing several, the clarification of water to flushing, after naturally drying, in convection oven, 110 DEG C are dried 8h, obtain active carbon CA1-0;
2, active carbon being soaked in 200ml concentration is 10h in 1.0mol/L lemon aqueous acid, soaked rear taking-up and in convection oven 110 DEG C dry 8h, obtain active carbon CA1-1;
3, the CoCl of cobalt salt: A, preparation 0.1mol/L is flooded
26H
2o solution 500ml, B, get 20g active carbon CA1-1, get the CoCl of the above-mentioned preparation of 240ml
26H
2active carbon CA1-1, in 500ml beaker, is put into CoCl by O solution
2in 6H2O solution, after standing dipping 8h, C, dipping terminate, remove unnecessary maceration extract, after naturally drying, with 120 DEG C of dry 10h in convection oven, obtain active carbon CA1-2;
4, roasting: by active carbon CA1-2 in a nitrogen atmosphere with the temperature calcination 10h of 280 DEG C, obtain active carbon CA1-3;
5, reduction activation: get proper amount of active carbon CA1-3 and load in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, until oxygen content is less than 0.3% in outlet tail gas; Then CO+H is passed into
2+ N
2mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:3, CO account for (CO+H
2) cumulative volume 3%, reduction pressure is 5bar; Reduction reaction adopts syllogic temperature programming, and heating rate is 5 DEG C/min, rises to 150 DEG C by room temperature, insulation 4h, is warming up to 250 DEG C by 150 DEG C, insulation 7h, be warming up to 270 DEG C by 250 DEG C, insulation 12h, obtains the catalyst CA1 of the embodiment of the present invention 1 after reduction reaction terminates;
6, the preparation of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane enters catalytic bed, opens tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge; The reaction condition of preparing dichlorosilane by trichlorosilane disproportionation is: reaction temperature is 150 DEG C, and reaction pressure is 0.6MPa.Every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 12.8% in the product.
embodiment 2
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing several, the clarification of water to flushing, after naturally drying, in convection oven, 100 DEG C are dried 8h, obtain active carbon CA2-0;
2, active carbon being soaked in 300ml concentration is 8h in 1.2mol/L lemon aqueous acid, soaked rear taking-up and in convection oven 100 DEG C dry 8h, obtain active carbon CA2-1;
3, the CoCl of cobalt salt: A, preparation 0.9mol/L is flooded
26H
2o solution 500ml, B, get 20g active carbon CA2-1, get the CoCl of the above-mentioned preparation of 300ml
26H
2active carbon CA2-1, in 500ml beaker, is put into CoCl by O solution
26H
2in O solution, after standing dipping 20h, C, dipping terminate, remove unnecessary maceration extract, after naturally drying, with 100 DEG C of dry 8h in convection oven, obtain active carbon CA2-2;
4, roasting: by active carbon CA2-2 in a nitrogen atmosphere with the temperature calcination 12h of 300 DEG C, obtain active carbon CA2-3;
5, reduction activation: get proper amount of active carbon CA2-3 and load in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, until oxygen content is less than 0.3% in outlet tail gas; Then CO+H is passed into
2+ N
2mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:4, CO account for (CO+H
2) cumulative volume 2%, reduction pressure is 8bar; Reduction reaction adopts syllogic temperature programming, and heating rate is 4 DEG C/min, rises to 150 DEG C by room temperature, insulation 4h, is warming up to 250 DEG C by 150 DEG C, insulation 6h, be warming up to 270 DEG C by 250 DEG C, insulation 24h, obtains the catalyst CA2 of the embodiment of the present invention 2 after reduction reaction terminates;
6, the preparation of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane enters catalytic bed, opens tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge; The reaction condition of preparing dichlorosilane by trichlorosilane disproportionation is: reaction temperature is 160 DEG C, and reaction pressure is 0.7MPa, 0.5L/min; Every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 12.8% in the product.
embodiment 3
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing several, the clarification of water to flushing, after naturally drying, in convection oven, 120 DEG C are dried 5h, obtain active carbon CA3-0;
2, active carbon being soaked in 200ml concentration is 12h in 0.4mol/L lemon aqueous acid, soaked rear taking-up and in convection oven 120 DEG C dry 5h, obtain active carbon CA3-1;
3, the CoCl of cobalt salt: A, preparation 0.5mol/L is flooded
26H
2o solution 500ml, B, get 20g active carbon CA3-1, get the CoCl of the above-mentioned preparation of 300ml
26H
2active carbon CA3-1, in 500ml beaker, is put into CoCl by O solution
26H
2in O solution, after standing dipping 36h, C, dipping terminate, remove unnecessary maceration extract, after naturally drying, with 120 DEG C of dry 5h in convection oven, obtain active carbon CA3-2;
4, roasting: by active carbon CA3-2 in a nitrogen atmosphere with the temperature calcination 10h of 320 DEG C, obtain active carbon CA3-3;
5, reduction activation: get proper amount of active carbon CA3-3 and load in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, until oxygen content is less than 0.3% in outlet tail gas; Then CO+H is passed into
2+ N
2mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:5, CO account for (CO+H
2) cumulative volume 4%, reduction pressure is 10bar; Reduction reaction adopts syllogic temperature programming, and heating rate is 5 DEG C/min, rises to 150 DEG C by room temperature, insulation 5h, is warming up to 250 DEG C by 150 DEG C, insulation 7h, be warming up to 270 DEG C by 250 DEG C, insulation 20h, obtains the catalyst CA3 of the embodiment of the present invention 3 after reduction reaction terminates;
6, the preparation of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane enters catalytic bed, opens tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge; The reaction condition of preparing dichlorosilane by trichlorosilane disproportionation is: reaction temperature is 180 DEG C, and reaction pressure is 0.8MPa, 0.5L/min; Every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 13.5% in the product.
embodiment 4
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing several, the clarification of water to flushing, after naturally drying, in convection oven, 110 DEG C are dried 8h, obtain active carbon CA4-0;
2, active carbon being soaked in 200ml concentration is 10h in 1.0mol/L lemon aqueous acid, soaked rear taking-up and in convection oven 110 DEG C dry 8h, obtain active carbon CA4-1;
3, the Co (NO of cobalt salt: A, preparation 0.1mol/L is flooded
3)
26H
2o solution 500ml, B, get 20g active carbon CA1-1, get the Co (NO of the above-mentioned preparation of 240ml
3)
26H
2active carbon CA1-1, in 500ml beaker, is put into Co (NO by O solution
3)
26H
2in O solution, after standing dipping 8h, C, dipping terminate, remove unnecessary maceration extract, after naturally drying, with 120 DEG C of dry 10h in convection oven, obtain active carbon CA4-2;
4, roasting: by active carbon CA4-2 in a nitrogen atmosphere with the temperature calcination 10h of 280 DEG C, obtain active carbon CA4-3;
5, reduction activation: get proper amount of active carbon CA4-3 and load in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, until oxygen content is less than 0.3% in outlet tail gas; Then CO+H is passed into
2+ N
2mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:3, CO account for (CO+H
2) cumulative volume 3%, reduction pressure is 5bar; Reduction reaction adopts syllogic temperature programming, and heating rate is 5 DEG C/min, rises to 150 DEG C by room temperature, insulation 4h, is warming up to 250 DEG C by 150 DEG C, insulation 7h, be warming up to 270 DEG C by 250 DEG C, insulation 12h, obtains the catalyst CA4 of the embodiment of the present invention 4 after reduction reaction terminates;
6, the preparation of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane enters catalytic bed, opens tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge; The reaction condition of preparing dichlorosilane by trichlorosilane disproportionation is: reaction temperature is 150 DEG C, and reaction pressure is 0.6MPa.Every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 12.0% in the product.
embodiment 5
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing several, the clarification of water to flushing, after naturally drying, in convection oven, 100 DEG C are dried 8h, obtain active carbon CA5-0;
2, active carbon being soaked in 300ml concentration is 8h in 1.2mol/L lemon aqueous acid, soaked rear taking-up and in convection oven 100 DEG C dry 8h, obtain active carbon CA2-1;
3, the C of cobalt salt: A, preparation 0.9mol/L is flooded
4h
6o
4co4H
2o solution 500ml, B, get 20g active carbon CA5-1, get the C of the above-mentioned preparation of 300ml
4h
6o
4co4H
2active carbon CA2-1, in 500ml beaker, is put into C by O solution
4h
6o
4co4H
2in O solution, after standing dipping 20h, C, dipping terminate, remove unnecessary maceration extract, after naturally drying, with 100 DEG C of dry 8h in convection oven, obtain active carbon CA2-2;
4, roasting: by active carbon CA5-2 in a nitrogen atmosphere with the temperature calcination 12h of 300 DEG C, obtain active carbon CA5-3;
5, reduction activation: get proper amount of active carbon CA5-3 and load in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, until oxygen content is less than 0.3% in outlet tail gas; Then CO+H is passed into
2+ N
2mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:4, CO account for (CO+H
2) cumulative volume 2%, reduction pressure is 8bar; Reduction reaction adopts syllogic temperature programming, and heating rate is 4 DEG C/min, rises to 150 DEG C by room temperature, insulation 4h, is warming up to 250 DEG C by 150 DEG C, insulation 6h, be warming up to 270 DEG C by 250 DEG C, insulation 24h, obtains the catalyst CA5 of the embodiment of the present invention 5 after reduction reaction terminates;
6, the preparation of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane enters catalytic bed, opens tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge; The reaction condition of preparing dichlorosilane by trichlorosilane disproportionation is: reaction temperature is 160 DEG C, and reaction pressure is 0.7MPa, 0.5L/min; Every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 12.4% in the product.
comparative example 1
Adopt existing macroporous weakly basic anion exchange resin (model is Amberlyst A-21) as catalyst preparing dichloro hydrogen silicon, the preparation process of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane carries out catalytic bed, in catalytic bed, add Amberlyst A-21 simultaneously, open tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge, reaction condition is: reaction temperature is 80 DEG C, and reaction pressure is 0.4MPa, every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 6.5% in the product.
comparative example 2
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing several, the clarification of water to flushing, after naturally drying, in convection oven, 110 DEG C are dried 8h, obtain active carbon DA1-0;
2, the CoCl of cobalt salt: A, preparation 0.1mol/L is flooded
26H
2o solution 500ml, B, get 20g active carbon DA1-0, get the CoCl of the above-mentioned preparation of 240ml
2active carbon DA1-0, in 500ml beaker, is put into CoCl by 6H2O solution
2in 6H2O solution, after standing dipping 8h, C, dipping terminate, remove unnecessary maceration extract, after naturally drying, with 120 DEG C of dry 10h in convection oven, obtain active carbon DA1-1;
3, roasting: by active carbon DA1-1 in a nitrogen atmosphere with the temperature calcination 10h of 280 DEG C, obtain active carbon DA1-2;
4, reduction activation: get proper amount of active carbon DA1-2 and load in reduction furnace, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, until oxygen content is less than 0.3% in outlet tail gas; Then H is passed into
2carry out reduction reaction, after reduction reaction terminates, obtain the catalyst DA1 of comparative example 1 of the present invention;
5, the preparation of dichloro hydrogen silicon: first close the valve between evaporimeter and catalytic bed, open head tank valve and pneumatic control valve, start to add trichlorosilane in evaporimeter, when pressure in head tank reaches requirement, open the valve between evaporimeter and catalytic bed, trichlorosilane enters catalytic bed, in catalytic bed, add catalyst DA1 simultaneously, open tail gas valve, regulate each thermometric instrument, predetermined value waited until by Pressure gauge; The reaction condition of preparing dichlorosilane by trichlorosilane disproportionation is: reaction temperature is 100 DEG C, and reaction pressure is 0.2MPa, 0.5L/min.Every stable after, start sampling and collect, test in chromatograph (manufacturer is Japanese Shimadzu, and model is: GC2014), dichloro hydrogen silicon accounts for 8% in the product.
test result
As can be seen from embodiment 1-5 above and comparative example 1-2, the catalyst that the preparation method that embodiments of the invention 1-5 provides obtains is significantly high compared to the catalytic efficiency of the catalyst of comparative example 1-2; Adopt this catalyst preparing dichloro hydrogen silicon, the productive rate of dichloro hydrogen silicon can be made to reach more than 12%.
Those skilled in the art easily know; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (9)
1., for the preparation of a preparation method for the catalyst of dichloro hydrogen silicon, it is characterized in that, comprise the steps:
Step 1: be soaked in by active carbon in lemon aqueous acid, has soaked rear taking-up and drying;
Step 2: impregnated in the aqueous solution of cobalt salt by the active carbon through soaking, has flooded rear taking-up and drying, has then carried out roasting;
Step 3: the active carbon through roasting is carried out reduction reaction, obtains described catalyst;
The temperature of described reduction reaction is 240-270 DEG C, and described reduction reaction adopts the method for segmented heating and heat preservation, and from room temperature temperature programming to the temperature of reduction reaction, heating rate controls at 0.5-5 DEG C/min, after temperature from ambient rises to 150 DEG C, and insulation 3-6h; After rising to 250 DEG C by 150 DEG C, insulation 6-8h; After rising to 270 DEG C by 250 DEG C, insulation 0.5-72h.
2. the preparation method of catalyst according to claim 1, is characterized in that, in step 1, employing concentration is the aqueous solution soaking active carbon 2-12h of the citric acid of 0.2-1.5mol/L.
3. the preparation method of catalyst according to claim 1, is characterized in that, in step 2, adopts CoCl
26H
2the aqueous impregnation active carbon of O, dip time is 0.5-48h, CoCl
26H
2coCl in the aqueous solution of O
26H
2the concentration of O is 0.01-1mol/L, and each gram of active carbon needs the CoCl of 0.1-2.5mmol
26H
2o.
4. the preparation method of catalyst according to claim 1, is characterized in that, in step 2, the atmosphere of described roasting is nitrogen atmosphere, and sintering temperature is 280-350 DEG C, and roasting time is 8-16h.
5. the preparation method of catalyst according to claim 1, is characterized in that, in step 3, described reduction reaction is carried out in the catalytic bed of the reactor for the preparation of dichloro hydrogen silicon.
6. the preparation method of catalyst according to claim 1, is characterized in that, in step 3, the atmosphere of described reduction reaction is mixed-gas atmosphere, and air pressure is 2-12bar; Described mist comprises reducing gas CO, H
2and inert gas N
2, wherein, reducing gas CO, H
2with inert gas N
2volume ratio be that 1:3-5, CO account for reducing gas CO, H
2the 1-5% of cumulative volume.
7. the preparation method of catalyst according to claim 1, it is characterized in that, in step 1, before being soaked in by active carbon in lemon aqueous acid, first pre-treatment is carried out to active carbon, described pre-treatment comprises first employing deionized water and cleans active carbon, adopt ultrasonic wave to carry out ultrasonic cleaning to active carbon again, and then adopt deionized water to clean active carbon, finally carry out drying.
8. for the preparation of a catalyst for dichloro hydrogen silicon, it is characterized in that, described catalyst adopts the method as described in claim 1-7 any one to prepare, and comprises active carbon and the cobalt metal being formed at described activated carbon surface.
9. a preparation method for dichloro hydrogen silicon, is characterized in that, trichlorosilane and catalyst is joined the disproportionated reaction of carrying out trichlorosilane in reactor, obtains dichloro hydrogen silicon after reaction terminates; Described catalyst is obtained by the preparation method as described in claim 1-7 any one.
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| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
| CN101347730A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst for refinement of crude terephthalic acid |
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| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
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