CN103285863A - 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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- CN103285863A CN103285863A CN2012100470671A CN201210047067A CN103285863A CN 103285863 A CN103285863 A CN 103285863A CN 2012100470671 A CN2012100470671 A CN 2012100470671A CN 201210047067 A CN201210047067 A CN 201210047067A CN 103285863 A CN103285863 A CN 103285863A
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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 is generally as the silicon source gas in semiconductor epitaxial and the chemical vapor deposition method, for the preparation of silane.Dichloro hydrogen silicon can make in several ways, for example: prepare dichloro hydrogen silicon and silicon tetrachloride by the trichlorosilane disproportionation, therefrom obtain required dichloro hydrogen silicon then.The disproportionated reaction of trichlorosilane is carried out under the condition that suitable catalyst exists.
In recent years; continuous aggravation along with energy crisis; worldwide photovoltaic industry obtains swift and violent development; cause the demand to the main raw material(s) polysilicon of solar cell sharply to increase; but polysilicon raw material supply deficiency constantly goes up by its price, has become the main bottleneck of restriction photovoltaic industry development.If can improve the conversion ratio that the trichlorosilane reaction generates dichloro hydrogen silicon, will effectively reduce the production cost of polysilicon.
The catalyst of Union Carbide Corporation's exploitation is adopted in the production of dichloro hydrogen silicon at present more; Described catalyst mostly is weak-base anion-exchange resin, and commercial disignation is respectively: Amberlyst A-21 and Dowex MWA-1.Because resin type catalyst has easily shortcomings such as wearing out, degrade, run off, stain product; in recent years; the Japan scientist has researched and developed new catalyst; it is noble metal supported active Pd/carbon catalyst; this catalyst tolerates HTHP is difficult for degradation with aging, and the selective conversion rate is all relatively good; but can be applied to not appear in the newspapers as yet in the production of dichloro hydrogen silicon of scale.
Existing noble metal load type active carbon Preparation of catalysts method is varied, topmost method is infusion process, active carbon needs to carry out pre-treatment before carried metal, mainly be with oxidant oxidation processes such as nitric acid, hydrogen peroxide, ozone, make activated carbon surface generate surface functional group, and then the anchoring metallic particles, for example: Au, Pt, Ag etc.; Yet, adopt above oxidant magnesium oxide/absorbent charcoal consuming time longer, and the adsorption effect of metallic particles on active carbon is not good enough, comes off easily, further cause the catalytic efficiency of catalyst low.
Summary of the invention
The present invention is not good enough for the adsorption effect of metallic particles on active carbon that solves the existing prepared noble metal supported active of Preparation of catalysts method Pd/carbon catalyst for the preparation of dichloro hydrogen silicon, comes off the technical problem that the catalytic efficiency of catalyst is low easily.
Accordingly, the invention provides a kind of Preparation of catalysts method for the preparation of dichloro hydrogen silicon, comprise the steps:
Step 1: active carbon is soaked in the lemon aqueous acid, takes out and drying after immersion is finished;
Step 2: will impregnated in the aqueous solution of cobalt salt through the active carbon that soaks, take out and drying after dipping is finished, carry out roasting then;
Step 3: will in reducing atmosphere, carry out reduction reaction through the active carbon of roasting, and obtain described catalyst.
Preferably, in step 1, adopting concentration is the aqueous solution soaking active carbon 2-12h of the citric acid of 0.2-1.5mol/L.
Preferably, in step 2, adopt CoCl
26H
2The aqueous solution Immesion active carbon of O, dip time are 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 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 ℃, and roasting time is 8-16h.
Preferably, in step 3, described reduction reaction is carried out in the catalytic bed for the preparation of the reactor 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 1:3-5, CO accounts for reducing gas CO, H
2The 1-5% of cumulative volume.
Preferably, the temperature of described reduction reaction is 240-270 ℃, and described reduction reaction adopts the method for segmented heating and heat preservation, temperature from the room temperature temperature programming to reduction reaction, heating rate control after temperature rises to 150 ℃ by room temperature, is incubated 3-6h at 0.5-5 ℃/min; After rising to 250 ℃ by 150 ℃, insulation 6-8h; After rising to 270 ℃ by 250 ℃, insulation 0.5-72h.
Preferably, in step 1, before active carbon being soaked in the lemon aqueous acid, earlier active carbon is carried out pre-treatment, described pre-treatment comprises adopts deionized water that active carbon is cleaned earlier, adopt ultrasonic wave that active carbon is carried out ultrasonic cleaning again, and then adopt deionized water that active carbon is cleaned, carry out drying at last.
The present invention also provides a kind of catalyst for the preparation of dichloro hydrogen silicon, and described catalyst adopts aforesaid method to prepare, and comprises active carbon and the cobalt metal that is scattered in described activated carbon surface.
The present invention further provides a kind of preparation method of dichloro hydrogen silicon, trichlorosilane and catalyst have been joined in the reactor react, reaction obtains dichloro hydrogen silicon after finishing; Described catalyst is made by aforesaid preparation method.
Preparation of catalysts method of the present invention adopts the lemon aqueous acid to handle active carbon before the aqueous solution Immesion active carbon that adopts cobalt salt earlier, make the oxygen-containing functional group of activated carbon surface increase, increased the application point between active carbon and the cobalt metallic particles, anchoring the position of metallic cobalt on active carbon, increased the decentralization of metallic cobalt at activated carbon surface, effectively reduce the granularity of cobalt metallic particles on active carbon, can effectively improve the catalytic activity of catalyst, make the catalytic efficiency height of catalyst; Adopt this Preparation of Catalyst dichloro hydrogen silicon, the productive rate of dichloro hydrogen silicon is reached more than 12%.
The specific embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The invention provides a kind of Preparation of catalysts method for the preparation of dichloro hydrogen silicon, comprise the steps: step 1: active carbon is soaked in the lemon aqueous acid, takes out and drying after immersion is finished.
In this step, active carbon is being soaked in citric acid (2-hydroxyl-1,2,3-three carboxyl propane) earlier active carbon was carried out pre-treatment before in the aqueous solution, described pre-treatment comprises and takes by weighing a certain amount of active carbon, adopts deionized water that active carbon is carried out repeated washing for several times earlier, adopt ultrasonic wave that active carbon was carried out ultrasonic cleaning 5-10 minute again, adopt the washed with de-ionized water active carbon for several times again, the clarification of water after cleaning obtains clean active carbon.Carry out drying then, described drying can adopt nature to dry or adopt oven for drying, and for example: the active carbon that cleans up is placed convection oven, and with 80-120 ℃ of baking 5-8h, the active carbon of dry back gained is labeled as active carbon CA-0.
In the prior art, active carbon adopts oxidants such as nitric acid, hydrogen peroxide, ozone that active carbon is carried out oxidation processes before carried metal usually, make activated carbon surface generate surface functional group, so that follow-up anchoring metallic particles, yet adopt above-mentioned oxidant magnesium oxide/absorbent charcoal, reach required effect, consuming time longer, and the adsorption effect of metallic particles on active carbon is not good enough, comes off easily.
In the present invention, get above-mentioned active carbon CA-0, adopt the aqueous solution soaking active carbon of an amount of certain density citric acid, preferably, adopting 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 soaking end, remove unnecessary citric acid, carry out drying then, described drying can adopt nature to dry or adopt oven for drying, for example: can earlier active carbon be dried naturally, and then place convection oven 80-120 ℃ of baking 5-12h, and the active carbon of dry back gained is labeled as active carbon CA-1, and this active carbon CA-1 has the active carbon of oxygen-containing functional group for the surface.
Though adopt existing oxidant, for example: the purpose of processing active carbon such as nitric acid, hydrogen peroxide and citric acid treatment active carbon all is to make activated carbon surface generate surface functional group, the position of metal nucleation is provided, but compared to existing oxidant, adopt citric acid that active carbon is handled, just can make activated carbon surface functionalized in short time, and citric acid treatment can make activated carbon surface produce more functional group, more be conducive to absorption and the anchoring of metal.
Preparation of catalysts method of the present invention adopts the lemon aqueous acid to handle active carbon before the aqueous solution Immesion active carbon that adopts cobalt salt earlier, make the oxygen-containing functional group of activated carbon surface increase, increased the application point between active carbon and the cobalt metallic particles, can be in the position of follow-up anchoring metallic cobalt on active carbon, increase the metallic cobalt particle at the decentralization of activated carbon surface, reduce the granularity of cobalt metallic particles on active carbon, effectively improve the catalytic activity of catalyst.
Step 2: will impregnated in the aqueous solution of cobalt salt through the active carbon that soaks, take out and drying after dipping is finished, carry out roasting then.
In this step, adopt infusion process that cobalt salt is impregnated on the active carbon, 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 the 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
2A kind of among the O, with the aqueous solution of the water-soluble formation cobalt salt of 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 an amount of active carbon CA-1 and CoCl
26H
2The aqueous solution of O, CA-1 impregnated in CoCl with active carbon
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 guarantee CoCl
26H
2The ratio of O and active carbon CA-1 satisfies 0.1-2.5mmol CoCl
26H
2The O:1g active carbon, dip time is 0.5-48h, after dipping finishes, remove unnecessary maceration extract, carry out drying then, described drying can adopt nature to dry or adopt oven for drying, for example: can earlier active carbon be dried naturally, and then place convection oven 50-120 ℃ of baking 5-12h, and the active carbon of dry back 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, described roasting can be adopted the common roasting apparatus in this area, for example: 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 ℃, and namely sintering temperature makes most of citric acid decompose more than the decomposition temperature of citric acid, reduces the pollution to the catalyst finished product.The sintering rotten possibility of while in order to reduce catalyst, sintering temperature also can not be too high, and in the preferred case, sintering temperature is controlled between 280-350 ℃, and roasting time is 8-16h.Calcination atmosphere is selected nitrogen atmosphere, under nitrogen atmosphere, citric acid decomposes when 150 ℃ of left and right sides, decompose even citric acid is most of during to 250 ℃. but temperature is crossed 600 ℃, citric acid still can not decompose under nitrogen atmosphere fully, and the residue after the decomposition (the heating citric acid does not decompose and the carbon deposit that produces fully) is still had an appointment 2wt%; And under air atmosphere, 460 ℃ of left and right sides citric acids decompose the carbon deposit complete oxidation combustion gas that the back produces, and do not have solid residue.Thereby the present invention selects nitrogen atmosphere to carry out roasting, under such atmosphere, an amount of citric acid and residue thereof (carbon distribution) contain more surface functional group, be conducive to the cobalt metal in dispersion and the anchoring of activated carbon surface, roasting makes the cobalt chloride of activated carbon surface be oxidized to cobalt oxide, the active carbon of gained is labeled as active carbon CA-3 after the roasting, and this active carbon CA-3 is the active carbon that surface distributed has cobalt oxide.
Step 3: will in reducing atmosphere, carry out reduction reaction through the active carbon of roasting, and obtain described catalyst.
Skilled in the art will recognize that, an important step in the noble metal load type active carbon Preparation of catalysts method 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 big, and LEL is less, therefore the manufacturing of reduction furnace is had relatively high expectations, this has just increased the manufacturing cost of catalyst, has namely increased the cost of equipment that dichloro hydrogen silicon is produced; And because the catalyst under the reducing condition can spontaneously react with airborne oxygen, therefore the unloading atmosphere to the catalyst after the reduction also has certain requirement, has increased the trouble in the catalyst preparation process.
In the present invention, described reduction activation step is carried out in for the preparation of the reactor of the dichloro hydrogen silicon catalytic bed of (or claiming the trichlorosilane disproportionation to prepare the pyrolysis furnace of dichloro hydrogen silicon).Described reduction reaction will place the catalytic bed of reactor through the active carbon of roasting, carry out reduction reaction in mixed-gas atmosphere, and described mist comprises reducing gas CO, H
2And inert gas N
2, described mist satisfies following condition: (CO+H
2): N
2=1:3-5, this is that the reduction of catalyst is more difficult because the shared volume ratio of inert gas is more big, for reduction in the suitable time generates the cobalt metal, control the addition of inert nitrogen gas; Simultaneously, because pure reducibility gas blasts easily, 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
2Reduction effect is best during the 2-4% of cumulative volume, reducibility gas CO and H
2Volume ratio to control well because CO is too much, the carbon distribution effect can take place, the interpolation of hydrogen can effectively reduce this carbon distribution effect, the experiment show that the volume ratio of mist satisfies above-mentioned condition, the reduction activation effect of catalyst is better.
In the present invention, the temperature of reduction reaction is 240-270 ℃, and this is that reduction temperature control 20 ℃ of left and right sides reduction effects more than critical reduction temperature are preferable because critical reduction temperature at 220-250 ℃, is tested to be confirmed, namely reduction temperature is at 240-270 ℃.And reduction reaction of the present invention adopts the method for segmented heating and heat preservation, and from the room temperature temperature programming to critical reduction temperature, heating rate is controlled at 0.5-5 ℃/min, after temperature rises to 150 ℃ by room temperature, and insulation 3-6h; After rising to 250 ℃ by 150 ℃, insulation 6-8h; After rising to 270 ℃ by 250 ℃, insulation 0.5-72h.In addition, in reduction process, high pressure more is conducive to the carrying out of reduction reaction, therefore, controls the pressure of mist in the pyrolysis furnace in the reduction process at 2-12bar.The temperature and pressure of above reduction activation reaction all satisfies operating temperature and the operating pressure of trichlorosilane pyrolysis furnace, thereby reduction reaction of the present invention can be carried out in the trichlorosilane disproportionation prepares the catalytic bed of pyrolysis furnace of dichloro hydrogen silicon.Obtain catalyst CA of the present invention through above-mentioned reduction reaction, described catalyst CA is the active carbon that area load has metallic cobalt simple substance, resulting catalyst results from the catalytic bed of trichlorosilane pyrolysis furnace, can be directly used in the trichlorosilane disproportionation and prepare dichloro hydrogen silicon.
As from the foregoing, reduction activation reactions steps of the present invention prepares catalyst directly carries out in catalytic bed, has saved the expense of reduction apparatus, and CO, H are adopted in the reduction activation reaction
2And N
2Mist, the adding of CO has improved the reducing power of metallic cobalt, has reduced by H
2The CH that generates during the reducing activity charcoal
4To the possibility of contamination of products, the adding of inert gas can suitably reduce the reduction rate of catalyst, the pressure when suitably improving reduction, thus can effectively 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 in the preparation facilities of dichloro hydrogen silicon, reduce, save equipment cost, reduce the unloading of catalyst and the number of times of loading, avoid the spontaneous oxidation of unloading back cobalt metal from reduction furnace, be conducive to large-scale production and the application of catalyst.
The present invention also provides a kind of catalyst that adopts above-mentioned preparation method to prepare, and comprises active carbon and the cobalt metal that is formed at described activated carbon surface.Cobalt metallic particles load on active carbon of catalyst of the present invention is firm, granularity is little and be evenly distributed, and has advantages of high catalytic activity.
The present invention also provides the preparation method of dichloro hydrogen silicon, and trichlorosilane and catalyst are joined the disproportionated reaction of carrying out trichlorosilane in the reactor, and reaction obtains dichloro hydrogen silicon after finishing; Described catalyst is made by preparation method of the present invention.
The preparation of dichloro hydrogen silicon adopts the 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 that makes 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 unloading back cobalt metal from reduction furnace.And the present invention adopts the metallic cobalt load type active carbon, can effectively improve reaction temperature and pressure that the trichlorosilane disproportionation prepares dichloro hydrogen silicon, can improve reaction temperature to 150-200 ℃, and pressure is increased to 0.6-0.8MPa.Skilled in the art will recognize that reaction temperature is up to 80 ℃ if adopt resin as catalyst, reaction pressure is up to 0.4MPa, because reaction temperature or hypertonia can make the resin inactivation.And adopting catalyst of the present invention, reaction temperature can be increased to 150-200 ℃, reaction pressure more can be increased to 0.6-0.8MPa, makes the production rate of dichloro hydrogen silicon to reach more than 12%.
The invention will be further elaborated below in conjunction with specific embodiment 1-5.
Embodiment 1
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing for several times, and the clarification of water after extremely washing, after drying naturally, 110 ℃ of baking 8h obtain active carbon CA1-0 in convection oven;
2, active carbon being soaked in 200ml concentration is 10h in the 1.0mol/L lemon aqueous acid, soak finish that the back is taken out and in convection oven 110 ℃ dry by the fire 8h, obtain active carbon CA1-1;
3, the CoCl of dipping cobalt salt: A, preparation 0.1mol/L
26H
2O solution 500ml, gets 20g active carbon CA1-1 at B, gets the CoCl of the above-mentioned preparation of 240ml
26H
2O solution is in the 500ml beaker, and CA1-1 puts into CoCl with active carbon
2In the 6H2O solution, leave standstill dipping 8h, after C, dipping finish, remove unnecessary maceration extract, after drying naturally, in convection oven, with 120 ℃ of dry 10h, obtain active carbon CA1-2;
4, roasting: with active carbon CA1-2 under nitrogen atmosphere with 280 ℃ temperature roasting 10h, obtain active carbon CA1-3;
5, reduction activation: get proper amount of active carbon CA1-3 and pack in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, and oxygen content is less than 0.3% in outlet tail gas; Feed CO+H then
2+ N
2Mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:3, CO accounts for (CO+H
2) cumulative volume 3%, reduction pressure is 5bar; Reduction reaction adopts the syllogic temperature programming, and heating rate is 5 ℃/min, rises to 150 ℃ by room temperature, insulation 4h is warming up to 250 ℃, insulation 7h by 150 ℃, be warming up to 270 ℃ by 250 ℃, insulation 12h obtains the catalyst CA1 of the embodiment of the invention 1 after reduction reaction finishes;
6, the preparation of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane enters catalytic bed, opens the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; The reaction condition that the trichlorosilane disproportionation prepares dichloro hydrogen silicon is: reaction temperature is 150 ℃, and reaction pressure is 0.6MPa.Behind every the stablizing, begin sampling and collect, (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 12.8% in product at chromatograph.
Embodiment 2
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing for several times, and the clarification of water after extremely washing, after drying naturally, 100 ℃ of baking 8h obtain active carbon CA2-0 in convection oven;
2, active carbon being soaked in 300ml concentration is 8h in the 1.2mol/L lemon aqueous acid, soak finish that the back is taken out and in convection oven 100 ℃ dry by the fire 8h, obtain active carbon CA2-1;
3, the CoCl of dipping cobalt salt: A, preparation 0.9mol/L
26H
2O solution 500ml, gets 20g active carbon CA2-1 at B, gets the CoCl of the above-mentioned preparation of 300ml
26H
2O solution is in the 500ml beaker, and CA2-1 puts into CoCl with active carbon
26H
2In the O solution, leave standstill dipping 20h, after C, dipping finish, remove unnecessary maceration extract, after drying naturally, in convection oven, with 100 ℃ of dry 8h, obtain active carbon CA2-2;
4, roasting: with active carbon CA2-2 under nitrogen atmosphere with 300 ℃ temperature roasting 12h, obtain active carbon CA2-3;
5, reduction activation: get proper amount of active carbon CA2-3 and pack in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, and oxygen content is less than 0.3% in outlet tail gas; Feed CO+H then
2+ N
2Mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:4, CO accounts for (CO+H
2) cumulative volume 2%, reduction pressure is 8bar; Reduction reaction adopts the syllogic temperature programming, and heating rate is 4 ℃/min, rises to 150 ℃ by room temperature, insulation 4h is warming up to 250 ℃, insulation 6h by 150 ℃, be warming up to 270 ℃ by 250 ℃, insulation 24h obtains the catalyst CA2 of the embodiment of the invention 2 after reduction reaction finishes;
6, the preparation of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane enters catalytic bed, opens the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; The reaction condition that the trichlorosilane disproportionation prepares dichloro hydrogen silicon is: reaction temperature is 160 ℃, and reaction pressure is 0.7MPa, 0.5L/min; Behind every the stablizing, begin sampling and collect, (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 12.8% in product at chromatograph.
Embodiment 3
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing for several times, and the clarification of water after extremely washing, after drying naturally, 120 ℃ of baking 5h obtain active carbon CA3-0 in convection oven;
2, active carbon being soaked in 200ml concentration is 12h in the 0.4mol/L lemon aqueous acid, soak finish that the back is taken out and in convection oven 120 ℃ dry by the fire 5h, obtain active carbon CA3-1;
3, the CoCl of dipping cobalt salt: A, preparation 0.5mol/L
26H
2O solution 500ml, gets 20g active carbon CA3-1 at B, gets the CoCl of the above-mentioned preparation of 300ml
26H
2O solution is in the 500ml beaker, and CA3-1 puts into CoCl with active carbon
26H
2In the O solution, leave standstill dipping 36h, after C, dipping finish, remove unnecessary maceration extract, after drying naturally, in convection oven, with 120 ℃ of dry 5h, obtain active carbon CA3-2;
4, roasting: with active carbon CA3-2 under nitrogen atmosphere with 320 ℃ temperature roasting 10h, obtain active carbon CA3-3;
5, reduction activation: get proper amount of active carbon CA3-3 and pack in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, and oxygen content is less than 0.3% in outlet tail gas; Feed CO+H then
2+ N
2Mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:5, CO accounts for (CO+H
2) cumulative volume 4%, reduction pressure is 10bar; Reduction reaction adopts the syllogic temperature programming, and heating rate is 5 ℃/min, rises to 150 ℃ by room temperature, insulation 5h is warming up to 250 ℃, insulation 7h by 150 ℃, be warming up to 270 ℃ by 250 ℃, insulation 20h obtains the catalyst CA3 of the embodiment of the invention 3 after reduction reaction finishes;
6, the preparation of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane enters catalytic bed, opens the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; The reaction condition that the trichlorosilane disproportionation prepares dichloro hydrogen silicon is: reaction temperature is 180 ℃, and reaction pressure is 0.8MPa, 0.5L/min; Behind every the stablizing, begin sampling and collect, (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 13.5% in product at chromatograph.
Embodiment 4
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing for several times, and the clarification of water after extremely washing, after drying naturally, 110 ℃ of baking 8h obtain active carbon CA4-0 in convection oven;
2, active carbon being soaked in 200ml concentration is 10h in the 1.0mol/L lemon aqueous acid, soak finish that the back is taken out and in convection oven 110 ℃ dry by the fire 8h, obtain active carbon CA4-1;
3, the Co (NO of dipping cobalt salt: A, preparation 0.1mol/L
3)
26H
2O solution 500ml, gets 20g active carbon CA1-1 at B, gets the Co (NO of the above-mentioned preparation of 240ml
3)
26H
2O solution is put into Co (NO with active carbon CA1-1 in the 500ml beaker
3)
26H
2In the O solution, leave standstill dipping 8h, after C, dipping finish, remove unnecessary maceration extract, after drying naturally, in convection oven, with 120 ℃ of dry 10h, obtain active carbon CA4-2;
4, roasting: with active carbon CA4-2 under nitrogen atmosphere with 280 ℃ temperature roasting 10h, obtain active carbon CA4-3;
5, reduction activation: get proper amount of active carbon CA4-3 and pack in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, and oxygen content is less than 0.3% in outlet tail gas; Feed CO+H then
2+ N
2Mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:3, CO accounts for (CO+H
2) cumulative volume 3%, reduction pressure is 5bar; Reduction reaction adopts the syllogic temperature programming, and heating rate is 5 ℃/min, rises to 150 ℃ by room temperature, insulation 4h is warming up to 250 ℃, insulation 7h by 150 ℃, be warming up to 270 ℃ by 250 ℃, insulation 12h obtains the catalyst CA4 of the embodiment of the invention 4 after reduction reaction finishes;
6, the preparation of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane enters catalytic bed, opens the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; The reaction condition that the trichlorosilane disproportionation prepares dichloro hydrogen silicon is: reaction temperature is 150 ℃, and reaction pressure is 0.6MPa.Behind every the stablizing, begin sampling and collect, (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 12.0% in product at chromatograph.
Embodiment 5
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing for several times, and the clarification of water after extremely washing, after drying naturally, 100 ℃ of baking 8h obtain active carbon CA5-0 in convection oven;
2, active carbon being soaked in 300ml concentration is 8h in the 1.2mol/L lemon aqueous acid, soak finish that the back is taken out and in convection oven 100 ℃ dry by the fire 8h, obtain active carbon CA2-1;
3, the C of dipping cobalt salt: A, preparation 0.9mol/L
4H
6O
4Co4H
2O solution 500ml, gets 20g active carbon CA5-1 at B, gets the C of the above-mentioned preparation of 300ml
4H
6O
4Co4H
2O solution is in the 500ml beaker, and CA2-1 puts into C with active carbon
4H
6O
4Co4H
2In the O solution, leave standstill dipping 20h, after C, dipping finish, remove unnecessary maceration extract, after drying naturally, in convection oven, with 100 ℃ of dry 8h, obtain active carbon CA2-2;
4, roasting: with active carbon CA5-2 under nitrogen atmosphere with 300 ℃ temperature roasting 12h, obtain active carbon CA5-3;
5, reduction activation: get proper amount of active carbon CA5-3 and pack in the catalytic bed of reactor, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, and oxygen content is less than 0.3% in outlet tail gas; Feed CO+H then
2+ N
2Mist carries out reduction reaction, wherein, and (CO+H
2): N
2=1:4, CO accounts for (CO+H
2) cumulative volume 2%, reduction pressure is 8bar; Reduction reaction adopts the syllogic temperature programming, and heating rate is 4 ℃/min, rises to 150 ℃ by room temperature, insulation 4h is warming up to 250 ℃, insulation 6h by 150 ℃, be warming up to 270 ℃ by 250 ℃, insulation 24h obtains the catalyst CA5 of the embodiment of the invention 5 after reduction reaction finishes;
6, the preparation of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane enters catalytic bed, opens the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; The reaction condition that the trichlorosilane disproportionation prepares dichloro hydrogen silicon is: reaction temperature is 160 ℃, and reaction pressure is 0.7MPa, 0.5L/min; Behind every the stablizing, begin sampling and collect, (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 12.4% in product at chromatograph.
Comparative Examples 1
Adopt existing macroporous weakly basic anion exchange resin (model is Amberlyst A-21) as Preparation of Catalyst dichloro hydrogen silicon, the preparation process of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane carries out catalytic bed, in catalytic bed, add Amberlyst A-21 simultaneously, open the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; Reaction condition is: reaction temperature is 80 ℃, and reaction pressure is 0.4MPa, behind every the stablizing, begins sampling and collects, and (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 6.5% in product at chromatograph.
Comparative Examples 2
1, the pre-treatment of active carbon: get active carbon 30g, with deionized water rinsing for several times, and the clarification of water after extremely washing, after drying naturally, 110 ℃ of baking 8h obtain active carbon DA1-0 in convection oven;
2, the CoCl of dipping cobalt salt: A, preparation 0.1mol/L
26H
2O solution 500ml, gets 20g active carbon DA1-0 at B, gets the CoCl of the above-mentioned preparation of 240ml
26H2O solution is in the 500ml beaker, and DA1-0 puts into CoCl with active carbon
2In the 6H2O solution, leave standstill dipping 8h, after C, dipping finish, remove unnecessary maceration extract, after drying naturally, in convection oven, with 120 ℃ of dry 10h, obtain active carbon DA1-1;
3, roasting: with active carbon DA1-1 under nitrogen atmosphere with 280 ℃ temperature roasting 10h, obtain active carbon DA1-2;
4, reduction activation: get proper amount of active carbon DA1-2 and pack in the reduction furnace, purge 4h with the nitrogen of heat, vacuum nitrogen is replaced repeatedly, and oxygen content is less than 0.3% in outlet tail gas; Feed H then
2Carry out reduction reaction, obtain the catalyst DA1 of Comparative Examples 1 of the present invention after reduction reaction finishes;
5, the preparation of dichloro hydrogen silicon: close the valve between evaporimeter and the catalytic bed earlier, open head tank valve and pneumatic control valve, beginning adds trichlorosilane in evaporimeter, when treating that pressure in the head tank reaches requirement, open the valve between evaporimeter and the catalytic bed, trichlorosilane enters catalytic bed, in catalytic bed, add catalyst DA1 simultaneously, open the tail gas valve, regulate each thermometric instrument, Pressure gauge is waited until predetermined value; The reaction condition that the trichlorosilane disproportionation prepares dichloro hydrogen silicon is: reaction temperature is 100 ℃, and reaction pressure is 0.2MPa, 0.5L/min.Behind every the stablizing, begin sampling and collect, (manufacturer is day island proper Tianjin, and model is: test GC2014), dichloro hydrogen silicon accounts for 8% in product at chromatograph.
Test result
From top embodiment 1-5 and Comparative Examples 1-2 as can be seen, the catalyst that the preparation method that embodiments of the invention 1-5 provides makes is significantly high compared to the catalytic efficiency of the catalyst of Comparative Examples 1-2; Adopt this Preparation of Catalyst dichloro hydrogen silicon, the productive rate of dichloro hydrogen silicon is reached more than 12%.
Those skilled in the art know easily; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace 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 (10)
1. the Preparation of catalysts method for the preparation of dichloro hydrogen silicon is characterized in that, comprises the steps:
Step 1: active carbon is soaked in the lemon aqueous acid, takes out and drying after immersion is finished;
Step 2: will impregnated in the aqueous solution of cobalt salt through the active carbon that soaks, take out and drying after dipping is finished, carry out roasting then;
Step 3: will carry out reduction reaction through the active carbon of roasting, and obtain described catalyst.
2. Preparation of catalysts method according to claim 1 is characterized in that, in step 1, adopting concentration is the aqueous solution soaking active carbon 2-12h of the citric acid of 0.2-1.5mol/L.
3. Preparation of catalysts method according to claim 1 is characterized in that, in step 2, adopts CoCl
26H
2The aqueous solution Immesion active carbon of O, dip time are 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 active carbon needs the CoCl of 0.1-2.5mmol
26H
2O.
4. Preparation of catalysts method 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 ℃, and roasting time is 8-16h.
5. Preparation of catalysts method according to claim 1 is characterized in that, in step 3, described reduction reaction is carried out in the catalytic bed for the preparation of the reactor of dichloro hydrogen silicon.
6. Preparation of catalysts method 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 1:3-5, CO accounts for reducing gas CO, H
2The 1-5% of cumulative volume.
7. Preparation of catalysts method according to claim 1, it is characterized in that, the temperature of described reduction reaction is 240-270 ℃, described reduction reaction adopts the method for segmented heating and heat preservation, temperature from the room temperature temperature programming to reduction reaction, heating rate control after temperature rises to 150 ℃ by room temperature, is incubated 3-6h at 0.5-5 ℃/min; After rising to 250 ℃ by 150 ℃, insulation 6-8h; After rising to 270 ℃ by 250 ℃, insulation 0.5-72h.
8. Preparation of catalysts method according to claim 1, it is characterized in that, in step 1, before active carbon being soaked in the lemon aqueous acid, earlier active carbon is carried out pre-treatment, described pre-treatment comprises adopts deionized water that active carbon is cleaned earlier, adopt ultrasonic wave that active carbon is carried out ultrasonic cleaning again, and then adopt deionized water that active carbon is cleaned, carry out drying at last.
9. the catalyst for the preparation of dichloro hydrogen silicon is characterized in that, described catalyst adopts and prepares as any described method of claim 1-8, comprises active carbon and the cobalt metal that is formed at described activated carbon surface.
10. the preparation method of a dichloro hydrogen silicon is characterized in that, trichlorosilane and catalyst are joined the disproportionated reaction of carrying out trichlorosilane in the reactor, and reaction obtains dichloro hydrogen silicon after finishing; Described catalyst is by making as any described preparation method of claim 1-8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467335A (en) * | 2013-09-22 | 2013-12-25 | 河南师范大学 | Method for synthesizing doxycycline hydrochloride intermediate alpha-6-deoxytetracycline based on hydrogenation of carbon-based rhodium catalyst |
| CN109088076A (en) * | 2018-07-13 | 2018-12-25 | 南京卡邦科技有限公司 | A kind of preparation method of non-precious metal catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63170209A (en) * | 1987-01-09 | 1988-07-14 | Osaka Titanium Seizo Kk | Disproportionating method for halogenated silane |
| JP2007268477A (en) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | Carbon monoxide reduction catalyst and its preparation method |
| 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 |
-
2012
- 2012-02-28 CN CN201210047067.1A patent/CN103285863B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63170209A (en) * | 1987-01-09 | 1988-07-14 | Osaka Titanium Seizo Kk | Disproportionating method for halogenated silane |
| JP2007268477A (en) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | Carbon monoxide reduction catalyst and its preparation method |
| 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 |
| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHEE KOK POHA，ET AL: ""Citric acid functionalized carbon materials for fuel cell applications"", 《JOURNAL OF POWER SOURCES》 * |
| ERMETE ANTOLINI: ""Carbon supports for low-temperature fuel cell catalysts"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 倪军，等: ""柠檬酸对Ru/AC氨合成催化剂结构和活性的影响"", 《物理化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467335A (en) * | 2013-09-22 | 2013-12-25 | 河南师范大学 | Method for synthesizing doxycycline hydrochloride intermediate alpha-6-deoxytetracycline based on hydrogenation of carbon-based rhodium catalyst |
| CN103467335B (en) * | 2013-09-22 | 2014-10-15 | 河南师范大学 | Method for synthesizing doxycycline hydrochloride intermediate alpha-6-deoxytetracycline based on hydrogenation of carbon-based rhodium catalyst |
| CN109088076A (en) * | 2018-07-13 | 2018-12-25 | 南京卡邦科技有限公司 | A kind of preparation method of non-precious metal catalyst |
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