CN102909006B - Catalyst for catalytic hydrogenation of silicon tetrachloride and preparation method thereof - Google Patents
Catalyst for catalytic hydrogenation of silicon tetrachloride and preparation method thereof Download PDFInfo
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- CN102909006B CN102909006B CN201210437980.2A CN201210437980A CN102909006B CN 102909006 B CN102909006 B CN 102909006B CN 201210437980 A CN201210437980 A CN 201210437980A CN 102909006 B CN102909006 B CN 102909006B
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Abstract
The invention discloses silicon a catalyst for reaction of silicon tetrachloride and hydrogen to prepare trichlorosilane. Nanometer platinum particles are active constituents of the catalyst, and silicon dioxide is a carrier. By the catalyst, the time of reaction of the silicon tetrachloride and the hydrogen to prepare the trichlorosilane can be greatly shortened, a reaction condition becomes more temperate, the conversion rate of the silicon tetrachloride reaches 28 to 35 percent on the condition of temperature of 200 DEG C and pressure of 0.2MPa, so that the production cost and equipment investment on transforming trichlorosilane from the silicon tetrachloride and the hydrogen are greatly reduced.
Description
Technical field
The invention belongs to chemical catalysis field, be specifically related to a kind of Catalysts and its preparation method that is trichlorosilane by hydrogenation of silicon tetrachloride.
Background technology
At present, polysilicon is mainly produced by improved Siemens.But, being subject to course of reaction process technology limit, this method produces a large amount of silicon tetrachloride as by-product (1 ton of polysilicon of every production can produce the silicon tetrachloride of 15-18 ton) in producing polysilicon.As with 150,000 tons of calculating of the whole of China, can produce ten thousand tons of silicon tetrachlorides of 225-270.The huge bottleneck that has been processed into restriction whole world polysilicon enterprise development of the huge silicon tetrachloride of quantity.In addition, silicon tetrachloride is a kind of poisonous and harmful liquid, processes and discharge arbitrarily if do not added, silicon tetrachloride will be combined by the steam in atmosphere, produces hydrogen chloride gas, thereby environment is caused to severe contamination, also cause the significant wastage of resource, strengthened the production cost of enterprise.Rationally recycle silicon tetrachloride, in reducing environmental pollution, greatly reduce the production cost of enterprise, be conducive to the sustainable development of production of polysilicon enterprise.
The best method of polysilicon business processes silicon tetrachloride is that silicon tetrachloride and hydrogen are converted into trichlorosilane under catalyst action, this process can not only make silicon tetrachloride effectively be processed, trichlorosilane and hydrogen chloride as production of polysilicon raw material have been obtained simultaneously, the secondary pollution of having avoided processing silicon chloride to bring, the green closed cycle that also makes polysilicon enterprise realize truly is simultaneously produced.
Course of reaction based on hot hydrogenation technology and mechanism, German goldschmidt chemical corporation has been developed a kind of new silicon tetrachloride catalytic hydrogenating reduction technique.In this technique, adopt a kind in the chloride calcium chloride, strontium chloride, barium chloride of in II main group alkaline earth elements ca, strontium, barium a kind and they, be mixed and made into catalyst activity component, with low aluminium zeolite, alkali-free glass, vitreous silica, active carbon or porous SiO
2prepare loaded catalyst as carrier.This catalyst has low conversion rate (below 23%), and catalyst preparation is complicated, and reaction temperature and pressure is the shortcoming such as higher (temperature is more than 500 DEG C, more than pressure 2.0MPa) still.
Summary of the invention
The object of the present invention is to provide that a kind of conversion ratio is high, reaction condition is gentle for silicon tetrachloride catalytic hydrogenation being become to the catalyst of trichlorosilane.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst.
It is as follows that the present invention realizes the technical scheme that above-mentioned purpose adopts:
A catalyst for catalytic hydrogenation silicon tetrachloride, the active component of this catalyst is nanometer platinum grain, carrier is silica.
Further, the particle diameter of described nanometer platinum grain is 3-10nm.
Further, described silica is spherical particle.
Further, the particle diameter of the spherical particle of described silica is 200-800nm.
Prepare the method for the catalyst of above-mentioned catalytic hydrogenation silicon tetrachloride: silica supports is scattered in water, add again chloroplatinic acid or chloroplatinate, react more than 10 hours existing under isopropyl alcohol and illumination condition, after separating, wash, being dried, at temperature 500-550 DEG C, calcining obtains described catalyst again.
Further, every 1g chloroplatinic acid or chloroplatinate use the isopropyl alcohol of 9-11ml.
Further, light application time is 10-20 hour.
Further, light application time is 10-15 hour.
Further, described silica supports is to obtain as follows: be 30-50 DEG C to mix with tetraethyl orthosilicate ethanolic solution in temperature by ammoniacal liquor alcohol mixeding liquid, product is through separating, wash, be drying to obtain silica supports, in described ammoniacal liquor alcohol mixeding liquid, the mol ratio of ammonia and ethanol is 1:(5-8), the volume ratio of described tetraethyl orthosilicate ethanolic solution mesosilicic acid tetra-ethyl ester and ethanol is 1:(5-10).
Further, the volume ratio of ammoniacal liquor alcohol mixeding liquid and tetraethyl orthosilicate ethanolic solution is (2-3): 1.
On silica supports, the load capacity of nanometer platinum grain can regulate by the consumption or the light application time that regulate chloroplatinic acid or chloroplatinate, light application time is longer, it is more complete that chloroplatinic acid or chloroplatinate decompose, usually, the silica supports of every 100g adds chloroplatinic acid or the chloroplatinate of 1-20g, and in the catalyst that makes finally to make, the mass percent of nanometer platinum grain reaches 0.5-5%.
Preferably, the silica supports of every 100g adds chloroplatinic acid or the chloroplatinate of 7-15g.
More preferably, the silica supports of every 100g adds chloroplatinic acid or the chloroplatinate of 10-12g.
Catalyst of the present invention is carried on Platinum Nanoparticles on silicon dioxide microsphere, make Platinum Nanoparticles keep good dispersiveness, improve the catalytic activity of platinum, this catalyst can shorten the time of silicon tetrachloride and hydrogen reaction generation trichlorosilane greatly, make that reaction condition is more gentle (compares existing reaction condition: temperature is more than 500 DEG C, more than pressure 2.0MPa), under 200 DEG C and 0.2MPa condition, the conversion ratio of silicon tetrachloride reaches 28-35%, is that production cost and the equipment investment of trichlorosilane greatly reduces thereby make silicon tetrachloride hydro-conversion.
Brief description of the drawings
Fig. 1 particle diameter is the SiO of 200nm
2transmission electron microscope (TEM) figure of carrier.
Fig. 2 is the HRTEM figure of catalyst.
Fig. 3 particle diameter is the SiO of 400nm
2the TEM figure of carrier.
Fig. 4 particle diameter is the SiO of 800nm
2the TEM figure of carrier.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 5:1, stir 10 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 5:1, and solution is mixed, after reacting completely in 30 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 200nm, as shown in Figure 1;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 3.2 g potassium chloroplatinates and 30ml isopropyl alcohol, illumination 10 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 500 DEG C of calcinings 1 hour, obtain catalyst, be designated as 1#, Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) figure of gained catalyst, from intergranular apart from finding out that silica surface load has platinum, nanoparticle platinum size is generally 3～10nm.
Embodiment 2
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 3.2 g chloroplatinic acids and 35 ml isopropyl alcohols, illumination 12 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 520 DEG C of calcinings 1.5 hours, obtains catalyst, be designated as 2#.
Embodiment 3
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 8:1, stir 15 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 10:1, and solution is mixed, after reacting completely in 50 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 800nm, as shown in Figure 4;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 3.2 g chloroplatinic acids and 35 ml isopropyl alcohols, illumination 15 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 550 DEG C of calcinings 2 hours, obtains catalyst, be designated as 3#.
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Embodiment 4
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 0.3g potassium chloroplatinate and 3 ml isopropyl alcohols, illumination 12 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 500 DEG C of calcinings 1 hour, obtains catalyst, be designated as 4#.
Embodiment 5
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 2.1g chloroplatinic acid and 25 ml isopropyl alcohols, illumination 12 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 520 DEG C of calcinings 1.5 hours, obtains catalyst, be designated as 5#.
Embodiment 6
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 4.5 g chloroplatinic acids and 45 ml isopropyl alcohols, illumination 12 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 550 DEG C of calcinings 2 hours, obtains catalyst, be designated as 6#.
Embodiment 7
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 6 g chloroplatinic acids and 61 ml isopropyl alcohols, illumination 12 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 550 DEG C of calcinings 2 hours, obtains catalyst, be designated as 7#.
Embodiment 8
Adding mol ratio is absolute ethyl alcohol and the ammoniacal liquor mixed solution 500ml altogether of 6:1, stir 12 min, solution is mixed, and then adding volume ratio is absolute ethyl alcohol and the tetraethyl orthosilicate 250 ml mixed solutions of 8:1, and solution is mixed, after reacting completely in 40 DEG C of waters bath with thermostatic control, centrifugation goes out silica white powder, then with absolute ethyl alcohol cyclic washing until solution is neutral, centrifugation goes out silica white powder, at 180 DEG C, be dried 180 minutes, obtain SiO
2white powder, gained SiO
2be spherical, particle diameter is 400nm, as shown in Figure 3;
Silica white powder 30 g of preparation are dispersed in 1000 ml high purity waters, add 3 g chlorine platinum sodium and 31 ml isopropyl alcohols, illumination 12 hours under high voltage mercury lamp radiation, then centrifugation, washing, dry, obtain grey black pressed powder, then this grey black pressed powder is placed on to 550 DEG C of calcinings 2 hours, obtains catalyst, be designated as 8#.
Get respectively 1#, 2#, 3#, 4#, 5#, 6#, 7#, 8# catalyst 100 g are dispersed in 1500 ml water, are 20 mm an internal diameter, external diameter is 24mm, and length is that the stainless-steel pipe of 1 m is immersed in the water of above-mentioned 1500 ml that are dispersed with 100 g catalyst, slowly rolls, after 30 minutes, take out, dry, then submergence, dry again, the tubular reactor that repeatedly can obtain being equipped with catalyst for three times like this.Then regulating the mol ratio of hydrogen and silicon tetrachloride is 6:1, and the temperature that regulates this tubular reactor is 200 DEG C, and pressure is 0.2MPa, obtains table 1
The conversion ratio of shown silicon tetrachloride.
Table 1
。
Adopting as can be seen from Table 1 100g particle diameter is the SiO of 200-800nm spherical particle
2carrier, the converting silicon tetrachloride rate obtaining with 10-12g chloroplatinic acid or chloroplatinate effect (being 1#, 2#, 3# test) is the highest.
Claims (8)
1. a catalyst for catalytic hydrogenation silicon tetrachloride, is characterized in that: the active component of described catalyst is nanometer platinum grain, and carrier is silica, wherein,
Described silica is spherical particle, and the particle diameter of the spherical particle of described silica is 200-800nm;
The particle diameter of described nanometer platinum grain is 3-10nm;
In described catalyst, the mass percent of nanometer platinum grain is 0.5-5%.
2. the preparation method of the catalyst of catalytic hydrogenation silicon tetrachloride described in preparation claim 1, it is characterized in that: silica supports is scattered in water, add again chloroplatinic acid or chloroplatinate, react more than 10 hours existing under isopropyl alcohol and illumination condition, after separating, wash, being dried, at temperature 500-550 DEG C, calcining obtains described catalyst again.
3. preparation method according to claim 2, is characterized in that: every 1g chloroplatinic acid or chloroplatinate use the isopropyl alcohol of 9-11ml.
4. preparation method according to claim 2, it is characterized in that, described silica supports is to obtain as follows: be 30-50 DEG C to mix with the ethanolic solution of tetraethyl orthosilicate in temperature by ammoniacal liquor alcohol mixeding liquid, product is through separating, wash, be drying to obtain silica supports, in described ammoniacal liquor alcohol mixeding liquid, the mol ratio of ammonia and ethanol is 1:(5-8), the volume ratio of described tetraethyl orthosilicate ethanolic solution mesosilicic acid tetra-ethyl ester and ethanol is 1:(5-10).
5. preparation method according to claim 4, is characterized in that: the volume ratio of ammoniacal liquor alcohol mixeding liquid and tetraethyl orthosilicate ethanolic solution is (2-3): 1.
6. the preparation method of the catalyst of catalytic hydrogenation silicon tetrachloride according to claim 2, is characterized in that: every 100g silica supports adds 1-20g chloroplatinic acid or chloroplatinate.
7. the preparation method of the catalyst of catalytic hydrogenation silicon tetrachloride according to claim 6, is characterized in that: every 100g silica supports adds 7-15g chloroplatinic acid or chloroplatinate.
8. the preparation method of the catalyst of catalytic hydrogenation silicon tetrachloride according to claim 7, is characterized in that: every 100g silica supports adds 10-12g chloroplatinic acid or chloroplatinate.
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| CN106276917A (en) * | 2015-05-28 | 2017-01-04 | 内蒙古盾安光伏科技有限公司 | polysilicon production process and system |
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| CN108439413B (en) * | 2018-05-16 | 2019-10-25 | 亚洲硅业（青海）有限公司 | A kind of method for hydrogenation of silicon tetrachloride |
| CN109957104A (en) * | 2019-04-03 | 2019-07-02 | 杭州硅途新材料科技有限公司 | A method of using the modified trisiloxanes of solid-borne platinum catalyst synthesizing polyether |
| CN112007634B (en) * | 2019-05-28 | 2023-08-29 | 新特能源股份有限公司 | Novel vinyl trichlorosilane catalyst, preparation method thereof and method for preparing vinyl trichlorosilane by catalysis of novel vinyl trichlorosilane catalyst |
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| CN101816946A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Preparation method and application of catalyst used in hydrogenation of silicon tetrachloride |
| CN102633263A (en) * | 2012-04-11 | 2012-08-15 | 洛阳晶辉新能源科技有限公司 | Method for preparing trichlorosilane by hydrogenating silicon tetrachloride |
| CN102838120A (en) * | 2012-09-18 | 2012-12-26 | 特变电工新疆硅业有限公司 | Method for catalyzing and hydrogenating silicon tetrachloride by using nano platinum |
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| CN102198929B (en) * | 2010-03-22 | 2013-05-01 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof |
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| CN101816946A (en) * | 2009-02-27 | 2010-09-01 | 比亚迪股份有限公司 | Preparation method and application of catalyst used in hydrogenation of silicon tetrachloride |
| CN102633263A (en) * | 2012-04-11 | 2012-08-15 | 洛阳晶辉新能源科技有限公司 | Method for preparing trichlorosilane by hydrogenating silicon tetrachloride |
| CN102838120A (en) * | 2012-09-18 | 2012-12-26 | 特变电工新疆硅业有限公司 | Method for catalyzing and hydrogenating silicon tetrachloride by using nano platinum |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106276917A (en) * | 2015-05-28 | 2017-01-04 | 内蒙古盾安光伏科技有限公司 | polysilicon production process and system |
| CN106276917B (en) * | 2015-05-28 | 2019-01-22 | 内蒙古盾安光伏科技有限公司 | Polysilicon production process and system |
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