CN109718781B - Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention provides a catalyst for preparing trichlorosilane by hydrogenation of silicon tetrachloride and a preparation method thereof. The catalyst comprises silicon dioxide, aluminum oxide, an active component and an auxiliary agent component; based on the weight of the catalyst, the content of alumina is 10-20%, the content of silicon dioxide is 15-25%, the content of active components calculated by metal oxides is 55-75%, and the content of auxiliary components calculated by oxides is 0.5-2.0%. Adding an acidic solution into a silicon source for acidification treatment, and adding an active component, an auxiliary agent soluble salt, pseudo-boehmite, a curing agent and deionized water to prepare slurry; and (3) forming the slurry in a spray forming mode, and preparing the catalyst through post-treatment. The catalyst has good activity stability, mechanical strength and wear resistance, increases the impact and friction capacity of the catalyst with silicon powder in the use process of a fluidized bed, and avoids the phenomenon of 'running loss' in the use process of the catalyst.
Description
Technical Field
The invention relates to a hydrogenation catalyst and a preparation method thereof, in particular to a catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and a preparation method thereof.
Background
With the gradual exhaustion of fossil energy and the increasing aggravation of environmental pollution problems, it is urgent to search for a pollution-free renewable energy source. Solar energy is the most abundant renewable energy, and compared with other energy sources, the solar energy has the advantages of cleanliness, safety, universality, resource sufficiency, potential economy and the like. The solar energy is fully utilized, and the method has important economic and strategic significance for realizing sustainable development in a low-carbon mode.
In recent years, the yield of polycrystalline silicon is increased sharply, and the main production processes of polycrystalline silicon comprise an improved siemens method, a silane method and a fluidized bed method, wherein the improved siemens method is the mainstream technology for producing polycrystalline silicon at present, is the most mature, minimum investment risk and easiest expansion process for producing polycrystalline silicon, and the produced polycrystalline silicon accounts for 70-80% of the total world production. At present, the polysilicon factory of the Siemens process adopts the synthesis of silicon powder and hydrogen chloride to prepare trichlorosilane. In the synthesized product, trichlorosilane accounts for 80 percent, and silicon tetrachloride accounts for 20 percent. In the process of reducing trichlorosilane at 1100 ℃ and decomposing to generate high-purity polysilicon products, the by-product silicon tetrachloride per ton of the products is nearly 6 t. Therefore, the silicon tetrachloride of the byproduct of each ton of polysilicon product in a polysilicon plant adopting the Siemens process is about 10 t.
Silicon tetrachloride is a toxic and harmful gas, and if the toxic and harmful gas is discharged randomly without treatment, the silicon tetrachloride can be combined with water vapor in the atmosphere to generate hydrogen chloride gas, so that the environment is seriously polluted, in addition, the resource waste is also caused, and the production cost of enterprises is increased. How to safely treat silicon tetrachloride becomes a bottleneck restricting the development of polysilicon, and finding a way for effectively treating silicon tetrachloride is a problem to be solved urgently at present. The silicon tetrachloride is reasonably recycled, so that the environmental pollution is reduced, the production cost of enterprises is reduced, and the sustainable development of polycrystalline silicon production enterprises is facilitated.
The silicon tetrachloride recycling mainly has two directions, namely, silicon tetrachloride is used as a raw material to produce other chemical products, including fumed silica, organic silicon products, optical fiber production and the like; and secondly, the silicon tetrachloride is hydrogenated and converted into trichlorosilane in the production process of the polysilicon for recycling. The former has limited demand, can not consume a large amount of silicon tetrachloride as a byproduct, and research focuses on recycling the silicon tetrachloride. The silicon tetrachloride hydrogenation technology mainly comprises a thermal hydrogenation method, a cold hydrogenation method, a plasma hydrogenation method and a catalytic hydrogenation method. The thermal hydrogenation method is to hydrogenate the silicon tetrachloride to trichlorosilane at 1250 ℃, the product is easy to separate, but the reaction temperature is high, and the energy consumption is large; the cold hydrogenation method is to react silicon tetrachloride, silicon powder and hydrogen in a fluidized bed reactor at 400 ℃ to produce trichlorosilane, wherein the reaction temperature is relatively low, but the product is difficult to separate, the conversion rate is low, and the reactor is seriously abraded; the plasma hydrogenation method is carried out under the conditions of normal pressure and 3000 ℃, the highest conversion rate of the silicon tetrachloride can reach 74 percent, but the energy consumption is very high, and the industrialization is difficult to realize; the catalytic hydrogenation method is characterized in that a catalyst is added on the basis of a thermal hydrogenation process, namely, silicon powder, hydrogen and silicon tetrachloride are used as raw materials, and a mixture of trichlorosilane, dichlorosilane and the like is generated under the conditions of the existence of the catalyst and the reaction temperature of 500-550 ℃ and the reaction pressure of 2.0-3.0 MPa.
Because the catalytic hydrogenation of silicon tetrachloride is carried out at a relatively low reaction temperature and reaction pressure, and meanwhile, the product is easy to separate and maintains a high conversion rate, the method becomes an ideal way for recovering silicon tetrachloride, and therefore, the selection and preparation of a catalyst in the catalytic hydrogenation process of silicon tetrachloride are particularly important.
CN105536789A discloses a method for preparing a catalyst for trichlorosilane by hydrodechlorination of silicon tetrachloride. The method directly mixes the calcined amorphous silica-alumina powder with a certain amount of cuprous chloride, carries out high-temperature treatment in an inert atmosphere, and cools the product to obtain the finished catalyst. Although the preparation method is simple and low in preparation cost, the activity of the obtained catalyst is low.
CN102626630A and CN105967189A disclose a method for preparing a trichlorosilane catalyst by hydrogenating silicon tetrachloride. The method comprises the steps of contacting soluble nickel salt, soluble salt compounds of metal M, a silicon source capable of providing silicon dioxide and a precipitator capable of precipitating nickel and/or metal M ions in a solvent, filtering a product obtained by the contact, and drying and roasting the obtained solid in sequence to obtain the catalyst. Wherein M is selected from one or more of IB, IIB, IIA and a group VIII metal other than Ni. The catalyst prepared by the method is powdery, and is easy to run and damage when used in a fluidized bed, thereby causing the loss of the catalyst and the reduction of the activity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing trichlorosilane by hydrogenating silicon tetrachloride and a preparation method thereof. The catalyst prepared by the method has centralized particle size distribution, higher activity, active metal dispersibility and wear resistance, meets the requirement of preparing trichlorosilane by hydrogenating silicon tetrachloride of an industrial fluidized bed, and has higher activity and stability in the process of preparing trichlorosilane by hydrogenating silicon tetrachloride.
The invention provides a catalyst for preparing trichlorosilane by silicon tetrachloride hydrogenation, which comprises silicon dioxide, alumina, an active component and an auxiliary agent component, wherein the active component is a metal in a VIII group, and the auxiliary agent component is a metal M; based on the weight of the catalyst, the content of alumina is 10-20%, the content of silica is 14.5-25%, the content of active components is 55-75% calculated by oxides, the content of auxiliary components is 0.5-2.0% calculated by oxides of metal M, and the metal M is one or more of Cu, Fe, Mg, Cr and Ba.
The catalyst for preparing trichlorosilane by hydrogenating silicon tetrachloride provided by the invention is a bulk phase catalyst.
In the catalyst of the invention, the active component group VIII metal is Ni and/or Co, preferably Ni.
In the catalyst of the invention, M1 and M2 are preferably adopted as the auxiliary component metal M, wherein M1 is one or more of Cu, Mg and Fe, preferably one or more of Cu and Mg, and M2 is one or more of Cr and Ba, preferably Ba. The molar ratio of M1 to M2 calculated by oxides is 1: 10-10: 1, preferably 2: 1-8: 1.
the properties of the catalyst of the invention are as follows: specific surface area >50 m2A specific ratio of 60 to 120 m/g2(ii) in terms of/g. In the present invention, the specific surface area is measured by a low-temperature liquid nitrogen adsorption method.
The particle size distribution of the catalyst of the invention is as follows (in volume fraction): the content of particles with the particle size of less than 150mm is less than 10%, preferably less than 8%; 75-95%, preferably 80-92% of particles with the particle diameter of 150-500 mm, and less than 15%, preferably less than 12% of particles with the particle diameter of more than 500 mm. In the present invention, the particle size is measured using a laser particle sizer.
The attrition rate of the catalyst of the invention is < 2.0 wt.%, preferably < 1.5 wt.%. In the invention, the abrasion rate is measured by a fluidized abrasion strength tester.
The invention also provides a preparation method of the catalyst for preparing trichlorosilane by hydrogenating silicon tetrachloride, which comprises the following steps:
(1) adding an acidic solution into a silicon source for acidification treatment;
(2) respectively adding soluble salt containing metal of the VIII group, soluble salt containing metal M, pseudo-boehmite, a curing agent and deionized water into the material obtained in the step (1) to prepare slurry;
(3) carrying out spray forming on the slurry obtained in the step (2) to obtain spherical gel;
(4) and (4) washing, drying and roasting the spherical gel obtained in the step (3) to obtain the catalyst.
In the method of the present invention, the silicon source in step (1) is water glass and/or silica sol, and the mass content of the silicon source is 20% to 40%, preferably 25% to 35%, calculated by silica. The acid solution is one or more of nitric acid, formic acid, acetic acid and citric acid, preferably nitric acid, wherein the mass concentration of the nitric acid is 55-75%, preferably 60-65%. The pH value of the silicon source after acidification treatment is 1.0-4.0, preferably 2.5-3.5.
In the process of the present invention, the group VIII metal in step (2) is Ni and/or Co, preferably Ni. The soluble salt of the metal in the VIII group is selected from one or more of nitrate, sulfate and chloride, preferably nitrate. The metal M is one or more of Cu, Fe, Mg, Cr and Ba, preferably M1 and M2, wherein M1 is one or more of Cu, Fe and Mg, preferably one or more of Cu and Mg, and M2 is one or more of Cr and Ba, preferably Ba. The soluble salt of the metal M is one or more of nitrate and sulfate, preferably nitrate.
In the method, the dry basis weight of the pseudo-boehmite in the step (2) is more than 70 percent, and the pseudo-boehmite is converted into gamma-Al by high-temperature roasting2O3The latter properties are as follows: the pore volume is more than 0.95mL/g, the preferable pore volume is 0.95-1.2 mL/g, and the specific surface area is 330m2More than g, preferably the specific surface area is 330-400 m2(ii) in terms of/g. The curing agent is one or more of urea and organic ammonium salt. The organic ammonium salt is hexamethinetetrammonium. The molar ratio of the addition amount of the curing agent to the active metal and the auxiliary agent is 0.5: 1.0-1.2: 1.0, preferably 0.6: 1.0-1.0: 1.0; the silicon source in the slurry obtained in the step (2) is calculated by silicon dioxide and pseudo-boehmiteThe total mass of the active component and the auxiliary component calculated by alumina and calculated by oxide accounts for 25-45 percent of the total weight of the slurry, and the total mass is preferably 30-35 percent.
In the method of the present invention, the spray forming in the step (3) is pressure type spray forming. The spray forming is carried out in a spray forming tower, the diameter of a spray nozzle is 0.3-1.2 mm, preferably 0.6-1.0 mm, the spraying pressure is 0.5-1.5 MPa, the formed product sprayed out of the spray nozzle is in countercurrent contact with a hot gas medium, the temperature of the hot gas medium is 70-200 ℃, preferably 90-120 ℃, the gas medium adopts ammonia-containing gas, and can adopt air containing ammonia, wherein NH is3The volume fraction of (A) is 5% -10%.
In the method, the washing in the step (4) is to wash the spherical gel to be neutral by using deionized water; the drying conditions are as follows: drying at 80-200 ℃ for 4-10 hours, preferably at 100-150 ℃ for 6-8 hours; the roasting conditions are as follows: roasting at 500-900 ℃ for 3-8 hours, preferably at 550-700 ℃ for 3-5 hours.
Compared with the prior art, the invention has the following advantages:
1. the catalyst adopts the silicon-aluminum composite material as the carrier component, under the synergistic effect of the auxiliary agent, the active metal component and the carrier component, the mechanical strength and the wear resistance of the catalyst are improved, the dispersion degree of the active metal and the auxiliary agent component is further improved, the activity and the stability of the catalyst are obviously improved, the application of the catalyst in a fluidized bed process is facilitated, the impact and the friction capacity of the catalyst and silicon powder are increased, and the phenomenon of 'running loss' in the use process of the catalyst is avoided.
2. The catalyst of the invention preferably adopts two assistants of M1 and M2, so that the dispersion degree of active metals and the wear resistance of the catalyst are further improved by the synergistic effect of the two assistants, and the activity stability of the catalyst are further improved.
3. In the preparation method of the catalyst, a silicon source is firstly acidified, then an active component, an auxiliary component, pseudo-boehmite, a curing agent and water are added to form slurry, and a spray forming mode is adopted to enable the components to act synergistically, so that the prepared catalyst has good strength and large specific surface area, more reaction sites are provided for reactants, and the activity of the catalyst can be effectively improved.
4. In the preparation method of the catalyst, the spray forming adopts pressure forming and the ammonia-containing gas is in countercurrent contact with the formed product, so that the formed product is cured under the dual actions of external ammonia gas and internal curing agent pyrolysis to form spherical gel, and the catalyst not only has good and uniform spherical shape and good wear resistance, but also has good pore structure, is beneficial to the reaction of producing trichlorosilane by silicon tetrachloride hydrogenation, and has higher activity and stability.
5. The preparation method of the catalyst integrates the molding of the catalyst and the loading of the active metal, thereby shortening the preparation process of the catalyst.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but is not limited to the following examples.
Example 1
57.1g of water glass with the mass content of 35 percent calculated by silicon oxide is added into a preparation tank, a stirring device is started, a nitric acid solution with the mass concentration of 62 percent is slowly added to ensure that the pH value of the acidified water glass solution is 2.5, 266.7g of nickel nitrate hexahydrate, 1.82g of copper nitrate trihydrate, 1.0g of barium nitrate and 21.4g of pseudo-boehmite (the property is as follows, the pore volume is 0.985mL/g, the specific surface area is 363 m) are added into the preparation tank after uniform mixing272 percent of dry basis), 53.6 grams of curing agent urea and deionized water, wherein the total mass of the water glass in terms of silicon dioxide, the pseudo-boehmite in terms of aluminum oxide, the nickel nitrate in terms of nickel oxide, the copper nitrate in terms of copper oxide and the barium nitrate in terms of barium oxide in the obtained slurry accounts for 33 percent of the total weight of the slurry.
Spraying the slurry with certain fluidity in a spray forming tower, setting the diameter of a nozzle to be 0.8mm, the spraying pressure to be 1.0MPa, and making the formed product sprayed from the nozzle contact with hot ammonia-containing air in countercurrent at 100 deg.C and NH in the ammonia-containing air3In a volume fraction of7%, solidifying and shrinking the material to obtain spherical gel;
the obtained spherical gel is washed to be neutral by deionized water, dried for 8 hours at 130 ℃, and then roasted for 3 hours at 600 ℃ to obtain the catalyst A, the properties of the catalyst are shown in table 1, and the evaluation results of the catalyst are shown in table 2.
Example 2
The preparation process was as in example 1, and 53.6g of urea as a curing agent was changed to 124g of hexamethynyltetramine, 2.62g of copper nitrate trihydrate and 0.56g of barium nitrate were added to prepare catalyst B of the present invention, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 2.
Example 3
The procedure of preparation was as in example 1, the nozzle diameter was changed to 1.0mm, the drying temperature in the spray drying tower was 120 ℃, catalyst C of the present invention was prepared, the properties are shown in table 1, and the catalyst evaluation results are shown in table 2.
Example 4
The procedure of example 1 was repeated, except that nickel nitrate hexahydrate was changed to cobalt nitrate hexahydrate and the amount of water glass added was changed to 43.8g, to prepare catalyst D of the present invention, the properties of which are shown in Table 1 and the evaluation results of which are shown in Table 2.
Example 5
The procedure of example 1 was followed, except that magnesium nitrate hexahydrate was used instead of the added copper nitrate trihydrate, and the amount of pseudoboehmite added was 21.83g, to prepare catalyst E of the present invention, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 2.
Example 6
The preparation process was as in example 1, the calcination temperature of the catalyst was changed to 700 ℃, the amount of copper nitrate trihydrate was changed to 2.90g, and the amount of barium nitrate was changed to 0.39g, to prepare catalyst F of the present invention, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 2.
Example 7
The procedure is as in example 1 except that no auxiliary barium nitrate is added to prepare catalyst G of the present invention, the properties are shown in Table 1, and the evaluation results are shown in Table 2.
Example 8
The procedure is as in example 1, except that no copper nitrate adjuvant is added, catalyst H according to the invention is prepared, the properties are shown in Table 1, and the evaluation results are shown in Table 2.
Example 9
The procedure is as in example 1 except that the drying medium is hot air and no ammonia is present, giving catalyst I, the catalyst properties are shown in Table 1 and the catalyst evaluation results are shown in Table 2.
Comparative example 1
The procedure is as in example 1 except that pseudoboehmite is not added and is replaced by water glass to give comparative catalyst J, the catalyst properties are shown in Table 1 and the catalyst evaluation results are shown in Table 2.
Comparative example 2
The catalyst was prepared by the method of example 2 in CN105967189A to obtain comparative catalyst K, the catalyst properties are shown in table 1, and the catalyst evaluation results are shown in table 2. The preparation process comprises the following steps:
dissolving 42.5 kg of nickel chloride hexahydrate and 18 kg of copper nitrate trihydrate into deionized water to prepare 500L of solution, adding 80 kg of silica sol with the solid content of 20 weight percent into the mixed salt solution, uniformly mixing to obtain slurry, and adjusting the pH value of the slurry to be 5 by using a 5 weight percent sodium hydroxide aqueous solution; dissolving 40 kg of ammonium carbonate with 400L of deionized water to obtain an ammonium carbonate aqueous solution;
the slurry and an aqueous ammonium carbonate solution were put into a 2000-liter reaction kettle and brought into contact at a temperature of 80 ℃ with the pH adjusted to 7 with a 5wt% aqueous sodium hydroxide solution, and after 4 hours of contact, a solid was obtained by filtration, and after drying, the solid was calcined at 500 ℃ for 6 hours in a muffle furnace to obtain catalyst K.
TABLE 1 Properties of catalysts prepared in examples and comparative examples
| Catalyst numbering | A | B | C | D | E | F |
| Catalyst shape | Microspheres | Microspheres | Microspheres | Microspheres | Microspheres | Microspheres |
| Specific surface area, m2/g | 78.1 | 79.0 | 80.5 | 82.2 | 80.9 | 70.2 |
| Abrasion of catalyst, wt% | 0.85 | 0.85 | 0.80 | 0.84 | 0.79 | 0.81 |
| Catalyst composition in wt% | ||||||
| Al2O3 | 15.12 | 15.13 | 15.23 | 15.31 | 15.71 | 15.30 |
| SiO2 | 19.41 | 19.45 | 19.56 | 15.70 | 19.86 | 19.51 |
| NiO or CoO | 64.30 | 64.21 | 64.04 | 67.82 | 63.55 | 63.99 |
| M1 oxide | 0.61 | 0.86 | 0.60 | 0.60 | 0.29 | 0.96 |
| M2 oxide | 0.56 | 0.35 | 0.57 | 0.57 | 0.59 | 0.24 |
| Particle size distribution of% | ||||||
| <150μm | 2.8 | 3.0 | 1.6 | 3.1 | 2.6 | 2.7 |
| 150～500μm | 90.1 | 89.7 | 88.9 | 90.0 | 90.0 | 89.5 |
| >500μm | 7.1 | 7.3 | 9.5 | 6.9 | 7.4 | 7.8 |
TABLE 1 Properties of catalysts prepared in examples and comparative examples
| Catalyst numbering | G | H | I | J | K |
| Catalyst shape | Microspheres | Microspheres | Microspheres | Microspheres | Amorphous form |
| Specific surface area, m2/g | 77.0 | 77.3 | 66.1 | 33.5 | 31.4 |
| Abrasion of catalyst, wt% | 0.91 | 0.86 | 4.31 | 1.56 | 4.8 |
| Catalyst composition in wt% | |||||
| Al2O3 | 15.21 | 15.21 | 15.12 | 0 | 0 |
| SiO2 | 19.52 | 19.51 | 19.41 | 34.53 | 49.7 |
| NiO or CoO | 64.66 | 64.72 | 64.3 | 64.3 | 40.2 |
| M1Oxide compound | 0.61 | - | 0.61 | 0.61 | 10.1 |
| M2Oxide compound | - | 0.56 | 0.56 | 0.56 | - |
| Particle size distribution of% | |||||
| <150μm | 1.8 | 1.7 | 17.5 | 2.9 | - |
| 150～500μm | 88.6 | 88.5 | 79.3 | 89.9 | - |
| >500μm | 9.6 | 9.8 | 3.2 | 7.2 | - |
The catalyst activity evaluation was carried out by using a fixed bed evaluation apparatus, the catalyst was packed in an amount of 10g, the reaction pressure was 1.2MPa, and the reaction pressure was H2/SiCl4(molar ratio) 25, silicon powder/SiCl4(molar ratio) is 10, and gas hourly space velocity is 30000h-1The reaction temperatures were 400 ℃ and 450 ℃ respectively, and the evaluation results are shown in Table 2.
TABLE 2 evaluation results of catalyst Activity and stability
| Numbering | Conversion (400 ℃, 10 hours)% | Conversion (400 ℃, 150 hours)% | Conversion (450 ℃, 10 hours)% | Conversion (450 ℃, 150 hours)% |
| A | 28.6 | 28.3 | 36.9 | 36.6 |
| B | 28.9 | 28.7 | 37.3 | 37.2 |
| C | 27.8 | 27.4 | 36.2 | 35.7 |
| D | 28.3 | 27.8 | 36.8 | 36.3 |
| E | 27.9 | 27.5 | 36.1 | 35.8 |
| F | 28.8 | 28.5 | 36.8 | 36.7 |
| G | 27.3 | 26.6 | 36.0 | 35.3 |
| H | 27.0 | 26.5 | 35.8 | 35.2 |
| I | 26.1 | 20.6 | 32.8 | 28.3 |
| J | 22.1 | 21.0 | 31.3 | 30.2 |
| K | 22.5 | 21.2 | 31.5 | 29.9 |
Claims (28)
1. A catalyst for preparing trichlorosilane by silicon tetrachloride hydrogenation is characterized by comprising silicon dioxide, alumina, an active component and an auxiliary agent component, wherein the active component is a metal in a VIII group, and the auxiliary agent component is a metal M; based on the weight of the catalyst, the content of alumina is 10-20%, the content of silica is 14.5-25%, the content of active components is 55-75% calculated by VIII group metal oxides, the content of auxiliary components is 0.5-2.0% calculated by metal M oxides, and the metal M is one or more of Cu, Fe, Mg, Cr and Ba.
2. The catalyst of claim 1, wherein: the group VIII metal is Ni and/or Co.
3. The catalyst of claim 2, wherein: the group VIII metal is Ni.
4. The catalyst of claim 1, wherein: the auxiliary component metal M adopts M1 and M2, wherein M1 is one or more of Cu, Mg and Fe, and M2 is one or more of Cr and Ba; the molar ratio of M1 to M2 calculated by oxides is 1: 10-10: 1.
5. the catalyst of claim 4, wherein: the M1 is Cu and/or Mg, the M2 is Ba; the molar ratio of M1 to M2 calculated by oxides is 2: 1-8: 1.
6. the catalyst according to claim 1 or 4, wherein: the properties of the catalyst are as follows: specific surface area >50 m2/g。
7. The catalyst of claim 6, wherein: the specific surface area of the catalyst is 60-120 m2/g。
8. The catalyst according to claim 1 or 4, wherein: the particle size of the catalyst is distributed by volume fraction as follows: the content of particles with the particle size of less than 150mm is less than 10 percent; 75-95% of particles with the particle diameter of 150-500 mm and less than 15% of particles with the particle diameter of more than 500 mm.
9. The catalyst of claim 8, wherein: the particle size of the catalyst is distributed by volume fraction as follows: the content of particles with the particle size of less than 150mm is less than 8 percent; 80-92% of particles with the particle size of 150-500 mm, and less than 12% of particles with the particle size of more than 500 mm.
10. The catalyst according to claim 1 or 4, wherein: the attrition rate of the catalyst is less than 2.0 wt%.
11. The catalyst of claim 10, wherein: the attrition rate of the catalyst is less than 1.5 wt%.
12. The preparation method of the catalyst for preparing trichlorosilane through hydrogenation of silicon tetrachloride according to any one of claims 1 to 11, which comprises the following steps:
(1) adding an acidic solution into a silicon source for acidification treatment;
(2) respectively adding soluble salt containing metal of the VIII group, soluble salt containing metal M, pseudo-boehmite, a curing agent and deionized water into the material obtained in the step (1) to prepare slurry; the curing agent is one or more of urea and organic ammonium salt, and the organic ammonium salt is hexamethylene tetramine;
(3) carrying out spray forming on the slurry obtained in the step (2) to obtain spherical gel;
(4) and (4) washing, drying and roasting the spherical gel obtained in the step (3) to obtain the catalyst.
13. The method according to claim 12, wherein the silicon source in step (1) is water glass and/or silica sol, and the mass content of the silicon source is 20-40% in terms of silica; the acid solution is one or more of nitric acid, formic acid, acetic acid and citric acid.
14. The process according to claim 13, wherein the silicon source is 25 to 35% by mass in terms of silicon oxide; the acid solution is nitric acid, and the mass concentration of the nitric acid is 60-65%.
15. The method according to claim 12, wherein the silicon source has a pH of 1.0 to 4.0 after the acidification treatment in the step (1).
16. The method according to claim 15, wherein the silicon source has a pH of 2.5 to 3.5 after the acidification treatment in the step (1).
17. The method according to claim 12, wherein in the step (2), the group VIII metal is Ni and/or Co; the soluble salt of the metal in the VIII family is selected from one or more of nitrate, sulfate and chloride; the metal M is one or more of Cu, Fe, Mg, Cr and Ba; the soluble salt of the metal M is one or more of nitrate and sulfate.
18. The method according to claim 17, wherein in step (2) the group viii metal is Ni; the soluble salt of the group VIII metal is selected from nitrates; the soluble salt of the metal M is nitrate.
19. The method according to claim 12, wherein the pseudoboehmite of the step (2) has a dry weight of 70% or more and is converted into γ -Al by high-temperature calcination2O3The latter properties are as follows: the pore volume is more than 0.95mL/g, the specific surface area is 330m2More than g.
20. The method according to claim 19, wherein the pseudoboehmite of the step (2) is converted into γ -Al by high-temperature calcination2O3The latter properties are as follows: the pore volume is 0.95-1.2 mL/gThe specific surface area is 330 to 400m2/g。
21. The method according to claim 12, wherein the molar ratio of the curing agent added in the step (2) to the reactive metal and the auxiliary agent is 0.5: 1.0-1.2: 1.0.
22. the method according to claim 21, wherein the molar ratio of the curing agent added in the step (2) to the reactive metal and the auxiliary agent is 0.6: 1.0-1.0: 1.0.
23. the preparation method according to claim 12, wherein the total mass of the silicon source in the slurry obtained in the step (2) calculated as silica, the pseudo-boehmite calculated as alumina, the active component and the auxiliary component calculated as oxides accounts for 25-45% of the total weight of the slurry.
24. The method according to claim 23, wherein the slurry obtained in step (2) contains 30-35% by mass of silicon source (silica), pseudoboehmite (alumina), active component(s) and auxiliary component(s) in terms of oxide, based on the total weight of the slurry.
25. The production method according to claim 12, wherein the spray forming in the step (3) is pressure type spray forming; the spray forming is carried out in a spray forming tower, the diameter of a nozzle is 0.3-1.2 mm, the spraying pressure is 0.5-1.5 MPa, the formed product sprayed out of the nozzle is in countercurrent contact with a hot gas medium, the temperature of the hot gas medium is 70-200 ℃, the gas medium adopts ammonia-containing gas, wherein NH is3The volume fraction of (A) is 5% -10%.
26. The method according to claim 25, wherein the nozzle has a diameter of 0.6mm to 1.0mm, the temperature of the hot gas medium is 90 ℃ to 120 ℃, and the gas medium is air containing ammonia.
27. The method according to claim 12, wherein the washing in the step (4) is to wash the spherical gel with deionized water to neutrality; the drying conditions are as follows: drying for 4-10 hours at 80-200 ℃; the roasting conditions are as follows: roasting for 3-8 hours at 500-900 ℃.
28. The method according to claim 27, wherein in the step (4), the drying conditions are: drying for 6-8 hours at 100-150 ℃; the roasting conditions are as follows: roasting at 550-700 ℃ for 3-5 hours.
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