阅读说明：本技术 用结构优化的硅颗粒生产三氯硅烷的方法 (Method for producing trichlorosilane with structurally optimized silicon particles ) 是由 K-H·里姆伯克 于 2019-04-29 设计创作，主要内容包括：本发明提供了一种在流化床反应器中生产通式1的氯硅烷的方法H-(n)SiCl-(4-n) (1),其中n为1至4,其中使包含氢气和四氯化硅的反应气体与含硅的颗粒接触物质在350℃-800℃的温度下反应,其中操作造粒颗粒理解为指引入该流化床反应器中的造粒颗粒或造粒颗粒混合物,其含有至少1质量％的由结构参数S描述的含硅颗粒S,其中S具有至少0的值并且如下计算： 其中,是对称加权球度因子ρ-(SD)是松装密度[g/cm～(3)]ρ-(F)是平均颗粒固体密度[g/cm～(3)]。(The invention provides a process H for producing chlorosilanes of the general formula 1 in a fluidized-bed reactor n SiCl 4‑n (1) Wherein n is 1 to 4, wherein a reaction gas comprising hydrogen and silicon tetrachloride is reacted with a silicon-containing particulate contact mass at a temperature of 350 ℃ to 800 ℃, wherein operating the prilled particles is understood as prilled particles or a mixture of prilled particles which contain at least 1 mass% of silicon-containing particles S described by the structural parameter S, wherein S has a value of at least 0 and is calculated as follows, which are directed into the fluidized bed reactor: wherein the content of the first and second substances, is a symmetrically weighted sphericity factor p SD Is apparent density [ g/cm ] 3 ]ρ F Is the average particle solid density [ g/cm 3 ]。)

1. Method for producing chlorosilanes of the general formula 1 in a fluidized bed reactor

H_nSiCl_4-n (1)，

Wherein n is a number from 1 to 3,

wherein a reaction gas comprising hydrogen and silicon tetrachloride is reacted with a silicon-containing particulate contact mass at a temperature of from 350 ℃ to 800 ℃, wherein operating the prilled particles is understood as prilled particles or a mixture of prilled particles which are directed into the fluidized bed reactor and which contain at least 1 mass% of silicon-containing particles S described by the structural parameter S, wherein S has a value of at least 0 and is calculated as follows:

wherein the content of the first and second substances,

is a symmetrically weighted sphericity factor

ρ_SDIs apparent density [ g/cm ]³]

ρ_FIs the average particle solid density [ g/cm³]。

2. The method of claim 1, wherein the symmetrically weighted sphericity factor of the particle SFrom 0.70 to 1, wherein the sphericity of the particle describes the ratio between the surface area and the perimeter of the image of the particle.

3. The method according to one or more of the preceding claims, wherein the particles having a structural parameter S ≧ 0 have an average particle solid density ρ_FIs 2.20 to 2.70g/cm³Wherein the determination is carried out in accordance with DIN 66137-2: 2019-03.

4. The process according to one or more of the preceding claims, wherein said operative granulated particles have a particle size parameter d comprised between 70 and 1500 μm₅₀Wherein the particle size parameters are determined according to DIN ISO 9276-2.

5. The process according to one or more of the preceding claims, wherein the reaction gas preferably comprises at least 10 volume% of hydrogen and silicon tetrachloride before entering the reactor.

6. The process of one or more of the preceding claims, wherein the molar ratio of hydrogen to silicon tetrachloride is from 1: 1 to 10: 1.

7. the process according to one or more of the preceding claims, wherein the chlorosilane of the general formula 1 produced is Trichlorosilane (TCS).

Examples

All examples used the same type of silicon in terms of purity, quality and content of minor elements and impurities. By crushing bulk Si_mg(98.9 mass% Si) and subsequent milling or generation of particulate Si by atomization techniques known to those skilled in the art_mg(98.9 mass% of Si), thereby producing a granule fraction for handling granulation granules. Optionally fractionating said fraction by sieving/screening. Thus producing in a targeted manner a particle fraction with certain values of the structural parameter S. A contact mass of silicon-containing particles having a defined mass fraction of a structural parameter S not less than 0 is subsequently blended by combining and mixing the particle fractions. The remaining particle fraction comprises silicon-containing particles having a structural parameter S of less than 0. These particle fractions were 100 mass%. Particle size parameter d of the granulated particles used in the experiment₅₀Is 330 and 350 μm. To ensure the greatest possible comparability between the individual experiments, no additional catalyst or promoter was added.

The following method was used in all examples. During the experiment, the operating temperature of the fluidized bed reactor was about 520 ℃. The temperature was kept approximately constant throughout the duration of the experiment using a heating device and heat exchanger. From H₂And STC (molar ratio 2.3: 1) were added in such a way that the height of the fluidized bed remained substantially constant throughout the experiment. The reactor was operated at a positive pressure of 1.5MPa throughout the experiment. Liquid and gas samples were taken at run times of 48h and 49h, respectively. The condensable proportion of the product gas stream (chlorosilane gas stream) was condensed at-40 ℃ using a cold trap and analyzed by Gas Chromatography (GC), from which the TCS selectivity and [ mass% ]weredetermined]. Detection is performed by a thermal conductivity detector. Furthermore, TCS selectively weighted production [ kg/(kg h)]I.e. the amount of granulated granules [ kg ] based on the operation used in the reactor, selectively weighted with TCS]The amount of chlorosilane produced per hour [ kg/h ]]Used as a basis. The values obtained after 48 and 49 hours were averaged in each case. After each run, the reactor was completely emptied and refilled with the granulation granules.

The contact materials used and the experimental results are summarized in table 1. ms is the mass fraction of particles with a structural parameter S > 0.

TABLE 1

Not according to the invention.