Synthesis method for co-production of disilane and trisilane

Abstract

The invention relates to the field of silane gas synthesis, in particular to a synthesis method for co-production of disilane and trisilane. The specific operation is as follows: monosilane is introduced into a metal pipeline reactor filled with a catalyst, a catalytic reaction is performed at the temperature of 450-550 DEG C and the pressure of 0.1-2 MPa to prepare a mixture of crude disilane and monosilane, and then the mixture enters an adsorption tower to collect disilane and trisilane with the purity greater than 99%. According to the method, the metal pipeline is used as a reactor, silane is pyrolyzed into SiH3 free radicals and H free radicals by regulating and controlling the temperature and ensuring the pressure and catalyst conditions, and the SiH3 free radicals and the H free radicals are mutually combined to form disilane and trisilane, so that the selectivity of the product is remarkably improved, and the purity of the collected product reaches 99% or above.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of silane gas synthesis, in particular to a method for synthesizing ethylsilane and propylsilane co-production. BACKGROUND

[0002] In the rapidly developing field of electronic information materials, the application of special electronic gases is particularly important. Among them, silicon-containing electronic gases occupy a crucial position in the manufacturing process of electronic information materials due to their unique chemical properties.

[0003] Ethylsilane is an inorganic compound with the chemical formula Si2H6. It is an important inorganic silicon compound with a wide range of applications. It plays an important role in the photovoltaic industry, semiconductor industry, surface coating, medical field, etc. In semiconductors, it can be used to prepare precursor materials for silicon, which can be converted into polycrystalline silicon and single-crystal silicon through chemical vapor deposition for the manufacture of semiconductor devices. By controlling the reaction conditions and adding appropriate dopants, the doping of silicon materials can be achieved, thereby changing the electrical properties.

[0004] Propylsilane is an inorganic compound with the chemical formula Si3H8. It is mainly used in the manufacture of semiconductor silicon thin films, amorphous silicon, and semiconductor silicon thin films and nanowires. It is an excellent special electronic gas

[0005] Currently, there are problems such as harsh reaction conditions, low yield, or low purity of products in the synthesis of ethylsilane and propylsilane. For example, Chinese Patent No. CN106672979A discloses a device and method for continuous preparation of methylsilane and ethylsilane by magnesium silicide method. The target product is collected by reacting magnesium silicide with ammonium chloride in liquid ammonia to generate a mixture of methylsilane and ethylsilane, and using condensation separation technology. This technology realizes continuous production, but has significant defects: the reaction product is mainly methylsilane and does not mention the generation of propylsilane; the separation of by-product magnesium chloride and liquid ammonia relies on a complex filtration system, which is prone to pipe blockage and increases energy consumption; it cannot realize the directional co-production of ethylsilane and propylsilane, limiting its application in the high-end electronic gas market. Chinese Patent No. CN112647085B discloses a method for electrocatalytic synthesis of high-purity ethylsilane, which proposes to use methylsilane as raw material to co-produce ethylsilane and propylsilane in a fixed bed reactor through electrocatalytic reaction, and collect the target components by fractional condensation of the reaction products. However, the reaction requires multi-stage condensation and adsorption purification, the process is long, and due to high temperature and high pressure, the yield of ethylsilane fluctuates greatly.

[0006] In summary, a new and efficient method for co-producing ethylsilane and propylsilane is urgently needed. SUMMARY

[0007] In view of the problems of harsh reaction conditions, low yield or low product purity in the synthesis method of ethylsilane and propylsilane in the prior art, the application provides a novel and efficient synthesis method of ethylsilane and propylsilane.

[0008] The technical scheme of the application is as follows:

[0009] The synthesis method of ethylsilane and propylsilane comprises the following steps: passing methylsilane into a metal pipeline reactor provided with a catalyst, and preparing a mixture of crude ethylsilane and methylsilane under the catalytic reaction conditions of a temperature of 450-550 DEG C and a pressure of 0.1-2 MPa, and then collecting ethylsilane and propylsilane with a purity of greater than 99% in an adsorption tower.

[0010] Preferably, the catalyst is a ruthenium-nickel co-supported catalyst, and the molar ratio of ruthenium to nickel is (2-3):1.

[0011] Preferably, the ruthenium-nickel co-supported catalyst has a Y-type zeolite as a carrier, and the specific preparation method is as follows:

[0012] Step S1. calcining the Y-type zeolite at 600 DEG C for 4 hours,

[0013] Step S2. adding the calcined Y-type zeolite into a mixed solution of RuCl3 and Ni(NO3)2, stirring uniformly, ultrasonic treatment for 30 min, and finally centrifuging, washing and drying to obtain the ruthenium-nickel co-supported catalyst.

[0014] Preferably, the concentration of the RuCl3 solution is 0.1 mol / L, the concentration of the Ni(NO3)2 solution is 0.2 mol / L, and the mass ratio of the Y-type zeolite to the mixed solution is 1:50.

[0015] Preferably, the addition amount of the catalyst is half of the volume of the metal pipeline reactor, and the reaction time is 15-120 s.

[0016] Preferably, the metal pipeline reactor is made of 316 stainless steel, hastelloy, titanium alloy, monel or manganese cadmium alloy.

[0017] Preferably, the adsorption tower is divided into a primary adsorption tower and a secondary adsorption tower.

[0018] Preferably, the primary adsorption tower is filled with activated carbon loaded with ZnCl2 and MgCl2, the specific surface area of which is greater than or equal to 1200 m 2 / g, the Cl- loading amount is 15 wt%, the mass ratio of ZnCl2 to MgCl2 is 1:1, the adsorption temperature is 25-30 DEG C, and the pressure is 0.8-1 MPa.

[0019] Preferably, the secondary adsorption tower is filled with silver ion exchanged 5A molecular sieve, wherein the exchange degree of silver ions is ≥80%; the adsorption temperature is -40 to -20℃, and the pressure is 0.5 to 1 MPa.

[0020] Preferably, the amount of silane introduced is stopped when the pressure of the reactor reaches -4.0 MPa.

[0021] The beneficial effects of the present application are as follows:

[0022] The present application adjusts the temperature to ensure that, under the conditions of pressure and ruthenium-nickel co-supported catalyst, silane is pyrolyzed into SiH3 free radicals and H free radicals, which combine into disilane and trisilane, thereby improving the selectivity of the products, making the purity of the collected products reach more than 99%, and the maximum yield of disilane can reach 74.85%, and the maximum yield of trisilane can reach 18.84%.

[0023] The reaction equipment of the present application is a metal pipeline, which improves the durability and safety of the reaction equipment, and the metal pipeline has good chemical stability and mechanical strength, effectively preventing leakage and safety accidents during the reaction; in addition, the silane produced by the present application can be recycled. DETAILED DESCRIPTION

[0024] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined purposes, the following preferred embodiments will be described in detail with respect to the specific implementation, structure, features and effects of the present application.

[0025] Embodiment 1

[0026] The present embodiment provides a method for synthesizing disilane and trisilane in combination, which specifically comprises the following steps:

[0027] I. Before passing silane gas, the catalyst is loaded into a 316 stainless steel metal pipeline reactor, and the loading amount of the catalyst is half of the volume of the metal pipeline reactor. After loading the catalyst (the catalyst is a nickel-based catalyst, which is a supported catalyst, the carrier is a zeolite ring, and the loading amount is 20%), a pressure maintaining experiment is performed for 48 hours. After the pressure maintaining experiment is completed, helium gas is introduced into the reactor, and the passing time of the helium gas is 25 minutes. The passing of the helium gas for 25 minutes can completely remove impurity gases such as O2 and H2O in the reactor, thereby avoiding catalyst poisoning.

[0028] The preparation method of the ruthenium-nickel co-supported catalyst is as follows: the molar ratio of ruthenium to nickel is (2-3):1.

[0029] The Y-type zeolite is calcined in a muffle furnace. After the muffle furnace is heated to 600℃, it is calcined for 4 hours, and finally cooled to 50℃. Then it is taken out and prepared for use.

[0030] The calcined Y-type zeolite was added to a mixture of RuCl3 (0.1 mol / L) solution and Ni(NO3)2 (0.2 mol / L) solution, and the molar ratio of ruthenium to nickel was controlled at 2:1. The mixture was stirred evenly, ultrasonically treated for 30 min, and finally centrifuged, washed and dried to obtain the ruthenium-nickel co-supported catalyst. The mass ratio of Y-type zeolite to the mixture was 1:50.

[0031] II. After completing the above preparatory experiments, the reactor temperature was heated to 500℃. Then, silane gas was introduced into the reactor until the pressure reached -4.0 MPa. The introduction of silane was then stopped, and a catalytic reaction was carried out at a pressure of 2 MPa for 30 seconds to prepare a mixture of crude silane and silane.

[0032] 3. The mixture of crude silane and silane prepared is transported to the primary adsorption tower via pipeline.

[0033] The primary adsorption tower is filled with activated carbon-supported ZnCl2 and MgCl2, with a specific surface area ≥1200 m². 2 / g, Cl - The loading was 15 wt%, with a ZnCl2 to MgCl2 mass ratio of 1:1, the adsorption temperature was 25℃, and the pressure was 1 MPa.

[0034] The secondary adsorption tower is filled with silver ion exchange 5A molecular sieve, in which the silver ion exchange degree is ≥80%, the adsorption temperature is -30℃, and the pressure is 0.5MPa.

[0035] After testing, the purity of both silane and propane was found to be greater than 99%, and the content of each component in the product is shown in Table 1 below.

[0036] Table 1

[0037] Component Methylsilane Disilane Propylsilane Content 6.85％ 74.85％ 18.30％

[0038] Example 2

[0039] This embodiment provides a method for the co-production of silane and propane, specifically including the following steps:

[0040] 1. Before passing silane gas, the catalyst is loaded into the metal pipe reactor with Hastelloy. The amount of catalyst loaded is half the volume of the metal pipe reactor. After loading the catalyst (zinc oxide), a pressure holding test is carried out for 48 hours. After the pressure holding is completed, helium gas is introduced into the reactor for 25 minutes. The helium gas is introduced for 25 minutes to completely remove impurities such as O2 and H2O in the reactor and avoid catalyst poisoning.

[0041] The preparation method of the ruthenium-nickel co-supported catalyst is as follows: the molar ratio of ruthenium to nickel is (2~3):1.

[0042] The Y zeolite was calcined in a muffle furnace, the muffle furnace was heated to 600℃ for 4 hours, and finally cooled to 50℃, and then taken out for standby use.

[0043] The calcined Y zeolite was added into a mixed solution of RuCl3(concentration of 0.1 mol / L) and Ni(NO3)2(concentration of 0.2 mol / L), the molar ratio of ruthenium to nickel was controlled to be 3:1, stirred uniformly, ultrasonically treated for 30 min, and finally centrifuged, washed and dried to obtain a ruthenium-nickel co-loaded catalyst, the mass ratio of Y zeolite to the mixed solution was 1:50.

[0044] After the above preparation test was completed, the temperature of the reactor was heated to 450℃, then silane gas was introduced into the reactor until the pressure was -4.0 MPa, the silane introduction was stopped, and a mixture of raw product disilane and silane was prepared under a catalytic reaction for 120 s at a pressure of 0.5 MPa,

[0045] Three, the prepared mixture of raw product disilane and silane was transported to a primary adsorption tower through a pipeline

[0046] The primary adsorption tower was filled with activated carbon loaded with ZnCl2 and MgCl2, the specific surface area was ≥1200 m 2 / g, the Cl - loading was 15wt%, and the mass ratio of ZnCl2 to MgCl2 was 1:1, the adsorption temperature was 28℃, and the pressure was 0.9 MPa.

[0047] The secondary adsorption tower was filled with silver ion exchanged 5A molecular sieve, the exchange degree of silver ion was ≥80%, the adsorption temperature was -20℃, and the pressure was 1 MPa.

[0048] After detection, the purity of disilane and trisilane was greater than 99%, and the content of the main components in the product was as shown in Table 2.

[0049] Table 2

[0050] Component Methylsilane Disilane Propylsilane Content 8.64％ 72.52％ 18.84％

[0051] Example 3

[0052] The embodiment provides a synthesis method for co-producing disilane and trisilane, which specifically comprises the following steps:

[0053] I. Before passing the silane gas, the catalyst is loaded into a 316 stainless steel metal pipe reactor, the loading amount of catalyst is half of the volume of the metal pipe reactor, after loading the catalyst (the catalyst is aluminum chloride), the pressure maintaining experiment is carried out for 48 hours, after the end of the pressure maintaining, the helium gas is passed into the reactor, the time of passing the helium gas is 25 minutes, the passing of the helium gas for 25 minutes can completely remove the impurity gases such as O2 and H2O in the reactor, and the catalyst poisoning is avoided.

[0054] The preparation method of the ruthenium-nickel co-supported catalyst is as follows: the molar ratio of the ruthenium to the nickel is (2-3):1.

[0055] The Y-type zeolite is calcined in a muffle furnace, the muffle furnace is heated to 600℃, and then calcined for 4 hours, and finally cooled to 50℃, and then taken out for standby.

[0056] The calcined Y-type zeolite is added into a mixed solution of RuCl3 (the concentration is 0.1 mol / L) and Ni(NO3)2 (the concentration is 0.2 mol / L), the molar ratio of the ruthenium to the nickel is controlled to be 2:1, the stirring is uniform, the ultrasonic treatment is carried out for 30 minutes, and finally the centrifugal washing and drying are carried out to obtain the ruthenium-nickel co-supported catalyst, and the mass ratio of the Y-type zeolite to the mixed solution is 1:50.

[0057] II. After the above preparation experiment is completed, the temperature of the reactor is heated to 550℃, then the silane gas is passed into the reactor until the pressure is-4.0 MPa, the passing of the silane is stopped, and the mixture of the crude ethylsilane and the silane is prepared by the catalytic reaction for 15 seconds under the pressure of 1.5 MPa.

[0058] III. The prepared mixture of the crude ethylsilane and the silane is transported to a primary adsorption tower through a pipe,

[0059] The primary adsorption tower is filled with activated carbon supported ZnCl2 and MgCl2, the specific surface area is ≥1200 m 2 / g, the Cl - loading amount is 15 wt%, and the mass ratio of the ZnCl2 to the MgCl2 is 1:1, the adsorption temperature is 30℃, and the pressure is 0.8 MPa.

[0060] The secondary adsorption tower is filled with silver ion exchanged 5A molecular sieve, the exchange degree of the silver ion is ≥80%, the adsorption temperature is-40℃, and the pressure is 0.8 MPa.

[0061] After the detection, the purity of the ethylsilane and the propylsilane is greater than 99%, and the content of the main components in the product is shown in Table 3.

[0062] Table 3

[0063] Component Methylsilane Disilane Propylsilane Content 9.17％ 73.69％ 17.14％

[0064] Comparative Example 1

[0065] The difference between this comparative example and Example 1 is that the temperature of the catalytic reaction is 1000°C.

[0066] Comparative Example 2

[0067] The difference between this comparative example and Example 1 is that the temperature of the catalytic reaction is 50°C.

[0068] Comparative Example 3

[0069] The difference between this comparative example and Example 1 is that the pressure of the catalytic reaction is 4 MPa.

[0070] Comparative Example 4

[0071] The catalyst used in this comparative example is a nickel-based catalyst, which is a supported catalyst, and the support is a zeolite with a loading of 20%.

[0072] The contents of monosilane, disilane and trisilane in Comparative Examples 1 to 4 were tested, and the results are shown in Table 4.

[0073] Table 4

[0074] Sample Methylsilane Disilane Propylsilane Comparative Example 1 22.15％ 63.55％ 14.30％ Comparative Example 2 18.65％ 65.36％ 15.99％ Comparative Example 3 23.12％ 62.47％ 14.41％ Comparative Example 4 28.95％ 60.55％ 10.50％

[0075] The above description is only the preferred embodiments of the present application and does not limit the present application in any form. Although the present application has been disclosed as the above preferred embodiments, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes, without departing from the scope of the technical solution of the present application. Any modification, change, equivalent change and modification of the above embodiments, which does not depart from the technical solution of the present application, is still within the scope of the technical solution of the present application.

Claims

1. A method for the synthesis of ethylsilane and propylsilane co-products, characterized in that, The mixture of crude ethylsilane and monosilane is prepared by catalytic reaction of monosilane in a metal pipe reactor with catalyst at a temperature of 450-550 DEG C and a pressure of 0.1-2 MPa, and then enters an adsorption tower to collect ethylsilane and propylsilane with a purity of more than 99%.

2. The method of claim 1, wherein the method is characterized by, The catalyst is a ruthenium-nickel co-supported catalyst, and the molar ratio of ruthenium to nickel is (2-3):

1.

3. The method of claim 2, wherein the method further comprises the step of: The ruthenium-nickel co-supported catalyst has a Y-type zeolite carrier, and the specific preparation method is as follows: ​ Step S1. Calcining the Y-type zeolite at 600 DEG C for 4 hours, Step S2. Adding the calcined Y-type zeolite into a mixed solution of RuCl3 and Ni(NO3)2, stirring uniformly, ultrasonic treatment for 30 min, and finally centrifuging, washing and drying to obtain the ruthenium-nickel co-supported catalyst.

4. The method of claim 3, wherein the method further comprises the step of: 4-1) removing the unreacted diethylsilane and the unreacted propylsilane from the reaction mixture. The concentration of the RuCl3 solution is 0.1 mol / L, the concentration of the Ni(NO3)2 solution is 0.2 mol / L, and the mass ratio of the Y-type zeolite to the mixed solution is 1:

50.

5. The method of claim 1, wherein the method further comprises: 5 separating the ethylsilane and propylsilane from the reaction mixture. 0 The added amount of the catalyst is half of the volume of the metal pipe reactor, and the catalytic reaction time is 15-120 s. ​ 6. The method of claim 5, wherein the method further comprises the step of: The material of the metal pipe reactor is 316 stainless steel, hastelloy, titanium alloy, monel or manganese cadmium alloy. ​ 7. The method for synthesizing ethylsilane and propane co-production according to claim 1, characterized in that, The adsorption tower is divided into a primary adsorption tower and a secondary adsorption tower.

8. The method of claim 7, wherein the method is characterized by, The primary adsorption tower is filled with activated carbon loaded with ZnCl2 and MgCl2, with a specific surface area of ≥1200 m 2 / g, Cl - The loading is 15 wt%, with a mass ratio of ZnCl2 to MgCl2 of 1:1, an adsorption temperature of 25-30°C, and a pressure of 0.8-1 MPa.

9. The method of claim 7, wherein the method further comprises the step of: 9a) purifying the mixture of ethylsilane and propylsilane by distillation. The secondary adsorption tower is filled with silver ion-exchanged 5A molecular sieves, wherein the exchange degree of silver ions is ≥80%, the adsorption temperature is -40 DEG C to -20 DEG C, and the pressure is 0.5-1 MPa.

10. The method of claim 7, wherein the method is characterized by: The monosilane is stopped when the pressure in the reactor reaches -4.0 MPa.