CN115650240A - Process for preparing monochlorosilane - Google Patents
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Abstract
The invention provides a preparation method of monochlorosilane, which comprises the following steps: step S1, reacting silane and chloride serving as raw materials in a reaction device under the action of a catalyst to obtain a reaction product; s2, separating and purifying the reaction product to obtain monochlorosilane; the catalyst contains metallic palladium, aluminum chloride and alumina. The method adopts a specific catalyst to directly synthesize the monochlorosilane through the silane and the chloride, has easily obtained raw materials, is different from a dichlorosilane disproportionation method and a silane and dichlorosilane symmetric disproportionation method, has mild requirements on reaction conditions, is not influenced by a balance reaction, has higher product content in a product, is easy to purify and obtain the high-purity monochlorosilane, has good catalytic effect and long service life, and effectively reduces the production cost of the monochlorosilane.
Description
Technical Field
The invention relates to the field of synthesis of monochlorosilane, and in particular relates to a preparation method of monochlorosilane.
Background
Monochlorosilane is a silicon-based precursor, is mainly used for synthesizing trisilyl ammonia by reacting with ammonia, is used as a silicon source for semiconductor manufacturing, is used for depositing silicon source materials of films such as silicon nitride and the like, and is widely applied to memories and logic chips because the monochlorosilane does not contain chlorine.
At present, the synthesis method of the monochlorosilane mainly comprises a silane and dichlorosilane neutralization method and a dichlorosilane disproportionation method.
Chinese patent application No. 201280008841.6 discloses a method and apparatus for preparing monochlorosilane by reacting silane with dichlorosilane in the presence of a catalyst, which is called a symmetric disproportionation reaction. Actually, the reverse reaction of the third step reaction of the process for preparing the silane by the disproportionation of the trichlorosilane is carried out, namely, the silane and the dichlorosilane are subjected to reverse disproportionation to generate the monochlorosilane; the catalyst is weak-base anion exchange resin, and the functional groups are mainly tertiary amino; finally, the rectification is utilized for separation and purification.
The Chinese patent application with the application number of 202011623031.4 discloses a system for producing silane, monochlorosilane, dichlorosilane and hexachlorodisilane, wherein a disproportionation reaction rectifying tower is adopted to prepare monochlorosilane, trichlorosilane is used as a raw material, a mixture containing monochlorosilane is prepared by two-step disproportionation, and then the monochlorosilane with the purity of 97 percent is prepared by multi-stage rectification and purification. The trichlorosilane is subjected to disproportionation reaction under the catalytic action of the catalyst, and meanwhile, the system also has reverse disproportionation reaction, and the reaction balance is broken through controlling the amount of different substances, so that the aim of preparing a target product is fulfilled.
The two methods are essentially disproportionation reactions or anti-disproportionation reactions of chlorosilane, and the main reaction formula is as follows.
The disproportionation reaction or the inverse disproportionation reaction is adopted, and under the action of a catalyst, the reaction balance is broken through controlling the amount of different substances, so that the preparation of the monochlorosilane is realized. Because the process involves three equilibrium reactions, directional control cannot be carried out on a certain reaction, and the reaction product always contains a mixture of trichlorosilane, silicon tetrachloride, dichlorosilane, monochlorosilane and the like. Because the mixture relates to a plurality of components, a multi-stage rectifying tower is needed to realize the separation of all the substances, and the main defects of the method are that the equilibrium reaction is not easy to control, side reaction exists, the separation and purification are difficult, and the process flow is complex.
Disclosure of Invention
The invention mainly aims to provide a synthesis method of monochlorosilane, which aims to solve the problems that in the prior art, monochlorosilane reaction balance is not easy to control, and the production cost is high due to complex process flow.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing monochlorosilane, the method comprising: step S1, under the action of a catalyst, taking silane and chloride as raw materials to react in a reaction device to obtain a reaction product; s2, separating and purifying the reaction product to obtain monochlorosilane; the catalyst contains metallic palladium, aluminum chloride and alumina.
Further, the catalyst also comprises a carrier, wherein the preferred carrier is any one or more of activated carbon, molecular sieve and aluminosilicate; preferably, the content of metal palladium in the catalyst is 0.1-10 wt%, the content of aluminum chloride is 1-20 wt%, and the content of aluminum oxide is 1-20 wt%; more preferably, the content of metallic palladium is 1.0 to 7.0wt%, the content of aluminum chloride is 2.0 to 5.0wt%, and the content of aluminum oxide is 2.0 to 5.0wt%.
Further, the preparation method of the catalyst comprises the following steps: mixing palladium salt, aluminum chloride and alumina with a carrier, and calcining for 2-10 h in a hydrogen atmosphere; preferably, the palladium salt is palladium acetate; preferably, the temperature of calcination is from 100 to 500 deg.C, more preferably from 200 to 300 deg.C.
The chloride is one or more of hydrogen chloride, carbon tetrachloride and chlorine, and the molar ratio of the chloride to the silane is preferably 1 to 10, more preferably 1 to 3.
Further, the reaction temperature in the step S1 is 10-300 ℃, and the reaction time is 10-60 min; preferably, the reaction temperature is 40-80 ℃ and the reaction time is 20-30 min.
Further, the pressure of the reaction in the step S1 is 10-500 kPa; the pressure of the reaction is preferably 200 to 300kPa.
Further, step S2 includes: and introducing the reaction product into a deep cooler, separating a liquid component containing the reaction product, and purifying the liquid component to obtain the monochlorosilane.
Furthermore, the temperature in the deep cooler is-60 to 0 ℃, preferably-50 to-40 ℃, and the pressure is 10 to 500kPa.
Further, the liquid phase component is purified by rectification; preferably, the rectification is carried out by connecting two rectification towers in series; more preferably, the first distillation column of the two-stage distillation column is used for removing light components, the second distillation column of the two-stage distillation column is used for removing heavy components, and methane chloride is distilled out of the top of the second distillation column.
Further, the pressure at the top of the first rectifying tower is 50-800 kPa, the temperature is-50 ℃, the preferable pressure is 100-200 kPa, and the temperature is-15-5 ℃; and/or the pressure at the top of the second rectifying tower is 50-800 kPa, the temperature is-50 ℃, the preferred pressure is 50-100 kPa, and the temperature is-20-10 ℃.
By applying the technical scheme of the invention, the specific catalyst is adopted to directly synthesize the monochlorosilane through the silane and the chloride, the raw materials are easy to obtain, the method is different from a dichlorosilane disproportionation method and a silane and dichlorosilane symmetric disproportionation method, the method has mild requirements on reaction conditions, is not influenced by equilibrium reaction, has high product content in the product, and is easy to purify to obtain the high-purity monochlorosilane. The catalyst contains metal palladium, aluminum chloride and aluminum oxide, wherein target and aluminum are active substances of the catalyst, and are coordinated with silane and the like to activate the catalyst and induce a chlorine source to attack so as to generate chlorination reaction, wherein aluminum trichloride can directly participate in catalytic reaction, aluminum oxide can be reacted with a carrier providing reaction in the reaction, and under certain conditions, the aluminum oxide can also be reacted and converted into the aluminum trichloride to participate in the catalytic reaction. The catalyst has good catalytic effect and long service life, and effectively reduces the production cost of the monochlorosilane.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic preparation scheme of example 1 according to the invention.
Wherein the figures include the following reference numerals: 1. a chloride; 2. silane; 3. a reaction product; 4. a gaseous component; 5. a liquid component; 6. light components; 7. heavy components; 8. methane chloride; 9. a high boiling residue; 100. a catalytic reactor; 200. a deep cooling device; 300. rectifying by a 1 tower; 400. and (3) rectifying by using a 2 tower.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed in the background art of the present application, the problem of prior art that the equilibrium is not easy to control, the product content in the product is low, the separation process is complex, and the production cost is high exists in the preparation of monochlorosilane by disproportionation reaction, and in order to solve the problem, the present application provides a method for preparing monochlorosilane, comprising: step S1, reacting silane and chloride serving as raw materials in a reaction device under the action of a catalyst to obtain a reaction product; s2, separating and purifying the reaction product to obtain monochlorosilane; the catalyst contains metallic palladium, aluminum chloride and alumina.
The method adopts a specific catalyst to directly synthesize the monochlorosilane through the silane and the chloride, has easily obtained raw materials, is different from a dichlorosilane disproportionation method and a silane and dichlorosilane symmetric disproportionation method, has mild requirements on reaction conditions, is not influenced by a balance reaction, has higher product content in a product, and is easy to purify to obtain the high-purity monochlorosilane. The catalyst contains metal palladium, aluminum chloride and aluminum oxide, wherein target and aluminum are active substances of the catalyst, and are coordinated with silane and the like to activate the catalyst and induce a chlorine source to attack so as to generate chlorination reaction, wherein aluminum trichloride can directly participate in catalytic reaction, aluminum oxide can be reacted with a carrier providing reaction in the reaction, and under certain conditions, the aluminum oxide can also be reacted and converted into the aluminum trichloride to participate in the catalytic reaction. The catalyst has good catalytic effect and long service life, and effectively reduces the production cost of the monochlorosilane.
In order to increase the specific surface area of the catalyst and further improve the catalytic efficiency, the catalyst also comprises a carrier, and metallic palladium, aluminum chloride and alumina are uniformly loaded on the carrier. The carrier of the above catalyst may be selected from the prior art, such as any one or more of activated carbon, molecular sieve and aluminosilicate, and the content of the carrier and each supported component may be determined according to the supporting ability of the carrier.
In some preferred embodiments of the present application, in order to further improve the catalytic efficiency of the catalyst, the content of metallic palladium in the catalyst is 0.1 to 10wt%, the content of aluminum chloride is 1 to 20wt%, and the content of aluminum oxide is 1 to 20wt%; more preferably, the content of metal palladium is 1.0 to 7.0wt%, the content of aluminum chloride is 2.0 to 5.0wt%, the content of aluminum oxide is 2.0 to 5.0wt%, and the catalytic efficiency is more preferable. The dosage of the catalyst can be determined according to the volume of the feeding amount, and the catalyst can be fully contacted with reaction raw materials. The above catalyst may be prepared according to the prior art, and in some preferred embodiments of the present application, the catalyst is prepared by a method comprising: the catalyst prepared by high-temperature reduction has the advantages of more stable structure, higher strength, strong metal adhesive force, uniform distribution, good catalytic effect and long service life. The palladium salt can be common palladium salts such as palladium chloride, palladium nitrate, palladium sulfate, palladium acetate and the like, preferably, the palladium salt is the palladium acetate, and the palladium acetate is soluble palladium salt, so that the palladium salt is easier to disperse during preparation and more uniform in distribution in a catalyst matrix. Meanwhile, the carbon is easy to decompose, and decomposed carbon escapes in the form of carbon dioxide gas without residual impurities. Preferably, the temperature for calcination is from 100 to 500 ℃, more preferably from 200 to 300 ℃.
The chloride may be selected from the prior art, and in some embodiments of the present application, the chloride is any one or more of hydrogen chloride, carbon tetrachloride, and chlorine, wherein when the chloride is hydrogen chloride and/or chlorine, the alumina in the catalyst may be reacted to convert to aluminum chloride to participate in the catalytic reaction. The molar ratio of chloride to silane can be referenced to a stoichiometric ratio, and in some embodiments herein, is from 1 to 10. Exemplary, the molar ratio of chloride to silane is 1, 2, 1, 3. The molar ratio of chloride to silane affects the type of product formed, which is advantageous in reducing the dichlorosilane, trichlorosilane, and tetrachlorosilane content of the product, and in some preferred embodiments, the molar ratio of chloride to silane is 1 to 3.
The reaction device can be a batch type or a continuous type, such as a coil type reactor or a fixed bed reactor, and can ensure that reaction materials and the catalyst are in good contact, and the reaction device has good sealing property and certain pressure resistance.
In some embodiments of the present application, in order to further improve the yield of the product, the temperature of the reaction in the step S1 is 10 to 300 ℃ and the time is 10 to 60min, and if the reaction is a continuous reaction device, the residence time of the material in the reaction device is 10 to 60min; preferably, the reaction temperature is 40-80 ℃ and the reaction time is 20-30 min, so that the conversion rate of raw materials and the yield of monochlorosilane can be further improved. In some exemplary embodiments of the present application, the catalytic reaction is performed under a certain pressure in order to increase the reaction yield, and generally, the pressure is increased, the number of molecules of the raw material per unit volume in the reactor is increased, and the raw material is more easily contacted and reacted with the catalyst, and the reaction yield is increased. The influence of the pressure is gradually balanced due to the limitation of the specific surface area of the catalyst, namely, the pressure is continuously increased, the conversion rate is not greatly influenced, and the structural stability of the catalyst is influenced by the overhigh pressure. Preferably, the pressure of the reaction in step S1 is 10 to 500kPa, and the pressure is a gauge pressure, and unless otherwise specified, the pressure means the gauge pressure; more preferably, the reaction pressure is 200 to 300kPa, and the yield of the target product is high.
After the reaction is finished, the separation and purification of the monochlorosilane product can refer to the prior art. In some embodiments of the present application, the step S2 includes: and introducing the reaction product into a deep cooler to obtain a liquid component containing the product, sending the gas component into a tail gas system for centralized treatment, and purifying the liquid component to obtain the monochlorosilane. In the reaction system, the boiling points of silane, hydrogen chloride, hydrogen and the like are low, the boiling points of monochlorosilane, carbon tetrachloride, carbon trichloride and the like are high, the silane, hydrogen chloride, hydrogen and the like are gas at a proper temperature and pressure, the silane, hydrogen chloride, carbon tetrachloride, carbon trichloride and the like can be conveniently separated from the monochlorosilane, carbon tetrachloride, carbon trichloride and the like, and the separated gas components can be treated according to a method in the prior art, such as being sent into a tail gas system for centralized treatment, and the classified recovery of materials is carried out.
In some embodiments of the present application, the temperature in the chiller is-60 to 0 ℃, preferably-50 to-40 ℃, and the pressure is 10 to 500kPa in order to better separate the gaseous components comprising the feedstock and the liquid components comprising the product in the chiller. The pressure in the deep cooler is increased, so that on one hand, the condensation temperature of substances such as Monochlorosilane (MCS) \ Dichlorosilane (DCS) \ tetrachlorosilane (STC) in the material can be increased, the temperature of the deep cooler can be controlled to be higher, and the energy consumption is saved; on the other hand, the pressure difference is kept between the rectification tower and the subsequent rectification tower, and the material is conveniently conveyed by means of the pressure difference.
The liquid component separated by cryogenic cooling can be further separated to obtain monochlorosilane according to the prior art, in some embodiments of the present application, the liquid component is purified by rectification, preferably, the rectification is performed by two rectification towers in series, a first rectification tower in the two rectification towers is used for removing light components, a second rectification tower in the two rectification towers is used for removing heavy components, and monochloromethane is distilled from the top of the second rectification tower.
The temperature and pressure of the two-stage rectifying tower can be determined according to the boiling point and the content of each component in the liquid components, in some embodiments of the present application, in order to separate high-purity monochlorosilane more efficiently, the pressure at the top of the first rectifying tower is 50-800 kPa, the temperature is-50 ℃, preferably the pressure is 100-200 kPa, and the temperature is-15-5 ℃; and/or the pressure at the top of the second rectifying tower is 50-800 kPa, the temperature is-50 ℃, the preferred pressure is 50-100 kPa, and the temperature is-20-10 ℃.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
Firstly, preparing a catalyst, wherein the weight ratio of palladium acetate, aluminum chloride, alumina and a carrier in the catalyst is 1. The catalyst is prepared according to the following steps: stirring and mixing 1 part by weight of palladium acetate, 3 parts by weight of aluminum chloride, 3 parts by weight of aluminum oxide and 93 parts by weight of activated carbon, uniformly mixing, and calcining at 200 ℃ for 5 hours in a hydrogen atmosphere to obtain the catalyst.
This example used an apparatus as shown in FIG. 1 to prepare monochlorosilane.
Filling 2500g of the catalyst into a catalytic reactor 100 with the diameter of DN100 and the length of 1500mm, wherein chloride 1 is hydrogen chloride, the molar ratio of fed chloride 1 to silane 2 is controlled to be 1, feeding the hydrogen chloride into the catalytic reactor 100, the feeding amount is 100kg/h, the reaction temperature is controlled to be 50 ℃, the pressure is controlled to be 200kPa, and the retention time is 20min, so as to obtain a reaction product 3. Detecting the composition of the reaction product by using an Agilent gas chromatography 7890B and a gas chromatography, wherein the content of monochlorosilane is 18 percent, the content of silane is 22 percent, the content of hydrogen chloride is 30 percent, the content of dichlorosilane is 2 percent, the content of trichlorosilane is 2 percent, the content of silicon tetrachloride is 1 percent and the content of hydrogen is 25 percent in terms of molar percentage.
Introducing the reaction product 3 into a deep cooler 200, controlling the temperature at-50 ℃ and the pressure at 200kPa, under the condition, dividing the reaction product 3 into a gaseous component 4 and a liquid component 5, wherein unreacted silane, hydrogen chloride and hydrogen generated by reaction mainly exist in the gaseous component 4, monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride and the like mainly exist in the liquid component 5, separating the gaseous component 4 from the liquid component 5, and sending the hydrogen, the silane and the hydrogen chloride in the obtained gaseous component 4 into a tail gas system for centralized treatment.
And (3) feeding the separated material of the liquid component 5 into a two-stage rectifying tower for rectification and purification. The rectifying towers are connected in series, the first rectifying tower 300 removes light components 6, the second rectifying tower 400 removes heavy components 9, and a chlorosilane product 8 is obtained at the top of the second rectifying tower 400. The top pressure of the first rectifying tower 300 is 200kPa, the top temperature of the first rectifying tower is 0-5 ℃, and light components 6, namely hydrogen chloride and silane, are extracted from the top of the first rectifying tower 300 and can be returned to the catalytic reactor 100 to be used as reaction raw materials. The tower bottom component is a heavy component 7 containing a mixture of monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride and enters a second rectifying tower 400. The second rectifying tower 400 is a de-heavy tower, the pressure is 50kPa, the temperature at the top of the tower is-20 ℃, the product monochlorosilane 8 is extracted from the top of the second rectifying tower 400, the purity is 99.5% (GC), and high-boiling-point substances 9 such as dichlorosilane, trichlorosilane, silicon tetrachloride and the like are extracted from the bottom of the tower.
Example 2
The difference from example 1 is that: chloride is hydrogen chloride, and the molar ratio of hydrogen chloride to silane is 3.
In terms of mole percentage, the content of monochlorosilane in the reaction product is 20%, the content of silane is 15%, the content of hydrogen chloride is 39%, the content of dichlorosilane is 4%, the content of trichlorosilane is 2%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 19%.
And introducing the reaction product into a deep cooler, controlling the temperature to be 50 ℃ below zero and the pressure to be 200kPa, separating a gaseous component from a liquid component, wherein the gaseous component contains unreacted silane, hydrogen chloride and hydrogen generated by the reaction, and the liquid component contains monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride and the like.
Adopting the same rectifying tower and rectifying conditions as those in the embodiment 1, the low-boiling-point substances such as hydrogen chloride, silane and the like are extracted from the top of the first rectifying tower and can be returned to the catalytic reactor as the raw materials for reaction; the top of the second rectifying tower is used for extracting chlorosilane with the purity of 99.5 percent (GC), and the bottom of the tower is used for extracting dichlorosilane, trichlorosilane, silicon tetrachloride and other high-boiling-point substances.
Example 3
The difference from example 1 is that: the chloride is chlorine gas, and the molar ratio of the chlorine gas to the silane is 1.
In terms of mole percentage, the reaction product contains 16 percent of monochlorosilane, 16 percent of silane, 25 percent of hydrogen chloride, 6 percent of dichlorosilane, 3 percent of trichlorosilane, 2 percent of silicon tetrachloride, 3 percent of hydrogen and 29 percent of chlorine.
And introducing the reaction product into a deep cooler, controlling the temperature to be-40 ℃ and the pressure to be 300kPa, separating a gaseous component from a liquid component, wherein the gaseous component contains unreacted silane, hydrogen and hydrogen chloride generated by reaction, and the liquid component contains monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride and the like.
Adopting the same rectifying tower and rectifying conditions as those in the embodiment 1, the hydrogen chloride, chlorine and silane are extracted from the top of the first rectifying tower and can be returned to the catalytic reactor as raw materials for reaction; the chlorosilane product is extracted from the top of the second rectifying tower, the purity of the chlorosilane product is 99 percent (GC), and high boiling point substances such as dichlorosilane, trichlorosilane, silicon tetrachloride and the like are extracted from the bottom of the second rectifying tower.
Example 4
The difference from example 1 is that: the molar ratio of hydrogen chloride to silane was 10.
The content of monochlorosilane in the reaction product is 9%, the content of silane is 4%, the content of hydrogen chloride is 68%, the content of dichlorosilane is 10%, the content of trichlorosilane is 4%, the content of silicon tetrachloride is 3%, and the content of hydrogen is 2%.
Example 5
The difference from example 1 is that: the weight ratio of palladium acetate, aluminum chloride, alumina and carrier in the catalyst is (2).
In the reaction product, the content of monochlorosilane is 28%, the content of silane is 16%, the content of hydrogen chloride is 21%, the content of dichlorosilane is 3%, the content of trichlorosilane is 2%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 29%.
Example 6
The difference from example 1 is that: the weight ratio of palladium acetate, aluminum chloride, alumina and the carrier in the catalyst is 5.
The content of monochlorosilane in the reaction product is 37%, the content of silane is 14%, the content of hydrogen chloride is 13%, the content of dichlorosilane is 3%, the content of trichlorosilane is 2%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 30%.
Example 7
The difference from example 1 is that: the weight ratio of palladium acetate, aluminum chloride, alumina and carrier in the catalyst is 7.
The content of monochlorosilane in the reaction product is 30%, the content of silane is 15%, the content of hydrogen chloride is 19%, the content of dichlorosilane is 2%, the content of trichlorosilane is 2%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 31%.
Example 8
The difference from example 1 is that: the weight ratio of palladium acetate, aluminum chloride, alumina and carrier in the catalyst is (2).
The content of monochlorosilane in the reaction product is 20%, the content of silane is 24%, the content of hydrogen chloride is 26%, the content of dichlorosilane is 1%, the content of trichlorosilane is 1%, the content of silicon tetrachloride is 0%, and the content of hydrogen is 28%.
Example 9
The difference from example 1 is that: the catalyst was prepared by replacing the activated carbon with the same parts by weight of a commercially available ZSM-5 (manufacturing company: jiangsu Jiehukang technologies Co., ltd.).
The content of monochlorosilane in the reaction product is 19%, the content of silane is 21%, the content of hydrogen chloride is 29%, the content of dichlorosilane is 1%, the content of trichlorosilane is 1%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 28%.
Comparative example 1
The difference from example 1 is that: palladium acetate is not added in the preparation process of the catalyst, and other components and proportions are not changed.
The content of monochlorosilane in the reaction product is 12%, the content of silane is 27%, the content of hydrogen chloride is 35%, the content of dichlorosilane is 1%, the content of trichlorosilane is 1%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 23%.
Comparative example 2
The difference from example 1 is that: the catalyst does not contain alumina, and the proportion of other components is not changed.
In the reaction product, the content of monochlorosilane is 16%, the content of silane is 25%, the content of hydrogen chloride is 32%, the content of dichlorosilane is 1%, the content of trichlorosilane is 1%, the content of silicon tetrachloride is 1%, and the content of hydrogen is 24%.
From the above description, it can be seen that, in the present application, the specific catalyst is adopted to directly synthesize the monochlorosilane through the silane and the chloride, the raw materials are easy to obtain, and different from the dichlorosilane disproportionation method and the silane and dichlorosilane symmetric disproportionation method, the method has mild requirements on reaction conditions, is not affected by equilibrium reaction, has high product content in the product, and is easy to purify to obtain high-purity monochlorosilane. The catalyst contains metal palladium, aluminum chloride and aluminum oxide, wherein a target and aluminum are active substances of the catalyst, and are coordinated with silane and the like to activate the catalyst and induce a chlorine source to attack so as to generate chlorination reaction.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing monochlorosilane, comprising:
step S1, under the action of a catalyst, taking silane and chloride as raw materials to react in a reaction device to obtain a reaction product;
s2, separating and purifying the reaction product to obtain monochlorosilane;
the catalyst contains metallic palladium, aluminum chloride and aluminum oxide.
2. The preparation method of claim 1, wherein the catalyst further comprises a carrier, preferably the carrier is any one or more of activated carbon, molecular sieve and aluminosilicate;
preferably, the content of the metal palladium in the catalyst is 0.1-10 wt%, the content of the aluminum chloride is 1-20 wt%, and the content of the aluminum oxide is 1-20 wt%;
more preferably, the content of metallic palladium is 1.0 to 7.0wt%, the content of aluminum chloride is 2.0 to 5.0wt%, and the content of aluminum oxide is 2.0 to 5.0wt%.
3. The method according to claim 2, wherein the method for preparing the catalyst comprises: mixing palladium salt, aluminum chloride and alumina with a carrier, and calcining for 2-10 h in a hydrogen atmosphere;
preferably, the palladium salt is palladium acetate;
preferably, the temperature of the calcination is from 100 to 500 ℃, more preferably from 200 to 300 ℃.
4. The preparation method according to claim 1, wherein the chloride is any one or more of hydrogen chloride, carbon tetrachloride and chlorine, and preferably the molar ratio of the chloride to the silane is 1-10.
5. The method according to claim 1, wherein the reaction in step S1 is carried out at a temperature of 10 to 300 ℃ for 10 to 60min;
preferably, the reaction temperature is 40-80 ℃ and the reaction time is 20-30 min.
6. The production method according to claim 1, wherein the pressure of the reaction in the step S1 is 10 to 500kPa; the pressure of the reaction is preferably 200 to 300kPa.
7. The method according to any one of claims 1 to 6, wherein the step S2 includes: and introducing the reaction product into a deep cooler, separating a liquid component containing the product, and purifying the liquid component to obtain the monochlorosilane.
8. The method according to claim 7, wherein the temperature in the deep-cooling device is-60 to 0 ℃, preferably-50 to-40 ℃, and the pressure is 10 to 500kPa.
9. The production method according to claim 7, wherein the liquid-phase component is purified by rectification;
preferably, the rectification is performed by connecting two rectification towers in series;
more preferably, a first rectifying column of the two-stage rectifying column is used for removing light components, a second rectifying column of the two-stage rectifying column is used for removing heavy components, and methane chloride is distilled out of the top of the second rectifying column.
10. The preparation method according to claim 9, characterized in that the pressure at the top of the first rectifying tower is 50-800 kPa, the temperature is-50 ℃, preferably the pressure is 100-200 kPa, and the temperature is-15-5 ℃;
and/or the pressure at the top of the second rectifying tower is 50-800 kPa, the temperature is-50 ℃, the preferred pressure is 50-100 kPa, and the temperature is-20-10 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117208913A (en) * | 2023-09-04 | 2023-12-12 | 全椒亚格泰电子新材料科技有限公司 | Method and equipment for preparing polychlorosilane by catalytic synthesis |
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| GB754552A (en) * | 1953-04-01 | 1956-08-08 | Exxon Research Engineering Co | Hydroforming catalyst and process |
| US3993594A (en) * | 1975-02-03 | 1976-11-23 | Phillips Petroleum Company | Activating Group VIII metal/alumina catalysts with halosilane |
| US5292909A (en) * | 1993-07-14 | 1994-03-08 | Dow Corning Corporation | Catalytic conversion of direct process high-boiling component to chlorosilane monomers in the presence of hydrogen chloride and hydrogen |
| US20110113628A1 (en) * | 2009-04-15 | 2011-05-19 | Air Products And Chemicals, Inc. | Method for Making a Chlorosilane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117208913A (en) * | 2023-09-04 | 2023-12-12 | 全椒亚格泰电子新材料科技有限公司 | Method and equipment for preparing polychlorosilane by catalytic synthesis |
| CN117208913B (en) * | 2023-09-04 | 2024-03-08 | 全椒亚格泰电子新材料科技有限公司 | Method and equipment for preparing polychlorosilane by catalytic synthesis |
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