CN115785143A - Production method and production device of diphenyl dichlorosilane - Google Patents
Production method and production device of diphenyl dichlorosilane Download PDFInfo
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- CN115785143A CN115785143A CN202111055706.4A CN202111055706A CN115785143A CN 115785143 A CN115785143 A CN 115785143A CN 202111055706 A CN202111055706 A CN 202111055706A CN 115785143 A CN115785143 A CN 115785143A
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Abstract
The invention discloses a production method and a production device of diphenyl dichlorosilane, wherein the method comprises the following steps: 1) Introducing a gas-phase raw material dichlorosilane and a gas-phase diluent silicon tetrachloride into a reactor, introducing a gas-phase initiator trichloromethane into the reactor, and introducing a gas-phase raw material chlorobenzene into the reactor; 2) Heating, and reacting dichlorosilane and chlorobenzene in a reactor to generate diphenyl dichlorosilane to obtain a reaction product. The production method of the invention uses chlorobenzene and dichlorosilane as raw materials, and has high activity and small relative steric hindrance under the high-temperature state of dichlorosilane, thus ensuring the reaction conversion rate, having high reaction conversion rate and reducing the cost; the process adopts gas-gas reaction to replace the existing solid-liquid reaction, has high conversion rate of raw materials, avoids equipment abrasion, simultaneously adopts trichloromethane as an initiator, avoids using solid catalysts such as copper and the like, and reduces environmental pollution; the production route has simple process flow and can realize continuous production.
Description
Technical Field
The invention belongs to the technical field of organic silicon materials, and particularly relates to a production method and a production device of diphenyldichlorosilane.
Background
Diphenyl dichlorosilane is an important synthetic monomer, has active property, can generate esterification reaction with alcohols to generate relative siloxane, and is an important organic compound intermediate. The most important application of the method is to prepare the diphenyl dimethoxy silane. The polymer molecule formed by the diphenyl dimethoxysilane prepared from diphenyl dichlorosilane and methanol contains hydrophobic hydrocarbon group and-Si-O-Si-chain with water and air permeability, thus having surface activity and weather resistance and being used as an auxiliary agent in the coating industry. For example, the coating containing 45 percent of diphenyldimethoxysilane has excellent waterproof performance, can reduce the hygroscopicity, the anti-sticking performance, the electromagnetic property and the like of the coating, and is widely applied to various fields of national defense, aerospace, construction and the like. Diphenyldimethoxysilane is introduced into the siloxane rubber as an anti-crosslinking agent, so that the rubber can be effectively prevented from being vulcanized, and during the storage process, a certain amount of diphenyldimethoxysilane is added so as to prevent the rubber from being hardened. In addition, diphenyl dimethoxy silane has wide application market in the aspects of cement, paint, lubrication, television screen films, copying, image sensing, liquid crystal display and the like.
In recent years, with the rapid development of the industrial fields in China, the demand for the diphenyldimethoxysilane is increasingly raised, the demand for the diphenyldichlorosilane is also increasingly increased, and few domestic manufacturers import parts of the diphenyldimethoxysilane, and the research on the diphenyldimethoxysilane is very little. Therefore, the further deep research on the technical process of the diphenyl dichlorosilane and the realization of the optimized operation have important practical significance.
In the prior art, diphenyl dichlorosilane is mainly prepared by a fluidized bed method or a reaction kettle mixing and stirring mode through silicon powder and chlorobenzene by a copper catalyst, and the product of the diphenyl dichlorosilane is mainly diphenyl dichlorosilane, inferior phenyl trichlorosilane and less triphenylchlorosilane, but the method has the following problems: (1) The single-pass conversion rate is lower, and the single-pass conversion rate of the obtained diphenyl dichloride is only 20-30%; (2) The waste catalyst contains copper as heavy metal, and certain pollution can be generated; (3) Due to the existence of Cu in the reaction process, part of polychlorinated biphenyl can be generated, and the substance is a carcinogenic substance which forbids import and export, so that part of downstream products are limited in export, and (4) the high-temperature and high-pressure operation is realized, so that the equipment has high safety leakage risk and high production cost.
In addition, some manufacturers react with chlorobenzene-formatted reagents to prepare diphenyl dichlorosilane, although polychlorinated biphenyl is not generated by the method, solvents such as tetrahydrofuran or diethyl ether are required to be used in the production process, the solvents can generate peroxide after long-time reaction, explosion risks exist, the conversion rate of the generated formatted reagents is high, meanwhile, the reaction of Si-Cl bonds and the Grignard reagents is uncontrollable, the reaction rate is too high, the heat release amount is large, unsafety exists, and industrial production conditions are not met.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a production method and a production device of diphenyldichlorosilane aiming at the defects in the prior art, wherein the production method shortens the reaction time, reduces the reaction temperature, improves the conversion rate and reduces the cost.
The technical scheme adopted for solving the technical problem of the invention is to provide a production method of diphenyl dichlorosilane, which comprises the following steps:
1) Introducing a gas-phase raw material dichlorosilane and a gas-phase diluent silicon tetrachloride into a reactor, introducing a gas-phase initiator trichloromethane into the reactor, and introducing a gas-phase raw material chlorobenzene into the reactor;
2) Heating, and reacting dichlorosilane and chlorobenzene in a reactor to generate diphenyl dichlorosilane to obtain a reaction product.
Preferably, the mass ratio of dichlorosilane to silicon tetrachloride in the step 1) is (1-1.8): 3.
preferably, the mass ratio of each substance in the step 1) is as follows: chloroform: chlorobenzene = (1 to 1.2): (0.04-0.06): 2.
preferably, the heating temperature in the step 2) is 300-400 ℃, the pressure is 200-220 Kpa, and the residence time in the reactor is at least 8-10 s.
Preferably, the step 1) is preceded by the following step a):
heating and vaporizing raw material dichlorosilane and gaseous diluent silicon tetrachloride at the temperature of 160-170 ℃ and the pressure of 200-220 Kpa;
heating and vaporizing trichloromethane serving as an initiator at the temperature of 160-170 ℃ and the pressure of 200-220 Kpa;
heating chlorobenzene to vaporize at 160-170 deg.c and 200-220 Kpa.
Preferably, the step 2) is preceded by the following step b): preheating the reactor to 350-400 deg.c, introducing nitrogen for replacement and eliminating oxidizing gas from the reactor.
Preferably, the following step c) is further included after the step 2):
condensing the reaction product through a cold source;
and sequentially removing dichlorosilane, silicon tetrachloride, benzene, chlorobenzene, phenyltrichlorosilane and diphenyldichlorosilane from the condensed reaction product through multi-stage rectification.
Preferably, the temperature of the reaction product after condensation is 130 to 180 ℃.
Preferably, the step c) of removing dichlorosilane, silicon tetrachloride, benzene, chlorobenzene, phenyltrichlorosilane and diphenyldichlorosilane sequentially from the condensed reaction product through multi-stage rectification specifically comprises:
removing dichlorosilane and silicon tetrachloride from the condensed reaction product through first-stage rectification, wherein the pressure range is 100-150 Kpa;
removing benzene by secondary rectification, wherein the pressure range is-30 to-50 Kpa;
removing chlorobenzene by third-stage rectification, wherein the pressure range is-60 to-80 Kpa;
removing phenyltrichlorosilane through fourth-stage rectification, wherein the pressure range is-85 to-95 Kpa;
removing the diphenyl dichlorosilane by a fifth stage of rectification, wherein the pressure range is-85 to-95 Kpa.
The invention also provides a production device of the diphenyl dichlorosilane, which comprises the following components:
the first storage tank is connected with the reactor and is used for storing raw material chlorobenzene;
the second storage tank is connected with the reactor and is used for storing raw materials of dichlorosilane and diluent silicon tetrachloride;
the third storage tank is connected with the reactor and is used for storing trichloromethane;
a feed heater for heating the feed;
and the reactor is connected with the feeding heater, and dichlorosilane and chlorobenzene react in the reactor to generate diphenyl dichlorosilane so as to obtain a reaction product.
Preferably, the reactor comprises three reactors in series.
Preferably, the apparatus for producing diphenyldichlorosilane further comprises:
the condenser is connected with the outlet of the reactor and is used for condensing the reaction product;
a crude product tank connected to the condenser, the crude product tank for receiving condensed reaction products;
the first-stage rectifying tower is connected with the crude product tank and is used for removing dichlorosilane and silicon tetrachloride in the condensed reaction products;
the second-stage rectifying tower is connected with the first-stage rectifying tower and is used for removing benzene;
the third-stage rectifying tower is connected with the second-stage rectifying tower and is used for removing chlorobenzene;
the fourth-stage rectifying tower is connected with the third-stage rectifying tower and is used for removing phenyltrichlorosilane;
and the fifth-stage rectifying tower is connected with the fourth-stage rectifying tower and is used for removing the diphenyl dichlorosilane.
Preferably, a gas phase outlet of the first-stage rectifying tower is connected with a second storage tank, and dichlorosilane and silicon tetrachloride separated from the first-stage rectifying tower are introduced into the second storage tank;
and a gas phase outlet of the third-stage rectifying tower is connected with the first storage tank, and the chlorobenzene channel separated from the third-stage rectifying tower is stored in the first storage tank.
Preferably, the apparatus for producing diphenyldichlorosilane further comprises:
a heat exchanger, comprising: the heat exchanger comprises a first heat exchanger pipeline and a second heat exchanger pipeline, wherein the first heat exchanger pipeline exchanges heat with the second heat exchanger pipeline, an inlet of the first heat exchanger pipeline is connected with a first storage tank, a second storage tank and a third storage tank respectively, an outlet of the first heat exchanger pipeline is connected with a feeding heater, an inlet of the second heat exchanger pipeline is connected with an outlet of a reactor, and an outlet of the second heat exchanger pipeline is connected with a condenser.
The production method and the production device of the diphenyl dichlorosilane have the following beneficial effects:
(1) Silicon tetrachloride is added into dichlorosilane, because the silicon tetrachloride is a compound with stable valence state, the silicon tetrachloride is difficult to react with other substances, the silicon tetrachloride plays a role in diluting and stabilizing dichlorosilane, and meanwhile, the reaction generates corresponding silicon tetrachloride byproducts in the reaction process, so that the related properties of the dichlorosilane can be stabilized, and the stability and the safety of mixed chlorosilane are improved;
(2) The initiator trichloromethane is added to replace the traditional metal catalyst at the initial stage of the reaction, so that the pollution is reduced, the initiator trichloromethane can generate corresponding free radicals at a lower temperature, dichlorosilane and chlorobenzene can be initiated to generate free radicals at a low temperature, the combination rate of the free radicals is improved, the reaction can be rapidly initiated, the reaction time is shortened, and the reaction temperature is reduced;
(3) Chlorobenzene and dichlorosilane are used as raw materials, and as dichlorosilane has high activity in a high-temperature state and small relative steric hindrance, the reaction conversion rate is ensured and can reach over 35 percent, and the cost can be reduced by at least 15 percent;
(4) The process adopts gas-gas reaction to replace the existing solid-liquid reaction, has high conversion rate of raw materials, avoids equipment abrasion, simultaneously adopts trichloromethane as an initiator, avoids using solid catalysts such as copper and the like, and reduces environmental pollution;
(5) The production line has simple process flow and can realize continuous production.
Drawings
FIG. 1 is a schematic view of the structure of a diphenyldichlorosilane production apparatus in example 2 of the present invention.
In the figure: 1-a first storage tank, 2-a second storage tank, 3-a third storage tank, 4-a heat exchanger, 5-a feeding heater, 6-a first reactor, 7-a second reactor, 8-a third reactor, 9-a condenser, 10-a crude product tank, 11-a first-stage rectifying tower, 12-a second-stage rectifying tower, 13-a third-stage rectifying tower, 14-a fourth-stage rectifying tower and 15-a fifth-stage rectifying tower.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail with reference to the accompanying drawings and the detailed description below.
Reference will now be made in detail to embodiments of the present patent, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the drawings are illustrative only for the purpose of explaining the present patent and are not to be construed as limiting the present patent.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Example 1
The embodiment provides a production method of diphenyl dichlorosilane, which comprises the following steps:
1) Introducing a gas-phase raw material dichlorosilane and a gas-phase diluent silicon tetrachloride into a reactor, introducing a gas-phase initiator trichloromethane into the reactor, and introducing a gas-phase raw material chlorobenzene into the reactor;
2) Heating, and reacting dichlorosilane and chlorobenzene in a reactor to generate diphenyl dichlorosilane to obtain a reaction product.
The embodiment also provides a production device of diphenyldichlorosilane used in the production method, which comprises:
the first storage tank is connected with the reactor and is used for storing raw material chlorobenzene;
the second storage tank is connected with the reactor and is used for storing raw materials of dichlorosilane and diluent silicon tetrachloride;
the third storage tank is connected with the reactor and is used for storing trichloromethane;
a feed heater for heating the feed;
and the reactor is connected with the feeding heater, and dichlorosilane and chlorobenzene react in the reactor to generate diphenyl dichlorosilane so as to obtain a reaction product.
The production method and the production device of the diphenyldichlorosilane in the embodiment have the following beneficial effects:
(1) Silicon tetrachloride is added into dichlorosilane, and is a compound with stable valence state, so that the silicon tetrachloride is difficult to react with other substances, dilution and stabilization effects are achieved in dichlorosilane, and meanwhile, a corresponding silicon tetrachloride byproduct is generated in the reaction process, so that the related properties of the dichlorosilane can be stabilized, and the stability and safety of mixed chlorosilane are improved;
(2) The initiator trichloromethane is added to replace the traditional metal catalyst at the initial stage of the reaction, so that pollution is reduced, the initiator trichloromethane can generate corresponding free radicals at a lower temperature, dichlorosilane and chlorobenzene can be initiated to generate free radicals at a low temperature, the combination rate of the free radicals is improved, the reaction can be initiated quickly, the reaction time is shortened, and the reaction temperature is reduced;
(3) Chlorobenzene and dichlorosilane are used as raw materials, and as dichlorosilane has high activity in a high-temperature state and small relative steric hindrance, the conversion rate is improved, and the cost is reduced;
(4) The process adopts gas-gas reaction to replace the existing solid-liquid reaction, has high conversion rate of raw materials, avoids equipment abrasion, simultaneously adopts trichloromethane as an initiator, avoids using solid catalysts such as copper and the like, and reduces environmental pollution;
(5) The production route has simple process flow and can realize continuous production.
Example 2
As shown in fig. 1, this embodiment provides a diphenyldichlorosilane production apparatus, including:
the first storage tank 1 is connected with the reactor, and the first storage tank 1 is used for storing raw material chlorobenzene;
the second storage tank 2 is connected with the reactor, and the second storage tank 2 is used for storing raw materials of dichlorosilane and diluent silicon tetrachloride;
the third storage tank 3 is connected with the reactor, and the third storage tank 3 is used for storing trichloromethane;
a feed heater 5 for heating the feed;
and the reactor is connected with the feeding heater 5, and dichlorosilane and chlorobenzene react in the reactor to generate diphenyldichlorosilane to obtain a reaction product.
Preferably, the reactor comprises three reactors in series. Specifically, the reactor comprises: a first reactor 6, a second reactor 7 linked to the first reactor 6, a third reactor 8 linked to the second reactor 7.
Specifically, the reactor in this example is a tubular reactor.
Preferably, the apparatus for producing diphenyldichlorosilane further comprises:
the condenser 9 is connected with the outlet of the reactor, and the condenser 9 is used for condensing the reaction product;
a crude product tank 10 connected to the condenser 9, the crude product tank 10 being adapted to receive condensed reaction products;
the first-stage rectifying tower 11 is connected with the crude product tank 10, and the first-stage rectifying tower 11 is used for removing dichlorosilane and silicon tetrachloride in the condensed reaction product;
a second-stage rectifying tower 12 connected to the first-stage rectifying tower 11, the second-stage rectifying tower 12 being used for removing benzene;
a third rectifying tower 13 connected to the second rectifying tower 12, wherein the third rectifying tower 13 is used for removing chlorobenzene;
the fourth-stage rectifying tower 14 is connected with the third-stage rectifying tower 13, and the fourth-stage rectifying tower 14 is used for removing phenyltrichlorosilane;
and the fifth-stage rectifying tower 15 is connected with the fourth-stage rectifying tower 14, and the fifth-stage rectifying tower 15 is used for removing the diphenyl dichlorosilane.
Preferably, a gas phase outlet of the first-stage rectifying tower 11 is connected with the second storage tank 2, and dichlorosilane and silicon tetrachloride separated from the first-stage rectifying tower 11 are introduced into the second storage tank 2;
the gas phase outlet of the third-stage rectifying tower 13 is connected with the first storage tank 1, and the chlorobenzene separated from the third-stage rectifying tower 13 is led into the first storage tank 1.
Preferably, the apparatus for producing diphenyldichlorosilane further comprises:
heat exchanger 4, comprising: the heat exchanger comprises a first heat exchanger pipeline and a second heat exchanger pipeline, wherein the first heat exchanger pipeline exchanges heat with the second heat exchanger pipeline, an inlet of the first heat exchanger pipeline is respectively connected with a first storage tank 1, a second storage tank 2 and a third storage tank 3, an outlet of the first heat exchanger pipeline is connected with a feeding heater 5, an inlet of the second heat exchanger pipeline is connected with an outlet of a reactor, and an outlet of the second heat exchanger pipeline is connected with a condenser 9.
The present example provides a method for producing diphenyldichlorosilane using the above production apparatus, comprising the steps of:
(1) A certain amount of raw material chlorobenzene is passed through a drying tower to remove moisture impurities in the raw material chlorobenzene, and then the raw material chlorobenzene is introduced into a first storage tank 1.
(2) And (3) removing moisture impurities in a certain amount of initiator trichloromethane through a drying tower, and introducing into a third storage tank 3.
(3) And (3) introducing the raw material dichlorosilane and the diluent silicon tetrachloride which are mixed in a certain ratio into a second storage tank 2, wherein the mass ratio of the raw material dichlorosilane to the diluent silicon tetrachloride is 1.5.
(4) And (3) opening the feeding heater 5, introducing nitrogen into the inlet position of the first pipeline of the heat exchanger, starting to heat the first reactor 6, the second reactor 7 and the third reactor 8 to raise the temperature to 350 ℃, introducing nitrogen into the reactors for replacement, removing oxidizing gases such as oxygen in the process, and the like, so that the feeding safety of the device is ensured, and the first reactor 6, the second reactor 7 and the third reactor 8 are arranged in an adiabatic heat-insulation facility to ensure that the temperature is not lost. And a temperature detector is added at the outlet of the reactor, and the replacement of the nitrogen gas with increased temperature is stopped when the integral temperature reaches 350 ℃.
(5) After the temperature of the reactor is stabilized, heating and vaporizing the chlorosilane in the step (3) through a feeding heater 5 at the flow of 200kg/h, the pressure of 200Kpa and the temperature of 170 ℃, and starting to introduce the chlorosilane into a first reactor 6, a second reactor 7 and a third reactor 8.
(6) After the flow of the chlorosilane in the step (5) is stable, heating and vaporizing the initiator trichloromethane in the step (2) through a feed heater 5, wherein the flow is 8kg/h, the pressure is 200KPa, the temperature is 170 ℃, and the trichloromethane and the chlorosilane in the step (5) are mixed and introduced into a reactor.
(7) After the flow rate and the pressure of the mixture in the step (6) are stabilized, heating and vaporizing the chlorobenzene in the step (1) by a feeding heater 5 at the pressure of 200Kpa and the temperature of 170 ℃, mixing the chlorobenzene with the mixed gas in the step (6), and introducing the mixture into a reactor at the flow rate of 400kg/h. The mass ratio of the materials introduced into the reactor is as follows: dichlorosilane: trichloromethane: chlorobenzene =1.
(8) In the whole reaction process, the power of a feeding heater 5 is adjusted to ensure that the temperature of the reactor is 300 ℃ and the pressure is 200Kpa, and the pressure of dichlorosilane: chloroform: chlorobenzene =1, and the total length of the reactor is about 50 meters, so that the retention time of the mixed raw materials in the reactor is at least 8 seconds, and the preferred pipe diameter of the reactor is DN25, the material 316 or the same temperature-resistant material. Wherein, the reaction product obtained from the outlet of the reactor comprises: 35% -38% of diphenyl dichlorosilane, 5% -6% of phenyl trichlorosilane, 25% -29% of chlorobenzene, 2% -5% of dichlorosilane, 15% -20% of silicon tetrachloride, 4% -6% of benzene and 7% -10% of HCl. And the high-temperature gas is condensed by a condenser 9 at the outlet of the reactor, cooling water is introduced into the condenser 9 for condensation, the high-temperature gas is condensed, the temperature after condensation is 130 ℃, the use temperature of subsequent materials is reduced, and the synthetic tail gas is condensed into liquid in the production process.
(9) The mixed gas after the reaction is preheated by the heat energy comprehensive utilization heat exchanger 4, the energy is recycled, the power of the feeding heater 5 is reduced, the energy consumption is reduced, the mixed gas after the primary cooling is cooled by the condenser 9 and then enters the crude product tank 10 for buffering, and the tail gas is sent to the alkali liquor absorption device for absorption.
(10) After the crude product tank 10 has a certain liquid level, starting rectification separation, introducing the crude product of the reaction product into a first-stage rectification tower 11 at a pressure range of 100-150 Kpa, removing dichlorosilane and silicon tetrachloride through the first-stage rectification tower 11, separating unreacted dichlorosilane, returning the separated dichlorosilane to a second storage tank 2 for use as a raw material, and conveying the tower kettle material to a second-stage rectification tower 12;
the pressure range of the second-stage rectifying tower 12 is-30 Kpa to-50 Kpa, benzene is removed through the second-stage rectifying tower 12, a high-purity by-product benzene is obtained at the tower top and sold, and the tower kettle material enters a third-stage rectifying tower 13;
the pressure range of the third-stage rectifying tower 13 is-60 Kpa to-80 Kpa, unreacted chlorobenzene is removed through the third-stage rectifying tower 13, the chlorobenzene on the tower top is continuously returned to the first-stage rectifying tower 11 to be used as a raw material, and the material in the tower kettle is sent to a fourth-stage rectifying tower 14;
the pressure of the fourth-stage rectifying tower 14 is in a range of-85 Kpa to-95 Kpa, phenyl trichlorosilane is removed through the fourth-stage rectifying tower 14, phenyl trichloro at the top of the tower is separated and then sent to a tank area for storage, after a certain liquid level is reached, the phenyl trichloro is sold, and the materials in the bottom of the tower are sent to a fifth-stage rectifying tower 15;
the pressure of the fifth-stage rectifying tower 15 is in the range of-85 Kpa to-95 Kpa, the diphenyl dichlorosilane product with the purity of more than 99.5mas percent is obtained at the tower top, and the high-boiling-point substances at the tower bottom are sent to incineration treatment.
The inlet of the fifth-stage rectifying tower 15 receives tower bottom materials of the fourth-stage rectifying tower 14, namely crude diphenyldichlorosilane, wherein the content of diphenyldichlorosilane in the crude diphenyldichlorosilane is 35-40mas%, and the content of phenyltrichlorosilane is 10-15mas%; after rectification, the purity of the diphenyl dimethoxy silane is 99.5mas percent.
The rectifying towers selected above are common wire mesh packing separation towers, are made of stainless steel and are resistant to negative pressure.
The reaction principle of the above reaction is as follows:
H 2 SiCl 2 +C 6 H 5 Cl——C 12 H 10 SiCl 2 +2HCl (exothermic reaction)
The chemical equation for the main side reaction is as follows:
2H 2 SiCl 2 ——HSiCl 3 +SiCl 4
HSiCl 3 +C 6 H 5 Cl——C 6 H 5 SiCl 3 + HCl (exothermic reaction)
HSiCl 3 +C 6 H 5 Cl——C 6 H 6 +SiCl 4
C 6 H 5 Cl→0.2H 2 + C (solid) + HCl
By researching the mechanism for preparing phenylchlorosilane and combining the principle of synthesizing phenyltrichlorosilane in production, dichlorosilane is adopted as a raw material to react with chlorobenzene in a tubular reactor to produce a corresponding diphenyldichlorosilane product accompanied by phenyltrichlorosilane and the like.
The production method and the production device of the diphenyl dichlorosilane in the embodiment have the following beneficial effects:
(1) Silicon tetrachloride is added into dichlorosilane, because the silicon tetrachloride is a compound with stable valence state, the silicon tetrachloride is difficult to react with other substances, the silicon tetrachloride plays a role in diluting and stabilizing dichlorosilane, and meanwhile, the reaction generates corresponding silicon tetrachloride byproducts in the reaction process, so that the related properties of the dichlorosilane can be stabilized, and the stability and the safety of mixed chlorosilane are improved;
(2) The initiator trichloromethane is added to replace the traditional metal catalyst at the initial stage of the reaction, so that pollution is reduced, the initiator trichloromethane can generate corresponding free radicals at a lower temperature, dichlorosilane and chlorobenzene can be initiated to generate free radicals at a low temperature, the combination rate of the free radicals is improved, the reaction can be initiated quickly, the reaction time is shortened, and the reaction temperature is reduced;
(3) Chlorobenzene and dichlorosilane are used as raw materials, and as dichlorosilane has high activity in a high-temperature state and small relative steric hindrance, the reaction conversion rate is ensured and can reach over 35 percent, and the cost can be reduced by at least 15 percent;
(4) The process adopts gas-gas reaction to replace the existing solid-liquid reaction, has high conversion rate of raw materials, avoids equipment abrasion, simultaneously adopts trichloromethane as an initiator, avoids using solid catalysts such as copper and the like, and reduces environmental pollution;
(5) The production line has simple process flow and can realize continuous production.
Example 3
This example provides a process for the production of diphenyldichlorosilane using the production apparatus of example 2, differing from that of example 2 by:
and (4) the mass ratio of the dichlorosilane to the silicon tetrachloride serving as the diluent in the step (3) is 1.
In the step (4), the first reactor 6, the second reactor 7 and the third reactor 8 are heated to 400 ℃. And adding a temperature detector at the outlet of the reactor, and stopping replacing and heating the nitrogen when the overall temperature reaches 400 ℃.
And (5) after the temperature of the reactor is stable, heating and vaporizing the chlorosilane in the step (3) through a feeding heater 5, wherein the flow is 210kg/h, the pressure is 210Kpa, the temperature is 160 ℃, and the chlorosilane is introduced into the first reactor 6, the second reactor 7 and the third reactor 8.
And (6) after the flow of the chlorosilane in the step (5) is stable, heating and vaporizing the initiator trichloromethane in the step (2) by using a feed heater 5, wherein the flow is 8kg/h, the pressure is 210KPa, the temperature is 160 ℃, and the trichloromethane and the chlorosilane in the step (5) are mixed and introduced into a reactor.
And (7) after the flow pressure of the mixture in the step (6) is stabilized, heating and vaporizing the chlorobenzene in the step (1) by using a feeding heater 5, mixing the chlorobenzene with the mixed gas in the step (6) at the pressure of 210Kpa and the temperature of 160 ℃, and introducing the mixture into a reactor at the flow of 400kg/h. The mass ratio of the materials introduced into the reactor is as follows: dichlorosilane: trichloromethane: chlorobenzene = 1.2.
In the step (8), in the whole reaction process, the temperature of the reactor is ensured to be 350 ℃ and the pressure is ensured to be 210Kpa by adjusting the power of the feeding heater 5, and the dichlorosilane: chloroform: chlorobenzene =1.2, total reactor length is about 50 meters, guarantee that the dwell time of the raw materials mixture in the reactor is at least 10 seconds, the preferred DN25 of pipe diameter of the reactor, material 316 or the same temperature resistant material. Wherein, the reaction product obtained from the outlet of the reactor comprises: 35% -38% of diphenyl dichlorosilane, 5% -6% of phenyl trichlorosilane, 25% -29% of chlorobenzene, 2% -5% of dichlorosilane, 15% -20% of silicon tetrachloride, 4% -6% of benzene and 7% -10% of HCl. And the high-temperature gas is condensed at the outlet of the reactor through a condenser 9, cooling water is introduced into the condenser 9 for condensation, the high-temperature gas is condensed, the temperature after condensation is 150 ℃, the use temperature of subsequent materials is reduced, and the synthetic tail gas is condensed into liquid in the production process.
In the embodiment, chlorobenzene and dichlorosilane are used as raw materials, and as dichlorosilane has high activity in a high-temperature state and small relative steric hindrance, the reaction conversion rate is ensured to be over 35 percent, and the cost can be reduced by at least 15 percent.
Example 4
This example provides a process for the production of diphenyldichlorosilane using the production apparatus of example 2, with the difference from example 2 that:
and (3) the mass ratio of the dichlorosilane to the silicon tetrachloride serving as the diluent in the step (3) is 1.8.
In the step (4), the first reactor 6, the second reactor 7 and the third reactor 8 are heated to 380 ℃. And adding a temperature detector at the outlet of the reactor, and stopping replacing and heating the nitrogen when the overall temperature reaches 380 ℃.
After the temperature of the reactor is stabilized in the step (5), heating and vaporizing the chlorosilane in the step (3) through a feed heater 5 at a flow of 220kg/h, a pressure of 220Kpa and a temperature of 165 ℃ and introducing the chlorosilane into a first reactor 6, a second reactor 7 and a third reactor 8.
And (6) after the flow of the chlorosilane in the step (5) is stable, heating and vaporizing the initiator trichloromethane in the step (2) by using a feed heater 5, wherein the flow is 8kg/h, the pressure is 220KPa, the temperature is 165 ℃, and the trichloromethane and the chlorosilane in the step (5) are mixed and introduced into a reactor.
And (7) after the flow pressure of the mixture in the step (6) is stabilized, heating and vaporizing the chlorobenzene in the step (1) by using a feeding heater 5, mixing the chlorobenzene with the mixed gas in the step (6) at the pressure of 220Kpa and the temperature of 165 ℃, and introducing the mixture into a reactor at the flow of 400kg/h. The mass ratio of the materials introduced into the reactor is as follows: dichlorosilane: trichloromethane: chlorobenzene = 1.1.
In the step (8), in the whole reaction process, the temperature of the reactor is ensured to be 400 ℃ and the pressure is ensured to be 220Kpa by adjusting the power of the feeding heater 5, and the dichlorosilane: trichloromethane: chlorobenzene =1.1, and the total length of the reactor is about 50 meters, so that the retention time of the mixed raw materials in the reactor is at least 9 seconds, and the preferred pipe diameter of the reactor is DN25, and the material 316 or the same temperature-resistant material. Wherein, the reaction product obtained from the outlet of the reactor comprises: 35% -38% of diphenyl dichlorosilane, 5% -6% of phenyl trichlorosilane, 25% -29% of chlorobenzene, 2% -5% of dichlorosilane, 15% -20% of silicon tetrachloride, 4% -6% of benzene and 7% -10% of HCl. And the high-temperature gas is condensed by a condenser 9 at the outlet of the reactor, cooling water is introduced into the condenser 9 for condensation, the high-temperature gas is condensed, the temperature after condensation is 180 ℃, the use temperature of subsequent materials is reduced, and the synthetic tail gas is condensed into liquid in the production process.
In the embodiment, chlorobenzene and dichlorosilane are used as raw materials, and as dichlorosilane has high activity in a high-temperature state and small relative steric hindrance, the reaction conversion rate is ensured to be over 35 percent, and the cost can be reduced by at least 15 percent.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and scope of the invention, and such modifications and improvements are also considered to be within the scope of the invention.
Claims (12)
1. The production method of the diphenyl dichlorosilane is characterized by comprising the following steps:
1) Introducing a gas-phase raw material dichlorosilane and a gas-phase diluent silicon tetrachloride into a reactor, introducing a gas-phase initiator trichloromethane into the reactor, and introducing a gas-phase raw material chlorobenzene into the reactor;
2) Heating, and reacting dichlorosilane and chlorobenzene in a reactor to generate diphenyl dichlorosilane to obtain a reaction product.
2. The production method of diphenyl dichlorosilane according to claim 1, characterized in that the mass ratio of dichlorosilane to silicon tetrachloride in the step 1) is (1-1.8): 3.
3. the production method of diphenyldichlorosilane according to claim 1 or 2, characterized in that the mass ratio of each substance in the step 1) is as follows: trichloromethane: chlorobenzene = (1 to 1.2): (0.04-0.06): 2.
4. the process for the production of diphenyldichlorosilane according to claim 1, wherein the heating temperature in step 2) is 300-400 ℃, the pressure is 200-220 Kpa, and the residence time in the reactor is at least 8-10 s.
5. The diphenyldichlorosilane production process according to claim 1, characterized in that said step 1) is preceded by the following step a):
heating and vaporizing raw material dichlorosilane and gaseous diluent silicon tetrachloride at the temperature of 160-170 ℃ and the pressure of 200-220 Kpa;
heating and vaporizing trichloromethane serving as an initiator at the temperature of 160-170 ℃ and the pressure of 200-220 Kpa;
heating chlorobenzene to vaporize at 160-170 deg.c and 200-220 Kpa.
6. The process for the production of diphenyldichlorosilane according to claim 1, further comprising the following step b) before said step 2): the reactor is preheated to 350-400 ℃, nitrogen is introduced into the reactor for replacement, and oxidizing gas in the reactor is removed.
7. The method for producing diphenyldichlorosilane according to any one of claims 1, 2, 4-6, wherein said step 2) is followed by the step c) of:
condensing the reaction product through a cold source;
and sequentially removing dichlorosilane, silicon tetrachloride, benzene, chlorobenzene, phenyltrichlorosilane and diphenyldichlorosilane from the condensed reaction product through multistage rectification.
8. The method for producing diphenyldichlorosilane according to claim 7, wherein the step c) of removing dichlorosilane and silicon tetrachloride, benzene, chlorobenzene, phenyltrichlorosilane, diphenyldichlorosilane sequentially by multi-stage rectification from the condensed reaction product comprises:
removing dichlorosilane and silicon tetrachloride from the condensed reaction product through first-stage rectification, wherein the pressure range is 100-150 Kpa;
removing benzene by secondary rectification, wherein the pressure is in a range of-30 to-50 Kpa;
removing chlorobenzene by third-stage rectification, wherein the pressure range is-60 Kpa to-80 Kpa;
removing phenyl trichlorosilane through fourth-stage rectification, wherein the pressure range is-85 to-95 Kpa;
removing the diphenyl dichlorosilane by a fifth stage of rectification, wherein the pressure range is-85 to-95 Kpa.
9. An apparatus for producing diphenyldichlorosilane used in the production method according to any one of claims 1 to 8, comprising:
the first storage tank is connected with the reactor and is used for storing raw material chlorobenzene;
the second storage tank is connected with the reactor and is used for storing raw materials of dichlorosilane and diluent silicon tetrachloride;
the third storage tank is connected with the reactor and is used for storing trichloromethane;
a feed heater for heating the feed;
and the reactor is connected with the feeding heater, and dichlorosilane and chlorobenzene react in the reactor to generate diphenyl dichlorosilane so as to obtain a reaction product.
10. The diphenyldichlorosilane production apparatus of claim 9, further comprising:
the condenser is connected with the outlet of the reactor and is used for condensing the reaction product;
a crude product tank connected to the condenser, the crude product tank for receiving condensed reaction products;
the first-stage rectifying tower is connected with the crude product tank and is used for removing dichlorosilane and silicon tetrachloride in condensed reaction products;
the second-stage rectifying tower is connected with the first-stage rectifying tower and is used for removing benzene;
the third-stage rectifying tower is connected with the second-stage rectifying tower and is used for removing chlorobenzene;
the fourth-stage rectifying tower is connected with the third-stage rectifying tower and is used for removing phenyltrichlorosilane;
and the fifth-stage rectifying tower is connected with the fourth-stage rectifying tower and is used for removing the diphenyl dichlorosilane.
11. The production device of diphenyl dichlorosilane according to claim 10, wherein a gas phase outlet of the first-stage rectifying tower is connected with a second storage tank, and dichlorosilane and silicon tetrachloride separated from the first-stage rectifying tower are introduced into the second storage tank;
and a gas phase outlet of the third-stage rectifying tower is connected with the first storage tank, and the chlorobenzene channel separated from the third-stage rectifying tower is stored in the first storage tank.
12. The apparatus for producing diphenyldichlorosilane according to claim 10, further comprising:
a heat exchanger, comprising: the heat exchanger comprises a first heat exchanger pipeline and a second heat exchanger pipeline, wherein the first heat exchanger pipeline exchanges heat with the second heat exchanger pipeline, an inlet of the first heat exchanger pipeline is connected with a first storage tank, a second storage tank and a third storage tank respectively, an outlet of the first heat exchanger pipeline is connected with a feeding heater, an inlet of the second heat exchanger pipeline is connected with an outlet of a reactor, and an outlet of the second heat exchanger pipeline is connected with a condenser.
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