CN112028937B - Preparation method and preparation system for synthesizing methyl phosphine dichloride through one-step method - Google Patents
Preparation method and preparation system for synthesizing methyl phosphine dichloride through one-step method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 87
- ONRKUGHFZWYUJP-UHFFFAOYSA-N methylphosphane dihydrochloride Chemical compound Cl.Cl.PC ONRKUGHFZWYUJP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 74
- 239000000047 product Substances 0.000 claims abstract description 50
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- 239000011780 sodium chloride Substances 0.000 claims abstract description 38
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- 229940050176 methyl chloride Drugs 0.000 claims abstract description 34
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- 238000003756 stirring Methods 0.000 claims abstract description 18
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- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 9
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention provides a preparation method and a preparation system for synthesizing methyl phosphine dichloride by a one-step method, wherein the preparation method comprises the following steps: aluminum powder, phosphorus trichloride, sodium chloride, a reaction solvent and a catalyst are put into a reaction device, nitrogen is adopted to replace air in the reaction device, chloromethane is introduced into the reaction device for mixed reaction, and the methyl phosphine dichloride is obtained after a reaction product is distilled and condensed. The invention uses reaction raw materials Al and PCl3NaCl and NaCl are preset in a reaction device, then nitrogen displacement and stirring are carried out, the mixture is fully dispersed and suspended, methyl chloride gas is introduced for reaction, the introduction flow of the methyl chloride is controlled according to the reaction temperature, the control is convenient, the safety is high, and the overall production efficiency and the product yield are high. After the reaction is finished, a methyl phosphine dichloride product is obtained by condensation.
Description
Technical Field
The invention belongs to the technical field of synthesis of methyl phosphine dichloride, and relates to a preparation method and a preparation system of methyl phosphine dichloride, in particular to a preparation method and a preparation system for synthesizing the methyl phosphine dichloride through a one-step method.
Background
The pure methyl phosphine dichloride is a colorless transparent liquid, has the boiling point of 82-84 ℃, has extremely active chemical properties, can explode when meeting water, is extremely easy to oxidize in air, is an important intermediate for synthesizing organic phosphorus compounds, can directly or indirectly synthesize hundreds of organic phosphorus compounds, and is widely applied to the industries of flame retardants, pesticides, medicines and the like. Particularly, methyl phosphine dichloride is used as an important intermediate of the second most transgenic herbicide-resistant glufosinate-ammonium worldwide, and with the rapid development of the glufosinate-ammonium market, the product has a very wide market prospect in the future.
The existing synthesis methods of methyl phosphorus dichloride mainly comprise a methyl aluminum chloride method, a Grignard method, a complex, a methane method and the like. Among them, the methane method is the best synthesis method so far:
CH4+PCl3→CH3PCl2+HCl
the advantages of this method are evident: (1) the economic utilization rate of atoms is as high as 76 percent, which is far higher than 48 percent and 25 percent of that of an aluminum method and a ternary complex method; (2) the byproduct is mainly hydrogen chloride and can be recycled; (2) gas phase homogeneous reaction, simple reaction process.
Of course, the disadvantages of this method are also evident: (1) the reaction conditions are harsh, the reaction needs to be carried out at 600 ℃ and under 0.4MPa, and the requirements on the material quality and the processing precision of reaction equipment are high; (2) the concentration of reaction products is only about 17 percent, the single-pass conversion rate of raw materials is low, a large amount of rectification separation is needed subsequently, and the separation process is very complicated; (3) the flammable and explosive raw materials react at high temperature and high pressure, and the chemical activity of the product is high, so the safety control requirement of the production process is very high.
CN202356087U discloses a fixed bed reactor for reacting methane with phosphorus trichloride and an initiator to produce methyl phosphine dichloride. The main body of the reactor is composed of a cylinder made of alloy steel or provided with an acid-resistant lining. The bottom of the reactor is provided with a sieve plate, and the sieve plate is provided with a filler which is spherical, ellipsoidal or special-shaped particles made of alloy steel, silicon carbide, graphite and other conductive acid-resistant materials. The outside of the reactor is provided with a conductive coil, alternating current is introduced into the coil, the filler inside the reactor is heated by inductance, and the filler transfers heat to the medium gas passing through the gap after the temperature of the filler is raised, so that the reaction gas can be rapidly heated to a specified temperature. The middle part of this reactor sets up certain empty bed section and lets the reaction fully go on, and the upper portion of empty bed section is installed a cooler and is cooled off high-temperature gas, cools off reaction gas to between 100 ~ 200 ℃. The reaction gas is passed through a cyclone separator after exiting the gas outlet to remove liquid and solid impurities.
The invention patent of CN106117267A provides a novel method for synthesizing methyl phosphine dichloride by a methane method, which comprises the steps of taking phosphorus pentachloride as a catalyst, heating phosphorus trichloride and phosphorus pentachloride into steam, mixing the steam with methane preheated to 150-250 ℃, then feeding the mixture into a tubular reactor, and reacting for 0.1-1.0 s under the conditions of the temperature of 400-500 ℃ and the pressure of 0.3-1.2 MPa to obtain the methyl phosphorus dichloride.
The above studies were in the pilot study stage. Many companies in China claim to master the process route of the methyl phosphine dichloride, but the industrial production is not realized yet.
In view of the difficulties in industrial production of methane-derived methyl dichlorophosphine, many scientific research institutes and enterprises both at home and abroad have developed the research on the synthesis process of the ternary complex-derived methyl dichlorophosphine. The main reaction principle of the method is as follows:
CH3Cl+AlCl3+PCl3→CH3PCl4·AlCl3(Complex reaction)
CH3PCl4·AlCl3+Al+2NaCl→CH3PCl2+2NaAlCl4(decomplexation reaction)
CN106565779B provides a new synthesis process of methyl phosphorus dichloride, which comprises the steps of heating a solid ternary complex obtained by the reaction of aluminum trichloride, chloromethane and phosphorus trichloride to 140 ℃, adding a small amount of aluminum powder, preserving the temperature for a period of time, then changing the ternary complex into slurry, slowly adding the slurry into mixed powder containing preheated sodium chloride and aluminum powder, and distilling while reacting to collect 80-82 ℃ fractions to obtain the high-purity methyl phosphorus dichloride.
Patent CN105669748B discloses a synthesis method of methyl phosphorus dichloride, which takes chloromethane, aluminum trichloride and phosphorus trichloride as raw materials and petroleum ether as a solvent to react to generate ligand CH3PCl4·AlCl3After petroleum ether is recovered by distillation, aluminium powder and sodium chloride are added, and the mixture is reduced under the action of catalyst to obtain the product methyl dichloro-methaneAnd (4) phosphorus melting.
The method comprises two main reaction steps of complex reaction and decomplexation reaction, wherein during the decomplexation reaction, aluminum powder is selected, and the simple substance can be strong reducing substances such as yellow phosphorus, iron and the like, for example, CN106967118A discloses a method for preparing dichloro-monoalkyl phosphine, wherein during the decomplexation reaction of binary complex of dichloro-monoalkyl aluminum or alkyl sesqui aluminum chloride and phosphorus trichloride by sodium chloride, alkane solvent is added, free dichloro-monoalkyl phosphine enters the alkane solvent, alkane solution of dichloro-monoalkyl phosphine and newly generated sodium tetrachloroaluminate NaAlCl4Filtering and separating solid; the mixture of the target product dichloro-alkyl phosphine and the alkane solvent can be separated by distillation, and can also directly enter the next application procedure without separation.
However, in the method, the product is a solid phase in the reaction process, so that pipelines and equipment are easy to block, a large amount of acidic substances such as hydrogen chloride and the like are generated in the reaction process, and the equipment is seriously corroded at high temperature, so that the engineering is very difficult. In addition, the method generates more solid waste sodium tetrachloroaluminate, and the development of the process is also limited. According to reports, domestic enterprises adopt the method to carry out project construction, but stable production is not realized until now because numerous engineering problems are not effectively solved.
With the rapid increase of the demand of industries such as glufosinate-ammonium and flame retardant on the methyl phosphine dichloride, domestic colleges and universities and enterprises further research and develop new industrial technical research on the methyl phosphine dichloride, the synthesis process of the methyl phosphine dichloride by the aluminum method is a typical method adopted in recent years, and the synthesis reaction principle is as follows:
2Al+3CH3Cl→(CH3)2AlCl+CH3AlCl2(sesquimer synthesis)
CH3AlCl2+(CH3)2AlCl+3PCl3→3CH3PCl2·2AlCl3(Complex Synthesis)
3CH3PCl2·2AlCl3+2NaCl→3CH3PCl2+2NaAlCl4(Synthesis of methyl phosphine dichloride)
Therefore, the synthesis process of the methyl phosphine dichloride by the aluminum method can be realized through three steps of reactions. The process is the mainstream production process of the national methyl phosphine dichloride at present, but the production process is complex to operate, the problems of solid material conveying, flammable and explosive intermediate transfer and the like are involved, the production can be carried out only by adopting an intermittent method at present, the production efficiency is low, the capacity of a single set of device is low, the process safety risk is great, and the production technology of the national methyl phosphine dichloride is urgently needed to be promoted through process innovation and device system integration optimization.
Disclosure of Invention
Aiming at the defects of the prior art for producing the methyl phosphine dichloride in China, the invention aims to provide a novel method for synthesizing the methyl phosphine dichloride, namely, the methyl phosphine dichloride can be quickly, efficiently and safely produced in the same device system by process integration optimization. The invention uses the reaction raw materials of aluminum powder Al and PCl3NaCl and NaCl are preset in a reaction device, then nitrogen displacement and stirring are carried out, the mixture is fully dispersed and suspended, methyl chloride gas is introduced for reaction, the introduction flow of the methyl chloride is controlled according to the reaction temperature, the control is convenient, the safety is high, and the overall production efficiency and the product yield are high. After the reaction is finished, the methyl phosphine dichloride product is obtained by distillation.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a one-step method for synthesizing methyl phosphine dichloride, wherein the preparation method comprises:
aluminum powder, phosphorus trichloride, sodium chloride, a reaction solvent and a catalyst are put into a reaction device, nitrogen is adopted to replace air in the reaction device, chloromethane is introduced into the reaction device for mixed reaction, and the methyl phosphine dichloride is obtained after a reaction product is distilled and condensed.
Namely, in the same device, the following reactions are realized in one step:
3CH3Cl+2Al+3PCl3+2NaCl→3CH3PCl2+2NaAlCl4
the main invention points of the invention are that:
(1) the invention is in productionThe one-step integration of three steps of reactions required by the original process is realized on the spatial level of the process. The invention converts the reaction which originally needs three steps into one step by deeply researching and analyzing the reaction mechanism and combining the physical properties of the main raw materials, but it is understood that the invention does not change the reaction mechanism, but integrates three spatially relatively separated steps into one space to realize the reaction. The main raw materials of Al and PCl are aluminum powder3And NaCl do not react with each other, and can coexist in the same space, which lays a principle foundation for the realization of the invention. The novel process of the 'one-step method' is formed by integrating innovation and process optimization, the complete synthesis of the methyl phosphine dichloride can be realized in the same reaction device, the operation of material transfer in the middle of reaction is greatly simplified, the realization of program control is facilitated, and the labor intensity of staff operation is reduced.
(2) The original step-by-step reaction with space isolation is optimized into synchronous reaction, and the reaction product of the previous step can rapidly participate in the synthesis of the subsequent step, so that the reaction is promoted to move towards the positive direction, the reaction rate is accelerated, and the production time is shortened. Specifically, the method comprises the following steps: after the aluminum powder reacts with chloromethane to generate methyl aluminum chloride sesqui-body, the methyl aluminum chloride sesqui-body can be directly reacted with PCl in the system3The reaction produces a complex (the reaction does not require catalysis, and the reaction can occur directly after reaching the reaction temperature), and the complex produced can undergo a dissociation reaction rapidly in the presence of NaCl. Because the three reactions are quickly connected in the same system and mutually promoted, the reaction is favorably carried out in the positive direction, and the reaction speed is accelerated.
(3) The sesquialter methyl aluminum chloride is very active and can be spontaneously combusted when meeting air and explode when meeting water, so that the production process has great safety risk. Especially, the methyl aluminum chloride times half body is difficult to avoid running, overflowing, dripping and leaking in the process of transferring between production devices, so the risk is higher. Therefore, from the safety point of view of process operation and process control, the methyl aluminum sesquichloride is not suitable for long-distance transportation and should be converted into safer intermediate products or products nearby. The invention controls the stable production operation of the whole system through methyl chloride, has no risk of transferring and storing hazardous material methyl aluminum chloride times half bodies, and greatly improves the safety of the process and the device.
(4) The one-step synthesis process designed by the invention improves the utilization rate of reaction heat and reduces the energy consumption of the comprehensive production of products. The reaction heat generated by the synthesis and the complex reaction of the sesquimer is directly used for gasifying the methyl phosphine dichloride product, and the gasification latent heat is utilized to quickly remove the reaction heat, so that the intrinsic safety of the reaction is ensured, and the heat utilization efficiency in the reaction process is improved.
As a preferable technical scheme of the invention, the mass ratio of the aluminum powder, the chloromethane, the phosphorus trichloride, the sodium chloride, the reaction solvent and the catalyst is (2.81-5.62): (7.64-15.28): (2.17-4.34): 1-10): 0.0001-0.1).
Preferably, the mass ratio of the aluminum powder, the chloromethane, the phosphorus trichloride, the sodium chloride, the reaction solvent and the catalyst is as follows: 1 (2.81-4.21), (7.64-11.46), (2.17-3.25), (2-5) and (0.001-0.01).
Preferably, the reaction solvent comprises one or a combination of at least two of an alkane, a chlorinated hydrocarbon or an aromatic hydrocarbon.
Preferably, the reaction solvent comprises one or a combination of at least two of isohexane, n-hexane, n-octane, dodecane, toluene, xylene or trimethylbenzene, and further preferably, the reaction solvent comprises one or a combination of at least two of toluene, xylene or dodecane.
Preferably, the catalyst comprises a halogen element and/or a halogenated hydrocarbon.
Preferably, the halogenated hydrocarbon comprises one or a combination of at least two of methyl iodide, ethyl iodide, methyl bromide, ethyl bromide or ethyl dibromide.
In the traditional methyl phosphine dichloride synthesis process, as a byproduct sodium tetrachloroaluminate is continuously generated, the solid content of materials in a kettle is continuously improved in the subsequent evaporation and extraction process of methyl phosphine dichloride, the wall sticking phenomenon is prominent, the extraction rate and the extraction degree of the methyl phosphine dichloride are influenced, and the discharging is difficult. In addition, the discharged sodium tetrachloroaluminate solid is very easy to harden after cooling down, which makes the subsequent transfer and treatment process difficult. In order to solve the problem, the invention adopts a method of adding a high-boiling point inert solvent, so that the flow state and the dispersion state of the product are improved, the subsequent discharge is simple, convenient and easy, more importantly, the discharge is a solid-liquid mixture which can be directly fed into solid-liquid separation equipment such as a centrifuge for separation, the obtained solid by-product sodium tetrachloroaluminate is uniform fine particles, the subsequent transfer and treatment are very facilitated, and the engineering problem of the traditional process is solved. The high boiling point solvent obtained after solid-liquid separation can be directly returned to the reaction system for recycling.
As a preferred technical scheme of the invention, aluminum powder, chloromethane, phosphorus trichloride, sodium chloride, a reaction solvent and a catalyst are fully mixed under the condition of stirring to react.
Preferably, the reaction temperature is controlled to 0 to 200 ℃ by controlling the amount of methyl chloride introduced, and may be, for example, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable. Further preferably, the reaction temperature is 50-120 ℃.
Preferably, the reaction pressure is 0 to 0.6MPa, and may be, for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6MPa, but is not limited to the values listed, and other values not listed in the numerical range are also applicable. Further preferably, the reaction pressure is 0.2-0.5 MPa.
The invention utilizes the operation design of normal pressure or micro-positive pressure, so that the raw material chloromethane is not only a reaction raw material, but also a carrier for strengthening the reaction process and accelerating the removal of the main product, and the reaction rate is improved.
Preferably, the introduction of methyl chloride is stopped when the introduction amount of methyl chloride reaches 1.1 times of the theoretical amount, and the heat is preserved for 0.5-24 h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable. Further preferably, the reaction time is 0.5-5 h.
As a preferable technical scheme of the invention, after the reaction is finished, the reaction product obtained in the reaction device is distilled, the gas-phase product generated by distillation is condensed to obtain the methyl phosphine dichloride product, and the non-condensable gas in the gas-phase product is returned to the reaction device for recycling.
Preferably, the non-condensable gas comprises methyl chloride.
Preferably, the distillation end temperature is 50 to 200 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable. Further preferably, the condensation temperature is 60-150 ℃.
Preferably, the distillation pressure is-0.01 to 0.1MPa, and may be, for example, -0.01MPa, 0MPa, 0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa or 0.1MPa, but is not limited to the values listed, and other values not listed within the range of values are also applicable. Further preferably, the condensation pressure is-0.05-0 MPa.
As a preferred technical scheme, liquid-solid phase products obtained by the reaction are discharged from the reaction device and then sequentially flow through a filtering device and a centrifugal separation device to respectively obtain a reaction solvent and sodium tetrachloroaluminate solids.
Preferably, the reaction solvent obtained by filtering is returned to the reaction device for recycling.
Preferably, the sodium tetrachloroaluminate obtained by centrifugal separation enters a post-treatment unit for recycling.
The process for recycling sodium tetrachloroaluminate is not particularly required and limited, and the recycling process disclosed in the prior art or the recycling process not disclosed in the new technology can be used for recycling sodium tetrachloroaluminate. Illustratively, the invention provides a process for preparing polyaluminum chloride by recycling optional sodium tetrachloroaluminate, which specifically comprises the following steps:
(1) solution separation: adding a decomposing agent into sodium tetrachloroaluminate, heating to 40-120 ℃ to generate aluminum trichloride and sodium chloride, dissolving the aluminum trichloride in the decomposing agent, and separating out the sodium chloride;
(2) solid filtration: filtering the mixed solution obtained in the step (1) while the mixed solution is hot, and removing sodium chloride solids to obtain an aluminum trichloride solution;
(3) cooling and precipitating: cooling the aluminum trichloride solution to room temperature, filtering and drying to obtain white aluminum trichloride solid, wherein the obtained aluminum trichloride meets the raw material conditions;
(4) and (3) reusing: taking the aluminum trichloride obtained in the step (3) as a raw material of glufosinate-ammonium, reacting with chloromethane and phosphorus trichloride to prepare a complex, carrying out decomplexation reduction on the complex to prepare methyl phosphine dichloride, and then forming ester with ethanol to obtain sodium tetrachloroaluminate solid again:
(5) and (3) recycling: repeating the steps (1) - (4), reducing the complexing capacity of the aluminum trichloride, the chloromethane and the phosphorus trichloride after multiple cycles, reducing the reaction titer, and carrying out the next step of processing the batch of aluminum trichloride;
(6) preparing polyaluminum chloride: and (3) adding a sodium hydroxide solution into the aluminum trichloride obtained in the step (5), controlling the reaction temperature to be 20-100 ℃, reacting for 0.5-10 h, quickly stirring to reach the required basicity of 45% -65%, and drying to obtain the product polyaluminium chloride.
In a second aspect, the present invention provides a one-step preparation system for synthesizing methyl phosphine dichloride, wherein the preparation system is used for completing the preparation method of the first aspect.
The preparation system comprises a reaction device and a condensing device connected with the top of the reaction device.
The invention designs an integrated preparation system of the methyl phosphine dichloride, reaction raw materials are added into a reaction device at one time, the centralized control of metering is convenient, the material loss in the process is small, and the operation risk factor is low. Because the viscosity and phase state change of the product exist in the reaction process, in order to ensure the rapid reaction, firstly, a high-power and high-shear mixing and stirring type is adopted, and secondly, the solid product is dispersed by adding the inert solvent with high boiling point, so that the phenomena of wall adhesion and the like caused by the increase of solid content in the subsequent extraction process of the methyl phosphine dichloride are avoided, and the engineering problem of product production is solved.
As a preferable technical scheme of the invention, the reaction device comprises a reaction device shell and a jacket arranged outside the reaction device shell, and a heating medium is introduced into the jacket.
Preferably, a stirring device is arranged inside the reaction device shell.
Preferably, reaction unit casing top independently access nitrogen pipeline, gas line and liquid line respectively, chloromethane let in reaction unit through gas line, phosphorus trichloride and reaction solvent let in reaction unit through liquid line.
Preferably, the top of the shell of the reaction device is further provided with a storage tank, and the storage tank is internally stored with aluminum powder and sodium chloride.
The reaction device provided by the invention integrates two engineering units of reaction heat removal and evaporation heat supply, utilizes the ordered connection of reaction processes to replace the artificial separation of the traditional production process, directly utilizes the generated heat generated in the synthesis and complexing reaction processes of the methyl aluminum sesquichloride to be used for gasifying a main product, namely the methyl phosphine dichloride, and simultaneously solves the two engineering problems of reaction heat removal and gasification latent heat supply, so that the reaction device provided by the invention has higher thermal efficiency and greatly reduces the energy consumption level in the production process of products.
As a preferable technical scheme of the invention, the preparation system further comprises a collecting device connected with the condensing device, a gas outlet of the collecting device is connected to a gas pipeline, and the non-condensable gas collected in the collecting device returns to the reaction device through the gas pipeline.
As a preferable technical scheme of the invention, the bottom of the shell of the reaction device is connected with a filtering device, a liquid outlet of the filtering device is connected with a liquid pipeline, and a reaction solvent obtained by filtering through the filtering device returns to the reaction device through the liquid pipeline for recycling.
Preferably, the discharge port of the filtering device is connected with a centrifugal separation device.
As a preferable technical scheme of the invention, the discharge hole of the centrifugal separation device is connected with the post-treatment unit.
The system refers to an equipment system, or a production equipment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention realizes one-step integration of reaction on the spatial level of the production process, converts the reaction which needs three steps to be carried out originally into one step by deeply analyzing and researching the reaction mechanism and combining the physical properties of the main raw materials, but needs to be understood that the invention does not change the reaction mechanism, but integrates three steps separated in space into one space to realize the reaction, and the main raw materials Al and PCl reacted in three steps in the original process3And NaCl do not react with each other, and can coexist in the same space, which lays a principle foundation for the realization of the invention. The novel process of the 'one-step method' is formed by integrating innovation and process optimization, the complete synthesis of the methyl phosphine dichloride can be realized in the same reaction device, the operation of transferring materials in the middle of reaction is greatly simplified, the realization of program control is facilitated, and the labor intensity of workers in operation is reduced.
(2) The original step-by-step reaction with space isolation is optimized into synchronous reaction, and the reaction product of the previous step can rapidly participate in the synthesis of the subsequent step, so that the reaction is promoted to move towards the positive direction, the reaction rate is accelerated, and the production time is shortened. Specifically, the method comprises the following steps: after the aluminum powder reacts with chloromethane to produce methyl aluminum chloride, the methyl aluminum chloride can be directly reacted with PCl in a system3The reaction produces a complex (the reaction does not require catalysis, and the reaction can occur directly after reaching the reaction temperature), and the produced complex is dissociated directly in the presence of NaCl. Because the three reactions are quickly connected in the same system and mutually promoted, the reaction is favorably carried out in the positive direction, and the reaction speed is accelerated.
(3) The sesquialter methyl aluminum chloride is very active and can be spontaneously combusted when meeting air and explode when meeting water, so that the production process has great safety risk. Especially, aluminum methyl chloride double half in the transfer process, the risk is greater. Therefore, from the safety point of view of process operation and process control, the methyl aluminum sesquichloride is not suitable for long-distance transportation and should be converted into safer intermediate products or products nearby. The invention controls the stable production operation of the whole system through methyl chloride, and has no risk of transferring and storing the methylaluminium chloride double half body of dangerous materials.
(4) The one-step synthesis process designed by the invention improves the utilization rate of reaction heat and reduces the energy consumption of the comprehensive production of products. The reaction heat generated by the complexation and dissociation reactions is directly used for gasifying the methyl phosphine dichloride product, and the gasification latent heat is utilized to quickly remove the reaction heat, so that the intrinsic safety of the reaction is ensured, and the heat utilization efficiency in the reaction process is improved.
Drawings
FIG. 1 is a schematic structural diagram of a preparation system according to an embodiment of the present invention.
Wherein, 1-a reaction device shell; 2-a jacket; 3-a stirring device; 4-a condensing unit; 5-a collecting device; 6-a storage tank; 7-a filtration device; 8-centrifugal separation device.
FIG. 2 is a flow chart of the synthesis process provided in comparative example 1 of the present invention.
Detailed Description
It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention.
It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In one embodiment, the invention provides a preparation system for synthesizing methyl phosphine dichloride by a one-step method, which is shown in figure 1 and comprises a reaction device and a condensing device 4 connected with the top of the reaction device. The reaction device comprises a reaction device shell 1 and a jacket 2 arranged on the outer side of the reaction device shell 1, and a heating medium is introduced into the jacket 2. The reaction device casing 1 is provided with a stirring device 3 inside. The top of the shell 1 of the reaction device is respectively and independently connected with a nitrogen pipeline, a gas pipeline and a liquid pipeline, chloromethane is introduced into the reaction device through the gas pipeline, and phosphorus trichloride and a reaction solvent are introduced into the reaction device through the liquid pipeline. The top of the reaction device shell 1 is also provided with a storage tank 6, and the storage tank 6 stores aluminum powder and sodium chloride.
The bottom of the reaction device shell 1 is connected with a filtering device 7, a liquid outlet of the filtering device 7 is connected with a liquid pipeline, and a reaction solvent obtained by filtering through the filtering device 7 returns to the reaction device through the liquid pipeline for recycling. The discharge port of the filtering device 7 is connected with a centrifugal separation device 8, and the discharge port of the centrifugal separation device 8 is connected with a post-processing unit.
The preparation system also comprises a collecting device 5 connected with the condensing device 4, a gas outlet of the collecting device 5 is connected with a gas pipeline, and the non-condensable gas collected in the collecting device 5 returns to the reaction device through the gas pipeline.
Example 1
In this embodiment, the preparation system provided by the specific embodiment is used to synthesize methyl phosphine dichloride, and the synthesis process specifically includes the following steps:
(1) 270g of aluminum powder, 0.1g of methyl iodide, 2065.5g of phosphorus trichloride, 614.25g of sodium chloride and 540g of xylene are added into a reaction device, a stirring device 3 is started, a heating medium is injected into a jacket 2 of the reaction device, and a cooling medium is injected into a condensing device 4. Introducing methyl chloride gas into the reaction device at a mass flow of 3g/min, controlling the reaction temperature in the reaction device at 50 ℃ and the reaction pressure at 0.2MPa by controlling the flow of the heating medium and the introduction rate of the methyl chloride. When the introduction amount of the methyl chloride reaches 1.1 times of the theoretical amount, the introduction of the methyl chloride is stopped, and the reaction temperature of 60 ℃ is maintained for 0.5 h.
(2) After the heat preservation is finished, the heating medium in the jacket 2 is utilized to carry out temperature rising distillation on the reaction product in the reaction device, the end temperature of the distillation is controlled to be 80 ℃, and the distillation pressure is controlled to be-0.1 MPa. And condensing a gas-phase product generated by distillation through a condensing device 4, then feeding the gas-phase product into a collecting device 5, recovering the condensed methyl phosphine dichloride product through the collecting device 5, and allowing the condensed non-condensable gas to escape from the collecting device 5 and return to the reaction device for recycling.
(3) After distillation is finished, slowly reducing the temperature in the reaction device to normal temperature, then opening a discharge valve at the bottom of the reaction device to discharge, discharging liquid-solid products in the reaction device out of the reaction device, sequentially flowing through a filtering device 7 and a centrifugal separation device 8 to respectively obtain a reaction solvent and sodium tetrachloroaluminate solids, returning the reaction solvent obtained by filtering to the reaction device for recycling, and allowing solid residues (mainly comprising sodium tetrachloroaluminate) obtained by centrifugal separation to enter a post-processing unit for recycling and synthesizing polyaluminium chloride.
1618.30g of a methyl phosphine dichloride sample and 1491.60g of fine granular solid slag are obtained after weighing. Through analysis, the methyl phosphine dichloride sample contains 98.50 wt% of methyl phosphine dichloride and 0.1 wt% of phosphorus trichloride; 95.20 wt% of sodium tetrachloroaluminate, 0.25 wt% of methyl phosphine dichloride and the balance of sodium chloride in the solid slag. By calculation, the yield of the methyl phosphine dichloride product is 90.83% when the synthesis process provided by the embodiment is adopted to prepare the methyl phosphine dichloride.
Comparative example 1
The comparative example provides a traditional preparation process for synthesizing methyl phosphine dichloride by a three-step method, and the preparation method is shown in figure 2 and specifically comprises the following steps:
(1) synthesis of aluminum sesquimethyl chloride: 270g of aluminum powder and 0.1g of iodomethane or bromomethane or dichloroethane as an initiator are put into the autoclave, and chloromethane is introduced while stirring for reaction. The heat is transferred by a cooling medium of an autoclave jacket 2, the reaction temperature is controlled at 100 ℃, the reaction pressure is controlled at 0.5MPa, and the reaction time is controlled at 12 h. After the reaction is finished, the temperature is reduced to 40 ℃, and the mixture is transferred to a sesquimethyl aluminum chloride intermediate tank through a hose for later use. About 25ml of aluminum sesquimethyl chloride remained in the autoclave.
(2) Synthesis of the complex: 4300g of phosphorus trichloride is added into a complex reaction kettle, a stirring and jacket heat transfer system is started, and a bottom valve of a middle tank of the sesquimethyl aluminum chloride is started to slowly drop the sesquimethyl aluminum chloride for complex reaction. The reaction temperature was controlled at 40 ℃ and normal pressure. The dropping time is about 10 hours, and the temperature is kept for 2 hours at 40 ℃ after the dropping is finished. And (4) distilling after the heat preservation is finished, recovering 2237.50g of phosphine trichloride, and obtaining the complex obtained by the reaction, wherein the residual viscous substance in the kettle is the phosphine.
(3) Synthesis of methyl phosphine dichloride: adding 851.50g of sodium chloride solid into the complexation kettle, stirring, heating, reacting and distilling. 1393g of phosphine methyldichloride sample are obtained after condensation in the gas phase, and analysis shows that: the content of methyl phosphine dichloride in the sample is 97.5%, and the content of phosphorus trichloride is 1.5%. The hard cake solid remaining in the kettle was 1670.65g total for a sample of sodium tetrachloroaluminate, analyzed: the content of sodium tetrachloroaluminate in the sample is 85%, the content of methyl phosphine dichloride is 2%, and the balance is sodium chloride and the like.
The product yield of the methyl phosphine dichloride prepared by the synthesis process of the three-step method provided by the comparative example is 77.40%.
Example 2
In this embodiment, the preparation system provided by the specific embodiment is used to synthesize methyl phosphine dichloride, and the synthesis process specifically includes the following steps:
(1) 270g of aluminum powder, 0.5g of iodine, 2065.5g of phosphorus trichloride, 614.25g of sodium chloride and 300g of trimethylbenzene are added into a reaction device, a stirring device 3 is started, a heating medium is injected into a jacket 2 of the reaction device, and a cooling medium is injected into a condensing device 4. Introducing methyl chloride gas into the reaction device at a mass flow of 3g/min, controlling the reaction temperature in the reaction device at 80 ℃ and the reaction pressure at 0.3MPa by controlling the flow of the heating medium and the introduction rate of the methyl chloride. When the introduction amount of the methyl chloride reaches 1.2 times of the theoretical amount, the introduction of the methyl chloride is stopped, and the reaction temperature of 80 ℃ is maintained for 1 hour.
(2) After the heat preservation is finished, the heating medium in the jacket 2 is utilized to carry out temperature rising distillation on the reaction product in the reaction device, the end temperature of the distillation is controlled to be 120 ℃, and the distillation pressure is controlled to be 0 MPa. And condensing a gas-phase product generated by distillation through a condensing device 4, then feeding the gas-phase product into a collecting device 5, recovering the condensed methyl phosphine dichloride product through the collecting device 5, and allowing the condensed non-condensable gas to escape from the collecting device 5 and return to the reaction device for recycling.
(3) After distillation is finished, slowly reducing the temperature in the reaction device to normal temperature, then opening a discharge valve at the bottom of the reaction device to discharge, discharging liquid-solid products in the reaction device out of the reaction device, sequentially flowing through a filtering device 7 and a centrifugal separation device 8 to respectively obtain a reaction solvent and sodium tetrachloroaluminate solids, returning the reaction solvent obtained by filtering to the reaction device for recycling, and allowing solid residues (mainly comprising sodium tetrachloroaluminate) obtained by centrifugal separation to enter a post-processing unit for recycling and synthesizing polyaluminium chloride.
1640.75g of a methyl phosphine dichloride sample and 1485.40g of fine granular solid slag are obtained after weighing. Through analysis, the content of the methyl phosphine dichloride in a methyl phosphine dichloride sample is 98.80 wt%, and the content of the phosphorus trichloride is 0.08 wt%; 96.10 wt% of sodium tetrachloroaluminate, 0.15 wt% of methyl phosphine dichloride and the balance of sodium chloride in the solid slag. By calculation, the yield of the methyl phosphine dichloride product prepared by the synthesis process provided by the embodiment is 92.36%.
Example 3
In this embodiment, the preparation system provided by the specific embodiment is used to synthesize methyl phosphine dichloride, and the synthesis process specifically includes the following steps:
(1) 270kg of aluminum powder, 100g of methyl iodide, 2065.5kg of phosphorus trichloride, 614.25kg of sodium chloride and 500kg of xylene are added into a reaction device, a stirring device 3 is started, a heating medium is injected into a jacket 2 of the reaction device, and a cooling medium is injected into a condensing device 4. Methyl chloride gas is introduced into the reaction device at a mass flow of 5kg/min, the reaction temperature in the reaction device is controlled at 120 ℃ and the reaction pressure is controlled at 0.4MPa by controlling the flow of the heating medium and the introduction rate of the methyl chloride. When the introduction amount of the methyl chloride reaches 1.05 times of the theoretical amount, the introduction of the methyl chloride is stopped, and the reaction temperature of 120 ℃ is maintained for 2 hours.
(2) After the heat preservation is finished, the heating medium in the jacket 2 is utilized to carry out temperature rise distillation on the reaction product in the reaction device, the end temperature of the distillation is controlled to be 150 ℃, and the distillation pressure is controlled to be-0.05 MPa. And condensing a gas-phase product generated by distillation through a condensing device 4, then feeding the gas-phase product into a collecting device 5, recovering the condensed methyl phosphine dichloride product through the collecting device 5, and allowing the condensed non-condensable gas to escape from the collecting device 5 and return to the reaction device for recycling.
(3) After distillation is finished, slowly reducing the temperature in the reaction device to normal temperature, then opening a discharge valve at the bottom of the reaction device to discharge, discharging liquid-solid products in the reaction device out of the reaction device, sequentially flowing through a filtering device 7 and a centrifugal separation device 8 to respectively obtain a reaction solvent and sodium tetrachloroaluminate solids, returning the reaction solvent obtained by filtering to the reaction device for recycling, and allowing solid residues (mainly comprising sodium tetrachloroaluminate) obtained by centrifugal separation to enter a post-processing unit for recycling and synthesizing polyaluminium chloride.
The samples were weighed to obtain 1685.20kg of phosphine methyldichloride and 1470.5kg of fine granular solid slag. By analysis, in the methyl phosphine dichloride sample, 98.60 wt% of methyl phosphine dichloride and 0.08 wt% of phosphorus trichloride are contained; 95.50 wt% of sodium tetrachloroaluminate, 0.1 wt% of methyl phosphine dichloride and the balance of sodium chloride in the solid slag. By calculation, the yield of the methyl phosphine dichloride product prepared by the synthesis process provided by the embodiment is 94.68%.
Example 4
In this embodiment, the preparation system provided by the specific embodiment is used to synthesize methyl phosphine dichloride, and the synthesis process specifically includes the following steps:
(1) 270kg of aluminum powder, 800g of a composition of methyl iodide and iodine, 2065.5kg of phosphorus trichloride, 614.25kg of sodium chloride and 500kg of xylene were charged into a reaction apparatus, a stirring apparatus 3 was started, a heating medium was injected into a jacket 2 of the reaction apparatus, and a cooling medium was injected into a condensing apparatus 4. And introducing methyl chloride gas into the reaction device at a rate of 1-5 kg/min, controlling the reaction temperature in the reaction device at 170 ℃ and the reaction pressure at 0.3MPa by controlling the flow of the heating medium and the introduction rate of the methyl chloride. When the introduction amount of the methyl chloride reaches 1.5 times of the theoretical amount, the introduction of the methyl chloride is stopped, and the reaction temperature of 150 ℃ is maintained for 2 hours.
(2) After the heat preservation is finished, the heating medium in the jacket 2 is utilized to carry out temperature rise distillation on the reaction product in the reaction device, the end temperature of the distillation is controlled to be 140 ℃, and the distillation pressure is controlled to be-0.08 MPa. And condensing a gas-phase product generated by distillation through a condensing device 4, then feeding the gas-phase product into a collecting device 5, recovering the condensed methyl phosphine dichloride product through the collecting device 5, and allowing the condensed non-condensable gas to escape from the collecting device 5 and return to the reaction device for recycling.
(3) After distillation is finished, slowly reducing the temperature in the reaction device to normal temperature, then opening a discharge valve at the bottom of the reaction device to discharge, discharging liquid-solid products in the reaction device out of the reaction device, sequentially flowing through a filtering device 7 and a centrifugal separation device 8 to respectively obtain a reaction solvent and sodium tetrachloroaluminate solids, returning the reaction solvent obtained by filtering to the reaction device for recycling, and allowing solid residues (mainly comprising sodium tetrachloroaluminate) obtained by centrifugal separation to enter a post-processing unit for recycling and synthesizing polyaluminium chloride.
The samples were weighed to obtain 1640.5kg of phosphine methyldichloride and 1458.6kg of fine granular solid slag. Through analysis, the content of the methyl phosphine dichloride in the sample is 97.60 percent by weight, and the content of the phosphorus trichloride is 0.22 percent by weight; 94.80 wt% of sodium tetrachloroaluminate, 0.36 wt% of methyl phosphine dichloride and the balance of sodium chloride in the solid slag. By calculation, the yield of the methyl phosphine dichloride product is 91.623% when the synthesis process provided by the embodiment is adopted to prepare the methyl phosphine dichloride.
Example 5
In this embodiment, the preparation system provided by the specific embodiment is used to synthesize methyl phosphine dichloride, and the synthesis process specifically includes the following steps:
(1) 270kg of aluminum powder, 500g of dichloroethane, 2065.5g of phosphorus trichloride, 614.25g of sodium chloride and 1000kg of dodecane were added to the reaction apparatus, the stirring apparatus 3 was started, a heating medium was injected into the jacket 2 of the reaction apparatus, and a cooling medium was injected into the condensing apparatus 4. Methyl chloride gas is fed into the reaction device at a rate of 5kg/min, the reaction temperature in the reaction device is controlled at 180 ℃ and the reaction pressure is controlled at 0.2MPa by controlling the flow rate of the heating medium and the feeding rate of the methyl chloride. When the introduction amount of the methyl chloride reaches 1.2 of the theoretical amount, the introduction of the methyl chloride is stopped, and the reaction temperature of 180 ℃ is maintained for 0.5 h.
(2) After the heat preservation is finished, heating medium in the jacket 2 is used for heating and distilling reaction products in the reaction device, the end temperature of the distillation is controlled to be 200 ℃, and the distillation pressure is controlled to be-0.05 MPa. And condensing a gas-phase product generated by distillation through a condensing device 4, then feeding the gas-phase product into a collecting device 5, recovering the condensed methyl phosphine dichloride product through the collecting device 5, and allowing the condensed non-condensable gas to escape from the collecting device 5 and return to the reaction device for recycling.
(3) After distillation is finished, slowly reducing the temperature in the reaction device to normal temperature, then opening a discharge valve at the bottom of the reaction device to discharge, discharging liquid-solid products in the reaction device out of the reaction device, sequentially flowing through a filtering device 7 and a centrifugal separation device 8 to respectively obtain a reaction solvent and sodium tetrachloroaluminate solids, returning the reaction solvent obtained by filtering to the reaction device for recycling, and allowing solid residues (mainly comprising sodium tetrachloroaluminate) obtained by centrifugal separation to enter a post-processing unit for recycling and synthesizing polyaluminium chloride.
The samples were weighed to obtain 1610kg of a phosphine methyldichloride sample and 1502.4kg of fine granular solid residues. Through analysis, the content of the methyl phosphine dichloride in the sample is 97.50 percent by weight, and the content of the phosphorus trichloride is 0.5 percent by weight; in the solid slag, 94.60 wt% of sodium tetrachloroaluminate, 0.45 wt% of methyl phosphine dichloride and the balance of sodium chloride are adopted. By calculation, the yield of the methyl phosphine dichloride product prepared by the synthesis process provided by the embodiment is 89.44%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (17)
1. A preparation method for synthesizing methyl phosphine dichloride through a one-step method is characterized by comprising the following steps:
aluminum powder, phosphorus trichloride, sodium chloride, a reaction solvent and a catalyst are put into a reaction device, and the aluminum powder, the chloromethane, the phosphorus trichloride, the sodium chloride, the reaction solvent and the catalyst are fully mixed under the stirring condition to react; replacing air in the reaction device with nitrogen, introducing methyl chloride into the reaction device for mixed reaction, controlling the reaction temperature to be 50-120 ℃ by controlling the introduction amount of the methyl chloride, controlling the reaction pressure to be 0-0.6 MPa, stopping introducing the methyl chloride when the introduction amount of the methyl chloride reaches 1.1 time of the theoretical amount, preserving the temperature for 0.5-24 h, and distilling and condensing a reaction product to obtain the methyl phosphine dichloride;
the mass ratio of the aluminum powder, the chloromethane, the phosphorus trichloride, the sodium chloride, the reaction solvent and the catalyst is 1 (2.81-5.62): (7.64-15.28): (2.17-4.34): 1-10): 0.0001-0.1; the reaction solvent comprises one or the combination of at least two of alkane, chlorohydrocarbon or aromatic hydrocarbon; the catalyst comprises halogen simple substance and/or halogenated hydrocarbon.
2. The method of claim 1, wherein the mass ratio of the aluminum powder, the chloromethane, the phosphorus trichloride, the sodium chloride, the reaction solvent and the catalyst is 1 (2.81-4.21): (7.64-11.46): (2.17-3.25): (2-5): 0.001-0.01).
3. The method of claim 1, wherein the reaction solvent comprises one or a combination of at least two of isohexane, n-hexane, n-octane, dodecane, toluene, xylene, or trimethylbenzene.
4. The method of claim 1, wherein the reaction solvent comprises one or a combination of at least two of toluene, xylene, or dodecane.
5. The method of claim 1, wherein the halogenated hydrocarbon comprises one or a combination of at least two of methyl iodide, ethyl iodide, methyl bromide, ethyl bromide and ethyl bromide.
6. The preparation method according to claim 1, wherein the reaction pressure is 0.2 to 0.5 MPa.
7. The preparation method according to claim 1, wherein the introduction of the methyl chloride is stopped when the introduction amount of the methyl chloride reaches 1.1 times of the theoretical amount, and the temperature is kept for 0.5-5 hours.
8. The preparation method according to claim 1, wherein the reaction product obtained in the reaction device is distilled after the reaction is finished, the gas-phase product generated by distillation is condensed to obtain the methyl phosphine dichloride product, and the non-condensable gas in the gas-phase product is returned to the reaction device for recycling.
9. The method of claim 8, wherein the non-condensable gas comprises methyl chloride.
10. The method according to claim 8, wherein the end point temperature of the distillation is 50 to 200 ℃.
11. The method according to claim 8, wherein the end point temperature of the distillation is 60 to 150 ℃.
12. The method according to claim 8, wherein the distillation pressure is from-0.01 MPa to 0.1 MPa.
13. The method according to claim 8, wherein the distillation pressure is-0.05 to 0 MPa.
14. The process according to claim 1, wherein the liquid-solid product obtained by the reaction is discharged from the reaction apparatus and then passed through a filtration apparatus and a centrifugal separation apparatus in this order to obtain the reaction solvent and the solid sodium tetrachloroaluminate, respectively.
15. The process according to claim 14, wherein the reaction solvent obtained by the filtration is returned to the reaction apparatus for recycling.
16. The method according to claim 14, wherein the sodium tetrachloroaluminate obtained by centrifugal separation is recycled by a post-treatment unit.
17. A one-step synthesis preparation system of methyl phosphine dichloride, which is characterized in that the preparation system is used for completing the preparation method of any one of claims 1 to 16;
the preparation system comprises a reaction device and a condensing device connected with the top of the reaction device;
the reaction device comprises a reaction device shell and a jacket arranged on the outer side of the reaction device shell, and a heating medium is introduced into the jacket;
a stirring device is arranged in the reaction device shell;
the top of the shell of the reaction device is respectively and independently connected with a nitrogen pipeline, a gas pipeline and a liquid pipeline, the chloromethane is introduced into the reaction device through the gas pipeline, and the phosphorus trichloride and the reaction solvent are introduced into the reaction device through the liquid pipeline;
the top of the shell of the reaction device is also provided with a storage tank, and the storage tank is internally stored with aluminum powder and sodium chloride;
the preparation system also comprises a collecting device connected with the condensing device, wherein a gas outlet of the collecting device is connected to a gas pipeline, and the non-condensable gas collected in the collecting device returns to the reaction device through the gas pipeline;
the bottom of the shell of the reaction device is connected with a filtering device, a liquid outlet of the filtering device is connected with a liquid pipeline, and a reaction solvent obtained by filtering through the filtering device returns to the reaction device through the liquid pipeline for recycling;
the discharge port of the filtering device is connected with a centrifugal separation device;
and a discharge port of the centrifugal separation device is connected with the post-processing unit.
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