WO2020000366A1 - Procédé de préparation d'halogénure d'hydrocarbyle phosphine et réacteur correspondant - Google Patents

Procédé de préparation d'halogénure d'hydrocarbyle phosphine et réacteur correspondant Download PDF

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WO2020000366A1
WO2020000366A1 PCT/CN2018/093672 CN2018093672W WO2020000366A1 WO 2020000366 A1 WO2020000366 A1 WO 2020000366A1 CN 2018093672 W CN2018093672 W CN 2018093672W WO 2020000366 A1 WO2020000366 A1 WO 2020000366A1
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weight
alloy
reactor
nickel
reaction
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Chinese (zh)
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邹应全
焦红军
郑朝俊
田传文
庞玉莲
何长云
何长华
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Hubei Gurun Technology Co Ltd
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Hubei Gurun Technology Co Ltd
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Priority to PCT/CN2018/093672 priority Critical patent/WO2020000366A1/fr
Priority to BR112020026755-4A priority patent/BR112020026755B1/pt
Priority to MYPI2020007073A priority patent/MY194553A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • 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

Definitions

  • the invention relates to a method for directly synthesizing a hydrocarbyl halophosphine under the condition of no catalyst, and a reactor specially used for implementing the method.
  • Diphenylphosphine chloride and phenyldichlorophosphine are important monomers for the synthesis of various organic phosphorus compounds. They are also intermediates for the preparation of pesticides, plasticizers, phosphorus flame retardants, and ultraviolet photoinitiators. The demand is vast.
  • the conventional method for preparing phenylphosphine dichloride is to use benzene and phosphorus trichloride to heat up the reaction for 2-6 hours in the presence of anhydrous aluminum trichloride catalyst.
  • the liquid organic phase was separated at a reduced temperature, and excess benzene and phosphorus trichloride were distilled off under reduced pressure in order. Finally, the product was distilled under reduced pressure to obtain the product phenylphosphine dichloride.
  • aluminum trichloride and phenylphosphine dichloride will form a complex and lose their activity. Therefore, it is necessary to add aluminum trichloride in an equimolar amount or more with benzene.
  • diphenylphosphine chloride is basically similar to that of phenylphosphine dichloride.
  • the conventional method is also obtained by using excess benzene and phosphorus trichloride in the presence of an anhydrous aluminum trichloride catalyst at high temperature. Its disadvantage is that it will generate a large amount of complex solid waste of aluminum trichloride, which has great environmental pressure (see http://www.docin.com/p-1372117195.html).
  • Organic decomplexing agents include phosphorus trichloride, phosphorus pentoxide, pyridine organic bases, ethyl acetate, ⁇ -chlorotriethyl phosphate, and dioxane.
  • the inorganic salt decomplexing agent is ground sodium chloride or potassium chloride.
  • Chinese patent application CN201110426418.5 discloses that benzene, phosphorus trichloride and aluminum trichloride are mixed vigorously and heated to 140-150 ° C for reaction; after the reaction is completed, the temperature is lowered to room temperature, and the decomplexing agent ⁇ -chlorophosphoric acid is added dropwise. Triethyl ester; the lower decomplexer layer was separated, and the upper organic layer was distilled under reduced pressure to obtain diphenylphosphine chloride.
  • Chinese patent application CN201210473945.6 discloses a method for synthesizing diphenylphosphine chloride. It uses a Lewis acid room temperature ionic liquid to catalyze the reaction of benzene and phosphorus trichloride to synthesize diphenylphosphine chloride. The method uses phosphorus trichloride and excess benzene as raw materials, and reacts under the action of a Lewis acid ionic liquid. After the reaction, the reaction liquid is divided into two layers, one is an ionic liquid layer, and the other is a mixed liquid layer.
  • the ionic liquid layer is extracted, and the extract and the mixed liquid layer are combined, and the pressure distillation and vacuum distillation are respectively performed to obtain the target product, diphenylphosphine chloride and by-product phenylphosphine dichloride.
  • Ionic liquids are often recovered by removing the impurities under reduced pressure and reduced pressure.
  • Chinese patent application CN201310099065.1 proposes a synthetic method of phenylphosphine dichloride. Benzene and phosphorus trichloride are used as raw materials, and sodium chloride and aluminum trichloride are simultaneously added as catalysts to obtain phenylphosphine dichloride, a mixed solution of benzene and phosphorus trichloride, and a solid residue. The solid residue is treated with an extractant, mixed with the mixed liquid, and often distilled under reduced pressure to obtain pure phenylphosphine dichloride. The catalyst AlCl 3 ⁇ XNaCl complex can be recycled.
  • US patent US3734958 discloses that chlorobenzene and yellow phosphorus are used as raw materials in the presence of phenylphosphine dichloride to raise the temperature to 340 ° C in a tantalum autoclave to react for 4 hours, and then discharged after cooling to obtain phosphorus trichloride, chlorobenzene, A mixture of phenyldichlorophosphine and diphenylphosphine chloride, often under pressure distillation and vacuum distillation to obtain the product-diphenylphosphine chloride.
  • Phosphorus trichloride, phenylphosphine dichloride, and diphenylphosphine chloride are very corrosive. Tantalum materials have Certain corrosion resistance, however, tantalum is expensive and cannot be industrialized, and the slightly cheaper tantalum-based alloy cannot achieve effective corrosion protection.
  • the inventors of the present invention have conducted extensive and in-depth studies on the materials of reactors and fittings for directly synthesizing hydrocarbon-based phosphine halide from yellow phosphorus and halogenated hydrocarbons as raw materials in the absence of a catalyst, It is hoped to find a special corrosion-resistant reactor and its accessories that can overcome the above-mentioned disadvantages of the prior art.
  • the inventors of the present invention have unexpectedly discovered that a nickel-based alloy as a corrosion-resistant alloy has a prominent anticorrosive effect on the reaction raw materials and reaction products of the above reaction at the same time, and a reactor made of the corrosion-resistant alloy and its accessories can be effectively implemented.
  • the present invention has been completed based on the foregoing findings.
  • an object of the present invention is to provide a method for synthesizing a hydrocarbon-based phosphine halide in a next step without catalyst in the presence of yellow phosphorus and a halogenated hydrocarbon as raw materials.
  • This method uses a nickel-based alloy as a corrosion resistant alloy as the material of the reactor and its accessories, so that it can achieve an improved anticorrosive effect than the existing reactor and its accessories, and the cost is acceptable, so that the foregoing can be implemented on an industrial scale. method.
  • Another object of the present invention is to provide a reactor that specifically implements the preparation method of the present invention.
  • the reactor uses a nickel-based alloy as a corrosion-resistant alloy as the material of the reactor, so that it can achieve improved corrosion protection than the existing reactor. Effect, so that the aforementioned method can be implemented on an industrial scale.
  • Yet another object of the present invention is to provide the use of a nickel-based alloy as a corrosion resistant alloy in the manufacture of the reactor of the present invention and its accessories.
  • X is halogen, preferably chlorine or bromine, and when two X are present in the same molecule, X may be the same or different, and
  • R is a hydrocarbon group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. When two R exist in the same molecule, R may be the same or different.
  • the material of the surface in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall. production.
  • nickel-based alloy as the corrosion resistant alloy is one or more alloys selected from the group consisting of:
  • Ni-Cu based alloy which contains 20-30% by weight Cu and 70-80% Ni based on its total weight
  • Ni-Mo based alloy which contains 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight;
  • a Ni-Cr based alloy comprising 50 to 65% by weight of Ni and 15% by weight or more of Cr, preferably 25% by weight or more of Cr, more preferably 35 to 50% by weight of Cr based on its total weight;
  • Ni-Si alloys which comprise 70-85% by weight of Ni and 3-10% by weight of Si, and Ni-Cr-Si alloys based on their total weight, It is a D-205 alloy, which contains 20% by weight of Cr, 5% by weight of Si, and 65% by weight of Ni based on its total weight.
  • the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of a Monel (Monel) alloy (e.g. Monel And Monel K500), Inconel (e.g. Inconel) Inconel And Inconel ), Incoloy (Incoloy) alloy And Incoloy ) And Hastelloy alloys (e.g. Hastelloy Hastelloy And Hastelloy ).
  • Monel Monel And Monel K500
  • Inconel e.g. Inconel
  • Inconel Inconel And Inconel
  • Hastelloy alloys e.g. Hastelloy Hastelloy And Hastelloy
  • R is the same or different, and each independently represents a straight-chain or branched alkyl group containing 1 to 20, preferably 1 to 8 carbon atoms (such as Methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl and octyl), C 6 -C 10 aryl, preferably C 6 -C 8 aryl (eg phenyl, o-toluene Radicals, m-tolyl and p-tolyl), and C 6 -C 10 aralkyl, preferably C 6 -C 8 aralkyl (such as benzyl).
  • R is the same or different, and each independently represents a straight-chain or branched alkyl group containing 1 to 20, preferably 1 to 8 carbon atoms (such as Methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, penty
  • reaction of yellow phosphorus with a compound of formula (III) is as one or more compounds selected from compounds of formula (I), (II) and (IV) Carried out in the presence of a co-solvent, preferably in the presence of a compound of formula (I) and / or (II) as a co-solvent,
  • R is as defined for the compounds of formula (I) and formula (II); preferably, the amount of the co-solvent is 1-50% by weight, preferably 5-30% by weight, based on the total weight of yellow phosphorus and the compound of formula (III).
  • reaction pressure is an autogenous pressure, for example, the reaction is performed at a gauge pressure of 0.01-8.0 MPa, preferably 0.01-6.0 MPa, more preferably 0.05-5.0 MPa; and / or, the reaction time is 2-10 h, preferably 2-6 h.
  • a reactor for carrying out the method according to any one of items 1-9 the reactor being a kettle reactor comprising: 1) a stirrer, 2) a kettle lid, and 3) a kettle body, 4) heating devices located outside and / or inside the reaction kettle, and 5) cooling devices located outside and / or inside the reaction kettle, wherein the kettle lid and optionally the upper part of the kettle are provided with openings, the kettle
  • the chamber formed by connecting the cover to the kettle body constitutes the reaction space of the reactor, and is characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor reacts throughout the reaction.
  • the thickness direction of the vessel wall is entirely made of a nickel-based alloy as a corrosion resistant alloy, and the volume of the reaction kettle is preferably 300L-5000L.
  • nickel-based alloy as the corrosion resistant alloy is one or more alloys selected from the group consisting of:
  • Ni-Cu based alloy which contains 20-30% by weight Cu and 70-80% Ni based on its total weight
  • Ni-Mo based alloy which contains 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight;
  • a Ni-Cr based alloy comprising 50 to 65% by weight of Ni and 15% by weight or more of Cr, preferably 25% by weight or more of Cr, more preferably 35 to 50% by weight of Cr based on its total weight;
  • Ni-Si alloys which comprise 70-85% by weight of Ni and 3-10% by weight of Si, and Ni-Cr-Si alloys based on their total weight, It is a D-205 alloy, which contains 20% by weight of Cr, 5% by weight of Si and 65% by weight of Ni based on its total weight.
  • the nickel-based alloy is one or more nickel-based alloys selected from the group consisting of a Monel (Monel) alloy (e.g. Monel Monel K500), Inconel alloy (e.g. Inconel Inconel Inconel ), Incoloy (Incoloy) alloy Incoloy ) And Hastelloy alloys (e.g. Hastelloy Hastelloy Hastelloy ).
  • Monel Monel Monel K500
  • Inconel alloy e.g. Inconel Inconel Inconel
  • Incoloy Incoloy
  • Hastelloy alloys e.g. Hastelloy Hastelloy Hastelloy Hastelloy
  • Figure 1 is a nickel-based alloy Hastelloy And Monel Photographs of the respective hanging pieces after being corroded in the gas phase.
  • Figure 2 shows the nickel-based alloy Hastelloy And Monel Photographs of the respective hanging pieces after being corroded in the liquid phase.
  • FIG. 3 is a photo of each hanging piece of tantalum, tantalum alloy Ta-2.5W and titanium-palladium alloy TA9 after being corroded in a gas phase.
  • FIG. 4 is a photo of each hanging piece of tantalum, tantalum alloy Ta-2.5W and titanium-palladium alloy TA9 after being corroded in a liquid phase.
  • X is halogen. When two X exist in the same molecule, X may be the same or different, and
  • R is a hydrocarbon group. When two R exist in the same molecule, R may be the same or different.
  • the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall .
  • variables X and R in formula (III) will be correspondingly transferred to the compounds of formula (I) and formula (II) after the reaction. Therefore, the definition of variables X and R in formula (III) is the same as that of formula (I) and formula ( II)
  • the corresponding definitions in the compounds have a corresponding relationship. If two compounds of formula (I) in which R is different from each other are to be prepared, two compounds of formula (III) in which R are different from each other can be introduced. If two compounds of formula (II) in which X are different from each other are to be prepared, two compounds of formula (III) in which X are different from each other can be introduced.
  • all R in the compound of formula (I) are the same, and / or all X in the compound of formula (II) are the same.
  • X is halogen, preferably chlorine or bromine.
  • X may be the same or different.
  • R is a hydrocarbon group.
  • R may be the same or different.
  • R is the same or different, and each is independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • R is an aliphatic hydrocarbon group, it may be the same or different, and each independently represents a linear or branched alkyl group containing 1-20, preferably 1-8 carbon atoms, such as methyl, ethyl, propyl Base, butyl, isobutyl, tert-butyl, pentyl and octyl.
  • R is an aromatic hydrocarbon group, it may be the same or different, and each independently represents a C 6 -C 10 aryl group, preferably a C 6 -C 8 aryl group, such as phenyl, o-tolyl, m-tolyl, and p-toluene And C 6 -C 10 aralkyl, preferably C 6 -C 8 aralkyl, such as benzyl.
  • X is chlorine and R in each formula is phenyl or tolyl.
  • reaction of yellow phosphorus with the compound of the formula (III) in the absence of a catalyst to obtain the compounds of the formula (I) and the formula (II) is conventional and can be carried out under conventional reaction conditions.
  • the reaction of yellow phosphorus with the compound of formula (III) can be advantageously carried out in the presence of a co-solvent.
  • Yellow phosphorus is solid at normal temperature, and the co-solvent can dissolve the yellow phosphorus.
  • co-solvents it is advantageous to use one or more compounds selected from the compounds of formulae (I), (II) and (IV) as described above,
  • the co-solvent may be selected from a combination of one or more of triphenylphosphine, diphenylphosphine chloride, and phenyldichlorophosphine, especially when the compound to be prepared is diphenylphosphine chloride and phenyl Phosphine dichloride.
  • the amount of the co-solvent is not particularly limited as long as the yellow phosphorus raw material used can be dissolved.
  • the amount of co-solvent is 1-50% by weight, preferably 5-30% by weight, based on the total weight of yellow phosphorus and the compound of formula (III).
  • the method of the present invention can be carried out in the presence of one or more compounds selected from compounds of formulae (I), (II) and (IV) as cosolvents
  • the variables X and R is consistent with the corresponding variables X and R in the compounds of formula (I) and formula (II) to be prepared.
  • the selected co-solvent is preferably one or more of triphenylphosphine, phenylphosphine dichloride and diphenylphosphine chloride.
  • phenylphosphine chloride and / or diphenylphosphine chloride This can reduce the cost of separating the components after the reaction is complete.
  • the amount of each reactant is conventional.
  • the molar ratio of yellow phosphorus (chemical formula P4) to the compound of formula (III) is 1: 6-1: 12, preferably 1: 6-1: 10, and more preferably 1: 6-1: 8.
  • the reaction temperature is conventional, and the reaction can be performed at a temperature of 200-800 ° C, preferably 200-600 ° C, more preferably 300-500 ° C, and particularly preferably 300-400 ° C.
  • the reaction pressure is also conventional and is usually carried out under autogenous pressure.
  • the reaction can be performed at a gauge pressure of 0.01 to 8.0 MPa, preferably 0.01 to 6.0 MPa, and more preferably 0.05 to 5.0 MPa.
  • the reaction time is also conventional, and the reaction usually lasts 2-10 h, preferably 2-6 h. Whether the reaction is complete can be judged by sampling and detecting yellow phosphorus.
  • reaction mixture comprising compounds of formula (I) and formula (II), optionally unreacted white phosphorus, optional compound of formula (III), and optional co-solvent.
  • the reaction mixture needs to be worked up. This workup is conventional as long as the compounds of formula (I) and formula (II) can be separated.
  • the reaction mixture obtained by the reaction is usually cooled to room temperature, and then transferred to a distillation kettle, and separated by distillation, such as first atmospheric distillation and then rectification under reduced pressure, to obtain compounds of formula (I) and formula (II).
  • Phosphorus trichloride, phenylphosphine dichloride and diphenylphosphine chloride are highly corrosive.
  • An important feature of the method of the present invention is that the material used for the surface in contact with the reaction space in the reactor of the method of the present invention is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely in the direction of the thickness of the entire reactor wall Made of a nickel-based alloy as a corrosion resistant alloy.
  • the prior art has various corrosion resistant material recommendations for various corrosive work or operating environments.
  • metal anti-corrosive materials there are mainly iron-based alloys, such as corrosion-resistant stainless steel. Active metals also have good anti-corrosion capabilities, typically represented by Ti, Zr, and Ta.
  • the reactor taught in US 3734958 is a tantalum autoclave.
  • the present inventors have found that when a tantalum autoclave is used to prepare a hydrocarbon-based phosphine halide, although it has a certain degree of corrosion resistance, when used in an industrial scale preparation, its corrosion resistance and durability are not enough, and the cost is high Therefore, the industrialized production of hydrocarbyl phosphine halide cannot be achieved.
  • the inventors have found that if the surface in the reactor that is in contact with the reaction space or even the entire thickness of the reactor wall is made of a nickel-based alloy as a corrosion-resistant alloy, the corrosion resistance of the reactor thus constructed is greatly improved, which is sufficient Corrosion resistance, and its price is far lower than tantalum materials, which provides a feasible reaction equipment for the industrialization of hydrocarbyl phosphine halide.
  • the material of the surface in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is entirely made of nickel as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
  • Base alloy the reaction space of a reactor has the meaning commonly understood by those skilled in the art. For example, taking a reaction kettle as an example, the reaction space refers to a three-dimensional space enclosed by the lid of the reaction kettle and the kettle body.
  • the reactor may be made entirely of a nickel-based alloy as a corrosion-resistant alloy in the entire thickness direction of the reactor wall.
  • those surfaces in the reactor that are in contact with the reaction space may be made of a nickel-based alloy as a corrosion resistant alloy.
  • the thickness of these surfaces it can be determined through routine tests according to the actual operating conditions and the design life of the reactor.
  • Nickel-based alloys which are corrosion-resistant alloys, generally contain more than 30% by weight of Ni, and common Ni-based alloys have a Ni content of more than 50% by weight. Because nickel-based alloys have superior high-temperature mechanical strength and corrosion resistance, they are collectively called superalloys with iron-based alloys and cobalt-based alloys.
  • the nickel-based alloy as the corrosion resistant alloy may be selected from one or more of the following groups:
  • Ni-Cu based alloy which contains 20-30% by weight of Cu and 70-80% of Ni based on its total weight.
  • Ni-Cu series alloys are represented by Monel (Monel) alloys.
  • Monel alloys have many of the advantages of Ni and Cu and can maintain a permanent metallic luster in the atmosphere.
  • Monel alloy is mainly used for corrosion-resistant parts and equipment under high temperature and load.
  • Monel alloy mention may be made of Monel And Monel K500.
  • Ni-Mo-based alloy containing 50 to 75% by weight of Ni and 15 to 50% by weight of Mo, preferably 28 to 50% by weight of Mo, based on its total weight.
  • molybdenum in this type of alloy greatly improves the corrosion resistance, strength, and high-temperature processability of nickel-based (solid solution). Adding more than 15% Mo to Ni can make the alloy have a high resistance to oxidizing acids.
  • Ni-Mo alloys containing about 28% Mo can withstand hydrochloric acid corrosion at any temperature and concentration under normal pressure, and can also withstand corrosion by sulfuric acid, acetic acid, phosphoric acid, formic acid, and hydrogen chloride gas.
  • the Ni-Mo corrosion resistant alloy includes a Hastelloy alloy. As an example of the Hastelloy alloy, mention may be made of Hastelloy Hastelloy And Hastelloy
  • Typical Ni-Cr corrosion resistant alloys include Inconel and Incoloy.
  • Inconel as an example of the Inconel alloy Inconel And Inconel Inconel Not only resistant to high temperature oxidation, but also used in aqueous solution, especially strong oxidizing aqueous solution, it can be used in room temperature sulfuric acid, phosphoric acid, low concentration of hydrochloric acid, hydrofluoric acid and other environments. Excellent performance, widely used in chemical industry, nuclear power industry, etc.
  • Incoloy alloy mention may be made of Incoloy And Incoloy
  • Ni-Si alloys 70-85% by weight of Ni and 3-10% by weight of Si are resistant to oxidation, sulfuric acid (arbitrary concentration and boiling point temperature), organic acids and salts.
  • Ni-Cr-Si alloy D-205 alloy in which Cr accounts for 20% by weight, Si accounts for 5% by weight, and Ni accounts for 65% by weight. This alloy is mainly used in the environment where superoxide substances exist.
  • the inner wall of the pipe that is in contact with the reaction raw material or reaction product or the pipe is entirely made of a nickel-based alloy as a corrosion resistant alloy in the wall thickness direction.
  • the valve in contact with the reaction raw material or reaction product or those surfaces of the valve in contact with the reaction raw material or reaction product are made of a nickel-based alloy as a corrosion resistant alloy.
  • the reactor according to the present invention may be designed to have a volume of 300L-5000L, that is, the volume of the internal space of the reaction kettle is 300L-5000L.
  • a reactor for carrying out the method of the present invention.
  • the reactor is a kettle reactor and includes: 1) a stirrer, 2) a kettle lid, and 3) a kettle body, 4 ) Heating devices located outside and / or inside the reaction kettle, and 5) cooling devices located outside and / or inside the reaction kettle, wherein the kettle lid of the reaction kettle and optionally, the upper part of the kettle body is provided with openings, the kettle lid
  • the chamber connected to the kettle body constitutes the reaction space of the reactor, and is characterized in that the material in contact with the reaction space in the reactor is a nickel-based alloy as a corrosion-resistant alloy, or the reactor is in the entire reactor
  • the wall thickness direction is made entirely of a nickel-based alloy as a corrosion resistant alloy.
  • the reactor of the present invention is provided with a stirrer for stirring the materials inside the reactor evenly.
  • Any stirrer that can achieve the function of stirring or agitation can be used, including mechanical stirrers, magnetic stirrers, etc.
  • the reactor needs to be kept in a sealed state, and the stirrer is preferably a magnetic stirrer.
  • the kettle-type reaction kettle at this time becomes a magnetic reaction kettle.
  • the stirrer usually has a motor reducer.
  • the stirrer is usually fixed on the lid of the kettle, and the magnetic piece of the stirrer or the stirring blade or the stirring belt is located in the reactor.
  • the kettle lid can be flat or project outward.
  • the kettle cover is preferably a flange cover, and the flange cover is connected to the kettle body through a flange plate. Accordingly, the agitator is fixed on the flange cover.
  • the reactor includes a flange cover, a flange plate and a kettle body from top to bottom.
  • the flange cover is connected with the kettle body through a flange to form a closed chamber, which constitutes a reaction space of the reactor.
  • the kettle lid may also have other openings, such as manholes, inlet and outlet holes.
  • the upper part of the reactor body can also be perforated, for example for feeding and discharging, sampling and testing.
  • the reaction kettle is preferably a vertical reactor.
  • the reactions involved in the process of the invention are generally carried out at elevated temperatures.
  • the reactor needs to be equipped with heating devices and cooling devices.
  • the heating means of the reactor it is located outside and / or inside the reactor, preferably outside.
  • a cooling device for the reactor it is located outside and / or inside the reactor, preferably outside.
  • the heating device can be heated by a molten salt electric heater or a far-infrared heating plate.
  • the cooling device can be cooled by air cooling or circulating water.
  • the material of the reactor of the present invention it is applicable to the material description of the reactor involved in the method of the present invention, which is not repeated here. Since the contact surface between the reactor and the stream of the invention or the entire reactor is made of a specific corrosion-resistant alloy, the industrial production of the method of the invention can be realized.
  • the working volume of the reactor is 300L-5000L.
  • a nickel-based alloy as a corrosion resistant alloy in the manufacture of the reactor of the invention and its accessories.
  • the description of the nickel-based alloy as the corrosion-resistant alloy is applicable to the material description of the reactor involved in the method of the present invention, and is not repeated here.
  • the fittings of the reactor include all pipes and valves in contact with the reaction raw materials or reaction products.
  • the method and reactor of the present invention have very important practical significance for the industrialized production of hydrocarbyl phosphine halide. At present, there is no such industrial production technology at home and abroad.
  • the present invention successfully realizes the industrialized production of hydrocarbyl phosphine halide in a green and environmentally friendly manner.
  • Advantages of the invention include:
  • a nickel-based alloy as a corrosion-resistant alloy as the material of the reactor and its accessories or as the material of the material contact surface of the reactor, it has obtained excellent corrosion resistance and can successfully achieve industrialization of 300-5000L per batch produce.
  • the yellow phosphorus used was purchased from Yunnan Huofa Phosphate Co., Ltd. with a purity of 95%; chlorobenzene was purchased from Wuhan Fengyao Tonghui Chemical Co., Ltd. with a purity of 98%.
  • Each corrosion-resistant metal is made into two identical metal pendants, and the size of the pendant is ⁇ 10cm ⁇ 10cm ⁇ 0.3cm or 10cm ⁇ 3cm ⁇ 0.3cm or 10cm ⁇ ⁇ 0.2cm wire.
  • Two pendants of each corrosion-resistant metal were placed in the gas phase of a 5 L closed-pressure axe containing a mixture of 20% by weight of phosphorus trichloride, 40% by weight of phenylphosphine dichloride, and 40% by weight of diphenylphosphine chloride.
  • the test temperature is 500 ° C
  • the pressure (gauge pressure) is 0.5 MPa
  • the test is continued for 10 hours. After the test time, remove the pendant to take a picture and weigh it to evaluate the anti-corrosion effect.
  • the tested corrosion-resistant metals include: pure tantalum metal sheet, tantalum alloy Ta-2.5W, pure metal zirconium sheet, Zr702 zirconium plate, titanium molybdenum nickel alloy TA10 and titanium palladium alloy TA9.
  • Figure 1 shows the nickel-based alloy Hastelloy And Monel Photographs of the respective hanging pieces after being corroded in the gas phase, of which Figure 1 (a) is Hastelloy Alloy, Figure 1 (b) is Monel alloy.
  • Figure 2 shows the nickel-based alloy Hastelloy And Monel Photographs of the respective hanging pieces after being corroded in the liquid phase, of which Figure 2 (a) is Hastelloy Alloy, Figure 2 (b) is Monel alloy.
  • Fig. 3 shows a photo of each hanging piece of tantalum, tantalum alloy Ta-2.5W, and titanium-palladium alloy TA9 after being corroded in the gas phase.
  • Fig. 3 (a) is tantalum
  • Fig. 3 (b) is tantalum alloy Ta-2.5. W
  • FIG. 3 (c) is a titanium-palladium alloy TA9.
  • Figure 4 shows the photos of the tantalum, tantalum alloy Ta-2.5W, and titanium-palladium alloy TA9 after corrosion in the liquid phase.
  • Figure 4 (a) is tantalum
  • Figure 4 (b) is tantalum alloy Ta-2.5. W
  • FIG. 4 (c) is a titanium-palladium alloy TA9.
  • the weight loss before and after corrosion is used to calculate the corrosion rate of each pendant, that is, the percentage of the weight that is eroded and the original weight before corrosion.
  • the corrosion resistance results of each corrosion resistant metal are summarized in Table 1 below.
  • Example 11 Production in a 500L reactor
  • Example 12 Production in a 300L reactor
  • Example 13 Production in a 500L reactor
  • Example 14 Production in a 500L reactor
  • Example 15 Production in a 1000L reactor
  • Example 16 Production in a 1000L reactor
  • Example 17 Production in a 5000L reactor
  • Example 18 Production in a 5000L reactor

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de composés de formules (I) et (II) suivantes, X étant un halogène, et R étant un hydrocarbyle, et un réacteur utilisé particulièrement pour la mise en œuvre du procédé. Le procédé consiste à faire réagir du phosphore jaune avec un composé de formule (III) dans le réacteur en l'absence d'un catalyseur, caractérisé en ce que, dans le réacteur, le matériau de la surface en contact avec l'espace de réaction est un alliage à base de nickel en tant qu'alliage résistant à la corrosion, ou le réacteur est entièrement constitué de l'alliage à base de nickel en tant qu'alliage résistant à la corrosion dans le sens de l'épaisseur de la paroi de l'ensemble du réacteur. La présente invention utilise un alliage à base de nickel, en tant qu'alliage résistant à la corrosion, comme matériau pour le réacteur et ses accessoires, ce qui permet d'obtenir une amélioration de l'effet de prévention contre la corrosion, par comparaison aux réacteurs et leurs accessoires existants, le coût est également acceptable, et le procédé peut ainsi être mis en œuvre à l'échelle industrielle.
PCT/CN2018/093672 2018-06-29 2018-06-29 Procédé de préparation d'halogénure d'hydrocarbyle phosphine et réacteur correspondant Ceased WO2020000366A1 (fr)

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PCT/CN2018/093672 WO2020000366A1 (fr) 2018-06-29 2018-06-29 Procédé de préparation d'halogénure d'hydrocarbyle phosphine et réacteur correspondant
BR112020026755-4A BR112020026755B1 (pt) 2018-06-29 Método para preparar haleto de hidrocarbil fosfina
MYPI2020007073A MY194553A (en) 2018-06-29 2018-06-29 Method for preparing hydrocarbyl phosphine halide and reactor used therefor

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121135769A (zh) * 2025-11-18 2025-12-16 山东艾科高分子材料有限公司 一种二苯基氧化膦和1,2-双(二苯基膦氧基)乙烷的联合生产方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3734958A (en) * 1968-09-09 1973-05-22 Rhone Poulenc Sa Process for the preparation of diorganochlorophines
CN105732708A (zh) * 2016-02-01 2016-07-06 东营美利达新型材料科技有限公司 一种生产苯基二氯化磷的方法
CN107912446A (zh) * 2017-12-02 2018-04-17 南通江山农药化工股份有限公司 含草甘膦、亚磷酸三甲酯的回收盐制备草铵膦复合农药的方法及其装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3734958A (en) * 1968-09-09 1973-05-22 Rhone Poulenc Sa Process for the preparation of diorganochlorophines
CN105732708A (zh) * 2016-02-01 2016-07-06 东营美利达新型材料科技有限公司 一种生产苯基二氯化磷的方法
CN107912446A (zh) * 2017-12-02 2018-04-17 南通江山农药化工股份有限公司 含草甘膦、亚磷酸三甲酯的回收盐制备草铵膦复合农药的方法及其装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121135769A (zh) * 2025-11-18 2025-12-16 山东艾科高分子材料有限公司 一种二苯基氧化膦和1,2-双(二苯基膦氧基)乙烷的联合生产方法

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