阅读说明：本技术 一种有机磷化合物的合成方法 (Synthetic method of organic phosphorus compound ) 是由 姜友法 王宝林 范剑峰 徐华星 宋晓春 李纪平 于 2020-08-11 设计创作，主要内容包括：本发明公开了一种有机磷化合物的合成方法,将甲烷通入到管式反应器中,且将管式反应器在甲烷氛围中升温至450-600℃；待温度平稳后,将三氯化磷与催化剂混合物通入到管式反应器中,三氯化磷、甲烷在催化剂的催化作用下、在450-600℃的条件下进行合成反应,反应0.1-1.0秒后得到产品甲基二氯化膦；催化剂的通式为C_nH_(2n+2-x)R_x或C_nH_(2n-x)R_x；其中：n、x为数字1、2、3、4、5、6、7、8；其中R为卤素氟、氯、溴或碘。本发明的催化剂主要用于代替破坏臭氧层的四氯化碳,本发明的催化剂应用于甲烷与三氯化磷合成甲基二氯化磷后,转化率15-25％、收率95％-98％,达到四氯化碳催化水平,可以安全替代催化剂四氯化碳。(The invention discloses a method for synthesizing an organic phosphorus compound, which comprises the steps of introducing methane into a tubular reactor, and heating the tubular reactor to 450-600 ℃ in a methane atmosphere; after the temperature is stable, introducing a mixture of phosphorus trichloride and a catalyst into a tubular reactor, and carrying out a synthetic reaction of phosphorus trichloride and methane under the catalytic action of the catalyst and at the temperature of 450-600 ℃ for 0.1-1.0 second to obtain a product, namely methyl phosphine dichloride; the general formula of the catalyst is C n H 2n+2‑x R x Or C n H 2n‑x R x (ii) a Wherein: n and x are numbers 1,2, 3, 4, 5, 6, 7 and 8; wherein R is halogen fluorine, chlorine, bromine or iodine. The catalyst is mainly used for replacing carbon tetrachloride damaging an ozone layer, after the catalyst is applied to synthesis of methyl phosphorus dichloride from methane and phosphorus trichloride, the conversion rate is 15-25%, the yield is 95% -98%, the catalytic level of the carbon tetrachloride is reached, and the catalyst can safely replace the carbon tetrachloride.)

1. A method for synthesizing an organophosphorus compound, comprising the steps of:

introducing methane into the tubular reactor, and heating the tubular reactor to 450-600 ℃ in the methane atmosphere; after the temperature is stable, introducing a mixture of phosphorus trichloride and a catalyst into a tubular reactor, and carrying out a synthetic reaction of phosphorus trichloride and methane under the catalytic action of the catalyst and at the temperature of 450-600 ℃ for 0.1-1.0 second to obtain a product, namely methyl phosphine dichloride;

the general formula of the catalyst is C_nH_2n+2-xR_xOr C_nH_2n-xR_x(ii) a Wherein: n and x are numbers 1,2, 3, 4, 5, 6, 7 and 8; wherein R is halogen fluorine, chlorine, bromine or iodine.

2. The synthesis method according to claim 1, characterized in that the catalyst is: the mixture is prepared by mixing any one, two or more than two of tetrachloroethylene, tetrabromoethylene, 1,1,1, 2-tetrachloroethane, 1,1,1, 2-tetrabromoethane, pentachloroethane, pentabromoethylene, hexachloroethane and hexabromoethane in any proportion.

3. The synthesis method of claim 1, wherein the catalyst is used in an amount of 1-12% by mass of the raw material phosphorus trichloride; the feeding ratio of the methane is 1 to 10 times of the equivalent of the molar weight of the phosphorus trichloride.

4. The synthesis method of claim 3, wherein the catalyst is used in an amount of 3-8% by mass based on the mass of the raw material phosphorus trichloride; the feeding ratio of the methane is 3-6 times of the equivalent of the molar weight of the phosphorus trichloride.

5. The method as claimed in claim 1, wherein the synthesis temperature is controlled to 480-580 ℃.

6. The synthesis method according to claim 1, wherein the tubular reactor is a synthesis column filled with nickel balls.

Technical Field

The invention relates to a synthesis method of an organic phosphorus compound, in particular to a green and environment-friendly catalyst used in the synthesis method, and belongs to the technical field of organic compound preparation.

Background

The structural formula of the methyl phosphine dichloride is as follows:the organic phosphorus compound is a basic organic phosphorus compound with wide application, is a colorless transparent liquid, and can be used for synthesizing chemicals such as pesticides, medicines, flame retardants and the like. The methyl phosphine dichloride is extremely active in chemical property and extremely easy to react with air and water, so that the compound is not easy to store and transport and cannot be bought in the market.

The research on the synthesis of the methyl phosphine dichloride is more in 70-80 years abroad, and the synthesis method mainly comprises the following steps:

B.J.Perry, J.B.Reesor, and, J.L.Ferron proposes a new method for synthesizing methyldichlorophosphine with high yield by reducing aluminum chloride-phosphorus chloride-chloromethane complex in diethyl phthalate solution by using fine powder antimony as a raw material.

Ludwig Maier proposes a method for synthesizing various methyl phosphine chlorides by taking red phosphorus and chloromethane or bromomethane as raw materials under the catalysis of copper.

H.e. ulmer, l.c.d. groenweghe, l.maier prepared CH by reaction of the corresponding thiophosphoryl derivative with tributylphosphine₃PCl₂，(CH₃)₂PCL and (CH)₃)(C₂H₅) PBr, and this method appears to have general applicability, yielding yields of 60-70%.

Patent US3210418 proposes the use of oxygen and nitrogen oxides to catalyze methane and phosphorus trichloride to produce methyl phosphine dichloride in gas phase at high temperature, and subsequently further perfects the process in US4101573, US4518538 and proposes carbon tetrachloride as a catalyst with better catalytic efficiency. The specific reaction conditions are as follows: adding 2-7% of carbon tetrachloride into phosphorus trichloride, heating the phosphorus trichloride and methane to 500-650 ℃ in a tubular reactor made of Hastelloy materials, staying for 0.1-0.9 seconds for a short time to obtain a phosphorus trichloride solution with the content of the methyl phosphine dichloride of 15-25%, and rectifying to obtain the methyl phosphine dichloride with the purity of 99%.

Because of the difficulty of industrial production of methyl phosphine dichloride, until now, only the Hessian company successfully industrializes the routes reported by the patents US4101573 and US4518538 in 1979, but the catalyst carbon tetrachloride used in the method has strong destructive effect on the Ozone Layer in the atmosphere and is limited by Montreal Protocol on substructures that is the Ozone Layer remover.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for synthesizing an organophosphorus compound, which uses a green and environment-friendly catalyst to synthesize the organophosphorus compound, aiming at the defects in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for synthesizing an organophosphorus compound, comprising the following steps:

introducing methane into the tubular reactor, and heating the tubular reactor to 450-600 ℃ in the methane atmosphere; after the temperature is stable, introducing a mixture of phosphorus trichloride and a catalyst into a tubular reactor, and carrying out a synthetic reaction of phosphorus trichloride and methane under the catalytic action of the catalyst and at the temperature of 450-600 ℃ for 0.1-1.0 second to obtain a product, namely methyl phosphine dichloride;

the general formula of the catalyst is C_nH_2n+2-xR_xOr C_nH_2n-xR_x(ii) a Wherein: n and x are numbers 1,2, 3, 4, 5, 6, 7 and 8; wherein R is halogen fluorine, chlorine, bromine or iodine.

In the above technical solution, the catalyst is preferably: the mixture is prepared by mixing any one, two or more than two of tetrachloroethylene, tetrabromoethylene, 1,1,1, 2-tetrachloroethane, 1,1,1, 2-tetrabromoethane, pentachloroethane, pentabromoethylene, hexachloroethane and hexabromoethane in any proportion.

In the technical scheme, the amount of the catalyst accounts for 1-12% of the mass of the raw material phosphorus trichloride, and preferably 3-8%.

In the technical scheme, the feeding ratio of the methane is 1-10 times of the equivalent of the molar weight of the phosphorus trichloride, and preferably 3-6 times of the equivalent.

In the above technical scheme, the synthesis temperature of the synthesis reaction is preferably controlled to be 480-580 ℃.

In the above technical solution, the tubular reactor is preferably a synthesis column filled with nickel balls inside.

The technical scheme of the invention has the advantages that: the catalyst is mainly used for replacing carbon tetrachloride damaging an ozone layer, after the catalyst is applied to synthesis of methyl phosphorus dichloride from methane and phosphorus trichloride, the conversion rate is 15-25%, the yield is 95% -98%, the catalytic level of the carbon tetrachloride is reached, and the catalyst can safely replace the carbon tetrachloride.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:

example 1

In the experiment, a set of synthetic columns made of DN25 hastelloy materials are filled with 4-6mm nickel balls, and the length of the column is 1 m. The raw material composition is a mixture of tetrachloroethylene and phosphorus trichloride, wherein the concentration of tetrachloroethylene is 10%. And (2) opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping a mixture of tetrachloroethylene and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, wherein the conversion rate of the phosphorus trichloride is 18.8 percent, and the yield is 93.5 percent calculated by the converted phosphorus trichloride.

Example 2

The raw material composition is a mixture of tetrachloroethylene and phosphorus trichloride, wherein the concentration of tetrachloroethylene is 8%. And (2) opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping a mixture of tetrachloroethylene and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, wherein the conversion rate of the phosphorus trichloride is 18.5 percent, and the yield is 93.1 percent calculated by the converted phosphorus trichloride.

Example 3

The raw material composition is a mixture of tetrachloroethylene and phosphorus trichloride, wherein the concentration of tetrachloroethylene is 6%. And (2) opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping a mixture of tetrachloroethylene and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, wherein the conversion rate of the phosphorus trichloride is 16.5 percent, and the yield is 93.7 percent calculated by the converted phosphorus trichloride.

Example 4

The raw material composition is a mixture of tetrachloroethylene and phosphorus trichloride, wherein the concentration of tetrachloroethylene is 4%. And (2) opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping a mixture of tetrachloroethylene and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, wherein the conversion rate of the phosphorus trichloride is 15.4 percent, and the yield is 93.5 percent calculated by the converted phosphorus trichloride.

Example 5

The raw material composition is a tetrabromoethylene and phosphorus trichloride mixture, wherein the concentration of the tetrabromoethylene is 8%. And (2) opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping the mixture of tetrabromoethylene and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, wherein the conversion rate of the phosphorus trichloride is 19.3 percent, and the yield is 94.1 percent in terms of the converted phosphorus trichloride.

Example 6

The raw material composition is a mixture of 1,1,1, 2-tetrachloroethane and phosphorus trichloride, wherein the concentration of the 1,1,1, 2-tetrachloroethane is 8%. And (2) opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping a mixture of 1,1,1, 2-tetrachloroethane and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, and obtaining the yield of 93.2 percent by the conversion of phosphorus trichloride, wherein the conversion rate of phosphorus trichloride is 15.7 percent.

Example 7

The raw material composition is a mixture of 1,1,1, 2-tetrabromoethane and phosphorus trichloride, wherein the concentration of the 1,1,1, 2-tetrabromoethane is 8%. Opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 550 ℃ in the methane atmosphere, pumping a mixture of 1,1,1, 2-tetrabromoethane and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, and obtaining the yield of 93.7 percent by the conversion of the phosphorus trichloride with the conversion rate of 16.3 percent.

Example 8

The raw material composition is a mixture of 1,1,1, 2-tetrabromoethane and phosphorus trichloride, wherein the concentration of the 1,1,1, 2-tetrabromoethane is 8%. Opening a methane inlet valve at the lower part of the synthesis column to control the methane inlet speed to be 120 liters/hour, heating the synthesis column to 500 ℃ in the methane atmosphere, pumping a mixture of 1,1,1, 2-tetrabromoethane and phosphorus trichloride into the synthesis column from a feed inlet at the lower part of the synthesis column after the temperature is stable, collecting the synthesis gas from the upper part of the synthesis column by a quenching tower, wherein the conversion rate of the phosphorus trichloride is 15.1 percent, and the yield is 94.2 percent based on the converted phosphorus trichloride.

The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.