阅读说明：本技术 一种苯基二氯化膦和二苯基氯化磷的联合生产方法 (Joint production method of phenyl phosphine dichloride and diphenyl phosphorus chloride ) 是由 储晓建 葛晓虎 周华平 汤和平 夏圣勤 于 2019-11-18 设计创作，主要内容包括：本发明公开了一种苯基二氯化膦和二苯基氯化磷的联合生产方法,本发明对苯基二氯化膦和二苯基氯化磷进行联合生产,并且充分回收了其中反映产生的副产物,提高了经济效益,降低了对环境的污染。(The invention discloses a joint production method of phenyl phosphine dichloride and diphenyl phosphorus chloride, which jointly produces the phenyl phosphine dichloride and the diphenyl phosphorus chloride, fully recycles byproducts generated by reaction in the phenyl phosphine dichloride and the diphenyl phosphorus chloride, improves economic benefit and reduces pollution to the environment.)

1. A joint production method of phenyl phosphine dichloride and diphenyl phosphorus chloride is characterized by comprising the following steps:

step one, putting 400-weight (weight portion) of aluminum trichloride and 1000-weight (weight portion) of phosphorus trichloride into a nitrogen replacement synthesis kettle, heating the kettle to 60-100 ℃, dropwise adding 500-weight (weight portion) of pure benzene when the reflux is normal, carrying out reflux reaction for 5-10 hours, and simultaneously absorbing hydrogen chloride generated by the reaction by using a hydrogen chloride falling film absorber to generate hydrochloric acid;

secondly, transferring the materials in the nitrogen replacement synthesis kettle to an extraction kettle after the reflux reaction is finished, standing for 3-8 hours, layering, dividing the lower-layer materials into a disproportionation kettle, and dividing the upper-layer materials into a desolventizing kettle;

step three, heating the desolventizing kettle to 100-200 ℃, distilling unreacted pure benzene and phosphorus trichloride out at normal pressure, synthesizing and recycling in batch, transferring the material in the desolventizing kettle to a rectifying tower after distillation, and distilling out a finished product of the phenylphosphonic dichloride under negative pressure; after the rectification is finished, transferring the kettle residue in the rectification kettle into a next disproportionation reaction kettle for use in the next batch;

heating the disproportionation kettle to 250 ℃ for 100 plus materials, distilling out residual pure benzene and phosphorus trichloride, synthesizing and recycling in next batch, preserving heat for 4-10 hours, cooling the materials in the disproportionation kettle to 50-150 ℃ by using cold oil, cooling to the proper position, adding 800 parts by weight of dried 60-100 mesh potassium chloride into the crude distillation kettle, regulating the negative pressure of the crude distillation kettle to-0.2-0.08 MPa, heating to 250 ℃ for 100 plus materials, and carrying out crude distillation on phenyl phosphine dichloride and diphenyl phosphorus chloride to obtain a distillate;

step five, after the distillation of the distillate before the crude distillation is finished, starting a Roots pump to achieve high vacuum, controlling the negative pressure to be-0.09 to-0.1 Mpa, heating the crude distillation kettle to 100 plus 260 ℃, distilling out the crude diphenyl phosphorus chloride, transferring the crude diphenyl phosphorus chloride to a rectifying tower, adjusting the high vacuum to be-0.095 to-0.1 Mpa, controlling the kettle temperature to be 150 plus 300 ℃, and distilling out the diphenyl phosphorus chloride; after the rectification, transferring the residue in the rectifying tower into a hydrolysis kettle;

putting the kettle residue in the rough steaming kettle into a hydrolysis kettle, cooling to 20-100 ℃, dropwise adding 1500 parts by weight of water into the hydrolysis kettle, completely hydrolyzing the kettle residue, standing the hydrolysis kettle for 1-5 hours after hydrolysis is finished, transferring the lower potassium chloride and aluminum trichloride aqueous solution into a cooling kettle, putting the upper diphenyl phosphoric acid into a centrifuge, spin-drying, bagging and selling, and transferring the aqueous solution thrown out by the centrifuge into the hydrolysis kettle for next hydrolysis for later use;

step seven, cooling the cooling kettle to 0-15 ℃, centrifugally drying potassium chloride in the materials in the kettle, and drying for recycling; transferring the centrifuged aluminum trichloride aqueous solution to a crystallization aluminum chloride kettle, maintaining the negative pressure of between minus 0.08 and minus 0.1Mpa, heating the crystallization kettle to 100 ℃ and 150 ℃, and transferring the excess water evaporated to a hydrolysis kettle for recycling; after the water evaporation is finished, putting the crystallized aluminum chloride in the crystallization kettle into a centrifuge for spin-drying, and bagging; the centrifugal mother liquor returns to the next crystallization aluminum chloride kettle for reuse.

2. The process for co-producing phenylphosphine dichloride and diphenylphosphine chloride according to claim 1, wherein in the first step, the mass ratio of aluminum trichloride to phosphorus trichloride is 4: 10.

3. The process for co-production of phenylphosphine dichloride and diphenylphosphine chloride as claimed in claim 1, wherein the temperature for distilling off the final phenylphosphine dichloride under negative pressure is 70-120 ℃ and the pressure is-0.1 MPa.

Technical Field

The invention relates to the field of chemical industry, and in particular relates to a joint production method of phenylphosphonic dichloride and diphenylphosphoryl chloride.

Background

Phenyl phosphine dichloride and diphenyl phosphorus chloride are important organic phosphorus chemical products, but side reaction products are more in the preparation process, the existing process cannot fully utilize the side products, and in addition, the yield of the diphenyl phosphorus chloride is lower.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, and the invention jointly produces the phenyl phosphine dichloride and the diphenyl phosphorus chloride, fully recycles the by-products generated by reaction, improves the economic benefit and reduces the pollution to the environment.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a joint production method of phenyl phosphine dichloride and diphenyl phosphorus chloride comprises the following steps:

step one, putting 400-weight (weight portion) of aluminum trichloride and 1000-weight (weight portion) of phosphorus trichloride into a nitrogen replacement synthesis kettle, heating the kettle to 60-100 ℃, dropwise adding 500-weight (weight portion) of pure benzene when the reflux is normal, carrying out reflux reaction for 5-10 hours, and simultaneously absorbing hydrogen chloride generated by the reaction by using a hydrogen chloride falling film absorber to generate hydrochloric acid;

secondly, transferring the materials in the nitrogen replacement synthesis kettle to an extraction kettle after the reflux reaction is finished, standing for 3-8 hours, layering, dividing the lower-layer materials into a disproportionation kettle, and dividing the upper-layer materials into a desolventizing kettle;

step three, heating the desolventizing kettle to 100-200 ℃, distilling unreacted pure benzene and phosphorus trichloride out at normal pressure, synthesizing and recycling in batch, transferring the material in the desolventizing kettle to a rectifying tower after distillation, and distilling out a finished product of the phenylphosphonic dichloride under negative pressure; after the rectification is finished, transferring the kettle residue in the rectification kettle into a next disproportionation reaction kettle for use in the next batch;

heating the disproportionation kettle to 250 ℃ for 100 plus materials, distilling out residual pure benzene and phosphorus trichloride, synthesizing and recycling in next batch, preserving heat for 4-10 hours, cooling the materials in the disproportionation kettle to 50-150 ℃ by using cold oil, cooling to the proper position, adding 800 parts by weight of dried 60-100 mesh potassium chloride into the crude distillation kettle, regulating the negative pressure of the crude distillation kettle to-0.2-0.08 MPa, heating to 250 ℃ for 100 plus materials, and carrying out crude distillation on phenyl phosphine dichloride and diphenyl phosphorus chloride to obtain a distillate;

step five, after the distillation of the distillate before the crude distillation is finished, starting a Roots pump to achieve high vacuum, controlling the negative pressure to be-0.09 to-0.1 Mpa, heating the crude distillation kettle to 100 plus 260 ℃, distilling out the crude diphenyl phosphorus chloride, transferring the crude diphenyl phosphorus chloride to a rectifying tower, adjusting the high vacuum to be-0.095 to-0.1 Mpa, controlling the kettle temperature to be 150 plus 300 ℃, and distilling out the diphenyl phosphorus chloride; after the rectification, transferring the residue in the rectifying tower into a hydrolysis kettle;

putting the kettle residue in the rough steaming kettle into a hydrolysis kettle, cooling to 20-100 ℃, dropwise adding 1500 parts by weight of water into the hydrolysis kettle, completely hydrolyzing the kettle residue, standing the hydrolysis kettle for 1-5 hours after hydrolysis is finished, transferring the lower potassium chloride and aluminum trichloride aqueous solution into a cooling kettle, putting the upper diphenyl phosphoric acid into a centrifuge, spin-drying, bagging and selling, and transferring the aqueous solution thrown out by the centrifuge into the hydrolysis kettle for next hydrolysis for later use;

step seven, cooling the cooling kettle to 0-15 ℃, centrifugally drying potassium chloride in the materials in the kettle, and drying for recycling; transferring the centrifuged aluminum trichloride aqueous solution to a crystallization aluminum chloride kettle, maintaining the negative pressure of between minus 0.08 and minus 0.1Mpa, heating the crystallization kettle to 100 ℃ and 150 ℃, and transferring the excess water evaporated to a hydrolysis kettle for recycling; after the water evaporation is finished, putting the crystallized aluminum chloride in the crystallization kettle into a centrifuge for spin-drying, and bagging; the centrifugal mother liquor returns to the next crystallization aluminum chloride kettle for reuse.

In the step one, the mass ratio of the aluminum trichloride to the phosphorus trichloride is 4: 10.

Further improved, the temperature for evaporating the finished product of the phenyl phosphine dichloride under negative pressure is 70-120 ℃, and the pressure is-0.1 Mpa.

The main equation is as follows:

Detailed Description