CN113772645A - Phosphorus pentafluoride synthesis process - Google Patents
Phosphorus pentafluoride synthesis process Download PDFInfo
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- CN113772645A CN113772645A CN202111236883.2A CN202111236883A CN113772645A CN 113772645 A CN113772645 A CN 113772645A CN 202111236883 A CN202111236883 A CN 202111236883A CN 113772645 A CN113772645 A CN 113772645A
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- phosphorus pentafluoride
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/10—Halides or oxyhalides of phosphorus
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Abstract
The invention provides a phosphorus pentafluoride synthesis process, and belongs to the field of chemical industry. The synthesis process comprises the steps of firstly, adding fluorine-containing waste residue powder into liquid-phase phosphorus trichloride to prepare a suspension; and then the suspension is sent into a reaction kettle after vacuum pumping, dry chlorine is introduced into the reaction kettle, the suspension is heated to be pasty, a phosphorus pentafluoride crude product is generated through reaction, impurities are removed through condensation, and finally high-purity phosphorus pentafluoride is obtained. The synthesis process recycles the fluorine-containing waste to synthesize the phosphorus pentafluoride, so that the environmental pollution can be reduced, the resource utilization rate is improved, and the production cost is reduced; the process has the advantages of cheap and easily available raw materials, relatively simple production process, high reaction efficiency and high product yield.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a phosphorus pentafluoride synthesis process.
Background
Phosphorus Pentafluoride (PF)5) It is colorless malodorous gas at normal temperature and pressure, and has strong irritation to skin, eyes and mucosa. Is a very active compound and can be violently hydrolyzed in humid air to generate toxic and corrosive white hydrogen fluoride smog. PF (particle Filter)5The method is widely applied to the fields of electronic industry, battery manufacturing, high polymer materials, catalysts and the like.
Lithium batteries are currently widely used in the fields of electric vehicles, portable computers, mobile phones, and the like. With PF5LiPF6 synthesized as a starting material is lithiumThe main electrolyte lithium salt of the battery has the advantages of strong electrochemical stability, high conductivity of the formed electrolyte and the like.
A large amount of fluorine-containing waste is generated in the production and manufacturing process of semiconductor integrated circuits, and the fluorine-containing waste can cause pollution to the environment and harm human health if being treated improperly. Most of the existing fluorine-containing waste residues are subjected to biochemical treatment or incineration, secondary pollutants generated are discharged in a liquid state up to the standard or buried in a solid state, and secondary pollution is generated and further the environment is seriously damaged due to improper treatment in an intermediate link. Therefore, it is important to treat the fluorine-containing waste without pollution, reduce the environmental pollution and ecological damage caused by unnecessary discharge, and reduce the possible adverse effects on animals, plants and human bodies.
In the prior art, PF5The common preparation method comprises the following steps: (1) phosphorus pentachloride and hydrogen fluoride are used as raw materials, and the phosphorus pentafluoride is synthesized in an organic solvent, in the method, the phosphorus pentachloride is easy to block a pipeline, and hydrogen chloride in the product is not easy to separate; (2) phosphorus pentoxide reacts with fluorine gas for preparation, the method has violent exothermic reaction, is difficult to control, has a plurality of byproducts, needs expensive fluorine gas and has higher cost; (3) red phosphorus or yellow phosphorus and fluorine gas are used as raw materials to generate phosphorus pentafluoride, and the method also needs expensive fluorine gas, so the cost is high; (4) calcium fluoride, phosphoric acid and sulfur trioxide are used as raw materials for reaction synthesis, and the method has low raw material utilization rate; (5) the method has the advantages that the fluorosulfonic acid is used for treating the phosphate ore to prepare the phosphorus pentafluoride and the phosphoric acid, and the fluorosulfonic acid is strong in corrosivity and high in requirement on equipment.
Disclosure of Invention
The invention aims to provide a phosphorus pentafluoride synthesis process, which has relatively simple process and low raw material cost, adopts fluorine-containing waste as one of the raw materials, and reduces environmental pollution and improves the resource utilization rate by recycling and reusing the fluorine-containing waste for synthesizing the phosphorus pentafluoride.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a phosphorus pentafluoride synthesis process comprises the following steps:
(1) adding fluorine-containing waste residue powder into liquid-phase phosphorus trichloride to prepare suspension;
(2) the suspension is sent into a reaction kettle after being vacuumized, and then dry chlorine is introduced into the reaction kettle for reaction;
(3) heating the suspension to a pasty state, reacting to generate a phosphorus pentafluoride crude product, and removing impurities through condensation to obtain high-purity phosphorus pentafluoride;
the reaction formula of the synthesis process is as follows:
2PCl3+2Cl2+3CaF2+2XSiF6→2PF5+3CaCl2+2XCl+2SiF4。
further, in some preferred embodiments of the present invention, the fluorine-containing waste residue powder is mainly obtained by neutralizing fluorine-containing waste acid in the fields of photovoltaic industry, glass etching and metallurgical industry with calcium hydroxide, drying and crushing, wherein the fluorine-containing waste residue powder mainly contains calcium fluoride and fluorosilicate, wherein the content of calcium fluoride is greater than or equal to 20%, the content of water is less than or equal to 100ppm, and the particle size D50 is less than or equal to 10.0 μm.
Further, in some preferred embodiments of the present invention, the suspension is prepared by any one or more of stirring, ultrasound, and high speed dispersion.
Further, in some preferred embodiments of the invention, the temperature of the chlorine gas introduced into the suspension for reaction is-10 to 30 ℃.
Further, in some preferred embodiments of the present invention, the temperature is raised to 300-500 ℃ for 3-5 h.
Further, in some preferred embodiments of the invention, the mass ratio of the liquid-phase phosphorus trichloride to the fluorine-containing waste residue powder in the suspension is 4-10: 1.
Compared with the prior art, the invention has the beneficial technical effects that: the fluorine-containing waste is recycled to synthesize the phosphorus pentafluoride, so that the environmental pollution can be reduced, the resource utilization rate is improved, and the production cost is reduced; the process has the advantages of cheap and easily available raw materials, relatively simple production process, high reaction efficiency and high product yield.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Adding 5kg of dried and crushed fluorine-containing waste residue powder (the content of calcium fluoride is 30%, the content of fluorosilicate is 40%, and D50 is 4.4 mu m) into 24kg of liquid-phase phosphorus trichloride, and carrying out ultrasonic treatment to obtain a suspension; starting a vacuum pump to vacuumize the reaction kettle to-0.09 MPa, introducing the suspension into the reaction kettle, slowly introducing dry chlorine, reacting at 10 ℃ for 2 hours, heating to 350 ℃, reacting for 3 hours to generate a phosphorus pentafluoride crude product, and removing impurities through condensation to obtain high-purity phosphorus pentafluoride; the reaction formula is as follows:
2PCl3+2Cl2+3CaF2+2XSiF6→2PF5+3CaCl2+2XCl+2SiF4。
the purity of the purified phosphorus pentafluoride gas is 99.9% by sampling test, and the rest gas is absorbed and treated by 1mol/L sodium hydroxide solution.
In this embodiment, during the ultrasonic treatment, liquid-phase phosphorus trichloride is uniformly dispersed on the surface of the fluorine-containing waste residue powder and permeates into the powder, phosphorus pentachloride is generated along with the introduction of chlorine gas, a large amount of phosphorus pentachloride is attached to the surface and the inside of the fluorine-containing waste residue powder, and after heating, the phosphorus pentachloride on the surface and the inside of the fluorine-containing waste residue powder and CaF contained in the fluorine-containing waste residue powder2、2XSiF6Directly reacting to generate a crude product of the phosphorus pentafluoride gas. The crude phosphorus pentafluoride gas can be purified by one or more of deep cooling, compression, rectification and washing.
Example 2
Adding 5kg of dried and crushed fluorine-containing waste residue powder (calcium fluoride content is 50%, fluorosilicate content is 30%, D50 is 5.6 mu m) into 30kg of liquid-phase phosphorus trichloride, and stirring to obtain a suspension; starting a vacuum pump to vacuumize the reaction kettle to-0.09 MPa, introducing the suspension into the reaction kettle, slowly introducing dry chlorine, reacting at room temperature for 2.5 hours, heating to 500 ℃, reacting for 2.5 hours to generate a phosphorus pentafluoride crude product, and removing impurities through condensation, rectification and separation to obtain high-purity phosphorus pentafluoride; the reaction formula is as follows:
2PCl3+2Cl2+3CaF2+2XSiF6→2PF5+3CaCl2+2XCl+2SiF4。
the purity of the purified phosphorus pentafluoride gas is 99.9% by sampling test, and the rest tail gas is absorbed and treated by 2mol/L sodium hydroxide solution.
Example 3
Adding 5kg of dried and crushed fluorine-containing waste residue powder (the content of calcium fluoride is 65%, the content of fluorosilicate is 20%, and D50 is 7.3 mu m) into 45kg of liquid-phase phosphorus trichloride, and carrying out ultrasonic treatment to obtain a suspension; starting a vacuum pump to vacuumize the reaction kettle to-0.09 MPa, introducing the suspension into the reaction kettle, slowly introducing dry chlorine, reacting at room temperature for 3 hours, heating to 400 ℃, reacting for 3 hours to generate a phosphorus pentafluoride crude product, and removing impurities through condensation, rectification and separation to obtain high-purity phosphorus pentafluoride; the reaction formula is as follows:
2PCl3+2Cl2+3CaF2+2XSiF6→2PF5+3CaCl2+2XCl+2SiF4。
the purity of the purified phosphorus pentafluoride gas is 99.9% by sampling test, and the rest tail gas is absorbed and treated by 2mol/L sodium hydroxide solution.
Example 4
Adding 5kg of dried and crushed fluorine-containing waste residue powder (calcium fluoride content is 70%, fluorosilicate content is 10%, D50 is 6.3 mu m) into 36kg of liquid-phase phosphorus trichloride, and carrying out ultrasonic treatment to obtain a suspension; starting a vacuum pump to vacuumize the reaction kettle to-0.09 MPa, introducing the suspension into the reaction kettle, slowly introducing dry chlorine, reacting at room temperature for 2.7 hours, heating to 400 ℃, reacting for 3 hours to generate a phosphorus pentafluoride crude product, and removing impurities through condensation, rectification and separation to obtain high-purity phosphorus pentafluoride; the reaction formula is as follows:
2PCl3+2Cl2+3CaF2+2XSiF6→2PF5+3CaCl2+2XCl+2SiF4。
the purity of the purified phosphorus pentafluoride gas is 99.9% by sampling test, and the rest tail gas is absorbed and treated by 2mol/L sodium hydroxide solution.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; based on the embodiments of the present invention, a person skilled in the art may modify the technical solutions described in the foregoing embodiments without creative efforts, or may substitute part of the technical features of the embodiments; however, such modifications and substitutions do not substantially depart from the spirit and scope of the present invention, and are intended to be included within the scope thereof.
Claims (6)
1. A phosphorus pentafluoride synthesis process, characterized by, add fluorine-containing waste residue powder into phosphorus trichloride of liquid phase to make into the suspension; sending the suspension into a reaction kettle after vacuumizing, then introducing dry chlorine into the reaction kettle, heating the suspension to be pasty, reacting to generate a phosphorus pentafluoride crude product, and removing impurities through condensation to obtain high-purity phosphorus pentafluoride; the reaction formula is as follows:
2PCl3+2Cl2+3CaF2+2XSiF6→2PF5+3CaCl2+2XCl+2SiF4。
2. the phosphorus pentafluoride synthesis process of claim 1, wherein: the fluorine-containing waste residue powder is mainly obtained by neutralizing fluorine-containing waste acid and calcium hydroxide in the fields of photovoltaic industry, glass etching and metallurgical industry and then drying and crushing, wherein the fluorine-containing waste residue powder mainly contains calcium fluoride and fluosilicate, the content of calcium fluoride is more than or equal to 20 percent, the content of water is less than or equal to 100ppm, and the granularity D50 is less than or equal to 10.0 mu m.
3. The phosphorus pentafluoride synthesis process of claim 1, wherein: the suspension is prepared by any one or more of stirring, ultrasonic and high-speed dispersion.
4. The phosphorus pentafluoride synthesis process of claim 1, wherein: the temperature of the chlorine gas introduced into the suspension for reaction is-10-30 ℃.
5. The phosphorus pentafluoride synthesis process of claim 1, wherein: heating to 300 ℃ and 500 ℃, and reacting for 3-5 h.
6. The phosphorus pentafluoride synthesis process of claim 1, wherein: the mass ratio of the liquid-phase phosphorus trichloride to the fluorine-containing waste residue powder in the suspension is 4-10: 1.
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Citations (7)
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| CN102320584A (en) * | 2011-10-26 | 2012-01-18 | 核工业理化工程研究院华核新技术开发公司 | Method for preparing phosphorus pentafluoride |
| JP2012126621A (en) * | 2010-12-17 | 2012-07-05 | Daikin Industries Ltd | Method for producing phosphorus pentafluoride |
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| CN103153847A (en) * | 2010-10-14 | 2013-06-12 | 大金工业株式会社 | Method for producing phosphorus pentafluoride |
| CN106241840A (en) * | 2016-09-08 | 2016-12-21 | 甘肃立焘新能源科技发展有限公司 | The preparation method of a kind of lithium hexafluoro phosphate and preparation system |
| CN109970084A (en) * | 2019-03-18 | 2019-07-05 | 张明东 | A kind of preparation method of high purity lithium hexafluorophosphate |
| CN110072807A (en) * | 2017-03-13 | 2019-07-30 | 关东电化工业株式会社 | The manufacturing method of phosphorus pentafluoride |
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- 2021-10-24 CN CN202111236883.2A patent/CN113772645A/en active Pending
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| CN103153847A (en) * | 2010-10-14 | 2013-06-12 | 大金工业株式会社 | Method for producing phosphorus pentafluoride |
| US20130177491A1 (en) * | 2010-10-14 | 2013-07-11 | Atsushi Suzuki | Method for producing phosphorus pentafluoride |
| JP2012126621A (en) * | 2010-12-17 | 2012-07-05 | Daikin Industries Ltd | Method for producing phosphorus pentafluoride |
| CN102583301A (en) * | 2011-01-18 | 2012-07-18 | 孟永 | Preparation method of lithium hexafluorophosphate |
| CN102320584A (en) * | 2011-10-26 | 2012-01-18 | 核工业理化工程研究院华核新技术开发公司 | Method for preparing phosphorus pentafluoride |
| CN106241840A (en) * | 2016-09-08 | 2016-12-21 | 甘肃立焘新能源科技发展有限公司 | The preparation method of a kind of lithium hexafluoro phosphate and preparation system |
| CN110072807A (en) * | 2017-03-13 | 2019-07-30 | 关东电化工业株式会社 | The manufacturing method of phosphorus pentafluoride |
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Application publication date: 20211210 |