Method a comprehensive selection of diperchlorate and hexaferrite

 

The invention relates to a method of separation of the products of pyrolysis of diperchlorate (DFHM) in the production of tetrafluoroethylene emitting high-purity hexaferrite (HFP) and return DFHM. Of pyrolysis gases emit high-boiling products, tetrafluoroethylene and the fraction containing diperchlorate, HEXAFLUOROPROPYLENE, tryptophanate and fluorocarbons. The resulting fraction is subjected to an absorption treatment with water at 20-40oC and 5-7 ATM. This is followed by extractive distillation using a separating agent on the basis of lower aliphatic halogen carbon, which is used as chloroform. Extractive distillation is carried out at 3-6 ATM flow in the column, taking the form of a light fraction at 5-20oC clean the GUF, as from the cube at 30-50oC chloroform with absorbed impurities, which is recovered by distillation at atmospheric pressure. Technical resultat - simplifying technology. 3 C.p. f-crystals, 6 tab., 1 Il.

The invention relates to the field of industrial synthesis of organofluorine, in particular to methods for separation of the products of pyrolysis of diperchlorate in the production of tetrafluoroethylene with the release of diperchlorate and exaft the th hillshade gaseous pyrolysis products from chloride and hydrogen fluoride, the compression and condensation of the neutral gases of pyrolysis and the multistage distillation under pressure. Gases of pyrolysis are multicomponent mixture that includes, along with the target product, unreacted tetrafluoroethylene, diperchlorate, and formed side when the pyrolysis triptorelin, deformity, HEXAFLUOROPROPYLENE, tryptophanate, fluorocarbons, OCTAFLUOROCYCLOBUTANE, tetraphthalate and others In the course of the distillation separation of the pyrolysis gases emit sequentially fraction containing tetrafluoroethylene, the fraction of unreacted diperchlorate that return on pyrolysis, and high-boiling by-products. The fraction of unreacted diperchlorate except diperchlorate contains HEXAFLUOROPROPYLENE, forming with diperchlorate azeotropic mixture, and the admixture of triptoreline and difenilamina. The return on the pyrolysis of diperchlorate containing HEXAFLUOROPROPYLENE, tryptophanate and fluorocarbons, unwanted, because co-pyrolysis of diperchlorate with HEXAFLUOROPROPYLENE, Cryptosporidium and diftorhinolonom characterized by the formation of highly toxic products, in particular PERFLUORO is. In addition, the HEXAFLUOROPROPYLENE is a valuable raw material for obtaining copolymers with tetrafluoroethylene and other personalname, so HEXAFLUOROPROPYLENE, as well as diperchlorate, you must select from the products of pyrolysis.

The number of known inventions allocation of diperchlorate and hexaferrite from a mixture of methods of absorption and extractive distillation. As separating agents used dimethylformamide [U.S. Pat. USA 3221070, CL 260-653.3, 1965], acetone [ed. St. USSR 327148, CL 07 With 21/18, 17/38, 1972], kalogeropoulou [U.S. Pat. Germany 1161877, CL 07, 1964], toluene, xylene or alkyl substituted benzene [U.S. Pat. The UK 886714, CL 07, 1962]. However, none of the above solutions solves the problem of allocation of both diperchlorate and hexaferrite high purity. In addition, dimethylformamide, acetone, aromatic compounds are flammable products.

A known method of separation of unreacted diperchlorate and hexaferrite of the pyrolysis products with the receipt of diperchlorate suitable for return to the pyrolysis. Of pyrolysis products after removal of acidic components and tetrafluoroethylene rectification allocate the fraction of unreacted diperchlorate is by reducing the pressure above the water solution to atmospheric. Nesorbiruyushchegosya when processing water gases is subjected to rectification with the release of hexaferrite [U.S. Pat. RF 2041195, CL 07 With 21/18, 17/38, 1995]. The method is characterized by the use of fire-separating agent. The disadvantage of this method is that allocated HEXAFLUOROPROPYLENE contaminated with Cryptosporidium and diftorhinolonom because of the formation of the azeotropic mixture of HEXAFLUOROPROPYLENE - tryptophanate and the closeness of the boiling points of hexaferrite and difenilamina.

Closest to the proposed technical essence is a way a comprehensive selection of diperchlorate and hexaferrite high purity gases from pyrolysis of diperchlorate production of tetrafluoroethylene, including the selection of the source gases of the pyrolysis of high-boiling products, tetrafluoroethylene and the fractions containing diperchlorate, HEXAFLUOROPROPYLENE, tryptophanate and fluorocarbons, which is subjected to extractive distillation using as the separating agent of the lower aliphatic kalogeropoulou (perftorsilanami, 1,1,2,2-tetrafluorodichloroethane or 1,1,2,2-TETRAFLUOROMETHANE) and the release of the concentrate of diperchlorate and mixtures containing getxattr will versaut distillation with removal of the separating agent, then the mixture of the first four components are subjected to absorption N-organic, acetone or dimethylformamide with a selection of hexaferrite and solvent absorbed by Cryptosporidium, diftorhinolonom, residual diperchlorate and part of hexaferrite. The selected solvent with absorbed impurities is heated to a temperature of 323-C, absorb impurities desorbed from the gas mixture by absorption of the above solvent and regenerate the solvent. Get HEXAFLUOROPROPYLENE high purity (content of difenilamina and triptoreline 430 and 14950 ppm, respectively) with exit 7386%, and diperchlorate suitable for re-pyrolysis [U.S. Pat. RF 2063952, class C 07 C 17/386, 19/08, 19/10, 1996].

The disadvantage of this method is that at the stage of allocation hexaferrite as absorbent materials are combustible or flammable liquids, the use of which will lead to the complication of the method and its implementation on an industrial scale. In addition, the disadvantages of this method include the choice of separating agents at the stage of selection of diperchlorate: perf the Tetra fluorine dibromine ethane are ozone-dangerous, and their production is now discontinued.

The technical problem solved by the present invention, simplification of the way by eliminating absorption handling flammable liquids.

The problem is solved in that in the method a comprehensive selection of diperchlorate and hexaferrite high purity gases from pyrolysis of diperchlorate production of tetrafluoroethylene, including the selection of the source gases of the pyrolysis of high-boiling products, tetrafluoroethylene and the fractions containing diperchlorate, HEXAFLUOROPROPYLENE, tryptophanate and fluorocarbons, and extractive distillation utilizing the separating agent on the basis of lower aliphatic kalogeropoulou, according to the invention by extractive distillation using a separating agent on the basis of lower aliphatic kalogeropoulou serves a mixture of HEXAFLUOROPROPYLENE, tryptophanate, fluorocarbons and residual diperchlorate resulting from the absorption of the treatment fractions containing diperchlorate, HEXAFLUOROPROPYLENE, tryptophanate and fluorocarbons, water at 20-40oAnd pressure of 5-7 bar.

In addition, as separating agents is ectification performed at a pressure of 3-6 bar in counter-current mode in the device column type with the selection in the light fraction with temperature 5-20oWith purified HEXAFLUOROPROPYLENE, and the heavy fraction with a temperature of 30-50oWith chloroform with absorbed impurities of triptoreline, difenilamina and diperchlorate.

The heavy fraction is sent for regeneration of chloroform, which is carried out by distillation at atmospheric pressure.

Schematic diagram of the allocation of diperchlorate and hexaferrite shown in the drawing.

The source gases of the pyrolysis of diperchlorate after release from the high-boiling products and the allocation of tetrafluoroethylene containing diperchlorate (R22), HEXAFLUOROPROPYLENE (R1216), tryptophanate (R1113) and fluorocarbons (R12), is fed under pressure into the bottom of absorption column 1, top of which is irrigated with water. From the upper part of the column in the gas phase output HEXAFLUOROPROPYLENE, tryptophanate, fluorocarbons and residual diperchlorate. From the bottom of the column output water with dissolved principal amount of diperchlorate, which is sent to the column 2 (desorber). In column 2 the pressure is reduced to atmospheric, causing the water is freed from dissolved diperchlorate. The water returns to irrigation of the column 1. Cleaned diperchlorate bring in dichlormethane and residual diperchlorate directed to the lower part of the extractive column 3, in the upper part of which serves extractant. In the light fraction from column 3 deduce purified HEXAFLUOROPROPYLENE, and as a bottom fraction - extractant containing tryptophanate, fluorocarbons and residual diperchlorate. Regeneration of the extractant is carried out in column 4, where in the light fraction output of tryptophanate, fluorocarbons and residual diperchlorate and cubic fraction regenerated extractant, which is cooled in the heat exchanger 5 and return in column 3.

The method was verified in the laboratory.

Example 1. Gases of pyrolysis of diperchlorate obtained in industrial conditions, is subjected to distillation separation with separation of fractions of tetrafluoroethylene, high-boiling products and the fraction of diperchlorate having the following composition, mol.%: Diperchlorate - 90,70 the HEXAFLUOROPROPYLENE Is 8.25 Fluorocarbons Is 0.60, Tryptophanate - 0,45 This fraction is directed to the absorption of the division of water on spetsstalej the Packed column 1 with an inner diameter of 24 mm and a height of the Packed part 950 mm, filled with a nozzle made of nichrome coils 23 mm Feed mixture of 36 g/HR, water supply 1440 g/H. the Absorption is carried out at 20oAnd 6 ATM. Top colormeter, which is directed to extractive distillation in column 3. The sorbate from the cube column 1 is directed in the Packed column 2 with a diameter of 24 mm and a height of 600 mm, filled with a nozzle made of nichrome coils 23 mm, where they perform the reduction of pressure to atmospheric and desorption of diperchlorate, which derive from the top of the column 2. Water after desorption of the dissolved components are returned to the column 1. The composition of the gases output from the column 1 and column 2 in table 1.

The gas phase from the column 1 is directed to the bottom of the Packed column from special steel with a diameter of 24 mm and a height of the Packed part 1200 mm, filled spiral nozzle 23 mm Column equipped with a reflux condenser, cooled by brine, and the cube, heated with hot water. In the upper part of the column served chilled chloroform. The flow rate of the gas mixture to extractive distillation is 115 g/h, consumption of chloroform - 450 g/H. the Extractive distillation is carried out at a pressure of 4 ATM, the temperature in the reflux condenser 10oAnd in the cube 30oC.

The composition of the light fraction and a bottom liquid (heavy fraction) column 3 in table 2.

Cubic liquid column 3 is sent to a distillation of ccih components. Regenerated chloroform is cooled in the heat exchanger 5 and return on irrigation columns 3.

In the end you get diperchlorate with purity to 99.6 mol.% and HEXAFLUOROPROPYLENE with a purity of 99.97 mol.%. Loss hexaferrite on stage extractive distillation is 14%.

Example 2. The experience carried out as described in example 1, but the absorption of the mixture of diperchlorate, hexaferrite, difenilamina and triptoreline carried out at a pressure of 7 bar and a temperature of 40oC. water Supply is 2100 g/h, the flow of the mixture of diperchlorate, hexaferrite, difenilamina and triptoreline - 36 g/H. the Compositions nenormirovannyj water gas (gas phase which is withdrawn from column 1) and purified of diperchlorate (gas phase column 2) in table 3.

The gas phase columns 1 further directed to extractive distillation using chloroform as the extractant. Extractive distillation is carried out at a pressure of 6 ATM, the temperature in the reflux condenser 20oAnd in Cuba 50oC. the Flow rate of the gas mixture to extractive distillation is 90 g/h, the flow rate of the extractant - 250 g/H. the composition of the light fraction and a bottom liquid of the column 3 in table 4.

Cubic liquid columns 3 pererestorani 99,93 mol.%. Loss hexaferrite on stage extractive distillation is about 9%.

Example 3. The experience carried out as described in example 1, but the absorption is carried out at a pressure of 5 ATM. Extractive rectification of unabsorbed water gas is performed at a pressure of 3 ATM, the temperature of the dephlegmator 5oWith Cuba and columns 30oC. the Compositions of the gas phase columns 1 and 2, and a light fraction and a bottom fraction column 3 are given in tables 5 and 6.

In the end you get diperchlorate with purity of 99.7 mol.% and HEXAFLUOROPROPYLENE with a purity of 99.97 mol.%. Loss hexaferrite on stage extractive distillation amounted to 17%.

Thus, the proposed method allows you to simultaneously select diperchlorate of a purity suitable for its return to the pyrolysis, and the HEXAFLUOROPROPYLENE content of the basic substance more than 99.9 mol.%, which can be used as feedstock for the synthesis of a wide class of compounds (OCTAFLUOROPROPANE, Heptafluoropropane, geksaftorpropilenom and products based on it and so on). The method is characterized by the use of fireproof, cheap and available, separating agents, which together simplifies the process.

Claims

oWith and 5-7 ATM.

2. The method according to p. 1, characterized in that the separating agent on the basis of lower aliphatic kalogeropoulou use chloroform.

3. The method according to p. 2, wherein the extractive distillation is carried out at 3-6 ATM in counter-current mode in the device column type with the selection in the light fraction with temperature 5-20oWith purified hexaferrite, and the heavy fraction with a temperature of 30-50oWith chloroform with poglosheniya fact, that the heavy fraction is sent for regeneration of chloroform, which is carried out by distillation at atmospheric pressure.

 

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