• 专利附录
  • 专利说明
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    • 专利摘要:
    A continuous process for fluorinating haloalkanes containing at least one nonfluorine halogen atom wherein antimony pentachloride is reacted (A) with HF to produce an antimony chlorofluoride. The antimony chlorofluoride thus produced is then transferred to a separate reaction zone (C) where it is reacted with the haloalkane, thereby replacing a portion of the nonfluorine halogen in the haloalkane with fluorine of the antimony chlorofluoride.
    公开号:SU1577693A3
    申请号:SU843752789
    申请日:1984-06-22
    公开日:1990-07-07
    发明作者:Уильям Мейдер Фредерик
    申请人:Е.И.Дюпон Де Немур, Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the preparation of chlorofluoromethanes or chlorofluoroethanes used as solvents and intermediates for fluorine-organic synthesis.
    The aim of the invention is to simplify the technology.
    Example 1. Continuous process of hydrofluorination of antimony tapenhloride by the continuous supply of antimony pentachloride: 1y to a part of the packed column and its interaction with hydrogen fluoride moved at the top of the specified column, a byproduct of the reaction is hydrogen chloride.
    Antimony (V) chlorofluoride is desorbed with nitrogen to remove dissolved hydrogen chloride before it is continuously fed to the reactor, where
    chloroform steps. Thus, chlorofluorhydromethanes are obtained which do not contain fluoride and hydrogen chloride.
    Figures 1 and 2 show a flow type reactor — packed column,
    Packed on column A is a metal pipe with a diameter (two inches), 5.08 cm with a nozzle height (27 inches) 68.58 cm, by means of stainless steel rings (1/4 inch) 0.63 cm thick. The reactor is a pipe with a diameter (3 inches) of 7.62 cm and a length (40 inches) of 101.60 cm, which is equipped with a steam jacket to control the reaction temperature. The liquid distillation pipe connected to the reactor is set to (4.75 inches) 12.05 cm below the top flange of the specified reactor. The reactor contains equally spaced sieve plates with an inaroM (3 inches) of 7.62 cm, which are designed to ensure the cascade of the reactor, thorough mixing and prevent bypass movement. Each of the cymbal plates is (three inches) in diameter of 7.62 cm and is equipped with a sealing gasket ring on the outer periphery to prevent retraction. There are five symmetrically drilled holes (1/4 inch) in size in each of the mesh plates 0 63 cm
    Antimony pentachloride is continuously supplied through conduit 1 at a feed rate of 18.144 or 27.941 kg / h (64–93 mol and distributed over column packing A. Liquid hydrogen fluoride is continuously fed at various speeds in the range of 0.990-1.998 kg / h 54-100 mol ) to the upper part, packed column A, via pipeline 2. The pressure is regulated in the range of 18.28 - 18.63 kg / cm, and the temperature in the range of 88-96 ° C. Hydrogen chloride gas, which is produced by reacting hydrogen fluoride with antimony pentachloride, moves up the column and undergoes countercurrent contact as the antimony pentachloride flows down to remove unreacted hydrogen fluoride contained in the vapor. Hydrogen chloride, containing on average 0.8 wt.% Hydrogen fluoride, is one way continuously released from
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    columns through conduit 3. Antimony chlorofluoride (V) formed in the column is continuously recovered through conduit 4 and accumulated in tank B, the contents of which are flushed with nitrogen introduced through conduit 5 to remove dissolved hydrogen chloride discharged through conduit 6.
    Antimony (V) chlorofluoride containing 3.6-4.4 wt.% Of fluoride is continuously fed from tank B through line 7 to tank 8, where it is mixed with chloroform fed through line 9. The reaction mixture is fed through line 10 into the reactor C, where the pressure of 13.50-1.85 kg / cm2 and the temperature of 90-110 ° C are regulated. The reaction mass, i.e. the mixture consisting of steam and liquid is removed from the reaction vessel C through line 11 and fed continuously to the vapor-liquid separator D. The steam is continuously withdrawn through line 12. The liquid phase containing spent antimony chlorofluoride is continuously separated from the separator pipeline 13 and accumulate in the tank E.
    In tab. 1 shows the data on the feed rate of the reactants; table 2 - data relating to the composition of the raw product "
    Table 1
    50
    Table 2
    Hydrogen fluoride
    Not Detected
    Table 2
    insufficient with respect to the molar amount of chloroform in the feed to convert all chloroform to chlorodifluoromethane, in experiment 2, the amount of fluoride contained in antimony chlorofluoride (V) relative to the molar amount of chloroform when fed exceeds the required amount of chloroform. None of the experiments revealed any presence of hydrogen fluoride in the gaseous raw products.
    EXAMPLE 2 The apparatus of Example 1 shown in Fig. 1 is used to demonstrate the continuous hydrofluorination of antimony pentachloride in packed column A with hydrogen fluoride followed by continuous fluorination of chloroform in reactor C by continuously passing antimony chlorofluoride (V) from the reactor. And in the reactor C - in the reactor for the synthesis of chlorofluoromethanes.
    Antimony pentachloride is continuously fed through conduit 1 at a feed rate of 22.2 kg / h (74 mol) and distributed over the packed material of the column A. Liquid hydrogen fluoride is supplied continuously at a speed of (3.4 pounds) 1.54 kg / h ( 76.7 mol) in the liquid phase of the distilled liquid in the upper part of the column. The pressure is set at 18.63 kg / cm2, and the temperature is 85 ° C. Hydrogen chloride produced by the interaction of hydrogen fluoride with antimony pentachloride passes upward in the column as a vapor and undergoes countercurrent contact with a descending stream of liquid antimony pentachloride for conversion.
    tirovani unreacted hydrogen fluoride. The content of hydrogen fluoride in the stream of hydrogen chloride leaving continuously from the column through the pipeline 3, 0.25 wt.%. When 99.7% of the use of hydrogen fluoride is fed into the reactor C of the synthesis of chlorofluoromethanes, antimony chlorofluoride (V) with a fluoride content of 6.63 wt.% (SbCl4F) is fed continuously through line 4 to the tank.
    Solubility of hydrogen chloride
    c in at different pressures and temperatures are determined in separate tests. Using these data, the calculated solubility of hydrogen chloride in antimony (V) chlorofluoride
    0 4.7% by weight. Under the conditions used, 63% of the hydrogen chloride obtained by reacting with hydrogen fluoride in reactor A is removed from the column via a pipeline, 3.37% remains diluted in antimony (V) chlorofluoride. To remove dissolved hydrogen chloride, antimony chlorofluoride (V) is not purged with nitrogen, as described in Example 1.
    Antimony chlorofluoride (V) is supplied continuously at 85 ° C from tank B via line 7 to tank 8, where it is mixed with chloroform fed through line 9 at 102 ° C. The resulting reaction mixture serves
    5 through the pipeline 10 with a steam jacket into the reaction vessel C, which operates at a pressure of 13.36 kg / cm and a temperature of 107 C. The resulting reaction product is continuously discharged from the reactor C through pipeline 10 to the vapor-liquid separator D.
    Spent antimony chlorofluoride (V) (fluoride content 1.4% by weight) is withdrawn from the separator via conduit 13 and accumulated in receiver E. The gas flow separated in the separator is withdrawn via conduit 12.
    In tab. 3 shows the data characterizing the feed rate of the components of the -R reactor; in tab. 4 - the composition of the crude product.
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    Table3
    55
    Method parameters
    I
    Indicators
    Feed rate, kg / h: antimony (fluoride content of 6.63 wt.%)
    22.2
    Continuation of table 3
    i
    Method Parameters Indicators
    TableA
    Components
    Quantity, mol.%
    Hydrogen fluoride Antimony chlorofluoride (1.44 wt.% Fluoride Hydrogen chloride Chlorine
    Chloroform Dphlorfluoromethane Chlorodifluoromethane Trifluorome tan
    The calculated data of this example shows that even without distilling the dissolved hydrogen chloride from antimony chlorofluoride (V) obtained in reactor A, the amount of inorganic fluoride that is contained in the vapor stream of the organic raw product is only 1.6% of the fluoride entering synthesis reactor. chlorofluoromethanes.
    PRI me R 3. Continuous process of hydrofluorizing antimony pentachloride with hydrogen fluoride in reactor A followed by continuous fluorination of carbon tetrachloride by continuously moving antimony chlorofluoride (2) from its synthesis reactor to the synthesis reactor of chlorofluoromethanes.
    Spent antimony (V) chlorofluoride, containing 0.4 wt.% Fluoride, is fed continuously through conduit 1 at a feed rate of 18.144 kg / h and is distributed along the packing of the column. Liquid hydrogen fluoride is fed at a feed rate of 1.45 kg / h to the top of the column via line 2. The pressure in the reaction system is adjusted to 16.43 kg / cmg and the temperature is 69-75 ° C. The hydrogen fluoride formed by the reaction of antimony chlorofluoride (V) and hydrogen chloride passes upwards in the form of steam and is countercurrently in contact with the bottom of the column.
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    A liquid stream of antimony chlorofluoride (V) to convert unreacted hydrogen fluoride. Hydrogen chloride is discharged from the column via line 3. The hydrogen fluoride content in the hydrogen chloride stream is 0.4% by weight with 99.2% use of hydrogen fluoride fed to the specified reactor. Antimony (V) chlorofluoride (fluoride content 8.14 wt.%), Formed in column A, is continuously fed through conduit 4 to the tank, but to remove hydrogen chloride dissolved in it, it is not purged with nitrogen, as described in Example 1 .
    The solubility of hydrogen chloride in antimony chlorofluoride (V) is determined in separate tests. Using the data obtained, the calculated content of hydrogen chloride contained in antimony chlorofluoride (V), 6, wt.%. Under these conditions, 57% hydrogen chloride, obtained as a result of interaction with hydrogen fluoride in reactor A, can be directly passed through line 3, with 43% remaining dissolved in antimony (V) chlorofluoride.
    Antimony chlorofluoride (V) is continuously fed at 69 ° C at a speed of 16.91 kg / h (separately) through conduit 7 to tank 8, where it is mixed with carbon tetrachloride fed at a speed of 6.895 kg / h via conduit 9 at 94 ° C . The resulting reaction mixture is continuously fed through a pipe 10 with a steam jacket into the tank of the reactor C, which operates at a pressure of 6.47 kg / cmg and a temperature of 100-103 ° C. The contents of the reactor are re- ent through pipeline 11 to the vapor-liquid separator.

    Spent antimony chlorofluoride (V) is withdrawn from tank D via line 13 to the receiver. The gas stream, which is separated in separator D, is discharged through line 12.
    The results of the experiment are given in table.5.
    Table5
    Hydrogen fluoride
    2.0
    Continuation of table.5
    The total amount of fluoride leaving the reactor in the form of hydrogen fluoride is 2.4 wt.%. 20
    PRI me R 4. Continuous fluorination process of recycled spent chlorofluoride (V) with hydrogen fluoride in reactor A (antimony chlorofluoride 25 is accumulated in tank B), followed by continuous fluorination of chloroform in reactor C by continuously supplying refluorinated antimony chlorofluoride (V) from the reactor and mixing it with the supplied chlorofor30
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    The reactor A operates at a pressure of 17.15 kg / cm2, and this pressure is controlled by blowing through the pipeline a by-product, hydrogen chloride, which contains 0.35 mol% of organic matter. Antimony (V) chlorofluoride obtained in the reactor, containing 8.05 wt.% Fluoride, is continuously discharged from reactor A at 72 ° C with its continuous flow through conduit 4 through inlet 5 to vessel B. Antimony chlorofluoride The level installed in tank B is fed continuously through line 7 at a feed rate of 57.51 kg / h to tank 8 and mixed with chloroform fed continuously through line 9 at a feed rate of 14.66 kg / h. Software C. The above mixture of reactants is fed through conduit 10 to the reactor, which operates at a pressure of 12.23 kg / cm and a temperature of 125 ° C. A mixture consisting of liquid and vapor is withdrawn from the reactor through conduit 11 to the vapor-liquid separator D. The separated vapor flow is withdrawn continuously via conduit 12.
    The data of the experiment are given in table.6.
    Table
    of separating liquid spent antimony chlorofluoride (V) from organic vapors formed in reactor C, and desorbing residual organic compounds and a solution of spent antimony chlorofluoride (V) in a stripping column before being recycled to the reactor to increase the fluorine content in the antimony chlorofluoride fluorinating agent (V)
    The stripping column (Fig.) Is a two-inch (5.98 cm) diameter stainless steel pipe with a packing height of 10 ft. (3.048 m) using 1/4 inch (0.60 cm) Raschig stainless steel rings.
    Spent antimony chlorofluoride (V) containing 1.4 wt.% Fluoride, is subjected to continuous recycling using a pump, and is continuously fed to reactor A via pipeline 1 at a feed rate of 60.80 kg / h. The supplied antimony chlorofluoride (V) after stripping it in the desorption column contains 0.2 mol.% Of residual chlorofor- | ma Hydrogen fluoride enters pipeline 2.
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    Spent antimony chlorofluoride (2), containing 10.1 mol.% Chloroform, 1.2 mol.% Dichloromethane, 7.5 mol.% Chlorofluoromethane and 0.4 mol.% Trifluoromethane, is continuously discharged from the top of the vapor-liquid separator D Moreover, the speed of its unloading is automatically controlled by means of a level control device located in separator D. In line 13, the pressure of waste is reduced.
    secret antimony chlorofluoride from 12.23 to 0.316 kg / cm2 - at 125 ° C and the resulting mixture consisting of liquid and steam is continuously fed into the upper part of the desorption column E. Nitrogen is fed continuously through conduit 14 at a feed rate of 0.907 kg / h in the direction of the dissolved organic substances that are desorbed by countercurrent from the descending stream of antimony chlorofluoride (V). The desorbed spent surmum (V) chlorofluoride is removed from the upper part of desorption column E and fed to tank F with a pump. Pairs from column E are taken along line 15.
    The analysis of this substance indicates that the organic substance that is present in the product is chloroform concentration only 0.2 mol%. Antimony (V) distilled chlorofluoride is recycled through pipeline 16 through pump G and pipeline 1 to reactor A at a feed rate of 60.83 kg / h. Of all the organic substances entering the desorption column, 99.1% is supplied to the pipeline 15.
    The composition of the effluent stream through conduit 15 is calculated from the material balance presented in table. 7
    Table 7
    The use of hydrogen fluoride to obtain fluorinated organic products, based on fluorine atoms, leaving the reactor and desorption column in the vapor of the raw product from the reactor is 97.1%. If desired, the percentage of use can be increased, even significantly, by further reducing the amount of dissolved hydrogen chloride in antimony chlorofluoride before it is fed into the chlorofluoromethane synthesis reactor, as shown in Example 1.
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    EXAMPLE 5: Continuous reaction between chloroform and antimony chlorofluoride in a packed column, in accordance with which chloroform gas contacts in countercurrent mode with antimony chlorofluoride, i
    1742 g of antimony chlorofluoride containing 5.05% fluorine at 85-90 ° С and prepared, as mentioned earlier, are continuously fed through a stainless steel pipe with a diameter of I / 4 inches (6.35 mm) into the upper part of the tube, Made of stainless steel, 2 cm in size, equipped with a 6.35 mm stainless steel extension nozzle. 1130 g of chloroform gas at 80 ° C is fed from the bottom up through the bottom of a stainless steel tube, and the chloroform gas is contacted with top-down antimony chlorofluoride. Contact time 2-40 s. Spent antimony chlorofluoride is collected in a vessel connected to the bottom of the reaction tube. The volatile products resulting from the reaction are removed from the reaction tube through a cooled refrigerator, a drain trap, two water scrubbers, a gas sampling device and a flow meter. Chloroform is administered over 250 minutes. The temperature in the reaction tube varies in the range of 50-90 ° C. Gas is sampled at 35, 60, 100, 120, 180, 210, 240 and 250 minutes and the samples thus taken are subjected to chromatographic analysis. The mean values of these analyzes, in eight measurements, expressed in terms of the percentage of surface area, indicate that the volatile products formed during the reaction consist of the components,%: trifluoromethane 0.6 (0.24-0.86%); mono-chlorodifluoromethane 10.5 (1.02-21.83%); dichlorofluoromethane 83.47 (73.21-93.27%); chloroform 3.1 (0.96-4.48%); trichloro-no-fluoromethane 1.54 (0.02-5.98%); dichlorodifluoromethane 0.25 (0.09-0.62%). Chloroform conversion 32%. Approximately 93% of the fluorine used in the reaction of fluorine in antimony chlorine lluoride is used (the initial concentration of fluorine is 5.05, the final concentration of fluorine is 0.33%).
    PRI me R 6. The process of iterating antimony pentachloride with
    liquid hydrogen fluoride is carried out in a Teflon polytetrafluoroethylene cylinder of a volume of ml. Antimony penta chloride in the amount of 70.6 g is placed in a cylinder and the latter is combined with a cylinder containing hydrofluoride. Antimony pentachloride in a Teflon cylinder is frozen by placing the bottom of this Teflon cylinder in solid carbon dioxide. After the antimony pentachloride is frozen, a Teflon cylinder is extracted from carbon dioxide and 49 g of hydrogen fluoride is introduced into the Teflon cylinder by distillation from a cylinder containing hydrogen fluoride. After stopping the supply of hydrogen fluoride from the cylinder, the teflon cylinder is connected to a drying tube, which is connected to a gas bubbler containing liquid trichlorotri-Ltoratan, in order to observe the release of hydrogen chloride. The teflon cylinder is kept for 12 hours, and after this time, the hydrogen chloride release process is stopped. Anhydrous nitrogen gas is pumped through the contents of the Teflon cylinder, and then the cylinder is placed in a vacuum to remove volatile materials. The weight of the residue in the cylinder is 66.6 g compared to a theoretical weight of the precipitate equal to 66.7 g, if one of the five antimony pentachloride chlorides is replaced by fluorine. The lower outer part of the Teflon cylinder is again placed in solid carbon dioxide, and then the cylinder is removed from carbon dioxide. Carbon tetrachloride in an amount of 29.6 g is fed by distillation into a Teflon cylinder, and the contents of this cylinder are heated to room temperature. The molar ratio between antimony chlorofluoride and carbon tetrachloride is 1.22. Output patrubo. the cylinder is connected to a water scrubber, which is connected to a receiver placed in a bath containing solid carbon dioxide and methanol. The cylinder is heated in an oil bath, with an initial heating temperature of 70 ° C and a final heating temperature of 80 ° C, and the heating process continues for 2 hours. The weight of the material collected in the cold receiver is 28.5 g. or-
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    of the material collected in the receiver, the following,%: monochlorotrifluoromethane 0.3; dichlorodifluoromethane 16.74 ;. trphlormonofluoromethane 81.3; carbon tetrachloride 1.42. The analysis of spent fluorinating agent - antimony chlorofluoride shows that 71.5% of the fluorine contained in the fluorinating agent has been used (from 7.0 to I, 95% Ltora).
    Example 7. Antimony chlorofluoride is prepared analogously to Example 1, except that instead of a Teflon cylinder, a cylinder made of stainless steel is used, and 82.6 g of antimony pentachloride and 62 g of hydrogen fluoride in liquid form are used.
    76.5 g of antimony chlorofluoride is reacted with 40 g of carbon tetrachloride / molar ratio between the fluorinating agent and carbon tetrachloride is 1.06, and the reaction is carried out at 85-90 ° C for 20 hours. At 88 ° C, the pressure is 8.3 kg / cm. After cooling, this cylinder is connected to a water scrubber and then to a receiver installed in a bath filled with solid carbon dioxide and methanol. The cylinder is heated to 42 ° C and 15.37 g of product is collected in the receiver. The analysis of the composition of the organic material collected in the receiver is as follows: dichlorodifluoromethane 43.94; trichloromonofluoromethane 49.77; carbon tetrachloride 4.76. An analysis of the spent fluorinating agent of antimony chlorofluoride proves that 94% of the fluorine contained in the fluorinating agent is used (the initial fluorine content is 9.34%, the final fluorine content is 0.56%).
    Example Antimony chlorofluoride is prepared according to the procedure described above, using 82.8 g of antimony pentachloride and 60.8 g of hydrogen fluoride. Hexachloroethane in the amount of 7 g adds in the solid state to antimony chlorofluoride. The molar ratio between fluoride fluoride and hexachloride is 3.86. The reaction is carried out at for 20 hours. After 14.5 hours at 146 ° C, the pressure is 4.570 ,
    After cooling the cylinder to 23 ° C, the pressure decreases to 1.406 kg / cm2. Using the described method, one collects
    6.27 g of material in the receiver, and the analysis of the composition of this organic material gives the following results,%: dichlorotetrafluoroethane 0.18; trichlorofluoroethane 71.77; tetrachlorofluoroethane 16.05; pentachloronofluoroethane 0.48; trichloromonofluoromethane 9.57; carbon tetrachloride, 1.72; Analysis of spent fluorinating agent — antimony chlorofluoride shows that 46.4% of the fluorine contained in the fluorinating agent is used (initial fluorine content is 10.45%, the end fluorine content is 5.6%).
    Limer 9. Antimony chlorofluoride is prepared, according to the described procedure, from 81.6 g of antimony pentachloride and 53.8 g of hydrogen fluoride. 24.6 g of chloroform was added to antimony chlorofluoride, and the mixture thus obtained was heated to 75-80 ° C for 17 hours. The molar ratio between antimony chlorofluoride and chloroform was 1.32. The pressure in the cylinder reaches, at 78 ° С, 13.07 kg / cm. After cooling to 35-40 ° C, the pressure decreases to 8.577 kg / cmg.
    After passing through a water scrubber to a receiver maintained in a bath cooled by a mixture of solid carbon dioxide and methanol, 4.88 g of product is obtained in this cooled receiver. Analysis of the composition of the organic product collected in the receiver, the following,%: trifluoromethane 10.16; monochlorodifluoromethane 85.46; dichloromonofluoromethane 2.2 chloroform 2.01. The analysis of spent fluorinating agent - antimony chlorofluoride shows that 80.2% of fluorine contained in chlorofluoride is used.
    Determined by dividing the peak area of the chromatogram for an individual component of the mixture by the total area of all peaks.
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    in antimony grade (initial fluorine content 7.44%, final fluoride content 1.47%).
    II g. And ri 10. 790 g (2.64 mol) of antimony pentachloride are placed in a 1 liter reaction vessel made of stainless steel, which is equipped with a condenser cooled with ice water. This container is heated to 90 ° C and 52 g (2.6 mol) of hydrogen fluoride gas bubbling through antimony pentachloride for 2 h, after the addition of hydrogen fluoride is stopped, the contents of the tank are flushed with nitrogen gas four times and the contents of the tank equilibrate for 1 hour between blows. The fluorine analysis shows that antimony chlorofluoride contains 6.35 wt.% Fluorine.
    227 g (0.8 mol) of the obtained antimony chlorofluoride are placed in a 1 liter tank made of stainless steel and equipped with a stirrer, and then 93 g (0.6 mol) of carbon tetrachloride are added over 40 minutes and the process is carried out with constant stirring. The reaction temperature in the vessel varies from 80-132 ° C. Volatile material released during the addition of carbon tetrachloride is sampled for analysis at different periods of time during the 40-minute reaction time interval. Total gas released 9 l
    Gas chromatographic analysis of gas samples, reaction time and temperature are presented in Table. eight.
    Table3
    The fluorine content in antimony fluorochloride is reduced from 6.45 to 0.1 wt.% The content of hydrogen chloride in the fluorinated product is 7.03 wt.%, The theoretical amount of hydrogen chloride released according to the previously developed technological processes with the combined supply of hydrogen fluoride and carbon tetrachloride to the catalyst - antimony pentachloride, 38 wt.%. Presence
    7.03 wt.% Hydrogen chloride in the product is caused by incomplete removal of hydrogen chloride from antimony chlorofluoride or by the presence of hydrogen fluoride in antimony chlorofluoride.
    Example 11. 229 g (0.8 mol) of antimony chlorofluoride, prepared analogously to example 10, are placed in a 1 liter stainless steel reactor equipped with a stirrer and then 45 g (0.38 mol) of chloroform are added 40 min with constant stirring. The temperature in the reaction vessel varies from 100 to 108 ° C. Volatile material released during this reaction is sampled at regular intervals and analyzed. Total gas released
    5.4l.
    These gas chromatography analysis of fluorinated products, the reaction time and the reaction temperature are given in Table. 9.
    In tab. 11 shows comparative
    Spent antimony chlorofluoride is co-50 with the results of a known method and contains 2.09% by weight of fluorine (the initial content is as follows (examples 1 and I).
    holding fluorine 6.35 wt.%). The content of hydrogen chloride in the fluorinated product is 3.8 wt.%, The theoretical amount of hydrogen chloride released during the technological processes, which are known, and during which the fluorine fluoride and chloroAorm are fed to the catalyst — antimony pentachloride, 46 wt.%
    Example 12 (comparative). The results of examples 1 and 2, which characterize the invention, are compared with the results obtained by the known technology, where hydrogen fluoride and chloroform are fed continuously and simultaneously to the reaction tank containing antimony pentachloride in a stationary state.
    The industrial reactor operates at 78 ° C and a pressure of 12.512 kg / cm. The gases discharged from the reactor are directly fractionated to return high boiling point compounds (antimony tapeamide, chloroLorm and dichlorofluoromethane) to the reaction tank. From the crude product leaving the distillation column, a sample is taken, which is analyzed to obtain the results presented in table. ten.
    Not detected
     100 97.8
    Not detected 32.8
    From tab. 11 shows that it is possible to drastically reduce the content of fluoride and hydrogen chloride in organic products of synthesis, which eliminates the need for complex processes of cleaning products, as well as the purification of hydrogen chloride. Simplification of the technology is also provided by increasing the use of fluorine, which eliminates the need to recycle hydrogen fluoride.
    PRI me R 13. Pentachloride is continuously fed through conduit 1 (FIG. 2) at a feed rate of 100 lb / h (0.334 lb-mol) and distributed over the load in zone A “Liquid HF is continuously supplied feeding 1.67 lb / h (0.0836 lb-mol) to the load in the lower part of the loaded zone A over pipe 2, therefore, the mole rTable 1
    12.5
    87.3 61.3
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    The HF / pentachloride ratio is 0.25. The pressure in the system is maintained at 0.5 at, and the temperature at 50 ° C. The gaseous HC1 formed during the reaction of HF with antimony pentachloride rises to the upper part of zone A and is countercurrently in contact with the liquid stream of antimony pentachloride flowing downwards in order to remove unreacted HF contained in the vapor. Hydrogen chloride, containing on average 0.8 wt.% HF, is continuously passed from zone A through conduit 3. Antimony chlorofluoride (V) is continuously removed through conduit 4, collected through inlet 5 in receptacle 6, and purified with nitrogen to remove the dissolved HC1
    Antimony (V) chlorofluoride, containing 1.6% by weight of fluoride, is continuously supplied from the vessel. Tarze pipeprogod 7 R
    20
    tank 8, where this mixture is mixed, with chloroform (0.042 lb-mol / h), which is fed through line 9. The molar ratio of fluoride to chloroform in the mixed feed material is 2.0. The resulting reaction mixture is continuously fed through line 10 into the reaction vessel C, which is maintained at 0.5 at and 50 ° C. The reaction mass, consisting of vapor and liquid, is discharged from vessel C through line 11 and continuously fed to separator D to separate vapor and liquid. The steam is removed, through line 12.
    The liquid phase containing spent antimony chlorofluoride (V) is continuously removed from vessel D through line 13 and accumulated in vessel E. The organic product is chlorodifluoromethane.
    Example 14. Antimony pentachloride is continuously fed through conduit 1 (Fig. 2): at a feed rate of 100 lb / h (0.334 lb-mol) and distributed over the load in zone A. Liquid HF is continuously fed at a feed rate of 21, 7 lb / h (1,086 lb-mol) per load in the lower part of the loaded zone A through line 2. Therefore, the molar ratio HF / antimony pentachloride is 3.25. The pressure in the system is maintained at 20 at, and the temperature at 120 ° C. The gaseous HC1 formed during the reaction of HF with antimony penchachloride rises to the upper part of zone A and contacts with the current downward liquid flow of penta-. Antimony chloride to remove unreacted HF contained in a pair. Hydrogen chloride containing an average of 2.0 May,% HF, is continuously passed from zone A through line 3. .d
    Antimony chlorofluoride (V), formed in zone A, is continuously removed through conduit 4 and collected in vessel B, purified with nitrogen to remove dissolved HC1 discharged through conduit 6.
    Antimony (V) chlorofluoride, containing 27.8 wt.% Fluoride, is continuously supplied from vessel B through line 7 to vessel 8, where this mixture is mixed with chloroform (0.362 lb-mol / h), which is continuously fed through pipe. 9. At the same time, the molar ratio of fluoride / chloroform in the mixed
    0
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    about ,. g
    the feed material is 3.0. The resulting reaction mixture is continuously fed through line 10 to reaction vessel C, which is maintained at 20 at and 60 ° C. The reaction mass, consisting of vapor and liquid, is discharged from the reaction vessel C through line 11 and continuously fed to separator D to separate the vapor and liquid. The liquid phase containing spent antimony chlorofluoride (V) s is continuously removed from vessel D through line 13 and collected in vessel E. Steam from vessel D is continuously removed through line 12. Organic product is chlorodifluoromethane.
    Example 15 Antimony pentachloride is continuously fed through conduit 1 (FIG. 2) at a feed rate of 100 lb / h (0.334 lb-mol) and distributed over the load in zone A. Liquid HF is continuously fed at a feed rate of 13.4 lb / h (0.67 lb-mol) to the load in the lower part of the loaded zone A through pipe 2. In this connection, the molar ratio of HF / antimony pentachloride is 2.0. The pressure in the system is maintained at 10.0 atm and the temperature at 125 C. The gaseous HC1 formed during the reaction of HF with antimony pentachloride rises to the upper part of zone A and is countercurrently in contact with the current down stream of antimony pentachloride to remove unreacted HF containing paired with. Hydrogen chloride, containing on average 0.7 wt.% HF, is continuously passed from zone A through conduit 3. Antimony chlorofluoride (V) formed in zone A is continuously removed through conduit 4 and collected in vessel B, purified with nitrogen.
    Antimony (V) chlorofluoride containing 14.3 wt.% Of fluoride is continuously fed into vessel B through line 2 into vessel 8, where this mixture is mixed with perchlorethylene (0.223 lb-mol / h) containing 0.223 lb-mol / h of chlorine (by this known method, hexachloroethane is produced in situ in a quantitative yield). This stream is fed continuously through an α-duct 9. In this case, the molar ratio fluoride / hexachloromethane in the mixed feed material is 3.0. The resulting reaction mixture is continuously fed through line 10 to reaction vessel C, which is maintained at 8.0 at and 60 ° C. The reaction mass, consisting of steam and liquid, is withdrawn from vessel C through line 11 and continuously fed to separator D to separate pagra and liquids. The liquid phase containing spent antimony chlorofluoride (V) is continuously removed from vessel D through conduit 13 and collected in vessel E. Steam from vessel D is continuously removed through conduit 12. The organic product is a mixture of 1.1 , 2-trichloro-1,2,2-trifluoroethane and 1,2-dichloro-1,1,2,2-tetrafluoroethane.
    Example 16. Antimony pentachloride is continuously fed through conduit 1 (FIG. 1) at a feed rate of 100 lb / h (0.334 lb-mol) and distributed over the column packing. A, Liquid HF is continuously fed at a feed rate of 6.68 lb / h (0.334 lb-mol) to the packing in the lower part of packed column A via conduit 2. For this reason, the molar ratio of HF / pentachloride to antimony is 1.0. The pressure in the system is maintained at 10 atm, and the temperature at 90 ° C. The gaseous HC1 formed by the reaction of HF with antimony pentechloride rises to the top of column A and is countercurrently contacted with the current stream of antimony pentachloride to remove unreacted HF contained in the vapor. Hydrogen chloride, containing on average 0.4 wt.% HF, is continuously discharged from column A through line 3, Antimony Chloride fluoride (V) formed in column A is continuously removed through line 4 and collected in tank B, the contents of which are blown. nitrogen injected through line 5 to remove dissolved HC1, which is discharged through line 6.
    Antimony (V) chlorofluoride containing 6.72% by weight of fluoride is continuously supplied from tank B via line 7 to tank 8, where this mixture is mixed with chloroform (0.334 lb-mol / h which is continuously fed through line 9. When this molar ratio of fluoride / chloroform with the mixed feed material is 3, 0. The resulting reaction mixture is continuously fed through line 10 to the reaction

    p 5 about 0
    -Q, 5
    five
    capacity of C. which is maintained at 20 at and 60 C. The reaction mass, i.e. the mixture consisting of vapor and liquid is removed from the reaction vessel C via line 11 and continuously fed to the separator D for the separation of vapor and liquid. The liquid phase containing spent antimony chlorofluoride (V) is continuously removed from tank D via conduit 13 and collected in tank E. Steam from the reservoir is continuously released via conduit 12, the organic product is difluorochloromethane.
    Thus, as can be seen from the examples, it is possible to drastically reduce the content of fluoride and hydrogen chloride in organic products of synthesis, which eliminates the need for complex processes for the purification of products, as well as the purification of hydrogen chloride. Simplification of the technology is also provided by increasing the use of fluorine, which eliminates the need to recycle fluoride.
    hydrogen,
    I
    The form, the invention
    1. A continuous process for the preparation of chlorofluoromethanes or chlorofluoroethanes by fluorinating chloroform or carbon tetrachloride or hexacloroethane at a temperature of 60-150 ° C and a pressure of 0.5-20 atm using hydrogen fluoride and antimony pentachloride in a flow-type reactor, characterized by that, in order to simplify the technology, hydrogen fluoride is preliminarily continuously reacted with antimony pentachloride at a molar ratio of reagents (0.25-3.25):, a temperature of 50-125 ° C and a pressure of 0.5-20 atm in a flow-type reactor at Simultaneously with the continuous removal of gaseous hydrogen chloride, the resulting mixture of antimony chlorofluorides containing 1.6-27.8% by weight of fluorine is continuously fed to a separate fluorination reaction zone with simultaneous supply of chloroform or tetrachloride of carbon, or hexahloroethane at a mole The ratio of the reactants is (1-3): 1, respectively, where the reactants are reacted with the partial replacement of chlorine in the starting chlorohydrocarbon by fluorine contained in antimony chlorofluoride, and the
    the resulting reaction products are chlorine-non-fluorinated chlorohydrocarbon ",
    fluoromethanes or chlorofluoroethanes. Antimony chlorofluoride is recycled to from2. The method according to p. 1, about t l and h and youn-yedny reactionary zone fluoridation
    w and and the fact that spent in zo-where hydrogen fluoride is supplied.
    FIG. 2
    Compiled by N. Gozalova Editor N. Gunko Tehred M. Khodanych
    BUT&
    Proofreader N. Revska
    权利要求:
    Claims (2)
    [1]
    Claim
    1, A continuous process for the production of chlorofluoromethanes or chlorofluoroethanes by fluorination of chloroform or carbon tetrachloride or hexachloroethane at a temperature of 60150 ° C and a pressure of 0.5-20 atm using hydrogen fluoride and. antimony pentachloride in a flow-type reactor, characterized in that, in order to simplify the technology, hydrogen fluoride is preliminarily continuously reacted with antimony pentachloride at a molar ratio of reactants (0.25-3.25): 1, temperature 50-125 ° C and pressure 0.5.20 atm in a flow-type reactor, while gaseous hydrogen chloride is continuously withdrawn, the resulting mixture of antimony chlorofluorides containing 1.6-27.8 mass% of fluorine is continuously fed into a separate fluorination reaction zone while feeding chlorine roforma or carbon tetrachloride or hexachloroethane at a molar ratio (1-3): 1, respectively, where. react reagents with. partial replacement of chlorine in the initial chlorohydrocarbon with fluorine contained in antimony chlorofluoride, and the resulting reaction products — chlorofluoromethanes or chlorofluoroethanes — are recovered
    [2]
    2. The method according to π, 1, on the basis of the assumption that the spent antimony chlorofluoride ’spent on the fluorination of chlorocarbon is recycled to the separate fluorination reaction zone to which hydrogen fluoride is fed.
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    同族专利:
    公开号 | 公开日
    BR8402990A|1985-05-28|
    DE3465184D1|1987-09-10|
    GR81632B|1984-12-11|
    JPS6019733A|1985-01-31|
    JPH0253414B2|1990-11-16|
    KR850000378A|1985-02-27|
    EP0129863B1|1987-08-05|
    EP0129863A1|1985-01-02|
    CA1247141A|1988-12-20|
    ZA844715B|1986-02-26|
    MX163998B|1992-07-07|
    ES8600180A1|1985-10-01|
    AU2971284A|1985-01-03|
    AU568365B2|1987-12-24|
    ES533561A0|1985-10-01|
    IN160224B|1987-07-04|
    KR870000955B1|1987-05-14|
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    PL383328A1|2004-11-17|2008-02-18|Minrad Inc.|Sevoflurane production method|
    EP2172441A1|2008-10-02|2010-04-07|Solvay Fluor GmbH|Process for the manufacture of hydrochlorofluorocarbons using trifluoromethane as fluorinating agent|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US50708483A| true| 1983-06-23|1983-06-23|
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