The way to obtain 1,1,1,2-tetrafluoroethane (hfc-134a)

 

(57) Abstract:

The invention relates to the production of ozone-safe refrigerants ethane series, in particular 1,1,1,2-Tetrafluoroethane, which is obtained by fluorination 1,1,1-triptorelin fluoride of a metal of variable valence in the presence of a diluent. The diluent serves as unreacted 1,1,1-trifluoroethane, Penta - or freon. As the metal fluoride use uranium hexafluoride or cobalt TRIFLUORIDE. The molar ratio of 1,1,1-triptorelin to uranium hexafluoride is 1.0 to 3.0:1 and the temperature of the fluorination 380-500oC. When using fluoride cobalt process temperature 250-350oWith the load 8-24 l/h 1,1,1-triptorelin per 1 kg of solid fluorinating agent. This results in the increased yield of the final product and reduces the energy consumption of the process. 2 C. p. F.-ly.

The invention relates to methods for producing fluorocarbons-ozone-safe refrigerants ethane series, in particular 1,1,1,2-Tetrafluoroethane (HFC-134a), which is an alternative refrigerant to replace existing refrigerants with high ozone depleting potential.

Known methods of producing 1,1,1,2-Tetrafluoroethane (HFC-134a) by catalytic hydroporinae carried out at elevated temperature and pressure in the two reaction zones. The process is characterized by a large excess of fluorinating agent, the low yield of the target product, accompanied by the release of significant quantities of hydrogen chloride and the formation of large amounts of by-products.

Known methods for the synthesis of 1,1,1,2-Tetrafluoroethane (HFC-134a) by fluorination of vinylidenefluoride fluoride (Japan's bid N 64-38034, 1987), as well as fluorides variable valence - cobalt TRIFLUORIDE (RF patent N 2051890, 1996) and uranium hexafluoride (RF patent N 2030380, 1995 - prototype).

These methods are based on adding fluoride to vinylidenefluoride double bond source organofluorine compounds

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For their implementation must obtain unsaturated organofluorine compounds - vinylidenefluoride. The fluorination process is accompanied by considerable polymerization of vinylidenefluoride and by-product formation, which complicates the technology of production of 1,1,1,2-Tetrafluoroethane (HFC-134a) and leads to increased energy costs and environmental impact on the environment.

Method for obtaining 1,1,1,2-Tetrafluoroethane by fluoridation source of organofluorine compounds fluoride metal variable alantolactone-143a). As a fluoride of a metal of variable valence using uranium hexafluoride, and fluoridation are in the gas phase at a molar ratio of HFC-143a: uranium hexafluoride = 1,0 - 3,0 : 1 and a temperature of 380 - 500oC, the uranium hexafluoride is used with a volume content of 20 - 100% in diluent. As a diluent for use excess triptorelin and freon-125, -116 if their education.

As a fluoride of a metal of variable valence, you can also use cobalt TRIFLUORIDE, fluoridation in this case are by contacting gaseous 1,1,1-triptorelin solid fluorinating agent cobalt TRIFLUORIDE at a temperature of 250 - 350oC and load 8 - 24 l/h 1,1,1-triptorelin per 1 kg of solid fluorinating agent. Unreacted 1,1,1-trifluoroethane is used as a diluent for the operation of fluoridation.

The proposed method is compared with the prototype has significant differences:

- as a source of organic compounds used 1,1,1-Tetrafluoroethane instead unsaturated vinylidenefluoride, eliminating the processes of polymerization and reduce the formation of by-products at the stage of synthesis of 1,1,1,2-tetraborates of vinylidenefluoride;

as diluent fluorinating agent is used an excess of 1,1,1-triptorelin and formed at the stage of synthesis of Penta - and HEXAFLUOROETHANE, resulting in preventing the use of inert diluent (nitrogen);

- simplified the synthesis technology of 1,1,1,2-Tetrafluoroethane;

- reduced impact on the environment.

Example 1. The process of obtaining of HFC-134a were continuously collecting tetrafluoride uranium capacity at pilot plant with a load of uranium hexafluoride to 200 g/H.

The HFC-143a was introduced in the response zone through the nozzle. Supplied in the response zone, the uranium hexafluoride was diluted. Received organofluorine the reaction products were purified from dust tetrafluoride uranium Nickel cermet filters, traces of uranium hexafluoride - in the sorption column with granules of sodium fluoride and are condensed in two traps cooled evaporating liquid nitrogen.

Quantitative and qualitative composition of the organic phase was determined by gas chromatography, infrared spectrometry and NMR (H,F19.

When the temperature in the synthesis reactor 450oC and a molar ratio of HFC-143a to uranium hexafluoride 1,1 : 1 volumetric maintained/P> Example 2. When the temperature in the synthesis reactor 500oC and a molar ratio of HFC-143a to uranium hexafluoride 1,1 : 1 volumetric content of HFC-134a in the organic phase was 38,0%, and the ratio of HFC-134a to HFC-143a was $ 0,84.

Example 3. Fluoridation of HFC-143a by uranium hexafluoride was carried out at a temperature of 400oC and a molar ratio of HFC-143a to uranium hexafluoride to 1.1 : 1. This volumetric content of HFC-134a in the organic phase was equal 23,7, and the ratio of HFC-134a to HFC-143a was 0,36.

Example 4. Synthesis of HFC-134a is carried out at a temperature of 400oC and a molar ratio of HFC-143a to uranium hexafluoride 2 : 1. Volumetric content of products of fluorination in organic phase, %:

Refrigerant-134a - 21,2

The HFC-143a - 77,0

Halon-116 - Tracks

The amount of impurities - 1,8

Conversion of 1,1,1-triptorelin reached 23,0%, output 1,1,1,2-Tetrafluoroethane - 92,2% converted to the original product.

Example 5. The HFC-134a synthesized at a temperature of 400oC and a molar ratio of HFC-143a to uranium hexafluoride 3 : 1. Volumetric content of the reaction products in the organic phase was equal, %:

Refrigerant-134a - 18,5

The HFC-143a - 81,2

Halon-116 - Traces of the tion of the original product.

Example 6. In the apparatus of stainless steel 12X18H10T downloaded 220 g of cobalt TRIFLUORIDE, warmed to 250oC, and then fed gaseous HFC-143a with a speed of 3 l/h In the products of the fluorination found,%:

Halon-116 - 0,10

The HFC-143a - 73,35

Refrigerant-134a - 25,77

The amount of impurities 0,78

Conversion of 1,1,1-triptorelin - 26,65%, output 1,1,1,2-Tetrafluoroethane - 96.7% of the converted original product. Mass fraction of cobalt TRIFLUORIDE in hours worked fluorinating agent is 20%. Load 1 kg fluorinating agent of 13.6 l/h 1,1,1-triptorelin.

Example 7. In the apparatus according to example 6 was downloaded 270 g of cobalt TRIFLUORIDE, warmed up to 300oC, and then fed the HFC-143a at the rate of 2 l/h (load 7.4 per 1 kg fluorinating agent).

In the products of the fluorination found,%:

Halon-116 - 2,08

The HFC-143a - 58,89

Refrigerant-134a - 38,19

The amount of impurities 0,84

Conversion of 1,1,1-triptorelin - 41,11%, output 1,1,1,2-Tetrafluoroethane - 92,9 converted to the original product. Mass fraction of cobalt TRIFLUORIDE in hours worked fluorinating agent 26%.

Example 8. In the apparatus according to example 6 was loaded with 250 g of cobalt TRIFLUORIDE, warmed up to 350oC, and then fed the HFC-143a with the speed 6 is -116 - 0,40

The HFC-143a - 40,56

Refrigerant-134a - 58,36

The amount of impurities was 0.68

Conversion of 1,1,1-triptorelin - 59,44%, output 1,1,1,2-Tetrafluoroethane of 98.2%. Mass fraction of cobalt TRIFLUORIDE in hours worked fluorinating agent 11%.

From the above examples that the use of 1,1,1-triptorelin as a source of organofluorine compounds allows

- significantly increase the output of 1,1,1,2-Tetrafluoroethane:

- to reduce the content of impurities in the raw 1,1,1,2-Tetrafluoroethane:

- to carry out the synthesis of 1,1,1,2-Tetrafluoroethane at atmospheric pressure, without the use of catalysts;

- to exclude the use of inert gases (nitrogen) to dilute the fluorinating agent;

- to reduce the impact on the environment.

1. The way to obtain 1,1,1,2-Tetrafluoroethane by fluorination of organofluorine compounds fluoride of a metal of variable valency at elevated temperature in the presence of a diluent with the separation of the target product by known methods, wherein as organofluorine compounds are used 1,1,1-trifluoroethane, and the diluent is unreacted 1,1,1-trifluoroethane and Penta - and freon.

2. The method according to p. 1, characterized in that howl phase at a molar ratio of 1,1,1-trifluoroethane : uranium hexafluoride, 1.0 to 3.0 : 1, and a temperature of 380 - 500oWith volumetric content of uranium hexafluoride in the diluent is 20 to 100%.

3. The method according to p. 1, characterized in that as a fluoride of a metal of variable valence using cobalt TRIFLUORIDE, and the fluoridation of conduct by contacting gaseous 1,1,1-triptorelin solid fluorinating agent cobalt TRIFLUORIDE at a temperature of 250 - 350oAnd load 8 - 24 l/h 1,1,1-triptorelin per 1 kg of solid fluorinating agent.

 

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EFFECT: method of increased yield.

3 cl, 4 ex

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