Distillation: processes – separatory – With disparate physical separation – Utilizing liquid-liquid extracting of distillation product
Reexamination Certificate
1998-09-11
2001-09-25
Manoharan, Virginia (Department: 1764)
Distillation: processes, separatory
With disparate physical separation
Utilizing liquid-liquid extracting of distillation product
C203S044000, C203S045000, C203S046000, C423S483000, C570S178000, C570S180000
Reexamination Certificate
active
06294055
ABSTRACT:
The present invention relates to a process for the separation of hydrogen fluoride from its mixtures with a hydrofluoroalkane containing from 3 to 6 carbon atoms.
Hydrofluoroalkanes can be prepared by reaction of a suitable chloro precursor with hydrogen fluoride, as disclosed, for example, in patent applications EP-A1-0,699,649 and WO-A1-97/15540 (in the name of Solvay) and in patent application WO-A1-97/05089. In such a process, on leaving the hydrofluorination reactor, the mixture of reaction products contains, besides the desired hydrofluoroalkane, hydrogen chloride originating from the elimination of the chlorine atom(s) from the starting chloro precursor, hydrogen fluoride and unconverted chloro precursor, optionally inert diluents, as well as low amounts of various by-products. Given that the process is usually performed with an excess of hydrogen fluoride relative to the chloro precursor, unconverted hydrogen fluoride usually remains in the mixture of reaction products. Although most of the constituents of the mixture of reaction products can readily be separated out completely by distillation, a complete separation between the hydrogen fluoride and the hydrofluoroalkane is generally very difficult to achieve by distillation, since these compounds often form azeotropic mixtures.
Patent application WO-A1-97/05089 discloses, inter alia, a process for the purification of hydro(chloro)fluoroalkanes (in particular 1,1,1,3,3-pentafluoropropane or HFC-245fa) from azeotropic mixtures with hydrogen fluoride, by a technique of azeotropic distillation comprising two successive steps of distillation at different temperatures and pressures.
However, this azeotropic distillation technique has the drawbacks of requiring a large temperature or pressure difference between the two columns, so as to have a sufficient separation potential (difference in composition between the azeotrope at low pressure/temperature and the azeotrope at high pressure/temperature) and to give rise to a large circulation flow rate between the two columns.
Patent application WO-A1-97/13719 discloses a process for the separation and recovery of hydrogen fluoride from its mixtures (azeotropic) with, inter alia, hydrofluoroalkanes containing from 1 to 6 carbon atoms (in particular HFC-245fa). The mixture is placed in contact with a solution of alkali metal fluoride (in particular potassium or caesium fluoride) and the organic phase is separated from the phase containing the hydrogen fluoride and the alkali metal fluoride.
Using this known process, there may be fear of contaminating the organic phase with the potassium or caesium fluoride and the risk of decomposing the hydrofluoroalkanes which this contamination might entail. Moreover, these alkali metal fluorides, and more particularly caesium fluoride, are very expensive.
The object of the present invention is to provide a process for the separation of hydrogen fluoride from its mixtures with a hydrofluoroalkane containing from 3 to 6 carbon atoms, which does not have the drawbacks of the abovementioned processes.
To this end, the invention relates to a process for the separation of hydrogen fluoride from its mixtures with at least one hydrofluoroalkane containing from 3 to 6 carbon atoms, according to which the separation is carried out by extraction using at least one organic solvent.
The organic solvent can be a halo or non-halo compound.
As examples of non-halo organic solvents, mention may be made of hydrocarbons containing from 5 to 10 carbon atoms, in particular n-pentane, n-hexane, n-heptane and n-octane.
Examples of halo-organic solvents are chloroform, trichloroethylene, tetrachloroethylene, tetrachloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1- or 1,1,2-trifluorotrichloroethane, 1,2,3-trichloropropane, perfluorohydrocarbons, bromobenzene, o-dichlorobenzene, p-chlorotoluene, p-chlorotrifluorobenzene and 1,2-dichloro-4-trifluorobenzene, as well as mixtures of these compounds.
In particular, when the process is applied to the separation of the hydrogen fluoride/1,1,1,3,3-pentafluorobutane (HFC-365mfc) mixture, the preferred extraction solvents are bromobenzene, o-dichlorobenzene and tetrachloroethylene. Bromobenzene and o-dichlorobenzene are particularly preferred.
The expression “hydrofluoroalkane containing from 3 to 6 carbon atoms” is understood to denote the hydrofluoroalkanes corresponding to the general formula C
a
H
(2a+2)−b
F
b
in which a=3 to 6 and b=1 to 2a+1. The hydrofluoroalkanes corresponding to the general formula C
a
H
(2a+2)−b
F
b
in which a=3 to 4 and b=5 to 2a+1 are preferred.
As examples of hydrofluoroalkanes containing from 3 to 6 carbon atoms which can be separated from their mixtures with hydrogen fluoride by the process according to the invention, mention may be made of 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3-pentafluoro-2-methylpropane (HFC-365mps), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff) and, 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-43-10mee). Compounds containing from 3 to 4 carbon atoms are preferred. 1,1,1,3,3-Pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) are particularly preferred.
The weight ratio of the hydrogen fluoride to the hydrofluoroalkane depends on the amount of hydrogen fluoride used in the hydrofluorination step of the process for the synthesis of the hydrofluoroalkane. In general, the hydrogen fluoride is in excess relative to the hydrofluoroalkane.
The extraction is preferably carried out on a mixture which has a hydrogen fluoride/hydrofluoroalkane weight ratio close to that of the azeotropic composition. If the initial mixture of hydrogen fluoride and hydrofluoroalkane differs from that in the azeotropic composition, it may be advantageous to carry out a predistillation in order to separate the HF/HFC azeotrope from the excess compound (HF or HFC). The azeotropic composition is then subjected to extraction.
In the separation process according to the invention, the weight ratio of the organic solvent to the mixture of hydrogen fluoride and hydrofluoroalkane is generally at least 0.1. Preferably, the process is performed with a weight ratio of at least 0.2. The weight ratio of the organic solvent to the mixture of hydrogen fluoride and hydrofluoroalkane does not generally exceed 10. Preferably, it does not exceed 5.
The temperature at which the extraction is carried out is generally at least −25° C. Preferably, it is about −10° C. The temperature generally does not exceed 40° C. Preferably, it does not exceed 30° C.
The process according to the invention is carried out at a pressure which is sufficient to keep the mixture in the liquid state. It can be carried out under the autogenous pressure of the mixture; in this case, the pressure is generally less than 3 bar. Alternatively, it can be carried out at a pressure above the autogenous pressure of the mixture by introducing an inert gas. In this case, the total pressure will generally be less than 10 bar; preferably, the pressure used will be less than 3 bar but greater than 1 bar. Any gaseous substance which does not react substantially under the extraction conditions, such as nitrogen, hydrogen chloride, argon or a mixture thereof, will be used as inert gas. Preferably, nitrogen will be used.
The mixture of hydrogen fluoride and hydrofluoroalkane is placed in contact with the organic extraction solvent in one or more steps, using any conventional liquid-liquid extraction device, for example by placing in intimate contact using a static mixer, a stirred reactor, a rotary-disc extractor, an extractor with centrifugation or a column with perforated plates, operating either counter-currentwise or co-currentwise. P
Brosch Carsten
Herkelmann Ralf
Wilmet Vincent
Manoharan Virginia
Schneller Marina V.
Solvay S.A.
Venable
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