Abstract:
The invention relates to a process for separating monochloro-trifluoropropenes such as HCFC-1233 from azeotrope or azeotrope like combinations with HF. The process employs a cold, liquid phase separations and multiple azeotropic distillation trains.

Description:
FIELD OF THE INVENTION 
     The present invention relates to a separation method for isolating monochloro-trifluoropropenes such as 1,1,1-trifluoro-3-chloro-2-propene (HCFC-1233zd) from azeotropic or near azeotropic streams of monochloro-trifluoropropenes and hydrogen fluoride. The method of the present invention makes use of chilled, liquid phase separation combined with azeotropic distillations to isolate pure monochloro-trifluoropropenes such as HCFC-1233zd. 
     BACKGROUND OF THE INVENTION 
     With continued regulatory pressure there is a growing need to produce more environmentally sustainable replacements for refrigerants, heat transfer fluids, foam blowing agents, solvents, and aerosols with lower ozone depleting and global warming potentials. Chlorofluorocarbon (CFC) and hydrochlorofluorocarbons (HCFC), widely used for these applications, are ozone depleting substances and are being phased out in accordance with guidelines of the Montreal Protocol. Hydrofluorocarbons (HFC) are a leading replacement for CFCs and HCFCs in many applications; though they are deemed “friendly” to the ozone layer they still generally possess high global warming potentials. One new class of compounds that has been identified to replace ozone depleting or high global warming substances are halogenated olefins, such as hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO). The HFOs and HCFOs provide the low global warming potential and zero or near zero ozone depletion properties desired. 
     Because of the presence of alkene linkage it is expected that the HFOs and HCFOs will be chemically unstable, relative to HCFCs or CFCs. The inherent chemical instability of these materials in the lower atmosphere results in short atmospheric lifetimes, which provide the low global warming potential and zero or near zero ozone depletion properties desired. 
     U.S. Pat. No. 6,013,846 discloses azeotropes of HF and 1233zd and methods for separating such azeotropes from mixtures of HF and 1233zd which are HF rich or 1233zd rich. The method comprises treating a mixture rich in HF relative to the azeotrope of 1233zd and HF in a distillation (rectification) column to obtain a distillate containing the azeotrope and a bottoms product of relatively pure HF 
     SUMMARY OF THE INVENTION 
     In the present invention, a method was discovered for separating azeotrope or near azeotrope compositions of monochloro-trifluoropropenes and HF, preferrably 1233zd and HF. The method of the present invention is also effective in separating other isomers of 1233, such as 1233xf (1,1,1-trifluoro-2-chloro-3-propene) from azeotrope or azeotrope like combinations with HF. The azotrope or near azeotrope combination of monochloro-trifluoropropenes and HF could be produced, for example, in a liquid phase fluorination reaction of 1,1,1,3,3-pentachloropropane (240fa) or 1,1,3,3-tetrachloro-2-propene (referred to hereinafter as (1230za). The 1230za is of special interest as a starting material since it has been shown to fluorinate readily in the liquid phase without a catalyst, as taught in U.S. Pat. No. 5,877,359. One of the problems associated with the production of the trans isomer of 1233zd, the preferred isomer of the present invention, is that it has nearly the same boiling point (18-20° C.) as HF and azeotropes or near azeotropes can form with HF. 
     The fluorination of 240fa or 1230za can take place in a catalyzed or uncatalyzed liquid phase reaction. Typically the liquid phase fluorination reactor is coupled to rectification a column(s). The feed to the fluorination reactor consists of an organic chlorocarbon and HF which react to form a hydrofluorocarbon (HFC) or hydrochlorofluorocarbon (HCFC) that is more volatile than the original chlorocarbon. The HFC or HCFC product can be removed from the reaction mixture as a gas along with by-product HCl and some unreacted HF. The rectification column is coupled to the reactor to separate unreacted HF, organic and under fluorinated organic compounds from HCl. The overhead from the rectification column is an azeotrope or near azeotrope combination of 1233zd and HF which also contains the HCl by-product of the reaction. In the case of 1233zd, the organic feedstock chlorocarbon to the fluorination reactor can be 1,1,3,3 tetrachloropropene (1230za) or 1,1,1,3,3 pentachloropropane (240fa). 
     In the present application “distillation column” and “rectification column” are sometimes used interchangeably. Actually, however, a rectification column is a specific type of distillation column. In most distillation columns the material to be distilled is fed to the middle of the column; below the feed point is called the stripping section and above the feed point is called the rectification section. Reference is made herein to a rectification column when the material to be distilled is fed to the bottom of the “distillation column.” 
     The process of the present invention uses azeotropic distillation columns to separate 1233zd from HF. The composition of the feed to the azeotropic distillation columns must have either HF or F1233zd in substantial excess of its azeotropic composition. In the method of the present invention, such streams are provided by first separating, by distillation, HCl from the azeotrope or near azeotrope of 1233zd/HF that exits from the overhead of the rectification column. The azeotrope or near azeotrope combination of 1233zd/HF is than cooled to a temperature sufficient to provide separation into an HF rich phase and a 1233zd rich phase. The HF rich phase is separated from the 1233zd rich phase in a liquid phase separator. Thereafter, the HF rich phase is fed to a first azeotropic distillation column that removes the azeotrope as an overhead and pure HF as the bottoms. The 1233zd rich phase is sent to a distillation train that includes a second azeotropic distillation column. The distillation train separates the 1233zd/HF azeotrope from 1233zd via azeotropic distillation and also separates impurities from the 1233zd to provide a stream of substantially pure 1233zd. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic of a typical process in accordance with the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The object of the present invention is to provide a means for separating monochloro-trifluoropropenes, preferably 1,1,1-trifluoro-3-chloro-2-propene (1233zd) and more preferably the trans isomer of 1233zd referred to hereinafter as “1233zd-t”, from HF when the two occur in an azeotrope or near azeotropic combinations. Azeotropic distillation is used to separate HF and 1233zd, preferably 1233zd-t, since they have very similar boiling points. The azeotropic mixture is typical of what is produced from liquid phase reactions that produce 1233zd from organic chlorocarbon feedstocks such as 1230za and 240fa. The azeotrope or near azeotrope compositions form when the reactor system uses a rectification column coupled to the reactor to separate out unreacted HF, unreacted feed organic, and under fluorinated organics from the vapor produced. The rectification column separates the vapor effluent from the reactor and produces a gas phase combination of HF and 1233zd, preferably 1233zd-t, in a ratio near the azeotropic ratio of HF and 1233zd. U.S. Pat. No. 6,013,846 discloses that this is ratio is about 2.33 moles HF per mole of 1233zd at 50° C. The overhead from such rectification columns would also contain HCl. 
     In accordance with the present invention, the azeotropic or near azeotropic combination of 1233zd, preferably 1233zd-t, and HF from the top of the rectification column is fed to a distillation column where HCl is removed. The HCl removal distillation column is typically operated at pressures of from about 100 psig to 300 psig. The bottoms from the HCl removal distillation column comprises the azeotrope or azeotrope like combination of 1233zd, preferably 1233zd-t, and HF. This bottoms stream is cooled sufficiently to provide that two phases form. Each phase contain the azeotrope or azeotrope like 1233zd/HF and independently HF or 1233zd. Thus the overall composition of each stream differs significantly from the azeotrope. One phase, the lighter phase, is rich in HF and the second phase, the heavier phase, is rich in 1233zd, preferably 1233zd-t,. The two phase mixture is fed to a liquid phase separator. The liquid phase separator can be operated at temperatures of from about −60° C. to +50° C., preferably from about −20° to +10° C. The lighter liquid phase has HF in substantial excess over the azeotrope composition. This HF rich phase is sent to a first azeotropic distillation column where azeotropic 1233zd/HF is removed as overhead and relatively pure HF removed as the bottoms. The azeotropic 1233zd/HF overhead is recycled to cooled and fed to the phase separator and the HF bottoms stream is recycled to the reactor. The heavy phase from the liquid phase separator comprises a substantial excess of 1233zd, preferably 1233zd-t, over the azeotropic composition. This stream is sent to a distillation train comprising a series of distillation columns. The first distillation column removes as an overhead any very volatile impurities such as HCl or over fluorinated HFC&#39;s. The bottoms of this column is sent to a second azeotropic distillation column. This second azeotropic distillation column removes a 1233zd/HF azeotrope as overhead and crude 1233zd, preferably 1233zd-t, as a bottoms. The overhead can be recycled to be cooled and fed to the liquid phase separator. The bottoms is sent to a product recovery distillation column that recovers pure 1233zd, preferably 1233zd-t, as overhead and any organic impurities such as the cis-isomer of 1233zd as a bottoms stream. The process of the present invention provides a method whereby relatively pure 1233zd, preferably 1233zd-t, can be separated from an azeotrope or azeotrope like combination of 1233zd and HF. 
       FIG. 1  show a schematic of a process in accordance with the present invention. The feeds to the reactor system are typically HF (Stream  1 ) and an organic stream, either 240fa or 1230za (Stream  2 ). The reactor (R 101  ) may or may not contain a catalyst. The selective products of the reaction are 1233zd and HCl. These would exit the reaction system from the top of a rectification Column (C 101 ) along with enough HF to be close to its azeotropic ratio with 1233zd (Stream  3 ). 
     Column C 102  removes the HCl as an overhead product (Stream  4 ). This could be done at pressures anywhere from 100 psig to 300 psig. The bottoms from this column (stream  5 ) would then be cooled in a heat exchanger (E 105 ) and sent to a liquid phase separator (V 102 ). The liquid phase separator could operate at temperatures from −60° C. to +50° C. A preferred temperature range would be −20° C. to 10° C. The lighter liquid phase (Stream  7 ) would have HF in substantial excess over the azeotropic composition. This phase is sent to a first azeotropic distillation column (C 103 ) that removes the HF/F1233zd azeotrope as overhead (Stream  8 ) and relatively pure HF as a bottoms (Stream  9 ). The azeotropic composition is recycled to be cooled and fed to the phase separator and the HF can be recycled to the reactor R 101 . 
     The heavy phase (Stream  6 ) from the phase separator contains 1233zd in substantial excess over the 1233zd/HF azeotropic composition. This stream is sent to a series of distillation columns. The first column (C 104 ) is a purification column which removes as an overhead (Stream  10 ) any very volatile impurities such as residual HCl or over fluorinated HFC&#39;s. The bottoms of the first column (Stream  11 ) is then sent to the second azeotropic distillation column (C 105 ). This azeotropic distillation column removes a 1233zd/HF azeotrope as overhead (Stream  12 ) and a crude 1233zd stream as bottoms (Stream  13 ). The overhead stream can be recycled to be cooled and fed to the liquid phase separator V 102 . The bottoms stream is sent to a product recovery distillation column (C 106 ) that recovers pure 1233zd, preferably 1233zd-t, as overhead (Stream  14 ) and any organic impurities such as the cis isomer of 1233zd as a bottoms (Stream  15 ). 
     EXAMPLES 
     Example 1 
     A set of experiments were conducted to determine the liquid-liquid equilibrium in an HF-F1233zd system. A mixture of F1233zd and HF were equilibrated at four different temperatures. Samples of bottom and top phases were analyzed. The following results were obtained: 
     
       
         
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                 T  
                 Upper Layer (wt %) 
                 Lower Layer (wt %) 
               
             
          
           
               
                   
                 (Deg C.) 
                 HF 
                 F1233zd-t 
                 HF 
                 F1233zd-t 
               
               
                   
                   
               
               
                   
                 −30 
                 75.72 
                 24.28 
                 0.85 
                 99.15 
               
               
                   
                 −15 
                 71.16 
                 28.84 
                 1.18 
                 98.82 
               
               
                   
                  0 
                 67.86 
                 32.14 
                 1.72 
                 98.28 
               
               
                   
                  30 
                 56.26 
                 43.74 
                 4.12 
                 95.88 
               
               
                   
                   
               
             
          
         
       
     
     Example 2 
     An example of a material balance of the relevant part of the process for a phase separator operated at −20C is shown in Table 2. The stream numbers refer to those used in  FIG. 1 . As the table shows, the phase separation will produce two phases far enough removed from the azeotropic composition that aeotropic distillation can be used to isolate both pure HF and pure 1233zd. 
     
       
         
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                   
                 kg/hr 
               
             
          
           
               
                   
                   
                   
                   
                 8 
                 9 
                 10 
                 11 
                 12 
                 13 
               
               
                   
                 5 
                 6 
                 7 
                 HF  
                 HF  
                 Lights 
                 Lights 
                 F12333zd 
                 F1233zd 
               
               
                   
                 Feed 
                 Org Ph 
                 HF Ph 
                 Ovhd 
                 Bttms 
                 Ovhd 
                 Btms 
                 Ovhd 
                 Bttms 
               
               
                   
               
             
          
           
               
                 1233zd-t 
                 130.45 
                 134.93 
                 25.32 
                 25.32 
                 0.00 
                 0.00 
                 134.93 
                 4.48 
                 130.45 
               
               
                 1233zd-c 
                 13.05 
                 13.40 
                 2.52 
                 2.52 
                 0.00 
                 0.00 
                 13.40 
                 0.36 
                 13.05 
               
               
                 245fa 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
                 0.00 
               
               
                 HF 
                 57.20 
                 1.79 
                 68.29 
                 11.10 
                 57.20 
                 0.00 
                 1.79 
                 1.79 
                 0.00 
               
               
                 HCl 
                 0.36 
                 0.36 
                 0.00 
                 0.00 
                 0.00 
                 0.36 
                 0.00 
                 0.00 
                 0.00 
               
               
                 Total 
                 201.06 
                 150.48 
                 96.13 
                 38.93 
                 57.20 
                 0.36 
                 150.11 
                 6.62 
                 143.50 
               
               
                 Temp (C.) 
                 −20 
                 −20 
                 −20 
                 47 
                 68 
                 −28 
                 80 
                 65 
                 65 
               
               
                 Press (psia) 
                 40 
                 40 
                 40 
                 65 
                 66 
                 130 
                 130 
                 50 
                 88 
               
               
                   
               
             
          
         
       
     
     While the present invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications, which are within the true spirit and scope of the present invention.