Abstract:
Provided is a process for making 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of hydrofluorinating 2-chloro-3,3,3-trifluoropropene in the presence of a catalyst selected from the group consisting of SbCl 3 , SbCl 5 , SbF 5 , TiCl 4 , SnCl 4 , Cr 2 O 3 , and fluorinated Cr 2 O 3 .

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a Continuation of U.S. application Ser. No. 12/631,728, filed Dec. 4, 2009, (now U.S. Pat. No. 9,024,092, issued May 5, 2015), which application is a Continuation-In-Part (CIP) of U.S. application Ser. No. 11/619,592, filed Jan. 3, 2007, (now U.S. Pat. No. 8,084,653, issued Dec. 27, 2011), which in turn, claims the priority benefit of U.S. Provisional Application No. 60/755,485, filed Jan. 3, 2006. application Ser. No. 12/631,728 is also a continuation of U.S. application Ser. No. 12/338,466, filed Dec. 18, 2008 (abandoned), which in turn claims the priority benefit of U.S. Provisional Application No. 61/021,121, filed Jan. 15, 2008. Each of these applications is incorporated herein by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to a process for making 2-chloro-1,1,1,2-tetrafluoropropane. The present invention further relates to a process for making 2-chloro-1,1,1,2-tetrafluoropropane via hydrofluorination of 2-chloro-3,3,3-trifluoropropene with high single-pass conversion. 
         [0004]    2. Description of the Related Art 
         [0005]    The refrigerant and blowing agent 2,3,3,3-tetrafluoropropene (1234yf) is produced from the dehydrochlorination of 2-chloro-1,1,1,2-tetrafluoropropane (244bb). 244bb may be manufactured from 2-chloro-3,3,3-trifluoropropene (1233xf). 
         [0006]    When conversion of 2-chloro-1,1,1,2-tetrafluoropropane from 2-chloro-3,3,3-trifluoropropene is low, 2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3,3-trifluoropropene are present in admixture in product streams. 2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3,3-trifluoropropene exhibit similar boiling points and azeotrope-like properties that make them difficult to separate via standard techniques such as conventional distillation. 
         [0007]    One method of addressing the problem of low conversion is to increase recycle of product streams to the reactor so that additional conversion is obtained. The increased recycle would require process equipment to be increased in size and scale to maintain a desired level or product output, and, thus significantly increase manufacturing cost. In addition, the separation of components in the product stream is difficult. 
         [0008]    It would be desirable to have a process for making 2-chloro-1,1,1,2-tetrafluoropropane from 2-chloro-3,3,3-trifluoropropene at higher single-pass conversion levels. 
       SUMMARY OF THE INVENTION 
       [0009]    Provided is a process for making 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of hydrofluorinating 2-chloro-3,3,3-trifluoropropene in the presence of a catalyst selected from the group consisting of SbCl 3 , SbCl 5 , SbF 5 , TiCl 4 , SnCl 4 , Cr 2 O 3 , and fluorinated Cr 2 O 3 . Preferably, the process is performed as a continuous process. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0010]    In the process of the present invention, selected catalysts are employed to enhance the single-pass conversion of 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane via HF addition across the double bond of 2-chloro-3,3,3-trifluoropropene. The catalysts are the following: SbCl 3 , SbCl 5 , SbF 5 , TiCl 4 , SnCl 4 , Cr 2 O 3 , and fluorinated Cr 2 O 3 . 
         [0011]    The catalyst may be supported or in bulk form (unsupported). Useful catalyst supports include carbon, alumina, fluorinated alumina, aluminum fluoride, alkaline earth metal oxides, fluorinated alkaline earth metals, zinc oxide, zinc fluoride, tin oxide, and tin fluoride. 
         [0012]    The catalyst optionally may be activated prior to and during use. Useful activating agents include anhydrous hydrogen fluoride and chlorine. The catalyst is kept activated by the continuous or batch addition of an oxidizing agent such as Cl 2 . 
         [0013]    The hydrofluorination process may be carried out in a vapor phase or a liquid phase. 
         [0014]    In vapor-phase hydrofluorination, HF (hydrogen fluoride gas) is fed continuously through the catalyst bed. After a short time with only the HF feed stream, 2-chloro-3,3,3-trifluoropropene is fed continuously through the catalyst bed at a ratio of about 1:1 to about 1:30 and preferably from about 1:2 to about 1:15 (2-chloro-3,3,3-trifluoropropene/HF mole ratio). The reaction between HF and 2-chloro-3,3,3-trifluoropropene is carried out at a temperature from about 30° C. to about 200° C. (preferably from about 50° C. to about 120° C.) and at a pressure of about 5 psia to about 200 psia (pounds per square inch absolute) (preferably from about 30 psia to about 175 psia). The catalyst may be supported on a substrate, such as on activated carbon, or may be unsupported or free-standing. The catalyst may (or may not) have to be activated with anhydrous hydrogen fluoride HF (hydrogen fluoride gas) and/or Cl 2  (chlorine gas) before use depending on the state of the catalyst. If necessary, the catalyst can be kept activated by the continuous or batch addition of Cl 2  or a similar oxidizing agent. 
         [0015]    In liquid phase hydrofluorination, the catalyst is charged in a liquid form to a reactor and optionally activated with HF. The activated catalyst is then heated to the desired reaction temperature of about 30° C. to about 200° C. (preferably from about 50° C. to about 120° C.) and the pressure is kept between about 15 psia to about 200 psia (preferably from about 50 psia to about 175 psia). After a short time with only HF feed, a 2-chloro-3,3,3-trifluoropropene feed stream is fed continuously through the catalyst bed at a ratio of about 1:1 to about 1:30 and preferably about 1:2 to about 1:15 (2-chloro-3,3,3-trifluoropropene/HF mole ratio). If necessary, the catalyst can be kept activated by the continuous or batch addition of Cl 2  or a similar oxidizing agent. 
         [0016]    Enhanced or improved single-pass conversion of 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane is an important feature of the present invention. The hydrofluorination reaction is preferably carried out to attain a conversion of about 70% or more, preferably about 90% or more, and most preferably about 93% or more. Conversion is calculated by the number of moles of reactant (2-chloro-3,3,3-trifluoropropene) consumed divided by number of moles of reactant (2-chloro-3,3,3-trifluoropropene) fed to the reactor multiplied by 100. The selectivity for 2-chloro-1,1,1,2-tetrafluoropropane attained is preferably about 60% or more and most preferably about 80% or more. Selectivity is calculated by number of moles of product (2-chloro-1,1,1,2-tetrafluoropropane) formed divided by number of moles of reactant consumed. 
         [0017]    Hydrofluorination is preferably carried out in a corrosion-resistant reaction vessel. Examples of corrosion-resistant materials are Hastelloy, Nickel, Incoloy, Inconel, Monel and fluoropolymer linings. The vessel may have a fixed or a fluidized catalyst bed. If desired, inert gases such as nitrogen or argon may be employed in the reactor during operation. 
         [0018]    The following are examples of the present invention and are not to be construed as limiting. Unless otherwise indicated, all percentages and parts are by weight. 
       EXAMPLES 
     Example 1 
       [0019]    The vapor phase fluorination of the 2-chloro-3,3,3-trifluoropropene (1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane (244bb) was carried out. The fluorination catalyst for the experiment was 50 wt % SbCl 5  impregnated on 50 wt % Calgon PCB activated carbon. 
         [0020]    Several kilograms of 50 weight % SbCl 5  on activated carbon were produced in the lab. The catalyst was first passed through a 10-mesh sieve to remove fines. A total of 2272.6 grams (or about 2800 cc) was charged to two 2-inch vapor-phase pipe reactors in series and installed in a sand bath for controlled heating. 
         [0021]    The catalyst was activated by adding a minimum of a 5:1 mole ratio of HF to SbCl 5 , followed by a Cl 2  addition of a minimum of a 3:1 mole ratio of Cl 2  to SbCl 5 . Finally, a large excess of HF was passed through the catalyst bed for 2 hours. 
         [0022]    The reaction was run using 2-chloro-3,3,3-trifluoropropene crude raw material with various compositions as organic feed to produce 2-chloro-1,1,1,2-tetrafluoropropane. The reactor effluent was collected in a distillation column before removal of excess HF. During the experiment, a 93.5% conversion of 2-chloro-3,3,3-trifluoropropene was achieved. The maximum selectivity of 2-chloro-1,1,1,2-tetrafluoropropane achieved was 98.4% on a molar basis. The reaction ran continuously for 76.5 hrs without attempting catalyst regeneration with Cl 2 . The catalyst began showing signs of deactivation after about 65 hours on-stream time. The experimental data and reaction conditions are shown below in Tables 1A to 1D. 
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1A 
               
               
                   
               
               
                 On- 
                   
                   
                   
                 1233xf 
                 1233xf 
                   
                 HF feed 
                   
                   
                 Contact 
               
               
                 stream time 
                 T 
                 P 
                   
                 feed rate 
                 feed rate 
                 HF feed rate 
                 rate 
                 mole ratio 
                 Catalyst 
                 Time 
               
               
                 (hrs) 
                 (° C.) 
                 (Mpa) 
                 Catalyst 
                 (mmole/min) 
                 (g/hr) 
                 (mmole/min) 
                 (g/hr) 
                 HF:1233xf 
                 (ml) 
                 (sec) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                  1-23 
                 72 
                 0.33 
                 SbCl 5 /C 
                 12.0 
                 95.3 
                 185.2 
                 222.3 
                 15.5 
                 2800 
                 99 
               
               
                 23-29 
                 72 
                 0.33 
                 SbCl 5 /C 
                 18.3 
                 145.2 
                 215.5 
                 258.6 
                 11.8 
                 2800 
                 84 
               
               
                 29-42 
                 72 
                 0.33 
                 SbCl 5 /C 
                 23.4 
                 186.0 
                 241.9 
                 290.3 
                 10.3 
                 2800 
                 74 
               
               
                 42-53 
                 74 
                 0.33 
                 SbCl 5 /C 
                 30.2 
                 240.4 
                 275.9 
                 331.1 
                 9.1 
                 2800 
                 64 
               
               
                 53-60 
                 76 
                 0.33 
                 SbCl 5 /C 
                 39.3 
                 322.1 
                 317.5 
                 381.0 
                 8.1 
                 2800 
                 54 
               
               
                   60-65.5 
                 77 
                 0.33 
                 SbCl 5 /C 
                 48.1 
                 394.6 
                 400.7 
                 480.8 
                 8.3 
                 2800 
                 43 
               
               
                 65.5-73.5 
                 80 
                 0.33 
                 SbCl 5 /C 
                 51.1 
                 408.2 
                 404.5 
                 485.4 
                 7.9 
                 2800 
                 42 
               
               
                 73.5-76.5 
                 79 
                 0.33 
                 SbCl 5 /C 
                 33.9 
                 281.2 
                 355.3 
                 426.4 
                 10.5 
                 2800 
                 49 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1B 
               
             
             
               
                   
                   
               
               
                   
                 Feed composition (GC area %) 
                   
               
             
          
           
               
                 On-stream 
                 1234yf/ 
                   
                   
                   
                   
                   
               
               
                 Time (hrs) 
                 245cb 
                 244bb 
                 1233xf 
                 1232xf 
                 1223xd 
                 others 
               
               
                   
               
             
          
           
               
                  1-23 
                 0 
                 0.31 
                 82.41 
                 17.03 
                 0 
                 0.25 
               
               
                 23-29 
                 0 
                 0.31 
                 82.41 
                 17.03 
                 0 
                 0.25 
               
               
                 29-42 
                 0 
                 0.31 
                 82.41 
                 17.03 
                 0 
                 0.25 
               
               
                 42-53 
                 0 
                 0.31 
                 82.41 
                 17.03 
                 0 
                 0.25 
               
               
                 53-60 
                 trace 
                 31.08 
                 68.92 
                 0 
                 0 
                 0 
               
               
                   60-65.5 
                 trace 
                 31.08 
                 68.92 
                 0 
                 0 
                 0 
               
               
                 65.5-73.5 
                   0.69 
                 21.41 
                 77.36 
                 0 
                 trace 
                 0.54 
               
               
                 73.5-76.5 
                   0.03 
                 38.86 
                 61.09 
                 0 
                 0 
                 0.02 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1C 
               
             
             
               
                   
                   
               
               
                   
                 Reactor Effluent Composition (GC area %) 
               
             
          
           
               
                 On-stream 
                 1234yf/ 
                   
                   
                   
                   
                   
               
               
                 Time (hrs) 
                 245cb 
                 244bb 
                 1233xf 
                 1232xf 
                 1223xd 
                 others 
               
               
                   
               
             
          
           
               
                  1-23 
                 3.0 
                 86.2 
                 7.5 
                 0.2 
                 0.1 
                 3.0 
               
               
                 23-29 
                 1.3 
                 91.7 
                 5.1 
                 0.2 
                 0.1 
                 1.7 
               
               
                 29-42 
                 0.9 
                 92.1 
                 4.8 
                 0.2 
                 0.0 
                 1.9 
               
               
                 42-53 
                 0.9 
                 91.3 
                 5.9 
                 0.1 
                 0.0 
                 1.8 
               
               
                 53-60 
                 0.6 
                 92.0 
                 7.1 
                 0.0 
                 0.0 
                 0.4 
               
               
                   60-65.5 
                 0.7 
                 90.0 
                 8.9 
                 0.0 
                 0.0 
                 0.5 
               
               
                 65.5-73.5 
                 1.6 
                 87.1 
                 10.2 
                 0.0 
                 trace 
                 1.1 
               
               
                 73.5-76.5 
                 1.4 
                 86.3 
                 11.6 
                 0.0 
                 0.0 
                 0.8 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 1D 
               
             
             
               
                   
               
               
                   
                   
                 Selectivities (molar basis 
               
               
                 1233xf 
                 1232xf 
                 presuming GC area % = wt %) 
               
             
          
           
               
                 Conver- 
                 Conver- 
                 1234yf/ 
                   
                   
                   
                   
               
               
                 sion 
                 sion 
                 245cb 
                 244bb 
                 1232xf 
                 1223xd 
                 others 
               
               
                   
               
               
                 89.9 
                 99.0 
                 3.9 
                 92.6 
                 NA 
                 0.1 
                 3.2 
               
               
                 93.2 
                 98.8 
                 1.6 
                 96.4 
                 NA 
                 0.0 
                 1.8 
               
               
                 93.5 
                 99.0 
                 1.2 
                 96.6 
                 NA 
                 0.0 
                 2.0 
               
               
                 92.0 
                 99.3 
                 1.1 
                 96.9 
                 NA 
                 0.0 
                 1.9 
               
               
                 83.8 
                 NA 
                 1.0 
                 98.4 
                 0.0 
                 0.0 
                 0.6 
               
               
                 82.8 
                 NA 
                 1.2 
                 98.1 
                 0.0 
                 0.0 
                 0.7 
               
               
                 81.5 
                 NA 
                 1.5 
                 97.8 
                 0.0 
                 0.0 
                 0.7 
               
               
                 75.1 
                 NA 
                 3.1 
                 95.5 
                 0.1 
                 0.0 
                 1.6 
               
               
                   
               
             
          
         
       
     
       Example 2 
       [0023]    The liquid phase fluorination reaction of 2-chloro-3,3,3-trifluoropropene (1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane (244bb) was carried out. The fluorination catalyst for the experiment was SbCl 5 . 
         [0024]    About 6100 grams of SbCl 5  were contained in a Teflon™-lined liquid phase reactor (Teflon is a trademark of E.I. duPont de Nemours &amp; Co) equipped with a 2-inch ID (inside diameter) packed column and a condenser. The reactor was 2.75-inch ID×36-inch L (length). Initially, a greater than 5:1 mole ratio of HF was added to the reactor to fluorinate the catalyst. A greater than 3:1 mole ratio of Cl 2  was then added to the reactor to ensure that the catalyst was brought back to a pentavalent state. The reactor was heated to about 85° C.-87° C. HF feed was started first. When an additional 1.3 lbs of HF had been added the 2-chloro-3,3,3-trifluoropropene feed was started. The purity of the 2-chloro-3,3,3-trifluoropropene feed stock was about 98 GC area % (gas chromatograph). The experiment ran continuously for 71 hours. For this run, chlorine was fed batchwise about every 4 hours throughout the run to keep the catalyst active. The HF and 2-chloro-3,3,3-trifluoropropene feeds were varied during the run. The feeds averaged 0.495 lbs/hr HF, and 0.408 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 5.4% by weight of organic) for a 7.9/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 135 seconds residence time at the beginning of the run. In the middle of the run, the feeds averaged 0.843 lbs/hr HF (pounds/hour) and 0.66 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 3.3% by weight of organic) for a 8.33/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 80 seconds residence time. For the end of the run, the rate was increased. The feeds for this period averaged 1.42 lbs/hr HF and 1.24 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 2% by weight of organic) for a 7.5/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 47 seconds residence time. The level of unreacted 2-chloro-3,3,3-trifluoropropene appeared to increase late in the run, which could have been the result of lower Cl 2  level or shorter residence time. 
         [0025]    The reactor temperature range for the experiment was 78-91° C. and the pressure range was 85 psig-115 psig (pounds per square inch gauge). 
         [0026]    The following Table 2 contains the 2-chloro-3,3,3-trifluoropropene conversion and product selectivity data: 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 (Conversion and Selectivity on a Molar Basis) 
               
             
          
           
               
                 elapsed 
                   
                   
                   
                   
                   
                   
                   
               
               
                 time 
                 HFC245cb 
                 HCFC244bb 
                 HCFC1233xf 
                 HCFC235da 
                 HCFC1223xd 
                 Others 
                 Temp 
               
               
                 (Hours) 
                 Selectivity 
                 Selectivity 
                 Conversion 
                 Selectivity 
                 Selectivity 
                 Selectivity 
                 ° C. 
               
               
                   
               
             
          
           
               
                 2 
                 64.8 
                 24.2 
                 99.3 
                 0.0 
                 0.0 
                 11.1 
                 87.1 
               
               
                 3 
                 68.2 
                 24.2 
                 99.2 
                 0.9 
                 4.8 
                 1.9 
                 90.5 
               
               
                 4 
                 67.5 
                 24.3 
                 99.8 
                 0.6 
                 3.6 
                 3.9 
                 90.2 
               
               
                 5 
                 64.6 
                 30.0 
                 99.9 
                 1.2 
                 3.1 
                 1.1 
                 90.4 
               
               
                 6 
                 67.4 
                 27.2 
                 99.8 
                 1.2 
                 3.1 
                 1.0 
                 85.7 
               
               
                 8 
                 82.8 
                 15.6 
                 99.7 
                 0.4 
                 0.8 
                 0.5 
                 78.9 
               
               
                 9 
                 78.5 
                 20.2 
                 99.9 
                 0.3 
                 0.6 
                 0.4 
                 78.9 
               
               
                 10 
                 65.4 
                 32.3 
                 99.6 
                 0.6 
                 1.0 
                 0.6 
                 83.2 
               
               
                 11 
                 61.8 
                 35.8 
                 99.0 
                 0.6 
                 1.0 
                 0.7 
                 78.5 
               
               
                 12 
                 64.8 
                 33.7 
                 99.3 
                 0.5 
                 0.6 
                 0.4 
                 79.6 
               
               
                 13.5 
                 61.6 
                 37.0 
                 99.8 
                 0.5 
                 0.5 
                 0.4 
                 80.9 
               
               
                 14 
                 62.1 
                 36.5 
                 99.7 
                 0.5 
                 0.5 
                 0.5 
                 81.3 
               
               
                 15 
                 61.9 
                 36.8 
                 99.6 
                 0.5 
                 0.4 
                 0.4 
                 78.9 
               
               
                 16 
                 29.1 
                 68.3 
                 99.5 
                 1.3 
                 0.6 
                 0.7 
                 86.9 
               
               
                 17 
                 30.5 
                 67.3 
                 98.6 
                 1.2 
                 0.5 
                 0.5 
                 88.5 
               
               
                 18 
                 24.4 
                 73.0 
                 98.8 
                 1.5 
                 0.6 
                 0.5 
                 84.5 
               
               
                 19 
                 31.0 
                 66.1 
                 98.3 
                 1.6 
                 0.7 
                 0.5 
                 87.5 
               
               
                 20 
                 28.7 
                 66.8 
                 99.8 
                 2.5 
                 1.2 
                 0.9 
                 84.5 
               
               
                 21 
                 33.8 
                 62.9 
                 99.7 
                 1.8 
                 0.9 
                 0.6 
                 86.9 
               
               
                 22 
                 51.6 
                 46.6 
                 99.5 
                 0.9 
                 0.5 
                 0.5 
                 86.6 
               
               
                 23 
                 54.3 
                 45.1 
                 99.7 
                 0.2 
                 0.1 
                 0.2 
                 85.6 
               
               
                 24 
                 28.3 
                 70.1 
                 99.5 
                 0.8 
                 0.4 
                 0.4 
                 86.9 
               
               
                 25 
                 23.0 
                 74.8 
                 99.0 
                 1.1 
                 0.6 
                 0.5 
                 86.4 
               
               
                 26 
                 16.0 
                 76.2 
                 98.3 
                 3.6 
                 2.8 
                 1.3 
                 86.3 
               
               
                 27 
                 20.8 
                 73.2 
                 98.3 
                 2.7 
                 2.1 
                 1.2 
                 85.5 
               
               
                 28 
                 12.0 
                 78.3 
                 99.0 
                 3.2 
                 2.7 
                 3.8 
                 87 
               
               
                 29 
                 11.9 
                 79.8 
                 98.7 
                 2.1 
                 2.0 
                 4.2 
                 87.9 
               
               
                 30 
                 11.0 
                 80.8 
                 98.6 
                 2.1 
                 2.0 
                 4.2 
                 87.1 
               
               
                 31 
                 13.9 
                 81.7 
                 98.2 
                 0.8 
                 1.0 
                 2.6 
                 86.2 
               
               
                 32 
                 10.2 
                 86.6 
                 99.3 
                 0.4 
                 0.7 
                 2.2 
                 85.9 
               
               
                 33 
                 9.4 
                 87.9 
                 98.8 
                 0.2 
                 1.4 
                 1.0 
                 85.5 
               
               
                 34 
                 12.6 
                 85.8 
                 98.5 
                 0.1 
                 0.7 
                 0.8 
                 85.4 
               
               
                 35 
                 15.1 
                 83.6 
                 98.1 
                 0.1 
                 0.5 
                 0.7 
                 85.3 
               
               
                 36 
                 4.3 
                 92.3 
                 98.2 
                 0.1 
                 2.2 
                 1.1 
                 85.2 
               
               
                 37 
                 4.7 
                 92.3 
                 97.9 
                 0.1 
                 1.8 
                 1.2 
                 84.9 
               
               
                 38 
                 4.8 
                 92.7 
                 97.9 
                 0.1 
                 1.5 
                 1.0 
                 85.4 
               
               
                 39.5 
                 8.6 
                 89.5 
                 97.8 
                 0.0 
                 0.1 
                 1.8 
                 85.1 
               
               
                 41.7 
                 17.1 
                 81.4 
                 98.1 
                 0.0 
                 0.6 
                 0.9 
                 85 
               
               
                 42.7 
                 14.0 
                 85.7 
                 97.8 
                 0.0 
                 0.1 
                 0.3 
                 83.6 
               
               
                 44.7 
                 20.4 
                 79.1 
                 98.1 
                 0.0 
                 0.0 
                 0.4 
                 80.6 
               
               
                 46 
                 6.0 
                 92.5 
                 98.3 
                 0.0 
                 0.9 
                 0.5 
                 84.2 
               
               
                 47.5 
                 6.1 
                 91.1 
                 99.7 
                 0.0 
                 1.5 
                 1.3 
                 86.2 
               
               
                 48 
                 6.2 
                 91.5 
                 99.9 
                 0.0 
                 1.3 
                 1.0 
                 87.1 
               
               
                 49 
                 10.6 
                 86.8 
                 98.9 
                 0.0 
                 1.7 
                 0.9 
                 86.9 
               
               
                 50 
                 7.2 
                 91.0 
                 98.1 
                 0.0 
                 1.1 
                 0.7 
                 86.6 
               
               
                 51 
                 10.9 
                 88.4 
                 97.7 
                 0.0 
                 0.3 
                 0.4 
                 86.7 
               
               
                 52 
                 13.9 
                 82.9 
                 98.7 
                 0.0 
                 2.3 
                 0.9 
                 89.3 
               
               
                 53 
                 12.7 
                 86.0 
                 97.9 
                 0.0 
                 0.6 
                 0.8 
                 87.5 
               
               
                 54 
                 9.5 
                 89.4 
                 97.7 
                 0.0 
                 0.5 
                 0.6 
                 88 
               
               
                 55 
                 6.6 
                 92.2 
                 98.3 
                 0.0 
                 0.6 
                 0.7 
                 87.1 
               
               
                 56 
                 6.8 
                 89.6 
                 98.1 
                 0.0 
                 2.7 
                 1.0 
                 87.4 
               
               
                 57 
                 7.5 
                 91.1 
                 97.6 
                 0.0 
                 0.7 
                 0.7 
                 87.7 
               
               
                 58.1 
                 5.4 
                 91.6 
                 99.8 
                 0.1 
                 1.4 
                 1.6 
                 87.6 
               
               
                 60 
                 6.2 
                 92.7 
                 98.8 
                 0.0 
                 0.2 
                 0.9 
                 87.8 
               
               
                 65.3 
                 0.0 
                 99.4 
                 96.9 
                 0.0 
                 0.2 
                 0.3 
                 88 
               
               
                 66 
                 5.2 
                 91.7 
                 99.7 
                 0.1 
                 2.0 
                 1.0 
                 87.2 
               
               
                 69 
                 3.3 
                 96.2 
                 96.1 
                 0.1 
                 0.2 
                 0.3 
                 88 
               
               
                 70 
                 3.0 
                 95.1 
                 95.3 
                 0.1 
                 1.3 
                 0.5 
                 87.9 
               
               
                 71 
                 2.8 
                 95.4 
                 96.8 
                 0.0 
                 0.4 
                 1.4 
                 88.5 
               
               
                   
               
             
          
         
       
     
       Example 3 
       [0027]    Example 3 used the same equipment as Example 2. 
         [0028]    About 5615 grams of SbCl 5  were contained in the same reactor as that of Example 2. The reactor was heated to about 85° C.-87° C. HF feed was started first. After about 1.5 lbs of HF had been added, the 2-chloro-3,3,3-trifluoropropene feed was started. The purity of the 2-chloro-3,3,3-trifluoropropene feed stock was about 97.3 GC area %. The experiment ran continuously for 71 hours. For this run, Cl 2  was fed batchwise about every 4 hours throughout the run to keep the catalyst active. 
         [0029]    The Run # for this experiment was 36b. Conversion was immediately above 98%, and remained that way throughout the rest of the run (through Friday shut-down). The catalyst charge was left hot over the weekend, and operation resumed on Monday (now called Run #37), and similar high conversion was observed throughout the week. About 123 pounds of acid-free 2-chloro-1,1,1,2-tetrafluoropropane crude was collected between runs #36b and its continuation as Run #37 the following week. 
         [0030]    The reactor temperature range for the experiment was 78° C.-86° C. and the pressure range was 70 psig-105 psig. The organic crude material collected from the run was run on a gas chromatograph and exhibited the following GC analysis. 
         [0031]    The following Tables 3A and 3B set forth the 2-chloro-3,3,3-trifluoropropene (1233xf) conversion and product selectivity data. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3A 
               
             
             
               
                   
               
               
                 (Run #36b, Conversion and Selectivity on a Molar Basis) 
               
             
          
           
               
                 Elapsed 
                   
                   
                 HF/Org 
                 molar 
                 molar 
                 molar 
                 molar 
                 molar 
                 molar 
               
               
                 Time 
                 Gas 
                 Temp 
                 mole 
                 selectivity 
                 selectivity 
                 conversion 
                 selectivity 
                 selectivity 
                 selectivity 
               
               
                 (Hours) 
                 Bag # 
                 (° C.) 
                 ratio 
                 HFC245cb 
                 HCFC244bb 
                 HCFC1233xf 
                 HCFC235da 
                 HCFC1232xf 
                 HCFC1223xd 
               
               
                   
               
             
          
           
               
                 35.3 
                 1 
                 84.1 
                 0.64 
                 0.26 
                 98.69 
                 0.01 
                 0.02 
                 0.06 
                 35.3 
               
               
                 36.3 
                 2 
                 85 
                 0.43 
                 0.54 
                 98.70 
                 0.01 
                 0.00 
                 0.01 
                 36.3 
               
               
                 37.3 
                 3 
                 85.2 
                 0.55 
                 0.41 
                 98.94 
                 0.01 
                 0.01 
                 0.02 
                 37.3 
               
               
                 38.6 
                 4 
                 85.6 
                 0.44 
                 0.51 
                 98.71 
                 0.01 
                 0.00 
                 0.02 
                 38.6 
               
               
                 39.2 
                 5 
                 83.6 
                 0.30 
                 0.63 
                 97.77 
                 0.01 
                 0.01 
                 0.03 
                 39.2 
               
               
                 39.7 
                 6 
                 85.5 
                 0.25 
                 0.70 
                 97.26 
                 0.01 
                 0.01 
                 0.02 
                 39.7 
               
               
                 40.8 
                 7 
                 86.9 
                 0.36 
                 0.59 
                 98.08 
                 0.01 
                 0.00 
                 0.03 
                 40.8 
               
               
                 41.6 
                 8 
                 83 
                 0.55 
                 0.44 
                 98.94 
                 0.00 
                 0.00 
                 0.01 
                 41.6 
               
               
                 42.4 
                 9 
                 85.9 
                 0.40 
                 0.58 
                 98.40 
                 0.00 
                 0.00 
                 0.01 
                 42.4 
               
               
                 43.4 
                 10 
                 85.3 
                 0.37 
                 0.61 
                 98.42 
                 0.00 
                 0.00 
                 0.00 
                 43.4 
               
               
                 44.75 
                 11 
                 83.1 
                 0.29 
                 0.70 
                 98.37 
                 0.00 
                 0.01 
                 0.01 
                 44.75 
               
               
                 45.5 
                 12 
                 80 
                 0.23 
                 0.76 
                 98.44 
                 0.00 
                 0.00 
                 0.00 
                 45.5 
               
               
                 46.5 
                 13 
                 81.7 
                 0.21 
                 0.76 
                 98.40 
                 0.00 
                 0.00 
                 0.01 
                 46.5 
               
               
                 47.5 
                 14 
                 81.3 
                 0.19 
                 0.79 
                 98.21 
                 0.00 
                 0.00 
                 0.01 
                 47.5 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3B 
               
             
             
               
                   
               
               
                 (Run #37, Conversion and Selectivity on a Molar Basis) 
               
             
          
           
               
                 Elapsed 
                   
                   
                 HF/Org 
                 molar 
                 molar 
                 molar 
                 molar 
                 molar 
                 molar 
               
               
                 Time 
                 Gas 
                 Temp 
                 mole 
                 selectivity 
                 selectivity 
                 conversion 
                 selectivity 
                 selectivity 
                 selectivity 
               
               
                 (Hours) 
                 Bag # 
                 (° C.) 
                 ratio 
                 HFC245cb 
                 HCFC244bb 
                 HCFC1233xf 
                 HCFC235da 
                 HCFC1232xf 
                 HCFC1223xd 
               
               
                   
               
             
          
           
               
                 1.3 
                 1 
                 87.5 
                 11.84 
                 0.16 
                 0.82 
                 98 
                 0.002 
                 0.002 
                 0.005 
               
               
                 2.4 
                 2 
                 85.2 
                 6.09 
                 0.10 
                 0.89 
                 98 
                 0.002 
                 0.002 
                 0.005 
               
               
                 3.25 
                 3 
                 86.5 
                 5.49 
                 0.13 
                 0.84 
                 98 
                 0.003 
                 0.002 
                 0.013 
               
               
                 4.4 
                 4 
                 83.2 
                 7.03 
                 0.10 
                 0.88 
                 98 
                 0.003 
                 0.002 
                 0.017 
               
               
                 5.4 
                 5 
                 83.3 
                 8.80 
                 0.10 
                 0.88 
                 98 
                 0.002 
                 0.001 
                 0.008 
               
               
                 6.4 
                 6 
                 81.5 
                 8.00 
                 0.08 
                 0.90 
                 98 
                 0.002 
                 0.001 
                 0.004 
               
               
                 7.4 
                 7 
                 79.9 
                 20.74 
                 0.08 
                 0.90 
                 98 
                 0.002 
                 0.001 
                 0.008 
               
               
                 8.3 
                 8 
                 80 
                 7.54 
                 0.07 
                 0.92 
                 98 
                 0.001 
                 0.001 
                 0.004 
               
               
                 9.3 
                 9 
                 81.3 
                 4.44 
                 0.09 
                 0.90 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 10.3 
                 10 
                 85.1 
                 3.57 
                 0.11 
                 0.88 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 11.3 
                 11 
                 88 
                 4.64 
                 0.15 
                 0.83 
                 98 
                 0.002 
                 0.002 
                 0.015 
               
               
                 12.6 
                 12 
                 85.5 
                 5.03 
                 0.14 
                 0.85 
                 98 
                 0.001 
                 0.002 
                 0.004 
               
               
                 13.4 
                 13 
                 85.3 
                 4.68 
                 0.10 
                 0.89 
                 98 
                 0.001 
                 0.002 
                 0.003 
               
               
                 14.3 
                 14 
                 82.8 
                 5.08 
                 0.08 
                 0.91 
                 98 
                 0.001 
                 0.002 
                 0.003 
               
               
                 15.3 
                 15 
                 83.7 
                 5.63 
                 0.09 
                 0.89 
                 98 
                 0.002 
                 0.001 
                 0.012 
               
               
                 16.25 
                 16 
                 84.2 
                 7.21 
                 0.08 
                 0.91 
                 98 
                 0.001 
                 0.001 
                 0.004 
               
               
                 17.4 
                 17 
                 86.1 
                 7.86 
                 0.09 
                 0.91 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 18.3 
                 18 
                 85.7 
                 8.33 
                 0.07 
                 0.92 
                 98 
                 0.001 
                 0.001 
                 0.002 
               
               
                 19.3 
                 19 
                 86 
                 7.38 
                 0.09 
                 0.88 
                 98 
                 0.003 
                 0.002 
                 0.018 
               
               
                 20.3 
                 20 
                 87.8 
                 8.27 
                 0.09 
                 0.90 
                 98 
                 0.002 
                 0.001 
                 0.003 
               
               
                 21.4 
                 21 
                 83.4 
                 10.48 
                 0.08 
                 0.88 
                 98 
                 0.002 
                 0.003 
                 0.003 
               
               
                 22.4 
                 22 
                 88.7 
                 18.21 
                 0.08 
                 0.91 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 23.3 
                 23 
                 83 
                 9.26 
                 0.08 
                 0.90 
                 98 
                 0.002 
                 0.001 
                 0.007 
               
               
                 24.3 
                 24 
                 82.9 
                 7.46 
                 0.06 
                 0.93 
                 98 
                 0.001 
                 0.001 
                 0.004 
               
               
                 25.3 
                 25 
                 81.3 
                 7.19 
                 0.06 
                 0.94 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 26.3 
                 26 
                 83.9 
                 8.05 
                 0.05 
                 0.94 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 27.3 
                 27 
                 81.9 
                 7.61 
                 0.06 
                 0.92 
                 98 
                 0.003 
                 0.001 
                 0.016 
               
               
                 28.3 
                 28 
                 83.8 
                 6.90 
                 0.06 
                 0.93 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 29.3 
                 29 
                 83.9 
                 7.18 
                 0.07 
                 0.93 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 30.3 
                 30 
                 85 
                 6.23 
                 0.08 
                 0.92 
                 97 
                 0.001 
                 0.001 
                 0.003 
               
               
                 31.3 
                 31 
                 83.4 
                 6.27 
                 0.06 
                 0.91 
                 98 
                 0.003 
                 0.002 
                 0.016 
               
               
                 32.3 
                 32 
                 82.8 
                 6.66 
                 0.05 
                 0.94 
                 98 
                 0.001 
                 0.001 
                 0.004 
               
               
                 34.3 
                 33 
                 85.2 
                 5.64 
                 0.06 
                 0.93 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 35.3 
                 34 
                 86 
                 5.30 
                 0.07 
                 0.91 
                 97 
                 0.001 
                 0.001 
                 0.008 
               
               
                 36.3 
                 35 
                 84.9 
                 7.23 
                 0.07 
                 0.92 
                 97 
                 0.001 
                 0.001 
                 0.003 
               
               
                 37.5 
                 36 
                 80.7 
                 7.58 
                 0.06 
                 0.94 
                 98 
                 0.001 
                 0.001 
                 0.002 
               
               
                 38.3 
                 37 
                 82.2 
                 5.81 
                 0.03 
                 0.97 
                 98 
                 0.001 
                 0.002 
                 0.003 
               
               
                 39.25 
                 38 
                 81.9 
                 6.32 
                 0.04 
                 0.94 
                 98 
                 0.002 
                 0.002 
                 0.013 
               
               
                 40.25 
                 39 
                 82 
                 6.32 
                 0.04 
                 0.95 
                 98 
                 0.002 
                 0.001 
                 0.006 
               
               
                 41.5 
                 40 
                 81.4 
                 5.77 
                 0.04 
                 0.94 
                 98 
                 0.001 
                 0.001 
                 0.004 
               
               
                 42.5 
                 41 
                 81 
                 6.20 
                 0.04 
                 0.95 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 43.8 
                 42 
                 81.4 
                 8.14 
                 0.03 
                 0.96 
                 98 
                 0.001 
                 0.001 
                 0.003 
               
               
                 44.7 
                 43 
                 80.7 
                 8.14 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.001 
                 0.001 
               
               
                 45.5 
                 44 
                 80.9 
                 6.88 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 47 
                 45 
                 82.8 
                 7.16 
                 0.14 
                 0.84 
                 98 
                 0.003 
                 0.002 
                 0.010 
               
               
                 47.8 
                 46 
                 82.3 
                 7.70 
                 0.03 
                 0.96 
                 98 
                 0.001 
                 0.000 
                 0.002 
               
               
                 48.8 
                 47 
                 82.3 
                 7.18 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 49.8 
                 48 
                 82.5 
                 6.67 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 50.8 
                 49 
                 82.8 
                 6.68 
                 0.03 
                 0.95 
                 98 
                 0.002 
                 0.001 
                 0.013 
               
               
                 51.8 
                 50 
                 82.7 
                 6.84 
                 0.03 
                 0.97 
                 98 
                 0.001 
                 0.000 
                 0.002 
               
               
                 53 
                 51 
                 81.3 
                 8.09 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 54.3 
                 52 
                 79.8 
                 8.60 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 54.8 
                 53 
                 81.2 
                 4.22 
                 0.03 
                 0.95 
                 98 
                 0.002 
                 0.001 
                 0.015 
               
               
                 56 
                 54 
                 81.6 
                 6.75 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.002 
               
               
                 56.8 
                 55 
                 83.6 
                 6.45 
                 0.03 
                 0.97 
                 97 
                 0.000 
                 0.000 
                 0.001 
               
               
                 57.8 
                 56 
                 84.9 
                 7.03 
                 0.03 
                 0.97 
                 97 
                 0.000 
                 0.000 
                 0.001 
               
               
                 58.8 
                 57 
                 81.5 
                 7.11 
                 0.04 
                 0.95 
                 98 
                 0.001 
                 0.001 
                 0.009 
               
               
                 59.8 
                 58 
                 82.8 
                 7.11 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.002 
               
               
                 60.8 
                 59 
                 81.1 
                 6.99 
                 0.02 
                 0.98 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 63 
                 60 
                 84.2 
                 7.51 
                 0.02 
                 0.96 
                 98 
                 0.001 
                 0.001 
                 0.010 
               
               
                 64 
                 61 
                 84 
                 8.79 
                 0.02 
                 0.97 
                 98 
                 0.001 
                 0.000 
                 0.004 
               
               
                 65 
                 62 
                 82.9 
                 8.79 
                 0.02 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 66 
                 63 
                 82.6 
                 6.44 
                 0.02 
                 0.98 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 67 
                 64 
                 83.2 
                 7.33 
                 0.03 
                 0.94 
                 98 
                 0.005 
                 0.001 
                 0.015 
               
               
                 68.25 
                 65 
                 82.1 
                 5.28 
                 0.04 
                 0.95 
                 98 
                 0.002 
                 0.001 
                 0.004 
               
               
                 69 
                 66 
                 83 
                 7.22 
                 0.03 
                 0.96 
                 98 
                 0.001 
                 0.000 
                 0.002 
               
               
                 70 
                 67 
                 82.6 
                 6.63 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 71 
                 68 
                 82.5 
                 4.98 
                 0.03 
                 0.96 
                 98 
                 0.001 
                 0.000 
                 0.001 
               
               
                 72 
                 69 
                 82.1 
                 5.28 
                 0.03 
                 0.95 
                 98 
                 0.002 
                 0.001 
                 0.020 
               
               
                 73 
                 70 
                 81.1 
                 4.75 
                 0.02 
                 0.97 
                 98 
                 0.000 
                 0.001 
                 0.002 
               
               
                 74.25 
                 71 
                 82.2 
                 4.77 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 75.1 
                 72 
                 87.1 
                 5.20 
                 0.03 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 75.8 
                 73 
                 81.3 
                 4.09 
                 0.03 
                 0.95 
                 98 
                 0.001 
                 0.001 
                 0.016 
               
               
                 78 
                 74 
                 81.4 
                 8.64 
                 0.02 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.002 
               
               
                 79.1 
                 75 
                 80.4 
                 7.16 
                 0.02 
                 0.98 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 80 
                 76 
                 83.2 
                 6.11 
                 0.03 
                 0.96 
                 98 
                 0.002 
                 0.000 
                 0.008 
               
               
                 81.1 
                 77 
                 83.4 
                 6.21 
                 0.02 
                 0.97 
                 98 
                 0.000 
                 0.000 
                 0.002 
               
               
                 83.25 
                 78 
                 84 
                 7.41 
                 0.02 
                 0.97 
                 97 
                 0.000 
                 0.000 
                 0.001 
               
               
                 84.3 
                 79 
                 85.5 
                 7.17 
                 0.02 
                 0.96 
                 98 
                 0.002 
                 0.000 
                 0.018 
               
               
                 85 
                 80 
                 84.4 
                 12.16 
                 0.02 
                 0.98 
                 98 
                 0.001 
                 0.000 
                 0.003 
               
               
                 86 
                 81 
                 82.1 
                 9.15 
                 0.02 
                 0.98 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 87 
                 82 
                 81.9 
                 7.69 
                 0.02 
                 0.98 
                 98 
                 0.001 
                 0.000 
                 0.001 
               
               
                 88.4 
                 83 
                 82.4 
                 4.58 
                 0.02 
                 0.94 
                 98 
                 0.007 
                 0.001 
                 0.031 
               
               
                 89 
                 84 
                 83.4 
                 9.46 
                 0.02 
                 0.97 
                 98 
                 0.001 
                 0.000 
                 0.004 
               
               
                 90 
                 85 
                 81.5 
                 7.22 
                 0.02 
                 0.98 
                 98 
                 0.001 
                 0.000 
                 0.001 
               
               
                 91.2 
                 86 
                 82.5 
                 7.09 
                 0.02 
                 0.98 
                 98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 92 
                 87 
                 83.4 
                 7.49 
                 0.01 
                 0.97 
                 98 
                 0.001 
                 0.001 
                 0.015 
               
               
                 93 
                 88 
                 82.4 
                 6.60 
                 0.02 
                 0.98 
                 98 
                 0.001 
                 0.000 
                 0.002 
               
               
                 94 
                 89 
                 82.3 
                 6.25 
                 0.01 
                 0.97 
                 98 
                 0.002 
                 0.000 
                 0.004 
               
               
                 95 
                 89.5 
                 82.4 
                 6.53 
                 0.02 
                 98 
                 0.98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 96.5 
                 90 
                 83.1 
                 4.76 
                 0.02 
                 96 
                 0.97 
                 0.002 
                 0.001 
                 0.016 
               
               
                 97 
                 91 
                 82.6 
                 5.01 
                 0.01 
                 95 
                 0.97 
                 0.003 
                 0.001 
                 0.021 
               
               
                 97.75 
                 92 
                 81 
                 7.29 
                 0.01 
                 97 
                 0.98 
                 0.001 
                 0.001 
                 0.015 
               
               
                 98.8 
                 93 
                 83.1 
                 6.74 
                 0.02 
                 98 
                 0.98 
                 0.000 
                 0.001 
                 0.012 
               
               
                 100.2 
                 94 
                 82.6 
                 9.05 
                 0.01 
                 98 
                 0.98 
                 0.002 
                 0.000 
                 0.004 
               
               
                 101.1 
                 95 
                 83.3 
                 5.98 
                 0.02 
                 98 
                 0.97 
                 0.000 
                 0.000 
                 0.003 
               
               
                 102.3 
                 96 
                 85.5 
                 5.11 
                 0.02 
                 97 
                 0.97 
                 0.000 
                 0.000 
                 0.001 
               
               
                 103.1 
                 97 
                 82.7 
                 5.22 
                 0.02 
                 97 
                 0.97 
                 0.001 
                 0.001 
                 0.007 
               
               
                 104 
                 98 
                 82.4 
                 5.11 
                 0.02 
                 97 
                 0.98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 107 
                 99 
                 80.4 
                 5.87 
                 0.02 
                 98 
                 0.98 
                 0.000 
                 0.000 
                 0.001 
               
               
                 109 
                 100 
                 82.6 
                 7.98 
                 0.02 
                 98 
                 0.97 
                 0.000 
                 0.000 
                 0.001 
               
               
                 110 
                 101 
                 93.3 
                 5.30 
                 0.03 
                 97 
                 0.85 
                 0.000 
                 0.001 
                 0.001 
               
               
                 111 
                 102 
                 88.8 
                 4.86 
                 0.03 
                 85 
                 0.82 
                 0.000 
                 0.001 
                 0.001 
               
               
                 112 
                 103 
                 89.4 
                 5.74 
                 0.03 
                 82 
                 0.96 
                 0.000 
                 0.000 
                 0.000 
               
               
                 113 
                 104 
                 82.8 
                 10.71 
                 0.02 
                 96 
                 0.97 
                 0.000 
                 0.000 
                 0.000 
               
               
                 114 
                 105 
                 82.1 
                 9.83 
                 0.01 
                 97 
                 0.97 
                 0.000 
                 0.001 
                 0.001 
               
               
                   
               
             
          
         
       
     
       Example 4  
     Liquid-Phase Catalytic Fluorination of CF 3 CCl═CH 2  (1233xf) with HF to CF 3 CFClCH 3  (244bb) 
       [0032]    About 327 grams of HF, about 50 grams 1233xf, and about 75 grams SbCl 5  were charged into a 1-L autoclave. The reaction mixture was stirred at a temperature of about 80° C. for about 3 hours under about 620 psig of pressure. After the reaction, the reactor was cooled to about 0° C. and about 300 ml water was then added slowly into the autoclave over a period of about 45 min. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF 3 CFClCH 3  was about 90% at a 1233xf conversion level of about 98%. The other major by-products were CF 3 CF 2 CH 3  (2%), and an unidentified isomer of a C4 compound of the general formula, C 4 H 3 Cl 3 F 4  (8%). 
       Example 5  
     Liquid-Phase Catalytic Fluorination of CF 3 CCl═CH 2  (1233xf) with HF to CF 3 CFClCH 3  (244bb) 
       [0033]    About 327 grams HF, about 50 grams 1233xf, and about 75 grams SbCl 5  were charged into a 1-L autoclave. The reaction mixture was stirred at 80° C. for about 3 hours under about 625 psig of pressure. After the reaction, the reactor was cooled to about 45° C. and then the overhead gas mixture was passed through a well dried KF, NaF, or Al 2 O 3  (350 g) packed column kept at about 80° C. to strip off HF from the gas stream. The gases coming out of the column are collected in a cylinder kept in dry ice (−70° C.) bath. The yield of CF 3 CFClCH 3  was 87% at a 1233xf conversion level of 93%. The other major by-products were CF 3 CF 2 CH 3  (1%), and an unidentified isomer of a C4 compound of the general formula, C 4 H 3 Cl 3 F 4  (7%). The product, CF 3 CFClCH 3  was isolated by distillation with 98% purity. 
       Example 6  
     Gas-Phase Catalytic Fluorination of CF 3 CCl=CH 2  (1233xf) with HF to CF 3 CFClCH 3  (244bb) 
       [0034]    A 22-inch (½ -inch diameter) Monel tube gas phase reactor was charged with about 120 cc of a catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by a custom made 5-point thermocouple kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about 300° C. by electrical heating. Organic (1233xf) was fed from a cylinder kept at 70° C. through a regulator, needle valve, and a gas mass-flow-meter. The organic line to the pre-heater was heat traced and kept at a constant temperature of about 73° C. by electrical heating to avoid condensation. N 2  was used as a diluent in some cases and fed from a cylinder through a regulator and a mass flow controller into the pre-heater. All feed cylinders were mounted on scales to monitor their weight by difference. The reactions were run at a constant reactor pressure of from about 0 to about 100 psig by controlling the flow of reactor exit gases by another research control valve. The gas mixtures exiting reactor was analyzed by on-line GC and GC/MS connected through a hotbox valve arrangements to prevent condensation. The conversion of 1233xf was from about 50% to about 65% and the selectivity to 244 isomer (CF 3 CFClCH 3 ) was from about 90% to about 93% depending on the reaction conditions using 120 cc of 50 wt % SbCl 5 /C as the catalyst at about 65° C. to about −85° C. with a HF flow of about 50 g/h and organic flow of about 15 g/h. No CF 3 CF 2 CH 3  was observed under the reaction conditions. The catalyst is pretreated at first with 50 g/h HF at about 65° C. for about 2 hours and then with about 50 g/h HF and about 200 sccm of Cl 2  at about 65° C. for about 4 hours. After pre-treatment, about 50 sccm of N 2  is flows over a period of about 40 minutes through the catalyst bed to sweep free chlorine from the catalyst surface prior to interacting with the organic feed (1233xf). Pretreatment is considered important to many embodiments of the invention. The products were collected by flowing the reactor exit gases through a 20-60 wt % aqueous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N 2 . The products were then isolated by distillation. About 50 wt % SbCl 5 /C, about 3 to about 6 wt % FeCl 3 /C, 20 wt % SnCl 4 /C, and about 23 wt % TiCl 4 /C, using 4 different kind of activated carbon such as Shiro saga, Calgon, Norit, and Aldrich were used as the catalyst at from about 60 to about 150° C. Among all the catalysts used for this reaction, Cl 2  and HF pre-treated SbCl 5 /C was found to be generally preferred in terms of activity. The results using SbCl 5  as the catalyst are shown in Table 2. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Catalyzed-gas-phase transformation 
               
               
                 of CF 3 CCl═CH 2  to CF 3 CFClCH 3   
               
             
          
           
               
                   
                   
                   
                 Conv. of 
                   
               
               
                   
                   
                 T 
                 CF 3 CCl═CH 2   
                 Selectivity for 
               
               
                 # 
                 Catalyst 
                 (° C.) 
                 (1233xf) 
                 CF 3 CFClCH 3   
               
               
                   
               
             
          
           
               
                 1 
                 10 wt % SbCl 5 /C 
                 60 
                 15 
                 100 
               
               
                 2 
                 20 wt % SbCl 5 /C 
                 60 
                 21 
                 98 
               
               
                 3 
                 30 wt % SbCl 5 /C 
                 60 
                 32 
                 98 
               
               
                 4 
                 50 wt % SbCl 5 /C 
                 60 
                 55 
                 97 
               
               
                 5 
                 50 wt % SbCl 5 /C 
                 80 
                 62 
                 93 
               
               
                 6 
                 50 wt % SbCl 5 /C 
                 100 
                 56 
                 87 
               
               
                 7 
                 60 wt % SbCl 5 /C 
                 60 
                 59 
                 91 
               
               
                 8 
                 50 wt % SbCl 5 /NORIT 
                 60 
                 34 
                 92 
               
               
                   
                 RFC3 Activated Carbon 
               
               
                 9 
                 50 wt % SbCl 5 /Shiro 
                 60 
                 56 
                 96 
               
               
                   
                 Saga Activated Carbon 
               
               
                 10 
                 50 wt % SbCl 5 /Aldrich 
                 60 
                 57 
                 94 
               
               
                   
                 Activated Carbon 
               
               
                   
               
               
                 Reaction conditions: 1233xf flow, 150 sccm; HF flow 50 g/h; pressure, 2.5-5.3 psig; in 1-5 reactions Calgon activated carbon is used as the catalyst support; catalyst, 120 cc. All catalysts are pre-treated with Cl 2  and HF prior to contacting with 1233xf. 
               
             
          
         
       
     
         [0035]    It should be understood that the foregoing description is only illustrative of the present invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances that fall within the scope of the appended claims.