Patent Publication Number: US-2022234971-A1

Title: Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes

Description:
FIELD OF THE INVENTION 
     The present invention relates to chemical processes for converting chlorofluoropropanes (HCFC) and chlorofluoropropenes (CFO) to more desirable fluoropropanes and fluoropropenes, especially propenes that are hydrofluoroolefins (HFO), i.e. free of Cl, and to intermediates from which these HFOs can be obtained. 
     BACKGROUND OF THE INVENTION 
     U.S. Pat. No. 8,399,722 discloses the hydrogenation of at least one of 1,1-dichloro-2,3,3,3-tetrafluoropropene (CF 3 CF=Cl 2 , 1214 ya) and 1-chloro-2,3,3,3-tetrafluoropropene (CF 3 CF=CHCl, 1224 yd) in the presence of catalyst composed of Pd supported on a carbon carrier to obtain 2,3,3,3,-tetrafluoropropene (CF 3 CF=CH 2 , 1234 yf), which is free of chlorine and which has promise at least as a refrigerant exhibiting both low ozone depletion potential and low global warming potential. Example 2 discloses the conversion rate 1214 ya to 1234 yf to be 75%, which can also be considered the selectivity of the process. In Example 3 the selectivity dropped to 69%. 
     Processes are desired to obtain better results in the production of HFO-1234 yf, and/or to obtain HFO-1234 ze (CF3CH=CHF), 1,3,3,3-tetrafluoropropene), which is also free of chlorine and has refrigerant application, and/or which opens up new routes for obtaining desirable HFOs such as HFO-1234 yf or HFO-1234 ze. 
     SUMMARY OF THE INVENTION 
     The present invention provides the process comprising contacting and reacting the compound CF 3 CF 2 CHXCl, wherein X is H or Cl, or the compound CF 3 CF=CXCl, wherein X is H or Cl, with hydrogen in the presence of a catalyst consisting essentially Cu, Ru, Cu—Pd, Ni—Cu, and Ni—Pd, to obtain as a result thereof reaction product comprising hydrofluoropropenes or intermediates convertible to said hydrofluoropropenes. When in the compound CF 3 CF 2 CHXCl, X is H, then the compound is HCFC-235 cb, and when Cl, the compound is HCFC-225 ca. When in the compound CF 3 CF=CXCl, X is H, the compound is HCFO-1224 yd, and when X is Cl, the compound is CFO-1214 ya. These are the reactant compounds in this Hydrogenation Process. 
     Another embodiment of the present invention is the Intermediates Process, i.e. the process for converting the intermediates obtained in the Hydrogenation Process to the desired hydrofluoropropenes. The Intermediates Process comprises such reactions as hydrogenation, dehydrochlorination, and dehydrofluorination. The catalysts used in the Hydrogenation Process are preferably those used in the hydrogenation reactions in the Intermediates Process. 
     The desired hydrofluoropropenes include HFO-1234 yf (CF 3 CF=CH 2 ), HFO-1234 ze (CF 3 CH=CHF), and HFO-1225 zc (CF 3 CH=CF 2 ). 
     Reaction pathways (reactant/reaction product) included in the Hydrogenation Process and Intermediates Process are as follows: 
     When the reactant compound is HCFC-225 ca, the reaction product comprises HFO-1234 yf (CF 2 CF=CH 2 ). The reaction product may also comprise at least one of HCFO-1224 yd, and HCFC-235 cb (CF 3 CF 2 CH 2 Cl) which are intermediates through which HFO-1234 yf can be obtained. HCFO-1224 yd can be converted directly to HFO-1234 yf. HCFC-235 cb can be converted indirectly to HFO-1234 yf by first being converted to HCFO-1224 yd, which is then converted to HFO-1234 yf. The HCFC-235 cb can also be converted directly to HFO-1234 yf, i.e. the reaction product of hydrogenating HCFC-235 cb comprises HFO-1234 yf. This direct conversion can result when the HCFC-235 cb is the reactant compound CF 3 CF 2 CHXCl, wherein X is H. 
     Typically, the reactant compound HCFC-225 ca will be mixed with HCFC-225 aa (CF 3 CCl 2 CHF 2 ), whereby the HCFC-225 aa will accompany the HCFC-225 ca in the contacting and reacting step. The resultant hydrogenation of the HCFC-225 aa forms the reaction product comprising at least one of HCFO-1224 xe (CF 3 CCl=CHF), HCFC-235 da (CF 3 CHClCHF 2 ), and HCFC-245 fa (CF 3 CH 2 CF 2 H), which are intermediates in the formation of HFO-1234 ze (CF 3 CH=CHF). The hydrogenation of HCFC-225 aa can also form HFO-1234 ze directly. 
     When the intermediate is HCFO-1234 xe, the reaction pathway to HFO-1234 ze is to first form HCFC-23 db (CF 3 CHCIHCH 2 F), which can be converted to HFO-1234 ze or 1234 ze can be formed directly from 1234 xe. When the intermediate is HCFC-235 da, this can be converted to HFO-1234 ze. When the intermediate is HCFC-245 fa, it can be converted to HFO-1234 ze directly. 
     When the reactant compound is either CFO-1214 ya or 1224 yd or a mixture thereof, the reaction product comprises HFO-1234 yf. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The hydrogenation reactions of the present invention (Hydrogenation Process and Intermediates Process) are preferably carried out in the gas phase in a corrosion-resistance reactor packed with a catalytically effective amount of the catalyst at temperatures and pressures and contact times effective to produce the reaction result desired for the particular reaction. The hydrogenation reactions are preferably carried out at atmospheric pressure or at higher or lower pressures. 
     The hydrogenation catalyst in each hydrogenation reaction in the Hydrogenation Process consists essentially or Cu, Ru, Cu—Pd, Ni—Cu, or Ni—Pd, with or without a support (carrier). These same catalysts are preferably used in the hydrogenation reactions in the Intermediates Process, although the catalyst used in a particular hydrogenation reaction in the Intermediates Process can be different from the catalyst used in a hydrogenation reaction in the Hydrogenation Process. The catalyst can include a support in each of the hydrogenation reactions. When a support is used as part of the catalyst, the Cu, Ru, Cu—Pd, Ni—Cu,or Ni—Pd can be loaded onto the support in a conventional manner used for loading metals onto supports, including combinations of metals. For example, the catalysts can be prepared by either precipitation or impregnation methods of the Cu, Ru, Cu—Pd, Ni—Cu,or Ni—Pd on a support as generally described in Satterfield on pp. 87-112 in  Heterogeneous Catalysts in Industrial Practice , 2 nd  ed. (McGraw-Hill, New York, 1991).The support is preferably inert, if not positively participative in the obtaining the desired result of the reaction, under the conditions of the reaction. The preferred support is carbon, which may be treated to enhance its support function for the catalyst loaded onto the carbon. One example of treatment is acid washing of the carbon. 
     When the catalyst is Cu—Pd or Ni—Pd, the Pd is preferably present in a minor amount as compared to the weight of the Cu or Ni. For, example, when the catalyst is Cu—Pd, the loading on the support in one embodiment is 0.1 to 20 wt % Cu and 0.1-1.0 wt % Pd. These same proportions can apply to the Ni—Pd catalyst. When the catalyst if Ni—Cu, the mole ratio of these metals can range from 1:99 to 99:1. In one embodiment, the molar ratio of these metals is about 1:1. 
     The foregoing description of catalysts applies to each of the hydrogenation reactions encompassed by the Hydrogenation Process and each of the hydrogenation reactions of the Intermediates Process, when these catalysts are used in the Intermediate Process. 
     Each of the reactant compounds HCFC-235 cb, HCFC-225 ca, HCFO-1224 yd, and CFO-1214 ya are commercially available or can be prepared by known processes in varying degrees of purity. Some impurities may participate in the hydrogenation reaction to form intermediates that can be converted directly or indirectly to the desired HFP propene. Other impurities may be unaffected by the reaction 
     When the compound is CF 3 CF 2 CHXCl, wherein X is Cl, i.e. HCFC-225 ca, the reaction product of the hydrogenation reaction in the presence of catalyst described above comprises the compound CF 3 CF=CH2 (HFO-1234 yf). 
     This reaction product may also comprise at least one of the compounds CF 3 CF=CHCl (HCFO-1224 yd) and CF 3 CF 2 CH 2 Cl (HCFC-235 cb). 
     When the compound CF 3 CF=CHCl is in the reaction product, this compound can be converted to the compound CF 3 CF=CH 2  by hydrogenation in the presence of a catalyst such as described above. The catalyst can be the same or different from the catalyst used to form the reaction product. The hydrogenation of the compound CF 3 CF=CHCl to a reaction product comprising CF 3 CF=CH 2  is in effect practice of the present invention when the reactant compound is CF 3 CF=CXCl, wherein X is H. 
     When the compound CF 3 CF 2 CH 2 Cl is in the reaction product, this compound can be converted to the compound CF 3 CF=CH 2 , first by dehydrofluorination of said compound CF 3 CF 2 CH 2 Cl to form the compound CF 3 CF=CHCI and then hydrogenation of said compound CF 3 CF=CHCl in the presence of catalyst as described above. 
     Alternatively, the compound CF 3 CF 2 CH 2 Cl can be converted to CF 3 CF=CH 2 by hydrogenation in the presence of catalyst as described above. 
     When the reactant compound comprises HCFC-225 ca, this compound will typically be accompanied by the compound CF 3 CCl 2 CHF 2  (HCFC-225 aa) in said contacting and reacting in the presence of the catalyst, whereby the reaction product will also comprise at least one of the compounds CF 3 CCl=CHF (HCFO-1224 xe), CF 3 CHClCHF 2  (HCFC-235 da), CF 3 CH 2 CF 2 H (HCFC-245 fa), and CF 3 CH=CHF(HFO-1234 ze) as reaction products of the hydrogenation of the HCFC-225 aa during the hydrogenation of the HCFC-225 ca. The HCFO-1234 xe and HFC-245 fa are both intermediates for the formation of CF 3 CH=CHF (HFO-1234 ze). The presence of HFO-1234 ze in the reaction product means this compound is formed directly from the hydrogenation of HCFC-225 aa. 
     When the reaction product compound is CF 3 CCl=CHF (HCFO-1234 xe), this compound is hydrogenated in the presence of catalyst as described above to form a reaction product comprising at least one of the compounds CF 3 CH=CHF (HFO-1234 ze) and CF 3 CHCICH 2 F (HCFC-234 db). 
     When the reaction product comprises the compound CF 3 CHClCH 2 F (HCFC-234 db), this compound is converted to the reaction product comprising the compound CF 3 CH=CHF by dehydrochlorination of the compound CF 3 CHCICH 2 F. 
     When the reaction product comprises the compound CF 3 CHCICHF 2  (HCFC-235 da) this compound is converted to reaction product comprising the compounds CF 3 CH=CF 2  or CF 3 CH=CHF. In one embodiment, the HCFC-235 da can be dehydrochlorinated to form reaction product comprising HFO-1225 zc (CF 3 CH=CF 2 ). In another embodiment, the HCFC-235 da is reacted with H 2  to remove both Cl and F (hydrodehalogenated) to form reaction product comprising HFO-1234 ze. 
     When the reaction product comprises the compound CF 3 CH 2 CF 2 H (HCFC-245 a), this compound can be dehydrofluorinated to form the reaction product comprising CF 3 CH=CHF (HFO-1234 ze). 
     When the reactant compound is CF 3 CF 2 CHXCl, wherein X is H, i.e. (HCFC-235 cb), the reaction product with H2 comprises the compound CF 3 CF=CH 2  (HFO-1234 yf). 
     When the reactant compound is CF 3 CF=CXCl, wherein X is Cl or CF 3 CF=CXCl, wherein X is H, or a mixture of these reactant compounds, the reaction product of the hydrogenation reaction in the presence of catalyst as described above comprises the compound CF 3 CF=CH 2 . Thus, CFO-1214 ya or HCFO 1224 yd can be the reactant compounds, one without the other, or these compounds can be present as a mixture of reactant compounds. 
     As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). 
     The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. 
     The transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term ‘consisting essentially of’ occupies a middle ground between “comprising” and ‘consisting of’. 
     Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.” 
     Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise. 
     EXAMPLES 
     The concepts described herein will be further described in the following Examples, which do not limit the scope of the invention as described in the claims. 
     Example 1—Hydrogenation of 225 ca to 1234 y, 1224 yd, and 235 cb 
     10 cc 10% Cu/C is loaded into a ½-inch (1.3 cm) Hastelloy® C 227 reactor. The catalyst is reduced at 250° C. with H 2  for 4 hours. Then HCFC-225 ca (GC analysis of HCFC-225 ca reactant mixture in Table 1), is fed at 3.11 sccm with H2 (10.5 sccm) at 325° C. and 350° C. at atmosphere pressure. The reaction product stream from the reactor is analyzed by GC and GC—MS. The result of the hydrogenation reaction is shown in Table 2. HFO-1234 yf, HCFO-1224 yd and HCFC-235 cb are reaction products made in this reaction. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 GC analysis of starting material 225ca mixture 
               
            
           
           
               
               
               
               
               
               
            
               
                 Compound 
                 235cb 
                 225ca 
                 225aa 
                 225cb 
                 Others 
               
               
                   
               
               
                 Mol % 
                 1.44 
                 83.25 
                 4.14 
                 11.14 
                 0.03 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 GC analysis of reaction product 
               
            
           
           
               
               
               
               
            
               
                 Temp 
                 Organic 
                 H 2   
                 mol % of product 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 ° C. 
                 sccm 
                 sccm 
                 1234yf 
                 1224yd 
                 1224xe 
                 235cb 
                 225ca 
                 225aa 
                 225cb 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 325 
                 3.11 
                 10.5 
                 1.51 
                 1.82 
                 2.07 
                 3.58 
                 73.87 
                 1.35 
                 11.52 
               
               
                 350 
                 3.11 
                 10.5 
                 4.71 
                 6.77 
                 2.48 
                 10.66 
                 49.0. 
                 ND 
                 12.66 
               
               
                   
               
            
           
         
       
     
     Example 2—Hydrogenation of HCFC-225 ca, Cu—Pd catalyst 
     10 cc 0.5% Pd-8.5% % Cu/C is loaded into a ½-inch (1.3 cm) Hastelloy® C 227 reactor. The catalyst is reduced at 400° C. with H2 for 4 hours. Then a 225 ca/cb mixture (GC analysis of HCFC-225 ca reactant mixture in Table 1), is fed at 3.11 sccm with H 2  (10.5 sccm) at 125, 140 and 160° C. at atmosphere pressure. The stream from the reactor is analyzed by GC and GC—MS. The result of the test is shown in Table 3. HFO-1234 yf, CFO-1224 yd and HCFC-235 cb are made in this reaction. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 GC analysis of reaction product 
               
            
           
           
               
               
            
               
                 Temp 
                 mol % of product 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 ° C. 
                 1234yf 
                 1224yd 
                 1224xe 
                 235cb 
                 225ca 
                 225aa 
                 225cb 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 125 
                 0.19 
                 14.49 
                 3.30 
                 16.03 
                 51.03 
                 0.95 
                 12.80 
               
               
                 140 
                 0.38 
                 29.17 
                 3.44 
                 34.29 
                 17.39 
                 0.82 
                 12.56 
               
               
                 160 
                 0.73 
                 36.64 
                 3.44 
                 41.11 
                 1.41 
                 ND 
                 12.5 
               
               
                   
               
            
           
         
       
     
     This Example shows the conversion of 225 ca and 1224 yd to 1234 yf in that the 1224 yd is an intermediate to the formation of 1234 yf. 
     Example 3—Hydrogenation of HCFC-235 cb to HFO-1234 yf 
     10 cc 10% Cu/C is loaded into a ½-inch (1.3 cm) Hastelloy® C 227 reactor. The catalyst is reduced at 250° C. with H 2  for 4 hours. Then the 235 cb was fed at 3.5 sccm with H 2  (6 sccm) at 325° C. and 350° C. at atmosphere pressure. The stream from the reactor is analyzed by GC and GC—MS. The result of the test is shown in Table 4. The 235 cb is converted to 1234 yf at a selectivity of 88 to 90%. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 GC analysis of reaction product 
               
            
           
           
               
               
               
            
               
                   
                 Temp 
                 mol % of product 
               
            
           
           
               
               
               
               
               
            
               
                   
                 ° C. 
                 1234yf 
                 245cb 
                 235cb 
               
               
                   
                   
               
               
                   
                 325 
                 14.85 
                 1.89 
                 82.98 
               
               
                   
                 350 
                 26.69 
                 2.71 
                 69.11 
               
               
                   
                   
               
            
           
         
       
     
     Example 4—Hydrogenation of 225 ca to 1234 y, 1224 yd and 235 cb, Ni—Cu catalyst 
     10 cc Johnson Matthey CP447 Ni—Cu/C is loaded into a ½-inch (1.3 cm) Hastelloy® C 227 reactor. The catalyst is reduced at 400° C. with H 2  for 4 hours. Then 225 ca (GC analysis of mixture in Table 5), is fed at 3.11 sccm with H2 (11 sccm) at 225, 250, 275 and 300 C at atmosphere pressure. The stream from the reactor is analyzed by GC and GC—MS. 
     The result of the test is shown in Table 6. The 1234 yf, 1224 yd and 235 cb are made in this reaction. 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 GC analysis starting 225ca mixture 
               
               
                 Mole Percent 
               
            
           
           
               
               
               
               
               
            
               
                   
                 225ca 
                 225aa 
                 225cb 
                 Others 
               
               
                   
                   
               
               
                   
                 47.43% 
                 3.09% 
                 48.53% 
                 0.95% 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 GC analysis of reaction product (F22E is CF 3 CF 2 CH═CHCF 2 CF 3 ) 
               
            
           
           
               
               
            
               
                   
                 Mole Percent 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Temp 
                   
                   
                   
                   
                 1224 
                   
                 1224 
                   
                   
                   
                   
               
               
                 ° C. 
                 1234yf 
                 1234ze 
                 F22E 
                 1224yd-E 
                 isomer 1 
                 235cb 
                 isomer 2 
                 225ca 
                 225aa 
                 225cb 
                 Others 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 225 
                 2.81% 
                 0.00% 
                 0.00% 
                 0.85% 
                 0.36% 
                 0.35% 
                 0.11% 
                 40.53% 
                 2.90% 
                 50.94% 
                 1.16% 
               
               
                 250 
                 4.92% 
                 0.00% 
                 0.08% 
                 1.72% 
                 0.60% 
                 0.74% 
                 0.23% 
                 35.32% 
                 2.53% 
                 50.92% 
                 2.94% 
               
               
                 275 
                 8.56% 
                 0.00% 
                 0.38% 
                 3.44% 
                 1.12% 
                 1.77% 
                 0.44% 
                 25.42% 
                 1.87% 
                 52.53% 
                 4.46% 
               
               
                 300 
                 11.66% 
                 0.16% 
                 1.40% 
                 5.82% 
                 1.53% 
                 3.39% 
                 0.70% 
                 13.63% 
                 1.13% 
                 54.30% 
                 6.27% 
               
               
                   
               
            
           
         
       
     
     Example 5—Hydrogenation of 1214 ya to 1234 y and 1224 yd, Ni—Cu catalyst 
     10cc Johnson Matthey CP447 Ni—Cu/C is loaded into a ½-inch (1.3 cm) Hastelloy® C 227 reactor. The catalyst is reduced at 400° C. with H 2  for 4 hours. Then 1214 ya is fed at 3.11 sccm with H 2  (11 sccm) at 225, 250, 275 and 300° C. at atmosphere pressure. The stream from the reactor is analyzed by GC and GC—MS. 1234 yf and 1224 yd are made in this reaction as shown in Table 7. 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 GC analysis of reaction product 
               
            
           
           
               
               
               
            
               
                 Temp 
                 Mole Percent 
                   
               
            
           
           
               
               
               
               
               
            
               
                 ° C. 
                 1234yf 
                 1224yd 
                 1214ya 
                 Others 
               
               
                   
               
               
                 225 
                  2% 
                  1% 
                 95% 
                 2% 
               
               
                 250 
                 18% 
                  6% 
                 70% 
                 6% 
               
               
                 275 
                 23% 
                 18% 
                 50% 
                 9% 
               
               
                 300 
                 45% 
                 23% 
                 25% 
                 7% 
               
               
                   
               
            
           
         
       
     
     Example 6—Hydrogenation of 1214 ya to 1234 yf and 1224 yd, Pd—Cu catalyst 
     10 cc 0.5%Pd-8.5% % Cu/C is loaded into a ½-inch (1.3 cm) Hastelloy® C 227 reactor. The catalyst is reduced at 400° C. with H 2  for 4 hours. Then 1214 ya is fed at 3.11 sccm with H 2 (10.5 sccm) at 125, 140 and 160° C. at atmosphere pressure. The stream from the reactor is analyzed by GC and GC—MS. The 1234 yf and 1224 yd are made as shown in Table 8. 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 GC analysis of reaction product 
               
            
           
           
               
               
               
            
               
                 Temp 
                 mol % of product 
                   
               
            
           
           
               
               
               
               
               
            
               
                 ° C. 
                 1234yf 
                 1224yd 
                 1214ya 
                 Others 
               
               
                   
               
               
                 125 
                 0.6% 
                 20% 
                 69.4% 
                 10% 
               
               
                 140 
                 1.2% 
                 40% 
                 38.8% 
                 20% 
               
               
                 160 
                     3% 
                 60% 
                     12% 
                 25%