Abstract:
Supported catalysts of the following formula (I) for preparing ethylene by conversion of methane or purified natural gas and preparation thereof, and process for preparation of ethylene by direct conversion of methane or purified natural gas using said catalysts: 
     
       Ma&#39;/S                                                      formula (I) 
     
     (wherein, M is a compound selected from the group of RuCl 2  (PPh 3 ) 3 , RuCl 2  (CO) 2  (PPh 3 ) 2 , Ru 3  (CO) 12 , RhCl(CO)(PPh 3 ) 2 , IrCl(CO)(PPh 3 ) 2 , Pd(PPh 3 ) 4 , Pt(PPh 3 ) 4 , RuCl 3  ·xH 2  O, RhCl 3  ·xH 2  O, IrCl 3  ·xH 2  O, PdCl 2  ·xH 2  O, H 2  PtCl 6  ·xH 2  O, S is an inorganic carrier selected from α-Al 2  O 3 , γ-Al 2  O 3 , SiO 2 , SiO 2  --Al 2  O 3 , Y-zeolite, MgO and TiO 2 , a&#39; is weight percentage of metal in catalyst, ranging from 0.25 to 5 wt %.)

Description:
FIELD OF THE INVENTION 
     The present invention relates to supported catalysts of the following formular (I) for producing ethylene which is used in basic reactions including polymerization, copolymerization and polycondensation reaction in the field of petrochemical industry and fine chemical industry, and preparation thereof. 
     
         Ma&#39;/S                                                      formula (I) 
    
     Further, the present invention is to provide a new process for preparation of ethylene by converting directly methane or purified natural gas, in the presence of the above catalyst with nitrogen, at a temperature of about 670° to 850° C., preferably in the range of 710° to 810° C., which is distinctly lower reaction temperature relative to that of conventional synthesis of hydrocarbon(s) by dehydrogenation. By this process, ethylene is obtained in short time, with high yield, and without by-product such as CO, CO 2 , contrary to oxidative coupling reaction where oxygen is introduced. 
     In Ma&#39;/S of above mentioned general formular (I), M is a compound selected from the group of RuCl 2  (PPh 3 ) 3 , RuCl 2  (CO) 2  (PPh 3 ) 2 , Ru 3  (CO) 12 , RhCl(CO)(PPh 3 ) 2 , IrCl(CO)(PPh 3 ) 2 , Pd(PPh 3 ) 4 , Pt(PPh 3 ) 4 , RuCl 3  ·xH 2  O, RhCl 3  ·xH 2  O, IrCl 3  ·xH 2  O, PdCl 2  ·xH 2  O, wherein x is 3-10, H 2  PtCl 6  ·xH 2  O, S is an inorganic carrier selected from α-Al 2  O 3 , γ-Al 2  O 3 , SiO 2 , SiO 2  --Al 2  O 3 , Y-zeolite, MgO and TiO 2 , a&#39; is weight percentage of metal in catalyst, ranging from 0.25 to 5 wt %. 
     BACKGROUND ART 
     Few of literatures and patents about the catalyst which can be used to produce ethylene by direct conversion of methane is disclosed; moreover, it is different in technical field from present invention. By conventional processes, large amounts of by-product such as carbon dioxide are produced, separation and removal thereof is difficult and environmental pollution is likely to be caused. Also, synthesis of hydrocarbon(s) by conventional dehydrogenation is conducted at relatively high temperature of about 1500° to 1550° C. through thermal or electric cracking reaction to cause some problems such as necessity of supply of high energy, expense of high temperature equipment (plan) as well as enormous loss of thermal energy expense, particulary severe corrosion of reactor. 
     As prior art describing synthesis of hydrocarbon by oxidative coupling or dehydrogenation reaction, there are U.S. Pat. Nos. 5,066,629, 5,068,486 and 5,118,654, Canadian patent no. 2016675 and Japanese patent nos. 04352730, 04368342. 
     SUMMARY OF THE INVENTION 
     Until now, new catalyst being able to conduct conversion reaction not at so (ultra) high temperature as that of process for synthesis of hydrocarbons by dehydrogenation but at distinctly lower (mid•low) temperature, and new process for producing said catalyst, and new process for conversion into ethylene using said catalyst have always been expected. 
     To meet the expectations above, as the result of study for years, the inventors completed development of a new catalyst, preparation thereof, and a simple process for obtaining ethylene in short time, with high yield and with trace amounts of impurities, by converting methane or purified natural gas in the presence of said catalyst at distinctly lower temperature compared to that of process for synthesis of hydrocarbon by dehydrogenation or oxidative coupling reaction; thus direct conversion of methane, being carried out at distinctly low temperature, causes to save enormous amount of thermal energy cost that was needed in synthesis reaction of hydrocarbon(s) by dehydrogenation or oxidative coupling reaction, and is sufficiently efficient to environmental pollution problems through reduced amounts of impurities, namely CO 2 . 
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention will be described in further detail with reference to Examples. 
     First, new desirable catalyst is produced by supporting organic transition metal compound on inorganic carriers, i.e., by supporting various metal cluster compound and organic metal complex on inorganic carriers. 
     In this method, process for synthesis and purification of catalyst is much easier than that in other processes. 
     Through development of this catalyst, reaction conditions such as reaction temperature, reaction pressure are mitigated considerably and ethylene is produced with high yield. 
     Further, due to development of process using catalyst of the present invention, the process for preparation of ethylene is simplified, as a result, productivity is enhanced. 
     The present invention is described in detail as follows. 
     In the present invention, by developing a new process where methane or purified natural gas is converted directly to ethylene, which is different from synthesis reaction of hydrocarbon by dehydrogenation or oxidative coupling reaction, overall process is simplified, further, reaction temperature is lowered to a temperature of about 670° to 850° C., preferably in the range of 710° to 810° C., and amounts of impurities such as carbon dioxide are greatly reduced. 
     In the present invention, by using RuCl 2  (PPh 3 ) 3 , RuCl 2  (CO) 2  (PPh 3 ) 2 , RhCl(CO)(PPh 3 ) 2  catalyst, ethylene is produced with high yield at a temperature of about 810° C. At this time, conversion rate is maintained in the range of about 7.5 to 8.3% and through continuous recirculation of raw material introduced, conversion rate is maximized. 
     That is to say, through solid surface reaction using heterogeneous catalyst, reaction conditions such as reaction temerature and pressure are considerably mitigated, at the same time, reaction equipment is simplified. 
     Process for preparing supported catalyst of the present invention is as follows. 
     Metal cluster (compound) and organic metal complex are dissolved in mixed solvent such as dichloromethane and acetone, etc. 
     Then, inorganic carrier is added to this solution, and metal cluster (compound) and organic metal complex are immersed into inorganic carrier by stirring at about 20° to 200° C., then dried in vacuum drier to prepare catalyst. 
     Inorganic carriers used here are α-Al 2  O 3 , γ-Al 2  O 3 , SiO 2 , SiO 2  --Al 2  O 3 , Y-zeolite, MgO and TiO 2 . 
     And metal cluster(compound) and organic metal complex compounds used are RuCl 2  (PPh 3 ) 3 , RuCl 2  (CO) 2  (PPh 3 ) 2 , Ru 3  (CO) 12 , RhCl(CO)(PPh 3 ) 2 , IrCl(CO)(PPh 3 ) 2 , Pd(PPh 3 ) 4 , Pt(PPh 3 ) 4 , RuCl 3  ·xH 2  O, RhCl 3  ·xH 2  O, IrCl 3  ·xH 2  O, PdCl 2  ·xH 2  O, H 2  PtCl 6  ·xH 2  O. 
     According to the experiments of the present invention, the optimum inorganic carriers for preparation of ethylene are α-Al 2  O 3  and MgO, and metal of VIII series are Ru, Rh. 
     Reaction conditions in the presence of new catalyst of the present invention are as follows. 
     Dilution ratio of nitrogen to methane or purified natural gas is 1 to 6, preferably 1 to 3, based on methane. 
     Reaction temperature is about 670° to 850° C., preferably in the range of 710° to 810° C. 
     Concentration of catalyst is below 5 wt %, prefarably 1 to 3 wt %. 
     Space velocity of source gas is about 75 to 1200 hr -1 , prefarably in the range of 150 to 600 hr -1 . 
     Reaction pressure is usually about 1 to 5 atm, preferably normal pressure. 
     Conversion rate of methane or purified natural gas, and yield and selectivity of ethylene are defined as follows. ##EQU1## 
     Reactants and products are analyzed by gas chromatograph. 
    
    
     Examples 1 to 8 relate to new catalyst and process for preparation thereof, Exmaples 9 to 31 relate to new process for producing ethylene by conversion reaction of methane or purified natural gas in the presence of new catalyst of the present invention. 
     EXAMPLE 1 
     α-Al 2  O 3  4.39 g, RuCl 2  (PPh 3 ) 3  0.85 g (0.886 mmol) are added to mixed solvent consisting of 20 ml of dichloromethane and 10 ml of acetone. This suspension is stirred for about 30 minutes at a temperature of around 40° C., and evaporated to dryness by distillation under reduced pressure, then dried in vacuum drier for about 20 hours to prepare RuCl 2  (PPh 3 ) 3  /α-Al 2  O 3  catalyst. 
     EXAMPLE 2 
     RuCl 2  (CO) 2  (PPh 3 ) 2  0.56 g (0.744 mmol) is added to mixed solvent consisting of 40 ml of dichloromethane and 10 ml of acetone and dissolved, then α-Al 2  O 3  3.68 g is added thereto. This suspension is stirred for about 30 minutes at a temperature of around 40° C. and solvent is evaporated by distillation under reduced pressure. Then residue obtained is dried in vacuum drier for about 20 hours to prepare RuCl 2  (CO) 2  (PPh 3 ) 2  /α-Al 2  O 3  catalyst. 
     EXAMPLE 3 
     α-Al 2  O 3  3.95 g, Ru 3  (CO) 12  0.17 g (0.266 mmol) are added to mixted solvent consisting of 10 ml of dichloromethane and 100 ml of acetone and dissolved. 
     This suspension is stirred for about 30 minutes at a temperature of around 40° C. and solvent is evaporated by distillation under reduced pressure. 
     Residue obtained is dried in vacuum drier for about 20 hours to prepare Ru 3  (CO) 12  /α-Al 2  O 3  catalyst. 
     EXAMPLE 4 
     α-Al 2  O 3  3.28 g, RhCl(CO)(PPh 3 ) 2  0.45 g (0.652 mmol) are added to mixted solvent consisting of 40 ml of dichloromethane and 20 ml of acetone and dissolved. 
     This suspension is stirred for about 30 minutes at a temperature of around 40° C. and solvent is evaporated by distillation under reduced pressure. 
     Residue obtained is dried in vacuum drier for about 20 hours to prepare RhCl(CO)(PPh 3 ) 2  /α-Al 2  O 3  catalyst. 
     EXAMPLE 5 
     α-Al 2  O 3  3.14 g, IrCl(CO)(PPh 3 ) 2  0.26 g (0.333 mmol) are added to mixed solvent consisting of 60 ml of dichloromethane and 10 ml of acetone and dissolved. 
     This suspension is stirred for about 30 minutes at a temperature of around 40° C. and solvent is evaporated by distillation under reduced pressure. 
     Residue obtained is dried in vacuum drier for about 20 hours to prepare IrCl(CO)(PPh 3 ) 2  /α-Al 2  O 3  catalyst. 
     EXAMPLE 6 
     α-Al 2  O 3  3.79 g, Pd(PPh 3 ) 4  0.84 g (0.727 mmol) are added to mixted solvent consisting of 20 ml of dichloromethane and 10 ml of acetone and dissolved. 
     This suspension is stirred for about 30 minutes at a temperature of around 40° C. and solvent is evaporated by distillation under reduced pressure. 
     Residue obtained is dried in vacuum drier for about 20 hours to prepare Pd(PPh 3 ) 4  /α-Al 2  O 3  catalyst. 
     EXAMPLE 7 
     α-Al 2  O 3  4.45 g, Pt(PPh 3 ) 4  0.58 g (0.466 mmol) are added to mixted solvent consisting of 20 ml of dichloromethane and 10 ml of acetone and dissolved. 
     This suspension is stirred for about 30 minutes at a temperature of around 40° C. and solvent is evaporated by distillation under reduced pressure. 
     Residue obtained is dried in vacuum drier for about 20 hours to prepare Pt(PPh 3 ) 4  /α-Al 2  O 3  catalyst. 
     EXAMPLE 8 
     γ-Al 2  O 3  4.39g, RuCl 2  (PPh 3 ) 3  0.85 g (0.886 mmol) are added to mixed solvent consisting of 20 ml of dichloromethane and 10 ml of acetone and stirred for about 30 minutes at a temperature of around 40° C. This suspension is evaporated to dryness by distillation under reduced pressure, then dried in vacuum drier for about 20 hours to prepare RuCl 2  (PPh 3 ) 3  /γ-Al 2  O 3  catalyst. 
     EXAMPLE 9 
     Except using SiO 2  4.39 g as inorganic carrier, Example 8 is repeated to prepare RuCl 2  (PPh 3 ) 3  /SiO 2  catalyst. 
     EXAMPLE 10 
     Except using SiO 2  --Al 2  O 3  4.39 g as inorganic carrier, Example 8 is repeated to prepare RuCl 2  (PPh 3 ) 3  /SiO 2  --Al 2  O 3  catalyst. 
     EXAMPLE 11 
     Except using Y-zeolite 4.39 g as inorganic carrier, Example 8 is repeated to prepare RuCl 2  (PPh 3 ) 3  /Y-zeolite catalyst. 
     EXAMPLE 12 
     Except using MgO 4.39 g as inorganic carrier, Example 8 is repeated to prepare RuCl 2  (PPh 3 ) 3  /MgO catalyst. 
     EXAMPLE 13 
     Except using TiO 2  4.39 g as inorganic carrier, Example 8 is repeated to prepare RuCl 2  (PPh 3 ) 3  /TiO 2  catalyst. 
     EXAMPLE 14 
     α-Al 2  O 3  5.01 g, RuCl 3  ·xH 2  O 0.21 g (1.012 mmol) are added to mixed solvent consisting of 20 ml of dichloromethane and 10 ml of acetone and stirred for about 30 minutes at a temperature of around 40° C. 
     This suspension is evaporated to dryness by distillation under reduced pressure, then dried in vacuum drier for about 20 hours to prepare RuCl 3  ·xH 2  O/α-Al 2  O 3  catalyst. 
     EXAMPLE 15 
     Except that α-Al 2  O 3  3.62 g, RhCl 3  ·xH 2  O 0.15 g (0.717 mmol) are added to mixed solvent consisting of 10 ml of dichloromethane and 20 ml of ethanol, Example 14 is repeated to prepare RhCl 3  ·xH 2  O/α-Al 2  O 3  catalyst. 
     EXAMPLE 16 
     Except α-Al 2  O 3  3.79 g, IrCl 3  ·xH 2  O 0.12 g (0.402 mmol) are added to 20 ml of N,N-Dimethylformamide, and stirred at a temperature of around 150° C., Example 14 is repeated to prepare IrCl 3  ·xH 2  O/α-Al 2  O 3  catalyst. 
     EXAMPLE 17 
     α-Al 2  O 3  3.53 g, PdCl 2  ·xH 2  O 0.12 g (0.677 mmol) are dissolved in mixed aqueous sollution of distilled water 30 ml and 35% conc. HCl 1 ml, then stirred for about 30 minutes at around 100° C. 
     This suspension is evaporated to dryness by distillation under reduced pressure, then dried in vacuum drier for about 20 hours to prepare PdCl 2  ·xH 2  O/α-Al 2  O 3  catalyst. 
     EXAMPLE 18 
     Except using H 2  PtCl 6  ·xH 2  O 0.15 g (0.366 mmol), Example 14 is repeated to prepare H 2  PtCl 6  ·xH 2  O/α-Al 2  O 3  catalyst. 
     EXAMPLE 19 
     Methane (or purified natural gas) and nitrogen are introduced each at the flow rate of about 10 ml/min into continuous stationary phase flow reactor (inner diameter: 0.70 cm; length: 40 cm; stuff: stainless steel 316) in the presence of the catalyst prepared in Example 1. Products are obtained by continuous reaction under about 1 atm at each reaction temperature which is given in following Table 1 and the results of analysis of them by gas chromatography is as following Table 1 (from this example to Example 31, raw material is continuously reintroduced to convesion reaction). 
     Below mentioned * mark represents reaction is conducted at surrounding temperature based on given value. 
     
                       TABLE 1______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 2.0 about 1.1                     about 0.9                            about 55.0                                   about 45.0730    about 2.9 about 2.1                     about 0.8                            about 72.4                                   about 27.6750    about 4.4 about 3.6                     about 0.8                            about 81.8                                   about 18.2770    about 5.4 about 4.8                     about 0.6                            about 88.9                                   about 11.1790    about 6.6 about 6.0                     about 0.6                            about 90.9                                   about 9.1810    about 7.5 about 6.8                     about 0.7                            about 90.7                                   about 9.3______________________________________ 
    
     EXAMPLE 20 
     Except using RuCl 2  (CO) 2  (PPh 3 ) 2  /α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 2. 
     
                       TABLE 2______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 2.1 about 1.2                     about 0.9                            about 57.1                                   about 42.9730    about 3.1 about 2.1                     about 1.0                            about 67.7                                   about 32.3750    about 4.5 about 3.7                     about 0.8                            about 82.2                                   about 17.8770    about 5.6 about 4.9                     about 0.7                            about 87.5                                   about 12.5790    about 6.5 about 5.9                     about 0.6                            about 90.8                                   about 9.2810    about 7.9 about 7.3                     about 0.6                            about 92.4                                   about 7.6______________________________________ 
    
     EXAMPLE 21 
     Except using Ru 3  (CO) 12  /α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 3. 
     
                       TABLE 3______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.4 about 0.5                     about 0.9                            about 35.7                                   about 64.3730    about 2.6 about 1.6                     about 1.0                            about 61.5                                   about 38.5750    about 3.8 about 2.8                     about 1.0                            about 73.7                                   about 26.3770    about 4.6 about 3.7                     about 0.9                            about 80.4                                   about 19.6790    about 6.4 about 5.1                     about 1.3                            about 79.7                                   about 20.3810    about 7.3 about 5.9                     about 1.4                            about 80.8                                   about 19.2______________________________________ 
    
     EXAMPLE 22 
     Except using RhCl(CO)(PPh 3 ) 2  /α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 4. 
     
                       TABLE 4______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 2.2 about 1.2                     about 1.0                            about 54.5                                   about 45.5730    about 2.6 about 1.8                     about 0.8                            about 69.2                                   about 30.8750    about 4.4 about 3.4                     about 1.0                            about 77.3                                   about 22.7770    about 5.5 about 4.7                     about 0.8                            about 85.5                                   about 14.5790    about 6.7 about 6.0                     about 0.7                            about 89.6                                   about 10.4810    about 8.3 about 7.6                     about 0.7                            about 91.6                                   about 8.4______________________________________ 
    
     EXAMPLE 23 
     Except using IrCl(CO)(PPh 3 ) 2  /α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 5. 
     
                       TABLE 5______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.3 about 0.6                     about 0.7                            about 46.2                                   about 53.8730    about 2.5 about 1.8                     about 0.7                            about 72.0                                   about 28.0750    about 3.6 about 2.6                     about 1.0                            about 72.2                                   about 27.8770    about 5.1 about 4.3                     about 0.8                            about 84.3                                   about 15.7790    about 6.1 about 5.4                     about 0.7                            about 88.5                                   about 11.5810    about 7.3 about 6.7                     about 0.6                            about 91.8                                   about 8.2______________________________________ 
    
     EXAMPLE 24 
     Except using Pd(PPh 3 ) 4  /α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 6. 
     
                       TABLE 6______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.1 about 0.5                     about 0.6                            about 45.5                                   about 54.5730    about 1.5 about 0.9                     about 0.6                            about 60.0                                   about 40.0750    about 3.6 about 2.6                     about 1.0                            about 72.2                                   about 27.8770    about 5.2 about 4.1                     about 1.1                            about 78.8                                   about 21.2790    about 5.9 about 5.1                     about 0.8                            about 86.4                                   about 13.6810    about 7.2 about 6.7                     about 0.6                            about 93.1                                   about 6.9______________________________________ 
    
     EXAMPLE 25 
     Except using Pt(PPh 3 ) 4  /α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 7. 
     
                       TABLE 7______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.2 about 0.6                     about 0.6                            about 50.0                                   about 50.0730    about 1.8 about 1.1                     about 0.7                            about 61.1                                   about 38.9750    about 3.0 about 2.3                     about 0.7                            about 76.7                                   about 23.3770    about 4.6 about 3.8                     about 0.8                            about 82.6                                   about 17.4790    about 5.8 about 5.1                     about 0.7                            about 87.9                                   about 12.1810    about 7.3 about 6.6                     about 0.7                            about 90.4                                   about 9.6______________________________________ 
    
     EXAMPLE 26 
     Except using RuCl 2  (PPh 3 ) 3  /γ-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 8. 
     
                       TABLE 8______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.4 about 1.0                     about 0.4                            about 71.4                                   about 28.6730    about 1.8 about 1.3                     about 0.5                            about 72.2                                   about 27.8750    about 2.3 about 1.7                     about 0.6                            about 73.9                                   about 26.1770    about 2.8 about 2.1                     about 0.7                            about 75.0                                   about 25.0790    about 4.7 about 3.9                     about 0.8                            about 83.0                                   about 17.0______________________________________ 
    
     EXAMPLE 27 
     Except using RuCl 2  (PPh 3 ) 3  /SiO 2  --Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 9. 
     
                       TABLE 9______________________________________Reaction  Conver-  Yield         SelectivityTemp.  sion     (%)           (%)*(°C.)  (%)      Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.3           about 1.3                    about 0.0                           about 100.0                                   about 0.0730    about 1.8           about 1.2                    about 0.6                           about 66.7                                   about 33.3750    about 3.2           about 2.2                    about 1.0                           about 68.8                                   about 31.2770    about 4.1           about 3.1                    about 1.0                           about 75.6                                   about 24.4790    about 5.7           about 4.9                    about 0.8                           about 86.0                                   about 14.0______________________________________ 
    
     EXAMPLE 28 
     Except using RuCl 2  (PPh 3 ) 3  /Y-zeolite as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 10. 
     
                       TABLE 10______________________________________Temp.            Yield         SelectivityReaction  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 1.9 about 1.4                     about 0.5                            about 73.7                                   about 26.3730    about 2.6 about 1.9                     about 0.7                            about 73.1                                   about 26.9750    about 4.0 about 3.0                     about 1.0                            about 75.0                                   about 25.0770    about 4.3 about 3.5                     about 0.8                            about 81.4                                   about 18.6790    about 4.8 about 4.0                     about 0.8                            about 83.3                                   about 16.7______________________________________ 
    
     EXAMPLE 29 
     Except using RuCl 2  (PPh 3 ) 3  /MgO as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 11. 
     
                       TABLE 11______________________________________Reaction         Yield         SelectivityTemp.  Conversion            (%)           (%)*(°C.)  (%)       Ethylene Ethane Ethylene                                   Ethane______________________________________710    about 2.4 about 1.3                     about 1.1                            about 54.2                                   about 45.8730    about 3.2 about 2.0                     about 1.2                            about 62.5                                   about 37.5750    about 4.1 about 3.1                     about 1.0                            about 75.6                                   about 24.4770    about 4.5 about 3.6                     about 0.9                            about 80.0                                   about 20.0790    about 5.9 about 5.1                     about 0.8                            about 86.4                                   about 13.6______________________________________ 
    
     EXAMPLE 30 
     Except using RuCl 3  ·xH 2  O/α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 12. 
     
                       TABLE 12______________________________________Reaction  Conver-  Yield         SelectivityTemp.  sion     (%)           (%)*(°C.)  (%)      Ethylene Ethane Ethylene                                  Ethane______________________________________710    about 0.0           about 0.0                    about 0.0                           about 0.0                                  about 0.0730    about 0.3           about 0.0                    about 0.3                           about 0.0                                  about 100.0750    about 1.0           about 0.2                    about 0.8                           about 20.0                                  about 80.0770    about 1.8           about 0.8                    about 1.0                           about 44.4                                  about 55.6790    about 2.7           about 1.7                    about 1.0                           about 63.0                                  about 37.0______________________________________ 
    
     EXAMPLE 31 
     Except using RhCl 3  ·xH 2  O/α-Al 2  O 3  as catalyst, Example 19 is repeated and the distribution of resultant products is as following Table 13. 
     
                       TABLE 13______________________________________Reaction  Conver-  Yield         SelectivityTemp.  sion     (%)           (%)*(°C.)  (%)      Ethylene Ethane Ethylene                                  Ethane______________________________________710    about 0.0           about 0.0                    about 0.0                           about 0.0                                  about 0.0730    about 0.0           about 0.0                    about 0.0                           about 0.0                                  about 0.0750    about 0.4           about 0.0                    about 0.4                           about 0.0                                  about 100.0770    about 1.7           about 0.9                    about 0.8                           about 52.9                                  about 47.1790    about 3.3           about 2.4                    about 0.9                           about 72.7                                  about 27.3______________________________________