Patent Publication Number: US-4319037-A

Title: Process for producing methyl formate

Description:
This is a continuation of application Ser. No. 786,408, filed Apr. 11, 1977, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to a process for producing methyl formate which comprises dehydrogenating methanol in vapor phase. 
     A process for producing methyl formate which comprises dehydrogenating methanol in the presence of a certain catalyst is known. For example, copper (French Pat. No. 673,337), catalyst obtained by reducing oxides of copper, nickel, chrome and iron (U.S. Pat. No. 1,400,195) and catalyst obtained by treating copper-aluminum alloy with an aqueous alkaline solution (U.S. Pat. No. 2,504,497) were known as such catalysts. However, these patents do not disclose the yield of methyl formate obtained. I have found that when methanol is dehydrogenated in the presence of copper, methyl formate can not be obtained with excellent selectivity. 
     SUMMARY OF THE INVENTION 
     The present invention has been proposed for overcoming such shortcoming in the prior art. 
     Therefore, an object of this invention is to provide a process for producing methyl formate from methanol with high selectivity. 
     This invention relates to a process for producing methyl formate by dehydrogenating of methanol in the vapor phase in the presence as a catalyst of copper and at least one element selected from the group consisting of elements of Group IIIA (including the rare earth elements) of the periodic table, elements of Group IVA of the periodic table and actinide elements; and more specifically to said process wherein the copper component in the catalyst is the one obtained by baking basic copper carbonate. 
     The periodic table employed in the present invention is the one given in THE ELEMENTS OF PHYSICAL CHEMISTRY, written by Samuel Glasstone, published by D. Van Nostrand Company, Inc. 
     In the catalyst components employed in the present invention, the atomic ratio of copper to the elements of Group IIIA (including the rare earths), the elements of Group IVA or actinide elements may be in the range of from about 1:0.01 to about 1:2, preferably from about 1:0.05 to about 1:1. 
     Examples of Group IIIA include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, promethium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutecium. Examples of the elements of Group IVA include titanium, zirconium and hafnium. Examples of actinides include thorium, protactinium, uranium, neptunium, plutonium and americium. 
     A process for producing the catalyst composed of copper and other element(s) is not critical. Conveniently, the catalyst may be prepared from compounds, such as hydroxides, oxides, carbonates, an inorganic acid salt or an organic acid salt containing copper and other element(s). The catalyst may also be prepared from a mixture of compounds containing copper and a compound containing other element(s). Preferably, the catalyst is prepared from a mixture of basic copper carbonate and a carbonate of other element(s). Water is added to the mixture of the compound containing copper and the compound containing other element(s) to form a paste, and thereafter a uniform mixture can be formed by kneading the paste. Alternatively, the catalyst can be formed by coprecipitation. The preparing operation is as follows: The mixture of the compound containing copper and the compound containing other elements is dried, and is baked at a temperature as high as about 400° C. in an atmosphere of air or nitrogen and then is reduced in a stream of H 2  or CO at 200° C. to activate the resulting catalyst. 
     The dehydrogenating of methenol is carried out by contacting the catalyst with methanol in vapor phase to produce methyl formate. The reaction conditions depend on the kind of the catalysts employed. Conveniently, the reaction temperature may be in the range from about 100° C. to about 400° C., preferably from about 150° C. to about 300° C.; and space velocity may be in the range of from about 100 hr -1  to about 50,000 hr -1 , preferably from about 500 hr -1  to about 30,000 hr -1  ; and the reaction may be carried out at an atmospheric pressure, a superpressure or a reduced pressure. About 0.1 mol to about 2 mol of a dilution gas, such as hydrogen, carbon monoxide or nitrogen which is non active to the reaction may be present in the reaction system per 1 mol of methanol. When methyl formate is produced from methanol, selectivity to methyl formate is relative to conversion of methanol. It is preferred to maintain the conversion of methanol at less than 60% in order to keep the selectivity to methyl formate high. When the yield of methyl formate is considered, it is preferred to maintain the conversion of methanol at more than 10%. 
     When methyl formate is produced by dehydrogenating methanol, the catalysts employed in the present invention give superior results to copper catalyst in respect of the selectivity to methyl formate. 
     The present invention is further illustrated by the following Examples. However, this invention should not be limited by these examples, and the changes and modification within the spirit and scope of this invention can be effected. 
     Parts and percent are by weight in the following Examples, unless otherwise specified. 
    
    
     EXAMPLE 1 
     Each of 1 mol of reagent grade (GR) copper nitrate and 1.17 mol of reagent grade (GR) anhydrous sodium carbonate was dissolved in 1l of deionized water separately, and two of the solutions were heated to 70° C. and were mixed with each other with strong stirring, and the resulting mixture was stirred while maintaining it at 70° C. for one and half hours. The resulting mixture was allowed to stand for one hour with stirring. The precipitate was suction-filtered from the mixture. The resulting cake was sufficiently washed with deionized water and was dried at 70° C. overnight. 
     Each of titanium oxide, zirconium carbonate, lanthanum oxide and yttrium oxide was added to 70 g of the resulting basic copper carbonate powder so that the atomic ratio of copper to titanium, zirconium, lanthanum or yttrium amounted to 1:0.1. Water was added to each mixture to form a paste. The pastes were blended and kneaded by a kneader for 30 minutes, and were allowed to stand at 70° C. overnight. The resulting dried mixtures were crushed to particles of 2 to 5 mm size. The particles were baked at 390° C. for one and half hours in air. 3 Percent of graphite was added to each mixture on the basis of the baked mixture. The mixtures were shaped to tablets having 6 mm in diameter and 5 mm high. The tablets were crushed to 1/8 size. The resulting particles containing copper compound and other element compound were charged in a pyrex glass pipe having 20 mm inner diameter, and were maintained at 200° C. for 6 hrs in a stream of hydrogen to reduce these compounds, separately. 
     Reactors having 20 mm inner diameter were filled with 10 ml of each of the activated catalysts and methanol vapor was charged at a space velocity of 3500 hr -1  from one edge of the reactor. The reaction was carried out at an atmospheric pressure at each temperature as given in Table 1. The results are shown in Table 1. 
     
                       TABLE 1                                                     
______________________________________                                    
                                      Yield of                            
Further catalyst   Conversion Selectivity                                 
                                      methyl                              
component Reaction of methanol                                            
                              to methyl                                   
                                      formate                             
added to copper                                                           
          temp. °C.                                                
                   %          formate %                                   
                                      %                                   
______________________________________                                    
          160      15.2       96.1    14.6                                
Titanium  181      29.0       86.9    25.2                                
          202      40.7       72.9    29.7                                
          180      24.8       94.3    23.4                                
          198      35.0       87.1    30.5                                
Zirconium 219      45.2       78.8    35.6                                
          242      52.9       73.6    38.9                                
          169      18.3       96.1    17.6                                
          180      26.0       94.6    24.6                                
          194      30.7       93.1    28.6                                
Lanthanum 211      37.4       89.2    33.4                                
          226      43.7       85.1    37.2                                
          243      49.5       79.4    39.3                                
          179      23.0       94.2    21.7                                
Yttrium   198      34.0       88.0    29.9                                
          219      43.6       77.6    33.8                                
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     EXAMPLE 2 
     The catalyst employed was the copper-lanthanum prepared in Example 1. The dehydrogenating reaction of Example 1 was repeated except that 0.13 mol of hydrogen or carbon monoxide coexisted in 1 mol of methanol, and the space velocity was 3750 hr -1 . The results are shown in Table 2. 
     
                       TABLE 2                                                     
______________________________________                                    
        Reaction   Conversion                                             
                             Selectivity                                  
                                     Yield of                             
Co-existing                                                               
        temperature                                                       
                   of methanol                                            
                             to methyl                                    
                                     methyl                               
gas     °C. %         formate %                                    
                                     formate %                            
______________________________________                                    
        170        17.2      97.0    16.7                                 
        180        24.4      95.1    23.2                                 
H.sub.2 195        29.4      93.0    27.3                                 
        213        35.3      88.8    31.3                                 
        226        39.2      86.3    33.8                                 
        173        19.3      97.0    18.7                                 
        181        27.8      94.3    26.2                                 
CO      195        32.0      92.8    29.7                                 
        210        39.5      89.3    35.2                                 
        225        46.5      85.5    39.7                                 
______________________________________                                    
 
    
     EXAMPLE 3 
     The dehydrogenating reaction of Example 1 was repeated using copper-lanthanum catalyst except that the space velocity was changed as shown in Table 3. The results are shown in Table 3. 
     
                       TABLE 3                                                     
______________________________________                                    
Space velocity                                                            
          Reaction Conversion                                             
                             Selectivity                                  
                                     Yield of                             
of methanol                                                               
          tempera- of methanol                                            
                             to methyl                                    
                                     methyl                               
vapor hr.sup.-1                                                           
          ture °C.                                                 
                   %         formate %                                    
                                     formate %                            
______________________________________                                    
          139       5.9      95.5     5.6                                 
          150      16.5      92.3    15.2                                 
500       164      21.9      90.0    19.7                                 
          180      27.7      85.2    23.6                                 
          200      28.6      78.8    22.5                                 
          170      17.5      96.3    16.8                                 
          182      26.8      94.0    25.2                                 
          195      31.4      94.1    29.5                                 
1,000     214      36.6      89.9    32.9                                 
          225      42.6      86.3    36.8                                 
          245      48.2      80.5    38.8                                 
          169      18.3      96.1    17.6                                 
          180      26.0      94.6    24.6                                 
          194      30.8      93.1    28.6                                 
3,500     211      37.4      89.2    33.4                                 
          226      43.7      85.1    37.2                                 
          243      49.5      79.4    39.3                                 
          200      25.4      95.0    24.1                                 
          215      30.7      93.1    28.6                                 
7,000     230      38.1      88.7    33.8                                 
          245      43.5      84.7    36.8                                 
          260      49.7      78.5    39.0                                 
          218      25.8      95.3    24.6                                 
          233      30.1      93.6    28.2                                 
10,000    249      38.2      89.7    34.3                                 
          265      43.8      85.1    37.3                                 
          280      48.5      81.5    39.5                                 
______________________________________                                    
 
    
     EXAMPLE 4 
     The dehydrogenating reaction of Example 1 was repeated using copper-zirconium catalyst, except that the atomic ratio of copper to zirconium was changed as shown in Table 4. 
     
                       TABLE 4                                                     
______________________________________                                    
Atomic ratio                                                              
         Reaction  Conversion                                             
                             Selectivity                                  
                                     Yield of                             
of copper to                                                              
         tempera-  of methanol                                            
                             to methyl                                    
                                     methyl                               
zirconium                                                                 
         ture °C.                                                  
                   %         formate %                                    
                                     formate %                            
______________________________________                                    
1:0.01   162       21.4      93.9    20.1                                 
         179       31.8      81.2    25.8                                 
1:0.1    180       24.8      94.3    23.4                                 
         198       35.0      87.1    30.5                                 
         219       45.2      78.8    35.6                                 
         242       52.9      73.6    38.9                                 
1:0.5    196       22.4      94.7    21.2                                 
         220       36.7      93.8    34.4                                 
         241       41.7      93.4    38.9                                 
         258       45.4      93.2    42.3                                 
         275       48.7      92.1    44.8                                 
         300       54.2      87.1    47.3                                 
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 1 
     The procedure of Example 3 was repeated except that the catalyst was Raney copper sold by Kawaken Fine Chemical Co. The results are shown in Table 5. 
     
                       TABLE 5                                                     
______________________________________                                    
Space velocity                                                            
          Reaction Conversion                                             
                             Selectivity                                  
                                     Yield of                             
of methanol                                                               
          tempera- of methanol                                            
                             to methyl                                    
                                     methyl                               
vapor hr.sup.-1                                                           
          ture °C.                                                 
                   %         formate %                                    
                                     formate %                            
______________________________________                                    
2,170     224      23.7      75.8    17.9                                 
          243      35.9      64.0    23.0                                 
7,700     242      17.7      71.0    12.6                                 
          270      30.3      50.7    15.3                                 
          291      41.0      28.9    11.8                                 
______________________________________                                    
 
    
     EXAMPLE 5 
     Each of cerium carbonate, neodymium carbonate, samarium oxide, thorium compound (precipitate obtained by adding sodium carbonate solution to thorium nitrate solution) and uranyl nitrate was added to 70 g of the basic copper carbonate powder obtained in Example 1 so that the atomic ratio of copper to cerium, neodymium, samarium, thorium or uranium amounted to 1:0.1. Water was added to each mixture to form a paste. The pastes were blended and kneaded by a kneader for 30 minutes, and were allowed to stand at 70° C. overnight. The resulting dried mixtures were crushed to particles of 2 to 5 mm size. The particles were baked at 390° C. for one and half hours in air. 3 Percent of graphite was added to each mixture on the basis of the baked mixture. The mixture was shaped to tablets having 6 mm in diameter and 5 mm high. The pellets were crushed to 1/8 size. The resulting particles containing copper compound and other element compounds were charged in a pyrex glass pipe having 20 mm inner diameter, and were maintained at 200° C. for 6 hrs in a stream of hydrogen to reduce these compounds. 
     Reactors having 20 mm inner diameter were filled with 10 ml of the activated catalysts, and methanol vapor was charged at space velocity of 3500 hr -1  from one edge of the reactor. The reaction was carried out at an atmospheric pressure at each temperature as given in Table 6. The results are shown in Table 6. 
     
                       TABLE 6                                                     
______________________________________                                    
Other metal                                                               
         Reaction  Conversion                                             
                             Selectivity                                  
                                     Yield of                             
added to tempera-  of methanol                                            
                             to methyl                                    
                                     methyl                               
copper   ture °C.                                                  
                   %         formate %                                    
                                     formate %                            
______________________________________                                    
Cerium   183       26.4      90.3    23.8                                 
         201       33.6      85.2    28.6                                 
         222       38.8      81.7    31.7                                 
         242       43.4      74.6    32.4                                 
Neodymium                                                                 
         189       30.8      92.9    28.6                                 
         210       41.0      87.2    35.8                                 
         229       49.6      80.0    39.6                                 
         245       55.7      70.6    39.3                                 
Samarium 184       31.6      92.5    29.2                                 
         205       40.4      85.7    34.7                                 
         224       49.0      80.0    39.2                                 
         243       56.5      70.3    39.7                                 
Thorium  147       11.6      94.2    10.9                                 
         159       21.7      89.1    19.3                                 
         171       31.6      74.9    23.7                                 
Uranium  170       22.8      93.5    21.3                                 
         188       31.2      88.5    27.6                                 
         212       40.8      82.6    33.7                                 
______________________________________                                    
 
    
     EXAMPLE 6 
     The procedure of Example 5 was repeated using copper-cerium catalyst except that 0.13 mol of hydrogen or carbon monoxide coexisted in 1 mol of methanol, and the space velocity was 3750 hr -1 . The results are shown in Table 7. 
     
                       TABLE 7                                                     
______________________________________                                    
        Reaction  Conversion                                              
                            Selectivity                                   
                                    Yield of                              
Co-existing                                                               
        tempera-  of methanol                                             
                            to methyl                                     
                                    methyl                                
gas     ture °C.                                                   
                  %         formate %                                     
                                    formate %                             
______________________________________                                    
H.sub.2 180       24.6      91.6    22.5                                  
        200       31.8      86.2    27.4                                  
        221       36.4      83.6    30.5                                  
        243       41.5      76.3    31.6                                  
CO      182       26.8      91.5    24.5                                  
        202       34.2      86.8    29.7                                  
        220       40.2      83.7    33.6                                  
        241       45.5      75.7    34.5                                  
______________________________________                                    
 
    
     EXAMPLE 7 
     The procedure of Example 5 was repeated using copper-cerium catalyst except that the space velocity was changed as shown in Table 8. 
     
                       TABLE 8                                                     
______________________________________                                    
Space velocity                                                            
          Reaction Conversion                                             
                             Selectivity                                  
                                     Yield of                             
of methanol                                                               
          tempera- of methanol                                            
                             to methyl                                    
                                     methyl                               
vapor hr.sup.-1                                                           
          ture °C.                                                 
                   %         formate %                                    
                                     formate %                            
______________________________________                                    
500       153      17.4      92.0    16.0                                 
          175      25.5      88.7    22.6                                 
          196      32.0      80.4    25.7                                 
1,000     180      25.5      90.3    23.0                                 
          202      32.6      85.7    27.9                                 
          220      37.8      82.6    31.2                                 
          243      41.9      75.7    32.1                                 
3,500     183      26.4      90.3    23.8                                 
          201      33.5      85.2    28.6                                 
          222      38.8      81.7    31.7                                 
          242      43.4      74.6    32.4                                 
7,000     220      31.6      91.7    29.0                                 
          241      36.2      87.6    31.7                                 
          263      38.6      85.6    33.1                                 
          280      43.8      80.2    35.2                                 
10,000    240      32.0      92.5    29.6                                 
          265      36.0      89.6    32.2                                 
          282      39.6      86.7    34.3                                 
          301      44.5      82.4    36.7                                 
______________________________________                                    
 
    
     COMPARATIVE EXAMPLE 2 
     The procedure of Example 7 was repeated except that the catalyst was Raney copper sold by Kawaken Fine Chemical Co. The results are shown in Table 9. 
     
                       TABLE 9                                                     
______________________________________                                    
Space velocity                                                            
          Reaction Conversion                                             
                             Selectivity                                  
                                     Yield of                             
of methanol                                                               
          tempera- of methanol                                            
                             to methyl                                    
                                     methyl                               
vapor hr.sup.-1                                                           
          ture °C.                                                 
                   %         formate %                                    
                                     formate %                            
______________________________________                                    
2,170     224      23.7      75.8    17.9                                 
          243      35.9      64.0    23.0                                 
7,700     242      17.7      71.0    12.6                                 
          270      30.3      50.7    15.3                                 
          291      41.0      28.9    11.8                                 
______________________________________