PROCESS FOR THE PRODUCTION OF MIXED ALCOHOLS

Abstract: A process for producing a mixed alcohol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by: calcining a mixture of (A) a copper or zinc compound, (B) a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II-VII of the Periodic Table; impregnating the above-calcined product with (D) an al­ kali metal compound and/or an alkaline earth metal com­ pound; calcining the resulting mixture; and reducing the thus-­ calcined product. The selectivity of the mixed alcohol is high in the process of the present invention. This is one of the advantages of the present invention. Furthermore the proportion of alcohols other than methanol in the mixed alcohol is relatively high, and thus the mixed alcohol is suitable for use as an alcohol compo­ nent to be compounded to gasoline.

Description: PROCESS FOR THE PRODUCTION OF MIXED ALCOHOLS BACKGROUND OF THE INVENTION In view of a rise in price of gasoline for cars due to the aggravation of oil situation, an attempt to pro duce inexpensive car fuel by adding mixed alcohols to gasoline have been made in recent years. The reason why mixed alcohols are used as an alcohol component to be added to gasoline is that if methanol alone is added to gasoline, it combines together with water in gasoline to form a water/methanol mixture, resulting in the formation of two layers, i.e., a gasoline layer and a water/methanol mixed layer, in a storage tank. Various methods of producing such mixed alcohols have been proposed. Japanese Patent Application Laid-Open No. 7727/1981, for example, discloses a process for producing mixed alcohols from synthesis gas by the use of a rhodium-base catalyst. This process, however, is not preferred in that large amounts of by-products such as acetic acid and aldehyde result. In addition, as catalysts for use in the production of mixed alcohols from synthesis gas, a ruthenium-base catalyst (Japanese PatentApplication Laid-Open No. 82327/1982), alkali metal-modified ones of a zinc-chromium catalyst and a copper-zinc catalyst (Japanese Patent Application Laid-Open No. 10689/1982), and a copper-cobalt catalyst (Japanese Patent Application Laid-Open No. 85530/1980) are known. Methods utilizing these catalysts, however, should be performed under elevated pressures. This will need expensive equipment and cause .many side reactions. Hence they cannot be said to be advantageous for practical use. SUMMARY OF THE INVENTION The present invention is intended to overcome the above-described problems of conventional methods, and an object of the invention is to provide a process for producing mixed alcohols from synthesis gas with efficiency under relatively low pressures. One embodiment of the present invention relates to a process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by: calcining a mixture of (A1) a copper compound, (B1) a nickel compound, and (C) a compound of at least one metal selected from the metals belonging to Groups II, III and IV and the fourth period of Groups V, VI and VII of the Periodic Table; impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound; calcining the resulting mixture; and reducing the thus-calcined product. The other embodiment of the present invention relates to a process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by: calcining a mixture of (A2) a zinc compound, (B2) a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II, ITI and IV and the fourth period of Groups V, VI and VII of the Periodic Table; impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound; calcining the resulting mixture; and reducing the thus-calcined product. DETAILED DESCRIPTION OF THE INVENTION A method of preparing the catalyst of the invention will hereinafter be explained in detail. In the preparation of the catalyst Compounds (A), (B) and (C) are first mixed and calcined. As Compound (A), Compound (A1) or Compound (A2) can be used. As Compound (A1) used herein, any suitable compound containing copper can be listed. Usually water-soluble compounds are preferred. Suitable examples of copper compounds include copper nitrate, copper sulfate, and copper chloride. As Compound (A2) used herein, any suitable compound containing zinc can be listed. Usually water-soluble compounds are preferred. Suitable examples of zinc compounds include zinc nitrate, zinc sulfate, and zinc chloride. As Compound (B), Compound (B1) or Compound (B2) can be used. Compound (B1) used herein, any suitable compound containing nickel can be listed. Particularly preferred are water-soluble compounds. Suitable examples of nickel compounds include nickel nitrate, nickel sulfate, and nickel chloride. Compound (B2) is a compound containing at least one of iron, cobalt, and nickel. Particularly preferred are water-soluble compounds. Suitable examples are the nitrates, sulfates, and chlorides of the metals. Compound (A1) can be used in combination with Compound (B1). Similar by, Compound (A2) can be used in combination with Compound (B2). Compound (C) is a compound of at least one metal selected from the metals belonging to Groups II, III and IV, and the fourth period of Groups V, VI and VII of the Periodic Table. Typical examples of the metals belonging to Groups II, III and IV of the Periodic Table are magnesium, calcium, zinc, boron, aluminum, gallium, lanthanum, silicon, germanium, titanium, tin, and zirconium. Suitable examples of the metals belonging to the fourth period of Groups V, VI and VII of the Periodic Table are vanadium, chromium, and manganese. As Compound (C), various compounds of the metals as described above, such as the titrates, sulfates, chlorides, and oxides thereof, can be used. Particularly preferred are water-soluble compounds. As Compound (C), salt of titanium is one of the preferable compounds. Especially sulfate of it is preferable. Other salts such as titanium tetrachloride are undesirable here. When dissolved into water, titanium tetrachloride, for instance, is difficult to treat since it fumes and is hydrolyzed not to be dispersed homogeneously. Moreover, other salts are insoluble in water. Titanium sulfate is a favourable salt for dispersing of titanium into catalyst as is described above, but sulfate radicals tend to remain in catalyst. When sulfur portion is 0.58 by weight or more, catalytic activity is scarcely observed. Accordingly, when titanium sulfate is employed for producing catalyst, it is inevitable to remove sulfate radicals to make sulfur portion less than 0.5% by weight after precipitate results. After earnest researches in removal of sulfate radicals, we have found that following two processes are desirable. One of the processes is to repeat washing with aqueous solution of sodium chloride after the precipitate results, and to exchange sulfate radicals with chlorine ions to reduce sulfate radicals, and thus make sulfur portion less than 0.5% by weight. Thereupon, the concentration of the aqueous solution of sodium chloride is desired to be 0.1 mole per liter - 5 mole per liter. Another process is to adjust pH at co-precipitating by addition of sodium carbonate. There, once co-precipitation is made at pH 9.0 or more, after that the washing with plain water can reduce the sulfate radicals to make the sulfur portion less than 0.5 & by weight. When pH is less than 9.0, activity does not arise sufficiently. In the preparation of the catalyst of the invention, Compounds (A), (B) and (C) are first mixed and calcined. Compounds (A), (B) and (C) can be mixed by techniques such as a co-precipitation method, a kneading method, and a dipping method. In accordance with the co-precipitation method, for example, they are added to water to form aqueous solutions or suspensions, which are then mixed and co-precipitated by adjusting the pH through addition of a co-precipitating agent such as sodium carbonate, sodium hydroxide, and potassium hydroxide at room temperature or at elevated temperatures. Then, the resulting precipitate is aged, if necessary, and washed with water, dried and calcined at a temperature of from 200 to 5000C. The above-calcinated product is then impregnated with Compound (D), i.e., an alkali metal compound and/or an alkaline earth metal compound. Compound (D) is preferably water-soluble. Suitable examples include sodium carbonate and magnesium acetate. In the impregnation of the calcined product, Compound (D) is used as an aqueous solution; that is, the calcined product is impregnated with an aqueous solution of Compound (D). After the process of impregnation, the resulting mixture should be calcined again. This calcination is usually performed at a temperature of from 100 to 5000C. Although the composition of the thus-calcined product varies with the amounts of Compounds (A), (B), (C) and (D) being added, it is necessary for the molar ratio of (A) to (B) to (C) to (D) (calculated as oxide) to be controlled so that 0.05 < (A) < 0.7, 0.01 < (B) < 0.7, 0.01 < (C) < 0.7, and 0.005 < (D) < 0.3. The calcined product is then reduced. This reduction is sufficient to be performed at a temperature of from 200 to 4000C by the use of a reducing atmosphere, for example, in the presence of hydrogen or carbon monoxide. The thus-prepared solid substance is used as the catalyst of the invention. Although Compounds (A), (B), (C) and (D) can be mixed and calcined simultaneously, Compound (D) of alkali or alkaline earth metal compound is dispersed only insufficiently and unevenly in the final product by such a procedure. Hence this procedure fails to produce the desired catalyst. In the process of the invention, the solid substance as prepared above is used as a catalyst, and synthesis gas, i.e., a mixed gas of hydrogen and carbon monoxide, is contacted with the catalyst to produce a mixed alcohol. The composition of the synthesis gas to be used as a feed in the process of the invention is not critical. In general, however, it is preferred to use synthesis gas in which the molar ratio of hydrogen to carbon monoxide is within the range of from 1:3 to 3:1. Other reaction conditions for the process of the invention are not critical and can be determined appropriately. The reaction temperature is usually from 200 to 5500C and preferably from 240 to 4500C; the reaction pressure may be relatively low, in general, ranges between 20 and 200 kilograms per square centimeter (by gauge) and preferably between 40 and 100 kilograms per square centimeter (by gauge); and the gas hourly space velocity (GHSV) is from 500 to 100,000 per hour and preferably from 1,000 to 50,000 per hour. The process of the invention as described above produces mixed alcohols comprising methanol and higher alcohols than methanol, such as ethanol, propanol, and butanol, and other compounds such as aldehydes and esters. The selectivity of the mixed alcohol is high in the process of the invention. This is one of the advantages of the present invention. Another advantage is that the costs of equipment and operation, for example, can be greatly reduced, since the reaction pressure in the process of the invention is sufficient to be relatively low. Furthermore the proportion of alcohols other than methanol in the mixed alcohol as produced by the process of the invention is relatively high, and thus the mixed alcohol is suitable for use as an alcohol component to be compounded to gasoline. The present invention is described in greater detail with reference to the following examples. EXAMPLE 1 An aqueous solution(Aqueous Solution I) (2.5 liters) containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 59.5 grams of zinc nitrate (6 hydrate) was prepared and heated to 600C. Separately 2.5 liters of an aqueous solution (Aqueous Solution II) containing 81.3 grams of sodium carbonate (anhydrous) was prepared and heated to 600C. These aqueous solutions were mixed rapidly and, after completion of precipitation, aged. Then the resulting mixture was filtered, and the pricipitate thus obtained was washed sufficiently with water, dried at 1200C for about 12 hours and then calcined at 4500C for 2 hours. The thus-calcined product was impregnated with an aqueous solution (Aqueous Solution III) containing 6.8 grams of sodium carbonate (anhydrous) and dried at 1200C for about 12 hours. Then graphite was added, and the resulting-mixture was pelletized and pulverized to produce 16-32 mesh grains. The thus-prepared catalyst precursor had a composition of Cu:Ni:Zn:Na=0.36:0.18: 0.36:0.10 (molar ratio). Then 1 milliliter of the catalyst precursor was packed in a reaction tube of stainless steel. While passing a 1:9 (molar ratio) mixture of carbon monoxide and nitrogen as a reducing gas through the reaction tube at a gas hourly space velocity (GHSV) of 4,000 per hour, the catalyst precursor was gradually heated and reduced at 2400C for 5-20 hours to produce a catalyst. A synthesis gas (carbon monoxide:hydrogen=l:2 (molar ratio)) was introduced into the reaction tube at a gas hourly space velocity (GHSV) of 4,000 per hour. The pressure was gradually increased to 50 kilograms per square centimeter (by gauge). Then the temperature was increased to a reaction temperature at which the conversion of carbon monoxide (excluding the one converted into carbon dioxide) reached about 20%. The reaction products were passed through a tube maintained at 2000C, without being condensed at the outlet of the reaction tube, and introduced into a gas chromatography instrument where they were analyzed. The column filler as used in this gas chromatography analysis was a mixture of activated carbon, Porapak-Q (produced by Water Co.) and Porapak R (produced by Water Co.). The results are shown in Table 1. EXAMPLE 2 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate),29.1 grams of nickel nitrate (6 hydrate), and 75.0 grams of aluminum nitrate (9 hydrate) was used as Aqueous Solution I and 2.5 liters of an aqueous solution containing 90.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Al:Na=0.36:0.18:0.36:0.l0 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 3 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 75.0 grams of aluminum nitrate (9 hydrate) was used as Aqueous Solution I, 2.5 liters of an aqueous solution containing 90.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and an aqueous solution containing 13.7 grams of magnesium acetate (4 hydrate) as Aqueous Solution III for the process of impregnation. This catalyst precursor had a composition of Cu:Ni:Al:SIg= 0.36:0.18:0.36:0.10 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 4 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 79.9 grams of gallium nitrate (8 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 91.6 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Ga:Na=0. 36:0.18:0.36:0.10 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 5 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate) and 29.1 grams of nickel nitrate (6 hydrate) was used as Aqueous- Solution I, and 2.5 liters of an aqueous solution containing 61.7 grams of water glass (SiO2 content: 28.6% by weight) and 37.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Si:Na=0.36:0.18:0. 36:0.10 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thusprepared catalysttthe-productionof mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 6 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 64.4 grams of zirconium oxychloride (8 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 63.7 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Zr:Na=0.36:0.l8:0.36: 0.10 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thusprepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 7 An aqueous solution (2.5 liters) containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 161.1 grams of titanium sulfate (Ti(SO4)2 content: 29.8% by weight) was prepared and heated to 600C. Separately 2.5 liters of an aqueous solution containing 128.0 grams of sodium carbonate (anhydrous) was prepared and heated to 600C. These aqueous solutions were mixed rapidly and, after completion of precipitation, aged. The resulting mixture was filtered, and the precipitate thus obtained was treated with an aqueous solution of sodium chloride (concentration: 0.5 mole per liter) and further washed sufficiently with water. Thereafter the same procedure as in Example 1 was performed to form a catalyst precursor. This catalyst precursor had a composition of Cu:Ni:Ti:Na=0.36:0.18:0.36: 0.10 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thusprepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner. as in Example 1. The results are shown in Table 1. EXAMPLE 8 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 80.0 grams of chromium nitrate was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 90.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Cr:Na=0.38:0.19:0.31:0.12 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thusprepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 9 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 86.6 grams of lanthanum nitrate (6 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 74.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:La:Na=0.36:0.18:0.36:0.10 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 10 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 86.6 grams of lanthanum nitrate (6 hydrate) was used as Aqueous Solution I, 2.5 liters of an aqueous solution containing 74.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and an aqueous solution containing 13.7 grams of magnesium acetate (4 hydrate) as Aqueous Solution III for the process of impregnation. This catalyst precursor had a composition of Cu:Ni:La:Mg=0.36:0.18:0.36.0.10 (molar ratio). The ata1yst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1. EXAMPLE 11 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 25.6 grams of magnesium nitrate (6 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 50.3 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Mg:Na=0.43:0.22:0.22:0.13 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed.in the same manner as in Example 1. The results are shown in Table 1. Table 1 Reaction Conversion Selectivity Composition of Mixed Alcohol (% by weight) Example Temperature of Carbon of Alcohol*ê Butanol and ( C) Monoxide*1 (%) Methanol Ethanol Propanol Higher Alcohols (%) than Butanol 1 311 20 70 88 8 3 1 2 305 22 55 55 29 8 8 3 315 21 68 89 8 2 1 4 307 19 53 58 27 8 7 5 312 21 52 53 28 11 8 6 333 21 43 82 10 4 4 7 307 19 46 45 37 10 8 8 335 20 69 87 9 3 1 9 331 20 55 77 15 1 1 10 334 19 52 78 14 6 2 11 319 21 47 57 30 8 5 Note: : *1 Conversion of Carbon Monoxide= Amount of Carbon Monoxide Converted - Amount of Carbon Dioxide into Alcohol (moles) Formed (moles) # 100 Amount of Carbon Monoxide Introduced (moles) *2 Selectivity of Alcohol= Amount of Carbon Monoxide Converted into Alcohol (moles) # 100 Amount of Carbon Monoxide Amount of Carbon Dioxide Converted (moles) Formed (moles) EXAMPLE 12 An aqueous solution (Aqueous Solution I) (1.5 liters) containing 24.2 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate (Ti(SO4)2 content: 29.8% by weight) was prepared and heated to 600C. Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 600C. These aqueous solutions were mixed rapidly and, after completion of precipitation, aged. The resulting mixture was filtered, and the thus-obtained precipitate was treated with an aqueous sodium chloride solution (concentration: 0.5 mole per liter) and washed sufficiently with water. The precipitate was dried at 1200C for about l2-hours and then calcined at 4500C for 2 hours. The thus-calcined product was impregnated with 38 milliliters of an aqueous solutiqn (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter), and dried at 1200C for about 12 hours. Then graphite was added, and the resulting mixture was pelletized and pul verized. to form 16-32 mesh grains. The thus-prepared catalyst precursor had a composition of Cu:Ni:Ti:Na= 1:1:1:0.38 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thusprepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 The results are shown in Table 2. EXAMPLE 13 A catalyst precursor was prepared in the same manner as in Example 12 except that 1.5 liters of an aqueous solution containing 16.1 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 106.7 grams of titanium sulfate (the same as used in Example 12) was used as Aqueous Solution I, and 1.5 liters of an aqueous solution containing 79.5 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Ti:Na= 2:3:4:1.15 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2. EXAMPLE 14 A catalyst precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous solution containing 24.1 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 28.7 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=1:1:1:0.38 (molar ratio). The¯catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2. EXAMPLE 15 A catalyst precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous solution containing 14.5 grams of copper nitrate (3 hydrate), 8.7 grams of nickel nitrate (6 hydrate), and 60.3 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=2:l:7:l.28 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the thusprepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2. EXAMPLE 16 A catalyst precursor was prepared In the same manner as in Example 1 except that 1.5 liters of an aqueous solution containing 50.7 grams of copper nitrate (3 hydrate), 8.7 grams of nickel nitrate (6 hydrate), and 17.2 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=7:l:2:l.28 (molar ratio). The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the thusprepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2. Table 2 Reaction Conversion Composition of Mixed Alcohol (% by weight) Exemple Temperature of Carbon Selectivity Butanol and ( C) Monoxide*1 of Alcohol*2 Methanol Ethanol Propanol Higher Alcohols (%) (%) than Butanol 12 318 21 51 31 41 13 15 13 308 20 50 33 39 12 16 14 251 19 62 43 49 6 2 15 284 20 80 56 33 1 10 16 256 20 64 45 48 2 5 Note: *1, *2 Same as in Table 1. EXAMPLE 17 An aqueous solution t2.5 liters) containing 59.5 grams of zinc nitrate (6 hydrate), 29.1 grams of cobalt nitrate ±6 hydrate), and 25.6 grams of magnesium nitrate was prepared and heated to 600C. Separately 2.5 liters of-an aqueous solution containing 88.3 grams of sodium carbonate (anhydrous) as a co-precipitating agent was prepared and heated to 600C. These aqueous solutions were mixed rapidly and, after completion of precipitation, aged. Then the resulting mixture was filtered, and the precipitate thus obtained was washed sufficiently with water. The thus-obtained co-precipitate was dried at 1200C for about 12 hours and then calcined at 4500C for 2 hours The thus-calcined product was impregnated with an aqueous solution containing 3.4 grams of sodium carbonate (anhydrous) and then dried at 1200C for about 12 hours. Then graphite was added, and the resulting mixture was pelletized and pulverized to form 16-32 mesh grains. This catalyst precursor had a composition of Zn:Co:Mg:Na= 0.43:0.22:0.22:0.13 (molar ratio). Then 1 milliliter of the catalyst precursor was packed in a reaction tube of stainless steel. While passing a 1:9 (molar ratio) mixture of carbon monoxide and nitrbgen as a reducing gas through the reaction tube at a gas hourly space velocity (GHSV) of 4,000 per hour, the catalyst precursor was gradually heated and reduced at 2400C for 12 hours to produce a catalyst. A synthesis gas (carbon monoxide:hydrogen=1:2 (molar ratio)) was introduced into the reaction tube at a gas hourly space velocity (GHSV) of 4,000 per hour. The pressure was increased to 50 kilograms per square centimeter (by gauge). Then the temperature was increased to a reaction temperature at which the conversion of carbon monoxide (excluding the one converted into carbon dioxide) reached about 20%. The reaction products were introduced, without being condensed at the outlet of the reaction tube, through a tube maintained at 2000C into a gas chromatography instrument where they were analyzed. The column filler as used in this gas chromatography analysis was a mixture of activated carbon, Porapak-Q (produced by Water Co.), and Porapak-N (produced by Water Co.). The results are shown in Table 3. EXAMPLE 18 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 90.2 grams (co-precipitating agent) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor: Zn:Co:Al:Na=0. 36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 19 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams spdium carbonate (anhydrous) 90.2 grams (for co-precipitation) magnesium acetate (4 hydrate) 13.7 grams Composition of catalyst precursor: Zn:Co:Al:Mg=0.36:0.l8:0.36:0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 20 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: Zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams gallium nitrate (8 hydrate) 79.9 grams sodium carbonate (anhydrous) 89.2 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor: Zn:Co:Ga:Na=0.36:0.18:0.36:0.10 (molar ratio) The'.results are shown in Table 3. EXAMPLE 21 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams water glass (SiO2 content: 61.7 grams 28.6% by weight) sodium carbonate (anhydrous) 35.3 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor: Zn:Co:Si:Na=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 22 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 63.8 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor: Zn:Co:Zr:K=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 23 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams chromium nitrate (9 hydrate) 80.0 grams sodium carbonate (anhydrous) 92.5 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor: Zn:Co:Cr:Na=0.36: 0.18:0.36:0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 24 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams lanthanum nitrate (6 hydrate) 86.6 grams sodium carbonate (anhydrous) 74.2 grams (for co-precipitation) magnesium acetate (4 hydrate) 13.7 grams Compqsition of catalyst precursor: Zn:Co:La:Mg=0.36:0.18:0.36:0.10 (molar ratio) results are shown in Table 3. EXAMPLE 25 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 81.3 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor: Zn:Ni:Al:Na=0.36:0.18:0.36: 0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 26 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 70.7 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor: Zn:Ni: Zr:Na=0. 36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 27 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams Aqueous titanium sulfate 161.1 grams solution (Ti(SO4)2 content: 29.8% by weight) sodium carbonate (anhydrous) 133.0 grams (for co-precipitation) (After co-precipitation followed by filtration, the resulting co-precipitate was washed with water and further with an aqueous solution of NaCl (0.5 mole per liter) to remove S042-). sodium carbonate (anhydrous) 4.2 grams -(for impregnation) Composition of catalyst precursor: Zn:Ni:Ti:Na=0.34:0.17:0.34:0.15 (molar ratio) The results are shown in Table 3. EXAMPLE 28 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams iron¯nitrate (9 hydrate) 40.4 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 93.4 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor: Zn:Fe:Al:Na=0.36:0.l8:0.36: 0.10 (molar ratio) The results are shown in Table 3. EXAMPLE 29 The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds: zinc nitrate (6 hydrate) 59.5 grams iron nitrate (9 hydrate) 40.4 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 89.3 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor: Zn:Fe:Zr:Na=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3. Table 3 Composition of Reaction Conversion of Selectivity Composition of Mixed Alcohol Example Catalyst Precursor Temperature Carbon Monoxide*1 of Alcohol*2 (% by weight) (molar ratio) ( C) (%) (%) Butanol and Metha- Etha- Propa- Higher Alcohols nol nol nol than butan 17 Zn.C0O.5.Mg.NaO.3 288 20 47 54 28 10 8 18 Zn.C0O.5.Al.NaO.3 310 20 56 50 31 11 8 19 Zn.C0O.5.Al.MgO.3 334 19 53 70 22 5 3 20 Zn.C0O.5.Ga.NaO.3 312 21 54 52 30 11 7 21 Zn.C0O.5.Si.NaO.3 320 22 50 51 29 12 8 22 Zn.C0O.5.Zr.KO.3 288 20 42 45 31 11 3 23 Zn.C0O.5.Cr.NaO.3 335 20 62 72 20 6 2 24 Zn.C0O.5.La.MgO.3 306 20 41 45 28 18 9 25 Zn.NiO.5.Al.KO.3 388 18 58 46 19 28 7 26 Zn.NiO.5.Zr.KO.3 367 19 64 50 25 20 5 27 Zn.NiO.5.Ti.NaO.3 360 21 65 75 14 8 3 28 Zn.FeO.5.Al.NaO.3 280 22 49 49 31 12 8 29 Zn.FeO.5.Zr.NaO.3 282 21 48 45 34 13 8 Note: *1, *2 Same as in Table 1. EXAMPLE 30 One and half liters of an aqueous solution (Aqueous Solution I) containing 24.2 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate solution (Ti(SO4)2 content: 30% by weight) was prepared and heated to 600C. Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 900C. These aqueous solutions I and II were mixed rapidly and maintained at 850C for about 2 hours with stirring vigorously to be precipitated. The pH of the above described solution was 9.2. Then the solution containing the precipitate was filtered, and the thus obtained precipitate was washed with water in 200 fold amount of the precipitate. The precipitate was dried at 1200C for about 10 hours and then was calcined at 4500C for 2 hours. The thus calcined product was cooled to a room temperature, and then the product was impregnated with 19.2 milliliters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter) in the water bath heated at 900C and evaporated to dryness. The thus-obtained product was dried at 1200C for about 5 hours. Then graphite of 2% by weight based on the product was added thereto, and the resulting mixture was pelletized (catalyst precursor). Sulfur content in the thus prepared catalyst precursor is 0.2% by weight. The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centimeter (by gauge). The results are shown in Table 4. EXAMPLE 31 A A catalyst precursor was prepared in the same manner as in Example 30 except that 1.5 liters of an aqueous solution containing 199.0 grams of sodium carbonate (anhydrous) was used as Aqueous Solution II and the pH of the above described solution was 9.9. Sulfur content in the thus-prepared catalyst precursor was 0.1E by weight. The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centimeter (by gauge). The results are shown in Table 4. EXAMPLE 32 One and half liters of an aqueous solution (Aqueous Solution I) containing 24.2 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate solution (Ti(SO4)2 content: 30% by weight) was prepared and heated to 600C. Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 900C. These aqueous solutions I and II were mixed rapidly and maintained at 850C for about 2 hours with stirring vigourously to be precipitated. The pH of the above described solution was 9.3. Then the solution containing the precipitate was filtered, and thus obtained precipitate was washed with water in 200 fold amount of the precipitate. The precipitate was sufficiently suspended in 2 liters of an aqueous solution (800C) of sodium chrolide (concentration: 0.5 mole per liter), and was separated by filtration. Then the precipitate was washed again with water in 200 fold amount of the precipitate. The precipitate was dried at 1200C for about 10 hours and then calcined at 4500C for 2 hours. The thuscalcined product was cooled to a room temperature, and then the product was impregnated with 19.2 milliliters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter) in the water bath heated at 900C and evaporated to dryness. The thus-obtained product was dried at 1200C for about 5 hours. Then graphite of 28 by.weight based on the product was added thereto, and the resulting mixture was pelletized (catalyst precursor). Sulfur content in the thus-prepared catalyst precursor is 0.2% by weight.- The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centimeter (by gauge). The-results are shown in Table 4. EXAMPLE 33 A catalyst precursor was prepared in the same manner as in Example 32 except that 1.5 liters of an aqueous solution containing 153.0 grams of sodium carbonate (anhydrous) was used as Aqueous Solution II and the pH-of the above solution was 8.0. Sulfur content in the thus-prepared catalyst precursor was 0.5% by weight. The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centimeter (by gauge). The results are shown in Table 4. Table 4 Reaction Conversion Selectivy Composition of Oxygen-containing compounds formed (% by weight) Exemple Temper- of Carbon of Oxygen- Buthanol ature Monoxide*1 containing Methanol Etanol Propanol and Higher Dimethyl Acetal- Methyl ( C) (%) Compounds*2 Alcohols ether dehye Acetone ethyl (%) than Buthanol ketone 30 297 19 58 56 31 4 4 1 2 2 1 31 297 19 65 57 23 11 6 1 1 0 1 32 307 20 54 55 33 5 4 0 1 2 1 33 307 19 53 59 24 12 3 0 0 2 0 Note: : *1 Conversion of Carbon Monoxide= Amount of Carbon Monoxide Converted Amount of Carbon Dioxide into Alcohol (moles) - Formed (moles) x100/ Amount of Carbon Monoxide Introduced (moles) *2 Selectivy of Oxygen-containing Compounds= Amount of Carbon Monoxide Converted into Oxygen-containing Compounds (moles) x100/ Amount of Carbon Monoxide Amount of Carbon Dioxide Converted (moles) - Formed (moles)

Claims: WHAT IS CLAIMED IS: 1. A process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by: calcining a mixture of (A1) a copper compound, (B1) a nickel compound, and (C) a compound of at least one metal selected from the metals belonging to Groups II, III and IV and the fourth period of Groups V, VI and VII of the Periodic Table; impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound; calcining the resulting mixture; and reducing the thus-calcined product. 2. The process for the production of mixed alcohols as claimed in Claim 1, wherein the Compound (C) is a compound of at least one metal selected from the groups consisting of magnesium, zinc,altinum, gallium, lanthanum, silicon, titanium, zirconium, chromium and manganese. 3. The process for the production of mixed alcohols as claimed in Claim 1, wherein the Compound (D) is sodium compound or magnesium compound. 4. A process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by: calcining a mixture of (A2) a zinc compound, (B2) a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II, III and IV and the fourth period of Groups V, VI and VII of the Periodic Table; impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound; calcining the resulting mixture; and reducing the thus-calcined product. 5. The process for the production of mixed alcohols as claimed in Claim 4, wherein the Compound (C). is a compound of at least one metal selected from the groups consisting of magnesium, fluminum, gallium, lanthanum, silicon, titanium, zirconium, chromium and manganese. 6. The process for the production of mixed alcohols as claimed in Claim 4, wherein the Compound (D) is a compound of at least one metal selected from the groups consisting of sodium, magnesium and potassium.

Inventors: AOKI, YOSHINOBU, SHIBATA, MASATOSHI, UCHIYAMA, SOICHI, UCHIYAMA, TSUTOMU
Applicants: RESEARCH ASSOCIATION FOR PETROLEUM ALTERNATIVES DEVELOPMENT
Application year: 1983
Main classification: C07C29
IPC codes: B01J23, C07C29