Abstract:
A catalyst for producing phenols consists essentially of; 
     an iron oxide; 
     a nickel oxide; 
     at least one first oxide selected from the group consisting of a vanadium oxide and a molybdenum oxide; and 
     at least one second oxide selected from the group consisting of an alkali metal oxide and an alkaline earth metal oxide. 
     The catalyst is used to produce phenols from benzoic acid or an alkyl benzoic acid.

Description:
This application is a Division of application Ser. No. 08/274,970, filed Jul. 14, 1994, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a catalyst for producing phenol or alkyl phenol and to a method for producing phenol or alkyl phenol by gas phase oxidation of benzoic acid or alkyl benzoic acid under the presence of the catalyst. 
     2. Description of the Related Art 
     Various methods and catalysts are known to produce phenol by gas phase contact oxidation of benzoic acid. 
     For example, JP-A-57-11932 (the term JP-A- referred to hereinafter signifies unexamined Japanese patent publication) disclosed a catalyst containing at least one of a copper compound, a vanadium compound, a silver compound, a lithium compound, a sodium compound, and a magnesium compound, and a method using the catalyst. 
     JP-B-59-20384 (the term JP-B- referred to hereinafter signifies examined Japanese patent publication) disclosed a method using a catalyst containing oxides of copper, zirconium, and alkali metal and being supported on α-alumina. JP-B-64-934 disclosed a method using an oxide catalyst containing a variety of metallic elements: namely, molybdenum as the essential component, at least one of vanadium, niobium, and tantalum, and at least one of copper, silver, manganese, iron, cobalt, nickel, rhodium, palladium, and platinum, and at least one of thallium, an alkali metal, and an alkaline earth metal. 
     The inventors conducted extensive study on the catalyst for phenol production and on the method for producing phenol, and provided the catalysts to produce phenol by gas phase contact oxidation of benzoic acid, which catalysts include the catalyst of a nickel compound supported on a metallic oxide such as titania, magnesia, and α-alumina (JP-A-4-5250), the catalyst containing an iron oxide and a nickel oxide (JP-A-4-330944), the catalyst containing an iron oxide, a nickel oxide, and an alkali earth metal compound (JP-A-4-330945), the catalyst containing an iron oxide, a nickel oxide, and an alkali metal compound (JP-A-4-104837), the catalyst containing an iron oxide, a nickel oxide, an alkali metal compound, and an alkaline earth metal compound (JP-A-4-330946), and the catalyst containing a composite metallic oxide having a spinel crystal structure. 
     Furthermore, the inventors provided a catalyst to produce phenol by gas phase oxidation of toluene, which catalyst contains a vanadium oxide, an iron oxide, and a nickel oxide (JP-A-4-277029). 
     However, the catalyst disclosed in JP-A-57-11932 is insufficient in both activity and selectivity, and the method for producing phenol using the catalyst gives the conversion of benzoic acid of 50.5% and the selectivity to phenol of 88.6% at the maximum. In addition, when an exothermic reaction such as oxidation of benzoic acid is carried out using a catalyst containing a copper compound, the catalyst bed likely induces hot spots which raises a problem of sintering of the catalyst and of significant degradation of the activity. The method for producing phenol disclosed in JP-B-59-20384 also shows an insufficient conversion and selectivity giving the conversion of benzoic acid of 63.7% and the selectivity to phenol of 82.2% at the maximum. Furthermore, the method induces the yield of a large amount of by-products such as diphenyl oxide, which significantly degrades the catalyst activity. The method also has an industrial disadvantage of necessity of refining stage for produced phenol. 
     The method for producing phenol disclosed in JP-B-64-934 also gives the conversion of benzoic acid of 75% and the selectivity to phenol of 89% at the maximum, which values are insufficient for industrial application. The method also has a problem of catalyst degradation with time. 
     All the three of above described methods gives a low space time yield of phenol (production amount of phenol per unit catalyst volume per unit time) not higher than 100, so the productivity is poor, and the methods are inapplicable to industrial process. 
     Regarding the production of cresol from toluic acid, which was disclosed in JP-B-64-934, the catalyst activity and the selectivity are insufficient giving the conversion of 45% and selectivity to m-cresol of 81% for the reaction of p-toluic acid (4-methyl benzoic acid), and gives the conversion of 48% and the selectivity to m-cresol of 79% for the reaction of o-toluic acid (2-methyl benzoic acid). M. Hronec, et al. pointed out a difficulty for obtaining a high yield of cresol species in the reaction system using a catalyst containing Cu owing to the unstable intermediate reaction products (Applied Catalysis, 69 (1991) pp201-204). In addition, the method has the problem of significant degradation of catalyst activity and of low space time yield, which is similar to the problem in the case of synthesis of phenol from benzoic acid. 
     The catalysts which were presented by the inventors improved the above described problems and improved the conversion of benzoic acid and the selectivity to phenol. Nevertheless, the development of catalysts which further improve the catalyst life and which are applicable to other reaction systems such as the ones to obtain alkyl phenol such as cresol from alkyl benzoic acid at a high yield have been wanted. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide a catalyst which gives a high conversion of benzoic acid and alkyl benzoic acid and a high selectivity to phenol and alkyl phenol for a long period with a high space time yield, and to provide a method for producing phenol and alkyl phenol using the catalyst. 
     The present invention provides a catalyst for producing phenols consisting essentially of; 
     an iron oxide; 
     a nickel oxide; 
     at least one first oxide selected from the group consisting of a vanadium oxide and a molybdenum oxide; and 
     at least one second oxide selected from the group consisting of an alkali metal oxide and an alkaline earth metal oxide. 
     Further, the present invention provides a method for producing phenols using a catalyst from a benzoic acid or an alkyl benzoic acid, the catalyst consisting essentially of; 
     an iron oxide; 
     a nickel oxide; 
     at least one first oxide selected from the group consisting of a vanadium oxide and a molybdenum oxide; and 
     at least one second oxide selected from the group consisting of an alkali metal oxide and an alkaline earth metal oxide. 
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The ratio of nickel oxide to iron oxide (NiO/Fe 2  O 3 ) in the catalyst is preferably in an approximate range of from 0.1 to 10.0 by weight, and most preferably from 0.3 to 5. When the ratio exceeds approximately 10.0 by weight, the yield of CO and CO 2  generated by complete combustion increases, and the selectivity to phenol or alkyl phenol decreases. When the ratio is lower than approximately 0.1, the yield of benzene or alkyl benzene becomes predominant, and the selectivity to phenol or alkyl phenol decreases. 
     The vanadium oxide is preferably vanadium pentoxide (V 2  O 5 ), and may include vanadium monoxide (VO), vanadium trioxide (V 2  O 3 ) and/or di-vanadium tetroxide (V 2  O 4 ). 
     A preferable range of vanadium oxide content is approximately from 0.1 to 10 wt. %, most preferably from 0.5 to 5 wt. %. When the content of vanadium oxide is less than 0.1 wt. %, the selectivity to phenol or alkyl phenol significantly degrades with time. When the content of vanadium oxide is above 10 wt. %, the yield of CO and CO 2  generated by complete combustion increases. 
     The molybdenum oxide is preferably molybdenum trioxide (MoO 3 ), and may include molybdenum dioxide (MnO 2 ). 
     A preferable range of molybdenum oxide content is from 0.1 to 10 wt. %, most preferably from 0.5 to 5 wt. %. When the content of molybdenum oxide is less than 0.1 wt. %, the selectivity to phenol or alkyl phenol significantly degrades with time. When the content of molybdenum oxide is above 10 wt. %, the yield of CO and CO 2  generated by complete combustion increases. 
     Presence of either one of the vanadium oxide or the molybdenum oxide is sufficient, and the sum of the content of these two oxides in a range of from 0.1 to 10 wt. % offers a satisfactory catalyst performance. Most preferable range of content of the sum of these oxides is from 0.5 to 5 wt. %. When the content of the sum of these oxides is less than 0.1 wt. %, the selectivity to phenol or alkyl phenol significantly degrades with time. When the content is above 10 wt. %, the yield of CO and CO 2  generated by complete combustion increases. 
     Alkali metal oxide includes Li 2  O, Na 2  O, K 2  O, Rb 2  O, Cs 2  O. Among them, the oxides of sodium and potassium are preferred because they yield less CO and CO 2  and give higher conversion of benzoic acid and alkyl benzoic acid. 
     A preferable range of alkali metal oxide content is approximately from 0.05 to 30 wt. %, most preferably from 0.05 to 10 wt. %. When the content of alkali metal oxide is less than 0.05 wt. %, the yield of CO and CO 2  increases and the selectivity to phenol or alkyl phenol significantly degrades. When the content of alkali metal oxide is above 10 wt. %, the conversion of benzoic acid and alkyl benzoic acid degrades. 
     Alkaline earth metal oxide includes MgO, CaO, SrO, BaO. Among them, the oxides of calcium are preferred because they yield less benzene and alkyl benzene and give higher conversion of benzoic acid and alkyl benzoic acid. 
     A preferable range of alkaline earth metal oxide content is approximately from 0.05 to 30 wt. %, most preferably from 0.05 to 10 wt. %. When the content of alkaline earth metal oxide is less than approximately 0.05 wt. %, the yield of CO and CO 2  increases and the selectivity to phenol or alkyl phenol degrades. When the content of alkaline earth metal oxide is above 30 wt. %, the conversion of benzoic acid and alkyl benzoic acid degrades, and the yield of benzene and alkyl benzene increases, and the selectivity to phenol and alkyl phenol degrades. 
     Presence of either one of the alkaline metal oxide or the alkali earth metal oxide is sufficient, or of both of them may be acceptable. The sum of the content of these two oxides in a range of from 0.05 to 30 wt. % is sufficient. 
     The catalyst of the present invention may contain various compounds, and it may be supported on a titanium oxide or silica support. 
     The preparation of the catalyst of the present invention may be carried out using a known method applied for that type of catalysts. For example, the applicable raw materials include the nitrate, carbonate, organic salt, halide, hydroxide, and oxide of iron, nickel, vanadium or molybdenum, and alkali metal or alkaline earth metal. The method for mixing the above-described compounds of iron, nickel, vanadium or molybdenum, and alkali metal or alkaline earth metal may be conducted by a known process of precipitation, kneading, or impregnation. For instance, a prepared gel mixture of iron hydroxide and nickel hydroxide is mixed with the compounds of vanadium or molybdenum, and alkali metal or alkaline earth metal, or mixed with their solution, followed by drying and calcining. Otherwise, the kneaded product of iron oxide and nickel oxide may be mixed with the compounds of vanadium or molybdenum, and alkali metal or alkaline earth metal. The mixed and calcined product of iron oxide and nickel oxide may be mixed with the compounds of vanadium or molybdenum, and alkali metal or alkaline earth metal. The mixed and calcined product of iron oxide and nickel oxide may be impregnated with the compound of vanadium or molybdenum, and alkali metal or alkaline earth metal. The iron oxide, nickel oxide, vanadium oxide or molybdenum oxide, and oxide of alkali metal or alkaline earth metal may be powdered to mix, followed by compression molding to form pellets. 
     The catalyst is preferably calcined in air or inert gas during the preparation stage after the mixing of iron oxide and nickel oxide and is crystallized to one or more of iron oxide, nickel oxide, and composite oxide of iron and nickel. Generally, when a catalyst prepared by a known method is further calcined at a temperature of approximately 600° C. or more, the specific surface area reduces and the catalyst activity degrades. However, within a temperature range of from approximately 600 to 900° C., the catalyst of the present invention reduces the specific surface area with the increase of calcining temperature, but the activity for yielding phenol and alkyl phenol increases, and gives a high conversion of benzoic acid and alkyl benzoic acid and a high selectivity to phenol and alkyl phenol. When the calcining temperature is lower than approximately 600° C., only the reaction to yield CO and CO 2  by complete combustion proceeds while generating very little phenol and alkyl phenol, and induces the deposition of carbon materials on the catalyst surface. When the calcining temperature exceeds approximately 900° C., the conversion of benzoic acid and alkyl benzoic acid becomes significantly low, and gives very slight amount of phenol and alkyl phenol generation. 
     The following is the method for producing phenol and alkyl phenol of the present invention. 
     The raw material is benzoic acid or mono-alkyl benzoic acid. The position of alkyl group substitution on mono-alkyl benzoic acid may be either one of ortho-, meta-, or para-position. The alkyl group preferably has 1 to 8 carbons, more preferably 1 to 5, and most preferably around 1 to 3. Examples of the substituted benzoic acid are toluic acid, ethyl benzoic acid, and iso-propylbenzoic acid. 
     According to the method of the present invention, oxygen is supplied along with the raw material benzoic acid or alkyl benzoic acid. The amount of oxygen may be at a theoretical quantity or more to the raw material benzoic acid or alkyl benzoic acid, and preferably in a range of from approximately 0.5 to 50 mole fold to the quantity of raw material. When the supply of oxygen exceeds approximately 50 mole fold, the complete oxidation of the raw material benzoic acid or alkyl benzoic acid is likely to occur. When the supply of oxygen is less than approximately 0.5 mole fold, sufficient conversion of benzoic acid or alkyl benzoic acid can not be attained. 
     The supplied oxygen may be in a form of molecular oxygen. Generally, however, air is used. The air may be diluted with an inert gas. 
     The reaction is usually conducted under the presence of water vapor. The water vapor supply is preferably in a range of from approximately 1 to 100 mole fold to the quantity of raw material benzoic acid or alkyl benzoic acid. When the supply of water vapor exceeds approximately 100 mole fold, the operation becomes uneconomical. When the supply of water vapor is less than approximately 1 mole fold, generally the selectivity of phenol and alkyl phenol decreases. 
     A preferable range of space velocity is in a range of from approximately 100 to 50000 hr -1 . When the space velocity is less than approximately 100 hr -1 , sufficient space time yield can not be obtained. When the space velocity exceeds approximately 50000 hr -1  the conversion of benzoic acid and alkyl benzoic acid decreases. 
     A preferable range of reaction temperature is approximately from 200 to 600° C., most preferably from approximately 300 to 500° C. When the reaction temperature is above approximately 600° C., the selectivity of phenol and alkyl phenol decreases. When the reaction temperature is below approximately 200° C., the conversion of benzoic acid and alkyl benzoic acid decreases. 
     The reaction pressure is not specifically limited if only the supplied raw material maintains gaseous phase under the reaction condition. Nevertheless, the reaction pressure is at atmospheric pressure or at a slightly positive pressure. 
     The method of the present invention may use either one of the fixed bed unit or the fluidized bed unit. 
    
    
     EXAMPLE 
     Example 1 
     Iron nitrate (Fe(NO 3 ) 3 .9H 2  O) 200 g and nickel nitrate (Ni(NO 3 ) 2 .6H 2  O) 144 g were dissolved to ion exchanged water 500 ml. Sodium hydroxide of approximately 100 g was dissolved to ion exchanged water 500 ml. Both solutions were added dropwise to an ion exchanged water 2 liter at room temperature while maintaining the pH in a range of from 7 to 8. After completing the dropwise addition, the resulted solution was agitated for approximately 1 hr. The generated precipitate was filtered and washed. 
     The obtained gel was mixed with aqueous solution 100 ml containing sodium carbonate (Na 2  CO 3 .10H 2  O) 2.24 g, and the mixture was agitated for approximately 1 hr. The gel was dried in air at 120° C. for 24 hrs., followed by calcining in air at 800° C. for 4 hrs. 
     The calcined product was put into an aqueous solution prepared by dissolving ammonium methavanadate (NH 4  VO 3 ) 2 g and oxalic acid ((COOH) 2 ) 4 g. The mixture was evaporated to dry, followed by drying at 120° C. for 24 hrs. and calcining at 500° C. for 3 hrs. to obtain the catalyst. 
     The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:V 2  O 5  =50.3:47.1:0.6:2.0 (by weight). 
     Examples 2-8 
     Catalysts containing several levels of vanadium oxide content were prepared by the same procedure with that in Example 1. The obtained catalysts were used in Examples 111 to 117, and the compositions are listed in Tables 7 and 8. 
     Examples 9-15 
     Catalysts containing several levels of sodium oxide content were prepared by the same procedure with that in Example 1. The obtained catalysts were used in Examples 118 to 124, and the compositions are listed in Tables 9 and 10. 
     Examples 16-20 
     Catalysts containing several levels of vanadium oxide content and sodium oxide content were prepared by the same procedure with that in Example 1. The obtained catalysts were used in Examples 125 to 129, and the compositions are listed in Table 11. 
     Examples 21-26 
     Catalysts containing several levels of composition ratio of Fe 2  O 3  to NiO were prepared by the same procedure with that in Example 1. The obtained catalysts were used in Examples 130 to 135, and the compositions are listed in Tables 12 and 13. 
     Examples 27-31 
     Catalysts were prepared by the same procedure with that in Example 1 except for varying the calcining temperature of Fe 2  O 3  --NiO--Na 2  O before supporting the vanadium component. The obtained catalysts were used in Examples 136 to 140, and the compositions are listed in Table 14. 
     Example 32 
     Iron nitrate (Fe(NO 3 ) 3 .9H 2  O) 200 g and nickel nitrate (Ni(NO 3 ) 2 .6H 2  O) 144 g were dissolved to ion exchanged water 500 ml. Sodium hydroxide of approximately 100 g was dissolved to ion exchanged water 500 ml. Both solutions were added dropwise to an ion exchanged water 2 liter at room temperature while maintaining the pH in a range of from 7 to 8. After completing the dropwise addition, the solution was agitated for approximately 1 hr. The generated precipitate was filtered and washed. 
     The obtained gel was mixed with aqueous solution 100 ml containing sodium carbonate (Na 2  CO 3 .10H 2  O) 3.68 g, and the mixture was agitated for approximately 1 hr. The gel was dried in air at 120° C. for 24 hrs., followed by calcining in air at 800° C. for 4 hrs. 
     The calcined product was put into an aqueous solution prepared by dissolving ammonium molybdate (NH 4 ) 6  Mo 7  O 24 .4H 2  O) 2.93 g. The mixture was evaporated to dry, followed by drying at 120° C. for 24 hrs. and calcining at 500° C. for 3 hrs. to obtain the catalyst. 
     The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:MoO 3  =49.6:46.4:1.0:3.0 (by weight). 
     Examples 33-38 
     Catalysts containing several levels of molybdenum oxide content were prepared by the same procedure with that in Example 32. The obtained catalysts were used in Examples 141 to 147, and the compositions are listed in Tables 15 and 16. 
     Examples 39-45 
     Catalysts containing several levels of sodium oxide content were prepared by the same procedure with that in Example 32. The obtained catalysts were used in Examples 148 to 154, and the compositions are listed in Tables 17 and 18. 
     Examples 46-50 
     Catalysts containing several levels of molybdenum oxide content and sodium oxide content were prepared by the same procedure with that in Example 32. The obtained catalysts were used in Examples 155 to 159, and the compositions are listed in Table 19. 
     Examples 51-56 
     Catalysts containing several levels of composition ratio of Fe 2  O 3  to NiO were prepared by the same procedure with that in Example 32. The obtained catalysts were used in Examples 160 to 165, and the compositions are listed in Tables 20 and 21. 
     Examples 57-61 
     Catalysts were prepared by the same procedure with that in Example 32 except for varying the calcining temperature of Fe 2  O 3  --NiO--Na 2  O before supporting the molybdenum component. The obtained catalysts were used in Examples 166 to 170, and the compositions are listed in Table 22. 
     Example 62 
     Iron nitrate (Fe(NO 3 ) 3 .9H 2  O) 200 g and nickel nitrate (Ni(NO 3 ) 2 .6H 2  O) 144 g were dissolved to ion exchanged water 500 ml. Sodium hydroxide of approximately 100 g was dissolved to ion exchanged water 500 ml. Both solutions were added dropwise to an ion exchanged water 2 liter at room temperature while maintaining the pH in a range of from 7 to 8. After completing the dropwise addition, the solution was agitated for approximately 1 hr. The generated precipitate was filtered and washed. 
     The obtained gel was mixed with aqueous solution 100 ml containing sodium carbonate (Na 2  CO 3 .10H 2  O) 3.70 g, and the mixture was agitated for approximately 1 hr. The gel was dried in air at 120° C. for 24 hrs., followed by calcining in air at 800° C. for 4 hrs. 
     The calcined product was put into an aqueous solution 25 ml prepared by dissolving ammonium methavanadate (NH 4  VO 3 ) 2.06 g and oxalic acid ((COOH) 2 ) 4 g and an aqueous solution 25 ml prepared by dissolving ammonium molybdate (NH 4 ) 6  Mo 7  O 24 .4H 2  O) 1.47 g. The mixture was evaporated to dry, followed by drying at 120° C. for 24 hrs. and calcining at 500° C. for 3 hrs. to obtain the catalyst. 
     The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:V 2  O 5  :MoO 3  =49.3:46.2:1.0:2.0:1.5 (by weight). 
     Examples 63-71 
     Catalysts containing several levels of vanadium oxide content and molybdenum oxide content were prepared by the same procedure with that in Example 69. The obtained catalysts were used in Examples 172 to 180, and the compositions are listed in Tables 23 to 25. 
     Example 72 
     Catalyst containing potassium carbonate (K 2  CO 3 ) 0.71 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 181, and the composition is listed in Table 26. 
     Example 73 
     Catalyst containing lithium carbonate (Li 2  CO 3 ) 1.20 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 182, and the composition is listed in Table 26. 
     Example 74 
     Catalyst containing rubidium carbonate (Rb 2  CO 3 ) 0.60 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 183, and the composition is listed in Table 26. 
     Example 75 
     Catalyst containing cesium carbonate (Cs 2  CO 3 ) 0.56 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 184, and the composition is listed in Table 26. 
     Example 76 
     Iron nitrate (Fe(NO 3 ) 3 .9H 2  O) 200 g and nickel nitrate (Ni(NO 3 ) 2 .6H 2  O) 144 g were dissolved to ion exchanged water 500 ml. Sodium hydroxide of approximately 100 g was dissolved to ion exchanged water 500 ml. Both solutions were added dropwise to an ion exchanged water 2 liter at room temperature while maintaining the pH in a range of from 7 to 8. After completing the dropwise addition, the solution was agitated for approximately 1 hr. The generated precipitate was filtered and washed. 
     The obtained gel was mixed with aqueous solution 100 ml containing sodium carbonate (Na 2  CO 3 .10H 2  O) 3.70 g, and with aqueous solution 25 ml prepared by dissolving ammonium methavanadate (NH 4  VO 3 ) 2.06 g and oxalic acid ((COOH) 2 ) 4 g, and with aqueous solution 25 ml prepared by dissolving ammonium molybdate (NH 4 ) 6  Mo 7  O 24 .4H 2  O) 1.47 g. The mixture was agitated for approximately 1 hr. to obtain a gel. The gel was dried in air at 120° C. for 24 hrs., followed by calcining in air at 800° C. for 4 hrs. to obtain the catalyst. 
     The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:V 2  O 5  :MoO 3  =49.3:46.2:1.0:2.0:1.5 (by weight). 
     Example 77 
     Iron nitrate (Fe(NO 3 ) 3 .9H 2  O) 200 g and nickel nitrate (Ni(NO 3 ) 2 .6H 2  O) 144 g were dissolved to ion exchanged water 500 ml. Sodium hydroxide of approximately 100 g was dissolved to ion exchanged water 500 ml. Both solutions were added dropwise to an ion exchanged water 2 liter at room temperature while maintaining the pH in a range of from 7 to 8. After completing the dropwise addition, the solution was agitated for approximately 1 hr. The generated precipitate was filtered and washed. 
     The obtained gel was mixed with aqueous solution 100 ml containing sodium carbonate (Na 2  CO 3 .10H 2  O) 3.70 g. The mixture was agitated for approximately 1 hr. The gel was dried in air at 120° C. for 24 hrs., followed by calcining in air at 800° C. for 4 hrs. 
     The calcined product was powdered, and was mixed with a vanadium pentoxide powder (V 2  O 5 ) 1.55 g. The mixture was compressed to form into cylindrical catalyst having the radius of 1 mm and the length of 5 mm. 
     The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:V 2  O 5  =50.3:47.1:0.6:2.0 (by weight). 
     Example 78 
     Iron nitrate (Fe(NO 3 ) 3 .9H 2  O) 200 g and nickel nitrate (Ni(NO 3 ) 2 .6H 2  O) 144 g were dissolved to ion exchanged water 500 ml. Sodium hydroxide of approximately 100 g was dissolved to ion exchanged water 500 ml. Both solutions were added dropwise to an ion exchanged water 2 liter at room temperature while maintaining the pH in a range of from 7 to 8. After completing the dropwise addition, the solution was agitated for approximately 1 hr. The generated precipitate was filtered and washed. 
     The obtained gel was dried in air at 120° C. for 24 hrs., followed by calcining in air at 800° C. for 4 hrs. 
     The fired product was put into an aqueous solution 100 ml containing sodium carbonate (Na 2  CO 3 .10H 2  O) 2.24 g. and an aqueous solution 50 ml prepared by dissolving ammonium methavanadate (NH 4  VO 3 ) 2 g and oxalic acid ((COOH) 2 ) 4 g. The mixture was evaporated to dry, followed by drying at 120° C. for 24 hrs. and calcining at 500° C. for 3 hrs. to obtain the catalyst. The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:V 2  O 5  =50.3:47.1:0.6:2.0 (by weight). 
     Example 79 
     Powders of hydroxyl-iron oxide (FeO(OH)) 43.98 g, nickel hydroxide (Ni(OH) 2 ) 45.9 g, sodium carbonate (Na 2  CO 3 .10H 2  O) 3.70 g, and vanadium pentoxide (V 2  O 5 ) 1.55 g were mixed together. The mixture was calcined in air at 800° C. for 4 hrs. The calcined product was compressed to form into cylindrical catalyst having the radius of 1 mm and the length of 5 mm. The catalyst had the composition of Fe 2  O 3  :NiO:Na 2  O:V 2  O 5  =50.3:47.1:0.6:2.0 (by weight). 
     Example 80 
     Catalyst containing magnesium nitrate (Mg(NO 3 ) 2 .6H 2  O) 3.09 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 189, and the composition is listed in Table 28. 
     Example 81 
     Catalyst containing calcium nitrate (Ca(NO 3 ) 2 .4H 2  O) 2.04 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 190, and the composition is listed in Table 28. 
     Example 82 
     Catalyst containing strontium nitrate (Sr(NO 3 ) 2 ) 0.99 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 191, and the composition is listed in Table 28. 
     Example 83 
     Catalyst containing barium nitrate(Ba(NO 3 ) 2 ) 0.83 g instead of sodium carbonate 2.24 g was prepared by the same procedure with that in Example 1. The obtained catalyst was used in Example 192, and the composition is listed in Table 28. 
     Example 84 
     Catalyst containing magnesium nitrate (Mg(NO 3 ) 2 .6H 2  O) 5.08 g instead of sodium carbonate 3.68 g was prepared by the same procedure with that in Example 32. The obtained catalyst was used in Example 193, and the composition is listed in Table 29. 
     Example 85 
     Catalyst containing calcium nitrate (Ca(NO 3 ) 2 .4H 2  O) 3.35 g instead of sodium carbonate 3.68 g was prepared by the same procedure with that in Example 32. The obtained catalyst was used in Example 194, and the composition is listed in Table 29. 
     Example 86 
     Catalyst containing barium nitrate (Ba(NO 3 ) 2 ) 1.36 g instead of sodium carbonate 3.68 g was prepared by the same procedure with that in Example 32. The obtained catalyst was used in Example 195, and the composition is listed in Table 29. 
     Comparative Example 1 
     A catalyst was prepared by the same procedure with that in Example 1 except for not using ammonium methavanadate and oxalic acid. 
     Comparative Example 2 
     A catalyst was prepared in accordance with the Example 1 described in JP-B-64-934. A γ-alumina 30 g was dipped into a solution of ion exchanged water 80 g containing ammonium molybdate 1.73 g, ammonium methavanadate 1.72 g, copper nitrate 4.14 g, 28% aqueous ammonia 75 g, and monoethanol amine 4 g. After heating the mixture at 80° C. for 10 min., the mixture was evaporated to dry in an evaporator under a reduced pressure for 1 hr., followed by calcining at 750° C. for 3 hrs. The obtained catalyst was dipped into an ion exchanged water 20 g containing sodium hydroxide 2.74 g. Then the catalyst was evaporated to dry in an evaporator, followed by calcining at 600° C. for 8 hrs. 
     Comparative Example 3 
     A catalyst was prepared in accordance with the Example 1 described in JP-B-59-20384. Copper sulfate 120 g and zirconium oxynitrate 18 g were dissolved to ion exchanged water 30 g. The mixture was heated to 70 to 80° C. An α-alumina 100 g was dipped into the solution. The solution was dried, and calcined at 750° C. for 2 hrs. The catalyst was dipped into an ion exchanged water 30 g containing potassium hydroxide 4.3 g, followed by drying and by calcining at 500° C. for 16 hrs. 
     II. Reaction Method 
     Each catalyst was pulverized to a specified size, which was then filled into a quartz tube having an inside diameter of 20 mm. to a specified quantity. A predetermined amount of benzoic acid, steam, and air were introduced to the tube to react them at a specified temperature. 
     III. Condition and Result of Reaction 
     Examples 87-90 
     The catalyst of Example 1 was used under various reaction temperature levels. The condition and result of the reaction are summarized in Table 1. 
     Examples 91-98 
     The catalyst of Example 1 was used under various Space Velocity. The condition and result of the reaction are summarized in Tables 2 and 3. 
     Examples 99-102 
     The catalyst of Example 1 was used under various air concentrations. The condition and result of the reaction are summarized in Table 4. 
     Examples 103-106 
     The catalyst of Example 1 was used under various steam quantities. The condition and result of the reaction are summarized in Table 5. 
     Examples 107-110 
     The catalyst of Example 1 was used under various raw materials. The condition and result of the reaction are summarized in Table 6. 
     Examples 111-114 
     Catalysts of Examples 2 through 5 were used. The condition and result of reaction are summarized in Table 7. 
     Examples 115-117 
     Catalysts of Examples 6 through 8 were used. The condition and result of reaction are summarized in Table 8. 
     Examples 118-121 
     Catalysts of Examples 9 through 12 were used. The condition and result of reaction are summarized in Table 9. 
     Examples 122-124 
     Catalysts of Examples 13 through 15 were used. The condition and result of reaction are summarized in Table 10. 
     Examples 125-129 
     Catalysts of Examples 16 through 20 were used. The condition and result of reaction are summarized in Table 11. 
     Examples 130-133 
     Catalysts of Examples 21 through 24 were used. The condition and result of reaction are summarized in Table 12. 
     Examples 134-135 
     Catalysts of Examples 25 and 26 were used. The condition and result of reaction are summarized in Table 13. 
     Examples 136-140 
     Catalysts of Examples 27 through 31 were used. The condition and result of reaction are summarized in Table 14. 
     Examples 141-144 
     Catalysts of Examples 32 through 35 were used. The condition and result of reaction are summarized in Table 15. 
     Examples 145-147 
     Catalysts of Examples 36 through 38 were used. The condition and result of reaction are summarized in Table 16. 
     Examples 148-151 
     Catalysts of Examples 39 through 42 were used. The condition and result of reaction are summarized in Table 17. 
     Examples 152-154 
     Catalysts of Examples 43 through 45 were used. The condition and result of reaction are summarized in Table 18. 
     Examples 155-159 
     Catalysts of Examples 46 through 50 were used. The condition and result of reaction are summarized in Table 19. 
     Examples 160-163 
     Catalysts of Examples 51 through 54 were used. The condition and result of reaction are summarized in Table 20. 
     Examples 164-165 
     Catalysts of Examples 55 and 56 were used. The condition and result of reaction are summarized in Table 21. 
     Examples 166-170 
     Catalysts of Examples 57 through 61 were used. The condition and result of reaction are summarized in Table 22. 
     Examples 171-174 
     Catalysts of Examples 62 through 65 were used. The condition and result of reaction are summarized in Table 23. 
     Examples 175-178 
     Catalysts of Examples 66 through 69 were used. The condition and result of reaction are summarized in Table 24. 
     Examples 179-180 
     Catalysts of Examples 70 and 71 were used. The condition and result of reaction are summarized in Table 25. 
     Examples 181-184 
     Catalysts of Examples 72 through 75 were used. The condition and result of reaction are summarized in Table 26. 
     Examples 185-188 
     Catalysts of Examples 76 through 79 were used. The condition and result of reaction are summarized in Table 27. 
     Examples 189-192 
     Catalysts of Examples 80 through 83 were used. The condition and result of reaction are summarized in Table 28. 
     Examples 193-195 
     Catalysts of Examples 84 through 86 were used with o-toluic acid as the raw material. The condition and result of reaction are summarized in Table 29. 
     Comparative Examples 4-6 
     Catalysts of Comparative Examples 1 through 3 were used. The condition and result of reaction are summarized in Table 30. 
     Example 196 and Comparative Examples 7 and 8 
     Catalysts of Example 62, Comparative Examples 2 and 3 were used with o-toluic acid as the raw material. The condition and result of reaction are summarized in Table 31. 
     
                                           TABLE 1__________________________________________________________________________             Example 87   Example 88__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          400conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             2150         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             93.7         90.5resultacid (%)Selectivity**       Phenol             91.0         90.9       Benzene             4.7          8.1       CO, CO.sub.2             4.3          0.8Space time yield of phenol             292          446(g/l · h)__________________________________________________________________________             Example 89   Example 90__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             300          500conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             27.5         100.0resultacid (%)Selectivity**       Phenol             95.9         84.3       Benzene             3.6          15.2       CO, CO.sub.2             0.3          0.4Space time yield of phenol             143          457(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 2__________________________________________________________________________             Example 91   Example 92__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             1250         3800Time after the start of reaction (h)             110          110ReactionConversion of benzoic             100.0        90.0resultacid (%)Selectivity**       Phenol             94.0         90.1       Benzene             2.5          8.4       CO, CO.sub.2             3.3          0.8Space time yield of phenol             187          496(g/l · h)__________________________________________________________________________             Example 93   Example 94__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             5500         8020Time after the start of reaction (h)             110          110ReactionConversion of benzoic             87.5         85.0resultacid (%)Selectivity**       Phenol             91.9         90.3       Benzene             7.6          8.2       CO, CO.sub.2             0.2          1.4Space time yield of phenol             705          982(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 3__________________________________________________________________________             Example 95   Example 96__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             9500         15000Time after the start of reaction (h)             110          110ReactionConversion of benzoic             76.9         50.6resultacid (%)Selectivity**       Phenol             91.0         90.4       Benzene             5.7          7.2       CO, CO.sub.2             3.3          1.8Space time yield of phenol             1060         1094(g/l · h)__________________________________________________________________________             Example 97   Example 98__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             18000        21000Time after the start of reaction (h)             110          110ReactionConversion of benzoic             47.3         27.4resultacid (%)Selectivity**       Phenol             90.5         92.3       Benzene             8.5          7.2       CO, CO.sub.2             0.3          0.5Space time yield of phenol             1229         847(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 4__________________________________________________________________________             Example 99   Example 100__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             1.9          7.6       Nitrogen             17.3         11.6Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             69.7         99.8resultacid (%)Selectivity**       Phenol             92.0         85.3       Benzene             3.7          10.1       CO, CO.sub.2             3.3          4.5Space time yield of phenol             348          461(g/l · h)__________________________________________________________________________             Example 101  Example 102__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          0.6concentration       Water vapor             76.9         11.7(%)    Oxygen             15.4         17.5       Nitrogen             3.8          70.2Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             100.0        100.0resultacid (%)Selectivity**       Phenol             85.9         80.2       Benzene             10.6         16.2       CO, CO.sub.2             3.5          3.6Space time yield of phenol             466          69(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 5__________________________________________________________________________             Example 103  Example 104__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             9.1          6.3concentration       Water vapor             45.5         62.5(%)    Oxygen             9.1          6.3       Nitrogen             36.3         24.9Space velocity (h.sup.-1)             1440         2090Time after the start of reaction (h)             110          110ReactionConversion of benzoic             90.5         92.8resultacid (%)Selectivity**       Phenol             85.8         88.4       Benzene             8.7          7.1       CO, CO.sub.2             3.2          2.5Space time yield of phenol             427          453(g/l · h)__________________________________________________________________________             Example 105  Example 106__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             2.8          1.8concentration       Water vapor             83.3         89.3(%)    Oxygen             2.8          1.8       Nitrogen             11.1         7.1Space velocity (h.sup.-1)             4710         7320Time after the start of reaction (h)             110          110ReactionConversion of benzoic             95.0         95.2resultacid (%)Selectivity**       Phenol             93.1         93.0       Benzene             3.2          3.4       CO, CO.sub.2             3.5          3.6Space time yield of phenol             489          490(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 6__________________________________________________________________________             Example 107  Example 108__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionAlkyl benzoic acid group as             o-toluic acid                          p-toluic acidconditionraw materialReaction Temperature (° C.)             420          420Feed gas    Alkyl 3.8          3.8concentration       benzoic acid(%)         Water vapor             76.9         76.9       Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of raw material             35.6         56.2result(%)Selectivity**       Alkyl 65.8         78.4       phenol group             (m-cresol)   (m-cresol)       CO, CO.sub.2             11.2         12.2Space time yield of phenol             146          275(g/l · h)__________________________________________________________________________             Example 109  Example 110__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.3:47.1:0.6:2.0)                          (50.3:47.1:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionAlkyl benzoic acid group as             p-isopropyl benzoic acid                          p-ethyl benzoic acidconditionraw materialReaction Temperature (° C.)             420          420Feed gas    Alkyl 3.8          3.8concentration       benzoic acid(%)         Water vapor             76.9         76.9       Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of raw material             25.9         33.2result(%)Selectivity**       Alkyl 53.1         33.0       phenol group             (m-isopropyl phenol)                          (m-ethyl phenol)       CO, CO.sub.2             22.1         24.1Space time yield of phenol             108          77(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 7__________________________________________________________________________             Example 111  Example 112__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (49.8:46.7:0.6:3.0)                          (49.2:44.8:0.6:4.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             6.5          6.5ReactionReaction Temperature (° C.)             410          410conditionFeed gas       Benzoic acid             3.2          3.2concentration       Water vapor             80.6         80.6(%)    Oxygen             3.2          3.2       Nitrogen             12.9         12.9Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             95           92ReactionConversion of benzoic             90.6         87.5resultacid (%)Selectivity**       Phenol             90.8         90.9       Benzene             8.2          8.6       CO, CO.sub.2             0.8          0.3Space time yield of phenol             376          363(g/l · h)__________________________________________________________________________             Example 113  Example 114__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (47.7:44.7:0.6:7.0)                          (46.1:43.3:0.6:10.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             6.5          5.5ReactionReaction Temperature (° C.)             410          420conditionFeed gas       Benzoic acid             3.1          3.8concentration       Water vapor             78.1         76.9(%)    Oxygen             3.1          3.8       Nitrogen             12.5         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             104          110ReactionConversion of benzoic             87.1         83.7resultacid (%)Selectivity**       Phenol             93.3         88.0       Benzene             6.2          6.7       CO, CO.sub.2             0.5          4.3Space time yield of phenol             359          399(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 8__________________________________________________________________________             Example 115  Example 116  Example 117__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5     Fe.sub.2 O.sub.3 --NiO--Na.sub                                       .2 O--V.sub.2 O.sub.5             (49.8:46.7:0.6:1.0)                          (49.2:44.8:0.6:0.5)                                       (47.7:44.7:0.6:0.1)Calcining temperature (° C.)*             800          800          800Use quantity (ml)             6.5          6.5          6.5ReactionReaction Temperature (° C.)             410          410          410conditionFeed gas       Benzoic acid             3.8          3.8          3.8concentration       Water vapor             76.9         76.9         76.9(%)    Oxygen             3.8          3.8          3.8       Nitrogen             15.4         15.4         15.4Space velocity (h.sup.-1)             3400         3400         3400Time after the start of reaction (h)             110          110          110ReactionConversion of benzoic             90.5         87.5         67.3resultacid (%)Selectivity**       Phenol             88.8         81.2         80.3       Benzene             10.2         14.6         15.2       CO, CO.sub.2             0.8          3.3          4.5Space time yield of phenol             436          385          293(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 9__________________________________________________________________________             Example 118  Example 119__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.5:47.4:0.05:2.0)                          (50.5:47.3:0.2:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          400conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             59.6         63.3resultacid (%)Selectivity**       Phenol             90.0         90.8       Benzene             6.3          7.2       CO, CO.sub.2             2.9          1.8Space time yield of phenol             291          312(g/l · h)__________________________________________________________________________             Example 120  Example 121__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (50.1:46.9:1.0:2.0)                          (46.5:46.5:2.0:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             300          500conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             90.2         94.4resultacid (%)Selectivity**       Phenol             92.3         91.0       Benzene             5.4          5.3       CO, CO.sub.2             2.3          2.9Space time yield of phenol             451          466(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 10__________________________________________________________________________             Example 122  Example 123  Example 124__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5     Fe.sub.2 O.sub.3 --NiO--Na.sub                                       .2 O--V.sub.2 O.sub.5             (48.0:45.0:5.0:2.0)                          (45.4:41.1:10.0:2.0)                                       (35.1:32.9:30.0:2.0)Calcining temperature (° C.)*             800          800          800Use quantity (ml)             5.5          5.5          5.5ReactionReaction Temperature (° C.)             420          400          300conditionFeed gas       Benzoic acid             3.8          3.8          3.8concentration       Water vapor             76.9         76.9         76.9(%)    Oxygen             3.8          3.8          3.8       Nitrogen             15.4         15.4         15.4Space velocity (h.sup.-1)             2150         3400         3400Time after the start of reaction (h)             110          110          110ReactionConversion of benzoic             93.4         66.3         47.5resultacid (%)Selectivity**       Phenol             90.1         77.9         64.9       Benzene             5.7          18.4         22.3       CO, CO.sub.2             3.9          2.9          12.2Space time yield of phenol             456          280          167(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 11__________________________________________________________________________             Example 125  Example 126  Example 127__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5     Fe.sub.2 O.sub.3 --NiO--Na.sub                                       .2 O--V.sub.2 O.sub.5             (50.0:46.9:1.0:3.0)                          (47.5:44.5:2.0:6.0)                                       (45.4:42.6:3.0:9.0)Calcining temperature (° C.)*             800          800          800Use quantity (ml)             6.5          6.5          6.5ReactionReaction Temperature (° C.)             410          410          410conditionFeed gas       Benzoic acid             3.1          3.1          3.2concentration       Water vapor             78.1         78.1         80.6(%)    Oxygen             3.1          3.1          3.2       Nitrogen             12.5         12.5         12.9Space velocity (h.sup.-1)             3400         3400         3400Time after the start of reaction (h)             104          101          93ReactionConversion of benzoic             87.1         88.4         53.8resultacid (%)Selectivity**       Phenol             93.3         92.1         88.0       Benzene             6.2          6.6          8.1       CO, CO.sub.2             0.5          1.1          3.8Space time yield of phenol             359          360          216(g/l · h)__________________________________________________________________________                          Example 128  Example 129__________________________________________________________________________        Catalyst             Composition (wt. ratio)                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5     Fe.sub.2 O.sub.3 --NiO--Na.sub                                       .2 O--V.sub.2 O.sub.5                          (46.4:42.0:0.05:10.0)                                       (36.1:33.8:30.0:0.1)             Calcining temperature (° C.)*                          800          800             Use quantity (ml)                          6.5          6.5        Reaction             Reaction Temperature (° C.)                          410          410        condition             Feed gas                    Benzoic acid                          3.2          3.2             concentration                    Water vapor                          80.6         80.6             (%)    Oxygen                          3.2          3.2                    Nitrogen                          12.9         12.9             Space velocity (h.sup.-1)                          3400         3400        Time after the start of reaction (h)                          110          110        Reaction             Conversion of benzoic                          24.0         14.0        result             acid (%)             Selectivity**                    Phenol                          95.5         52.5                    Benzene                          0.8          22.7                    CO, CO.sub.2                          3.6          23.4             Space time yield of phenol                          105          34             (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 12__________________________________________________________________________             Example 130  Example 131__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (8.3:89.1:0.6:2.0)                          (20.5:76.9:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             43.6         70.5resultacid (%)Selectivity**       Phenol             73.4         80.9       Benzene             3.3          7.1       CO, CO.sub.2             23.0         11.8Space time yield of phenol             174          309(g/l · h)__________________________________________________________________________             Example 132  Example 133__________________________________________________________________________CatalystComposition (wt. ratio)             Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2 O.sub.5                          Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O--V.sub.2                           O.sub.5             (40.5:56.9:0.6:2.0)                          (59.9:37.5:0.6:2.0)Calcining temperature (° C.)*             800          800Use quantity (ml)             5.5          5.5ReactionReaction Temperature (° C.)             420          420conditionFeed gas       Benzoic acid             3.8          3.8concentration       Water vapor             76.9         76.9(%)    Oxygen             3.8          3.8       Nitrogen             15.4         15.4Space velocity (h.sup.-1)             3400         3400Time after the start of reaction (h)             110          110ReactionConversion of benzoic             87.5         95.0resultacid (%)Selectivity**       Phenol             90.9         82.7       Benzene             3.1          15.2       CO, CO.sub.2             1.3          0.4Space time yield of phenol             431          426(g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                       TABLE 13______________________________________            Example 134                     Example 135______________________________________Catalyst  Composition     Fe.sub.2 O.sub.3 --NiO--                             Fe.sub.2 O.sub.3 --NiO--  (wt. ratio)     Na.sub.2 O--V.sub.2 O.sub.5                             Na.sub.2 O--V.sub.2 O.sub.5                  (78.9:18.5:                             (91.0:6.4:                  0.6:2.0)   0.6:2.0)  Calcining temperature                  800        800  (° C.)*  Use quantity (ml)                  5.5        5.5Reaction  Reaction        420        420condition  Temperature (° C.)Feed gas      Benzoic  3.8        3.8concentration acid(%)           Water    76.9       76.9         vapor         Oxygen   3.8        3.8         Nitrogen 15.4       15.4Space velocity (h.sup.-1)              3400       3400Time after the start of reaction (h)              110        110Reaction  Conversion of   99.5       100.0result benzoic acid (%)Selectivity** Phenol   71.0       60.2         Benzene  22.9       38.1         CO,CO.sub.2                  4.2        0.7Space time yield   383        326of phenol (g/l · h)______________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 14__________________________________________________________________________             Example 136                    Example 137                           Example 138                                  Example 139                                         Example 140__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--                                         Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--V.sub.2 O.sub.5                    Na.sub.2 O--V.sub.2 O.sub.5                           Na.sub.2 O--V.sub.2 O.sub.5                                  Na.sub.2 O--V.sub.2 O.sub.5                                         Na.sub.2 O--V.sub.2                                         O.sub.5             (50.3:47.1:                    (50.3:47.1:                           (50.3:47.1:                                  (50.3:47.1:                                         (50.3:47.1:             0.6:2.0)                    0.6:2.0)                           0.6:2.0)                                  0.6:2.0)                                         0.6:2.0)Calcining temperature (° C.)*             550    600    700    900    950Use quantity (ml)             5.5    5.5    5.5    5.5    5.5ReactionReaction     420    420    420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400   3400   3400Time after the start of reaction (h)             110    110    110    110    110ReactionConversion of             100.0  100.0  99.5   55.3   6.5resultbenzoic acid (%)Selectivity**       Phenol             33.1   60.3   70.5   91.2   74.6       Benzene             25.3   20.3   13.5   2.3    14.3       CO,CO.sub.2             40.3   16.5   12.3   6.5    11.1Space time yield  179    327    380    273    26of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 15__________________________________________________________________________             Example 141                    Example 142                           Example 143                                  Example 144__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3                                  Na.sub.2 O--MoO.sub.3             (49.6:46.4:                    (51.0:47.9:                           (50.6:47.4:                                  (50.1:46.9:             1.0:3.0)                    1.0:0.1)                           1.0:1.0)                                  1.0:2.0)Calcining temperature (° C.)*             800    800    800    800Use quantity (ml)             5.5    5.5    5.5    5.5ReactionReaction     420    420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             2170   3400   3400   3400Time after the start of reaction (h)             92     110    110    110ReactionConversion of             60.1   70.5   60.2   62.3resultbenzoic acid (%)Selectivity**       Phenol             85.1   65.2   77.3   85.9       Benzene             8.2    22.5   11.3   8.9       CO,CO.sub.2             6.7    11.2   10.2   5.2Space time yield  177    249    252    290of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 16__________________________________________________________________________             Example 145                    Example 146                           Example 147__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3             (48.5:45.5:                    (47.0:44.0:                           (45.9:43.1:             1.0:5.0)                    1.0:8.0)                           1.0:10.0)Calcining temperature (° C.)*             800    800    800Use quantity (ml)             5.5    5.5    5.5ReactionReaction     420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9       Oxygen             3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400Time after the start of reaction (h)             110    110    110ReactionConversion of             65.4   59.2   53.6resultbenzoic acid (%)Selectivity**       Phenol             83.6   82.3   70.6       Benzene             5.7    10.4   21.6       CO,CO.sub.2             10.4   6.9    6.9Space time yield  296    264    205of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 17__________________________________________________________________________             Example 148                    Example 149                           Example 150                                  Example 151__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3                                  Na.sub.2 O--MoO.sub.3             (50.5:46.9:                    (49.9:46.9:                           (49.7:46.7:                                  (49.0:46.0:             0.05:3.0)                    0.2:3.0)                           0.6:3.0)                                  2.0:3.0)Calcining temperature (° C.)*             800    800    800    800Use quantity (ml)             5.5    5.5    5.5    5.5ReactionReaction     420    420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400   3400Time after the start of reaction (h)             110    110    110    110ReactionConversion of             33.5   42.1   65.8   67.5resultbenzoic acid (%)Selectivity**       Phenol             75.1   75.2   86.3   88.6       Benzene             8.9    12.9   5.9    5.9       CO,CO.sub.2             13.5   8.2    7.2    6.3Space time yield  136    172    308    324of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 18__________________________________________________________________________             Example 152                    Example 153                           Example 154__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3             (47.5:44.5:                    (44.9:42.1:                           (34.6:32.4:             5.0:3.0)                    10.0:3.0)                           30.0:3.0)Calcining temperature (° C.)*             800    800    800Use quantity (ml)             5.5    5.5    5.5ReactionReaction     410    410    410conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9       Oxygen             3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400Time after the start of reaction (h)             110    110    100ReactionConversion of             63.5   52.3   36.9resultbenzoic acid (%)Selectivity**       Phenol             80.6   65.8   64.5       Benzene             11.4   30.3   23.8       CO,CO.sub.2             7.2    4.2    8.3Space time yield  277    187    129of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 19__________________________________________________________________________             Example 155                    Example 156                           Example 157                                  Example 158                                         Example 159__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--                                         Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3                                  Na.sub.2 O--MoO.sub.3                                         Na.sub.2 O--MoO.sub.3             (50.3:47.1:                    (49.9:45.5:                           (47.5:44.5:                                  (46.4:42.0:                                         (36.1:33.8:             0.6:2.0)                    0.6:4.0)                           2.0:6.0)                                  0.05:10.0)                                         30.0:0.1)Calcining temperature (° C.)*             800    800    800    800    800Use quantity (ml)             5.5    5.5    5.5    5.5    5.5ReactionReaction     410    410    410    410    410conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.2    3.1    3.8    3.8concentration       acid(%)         Water vapor             76.9   80.6   78.1   76.9   76.9       Oxygen             3.8    3.2    3.1    3.8    3.8       Nitrogen             15.4   12.9   12.5   15.4   15.4Space velocity (h.sup.-1)             2180   3400   3400   3400   3400Time after the start of reaction (h)             95     100    93     110    110ReactionConversion of             54.2   48.5   40.3   32.0   21.0resultbenzoic acid (%)Selectivity**       Phenol             87.8   88.1   86.3   61.2   50.2       Benzene             7.9    7.5    8.1    19.5   40.3       CO,CO.sub.2             4.3    4.4    5.6    18.5   6.5Space time yield  165    195    154    106    57of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 20__________________________________________________________________________             Example 160                    Example 161                           Example 162                                  Example 163__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3                                  Na.sub.2 O--MoO.sub.3             (8.3:89.1:                    (20.5:76.9:                           (40.5:56.9:                                  (59.9:37.5:             0.6:2.0)                    0.6:2.0)                           0.6:2.0)                                  0.6:2.0)Calcining temperature (° C.)*             800    800    800    800Use quantity (ml)             5.5    5.5    5.5    5.5ReactionReaction     420    420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400   3400Time after the start of reaction (h)             110    110    110    110ReactionConversion of             29.9   40.6   50.3   76.2resultbenzoic acid (%)Selectivity**       Phenol             80.3   86.2   89.6   83.2       Benzene             2.9    7.6    3.1    10.3       CO,CO.sub.2             11.5   5.9    5.6    6.3Space time yield  130    190    244    343of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                       TABLE 21______________________________________            Example 164                     Example 165______________________________________Catalyst  Composition     Fe.sub.2 O.sub.3 --NiO--                             Fe.sub.2 O.sub.3 --NiO--  (wt. ratio)     Na.sub.2 O--MoO.sub.3                             Na.sub.2 O--MoO.sub.3                  (78.9:18.5:                             (91.0:6.4:                  0.6:2.0)   0.6:2.0)  Calcining temperature                  800        800  (° C.)*  Use quantity (ml)                  5.5        5.5Reaction  Reaction        420        420condition  Temperature (° C.)Feed gas      Benzoic  3.8        3.8concentration acid(%)           Water    76.9       76.9         vapor         Oxygen   3.8        3.8         Nitrogen 15.4       15.4Space velocity (h.sup.-1)              3400       3400Time after the start of reaction (h)              110        110Reaction  Conversion of   88.5       95.3result benzoic acid (%)Selectivity** Phenol   74.2       55.3         Benzene  12.9       22.3         CO,CO.sub.2                  10.3       20.9Space time yield   356        286of phenol (g/l · h)______________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 22__________________________________________________________________________             Example 166                    Example 167                           Example 168                                  Example 169                                         Example 170__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--                                         Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--MoO.sub.3                    Na.sub.2 O--MoO.sub.3                           Na.sub.2 O--MoO.sub.3                                  Na.sub.2 O--MoO.sub.3                                         Na.sub.2 O--MoO.sub.3             (50.3:47.1:                    (50.3:47.1:                           (50.3:47.1:                                  (50.3:47.1:                                         (50.3:47.1:             0.6:2.0)                    0.6:2.0)                           0.6:2.0)                                  0.6:2.0)                                         0.6:2.0)Calcining temperature (° C.)*             550    600    700    900    950Use quantity (ml)             5.5    5.5    5.5    5.5    5.5ReactionReaction     420    420    420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400   3400   3400Time after the start of reaction (h)             110    110    110    110    110ReactionConversion of             100.0  98.8   90.2   43.2   8.9resultbenzoic acid (%)Selectivity**       Phenol             61.2   62.1   70.9   86.5   72.1       Benzene             15.6   13.3   8.5    6.3    14.0       CO,CO.sub.2             22.3   16.4   21.5   3.5    11.1Space time yield  331    332    347    202    35of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 23__________________________________________________________________________             Example 171                     Example 172                             Example 173                                     Example 174__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                     Fe.sub.2 O.sub.3 --NiO--                             Fe.sub.2 O.sub.3 --NiO--                                     Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--V.sub.2 O.sub.5 --                     Na.sub.2 O--V.sub.2 O.sub.5 --                             Na.sub.2 O--V.sub.2 O.sub.5 --                                     Na.sub.2 O--V.sub.2 O.sub.5 --             MoO.sub.3                     MoO.sub.3                             MoO.sub.3                                     MoO.sub.3             (49.3:46.2                     (47.5:44.5                             (47.5:44.5                                     (50.1:46.9             1.0:2.0:1.5)                     1.0:4.0:3.0)                             2.0:4.0:3.0)                                     2.0:0.5:0.5)Calcining temperature (° C.)*             800     800     800     800Use quantity (ml)             5.5     5.5     5.5     5.5ReactionReaction     420     420     420     420conditionTemperature (° C.)Feed gas    Benzoic             3.8     3.8     3.8     3.8concentration       acid(%)         Water vapor             76.9    76.9    76.9    76.9       Oxygen             3.8     3.8     3.8     3.8       Nitrogen             15.4    15.4    15.4    15.4Space velocity (h.sup.-1)             3400    3400    3400    3400Time after the start of reaction (h)             110     110     110     110ReactionConversion of             83.9    88.9    95.3    62.5resultbenzoic acid (%)Selectivity**       Phenol             93.5    94.1    88.6    80.5       Benzene             3.5     4.4     2.6     15.8       CO,CO.sub.2             1.4     0.5     8.1     5.1Space time yield  425     453     458     273of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 24__________________________________________________________________________             Example 175                     Example 176                             Example 177                                     Example 178__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                     Fe.sub.2 O.sub.3 --NiO--                             Fe.sub.2 O.sub.3 --NiO--                                     Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--V.sub.2 O.sub.5 --                     Na.sub.2 O--V.sub.2 O.sub.5 --                             Na.sub.2 O--V.sub.2 O.sub.5 --                                     Na.sub.2 O--V.sub.2 O.sub.5 --             MoO.sub.3                     MoO.sub.3                             MoO.sub.3                                     MoO.sub.3             (50.5:47.3                     (45.4:42.6                             (40.2:37.8                                     (25.8:24.2             2.0:0.1:0.1)                     2:5:5)  2:10:10)                                     30:10:10)Calcining temperature (° C.)*             800     800     800     800Use quantity (ml)             5.5     5.5     5.5     5.5ReactionReaction     420     420     420     420conditionTemperature (° C.)Feed gas    Benzoic             3.8     3.8     3.8     3.8concentration       acid(%)         Water vapor             76.9    76.9    76.9    76.9       Oxygen             3.8     3.8     3.8     3.8       Nitrogen             15.4    15.4    15.4    15.4Space velocity (h.sup.-1)             3400    3400    3400    3400Time after the start of reaction (h)             110     110     110     110ReactionConversion of             44.3    77.7    85.4    55.5resultbenzoic acid (%)Selectivity**       Phenol             71.5    84.3    89.8    51.0       Benzene             21.1    8.4     3.3     15.4       CO,CO.sub.2             5.9     5.6     5.0     31.8Space time yield  172     355     416     153of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                       TABLE 25______________________________________            Example 179                     Example 180______________________________________Catalyst  Composition     Fe.sub.2 O.sub.3 --NiO--                             Fe.sub.2 O.sub.3 --NiO--  (wt. ratio)     Na.sub.2 O--                             Na.sub.2 O--                  V.sub.2 O.sub.5 --                             V.sub.2 O.sub.5 --                  MoO.sub.3  MoO.sub.3                  (51.5:48.3 (45.4:42.6                  0.05:0.1:0.1)                             1:10:1)  Calcining temperature                  800        800  (° C.)*  Use quantity (ml)                  5.5        5.5Reaction  Reaction        420        420condition  Temperature (° C.)Feed gas      Benzoic  3.8        3.8concentration acid(%)           Water    76.9       76.9         vapor         Oxygen   3.8        3.8         Nitrogen 15.4       15.4Space velocity (h.sup.-1)              3400       3400Time after the start of reaction (h)              110        110Reaction  Conversion of   35.1       55.9result benzoic acid (%)Selectivity** Phenol   76.6       86.1         Benzene  12.9       7.4         CO,CO.sub.2                  10.0       4.6Space time yield   146        261of phenol (g/l · h)______________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 26__________________________________________________________________________             Example 181                    Example 182                           Example 183                                  Example 184__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  K.sub.2 O--V.sub.2 O.sub.5                    Li.sub.2 O--V.sub.2 O.sub.5                           Rb.sub.2 O--V.sub.2 O.sub.5                                  Cs.sub.2 O--V.sub.2 O.sub.5             (50.3:47.1:                    (50.3:47.1:                           (50.3:47.1:                                  (50.3:47.1:             0.6:2.0)                    0.6:2.0)                           0.6:2.0)                                  0.6:2.0)Calcining temperature (° C.)*             800    800    800    800Use quantity (ml)             5.5    5.5    5.5    5.5ReactionReaction     420    420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400   3400Time after the start of reaction (h)             110    110    110    110ReactionConversion of             85.9   66.8   54.3   44.3resultbenzoic acid (%)Selectivity**       Phenol             90.6   90.1   83.6   70.6       Benzene             5.4    3.3    7.5    16.3       CO,CO.sub.2             2.3    6.4    8.5    10.3Space time yield  422    326    246    170of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 27__________________________________________________________________________             Example 185                     Example 186                            Example 187                                   Example 188__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                     Fe.sub.2 O.sub.3 --NiO--                            Fe.sub.2 O.sub.3 --NiO--                                   Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  Na.sub.2 O--V.sub.2 O.sub.5 --                     Na.sub.2 O--V.sub.2 O.sub.5                            Na.sub.2 O--V.sub.2 O.sub.5                                   Na.sub.2 O--V.sub.2 O.sub.5             MoO.sub.3                     (50.3:47.1:                            (50.3:47.1:                                   (50.3:47.1:             (49.3:46.2                     0.6:2.0)                            0.6:2.0)                                   0.6:2.0)             1.0:2.0:1.5)Use quantity (ml)             5.5     5.5    5.5    5.5ReactionReaction     420     420    420    420conditionTemperature (° C.)Feed gas    Benzoic             3.8     3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9    76.9   76.9   76.9       Oxygen             3.8     3.8    3.8    3.8       Nitrogen             15.4    15.4   15.4   15.4Space velocity (h.sup.-1)             3400    3400   3400   3400Time after the start of reaction (h)             110     110    110    110ReactionConversion of             94.9    65.9   41.3   31.5resultbenzoic acid (%)Selectivity**       Phenol             93.2    96.3   98.0   80.0       Benzene             5.3     1.2    1.0    13.2       CO,CO.sub.2             1.1     1.3    0.6    5.4Space time yield  480     344    219    137of phenol (g/l · h)__________________________________________________________________________ 
    
     
                                           TABLE 28__________________________________________________________________________             Example 189                    Example 190                           Example 191                                  Example 192__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O.sub.3 --NiO--                           Fe.sub.2 O.sub.3 --NiO--                                  Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  MgO--V.sub.2 O.sub.5                    CaO--V.sub.2 O.sub.5                           SrO--V.sub.2 O.sub.5                                  BaO--V.sub.2 O.sub.5             (50.3:47.1:                    (50.3:47.1:                           (50.3:47.1:                                  (50.3:47.1:             0.6:2.0)                    0.6:2.0)                           0.6:2.0)                                  0.6:2.0)Calcining temperature (° C.)*             800    800    800    800Use quantity (ml)             5.5    5.5    5.5    5.5ReactionReaction     420    400    300    500conditionTemperature (° C.)Feed gas    Benzoic             3.8    3.8    3.8    3.8concentration       acid(%)         Water vapor             76.9   76.9   76.9   76.9       Oxygen             3.8    3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4   15.4Space velocity (h.sup.-1)             2150   3400   3400   3400Time after the start of reaction (h)             110    110    110    110ReactionConversion of             63.5   55.3   43.2   50.3resultbenzoic acid (%)Selectivity**       Phenol             90.3   90.4   89.3   88.8       Benzene             2.3    5.1    1.5    10.2       CO,CO.sub.2             7.3    3.8    8.1    1.3Space time yield  196    271    209    242of phenol (g/l · h)__________________________________________________________________________ *Calcining temperature of Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O before supporting V.sub.2 O.sub.5. **Cmol % 
    
     
                                           TABLE 29__________________________________________________________________________             Example 193                    Example 194                           Example 195__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                    Fe.sub.2 O--NiO--                           Fe.sub.2 O.sub.3 --NiO--(wt. ratio)  MgO--MoO.sub.3                    CaO--MoO.sub.3                           BaO--MoO.sub.3             (49.6:46.4:                    (51.0:47.9:                           (50.6:47.4:             1.0:3.0)                    1.0:0.1)                           1.0:1.0)Use quantity (ml) 5.5    5.5    5.5ReactionAlkyl benzoic acid group             o-toluic acid                    o-toluic acid                           o-toluic acidconditionas raw materialReaction          420    420    420Temperature (° C.)Feed gas    Alkyl 3.8    3.8    3.8concentration       benzoic(%)         acid       Water vapor             76.9   76.9   76.9       Oxygen             3.8    3.8    3.8       Nitrogen             15.4   15.4   15.4Space velocity (h.sup.-1)             3400   3400   3400Time after the start of reaction (h)             110    110    110ReactionConversion of             59.6   42.5   40.3resultraw material (%)Selectivity**       Alkyl 70.2   66.6   72.2       phenol             (m-cresol)                    (m-cresol)                           (m-cresol)       group       CO,CO.sub.2             11.6   13.5   10.2Space time yield  261    177    181of phenol (g/l · h)__________________________________________________________________________ **C-mol % 
    
     
                                           TABLE 30__________________________________________________________________________             Comparative                       Comparative                                  Comparative             example 4 example 5  example 6__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--Na.sub.2 O                       MoO.sub.3 --V.sub.2 O.sub.5 --CuO--                                  CuO--ZnO--K.sub.2 O--Al.sub.2                                  O.sub.3(wt. ratio)  (51.3:48.1:0.6)                       Na.sub.2 O--Al.sub.2 O.sub.3                                  (4.0:3.0:3.6:89.4)                       (3.9:3.7:3.8:5.9:82.7)Use quantity (ml)             6.5       5.9        5.3ReactionReaction     410       300        300conditionTemperature (° C.)Feed gas    Benzoic             2.7       2.3        2.3concentration       acid(%)         Water vapor             69.4      69.9       69.9       Oxygen             5.6       4.7        4.7       Nitrogen             22.2      23.1       23.1Space velocity (h.sup.-1)             3950      2640       2960Time after the start of reaction (h)             91        83         87ReactionConversion of             31.2      35.6       12.2resultbenzoic acid (%)Selectivity**       Phenol             24.0      51.9       26.3       Benzene             38.9      18.7       53.6       CO,CO.sub.2             36.7      29.4       20.1Space time yield  21        47         9of phenol (g/l · h)__________________________________________________________________________ **C-mol % 
    
     
                                           TABLE 31__________________________________________________________________________                     Comparative                                Comparative             Example 196                     example 7  example 8__________________________________________________________________________CatalystComposition  Fe.sub.2 O.sub.3 --NiO--                     MoO.sub.3 --V.sub.2 O.sub.5 --CuO--                                CuO--ZnO--K.sub.2 O--(wt. ratio)  Na.sub.2 O--V.sub.2 O.sub.5 --                     Na.sub.2 O--Al.sub.2 O.sub.3                                Al.sub.2 O.sub.3             MoO.sub.3                     (3.9:3.7:3.8:                                (4.0:3.0:3.6:             (49.3:46.2                     5.9:82.7)  89.4)             1.0:2.0:1.5)                     :0.6:2.0)  :0.6:2.0)Use quantity (ml)             5.5     5.5        5.5ReactionAlkyl benzoic acid group             o-toluic acid                     o-toluic acid                                o-toluic acidconditionas raw materialReaction          420     300        300Temperature (° C.)Feed gas    Alkyl 3.8     3.8        3.8concentration       benzoic(%)         acid       Water vapor             76.9    76.9       76.9       Oxygen             3.8     3.8        3.8       Nitrogen             15.4    15.4       15.4Space velocity (h.sup.-1)             3400    3400       3400Time after the start of reaction (h)             110     110        110ReactionConversion of             42.5    23.5       11.5resultraw material (%)Selectivity**       Alkyl 63.2    2.8        1.9       phenol             (m-cresol)                     (m-cresol) (m-cresol)       group       CO,CO.sub.2             10.9    28.9       31.6Space time yield  167     4          1of phenol (g/l · h)__________________________________________________________________________ **C-mol %