Catalyst and method for producing phenols

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 .alpha.-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 .alpha.-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.sub.2 O.sub.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.sub.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.sub.2 O.sub.5), and may include vanadium monoxide (VO), vanadium trioxide (V.sub.2 O.sub.3) and/or di-vanadium tetroxide (V.sub.2 O.sub.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.sub.2 generated by complete combustion increases.
The molybdenum oxide is preferably molybdenum trioxide (MoO.sub.3), and may include molybdenum dioxide (MnO.sub.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.sub.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.sub.2 generated by complete combustion increases.
Alkali metal oxide includes Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O. Among them, the oxides of sodium and potassium are preferred because they yield less CO and CO.sub.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.sub.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.sub.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.degree. C. or more, the specific surface area reduces and the catalyst activity degrades. However, within a temperature range of from approximately 600 to 900.degree. 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.degree. C., only the reaction to yield CO and CO.sub.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.degree. 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.sup.-1. When the space velocity is less than approximately 100 hr.sup.-1, sufficient space time yield can not be obtained. When the space velocity exceeds approximately 50000 hr.sup.-1 the conversion of benzoic acid and alkyl benzoic acid decreases.
A preferable range of reaction temperature is approximately from 200 to 600.degree. C., most preferably from approximately 300 to 500.degree. C. When the reaction temperature is above approximately 600.degree. C., the selectivity of phenol and alkyl phenol decreases. When the reaction temperature is below approximately 200.degree. 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.sub.3).sub.3.9H.sub.2 O) 200 g and nickel nitrate (Ni(NO.sub.3).sub.2.6H.sub.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.sub.2 CO.sub.3.10H.sub.2 O) 2.24 g, and the mixture was agitated for approximately 1 hr. The gel was dried in air at 120.degree. C. for 24 hrs., followed by calcining in air at 800.degree. C. for 4 hrs.
The calcined product was put into an aqueous solution prepared by dissolving ammonium methavanadate (NH.sub.4 VO.sub.3) 2 g and oxalic acid ((COOH).sub.2) 4 g. The mixture was evaporated to dry, followed by drying at 120.degree. C. for 24 hrs. and calcining at 500.degree. C. for 3 hrs. to obtain the catalyst.
The catalyst had the composition of 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 (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.sub.2 O.sub.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.sub.2 O.sub.3 --NiO--Na.sub.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.sub.3).sub.3.9H.sub.2 O) 200 g and nickel nitrate (Ni(NO.sub.3).sub.2.6H.sub.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.sub.2 CO.sub.3.10H.sub.2 O) 3.68 g, and the mixture was agitated for approximately 1 hr. The gel was dried in air at 120.degree. C. for 24 hrs., followed by calcining in air at 800.degree. C. for 4 hrs.
The calcined product was put into an aqueous solution prepared by dissolving ammonium molybdate (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O) 2.93 g. The mixture was evaporated to dry, followed by drying at 120.degree. C. for 24 hrs. and calcining at 500.degree. C. for 3 hrs. to obtain the catalyst.
The catalyst had the composition of Fe.sub.2 O.sub.3 :NiO:Na.sub.2 O:MoO.sub.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.sub.2 O.sub.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.sub.2 O.sub.3 --NiO--Na.sub.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.sub.3).sub.3.9H.sub.2 O) 200 g and nickel nitrate (Ni(NO.sub.3).sub.2.6H.sub.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.sub.2 CO.sub.3.10H.sub.2 O) 3.70 g, and the mixture was agitated for approximately 1 hr. The gel was dried in air at 120.degree. C. for 24 hrs., followed by calcining in air at 800.degree. C. for 4 hrs.
The calcined product was put into an aqueous solution 25 ml prepared by dissolving ammonium methavanadate (NH.sub.4 VO.sub.3) 2.06 g and oxalic acid ((COOH).sub.2) 4 g and an aqueous solution 25 ml prepared by dissolving ammonium molybdate (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O) 1.47 g. The mixture was evaporated to dry, followed by drying at 120.degree. C. for 24 hrs. and calcining at 500.degree. C. for 3 hrs. to obtain the catalyst.
The catalyst had the composition of Fe.sub.2 O.sub.3 :NiO:Na.sub.2 O:V.sub.2 O.sub.5 :MoO.sub.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.sub.2 CO.sub.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.sub.2 CO.sub.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.sub.2 CO.sub.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.sub.2 CO.sub.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.sub.3).sub.3.9H.sub.2 O) 200 g and nickel nitrate (Ni(NO.sub.3).sub.2.6H.sub.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.sub.2 CO.sub.3.10H.sub.2 O) 3.70 g, and with aqueous solution 25 ml prepared by dissolving ammonium methavanadate (NH.sub.4 VO.sub.3) 2.06 g and oxalic acid ((COOH).sub.2) 4 g, and with aqueous solution 25 ml prepared by dissolving ammonium molybdate (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.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.degree. C. for 24 hrs., followed by calcining in air at 800.degree. C. for 4 hrs. to obtain the catalyst.
The catalyst had the composition of Fe.sub.2 O.sub.3 :NiO:Na.sub.2 O:V.sub.2 O.sub.5 :MoO.sub.3 =49.3:46.2:1.0:2.0:1.5 (by weight).
Example 77
Iron nitrate (Fe(NO.sub.3).sub.3.9H.sub.2 O) 200 g and nickel nitrate (Ni(NO.sub.3).sub.2.6H.sub.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.sub.2 CO.sub.3.10H.sub.2 O) 3.70 g. The mixture was agitated for approximately 1 hr. The gel was dried in air at 120.degree. C. for 24 hrs., followed by calcining in air at 800.degree. C. for 4 hrs.
The calcined product was powdered, and was mixed with a vanadium pentoxide powder (V.sub.2 O.sub.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.sub.2 O.sub.3 :NiO:Na.sub.2 O:V.sub.2 O.sub.5 =50.3:47.1:0.6:2.0 (by weight).
Example 78
Iron nitrate (Fe(NO.sub.3).sub.3.9H.sub.2 O) 200 g and nickel nitrate (Ni(NO.sub.3).sub.2.6H.sub.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.degree. C. for 24 hrs., followed by calcining in air at 800.degree. C. for 4 hrs.
The fired product was put into an aqueous solution 100 ml containing sodium carbonate (Na.sub.2 CO.sub.3.10H.sub.2 O) 2.24 g. and an aqueous solution 50 ml prepared by dissolving ammonium methavanadate (NH.sub.4 VO.sub.3) 2 g and oxalic acid ((COOH).sub.2) 4 g. The mixture was evaporated to dry, followed by drying at 120.degree. C. for 24 hrs. and calcining at 500.degree. C. for 3 hrs. to obtain the catalyst. The catalyst had the composition of 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 (by weight).
Example 79
Powders of hydroxyl-iron oxide (FeO(OH)) 43.98 g, nickel hydroxide (Ni(OH).sub.2) 45.9 g, sodium carbonate (Na.sub.2 CO.sub.3.10H.sub.2 O) 3.70 g, and vanadium pentoxide (V.sub.2 O.sub.5) 1.55 g were mixed together. The mixture was calcined in air at 800.degree. 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.sub.2 O.sub.3 :NiO:Na.sub.2 O:V.sub.2 O.sub.5 =50.3:47.1:0.6:2.0 (by weight).
Example 80
Catalyst containing magnesium nitrate (Mg(NO.sub.3).sub.2.6H.sub.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.sub.3).sub.2.4H.sub.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.sub.3).sub.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.sub.3).sub.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.sub.3).sub.2.6H.sub.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.sub.3).sub.2.4H.sub.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.sub.3).sub.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 .gamma.-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.degree. 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.degree. 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.degree. 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.degree. C. An .alpha.-alumina 100 g was dipped into the solution. The solution was dried, and calcined at 750.degree. 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.degree. 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__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 400condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 93.7 90.5result acid (%)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 .multidot. h)__________________________________________________________________________ Example 89 Example 90__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 300 500condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 27.5 100.0result acid (%)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 .multidot. 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__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 100.0 90.0result acid (%)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 .multidot. h)__________________________________________________________________________ Example 93 Example 94__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 87.5 85.0result acid (%)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 .multidot. 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__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 76.9 50.6result acid (%)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 .multidot. h)__________________________________________________________________________ Example 97 Example 98__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 47.3 27.4result acid (%)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 .multidot. 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__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 69.7 99.8result acid (%)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 .multidot. h)__________________________________________________________________________ Example 101 Example 102__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 0.6 concentration 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 110Reaction Conversion of benzoic 100.0 100.0result acid (%)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 .multidot. 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__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 9.1 6.3 concentration 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 110Reaction Conversion of benzoic 90.5 92.8result acid (%)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 .multidot. h)__________________________________________________________________________ Example 105 Example 106__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 2.8 1.8 concentration 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 110Reaction Conversion of benzoic 95.0 95.2result acid (%)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 .multidot. 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__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Alkyl benzoic acid group as o-toluic acid p-toluic acidcondition raw material Reaction Temperature (.degree. 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 110Reaction Conversion 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 .multidot. h)__________________________________________________________________________ Example 109 Example 110__________________________________________________________________________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 (50.3:47.1:0.6:2.0) (50.3:47.1:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Alkyl benzoic acid group as p-isopropyl benzoic acid p-ethyl benzoic acidcondition raw material Reaction Temperature (.degree. 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 110Reaction Conversion 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 .multidot. 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__________________________________________________________________________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 (49.8:46.7:0.6:3.0) (49.2:44.8:0.6:4.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 6.5 6.5Reaction Reaction Temperature (.degree. C.) 410 410condition Feed gas Benzoic acid 3.2 3.2 concentration 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 92Reaction Conversion of benzoic 90.6 87.5result acid (%)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 .multidot. h)__________________________________________________________________________ Example 113 Example 114__________________________________________________________________________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 (47.7:44.7:0.6:7.0) (46.1:43.3:0.6:10.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 6.5 5.5Reaction Reaction Temperature (.degree. C.) 410 420condition Feed gas Benzoic acid 3.1 3.8 concentration 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 110Reaction Conversion of benzoic 87.1 83.7result acid (%)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 .multidot. 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__________________________________________________________________________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 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 (.degree. C.)* 800 800 800 Use quantity (ml) 6.5 6.5 6.5Reaction Reaction Temperature (.degree. C.) 410 410 410condition Feed gas Benzoic acid 3.8 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 90.5 87.5 67.3result acid (%)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 .multidot. 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__________________________________________________________________________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 (50.5:47.4:0.05:2.0) (50.5:47.3:0.2:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 400condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 59.6 63.3result acid (%)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 .multidot. h)__________________________________________________________________________ Example 120 Example 121__________________________________________________________________________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 (50.1:46.9:1.0:2.0) (46.5:46.5:2.0:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 300 500condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 90.2 94.4result acid (%)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 .multidot. 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__________________________________________________________________________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 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 (.degree. C.)* 800 800 800 Use quantity (ml) 5.5 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 400 300condition Feed gas Benzoic acid 3.8 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 93.4 66.3 47.5result acid (%)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 .multidot. 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__________________________________________________________________________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 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 (.degree. C.)* 800 800 800 Use quantity (ml) 6.5 6.5 6.5Reaction Reaction Temperature (.degree. C.) 410 410 410condition Feed gas Benzoic acid 3.1 3.1 3.2 concentration 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 93Reaction Conversion of benzoic 87.1 88.4 53.8result acid (%)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 .multidot. 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 (.degree. C.)* 800 800 Use quantity (ml) 6.5 6.5 Reaction Reaction Temperature (.degree. 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 .multidot. 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__________________________________________________________________________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 (8.3:89.1:0.6:2.0) (20.5:76.9:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 43.6 70.5result acid (%)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 .multidot. h)__________________________________________________________________________ Example 132 Example 133__________________________________________________________________________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 (40.5:56.9:0.6:2.0) (59.9:37.5:0.6:2.0) Calcining temperature (.degree. C.)* 800 800 Use quantity (ml) 5.5 5.5Reaction Reaction Temperature (.degree. C.) 420 420condition Feed gas Benzoic acid 3.8 3.8 concentration 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 110Reaction Conversion of benzoic 87.5 95.0result acid (%)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 .multidot. 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 (.degree. C.)* Use quantity (ml) 5.5 5.5Reaction Reaction 420 420condition Temperature (.degree. 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 550 600 700 900 950 Use quantity (ml) 5.5 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 100.0 100.0 99.5 55.3 6.5result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 60.1 70.5 60.2 62.3result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 Use quantity (ml) 5.5 5.5 5.5Reaction Reaction 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 65.4 59.2 53.6result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 33.5 42.1 65.8 67.5result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 Use quantity (ml) 5.5 5.5 5.5Reaction Reaction 410 410 410condition Temperature (.degree. 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 100Reaction Conversion of 63.5 52.3 36.9result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5 5.5Reaction Reaction 410 410 410 410 410condition Temperature (.degree. 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 110Reaction Conversion of 54.2 48.5 40.3 32.0 21.0result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 29.9 40.6 50.3 76.2result benzoic 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 .multidot. 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 (.degree. C.)* Use quantity (ml) 5.5 5.5Reaction Reaction 420 420condition Temperature (.degree. 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 550 600 700 900 950 Use quantity (ml) 5.5 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 100.0 98.8 90.2 43.2 8.9result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 83.9 88.9 95.3 62.5result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 44.3 77.7 85.4 55.5result benzoic 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 .multidot. 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 (.degree. C.)* Use quantity (ml) 5.5 5.5Reaction Reaction 420 420condition Temperature (.degree. 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 85.9 66.8 54.3 44.3result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 5.5Reaction Reaction 420 420 420 420condition Temperature (.degree. 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 110Reaction Conversion of 94.9 65.9 41.3 31.5result benzoic 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 .multidot. h)__________________________________________________________________________
TABLE 28__________________________________________________________________________ Example 189 Example 190 Example 191 Example 192__________________________________________________________________________Catalyst Composition 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 (.degree. C.)* 800 800 800 800 Use quantity (ml) 5.5 5.5 5.5 5.5Reaction Reaction 420 400 300 500condition Temperature (.degree. 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 110Reaction Conversion of 63.5 55.3 43.2 50.3result benzoic 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 .multidot. 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__________________________________________________________________________Catalyst Composition 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 5.5Reaction Alkyl benzoic acid group o-toluic acid o-toluic acid o-toluic acidcondition as raw materialReaction 420 420 420Temperature (.degree. 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 110Reaction Conversion of 59.6 42.5 40.3result raw 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 .multidot. h)__________________________________________________________________________ **C-mol %
TABLE 30__________________________________________________________________________ Comparative Comparative Comparative example 4 example 5 example 6__________________________________________________________________________Catalyst Composition 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 5.3Reaction Reaction 410 300 300condition Temperature (.degree. 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 87Reaction Conversion of 31.2 35.6 12.2result benzoic 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 .multidot. h)__________________________________________________________________________ **C-mol %
TABLE 31__________________________________________________________________________ Comparative Comparative Example 196 example 7 example 8__________________________________________________________________________Catalyst Composition 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 5.5Reaction Alkyl benzoic acid group o-toluic acid o-toluic acid o-toluic acidcondition as raw materialReaction 420 300 300Temperature (.degree. 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 110Reaction Conversion of 42.5 23.5 11.5result raw 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 .multidot. h)__________________________________________________________________________ **C-mol %

Number	Name	Date
3926853	Senes et al.	Dec 1975
4060545	Miller et al.	Nov 1977
4390736	Inoue et al.	Jun 1983
4620043	Lam et al.	Oct 1986
5268512	Miki et al.	Dec 1993

Number	Date	Country
0 052 839	Jun 1982	EPX
0 226 640	Jul 1987	EPX
0 452 695	Oct 1991	EPX
0 538 912	Apr 1993	EPX
57-11932	Jan 1982	JPX
4-277029	Oct 1992	JPX
59-20384	May 1994	JPX

Catalyst and method for producing phenols

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