JP2522929B2 - Process for producing vanadium / antimony-containing oxide catalyst for nitrile production - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a vanadium antimony-containing catalyst suitable for producing nitriles.

The catalyst according to the present invention can be effectively used in the method for producing the corresponding nitriles by ammoxidation of alkyl-substituted aromatic compounds, alkyl-substituted heterocyclic compounds, alkyl-substituted alicyclic compounds, alcohols, aldehydes and the like.

[Conventional technology]

In the ammoxidation reaction of the organic compound, a catalyst mainly containing vanadium oxide has been conventionally used.

For example, the production of benzonitrile by ammoxidation of toluene (Japanese Patent Publication Nos. 34-8714, 42-13770, 56-37979), phthalonitrile, isophthalonitrile, terephthalonitrile by ammoxidation of xylene. Production of nitrile (Japanese Patent Publication No. 34-8714, Japanese Patent Publication No. 35-15689,
Japanese Patent Publication No. 42-13717, Japanese Patent Publication No. 43-10624, Japanese Patent Publication No. 45-19
No. 284, Japanese Patent Publication No. 56-37980), o-, m-, p-halogenated benzonitrile by ammoxidation of halogenated toluene, 2,4-, 2,5-, 2,6-dihalogenated benzene Production of nitrile (Japanese Patent Publication No. 38-15371, Japanese Patent Publication No. 42-790)
2, Japanese Patent Publication No. 43-5386, Japanese Patent Publication No. 43-10623)
Cyanonaphthalene by ammoxidation of methylnaphthalene (JP-B-56-35663 and JP-B-57-54501), production of tricyanobenzene by ammoxidation of mesitylene (JP-B-56-35663), of aminotoluene Production of aminobenzonitrile by ammoxidation (Japanese Patent Publication No. 57-25031), production of hydroxybenzonitrile by ammoxidation of cresol (British Patent Specification 1244)
149), in the ammoxidation of alkyl-substituted heterocyclic compounds, ammoxidation of alkyl-substituted furan, pyrrole, indole, thiophene, pyrazole, imidazole, thiazole, oxazole, pyran, pyridine, quinoline, isoquinoline, pyrimidine, pyridazine, pyridine. Production of nitriles (JP-B-56-35556, JP-A-57-87838, JP-B-57-19706, JP-B-52-1115)
No. 65, Japanese Patent Publication No. 61-4388, JP-A No. 55-145672), ammoxidation of alkyl-substituted alicyclic compounds includes ammoxidation of methylcyclopentane, methylcyclohexane, alkyl-substituted decalin (simultaneous dehydrogenation). Corresponding nitriles produced by reaction (Japanese Patent Publication No. 56-35663)
JP-A-57-134454) and the production of corresponding nitriles by ammoxidation of linear hydrocarbons. In these reactions, vanadium alone or a catalyst supported on a carrier together with other elements is used, but its activity and physical properties are not necessarily satisfactory. As a catalyst for these reactions, a catalyst containing antimony together with vanadium gives relatively good performance.
However, it has been difficult to manufacture a touch panel containing vanadium and antimony at the same time with high reproducibility and high performance.

Since vanadium oxide has a low melting point, a method of impregnating vanadium with a compound on an alumina carrier which has been fired at a high temperature has been usually used for producing a catalyst. However, it is not easy to impregnate the antimony component at the same time because the amount of the water-soluble antimony compound is small. The use of chloride causes problems such as equipment corrosion and reproducibility due to the escape of components during drying and firing, and the use of antimony trioxide tartaric acid and ethylene glycol complex salts requires complicated preparation and dispersion of organic substances. Due to the complexity of the conditions, catalyst reproducibility problems were likely to occur.

As a carrier for a vanadium-based catalyst, a high temperature (for example, 10
Alumina fired at around 00 ° C is often used. Even if there are problems as described above, it is possible to prepare a vanadium-antimony-containing oxide catalyst by impregnating an alumina carrier with a vanadium component and an antimony component, drying and firing. However, since the antimony component easily reacts with alumina, the reproducibility of the catalyst is poor, and there are various problems in terms of aging.
Especially the activity that contains vanadium and antimony at the same time.
It was difficult to produce a fluidized bed catalyst having good physical properties.

On the other hand, it is known that it is difficult to produce an antimony-containing oxide catalyst having excellent strength. To solve this problem, there are proposals such as the methods described in JP-B-42-22476, JP-B-47-18722 and JP-B-18723. However, these methods also did not provide a sufficient solution for the strength of the catalyst containing vanadium together with antimony.

[Problems to be Solved by the Present Invention]

An object of the present invention is to provide a method of preparing a catalyst having good activity and physical properties with good reproducibility when preparing a catalyst containing vanadium and antimony which are suitable for producing the nitriles.

[Means for solving problems]

According to the present invention, an alkyl-substituted aromatic compound, an alkyl-substituted heterocyclic compound, an alkyl-substituted alicyclic compound, a method for producing a vanadium-antimony-containing oxide catalyst for producing a corresponding nitrile by ammoxidation of an alcohol or an aldehyde is antimony and iron, A metal oxide composition containing at least one element selected from the group consisting of cobalt, nickel, tin, uranium, chromium, copper, titanium, thorium and cerium and silica as essential components is fired at 500 ° C to 950 ° C. Thus, a base catalyst was prepared, and vanadium or vanadium and iron, cobalt were adjusted so that the ratio V / Sb (atomic ratio) between the amount of impregnated vanadium component and the amount of antimony component in the base catalyst was 0.005 to 5. Nickel, chromium, copper, manganese, cerium, lanthanum,
At least one element selected from the group consisting of zirconium, magnesium, calcium, strontium, barium, silver, zinc, cadmium, aluminum, gallium, germanium, lead, lithium, sodium, potassium, rubidium, cesium, boron, phosphorus and bismuth. Impregnated with an aqueous solution containing and dried at 300 ℃ to 800 ℃
It is characterized by being fired at the temperature of.

 The present invention will be specifically described below.

First, a substrate catalyst containing antimony, at least one element selected from the group consisting of iron, cobalt, nickel, tin, uranium, chromium, copper, titanium, thorium and cerium and silica as essential components is produced. It includes the Japanese Patent Publications 42-22476, 47-18722, and
The methods described in each publication such as 18723 can be used.

Especially in the case of fluidized bed catalysts, antimony compounds,
A slurry containing iron, cobalt, nickel, tin, uranium, chromium, copper, titanium, a compound of at least one element selected from the group consisting of thorium and cerium, and silica sol is prepared to have a pH of 7 or less, and then the slurry is heated to a temperature of After heat treatment at 40 ℃ or more, dry, 500 ℃ to 950 ℃
It is preferred to produce the base catalyst by calcining at a temperature of.

As the base catalyst, one having a composition represented by the following empirical formula is preferable.

Me _a Sb _b X _c Q _d R _e S _f O _g (SiO ₂ ) _h , selected from the group consisting of Me = Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th and Ce. At least one element, at least one element selected from the group consisting of X = V and Mo, Q = Be, Mg, Ca, Sr, Ba, Y, La, Zr, Hf, W, Nb, Ta , Re, Ru, Os, Rh,
At least one element selected from the group consisting of Ir, Pd, Pt, Ag, Zn, Cd, Al, Ca, In, Ge and Pb, R = B, P, Te, Bi, As and Se group At least one element selected from the group consisting of S = Li, Na, K, Rb, Cs and Tl, and subscripts a, b, c, d, e, f, g and h represent atomic ratios and are in the following ranges respectively.

a = 5-15 b = 5-100 (preferably 10-50) c = 0-15 (preferably 0.01-10) d = 0-20 (preferably 0.05-15) e = 0-10 (preferably 0.1) ~ 7) f = 0 to 5 (preferably 0.05 to 3) h = 10 to 200, preferably 20 to 150 In addition, O represents an oxygen atom, and g corresponds to an oxide formed by combining the respective component elements. Indicates the number of oxygen atoms.

The base catalyst thus prepared is impregnated with an aqueous solution containing a vanadium compound.

Examples of the vanadium compound used in the preparation of the impregnating solution include ammonium metavanadate, vanadyl oxalate, vanadyl sulfate, vanadyl phosphate, vanadyl acetylacetonate, vanadium-containing heteropolyacids and salts thereof. Alternatively, an aqueous hydrogen peroxide solution of vanadium oxide or vanadic acid (salt) can be used.

It is also possible to impregnate components other than vanadium at the same time. In that case, a water-soluble compound of those components may be used. A nitrate is preferably used for iron, cobalt, nickel, chromium, copper, manganese, cerium, lanthanum, zirconium, magnesium, calcium, strontium, barium, silver, zinc, cadmium, aluminum, gallium, germanium, lead and the like. It is also good to use an organic acid salt. For lithium, sodium, potassium, rubidium and cesium, it is preferable to use hydroxide or nitrate. Boron is boric acid, or glycerin,
Propylene glycol, tartaric acid, lactic acid, malic acid, etc. may be used after enhancing the solubility. Phosphorus is phosphoric acid,
Bismuth is preferably nitrate.

The above compound is dissolved in water to prepare an impregnating solution containing vanadium or vanadium and other elements.

The amount of these impregnating liquids is adjusted to a liquid amount corresponding to the pore volume of the base catalyst measured in advance, and the base catalyst is impregnated with the liquid. At that time, if the impregnated amount of vanadium is too small, sufficient activity cannot be obtained, and if it is too large, the activity is large but the selectivity of the target product decreases. In the case of a fluidized bed catalyst, the catalyst adhesion increases and the fluidized state deteriorates, which causes a disadvantage such as a decrease in the yield of the target product.

The amount of vanadium to be impregnated is preferably in the range specified below. The ratio V / Sb (atomic ratio) of the impregnated vanadium component amount to the antimony component amount in the base catalyst is 0.005 to 5,
It is preferably 0.01 to 2, and more preferably 0.03 to 1.5.

When impregnating components other than vanadium, it is preferable to do as follows. When T is a component other than vanadium, T is Fe, Co, Ni, Cr, Cu, Mn, Ce, La, Zr, Mg, Ca, Sr, Ba, A.
g, Zn, Cd, Al, Ga, Ge, Pb, Li, Na, K, Rb, Cs, B, P, Bi is at least one element selected, T / V (atomic ratio) is 0.0
It is preferably in the range of 1 to 10, particularly in the range of 0.05 to 5.

It is economical to perform the impregnation in a single time by forming a uniform solution containing the required amounts of components, but if necessary, lower the concentration of the impregnating solution to impregnate and dry (baking if necessary), and repeat this multiple times. You can also Further, it is also possible to prepare impregnating liquids having different kinds or amounts of components and sequentially carry out the operations of impregnation and drying (calcination if necessary). When the impregnation amount is relatively high, multiple impregnations are recommended.

In this manner, the base catalyst is impregnated with vanadium or an aqueous solution of vanadium and other component elements, dried, and then calcined at a temperature of 300 ° C. to 800 ° C. to complete a catalyst.

The catalyst thus obtained is a vanadium-antimony-containing oxide catalyst suitable for the production of the above-mentioned nitriles and having good activity and physical properties. Generally, the catalyst composition of the finished catalyst preferably has the following composition.

In Me _i Sb _j V _k Mo _L Q _m R _n S _o O _p (SiO ₂ ) _q , Me = Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th and Ce. At least one element, Q ＝ Be, Mg, Ca, Sr, Ba, Y, La, Zr, Hf, W, Nb, Ta, Re, Ru, Os, Rh,
Ir, Pd, Pt, Ag, Zn, Cd, Al, Ga, In, Ge and at least one element selected from the group consisting of Pb and Pb, R = B, P, Te, Bi, As and Se At least one element selected from the group, at least one element selected from the group consisting of S = Li, Na, K, Rb, Cs and Th, and subscripts i, j, k, l, m, n, o, p, and q represent atomic ratios and are in the following ranges, respectively.

i = 5 to 15 j = 5 to 100 (preferably 10 to 50) k = 0.01 to 15 (preferably 0.1 to 10) l = 0 to 10 (preferably 0.05 to 7) m = 0 to 20 (preferably 0.05) -15) n = 0-10 (preferably 0.1-7) o = 0-5 (preferably 0.05-3) q = 10-200 (preferably 20-150) In addition, O represents an oxygen atom and P is The number of oxygen atoms corresponding to the oxide formed by combining the component elements is shown.

According to the present invention, a method for producing nitriles is a starting material compound such as an alkyl-substituted aromatic compound, an alkyl-substituted heterocyclic compound, an alkyl-substituted alicyclic compound in a reactor filled with a catalyst, a molar ratio of ammonium and oxygen of 1: 1-30:
The 1.5-30 mixture is passed in the temperature range up to 300 to 550 ° C.

The reaction pressure is usually from atmospheric pressure to 5 kg / cm ² G.

The reaction may be either a fixed bed or a fluidized bed, but a fluidized bed is particularly preferable.

[Action and effect]

The conventional method of mixing the vanadium component and the antimony component from the beginning and calcining generally does not provide a catalyst with good strength, and especially the change in the activity and physical properties is large due to the change in the calcining temperature, and reproducibility is also a problem. On the contrary, according to the method of the present invention, a catalyst having good activity and physical properties can be prepared with good reproducibility. Since no alumina is used as the carrier, the antimony component and alumina do not react during the preparation of the catalyst, so that the reproducibility is good and the reaction is stable even at a high temperature. Therefore, a catalyst with little change over time can be obtained.

However, the process of the present invention is generally unsuitable for the production of unsaturated nitriles by ammoxidation of olefins. Byproducts such as carbon dioxide gas increase and the selectivity of the target product decreases, which is not desirable.

Hereinafter, the effects of the present invention will be specifically shown by examples.

[1] Catalyst activity test The activity test was conducted by passing the starting compound, air and ammonia to the catalyst bed packed in a fluidized bed reactor having an inner diameter of 2.5 cm and a height of 40 cm in the catalyst fluidized section.

 The reaction pressure is normal pressure.

However, the conversion rate of the raw material compounds, the yield of the target product, and the selectivity in Examples and Comparative Examples are defined as follows.

[2] Catalyst strength test (1) Abrasion resistance test “TEST” is known as a test method for fluid catalytic cracking catalysts.
METHOD FOR SYNTHETIC CRACKING CATALYSTS "American
It was obtained by the method described in Cyanamid Co., Ltd. 6 / 31-4m-1 / 57.

However, A = weight of catalyst [g] lost and worn in 0 to 5 hours B = weight of catalyst worn and lost in 5 to 20 hours [g] C = weight of catalyst used in test [g] This test was conducted at C = 50 [g].

 It can be said that the larger the R value, the smaller the catalyst strength.

(2) Crush strength test Sieve through a micromesh sieve and take a catalyst sample with a particle size in the range of 35-40μ.

This 0.025 g was put together with a steel ball with a diameter of 2 mm into a polystyrene container with a volume of 4 CC, and this was mixed with a mixer / mill (SPEX
Mill) for 90 seconds.

Measure the particle size distribution of the crushed sample and
The ratio K [%] of the amount that becomes less than or equal to μ to the charged amount is calculated.

 It can be said that the larger the K value, the smaller the catalyst strength.

Example 1 A catalyst whose empirical formula was Fe _8.8 Cu _3.2 Sb ₂₀ V ₂ O _61.4 (SiO ₂ ) ₄₈ was prepared as follows.

Take 73.0g of electrolytic iron powder. Mix 600 ml of nitric acid (specific gravity 1.38) with 750 ml of pure water and heat. Add electrolytic iron powder little by little to this. Make sure it is completely dissolved. Copper nitrate
Add 115 g and dissolve. To this iron / copper solution, silica sol
Add 1785g. Take 433 g of antimony trioxide and add to the above solution. To this slurry, add 15% ammonia water little by little to adjust the PH to 2.5. This is refluxed at 95 ° C for 5
Heated for hours. Then spray-dry it by the usual method, 200 ℃ 4
After firing at 400 ° C for 4 hours, finally firing at 850 ° C for 4 hours.

This is the base catalyst. The composition is Fe _8.8 Cu _3.2 Sb ₂₀ O _70.5
(SiO ₂ ) ₄₀ .

On the other hand, 27.0 g of vanadium pentoxide is suspended in 200 ml of pure water, heated to 90 ° C., and oxalic acid is added little by little to dissolve it. The vanadium-containing solution was impregnated into the iron-antimony-copper-silica substrate catalyst prepared above and calcined at 200 ° C for 4 hours and 450 ° C for 4 hours. The ratio V / Sb (atomic ratio) between the amount of vanadium component in the impregnating liquid and the amount of antimony component in the base catalyst was 0.1.

This catalyst was charged into the reactor, and a mixture of toluene, ammonia and oxygen in a molar ratio of 1: 5: 8 was fed and the reaction was carried out at 410 ° C.

The conversion of toluene is 97.4% and the benzonitrile yield is 7
8.3%.

* Oxygen is sent as air. The same applies to the following examples and comparative examples.

Example 2 A catalyst whose empirical formula was Fe ₁₀ Sb ₂₀ V ₁ Mo _0.2 P _0.2 O _68.6 (SiO ₂ ) ₆₀ was prepared in the same manner as in Example 1.

The basic catalyst composition is Fe ₁₀ Sb ₂₀ Mo _0.2 P _0.2 O _56.1 (SiO ₂ )
_{It was set to 60} and was impregnated with a vanadium component. V / Sb is 0.
05.

This catalyst was charged into the reactor, and a mixture of toluene, ammonia and oxygen in a molar ratio of 1: 5: 8 was fed and reacted at 390 ° C.

Toluene conversion is 95.2%, benzonitrile yield is 7
It was 6.1%.

Example 3 The empirical formula is Fe _9.6 Cu _2.4 Sb ₂₀ V _3.2 Mo _0.4 Zn _0.8 Te _0.96 B
_A catalyst that was _0.4 O _64.5 (SiO ₂ ) ₄₈ was prepared in the same manner as in Example 1.

The base catalyst composition is Fe _9.6 Cu _2.4 Sb ₂₀ Mo _0.4 Zn _0.8 Te _0.96 B
_0.4 O _41.3 (SiO ₂ ) ₄₈ , which was impregnated with a vanadium component. V / Sb is 0.16.

The catalyst was charged into the reactor and charged with a mixture of metaxylene, ammonia and oxygen in a molar ratio of 1:10:10, 4
The reaction was allowed to proceed at 00 ° C.

The conversion of metaxylene was 92.2% and the yield of isophthalonitrile was 78.8%.

Example 4 A catalyst whose test formula is Fe ₁₂ Sb ₂₅ V ₅ Mg ₄ Bi ₁ O ₈₆ (SiO ₂ ) ₅₀ was prepared in the same manner as in Example 1.

The base catalyst composition was Fe ₁₂ Sb ₂₅ Mg ₄ Bi ₁ O _73.5 (SiO ₂ ) ₅₀ , which was impregnated with a vanadium component. V / Sb is 0.2.

The catalyst was charged into the reactor and charged with a mixture of metaxylene, ammonia and oxygen in a molar ratio of 1:10:10, 4
The reaction was allowed to proceed at 10 ° C.

The conversion of metaxylene was 95.4% and the yield of isophthalonitrile was 76.3%.

Example 5 The empirical formula is Fe _10.4 Ni _1.6 Co _0.8 Sb ₂₀ V _2.4 Zr _0.4 P _0.4 O
A catalyst that was _65.8 (SiO) ₆₄ was prepared in the same manner as in Example 1.

The base catalyst composition is Fe _10.4 Ni _1.6 Co _0.4 Sb ₂₀ V _0.16 Zr _0.4 P
_0.4 O _59.8 (SiO ₂ ) ₆₄ , which was impregnated with a solution containing a vanadium component and a cobalt component. V / Sb is 0.112 and Co / V is 0.357. Cobalt nitrate was used as the cobalt component raw material.

The catalyst was charged in the reactor, and a mixture of 3-methylpyridine, ammonia and oxygen in a molar ratio of 1: 3: 15 was fed and the reaction was carried out at 360 ° C.

The conversion rate of 3-methylpyridine was 92.7%, and the yield of 3-cyanopyridine was 79.5%.

Example 6 empirical _{formula, Fe 10 Sn 2 Cr 2 Sb} 20 V 2 Mo 0.1 O 58.55 (SiO 2) 50
Was prepared in the same manner as in Example 1.

The base catalyst composition is Fe _9.5 Sn ₂ Sb ₂₀ Mo _0.1 O _59.3 (SiO ₂ )
_{It was set to 50} and was impregnated with a solution containing a vanadium component, a chromium component and an iron component. V / Sb is 0.1 and Fe / V is
It is 1.25. Ferric nitrate was used as the iron component raw material.

The catalyst was charged in the reactor, and a mixture of 3-methylpyridine, ammonia and oxygen in a molar ratio of 1: 3: 15 was fed and the reaction was carried out at 360 ° C.

The conversion rate of 3-methylpyridine was 96.4%, and the yield of 3-cyanopyridine was 80.8%.

Example 7 The empirical formula is Fe _9.6 Cu _2.4 Cr _1.6 Sb ₂₀ V _3.2 Mo _0.4 W _0.2 Te
_The catalyst, _0.96 O _32.5 (SiO ₂ ) ₄₈ , was prepared in a similar manner to the examples.

The base catalyst composition was Fe _9.6 Cu _2.4 Sb ₂₀ Mo _0.4 W _0.2 Te _0.96 O
_22.1 (SiO ₂ ) ₄₈ , which was impregnated with a solution containing a vanadium component and a chromium component. V / Sb is 0.16, Cr / V
Is 0.5. Chromium nitrate was used as the chromium component raw material.

This catalyst was charged into the reactor, and a mixture of orthochlorotoluene, ammonia and oxygen in a molar ratio of 1: 5: 4 was fed and reacted at 360 ° C.

The ortho-chlorotoluene conversion rate was 97.5%, and the ortho-chlorobenzonitrile yield was 80.5%.

Example 8 The empirical formula is Fe ₁₀ Cu _3.2 Sb ₂₀ V ₄ Mo _0.56 W _0.08 Te _1.36 O
_A catalyst that was _72.8 (SiO ₂ ) ₅₆ was prepared in the same manner as in Example 1.

The base catalyst composition was Fe ₁₀ Cu _3.2 Sb ₂₀ V _0.16 Mo _0.56 W _0.08 Te.
_1.36 O _63.2 (SiO ₂ ) ₅₆ , which was impregnated with a vanadium component. V / Sb is 0.192.

This catalyst was charged into the reactor, and a mixture of 2,6-dichlorotoluene, ammonia, and oxygen in a molar ratio of 1: 5: 4 was introduced and reacted at 360 ° C.

The conversion of 2,6-dichlorotoluene was 97.1% and the yield of 2,6-dichlorobenzonitrile was 79.8%.

Example 9 empirical _{formula, Fe 10 Sb 30 V 5 O} 87.5 The catalyst is a (SiO _{2) 30,} was prepared in the same manner as in Example 1.

The base catalyst composition was Fe ₁₀ Sb ₃₀ O ₇₅ (SiO ₂ ) ₃₀ and was impregnated with a vanadium component. V / Sb is 0.17.

This catalyst was charged into the reactor, and a mixture of toluene, ammonia and oxygen in a molar ratio of 1: 5: 8 was fed and reacted at 400 ° C.

Conversion of toluene is 97.5%, benzonitrile yield is 8
0.2%.

Example 10 The empirical formula is Fe ₁₀ Sb ₁₅ V ₁₀ P ₂ B _0.5 K _0.2 O _75.9 (SiO ₂ ).
A catalyst of ₁₀₀ was prepared in a similar manner to Example 1.

The base catalyst composition was Fe ₁₀ Sb ₁₅ B _0.5 O _45.8 (SiO ₂ ) _100, and this was impregnated with a solution containing a vanadium component, a phosphorus component, and a potassium component. V / Sb is 0.67, (P +
K) / V is 0.22. Phosphoric acid is used as the raw material for the phosphorus component,
Potassium nitrate was used as the potassium component raw material.

This catalyst was charged into the reactor, and a mixture of toluene, ammonia and oxygen in a molar ratio of 1: 5: 8 was fed and reacted at 400 ° C.

Conversion of toluene is 94.2%, benzonitrile yield is 7
5.7%.

Comparative Example 1 A catalyst having an empirical formula of Fe _8.8 Cu _3.2 Sb ₂₀ V _0.02 O _56.4 (SiO ₂ ) ₄₀ was prepared in the same manner as in Example 1.

The base catalyst composition is the same as in Example 1, but the ratio V / Sb (atomic ratio) of the vanadium component amount in the impregnating liquid to the antimony component amount in the base catalyst is 0.001.

This catalyst was filled in the reactor, and an ammoxidation reaction of toluene was carried out in the same manner as in Example 1.

Toluene conversion is 74.9%, benzonitrile yield is 2
It was 8.1%.

Comparative Example 2 A catalyst having the same empirical formula as that of Example 1 was prepared as follows.

Take 73.0g of electrolytic iron powder. Mix 600 ml of nitric acid (specific gravity 1.38) with 750 ml of pure water and heat. Add electrolytic iron powder little by little to this. Make sure it is completely dissolved. Copper nitrate
Add 115 g and dissolve. Silica sol 17 in this iron / copper solution
Add 85g. 433 g of antimony trioxide and 27.0 g of vanadium pentoxide are sequentially added to the above slurry and mixed well.
This was heated under reflux for 5 hours at 95 ° C. Then, it is spray-dried by a conventional method, baked at 200 ° C. for 4 hours and 400 ° C. for 4 hours and finally baked at 450 ° C. for 4 hours.

This catalyst was filled in the reactor, and an ammoxidation reaction of toluene was carried out in the same manner as in Example 1.

Conversion of toluene is 84.6%, benzonitrile yield is 5
It was 3.2%.

Comparative Example 3 In the empirical formula, the same catalyst was used as the base catalyst of Example 8
It was prepared in the same manner as described above.

This catalyst was charged into the reactor, and the ammoxidation reaction of 2,6-dichlorotoluene was carried out in the same manner as in Example 8.

The conversion of 2,6-dichlorotoluene was 77.1% and the yield of 2,6-dichlorobenzonitrile was 31.7%.

Comparative Example _{4 V 2 O 5 -Al 2 O} 3 catalyst was prepared.

A commercially available alumina carrier was impregnated with the same amount of the vanadium component as in Example 8.

 It is 8.52% by weight as vanadium pentoxide.

This catalyst was charged into the reactor, and the ammoxidation reaction of 2,6-dichlorotoluene was carried out in the same manner as in Example 8.

The conversion of 2,6-dichlorotoluene was 90.4%, and the yield of 2,6-cyclolobenzonitrile was 68.2%.

Comparative Example 5 A catalyst having an empirical formula of Fe ₁₀ Sb ₃₀ V ₅ O _87.5 (Al ₂ O ₃ ) ₃₀ was prepared in the same manner as in Example 1. However, alumina sol was used instead of silica sol.

The base catalyst composition was Fe ₁₀ Sb ₃₀ O ₇₅ (Al ₂ O ₃ ) ₃₀ and was impregnated with a vanadium component. When X-ray diffraction of this catalyst was taken, the antimony component reacted with alumina and
It was found that bO ₄ was formed. In the catalyst of Example 9, the reaction between the antimony component and silica is not recognized.

This catalyst was charged into the reactor, and the ammoxidation reaction of toluene was carried out in the same manner as in Example 9.

Toluene conversion is 78.5%, benzonitrile yield is 4
2.3%.

The activity test results using the catalysts shown in the above Examples and Comparative Examples, and their physical properties (strength test results) are shown in Table 1 below.
Are summarized in.

In Comparative Example 1, even if a catalyst was prepared by the same method as in the present invention, the yield of nitrile was low when the impregnation amount of the vanadium component was low.

In Comparative Example 2, even if the catalyst having the same composition as that of Example 1 of the present invention was not used according to the method of the present invention, the yield of the target nitrile was low and the strength of the catalyst was low, so that it was practically used. Do not get it.

In Comparative Example 3, when the vanadium component content is low,
Although a catalyst with good physical properties may be obtained, the target nitrile yield is low.

In Comparative Example 4, the catalyst using an alumina carrier in place of the antimony-containing base catalyst has a low nitrile yield, which is a target, and inferior catalyst physical properties.

In Comparative Example 5, an alumina sol was used in place of the silica sol for the preparation of the base catalyst, but in this case, the one having good physical properties was not obtained. Therefore, the catalyst was completed by impregnating it with a vanadium component. However, it has been shown that the desired nitrile yield is low and the physical properties of the catalyst are inferior.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 255/51 9357-4H C07C 255/51 C07D 213/85 C07D 213/85 (56) References Kai 51-17194 (JP, A) JP-A-56-126448 (JP, A)

Claims (3)

(57) [Claims] 1. A metal oxide composition containing antimony, at least one element selected from the group consisting of iron, cobalt, nickel, uranium, chromium, copper, titanium, thorium and cerium, and silica as essential components, 500 A base catalyst is prepared by calcining at a temperature of ℃ to 950 ℃, and the ratio V / Sb (atomic ratio) of the amount of impregnated vanadium component and the amount of antimony component in the base catalyst is adjusted to 0.005 to 5 Vanadium or vanadium and iron, cobalt, nickel, chromium, copper, manganese, cerium, lanthanum, zirconium, magnesium, calcium, strontium, barium, silver, zinc, cadmium, aluminum, gallium, germanium, lead, lithium, sodium, potassium , Rubidium, cesium, boron,
Alkyl-substituted aromatic compounds and alkyl-substituted heterocyclic compounds characterized by being impregnated with an aqueous solution containing at least one element selected from the group consisting of phosphorus and bismuth, dried, and then calcined at a temperature of 300 ° C to 800 ° C. , A process for producing vanadium-antimony-containing oxide catalysts for the production of corresponding nitriles by ammoxidation of alkyl-substituted alicyclic compounds, alcohols or aldehydes. 2. The method according to claim 1, wherein the composition of the base catalyst is represented by the following empirical formula. Me _a Sb _b X _c Q _{d Re} S _f O _g (SiO ₂ ) _h However, in the above formula, from Me ＝ Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th and Ce At least one element selected from the group consisting of X = V and at least one element selected from the group consisting of Mo, Q = Be, Mg, Ca, Sr, Ba, Y, La, Zr, Hf, W, Nb, Ta, Re, Ru, Os, Rh,
At least one element selected from the group consisting of Ir, Pd, Pt, Ag, Zn, Cd, Al, Ca, In, Ge and Pb, R = B, P, Te, Bi, As and Se group At least one element selected from the group consisting of S = Li, Na, K, Rb, Cs and Tl, subscripts a, b, c, d, e, f, g and h represents an atomic ratio and is in the following range, respectively. a = 5-15 b = 5-100 c = 0-15 d = 0-20 e = 0-10 f = 0-5 h = 10-200 In addition, O represents an oxygen atom and g represents each component element. The number of oxygen atoms corresponding to the oxide formed by bonding is shown. 3. A metal oxide composition comprising at least one selected from the group consisting of (i) antimony compounds, (ii) iron, cobalt, nickel, tin, uranium, chromium, copper, titanium, thorium and cerium. PH7 is a slurry containing the compound of the element of (iii) and silica sol as an essential component.
The method according to claim 1, characterized in that the slurry is heat-treated at a temperature of 40 ° C. or higher, dried and calcined to obtain a substrate catalyst, which is adjusted as follows.