JPH05279313A - Production of nitrile - Google Patents

Abstract

PURPOSE:To produce a nitrile from an alkane in high yield in the absence of halide, water, etc., in the reaction system at a relatively low temperature, i.e., about 400-450 deg.C. CONSTITUTION:A nitrile is produced in high yield by the vapor-phase catalytic oxidation reaction of an alkane (preferably propane and/or isobutane) at e.g. 340-480 deg.C (especially 380-440 deg.C) in the presence of a solid catalyst produced by adding one or more kinds of oxides of Sb, Bi, Ce or B to a multiple oxide expressed by formula (X is one or more elements selected from Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sb, Bi, B and Se; (b) is 0.01-1.0, (c) is 0.01-1.0 and (x) is 0.01-1.0 when a is 1; (n) is a number determined by the oxidation states of other elements) and preferably baking the mixture. A substance produced by adding an organic compound containing Sb, Bi, Ce and/or B to the above multiple oxide and baking the mixture may be used as the solid catalyst for the objective process.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing nitrile. More particularly, it relates to an improved nitrile production method using alkane as a raw material.

[0002]

2. Description of the Related Art Nitriles such as acrylonitrile and methacrylonitrile are industrially produced as important intermediates for fibers, synthetic resins and synthetic rubbers. Conventional production methods include propylene and isobutene. The most general method is a method in which an olefin such as the above is catalytically reacted with ammonia and oxygen in the presence of a catalyst in a gas phase at a high temperature.

On the other hand, due to the price difference between propane and propylene or the price difference between isobutane and isobutene, lower alkanes such as propane and isobutane are used as starting materials, and ammonia and oxygen are used in the presence of a catalyst. There is an increasing interest in the development of a method for producing acrylonitrile and methacrylonitrile by a so-called ammoxidation reaction method in which they are catalytically reacted with each other in the gas phase.

As an example of these reports, Mo-Bi-P
-O catalyst (Japanese Patent Laid-Open No. 48-16887), V-Sb-
O-based catalyst (JP-A-47-33783, JP-B-50-2)
No. 3016, JP-A-1-268668), Sb-U-
V-Ni-O catalyst (Japanese Patent Publication No. 47-14371), S
b-Sn-O type catalyst (Japanese Patent Publication No. 50-28940), V
-Sb-W-P-O catalyst (Japanese Patent Laid-Open No. 95439/1990)
No.), V-Sb-W-O-based oxide and Bi-Ce-Mo-
A catalyst obtained by mechanically mixing W—O type oxides (Japanese Patent Application Laid-Open No. Sho 6-96).
4-38051) and the present inventors
o-V-Te-Nb-O based catalyst (JP-A-2-257)
Is reported.

[0005]

However, none of these methods can sufficiently satisfy the target yield of nitriles. Further, in order to improve the yield of nitriles, a method of adding a small amount of an organic halide, an inorganic halide, a sulfur compound, or water to the reaction system has been attempted, but the former three are not There is a problem of corrosion, and water has a problem of generation of a by-product due to a side reaction and its treatment, which are both difficult in industrial implementation.

Further, the conventional method using a catalyst system generally requires an extremely high reaction temperature of about 500 ° C. or higher except for the Mo-V-Te-Nb-O catalyst reported by the present inventors. Therefore, it is not advantageous in terms of reactor material, manufacturing cost, and the like.

[0007]

Means for Solving the Problems The present inventors
As a result of further studying a method for producing a nitrile using an alkane as a raw material, focusing on improvement of an o-V-Te-Nb-O-based catalyst, a Mo-V-Te-X-O-based catalyst (X is one or It has been found that it represents a plurality of kinds of specific elements and may contain Nb as X. (Japanese Patent Application No. 10438/1993)
2). Furthermore, it has been found that the yield of nitrile is remarkably improved when the same Mo-V-Te-X-O-based catalyst having a specific crystal structure is used (Japanese Patent Application No. 3-199573). ).

The inventors of the present invention have been focusing on further study based on the recent research results, and found that Mo-V-Te-X
After preparing a —O-based composite oxide, the composite oxide is further
In the presence of a solid catalyst obtained by adding a specific substance such as antimony oxide, by reacting an alkane with ammonia in a gas phase, the reaction system does not have a halide, water, etc. The inventors have found that the target nitrile can be produced in a higher yield than the conventional method at a relatively low temperature of about 450 ° C. and have reached the present invention.

[0009] That is, the gist of the present invention, in the empirical formula _{(1) Mo a V b Te} c X x O n (1) ( Formula (1), X is Nb, Ta, W, Ti, A
1, Zr, Cr, Mn, Fe, Ru, Co, Rh, N
represents one or more elements selected from i, Pd, Pt, Sb, Bi, B and Ce, and when a = 1, b = 0.01 to 1.0 c = 0.01 .About.1.0 x = 0.01 to 1.0, and n is determined by the oxidation states of other elements. ) In the presence of a solid catalyst formed by adding an antimony oxide or the like to the complex oxide represented by the formula (1), a method for producing a nitrile characterized by subjecting an alkane to a gas phase catalytic oxidation reaction with ammonia.

The present invention will be described in detail below. In the complex oxide of the above formula (1) prepared first in the present invention, the above element is used as X, but preferably Nb, Ta,
W and Ti, and particularly preferably Nb. Further, as a coefficient of the equation (1), when a = 1, b = 0.1
0.6, c = 0.05 to 0.4, x = 0.01 to 0.6
Is particularly preferable.

Further, the complex oxide preferably has a specific crystal structure. Specifically, as the pattern of the X-ray diffraction peak (using Cu-Kα ray as the X-ray source) of the composite oxide, the following five main diffraction peaks are observed at a specific diffraction angle 2θ. ..

[0012]

[Table 1] X-ray grating plane diffraction angle 2θ (°) Interval median value (Å) Relative intensity 22.1 ± 0.3 4.02 100 28.2 ± 0.3 3.16 20 to 150 36.2 ± 0.3 2.48 5-60 45.2 ± 0.3 2.00 2-40 50.0 ± 0.3 1.82 2-40

The X-ray diffraction peak intensity may deviate depending on the measurement conditions of each crystal, but the relative intensity is usually in the above range when the peak intensity at 2θ = 22.1 ° is 100. Also, in general, 2θ = 22.1 ° and 28.2.
The peak intensity at ° appears significantly. Even if a small amount of an antimony compound described later is added to the composite oxide having such a crystal structure and subjected to treatments such as mixing and firing, the X-ray diffraction pattern of the obtained substance is almost the same. No change is observed.

The method for preparing the composite oxide is as follows.
For example, Mo_aV_bTe_cNb_xO _nIn case of
Tellurium was added to an aqueous solution containing ammonium metavanadate.
Aqueous acid solution, Niobium oxalate ammonium salt solution
And an aqueous solution of ammonium paramolybdate
Sequentially in a quantitative ratio such that the atomic ratio of metal elements is a predetermined ratio
Add and dry by evaporation drying method, spray drying method, vacuum drying method, etc.
And finally, the remaining dried product is usually heated to 350 to 700.
℃, preferably at a temperature of 400 ~ 650 ℃, usually 0.5
For 30 to 30 hours, preferably 1 to 10 hours, after firing,
It is a composite oxide.

Regarding the above-mentioned calcination method, the most general method is to carry out in an oxygen atmosphere, but in order to obtain the composite oxide having the above-mentioned specific structure, the calcination atmosphere is rather oxygen-free. It is preferable to set it below. Specifically, it is carried out in an atmosphere of an inert gas such as nitrogen, argon or helium, or in vacuum. The raw material of the above-mentioned composite oxide is not limited to the above-mentioned ones. Instead of ammonium metavanadate, for example, V
₂ O ₅ , V ₂ O ₃ , VOCl ₃ or VCl ₄ can be used, TeO ₂ or the like can be used instead of telluric acid, and N ₂ O ₃ can be used instead of niobium ammonium oxalate.
bCl ₅ , Nb ₂ O ₅ , niobate, etc. are used, and instead of ammonium paramolybdate, MoO ₃ , MoC is used.
l ₅ etc. can be used.

The composite oxide of the formula (1) prepared as described above has activity as a solid catalyst as it is, but in the present invention, in order to further enhance the selectivity and yield of nitrile. In addition, it is characterized in that a substance obtained by adding a specific oxide to the composite oxide is used as a solid catalyst. As the specific oxide, an oxide containing at least one of antimony, bismuth, cerium and boron is used, and antimony oxide is particularly preferable.

As the antimony oxide to be added, Sb
The antimony oxides of ₂ O ₃ , Sb ₂ O ₄ , and Sb ₂ O ₅ are exemplified, and a mixed oxide having a composition such as SbO ₂ (Sb ₂ O ₄ ) may be used. These oxides may be used alone or as a mixture of two or more kinds, and may be used in the form of hydrate. In some cases, an organic compound containing antimony, such as antimonylammonium tartrate and antimony oxalate, may be added to the composite oxide of formula (1), and the calcined substance may be used as a solid catalyst. In this case, the organic compound containing antimony is converted into antimony oxide by firing.

The bismuth oxide to be added is
Bi ₂ O ₃ and Bi ₂ O ₄ bismuth oxides are exemplified,
Also, a hydrate such as Bi ₂ O ₄ .2H ₂ O may be used. These oxides may be one kind or a mixture of plural kinds. In addition, in some cases, organic acid or inorganic acid salts containing bismuth such as bismuth hydroxide, bismuth nitrate, bismuth nitrate, bismuth acetate, etc., hydroxides, etc. are added to the composite oxide of the formula (1) and fired. The material can also be used as a solid catalyst. In these cases, the salt or hydroxide containing bismuth is converted into bismuth oxide by firing.

Further, as the cerium oxide, Ce ₂ O is used.
An example is cerium oxide of ₃ , CeO ₂ , and these oxides may be one kind or a mixture of plural kinds. In some cases, cerium nitrate, cerium hydroxide, cerium oxalate, cerium acetate, and other organic acids containing cerium, salts of inorganic acids, hydroxides, etc. are added to the composite oxide of formula (1) and fired. The above substances can also be used as a solid catalyst. In these cases, the salt or hydroxide containing cerium is converted into cerium oxide by firing.

The boron oxide is generally B ₂ O _3, but boric acid such as orthoboric acid, metaboric acid, ethyl borate, propyl borate or boric acid ester is used as a complex oxide of the formula (1). It is also possible to use the substance added to the above and calcined as a solid catalyst. In these cases, it is presumed that boric acid or boric acid ester is converted into boron oxide by firing.

The above-mentioned method of adding the specific oxide to the composite oxide is carried out while pulverizing and mixing both of them so that the contact of the specific oxide with the composite oxide is effectively performed.
The amount of the specific oxide added to the composite oxide is usually 0.0001 to 0.2, preferably 0.001 to 0.05, by weight ratio with respect to the composite oxide. After the addition, it may be used as it is in a reaction for producing nitriles from alkane, but it is preferably usually 300 to 650 ° C., particularly 35.
Bake at 0-600 ° C. The firing is preferably carried out in an atmosphere of an inert gas such as nitrogen, argon or helium, and the gas may contain a reducing gas such as hydrogen, ammonia or hydrocarbon, or steam, or is carried out in vacuum.

The substance composed of the complex oxide of the formula (1) and the oxide of antimony thus obtained can be used alone as a solid catalyst, but it is a well-known carrier such as silica, alumina, titania, It can also be used with aluminosilicate, diatomaceous earth and the like. In this case, the carrier as described above may be used when preparing the complex oxide of the formula (1) or may be used when adding antimony oxide. Further, it is molded into an appropriate shape and particle size depending on the scale of reaction, method and the like.

The method of the present invention is to produce a nitrile by subjecting an alkane to a gas phase catalytic oxidation reaction with ammonia in the presence of the above-mentioned oxide. In the present invention, the alkane as a raw material is not particularly limited, and examples thereof include methane, ethane, propane, butane, isobutane, pentane, hexane, heptane, cyclohexane, and the like. Then, it is preferable to use a lower alkane having 1 to 4 carbon atoms, particularly propane or isobutane.

Although the details of the mechanism of the oxidation reaction in the present invention are not clear, it is carried out by oxygen atoms present in the above oxides or molecular oxygen present in the feed gas. When the molecular oxygen is present in the feed gas, the molecular oxygen may be pure oxygen gas, but it is generally economical to use an oxygen-containing gas such as air because purity is not particularly required. Alkane, a mixed gas of ammonia and an oxygen-containing gas is usually used as the supply gas, but a mixed gas of an alkane and ammonia and an oxygen-containing gas may be alternately supplied.

It is also possible to carry out a gas phase catalytic reaction using only alkane and ammonia, which are substantially free of molecular oxygen, as feed gases. In such a case, it is preferable that a part of the catalyst is appropriately withdrawn from the reaction zone, the catalyst is fed into an oxidation regenerator, and after regeneration, the catalyst is re-supplied to the reaction zone. As a method of regenerating the catalyst, the catalyst is oxygen, air,
Oxidizing gas such as nitric oxide to the catalyst in the regenerator,
A typical method is to circulate at 300 to 600 ° C.

In the case of using propane as the alkane and air as the oxygen source, the present invention will be described in more detail. As the reactor system, either a fixed bed or a fluidized bed can be adopted, but since it is an exothermic reaction, It is easier to control the reaction temperature in the fluidized bed method. The ratio of air supplied to the reaction is important with respect to the selectivity of acrylonitrile to be produced, and the air usually shows a high acrylonitrile selectivity in a range of 25 mol times or less, particularly 1 to 15 mol times with respect to propane. . The proportion of ammonia supplied to the reaction is 0.2 to 5 times the molar amount of propane, particularly 0.1.
A range of 5 to 3 molar times is suitable. The reaction is usually carried out under atmospheric pressure, but it can also be carried out under slightly elevated pressure or reduced pressure. For other alkanes, the composition of the feed gas is selected according to the conditions for propane.

In the method of the present invention, the temperature is lower than that in the conventional ammoxidation reaction of alkane, for example, 34
It can be carried out at 0 to 480 ° C, particularly preferably at about 380 to 440 ° C. Even at such a low temperature, nitriles can be produced in a high yield as compared with conventional techniques. The gas space velocity SV in the gas phase reaction is usually 100 to 10000 h ^-1 , preferably 30.
It is in the range of ⁰ to 2000 h ⁻¹ . An inert gas such as nitrogen, argon, or helium can be used as a diluent gas for adjusting the space velocity and the oxygen partial pressure. When the ammoxidation reaction of propane is carried out by the method of the present invention, carbon monoxide, carbon dioxide, acetonitrile, hydrocyanic acid, and the like are by-produced in addition to acrylonitrile, but the amount produced is extremely small.

[0028]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded. The conversion rate (%) in the following examples and comparative examples,
The selectivity (%) and the yield (%) are respectively shown by the following equations.

[0029]

## EQU1 ## Alkane conversion rate (%) = (mol number of consumed alkane / mol number of supplied alkane) × 100 Selectivity of target nitrile (%) = (mol number of nitrile to be produced / mol number of consumed alkane) × 100 Yield of target nitrile (%) = (number of moles of nitrile to be produced / number of moles of alkane supplied) × 100

Example 1 A composite oxide having the empirical formula Mo ₁ V _0.3 Te _0.23 Nb _0.12 O _n was prepared as follows. 15.7 g of ammonium metavanadate was dissolved in 325 ml of warm water, and 23.6 g of telluric acid and 78.9 g of ammonium paramolybdate were sequentially added thereto to prepare a uniform aqueous solution. Furthermore, 117.5 g of a niobium ammonium oxalate aqueous solution having a niobium concentration of 0.456 mol / kg was mixed to prepare a slurry. The slurry was evaporated to dryness to give a solid. 5 mm of this solid using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 600 ° C. for 2 hours in a nitrogen stream.

Powder X-ray diffraction measurement of the thus obtained composite oxide (using Cu-Kα ray) revealed that the diffraction angles 2θ (°) were 22.1 (100), 28.2.
(90.0), 36.2 (25.7), 45.1 (1
The major diffraction peaks were observed at 5.2) and 50.0 (16.3) (the number in parentheses indicates the peak at 22.1 ° is 1).
The relative peak intensity when 00 is shown. ).

Next, 30 g of the complex oxide is crushed in a mortar.
Furthermore, tetravalent antimony oxide (Sb ₂O_Four) 0.3 g
Added and mixed. 5m of this mixture using a tablet press
After molding into mΦ × 3mmL, it is crushed and
Sieve into ash and bake at 500 ° C for 2 hours in a nitrogen stream
It was 0.5 ml of the solid catalyst thus obtained was placed in a reactor.
Fill, reaction temperature 410 ℃, space velocity SV 1000h
^-1Fixed to propane: ammonia: air = 1: 1.
Gas is supplied at a molar ratio of 2:15 to carry out a gas phase catalytic reaction.
The results obtained are shown in Table-1.

Example 2 Tetravalent antimony oxide (Sb ₂ O ₄ ) in Example 1
Table 1 shows the results obtained by producing a solid catalyst in the same manner as in Example 1 except that the amount added was 0.15 g, and further conducting the reaction under the same conditions as in Example 1.

Example 3 A solid catalyst was produced in the same manner as in Example 2 except that the calcination after adding the tetravalent antimony oxide in Example 2 was carried out in a nitrogen stream at 550 ° C. for 2 hours, and further carried out. The results of the reaction carried out under the same conditions as in Example 1 are shown in Table 1.

Example 4 30 g of the same complex oxide as in Example 1 was crushed in an agate mortar and an antimonylammonium tartrate aqueous solution (Sb ₂ O) was added.
₃ g (corresponding to a concentration of 10 wt% in terms of ₃ ) was added and mixed. This mixture is solid 5 mmΦ using a tablet press
After being molded into 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired in an air stream at 300 ° C for 1 hour and further in a nitrogen stream at 500 ° C for 2 hours. Table 1 shows the results of the reaction carried out under the same conditions as in Example 1, using the solid catalyst thus obtained.

Comparative Example 1 In Example 1, without adding antimony oxide, Mo,
Table 1 shows the results obtained by carrying out the reaction under the same conditions as in Example 1 using only the composite oxide containing V, Te, and Nb.

Comparative Example 2 The catalyst composition was the same as in Example 1, but the empirical formula Mo ₁ V was used.
After preparing a composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n , tetravalent antimony oxide (Sb ₂ O ₄ ) was not added, but tetravalent antimony oxide (Sb
_The composite oxide was prepared in the presence of ₂ O ₄ ). That is, 15.7 g of ammonium metavanadate salt was dissolved in 325 ml of warm water, and 23.6 g of telluric acid and ammonium paramolybdate 78.
9 g were sequentially added to prepare a uniform aqueous solution. Further, 117.5 g of an aqueous solution of ammonium niobium oxalate having a niobium concentration of 0.456 mol / kg was mixed to prepare a slurry. Further, 0.98 g of tetravalent antimony oxide (Sb ₂ O ₄ ) was added to this slurry and mixed. The slurry was evaporated to dryness to give a solid. This solid was molded into a size of 5 mmΦ × 3 mmL using a tablet molding machine, crushed, and sieved to 16 to 28 mesh, and the temperature was 600 ° C. in a nitrogen stream.
It was baked for 2 hours. Using the solid catalyst thus obtained, the reaction was carried out under the same conditions as in Example 1. Table of results
Shown in 1.

Comparative Example 3 A composite oxide was prepared in the same manner as in Comparative Example 2 except that the firing in a nitrogen stream in Comparative Example 2 was carried out at 500 ° C. for 2 hours, and the reaction was carried out under the same conditions as in Example 1. It was The results are shown in Table-1.

[0039]

[Table 2]

Examples 5 to 33 Table 2 shows the results of the reaction under various conditions using the solid catalyst produced in Example 1.

Examples 34 to 67 Table 3 shows the results of carrying out reactions under various conditions using the solid catalyst produced in Example 2.

Comparative Examples 4 to 10 Table 4 shows the results of carrying out the reaction under various conditions using the solid catalyst produced in Comparative Example 1. Under these same reaction conditions, it is understood that the yields of these comparative examples do not reach those of the examples shown in Tables 2 and 3.

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

[Table 6]

[0047]

[Table 7]

[0048] was prepared a composite oxide having Examples 68-72 empirical formula _{Mo 1 V 0.4 Te 0.2 Nb 0.1} O n as follows. 4.21 g of ammonium metavanadate was dissolved in 117 ml of warm water, and 4.13 g of telluric acid and 15.9 g of ammonium paramolybdate were sequentially added thereto to prepare a uniform aqueous solution. Further, 21.9 g of an aqueous solution of ammonium niobium oxalate having a niobium concentration of 0.41 mol / kg was mixed,
A slurry was prepared. The slurry was evaporated to dryness to give a solid. 5 mmΦ x 3 of this solid using a tablet press
After molding into mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 600 ° C for 2 hours in a nitrogen stream.

Powder X-ray diffraction measurement of the thus obtained composite oxide (using Cu-Kα ray) revealed that the diffraction angles 2θ (°) were 22.1 (100), 28.2.
(79.5), 36.2 (21.0), 45.2 (1
The major diffraction peaks were observed at 0.9) and 50.0 (12.3) (the number in parentheses indicates the peak at 22.1 ° is 1).
The relative peak intensity when 00 is shown.

Next, 10 g of the composite oxide was crushed in a mortar, and trivalent antimony oxide (Sb ₂ O ₃ ) 0.1 was added.
g was added and mixed. This mixture was molded into 5 mmΦ × 3 mmL using a tablet molding machine, and then pulverized to 16 to 2
It was sieved to 8 mesh and baked at 600 ° C. for 2 hours in a nitrogen stream. Table 5 shows the results of charging 0.5 ml of the thus obtained solid catalyst into a reactor and conducting the reaction under various conditions.

Comparative Examples 11 to 14 In Example 68, antimony oxide was not added, and Mo,
Table 5 shows the results of the reaction carried out under various conditions using only the composite oxide composed of V, Te and Nb. Even if the reaction temperature is raised 10 ° C. higher than that of Example 68 to increase the conversion rate of propane, it can be seen that, in comparison with Examples having the same reaction gas composition, all Comparative Examples are lower than the yield of Examples.

[0052]

[Table 8]

Examples 73 to 76 Example 68 was repeated except that the conversion of antimony oxide to the composite oxide consisting of Mo, V, Te and Nb in Example 68 was carried out using tetravalent antimony oxide (Sb ₂ O ₄ ). Table 6 shows the results of producing a solid catalyst in the same manner as above, and further conducting the reaction under various conditions.

Comparative Example 15 The catalyst composition was the same as in Example 68, but the empirical formula Mo ₁
After the composite oxide was prepared having a _{V 0.4 Te 0.2 Nb 0. 1 O} n, instead of adding a tetravalent antimony oxide (Sb ₂ O _4), starting from tetravalent antimony oxide (S
The oxide was prepared in the presence of b ₂ O ₄ ).
That is, 4.21 g of ammonium metavanadate is dissolved in 117 ml of warm water, and 4.13 g of telluric acid and ammonium paramolybdate 15.9 are added to the solution.
g was sequentially added to prepare a uniform aqueous solution. Further, 21.9 g of an aqueous solution of ammonium niobium oxalate having a niobium concentration of 0.41 mol / kg was mixed to prepare a slurry. Furthermore, tetravalent antimony oxide (Sb
0.2 g of ₂ O ₄ ) was added and mixed. The slurry was evaporated to dryness to give a solid. This solid was molded into a size of 5 mmΦ × 3 mmL using a tablet molding machine, and then crushed to obtain 16-
The mixture was sieved to 28 mesh and fired in a nitrogen stream at 600 ° C for 2 hours. Using the solid catalyst thus obtained, the reaction was carried out under the conditions shown in Table-6. The results are also shown in the table.

Comparative Example 16 Firing in a nitrogen stream in Comparative Example 15 was carried out at 500 ° C. for 2
A composite oxide was prepared in the same manner as in Comparative Example 15 except that the time was set, and the reaction was performed under the conditions shown in Table-6. The results are also shown in the table.

[0056]

[Table 9]

Example 77 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of a composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was crushed, and 0.3 g of orthoboric acid (H ₃ BO ₃ ) was added and mixed. 5 mm of this mixture using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 600 ° C. for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, the reaction temperature was 410 ° C., the space velocity SV was fixed at 1000 h ⁻¹ , and propane: ammonia: air = 1: 1.2:
The results of carrying out the gas phase catalytic reaction by supplying gas at a molar ratio of 15 are shown in Table 7.

Comparative Example 78 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of a composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was pulverized, and 0.6 g of orthoboric acid (H ₃ BO ₃ ) was further added and mixed. 5 mm of this mixture using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired in a nitrogen stream at 550 ° C. for 2 hours. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the gas phase catalytic oxidation reaction of propane was conducted under the same reaction conditions as in Example 125. The results are shown in Table 7.

Example 79 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of a composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was crushed, and 0.9 g of orthoboric acid (H ₃ BO ₃ ) was further added and mixed. 5 mm of this mixture using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired in a nitrogen stream at 550 ° C. for 2 hours. 0.5 ml of the solid catalyst thus obtained is charged into a reactor, and the results of gas phase catalytic oxidation reaction of propane under the same reaction conditions as in Example 77 are shown in Table 7.

[0060]

[Table 10]

Example 80 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of a composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was crushed, and 0.3 g of bismuth oxide (Bi ₂ O ₃ ) was further added and mixed. 5 mm of this mixture using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired in a nitrogen stream at 550 ° C. for 2 hours. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, the reaction temperature was 410 ° C., the space velocity SV was fixed at 1000 h ⁻¹ , and propane: ammonia: air = 1: 1.2:
Table 8 shows the results of gas-phase catalytic reaction performed by supplying gas at a molar ratio of 15.

Example 81 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of the composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was pulverized, and 0.6 g of bismuth oxide (Bi ₂ O ₃ ) was further added and mixed. 5 mm of this mixture using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired in a nitrogen stream at 550 ° C. for 2 hours. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the results of gas phase catalytic oxidation reaction of propane under the same reaction conditions as in Example 80 are shown in Table-8.

Example 82 A solid catalyst was prepared in the same manner as in Example 81 except that the calcination temperature in a nitrogen stream after the addition of bismuth oxide was changed to 600 ° C. in Example 81. The results of the phase contact oxidation reaction are shown in Table-8.

Example 83 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of the composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was crushed, and 0.9 g of bismuth oxide (Bi ₂ O ₃ ) was further added and mixed. 5 mm of this mixture using a tablet press
After being molded into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired in a nitrogen stream at 550 ° C. for 2 hours. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the results of gas phase catalytic oxidation reaction of propane under the same reaction conditions as in Example 80 are shown in Table-8.

Example 84 0.5 ml of the solid catalyst prepared as described in Example 80 was charged to a reactor at a reaction temperature of 400.
Table-8 shows the results of the gas phase catalytic reaction with the gas supplied at a molar ratio of propane: ammonia: air = 1: 0.75: 15 with the space velocity SV fixed at 1000 h ^-1 at ℃. ..

Examples 85 to 92 Table 8 shows the results of the vapor phase catalytic oxidation reaction of propane under various reaction conditions using the solid catalyst prepared by the method described in Example 81.

[0067]

[Table 11]

Example 93 Empirical formula Mo ₁ V prepared as described in Example 1
30 g of a composite oxide containing _0.3 Te _0.23 Nb _0.12 O _n was pulverized, and 0.3 g of cerium oxide (CeO ₂ ) was further added and mixed. 5 mmΦ of this mixture using a tablet press
After molding to × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 600 ° C for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor,
The reaction temperature is 420 ° C., the space velocity SV is fixed at 1000 h ⁻¹ , and propane: ammonia: air = 1: 1.2: 15.
Table 9 shows the results of the gas-phase catalytic reaction performed by supplying the gas at a molar ratio of.

Example 94 0.5 m of solid catalyst prepared as in Example 93
1 was charged into a reactor, reaction temperature was 430 ° C., space velocity SV
Is fixed at 1500 h ⁻¹ , gas is supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15, and a gas phase catalytic reaction is carried out. The results are shown in Table-9.

Example 95 A solid catalyst was prepared in the same manner as in Example 93 except that the amount of bismuth oxide added in Example 93 was changed to 0.6 g. 0.5 ml of the thus prepared solid catalyst was charged into a reactor, the reaction temperature was 430 ° C., and the space velocity SV was 1000 h.
Fixed to ^-1 , propane: ammonia: air = 1: 1.
Table 9 shows the results of gas-phase catalytic reaction performed by supplying gas at a molar ratio of 2:15.

Example 96 0.5 m of solid catalyst prepared as in Example 95
1 was charged into a reactor, reaction temperature was 440 ° C., space velocity SV
Is fixed at 1500 h ⁻¹ , gas is supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15, and a gas phase catalytic reaction is carried out. The results are shown in Table-9.

Comparative Examples 17 to 19 In Examples 93 to 95, M was added without adding cerium oxide.
Table 9 shows the results of the gas phase catalytic oxidation reaction of propane carried out under the same conditions as in Examples 93 to 95 using only the composite oxide consisting of o, V, Te and Nb.

[0073]

[Table 12]

Example 97 Empirical formula Mo prepared as described in Example 1₁V
_0.3Te_0.23Nb_0.12O_n30g of complex oxide having
Crushed and further tetravalent antimony oxide (Sb₂O _Four) 0.
225 g, bismuth oxide (Bi₂O₃) Add 0.6 g
And mixed. 5 mmΦ of this mixture using a tablet press
× 3mmL, then crushed and 16-28 mesh
After sieving, the mixture was calcined in a nitrogen stream at 550 ° C. for 2 hours. this
0.5 ml of the solid catalyst thus obtained was charged into a reactor,
Reaction temperature 410 ℃, space velocity SV 1000h^-1Fixed to
Then, propane: ammonia: air = 1: 1.2: 15
Results of gas-phase catalytic reaction by supplying gas at a molar ratio of
Is shown in Table-10.

Example 98 Empirical formula Mo prepared as described in Example 1₁V
_0.3Te_0.23Nb_0.12O_n30g of complex oxide having
Crushed and further tetravalent antimony oxide (Sb₂O _Four) 0.
1125 g, bismuth oxide (Bi₂O₃) Add 0.3 g
Add and mix. 5 mm of this mixture using a tablet press
After molding into Φ × 3mmL, crushed and 16-28 mesh
And screened for 2 hours at 550 ° C. in a nitrogen stream. This
0.5 ml of the solid catalyst obtained as described above was charged into the reactor.
Then, the reaction temperature is 400 ° C and the space velocity SV is 1000h.^-1To
Fixed, propane: ammonia: air = 1: 1.2:
Gas was supplied at a molar ratio of 15 to carry out a gas phase catalytic reaction.
The results are shown in Table-10.

Example 99 0.5 m of solid catalyst prepared as in Example 98
1 was charged into a reactor, reaction temperature was 410 ° C., space velocity SV
Is fixed at 1500 h ⁻¹ , gas is supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15, and a gas phase catalytic reaction is carried out. The results are shown in Table-10.

Example 100 Bismuth nitrate pentahydrate (Bi (NO₃)₃
・ 5H₂O) 0.277 g is added, and tetravalent oxidation is further performed.
Antimony (Sb₂O_Four) 0.167g are mixed and evaporated to dryness
Solidified The solid was calcined at 600 ° C for 2 hours under air flow.
It was The solid thus obtained was prepared as described in Example 1.
Experimental formula Mo prepared by ₁V_0.3Te_0.23Nb_0.12O
_n30 g of the complex oxide having the above formula was added and mixed. this
Mold the mixture into 5mmΦ x 3mmL using a tablet molding machine
After that, it is pulverized and sieved to 16-28 mesh, and nitrogen gas is added.
It was calcined at 550 ° C. for 2 hours in the flow. It exists here
The atomic ratio of Sb to Bi is 2: 1. In this way
0.5 ml of the obtained solid catalyst was charged into a reactor, and the reaction temperature was 4
10 ℃, space velocity SV 1000h^-1Fixed to a professional
Bread: ammonia: air = 1: 1.2: 15 molar ratio
Table 10 shows the results of gas-phase contact reaction with gas supply.
Shown in.

Example 101 0.5% solid catalyst prepared as in Example 100
ml was charged into the reactor, the reaction temperature was 410 ° C, the space velocity S
V was fixed at 1500 h ^-1 , and propane: ammonia:
Table-10 shows the results of the gas-phase catalytic reaction performed by supplying gas at a molar ratio of air = 1: 1.2: 15.

[0079]

[Table 13]

Example 102 Empirical formula Mo prepared as described in Example 1₁V
_0.3Te_0.23Nb_0.12O_n30g of complex oxide having
Crushed and further tetravalent antimony oxide (Sb₂O _Four) 0.
225g was added and mixed. Press this mixture into a tablet press
After molding to 5mmΦ x 3mmL, it is crushed to 16
Sieve to ~ 28 mesh and nitrogen gas flow at 550 ° C for 2 hours
Baked. 0.5 ml of the solid catalyst obtained in this way
Fill the reactor, reaction temperature 420 ℃, space velocity SV 10
00h^-1Fixed to, isobutane: ammonia: air =
Gas is supplied at a molar ratio of 1: 1.2: 15 to prevent gas phase contact reaction.
I responded. As a result, the conversion rate of isobutane was 61.
4%, methacrylonitrile selectivity 33.0%, methacrylonitrile
The yield of lilonitrile was 20.3%.

Comparative Example 20 In Example 102, M was not added without antimony oxide.
The vapor phase catalytic oxidation reaction of isobutane was performed under the same reaction conditions as in Example 102, using only the composite oxide composed of o, V, Te, and Nb. As a result, the conversion rate of isobutane was 64.1.
%, The methacrylonitrile selectivity was 29.7%, and the methacrylonitrile yield was 19.1%.

[0082]

According to the method of the present invention, alkane is used as a raw material in the reaction system at a relatively low temperature of about 400 to 450 ° C. in a high yield without halide and water being present in the reaction system. The nitrile can be produced.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Sawaki, No. 1 Higashinamachi, Yokkaichi, Mie Prefecture Yokkaichi Plant, Mitsubishi Kasei Co., Ltd.

Claims (4)

[Claims] 1. A following empirical formula _{(1) Mo a V b Te} c X x O n (1) ( Formula (1), X is Nb, Ta, W, Ti, A
1, Zr, Cr, Mn, Fe, Ru, Co, Rh, N
represents one or more elements selected from i, Pd, Pt, Sb, Bi, B and Ce, and when a = 1, b = 0.01 to 1.0 c = 0.01 .About.1.0 x = 0.01 to 1.0, and n is determined by the oxidation states of other elements. In the presence of a solid catalyst prepared by adding one or more oxides of antimony, bismuth, cerium and boron to the complex oxide represented by Manufacturing method. 2. The solid catalyst is a composite oxide and antimony,
2. The method for producing a nitrile according to claim 1, wherein the nitrile is a substance obtained by adding one or more oxides of bismuth, cerium and boron and firing the mixture. 3. The composite oxide according to claim 1 containing antimony,
A method for producing a nitrile, characterized in that an alkane is subjected to a gas phase catalytic oxidation reaction with ammonia in the presence of a solid catalyst formed by adding an organic compound containing at least one of bismuth, cerium and boron and firing the mixture. 4. The method according to claim 1, wherein the alkane is propane and / or isobutane.
The method for producing a nitrile according to any one of 1.