JP3168716B2 - Nitrile manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a nitrile. More specifically, the present invention relates to a method for producing an improved nitrile using alkane as a raw material.

[0002]

2. Description of the Related Art Nitriles such as acrylonitrile and methacrylonitrile are industrially manufactured as important intermediates such as fibers, synthetic resins and synthetic rubbers. Is known as the most common method of contacting olefins such as with ammonia and oxygen in the gas phase at a high temperature in the presence of a catalyst.

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

[0004] As an example of these reports, Mo-Bi-P
-O-based catalyst (JP-A-48-16887), V-Sb-
O-based catalysts (JP-A-47-33783, JP-B-50-2)
No. 3016, JP-A-1-268668), Sb-U-
V-Ni-O catalyst (JP-B-47-14371), S
b-Sn-O type catalyst (JP-B-50-28940), V
-Sb-WPO catalyst (Japanese Patent Laid-Open No. 2-95439)
No.), V-Sb-WO-based oxide and Bi-Ce-Mo-
Catalysts obtained by mechanically mixing WO oxides
4-38051) is known, and the present inventors have
o-V-Te-Nb-O-based catalyst (JP-A-2-257)
Has been reported.

[0005]

However, none of these methods has a satisfactory yield of the desired nitrile. 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. Water has a problem of corrosion, and water has a problem of generation of by-products due to side reactions and treatment thereof, and all have problems in industrial implementation.

Furthermore, the conventional method using a catalyst system 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 the material of the reactor, the production cost and the like.

[0007]

Means for Solving the Problems The present inventors have proposed the above-mentioned M
As a result of further study on 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, as a result, a Mo-V-Te-X-O-based catalyst (X is one or A plurality of specific elements are represented, and X may include Nb.) (Japanese Patent Application No. 3-10438).
2). Furthermore, it has been found that when the same Mo-V-Te-X-O-based catalyst having a specific crystal structure is used, the yield of nitrile is remarkably improved (Japanese Patent Application No. 3-199573). ).

The present inventors have focused on further studies based on the results of the recent research described above, and found that Mo-V-Te-X
After preparing the -O-based composite oxide, the composite oxide further comprises
By reacting the alkane with ammonia in the gas phase in the presence of a solid catalyst obtained by adding a specific substance such as antimony oxide and the like, the reaction system is free from halides, water, etc. The inventors have found that the desired nitrile can be produced at a relatively low temperature of about 450 ° C. with a higher yield than the conventional method, 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 1.0x = 0.01 to 1.0, and n is determined by the oxidation state of other elements. ), A gaseous catalytic oxidation reaction of alkane with ammonia in the presence of a solid catalyst obtained by adding antimony oxide or the like to the composite oxide represented by the formula (1).

Hereinafter, the present invention will be described in detail. In the composite oxide of the above-mentioned formula (1) prepared first in the present invention, the above-mentioned elements are used as X, and preferably, Nb, Ta,
W and Ti, particularly preferably Nb. Further, when a = 1 as a coefficient of the equation (1), b = 0.1 to
0.6, c = 0.05-0.4, x = 0.01-0.6
Is particularly preferred.

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

[0012]

Table 1 X-ray grating surface diffraction angle 2θ (°) Median interval (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 when the peak intensity at 2θ = 22.1 ° is 100 is usually in the above range. In general, 2θ = 22.1 ° and 28.2
° peak intensity is large. Note that, even when a small amount of an antimony compound described below is added to the composite oxide having such a crystal structure, and a treatment such as mixing and baking is performed, the X-ray diffraction pattern of the obtained substance is almost the same. No change is observed.

The preparation method of the composite oxide is as follows.
For example, Mo_aV_bTe_cNb_xO _nIn the case of
Tellurium solution in an aqueous solution containing ammonium metavanadate
Aqueous solution of acid, aqueous solution of niobium ammonium oxalate
And aqueous solutions of ammonium paramolybdate
In order to achieve a predetermined ratio of metal element atomic ratio
Add and dry by evaporation to dryness, spray drying, vacuum drying, etc.
And finally, the remaining dried product is usually 350 to 700
° C, preferably at a temperature of 400-650 ° C, usually 0.5
For 30 to 30 hours, preferably 1 to 10 hours
It is a composite oxide.

The above-mentioned firing method is most commonly performed in an oxygen atmosphere. However, in order to obtain the above-mentioned composite oxide having a specific structure, the firing atmosphere is preferably changed to a state in which oxygen is not present. It is preferred to be below. Specifically, it is performed in an atmosphere of an inert gas such as nitrogen, argon, and helium, or in a vacuum. In addition, the raw material of the above-mentioned composite oxide is not limited to the above-mentioned one, and 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 is used in place of telluric acid, and Nb in place of niobium ammonium oxalate is used.
bCl ₅ , Nb ₂ O ₅ , niobate, etc. are used, and instead of ammonium paramolybdate, MoO ₃ , MoC
it is possible to use the l ₅ and the like.

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

The antimony oxide to be added is Sb
Antimony oxides of ₂ O ₃ , Sb ₂ O ₄ and Sb ₂ O ₅ are exemplified, and mixed oxides 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, or may be used in the form of a hydrate. In some cases, an organic compound containing antimony such as antimony ammonium tartrate or antimony oxalate may be added to the composite oxide of the 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 includes:
Bismuth oxides _{Bi 2 O 3, Bi 2 O} 4 and the like,
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 some cases, bismuth hydroxide, bismuth nitrate, bismuth nitrate oxide, bismuth-containing organic or inorganic acid salts or hydroxides containing bismuth are added to the composite oxide of formula (1) and calcined. The substance can also be used as a solid catalyst. In these cases, the salts and hydroxides containing bismuth are converted to bismuth oxide by firing.

As the cerium oxide, Ce ₂ O is used.
₃ , cerium oxides of CeO ₂ are exemplified, and these oxides may be one kind or a mixture of plural kinds. In some cases, cerium-containing organic acids and inorganic acid salts such as cerium nitrate, cerium hydroxide, cerium oxalate, and cerium acetate, and hydroxides are added to the composite oxide of the formula (1), followed by firing. The obtained substance can be used as a solid catalyst. In these cases, the salt or hydroxide containing cerium is converted to cerium oxide by firing.

The boron oxide is generally B ₂ O _3, but boric acid or boric acid ester such as orthoboric acid, metaboric acid, ethyl borate, propyl borate, etc. is a complex oxide of the formula (1). And the calcined substance can be used as a solid catalyst. In these cases, it is presumed that boric acid or borate is converted to boron oxide by firing.

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

The substance comprising the composite oxide of the formula (1) and the oxide of antimony thus obtained can be used alone as a solid catalyst, but may be a known carrier such as silica, alumina, titania, It can also be used with aluminosilicate, diatomaceous earth and the like. In this case, the above-mentioned carrier 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 according to the scale and system of the reaction.

In the method of the present invention, a nitrile is produced by subjecting an alkane to a gas-phase catalytic oxidation reaction with ammonia in the presence of the above-mentioned oxide. The alkane as a raw material in the present invention is not particularly limited, and includes, for example, methane, ethane, propane, butane, isobutane, pentane, hexane, heptane, cyclohexane, and the like, and the industrial use of the obtained nitrile is considered. 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, the oxidation reaction is carried out by oxygen atoms present in the above-described oxide or molecular oxygen present in the supply gas. When molecular oxygen is present in the feed gas, the molecular oxygen may be pure oxygen gas, but since purity is not particularly required, it is generally economical to use an oxygen-containing gas such as air. Usually, a mixed gas of alkane, ammonia and an oxygen-containing gas is used as a supply gas, but a mixed gas of alkane and ammonia and an oxygen-containing gas may be supplied alternately.

It is also possible to carry out a gas phase contact reaction using only an alkane substantially free of molecular oxygen and ammonia as feed gases. In such a case, a method is preferable in which a part of the catalyst is appropriately extracted from the reaction zone, the catalyst is sent to an oxidation regenerator, and after regeneration, the catalyst is re-supplied to the reaction zone. As a method for regenerating the catalyst, oxygen, air,
An oxidizing gas such as nitric oxide is supplied to the catalyst in the regenerator,
A method of flowing at a temperature of usually 300 to 600 ° C. is exemplified.

In the case where propane is used as the alkane and air is used as the oxygen source, the present invention will be described in more detail. In the reactor system, any of a fixed bed, a fluidized bed and the like can be adopted. The fluidized bed system makes it easier to control the reaction temperature. The proportion of air supplied to the reaction is important with respect to the selectivity of acrylonitrile to be produced, and air generally exhibits a high acrylonitrile selectivity in the range of 25 mol times or less, particularly in the range of 1 to 15 mol times, relative to propane. . The proportion of ammonia to be supplied to the reaction is 0.2 to 5 times the molar amount of propane, especially 0.1 to 0.5.
A range of 5 to 3 molar times is preferred. This reaction is usually carried out under atmospheric pressure, but can also be carried out under low pressure or low 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 alkane ammoxidation reaction, for example, 34.
It can be carried out at 0 to 480 ° C, particularly preferably about 380 to 440 ° C. Even at such a low temperature, nitriles can be produced with a higher yield than conventional techniques. The gas hourly space velocity SV in the gas phase reaction is usually 100 to 10,000 h ^-1 , preferably 30
It is in the range of ⁰ to 2000 h ^-1 . Note that 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 propane is subjected to an ammoxidation reaction by the method of the present invention, carbon monoxide, carbon dioxide, acetonitrile, hydrocyanic acid, and the like are produced as by-products in addition to acrylonitrile, but the amount produced is extremely small.

[0028]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples without departing from the gist thereof. The conversion (%) in the following Examples and Comparative Examples,
The selectivity (%) and the yield (%) are represented by the following formulas, respectively.

[0029]

## EQU00001 ## Alkane conversion (%) = (moles of alkane consumed / moles of supplied alkane) .times.100 Selectivity of target nitrile (%) = (moles of target nitrile formed / moles of alkane consumed) × 100 Yield (%) of target nitrile = (moles of target nitrile formed / moles of alkane supplied) × 100

[0030] was prepared in Example 1 empirical formula Mo ₁ complex oxide having a V _0.3 Te _0.23 Nb _0.12 O _n 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. Further, 117.5 g of an aqueous niobium ammonium oxalate 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. This solid was compressed to 5 mm using a tableting machine.
After shaping to Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 600 ° C. for 2 hours in a nitrogen stream.

The composite oxide thus obtained was subjected to powder X-ray diffraction measurement (using a Cu-Kα ray). The diffraction angle 2θ (°) was 22.1 (100) and 28.2.
(90.0), 36.2 (25.7), 45.1 (1
5.2), a major diffraction peak was observed at 50.0 (16.3) (in parentheses in the figures, the peak at 22.1 ° was 1).
The relative peak intensity when the value is set to 00 is shown. ).

Next, 30 g of the composite oxide was crushed in a mortar.
And tetravalent antimony oxide (Sb _TwoO_Four) 0.3g
Added and mixed. This mixture was compressed to 5 m using a tablet press.
After molding to mΦ × 3mmL, pulverize,
And calcined in a nitrogen stream at 500 ° C for 2 hours.
Was. 0.5 ml of the solid catalyst thus obtained is placed in a reactor.
Filling, reaction temperature 410 ° C, space velocity SV 1000h
^-1And propane: ammonia: air = 1: 1.
A gas is supplied at a molar ratio of 2:15 to perform 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
A solid catalyst was produced in the same manner as in Example 1 except that the addition amount of was 0.15 g, and the reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 3 A solid catalyst was prepared in the same manner as in Example 2 except that the calcination in Example 2 after adding tetravalent antimony oxide was performed at 550 ° C. for 2 hours in a nitrogen stream. Table 1 shows the results of the reaction performed under the same conditions as in Example 1.

Example 4 30 g of the same composite oxide as in Example 1 was ground in an agate mortar, and an aqueous solution of antimony ammonium ammonium tartrate (Sb ₂ O) was used.
₃ g was added and mixed. This mixture was solidified into a solid of 5 mmφ × using a tableting machine.
After shaping to 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 300 ° C. for 1 hour in an air stream and further for 2 hours at 500 ° C. in a nitrogen stream. Using the solid catalyst thus obtained, the reaction was carried out under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example 1 In Example 1, no antimony oxide was added, and Mo,
Table 1 shows the results of a reaction performed under the same conditions as in Example 1 using only the composite oxide composed of V, Te, and Nb.

Comparative Example 2 The same catalyst composition as in Example 1 was used, but the empirical formula Mo ₁ V
_0.3 Te _0.23 Nb _0.12 O _n After the composite oxide was prepared with, rather than adding a tetravalent antimony oxide (Sb ₂ O _4), starting from tetravalent antimony oxide (Sb
_A composite oxide was prepared in the presence of ₂ O ₄ ). That is, 15.7 g of ammonium metavanadate 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 niobium ammonium oxalate solution 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 the slurry and mixed. The slurry was evaporated to dryness to give a solid. This solid was molded into 5 mmΦ × 3 mmL using a tablet molding machine, then crushed, sieved to 16 to 28 mesh, and placed in a nitrogen stream at 600 ° C.
For 2 hours. Using the solid catalyst thus obtained, a reaction was carried out under the same conditions as in Example 1. Table-Results
It is shown in FIG.

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

[0039]

[Table 2]

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

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

Comparative Examples 4 to 10 Using the solid catalyst prepared in Comparative Example 1, the reaction was carried out under various conditions. It can be seen that, under the same reaction conditions, the yields of these comparative examples are not as high as 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 niobium ammonium oxalate solution 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. Using a tableting machine, this solid is 5mmΦ × 3
After being molded into mmL, it was pulverized, sieved to 16 to 28 mesh, and calcined at 600 ° C. for 2 hours in a nitrogen stream.

The composite oxide thus obtained was subjected to powder X-ray diffraction measurement (using Cu-Kα radiation), and it was found that the diffraction angle 2θ (°) was 22.1 (100), 28.2.
(79.5), 36.2 (21.0), 45.2 (1
0.9) and 50.0 (12.3), major diffraction peaks were observed (in parentheses in the figures, the peak at 22.1 ° was 1).
The relative peak intensity when the value is set to 00 is shown.

Next, 10 g of the composite oxide was ground in a mortar, and trivalent antimony oxide (Sb ₂ O ₃ ) 0.1 g was further added.
g was added and mixed. This mixture was molded into 5 mmφ × 3 mmL using a tablet molding machine, and then pulverized,
The mixture was sieved to 8 mesh and calcined at 600 ° C. for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor and reacted under various conditions. The results are shown in Table-5.

Comparative Examples 11 to 14 In Example 68, no antimony oxide was added and Mo,
Table 5 shows the results of the reaction performed under various conditions using only the composite oxide composed of V, Te, and Nb. Even when the conversion temperature of propane is increased by increasing the reaction temperature by 10 ° C. as compared with Example 68, 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 tetravalent antimony oxide (Sb ₂ O ₄ ) was used for the conversion of antimony oxide into the composite oxide comprising Mo, V, Te, and Nb. Table 6 shows the results of producing a solid catalyst in the same manner as described above, and further performing the reaction under various conditions.

Comparative Example 15 The catalyst had the same composition as that of Example 68, but had 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 was dissolved in 117 ml of warm water, and 4.13 g of telluric acid and 15.9 g of ammonium paramolybdate were dissolved therein.
g were sequentially added to prepare a uniform aqueous solution. Further, 21.9 g of an aqueous niobium ammonium oxalate solution 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 tableting machine, and then crushed.
The mixture was sieved to 28 mesh and calcined at 600 ° C. for 2 hours in a nitrogen stream. Using the solid catalyst thus obtained, a reaction was carried out under the conditions shown in Table-6. The results are also shown in the table.

Comparative Example 16 The sintering in Comparative Example 15 was performed at 500 ° C.
A composite oxide was prepared in the same manner as in Comparative Example 15 except that the time was changed, 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 Experimental formula Mo ₁ V prepared as described in Example 1
The _0.3 Te _0.23 Nb composite oxide 30g having _0.12 O _n was pulverized after further addition of orthoboric acid (H ₃ BO ₃₎ 0.3g mixing. The mixture was compressed to 5 mm using a tableting machine.
After shaping 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 gas was supplied at a molar ratio of 15 to perform a gas phase contact reaction, and the results are shown in Table-7.

Example 78 Empirical formula Mo ₁ V prepared as described in Example 1.
The _0.3 Te _0.23 Nb composite oxide 30g having _0.12 O _n was pulverized after further addition of orthoboric acid (H ₃ BO ₃₎ 0.6g mixing. This mixture was mixed with a tableting machine at 5 mmФ ×
After shaping to 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 550 ° C. for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the gas phase catalytic oxidation reaction of propane was performed under the same reaction conditions as in Example 125. Table 7 shows the results.

Example 79 Experimental formula Mo ₁ V prepared as described in Example 1.
The _0.3 Te _0.23 Nb composite oxide 30g having _0.12 O _n was pulverized after further addition of orthoboric acid (H ₃ BO ₃₎ 0.9g mixing. The mixture was compressed to 5 mm using a tableting machine.
After shaping into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 550 ° C. for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the gas phase catalytic oxidation reaction of propane was carried out under the same reaction conditions as in Example 77. Table 7 shows the results.

[0060]

[Table 10]

Example 80 Empirical formula Mo ₁ V prepared as described in Example 1.
The _0.3 Te _0.23 Nb _0.12 composite oxide 30g having O _n milled and added further bismuth oxide (Bi ₂ O ₃₎ 0.3g mixing. The mixture was compressed to 5 mm using a tableting machine.
After shaping into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 550 ° 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 gas was supplied at a molar ratio of 15 to perform a gas phase contact reaction, and the results are shown in Table-8.

Example 81 The empirical formula Mo ₁ V prepared as described in Example 1
The _0.3 Te _0.23 Nb _0.12 composite oxide 30g having O _n milled and added further bismuth oxide (Bi ₂ O ₃₎ 0.6g mixing. The mixture was compressed to 5 mm using a tableting machine.
After shaping into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 550 ° C. for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the gas phase catalytic oxidation reaction of propane was carried out under the same reaction conditions as in Example 80. Table 8 shows the results.

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

Example 83 Empirical formula Mo ₁ V prepared as described in Example 1
The _0.3 Te _0.23 Nb _0.12 composite oxide 30g having O _n milled and added further bismuth oxide (Bi ₂ O ₃₎ 0.9g mixing. The mixture was compressed to 5 mm using a tableting machine.
After shaping into Φ × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 550 ° C. for 2 hours in a nitrogen stream. 0.5 ml of the solid catalyst thus obtained was charged into a reactor, and the gas phase catalytic oxidation reaction of propane was carried out under the same reaction conditions as in Example 80. Table 8 shows the results.

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

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

[0067]

[Table 11]

Example 93 The empirical formula Mo ₁ V prepared as described in Example 1
The _0.3 Te _0.23 Nb composite oxide 30g having _0.12 O _n was pulverized after addition of further cerium oxide (CeO ₂₎ 0.3 g mixture. This mixture was compressed to 5 mmφ using a tableting machine.
After shaping to × 3 mmL, it was pulverized, sieved to 16 to 28 mesh, and fired at 600 ° C. for 2 hours in a nitrogen stream. The reactor was filled with 0.5 ml of the solid catalyst thus obtained,
At a reaction temperature of 420 ° C. and a space velocity SV of 1000 h ⁻¹ , propane: ammonia: air = 1: 1.2: 15
Table 9 shows the results obtained by supplying a gas at the following molar ratio and performing a gas phase contact reaction.

Example 94 The solid catalyst prepared as in Example 93 was treated with 0.5 m
into a reactor at a reaction temperature of 430 ° C. and a space velocity SV
Was fixed at 1500 h ^-1 , and a gas was supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15 to perform a gas phase contact reaction. Table 9 shows the results.

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

Example 96 The solid catalyst prepared as in Example 95 was treated with 0.5 m
into a reactor at a reaction temperature of 440 ° C. and a space velocity SV
Was fixed at 1500 h ^-1 , and a gas was supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15 to perform a gas phase contact reaction. Table 9 shows the results.

Comparative Examples 17 to 19 In Examples 93 to 95, no cerium oxide was added and M
Table 9 shows the results of the gas phase catalytic oxidation reaction of propane performed using only the composite oxide consisting of o, V, Te, and Nb under the same conditions as in Examples 93 to 95.

[0073]

[Table 12]

Example 97 An empirical formula Mo prepared as described in Example 1.₁V
_0.3Te_0.23Nb_0.12O_n30 g of the composite oxide having
Pulverized, and furthermore tetravalent antimony oxide (Sb_TwoO _Four) 0.
225 g, bismuth oxide (Bi_TwoO_Three) Add 0.6g
And mixed. This mixture was compressed to 5 mmφ using a tableting machine.
× 3mmL, then pulverized, 16-28 mesh
And calcined at 550 ° C. for 2 hours in a nitrogen stream. this
0.5 ml of the solid catalyst thus obtained was charged into a reactor,
Reaction temperature 410 ° C, space velocity SV 1000h^-1Fixed to
And propane: ammonia: air = 1: 1.2: 15
Gas was supplied at the molar ratio of
Is shown in Table-10.

Example 98 An empirical formula Mo prepared as described in Example 1.₁V
_0.3Te_0.23Nb_0.12O_n30 g of the composite oxide having
Pulverized, and furthermore tetravalent antimony oxide (Sb_TwoO _Four) 0.
1125 g, bismuth oxide (Bi_TwoO_Three) Add 0.3g
And mixed. The mixture was compressed to 5 mm using a tableting machine.
After shaping into Φ × 3mmL, crushed, 16-28 mesh
And baked at 550 ° C. for 2 hours in a nitrogen stream. This
Fill the reactor with 0.5 ml of the solid catalyst obtained as above
The reaction temperature is 400 ° C. and the space velocity SV is 1000 h^-1To
Fixed, propane: ammonia: air = 1: 1.2:
A gas was supplied at a molar ratio of 15 to perform a gas phase contact reaction.
The results are shown in Table-10.

Example 99 The solid catalyst prepared as in Example 98 was treated with 0.5 m
into a reactor, at a reaction temperature of 410 ° C. and a space velocity SV
Was fixed at 1500 h ^-1 , and a gas was supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15 to perform a gas phase contact reaction. Table 10 shows the results.

Example 100 Bismuth nitrate pentahydrate (Bi (NO_Three)_Three
・ 5H_TwoO) 0.277 g was added, and tetravalent oxidation was further performed.
Antimony (Sb_TwoO_Four) 0.167g mixed and evaporated to dryness
Hardened. This solid is fired at 600 ° C. for 2 hours under air flow.
Was. The solid obtained in this way is as described in Example 1.
Formula Mo prepared by ₁V_0.3Te_0.23Nb_0.12O
_nWas added and mixed. this
Mold the mixture to 5mmΦ × 3mmL using a tableting machine
After crushing, sieving to 16-28 mesh, nitrogen
It was calcined at 550 ° C. for 2 hours in a stream. It exists here
The atomic ratio between Sb and Bi is 2: 1. Like this
0.5 ml of the obtained solid catalyst was charged into a reactor, and a reaction temperature of 4 ml.
10 ° C, space velocity SV 1000h^-1To the professional
Pan: Ammonia: Air = 1: 1.2: 15 molar ratio
Table 10 shows the results of the gas-phase contact reaction when the gas was supplied.
Shown in

Example 101 The solid catalyst prepared as in Example 100
into a reactor, at a reaction temperature of 410 ° C. and a space velocity S
V was fixed at 1500 h ^-1 and propane: ammonia:
The gas was supplied at a molar ratio of air = 1: 1.2: 15, and the gas phase contact reaction was carried out. The results are shown in Table-10.

[0079]

[Table 13]

Example 102 The empirical formula Mo prepared as described in Example 1₁V
_0.3Te_0.23Nb_0.12O_n30 g of the composite oxide having
Pulverized, and furthermore tetravalent antimony oxide (Sb_TwoO _Four) 0.
225 g were added and mixed. This mixture is made into a tablet press
After shaping into 5mmΦ × 3mmL using crushing,
２８28 mesh at 550 ° C for 2 hours in a nitrogen stream
Fired. 0.5 ml of the solid catalyst thus obtained was
The reaction temperature was 420 ° C and the space velocity SV was 10
00h^-1And isobutane: ammonia: air =
Gas was supplied at a molar ratio of 1: 1.2: 15, and gas phase contact reaction was performed.
Response. As a result, the conversion of isobutane was 61.
4%, methacrylonitrile selectivity 33.0%, methacrylonitrile
The yield of rilonitrile was 20.3%.

Comparative Example 20 In Example 102, no antimony oxide was added and M
A gas phase catalytic oxidation reaction of isobutane was carried out under the same reaction conditions as in Example 102, using only the composite oxide consisting of o, V, Te, and Nb. As a result, the conversion of isobutane was 64.1.
%, Methacrylonitrile selectivity was 29.7%, and the yield of methacrylonitrile was 19.1%.

[0082]

According to the method of the present invention, an alkane as a raw material can be used in a high yield at a relatively low temperature of about 400 to 450 ° C. without the presence of halides or water in the reaction system. Can be produced.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Itaru Sawaki 1 Tona-cho, Yokkaichi-shi, Mie Mitsubishi Kasei Co., Ltd. Yokkaichi Plant (56) References JP-A-2-257 (JP, A) Japanese Patent Publication No. 45- 4733 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 253/24 B01J 27/057 C07C 255/00-255/67 C07B 61/00 300 C07B 43/08

Claims (1)

(57) [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. When a = 1, b = 0.01 to 1.0, c = 0. 01-1.0, x
= 0.01 to 1.0, and n is determined by the oxidation state of another element. ), An oxide of at least one of antimony, bismuth, cerium, and boron is added to the composite oxide in a weight ratio to the composite oxide.
Wherein the alkane is subjected to a gas-phase catalytic oxidation reaction with ammonia in the presence of a solid catalyst to which an amount of 0.0001 to 0.2 has been added.