JP2000344724A - Production of unsaturated nitrile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an unsaturated nitrile in a high yield, by conducting ammoxidation reaction by the use of a specific metal oxide catalyst containing molybdenum, bismuth, iron, nickel, potassium, etc. SOLUTION: This method for producing an unsaturated nitrile comprises subjecting an organic compound to ammoxidation reaction at, preferably, 370-500 deg.C by the use of a metal oxide catalyst of the formula: MoaBibFecNidKeAfBgChQiRjOk (SiO2)l A is at least one element selected from the group comprising Mg, Ca, Sr and so on; B is at least one element selected from the group comprising Cd, Al, Ga, Sn, Sb and so on; C is at least one element selected from the group comprising Cu, Ag, In, Ge, Nb and so on; Q is at least one element selected from the group comprising P, B(boron) and Te; R is at least one element selected from the group comprising Li, Na, Rb and Cs; (a) to (l) express each an atomic ratio of each element and satisfy (b)=0.2-1.2, (c)=0.1-15, (d)=38, (e)=0.3-0.8, (f)=0-5, (g)=0-8, (h)=0-2, (i)=0-2, (j)=0-0.3, (k) is a number of oxygen atoms required for satisfying atomic valences of each element, (l)=0-200, (e)/(b)=0.6-5, (e)/[(d)+(f)]=0.06-0.2, when (a)=10}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing unsaturated nitrile by an ammoxidation method using a metal oxide catalyst.

[0002]

2. Description of the Related Art As a method for producing unsaturated nitriles by an ammoxidation method, there is known a method for producing acrylonitrile, methacrylonitrile and the like by reacting propylene, isobutene or tertiary butanol with oxygen and ammonia. And various catalysts are disclosed. For example, JP-B-38-17967 discloses an oxide catalyst containing molybdenum, bismuth and iron.
In this publication, an oxide catalyst containing iron and antimony is disclosed.

[0003] Thereafter, these improvements continued vigorously,
JP-A-7-48334 discloses an oxide catalyst containing molybdenum, bismuth, iron, nickel, praseodymium, neodymium and an alkali metal. JP-A-6-9530 discloses molybdenum, bismuth, iron, cobalt, nickel, chromium, Oxide catalyst containing phosphorus, antimony and alkali metal, JP-A-7-47271 discloses iron, bismuth,
Oxide catalysts containing molybdenum, nickel, magnesium, cesium and potassium. JP-A-8-266899 discloses an oxide catalyst containing at least one element selected from molybdenum, bismuth, iron and rare earth elements and yttrium. Japanese Patent Laid-Open No. 4-118051 discloses an oxide catalyst containing iron, antimony, molybdenum, bismuth, tellurium and potassium.

[0004]

Although these prior art catalysts have gradually improved the yield of unsaturated nitriles, they still do not always provide satisfactory yields.
A catalyst that suppresses the generation of unnecessary by-products such as carbon dioxide and carbon monoxide, and that has a high by-product yield of hydrocyanic acid, which is a useful by-product, with further improvement in the yield of unsaturated nitriles has been desired. . It was also a point to be improved that the ammonia flammability generally found in a catalyst having a high molybdenum content was high. At the same time, particularly for use in fluidized bed reactions, improvement of the catalyst strength was also an important issue.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the present invention contains molybdenum, bismuth, iron, nickel and potassium as essential components, and contains bismuth, nickel and A By setting the potassium content to be relatively high relative to the components, a catalyst having a high yield of useful by-product hydrocyanic acid as well as a yield of unsaturated nitrile was successfully developed. In addition, catalysts containing a relatively large amount of molybdenum usually have high ammonia flammability, so the efficiency of ammonia is low, and there are many by-products such as aldehydes, acids, and NOx. However, the catalyst of the present invention is also excellent in this respect. When used as a fluidized bed catalyst,
Although the strength is particularly important in practical use, the catalyst of the present invention has sufficient strength at a relatively low calcination temperature.

That is, the present invention relates to a method for producing an unsaturated nitrile using a metal oxide catalyst having a composition represented by the following empirical formula when producing an unsaturated nitrile by ammoxidation. MoaBibFecNidKeAfBgChQiRjO
k (SiO2) l (wherein, Mo, Bi, Fe, Ni, K, O, and Si represent molybdenum, bismuth, iron, nickel, potassium, oxygen, and silicon, respectively, and A represents magnesium, calcium, strontium, barium, Manganese, cobalt, at least one element selected from the group consisting of zinc, B is cadmium, aluminum, gallium, tin,
Lead, antimony, titanium, zirconium, vanadium,
At least one element selected from the group consisting of chromium and tungsten, C is copper, silver, indium, germanium, niobium, tantalum, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, thorium, yttrium, lanthanum, cerium , At least one element selected from the group consisting of praseodymium, neodymium, samarium, europium and gadolinium, Q
Represents at least one element selected from the group consisting of phosphorus, boron and tellurium, and R represents at least one element selected from the group consisting of lithium, sodium, rubidium and cesium. Where subscripts a, b, c, d, e, f,
g, h, i, j, k and l represent the atomic ratio of each element, and a
= 10, b = 0.1-1.2, preferably 0.2-
1.0, more preferably 0.3-0.8, c = 0.1-
15, preferably 0.2 to 10, more preferably 0.5
-8, d = 3-8, preferably 4-7, e = 0.3-
0.8, f = 0-5, g = 0-8, h = 0-2, i = 0
2, j = 0 to 0.3, k = the number of oxygen atoms necessary to satisfy the valence of each component, l = 0 to 200, and e / b = 0.6 to 5, e /(D+f)=0.06-
0.2. )

In the present invention, molybdenum, bismuth,
Iron, nickel and potassium are essential components, and the objects of the present invention cannot be achieved unless each of the components is within the above-mentioned composition range. In particular, the present invention is characterized in that it has been found that a preferable composition range exists in a region where the amount of potassium is large in a region where bismuth is small as compared with a conventionally known catalyst, and at the same time a region where a potassium is relatively large in a region where nickel is large.

By using a catalyst adjusted to the composition range of the present invention, not only the yield of the target product is not only good, but also a small amount of by-products, especially acrylic acid, which are often present in the catalysts of this system are suppressed. It is emphasized that it is preferable in terms of environmental measures, that the catalyst strength is improved, and that it is advantageous in industrial use.

The iron component is described in the above-mentioned Japanese Patent Application Laid-Open No.
In the case where iron antimonate is contained as in the case of JP-A-8051, the content increases and antimony is inevitably contained. Silica is added in the above range in order to provide preferable physical properties. In the region where the potassium content is large, the catalyst performance is reduced when the added amount of the R component is large.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The method for preparing a catalyst of the present invention can be applied by selecting from the conventional methods disclosed in the above-mentioned patent publications.

The starting material for each element constituting the catalyst of the present invention is not particularly limited. For example, the starting material for the molybdenum component may be molybdenum oxide such as molybdenum trioxide, molybdic acid, paramolybdic acid. Ammonium, molybdic acid or a salt thereof such as ammonium metamolybdate, phosphomolybdic acid, heteropolyacid containing molybdenum such as silico-molybdic acid or a salt thereof, and the like, as a raw material of the bismuth component, bismuth nitrate, bismuth carbonate, bismuth sulfate, Bismuth salts such as bismuth acetate, bismuth trioxide, bismuth metal, etc. are used as raw materials for iron components such as metallic iron, ferrous oxide, ferric oxide, ferric oxide, ferrous nitrate, and ferric nitrate sulfate. Raw materials for nickel components such as iron chloride, iron organic acid salts and iron hydroxide Kell, nickel nitrate, etc., as the raw material for the potassium component may be used potassium hydroxide, potassium nitrate or the like alone or in combination. As a raw material for the other elements, an oxide or a nitrate, a carbonate, an organic acid salt, a hydroxide, or the like, which can be converted to an oxide by firing, or a mixture thereof is usually used.

It is preferable to use silica as the carrier. It is convenient to use silica sol as the raw material. It is preferable to use a silica sol having a low sodium content.

In the present invention, the desired catalyst is obtained by mixing these raw materials, drying and calcining.

At this time, the slurry prepared by mixing the raw materials is preferably prepared according to the method described in Japanese Patent No. 2749920. That is, the pH is adjusted to 6 or more, and at the time of mixing the raw materials, the viscosity of the slurry is reduced by mixing a chelating agent into the slurry to improve the operability. In this case, chelating agents that are easy to use include ethylenediamine, lactic acid, tartaric acid, citric acid, gluconic acid and the like.

When iron antimonate is contained in the catalyst composition, it is preferable that iron antimonate is prepared in advance and then mixed with molybdenum and other components to form a slurry.

By drying and calcining the slurry thus prepared, a catalyst having excellent activity and physical properties can be obtained. When using the catalyst of the present invention in a fluidized bed reactor,
The granulation is preferably performed by a spray drying method. 200 after dry granulation
After firing at 500 to 650C, firing is further performed at 500 to 650C. The firing time may be 0.1 to 20 hours. The firing atmosphere is preferably an oxygen-containing gas. Although it is convenient to carry out in air, a gas in which oxygen and nitrogen, carbon dioxide gas, water vapor, an organic compound and the like are appropriately mixed can also be used.
For firing, a box furnace, a tunnel furnace, a rotary firing furnace, a fluidized firing furnace, or the like is used. When the catalyst is a fluidized bed catalyst, it is particularly preferable to use a fluidized calciner for final calcination. This facilitates strict control of the final firing conditions, and makes it possible to produce a fluidized bed catalyst having excellent performance with good reproducibility. The fluidized bed catalyst thus produced has a particle size of 10
To 200 μm.

In the ammoxidation reaction of the present invention, the starting organic compound / ammonia / oxygen = 1 / 0.9-1.3 / 1.6-
It is preferable to carry out in the range of 2.6 (molar ratio). The use of air as an oxygen source is industrially advantageous. The raw material gas may be diluted with an inert gas such as nitrogen or water vapor, or may be used by adding pure oxygen to increase the oxygen concentration. Reaction temperature is 370-500 ° C, reaction pressure is normal pressure-400 kPa
Is preferable. The contact time is preferably adjusted to 0.1 to 20 seconds.

The starting organic compounds that can be used in the ammoxidation reaction of the present invention include propylene, isobutene,
Tertiary butanol, methyl tertiary butyl ether and the like are mentioned, and they produce unsaturated nitriles such as acrylonitrile and methacrylonitrile.

[0019]

EXAMPLES Hereinafter, the effects of the present invention will be described specifically with reference to examples, but the present invention is not limited to the following examples.

The activity test of the catalyst was carried out as follows, taking an ammoxidation reaction of propylene as an example. 25mm inner diameter catalyst
A fluidized bed reactor having a diameter of 40 cm and a height of 40 cm was packed so as to have a specified contact time, and maintained at a reaction temperature of 430 ° C. In this reactor, a mixed gas of propylene, ammonia, air and steam having a molar ratio of propylene: ammonia: oxygen: water of 1: 1.2: 2.1: 0.5 was added at 6.5 l / h (NTP). Conversion) supplied. Reaction pressure is 20
0 kPa was set. The acrylonitrile yield, acrylic acid yield, conversion rate of raw material propylene, and ammonia combustion rate in the examples are defined by the following equations.

Acrylonitrile yield (%) = moles of acrylonitrile produced / moles of propylene fed × 100 Acrylic acid yield (%) = moles of acrylic acid produced /
Number of moles of supplied propylene × 100 Conversion ratio of propylene (%) = Number of moles of propylene reacted / Number of moles of supplied propylene × 100 Ammonia combustion rate (%) = 100 − [(weight of nitrogen in product) + Weight of nitrogen in unreacted ammonia) / weight of nitrogen in supplied ammonia x 100]

The particle strength was measured by a micro compression tester M manufactured by Shimadzu Corporation.
Using CTM-200, particles 30 having a diameter of 45 to 50 μm
The intensity of the points was measured and the average value was determined. The results of the activity test are shown in Tables 1 and 2, and the results of the particle strength measurement are shown in Table 3.

Example 1 The composition was Mo10Bi0.3Fe0.6Ni6K0.7P
0.2Te0.25 (SiO2) 40Ox (atomic ratio, x
Is a value naturally determined by the valence of another element, and hence the description of oxygen is omitted. ) Was prepared by the following method. 5.68 g of metal tellurium powder in 250 g of pure water and 4.71 of ammonium paramolybdate
g, 35% hydrogen peroxide solution 16g, 95 ~ 100 ℃
To dissolve. The solution was cooled to room temperature, and 20 g of citric acid and 43.1 g of ferric nitrate were dissolved. While stirring, 15% aqueous ammonia was added to the solution to adjust the pH to 9.2, and further 121.0 g of ammonium paramolybdate was added.
Was added little by little to dissolve. Thereafter, 15% aqueous ammonia was added to adjust the pH to 7.0 (Solution A).

Separately, 188.5 g of ammonium paramolybdate was dissolved in 2500 g of pure water, and 4.10 g of 85% phosphoric acid was added. Under stirring, a solution of 310.5 g of nickel nitrate in 300 g of pure water, a solution of 12.6 g of potassium nitrate in 10 g of pure water, 25.9 g of bismuth nitrate and 20 g of citric acid in 200 g of 10% nitric acid
And 2138.3 g of a 20% silica sol were sequentially added. Further, the pH was adjusted to 7.7 by adding 15% aqueous ammonia, and the slurry was heated at 100 ° C. for 2 hours under reflux (Solution B).

The solution A was mixed with the solution B under stirring, and the obtained slurry was spray-dried with a rotating disk type spray dryer while controlling the inlet temperature to 320 ° C. and the outlet temperature to 160 ° C.
The obtained spherical particles are heat-treated at 250 ° C.
Baking was performed at 0 ° C. for 2.5 hours and further at 590 ° C. for 3 hours.

Example 2 The composition is Mo10Bi0.5Fe0.6Ni6K0.7Z
A catalyst represented by r0.1La0.1 (SiO2) 40 (atomic ratio) was prepared in the same manner as in Example 1. However, zirconium oxynitrate as zirconium raw material,
Using lanthanum nitrate as a lanthanum raw material, nickel nitrate was added sequentially, and the final baking was performed at 600 ° C.

Example 3 The composition was Mo10Bi0.4Fe0.6Ni5.5K0.
7Cr0.5P0.2Cs0.05 (SiO2) 40
A catalyst represented by (atomic ratio) was prepared in the same manner as in Example 1. However, it was added after nickel nitrate using chromium nitrate as a chromium raw material and after potassium nitrate using cesium nitrate as a cesium raw material.

Example 4 The composition is Mo10Bi0.7Fe0.6Ni6K0.7T
e A catalyst represented by 0.25 (SiO 2) 60 (atomic ratio) was prepared in the same manner as in Example 1.

Example 5 The composition is Mo10Bi0.4Fe0.6Ni4K0.7M
A catalyst represented by g2Na0.05 (SiO2) 40 (atomic ratio) was prepared in the same manner as in Example 1. However, after adding nickel nitrate using magnesium nitrate as a magnesium raw material, and then adding potassium nitrate using sodium nitrate as a sodium raw material, the final firing temperature was 600 ° C.

Example 6 The composition is Mo10Bi0.4Fe0.6Ni6K0.7M
n0.5Pr0.1Nd0.1P0.2Rb0.05
A catalyst represented by (SiO 2) 40 (atomic ratio) was prepared by the following method. 310.8 g of ammonium paramolybdate was dissolved in 2500 g of pure water, and then 4.06 g of 85% phosphoric acid was added. Under stirring, 307.1 g of nickel nitrate, 25.3 g of manganese nitrate, 12.5 g of potassium nitrate, 1.30 g of rubidium nitrate, 7.66 g of praseodymium nitrate, 7.72 g of neodymium nitrate, 20 g of citric acid and 34.2 g of bismuth nitrate were added to this solution. To 10% nitric acid 210
g and solution of 20% silica sol 2115.0 g
Were sequentially added. Add 15% ammonia water and adjust the pH
Was adjusted to 7.7 and the slurry was refluxed at 100 ° C.
For 1.5 hours.

Under stirring, the slurry was mixed with ferric nitrate.
A solution of 4 g and 20 g of citric acid dissolved in 200 g of pure water was added, and the resulting slurry was spray-dried with a rotating disk type spray dryer while controlling the inlet temperature to 320 ° C and the outlet temperature to 160 ° C. The resulting spherical particles are heat-treated at 250 ° C., followed by 400 ° C. for 2.5 hours,
Calcination was performed at 3 ° C. for 3 hours.

Example 7 The composition is Mo10Bi0.4Fe0.4Ni6K0.7C
o0.5Zr0.2Na0.05Cs0.05 (SiO
2) A catalyst represented by 40 (atomic ratio) was prepared in the same manner as in Example 6. However, cobalt nitrate was used as a cobalt source, nickel nitrate was used as zirconium oxynitrate as a zirconium source, sodium nitrate was used as a sodium source, and potassium nitrate was used as a cesium source using cesium nitrate. The final firing temperature was 550. ° C.

Example 8 The composition is Mo10Bi0.6Fe1.5Ni6K0.6Z
A catalyst represented by n0.5La0.1Rb0.1 (SiO2) 50 (atomic ratio) was prepared by the following method. Ammonium paramolybdate 269.3 in 2,500 g of pure water
g was dissolved. Under stirring, add nickel nitrate 26 to this solution.
6.1 g, zinc nitrate 22.7 g, potassium nitrate 9.25
g, rubidium nitrate 2.25 g, lanthanum nitrate 6.60
g, 20 g of citric acid and 44.4 g of bismuth nitrate in 10
Solution in 210 g of 20% nitric acid and 20% silica sol 2
290.7 g were added sequentially. Further, the pH was adjusted to 8.0 by adding 15% aqueous ammonia, and the slurry was heated at 100 ° C. for 1.5 hours under reflux.

Under stirring, a solution prepared by dissolving 92.4 g of ferric nitrate and 20 g of citric acid in 200 g of pure water was added to the slurry, and the obtained slurry was subjected to a rotating disk type spray dryer at an inlet temperature of 320 ° C. and an outlet temperature of 320 ° C. Spray drying was performed while controlling the temperature at 160 ° C. The obtained spherical particles are heat-treated at 250 ° C., followed by 400 ° C. for 2.5 hours and further 630 ° C.
Calcination was performed at 3 ° C. for 3 hours.

Example 9 The composition was Mo10Bi1Fe1Ni6.5K0.6Ce.
A catalyst represented by 0.05Te0.1Cs0.1 (SiO2) 30 (atomic ratio) was prepared in the same manner as in Example 8. However, cerium nitrate was used as a cerium raw material, cesium nitrate was used as a cesium raw material, and potassium nitrate was added sequentially, and the final firing temperature was 600 ° C.

Example 10 The composition was Mo10Bi0.3Fe0.6Ni6K0.7S.
A catalyst represented by m0.05Cs0.05 (SiO2) 40 (atomic ratio) was prepared in the same manner as in Example 8.
However, samarium nitrate was used as a samarium raw material, and cesium nitrate was used as a cesium raw material, followed by potassium nitrate, and the final firing temperature was 610 ° C.

Example 11 The composition was Mo10Bi0.2Fe8Ni6.25K0.7.
Sb7.7W0.1P0.49B0.49 (SiO2)
A catalyst represented by 40 (atomic ratio) was prepared by the following method. 99.3 g of electrolytic iron powder was added little by little to a solution in which 808 g of 61% nitric acid and 808 g of pure water were mixed and dissolved, and 285.0 g of antimony trioxide powder was further added. This slurry was heated at 100 ° C. for 2 hours while being well stirred. X-ray diffraction measurement of the solid content of the slurry revealed the presence of iron antimonate. A solution of 7.70 g of orthoboric acid dissolved in 150 g of pure water and 14.3 g of 85% phosphoric acid were sequentially added to the slurry. This was sprayed with a rotating disk type spray dryer at an inlet temperature of 320 ° C and an outlet temperature of 16 ° C.
Spray drying was performed while controlling at 0 ° C. The obtained spherical particles are heat-treated at 250 ° C. and subsequently at 400 ° C.
Baking was performed for 5 hours and further at 950 ° C. for 3 hours. The obtained particles were pulverized to obtain a boron- and phosphorus-containing iron antimonate powder.

224.2 g of ammonium paramolybdate was dissolved in 2500 g of pure water. Under stirring, a solution of 230.8 g of nickel nitrate, 8.99 g of potassium nitrate and 12.3 g of bismuth nitrate in 210 g of 10% nitric acid, 3.31 g of ammonium paratungstate and 1525.6 g of 20% silica sol were sequentially added to this solution. . The resulting slurry was adjusted to pH 7.7 with 15% aqueous ammonia, and then heated at 100 ° C. under reflux for 1.5 hours.

Under stirring, ferric nitrate was added to the slurry.
A solution in which 3 g and 20 g of citric acid were dissolved in 200 g of pure water, and 227.9 g of a boron- and phosphorus-containing iron antimonate powder previously prepared were sequentially added. The obtained slurry was subjected to a rotating disk type spray dryer at an inlet temperature of 320 ° C. and an outlet temperature of 160 ° C.
Spray drying was performed while controlling the temperature at 0 ° C. The obtained spherical particles are heat-treated at 250 ° C., followed by 2.5 ° C. at 400 ° C.
Baked at 600 ° C. for 3 hours.

Example 12 The composition was Mo10Bi0.3Fe4.5Ni6K0.5S.
b4V0.05Nb0.1Pr0.1Nd0.1P0.
47B0.27Rb0.1 (SiO2) 40 (atomic ratio)
Was prepared by the following method. Pure water 25
257.3 g of ammonium paramolybdate was dissolved in 00 g, and then 3.36 g of 85% phosphoric acid was added. Under stirring, a solution obtained by dissolving 254.2 g of nickel nitrate, 7.37 g of potassium nitrate, 2.15 g of rubidium nitrate, 6.34 g of praseodymium nitrate, 6.39 g of neodymium nitrate and 21.2 g of bismuth nitrate in 210 g of 10% nitric acid, 0.85 g of ammonium metavanadate is added to pure water 10
Solution in 0 g, 1.94 g niobium oxide and 20%
1750.0 g of silica sol was added sequentially. The resulting slurry was adjusted to pH 7.7 with 15% aqueous ammonia,
Heat treatment was performed at 100 ° C. for 2 hours under reflux.

Under stirring, ferric nitrate was added to the slurry.
A solution of 2 g and 20 g of citric acid dissolved in 200 g of pure water and 143.0 g of a boron- and phosphorus-containing iron antimonate powder prepared in the same manner as in Example 11 were sequentially added. The obtained slurry was fed to a rotary disk type spray dryer at an inlet temperature of 320.
The spray drying was performed while controlling the temperature at 160 ° C. and the outlet temperature at 160 ° C. The obtained spherical particles were heat-treated at 250 ° C., and subsequently calcined at 400 ° C. for 2.5 hours and further at 570 ° C. for 3 hours.

Comparative Example 1 The composition was Mo10Bi0.08Fe0.6Ni6K0.7
A catalyst represented by P0.2Te0.25 (SiO2) 40 was prepared in the same manner as in Example 1. The content of bismuth is set to be less than 0.1 with respect to molybdenum at an atomic ratio of e / b (e is potassium, b is atomic ratio of bismuth)
Was made larger than 5, the acrylonitrile yield decreased.

Comparative Example 2 The composition was Mo10Bi1.5Fe0.6Ni6K0.7P
A catalyst represented by 0.2Te0.25 (SiO2) 40 was prepared in the same manner as in Example 1. Increasing the content of bismuth to more than 1.2 in terms of atomic ratio with respect to molybdenum 10;
When e / b (e is the atomic ratio of potassium and b is the atomic ratio of bismuth) was made smaller than 0.6, the acrylonitrile yield decreased.

Comparative Example 3 The composition was Mo10Bi0.3Fe0.6Ni2K0.7M
A catalyst represented by g2Na0.05 (SiO2) 40 was prepared in the same manner as in Example 1. When the content of nickel was made less than 3 in terms of atomic ratio with respect to 10 of molybdenum, the acrylonitrile yield was reduced.

Comparative Example 4 The composition was Mo10Bi0.3Fe0.6Ni10K0.7
A catalyst represented by P0.2Te0.25 (SiO2) 40 was prepared in the same manner as in Example 1. When the content of nickel was set to be greater than 8 in terms of atomic ratio with respect to molybdenum 10, the acrylonitrile yield decreased.

Comparative Example 5 The composition was Mo10Bi0.3Fe0.6Ni6K0.1P
A catalyst represented by 0.2Te0.25 (SiO2) 40 was prepared in the same manner as in Example 1. When the content of potassium was made smaller than 0.3 with respect to molybdenum at an atomic ratio of 10 and the ratio of e / b (e was an atomic ratio of potassium and b was an atomic ratio of bismuth) was made smaller than 0.6, the acrylonitrile yield was reduced.

Comparative Example 6 The composition was Mo10Bi0.3Fe0.6Ni6K1.5P
A catalyst represented by 0.2Te0.25 (SiO2) 40 was prepared in the same manner as in Example 1. The content of potassium is set to be more than 1 with respect to molybdenum 10 in atomic ratio, and e /
When (d + f) (e is potassium, d is nickel, and f is the atomic ratio of the A component) was larger than 0.2, the acrylonitrile yield decreased.

Comparative Example 7 The composition was Mo10Bi0.7Fe0.6Ni6K0.4T
e A catalyst represented by 0.25 (SiO 2) 60 (atomic ratio) was prepared in the same manner as in Example 1. When e / b (e is the atomic ratio of potassium and b is the atomic ratio of bismuth) was made smaller than 0.6, the acrylonitrile yield decreased.

Comparative Example 8 The composition was Mo10Bi0.4Fe0.4Ni6K0.3C
o0.5Zr0.2Na0.05Cs0.05 (SiO
2) A catalyst represented by 40 (atomic ratio) was prepared in the same manner as in Example 7. e / (d + f) (e is potassium,
When d was nickel and f was the atomic ratio of the A component) smaller than 0.06, the acrylonitrile yield was reduced.

Comparative Example 9 The composition was Mo10Bi0.2Fe0.6Ni6K0.7S
A catalyst represented by m0.05Cs0.5 (SiO2) 40 (atomic ratio) was prepared in the same manner as in Example 10.
The content of the R component is set to 0.3 with respect to molybdenum 10 in atomic ratio.
With more, the acrylonitrile yield decreased.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

According to the present invention, when an unsaturated nitrile is produced by an ammoxidation reaction, molybdenum, bismuth, iron,
By using a metal oxide catalyst containing nickel and potassium as essential components and setting the content of potassium with respect to bismuth and the nickel and A components to be considerably high, useful by-product hydrocyanic acid can be obtained together with unsaturated nitrile yield. Can also be increased. Further, despite the fact that the catalyst contains a relatively large amount of molybdenum, it has a low ammonia flammability and a high efficiency of ammonia, and can be used for aldehydes, acids, NO
It has few by-products such as x, and has a great effect on environmental measures as well as a yield improving effect. Further, when used as a fluidized bed catalyst, its strength is particularly important in practical use, but the catalyst of the present invention has sufficient strength at a relatively low calcination temperature.

Continued on the front page F-term (reference) 4G069 AA01 AA08 AA15 BA25A BB04A BB04B BB12B BB14B BC02A BC02B BC03A BC03B BC04A BC05A BC05B BC06A BC06B BC09A BC10A BC10B BC12A BC13A BC16A BC31 BC18 BCA BC A BC BC A BC A BC BC BC40A BC41A BC41B BC42A BC42B BC43A BC43B BC44A BC44B BC45A BC46A BC50A BC51A BC51B BC54A BC55A BC55B BC56A BC58A BC58B BC59A BC59B BC60A BC60B BC62A BC64A BC65A BC66A BC66B BC67A BC67B BC68A BC68B BC71A BC72A BC73A BC73B BC74A BC75A BD03A BD03B BD05A BD05B BD07A BD07B CB54 DA08 EA04Y FB15 FB30 FB57 FC09 4H006 AA02 AC54 BA02 BA03 BA04 BA05 BA06 BA07 BA08 BA09 BA10 BA11 BA12 BA13 BA14 BA16 BA19 BA20 BA21 BA22 BA23 BA24 BA25 BA26 BA27 BA30 BA31 BA35 BA81 BA82 BE14 BE30 BE60 4H039 CA70 CD10 CL50

Claims (4)

[Claims] 1. An unsaturated nitrile production method using a metal oxide catalyst having a composition represented by the following empirical formula when producing an unsaturated nitrile by ammoxidation. MoaBibFecNidKeAfBgChQiRjO
k (SiO2) l (wherein, Mo, Bi, Fe, Ni, K, O, and Si represent molybdenum, bismuth, iron, nickel, potassium, oxygen, and silicon, respectively, and A represents magnesium, calcium, strontium, barium, Manganese, cobalt, at least one element selected from the group consisting of zinc, B is cadmium, aluminum, gallium, tin,
Lead, antimony, titanium, zirconium, vanadium,
At least one element selected from the group consisting of chromium and tungsten, C is copper, silver, indium, germanium, niobium, tantalum, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, thorium, yttrium, lanthanum, cerium , At least one element selected from the group consisting of praseodymium, neodymium, samarium, europium and gadolinium, Q
Represents at least one element selected from the group consisting of phosphorus, boron and tellurium, and R represents at least one element selected from the group consisting of lithium, sodium, rubidium and cesium. Where subscripts a, b, c, d, e, f,
g, h, i, j, k and l represent the atomic ratio of each element, and a
= 10, b = 0.1-1.2, c = 0.1-15,
d = 3-8, e = 0.3-0.8, f = 0-5, g = 0
-8, h = 0-2, i = 0-2, j = 0-0.3, k =
The number of oxygen atoms required to satisfy the valence of each component,
l = 0 to 200, and e / b = 0.6 to 5, e / b
(D + f) = 0.06 to 0.2. ) 2. A fluidized bed prepared by spray-drying and calcining an aqueous slurry having a pH of 6 or more, wherein the metal oxide catalyst contains at least molybdenum, bismuth, iron, nickel and potassium raw materials and a chelating agent. The method for producing an unsaturated nitrile according to claim 1, wherein the method is a catalyst. 3. The process for producing an unsaturated nitrile according to claim 1, wherein the metal oxide catalyst is a fluidized bed catalyst prepared by using a fluidized-bed kiln in the final baking. 4. The method for producing an unsaturated nitrile according to claim 1, wherein the unsaturated nitrile is acrylonitrile.