WO1999054037A1

WO1999054037A1 - Catalyst for producing unsaturated nitrile

Info

Publication number: WO1999054037A1
Application number: PCT/JP1999/002146
Authority: WO
Inventors: Yutaka Sasaki; Kunio Mori; Yoshimi Nakamura; Takao Shimizu; Yuichi Tagawa; Kenichi Miyaki; Seiichi Kawatou
Original assignee: Mitsubishi Rayon Co., Ltd.
Priority date: 1998-04-23
Filing date: 1999-04-22
Publication date: 1999-10-28

Abstract

A catalyst composition represented by the following experimental formula: Mo10BiaFebSbcNidCreFfGgHhKkXxYyOi(SiO2)j, which is for use in producing an usaturated nitrile through ammoxidation wherein F represents at least one element selected from the group consisting of zirconium, lanthanum, and cerium; G represents at least one element selected from the group consisting of magnesium, cobalt, manganese, and zinc; H represents at least one element selected from the group consisting of vanadium, niobium, tantalum, and tungsten; X represents at least one element selected from the group consisting of phosphorus, boron, and tellurium; Y represents at least one element selected from the group consisting of lithium, sodium, rubidium, and cesium; and the subscripts a to k, x, and y, which represent proportions of the atoms and the group of atoms, are such numbers that a=0.1 to 3, b=0.3 to 15, c=0 to 20, d=3 to 8, e=0.2 to 2, f=0.05 to 1, e/f > 1, g=0 to 5, h=0 to 3, k=0.1 to 1, x=0 to 3, y=0 to 1, i is the number of oxygen atoms resulting from the bonding of the above ingredients, and j=0 to 100.

Description

Description Catalyst for the production of unsaturated nitriles Technical field

The present invention relates to a metal oxide catalyst used for producing unsaturated nitrile by ammoxidation.

Conventional technology

Conventionally, various catalysts suitable for the production of unsaturated nitrile by ammoxidation, for example, the production of acrylonitrile by the ammoxidation of propylene, the production of methacrylonitrile by the ammoxidation of isobutylene or tert-butanol, etc. A composition of the catalyst is disclosed. For example, U.S. Pat. No. 3,226,422 discloses an oxide catalyst containing molybdenum, bismuth and iron, and Japanese Patent Publication No. 38-1991 includes iron and antimony. An oxide catalyst is disclosed. Thereafter, the improvement of these catalysts continued energetically. For example, US Pat. No. 4,290,922 includes molybdenum, cobalt, nickel, bismuth, vanadium, calcium, and potassium as essential components. Oxide catalyst containing zirconium and zirconium and / or chromium as optional components; Patent No. 2,640,356 discloses an oxide catalyst containing molybdenum, bismuth, iron, nickel, and metal alloys; U.S. Patent No. 5,093,299 and US Pat. No. 5,175,334 describe oxides containing molybdenum, bismuth, iron, nickel, magnesium, potassium and cesium. Catalysts and Japanese Patent Publication No. 7-47272 disclose at least one element selected from the group consisting of molybdenum, bismuth, iron, nickel, chromium and indium, and alkalis such as potassium. Oxide catalyst containing a metal element as an essential component and at least one element selected from the group consisting of manganese, magnesium, zinc, cerium, sodium and phosphorus as an optional component No. 5,132,269 discloses iron, antimony, and molybdenum, bismuth, cerium, iron, nickel, and oxide catalysts containing magnesium or zinc, and alkali metals. , Molybdenum, and oxide catalysts containing bismuth or tellurium, potassium, etc. Is disclosed.

While these prior art catalysts have had some effect in improving the yield of unsaturated nitriles, they have not been satisfactory. In the technical field, while further increasing the yield of unsaturated nitrile, suppressing the flammability of ammonia, which is likely to occur in catalysts containing a large amount of molybdenum, the generation of by-products such as nitrogen oxides, which are problematic in environmental measures It was desired to reduce the number.

Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that a catalyst containing molybdenum, bismuth, iron, antimony, or the like comprises chromium, zirconium, lanthanum, and cerium. By coexisting at least one element selected from the group, it has been found that a high unsaturated nitrile yield that cannot be obtained by adding each element alone can be obtained.

These additional elements synergistically exhibited favorable effects. Titanium and hafnium, which are related to zirconium, did not show such an effect. Rare earth metal elements of lanthanum other than lanthanum and cerium did not show such a special effect.

At least one element selected from the group consisting of chromium, zirconium, lanthanum and cerium has a clear effect when added in a relatively small amount, and excessive addition rather decreases the yield of the target product sharply . In addition, it is preferable that the ratio of zirconium, lanthanum, cerium, and the like to chromium is small. If the ratio is large, ammonia flammability increases and the yield of the target product decreases. Chromium is used in combination with at least one element selected from the group consisting of zirconium, lanthanum and cerium, and by finding a favorable quantitative relationship at the time of addition, the yield of the target product is improved, and The flammability was suppressed and the yield of by-products was also reduced.

That is, the present invention provides a catalyst composition represented by the following empirical formula, which is used when producing unsaturated nitrile by ammoxidation:

M o ₁₀ B i _a F e _b S b _c N i _d C r _e F _f G _g H _h K _k X _x Y _y O _¾

(S i 0 ₂ ) In the formula, Mo, Bi, Fe, Sb, Ni, Cr, and K represent molybdenum, bismuth, iron, antimony, nickel, chromium, and potassium, respectively, and F represents zirconium, lanthanum, and cerium. At least one element selected from the group consisting of magnesium, cobalt, manganese, and zinc; andH is at least one element selected from the group consisting of vanadium, niobium, tantalum, and tungsten. Element, X is at least one element selected from the group consisting of phosphorus, boron and tellurium, Y is at least one element selected from the group consisting of lithium, sodium, rubidium and cesium, O is oxygen, and Si ₂ is Represents silica, and the subscripts a, b, c, d, e, f, g, h, i, j, k, x, and y represent the ratio of atoms or groups of atoms. Then, when Mo = 10, a = 0.:! ~ 3, b = 0.3 ~: L5, c = 0 ~ 20, d = 3 ~ 8, e = 0.2-2 ~, f = 0.05 ~; 1, e Zf> l, g = 0 ~ 5, h = 0 ~ 3, k = 0. 11, x = 0 y3, y = 0 i: 1, i = the number of oxygen generated by combining the above components, and j = 00〜10100.

On the other hand, efforts have been made to improve the yield of the target oxidation product by improving the catalyst preparation method. For example, U.S. Pat. No. 3,350,323 discloses a method of adding an aqueous solution of bismuth citrate to an aqueous solution of molybdic acid, JP-A-53-10387, JP-A-53-10388, and U.S. Pat. No. 4,847,831 describes a method of adding a bismuth compound in a solid state to an aqueous molybdic acid solution, and US Pat. No. 4,418,007 discloses a method in which the pH is in the range of 6 to 8. A method in which an aqueous solution of bismuth salt and aqueous ammonia are simultaneously added to an aqueous solution of lybdic acid. U.S. Pat. No. 4,388,226 describes a method of adding an aqueous solution of a bismuth salt to a suspension of a molybdenum compound; U.S. Pat. No. 4,212,766; U.S. Pat. No. 4,148 No. 4,040,978 and US Pat. No. 4,040,978 describe a method for preforming various molybdite, Japanese Patent Publication No. 52-22359, and US Pat. No. 3,872,148. US Pat. No. 4,803,190 describes a method of using bismuth oxide or bismuth subcarbonate as a bismuth source, and US Pat. No. 4,803,190 describes a method of forming bismuth compounds in advance. Adjusting a slurry containing at least one selected from the group consisting of: bismuth and tellurium and a molybdenum compound to a pH range above pH 7, US Pat. Japanese Patent No. 5,071,814 discloses a method in which a chelating agent is added to a slurry containing molybdenum compound containing silicide to adjust ^ 1 to 1 ^ 6 or more. The specification discloses a method of mixing a bismuth compound after a slurry containing molybdenum is adjusted to pH 6 or more.

As described above, various methods have been proposed to improve the performance of the catalyst, such as devising a method of mixing an aqueous solution of molybdenum and a bismuth compound, and selecting a special raw material of bismuth. However, when these methods are applied to the production of a molybdenum-bismuth-containing composite oxide catalyst containing at least one metal element selected from the group consisting of divalent metal elements and trivalent metal elements, Product yields were not always satisfactory.

BEST MODE FOR CARRYING OUT THE INVENTION

Molybdenum, bismuth, iron, nickel, chromium, potassium, and the metal elements represented by F are essential components, and the objects of the present invention cannot be achieved unless each of the above composition ranges.

When the catalyst composition of the present invention contains iron antimonate, it necessarily contains antimony. In this case, in particular, the selectivity of the target product is improved, and the physical properties of the catalyst are improved. Advantages are noted.

When the catalyst of the present invention is used as a fluidized bed catalyst, silica is preferably used as a carrier. In this case, j is preferably in a range of 20 to 80.

The catalyst composition of the present invention may be prepared by appropriately selecting and applying the preparation method disclosed as the above-mentioned prior art.

The raw materials for the molybdenum component include dimethyl molybdenum acid and ammonium paramolybdate; the raw materials for the bismuth component include bismuth trioxide, bismuth nitrate, bismuth carbonate, and bismuth oxalate; and the raw material for the iron component include nitric acid. Iron, iron oxalate, and the like, chromium nitrate and chromic acid are used as raw materials for the chromium component, and potassium hydroxide and potassium nitrate are used as the raw material for the potassium component.

The raw materials of the zirconium component include zirconium oxide and zirconium oxynitrate; the raw materials of the lanthanum component include lanthanum oxide and lanthanum nitrate; and the raw materials of the cerium component include cerium oxide and cerium ammonium nitrate. Etc. are for Also, organic acid salts of these elements can be used.

It is convenient to use the respective nitrates as the raw materials for the components such as nickel, cobalt, magnesium, manganese and zinc, but it is also possible to use the respective organic acid salts, hydroxides and oxides.

When the tellurium component is added, as a raw material of the tellurium component, a material capable of using telluric acid or a salt thereof or tellurous acid or a salt thereof, or a solution obtained by dissolving metallic tellurium in a heated aqueous hydrogen peroxide solution. May be used.

As raw materials for other components, oxides, hydroxides, nitrates, organic acid salts, etc. of the respective elements are used.

As a raw material of silica, silica sol, fumed silica and the like are used, and silica sol is particularly preferable. As the silica sol, one having a low sodium content is preferably used.

The catalyst composition of the present invention is prepared by mixing these raw materials, drying and calcining. The slurry prepared by mixing the raw materials preferably has a pH of 6 or more. This operation reduces the ammonia flammability during the reaction and improves the yield of the target product. In that case, the viscosity of the slurry can be reduced by mixing the chelating agent into the slurry, and the operability can be improved. When the present catalyst composition was prepared with a pH of 6 or more, it was found that the presence of the chromium component contributed to lowering the viscosity of the slurry. This is an advantage for improving operability, and it is noteworthy.

Further heat treatment of the prepared slurry may be advantageous in that the stability of the slurry is increased and the reproducibility is improved.

Examples of chelating agents that can be used here include ethylenediaminetetraacetic acid, lactic acid, citric acid, tartaric acid, and dalconic acid.

The amount of the chelating agent is preferably in the range of 0.1 to 10%, preferably 0.5 to 8% by weight of the oxide catalyst to be produced. More preferably, it is used in the range of / ₀ . If the amount of the chelating agent is less than 0.1% by weight with respect to the oxide catalyst, the effect is not sufficiently exhibited, and if the amount exceeds 10% by weight, a large number of cracks may be formed in the completed catalyst. When preparing a solution containing iron ions and a chelating agent, the chelating agent is iron 1 0.1 to 2 gram molecules are preferred for gram ions.

When iron antimonate is contained, it is preferable to prepare iron antimonate in advance and then mix it with a raw material of other components such as molybdenum to form a slurry. .

Further, as a further improved preparation method, a molybdenum raw material and / or a raw material of at least one element selected from the group consisting of nickel, cobalt, magnesium, chromium, manganese and zinc and having a pH of 6 or more are contained. A method is also preferable in which a certain aqueous slurry is mixed with a solution or slurry containing a tellurium raw material and a Z or iron raw material, and then the mixture is dried and fired. In particular, in the case of a catalyst containing both tellurium and iron, a solution or slurry containing a raw material of iron and a solution containing a raw material of tellurium are mixed with the aqueous slurry having a pH of 6 or more, or Also preferred is a method of mixing a mixed solution or slurry containing a raw material and a tellurium raw material with the aqueous slurry having a pH of 6 or more, followed by drying and firing the mixture.

An aqueous slurry containing at least a part of a molybdenum raw material and a raw material of at least one element selected from the group consisting of nickel, cobalt, magnesium, chromium, manganese, and zinc, and having a pH of 6 or more, is heated to a temperature of 50 °. After heating for at least 10 minutes in the range of C to 120 ° C, preferably 60 ° C to 120 ° C, tellurium raw material or iron raw material, or tellurium raw material and iron raw material It is also preferable to mix both of them into the heat-treated slurry, and then dry and bake the mixture.

Ferrous oxide, ferric oxide, ferric oxide, ferrous nitrate, ferric nitrate, iron sulfate, iron chloride, iron organic acid salt, iron hydroxide, etc. Alternatively, metallic iron may be used by dissolving it in heated nitric acid. The solution containing the iron component may be used after adjusting the pH with ammonia water or the like. When adjusting the pH, coexistence of a chelating agent in a solution containing an iron component can prevent precipitation of the iron component, and a highly active catalyst can be obtained. Examples of chelating agents that can be used here include ethylenediaminetetraacetic acid, lactic acid, citric acid, tartaric acid, and glyconic acid.

In any of the above methods, the drying of the slurry mixture is preferably carried out by a spray drying method in the case of producing a fluidized bed catalyst, and granulation is carried out simultaneously with drying. Thereby, fine spherical particles can be obtained. After drying, the mixture is preferably calcined at 200 to 500 ° C, and more preferably calcined at 500 to 700 ° C. The firing time may be 1 to 20 hours. The atmosphere during firing is preferably an oxygen-containing gas. The baking is conveniently performed in the air, but may be performed in an atmosphere in which oxygen and nitrogen, carbon dioxide, water vapor, organic compounds, and the like are appropriately mixed. Box furnaces, tunnel furnaces, rotary furnaces, fluidized furnaces, etc. are used for baking. When the catalyst is a fluidized bed catalyst, the final calcination is preferably performed in a fluidized furnace. This makes it easier to strictly control the final firing conditions, and makes it possible to produce fluidized bed catalysts with excellent performance with good reproducibility. The particle size of the fluidized bed catalyst produced in this way is preferably from 10 to 200 μm.

The catalyst composition of the present invention or the catalyst composition produced by the production method of the present invention as described above is suitable for producing unsaturated nitrile by ammoxidation of olefin. The ammoxidation reaction is usually carried out using a feed gas in the composition range of raw material organic compound / ammonia Z air = 10.9 to 1.3 to 8 to 12 (molar ratio), reaction temperature 370 to 500 ° C, reaction pressure Perform at normal pressure to 500 kPa. The apparent contact time is 0.1 to 20 seconds.

Hereinafter, the present invention will be described specifically with reference to examples.

Catalyst activity test

Ammoxidation of propylene was performed as an example of the gamma oxidation reaction.

A catalyst is packed in a fluidized bed reactor with an inner diameter of the catalyst flowing section of 25 mm and a height of 400 mm, and a mixed gas having the composition of propylene ammonia Z air Z steam = 1Zl. 2/1 0 / 0.5 (molar ratio) At a gas linear velocity of 4.5 cm / sec. The reaction pressure was 20 ° kPa.

Contact time (sec) = catalyst volume based on apparent bulk density (ml) / supply gas flow rate converted to reaction conditions (m1Zsec)

Atarilonitrile yield (%) = number of moles of acrylonitrile produced Number of moles of propylene supplied / number of moles X 100

Acrylonitrile selectivity (%) = number of moles of atarilonitrile produced, number of moles of propylene reacted x 100

Propylene conversion (%) = number of moles of propylene reacted / propylene supplied Number of monoles of X 100

Ammonia combustion rate (%) = 100- [(weight of nitrogen in product + weight of nitrogen in unreacted ammonia) Z weight of nitrogen in supplied ammonia X loo]

Example 11

Composition _{_{Mo ioB i 0. 3 F e}} 4. 4 S b 4. 2 N i 5. 7 5 c r 0. 5 Z r 0. 2

^A catalyst having a ^{K of} 0.7 ^P 0.2 ^{T e} 0.25 ° 53.7 ^ i ° 2) 40 (atomic ratio) was prepared.

In 1730 g of pure water, 25.6 g of ammonium paramolybdate were dissolved, and then 3.3 g of 85% phosphoric acid was added. This solution was mixed with 1750 g of 20% silica sol. To this solution was added 243.7 g of nickel nitrate in 216 g of 3.3% nitric acid, 29.1 g of chromium nitrate, 7.79 g of zirconium oxynitrate, 10.32 g of potassium nitrate, 40 g of citric acid, and nitric acid A solution obtained by dissolving 35.33 g of iron and 21.21 g of bismuth nitrate was mixed to obtain a slurry. To this slurry, add 4.65 g of metal tellurium, 3.9 g of ammonium paramolybdate and 16 g of hydrogen peroxide in 208 g of water, stir at 95 to 100 ° C, dissolve The obtained liquid was added. 15% ammonia water was added to the slurry while stirring to adjust the pH to 7.7, and 138.3 g of iron antimonate powder was mixed with the slurry to obtain a mixture.

The above mixture was spray-dried with a rotating disk spray dryer at an inlet temperature of 330 ° C and an outlet temperature of 160 ° C. The particles were heat-treated at 250 ° C. for 2 hours and 400 ° C. for 2 hours, and finally fluidized at 590 ° C. for 3 hours.

Example 11

Example 11 A catalyst having the same composition as in Example 1 was prepared by the following method.

154.4 g of ammonium paramolybdate was dissolved in 1730 g of pure water, and 3.3 g of 85% phosphoric acid was added. This solution was mixed with 1750 g of a 20% sily sol. To this solution was added 243.7 g of nickel nitrate, 29.1 g of chromium nitrate, 7.79 g of zirconium oxynitrate, 10.79 g of potassium nitrate, 20 g of citric acid, 20 g of nitric acid and 216 g of 3.3% nitric acid. A solution in which 21.21 g of bismuth was dissolved was mixed to obtain a slurry. This slurry was adjusted to pH 7.7 by adding 15% aqueous ammonia with stirring, and then heat-treated at 100 ° C. for 1.5 hours under reflux. To 208 g of water were added 4.65 g of metal tellurium, 3.9 g of ammonium paramolybdate, and 16 g of hydrogen peroxide solution, and the mixture was stirred at 95 to 100 ° C. and dissolved. The solution was cooled to room temperature, and 20 g of citric acid and 35.33 g of iron nitrate were dissolved. While stirring this, 15% aqueous ammonia was added to adjust the pH to 9.2, and 99.1 g of ammonium paramolybdate was added little by little to dissolve. Here, ammonia water was added to adjust the pH to 7. This solution was mixed with the slurry previously heated, and 138.3 g of iron antimonate powder was mixed.

The mixture was spray-dried and heat-treated in the same manner as in Example 11-11, and finally fluidized at 580 ° C for 3 hours.

Example 2-1

Composition ^{Mo 10 B i 0. 3 F e} 4. 5 S b 7 N i 5. 75 C Γ o. 7 L a 0. 2 V 0. 05 K 0. 7 P 0. 2 Te o. 25 0 5 _9.8 the (S i 0 ₂₎ 40 catalyst is (atomic ratio) was prepared by the following method.

237.2 g of ammonium paramolybdate was dissolved in 1730 g of pure water, and then 3.10 g of 85% phosphoric acid was added. This solution was mixed with 1615 g of 20% silica sol. To this solution was added 224.6 g of nickel nitrate in 210 g of 3.3% nitric acid, 37.6 g of chromium nitrate, 11.63 g of lanthanum nitrate, 9.51 g of potassium nitrate, 40 g of citric acid, and 32. A slurry in which 56 g and 19.55 g of bismuth nitrate were dissolved was mixed to obtain a slurry. The slurry was adjusted to pH 7.7 by adding 15% aqueous ammonia with stirring, and then heated under reflux at 100 ° C. for 1.5 hours.

7.71 g of tellurium was dissolved in 200 g of water. This solution was mixed with the slurry previously heated, and 186.4 g of iron antimonate powder was mixed.

The above mixture was spray-dried and heat-treated in the same manner as in Example 1-11, and finally fluidized-fired at 590 ° C for 3 hours.

Example 2-2

A catalyst having the same composition as in Example 2-1 was prepared by the following method.

237.2 g of ammonium paramolybdate was dissolved in 1730 g of pure water, and then 3.10 g of 85% phosphoric acid was added. This solution was mixed with 1615 g of 20% silica sol. To this solution, add 22.6 g of nickel nitrate to 216 g of 3.3% nitric acid, nitric acid A solution obtained by dissolving 37.6 g of chromium, 1.63 g of lanthanum nitrate, 9.51 g of potassium nitrate, 20 g of citric acid and 19.55 g of bismuth nitrate was mixed to obtain a slurry. This slurry was adjusted to pH 7.7 by adding 15% aqueous ammonia with stirring, and then heat-treated at 100 ° C. for 1.5 hours under reflux.

7.71 g of telluric acid, 20 g of citric acid and 32.56 g of iron nitrate were dissolved in 200 g of water. This solution was mixed with the previously heated slurry, and 186.4 g of iron antimonate powder was mixed.

Example 3 composition _{_{M o 10 B i 0. 4}} F e 4. 5 S b l 0 N i 5. 7 5 C r 1. 0 C e 0. 2 a 0. 05 K 0. 5 P 0. 2 It was prepared by _{C s o. i0 65. 8} (S i 0 2) 40 following way catalyst is (atomic ratio).

219.2 g of ammonium paramolybdate was dissolved in 1730 g of pure water, and then 2.86 g of 85% phosphoric acid was added. This solution was mixed with 1490 g of 20% silica sol. To this solution, add 207.6 g of nickel nitrate to 210 g of 3.3% nitric acid, 49.67 g of chromium nitrate, 10.78 g of cerium nitrate, 8.79 g of potassium nitrate, 2.42 g of cesium nitrate, and tantalum oxide A solution obtained by dissolving 1.32 g, 20 g of citric acid, and 21.21 g of bismuth nitrate was mixed to obtain a slurry. The slurry was adjusted to pH 7.7 by adding 15% aqueous ammonia with stirring, and then heat-treated at 100 ° C for 1.5 hours under reflux.

20 g of citrate and 35.33 g of iron nitrate were dissolved in 100 g of water. The solution was adjusted to pH 8 by adding 15% aqueous ammonia while stirring. This solution was mixed with the slurry that had been previously heat-treated, and 138.3 g of iron antimonate powder was mixed.

The above mixture was spray-dried and heat-treated in the same manner as in Example 11-11, and finally fluidized-fired at 600 ° C for 3 hours.

Example 4 1 1 The composition is Mo! _{_{^{0 B i 0. 4 F e o}}} . EN i 5. 75 C r 0. 5 Z r 0. 2 K o. 7

P _0. The catalyst was prepared a ^{2 T e 0. 25O39. 8 (} S i 0 2) 40 ( atomic ratio). 309.5 g of ammonium paramolybdate was dissolved in 1800 g of pure water, and then 4.04 g of 85% phosphoric acid was added. To this solution was added 293.2 g of nickel nitrate to 250 g of 3.3% nitric acid, 35.08 g of chromium nitrate, 9.37 g of zirconium oxynitrate, 12.41 g of potassium nitrate, and 34.02 of bismuth nitrate g was dissolved and then 2107 g of 20% silica sol was mixed to obtain a slurry. The slurry was adjusted to pH 8 by adding 15% aqueous ammonia while stirring. A solution of 10.1 g of telluric acid and 35.33 g of iron nitrate dissolved in 200 g of pure water was added to the slurry and mixed.

Example 4-1

Example 4 A catalyst having the same composition as in Example 11 was prepared by the following method.

185.7 g of ammonium paramolybdate was dissolved in 1730 g of pure water, and then 4.04 g of 85% phosphoric acid was added. In this solution, 216 g of 3.3% nitric acid, 293.2 g of nickel dinitrate, 35.08 g of chromium nitrate, 9.37 g of zirconium oxynitrate, 12.41 g of potassium nitrate, 24 g of citric acid, and A solution in which 34.02 g of bismuth nitrate was dissolved was mixed, and then 2107 g of a 20% silicic acid sol was mixed to obtain a slurry. The slurry was adjusted to pH 7.7 by adding 15% aqueous ammonia with stirring, and then heated under reflux at 100 ° C. for 1.5 hours.

5.59 g of metallic tellurium powder in 208 g of pure water, ammonium paramolybdate 4.

6 g, 31% hydrogen peroxide and 19 g of water were added, and the mixture was dissolved by stirring at 95 to 100 ° C. The solution was cooled to room temperature, and 20 g of citrate and 35.33 g of iron nitrate were dissolved. While stirring, 15% aqueous ammonia was added to adjust the pH to 9.2. Then, 11.9.2 g of ammonium paramolybdate was added little by little to dissolve, and further, 15% aqueous ammonia was added. In addition, the pH was set to 7. This liquid was added to and mixed with the slurry previously heated.

The mixture was spray-dried and heat-treated in the same manner as in Examples 13 to 13, and finally fluidized at 580 ° C for 3 hours.

Example 5 Composition _{_{Mo 10 B i 0. 4 F}} e o_ 6 N i 5. 75 C r x. 5 L a 0 _ 2 Mn 0. 2

_{_{K 0. 7 P o. 2}} T e 0. 25 ° 41. 6 (S i 0 2) 40 was prepared analogously to catalyst (atomic ratio) in the method of Example 4-2.

Example 6

Composition _{_{_{Μθ ι 0 Β ί 0 · 8}}} F e 4. 5 S b 4 N i 6. 5 C r 0. 6 Z r 0. 1

_{_{L a 0. IKo. 7 P}} 0. 5 B 0. 3 0 5 5. 8 (S i 0 2) was ₅₀ catalysts are (atomic ratio) was prepared according to the method of Example 1 2. However, iron antimonate containing phosphorus and boron (atomic ratio of 0.075 to Sb, respectively) was used.

Example 7

The composition is Mo! _{0 B i 1 F e 4. 5} S b 4 N i 6 C r 0. 5 zr o. I zn o. 2 b o. O 5 K 0. 6 P 0. 5 B 0. 3 T e 0. 25 A catalyst having a temperature of 56.0 (Si ₂ ) ₄₀ (atomic ratio) was prepared according to the method of Example 6.

Example 8

The composition is Mo! 0 B i! _{_{F e 4. 5 S b 4 N}} i 5. 5 C r 0. 5 L a 0. l ^ g 0. 5

_{^{^{K 0. 6 P 0. 2 T}}} e 0. 25 ° 54. 5 (S i 0 2) 4 0 was prepared according to catalyst is (atomic ratio) in actual Example 1 one 2 ways.

Example 9

The composition is Mo! _{_{^{0 B i!. 5 F e}}} 4. 5 S b 4 N 1 5 C r 0. 3 L a 0. 07 C o 1 K 0. 6 P 0. 2 T e 0. 25 ° 55. 3 (S i It was prepared 〇 ₂₎ ₄₀ (according to the catalyst an atomic ratio) in actual Example 1 one 2 ways.

Example 10

Composition _{_{_{Mo 10 B i 0. 4 F}}} e 4. 5 S b 4 N i 7 C r 0. 4 L a 0. IW 0. 1

_{_{K 0. 5 P 0. 5 B}} 0. 3 Rb o. The _{_{ι0 55 · 4 (S i 0}} 2) 40 catalysts is (atomic ratio) was prepared according to the method of Example 6.

Example 1 1

Composition _{_{Mo i 0 B i 0. 3}} F e 7. 6 S b 7. 7 N 1 6 C r 0. 5 Z r 0. 1 La 0.! KQ. 6 P 0. 2_Rei_65. 5 (S A catalyst having i 0 ₂ ) 60 (atomic ratio) was prepared according to the method of Example 1-2. Comparative Example 1

Composition Mo i oB i o. 3 F e 4 4 S b 4, 2 N i 5. 75 C r o. 5 K 0. 7

_{^{. P 0 2 T e 0. 25}} ° 53. 3 (S i 0 2) 40 implementing the catalyst is (atomic ratio) Example 1 - were prepared in accordance with the second method. However, no zirconium component was added.

Comparative Example 2 composition ^ 40 10: 6 1 0. 3 F e 4. 4 S b 4. 2 Ν ί 5. 75 Z r 0. 2 K 0. 7 P 0. 2 T e 0. 25 ° 53. A catalyst having a ratio of 0 (S 10 ₂ ) 40 (atomic ratio) was prepared according to the method of Example 12-12. However, no kumumu component was added.

Comparative Example 3

Composition _{Mo i oB i o. 3 F} e 4. 4 S b 4. 2 N i 5. 75 Ce 0. 2 K 0. 7

A catalyst having a ratio of P 0.2 ^{T e} 0.25 455.4 (S i〇 ₂ ) ₄₀ (atomic ratio) was prepared according to the method of Example 1-2.

The catalysts of the above Examples and Comparative Examples were subjected to the above-mentioned catalytic activity test, and the results are shown in Table 1.

Industrial applicability

INDUSTRIAL APPLICABILITY The catalyst of the present invention can provide a high acrylonitrile yield in the production of atarilonitrile by ammoxidation of olefin, in particular, ammoxidation of propylene, and can suppress the flammability of ammonia.

Conditions

Firing Reaction Contact ANC 3 ANN, H :. Catalyst composition (atomic ratio) Temperature Temperature Time Yield ¹ > Teidani rate ² ) ³⁾ Burn rate

Mo Bi Fe Sb Ni Cr F G H

Example K X Y Si02 ° C sec%%%%

1-1 10 0.3 4.4 4.2 5.75 0.5 Zr 0.2 1 0.7 P 0.2 Te 0.25 1 40 590 440 2.25 84.5 98.5 85.9 11

1-2 10 0.3 4.4 4.2 5.75 0.5 Zr 0.2--0.7 P 0.2 Te 0.25-40 590 440 2.25 85.7 98.5 87.0 10

2-1 10 0.3 4.5 7.0 5.75 0.7 0.2 V 0.05 0.7 P 0.2 Te 0.25 1 40 590 435 2.50 84.5 98.5 85.7 9

2-2 10 0.3 4.5 7.0 5.75 0.7 La 0.2 ― V 0.05 0.7 P 0.2 Te 0.25-40 590 435 2.50 84.7 98.6 85.9 8

3 10 0.4 4.5 10.0 5.75 1.0 Ce 0.2 i Ta 0.05 0.5 P 0.2 Cs 0.1 40 600 440 2.50 85.1 98.5 86.4 7

4-1 10 0.4 0.6 one 5.75 0.5 Zr 0.2 one-0.7 P 0.2 Te 0.25 one 40 580 440 2.50 84.2 98.2 85.7 15

4-2 10 0.4 0.6 1 5, 75 0.5 Zr 0.2-1 0.7 P 0.2 Te 0.25 ― 40 580 440 2.25 84.8 98.6 86.0 13

5 10 0.4 0.6-5.75 1.5 La 0.2 Mn 0.2-0.7 P 0.2 Te 0.25 ― 40 580 435 2.50 84.1 98.9 85.0 10

6 10 0.8 4.5 4.0 6.50 0.6 Zr 0.1 0.1--0.7 P 0.5 B 0.3 1 40 560 440 2.50 84.2 98.1 85.8 12

7 10 1.0 4.5 4.0 6.00 0.5 Zr 0.1 Zn 0.2 Nb 0.05 0.6 P 0.5 Te 0.25 B 0.3 ― 50 560 440 2.50 83.9 98.0 85.6 11

8 10 1.0 4.5 4.0 5.50 0.5 La 0.1 Mg 0.5-0.6 P 0.2 Te 0.25 40 555 440 2.25 84.1 98.8 85.1 10

9 10 1.5 4.5 4.0 5.00 0.3 La 0.07 Co 1.0-0.6 P 0.2 Te 0.25-40 535 440 2.25 83.9 98.5 85.2 16

10 10 0.4 4.5 4.0 7.00 0.4 0.1 W 0.1 0.5 P 0.5 B 0.3 Rb 0.1 40 600 440 100 85.5 98.3 87.0 6

11 10 0.3 7.6 7.7 6.00 0.5 Zr 0.1 La 0.1 0.6 P 0.2 60 590 440 2.50 85.6 98.7 86,7 9 Comparative example

1 10 0.3 4.4 4.2 5.75 0.5 0.7 P 0.2 Te 0.25 40 590 440 1.50 82.1 98.3 83.5 5

2 10 0.3 4.4 4.2 5.75 Zr 0.2 0.7 P 0.2 Te 0.25 ΊΟ 550 440 1.75 83.1 98.5 84.4 18

3 10 0.3 4.4 4.2 5.75 Ce 0.2 0.7 P 0.2 Te 0, 25 40 570 1 440 2.50 83.6 98.6 84.8 25 Note) 1) AN: Atarilonitrino

2) C 3: propylene

Claims

The scope of the claims

1. A catalyst composition represented by the following empirical formula used in the production of unsaturated nitrile by ammoxidation:

Mo _{1 0} B i _a F e _b S b _c N i _d C r _e F _f G _g H _h K _k X _x Y _y O _i

(S i 0 ₂ ) j

In the formula, Mo, Bi, Fe, Sb, Ni, Cr, and K represent molybdenum, bismuth, iron, antimony, nickel, chromium, and potassium, respectively, and F represents zirconium, lanthanum, and cerium. At least one element selected from the group consisting of magnesium, cobalt, manganese, and zinc; andH is at least one element selected from the group consisting of vanadium, niobium, tantalum, and tungsten. element, X is phosphorus, at least one element selected from the group consisting of boron and tellurium, Y is lithium, sodium, at least one element selected from the group consisting of rubidium及beauty cesium, O represents oxygen, S i 0 ₂ is Represents silica, and the subscripts a, b, c, d, e, f, g, h, i, j, k, x, and y represent the ratio of atoms or groups of atoms. , When Mo = 10, a = 0.:! ~ 3, b = 0.

3 to 15, c = 0 to 20, d = 3 to 8, e = 0.2 to 2, f = 0.05.05 to: 1, ef> 1, g = 0 to 5, h = 0 to 3, k = 0. 1 to: 1, x = 0 to 3, y = 0 to 1 _Λ i = the number of oxygen generated by combining the above components, and〗 = 0 to 100.

2. The catalyst composition according to claim 1, comprising iron antimonate.

3. The metal oxide catalyst is a fluidized bed catalyst prepared by spray-drying and calcining an aqueous slurry containing at least molybdenum, bismuth and iron raw materials and a chelating agent and having a pH of 6 or more. 3. The catalyst composition according to 1 or 2.

4. an aqueous slurry containing at least a part of a molybdenum raw material, and a raw material of at least one element selected from the group consisting of nickel, cobalt, magnesium, chromium, manganese and zinc, and having a pH of 6 or more; 3. The method for producing a catalyst composition according to claim 1, comprising mixing a solution or slurry containing a tellurium raw material or an iron raw material, and then drying and calcining the mixture.

5. At least a part of molybdenum raw material and nickel, cobalt, magnesium Aqueous slurry containing at least one element selected from the group consisting of aluminum, chromium, manganese, and dumbbell and having a pH of 6 or more at a temperature of 50 to 120 ° C and at least 10 ° C. The method for producing a catalyst composition according to claim 1 or 2, further comprising mixing a tellurium raw material or an iron raw material with the calo-heat-treated slurry, followed by drying and calcining the mixture. .

6. An aqueous slurry containing at least a part of a molybdenum raw material, and a raw material of at least one element selected from the group consisting of nickel, cobalt, magnesium, chromium, manganese, and zinc, and having a pH of 6 or more. 3. The method for producing a catalyst composition according to claim 1, comprising mixing a solution or slurry containing a tellurium raw material and an iron raw material, and then drying and calcining the mixture.

7. An aqueous slurry containing at least a part of a molybdenum raw material and a raw material of at least one element selected from the group consisting of nickel, cobalt, magnesium, chromium, manganese, and zinc, and having a pH of 6 or more. After a heat treatment at a temperature of 50 to 120 ° C. for at least 10 minutes, a tellurium raw material and an iron raw material are mixed with the heat-treated slurry, and then the mixture is dried and fired. 3. The method for producing a catalyst composition according to claim 1, comprising: