KR20120022559A - Catalyst for producing methacrolein and methacrylic acid, and process for producing the same - Google Patents

Abstract

PURPOSE: A catalyst for manufacturing metacrolein and metharylic acid and a method for manufacturing the same are provided to reduce the further generation of compounds with high activity and high boiling points by adjusting the ratio of acid amount in the catalyst. CONSTITUTION: A catalyst for manufacturing metacrolein and metharylic acid includes molybdenum and bismuth as component elements. The ratio of the acid amount of the catalyst at a low temperature side to the acid amount of the catalyst at a high temperature side based on the ammonia thermal desorption method is 0.14 or less. A method for manufacturing the catalyst includes an organic acid adding process.

Description

Catalysts for producing methacrolein and methacrylic acid, and methods for preparing the same {CATALYST FOR PRODUCING METHACROLEIN AND METHACRYLIC ACID, AND PROCESS FOR PRODUCING THE SAME}

The present invention is a molybdenum-containing composite used for producing methacrolein by gas phase contact oxidation of at least one selected from the group consisting of isobutylene and t-butyl alcohol using a molecular oxygen-containing gas. An oxide catalyst and a method for producing the same.

At least one selected from isobutylene and t-butyl alcohol is subjected to gas phase catalytic oxidation, and when methacrylic acid is produced, at least one selected from isobutylene and t-butyl alcohol is subjected to catalytic gas phase oxidation. Converted to methacrolein (hereinafter, this reaction is called a "shear reaction" and the catalyst used therein is called a "shear catalyst"), and then this methacrolein is subjected to catalytic gas phase oxidation to methacrylic acid. The so-called two-stage oxidation reaction which converts (hereinafter, this reaction is called "post-stage reaction" and the catalyst used for this is called "post-stage catalyst") is generally employ | adopted. As the catalyst used for the shear catalyst, molybdenum and bismuth-containing complex oxide catalysts are generally used. Numerous proposals have been made regarding molybdenum and bismuth-containing composite oxide catalysts used in the production of methacrolein by gas phase catalytic oxidation of at least one selected from isobutylene and t-butyl alcohol.

On the other hand, efforts to improve the target oxidation product yield have been continued by adding various additives. For example, Patent Literature 1 discloses a method in which salts such as nitrate and ammonium salt are contained in a catalyst precursor, Patent Literature 2 adds a chelating agent to a molybdenum-containing slurry, and Patent Literature 3 integrates a molybdenum compound and a bismuth compound. A method of adding ammonia water at the time is disclosed. In addition, Patent Document 4 discloses a method that does not generate metal precipitation during suspension preparation using various acids. However, the above method has a problem in that physical properties and performance of the catalyst are deteriorated because additives are rapidly decomposed in the firing process.

In order to solve such a problem, Patent Literature 5 or Non-Patent Literature 1 discloses a method of chelating an aqueous solution of a metal salt with an organic acid to completely dissolve it, and then adding a drying control additive to vacuum drying and pulverizing. However, from the industrial point of view, the composite oxide catalyst containing molybdenum and bismuth produced by these conventional methods is required to further improve the yield of the desired oxidation product. In addition, in view of simplicity and safety in the preparation of the catalyst, reproducibility in the preparation of the catalyst, mechanical strength of the catalyst, and even environmental problems, it is impossible to say that the conventional catalyst is still sufficient. .

When at least one selected from isobutylene and t-butyl alcohol is subjected to gas phase catalytic oxidation, relatively high-boiling compounds such as maleic acid and terephthalic acid, as well as methacrolein as the main product, are byproducts. At the same time, a polymer or tar-like substance is contained in the reaction product gas. When the reaction product gas containing such a substance is provided to the rear end reaction as it is, these substances cause clogging in the piping or the rear end catalyst packed bed, resulting in an increase in pressure loss, a decrease in catalyst activity, and methacrylic acid. Causes a decrease in selectivity. Such troubles often occur when the supply amount of isobutylene and / or t-butyl alcohol is increased or the isobutylene and / or t-butyl alcohol concentration is increased to increase the productivity of methacrylic acid.

As a method generally employed to prevent such troubles, the reaction is stopped at regular intervals, and the inert material charged in order to prevent blockage in the catalyst layer or deactivation of the catalyst at the gas inlet side of the rear catalyst is removed and replaced, or By separating the methacrolein from the shear reaction product gas once, and supplying this separated methacrolein to the post reaction again, an optimization process of the oxidation reaction is adopted, or further, the source gas concentration is diluted more than necessary, and the byproduct concentration is increased. A method of lowering and reacting has been proposed. Patent Literature 6 discloses a method of keeping the portion at a temperature above the boiling point of maleic anhydride, a method for taking the gas line speed very large, in order to prevent clogging such as piping at the intermediate portion of the front end and the rear end reactions. For example, a method of specifying the shape of the catalyst used for the post-stage reaction, increasing the porosity between the catalysts, and suppressing the blockage of solids from the shear reactor is proposed. However, these methods are also not satisfactorily satisfactory as industrial methods, and development of catalysts with less by-products of high boiling point materials is desired.

Japanese Laid-Open Patent Publication No. 2003-251183 Japanese Patent Application Laid-Open No. 2-214543 Japanese Laid-Open Patent Publication No. 2003-220335 Korean Patent Publication No. 2002-27023 WO 2005/079980 publication Japanese Laid-Open Patent Publication No. 50-126605 Japanese Laid-Open Patent Publication No. 61-221149

 Applied Catalsis A: General Vol.332 (2007) P.257-262

The present invention provides molybdenum used for producing methacrolein by gas phase contact oxidation of at least one selected from the group consisting of isobutylene and t-butyl alcohol in the presence of an oxidation catalyst composition using a molecular oxygen-containing gas. It is related with the containing complex oxide catalyst, It is high activity, and there are few by-products of a high boiling point compound, It is providing the catalyst which supplies methacrolein stably in a high yield, and its manufacturing method.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, at least 1 sort (s) selected from the group which consists of isobutylene and t-butyl alcohol is gas-phase-contact-oxidized using molecular oxygen containing gas in presence of an oxidation catalyst composition, When preparing a composite oxide catalyst containing molybdenum and bismuth used in the production of lanes, a method of preparing a catalyst by adding an organic acid in the step of integrating the source compound of molybdenum and bismuth in an aqueous system Polite review. As a result, the composite oxide catalyst containing molybdenum and bismuth produced by the method of the present invention is more active than conventional catalysts, and has less by-products of the high-boiling point compounds, resulting in stable high yield of methacrolein. We found that we could manufacture. This invention is completed based on this knowledge.

That is, the present invention

(a) A catalyst containing at least molybdenum and bismuth as a component element, wherein the ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method is 0.14. A catalyst for methacrolein and / or methacrylic acid production, characterized by the following

(b) In the integration process in the aqueous system of the source compound containing at least molybdenum and bismuth as a component element, an organic acid is added, The methacrolein and / or methacrylic acid manufacturing catalyst of (a) characterized by the above-mentioned.

(c) The ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the above-mentioned ammonia elevated temperature desorption method is 0.12 or less, The meta-described as described in (b) Catalysts for Crawlane and / or Methacrylic Acid Production

(d) The ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the above-mentioned ammonia elevated temperature desorption method is 0.10 or less, Meta as described in (b) Catalysts for Crawlane and / or Methacrylic Acid Production

(e) The catalyst for producing methacrolein and / or methacrylic acid according to any one of (b) to (d), wherein the boiling point of the organic acid is 110 ° C or higher.

(f) The catalyst for producing methacrolein and / or methacrylic acid according to any one of (b) to (e), wherein the organic acid is a fatty acid.

(g) The catalyst for producing methacrolein and / or methacrylic acid according to any one of (b) to (f), wherein the organic acid is a fatty acid having 1 to 10 carbon atoms.

(h) The catalyst for producing methacrolein and / or methacrylic acid according to any one of (b) to (g), wherein the organic acid is acetic acid, propionic acid, butyric acid or valeric acid.

(i) The catalyst for producing methacrolein and methacrylic acid according to any one of (a) to (h), wherein the catalyst is a molding catalyst.

(j) The catalyst for production of methacrolein and methacrylic acid according to any one of (a) to (i), wherein the amount of the organic acid added is 0.1 to 20 parts by mass with respect to 100 parts by mass of the molybdenum raw material.

(k) The ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method containing at least molybdenum and bismuth as a component element is 0.14 or less. Method for producing composite oxide catalyst

(l) In the integration process in the aqueous system of the source compound which contains molybdenum and bismuth at least as a component element, it relates to the manufacturing method of the composite oxide catalyst as described in (k) characterized by adding an organic acid.

The composite oxide catalyst containing molybdenum and bismuth produced by the method of the present invention is prepared by subjecting at least one selected from the group consisting of isobutylene and t-butyl alcohol to gas-phase catalytic oxidation using a molecular oxygen-containing gas. As a catalyst used when producing a crawl lane, it is highly active and there are few by-products of a high boiling point compound, and methacrolein can be obtained stably in high yield.

(Form to carry out invention)

The composite oxide catalyst containing molybdenum and bismuth to which the production method of the present invention can be applied is gas-phase contacted with at least one selected from the group consisting of isobutylene and t-butyl alcohol using a molecular oxygen-containing gas. Although there will be no restriction | limiting in particular if it is a catalyst for oxidation and manufacturing methacrolein and methacrylic acid, The complex oxide catalyst represented by following General formula (1) is preferable.

Mo _a Bi _b Fe _c A _d B _e C _f D _g E _h O _x (1)

(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from sodium, potassium, rubidium, cesium and thallium, C is at least one element selected from boron, phosphorus, chromium, manganese, zinc, arsenic, niobium, tin, antimony, tellurium, cerium and lead, D is at least one kind selected from silicon, aluminum, titanium and zirconium Element, E is at least one element selected from alkaline earth metals, and O is oxygen, and a, b, c, d, e, f, g, h and x are Mo, Bi, Fe, A, B, Represents the atomic ratio of C, D, E and O, and when a = 12, 0.1 ≦ b ≦ 10, 0.1 ≦ c ≦ 20, 1 ≦ d ≦ 20, 0.001 ≦ e ≦ 5, 0 ≦ f ≦ 10, 0 ≤ g ≤ 30, 0 ≤ h ≤ 5, and x is a numerical value determined according to the oxidation state of each element.

Although it does not specifically limit as a starting material of each element which comprises the catalyst of this invention, For example, as a raw material of a molybdenum component, molybdenum oxides, such as molybdenum trioxide, molybdate, ammonium paramolybdate, and molybdenum, such as ammonium metamolybdate Acids or salts thereof, heteropolyacids containing molybdenum such as phosphorus molybdate and silicon molybdate, or salts thereof.

As a raw material of the bismuth component, bismuth nitrate, bismuth carbonate, bismuth sulfate, bismuth salts such as bismuth acetate, bismuth trioxide, metal bismuth and the like can be used. Although these raw materials can be used as a solid or as a slurry of the bismuth compound which arises from aqueous solution, nitric acid solution, or those aqueous solution, it is preferable to use nitrate or its solution, or the slurry generated from this solution.

As a starting material of other component elements, it is generally good to use a combination of ammonium salts, nitrates, carbonates, chlorides, sulfates, hydroxides, organic acid salts, oxides or mixtures thereof which are metal elements used in this kind of catalyst, but ammonium salts and nitrates This is suitably used.

Integration in the aqueous system of the source compound of each component element means mixing or aging treatment of the aqueous solution or aqueous dispersion of the source compound of each component element in batch or stepwise. That is, (a) a method of collectively mixing each of the above source compounds, (b) a method of aging treatment after collectively mixing each of the above source compounds, and (c) a method of mixing each of the above source compounds stepwise. (D) The method of repeating mixing and maturing the above source compounds step by step, and the method of combining (a) and (d), are all concepts of integration in the aqueous system of the source compounds of the respective elemental elements. Included in Here, the above-mentioned aging means "operation which processes industrial raw materials or semi-finished products under specific conditions, such as a fixed time and a certain temperature, and acquires the physical property and chemical property which are needed, and raises a progress of a predetermined reaction, etc." Say. In addition, in this invention, said constant time means the range of 5 minutes-24 hours, and said constant temperature means the range of the boiling point of room temperature aqueous solution-aqueous dispersion.

Since the added organic acid may evaporate during aging, as the organic acid to be added in the integration process in the aqueous system of the source compound of each component element, an organic acid having a boiling point of 110 ° C. or higher is preferable. For example, acetic acid, propanoic acid, butyric acid, isobutyric acid, pentanic acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, ethane2 acid, propanoic acid, lactic acid, tartaric acid, maleic acid, fumaric acid, malonic acid, Succinic acid, citric acid, malic acid, adipic acid, cinnamic acid, pyruvic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, etc. are mentioned.

When the amount of the organic acid added in the integration step is large, since the organic acid added in the firing step is rapidly decomposed, the physical properties and performance of the catalyst may be lowered. Therefore, the amount of the organic acid added is 0.1? To 100 parts by mass of the molybdenum raw material. 20 mass parts is preferable, and 0.5-15 mass parts is more preferable.

Although the method of adding an organic acid in the said integration process is not specifically limited, For example, the method of adding in a solvent before mixing the source compound of each component element, and before mixing the source compound of each component element to any component element is mixed. The method of adding, the method of mixing the source compound and organic acid of each component element collectively, The method of adding in each step of mixing each source compound in steps, The addition of each source compound in the step which repeats mixing and aging process step by step How to do this. The addition conditions (time, temperature, pressure, pH, and the like) are not particularly limited and may be appropriately determined.

Then, all the solutions or slurries obtained in this way are dried.

As a drying method, for example, evaporation drying method, spray drying method, drum drying method, airflow drying method, etc. are mentioned, About the model of a dryer, conditions, such as temperature and time at the time of drying, and a form of a catalyst precursor, It does not specifically limit, It can change suitably.

By firing the catalyst precursor obtained as described above, a target complex oxide catalyst is obtained. In addition, after pulverizing a catalyst precursor as needed, it may be baked without shaping | molding, and may be shape | molded subsequently, and may be baked after shape | molding. Moreover, what was shape | molded after baking may be baked again.

The shaping | molding can also employ | adopt any shaping | molding method of the supported shaping | molding supported on support | carriers, such as a silica, and the unsupported shaping | molding which does not use a support | carrier. As a specific shaping | molding method, tableting molding, press molding, extrusion molding, granulation molding, etc. are mentioned, for example. As the shape of the molded article, for example, a cylindrical shape, a ring shape, a spherical shape, and the like can be appropriately selected in consideration of operating conditions, but the catalyst active component is supported on a spherical carrier, particularly an inert carrier such as silica or alumina. A supported catalyst having a particle size of 3 to 8 mm is preferable. In addition, when shaping | molding, you may add a small amount of well-known additives, such as graphite and talc, for example.

Although a baking method and baking conditions are not specifically limited, Well-known processing methods and conditions can be applied. The optimum conditions for firing differ depending on the catalyst raw material used, the catalyst composition, the preparation method, and the like, but are usually 0.5 to 600 ° C., preferably 300 to 550 ° C. under oxygen-containing gas flow such as air or inert gas flow. More than hour, Preferably it is 1-40 hours. Here, an inert gas means the gas which does not reduce the reaction activity of a catalyst, Specifically, nitrogen, a carbon dioxide gas, helium, argon, etc. are mentioned.

The composite oxide catalyst thus obtained satisfies a specific relationship with respect to the amount of acid measured from the ammonia adsorption amount by the ammonia elevated temperature desorption method. That is, when the amount of acid is measured by the ammonia elevated temperature desorption method for the composite oxide catalyst, there are two types of peaks observed on the high temperature side (400 to 800 ° C) and the low temperature side (100 to 400 ° C). The ratio of the acid amount of the catalyst on the low temperature side to the acid amount of the catalyst on the high temperature side is 0.14 or less, more preferably 0.12 or less. In order to make this ratio 0.14 or less, the kind and addition amount of the organic acid to add are suitably selected / adjusted according to catalyst preparation conditions, such as a catalyst raw material, a preparation liquid temperature, and pH, but the addition amount of an organic acid is 0.1 with respect to 100 mass parts of molybdenum raw materials. -20 mass parts is preferable, and 0.5-15 mass parts is more preferable.

It is clear that the catalyst performance is improved by setting the ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method of the complex oxide catalyst to 0.14 or less. However, the acid amount of the catalyst on the low temperature side by the ammonia temperature desorption method contributes to side reactions other than the oxidation reaction to the target compound, resulting in a reduction in by-products other than the target compound, resulting in catalytic performance, in particular to the target compound. It is inferred that the selectivity is improved.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples. In addition, in the Example, conversion rate, yield, and selectivity were computed according to the following formula | equation.

Raw material conversion rate (%) = (moles of reacted t-butyl alcohol or isobutylene) / (moles of supplied t-butyl alcohol or isobutylene) * 100

Methacrolein yield (%) = (mole number of produced methacrolein) / (mole number of t-butyl alcohol or isobutylene supplied) * 100

Methacrylic acid yield (%) = (mole number of methacrylic acid produced) / (mole number of t-butyl alcohol or isobutylene supplied) * 100

Effective selectivity (%) = (methacrolein yield + methacrylic acid yield) / (raw material conversion rate) * 100

The acid amount of the catalyst was measured using an ammonia desorption apparatus. After precisely weighing 0.1 g of the catalyst, it was charged into a measuring tube, and the catalyst was pretreated for 1 hour at a processing temperature of 500 ° C. under a helium atmosphere, and the ammonia gas was adsorbed at an adsorption temperature of 100 ° C., 30 It vacuum-exhausted for minutes, it heated up at 600 degreeC at the speed of 10 degree-C / min, and measured the ammonia desorption amount.

The ratio of the acid amount of the catalyst at the low temperature side by the ammonia elevated temperature desorption method with respect to the acid amount of the catalyst at the high temperature side by the ammonia temperature rising desorption method of the catalyst was computed with the following method.

L / H = (acid amount of catalyst on low temperature side) / (acid amount of catalyst on high temperature side)

That is, the smaller the numerical value, the smaller the ratio of the acid amount of the catalyst on the low temperature side.

In addition, quantification of the high boiling point substance was performed using liquid chromatography. The said high boiling point substance is an aromatic compound represented by terephthalic acid. In the Example, the high boiling point material yield was computed according to the following formula | equation.

High boiling point yield (%) = (molar number of generated high boiling point substance) / (molar number of t-butyl alcohol or isobutylene supplied) * 100

(Oxidation reaction test)

An oxidation catalyst (E) was charged to 310 cm in a stainless steel reactor having an inner diameter of 23 mm provided with a jacket for circulating the molten salt as a thermal catalyst and a thermocouple for measuring the temperature of the catalyst bed on the tube shaft. Reaction bath temperature (Tb) was set to 345 degreeC. Here, a gas having a supply amount of t-butyl alcohol, air, nitrogen, and water is introduced into the oxidation reactor at a space velocity of 1000 h ^-1 so that the raw material molar ratio is isobutylene: oxygen: nitrogen: water = 1: 2: 10: 1.6. Reaction was carried out.

Example 1

3000 g of ammonium molybdate and 55.2 g of cesium nitrate were dissolved while heating and stirring 12000 ml of distilled water to obtain an aqueous solution (A). Separately, 2782 g of cobalt nitrate, 1144 g of ferric nitrate, and 412 g of nickel nitrate were dissolved in 2300 ml of distilled water, an aqueous solution (B) was added, and 292 ml of concentrated nitric acid was added to dissolve 1167 g of bismuth nitrate in 1215 ml of acidic distilled water. (C) was prepared respectively. (B) and (C) were mixed sequentially with vigorous stirring to the aqueous solution (A), and finally 60 g of acetic acid was added, and the resulting suspension was dried using a spray dryer and calcined at 460 ° C. for 5 hours. The obtained calcined powder (D) was obtained. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.7, Fe = 2.0, Co = 6.75, Ni = 1.0, and Cs = 0.20 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E1). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 2

While stirring 2000 mL of distilled water, 450 g of ammonium molybdate and 3.8 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 456 g of cobalt nitrate and 158 g of ferric nitrate were dissolved in 500 ml of distilled water to add an aqueous solution (B), and 48 ml of concentrated nitric acid was added to dissolve 190 g of bismuth nitrate in 200 ml of acidic distilled water to give an aqueous solution (C). Prepared. (B) and (C) are sequentially mixed with vigorous stirring to the aqueous solution (A), and finally 35 g of propionic acid is added, and the resulting suspension is dried using a spray dryer and calcined at 460 ° C. for 5 hours. The obtained calcined powder (D) was obtained. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 13, Bi = 2.0, Fe = 2.0, Co = 8.0, and Cs = 0.1 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 40 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E2). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 3

3000 g of distilled water in which 40 g of propionic acid was dissolved was dissolved in 500 g of ammonium molybdate and 10.2 g of cesium nitrate while heating and stirring to obtain an aqueous solution (A). Separately, 485 g of cobalt nitrate, 190 g of ferric nitrate, and 72 g of nickel nitrate were dissolved in 395 ml of distilled water, an aqueous solution (B) was added, and 50 ml of concentrated nitric acid was added to dissolve 196 g of bismuth nitrate in 206 ml of acidic distilled water. (C) was prepared respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.8, Fe = 2.0, Co = 7.75, Ni = 1.5, and Cs = 0.30 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E3). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 4

While 2500 ml of distilled water was heated and stirred, 450 g of ammonium molybdate and 8.2 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 482 g of cobalt nitrate, 103 g of ferric nitrate, and 74 g of nickel nitrate were dissolved in 341 ml of distilled water, an aqueous solution (B) was added, and 42 g of propionic acid and 32 ml of concentrated nitric acid were added, and 103 g of bismuth nitrate was added to 182 ml of acidic distilled water. It melt | dissolved and prepared the aqueous solution (C), respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.0, Fe = 1.2, Co = 7.80, Ni = 1.2, and Cs = 0.20 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E4). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 5

While dissolving 2000 ml of distilled water, 450 g of ammonium molybdate and 12.4 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 417 g of cobalt nitrate and 128 g of ferric nitrate were dissolved in 341 ml of distilled water in which 35 g of propionic acid was dissolved, an aqueous solution (B) was added, and 52 ml of concentrated nitric acid was added to dissolve 206 g of bismuth nitrate in 182 ml of acidic distilled water. Aqueous solutions (C) were prepared, respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. Composition ratios except oxygen of the catalytically active component at this time were Mo = 12, Bi = 2.0, Fe = 1.5, Co = 6.75 and Cs = 0.3 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 40 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E5). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 6

While dissolving 2000 ml of distilled water, 500 g of ammonium molybdate and 12.4 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 390 g of cobalt nitrate, 189 g of ferric nitrate, and 68 g of nickel nitrate were dissolved in 341 ml of distilled water, an aqueous solution (B) was added, and 47 ml of concentrated nitric acid was added to dissolve 185 g of bismuth nitrate in 182 ml of acidic distilled water. (C) was prepared respectively. 40 g of propionic acid, (B), and (C) are mixed with the aqueous solution (A) in sequential order with vigorous stirring, and the resulting suspension is dried using a spray dryer and calcined at 460 ° C. for 5 hours to be prebaked powder ( D) was obtained. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.8, Fe = 2.2, Co = 6.3, Ni = 1.1, and Cs = 0.30 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E6). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 7

While 2500 ml of distilled water was heated and stirred, 450 g of ammonium molybdate and 8.2 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 482 g of cobalt nitrate, 103 g of ferric nitrate, and 74 g of nickel nitrate were dissolved in 341 ml of distilled water, an aqueous solution (B) was added, and 52 g of butyric acid and 32 ml of concentrated nitric acid were added to 103 g of bismuth nitrate in 182 ml of acidic distilled water. It melt | dissolved and prepared the aqueous solution (C), respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.0, Fe = 1.2, Co = 7.80, Ni = 1.2, and Cs = 0.20 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E7). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Example 8

3000 g of distilled water in which 15 g of lactic acid was dissolved was dissolved in 500 g of ammonium molybdate and 10.2 g of cesium nitrate while heating and stirring to obtain an aqueous solution (A). Separately, 485 g of cobalt nitrate, 190 g of ferric nitrate, and 72 g of nickel nitrate were dissolved in 395 ml of distilled water, an aqueous solution (B) was added, and 50 ml of concentrated nitric acid was added to dissolve 196 g of bismuth nitrate in 206 ml of acidic distilled water. (C) was prepared respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.8, Fe = 2.0, Co = 7.75, Ni = 1.5, and Cs = 0.30 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E8). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Comparative Example 1

3000 g of ammonium molybdate and 55.2 g of cesium nitrate were dissolved while heating and stirring 12000 ml of distilled water to obtain an aqueous solution (A). Separately, 2782 g of cobalt nitrate, 1144 g of ferric nitrate, and 412 g of nickel nitrate were dissolved in 2300 ml of distilled water, an aqueous solution (B) was added, and 292 ml of concentrated nitric acid was added to dissolve 1167 g of bismuth nitrate in 1215 ml of acidic distilled water. (C) was prepared respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.7, Fe = 2.0, Co = 6.75, Ni = 1.0, and Cs = 0.20 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E9). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Comparative Example 2

While dissolving 2000 ml of distilled water, 450 g of ammonium molybdate and 12.4 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 417 g of cobalt nitrate and 128 g of ferric nitrate were dissolved in 341 ml of distilled water, an aqueous solution (B) was added thereto, and 52 ml of concentrated nitric acid was added to dissolve 206 g of bismuth nitrate in 182 ml of acidic distilled water. Each prepared. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. Composition ratios except oxygen of the catalytically active component at this time were Mo = 12, Bi = 2.0, Fe = 1.5, Co = 6.75 and Cs = 0.3 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 40 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E10). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Comparative Example 3

While 2500 ml of distilled water was heated and stirred, 450 g of ammonium molybdate and 8.2 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 482 g of cobalt nitrate, 103 g of ferric nitrate, and 74 g of nickel nitrate were dissolved in 341 ml of distilled water, an aqueous solution (B) was added, and 32 ml of concentrated nitric acid was added to dissolve 103 g of bismuth nitrate in 182 ml of acidic distilled water. C) was prepared respectively. (B) and (C) are mixed with the said aqueous solution (A) in order, stirring vigorously, the produced suspension is dried using a spray dryer, and it calcined at 460 degreeC for 5 hours, and prebaked powder (D) is carried out. Got it. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.0, Fe = 1.2, Co = 7.80, Ni = 1.2, and Cs = 0.20 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E11). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Examples 1 to 8 and Comparative Examples 1 to 3 Table 1 shows the ratio (L / H) of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the organic acid addition condition and the ammonia elevated temperature desorption method. Moreover, the result of the oxidation reaction test of the catalyst obtained in Examples 1-8 and Comparative Examples 1-3 was shown in Table 2.

Example 9

While stirring 2000 mL of distilled water, 450 g of ammonium molybdate and 3.8 g of cesium nitrate were dissolved to obtain an aqueous solution (A). Separately, 456 g of cobalt nitrate and 158 g of ferric nitrate were dissolved and dissolved in 500 ml of distilled water. An aqueous solution (B) was added. Furthermore, 48 ml of concentrated nitric acid was added to dissolve 190 g of bismuth nitrate in 200 ml of acidic distilled water. Prepared each. (B) and (C) were mixed sequentially with vigorous stirring to the aqueous solution (A), and finally the suspension produced by adding 43 g of oxalic acid was dried using a spray dryer and calcined at 460 ° C. for 5 hours. Prebaked powder (D) was obtained. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 13, Bi = 2.0, Fe = 2.0, Co = 8.0, and Cs = 0.1 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert carrier (alumina, particle diameter 4.0mm) at the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E12). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

Comparative Example 4

3000 g of ammonium molybdate and 55.2 g of cesium nitrate were dissolved while heating and stirring 12000 ml of distilled water to obtain an aqueous solution (A). Separately, 2782 g of cobalt nitrate, 1144 g of ferric nitrate, and 412 g of nickel nitrate were dissolved in 2300 ml of distilled water, an aqueous solution (B) was added, and 292 ml of concentrated nitric acid was added to dissolve 1167 g of bismuth nitrate in 1215 ml of acidic distilled water. C) was prepared respectively. (B) and (C) were mixed sequentially with vigorous stirring to the aqueous solution (A), and finally the suspension produced by adding 3000 g of citric acid was dried using a spray dryer and calcined at 460 ° C. for 5 hours. Prebaked powder (D) was obtained. The composition ratio excluding oxygen of the catalytically active component at this time was Mo = 12, Bi = 1.7, Fe = 2.0, Co = 6.75, Ni = 1.0, and Cs = 0.20 in atomic ratio.

Then, the powder which mixed 5 mass parts of crystalline celluloses with 100 mass parts of prebaked powders (D) was supported by an inert support (particle diameter of 4.0 mm) in the ratio which occupies 45 mass% with respect to the catalyst after shaping | molding. The molded product thus obtained was calcined at 520 ° C. for 5 hours to obtain an oxidation catalyst (E13). As a result of measuring the ammonia elevated temperature desorption spectrum of the obtained catalyst, it had one peak in the range of 100-400 degreeC, and had one peak in the range of 400 degreeC or more. The peak of the peak of the range of 100-400 degreeC exists in the vicinity of 200 degreeC, and the peak of the peak of the range of 400 degreeC or more existed in the vicinity of 600 degreeC.

The ratio (L / H) of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the organic acid addition conditions of Example 9 and Comparative Example 4 by the ammonia elevated temperature desorption method Table 3 shows. Moreover, the result of the oxidation reaction test of the catalyst obtained in Example 9 and the comparative example 4 is shown in Table 4.

Test Example

The high boiling point substance contained in the reaction product obtained by the oxidation reaction test of the catalyst obtained in Example 1 and the comparative example 1 was quantified. The high boiling point material yield of the catalyst obtained in Example 1 was 0.05%, while the high boiling point material yield of the catalyst obtained in Comparative Example 1 was 0.12%. In addition, the high boiling point material yields of the catalysts obtained in Examples 6 and 7 were 0.04% and 0.05%.

The composite oxide catalyst containing molybdenum and bismuth produced by the method of the present invention is at least one selected from the group consisting of isobutylene and t-butyl alcohol, and a molecular oxygen-containing gas in the presence of an oxidation catalyst composition. It is a highly active catalyst used for producing methacrolein by gas phase catalytic oxidation by use, and there is little by-product of a high boiling point compound, and methacrolein can be stably obtained in a high yield.

Claims (12)

A catalyst containing at least molybdenum and bismuth as component elements, wherein the ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method is 0.14 or less. A catalyst for producing methacrolein or methacrylic acid. The method of claim 1,
A catalyst for producing methacrolein or methacrylic acid, wherein an organic acid is added in an integration process in an aqueous system of a source compound containing at least molybdenum and bismuth as component elements. The method of claim 2,
A catalyst for producing methacrolein or methacrylic acid, wherein the ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method is 0.12 or less. The method of claim 2,
A catalyst for producing methacrolein or methacrylic acid, characterized in that the ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method is 0.10 or less. . The method of claim 2,
A catalyst for producing methacrolein or methacrylic acid, wherein the boiling point of the organic acid is 110 ° C. or higher. The method of claim 2,
A catalyst for producing methacrolein or methacrylic acid, wherein the organic acid is a fatty acid. The method of claim 2,
A catalyst for producing methacrolein or methacrylic acid, wherein the organic acid is a fatty acid having 1 to 10 carbon atoms. The method of claim 2,
A catalyst for producing methacrolein or methacrylic acid, wherein the organic acid is acetic acid, propionic acid, butyric acid or valeric acid. The method according to any one of claims 1 to 8,
The catalyst for methacrolein or methacrylic acid production, characterized in that the catalyst is a molding catalyst. The method according to any one of claims 1 to 8,
The addition amount of the said organic acid is 0.1-20 mass parts with respect to 100 mass parts of molybdenum raw materials, The catalyst for manufacturing methacrolein or methacrylic acid. The ratio of the acid amount of the catalyst on the low temperature side by the ammonia elevated temperature desorption method to the acid amount of the catalyst on the high temperature side by the ammonia elevated temperature desorption method containing at least molybdenum and bismuth as a component element is characterized by the above-mentioned. Method for producing a composite oxide catalyst. The method of claim 11,
An organic acid is added in the integration process in the aqueous system of the source compound which contains molybdenum and bismuth as a component element, The manufacturing method of the complex oxide catalyst characterized by the above-mentioned.