JP5269046B2 - Method for producing a catalyst for methacrylic acid production - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easy method for producing a catalyst which is used for producing methacrylic acid in high yield and with high selectivity by subjecting methacrolein, isobutyl aldehyde or isobutyric acid to vapor-phase catalytic oxidation and can keep stable yield of methacrylic acid over a long period of time and to provide a method for easily controlling the catalytic activity so that the catalyst copes with various reaction conditions. <P>SOLUTION: The method for producing the catalyst for producing methacrylic acid, the catalyst containing molybdenum, phosphorus, vanadium, cesium, antimony and ammonium as essential active components, includes the steps of: preparing slurry, which includes the essential active components other than antimony and in which the essential active components are converted into a compound oxide thereof when a heating step is performed on the slurry; mixing an antimony compound with the slurry at 0-20&deg;C; drying the obtained mixture to obtain dried powder; molding the dried powder; and firing the obtained compact. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a catalyst for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, isobutyraldehyde or isobutyric acid using a catalyst having high activity and high selectivity, and a method for producing the same.

Many catalysts have been proposed as catalysts used for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, isobutyraldehyde or isobutyric acid. Most of these catalysts are mainly composed of molybdenum and phosphorus, and have a heteropolyacid and / or salt structure.

For example, Patent Document 1 describes in detail the role of each element in a catalyst containing molybdenum, vanadium, phosphorus, arsenic, and copper as essential components, and a method for preparing the catalyst. Patent Document 2 describes in detail the role of each element in a catalyst containing molybdenum, phosphorus, vanadium, antimony, and copper as essential components and the preparation method of the catalyst. The vanadium and antimony prepared by a specific method are described in detail. It is described that the catalyst including both has a combination of reaction activity, methacrylic acid selectivity, and catalyst life. In addition, in Patent Document 3, when preparing a molybdenum, phosphorus, vanadium, antimony, or copper-based catalyst, a catalyst raw material, except for the vanadium raw material and / or the antimony raw material, is dissolved or suspended in water to prepare an ammonium root. In the present invention, after heat treatment at a temperature of 80 to 200 ° C. for 1 to 24 hours in the presence of vanadium, a vanadium raw material and / or an antimony raw material is added, and the heat treatment is performed again at a temperature of 80 to 200 ° C. for 1 to 24 hours, followed by firing. Is described.

Patent Document 4 uses, as a catalyst raw material, an antimony component and a molybdenum, vanadium and / or copper component previously mixed and heat-treated at 400 to 800 ° C. in preparing a molybdenum, phosphorus, vanadium, antimony, or copper-based catalyst. The invention to be described is described.

In these known techniques, the addition process of the antimony compound is devised in various ways to increase the activity of the resulting catalyst. However, the addition process of the antimony compound is complicated or requires a long time, so that it is simple. There is a need to establish manufacturing methods.
Furthermore, when compared with the molybdenum-vanadium catalyst proposed to produce acrylic acid by oxidation of acrolein known as a reaction similar to the gas phase catalytic oxidation reaction of methacrolein, isobutyraldehyde or isobutyric acid, the reaction Although the activity is low, the selectivity to the target substance is low, and the lifetime is short, some of the proposed catalysts have been industrialized, but there is a demand for improvement of these catalyst performances.

Further, the optimum activity of the catalyst (conversion rate of the raw material) varies depending on the reaction conditions (space velocity, raw material gas molar ratio, reaction tube diameter, etc.). If the catalytic activity is too strong, the yield of methacrylic acid decreases due to the progress of the sequential oxidation reaction. On the other hand, if the catalytic activity is too weak, the reaction bath temperature will not rise and it will not be able to withstand prolonged use. Therefore, establishment of a method for controlling the catalyst activity is also required in order to cope with many reaction conditions.

In Patent Document 5, a plurality of catalysts having different activities are provided in a plurality of reaction zones provided by dividing the reactor into two or more layers in the tube axis direction, and the activity is higher from the raw material gas inlet side to the outlet side. A method of filling is described. Thereby, the heat generation in the reactor can be suppressed to some extent, but the catalyst filling operation becomes complicated. Further, in Examples and Comparative Examples of Patent Document 5, the reaction is carried out by charging two kinds of catalysts whose catalytic activities are controlled by controlling the amount of antimony. When these catalysts are used in a single layer, the amount of antimony is increased. It is described that a catalyst having a small amount of activity has a very low activity, and a catalyst having a large amount of antimony has a high activity but has a low selectivity and a low yield. Further, it is described that even a catalyst having an intermediate composition between these two has a low yield and a high ΔT (hot spot temperature−heat medium bath temperature), and there is a concern about deterioration due to heat load.

Japanese Patent No. 3146486 Japanese Patent Laid-Open No. 9-24277 Japanese Patent No. 3482476 JP-A-6-91172 Japanese Patent No. 2574948

The present invention provides a simple catalyst that can maintain methacrolein, isobutyraldehyde or isobutyric acid in a gas phase catalytic oxidation to maintain a stable yield of methacrylic acid over a long period of time with high yield and high selectivity. It is an object of the present invention to provide a simple production method and a method for easily controlling the catalyst activity to cope with various reaction conditions.

The present inventors, it has molybdenum, phosphorus, vanadium, cesium, catalyst was added antimony compound in a specific manner in heteropolyacids partially neutralized salts and antimony and ammonium um essential components a very high catalytic performance and The inventors have found that the catalytic activity can be easily and accurately controlled by adding antimony by a specific method, and that antimony has an effect completely opposite to that of Patent Document 5, thereby completing the present invention.
That is, the present invention
(1) molybdenum, phosphorus, vanadium, cesium, a process for preparing a catalyst to antimony and ammonium um an essential active ingredient, of the catalyst the essential active ingredient, by going through the heating step comprise the active ingredient other than antimony A slurry that can be converted into a composite oxide and an antimony compound are mixed at 0 to 20 ° C., and then dried to obtain a dry powder, which is then molded and fired, for producing methacrylic acid Catalyst production method
(2) The method for producing a catalyst for methacrylic acid production according to the above (1), wherein the mixing step includes an aging step (3) The molding step coats the dry powder on the inert carrier using a binder, and coats it. The production method according to the above (1) or (2), which is a step for forming a catalyst (4) The binder is at least one selected from the group consisting of water and an organic compound having a boiling point of 150 ° C. or less under 1 atm. The manufacturing method according to (3), which is a liquid (5) The manufacturing method according to any one of (1) to (4), wherein the firing temperature is 300 to 450 ° C. (6) The above (1) to (1) The present invention relates to a method for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, isobutyraldehyde or isobutyric acid, which uses the catalyst obtained by the production method according to any one of (5) .

According to the present invention, molybdenum, phosphorus, vanadium, cesium, highly active and antimony and ammonium um an essential component, it is possible to produce a high selectivity catalyst, it is easy to control the catalytic activity, diverse reactive It is possible to provide a catalyst that can meet the conditions.

Production method of the present invention, the active component of the catalyst aqueous dispersion of aqueous solution or the compound containing (molybdenum, phosphorus, vanadium, cesium, and ammonium um) compounds containing (hereinafter, referred to as slurry together both) and antimony compound The process of mixing.
Namely, molybdenum, phosphorus, vanadium, cesium, and ammonium dissolved um and compounds respectively or a plurality containing other elements necessary water and / or dispersing (step (f)) is, to prepare a slurry, to which antimony The compound is mixed (step (g)), dried (step (h)), molded (step (i)), and fired (step (j)) for use.
In the present invention, molybdenum, phosphorus, vanadium, cesium, as the active ingredient other than antimony and ammonium um, copper, arsenic, silver, manganese, zinc, aluminum, boron, germanium, tin, lead, titanium, zirconium, chromium, rhenium , Bismuth, tungsten, iron, cobalt, nickel, cerium, thorium, potassium, and rubidium. The method for adding components other than the essential components is not particularly limited as long as a uniform slurry can be obtained, and may be before the antimony compound is added or after the antimony compound is added.
In the present invention, the use ratio of the active ingredient-containing compound is such that the atomic ratio is usually 0.1 or more and 6 or less, preferably 0.3 or more and 2.0 or less, and phosphorus is usually 0 or less with respect to molybdenum 10. 0.5 or more and 6 or less, preferably 0.7 or more and 2.0 or less, cesium is usually 0.01 or more and 4.0 or less, preferably 0.1 or more and 2.0 or less, and ammonium is usually 0.1 The above is 10.0 or less, preferably 0.5 or more and 5.0 or less, and antimony is usually 0.01 or more and 5 or less, preferably 0.05 or more and 2.0 or less. The types of other active ingredients to be used as necessary and the usage ratio thereof are appropriately determined so as to obtain a catalyst exhibiting optimum performance in accordance with the usage conditions of the catalyst. The atomic ratios of the catalytically active components described in the present invention are those at the raw material charging stage, and are values excluding oxygen.

Hereinafter, embodiments will be described according to the above-described steps.
Step (f): Preparation of Slurry In the present invention, examples of the active component-containing compound used for catalyst preparation include chlorides, sulfates, nitrates, oxides or acetates of active component elements. Specific examples of preferred compounds include nitrates such as potassium nitrate and cobalt nitrate, oxides such as molybdenum oxide, vanadium pentoxide, cerium oxide, zinc oxide and germanium oxide, orthophosphoric acid, phosphoric acid, boric acid, aluminum phosphate or Examples include acids (or salts thereof) such as 12 tungstophosphoric acid. Moreover, it is preferable to use cesium acetate or cesium hydroxide and a cesium weak acid salt as a cesium compound, and ammonium acetate or ammonium hydroxide as an ammonium compound. The compounds containing these active ingredients may be used alone or in combination of two or more. The slurry can be obtained by uniformly mixing each active ingredient-containing compound and water. The order of addition of the active ingredient-containing compound when preparing the slurry is preferably that the compound containing molybdenum, vanadium, phosphorus, and other metal elements as necessary is sufficiently dissolved, and then the cesium compound and ammonium compound are added to the slurry. . After preparing the slurry, an antimony compound is mixed. Examples of the antimony compound include antimony trioxide, antimony pentoxide, and antimony acetate, and antimony trioxide is particularly preferable. In addition, as a metal compound other than the essential active component, for example, as a copper compound, copper acetate (cuprous acetate, cupric acetate, basic copper acetate, cupric oxide, etc., preferably cupric acetate) or copper oxide When (cuprous oxide, cupric oxide) is used, there may be a preferable effect.
The temperature at which the slurry is prepared is preferably heated to a temperature at which the compound containing molybdenum, phosphorus, vanadium and, if necessary, other metal elements can be sufficiently dissolved. The temperature at which the cesium compound and the ammonium compound are added is usually in the range of 0 to 35 ° C., preferably about 10 to 30 ° C., and the resulting catalyst tends to be highly active. The amount of water used in the slurry is not particularly limited as long as the total amount of the compound to be used can be completely dissolved or can be uniformly mixed, but is appropriately determined in consideration of the drying method and drying conditions. Usually, it is about 200 to 2000 parts by mass with respect to 100 parts by mass of the total mass of the compound for slurry preparation. The amount of water may be large, but if it is too large, the energy cost of the drying process becomes high, and there are many disadvantages such as the case where it cannot be completely dried.

Step (g): Mixing and aging of slurry and antimony compound The temperature during mixing and aging of the slurry and antimony compound is 0 to 20C . In addition, when the slurry before adding a cesium compound and an ammonium compound, especially the slurry of 35 degreeC or more, and an antimony compound are mixed, a catalyst with low activity may be obtained and it is unpreferable.

Step (h): drying then dried slurry obtained in the step (g), and dry powder (complex oxide). The drying method is not particularly limited as long as the slurry can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness. Among these, in the present invention, spray drying which can be dried from a slurry state into powder or granules in a short time is particularly preferable.
The drying temperature of spray drying varies depending on the slurry concentration, the liquid feeding speed, etc., but the temperature at the outlet of the dryer is generally 70 to 150 ° C. Moreover, it is preferable to dry so that the average particle diameter of the slurry dry body obtained in this case may be 30-700 micrometers.

Step (i): The dry powder obtained in the molding step (h) is used after being molded into a columnar product, a tablet, a ring shape, a spherical shape or the like in order to reduce the pressure loss of the reaction gas in the oxidation reaction. Of these, it is particularly preferable to coat an inert carrier to form a coated catalyst, since selectivity can be improved and reaction heat can be removed.
This coating step (step (i)) is preferably the rolling granulation method described below. In this method, for example, in a device having a flat or uneven disk at the bottom of a fixed container, the support in the container is vigorously agitated by repeated rotation and revolution movements by rotating the disk at high speed. This is a method in which a carrier is coated with a binder and a mixture or a dry powder and a coating mixture to which other additives such as a molding aid and a strength improver are added if necessary. The method of adding the binder is as follows: 1) Preliminarily mix with the coating mixture 2) Add at the same time as adding the coating mixture into the fixed container 3) Add after adding the coating mixture into the fixed container 4) Addition of the coating mixture before it is added to the fixed container, 5) Dividing the coating mixture and the binder, respectively, and combining 2) to 4) as appropriate, and adding the total amount, etc. can be arbitrarily adopted. . In 5), for example, the coating rate is adjusted by using an auto-feeder or the like so that the coating mixture adheres to the fixed container wall and the coating mixture does not agglomerate and a predetermined amount is supported on the carrier. Is preferred.
The binder is not particularly limited as long as it is at least one selected from the group consisting of water and an organic compound having a boiling point of 150 ° C. or less at 1 atm. Specific examples of binders other than water include alcohols such as methanol, ethanol, propanols and butanols, preferably alcohols having 1 to 4 carbon atoms, ethers such as ethyl ether, butyl ether or dioxane, and esters such as ethyl acetate or butyl acetate. , Ketones such as acetone or methyl ethyl ketone, and aqueous solutions thereof, with ethanol being particularly preferred. When ethanol is used as the binder, ethanol / water = 10/0 to 0/10 (mass ratio), preferably 9/1 to 1/9 (mass ratio) by mixing with water. The usage-amount of these binders is 2-60 mass parts normally with respect to 100 mass parts of coating mixtures, Preferably it is 10-50 mass parts.

Specific examples of the carrier that can be used in the present invention include a spherical carrier having a diameter of 1 to 15 mm, preferably 2.5 to 10 mm, such as silicon carbide, alumina, silica alumina, mullite, and alundum. These carriers are usually those having a porosity of 10 to 70%. The ratio of the carrier to the coating mixture is usually used in such an amount that the coating mixture / (coating mixture + carrier) = 10 to 75% by mass, preferably 15 to 60% by mass.
When the ratio of the coating mixture is large, the reaction activity of the coated catalyst increases, but the mechanical strength tends to decrease. On the contrary, when the ratio of the coating mixture is small, the mechanical strength is large (the degree of abrasion is small), but the reaction activity tends to be small.
In addition, silica gel, diatomaceous earth, an alumina powder etc. are mentioned as a shaping | molding adjuvant used as needed in the above. The usage-amount of a shaping | molding adjuvant is 1-60 mass parts normally with respect to 100 mass parts of a mixture or dry powder.
Further, if necessary, it is useful to improve the mechanical strength of the catalyst by using inorganic fibers such as ceramic fibers and whiskers that are inert to the catalytically active component and the reaction gas as necessary. However, fibers that react with catalyst components such as potassium titanate whiskers and basic magnesium carbonate whiskers are not preferred. The amount of these fibers used is usually 1 to 30 parts by mass with respect to 100 parts by mass of the mixture or dry powder.
The mixture or dry powder is coated on the carrier in this way, and the coated product obtained at this time is usually about 3 to 15 mm in diameter.

Step (j): Calcination The coated catalyst obtained as described above can be directly subjected to a gas phase catalytic oxidation reaction as a catalyst, but calcination is preferred because the catalyst activity may be improved. In this case, the firing temperature is usually 100 to 450 ° C., preferably 250 to 420 ° C., and the firing time is 1 to 20 hours.
The firing is usually performed in an air atmosphere, but may be performed in an inert gas atmosphere such as nitrogen or a reducing gas atmosphere such as ethanol. If necessary, baking may be performed in an air atmosphere after baking in an inert gas or reducing gas atmosphere.
The catalyst obtained as described above (hereinafter referred to as the catalyst of the present invention) is used for production of methacrylic acid by gas phase catalytic oxidation of methacrolein, isobutyraldehyde or isobutyric acid.
Hereinafter, the gas phase catalytic reaction using methacrolein, which is the most preferable raw material for using the catalyst of the present invention, will be described.
Molecular oxygen or a molecular oxygen-containing gas is used for the gas phase catalytic oxidation reaction. The molar ratio of molecular oxygen to methacrolein is preferably in the range of 0.5 to 20, and particularly preferably in the range of 1 to 10. For the purpose of allowing the reaction to proceed smoothly, water is preferably added to the raw material gas in a molar ratio of 1 to 20 with respect to methacrolein.
The raw material gas may contain oxygen, if necessary, a gas inert to the reaction such as nitrogen, carbon dioxide, saturated hydrocarbon, etc. in addition to water (usually included as water vapor).
As for methacrolein, a gas obtained by oxidizing isobutylene, tertiary butanol, and methyl tertiary butyl ether may be supplied as it is.
The reaction temperature is usually 200 to 400 ° C. in a gas phase catalytic oxidation reaction, preferably two hundred sixty to three hundred sixty ° C., the supply amount of the raw material gas in the space velocity (SV), usually 100～6000Hr ^-1, preferably 300～3000Hr ^-1 It is.
The gas phase catalytic oxidation reaction can be performed under pressure or under reduced pressure, but generally a pressure around atmospheric pressure is suitable.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the examples.
In the following, the conversion rate, selectivity and yield are defined as follows.
Conversion = number of moles of reacted methacrolein / number of moles of methacrolein fed × 100
Selectivity = number of moles of methacrylic acid produced / number of moles of reacted methacrolein × 100
Yield = number of moles of methacrylic acid produced / number of moles of methacrolein fed × 100

Example 1
1) Preparation of catalyst To 5680 ml of pure water, 800 g of molybdenum trioxide, 40.43 g of vanadium pentoxide, and 73.67 g of 85 mass% orthophosphoric acid were added, and the mixture was heated and stirred at 92 ° C. for 3 hours to obtain a reddish brown transparent A solution was obtained. Subsequently, the solution was cooled to 15 to 20 ° C., and 458.2 g of 9.1% by mass cesium hydroxide aqueous solution and 629.1 g of 14.3% by mass ammonium acetate aqueous solution were gradually added simultaneously with stirring. The mixture was aged at 15 to 20 ° C. for 1 hour to obtain a yellow slurry.
Subsequently, 709.9 g of a 6.3% by mass cupric acetate aqueous solution was gradually added to the slurry, followed by further aging at 15 to 20 ° C. for 30 minutes. Subsequently, 32.4 g of antimony trioxide was mixed with this slurry, and further aged at 15 to 20 ° C. for 30 minutes. Next, this slurry was spray-dried to obtain a dry powder. The composition of the obtained composite powder was Mo ₁₀ V _0.8 P _1.15 Cu _0.4 Cs _0.5 (NH ₄ ) _2.1 Sb _0.4
It is.
Next, 320 g of the dry powder and 45 g of the strength improving material (ceramic fiber) were uniformly mixed, and 300 g of a spherical porous alumina support (particle size: 3.5 mm) was coated and molded using about 80 g of a 90% by mass ethanol aqueous solution as a binder. Subsequently, the obtained molded product was calcined at 380 ° C. for 5 hours under an air flow to obtain a target coated catalyst (the catalyst of the present invention).

2) Catalytic oxidation reaction of methacrolein
10.3 ml of the obtained coated catalyst was filled in a stainless steel reaction tube having an inner diameter of 18.4 mm, and a raw material gas (composition (molar ratio); methacrolein: oxygen: water vapor: nitrogen = 1: 2: 4: 18.6), The methacrolein oxidation reaction was carried out under conditions of a space velocity (SV) of 1200 hr-1 and a reaction bath temperature of 310 ° C. The reaction was first continued for 3 hours at a reaction bath temperature of 310 ° C., then the reaction bath temperature was raised to 350 ° C. and the reaction was continued for 15 hours (hereinafter this treatment is referred to as a high temperature reaction treatment). Next, the reaction bath temperature was lowered to 310 ° C., and the reaction results were measured.
The results are shown in Table 1.

Comparative Example 1
To 5680 ml of pure water were added 800 g of molybdenum trioxide, 40.43 g of vanadium pentoxide, and 73.67 g of 85 mass% orthophosphoric acid, and the mixture was heated and stirred at 92 ° C. for 3 hours to obtain a reddish brown transparent solution. Subsequently, 32.4 g of antimony trioxide was added thereto, and the mixture was further heated and stirred at 92 ° C. for 2 hours to obtain a dark blue solution. Subsequently, the solution was cooled to 15 to 20 ° C., and 458.2 g of 9.1% by mass cesium hydroxide aqueous solution and 629.1 g of 14.3% by mass ammonium acetate aqueous solution were gradually added simultaneously with stirring. And aged at 15 to 20 ° C. for 1 hour to obtain a slurry.
Subsequently, 709.9 g of a 6.3% by mass cupric acetate aqueous solution was gradually added to the slurry and further aged at 15 to 20 ° C. for 30 minutes.
Subsequently, this slurry was spray-dried to obtain a composite oxide powder. The composition of the obtained powder was Mo ₁₀ V _0.8 P _1.15 Cu _0.4 Cs _0.5 (NH ₄ ) _2.1 Sb _0.4
It is.
Next, 320 g of this composite oxide powder and 45 g of a strength improving material (ceramic fiber) were uniformly mixed, and 300 g of a spherical porous alumina carrier (particle size 3.5 mm) was coated and molded using about 80 g of a 90 mass% aqueous ethanol solution as a binder. . Next, the obtained molded product was calcined at 380 ° C. for 5 hours under air flow to obtain a comparative coated catalyst. Except for the use of this coated catalyst, the methacrolein oxidation reaction was carried out in the same manner as in Example 1. As a result, the methacrolein conversion rate at the initial stage of the reaction was as very low as 15% and could not be used as a practical catalyst.

Claims (6)

Molybdenum, phosphorus, vanadium, cesium, a process for preparing a catalyst to antimony and ammonium um an essential active ingredient, of the catalyst the essential active ingredient a composite oxide by passing through a heating step comprise the active ingredient other than antimony A slurry that can be converted into an antimony compound and an antimony compound are mixed at 0 to 20 ° C., and then dried to obtain a dry powder, which is then molded and fired to produce a catalyst for producing methacrylic acid Method. The method for producing a catalyst for producing methacrylic acid according to claim 1, wherein the mixing step includes an aging step. The production method according to claim 1 or 2, wherein the molding step is a step of coating a dry powder on an inert carrier using a binder to form a coated catalyst. The production method according to claim 3, wherein the binder is at least one liquid selected from the group consisting of water and an organic compound having a boiling point of 150 ° C or less at 1 atm. The method according to any one of claims 1 to 4, wherein the firing temperature is 300 to 450 ° C. A method for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, isobutyraldehyde or isobutyric acid, wherein the catalyst obtained by the production method according to any one of claims 1 to 5 is used.