METHOD FOR PRODUCING UNSATURATED ALDEHYDE AND/OR UNSATURATED CARBOXYLIC ACID

Abstract

Provided is a method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid, which enables one to achieve an operation stably over a long period of time while improving an effective yield, even in a high-load reaction, and in the method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid, multilayer filling of stacking two or more catalyst layers each containing a complex metal oxide catalyst in the axial direction of the tube under specified conditions is performed, and the catalyst layer on the most gas outlet side in the tube axis contains a catalyst containing a compound represented by a specified formulation formula.

Claims

1. A method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid, the method comprising subjecting an alkene to gas-phase catalytic partial oxidation with molecular oxygen by using a multitubular reactor having a complex metal oxide catalyst filled therein, thereby obtaining a corresponding unsaturated aldehyde and/or unsaturated carboxylic acid, wherein two or more catalyst layers each containing a complex metal oxide catalyst are stuck in an axial direction of the tube, thereby achieving multilayer filling; a formulation of the complex metal oxide catalyst contained in one catalyst layer is different from a formulation of the complex metal oxide catalyst contained in at least one of other catalyst layers; a ratio of a component amount of bismuth to a component amount of molybdenum of the catalyst layer on the most gas inlet side in the tube axis is larger than a ratio of a component amount of bismuth to a component amount of molybdenum of the catalyst layer on the most gas outlet side in the tube axis; in all of the two catalyst layers adjacent to each other, a ratio of a component amount of bismuth to a component amount of molybdenum of the catalyst layer on the gas inlet side in the tube axis is equal to or larger than a ratio of a component amount of bismuth to a component amount of molybdenum of the catalyst layer on the gas outlet side in the tube axis; and the catalyst layer on the most gas outlet side in the tube axis contains a catalyst containing a compound represented by the following formula (1):
Mo.sub.12Bi.sub.aFe.sub.bCo.sub.cNi.sub.dX.sub.eY.sub.fZ.sub.gO.sub.h(1) wherein X is at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), manganese (Mn), copper (Cu), zinc (Zn), cerium (Ce) and samarium (Sm); Y is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As), antimony (Sb), tungsten (W), silicon (Si) and aluminum (Al); Z is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs); a to h represent atomic ratios of the respective components; a=0.40 or more and less than 0.80; b=1.0 to 2.5; c=3.0 to 7.5; d=2.0 to 3.5; e=0 to 10; f=0 to 10; g=0.01 to 1.0; h is expressed by a numerical value satisfying oxidation states of other elements; d/a is more than 2.5 and 8.8 or less; d/g is 2.0 or more and 350 or less; and a/g is 0.4 or more and less than 80.

2. The method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1, wherein in a step of preparing the compound represented by the formula (1), a molybdenum component raw material is constituted of only an ammonium molybdate, and a weight of water for dissolution is 8.5 times or less relative to a weight of molybdenum contained in the ammonium molybdate; and a bismuth component raw material is constituted of only bismuth nitrate, a weight of a nitric acid aqueous solution for dissolution is 2.3 times or more relative to a weight of bismuth contained in the bismuth nitrate, and a concentration of nitric acid of the nitric acid aqueous solution for dissolving bismuth nitrate therein is 10% by weight or more.

3. The method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1, wherein the complex metal oxide catalyst is a spherical coating catalyst in which catalytic active components are supported on a surface of an inert carrier.

4. The method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1, wherein a load of the alkene in the raw material gas to be supplied into the multitubular reactor is 100 times or more (converted in a standard state) relative to a unit catalyst volume per hour.

5. The method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1, wherein a load of the alkene in the raw material gas to be supplied into the multitubular reactor is 150 times or more (converted in a standard state) relative to a unit catalyst volume per hour.

6. The method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1, wherein a concentration of the alkene contained in the raw material gas to be supplied into the multitubular reactor is 8.5% by volume or less.

7. The method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1, wherein all of the catalyst layers filled in the multitubular reactor are not diluted by physical mixing of the complex metal oxide catalyst and an inert substance.

8. A method for producing acrolein and/or acrylic acid, or methacrolein and/or methacrylic acid, by the method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid according to claim 1.

Description

EXAMPLES

[0054] Examples are hereunder described by reference to specific examples, but it should be construed that the present invention is not limited to these Examples so long as the gist of the present invention is hot deviated.

Catalyst 1

[0055] 2,000 parts by weight of ammonium heptamolybdate was completely dissolved in 7,600 parts by weight of pure water warmed at 60? C. Subsequently, 9.2 parts by weight of potassium nitrate was dissolved in 104.1 parts by weight of pure water and added to the above-described solution. Subsequently, 686.4 parts by weight of ferric nitrate, 1,428.8 parts by weight of cobalt nitrate, and 768.6 parts by weight of nickel nitrate were dissolved in 1,528.4 mL of pure water warmed at 60? C. These solutions were gradually mixed while stirring. Subsequently, a solution prepared by adding 198.2 parts by weight of nitric acid (60% by weight) to 825.2 mL of pure water, to Which was then added 778.4 parts by weight of bismuth nitrate and completely dissolved, was added to the above-described solution, followed by stirring and mixing. This slurry was dried by the spray drying method, and the resulting dry powder was preliminarily calcined at a maximum temperature 440? C. for 6 hours. Crystalline cellulose was added in a proportion of 5% by weight relative to the preliminarily calcined powder and thoroughly mixed. Subsequently, the mixture was supported and molded in a spherical form at a supporting rate of 50% by weight on an inert spherical carrier composed mainly of silica and alumina and having a diameter of 4.5 mm by using a 30% by weight glycerin solution as a binder by the tumbling granulation method. Subsequently, calcination was carried out at 560? C. for 4 hours, thereby obtaining Spherical Catalyst 1 having an average particle diameter of 5.2 mm. The catalyst calculated from the charged raw materials was found to be a complex metal oxide having the following atomic ratios.

d/a=1.6, d/g=28, a/g=17

Mo:Bi:Fe:Co:Ni:K=12:1.7:1.8:5.2:2.8:0.10

Catalyst 2

[0056] 2,000 parts by weight of ammonium heptamolybdate was completely dissolved in 7,600 parts by weight of pure water (in a weight of 7.0 times the weight of molybdenum) warmed at 60? C. Subsequently, 4.4 parts by weight of potassium nitrate was dissolved in 50.1 parts by weight of pure water and added to the above-described solution. Subsequently, 762.7 parts by weight of ferric nitrate, 1,786.0 parts by weight of cobalt nitrate, and 823.5 parts by weight of nickel nitrate were dissolved in 1,787.3 mL of pure water warmed at 60? C. These solutions were gradually mixed while stirring. Subsequently, a solution prepared by adding 320.5 parts by weight of bismuth nitrate to a nitric acid aqueous solution (in a weight of 2.3 times the weight of bismuth in bismuth nitrate to be dissolved) which had been prepared by adding 81.6 parts by weight of nitric acid (60% by weight) to 339.8 mL of pure water, thereby regulating a nitric acid concentration to 12% by weight and then completely dissolving was added to the above-described solution and mixed with stirring. This slurry was dried by the spray drying method, and the resulting dry powder was preliminarily calcined so as to keep the maximum temperature at 440? C. for 4 hours. Crystalline cellulose was added in proportion of 5% by weight relative to the preliminarily calcined powder and thoroughly mixed. Thereafter, the mixture was supported and molded in a spherical form at a supporting rate of 50% by weight on an inert spherical carrier by using a 30% by weight glycerin solution as a binder by the tumbling granulation method. Subsequently, calcination was carried out so as to be held at a maximum temperature of 520? C. for 4 hours, thereby obtaining Spherical Catalyst 2 having an average particle diameter of 5.2 mm. The catalyst calculated from the charged raw materials was found to be a complex metal oxide having the following atomic ratios.

d/a=4.3, d/g=60, a/g=14

Mo:Bi:Fe:Co:Ni:K=12:0.7:2.0:6.5:3.0:0.05

Catalyst 3

[0057] 2,000 parts by weight of ammonium heptamolybdate was completely dissolved in 7,600 parts by weight of pure water warmed at 60? C. Subsequently, 5.5 parts by weight of cesium nitrate was dissolved in 62.2 parts by weight of pure water and added to the above-described solution. Subsequently, 762.7 parts by weight of ferric nitrate, 1,786.0 parts by weight of cobalt nitrate, and 823.5 parts by weight of nickel nitrate were dissolved in 1,787.3 mL of pure water warmed at 60? C. These solutions were gradually mixed while stirring. Subsequently, a solution prepared by adding 116.6 parts by weight of nitric acid (60% by weight) to 485.5 mL of pure water, to which was then added 457.9 parts by weight of bismuth nitrate and completely dissolved, was added to the above-described solution, followed by stirring and mixing. This slurry was dried by the spray drying method, and the resulting dry powder was preliminarily calcined at a maximum temperature 440? C. for 6 hours. Crystalline cellulose was added in a proportion of 5% by weight relative to the preliminarily calcined powder and thoroughly mixed. Thereafter, the mixture was supported and molded in a spherical form at a supporting rate of 50% by weight on an inert spherical carrier composed mainly of silica and alumina and having a diameter of 4.5 mm by using a 30% by weight glycerin solution as a hinder by the tumbling granulation method. Subsequently, calcination was carried out at 540? C. for 4 hours, thereby obtaining Spherical Catalyst 3 having an average particle diameter of 5.2 mm. The catalyst calculated from the charged raw materials was found to be a complex metal oxide having the following atomic ratios.

d/a=3.0, d/g=100, a/g=33

Mo:Bi:Fe:Co:Ni:Cs=12:1.0:2.0:6.5:3.0:0.03

Catalyst 4

[0058] Catalyst 4 was obtained in the same manner as in Catalyst 2, except that only the calcination step temperature after molding was changed to 540? C.

Catalyst 5

[0059] 2,000 parts by weight of ammonium heptamolybdate was completely dissolved in 7,600 parts by weight of pure water warmed at 60? C. Subsequently, 4.4 parts by weight of potassium nitrate was dissolved in 50.1 parts by weight of pure water and added to the above-described solution. Subsequently, 762.7 parts by weight of ferric nitrate, 1,786.0 parts by weight of cobalt nitrate, and 823.5 parts by weight of nickel nitrate were dissolved in 1,787.3 mL of pure water warmed at 60? C. These solutions were gradually mixed while stirring. Subsequently, a solution prepared by adding 116.6 g of nitric acid (60% by weight) to 485.5 mL of pure water, to which was then added 457.9 parts by weight of bismuth nitrate and completely dissolved, was added to the above-described solution, followed by stirring and mixing. This slurry was dried by the spray drying method, and the resulting dry powder was preliminarily calcined at a maximum temperature 440? C. for 6 hours. Crystalline cellulose was added in a proportion of 5% by weight relative to the preliminarily calcined powder and thoroughly mixed. Thereafter, the mixture was supported and molded in a spherical form at a supporting rate of 50% by weight on an inert spherical carrier composed mainly of silica and alumina and having a diameter of 4.5 mm by using a 30% by weight glycerin solution as a binder by the tumbling granulation method. Subsequently, calcination was carried out at 550? C. for 4 hours, thereby obtaining Spherical Catalyst 5 having an average particle diameter of 5.2 mm. The catalyst calculated from the charged raw materials was found to be a complex metal oxide having the following atomic ratios.

d/a=3.0, d/g=60, a/g=20

Mo:Bi:Fe:Co:Ni:K=12:1.0:2.0:6.5:3.0:0.05

Catalyst 6

[0060] 2,000 parts by weight of ammonium heptamolybdate was completely dissolved in 7,600 parts by weight of pure water warmed at 60? C. Subsequently, 9.2 parts by weight of potassium nitrate was dissolved in 104.1 parts by weight of pure water and added to the above-described solution. Subsequently, 877.1 parts by weight of ferric nitrate, 1,373.9 parts by weight of cobalt nitrate, and 768.6 parts by weight of nickel nitrate were dissolved in 1,600.4 mL of pure water warmed at 60? C. These solutions were gradually mixed while stirring. Subsequently, a solution prepared by adding 151.6 g of nitric acid (60% by weight) to 631.1 mL of pure water, to which was then added 595.3 parts by weight of bismuth nitrate and completely dissolved, was added to the above-described solution, followed by stirring and mixing. This slurry was dried by the spray drying method, and the resulting dry powder was preliminarily calcined at a maximum temperature 440? C. for 6 hours. Crystalline cellulose was added in a proportion of 5% by weight relative to the preliminarily calcined powder and thoroughly mixed. Thereafter, the mixture was supported and molded in a spherical form at a supporting rate of 50% by weight on an inert spherical carrier composed mainly of silica and alumina and having a diameter of 4.5 mm by using a 30% by weight glycerin solution as a binder by the tumbling granulation method. Subsequently, calcination was carried out at 530? C. for 4 hours, thereby obtaining Spherical Catalyst 6 having an average particle diameter of 5.2 mm. The catalyst calculated from the charged raw materials was found to be a complex metal oxide having the following atomic ratios.

d/a=2.2, d/g=29, a/g=13

Mo:Bi:Fe:Co:Ni:K=12:1.3:2.3:5.0:2.8:0.10

Example 1

[0061] A gas-phase catalytic oxidation reaction of propylene was carried out by using Catalyst 1 and Catalyst 2, thereby determining catalytic performances represented by a propylene conversion, an acrolein yield (A), an acrylic acid yield (B), and an effective yield (A+B). Catalyst 1 was filled in a length of 1,500 mm on the raw material gas inlet side of a stainless steel-made reaction tube having a diameter of 25.2 mm, in which a thermocouple protection tube having an outer diameter of 3.2 mm was placed; and the above-described Catalyst 2 was filled in a filling length of 2,000 mm on the raw material gas outlet side. A mixed gas composed of 7.4% by volume of propylene, 63.2% by volume of air, 7.4% by volume of steam, and 22.1% by volume of nitrogen as a raw material gas was introduced at a propylene space velocity (SV.sub.0) of 165 hr.sup.?from the reaction tube inlet, a pressure on the gas outlet side was adjusted at 95 kPaG, and the gas-phase catalytic partial oxidation reaction of propylene was carried out. The results When the propylene conversion at the moment when the reaction elapsed about 300 hours after commencement of the reaction became 98% are shown in Table 1.

Example 2

[0062] A gas-phase catalytic oxidation reaction of propylene was carried out by using Catalyst 3 and Catalyst 4, thereby determining catalytic performances represented by a propylene conversion, an acrolein yield (A), an acrylic acid yield (B), and an effective yield (A+B). Catalyst 3 was filled in a filling length of 1,200 mm on the raw material gas inlet side of a stainless steel-made reaction tube having a diameter of 27.2 mm, in which a thermocouple protection tube having an outer diameter of 6.0 mm was placed; and the above-described Catalyst 4 was filled in a filling length of 1,700 mm on the raw material gas outlet side. A mixed gas composed of 8.2% by volume of propylene, 64.0% by volume of air, 24.4% by volume of steam, and 3.4% by volume of nitrogen as a raw material gas was introduced at a propylene space velocity (SV.sub.0) of 140 hr.sup.?1 from the reaction tube inlet, a pressure on the gas outlet side was adjusted at 80 kPaG, and the gas-phase catalytic partial oxidation reaction of propylene was carried out. The results when the propylene conversion at the moment when the reaction elapsed about 300 hours after commencement of the reaction became 98% are shown in Table 1.

Example 3

[0063] The oxidation reaction of propylene was carried out in the same manner as in Example 2, except that the filling was changed to diluted three-layer filling with Catalyst 3 and Catalyst 4. The diluted three-layer filling was carried out in such a manner that the catalyst concentration became high in the order of the upper layer to the intermediate layer to the lower layer, from the gas inlet side toward the gas outlet side. As for the upper layer, Catalyst 3 was diluted with an inert substance composed mainly of silica and alumina and having an average particle diameter of 5.2 mm such that the catalyst weight was 90% by weight, and then filled in a filling length of 650 mm. Subsequently, as for the intermediate layer, Catalyst 3 was filled such that the catalyst weight was 100% by weight; and that the filling length was 650 mm. Finally, as for the lower layer, Catalyst 4 was filled such that the catalyst weight was 100% by weight; and that the filling length was 1,600 mm. The results when the propylene conversion at the moment when the reaction elapsed about 300 hours after commencement of the reaction became 98% are shown in Table 1.

Comparative Example 1

[0064] The oxidation reaction of propylene was carried out in the same manner as in Example 1, except for changing Catalyst 2 to Catalyst 5. The results when the propylene conversion at the moment when the reaction elapsed about 300 hours after commencement of the reaction became 98% are shown in Table 1.

Comparative Example 2

[0065] The oxidation reaction of propylene was carried out in the same manner as in Example 2, except for changing Catalyst 4 to Catalyst 5. The results when the propylene conversion at the moment when the reaction elapsed about 300 hours after commencement of the reaction became 98% are shown in Table 1.

Comparative Example 3

[0066] The oxidation reaction of propylene was carried out in the same manner as in Example 2, except that the filling was changed to diluted three-layer filling with Catalyst 6. The diluted three-layer filling was carried out in such a manner that the catalyst concentration became high in the order of the upper layer to the intermediate layer to the lower layer, from the gas inlet side toward the gas outlet side. As for the upper layer, the catalyst was diluted with an inert substance composed mainly of silica and alumina and having an average particle diameter of 5.2 mm such that the catalyst weight was 70% by weight, and then filled in a filling length of 700 mm. Subsequently, as for the intermediate layer, the catalyst was diluted with the above-described inert substance such that the catalyst weight was 80% by weight, and then tilled in a filling length of 700 mm. Finally, as for the lower layer, the catalyst was filled such that the catalyst weight was 100% by weight; and that the filling length was 1,500 mm. The results when the effective yield at the moment when the reaction elapsed about 300 hours after commencement of the reaction became maximum are shown in Table 1. It is to be noted that in Comparative Example 3, in the case where the reaction was carried out such that the propylene conversion became 98%, the hot spot temperature became excessively high, so that it was difficult to keep the stable reaction state.

TABLE-US-00001 TABLE 1 Maximum Effective Reaction bath reaction yield temperature temperature (A + B) Catalyst (? C.) (? C.) (%) Example 1 Catalyst 1, 326 421 90.7 Catalyst 2 Example 2 Catalyst 3, 328 425 90.3 Catalyst 4 Example 3 Catalyst 3, 327 393 90.4 Catalyst 4 Comparative Catalyst 1, 331 420 90.2 Example 1 Catalyst 5 Comparative Catalyst 3, 326 406 90.0 Example 2 Catalyst 5 Comparative Catalyst 6 330 439 89.5 Example 3 Effective yield = (Acrolein yield, A %) + (Acrylic acid yield, B %)

[0067] In the light of the above, by using the technique of the present invention, even in a high-load reaction, a target product can be obtained stably over a long period of time while not only controlling the reaction bath temperature at a low level but also improving the effective yield.

[0068] While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

[0069] It is to be noted that the present application is based on a Japanese patent application filed on Jul. 10, 2015 (Japanese Patent Application No. 2015-138375), the entireties of which are incorporated by reference. In addition, all references cited herein are incorporated as a whole.

INDUSTRIAL APPLICABILITY

[0070] The present invention is useful for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid.