CN111727085A - Molded catalyst, and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same - Google Patents
Molded catalyst, and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same Download PDFInfo
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- CN111727085A CN111727085A CN201980013549.5A CN201980013549A CN111727085A CN 111727085 A CN111727085 A CN 111727085A CN 201980013549 A CN201980013549 A CN 201980013549A CN 111727085 A CN111727085 A CN 111727085A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- C07B61/00—Other general methods
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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Abstract
Disclosed is a catalyst molded body having high yield and high mechanical strength, which contains a cellulose nanofiber having an average fiber diameter of 1-300 nm and a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid or a catalyst for producing an unsaturated carboxylic acid.
Description
Technical Field
The present invention relates to a catalyst molded body containing a catalyst and cellulose nanofibers, and a method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid using the catalyst molded body.
Background
In the production process of unsaturated aldehyde and unsaturated carboxylic acid, the catalyst molded body is generally molded into a cylindrical or cylindrical molded body having a diameter of 2 to 10mm and a length of about 2 to 20mm, and the molded body is used by filling the reactor with the molded body.
For example, patent document 1 proposes a catalyst for synthesizing an unsaturated aldehyde and an unsaturated carboxylic acid by vapor-phase catalytic oxidation of propylene, isobutylene, tert-butyl alcohol or methyl tert-butyl ether with molecular oxygen, the catalyst comprising a catalyst component containing molybdenum and bismuth, and a scaly inorganic substance having an average particle diameter of 10 μm to 2mm and an average thickness of 0.005 to 0.3 times the average particle diameter.
Patent document 2 proposes an oxide catalyst containing molybdenum, bismuth, cobalt and iron, which is used for producing methacrolein, and which has a mixing ratio of 0.5m in surface area in a catalyst precursor powder2A crystalline cellulose of at least one gram and molding the molded article, and removing the crystalline cellulose by heat treatment of the molded article.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-224482
Patent document 2: japanese laid-open patent publication No. 2007-061763
Disclosure of Invention
However, from an industrial point of view, further improvement in mechanical strength of the catalyst molded body is desired. The purpose of the present invention is to provide a catalyst molded body having high yield and high mechanical strength.
The present invention is [1] to [13] below.
[1] A catalyst molded body comprising a catalyst component capable of producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by gas-phase catalytic oxidation using molecular oxygen and cellulose nanofibers having an average fiber diameter of 1 to 300 nm.
[2] The molded catalyst according to [1], wherein the cellulose nanofiber content calculated by the following formula (III) is 0.1 to 5% by mass when the mass of the molded catalyst is M1[ g ] and the mass of the cellulose nanofiber is M2[ g ].
Cellulose nanofiber content [% by mass ] (M2/M1) × 100 (III)
[3] The catalyst molded body according to [1] or [2], which further comprises a binder.
[4] The catalyst molded body according to [3], wherein the binder is water-soluble.
[5] The catalyst molded body according to [3], wherein the binder is a water-soluble organic binder.
[6] A molded catalyst article obtained by calcining the molded catalyst article according to any one of [1] to [5 ].
[7] The molded catalyst according to any one of [1] to [6], which is produced by a process including extrusion molding.
[8] The molded catalyst according to any one of [1] to [7], wherein the catalyst component has a composition represented by the following formula (I), and is a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which is obtained by vapor-phase catalytic oxidation of propylene, isobutylene, primary butanol, tertiary butanol, or methyl tertiary butyl ether with molecular oxygen.
Moa1Bib1Fec1Ad1E1e1G1f1J1g1Sih1(NH4)i1Oj1(I)
(in the formula (I), Mo, Bi, Fe, Si, NH4And O respectively represents molybdenum, bismuth, iron, silicon, ammonium group and oxygen, a represents at least 1 element selected from cobalt and nickel, E1 represents at least 1 element selected from chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, thallium, tantalum and zinc, G1 represents at least 1 element selected from phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium, and J1 represents at least 1 element selected from lithium, sodium, potassium, rubidium and cesium. a1, b1, c1, d1, e1, f1, g1, h1, i1 and j1 represent molar ratios of the components, when a1 is 12, b1 is 0.01 to 3, c1 is 0.01 to 5, d1 is 0.01 to 12, e1 is 0 to 8, f1 is 0 to 5, g1 is 0.001 to 2, h1 is 0 to 20, i1 is 0 to 30, and j1 represents a molar ratio of oxygen necessary to satisfy the valence number of each component. )
[9] The catalyst molded body according to any one of [1] to [7], wherein the catalyst component has a composition represented by the following formula (II), and is a catalyst for producing an unsaturated carboxylic acid, which is obtained by gas-phase catalytic oxidation of (meth) acrolein with molecular oxygen.
Pa2Mob2Vc2Cud2E2e2G2f2J2g2(NH4)h2Oi2(II)
(in the formula (II), P, Mo, V, Cu, NH4And O represents phosphorus, molybdenum, vanadium, copper, ammonium, and oxygen, respectively. E2 represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. G2 represents at least 1 element selected from iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, thallium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. J2 represents at least 1 element selected from potassium, rubidium and cesium. a2, b2, c2, d2, e2, f2, g2, h2 and i2 represent molar ratios of the respective components, and when b2 is 12, a2 is 0.1 to 3, c2 is 0.01 to 3, d2 is 0.01 to 2, e2 is 0 to 3, f2 is 0 to 3, g2 is 0.01 to 3, h2 is 0 to 30, and i2 represents a molar ratio of oxygen necessary to satisfy the valence number of the respective components. )
[10] A process for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which comprises subjecting propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether to vapor-phase catalytic oxidation with molecular oxygen in the presence of the molded catalyst as described in [8 ].
[11] A process for producing an unsaturated carboxylic acid, which comprises subjecting (meth) acrolein to gas-phase catalytic oxidation with molecular oxygen in the presence of the catalyst molded body as described in [9 ].
[12] A method for producing an unsaturated carboxylic acid ester, comprising esterifying an unsaturated carboxylic acid produced by the method of [10] or [11 ].
[13] A method for producing an unsaturated carboxylic acid ester, comprising the step of producing an unsaturated carboxylic acid by the method according to [10] or [11], and the step of esterifying the unsaturated carboxylic acid.
According to the present invention, a catalyst molded body having high yield and high mechanical strength can be provided. Further, a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which can maintain a high yield for a long period of time, can be provided.
Detailed Description
The catalyst molded body of the present invention contains cellulose nanofibers having an average fiber diameter of 1 to 300 nm. The molded catalyst body of the present invention further comprises: specifically, the catalyst component used in the production of unsaturated aldehyde and unsaturated carboxylic acid by the vapor phase catalytic oxidation of propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether with molecular oxygen or the catalyst component used in the production of unsaturated carboxylic acid by the vapor phase catalytic oxidation of (meth) acrolein with molecular oxygen.
The catalyst molded body of the present invention contains cellulose nanofibers having a specific fiber diameter, and thus can achieve both a high yield of a target product and high mechanical strength. Thus, since the pulverization and cracking of the catalyst are reduced in the long-term continuous operation of the industrial process, the increase in the differential pressure can be suppressed, and the high yield can be maintained for a long period of time. Therefore, the catalyst life is also long, and the frequency of catalyst exchange can be reduced.
The mechanical strength of the molded catalyst can be evaluated by, for example, the falling powder ratio measured by the following method. The catalyst molded body 100g was dropped from the upper opening of a stainless steel cylinder having an inner diameter of 27.5mm and a length of 6m, the lower opening of which was sealed with a stainless steel plate, and filled into the cylinder. The catalyst molded bodies were recovered by opening the lower openings, and the falling powder yield was calculated by the following formula, assuming that the mass of the catalyst molded bodies which did not pass through a mesh having a mesh size of 1mm among the recovered catalyst molded bodies was α g. The smaller the falling pulverization rate is, the higher the mechanical strength is; the larger the falling powder ratio, the lower the mechanical strength.
Drop pulverization rate (%) { (100- α)/100} × 100
[ cellulose nanofibers ]
The cellulose nanofibers used in the present invention have an average fiber diameter of 1 to 300 nm. The lower limit of the average fiber diameter is preferably 2nm or more, and more preferably 3nm or more. The upper limit of the average fiber diameter is preferably 100nm or less, and more preferably 50nm or less. The cellulose nanofibers mean fibrous cellulose having an average aspect ratio of 100 or more. The average aspect ratio is preferably 100 to 10000, more preferably 100 to 2000. The average aspect ratio refers to the ratio of the average fiber length to the average fiber diameter of the cellulose nanofibers (average fiber length/average fiber diameter).
In the present invention, the average fiber diameter and average fiber length of the cellulose nanofibers are values obtained for the cellulose nanofibers in a dry state. The average fiber diameter and average fiber length of the cellulose nanofibers in a dried state of the present invention can be measured by a scanning electron microscope or a transmission electron microscope (with electron staining). For example, a dispersion having a cellulose nanofiber content of 0.05 to 0.1 mass% is cast onto a substrate such as a Si wafer, dried, and then observed with a scanning electron microscope. An axis having an arbitrary image width in the vertical and horizontal directions is assumed in an observation field, and a sample, magnification, and the like are adjusted so that 20 to 100 fibers intersect the axis to obtain an image. After obtaining the images, 2 random axes in the vertical and horizontal directions were drawn for 1 image, and the values of the fiber diameter and the fiber length were read from 20 arbitrary pairs of fibers intersecting each axis. In this manner, 3 images of the surface portion without repetition were taken by the scanning electron microscope, and the values of the fiber diameter and the fiber length of 20 fibers intersecting with the 2 axes were read, respectively. Thus, information on the fiber diameter and the fiber length of 120 fibers in total of 20 × 2 × 3 fibers was obtained. The average fiber diameter can be calculated from the arithmetic mean of the obtained fiber diameters, and the average fiber length can be calculated from the arithmetic mean of the fiber lengths. In the case of branched fibers, if the length of the branched portion is 50nm or more, the branched portion is taken as 1 fiber to be incorporated in the calculation of the fiber diameter. In this case, the length of the longest portion of the fiber is defined as the fiber length.
The average aspect ratio of the present invention can be calculated by a method other than the above method if the average aspect ratio is a method for obtaining a value equivalent to that of a scanning electron microscope or a transmission electron microscope (with electron staining). In the present invention, the dried state is a state in which the liquid is removed by a conventionally known method such as natural drying or freeze-drying under reduced pressure, and the liquid content of the cellulose nanofibers is 1 mass% or less.
The cellulose nanofibers used in the present invention are not particularly limited, and commercially available cellulose nanofibers produced by a known production method can be used. In general, a material containing cellulose fibers can be produced by defibering or refining a material by grinding or beating the material with a refiner, a high-pressure homogenizer, a media-stirring mill, a stone mortar, a grinder, or the like. Further, the resin composition can be produced by a known method such as the method described in, for example, Japanese patent application laid-open No. 2005-42283. In addition, the microorganism can be also used for production (for example, acetic acid bacteria (acetobacter) bacteria). Further, commercially available products can be used. As the material containing cellulose fibers, materials derived from plants (e.g., wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp, recycled pulp, waste paper), animals (e.g., ascidians), algae, microorganisms (e.g., acetobacter), microbial products, and the like are known, and any of them can be used in the present invention. Preferably cellulose nanofibers derived from plants or microorganisms, more preferably cellulose nanofibers derived from plants.
The cellulose nanofibers used in the present invention can be, for example, so-called modified cellulose nanofibers to be subjected to a certain chemical modification as described in jp 2013-181167 a and jp 2010-216021, and commercially available cellulose nanofibers or unmodified cellulose nanofibers produced by the method described in jp 2011-056456 a can be used. Examples of commercially available unmodified cellulose nanofibers include bionanofibers "BiNFi-s" series from Sequoia mechanical Co., Ltd, "Celish" series from Daicel FineChem Co., Ltd, and "CNF" series from Mitsuka pulp. These cellulose nanofibers may be used alone, or 2 or more kinds may be mixed and used.
[ catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid ]
From the viewpoint of the yield of unsaturated aldehyde and unsaturated carboxylic acid, the catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid of the present invention preferably has a composition represented by the following formula (I). The molar ratio of each element is a value obtained by analyzing a component obtained by dissolving a catalyst component in ammonia water by an ICP emission spectrometry. The molar ratio of ammonium groups is a value obtained by analyzing the catalyst component by the kyerda method.
Moa1Bib1Fec1Ad1E1e1G1f1J1g1Sih1(NH4)i1Oj1(I)
In the formula (I), Mo, Bi, Fe, Si, NH4And O respectively represents molybdenum, bismuth, iron, silicon, ammonium group and oxygen, a represents at least 1 element selected from cobalt and nickel, E1 represents at least 1 element selected from chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, thallium, tantalum and zinc, G1 represents at least 1 element selected from phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium, and J1 represents at least 1 element selected from lithium, sodium, potassium, rubidium and cesium. a1, b1, c1, d1, e1, f1, g1, h1, i1 and j1 represent molar ratios of the components, when a1 is 12, b1 is 0.01 to 3, c1 is 0.01 to 5, d1 is 0.01 to 12, and e1 is 0 to 8F1 is 0 to 5, g1 is 0.001 to 2, h1 is 0 to 20, i1 is 0 to 30, and j1 is the molar ratio of oxygen necessary to satisfy the valence of each component.
The molar ratio of each component is more preferably 0.05 to 2 for b1, 0.1 to 4 for c1, 0.1 to 10 for d1, 0 to 5 for e1, 0 to 3 for f1, 0.01 to 1 for g1, 0 to 10 for h1, and 0 to 20 for i 1.
In the present invention, "ammonium group" may be an ammonium ion (NH)4 +) Ammonia (NH)3) And ammonium contained in an ammonium-containing compound such as an ammonium salt.
[ catalyst for producing unsaturated Carboxylic acid ]
From the viewpoint of the yield of unsaturated carboxylic acid, the catalyst for producing unsaturated carboxylic acid of the present invention preferably has a composition represented by the following formula (II).
Pa2Mob2Vc2Cud2E2e2G2f2J2g2(NH4)h2Oi2(II)
In the formula (II), P, Mo, V, Cu, NH4And O represents phosphorus, molybdenum, vanadium, copper, ammonium, and oxygen, respectively. E2 represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. G2 represents at least 1 element selected from iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, thallium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. J2 represents at least 1 element selected from potassium, rubidium and cesium. a2, b2, c2, d2, e2, f2, g2, h2 and i2 represent molar ratios of the respective components, and when b2 is 12, a2 is 0.1 to 3, c2 is 0.01 to 3, d2 is 0.01 to 2, e2 is 0 to 3, f2 is 0 to 3, g2 is 0.01 to 3, h2 is 0 to 30, and i2 represents a molar ratio of oxygen necessary to satisfy the valence number of the respective components.
The molar ratio of the components is more preferably 0.5 to 2 for a2, 0.05 to 2 for c2, 0.05 to 1.5 for d2, 0.01 to 2 for e2, 0 to 2 for f2, 0 to 2 for g2, and 0 to 20 for h 2.
[ molded catalyst ]
When the mass of the molded catalyst is M1[ g ] and the mass of the cellulose nanofibers is M2[ g ], the cellulose nanofiber content calculated by the following formula (III) is preferably 0.1 to 5% by mass. M1 and M2 are masses calculated from the amounts charged. For example, M1 is the total mass of the molded catalyst containing cellulose nanofibers, and is calculated from the total of the dried catalyst, the binder, and other solid components described below.
Cellulose nanofiber content [% by mass ] (M2/M1) × 100 (III)
The mechanical strength of the molded catalyst can be further improved by setting the cellulose nanofiber content to 0.1 mass% or more.
Further, by setting the cellulose nanofiber content to a value of 5 mass% or less, a sufficient amount of the catalyst component can be charged into the reactor, and therefore, a high yield can be maintained for a long period of time during continuous operation. Therefore, the catalyst life is also long, and the frequency of catalyst exchange can be reduced. The lower limit of the cellulose nanofiber content is more preferably 0.2 mass% or more, and still more preferably 0.3 mass% or more. The upper limit of the cellulose nanofiber content is more preferably 4% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
The catalyst molded body preferably contains a binder in addition to the cellulose nanofibers. When the catalyst molded body contains both cellulose nanofibers and a binder, moldability in a molding step described later is improved, and a molded body having a desired shape can be stably obtained. When the mass of the binder is M3[ g ], the binder content calculated by the following formula (IV) is preferably 0.05 to 10 mass%, and the lower limit is more preferably 0.1 mass% or more, and still more preferably 1 mass% or more. The upper limit is more preferably 8% by mass or less, and still more preferably 5% by mass or less.
Content of binder [% by mass ] - (M3/M1) × 100 (IV)
The binder is not particularly limited as long as it has a function of binding the dried catalyst or the calcined catalyst, and a water-soluble binder or a water-insoluble binder can be used.
Examples of the water-soluble binder include water-soluble polymer compounds such as polyvinyl alcohol, organic binders such as water-soluble α glucan derivatives and water-soluble β glucan derivatives, and inorganic binders such as water-soluble silicic acid compounds and ammonium salts of inorganic acids. One kind of these may be used, or two or more kinds may be used in combination.
The α glucan derivative in the present invention means a polysaccharide composed of glucose in which glucose is bound in an α -form structure. Specific examples of the water-soluble α -glucan derivative include amylose, glycogen, pullulan, dextrin, and cyclodextrin. One kind of these may be used, or two or more kinds may be used in combination. In the present invention, the β -glucan derivative represents a polysaccharide composed of glucose in which glucose is bound in a β -type structure. Specific examples of the water-soluble β -glucan derivative include methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methyl cellulose, ethyl hydroxyethyl cellulose, and scleroglucan.
Specific examples of the water-soluble silicic acid compound include sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, lithium silicate, ammonium silicate, and alkyl silicate. Examples of the ammonium salt of the inorganic acid include ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium chlorite, ammonium hydrogen carbonate, ammonium thiosulfate, ammonium dithionite, and ammonium chloride salt. One kind of these may be used, or two or more kinds may be used in combination.
Examples of the water-insoluble binder include organic binders such as water-insoluble α glucan derivatives and water-insoluble β glucan derivatives, and inorganic binders such as water-insoluble inorganic compounds and water-insoluble inactive carriers. One kind of these may be used, or two or more kinds may be used in combination.
Specific examples of the water-insoluble α -glucan derivative include pullulan and the like. Specific examples of the water-insoluble β -glucan derivative include ethyl cellulose, crystalline cellulose, curdlan (curdlan), paramylon (paramylon), and the like. One kind of these may be used, or two or more kinds may be used in combination.
Specific examples of the water-insoluble inorganic compound include silica, alumina, silica-alumina, silicon carbide, titania, magnesia, graphite, and diatomaceous earth. Specific examples of the water-insoluble inert carrier include inorganic fibers such as ceramic beads, stainless steel, glass fibers, ceramic fibers, and carbon fibers. One kind of these may be used, or two or more kinds may be used in combination.
From the viewpoint of the mechanical strength of the catalyst molded body, the binder is preferably water-soluble, more preferably a water-soluble organic binder, and particularly preferably a water-soluble β glucan derivative. In the present invention, water solubility means a property of dissolving 5g or more in 100g of water at 20 ℃.
[ method for producing molded catalyst ]
The catalyst molded body of the present invention can be produced by a known catalyst production method, in addition to containing cellulose nanofibers.
The method of incorporating cellulose nanofibers into the catalyst molded body is not particularly limited, and examples thereof include a method of adding cellulose nanofibers to a catalyst raw material liquid in a catalyst raw material liquid preparation step described later, a method of adding cellulose nanofibers to a catalyst dried body in a molding step described later and molding, and a method of using these methods in combination.
(catalyst stock solution preparation step)
In the present invention, the method for preparing the catalyst component is not particularly limited, and various methods known in the art, such as a precipitation method and an oxide mixing method, may be used as long as the method does not involve significant uneven distribution of the component. For example, in the production of a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, it is preferable to prepare a solution or slurry (hereinafter also referred to as a catalyst raw material liquid) containing at least molybdenum and bismuth by dissolving or suspending a raw material compound of a catalyst component of the catalyst for producing a saturated aldehyde and an unsaturated carboxylic acid in an appropriately selected solvent. In the production of the catalyst for unsaturated carboxylic acid production, it is preferable to prepare a catalyst raw material liquid containing at least molybdenum and phosphorus by dissolving or suspending a raw material compound of a catalyst component of the catalyst for unsaturated carboxylic acid production in an appropriately selected solvent.
The raw material compound used for preparing the catalyst raw material liquid is not particularly limited, and two or more kinds of organic acid salts such as oxides, sulfates, nitrates, carbonates, hydroxides, and acetates, ammonium salts, halides, oxoacids, oxoacid salts, and alkali metal salts of each constituent element of the catalyst may be used alone or in combination. Examples of the raw material compound of molybdenum include molybdenum oxides such as molybdenum trioxide, ammonium molybdates such as ammonium paramolybdate and ammonium dimolybdate, molybdic acid, molybdenum chloride, and the like. Examples of the raw material compound of bismuth include bismuth nitrate, bismuth oxide, bismuth acetate, and bismuth hydroxide. Examples of the phosphorus raw material compound include phosphoric acid, phosphorus pentoxide, and phosphates such as ammonium phosphate. Examples of the raw material compound of vanadium include ammonium vanadate, ammonium metavanadate, vanadium pentoxide, vanadium chloride, vanadyl oxalate, and the like. The raw material compound may be used alone in an amount of 1 kind or in combination of 2 or more kinds for each element constituting the catalyst component.
Examples of the solvent include water, ethanol, and acetone, and water is preferably used.
(drying Process)
In the drying step, the catalyst raw material liquid obtained in the catalyst raw material liquid preparation step is dried to obtain a catalyst dried body. The method for drying the catalyst raw material liquid is not particularly limited, and for example, a method of drying using a spray dryer, a method of drying using a slurry dryer, a method of drying using a drum dryer, a method of evaporating a solid, and the like can be applied. Among these, a method of drying using a spray dryer is preferable in terms of obtaining particles simultaneously with drying and obtaining particles having a completely spherical shape. The drying conditions vary depending on the drying method, but when a spray dryer is used, the dryer inlet temperature is preferably 100 to 500 ℃, the lower limit is more preferably 200 ℃ or more, and still more preferably 220 ℃ or more. The upper limit is more preferably 400 ℃ or lower, and still more preferably 370 ℃ or lower. The outlet temperature of the dryer is preferably 100 to 200 ℃, and the lower limit is more preferably 105 ℃ or higher. The drying is preferably performed so that the moisture content of the obtained dried catalyst body is 0.1 to 4.5 mass%. Such conditions can be appropriately selected depending on the shape and size of the desired catalyst.
When a spray dryer is used, the average particle diameter of the dried catalyst is preferably 1 to 250 μm. By making the average particle diameter 1 μm or more, fine pores having a diameter preferable for producing the target product are formed, and the target product is obtained in a high yield. Further, by setting the average particle diameter to 250 μm or less, the number of contact points between the catalyst dried particles per unit volume can be maintained, and sufficient mechanical strength of the catalyst can be obtained. The lower limit of the average particle diameter of the dried catalyst is more preferably 5 μm or more and the upper limit thereof is more preferably 150 μm or less. The average particle size is a volume average particle size and is a value measured by a laser particle size distribution measuring apparatus.
The contact manner of the sprayed droplets with the hot air may be any of cocurrent, countercurrent, and cocurrent and countercurrent (mixed flow), and in any case, drying can be suitably performed.
(Molding Process)
In the molding step, the dried catalyst body obtained in the drying step is molded to obtain a molded catalyst body. When the dried catalyst body contains cellulose nanofibers, the dried catalyst body may be molded as it is, or may be molded after adding cellulose nanofibers. When the dried catalyst body does not contain cellulose nanofibers, cellulose nanofibers are added to the dried catalyst body and the dried catalyst body is molded to obtain a catalyst molded body. The molding may be performed by adding cellulose nanofibers after the calcination step described later.
The dried catalyst body obtained in the drying step exhibits catalytic performance, and the molded body obtained by molding the dried catalyst body can be used as a molded catalyst body, but it is preferable because the performance as a catalyst is improved by the calcination. In the present invention, the calcined material is collectively referred to as a catalyst molded body.
The molding method is not particularly limited, and examples thereof include known methods such as extrusion molding, tablet molding, carrier molding, and rotary granulation. Among these, tablet forming and extrusion forming are preferable from the viewpoint of productivity of the catalyst, and extrusion forming is more preferable from the viewpoint of formation of fine pores in the catalyst molded body, which is advantageous for production of the target product. The shape of the catalyst molded body is not particularly limited, and examples thereof include spherical, cylindrical, annular (cylindrical), star-shaped, and the like, and among them, spherical, cylindrical, and annular shapes having high mechanical strength are preferable.
The catalyst molded body of the present invention can improve moldability by containing a binder in addition to the cellulose nanofibers, and can stably obtain a molded body having a desired shape.
(calcination Process)
From the viewpoint of the yield of the target product, it is preferable to calcine the dried catalyst obtained in the drying step or the molded catalyst obtained in the molding step. The calcination temperature is usually 200 to 600 ℃, preferably 300 ℃ or higher at the lower limit and 500 ℃ or lower at the upper limit. The calcination conditions are not particularly limited, but calcination is usually carried out under a flow of oxygen, air or nitrogen. The calcination time is suitably set in accordance with the target catalyst, and is preferably 0.5 to 40 hours, and more preferably 1 to 40 hours.
[ Process for producing unsaturated aldehyde and unsaturated carboxylic acid ]
The process for producing an unsaturated aldehyde and an unsaturated carboxylic acid of the present invention comprises subjecting propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether to vapor phase catalytic oxidation with molecular oxygen in the presence of a molded catalyst containing the catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid of the present invention. According to these methods, an unsaturated aldehyde and an unsaturated carboxylic acid can be produced in high yield.
The unsaturated aldehyde and the unsaturated carboxylic acid to be produced are compounds corresponding to propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether, respectively. For example, the unsaturated aldehyde corresponding to propylene is acrolein, and the unsaturated carboxylic acid corresponding to propylene is acrylic acid. The unsaturated aldehyde corresponding to isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether is methacrolein, and the unsaturated carboxylic acid corresponding to isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether is methacrylic acid.
From the viewpoint of the yield of the target product, the unsaturated aldehyde and the unsaturated carboxylic acid are preferably methacrolein and methacrylic acid, respectively.
Hereinafter, a method for producing methacrolein and methacrylic acid by the gas phase catalytic oxidation of isobutylene with molecular oxygen in the presence of the catalyst molded product produced by the method of the present invention will be described as a representative example.
In the method, methacrolein and methacrylic acid are produced by bringing a raw material gas containing isobutylene and molecular oxygen into contact with the catalyst molded body of the present invention. A fixed bed type reactor may be used in the reaction. The reaction can be carried out by filling a catalyst molded body in a reaction tube and supplying a raw material gas to the reactor. The catalyst molded body layer may be 1 layer, or a plurality of catalyst molded bodies having different activities may be divided into a plurality of layers and filled. In order to control the activity, the catalyst molded body may be diluted with an inactive carrier and filled.
The concentration of isobutylene in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, the lower limit is more preferably 3% by volume or more, and the upper limit is 10% by volume or less.
The concentration of molecular oxygen in the raw material gas is preferably 0.1 to 5 mol based on 1 mol of isobutylene, and the lower limit is preferably 0.5 mol or more and the upper limit is 3 mol or less. The molecular oxygen source is preferably air from the viewpoint of economy. If necessary, a gas rich in molecular oxygen by adding pure oxygen to air may be used.
The raw material gas may be a gas obtained by diluting isobutylene and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the raw material gas.
The contact time between the raw material gas and the catalyst molded body is preferably 0.5 to 10 seconds, and more preferably 1 second or more as a lower limit and 6 seconds or less as an upper limit. The reaction pressure is preferably 0.1 to 1MPa (G). Wherein (G) represents gauge pressure. The reaction temperature is preferably 200 to 420 ℃, and more preferably, the lower limit is 250 ℃ or higher and the upper limit is 400 ℃ or lower.
[ Process for producing unsaturated Carboxylic acid ]
The method for producing an unsaturated carboxylic acid of the present invention comprises subjecting (meth) acrolein to gas-phase catalytic oxidation with molecular oxygen in the presence of a catalyst molded body containing the catalyst for producing an unsaturated carboxylic acid of the present invention. According to these methods, an unsaturated carboxylic acid can be produced in high yield.
The unsaturated carboxylic acid to be produced is an unsaturated carboxylic acid in which the aldehyde group of (meth) acrolein is changed to a carboxyl group, and specifically (meth) acrylic acid can be obtained.
In addition, "(meth) acrolein" represents acrolein and methacrolein, and "(meth) acrylic acid" represents acrylic acid and methacrylic acid. From the viewpoint of the yield of the target product, (meth) acrolein and (meth) acrylic acid are preferably methacrolein and methacrylic acid, respectively.
Hereinafter, a method for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst molded product produced by the method of the present invention will be described as a representative example.
In the method, methacrylic acid is produced by bringing a raw material gas containing methacrolein and molecular oxygen into contact with the catalyst molded body of the present invention. A fixed bed type reactor may be used in the reaction. The reaction can be carried out by filling the catalyst molded body in the reaction tube and supplying the raw material gas to the reactor. The catalyst molded body layer may be 1 layer, or a plurality of catalyst molded bodies having different activities may be divided into a plurality of layers and filled. In order to control the activity, the catalyst molded body may be diluted with an inactive carrier and filled.
The concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, more preferably 3% by volume or more at the lower limit and 10% by volume or less at the upper limit. The methacrolein as the raw material may contain a small amount of impurities such as lower saturated aldehydes which do not substantially affect the main reaction.
The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol based on 1 mol of methacrolein, and more preferably 0.5 mol or more at the lower limit and 3 mol or less at the upper limit. The molecular oxygen source is preferably air from the viewpoint of economy. If necessary, a gas rich in molecular oxygen by adding pure oxygen to air can be used.
The raw material gas may be a gas obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the raw material gas. By carrying out the reaction in the presence of water vapor, methacrylic acid can be obtained in a higher yield. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, and more preferably, the lower limit is 1% by volume or more and the upper limit is 40% by volume or less.
The contact time of the raw material gas with the methacrylic acid production catalyst is preferably 1.5 to 15 seconds. The reaction pressure is preferably 0.1 to 1MPa (G). Wherein (G) is gauge pressure. The reaction temperature is preferably 200 to 450 ℃, more preferably, the lower limit is 250 ℃ or higher and the upper limit is 400 ℃ or lower.
[ Process for producing unsaturated Carboxylic acid ester ]
The method for producing an unsaturated carboxylic acid ester of the present invention is a method for esterifying an unsaturated carboxylic acid produced by the method of the present invention. That is, the method for producing an unsaturated carboxylic acid ester of the present invention includes a step of producing an unsaturated carboxylic acid by the method of the present invention and a step of esterifying the unsaturated carboxylic acid. According to these methods, an unsaturated carboxylic acid ester can be obtained using an unsaturated carboxylic acid obtained by gas-phase catalytic oxidation of propylene, isobutylene, primary butanol, tertiary butanol, or methyl tertiary butyl ether, or by gas-phase catalytic oxidation of (meth) acrolein.
The alcohol to be reacted with the unsaturated carboxylic acid is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the unsaturated carboxylic acid ester to be obtained include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. The reaction may be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50-200 ℃.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "part" means "part by mass".
(falling powdering ratio)
The falling powder ratio, which is an index of the mechanical strength of the molded catalyst, was measured by the following method. The catalyst molded body 100g was dropped from the upper opening of a stainless steel cylinder having an inner diameter of 27.5mm and a length of 6m, the lower opening of which was sealed with a stainless steel plate, and filled into the cylinder. The catalyst molded bodies were recovered by opening the lower openings, and the falling powder rate was calculated from the following formula, assuming that the mass of the catalyst molded bodies which did not pass through a mesh having a mesh size of 1mm among the recovered catalyst molded bodies was α g. The smaller the falling pulverization rate is, the higher the mechanical strength is; the larger the falling powder ratio, the lower the mechanical strength. The falling powder ratios in table 1 are average values of falling powder ratios measured for each catalyst molded body after 10 times of production of catalyst molded bodies under the same conditions.
Drop pulverization rate (%) { (100- α)/100} × 100
(analysis of raw gas and product)
The raw material gas and the product were analyzed by gas chromatography. In examples 1 to 3 and comparative examples 1 to 3, the total yield of methacrolein and methacrylic acid was calculated by the following formula.
Total yield (%) of methacrolein and methacrylic acid (B + C)/ax100
Wherein A is the number of moles of isobutylene supplied, B is the number of moles of methacrolein formed, and C is the number of moles of methacrylic acid formed.
In examples 1 to 3 and comparative examples 1 to 3, only the case where isobutylene was used as a raw material was shown, and in the case where tert-butanol was used as a raw material, the isobutylene was rapidly dehydrated in the inlet portion of the reactor, and the same results as those obtained in the case where isobutylene was used as a raw material were obtained.
In example 4 and comparative examples 4 to 6, the yield of methacrylic acid produced was defined as follows.
Yield (%) of methacrylic acid (E/D) × 100
Here, D is the number of moles of methacrolein supplied, and E is the number of moles of methacrylic acid produced.
(average fiber diameter)
The average fiber diameter of the cellulose nanofibers was calculated from the analysis result by a scanning electron microscope. Specifically, a dry product obtained by casting a dispersion liquid, in which the cellulose nanofibers were dispersed in pure water so that the content of the cellulose nanofibers became 0.05 mass%, on a wafer and drying the casting liquid was observed by a scanning electron microscope. An axis having an arbitrary image width in the vertical and horizontal directions is assumed in the observation field, and the sample and the magnification are adjusted so that 20 to 100 fibers intersect the axis to obtain an image. After obtaining the images, 2 random vertical and horizontal axes are drawn for 1 image, and the fiber diameter value is read from 20 arbitrary fiber pairs intersecting each axis. In this way, 3 images of the surface portion not overlapping each other were taken by the scanning electron microscope, and the fiber diameters of the fibers intersecting the 2 axes were read to obtain information on the fiber diameters of 120 fibers. The average fiber diameter with 2 significant figures was calculated from the arithmetic mean of the fiber diameters obtained.
(composition ratio of catalyst component)
The molar ratio of each element was determined by analyzing a component obtained by dissolving a catalyst component in ammonia water by ICP emission spectrometry. The molar ratio of ammonium groups was determined by analyzing the catalyst components by the kyerda method.
(cellulose nanofiber content)
The content of cellulose nanofibers in the catalyst molded article was calculated from the following formula (III).
Cellulose nanofiber content [% by mass ] (M2/M1) × 100 (III)
In the formula (III), the mass M1 of the catalyst molded article is the total amount of the catalyst dried product, the hydroxypropyl methylcellulose, and the cellulose nanofibers charged. The mass M2 of the cellulose nanofibers is the amount of the cellulose nanofibers to be charged.
[ example 1]
To 1000 parts of pure water were added 500 parts of ammonium paramolybdate, 12.4 parts of ammonium paratungstate, 2.3 parts of potassium nitrate, 27.5 parts of antimony trioxide and 66.0 parts of bismuth trioxide, followed by heating and stirring (solution A). In addition, 114.4 parts of iron nitrate, 274.7 parts of cobalt nitrate, and 35.1 parts of zinc nitrate were added to 1000 parts of pure water in this order and dissolved (solution B). The catalyst raw material solution obtained by adding solution B to solution A was dried using a parallel flow type spray dryer at a dryer inlet temperature of 250 ℃ at 13000rpm of a rotating disk for slurry spray, to obtain a catalyst dried body having an average particle diameter of 46 μm. The oxygen-removed catalyst composition of the dried catalyst body is Mo12W0.2Bi1.2Fe1.2Sb0.8Co4.0Zn0.5K0.1(NH4)12.3。
A dispersion liquid in which 4 parts of hydroxypropylmethylcellulose and 1 part of cellulose nanofibers having an average fiber diameter of 40nm were dispersed in 45 parts of pure water per 100 parts of the dried catalyst body was kneaded into a clay-like state by a batch kneader equipped with a double-arm sigma plate to obtain a mixture.
The resulting mixture was extrusion-molded using a ram extruder into a ring shape having an outer diameter of 5mm, an inner diameter of 2mm and a length of 5.5mm, and then dried at 90 ℃ for 12 hours by a hot air dryer to obtain a molded catalyst. The results of measuring the falling powder rate of the molded catalyst are shown in table 1.
The catalyst molded body was then filled in a reaction tube and calcined at 450 ℃ for 3 hours under air circulation. Subsequently, a raw material gas containing 5 vol% of isobutylene, 12 vol% of oxygen, 10 vol% of water vapor and 73 vol% of nitrogen was passed through the reactor at a reaction temperature of 340 ℃ for 3.6 seconds under normal pressure to conduct a vapor-phase catalytic oxidation reaction of isobutylene. The product was collected and analyzed by gas chromatography to determine the total yield of methacrolein and methacrylic acid. The results are shown in Table 1.
[ example 2]
A catalyst compact was produced in the same manner as in example 1 except that the amount of cellulose nanofibers dispersed in pure water was changed to 0.5 part in example 1, the falling powder ratio was measured, and then the catalyst compact was calcined and the reaction was evaluated. The results are shown in Table 1.
[ example 3]
A catalyst compact was produced in the same manner as in example 1 except that the amount of cellulose nanofibers dispersed in pure water was changed to 0.25 parts in example 1, the falling powder ratio was measured, and then the catalyst compact was calcined and the reaction was evaluated. The results are shown in Table 1.
Comparative example 1
In example 1, a catalyst compact was produced in the same manner as in example 1 except that 45 parts of pure water was mixed instead of the cellulose nanofiber dispersion in the dried catalyst body, and the falling powder ratio was measured, followed by calcination of the catalyst compact and evaluation of the reaction. The results are shown in Table 1.
Comparative example 2
A catalyst compact was produced in the same manner as in example 1 except that in example 1, a cellulose nanofiber dispersion was not mixed with the catalyst compact, and 45 parts of pure water and 1 part of crystalline cellulose having an average particle diameter of 50 μm were mixed instead, and the falling powder ratio was measured, followed by calcination of the catalyst compact and reaction evaluation. The results are shown in Table 1.
Comparative example 3
A catalyst compact was produced in the same manner as in example 1 except that 45 parts of pure water and 5.0 parts of crystalline cellulose having an average particle diameter of 50 μm were mixed instead of the cellulose nanofiber dispersion in example 1, and the falling powder ratio was measured, followed by calcination and reaction evaluation of the catalyst compact. The results are shown in Table 1.
[ example 4]
1000 parts of molybdenum trioxide, 34 parts of ammonium metavanadate and 85 mass percent in 4000 parts of pure water80 parts of phosphoric acid aqueous solution and 7 parts of copper nitrate were stirred while raising the temperature to 95 ℃ and stirred for 3 hours while keeping the liquid temperature at 95 ℃. After cooling to 90 ℃, a solution of 124 parts of cesium bicarbonate in 200 parts of pure water was added thereto and stirred for 15 minutes while stirring with a rotary paddle stirrer. Next, a solution prepared by dissolving 92 parts of ammonium carbonate in 200 parts of pure water was added thereto, and the mixture was further stirred for 20 minutes. The catalyst raw material liquid thus obtained was dried by a parallel flow spray dryer at a dryer inlet temperature of 300 ℃ and a rotating disk for slurry spraying of 18000rpm to obtain a dried catalyst body having an average particle diameter of 25 μm. The oxygen-removed catalyst composition of the dried catalyst body is P1.2Mo12V0.5Cu0.05Cs1.1(NH4)3.8。
A dispersion liquid in which 4 parts of hydroxypropylmethyl fiber and 0.5 part of cellulose nanofiber having an average fiber diameter of 20nm were dispersed in 30 parts of pure water per 100 parts of the dried catalyst body was kneaded into a clay-like state by a batch kneader equipped with a double-arm sigma plate to obtain a mixture.
The resulting mixture was extrusion-molded by using a ram extruder into a cylindrical shape having an outer diameter of 6mm and a length of 5mm, and then calcined at 90 ℃ for 12 hours by a hot air dryer to obtain a molded catalyst. The results of measuring the falling powder rate of the molded catalyst are shown in Table 2.
The catalyst molded body was then charged into a reaction tube and calcined at 380 ℃ for 10 hours under air circulation. Then, a raw material gas containing 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen was passed through the reactor at a reaction temperature of 305 ℃ for 7.1 seconds under normal pressure to perform a gas phase catalytic oxidation reaction of methacrolein. The yield of methacrylic acid was determined by collecting the product and analyzing the product by gas chromatography. The results are shown in Table 2.
Comparative example 4
In example 4, a catalyst compact was produced in the same manner as in example 4 except that 30 parts of pure water was mixed instead of the cellulose nanofiber dispersion in the dried catalyst body, and the falling powder ratio was measured, followed by calcination and reaction evaluation of the catalyst compact. The results are shown in Table 2.
Comparative example 5
In example 4, a catalyst compact was produced in the same manner as in example 4 except that 45 parts of pure water and 1 part of crystalline cellulose having an average particle diameter of 50 μm were mixed instead of mixing the cellulose nanofiber dispersion with the dried catalyst compact, and the falling powder ratio was measured, followed by calcination of the catalyst compact and reaction evaluation. The results are shown in Table 2.
Comparative example 6
A catalyst compact was produced in the same manner as in example 1 except that in example 1, a cellulose nanofiber dispersion was not mixed with the catalyst compact, and 45 parts of pure water and 8 parts of crystalline cellulose having an average particle diameter of 50 μm were mixed instead, and the falling powder ratio was measured, followed by calcination of the catalyst compact and reaction evaluation. The results are shown in Table 1.
[ Table 1]
[ Table 2]
As shown in Table 1, Mo contained in the formula (I) was used12W0.2Bi1.2Fe1.2Sb0.8Co4.0Zn0.5K0.1(NH4)12.3In the case of the catalyst components having the composition ratios of (1) to (3), the catalyst molded bodies containing the cellulose nanofibers having an average fiber diameter of 1 to 300nm were low in falling powder percentage and high in mechanical strength, and the total yield of methacrolein and methacrylic acid was high. On the other hand, comparative examples 1 and 2, in which the molded catalyst did not contain cellulose nanofibers, were methacrolein of the same degree as in examples 1 to 3And methacrylic acid, but has a high falling powder rate and a low mechanical strength. Therefore, as shown in comparative example 3, when the mechanical strength was formed by a binder other than cellulose nanofibers to the same extent as in example 1, the total yield of methacrolein and methacrylic acid was significantly reduced.
The molded catalyst bodies of examples 1 to 3 had high yields of methacrolein and methacrylic acid and also had high mechanical strength, and therefore, the catalyst was less pulverized and cracked during continuous operation, and therefore, the increase in differential pressure was suppressed, and high yields could be maintained for a long period of time. Therefore, the catalyst life is also long, and the frequency of catalyst exchange can be reduced.
Likewise, P contained in the formula (II) is used1.2Mo12V0.5Cu0.05Cs1.1(NH4)3.81In the case of the catalyst component of the composition ratio (B) of (A), in example 4 in which the molded catalyst contains cellulose nanofibers having an average fiber diameter of 1 to 300nm, a molded catalyst having a low falling powder rate and high mechanical strength can be obtained, and the yield of methacrylic acid is also high. On the other hand, comparative example 4, in which the catalyst molded body did not contain cellulose nanofibers, had a high falling powder rate and low mechanical strength, and the yield of methacrylic acid was also slightly low. In comparative example 5, the yield of methacrylic acid was about the same as that in example 4, but the falling powder ratio was high and the mechanical strength was low. Therefore, as shown in comparative example 6, when the mechanical strength was formed by a binder other than cellulose nanofibers to the same extent as in example 4, the yield of methacrylic acid was lowered.
Since the yield of methacrylic acid in the molded catalyst of example 4 was high and the mechanical strength was also high, the catalyst was less pulverized and cracked during continuous operation, and therefore, the increase in differential pressure was suppressed, and the high yield could be maintained for a long period of time. Therefore, the catalyst life is also long, and the frequency of catalyst exchange can be reduced.
Methacrylic acid esters can be obtained by esterifying methacrylic acid obtained in this example.
Industrial applicability
According to the present invention, a catalyst molded body having high yield and high mechanical strength can be provided. By using such a molded catalyst, a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which can maintain a high yield for a long period of time, can be provided.
The present invention has been described specifically by way of the embodiments and examples, but the present invention is not limited thereto, and various modifications can be made in the configuration and details of the present invention within the scope of the present invention as will be apparent to those skilled in the art.
The present application claims priority based on Japanese application laid-open application No. 2018-046637, filed on 3/14/2018, the entire disclosure of which is incorporated herein by reference.
Claims (13)
1. A catalyst molded body comprising a catalyst component capable of producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by gas-phase catalytic oxidation using molecular oxygen and cellulose nanofibers having an average fiber diameter of 1 to 300 nm.
2. The molded catalyst according to claim 1, wherein the cellulose nanofiber content calculated by the following formula (III) is 0.1 to 5% by mass when M1[ g ] is the mass of the molded catalyst and M2[ g ] is the mass of the cellulose nanofiber,
the cellulose nanofiber content [% by mass ] (M2/M1) × 100 (III).
3. The catalyst molded body according to claim 1 or 2, further comprising a binder.
4. The catalyst shaped body according to claim 3, wherein the binder is water-soluble.
5. The catalyst shaped body according to claim 3, wherein the binder is a water-soluble organic binder.
6. A molded catalyst body obtained by calcining the molded catalyst body according to any one of claims 1 to 5.
7. A molded catalyst according to any one of claims 1 to 6, which is produced by a process comprising extrusion molding.
8. The molded catalyst according to any one of claims 1 to 7, wherein the catalyst component has a composition represented by the following formula (I) and is a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which is obtained by vapor-phase catalytic oxidation of propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether with molecular oxygen,
Moa1Bib1Fec1Ad1E1e1G1f1J1g1Sih1(NH4)i1Oj1(I)
in the formula (I), Mo, Bi, Fe, Si, NH4And O represents molybdenum, bismuth, iron, silicon, ammonium and oxygen, respectively, a represents at least 1 element selected from cobalt and nickel, E1 represents at least 1 element selected from chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, thallium, tantalum and zinc, G1 represents at least 1 element selected from phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium, J1 represents at least 1 element selected from lithium, sodium, potassium, rubidium and cesium, a1, b1, c1, d1, E1, f1, G1, h1, i1 and J1 represent molar ratios of the respective components, b1 is 0.01 to 3 when a1 is 12, c1 is 0.01 to 5, d 5 is 0.01 to 12, E1 is 0 f 24, f1 is 1 to 24, J is 590.599, and J is 5930 to 5920, which satisfy the molar ratios of the stated components.
9. The molded catalyst according to any one of claims 1 to 7, wherein the catalyst component has a composition represented by the following formula (II) and is a catalyst for producing an unsaturated carboxylic acid, which is obtained by subjecting (meth) acrolein to gas-phase catalytic oxidation with molecular oxygen,
Pa2Mob2Vc2Cud2E2e2G2f2J2g2(NH4)h2Oi2(II)
in the formula (II), P, Mo, V, Cu, NH4And O represents phosphorus, molybdenum, vanadium, copper, ammonium and oxygen, respectively, E2 represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron, G2 represents at least 1 element selected from iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, thallium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum, J2 represents at least 1 element selected from potassium, rubidium and cesium, a2, b2, c2, d2, E2, f2, G2, h2 and i2 represent molar ratios of the respective components, when b 8 is 12, a2 is 0.1 to 3, c2 is 0.01 to 3, d2 is 0.01 to 2, E2 is 0.84 is 0 to 3, f2 is 373, and i is 0.2, and the molar ratio of the required components is 3945 to satisfy the valence ratios of a.
10. A process for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which comprises subjecting propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether to vapor-phase catalytic oxidation with molecular oxygen in the presence of the molded catalyst as claimed in claim 8.
11. A process for producing an unsaturated carboxylic acid, which comprises subjecting (meth) acrolein to gas-phase catalytic oxidation with molecular oxygen in the presence of the molded catalyst as claimed in claim 9.
12. A method for producing an unsaturated carboxylic acid ester, comprising esterifying an unsaturated carboxylic acid produced by the method according to claim 10 or 11.
13. A method for producing an unsaturated carboxylic acid ester, comprising the step of producing an unsaturated carboxylic acid by the method according to claim 10 or 11, and the step of esterifying the unsaturated carboxylic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018046637 | 2018-03-14 | ||
| JP2018-046637 | 2018-03-14 | ||
| PCT/JP2019/010294 WO2019177031A1 (en) | 2018-03-14 | 2019-03-13 | Catalyst molded body, and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same |
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| CN111727085A true CN111727085A (en) | 2020-09-29 |
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| JP (1) | JP6973618B2 (en) |
| KR (1) | KR102547450B1 (en) |
| CN (1) | CN111727085A (en) |
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| KR102547450B1 (en) | 2023-06-23 |
| KR20200128734A (en) | 2020-11-16 |
| WO2019177031A1 (en) | 2019-09-19 |
| SG11202008534XA (en) | 2020-10-29 |
| JPWO2019177031A1 (en) | 2021-03-11 |
| JP6973618B2 (en) | 2021-12-01 |
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