JP6973618B2 - A catalyst molded product and a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the catalyst molded product. - Google Patents

Description

The present invention relates to a catalyst molded product containing a catalyst and cellulose nanofibers, and a method for producing an unsaturated aldehyde and / or an unsaturated carboxylic acid using the catalyst.

In the process of producing unsaturated aldehydes and unsaturated carboxylic acids, the catalyst molded body is generally formed into a cylindrical or cylindrical molded body having a diameter of 2 to 10 mm and a length of about 2 to 20 mm, and this is filled in a reactor. Will be used.

For example, Patent Document 1 describes a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids by vapor-phase catalytic oxidation of propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen. , Molybdenum and bismuth, and a catalyst containing a scaly inorganic substance having an average particle size of 10 μm to 2 mm and an average thickness of 0.005 to 0.3 times the average particle size have been proposed.

Patent Document 2 describes an oxide catalyst containing molybdenum, bismuth, cobalt and iron used for producing metachlorine, in which ^{crystalline cellulose having a specific surface area of 0.5 m 2} / g or more is mixed with a catalyst precursor powder. An oxide catalyst obtained by molding and heat-treating the obtained molded body to remove crystalline cellulose has been proposed.

Japanese Unexamined Patent Publication No. 2011-224482 JP-A-2007-061763

However, from an industrial point of view, further improvement in mechanical strength of the catalyst molded product is desired. An object of the present invention is to provide a catalyst molded product having a high yield and high mechanical strength.

The present invention is the following [1] to [ 17 ].
[1] A catalyst molded body containing a catalyst component capable of producing an unsaturated aldehyde and / or an unsaturated carboxylic acid by vapor-phase catalytic oxidation with molecular oxygen, and cellulose nanofibers having an average fiber diameter of 1 to 300 nm.
[2] When the mass of the catalyst molded product is M1 [g] and the mass of the cellulose nanofibers is M2 [g], the cellulose nanofiber content calculated by the following formula (III) is 0.1 to 5 The catalyst molded body according to [1], which is by mass%.
Cellulose nanofiber content [% by mass] = (M2 / M1) × 100 (III)
[3] The catalyst molded product according to [1] or [2], which further contains a binder.
[4] The catalyst molded product according to [3], wherein the binder is water-soluble.
[5] The catalyst molded product according to [3], wherein the binder is a water-soluble organic binder .

[ 6 ] The catalyst component has a composition represented by the following formula (I), and propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether is vapor-phase contacted with molecular oxygen. The catalyst molded product according to any one of [1] to [5 ], which is a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid to be oxidized.
Mo _a1 Bi _b1 Fe _c1 A _d1 E1 _e1 G1 _f1 J1 _g1 Si _h1 (NH ₄ ) _i1 O _j1 (I)
In formula (I), Mo, Bi, Fe, Si, NH ₄ and O represent molybdenum, bismuth, iron, silicon, ammonium root and oxygen, respectively, and A is selected from the group consisting of cobalt and nickel. Represents at least one element, E1 represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, nihonium, silver, barium, tin, thallium, thallium and zinc, G1 Represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium, and J1 is from the group consisting of lithium, sodium, potassium, rubidium and cesium. Represents at least one selected element. A1, b1, c1, d1, e1, f1, g1, h1, i1 and j1 represent the molar ratio of each component, and when a1 = 12, b1 = 0.01 to 3, c1 = 0.01 to 5, d1 = 0.01 to 12, e1 = 0 to 8, f1 = 0 to 5, g1 = 0.001 to 2, h1 = 0 to 20, i1 = 0 to 30 Yes, j1 is the molar ratio of oxygen required to satisfy the valence of each component.)

[ 7 ] The catalyst component is a catalyst for producing an unsaturated carboxylic acid having a composition represented by the following formula (II) and in which (meth) acrolein is vapor-phase catalytically oxidized with molecular oxygen. [1] to [ 5 ] The catalyst molded product according to any one of the above items.
P _a2 Mo _b2 V _c2 Cu _d2 E2 _e2 G2 _f2 J2 _g2 (NH ₄ ) _h2 O _i2 (II)
(In the formula (II), P, Mo, V, Cu, NH4 and O represent phosphorus, molybdenum, vanadium, copper, ammonium root and oxygen, respectively. E2 represents antimony, bismuth, arsenic, germanium, zirconium, respectively. Represents at least one element selected from the group consisting of tellurium, silver, selenium, silicon, tungsten and boron. G2 represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, Represents at least one element selected from the group consisting of titanium, tin, tarium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. J2 represents at least one selected from the group consisting of potassium, rubidium and cesium. Represents one kind of element. A2, b2, c2, d2, e2, f2, g2, h2 and i2 represent the molar ratio of each component, and when b2 = 12, a2 = 0.1 to 3, c2 = 0. .01-3, d2 = 0.01-2, e2 is 0-3, f2 = 0-3, g2 = 0.01-3, h2 = 0-30, and i2 is the valence of each of the above components. The molar ratio of oxygen required to be satisfied.)

[8] The method for producing a catalyst molded product according to any one of [1] to [6], which comprises a firing step.
[9] The method for producing a catalyst molded product according to [8], which comprises an extrusion molding step.
[10] The method for producing a catalyst molded product according to [7], which comprises a firing step.
[11] The method for producing a catalyst molded product according to [10], which comprises an extrusion molding step.
[ 12 ] In the presence of the catalyst molded product according to [6 ], propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether is vapor-phase catalytically oxidized with molecular oxygen, unsaturated. A method for producing an aldehyde and an unsaturated carboxylic acid.
[ 13 ] A method for producing an unsaturated carboxylic acid, which comprises vapor-phase catalytic oxidation of (meth) acrolein with molecular oxygen in the presence of the catalyst molded product according to [7].
[ 14 ] A method for producing an unsaturated carboxylic acid ester that esterifies an unsaturated carboxylic acid produced by the method according to [12 ] or [ 13].
[ 15 ] A method for producing an unsaturated carboxylic acid ester, which comprises a step of producing an unsaturated carboxylic acid by the method according to [12 ] or [ 13], and a step of esterifying the unsaturated carboxylic acid.
[16] Molecular oxygen of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether in the presence of the catalyst compact produced by the method according to [8] or [9]. A method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which is subjected to gas-phase catalytic oxidation.
[17] A method for producing an unsaturated carboxylic acid, which comprises vapor-phase catalytic oxidation of (meth) acrolein with molecular oxygen in the presence of the catalyst molded product produced by the method according to [10] or [11].

According to the present invention, it is possible to provide a catalyst molded product having a high yield and high mechanical strength. Further, it is possible to provide a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid that can maintain a high yield for a long period of time.

The catalyst molded body of the present invention contains cellulose nanofibers having an average fiber diameter of 1 to 300 nm. Further, the catalyst molded product of the present invention is a catalyst component capable of producing unsaturated aldehyde and / or unsaturated carboxylic acid by vapor phase catalytic oxidation with molecular oxygen, particularly propylene, isobutylene, primary butyl alcohol and tertiary butyl. Molecular oxygen is the catalytic component used in the production of unsaturated aldehydes and unsaturated carboxylic acids corresponding to each by gas-phase catalytic oxidation of alcohol or methyl tertiary butyl ether with molecular oxygen, or (meth) acrolein. Contains catalytic components used in the production of unsaturated carboxylic acids by vapor-phase catalytic oxidation.
By containing cellulose nanofibers having a specific fiber diameter, the catalyst molded product of the present invention can achieve both a high yield of a target product and a high mechanical strength. As a result, in the long-term continuous operation of the industrial process, the catalyst is less likely to be pulverized or cracked, so that the increase in the differential pressure is suppressed and the high yield can be maintained for a long period of time. Therefore, the catalyst life is long, and the frequency of catalyst replacement can be reduced.
The mechanical strength of the catalyst molded product can be evaluated by, for example, the falling powdering rate measured by the following method. 100 g of the catalyst molded body is dropped from the upper opening of a stainless steel cylinder having an inner diameter of 27.5 mm and a length of 6 m, which is installed so as to be vertical in the longitudinal direction and whose lower opening is closed by a stainless steel plate. Fill in a cylinder. Of the catalyst molded bodies recovered by opening the lower opening, the mass of the one that does not pass through the sieve with a mesh opening of 1 mm is defined as αg, and the falling powdering rate is calculated by the following formula. The smaller the falling powder ratio, the higher the mechanical strength, and the larger the fall powder rate, the lower the mechanical strength.
Fall powder 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 2 nm or more, more preferably 3 nm or more. The upper limit of the average fiber diameter is preferably 100 nm or less, more preferably 50 nm or less. The cellulose nanofibers are fibrous celluloses 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 means the ratio of the average fiber length to the average fiber diameter (average fiber length / average fiber diameter) of the cellulose nanofibers.

In the present invention, the average fiber diameter and the average fiber length of the cellulose nanofibers are the values obtained for the dry cellulose nanofibers. The average fiber diameter and average fiber length of the dry cellulose nanofibers in 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% by mass is cast on a substrate such as a Si wafer and dried, and then observed with a scanning electron microscope. An axis with an arbitrary vertical and horizontal image width is assumed in the observation field of view, and an image is acquired by adjusting the sample, magnification, etc. so that 20 to 100 fibers intersect the axis. After obtaining an image, two random axes in the vertical and horizontal directions are drawn per image, and the values of the fiber diameter and the fiber length are read for any 20 fibers from the fibers intersecting each axis. In this way, images of three non-overlapping surface portions are taken with a scanning electron microscope, and the fiber diameter and fiber length values of 20 fibers intersecting each of the two axes are read. Therefore, information on the fiber diameter and fiber length of a total of 120 fibers of 20 fibers × 2 axes × 3 fibers is 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. For the branched fiber, if the length of the branched portion is 50 nm or more, that portion is incorporated into the calculation of the fiber diameter as one fiber. At this time, the length of the longest portion of the fiber is defined as the fiber length.
The average aspect ratio in the present invention may be calculated by a method other than the above as long as it is a method capable of obtaining a value equivalent to that of a scanning electron microscope or a transmission electron microscope (with electron staining). In the present invention, the dry state is a state in which the liquid is removed by a conventionally known method such as natural drying or freezing and vacuum drying, and the liquid content of the cellulose nanofibers is 1% by mass or less.

The cellulose nanofibers used in the present invention are not particularly limited, and commercially available products or those manufactured by a known manufacturing method can be used. Generally, the cellulose fiber-containing material is defibrated or refined by grinding or beating with a refiner, a high-pressure homogenizer, a medium stirring mill, a stone mill, a grinder, or the like. Further, it can also be produced by a known method such as the method described in JP-A-2005-42283. It can also be produced using microorganisms (for example, acetic acid bacteria (Acetobacter)). Further, it is also possible to use a commercially available product. Cellulose fiber-containing materials include plants (eg wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp, recycled pulp, waste paper), animals (eg squirrels), algae, microorganisms (eg acetic acid bacteria (acetobacter)). )), Those originating from microbial products and the like are known, and any of them can be used in the present invention. Cellulose nanofibers derived from plants or microorganisms are preferable, and cellulose nanofibers derived from plants are more preferable.

As the cellulose nanofibers used in the present invention, so-called modified cellulose nanofibers having undergone some chemical modification, such as those described in JP2013-181167A and JP2010-216201, may be used, for example, special feature. So-called unmodified cellulose nanofibers produced by the method described in Japanese Patent Publication No. 2011-056456 or commercially available unmodified cellulose nanofibers may be used. Examples of commercially available products of unmodified cellulose nanofibers include the bio-nanofiber "BiNFi-s" series of Sugino Machine Limited, the "Cerish" series of Daicel FineChem Co., Ltd., and the "CNF" series of Chuetsu Pulp & Paper. These cellulose nanofibers can be used alone or in combination of two or more.

[Catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids]
The catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to the present invention preferably has a composition represented by the following formula (I) from the viewpoint of the yield of the unsaturated aldehyde and the unsaturated carboxylic acid. The molar ratio of each element is a value obtained by analyzing a component obtained by dissolving a catalyst component in aqueous ammonia by an ICP emission spectrometry method. The molar ratio of ammonium roots is a value obtained by analyzing the catalyst component by the Kjeldahl method.
Mo _a1 Bi _b1 Fe _c1 A _d1 E1 _e1 G1 _f1 J1 _g1 Si _h1 (NH ₄ ) _i1 O _j1 (I)
In formula (I), Mo, Bi, Fe, Si, NH ₄ and O represent molybdenum, bismuth, iron, silicon, ammonium root and oxygen, respectively, and A is at least selected from the group consisting of cobalt and nickel. Represents one element, E1 represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, thallium, tantalum and zinc, and G1 represents. Represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and tantalum, where J1 is selected from the group consisting of lithium, sodium, potassium, rubidium and cesmuth. Represents at least one element. a1, b1, c1, d1, e1, f1, g1, h1, i1 and j1 represent the molar ratio of each component, and when a1 = 12, b1 = 0.01-3, c1 = 0.01-5, d1. = 0.01 to 12, e1 = 0 to 8, f1 = 0 to 5, g1 = 0.001 to 2, h1 = 0 to 20, i1 = 0 to 30, and j1 is the valence of each of the above components. The molar ratio of oxygen required to be satisfied.
The molar ratio of each component is b1 = 0.05 to 2, c1 = 0.1 to 4, d1 = 0.1 to 10, e1 = 0 to 5, f1 = 0 to 3, g1 = 0.01 to 1. , H1 = 0 to 10, i1 = 0 to 20 are more preferable.
Note that the "ammonium ions" in the present invention, ammonia (NH 3) can become an ammonium ion (NH 4 ^_+), and ammonium salts is a general term of ammonium contained in the ammonium-containing compound such.

[Catalyst for producing unsaturated carboxylic acid]
The catalyst for producing an unsaturated carboxylic acid according to the present invention preferably has a composition represented by the following formula (II) from the viewpoint of the yield of unsaturated carboxylic acid.
P _a2 Mo _b2 V _c2 Cu _d2 E2 _e2 G2 _f2 J2 _g2 (NH ₄ ) _h2 O _i2 (II)
In the formula (II), P, Mo, V, Cu, NH ₄ and O represent phosphorus, molybdenum, vanadium, copper, ammonium root and oxygen, respectively. E2 represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. G2 is from the group consisting of iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, thallium, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. Represents at least one element selected. J2 represents at least one element selected from the group consisting of potassium, rubidium and cesium. a2, b2, c2, d2, e2, f2, g2, h2 and i2 represent the molar ratio of each component, and when b2 = 12, a2 = 0.1 to 3, c2 = 0.01-3, d2 = 0.01 to 2, e2 are 0 to 3, f2 = 0 to 3, g2 = 0.01 to 3, h2 = 0 to 30, and i2 is the oxygen required to satisfy the valence of each component. The molar ratio of.
The molar ratio of each component is a2 = 0.5 to 2, c2 = 0.05 to 2, d2 = 0.05 to 1.5, e2 = 0.01 to 2, f2 = 0 to 2, g2 = 0. .05-2, h2 = 0-20 are more preferable.

[Catalyst molded product]
The content of the cellulose nanofibers in the catalyst molded body is calculated by the following formula (III) when the mass of the catalyst molded body is M1 [g] and the mass of the cellulose nanofibers is M2 [g]. The fiber content is preferably 0.1 to 5% by mass. In addition, M1 and M2 are masses calculated from the charged amount. For example, M1 is the total mass of the catalyst molded body containing the cellulose nanofibers, and is calculated from the total of the catalyst dried body, the binder and other solid contents described later.
Cellulose nanofiber content [% by mass] = (M2 / M1) × 100 (III)
By setting the value of the cellulose nanofiber content to 0.1% by mass or more, the mechanical strength of the catalyst molded body can be further increased.
Further, when the value of the cellulose nanofiber content is 5% by mass or less, the reactor can be filled with a sufficient amount of the catalyst component, so that a high yield can be maintained for a long period of time in continuous operation. Therefore, the catalyst life is long, and the frequency of catalyst replacement can be reduced. The lower limit of the cellulose nanofiber content is more preferably 0.2% by mass or more, further preferably 0.3% by mass or more. The upper limit of the cellulose nanofiber content is more preferably 4% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less.

Further, it is preferable that the catalyst molded product further contains a binder in addition to the cellulose nanofibers. When the catalyst molded product contains both the cellulose nanofibers and the binder, the moldability is improved in the molding process described later, and the molded product 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% by mass, and the lower limit is more preferably 0.1% by mass or more. 1% by mass or more is more preferable. The upper limit is more preferably 8% by mass or less, further preferably 5% by mass or less.
Binder content [% by mass] = (M3 / M1) × 100 (IV)

The binder is not particularly limited as long as it has a function of adhering a dried catalyst or a catalyst after firing, 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. Can be mentioned. These may be used alone or in combination of two or more.

In the present invention, the α-glucan derivative refers to a polysaccharide composed of glucose to which glucose is bound in an α-type structure. Specific examples of the water-soluble α-glucan derivative include amylose, glycogen, pullulan, dextrin, and cyclodextrin. These may be used alone or in combination of two or more. Further, in the present invention, the β-glucan derivative refers to a polysaccharide composed of glucose to which glucose is bound in a β-type structure. Specific examples of the water-soluble β-glucan derivative include methyl cellulose, carboxyl methyl cellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxybutyl methyl cellulose, ethyl hydroxyethyl cellulose, scleroglucan and the like. Can be mentioned.

Specific examples of the water-soluble silicic acid compound include sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, lithium silicate, ammonium silicate, and alkyl silicates. Examples of the ammonium salt of the inorganic acid include ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium sulphate, ammonium hydrogencarbonate, ammonium thiosulfate, ammonium hyposulfate, ammonium chlorate and the like. These may be used alone or in combination of two or more.

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. These may be used alone or in combination of two or more.
Specific examples of the water-insoluble α-glucan derivative include amylopectin and the like. Specific examples of the water-insoluble β-glucan derivative include ethyl cellulose, crystalline cellulose, curdlan, paramylon and the like. These may be used alone or in combination of two or more.

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 ceramic balls, stainless steel, and inorganic fibers such as glass fibers, ceramic fibers, and carbon fibers. These may be used alone or in combination of two or more.

From the viewpoint of the mechanical strength of the catalyst molded product, 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-soluble means a property of dissolving 5 g or more in 100 g of water at 20 ° C.

[Manufacturing method of catalyst molded product]
The catalyst molded product of the present invention can be produced according to a known method for producing a catalyst, except that it contains cellulose nanofibers.
The method of incorporating the cellulose nanofibers into the catalyst molded body is not particularly limited. For example, in the catalyst raw material liquid preparation step described later, the method of adding the cellulose nanofibers to the catalyst raw material liquid, and in the molding step described later, the catalyst dry body is used. Examples thereof include a method of adding and molding cellulose nanofibers and a method of using these methods in combination.

(Catalyst raw material liquid preparation process)
In the present invention, the method for preparing the catalyst component is not particularly limited, and various methods such as a conventionally well-known precipitation method and oxide mixing method can be used as long as the components are not significantly unevenly distributed. For example, in the production of a catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid, the raw material compound of the catalyst component of the catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid is dissolved or suspended in an appropriately selected solvent, and at least molybdenum is used. It is preferable to prepare a solution or slurry containing bismuth (hereinafter, also referred to as a catalyst raw material solution). Further, in the production of the catalyst for producing an unsaturated carboxylic acid, the raw material compound of the catalyst component of the catalyst for producing an unsaturated carboxylic acid is dissolved or suspended in an appropriately selected solvent, and a catalyst raw material solution containing at least molybdenum and phosphorus is prepared. It is preferable to prepare.

The raw material compound used for preparing the catalyst raw material liquid is not particularly limited, and organic acid salts such as oxides, sulfates, nitrates, carbonates, hydroxides and acetates of each constituent element of the catalyst, ammonium salts and halides are used. , Oxo acid, oxo acid salt, alkali metal salt and the like can be used alone or in combination of two or more. Examples of the raw material compound for molybdenum include molybdenum oxides such as molybdenum trioxide, ammonium molybdates such as ammonium paramolybdate and ammonium dimolybdate, molybdic acid, and molybdenum chloride. Examples of the raw material compound of bismuth include bismuth nitrate, bismuth oxide, bismuth acetate, and bismuth hydroxide. Examples of the raw material compound for phosphorus include phosphates such as phosphoric acid, phosphorus pentoxide, and ammonium phosphate. Examples of the raw material compound of vanadium include ammonium vanadate, ammonium metavanadate, vanadium pentoxide, vanadium chloride, vanadyl oxalate and the like. As the raw material compound, only one kind may be used for each element constituting the catalyst component, or two or more kinds may be used in combination.
Examples of the solvent include water, ethyl alcohol, acetone and the like, but it is preferable to use water.

(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 product. The method for drying the catalyst raw material liquid is not particularly limited, and examples thereof include a method of drying using a spray dryer, a method of drying using a slurry dryer, a method of drying using a drum dryer, and a method of evaporating to dryness. Applicable. Among these, the method of drying using a spray dryer is preferable because the particles can be obtained at the same time as drying and the obtained particles have a regular spherical shape. The drying conditions differ depending on the drying method, but when a spray dryer is used, the dryer inlet temperature is preferably 100 to 500 ° C, the lower limit is more preferably 200 ° C or higher, and even more preferably 220 ° C or higher. Further, the upper limit is more preferably 400 ° C. or lower, further preferably 370 ° C. or lower. The dryer outlet temperature is preferably 100 to 200 ° C, and the lower limit is more preferably 105 ° C or higher. The drying is preferably performed so that the water content of the obtained dried catalyst is 0.1 to 4.5% by mass. These conditions can be appropriately selected depending on the shape and size of the desired catalyst.
When a spray dryer is used, the average particle size of the obtained catalyst dry body is preferably 1 to 250 μm. When the average particle size is 1 μm or more, pores having a diameter preferable for producing the target product are formed, and the target product can be obtained in a high yield. Further, when the average particle size is 250 μm or less, the number of contact points between the catalyst dry body particles per unit volume can be maintained, and sufficient mechanical strength of the catalyst can be obtained. It is more preferable that the lower limit of the average particle size of the dried catalyst is 5 μm or more and the upper limit is 150 μm or less. The average particle size means a volume average particle size, and is a value measured by a laser particle size distribution measuring device.
Further, the contact method between the sprayed droplets and the hot air may be any of parallel flow, countercurrent flow, and parallel flow (mixed flow), and in any case, drying can be suitably performed.

(Molding process)
In the molding step, the catalyst dried body obtained in the drying step is molded to obtain a catalyst molded body. When the dried catalyst contains cellulose nanofibers, it may be molded as it is, or it may be molded after additional addition of cellulose nanofibers. When the catalyst dry body does not contain cellulose nanofibers, cellulose nanofibers are added and molded to obtain a catalyst molded body. The molding may be performed after adding the cellulose nanofibers after the firing step described later.
The catalyst dried product obtained in the drying step exhibits catalytic performance, and a molded product thereof can be used as a catalyst molded product, but it is preferable because the performance as a catalyst is improved by firing. In the present invention, those after firing are collectively referred to as catalyst molded products.
The molding method is not particularly limited, and examples thereof include known extrusion molding, tableting molding, support molding, rolling granulation, and the like. Of these, tableting and extrusion molding are preferable from the viewpoint of catalyst productivity, and extrusion molding is more preferable from the viewpoint of forming pores advantageous for producing the target product in the catalyst molded body. The shape of the catalyst molded product is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a ring shape (cylindrical shape), a star shape, and the like, and among them, a spherical shape, a cylindrical shape, and a ring shape having high mechanical strength are preferable. ..
By further containing a binder in addition to the cellulose nanofibers, the catalyst molded body of the present invention has improved moldability and can stably obtain a molded body having a desired shape.

(Baking process)
It is preferable to bake the catalyst-dried product obtained in the drying step or the catalyst-molded product obtained in the molding step from the viewpoint of the yield of the target product. The firing temperature is usually 200 to 600 ° C., the lower limit is preferably 300 ° C. or higher, and the upper limit is preferably 500 ° C. or lower. The calcination conditions are not particularly limited, but the calcination is usually carried out under oxygen, air or nitrogen flow. The firing time is appropriately set depending on the target catalyst, but is preferably 0.5 to 40 hours, more preferably 1 to 40 hours.

[Method for producing unsaturated aldehydes and unsaturated carboxylic acids]
The method for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to the present invention is propylene, isobutylene, and primary in the presence of a catalyst molded product containing the unsaturated aldehyde and the catalyst for producing the unsaturated carboxylic acid according to the present invention. Gas-phase catalytic oxidation of butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen. According to these methods, unsaturated aldehydes and unsaturated carboxylic acids can be produced in high yields.
The unsaturated aldehydes and unsaturated carboxylic acids produced correspond to propylene, isobutylene, primary butyl alcohols, tertiary butyl alcohols or methyl tertiary butyl ethers, 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 butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether is methacrolein, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether. The unsaturated carboxylic acid corresponding to 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, as a representative example, a method for producing methacrolein and methacrylic acid by gas-phase catalytic oxidation of isobutylene with molecular oxygen in the presence of a catalyst molded product produced by the method according to the present invention will be described.
In the above method, methacrolein and methacrylic acid are produced by contacting a raw material gas containing isobutylene and molecular oxygen with a catalyst molded product according to the present invention. A fixed bed reactor can be used for this reaction. The reaction can be carried out by filling the reaction tube with a catalyst molded product and supplying the raw material gas to the reactor. The catalyst molded body layer may be one layer, or a plurality of catalyst molded bodies having different activities may be divided into a plurality of layers and filled. Further, the catalyst molded product may be diluted with an inert carrier and filled in order to control the activity.
The concentration of isobutylene 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 concentration of molecular oxygen in the raw material gas is preferably 0.1 to 5 mol with respect to 1 mol of isobutylene, the lower limit is 0.5 mol or more, and the upper limit is more preferably 3 mol or less. As the molecular oxygen source, air is preferable from the viewpoint of economy. If necessary, a gas enriched with molecular oxygen by adding pure oxygen to air may be used.
The raw material gas may be isobutylene and molecular oxygen diluted 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 product is preferably 0.5 to 10 seconds, the lower limit is 1 second or more, and the upper limit is 6 seconds or less. The reaction pressure is preferably 0.1 to 1 MPa (G). However, (G) means that it is a gauge pressure. The reaction temperature is preferably 200 to 420 ° C., the lower limit is 250 ° C. or higher, and the upper limit is 400 ° C. or lower.

[Method for producing unsaturated carboxylic acid]
In the method for producing an unsaturated carboxylic acid according to the present invention, (meth) acrolein is vapor-phase catalytically oxidized with molecular oxygen in the presence of a catalyst molded product containing the unsaturated carboxylic acid production catalyst according to the present invention. According to these methods, unsaturated carboxylic acids can be produced in high yield.
The unsaturated carboxylic acid 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" indicates acrolein and methacrolein, and "(meth) acrylic acid" indicates acrylic acid and methacrylic acid. From the viewpoint of the yield of the target product, it is preferable that the (meth) acrolein and the (meth) acrylic acid are methacrolein and methacrylic acid, respectively.

Hereinafter, as a representative example, a method for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of a catalyst molded product produced by the method according to the present invention will be described.
In the above method, methacrylic acid is produced by contacting a raw material gas containing methacrolein and molecular oxygen with a catalyst molded product according to the present invention. A fixed bed reactor can be used for this reaction. The reaction can be carried out by filling the reaction tube with a catalyst molded product and supplying the raw material gas to the reactor. The catalyst molded body layer may be one layer, or a plurality of catalyst molded bodies having different activities may be divided into a plurality of layers and filled. Further, the catalyst molded product may be diluted with an inert carrier and filled in order to control the activity.

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 raw material, methacrolein, may contain a small amount of impurities such as lower saturated aldehydes that do not substantially affect this reaction.
The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol per 1 mol of methacrolein, more preferably 0.5 mol or more at the lower limit and 3 mol or less at the upper limit. As the molecular oxygen source, air is preferable from the viewpoint of economy. If necessary, a gas enriched with molecular oxygen by adding pure oxygen to air may 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 higher yield. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, more preferably 1% by volume or more at the lower limit and 40% by volume or less at the upper limit.
The contact time between the raw material gas and the catalyst for producing methacrylic acid is preferably 1.5 to 15 seconds. The reaction pressure is preferably 0.1 to 1 MPa (G). However, (G) means that it is a gauge pressure. The reaction temperature is preferably 200 to 450 ° C., the lower limit is 250 ° C. or higher, and the upper limit is 400 ° C. or lower.

[Manufacturing method of unsaturated carboxylic acid ester]
The method for producing an unsaturated carboxylic acid ester according to the present invention esterifies the unsaturated carboxylic acid produced by the method according to the present invention. That is, the method for producing an unsaturated carboxylic acid ester according to the present invention includes a step of producing an unsaturated carboxylic acid by the method according to the present invention and a step of esterifying the unsaturated carboxylic acid. According to these methods, unsaturated carboxylic acids obtained by vapor phase catalytic oxidation of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether, or vapor phase catalytic oxidation of (meth) acrolein. Unsaturated carboxylic acid esters can be obtained using acids.
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 obtained unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. The reaction can 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 to 200 ° C.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" indicates "mass part".

(Falling powder rate)
The falling pulverization rate, which is an index of the mechanical strength of the catalyst molded product, was measured by the following method. 100 g of the catalyst molded body is dropped from the upper opening of a stainless steel cylinder having an inner diameter of 27.5 mm and a length of 6 m, which is installed so as to be vertical in the longitudinal direction and whose lower opening is closed by a stainless steel plate. It was filled in a cylinder. Of the catalyst molded bodies recovered by opening the lower opening, the mass of the one that did not pass through the sieve having a mesh opening of 1 mm was defined as αg, and the falling powdering rate was calculated by the following formula. The smaller the falling powder ratio, the higher the mechanical strength, and the larger the fall powder rate, the lower the mechanical strength. The falling pulverization rate in Table 1 is an average value of the falling pulverization rates measured for each catalyst molded body after producing the catalyst molded body 10 times under the same conditions.
Fall powder rate (%) = {(100-α) / 100} × 100

(Analysis of raw material gas and products)
Analysis of the source gas and products was performed using 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) / A × 100
Here, A is the number of moles of isobutylene supplied, B is the number of moles of methacrolein produced, and C is the number of moles of methacrylic acid produced.
In Examples 1 to 3 and Comparative Examples 1 to 3, only the case where the raw material is isobutylene is shown, but even when tertiary butyl alcohol is used as the raw material, it is rapidly dehydrated to isobutylene at the inlet portion of the reactor. The same result as when isobutylene is used as a raw material can be obtained.
Further, in Example 4 and Comparative Examples 4 to 6, the yield of methacrylic acid produced is 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 results by a scanning electron microscope. Specifically, a dispersion liquid dispersed in pure water so that the content of cellulose nanofibers was 0.05% by mass was cast on a wafer and dried, and observed with a scanning electron microscope. An axis of arbitrary vertical and horizontal image width was assumed in the observation field of view, and the sample and the magnification were adjusted so that 20 to 100 fibers intersected the axis, and the image was acquired. After obtaining the images, two random axes in the vertical and horizontal directions were drawn per image, and the fiber diameter values were read for any 20 fibers from the fibers intersecting each axis. In this way, images of three non-overlapping surface portions are taken with a scanning electron microscope, and the value of the fiber diameter of the fiber intersecting each of the two axes is read to obtain information on the fiber diameter of 120 fibers. rice field. The average fiber diameter was calculated from the arithmetic mean of the obtained fiber diameters with two significant figures.

(Composition ratio of catalyst components)
The molar ratio of each element was determined by analyzing the component in which the catalyst component was dissolved in aqueous ammonia by ICP emission spectrometry. The molar ratio of ammonium roots was determined by analyzing the catalytic components by the Kjeldahl method.

(Cellulose nanofiber content)
The content of cellulose nanofibers in the catalyst molded product was calculated by the following formula (III).
Cellulose nanofiber content [% by mass] = (M2 / M1) × 100 (III)
In the above formula (III), the mass M1 of the catalyst molded body was taken as the total amount of the catalyst dry body, hydroxypropylmethylcellulose and cellulose nanofibers charged. The mass M2 of the cellulose nanofibers was taken as the amount of the cellulose nanofibers charged.

[Example 1]
To 1000 parts of pure water, 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 were added and stirred by heating (Liquid A). ). Separately, 114.4 parts of ferric nitrate, 274.7 parts of cobalt nitrate and 35.1 parts of zinc nitrate were sequentially added and dissolved in 1000 parts of pure water (Liquid B). The catalyst raw material liquid obtained by adding the liquid B to the liquid A is dried using a parallel flow type spray dryer under the conditions of a dryer inlet temperature of 250 ° C. and a rotary disk for slurry spraying of 13,000 rpm, and average particles are obtained. A dried catalyst having a diameter of 46 μm was obtained. The composition of the catalyst excluding oxygen in the dried catalyst is Mo ₁₂ W _0.2 Bi _1.2 Fe _1.2 Sb _0.8 Co _4.0 Zn _0.5 K _0.1 (NH ₄ ) _12. It was _3.3.
A dual-arm type sigma blade is provided with a dispersion liquid in which 4 parts of hydroxypropylmethylcellulose and 1 part of cellulose nanofibers having an average fiber diameter of 40 nm are dispersed in 45 parts of pure water with respect to 100 parts of the catalyst dry body. The mixture was kneaded with a batch-type kneader until it became clay-like, and a mixture was obtained.
The obtained mixture was extruded using a plunger type extruder to form a ring having an outer diameter of 5 mm, an inner diameter of 2 mm and a length of 5.5 mm, and then dried at 90 ° C. for 12 hours in a hot air dryer. A catalyst molded product was obtained. Table 1 shows the measurement results of the falling powdering rate of the catalyst molded product.
Subsequently, the catalyst molded product was filled in a reaction tube and calcined at 450 ° C. for 3 hours under air flow. Then, using raw materials gas of 5% by volume of isobutylene, 12% by volume of oxygen, 10% by volume of water vapor and 73% by volume of nitrogen, the gas phase contact oxidation of isobutylene was carried out under normal pressure at a reaction temperature of 340 ° C. and a contact time of 3.6 seconds. The reaction was carried out. 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]
In Example 1, a catalyst molded body was produced in the same manner as in Example 1 except that the amount of cellulose nanofibers dispersed in pure water was 0.5 part, and the falling pulverization rate was measured, followed by The catalyst molded body was fired and the reaction was evaluated. The results are shown in Table 1.

[Example 3]
In Example 1, a catalyst molded body was produced in the same manner as in Example 1 except that the amount of cellulose nanofibers dispersed in pure water was 0.25 parts, and the falling pulverization rate was measured, followed by The catalyst molded body was fired and the reaction was evaluated. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, a catalyst molded product was produced in the same manner as in Example 1 except that the cellulose nanofiber dispersion was not mixed with the dried catalyst, but 45 parts of pure water was mixed instead. Was subsequently measured, and then the catalyst molded product was fired and the reaction was evaluated. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, the same as in Example 1 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 liquid with the catalyst molded body. A catalyst molded body was manufactured, the falling pulverization rate was measured, and then the catalyst molded body was fired and the reaction was evaluated. The results are shown in Table 1.

[Comparative Example 3]
Same as 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 liquid in the catalyst molded body. The catalyst molded body was produced and the falling pulverization rate was measured, and then the catalyst molded body was fired and the reaction was evaluated. The results are shown in Table 1.

[Example 4]
1000 parts of molybdenum trioxide, 34 parts of ammonium metavanadate, 80 parts of 85 mass% phosphoric acid aqueous solution and 7 parts of copper nitrate are dissolved in 4000 parts of pure water, and the temperature is raised to 95 ° C. with stirring to raise the liquid temperature to 95. The mixture was stirred for 3 hours while maintaining the temperature at ° C. After cooling to 90 ° C., a solution prepared by dissolving 124 parts of cesium-polycarbonate in 200 parts of pure water was added and stirred for 15 minutes while stirring using a rotary blade stirrer. Then, a solution prepared by dissolving 92 parts of ammonium carbonate in 200 parts of pure water was added, and the mixture was further stirred for 20 minutes. The catalyst raw material liquid obtained as described above was dried using a parallel flow type spray dryer under the conditions of a dryer inlet temperature of 300 ° C. and a rotary disk for slurry spraying of 18,000 rpm to have an average particle diameter of 25 μm. A catalyst dried product was obtained. The composition of the catalyst of the dried catalyst excluding oxygen is P _1.2 Mo ₁₂ V _0.5 Cu _0.05 Cs _1.1 (NH ₄ ) _3.8 .
For 100 parts of the catalyst dry body, 4 parts of hydroxypropyl cellmethylrose and 0.5 part of cellulose nanofibers having an average fiber diameter of 20 nm are dispersed in 30 parts of pure water in a double-armed type. The mixture was kneaded with a batch-type kneader equipped with a sigma blade until it became clay-like, and a mixture was obtained.
The obtained mixture is extruded using a plunger type extruder, formed into a cylinder having an outer diameter of 6 mm and a length of 5 mm, and then catalyst-molded by firing at 90 ° C. for 12 hours in a hot air dryer. I got a body. Table 2 shows the measurement results of the falling powdering rate of the catalyst molded product.
Subsequently, the catalyst molded product was filled in a reaction tube and calcined at 380 ° C. for 10 hours under air flow. Next, using raw materials gas of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor, and 55% by volume of nitrogen, gas phase contact of methacrolein was carried out under normal pressure at a reaction temperature of 305 ° C. and a contact time of 7.1 seconds. An oxidation reaction was carried out. The product was collected and analyzed by gas chromatography to determine the yield of methacrylic acid. The results are shown in Table 2.

[Comparative Example 4]
In Example 4, the catalyst molded body was produced in the same manner as in Example 4 except that the cellulose nanofiber dispersion was not mixed with the dried catalyst, but 30 parts of pure water was mixed instead. Was subsequently measured, and then the catalyst molded product was fired and the reaction was evaluated. The results are shown in Table 2.

[Comparative Example 5]
In Example 4, the same 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 liquid with the catalyst dry body. A catalyst molded body was manufactured, the falling pulverization rate was measured, and then the catalyst molded body was fired and the reaction was evaluated. The results are shown in Table 2.

[Comparative Example 6]
In Example 1, the same as in Example 1 except that 45 parts of pure water and 8 parts of crystalline cellulose having an average particle diameter of 50 μm were mixed instead of mixing the cellulose nanofiber dispersion liquid with the catalyst molded body. A catalyst molded body was manufactured, the falling pulverization rate was measured, and then the catalyst molded body was fired and the reaction was evaluated. The results are shown in Table 1.

_{As shown in Table 1, Mo 12} W _0.2 Bi _1.2 Fe _1.2 Sb _0.8 Co _4.0 Zn _0.5 K _0.1 (NH ₄ ) ₁₂ contained in the formula (I). _In Examples 1 to 3 containing cellulose nanofibers having an average fiber diameter of 1 to 300 nm in the catalyst molded body when the catalyst component having a composition ratio of 3 was used, the falling powder ratio was low and the mechanical strength was high. A catalyst molded product was obtained, and the total yields of methacrolein and methacrolein were also high. On the other hand, Comparative Examples 1 and 2 in which the catalyst molded product did not contain cellulose nanofibers had the same total yields of methacrolein and methacrylic acid as in Examples 1 to 2, but had a high falling powder ratio and low mechanical strength. rice field. Therefore, as shown in Comparative Example 3, when the mechanical strength was set to the same level as in Example 1 with a binder other than cellulose nanofibers, the total yield of methacrolein and methacrylic acid was significantly reduced.
Since the catalyst compacts of Examples 1 to 3 have high yields of methacrolein and methacrylic acid and high mechanical strength, the catalyst is less likely to be pulverized or cracked in continuous operation, so that the increase in differential pressure is suppressed. High yield can be maintained for a long period of time. Therefore, the catalyst life is long, and the frequency of catalyst replacement can be reduced.

_{Similarly, when a catalyst component having a composition ratio of P 1.2} Mo ₁₂ V _0.5 Cu _0.05 Cs _1.1 (NH ₄ ) _3.81 contained in the formula (II) is used, the catalyst molded product is used. In Example 4 containing cellulose nanofibers having an average fiber diameter of 1 to 300 nm, a catalyst molded product having a low falling powder ratio and high mechanical strength was obtained, and the methacrylic acid yield was also high. On the other hand, in Comparative Example 4 in which the catalyst molded product did not contain cellulose nanofibers, the falling powdering rate was high, the mechanical strength was low, and the methacrylic acid yield was also slightly low. In Comparative Example 5, the yield of methacrylic acid was about the same as that of Example 4, but the falling powdering rate was high and the mechanical strength was low. Therefore, as shown in Comparative Example 6, when the mechanical strength was set to the same level as in Example 4 with a binder other than cellulose nanofibers, the yield of methacrylic acid decreased.
Since the catalyst molded product of Example 4 has a high yield of methacrylic acid and high mechanical strength, the catalyst is less likely to be pulverized or cracked in continuous operation, so that an increase in differential pressure is suppressed and a high yield is obtained over a long period of time. Can be maintained. Therefore, the catalyst life is long, and the frequency of catalyst replacement can be reduced.
A methacrylic acid ester can be obtained by esterifying the methacrylic acid obtained in this example.

According to the present invention, it is possible to provide a catalyst molded product having a high yield and high mechanical strength. By using such a catalyst molded product, it is possible to provide a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid that can maintain a high yield for a long period of time.

Although the present invention has been specifically described above with reference to embodiments and examples, the present invention is not limited thereto, and those skilled in the art will understand the configuration and details of the present invention within the scope of the present invention. You can make various possible changes.
This application claims priority on the basis of Japanese application Japanese Patent Application No. 2018-046637 filed on March 14, 2018 and incorporates all of its disclosures herein.

Claims (17)

A catalyst molded body containing a catalyst component capable of producing an unsaturated aldehyde and / or an unsaturated carboxylic acid by vapor phase catalytic oxidation with molecular oxygen, and cellulose nanofibers having an average fiber diameter of 1 to 300 nm. When the mass of the catalyst molded product is M1 [g] and the mass of the cellulose nanofibers is M2 [g], the cellulose nanofiber content calculated by the following formula (III) is 0.1 to 5% by mass. The catalyst molded body according to claim 1.
Cellulose nanofiber content [% by mass] = (M2 / M1) × 100 (III) The catalyst molded product according to claim 1 or 2, further containing a binder. The catalyst molded product according to claim 3, wherein the binder is water-soluble. The catalyst molded product according to claim 3, wherein the binder is a water-soluble organic binder. The catalyst component has a composition represented by the following formula (I), and is not capable of gas-phase catalytic oxidation of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen. The catalyst molded product according to any one of claims 1 to 5 , which is a catalyst for producing a saturated aldehyde and an unsaturated carboxylic acid.
Mo _a1 Bi _b1 Fe _c1 A _d1 E1 _e1 G1 _f1 J1 _g1 Si _h1 (NH ₄ ) _i1 O _j1 (I)
In formula (I), Mo, Bi, Fe, Si, NH ₄ and O represent molybdenum, bismuth, iron, silicon, ammonium root and oxygen, respectively, and A is selected from the group consisting of cobalt and nickel. Represents at least one element, E1 represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, nihonium, silver, barium, tin, thallium, thallium and zinc, G1 Represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium, and J1 is from the group consisting of lithium, sodium, potassium, rubidium and cesium. Represents at least one selected element. A1, b1, c1, d1, e1, f1, g1, h1, i1 and j1 represent the molar ratio of each component, and when a1 = 12, b1 = 0.01 to 3, c1 = 0.01 to 5, d1 = 0.01 to 12, e1 = 0 to 8, f1 = 0 to 5, g1 = 0.001 to 2, h1 = 0 to 20, i1 = 0 to 30 Yes, j1 is the molar ratio of oxygen required to satisfy the valence of each component.) Any of claims 1 to 5 , wherein the catalyst component has a composition represented by the following formula (II) and is a catalyst for producing an unsaturated carboxylic acid in which (meth) acrolein is vapor-phase catalytically oxidized by molecular oxygen. The catalyst molded body according to item 1.
P _a2 Mo _b2 V _c2 Cu _d2 E2 _e2 G2 _f2 J2 _g2 (NH ₄ ) _h2 O _i2 (II)
(In the formula (II), P, Mo, V, Cu, NH ₄ and O represent phosphorus, molybdenum, vanadium, copper, ammonium root and oxygen, respectively. E2 represents antimony, bismuth, arsenic, germanium and zirconium. Represents at least one element selected from the group consisting of, tellurium, silver, selenium, silicon, tungsten and boron. G2 represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium. , Titanium, tin, tarium, lead, nihonium, indium, sulfur, palladium, gallium, cerium and lanthanum represents at least one element selected from the group. J2 is selected from the group consisting of potassium, rubidium and cesium. It represents at least one kind of element. A2, b2, c2, d2, e2, f2, g2, h2 and i2 represent the molar ratio of each component, and when b2 = 12, a2 = 0.1 to 3, c2 = 0.01 to 3, d2 = 0.01 to 2, e2 is 0 to 3, f2 = 0 to 3, g2 = 0.01 to 3, h2 = 0 to 30, and i2 is the valence of each of the above components. The molar ratio of oxygen required to satisfy.) A method of manufacturing a shaped catalyst body according to any one of claims 1 to 6 comprising the firing step, the manufacturing method of the catalyst bodies. The method for producing a catalyst molded product according to claim 8 , which comprises an extrusion molding step. The method for producing a catalyst molded product according to claim 7, wherein the method for producing the catalyst molded product includes a firing step. The method for producing a catalyst molded product according to claim 10, which comprises an extrusion molding step. Unsaturated aldehydes and unsaturated aldehydes that undergo gas-phase catalytic oxidation of propylene, isobutylene, primary butyl alcohols, tertiary butyl alcohols or methyl tertiary butyl ethers with molecular oxygen in the presence of the catalyst compact according to claim 6. A method for producing a saturated carboxylic acid. A method for producing an unsaturated carboxylic acid, which comprises vapor-phase catalytic oxidation of (meth) acrolein with molecular oxygen in the presence of the catalyst molded product according to claim 7. A method for producing an unsaturated carboxylic acid ester that esterifies an unsaturated carboxylic acid produced by the method according to claim 12 or 13. A method for producing an unsaturated carboxylic acid ester, which comprises a step of producing an unsaturated carboxylic acid by the method according to claim 12 or 13, and a step of esterifying the unsaturated carboxylic acid. Gas-phase catalytic oxidation of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen in the presence of the catalyst compact produced by the method according to claim 8 or 9. A method for producing an unsaturated aldehyde and an unsaturated carboxylic acid. A method for producing an unsaturated carboxylic acid, which comprises vapor-phase catalytic oxidation of (meth) acrolein with molecular oxygen in the presence of the catalyst molded product produced by the method according to claim 10 or 11.