CN113613785B - Catalyst molded body and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same - Google Patents

Catalyst molded body and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same Download PDF

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Publication number
CN113613785B
CN113613785B CN202080023586.7A CN202080023586A CN113613785B CN 113613785 B CN113613785 B CN 113613785B CN 202080023586 A CN202080023586 A CN 202080023586A CN 113613785 B CN113613785 B CN 113613785B
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catalyst
molded body
catalyst molded
carboxylic acid
unsaturated carboxylic
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CN113613785A (en
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渡边拓朗
井口敏行
菅野充
近藤正英
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B01J35/60—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • C07C51/23—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Abstract

A catalyst molded body for use in producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by an oxidation reaction, which satisfies both the following requirements (A) and (B). (A) The molded article density of the catalyst molded article is 2.25g/mL or less in a state before filling the catalyst molded article in the reactor. (B) At least one of the following conditions (B-1) and (B-2) is satisfied: (B-1) the surface of the catalyst molded body has an arithmetic average roughness (Ra) of 3.0 μm or less as defined in JIS B-0601-2001. (B-2) the maximum height (Rz) defined in JIS B-0601-2001 of the surface of the catalyst molded body is 15 μm or less.

Description

Catalyst molded body and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same
Technical Field
The present invention relates to a catalyst molded body and a method for producing an unsaturated aldehyde and/or an unsaturated carboxylic acid using the catalyst molded body.
Background
In the process for producing an unsaturated aldehyde or an unsaturated carboxylic acid, the catalyst is generally molded into a spherical shape having a diameter of about 2 to 20mm, a cylindrical or columnar molded body having a diameter of about 2 to 10mm and a length of about 2 to 20mm, and is used for the reaction.
As a method for improving the method for producing a catalyst molded article to increase the yields of unsaturated aldehydes and unsaturated carboxylic acids, for example, patent document 1 proposes a method for producing a catalyst in which a catalyst component containing molybdenum and bismuth is mixed with 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 and molded.
Patent document 2 proposes a method for producing a catalyst for methacrylic acid production, comprising: a step of drying an aqueous mixture of a raw material compound containing at least molybdenum and phosphorus as catalyst components and containing the catalyst components to produce a dried product having an apparent density (X) of 1.00 to 1.80kg/L, and a step of molding the dried product or a mixture containing the dried product to produce a molded product having a density (Y) of 1.60 to 2.40kg/L and a ratio (X/Y) of the apparent density (X) to the molded product density (Y) of 0.50 to 0.80.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2007-000803
Patent document 2: international publication No. 2012/141076
Disclosure of Invention
However, the yields of unsaturated aldehydes and unsaturated carboxylic acids are improved, and even when the catalyst molded article modified by the above method is used, the production is still insufficient. Therefore, further improvement in yield is desired.
The purpose of the present invention is to provide a catalyst molded body that can produce an unsaturated aldehyde and an unsaturated carboxylic acid in high yields. The present invention also provides a method for producing an unsaturated aldehyde, an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester using the catalyst molded body.
The present inventors have made intensive studies in view of the above problems, and as a result, have found that the above problems can be solved by using a catalyst molded body having a specific molded body density and surface characteristics, and have completed the present invention.
Specifically, the present invention is the following [1] to [10].
[1] A catalyst molded body for use in producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by an oxidation reaction, which satisfies both the following requirements (A) and (B):
(A) The molded article density of the catalyst molded article is 2.25g/mL or less in a state before filling the catalyst molded article in the reactor.
(B) At least one of the following conditions (B-1) and (B-2) is satisfied:
(B-1) the surface of the catalyst molded body has an arithmetic average roughness (Ra) of 3.0 μm or less as defined in JIS B-0601-2001.
(B-2) the maximum height (Rz) defined in JIS B-0601-2001 of the surface of the catalyst molded body is 15 μm or less.
[2] The catalyst molded body according to [1], wherein at least a part of the surface of the catalyst molded body has a coating layer of an organic polymer compound.
[3] The catalyst molded article according to [2], wherein the organic polymer compound is contained in an amount of 0.001 to 2% by mass.
[4] The catalyst molded body according to any one of [1] to [3], wherein the molded body is an extrusion molded body.
[5] The catalyst molded article according to any one of [1] to [4], which contains a catalyst component having a composition represented by the following formula (I).
Mo a1 Bi b1 Fe c1 A d1 E1 e1 G1 f1 J1 g1 Si h1 (NH 4 ) i1 O j1 (I)
(in the formula (I), mo, bi, fe, si, NH) 4 And 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, 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, j1 is a molar ratio of oxygen required to satisfy the valence of the respective components. )
[6] The catalyst molded article according to any one of [1] to [4], which contains a catalyst component having a composition represented by the following formula (II).
P a2 Mo b2 V c2 Cu d2 E2 e2 G2 f2 J2 g2 (NH 4 ) h2 O i2 (II)
(P, mo, V, cu, NH in the above formula (II)) 4 And O represents phosphorus, molybdenum, vanadium, copper, ammonium and oxygen, respectively. E2 represents at least 1 element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. G2 represents at least 1 element selected 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. J2 represents at least 1 element selected from potassium, rubidium and cesium. a2, b2, c2, d2, e2, f2,g2, h2 and i2 represent the molar ratio of the components, 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 molar ratio of oxygen required to satisfy the valence of the above components when b2=12. )
[7] A process for producing an unsaturated aldehyde and an unsaturated carboxylic acid, wherein propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether is subjected to vapor phase catalytic oxidation with molecular oxygen in the presence of the catalyst molded body described in [5 ].
[8] A process for producing an unsaturated carboxylic acid, wherein (meth) acrolein is subjected to gas-phase catalytic oxidation with molecular oxygen in the presence of the catalyst molded article described in [6 ].
[9] A process for producing an unsaturated carboxylic acid ester, wherein the unsaturated carboxylic acid produced by the process of [7] or [8] is esterified.
[10] A method for producing an unsaturated carboxylic acid ester, comprising:
the process for producing an unsaturated carboxylic acid by the method of [7] or [8], and
and esterifying the unsaturated carboxylic acid.
According to the present invention, a catalyst molded body capable of producing an unsaturated aldehyde and/or an unsaturated carboxylic acid in high yield can be provided.
Detailed Description
[ catalyst molded body ]
One embodiment of the catalyst molded body of the present invention is a catalyst molded body used in producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by an oxidation reaction, wherein the catalyst molded body has a molded body density of 2.25g/mL or less in a state before being filled in a reactor, and the surface of the catalyst molded body has an arithmetic average roughness (Ra) of 3.0 μm or less as specified in JIS B-0601-2001.
In addition, another embodiment of the catalyst molded body of the present invention is a catalyst molded body used in producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by an oxidation reaction, wherein the molded body density of the catalyst molded body is 2.25g/mL or less in a state before filling in a reactor, and the maximum height (Rz) specified in JIS B-0601-2001 on the surface of the catalyst molded body is 15 μm or less.
In addition, another embodiment of the catalyst molded body of the present invention is a catalyst molded body used in producing an unsaturated aldehyde and/or an unsaturated carboxylic acid by an oxidation reaction, wherein the molded body density of the catalyst molded body is 2.25g/mL or less in a state before filling in a reactor, and the arithmetic average roughness (Ra) defined in JIS B-0601-2001 of the surface of the catalyst molded body is 3.0 μm or less and the maximum height (Rz) defined in JIS B-0601-2001 is 15 μm or less.
When such a catalyst molded body is filled in a reactor, the number of catalyst molded bodies that can be filled per unit volume increases, and thus the amount of catalyst active ingredient per unit volume in the reactor increases. As a result, the reactivity in the production of unsaturated aldehyde and/or unsaturated carboxylic acid is improved, and the yield of the target product obtained is improved. In addition, by increasing the amount of the catalyst active ingredient per unit volume, an effect of increasing the continuous reaction time is also obtained.
(element A: molded article Density of catalyst molded article)
The molded article density of the catalyst molded article of the present invention is 2.25g/mL or less in the state before filling in the reactor. Thus, a large number of pores are formed in the catalyst molded body, and the selectivity of the target product is improved. The density of the molded article is more preferably 2.20g/mL or less, and still more preferably 2.15g/mL or less. The density of the molded article is usually 1.0g/mL or more.
Here, the molded article density is a value calculated by dividing the mass (g) of each 1 catalyst molded article by the volume (mL), and performing arithmetic average on 100 catalyst molded articles by this calculation.
( Element (B): arithmetic average roughness (Ra) and maximum height (Rz) of the surface of the catalyst molded body )
As described above, the selectivity of the target product is improved by the molded body density of the catalyst molded body being 2.25g/mL or less, but the more pores are formed inside the catalyst molded body, the smaller the amount of the catalyst active ingredient per 1 catalyst molded body, and the lower the reactivity. In other words, when the same number of catalyst molded bodies having the same shape and size are used, the reaction rate of the raw material decreases in the case of filling the catalyst molded bodies having a molded body density of 2.25g/mL or less and the case of filling the catalyst molded bodies having a molded body density of more than 2.25g/mL and carrying out the reaction, although the selectivity of the former target product increases, the reaction activity is low. Further, since the total amount of the catalyst active ingredient is reduced, there is also a problem that the continuous reaction time is shorter than that of the conventional catalyst molded body.
In order to solve the above problems, the present inventors have focused on the surface characteristics of the catalyst molded body, and have found that when the arithmetic average roughness (Ra) of the surface of the catalyst molded body in the state before filling in the reactor is 3.0 μm or less (element (B-1)) or when the maximum height (Rz) of the surface is 15 μm or less (element (B-2)) in addition to the molded body density of the catalyst molded body being 2.25g/mL or less, the number of catalyst molded bodies that can be filled per unit volume can be increased, and thus the problem that the total amount of the catalyst active components that can be filled in the reactor is small can be solved. More specifically, it was found that when the molded catalyst body had a molded catalyst density of more than 2.25g/mL, the molded catalyst was densely packed under the weight of the catalyst, whereas when the molded catalyst had a molded catalyst density of 2.25g/mL or less, the molded catalyst was light and could not be densely packed under the weight of the catalyst. However, it was found that when the catalyst molded body has specific surface characteristics as described above, the catalyst molded body can be densely packed, and the number of the packed catalyst molded body in the reactor can be increased. This achieves both effects of an improvement in selectivity and an improvement in yield, and can solve the problem of the reaction duration.
From the viewpoint of the number of catalyst molded bodies that can be filled in a unit volume, the surface of the catalyst molded body preferably has an arithmetic average roughness (Ra) of 3.0 μm or less and a maximum height (Rz) of 15 μm or less. The upper limit of the arithmetic average roughness (Ra) of the surface of the catalyst molded body is preferably 2.8 μm or less, more preferably 2.6 μm or less. However, the arithmetic average roughness (Ra) of the surface is usually 0.5 μm or more. The upper limit of the maximum height (Rz) of the surface is preferably 14 μm or less, more preferably 13 μm or less. However, the maximum height (Rz) of the surface is usually 3 μm or more.
Here, the arithmetic average roughness (Ra) is an average representing an absolute value at a reference length. The maximum height (Rz) is the sum of the height of the highest mountain and the depth of the deepest valley obtained from the contour curve at the reference length. Both can be measured in accordance with JISB-0601-2001.
The measurement positions of the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the molded catalyst of the present invention are measured on the surface having the largest surface area in the surface that can be in contact with other molded articles when the molded article has a shape having a plurality of surfaces. For example, if the catalyst molded body is cylindrical, the surface area of the circular portion is compared with the surface area of the side portion, and the measurement is performed on a surface having a large surface area. In addition, if the catalyst molded body is cylindrical, the surface area of the annular portion and the surface area of the portion of the cylindrical side surface are compared with each other as a surface that can be in contact with other molded bodies, and measurement is performed on a surface having a large surface area. This measurement was performed on 10 molded catalyst bodies, and calculated from the arithmetic average thereof.
(surface of catalyst molded body)
The catalyst molded article of the present invention may be subjected to surface treatment as needed, and the arithmetic average roughness (Ra) and the maximum height (Rz) may be adjusted. From the viewpoint of mechanical strength of the surface of the catalyst molded body, it is preferable that at least a part of the surface has a coating layer of an organic polymer compound. Further, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the catalyst molded body can be adjusted to desired values by forming the coating layer.
Specific examples of the organic polymer compound include saccharides and synthetic resins. Examples of the saccharides include monosaccharides such as threose, arabinose, xylose, galactose, ribose, glucose, sorbose, fructose, and mannose, sugars such as sucrose, lactose, maltose, trehalose, cellobiose, isomaltose, isotrehalose, neotrehalose, disaccharides such as isolactose, melibiose, and palatinose, and polysaccharides such as starch, glycogen, pullulan, water-soluble cellulose, and water-insoluble cellulose. Examples of the synthetic resin include polyvinyl alcohol, polyethylene, polypropylene, polystyrene, phenolic resin, and epoxy resin. One kind of these may be used, or two or more kinds may be used in combination. The molecular weight of the organic polymer compound is preferably 2 to 40 tens of thousands, the lower limit is more preferably 3 tens of thousands or more, and the upper limit is more preferably 30 tens of thousands or less.
From the viewpoint of mechanical strength of the catalyst molded body, it is more preferable to have a coating layer of saccharide on at least a part of the surface of the catalyst molded body, and it is further preferable to have a coating layer of polysaccharide, and it is particularly preferable to have at least 1 coating layer selected from pullulan and water-soluble cellulose.
Specific examples of the water-soluble cellulose include methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethyl cellulose, hydroxyethylmethyl cellulose, hydroxybutyl methylcellulose, ethylhydroxyethyl cellulose, and salts thereof. One kind of these may be used, or two or more kinds may be used in combination.
The catalyst molded article preferably contains 0.001 to 2 mass% of an organic polymer compound. The mechanical strength of the catalyst molded body is increased by setting the content of the organic polymer compound to 0.001 mass% or more. In addition, the content of the organic polymer compound is set to 2 mass% or less, whereby a sufficient amount of the catalyst active ingredient is contained in the catalyst molded body. The upper limit of the content of the organic polymer compound is more preferably 1.5 mass% or less, and still more preferably 1 mass% or less.
(type and shape of catalyst molded body)
The type of the catalyst molded body is not particularly limited, and examples thereof include extrusion molded bodies, tabletting molded bodies, supporting molded bodies, rotary granulating bodies, and the like. Among them, extrusion molded articles are preferable in terms of the ease with which the density of the molded articles can be adjusted. Here, the extrusion molded body means a molded body molded into a predetermined shape by extrusion under pressure of a catalyst placed in a mold frame. The shape of the catalyst molded body is not particularly limited, and examples thereof include spherical, cylindrical (annular), star-shaped, and the like, and among them, spherical, cylindrical with high mechanical strength are preferable.
(catalyst component in catalyst molded article for production of unsaturated aldehyde and unsaturated carboxylic acid)
From the viewpoint of the yields of unsaturated aldehydes and unsaturated carboxylic acids, the catalyst molded body used in the production of unsaturated aldehydes and unsaturated carboxylic acids of the present invention preferably contains a catalyst component having 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 ICP emission analysis. The molar ratio of ammonium groups 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)
Mo, bi, fe, si, NH in formula (I) 4 And 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, 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, j1 is a molar ratio of oxygen required to satisfy the valence of the respective components.
In the present invention, "ammonium group" means a group which is changed to an ammonium ion (NH) 4 + ) Ammonia (NH) 3 ) And ammonium contained in an ammonium-containing compound such as an ammonium salt.
(catalyst component in molded catalyst for unsaturated carboxylic acid production)
From the viewpoint of the yield of unsaturated carboxylic acid, the catalyst molded body used in the production of unsaturated carboxylic acid of the present invention preferably contains a catalyst component having a composition represented by the following formula (II).
P a2 Mo b2 V c2 Cu d2 E2 e2 G2 f2 J2 g2 (NH 4 ) h2 O i2 (II)
P, mo, V, cu, NH in the above formula (II) 4 And O represents phosphorus, molybdenum, vanadium, copper, ammonium and oxygen, respectively. E2 represents at least 1 element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. G2 represents at least 1 element selected 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. J2 represents at least 1 element selected from potassium, rubidium and cesium. a2, b2, c2, d2, e2, f2, g2, h2 and i2 represent the molar ratio of each component, a2=0.1 to 3, c2=0.01 to 3, d2=0.01 to 2, e2 is 0 to 3, preferably 0.01 to 3, f2=0 to 3, g2=0.01 to 3, h2=0 to 30, and i2 is the molar ratio of oxygen required to satisfy the valence of each component.
[ method for producing molded catalyst body ]
The catalyst molded article of the present invention can be produced according to a known method for producing a catalyst molded article, preferably by a method comprising the following steps (i) to (iii), as long as the density of the molded article is 2.25g/mL or less and the arithmetic average roughness (Ra) of the surface is 3.0 μm or less or the density of the molded article is 2.25g/mL or less and the maximum height (Rz) of the surface is 15 μm or less in the state before filling the catalyst molded article into the reactor.
(i) And a step of preparing a catalyst raw material liquid by mixing a raw material compound of the catalyst component with a solvent.
(ii) And a step of drying the catalyst raw material liquid to obtain a catalyst dried body.
(iii) And a step of molding the catalyst dried body and optionally subjecting the catalyst molded body to a surface treatment to obtain a catalyst molded body.
(Process (i))
In the step (i), a raw material compound of the catalyst component is mixed with a solvent to prepare a catalyst raw material liquid. For example, in the production of a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, a catalyst raw material liquid containing at least molybdenum and bismuth is prepared by mixing a raw material compound of a catalyst component of the catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid with a properly selected solvent. In addition, in the production of a catalyst for producing an unsaturated carboxylic acid, a catalyst raw material liquid containing at least molybdenum and phosphorus is prepared by mixing a raw material compound of a catalyst component of the catalyst for producing an unsaturated carboxylic acid with a properly 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, acetates, ammonium salts, halides, oxy-acids, oxy-acid salts, alkali metal salts, and the like of the respective constituent elements of the catalyst may be used singly 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, bismuth hydroxide, and the like. Examples of the raw material compound of 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. The starting material compound may be used in combination of 1 or 2 or more of the elements constituting the catalyst component.
Examples of the solvent include water, ethanol, and acetone, and water is preferably used from an industrial point of view.
In the production of the catalyst for producing an unsaturated carboxylic acid, the catalyst raw material liquid preferably contains a Keggin-type heteropolyacid containing at least molybdenum and phosphorus from the viewpoint of the selectivity to an unsaturated carboxylic acid. For example, by using an appropriate choice of the addition of the starting compoundsThe Keggin-type heteropoly acid can be stably formed by adjusting the pH of the catalyst raw material liquid to 4 or less, preferably 3 or less by adding nitric acid, oxalic acid or the like appropriately. The structure of the obtained heteropolyacid was determined by infrared absorption analysis using NICOLET6700FT-IR (product name, manufactured by Thermo electronics Co.). When the heteropolyacid salt has a Keggin structure, the obtained infrared absorption spectrum is 1060, 960, 870 and 780cm －1 With characteristic peaks in the vicinity.
(step (ii))
In the step (ii), the catalyst raw material liquid obtained in the step (i) is dried to obtain a catalyst dried body. The method of 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 dry solids, and the like can be employed. Among them, a method of drying using a spray dryer is preferable because particles are obtained simultaneously with drying and the shape of the obtained particles is uniform spherical. The drying conditions vary depending on the drying method, and when a spray dryer is used, the inlet temperature of the dryer is preferably 100 to 500 ℃, and the lower limit is more preferably 200 ℃ or higher, and further preferably 220 ℃ or higher. The upper limit is more preferably 400℃or lower, and still more preferably 370℃or lower. The lower limit of the outlet temperature of the dryer is preferably 100℃or higher, more preferably 105℃or higher. The upper limit is preferably 200℃or lower. The catalyst dried body is preferably dried so that the moisture content is 0.1 to 4.5 mass%. These conditions may be appropriately selected according to the desired shape and size of the catalyst.
When a spray dryer is used, the average particle diameter of the catalyst dried body obtained is preferably 1 to 250. Mu.m. By setting the average particle diameter to 1 μm or more, pores having a diameter suitable for the formation of the target product are formed in the step (iii) described later, 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 body particles per unit volume can be maintained, and the mechanical strength of the catalyst molded body obtained in the step (iii) described later can be improved. The lower limit of the average particle diameter of the catalyst dried body is more preferably 5 μm or more, and the upper limit is more preferably 150 μm or less. The average particle diameter is a volume average particle diameter, and is a value measured by a laser particle size distribution measuring apparatus.
The contact between the sprayed droplets and the hot air may be any of parallel flow, convection, and convection (mixed flow), and in any case, the droplets may be properly dried.
(Process (iii))
In the step (iii), the dried catalyst body obtained in the step (ii) is molded to obtain a molded catalyst body. The catalyst molded body may be surface-treated as needed.
< shaping of catalyst Dry body >
The catalyst dried body is preferably molded after being mixed with a solvent, from the viewpoint of being able to adjust the molded body density of the catalyst molded body. The amount of the solvent to be used is appropriately selected depending on the type of the catalyst dried body, the shape of the particles, and the type of the solvent, and the amount of the solvent to be used is reduced to increase the density of the molded catalyst molded body obtained by decreasing the amount of the solvent to be used relative to the catalyst dried body, and the amount of the solvent to be used relative to the catalyst dried body is increased to decrease the density of the molded catalyst molded body obtained by increasing the amount of the solvent to be used relative to the catalyst dried body. The amount of the solvent to be used is preferably adjusted to be in the range of 10 to 70 parts by mass relative to 100 parts by mass of the catalyst-dried body. When the amount of the solvent to be used is 10 parts by mass or more based on 100 parts by mass of the catalyst-dried body, moldability tends to be improved, and pores effective for production of methacrylic acid in the obtained catalyst molded body tend to be increased. In addition, the use amount of the solvent is 70 parts by mass or less, whereby the adhesion during molding is reduced and the handleability is improved. More preferably, the amount of the solvent to be used is adjusted so that the lower limit is 15 parts by mass or more and the upper limit is 60 parts by mass or less relative to 100 parts by mass of the catalyst-dried body.
The type of the solvent is not particularly limited, and water and an organic solvent are preferable. Examples of the organic solvent include lower alcohols such as methanol, ethanol, propanol, butanol, and isopropanol, acetone, methyl ether, diethyl ether, methyl ethyl ketone, and ethyl acetate. These solvents may be used in an amount of 1 or 2 or more kinds. The solvent preferably contains at least an organic solvent.
In addition, polyvinyl alcohol, an α -glucan derivative, a β -glucan derivative, stearic acid, ammonium nitrate, graphite, water, alcohol, and the like, which are generally used as a molding aid, may be used as needed in molding.
The method for molding the catalyst dried body is not particularly limited. For example, known methods such as extrusion molding, tablet molding, support molding, and rotary granulation are mentioned. Among them, extrusion molding is preferable in that the molded body density of the catalyst molded body can be easily adjusted. As the extrusion molding machine, for example, a screw type extrusion molding machine, a ram type extrusion molding machine, or the like can be used, and a ram type extrusion molding machine can be preferably used.
In extrusion molding, the molded body density of the obtained catalyst molded body is increased by increasing the extrusion pressure, and the molded body density of the obtained catalyst molded body is decreased by decreasing the extrusion pressure. The extrusion pressure is preferably adjusted in the range of 0.1 to 30MPa (G). Wherein, (G) refers to gauge pressure. The extrusion pressure is 0.1MPa (G) or more, whereby a catalyst molded article can be stably produced. In addition, when the extrusion pressure is 30MPa or less, the pores effective for producing methacrylic acid tend to increase in the obtained catalyst molded body. The lower limit of the extrusion pressure is more preferably 0.5MPa (G) or more, still more preferably 1MPa (G) or more, and particularly preferably 2MPa (G) or more. The upper limit of the extrusion pressure is more preferably 20MPa (G) or less, still more preferably 15MPa (G) or less, and particularly preferably 10MPa (G) or less.
Surface treatment of catalyst molded body
The catalyst molded article of the present invention may be treated as necessary to adjust the arithmetic average roughness (Ra) and the maximum height (Rz). Examples of the surface treatment method of the catalyst molded body include a method of coating the surface with an organic polymer compound and a method of spraying a solvent onto the surface and drying the surface. From the viewpoints of imparting mechanical strength and adjusting the arithmetic average roughness (Ra) and maximum height (Rz) of the surface of the catalyst molded body, a method of coating the surface of the catalyst molded body with an organic polymer compound is preferably used, and a method of coating the surface with an organic polymer compound, then spraying a solvent onto the surface, and drying is more preferably used.
Examples of the method of coating the surface of the catalyst molded body with the organic polymer compound include a method of spraying a coating liquid in which the organic polymer compound is dissolved in a solvent into a mist, adhering the coating liquid to the catalyst molded body, and vaporizing and evaporating the solvent. According to this method, coating can be easily and uniformly performed.
Examples of the solvent used in the coating liquid and the solvent sprayed further after the coating include water, alcohol, and an alkaline solution, and water is preferable. The concentration of the organic polymer compound in the coating liquid is preferably 10 mass% or less. This reduces adhesion between the catalyst molded bodies, which is advantageous in terms of handling. The concentration of the organic polymer compound in the coating liquid is usually 0.1 mass% or more. The amount of the solvent sprayed further after spraying of the coating liquid is preferably 0.1 to 3 mass% with respect to the molded catalyst, and the lower limit is more preferably 0.2 mass% or more, and the upper limit is more preferably 2 mass% or less.
As the coating device, a device in which a rotating mechanism is simply attached to a container called a disk such as a coating disk is preferable. By using such an apparatus, the solvent can be removed by spraying the coating liquid into a mist while rotating the catalyst molded body, adhering the coating liquid to the catalyst molded body, and blowing hot air. As the coating device, a sugar coating machine, a coater, or the like for tablets used in the pharmaceutical industry and the food industry can be used.
[ method for producing unsaturated aldehyde and/or unsaturated carboxylic acid ]
In the production of the unsaturated aldehyde and/or unsaturated carboxylic acid, the catalyst molded body obtained in the step (iii) is preferably calcined and used from the viewpoint of the yield of the target product. The calcination may be performed on the dried catalyst body obtained in the step (ii). The calcination temperature is usually 200 to 600 ℃, preferably 300 ℃ or more in the lower limit and 500 ℃ or less in the upper limit. The calcination conditions are not particularly limited, and calcination is usually performed under oxygen, air or nitrogen flow. The calcination time is appropriately set according to the target catalyst, and is preferably 0.5 to 40 hours, more preferably 1 hour or more as the lower limit, and more preferably 40 hours or less as the upper limit.
(Process for producing unsaturated aldehyde and unsaturated carboxylic acid)
The process for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to 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 the molded catalyst body used in the production of an unsaturated aldehyde and an unsaturated carboxylic acid according to the present invention. According to these methods, unsaturated aldehydes and unsaturated carboxylic acids can be produced in high yields.
The unsaturated aldehyde and unsaturated carboxylic acid produced are those corresponding to propylene, isobutylene, primary butanol, tertiary butanol 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 vapor-phase catalytic oxidation of isobutylene with molecular oxygen in the presence of the catalyst molded body produced by the method of the present invention will be described as a representative example.
In the above 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 reactor may be used for this reaction. The reaction can be carried out by filling the reactor with a catalyst molded body 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 packed by dividing them into a plurality of layers. The catalyst molded body may be diluted with an inactive carrier and filled 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 as the lower limit, and still more preferably 10% by volume or less as the upper limit.
The concentration of molecular oxygen in the raw material gas is preferably 0.1 to 5 moles, more preferably 0.5 mole or more in the lower limit, and still more preferably 3 moles or less in the upper limit, relative to 1 mole of isobutylene. As the source of molecular oxygen, air is preferred from the viewpoint of economy. If necessary, a gas in which pure oxygen is added to air to enrich molecular oxygen may be used.
The raw material gas may be a gas obtained by diluting isobutene and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Steam may be further 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, the lower limit is more preferably 1 second or more, and the upper limit is more preferably 6 seconds or less. The reaction pressure is preferably 0.1 to 1MPa (G). Wherein, (G) refers to gauge pressure. The reaction temperature is preferably 200 to 420 ℃, the lower limit is more preferably 250 ℃ or higher, and the upper limit is more preferably 400 ℃ or lower.
(method for producing unsaturated carboxylic acid)
The method for producing an unsaturated carboxylic acid of the present invention is a method in which (meth) acrolein is subjected to gas-phase catalytic oxidation with molecular oxygen in the presence of the molded catalyst used in the production of 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 produced is an unsaturated carboxylic acid obtained by converting an aldehyde group of (meth) acrolein into a carboxyl group, and specifically, (meth) acrylic acid is obtained.
The "(meth) acrolein" means acrolein and methacrolein, and the "(meth) acrylic acid" means 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 vapor-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst molded body produced by the method of the present invention will be described as a representative example.
In the above 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 reactor may be used for this reaction. The reaction can be carried out by filling the reactor with a catalyst molded body 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 packed by dividing them into a plurality of layers. The catalyst molded body may be diluted with an inactive carrier and filled 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, and still more preferably 10% by volume or less. The methacrolein as the raw material may contain a small amount of an impurity that does not substantially affect the reaction, such as a lower saturated aldehyde.
The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 moles, more preferably 0.5 mole or more in the lower limit, and still more preferably 3 moles or less in the upper limit, relative to 1 mole of methacrolein. As the source of molecular oxygen, air is preferred from the viewpoint of economy. The gas enriched in molecular oxygen by adding pure oxygen to air can be used as needed.
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. Steam may be further added to the raw material gas. Methacrylic acid can be obtained in a higher yield by carrying out the reaction in the presence of water vapor. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, and the lower limit is more preferably 1% by volume or more, and the upper limit is more preferably 40% by volume.
The contact time between the raw material gas and the methacrylic acid production catalyst is preferably 1.5 to 15 seconds, the lower limit is more preferably 2 seconds or more, and the upper limit is more preferably 10 seconds or less. The reaction pressure is preferably 0.1 to 1MPa (G). Wherein, (G) refers to gauge pressure. The reaction temperature is preferably 200 to 450 ℃, the lower limit is more preferably 250 ℃ or higher, and the upper limit is more preferably 400 ℃ or lower.
[ method for producing unsaturated carboxylic acid ester ]
The method for producing an unsaturated carboxylic acid ester of the present invention is to esterify 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 comprises: 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 obtained by vapor-phase catalytic oxidation of propylene, isobutylene, primary butanol, tertiary butanol or methyl tertiary butyl ether or vapor-phase catalytic oxidation of (meth) acrolein can be used to obtain an unsaturated carboxylic acid ester.
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 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 to 200 ℃.
Examples
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. The term "parts" means "parts by mass".
(composition ratio of catalyst component)
The molar ratio of each element was determined by analyzing a component in which the catalyst component was dissolved in ammonia water by ICP emission analysis. The molar ratio of ammonium ions was determined by analyzing the catalyst component by the Kjeldahl method.
(content of organic Polymer Compound)
The content of the organic polymer compound in the coated catalyst molded body is calculated from the mass M2 of the coated catalyst molded body and the mass M3 of the organic polymer compound used in the coating liquid according to the following formula.
Content of organic polymer compound [ mass% ] = (M3/M2) ×100
M2 is the sum of the amount of the catalyst molded body used for coating and the amount of the organic polymer compound used in the coating liquid. The amount of the catalyst molded body used for coating is an amount of the catalyst molded body in a state where the liquid is removed by a known drying method such as natural drying or hot air drying to have a liquid content of 1 mass% or less. M3 is the amount of the organic polymer compound used in the coating liquid.
(molded body Density of catalyst molded body)
The molded body density of the catalyst molded body was calculated from the mass M1 (g) per 1 catalyst molded body and the volume V1 (mL) per 1 catalyst molded body according to the following formula.
Molded body density (g/mL) =m1/V1 of catalyst molded body
The molded body density of the catalyst molded body is an average value obtained by calculating 100 molded bodies of the catalyst molded body produced under the same conditions.
(arithmetic average roughness (Ra) and maximum height (Rz))
The surface roughness of the catalyst molded article was measured using "SURFCOM1900SD" (trade name) manufactured by tokyo precision. The measurement position was a side surface when the molded body was cylindrical, and a cylindrical side surface when the molded body was cylindrical, and was measured in the axial direction under the conditions of a measurement distance of 4.0mm, a cutoff value of 0.8mm, and 4λ. This measurement was performed on 10 molded catalyst bodies, and calculated from the arithmetic average thereof.
(falling pulverization Rate of catalyst molded body)
As an index of the mechanical strength of the catalyst molded body, the falling pulverization rate of the catalyst molded body was used. The smaller the falling dusting rate, the higher the mechanical strength, the larger the falling dusting rate, the lower the mechanical strength. The falling pulverization rate of the catalyst molded body 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, which was provided so as to be perpendicular to the longitudinal direction and the lower opening was closed with a stainless steel plate, and filled in the cylinder. In the catalyst molded article recovered by opening the lower opening, the mass of the molded article which failed to pass through the sieve having a mesh of 1mm was denoted by M4g, and the falling powder percentage was calculated by the following formula. The falling powder ratio in the examples was an average value of the falling powder ratios measured for each catalyst molded body obtained by producing 10 catalyst molded bodies under the same conditions.
Falling pulverization ratio (%) = { (100-M4)/100 } ×100
(number of catalyst molded bodies to be packed in the reactor)
The number of catalyst molded bodies filled in the reactor was calculated from the mass M1 (g) of each catalyst molded body, the mass M5 (g) of the catalyst molded body filled in the reactor, and the filling volume V2 (mL) of the reactor according to the following formula.
The number of catalyst molded bodies filled in the reactor [ number/mL ] =m5/M1/V2
(analysis of raw gas and product)
Analysis of the raw material gas and the product was performed by using a gas chromatograph (apparatus: GC-2014 manufactured by Shimadzu corporation, column: DB-FFAP manufactured by J & W Co., ltd., 30 m. Times.0.32 mm, film thickness 1.0 μm). In example 1 and comparative example 1, the total yield of methacrolein and methacrylic acid produced was calculated from the following formula.
Total yield (%) = (n2+n3)/n1×100 of methacrolein and methacrylic acid
Here, N1 is the number of moles of isobutylene supplied, N2 is the number of moles of methacrolein produced, and N3 is the number of moles of methacrylic acid produced.
In example 1 and comparative example 1, only the case where isobutylene was used as the raw material was shown, but in the case where tert-butanol was used as the raw material, the same results as in the case where isobutylene was rapidly dehydrated to form isobutylene at the inlet portion of the reactor and was used as the raw material were obtained.
In examples 2 to 5 and comparative example 2, the yield of methacrylic acid produced was calculated from the following formula.
Yield (%) = (N5/N4) ×100 of methacrylic acid
Here, N4 is the number of moles of methacrolein supplied, and N5 is the number of moles of methacrylic acid produced.
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 the mixture was heated and stirred (liquid A). Further, 114.4 parts of ferric 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 the mixture was dissolved (solution B). The catalyst raw material liquid obtained by adding the liquid B to the liquid A was dried using a parallel flow spray dryer at a dryer inlet temperature of 250℃and a rotating disc for slurry spraying of 15000rpm, to obtain a catalyst dried body having an average particle diameter of 42. Mu.m. The composition of the catalyst excluding oxygen in the catalyst dried body was 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 ) 12.3 。
The mixture was obtained by kneading 4 parts of hydroxypropyl methylcellulose and 45 parts of pure water with 100 parts of the catalyst dried body in a clay-like manner using a batch kneader equipped with double-arm sigma blades (sigma blade).
The obtained mixture was extruded using a ram extruder to form a cylinder having an outer diameter of 6mm, an inner diameter of 2mm and a length of 5.5mm, and then dried at 90℃for 14 hours using a hot air dryer to obtain a catalyst molded body.
Next, the obtained catalyst molded body was filled in a coating pan, the catalyst molded body was rotated by rotation of the coating pan, and a coating liquid prepared as a 4 mass% aqueous solution with respect to 100 parts of the catalyst molded body of methyl cellulose was sprayed while blowing hot air at 95 ℃, and then pure water was sprayed with respect to 100 parts of the catalyst molded body. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface, and the falling dusting rate of the catalyst molded body after the coating are shown in table 1.
Next, the coated catalyst molded body was packed so that the packed volume in the reactor was 2500mL, and calcined at 450 ℃ for 5 hours under air ventilation. Then, a gas-phase catalytic oxidation reaction of isobutene was carried out by passing a raw material gas containing 5% by volume of isobutene, 12% by volume of oxygen, 10% by volume of steam and 73% by volume of nitrogen at a reaction temperature of 320℃for a contact time of 2.9 seconds. The product was collected and analyzed by a gas chromatograph, whereby the total yield of methacrolein and methacrylic acid was obtained. The number of the above-mentioned coated catalyst molded bodies filled in the reactor and the reaction results are shown in Table 1.
Comparative example 1
A catalyst molded body was produced in the same manner as in example 1. The step of spraying the coating liquid and pure water on the catalyst molded body by using a coating pan is not performed. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the molded catalyst body, and the falling powder percentage are shown in table 1.
Next, the catalyst molded body was filled in a reactor in the same manner as in example 1, and calcination and a vapor-phase catalytic oxidation reaction of isobutylene were performed. The number of the catalyst molded bodies filled in the reactor and the reaction results are shown in Table 1.
TABLE 1
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Example 2
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 were dissolved in 4000 parts of pure water, and the temperature was raised to 95 ℃ while stirring, and the liquid temperature was maintained at 95 ℃ and stirred for 3 hours. After cooling to 90 ℃, a solution obtained by dissolving 124 parts of cesium bicarbonate in 200 parts of pure water was added and stirred for 15 minutes while stirring with a rotating blade stirrer. Next, a solution obtained by dissolving 92 parts of ammonium carbonate in 200 parts of pure water was added, and the mixture was further stirred for 20 minutes to obtain a catalyst raw material liquid containing a Keggin-type heteropoly acid containing molybdenum and phosphorus. The catalyst raw material liquid is used for preparingThe slurry 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 catalyst dried body having an average particle diameter of 25. Mu.m. The composition of the catalyst excluding oxygen in the catalyst dried body was P 1.2 Mo 12 V 0.5 Cu 0.05 Cs 1.1 (NH 4 ) 3.8 。
The mixture was obtained by kneading 4 parts of hydroxypropyl cellulose and 18 parts of ethanol with 100 parts of the above-mentioned catalyst dried body in a clay-like state using a batch kneader equipped with double-arm sigma blades (sigma blade).
The obtained mixture was extruded using a ram extruder to form a cylindrical shape having an outer diameter of 5.5mm and a length of 5.5mm, and then dried at 90℃for 8 hours using a hot air dryer to obtain a catalyst molded body.
Next, the obtained catalyst molded body was filled in a coating pan, and the catalyst molded body was rotated by rotation of the coating pan, and a coating liquid prepared as a 4 mass% aqueous solution with respect to 100 parts of the catalyst molded body of methyl cellulose was sprayed while blowing hot air at 95 ℃, and then pure water was sprayed with respect to 100 parts of the catalyst molded body. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface, and the falling dusting rate of the catalyst molded body after the coating are shown in table 2.
Next, the catalyst molded article after the coating was packed so that the packed volume in the reactor was 2500mL, and calcined at 380 ℃ for 11 hours under air circulation. Then, a gas-phase catalytic oxidation reaction of methacrolein was carried out by using a raw material gas comprising 6% by volume of methacrolein, 12% by volume of oxygen, 10% by volume of water vapor, and 72% by volume of nitrogen, and passing the mixture at a reaction temperature of 290℃for a contact time of 2.9 seconds. The product was collected and analyzed by a gas chromatograph, whereby the yield of methacrylic acid was obtained. The number of the coated catalyst molded bodies packed in the reactor and the reaction results are shown in Table 2.
Example 3
A coated catalyst molded body was produced in the same manner as in example 2, except that the amount of methyl cellulose used in the coating liquid was changed to 0.3 part with respect to 100 parts of the catalyst molded body in example 2. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface, and the falling dusting rate of the coated catalyst molded body are shown in table 2.
Next, the catalyst molded body after the coating was filled in a reactor in the same manner as in example 2, and calcination and a gas-phase catalytic oxidation reaction of methacrolein were performed. The number of the coated catalyst molded bodies packed in the reactor and the reaction results are shown in Table 2.
Example 4
A coated catalyst molded body was produced in the same manner as in example 2, except that the amount of methyl cellulose used in the coating liquid was changed to 0.2 part with respect to 100 parts of the catalyst molded body in example 2. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface and the falling dusting rate of the coated catalyst molded body are shown in table 2.
Next, the catalyst molded body after the coating was filled in a reactor in the same manner as in example 2, and calcination and a gas-phase catalytic oxidation reaction of methacrolein were performed. The number of the coated catalyst molded bodies packed in the reactor and the reaction results are shown in Table 2.
Example 5
The catalyst molded body obtained was filled in a coating pan in the same manner as in example 2, and the catalyst molded body was rotated by rotating the coating pan, and a coating liquid prepared as a 4 mass% aqueous solution with respect to 100 parts of the catalyst molded body was sprayed while blowing hot air at 95℃and then 1 part of pure water was sprayed with respect to 100 parts of the catalyst molded body. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface, and the falling dusting rate of the catalyst molded body after the coating are shown in table 2.
Next, the catalyst molded body after the coating was filled in a reactor in the same manner as in example 2, and calcination and a gas-phase catalytic oxidation reaction of methacrolein were performed. The number of the coated catalyst molded bodies packed in the reactor and the reaction results are shown in Table 2.
Comparative example 2
A catalyst molded body was produced in the same manner as in example 2. The step of spraying the coating liquid and pure water on the catalyst molded body by using a coating pan is not performed. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the molded catalyst body, and the falling powder percentage are shown in table 2.
Next, the catalyst molded body was filled in a reactor in the same manner as in example 2, and calcination and a gas-phase catalytic oxidation reaction of methacrolein were performed. The number of the catalyst molded bodies filled in the reactor and the reaction results are shown in Table 2.
Comparative example 3
A catalyst dried body was produced in the same manner as in example 2.
3 parts of graphite was mixed with 100 parts of the above-mentioned catalyst dried body, and the mixture was molded into a cylindrical shape having an outer diameter of 5.5mm and a length of 5.5mm by a tablet molding machine, to obtain a catalyst molded body.
Next, the obtained catalyst molded body was filled in a coating pan, and the catalyst molded body was rotated by rotation of the coating pan, and a coating liquid prepared as a 4 mass% aqueous solution with respect to 100 parts of the catalyst molded body of methyl cellulose was sprayed while blowing hot air at 95 ℃, and then pure water was sprayed with respect to 100 parts of the catalyst molded body. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface, and the falling dusting rate of the catalyst molded body after the coating are shown in table 2.
Then, the catalyst molded body thus coated was charged in a reactor in the same manner as in example 2, and calcination and a vapor-phase catalytic oxidation reaction of methacrolein were performed. The number of the coated catalyst molded bodies packed in the reactor and the reaction results are shown in Table 2.
Comparative example 4
A catalyst molded body was produced in the same manner as in comparative example 3. The step of spraying the coating liquid and pure water on the catalyst molded body by using a coating pan is not performed. The measurement results of the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the molded catalyst body, and the falling powder percentage are shown in table 2.
Next, the catalyst molded body was filled in a reactor in the same manner as in example 2, and calcination and a gas-phase catalytic oxidation reaction of methacrolein were performed. The number of the catalyst molded bodies filled in the reactor and the reaction results are shown in Table 2.
TABLE 2
As is clear from Table 1, the alloy contains 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 ) 12.3 In the case of the catalyst component having the composition ratio of (a), the number of charges of the catalyst molded body into the reactor was increased, and the total yield of methacrolein and methacrylic acid was higher, as compared with comparative example 1 in which the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the catalyst molded body were outside the predetermined ranges, in example 1 in which the molded body density, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the catalyst molded body were values within the predetermined ranges. In addition, it can be said that the increase in the number of catalyst molded bodies to be charged into the reactor is also advantageous from the viewpoint of continuous reaction time.
Also, as can be seen from Table 2, the composition contains a polypeptide having P 1.2 Mo 12 V 0.5 Cu 0.05 Cs 1.1 (NH 4 ) 3.81 Examples 2 to 5, in which the density of the molded catalyst and the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the molded catalyst were values within the predetermined ranges, showed higher methacrylic acid yield as compared with comparative example 2, in which the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the molded catalyst were outside the predetermined ranges, in which the number of the catalyst molded catalyst to be charged into the reactor was increased. In addition, anotherIn addition, it can be said that the increase in the number of catalyst molded bodies to be charged into the reactor is also advantageous from the viewpoint of continuous reaction time.
In comparative examples 3 and 4, the arithmetic average roughness (Ra) and the maximum height (Rz) of the surface of the catalyst molded body were values within the predetermined ranges, but the molded body density was outside the predetermined range. In this case, the number of catalyst molded bodies to be charged into the reactor was the same as in examples 2 to 5, but the yield of methacrylic acid was lower than in examples 2 to 5. This is considered to be due to the reduction of pores in the catalyst molded body, which are advantageous for the production of methacrylic acid.
The methacrylic acid obtained in this example was esterified to obtain a methacrylic acid ester.

Claims (8)

1. A catalyst molded article for use in producing an unsaturated aldehyde and/or unsaturated carboxylic acid by an oxidation reaction, which satisfies both the following requirements (A) and (B), contains a catalyst component having a composition represented by the following formula (I),
(A) The molded body density of the catalyst molded body is 2.25g/mL or less in a state before filling in the reactor,
(B) The following requirements (B-1) and (B-2) are satisfied:
the catalyst molded body of (B-1) has an arithmetic average roughness Ra of 3.0 μm or less as defined in JIS B-0601-2001,
(B-2) the maximum height Rz specified in JIS B-0601-2001 of the surface of the catalyst molded body is 15 μm or less;
Mo a1 Bi b1 Fe c1 A d1 E1 e1 G1 f1 J1 g1 Si h1 (NH 4 ) i1 O j1 (I)
mo, bi, fe, si, NH in formula (I) 4 And 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 zincWherein 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=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, J1 is a molar ratio of oxygen required to satisfy valence numbers of the respective components when a1=12.
2. A catalyst molded article for use in producing an unsaturated aldehyde and/or unsaturated carboxylic acid by an oxidation reaction, which satisfies both the following requirements (A) and (B), contains a catalyst component having a composition represented by the following formula (II),
(A) The molded body density of the catalyst molded body is 2.25g/mL or less in a state before filling in the reactor,
(B) The following requirements (B-1) and (B-2) are satisfied:
the catalyst molded body of (B-1) has an arithmetic average roughness Ra of 3.0 μm or less as defined in JIS B-0601-2001,
(B-2) the maximum height Rz specified in JIS B-0601-2001 of the surface of the catalyst molded body is 15 μm or less;
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 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, a2=0.1 to 3, c2=0.01 to 3, d2=0.01 to 2 when b2=12 E2 is 0 to 3, f2=0 to 3, g2=0.01 to 3, h2=0 to 30, and i2 is the molar ratio of oxygen required to satisfy the valence of each component.
3. The catalyst molded body according to claim 1 or 2, wherein at least a part of a surface of the catalyst molded body has a coating layer of an organic polymer compound.
4. The molded catalyst according to claim 3, wherein the organic polymer compound is contained in an amount of 0.001 to 2% by mass.
5. The catalyst molded body according to claim 1 or 2, wherein the molded body is an extrusion molded body.
6. A process for producing an unsaturated aldehyde and an unsaturated carboxylic acid, comprising 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 catalyst molded body according to claim 1.
7. A process for producing an unsaturated carboxylic acid, comprising subjecting (meth) acrolein to gas-phase catalytic oxidation with molecular oxygen in the presence of the catalyst molded body according to claim 2.
8. A process for producing an unsaturated carboxylic acid ester, wherein the unsaturated carboxylic acid produced by the process according to claim 6 or 7 is esterified.
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