WO2004073857A1 - メタクリル酸製造用触媒及びその製法 - Google Patents
メタクリル酸製造用触媒及びその製法 Download PDFInfo
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- WO2004073857A1 WO2004073857A1 PCT/JP2004/001999 JP2004001999W WO2004073857A1 WO 2004073857 A1 WO2004073857 A1 WO 2004073857A1 JP 2004001999 W JP2004001999 W JP 2004001999W WO 2004073857 A1 WO2004073857 A1 WO 2004073857A1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
Definitions
- the present invention relates to a method for producing methacrylic acid by gas phase catalytic oxidation of methachlorin, isobutyl aldehyde, or isobutyric acid having a long life and having high activity and high selectivity. It relates to a catalyst and its production method.
- catalysts have been proposed as catalysts for the production of methacrylic acid by gas phase catalytic oxidation of methacrylone, isobutyl aldehyde or isobutyric acid. .
- Most of these catalysts are mainly composed of molybdenum and phosphorus, and have a structure of heteropolyacid and / or a salt thereof.
- the catalyst used in this reaction is known to be a similar reaction to this reaction.
- the reaction activity is lower and the selectivity to the target substance is lower. Although they are low and have short lifespans, they are partially industrialized, but there is a need for improved catalytic performance.
- the present inventors have previously attempted to improve the low activity, low selectivity, and short life of the conventional metal-mouthed, gas-phase catalytic oxidation catalyst, and added various elements to Mo, V, and P. It was discovered that the catalyst with vapor-phase gas-phase contact oxidation has a heteropolyacid (salt) structure, is highly active, has high selectivity, and is particularly stable over its life. Publication No. 58-1 1 4 16 No. 6, Special Publication No. 5 9-2 4 140, Japanese Patent Publication No. 62-1 4 3 5 No. 5, Special Publication No. 62-310 7 7 The catalyst described in the publication is proposed.
- 11-226441 discloses that purified starch is used when granulating a catalytically active component, and the starch is burned off in a calcination step, whereby the pore volume of the catalyst is reduced. Improve A method for producing a shaped catalyst is described.
- the catalyst powder is usually formed into a column, a tablet, a ring, a sphere, or the like, or an active catalyst substance is impregnated or coated on an inert carrier.
- this coated catalyst having an inert carrier as the core are as follows: (1) the effective utilization of the catalytically active component can be increased; (2) the residence time distribution of the reactants in the catalyst becomes uniform. (3) Improvement of the thermal conductivity of the catalyst or dilution of the inert carrier makes it easier to remove the heat of reaction.
- the present invention relates to a catalyst or a coated catalyst for producing methacrylic acid with high yield and high selectivity by gas phase catalytic oxidation of methacrolein, isobutyl aldehyde or isobutyric acid, and their catalysts.
- the purpose is to provide a manufacturing method.
- the present inventors have attempted to improve the low activity, low selectivity, and short life of the conventional gas-phase catalytic oxidation catalyst for methacrolein as a method for solving the above-mentioned problems.
- P the preparation of the catalysts C u, C s and NH 4 as essential components, i.e., in preparing the hetero Po Li acid (salt) containing the essential components, cesium weak acid and a C s material
- salt or cesium hydroxide is added, and ammonium acetate or ammonium hydroxide is added as the NH 4 raw material, respectively, high activity, high selectivity, and particularly stable life and high stability are obtained.
- the inventors have found that a high-performance industrial catalyst can be obtained, and have completed the present invention.
- M o, V, P, C u a catalyst hetero port Li salt as a catalyst active component containing a hetero Po Li acid to C s and NH 4 the essential active ingredient, the catalyst activity Cs as a raw material Methachlorin, isobutyl aldehyde or methacrylic acid, characterized by being obtained using a weak acid salt or cesium hydroxide, and ammonium acetate as a NH 4 raw material, respectively.
- composition of the catalytically active component is represented by the following formula (1)
- X is SbAs, Ag, M g, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce, Th , K and Rb each represent one or more elements selected from the group consisting of: a to g represent the atomic ratio of each element, and a represents 0.1 ⁇ a ⁇ 6.0.
- b is a positive number of 0.5 ⁇ b ⁇ 6.0
- c is 0 ⁇ c ⁇ 3.0 positive integer
- d is 0.0.1 ⁇ d ⁇ 3.0 positive integer
- e is 0.1 ⁇ e ⁇ 3.0 positive integer
- ⁇ is 0 ⁇ 0 ⁇ 3.0
- Represent the positive numbers of g is a value determined by the acid-acid value of each element.
- a is a positive number of 0.5 ⁇ a ⁇ l.2, a positive number of b power 0.9 ⁇ b ⁇ 1.5, a positive number of c power 0.2 ⁇ c ⁇ 0.8, and d is A catalyst according to the above (5), wherein a positive number of 0.2 ⁇ d ⁇ 0.8, a positive number of e force S 1.0 ⁇ e ⁇ 2.2, and a f force S 0 ⁇ f ⁇ 0.8;
- the following compounds A-1 to A-3 and, if necessary, the compound A-4 are mixed with water, and an aqueous solution or dispersion of these compounds (hereinafter a slurry solution containing both) is prepared.
- step (A) A step of drying the slurry obtained in step (A) to obtain a dried slurry
- a process for producing a catalyst for the production of methacrylic acid by gas phase catalytic oxidation of methacrolein, isobutyl aldehyde or isobutyric acid characterized by comprising:
- S b As, Ag, Mg, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, B at least one compound selected from the group consisting of compounds having i, W, Fe, Co, Ni, Ce, Th, K, or Rb step (b)
- the following compounds a-1 to a_3 and, if necessary, disulfide compound a-4 are mixed with water to prepare a slurry of these compounds.
- step (a) The slurry obtained in step (a) is dried and slurry dried.
- step (b) Mixing the compound having solid copper with the dried slurry obtained in step (b) to obtain a powder
- step (c) Calcining the coated molded product obtained in step (c), characterized in that the method comprises the steps of gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or isobutyric acid. Production method of coated catalyst for crylic acid production,
- binder at least one selected from the group consisting of water and organic compounds having a boiling point of 150 ° C. or less at 1 atm is used.
- the catalyst of the present invention can produce methacrylic acid from methachlorin, isobutyl aldehyde or isoacetic acid with high yield and low selectivity. Extremely high industrial value because it can be used for reactions. ' BEST MODE FOR CARRYING OUT THE INVENTION
- One catalyst for obtaining good or correct the process of the present invention M o, V, P, C u, C s and NH 4 and good necessary Ri plurality of compounds having multiple rather by young other elements, respectively (hereinafter
- a compound having these active ingredients is also referred to as an “active ingredient-containing compound” in water and dissolved or dispersed in water (step (A)) to prepare a slurry.
- Cesium weak acid salt or cesium hydroxide was used as the cesium compound, and ammonium acetate was used as the ammonium conjugate, and the slurry was dried (step (B)).
- the active ingredient-containing compound used for preparing a one-part slurry other than cesium weak acid salt or cesium hydroxide and ammonium acetate is dried (step (B)) or calcined. More preferred are compounds that form heteropolyacid or a salt thereof. Examples of the compound include chlorides, sulfates, nitrates, oxides and acetates of the active ingredient elements.
- nitrates such as potassium nitrate or cobalt nitrate, oxides such as molybdenum oxide, vanadium pentoxide, antimony trioxide, cerium oxide, zinc oxide or germanium oxide, positive phosphorus
- An acid or a salt thereof
- an acid such as an acid, phosphoric acid, boric acid, aluminum phosphate or 12-tungstic acid, and the like
- copper acetate copper acetate, cupric acetate, basic copper acetate, cupric oxide, or the like, preferably cupric acetate
- copper raw material has a favorable effect. May be. These may be used alone or as a mixture of two or more.
- the cesium weak acid salt is not particularly limited as long as it is a salt of a weak acid generally known as cesium, and examples thereof include cesium hydrogen carbonate, cesium carbonate, and cesium acetate. Cesium acetate is preferred. Of these, commercially available cesium acetate can be used as it is. For example, an aqueous solution of a water-soluble salt of cesium such as cesium hydroxide or cesium carbonate can be used. An equivalent amount or more of acetic acid may be added to the mixture and added as an aqueous solution of cesium acetate.
- the active component other than Mo, V, P, Cu, Cs, and NH 4 is a compound known as a component element of a catalyst for producing methacrylic acid. If there are no restrictions, S b, A s, A g, M g, Z n, A l, B, G e, S n, P b, T i, Z r, C r, R e, B i, W, F e, C o, N i, C One or more members selected from the group consisting of e, Th, K and Rb are listed, and among these, elements other than As are preferred.
- the ratio of each active component of the catalyst in the present invention is such that the atomic ratio of vanadium to molybdenum 10 is usually 0.1 or more and 6.0 or less, preferably 0.3 or more and 2.0 or less. 0 or less, especially preferred
- the ring is usually 0.5 or more and less than or equal to 6.0, preferably 0.9 or more and less than or equal to 1.5, and copper is usually greater than 0 and more than 3.
- ammonia is usually more than 0.1 and less than or equal to 3.0.
- the type of the other active components and the use ratio thereof used as necessary are appropriately determined in accordance with the conditions of use of the catalyst and the like so that a catalyst having optimum performance can be obtained.
- the preferred correct catalysts used in normal conditions the following formula (1) M o 1 0 V a P b C u c C s d (NH 4) e X f O "(1) (In the formula, Mo is molybdenum, V is vanadium, ⁇ is phosphorus, Cu is copper, Cs is cesium, (NH 4 ) is an ammonium group, X is Sb.As, Ag , M g, Z n, A l, B, G e, Sn, P b, T i, Z r, C r, R e, B i, W, F e, C o, N i, C e, Each of one or more elements selected from the group consisting of Th, K, and Rb, a to
- a positive number of 0, b is a positive number of 0.5 ⁇ b ⁇ 6.0, c is a positive number of 0 and c ⁇ 3.0, d is a positive number of 0.0 1 ⁇ d ⁇ 3.0, e Is a positive number of 0.1 ⁇ e ⁇ 3.0, and f is a positive number of 0 f 3.0.
- G is a value determined by the acid-acid valency of each element.) It has a component composition.
- This active ingredient composition means the composition in the slurry slurry described below, and does not necessarily reflect the composition of the powder after the step (d).
- the NH 4 component volatilizes and is replaced by a hydrogen atom or a metal atom.
- the NH 4 component in the dried slurry may be volatilized through the firing step.
- the extent of volatilization of NH 4, the calcination temperature, firing time, firing atmosphere (although different I'm in or in the air nitrogen force, up to 9 0 It evaporates about mol%.
- S b is preferable as the element X.
- S b is used as required in the above formula (1) in a range from 0 to 2.2, preferably from 0.01 to 0.8.
- the catalyst can be obtained by the following procedure.
- an aqueous solution or aqueous dispersion of the active ingredient-containing compound (hereinafter, referred to as a slurry solution including both) is prepared.
- the slurry solution can be obtained by uniformly mixing a plurality of compounds having each active ingredient and a solvent, preferably water.
- the slurry preferably contains all of the necessary active ingredient-containing compounds in the required amount of the catalyst.
- the order of adding the active ingredient-containing compound when preparing a slurry solution is not particularly limited, but the compound having Mo, V and P is first used as a slurry solution, and then the cesium weak acid salt or water is used. It is preferable to add a compound having cesium oxide, ammonium acetate and copper to the slurry.
- the temperature at which the slurry is prepared is not particularly limited as long as it does not interfere with the preparation, but a compound containing cesium weak acid salt or cesium hydroxide, ammonium acetate, and copper is added.
- the temperature is usually between 0 and 35 ° C, preferably between 10 and 30 ° C
- the resulting catalyst may be highly active. Since this tendency becomes remarkable when copper acetate is used as a compound having copper, the slurry liquid is prepared more efficiently by using the above-mentioned preferred addition method. .
- the slurry solution is preferably an aqueous solution.
- the use ratio of the compound of each active ingredient in one slurry is not particularly limited as long as the atomic ratio of each active ingredient is in the above range.
- the amount of water used is not particularly limited as long as it can completely dissolve the entire amount of the compound to be used or can be uniformly mixed, but is appropriately determined in consideration of the drying method and drying conditions described below. Is done. That is, it is about 200 to 2000 parts by mass with respect to 100 parts by mass of the compound for preparation of the slurry. Although the amount of water may be large, too much water increases the energy cost of the drying process and may not be completely dried, and has many disadvantages. Not suitable, so an appropriate amount is preferred.
- the drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness. Of these, in the present invention, It is possible to dry the slurry from powder to granules in a short time from the liquid state. It is preferable to use the evaporation drying method, which is easy to dry the slurry liquid directly. Evaporation drying is particularly preferable. New
- the drying temperature in the case of spray drying differs depending on the slurry concentration, the feed rate, etc., but the temperature at the outlet of the dryer is generally 70 to 150 ° C.
- the evaporation to dryness may be carried out according to a standard method.
- pulverization since the slurry-dried product is obtained as a lump or a large particle, pulverization may be appropriately performed, preferably 3 OO / Pulverize to less than zm.
- a dried slurry such a crushed one is included in the dried slurry.
- the slurry slurry thus obtained can be subjected to a gas-phase catalytic oxidation reaction as the catalyst of the present invention, but as described above, in order to reduce the pressure loss of the reaction gas.
- step (A) one slurry was prepared without using a compound having copper, and After this is subjected to a drying step, a mixture of the obtained dried product and a powder of a compound containing copper can be used as the catalyst of the present invention.
- the coated catalyst of the present invention further comprises selecting an ammonium hydroxide as an ammonium source in the step (A).
- the starting compound is dissolved and Z or dispersed in water (step (a)) to prepare a slurry solution, which is dried (step (b)) to obtain a slurry slurry.
- step (a) there is no particular restriction on the order of addition of each starting compound, but as in step (A), the compound having Mo, V, and P is first converted into a slurry, and then the slurry is added. It is preferable to add a compound which is a source of ummonium, ammonium and copper to the slurry.
- the temperature at which the compounds serving as a cesium source, an ammonium source and a copper source are added is usually 0 to 35 ° C, preferably 10 to 30 ° C. Is preferred.
- a slurry was prepared in step (a) without using a compound having copper, and the slurry was subjected to a drying step. After that, a mixture obtained by mixing the obtained dried product and a powder of a compound having copper was used. (Step (b ')) Thus, the coated catalyst of the present invention can be obtained.
- step (c) The obtained dried slurry (or the mixture; hereinafter, the dried slurry contains the mixture) is subjected to the following coating step (step (c)).
- the tumbling granulation method described below is preferred.
- the disk is rotated at high speed, and the carrier in the container is rotated and revolved. 'Repeat repeatedly.' Stir vigorously, and add the binder and dried slurry and, if necessary, other additives such as a mixture of a molding aid and a strength improving material.
- a method for coating the mixture on a carrier by The method for adding the binder is as follows: 1) Premix the mixture with the above mixture, 2) Add the mixture at the same time as adding the mixture into the fixed container, 3) Add the mixture into the fixed container, and then add the mixture.
- the addition rate is adjusted using an auto feeder or the like so that the mixture is not attached to the wall of the fixed container, and the mixture is not agglomerated, and a predetermined amount is supported on the carrier. I prefer to adjust it New
- the binder is not particularly limited as long as it is at least one selected from the group consisting of water and organic compounds having a boiling point at 150 ° C or less at 1 atm. Considering the above factors, those having a boiling point of 100 ° C or lower are preferred.
- Specific examples of binders other than water include alcohols such as methanol, ethanol, pronools, and butanols, preferably alcohols having 1 to 4 carbon atoms. Examples thereof include ethers such as coal, ethyl ether, butyl ether and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetate and methylethyl ketone; and aqueous solutions thereof.
- ethanol is preferred.
- the ratio of ethanol / water is 10/0 to 5/5 (weight ratio), preferably 100 to 7/3 (weight ratio).
- an ethanol concentration of about 10 to 30% by mass is particularly preferred.
- the amount of the binder used is usually 2 to 60 parts by mass, preferably 5 to 25 parts by mass, based on 100 parts by mass of the slurry slurry.
- the carrier used in the present invention include silicon carbide, alumina, silica alumina, mullite, arandom and the like having a diameter of 1 to 15 mm, preferably 2.5 to 1 Omm. , Especially preferred 2.
- a spherical carrier having a diameter of 5 to 4.5 mm is exemplified.
- These carriers usually have a porosity of 10 to 70%.
- the porosity of the carrier is calculated assuming that the dry weight of the carrier is W, the weight in water is W 2 , and the saturated water absorption weight is W 3 (W 3 — / (W a-W 2 ) XI
- the range is from 10 to 75% by mass, preferably from 15 to 60% by mass.
- the reaction activity of the coated catalyst is large, but the mechanical strength tends to be low (the friability is high). Conversely, when the percentage of the dried slurry to be coated is small, the mechanical strength is high (the friability is small), but the reaction activity tends to be low.
- a molding aid such as silica gel, diatomaceous earth, or alumina powder may be used, if necessary.
- the amount of the molding aid used is usually 5 to 60 parts by mass based on 100 parts by mass of the slurry slurry.
- inorganic fibers such as ceramic fibers and whiskers, which are inert to the catalyst component, are used as the strength improving material. This is useful for improving the mechanical strength of the catalyst.
- fibers that react with catalytic components such as titanic acid reamed whiskers and basic magnesium carbonate whiskers, are not preferred. The amount of these fibers used is usually 1 to 30 parts by mass relative to 100 parts by mass of the dried slurry.
- additives such as a molding aid and a strength improving material are usually added to a granulator together with a carrier, a slurry slurry, a binder and the like in a coating step and used for coating the carrier.
- the dried slurry is coated on a carrier, and the coated product obtained at this time usually has a diameter of about 3 to 15 mm, preferably about 3.2 to 5 mm.
- the coated catalyst thus obtained can be used as it is as a catalyst in the gas phase catalytic oxidation reaction, but firing (step (d)) may improve the catalytic activity. I like it.
- the firing temperature in this case is usually 100 to 420 ° C, preferably 250 to 400 ° C, and the firing time is 1 to 20 hours.
- the firing is usually performed in an air atmosphere, but may be performed in an inert gas atmosphere such as nitrogen, or may be further performed in an air atmosphere as necessary after the firing in the inert gas atmosphere. Perform firing in May be. Further, if calcination is carried out in an inert gas atmosphere or preferably in the presence of a reducing agent, a more active catalyst may be obtained, which is preferable.
- the reducing agent is not particularly limited as long as it is preferably a gas at the calcination temperature, and includes alcohols, aldehydes, ketones, and organic acids having 2 to 5 carbon atoms. Among them, ethanol is particularly preferred.
- the catalyst of the present invention obtained as described above is used in the production of methacrylic acid by gas phase catalytic oxidation of methanol mouth lane, isobutyl aldehyde or isobutyric acid. You. When the catalyst of the present invention is used, unless otherwise specified, the slurry slurry obtained through the steps (A) to (B) or the slurry (a) to (c) (and preferably Or the coated catalyst obtained through the step (d)).
- molecular oxygen or a gas containing molecular oxygen is used for the gas phase catalytic oxidation reaction.
- the molar ratio of the molecular oxygen to the metal-carrying lane is preferably in the range of 0.5 to 20 and particularly preferably in the range of 1 to 10.
- water is preferable to add water to the raw material gas in a molar ratio of 1 to 20 with respect to the metal-carrying lane.
- the raw material gas may contain, in addition to oxygen and, if necessary, water (including usually as steam), a gas inert to the reaction such as nitrogen, carbon dioxide, and saturated hydrocarbon.
- a gas inert to the reaction such as nitrogen, carbon dioxide, and saturated hydrocarbon.
- the gas obtained by oxidizing isoptilene, tertiary butanol, and methyl tert-butyl ether may be supplied as it is to methacrolein.
- the reaction temperature in the gas phase catalytic oxidation reaction is usually from 200 to 400 ° C, preferably from 260 to 360 ° C, and the supply amount of the raw material gas is usually 1 space velocity (SV). 0 0 ⁇ 6 0 0 0 hr - 1, and preferred rather is a 4 0 0 ⁇ 3 0 0 0 hr _ 1.
- the catalyst according to the present invention When the catalyst according to the present invention is used, there is no significant change in the reaction result even when the SV is increased, and the reaction can be performed at a high space velocity.
- the catalytic oxidation reaction can be performed under increased or reduced pressure, but generally, a pressure near the atmospheric pressure is suitable.
- Example hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
- compositions of the catalytically active components in the examples are all ratios calculated from the charged raw materials. In the formula, oxygen is omitted.
- the solution was cooled to 15 to 20 ° C, and while stirring, a solution obtained by dissolving 13.33 g of cesium acetate in 15 O ml of pure water was added thereto.
- a solution obtained by dissolving 16.06 g of ammonium acetate in 5 O ml was gradually added at the same time, and then the slurry was further added to 170 ml of pure water with 170 ml of pure water.
- a solution of 11.09 g of cupric monohydrate was added, and the mixture was aged at 15 to 20 ° C. for 1 hour to obtain a green-blue slurry.
- the slurry was dried by evaporating to dryness with hot water and crushed in a mortar to 300 / im or less to obtain a dried slurry.
- the composition of the dried slurry obtained is
- the obtained coated molded article was calcined at 310 ° C. for 5 hours under air flow to obtain a coated catalyst of the present invention.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- the reaction performance was measured at a reaction bath temperature of 310 ° C, and then the reaction bath temperature was raised to 350 ° C and the reaction was continued for 15 hours. Next, the reaction bath temperature was lowered to 310 ° C., and the reaction results were measured. Table 1 shows the results of the reaction.
- the solution was cooled to 15 to 20 ° C, and a solution obtained by dissolving 23.33 g of cesium acetate in 17 O ml of pure water while stirring was added to a solution of 170 ml of pure water.
- a solution of 33.73 g of ammonium acetate was gradually added to the mixture, and the mixture was gradually aged at 15 to 20 ° C. for 1 hour to obtain a green-blue slurry.
- the slurry was dried by evaporating to dryness with hot water and pulverized to 300 / Xm or less in a mortar to obtain a powder.
- the composition of the obtained powder is
- cupric acetate monohydrate powder in such an amount that the atomic ratio becomes Cu 0.4 with respect to Mo 10 was added to the above powder and a strength improving material (Cera). 66.1 g) and uniformly mixed with a spherical porous alumina carrier (particle diameter: 3.5 mm, porosity: 25.5%) to 44.1 g. 0 mass. Coating was performed by a rolling granulation method using an aqueous solution of / 0 ethanol as a binder to obtain a coated molded product. The particle size of the obtained coated catalyst was 4.3 mm (average value).
- the obtained coated molded product was subjected to 380 liters of ethanol (20 g Zh) as a reducing agent under nitrogen flow (SL Zmin.).
- the coated catalyst of the present invention was obtained by firing at 10 ° C. for 10 hours.
- the active component composition of the obtained coated catalyst is
- the obtained coated molded product was treated with ethanol (20 g Zh) as a reducing agent under nitrogen flow (5 L / min.).
- the coated catalyst of the present invention was obtained by firing at 80 ° C for 10 hours.
- the active ingredient composition of the resulting coated catalyst is
- a solution obtained by diluting 26.08 g of an 28% aqueous ammonia solution in 150 ml of pure water is gradually added at the same time, and the mixture is aged at 15 to 20 ° C for 1 hour to obtain a green-blue slurry. I got a liquid
- the slurry was dried by evaporating to dryness in a hot water bath.
- the powder was crushed in a pot to a size of 300 m or less to obtain a powder.
- the composition of the obtained powder is
- cupric acetate monohydrate powder in an amount of 0.4 in atomic ratio to Mo 10 was added to the above powder and a strength improving material (ceramics). 34.7 g) and uniformly mixed with each other to obtain a spherical porous alumina carrier (particle size: 3.5 mm, porosity: 25.5%), 90 mass per 23,2,6 g .
- a coating was formed by a rolling granulation method using an aqueous solution of / 0 ethanol as a binder to obtain a coated molded product. The particle size of the obtained coated molded product was 4.3 mm (average value).
- the obtained coated molded product was calcined at 310 ° C. for 5 hours under an air flow to obtain a coated catalyst for comparison.
- the composition of the obtained coated catalyst is
- the amount of antimony trioxide was changed to 22.14 g, the amount of ammonium acetate was changed to 26.23 g, and the calcination process was changed to 310 ° C and 5 hours under air flow. Except for this, the coated catalyst of the present invention was obtained in the same manner as in Example 2. The particle size of the obtained coated catalyst was 4.3 mm (average value).
- Example 6 The amount of vanadium pentoxide to 15.48 g, 85 mass. /. Except that the amount of orthophosphoric acid was changed to 31.7 g, the amount of ammonium acetate was changed to 31.886 g, and the calcination process was changed to 310 ° C and 5 hours under air flow, respectively.
- a coated catalyst of the present invention was obtained in the same manner as in Example 2. The particle size of the obtained coated catalyst was 4.3 mm (average value).
- Cesium acetate 23.33 g Z water 170 ml aqueous solution was mixed with cesium hydroxide 'monohydrate 20.4 lg / water 17 ml aqueous solution ( s O .5), except that The coated catalyst of the present invention was obtained.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- Aqueous solution of cesium acetate 23.3.3 g Z water 170 m 1 was added to cesium hydroxide.monohydrate 20.4 1 g Z water 123 ml and acetic acid 7.30 g Z water 5
- a coated catalyst of the present invention was obtained in the same manner as in Example 2 except that 2.5 m 1 was changed to a stronger one.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- a coated catalyst of the present invention was obtained in the same manner as in Example 2, except that the amount of antimony trioxide was changed to 2.21 g.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- the coated catalyst of the present invention was obtained in the same manner as in Example 3 except that the amount of ammonium acetate was changed to 21.4 lg, and ammonium trioxide was not used.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- the cooling temperature of the dark blue solution in which antimony trioxide is dissolved is 26-
- a coated catalyst of the present invention was obtained in the same manner as in Example 2, except that the temperature was changed to 30 ° C.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- a coating for comparison was made in the same manner as in Example 2 except that cesium acetate and ammonium acetate were not used and the amount of cupric acetate-monohydrate was changed to 24.26 g.
- a catalyst was obtained.
- the particle size of the obtained coated catalyst was 4.3 mm (average value). '' Comparative Example 4
- a coated catalyst for comparison was obtained in the same manner as in Example 2 except that cesium acetate was not used.
- the particle size of the obtained coated catalyst is 4.3 mm
- the amount of 85% by mass orthophosphoric acid was increased to 19.22 g, and cesium nitrate A coated catalyst for comparison was obtained in the same manner as in Comparative Example 1 except that 54 g was changed to 7.02 g of potassium acetate.
- the particle size of the obtained coated catalyst was 4.3 mm (average value).
- Example 4 to 10 and Comparative Examples 2 to 6 were subjected to an oxidation reaction in the same manner as in Example 1 under the conditions of a bath temperature of 350 ° C. and 15 hours, and then the bath temperature was changed to 31. The temperature was lowered to 0 ° C and the reaction results were measured. The results are shown in Table 5 together with the atomic ratio of each catalytically active component of the coated catalyst.
- Catalyst active component composition Catalyst performance
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Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US10/545,699 US7825061B2 (en) | 2003-02-20 | 2004-02-20 | Catalyst for producing methacrylic acid and preparation method thereof |
EP04713199.0A EP1595600B1 (en) | 2003-02-20 | 2004-02-20 | Process for producing a catalyst for methacrhylic acid synthesis |
MXPA05008754A MXPA05008754A (es) | 2003-02-20 | 2004-02-20 | Catalizador para producir acido metacrilico y metodo de preparacion del mismo. |
JP2005502792A JP4478107B2 (ja) | 2003-02-20 | 2004-02-20 | メタクリル酸製造用触媒及びその製法 |
BR0407442-4A BRPI0407442A (pt) | 2003-02-20 | 2004-02-20 | Catalisador para produzir ácido metacrìlico e método para sua preparação |
Applications Claiming Priority (2)
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JP2003042259 | 2003-02-20 | ||
JP2003-042259 | 2003-02-20 |
Publications (1)
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WO2004073857A1 true WO2004073857A1 (ja) | 2004-09-02 |
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ID=32905345
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PCT/JP2004/001999 WO2004073857A1 (ja) | 2003-02-20 | 2004-02-20 | メタクリル酸製造用触媒及びその製法 |
Country Status (11)
Country | Link |
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US (1) | US7825061B2 (ja) |
EP (2) | EP2374538A1 (ja) |
JP (1) | JP4478107B2 (ja) |
KR (1) | KR100972813B1 (ja) |
CN (1) | CN100457264C (ja) |
BR (1) | BRPI0407442A (ja) |
MX (1) | MXPA05008754A (ja) |
MY (1) | MY144325A (ja) |
TW (1) | TWI341219B (ja) |
WO (1) | WO2004073857A1 (ja) |
ZA (1) | ZA200507363B (ja) |
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MY144325A (en) * | 2003-02-20 | 2011-08-29 | Nippon Kayaku Kk | Catalyst for producing methacrylic acid and preparation method thereof |
US7273829B2 (en) * | 2005-12-22 | 2007-09-25 | Saudi Basic Industries Corporation | Catalyst for oxidation of saturated and unsaturated aldehydes to unsaturated carboxylic acid, method of making and method of using thereof |
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- 2004-02-19 TW TW093104115A patent/TWI341219B/zh not_active IP Right Cessation
- 2004-02-20 EP EP11173250A patent/EP2374538A1/en not_active Withdrawn
- 2004-02-20 JP JP2005502792A patent/JP4478107B2/ja not_active Expired - Lifetime
- 2004-02-20 EP EP04713199.0A patent/EP1595600B1/en not_active Expired - Lifetime
- 2004-02-20 MX MXPA05008754A patent/MXPA05008754A/es active IP Right Grant
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US8716523B2 (en) | 2005-03-29 | 2014-05-06 | Nippon Kayaku Kabushiki Kaisha | Catalyst for use in production of methacrylic acid and method for manufacturing the same |
US8148291B2 (en) | 2005-05-12 | 2012-04-03 | Nippon Kayaku Kabushiki Kaisha | Method for manufacturing catalyst for use in production of methacrylic acid |
JP2006314923A (ja) * | 2005-05-12 | 2006-11-24 | Nippon Kayaku Co Ltd | メタクリル酸製造用触媒の製造方法 |
WO2006121100A1 (ja) * | 2005-05-12 | 2006-11-16 | Nippon Kayaku Kabushiki Kaisha | メタクリル酸製造用触媒の製造方法 |
US8017547B2 (en) | 2005-05-12 | 2011-09-13 | Nippon Kayaku Kabushiki Kaisha | Method for manufacturing catalyst for use in production of methacrylic acid |
JP2009502481A (ja) * | 2005-07-25 | 2009-01-29 | サウディ ベーシック インダストリーズ コーポレイション | メタクロレインを酸化するための触媒およびその製造方法と使用方法 |
JP2008302313A (ja) * | 2007-06-08 | 2008-12-18 | Mitsubishi Rayon Co Ltd | メタクリル酸製造用触媒及びその製造方法並びにメタクリル酸の製造方法 |
WO2010052909A1 (ja) * | 2008-11-06 | 2010-05-14 | 日本化薬株式会社 | メタクリル酸の製造方法及びメタクリル酸製造用触媒 |
JP5574434B2 (ja) * | 2008-11-06 | 2014-08-20 | 日本化薬株式会社 | メタクリル酸の製造方法及びメタクリル酸製造用触媒 |
JP2011152543A (ja) * | 2011-04-28 | 2011-08-11 | Nippon Kayaku Co Ltd | メタクリル酸製造用触媒の製造方法 |
JPWO2013073691A1 (ja) * | 2011-11-17 | 2015-04-02 | 日本化薬株式会社 | メタクリル酸製造用触媒及びそれを用いたメタクリル酸の製造方法 |
JP2018111720A (ja) * | 2013-10-10 | 2018-07-19 | 日本化薬株式会社 | 不飽和カルボン酸の製造方法、及び担持触媒 |
WO2015163020A1 (ja) * | 2014-04-22 | 2015-10-29 | 株式会社ダイセル | アルデヒド類製造用固体触媒、及びアルデヒド類の製造方法 |
JPWO2015163020A1 (ja) * | 2014-04-22 | 2017-04-13 | 株式会社ダイセル | アルデヒド類製造用固体触媒、及びアルデヒド類の製造方法 |
EP3892367A1 (en) | 2020-04-09 | 2021-10-13 | Röhm GmbH | A tube bundle reactor and method for the production of methacrylic acid through the partial oxidation of methacrolein |
CN115999610A (zh) * | 2022-12-28 | 2023-04-25 | 陕西科技大学 | 一种具有不饱和中心的nc负载渗碳体aop催化剂及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1595600B1 (en) | 2014-06-25 |
KR20050098919A (ko) | 2005-10-12 |
EP1595600A1 (en) | 2005-11-16 |
JP4478107B2 (ja) | 2010-06-09 |
CN100457264C (zh) | 2009-02-04 |
US7825061B2 (en) | 2010-11-02 |
EP2374538A1 (en) | 2011-10-12 |
MXPA05008754A (es) | 2005-10-05 |
BRPI0407442A (pt) | 2006-01-31 |
ZA200507363B (en) | 2006-10-25 |
TWI341219B (en) | 2011-05-01 |
TW200425951A (en) | 2004-12-01 |
US20060154811A1 (en) | 2006-07-13 |
KR100972813B1 (ko) | 2010-07-28 |
EP1595600A4 (en) | 2007-03-21 |
JPWO2004073857A1 (ja) | 2006-06-01 |
CN1750878A (zh) | 2006-03-22 |
MY144325A (en) | 2011-08-29 |
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