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WO2018150797A1 - Catalyseur pour fabrication d'acide méthacrylique, précurseur de catalyseur pour fabrication d'acide méthacrylique, procédés de fabrication de ceux-ci, procédé de fabrication d'acide méthacrylique, et procédé de fabrication d'ester d'acide méthacrylique - Google Patents

Catalyseur pour fabrication d'acide méthacrylique, précurseur de catalyseur pour fabrication d'acide méthacrylique, procédés de fabrication de ceux-ci, procédé de fabrication d'acide méthacrylique, et procédé de fabrication d'ester d'acide méthacrylique Download PDF

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Publication number
WO2018150797A1
WO2018150797A1 PCT/JP2018/001397 JP2018001397W WO2018150797A1 WO 2018150797 A1 WO2018150797 A1 WO 2018150797A1 JP 2018001397 W JP2018001397 W JP 2018001397W WO 2018150797 A1 WO2018150797 A1 WO 2018150797A1
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Prior art keywords
methacrylic acid
catalyst
producing
slurry
catalyst precursor
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PCT/JP2018/001397
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English (en)
Japanese (ja)
Inventor
純 平田
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三菱ケミカル株式会社
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Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020197021407A priority Critical patent/KR102310395B1/ko
Priority to MYPI2019003714A priority patent/MY192057A/en
Priority to JP2018568053A priority patent/JP6819699B2/ja
Priority to CN201880012149.8A priority patent/CN110300622B/zh
Publication of WO2018150797A1 publication Critical patent/WO2018150797A1/fr

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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
    • 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
    • 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
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a catalyst for producing methacrylic acid, a catalyst precursor for producing methacrylic acid, a method for producing them, a method for producing methacrylic acid, and a method for producing a methacrylic acid ester.
  • Examples of a catalyst for producing methacrylic acid used in the production of methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen include, for example, a heteropolyacid containing molybdenum element and phosphorus element System catalysts.
  • heteropolyacid catalyst examples include a proton type heteropolyacid whose counter cation is a proton and a heteropoly acid salt obtained by substituting a part of the proton with a cation other than a proton (hereinafter referred to simply as “heteropolyacid” and Also referred to as “heteropolyacid salt.” Both are also referred to as “heteropolyacid (salt).”
  • Non-Patent Document 1 discloses that the heteropolyacid (salt) has a heterogeneous element (hereinafter referred to as a central element) at the center, and the condensed acid group is condensed by sharing oxygen. It describes that it has a mononuclear or binuclear complex ion to be formed, several types of condensation are known, and that phosphorus, arsenic, silicon, germanium, titanium, and the like can be the central element.
  • Non-Patent Document 2 various structures such as keggin, deficient keggin, dawson, deficient dawson exist as the structure of the heteropolyacid (salt), and these structures are controlled by controlling the pH during the preparation process. It is described that Keggin type heteropolyacid (salt) can be prepared by adjusting the pH of the preparation process to 6 or less.
  • Patent Document 1 discloses a catalyst represented by the following formula (I) as a catalyst having a high selectivity for methacrylic acid.
  • Mo a P b V c Cu d Sb e Nb f X g Y h Z i O j (I) (In the formula (I), Mo, P, V, Cu, Sb, Nb and O each represent molybdenum, phosphorus, vanadium, copper, antimony, niobium and oxygen, and X is a group consisting of iron, cobalt, nickel and zinc.
  • J is the atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.
  • the present invention relates to a catalyst capable of producing methacrylic acid with high selectivity by gas phase catalytic oxidation of methacrolein, a catalyst precursor, a production method thereof, a production method of methacrylic acid using the catalyst, and a methacrylate ester.
  • An object is to provide a manufacturing method.
  • the present invention includes the following [1] to [11].
  • a catalyst for producing methacrylic acid having a composition represented by the following formula (1), which is used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen.
  • a catalyst precursor for producing methacrylic acid having a composition
  • [5] A method for producing a catalyst precursor for producing methacrylic acid according to [2] or [4], (I) preparing a slurry (I) or a solution (I) containing at least a raw material of molybdenum; (Ii) adding an ammonium compound to the slurry (I) or the solution (I) to prepare a slurry (II) containing an ammonium salt; (Iii) drying the slurry (II) to obtain a catalyst precursor for producing methacrylic acid having the Keggin structure; Including A catalyst for producing methacrylic acid, which maintains the pH of the slurry (I), the solution (I), and the slurry (II) within the range of 0.1 to 6.5 in the steps (i) and (ii) A method for producing a precursor.
  • a method for producing a catalyst for producing methacrylic acid comprising a step of calcining a catalyst precursor for producing methacrylic acid produced by the method according to [5].
  • [7] A method for producing methacrylic acid, which uses the catalyst for producing methacrylic acid according to [1] or [3] to produce methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen.
  • a catalyst for producing methacrylic acid is produced by the method according to [6], and methacrolein is produced in a gas phase catalytic oxidation with molecular oxygen using the catalyst for producing methacrylic acid to produce methacrylic acid. Production method.
  • [10] A method for producing a methacrylic acid ester obtained by esterifying methacrylic acid produced by the method according to any one of [7] to [9].
  • [11] A method for producing methacrylic acid ester, wherein methacrylic acid is produced by the method according to any one of [7] to [9], and the methacrylic acid is esterified.
  • a catalyst capable of producing methacrylic acid with high selectivity by gas phase catalytic oxidation of methacrolein, a catalyst precursor, a production method thereof, a production method of methacrylic acid using the catalyst, and methacrylic acid A method for producing an ester can be provided.
  • the catalyst for producing methacrylic acid according to the present invention is used when producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen and has a composition represented by the following formula (1).
  • P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively.
  • A represents at least one element selected from the group consisting of silicon, germanium, arsenic and antimony.
  • E is bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, indium, sulfur, palladium, And at least one element selected from the group consisting of gallium, cerium, and lanthanum.
  • G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
  • ammonium root is a general term for ammonium (NH 3 ) that can be an ammonium ion (NH 4 + ) and ammonium contained in an ammonium-containing compound such as an ammonium salt.
  • the molar ratio of each element is a value obtained by analyzing a component in which a catalyst or a catalyst precursor is dissolved in aqueous ammonia by ICP emission analysis.
  • the molar ratio of the ammonium radical is a value obtained by analyzing the catalyst or catalyst precursor by the Kjeldahl method.
  • the selectivity of methacrylic acid is improved by using the catalyst having the composition represented by the formula (1).
  • the catalyst according to the present invention suppresses this sequential oxidation reaction, it is considered that the selectivity of methacrylic acid is improved.
  • the selectivity of methacrylic acid as the target product is lowered.
  • a + f which is the total amount of phosphorus and A satisfies 0.5 ⁇ a + f ⁇ 2.1.
  • the lower limit of a + f is preferably 0.6 or more, more preferably 0.8 or more, further preferably 0.9 or more, and most preferably 1.3 or more.
  • the upper limit of a + f is preferably 2.0 or less, more preferably 1.9 or less, and even more preferably 1.8 or less.
  • a satisfies 0.5 ⁇ a.
  • the lower limit of a is preferably 0.6 or more, and more preferably 0.7 or more.
  • the upper limit of a is preferably 1.9 or less, and more preferably 1.8 or less.
  • f satisfies 0 ⁇ f.
  • the lower limit of f is preferably 0.01 or more, and more preferably 0.1 or more.
  • the upper limit of f is preferably 1.0 or less, and more preferably 0.9 or less.
  • c + d which is the total amount of V and Nb, satisfies 0.01 ⁇ c + d ⁇ 3.
  • the catalyst contains at least Nb, and 0 ⁇ c and 0.01 ⁇ d ⁇ 3.
  • the lower limit of c + d is preferably 0.1 or more, more preferably 0.15 or more, and further preferably 0.2 or more.
  • the upper limit of c + d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less.
  • the lower limit of d is preferably 0.1 or more, more preferably 0.15 or more, and further preferably 0.2 or more.
  • the upper limit of d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less.
  • d / (c + d) preferably satisfies 0.35 ⁇ d / (c + d) ⁇ 1. This further improves the selectivity of methacrylic acid.
  • the lower limit of d / (c + d) is more preferably 0.5 or more, further preferably 0.75 or more, and particularly preferably 0.9 or more.
  • E satisfies 0.005 ⁇ e ⁇ 3.
  • the lower limit of e is preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.05 or more.
  • the upper limit of e is preferably 2 or less, more preferably 1 or less, and further preferably 0.5 or less.
  • G satisfies 0 ⁇ g ⁇ 3.
  • h satisfies 0.01 ⁇ h ⁇ 3.
  • the lower limit of h is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.5 or more.
  • the upper limit of h is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less.
  • i satisfies 0 ⁇ i ⁇ 5.
  • the upper limit of i is preferably 3 or less, and more preferably 2 or less.
  • the catalyst precursor for producing methacrylic acid according to the present invention (hereinafter also referred to as catalyst precursor) is a precursor of a catalyst used when producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. And it has a Keggin structure and has a composition represented by the following formula (2).
  • P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively.
  • A represents at least one element selected from the group consisting of silicon, germanium, arsenic and antimony.
  • E is bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, indium, sulfur, palladium, And at least one element selected from the group consisting of gallium, cerium, and lanthanum.
  • G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
  • a to j represent the molar ratio of each component.
  • the selectivity of methacrylic acid is improved by using a catalyst obtained from the catalyst precursor having the composition represented by the formula (2).
  • a catalyst obtained from the catalyst precursor having the composition represented by the formula (2) Normally, after methacrolein is oxidized to methacrylic acid, a sequential oxidation reaction occurs in which the oxidation reaction is continued to produce carbon monoxide, carbon dioxide, and the like.
  • the catalyst obtained from the catalyst precursor according to the present invention suppresses this sequential oxidation reaction, it is considered that the selectivity of methacrylic acid is improved.
  • the selectivity of the target product methacrylic acid decreases.
  • a + f which is the total amount of phosphorus and A satisfies 0.5 ⁇ a + f ⁇ 2.4.
  • the selectivity for methacrylic acid is significantly reduced.
  • the lower limit of a + f is preferably 0.6 or more, more preferably 0.8 or more, further preferably 0.9 or more, and most preferably 1.3 or more.
  • the upper limit of a + f is preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.8 or less.
  • a satisfies 0.5 ⁇ a.
  • the lower limit of a is preferably 0.6 or more, and more preferably 0.7 or more.
  • the upper limit of a is preferably 1.9 or less, and more preferably 1.8 or less.
  • f satisfies 0 ⁇ f.
  • the lower limit of f is preferably 0.01 or more, and more preferably 0.1 or more.
  • the upper limit of f is preferably 1.0 or less, and more preferably 0.9 or less.
  • c + d which is the total amount of V and Nb, satisfies 0.01 ⁇ c + d ⁇ 3.
  • the catalyst precursor contains at least Nb, and 0 ⁇ c and 0.01 ⁇ d ⁇ 3.
  • the lower limit of c + d is preferably 0.1 or more, more preferably 0.15 or more, and further preferably 0.2 or more.
  • the upper limit of c + d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less.
  • the lower limit of d is preferably 0.1 or more, more preferably 0.15 or more, and further preferably 0.2 or more.
  • the upper limit of d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less.
  • d / (c + d) preferably satisfies 0.35 ⁇ d / (c + d) ⁇ 1. This further improves the selectivity of methacrylic acid.
  • the lower limit of d / (c + d) is more preferably 0.5 or more, further preferably 0.75 or more, and particularly preferably 0.9 or more.
  • E satisfies 0.005 ⁇ e ⁇ 3.
  • the lower limit of e is preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.05 or more.
  • the upper limit of e is preferably 2 or less, more preferably 1 or less, and further preferably 0.5 or less.
  • G satisfies 0 ⁇ g ⁇ 3.
  • h satisfies 0.01 ⁇ h ⁇ 3.
  • the lower limit of h is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.5 or more.
  • the upper limit of h is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less.
  • i satisfies 0.1 ⁇ i ⁇ 20.
  • the lower limit of i is preferably 0.5 or more, and more preferably 1 or more.
  • the upper limit of i is preferably 18 or less, and more preferably 16 or less.
  • the catalyst precursor for methacrylic acid production according to the present invention has a Keggin type structure.
  • methacrolein exhibits high activity when producing methacrylic acid by vapor-phase catalytic oxidation with molecular oxygen.
  • the structure of the catalyst precursor can be determined by infrared absorption analysis measurement.
  • the catalyst precursor has a Keggin structure, the obtained infrared absorption spectrum has characteristic peaks in the vicinity of 1060, 960, 870, and 780 cm ⁇ 1 .
  • the catalyst for methacrylic acid production according to the present invention has a composition represented by the following formula (3), it is preferable to satisfy the following atomic ratio.
  • P, Mo, V, Nb, Cu, Sb, and O represent phosphorus, molybdenum, vanadium, niobium, copper, antimony, and oxygen, respectively.
  • X represents at least one element selected from the group consisting of silicon, titanium, germanium, arsenic, tellurium and selenium.
  • Z represents at least one element selected from the group consisting of potassium, rubidium and cesium.
  • a to h represent the atomic ratio of each element.
  • a satisfies 0.5 ⁇ a ⁇ 3, preferably satisfies 0.6 ⁇ a ⁇ 2.5, and more preferably satisfies 0.8 ⁇ a ⁇ 2. More preferably 0.9 ⁇ a ⁇ 1.3.
  • c + d satisfies 0.01 ⁇ c + d ⁇ 3, preferably satisfies 0.1 ⁇ c + d ⁇ 2.5, more preferably satisfies 0.15 ⁇ c + d ⁇ 2, and further preferably satisfies 0.2 ⁇ c + d ⁇ 1.
  • d satisfies 0.01 ⁇ d ⁇ 3, preferably satisfies 0.1 ⁇ d ⁇ 2.5, more preferably satisfies 0.15 ⁇ d ⁇ 2, more preferably 0.2 ⁇ d ⁇ 1.
  • e satisfies 0.01 ⁇ e ⁇ 2, preferably satisfies 0.03 ⁇ e ⁇ 1.5, more preferably satisfies 0.04 ⁇ e ⁇ 1, and more preferably 0.05 ⁇ e ⁇ 0. .5 is satisfied.
  • g satisfies 0.01 ⁇ g ⁇ 3, preferably satisfies 0.1 ⁇ g ⁇ 2.5, more preferably satisfies 0.3 ⁇ g ⁇ 2, and more preferably 0.5 ⁇ g ⁇ 1.
  • h satisfies 0.01 ⁇ h ⁇ 3, preferably satisfies 0.1 ⁇ h ⁇ 2.5, more preferably satisfies 0.3 ⁇ h ⁇ 2, and more preferably 0.5 ⁇ h ⁇ 1. .5 is satisfied.
  • the selectivity of methacrylic acid that is the target product may decrease.
  • the reaction rate of methacrolein decreases.
  • d / (c + d) preferably satisfies 0.5 ⁇ d / (c + d) ⁇ 1, more preferably satisfies 0.75 ⁇ d / (c + d) ⁇ 1, and 0.9 ⁇ More preferably, d / (c + d) ⁇ 1 is satisfied.
  • 0.5 ⁇ d / (c + d) ⁇ 1 the selectivity of methacrylic acid is further improved.
  • the method for producing a catalyst precursor for producing methacrylic acid according to the present invention includes the following steps (i) to (iii), and in the steps (i) and (ii), the slurry (I), the solution ( The pH of I) and the slurry (II) is maintained within the range of 0.1 to 6.5.
  • a step of drying the slurry (II) to obtain a catalyst precursor for producing methacrylic acid having the Keggin structure.
  • the method for producing a catalyst precursor for producing methacrylic acid according to the present invention may further include a molding step described later. According to this method, the catalyst precursor for methacrylic acid production according to the present invention can be suitably produced.
  • slurry (I) or solution (I) containing at least a raw material of molybdenum is prepared.
  • the slurry (I) or the solution (I) may be either, for example, the slurry (I) is dissolved in the solvent by suspending the raw material compound of the catalyst component in the solvent using a preparation container.
  • Solution (I) can be prepared respectively.
  • the slurry (I) or the solution (I) contains at least a molybdenum raw material, can contain a component contained in the composition represented by the formula (2), and preferably contains a niobium raw material.
  • the raw material compound used is not particularly limited, and examples thereof include nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxoacids and oxoacid salts of each element, which may be used in combination. it can.
  • the molybdenum raw material include ammonium paramolybdate, molybdenum trioxide, molybdic acid, and molybdenum chloride.
  • Examples of the phosphorus raw material include orthophosphoric acid, phosphorus pentoxide, or phosphates such as ammonium phosphate and cesium phosphate.
  • Examples of the copper raw material include copper sulfate, copper nitrate, copper oxide, copper carbonate, copper acetate, and copper chloride.
  • Examples of the vanadium raw material include phosphovanadomolybdic acid, ammonium metavanadate, vanadium pentoxide, and vanadium chloride.
  • phosphovanadomolybdic acid is used as the vanadium raw material, since molybdenum element and phosphorus element are simultaneously contained in phosphovanadmolybdic acid, the target catalyst precursor composition is obtained according to the amount of phosphovanadomolybdic acid added.
  • the addition amount of molybdenum raw material and phosphorus raw material is adjusted.
  • niobium raw material examples include niobic acid, niobium pentoxide, niobium chloride, niobium hydrogen oxalate, and ammonium oxalate niobate.
  • a water-soluble raw material such as niobium hydrogen oxalate or ammonium niobate oxalate is preferably used as the niobium raw material.
  • a water-insoluble raw material such as niobium pentoxide
  • a preparation method in which the niobium raw material is dissolved in water such as by adding oxalic acid or hydrogen peroxide to water.
  • the slurry (I) or the solution (I) can be obtained by adding a raw material containing an element constituting the catalyst precursor to a solvent and mixing it.
  • a solvent water, an organic solvent or the like can be used, but water is preferably used from an industrial viewpoint. Moreover, you may heat-process the said slurry (I) or the said solution (I) as needed.
  • the order of addition of the raw materials during the preparation is not particularly limited, but in the step (i), the raw material is prepared while maintaining the pH of the slurry (I) or the solution (I) at 0.1 to 6.5. This improves the selectivity of methacrylic acid.
  • the lower limit of the pH is preferably 0.5 or more, and more preferably 1.0 or more.
  • the upper limit of the pH is preferably 6 or less.
  • the pH of the slurry (I) or the solution (I) can be measured with a portable pH meter D-72 (trade name) manufactured by HORIBA.
  • a method for controlling the pH of the slurry (I) or the solution (I) the raw material of each component constituting the catalyst precursor, the addition amount of ammonium root, etc. are appropriately selected, and nitric acid, oxalic acid, etc. are added as appropriate. The method of doing is mentioned.
  • step (ii) an ammonium compound is added to the slurry (I) or the solution (I) to prepare a slurry (II) containing an ammonium salt.
  • the ammonium compound include ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrate, and aqueous ammonia. These ammonium compounds may be used alone or in combination of two or more.
  • a metal cation-containing compound in addition to the ammonium compound.
  • the metal cation-containing compound a compound containing at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium (corresponding to G in the formula (2)) is preferably used.
  • the temperature of the heat treatment is not particularly limited, but it is preferable to heat to a temperature at which the compound containing molybdenum, niobium, copper, phosphorus and, if necessary, other metal elements can be dissolved or reacted with other compounds. ⁇ 130 ° C is preferable, and 95-130 ° C is more preferable. Depending on the vapor pressure of the solvent used, it may be concentrated and refluxed during heating, or may be heat-treated under pressure conditions by operating in a closed container.
  • the rate of temperature increase is not particularly limited, but is preferably 0.8 to 15 ° C./min. When the rate of temperature increase is 0.8 ° C./min or more, the slurry preparation time can be shortened. Moreover, when the rate of temperature increase is 15 ° C./min or less, the temperature can be increased using normal temperature increasing equipment.
  • the slurry (II) is prepared while maintaining the pH at 0.1 to 6.5. This improves the selectivity of methacrylic acid.
  • the lower limit of the pH is preferably 0.5 or more, and more preferably 1.0 or more.
  • the upper limit is preferably 6.0 or less.
  • the pH of the resulting slurry (II) after heat treatment is preferably 0.1 to 3.0, the lower limit is 1.0 or more, and the upper limit is 2. 5 or less is more preferable.
  • the pH of the slurry (II) can be measured with a portable pH meter D-72 (trade name) manufactured by HORIBA.
  • Examples of a method for controlling the pH of the slurry (II) include a method in which raw materials of the respective components constituting the catalyst precursor, an addition amount of ammonium root, and the like are appropriately selected, and nitric acid, oxalic acid, and the like are appropriately added. Thereby, the catalyst precursor which has a preferable structure in the process (iii) mentioned later can be obtained.
  • step (iii) the slurry (II) is dried to obtain a catalyst precursor for producing methacrylic acid having the Keggin structure.
  • drying method There is no particular limitation on the drying method, and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness. Of these, drum drying, spray drying or evaporation to dryness is preferred in the method according to the present invention.
  • the pH of the slurry (II) after the heat treatment obtained in the step (ii) is adjusted to 3 or less, preferably 2.5 or less.
  • the method of doing is mentioned.
  • the structure of the catalyst precursor can be determined by infrared absorption analysis measurement. When the catalyst precursor has a Keggin structure, the obtained infrared absorption spectrum has characteristic peaks in the vicinity of 1060, 960, 870, and 780 cm ⁇ 1 .
  • the catalyst precursor or the catalyst after calcination obtained in the calcination step described later is formed.
  • the shape of the catalyst is appropriately selected from shapes suitable for each reaction mode. do it.
  • the method for forming the catalyst used in the fixed bed reactor is not particularly limited, and can be appropriately selected from known methods. However, it is preferable to form the catalyst so that the pressure loss during the reaction does not increase.
  • the molding method include tableting molding, wet molding, pressure molding, rolling granulation, and the like, and a suitable size and shape may be used depending on the use conditions.
  • the method for producing a catalyst for producing methacrylic acid comprises a catalyst precursor obtained in the step (iii) or a molded product of the catalyst precursor obtained in the molding step (hereinafter collectively referred to as catalyst precursor).
  • Step) (hereinafter also referred to as a firing step).
  • the catalyst precursor is fired to obtain a catalyst for producing methacrylic acid.
  • a suitable method may be appropriately selected from stationary firing, fluidized firing, and the like.
  • the stationary firing include a firing method using a box-type electric furnace, an annular firing furnace, or the like.
  • fluidized firing include a method of firing using a fluidized firing furnace, a rotary kiln, or the like.
  • the firing gas can be appropriately selected from air, nitrogen and the like. If the desired firing gas atmosphere can be maintained, the firing gas may or may not be circulated.
  • the firing temperature is preferably 200 to 500 ° C, the lower limit is preferably 300 ° C or higher, and the upper limit is more preferably 450 ° C or lower.
  • the firing time is preferably 0.5 to 40 hours, more preferably 1 to 40 hours, and even more preferably 2 to 40 hours.
  • the obtained catalyst may be used alone, but may be supported on an inert carrier such as silica, alumina, silica / alumina, silicon carbide, or mixed with these. Moreover, you may mix and use with the catalyst manufactured by methods other than the manufacturing method which concerns on this invention.
  • the method for producing methacrylic acid according to the present invention produces methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen using the catalyst for methacrylic acid production according to the present invention.
  • the method for producing methacrylic acid according to the present invention comprises producing a catalyst for producing methacrylic acid by the method according to the present invention, and subjecting methacrolein to gas phase catalytic oxidation with molecular oxygen using the catalyst for producing methacrylic acid. Produces methacrylic acid.
  • the method for producing methacrylic acid according to the present invention produces methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen using the methacrylic acid production catalyst produced by the method according to the present invention. According to these methods, methacrylic acid can be produced with high selectivity.
  • the method can be carried out by bringing a raw material gas containing methacrolein and molecular oxygen into contact with the methacrylic acid production catalyst.
  • concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, more preferably 3 to 10% by volume.
  • the raw material methacrolein may contain a small amount of impurities such as water and lower saturated aldehydes that do not substantially affect the present reaction.
  • the concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol, more preferably 0.5 to 3 mol, per 1 mol of methacrolein.
  • the molecular oxygen source is preferably air from the viewpoint of economy. If necessary, a gas enriched with molecular oxygen by adding pure oxygen to air may be used.
  • the raw material gas may be obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the source gas. By performing the reaction in the presence of water, methacrylic acid can be obtained with higher selectivity and higher yield.
  • concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, more preferably 1 to 40% by volume.
  • the contact time between the raw material gas and the catalyst for producing methacrylic acid is preferably 1.5 to 15 seconds, and more preferably 2 to 10 seconds.
  • the reaction pressure is preferably 0.1 to 1 MPa (G). However, (G) means a gauge pressure.
  • the reaction temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
  • methacrylic acid produced by the method according to the present invention is esterified.
  • the manufacturing method of the methacrylic acid ester which concerns on this invention manufactures methacrylic acid by the method which concerns on this invention, and esterifies this methacrylic acid.
  • a methacrylic acid ester can be obtained using methacrylic acid obtained by gas phase catalytic oxidation of methacrolein.
  • the alcohol to be reacted with methacrylic acid is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol.
  • Examples of the resulting methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
  • the reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin.
  • the reaction temperature is preferably 50 to 200 ° C.
  • composition ratio of each element in the catalyst precursor and the catalyst was determined by analyzing the catalyst or a component obtained by dissolving the catalyst precursor in aqueous ammonia by ICP emission analysis.
  • the molar ratio of the ammonium root was determined by analyzing the catalyst or catalyst precursor by the Kjeldahl method. Further, the pH of the slurry and the solution was measured using a portable pH meter D-72 (trade name) manufactured by HORIBA.
  • the raw material gas and the product were analyzed using gas chromatography. From the results of gas chromatography, the reaction rate of methacrolein and the selectivity of methacrylic acid were determined by the following formula.
  • Reaction rate (%) of methacrolein number of moles of reacted methacrolein / number of moles of methacrolein supplied ⁇ 100
  • Methacrylic acid selectivity (%) number of moles of methacrylic acid produced / number of moles of reacted methacrolein ⁇ 100.
  • Example 1 A diluted product of 1200 parts of pure water at room temperature, 300 parts of molybdenum trioxide, 21 parts of ammonium niobate oxalate, and 20.1 parts of 85 mass% phosphoric acid aqueous solution with 18 parts of pure water, 24 mass% arsenic acid aqueous solution A dilution obtained by diluting 6 parts with 18 parts of pure water and a solution obtained by dissolving 4.2 parts of copper (II) nitrate trihydrate in 9.0 parts of pure water were mixed to obtain slurry (I). It was.
  • the pH was in the range of 1.4 to 2.5.
  • the slurry (II) was heated and evaporated to dryness to obtain a catalyst precursor.
  • Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. Further, the catalyst precursor had a Keggin type structure.
  • the obtained catalyst precursor is pressure-molded, crushed, and classified using a sieve so that the particle size is in the range of 710 ⁇ m to 2.36 mm, and calcined at 380 ° C. for 5 hours under air flow.
  • Table 2 shows the composition ratio of the obtained catalyst excluding oxygen.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • the catalyst was charged into the reactor, and a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen was circulated, and the reaction was evaluated at a reaction temperature of 285 ° C.
  • the catalyst loading was adjusted so that the reaction rate of methacrolein was within a range of 13 to 27%.
  • the gas after the reaction was collected and analyzed by gas chromatography to calculate methacrolein reaction rate and methacrylic acid selectivity. The results are shown in Table 2.
  • Example 2 the catalyst precursor was prepared in the same manner as in Example 1, except that the amount of ammonium niobate oxalate was changed to 17 parts and the amount of 60% by mass aqueous arsenic acid solution was changed to 20.5 parts. Manufactured. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) was changed within the range of 1.4 to 5.6, and the slurry (II) obtained after heating and stirring was changed. The pH was in the range of 1.4 to 2.5. The composition ratio of the obtained catalyst precursor excluding oxygen is shown in Table 1. Further, the catalyst precursor had a Keggin type structure.
  • the resulting catalyst precursor was molded and calcined in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated in the same manner as in Example 1 using this catalyst.
  • Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • Example 3 Diluted product obtained by diluting 300 parts of molybdenum trioxide, 0.22 part of ammonium metavanadate, 13 parts of ammonium niobate oxalate, and 20.1 parts of 85 mass% phosphoric acid aqueous solution with 18 parts of pure water to 1200 parts of pure water at room temperature , 24.6 parts of a 60 mass% arsenic acid aqueous solution diluted with 18 parts of pure water, and a solution obtained by dissolving 4.2 parts of copper (II) nitrate trihydrate in 9.0 parts of pure water Thus, slurry (I) was obtained.
  • slurry (I) While the slurry (I) is stirred at room temperature, a solution obtained by dissolving 33.6 parts of cesium bicarbonate in 60 parts of pure water at room temperature and a solution obtained by dissolving 27.5 parts of ammonium carbonate in 73 parts of pure water at room temperature was added dropwise to obtain slurry (II).
  • the resulting slurry (II) was heated at 2 ° C./min, and heated and stirred at 95 ° C. for 2 hours.
  • the pH of the slurry (I) and the slurry (II) was changed within the range of 1.4 to 5.6, and the slurry (II) obtained after heating and stirring was changed.
  • the pH was in the range of 1.4 to 2.5.
  • the slurry (II) was heated and evaporated to dryness to obtain a catalyst precursor.
  • Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. Further, the catalyst precursor had a Keggin type structure.
  • the resulting catalyst precursor was molded and calcined in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated in the same manner as in Example 1 using this catalyst.
  • Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • Example 4 In Example 3, a catalyst precursor was produced in the same manner as in Example 3 except that the amount of ammonium metavanadate was changed to 2 parts.
  • the pH of the slurry (I) and the slurry (II) was changed within the range of 1.5 to 5.7, and the slurry (II) obtained after heating and stirring was changed.
  • the pH was in the range of 1.5 to 2.5.
  • Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. Further, the catalyst precursor had a Keggin type structure.
  • the resulting catalyst precursor was molded and calcined in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated in the same manner as in Example 1 using this catalyst.
  • Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • Example 5 To 1200 parts of pure water at room temperature, 300 parts of molybdenum trioxide, 4.1 parts of ammonium metavanadate, 10.5 parts of ammonium niobate oxalate, and 20.1 parts of 85 mass% phosphoric acid aqueous solution were diluted with 18 parts of pure water. Diluted product, diluted product obtained by diluting 24.6 parts of 60 mass% arsenic acid aqueous solution with 18 parts of pure water, and dissolved product obtained by dissolving 4.2 parts of copper (II) nitrate trihydrate in 9.0 parts of pure water Were mixed to obtain slurry (I).
  • the resulting catalyst precursor was molded and calcined in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated in the same manner as in Example 1 using this catalyst.
  • Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • Example 5 In Example 5, the amount of ammonium metavanadate was changed to 8.2 parts, the amount of cesium bicarbonate was changed to 23.5 parts, and the amount of potassium bicarbonate was changed to 5.2 parts.
  • a catalyst precursor was produced in the same manner as in Example 5 except that ammonium was not used.
  • the pH of the slurry (I) and the slurry (II) was changed within the range of 1.5 to 5.7, and the slurry (II) obtained after heating and stirring was changed. The pH was in the range of 1.5 to 2.5.
  • Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. Further, the catalyst precursor had a Keggin type structure.
  • the resulting catalyst precursor was molded and calcined in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated in the same manner as in Example 1 using this catalyst.
  • Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • the resulting catalyst precursor was molded and calcined in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated in the same manner as in Example 1 using this catalyst.
  • Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results.
  • the molar ratio of ammonium radicals in the catalyst was 0 ⁇ i ⁇ 1.
  • a methacrylic acid ester can be obtained by esterifying the methacrylic acid obtained in this example.
  • the catalyst for producing methacrylic acid according to the present invention can produce methacrylic acid with high selectivity, it is useful when producing methacrylic acid industrially.

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Abstract

L'invention fournit un catalyseur permettant de fabriquer selon une sélectivité élevée un acide méthacrylique par oxydation catalytique en phase gazeuse d'une méthacroléine. Plus précisément, l'invention concerne un Catalyseur pour fabrication d'acide méthacrylique qui est mis en œuvre lors de la fabrication d'un acide méthacrylique par oxydation catalytique en phase gazeuse d'une méthacroléine à l'aide d'un oxygène moléculaire, et qui présente une composition représentée par la formule suivante. ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ (A représente au moins un élément parmi Ｓｉ, Ｇｅ, Ａｓ et Ｓｂ, E représente au moins un élément parmi Ｂｉ, Ｚｒ, Ｔｅ, Ａｇ, Ｓｅ, Ｗ, Ｂ, Ｆｅ, Ｚｎ, Ｃｒ, Ｍｇ, Ｃａ, Ｓｒ, Ｔａ, Ｃｏ, Ｎｉ, Ｍｎ, Ｂａ, Ｔｉ, Ｓｎ, Ｐｂ, Ｉｎ, Ｓ, Ｐｄ, Ｇａ, Ｃｅ et Ｌａ, et G représente au moins un élément parmi Ｌｉ, Ｎａ, Ｋ, Ｒｂ, Ｃｓ et Ｔｌ. Lorsque ｂ＝１２, ０,５≦ａ＋ｆ≦２,１, ０,０１≦ｃ＋ｄ≦３, ０,５≦ａ, ０≦ｃ, ０,０１≦ｄ≦３, ０,００５≦ｅ≦３, ０≦ｆ, ０≦ｇ≦３, ０,０１≦ｈ≦３ et ０≦ｉ≦５ sont satisfaits. J représente le rapport molaire de l'oxygène satisfaisant la valence de chaque composant.)
PCT/JP2018/001397 2017-02-17 2018-01-18 Catalyseur pour fabrication d'acide méthacrylique, précurseur de catalyseur pour fabrication d'acide méthacrylique, procédés de fabrication de ceux-ci, procédé de fabrication d'acide méthacrylique, et procédé de fabrication d'ester d'acide méthacrylique WO2018150797A1 (fr)

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MYPI2019003714A MY192057A (en) 2017-02-17 2018-01-18 Catalyst for production of methacrylic acid, catalyst precursor for production of methacrylic acid, method for producing said catalyst and catalyst precursor, method for producing methacrylic acid, and method for producing methacrylate ester
JP2018568053A JP6819699B2 (ja) 2017-02-17 2018-01-18 メタクリル酸製造用触媒、メタクリル酸製造用触媒前駆体、およびそれらの製造方法、メタクリル酸の製造方法、並びにメタクリル酸エステルの製造方法
CN201880012149.8A CN110300622B (zh) 2017-02-17 2018-01-18 甲基丙烯酸制造用催化剂、甲基丙烯酸制造用催化剂前体和它们的制造方法、甲基丙烯酸的制造方法以及甲基丙烯酸酯的制造方法

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WO2021226172A1 (fr) * 2020-05-08 2021-11-11 Air Company Holdings, Inc. Catalyseurs à base de molybdène pour la conversion de dioxyde de carbone

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JP7441474B2 (ja) * 2020-03-31 2024-03-01 三菱ケミカル株式会社 触媒、イソブチルアルデヒドおよびメタクロレインの製造方法、メタクリル酸の製造方法、及びメタクリル酸エステルの製造方法
CN113976179B (zh) * 2021-11-04 2024-02-09 淄博市翔力致高新材料有限责任公司 一种空心结构催化剂及其制备方法和用途

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