WO2000072964A1 - Production d'acide methacrylique et catalyseur a cet effet - Google Patents

Production d'acide methacrylique et catalyseur a cet effet Download PDF

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Publication number
WO2000072964A1
WO2000072964A1 PCT/JP2000/003311 JP0003311W WO0072964A1 WO 2000072964 A1 WO2000072964 A1 WO 2000072964A1 JP 0003311 W JP0003311 W JP 0003311W WO 0072964 A1 WO0072964 A1 WO 0072964A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
methacrylic acid
methacrolein
group
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2000/003311
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English (en)
Japanese (ja)
Inventor
Hiroyuki Naito
Motomu Oh-Kita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Publication of WO2000072964A1 publication Critical patent/WO2000072964A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum

Definitions

  • the present invention provides a catalyst for producing methacrylic acid by gas phase catalytic oxidation of methacrolein with molecular oxygen, a method for producing the catalyst, a method for producing methacrylic acid using the catalyst, and a method for producing methacrylic acid using the catalyst. It relates to the method used for manufacturing.
  • the present invention provides a catalyst capable of producing methacrylic acid in high yield by gas phase catalytic oxidation of methacrolein with molecular oxygen, a method for producing the catalyst, a method for producing methacrylic acid using the catalyst, and a method for producing the same.
  • the purpose is to provide a method for using the catalyst for the production of methacrylic acid.
  • the present invention provides the following formula (1):
  • a methacrylic acid production catalyst having a composition represented by the formula: and having an ammonia adsorption amount at 0 ° C of 1 000 // mo 1 / g-catalyst or more;
  • a method for producing the catalyst for producing methacrylic acid comprising: mixing raw materials of the constituent elements of the catalyst, drying the obtained mixture, and calcining the obtained dried product.
  • a method for producing methacrylic acid using the catalyst a method for producing methacrylic acid, and a method for using the catalyst for producing methacrylic acid.
  • the present invention relates to a catalyst for producing methacrylic acid having a composition represented by the above formula (1), which is used in the gas-phase catalytic oxidation of methacrolein with molecular oxygen, and comprises an ammonia adsorption amount at 0 ° C. Is greater than 100 OO i mo 1 Zg—catalyst.
  • the ammonia adsorption amount at 0 ° C. is preferably at least 1,500 ⁇ 1 Zg—catalyst, particularly preferably 2,000 to 10,000 zmol / g—catalyst.
  • methacrylic acid can be obtained in high yield, but an ammonia adsorption of 1 000 // mo 1 / g— If the amount is less than the catalyst, the yield of methacrylic acid tends to decrease.
  • methacrylic acid can be obtained in high yield by using a catalyst having an ammonia adsorption amount at 0 ° C of 1 000 mo 1 / g or more is that the ammonia adsorption amount of 1 000/1 It is speculated that the adsorption and desorption of the reactant (methacrolein) and the product (methacrylic acid) on the active site of the catalyst are performed more smoothly than when the catalyst is less than mo 1 Zg—catalyst.
  • the ammonia adsorption amount in the present invention refers to the ammonia adsorbed on 1 g of the catalyst at 0 ° C.
  • Amount refers to the total amount of chemical adsorption and physical adsorption. The larger the amount of adsorbed ammonia, the larger the number of acid sites per g of catalyst.
  • the inside of the vessel filled with the catalyst was evacuated in advance, and ammonia was adsorbed at 0 ° C for 30 minutes, and then the temperature was raised to 600 ° C. From the amount of ammonia desorbed from the catalyst.
  • the amount of ammonia adsorbed thus determined is the amount of adsorption obtained by combining the amount of chemical adsorption and the amount of physical adsorption at o ° c.
  • the catalyst of the present invention is not particularly limited as long as it satisfies the composition of the above formula (1).
  • the X element is potassium, rubidium and cesium
  • the Y element is zirconium, silver, iron, zinc, palladium, titanium.
  • tin, and the Z elements are antimony, arsenic, germanium, tellurium, silicon and tantalum. More preferably, element X is potassium and cesium, element Y is zirconium, silver, iron, zinc, titanium and tin, and element Z is antimony, arsenic, germanium, tellurium and tantalum.
  • the method for producing the catalyst of the present invention is not particularly limited.
  • a raw material containing a catalyst constituent element is mixed to prepare a mixed solution or an aqueous slurry containing the catalyst constituent element, and the mixed solution or the aqueous slurry is dried. Then, a solvent such as water is removed, and the obtained dried catalyst precursor is calcined to produce the catalyst of the present invention.
  • a method for preparing a mixed solution or an aqueous slurry containing the catalyst constituent elements does not need to be limited to a special method, and it is well known to the art unless a significant uneven distribution of components is involved.
  • Various methods such as a precipitation method and an oxide mixing method can be used.
  • Preparation conditions such as mixing means, temperature, pressure, and atmosphere for preparing this mixed solution or aqueous slurry are not particularly limited.
  • an oxide, a nitrate, a carbonate, a bicarbonate, an ammonium salt, an acid compound or the like of each element can be appropriately selected and used.
  • Various types of ammonium molybdate such as ammonium paramolybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum trioxide, molybdic acid, and the like can be used as raw materials for molybdenum.
  • Phosphorus oxide, ammonium phosphate and the like can be used, and as a raw material of vanadium, ammonium metavanadate, vanadium pentoxide and the like can be used.
  • a heteropoly acid such as phosphomolybdic acid, molybdovanadophosphoric acid, and ammonium phosphomolybdate can also be used.
  • a raw material for copper the X component, the Y component, and the z component, oxides, nitrates, carbonates, bicarbonates, ammonium salts, acid compounds, and the like of each element can be appropriately selected and used.
  • a raw material of molybdenum ammonium paramolybdate and molybdenum trioxide
  • a phosphorus raw material orthophosphoric acid can be used
  • a raw material of vanadium, ammonium metavanadate and vanadium pentoxide can be used.
  • Copper nitrate and copper oxide can be used as copper raw materials
  • nitrate, bicarbonate and acid compounds can be used as X component raw materials
  • nitrate and oxide compounds can be used as Y component raw materials
  • Oxides and acid compounds can be used as raw materials for the Z component. The ratio of these raw materials used is appropriately changed according to the composition ratio of each element in the obtained final catalyst.
  • various methods can be used as a method for drying the mixed solution or the aqueous slurry containing the constituent elements of the catalyst, for example, an evaporative drying method, a spray drying method, and a drum drying method. And a flash drying method.
  • the type of dryer used for drying, the temperature, pressure, atmosphere, etc., and the presence or absence of stirring during drying are not particularly limited, and a dried product of the catalyst precursor according to the purpose can be obtained by appropriately changing the drying conditions. be able to.
  • the molding method is not particularly limited, and various known dry and wet molding methods can be applied, but a method of molding only with the catalyst component without including a carrier or the like is preferable.
  • the molding conditions such as temperature, pressure, atmosphere and the like during molding are not particularly limited. Specific molding methods include, for example, tablet molding, press molding, extrusion molding, granulation molding, and the like.
  • the shape of the molded article is not particularly limited, either. It can be formed into a desired shape such as a ring or a sphere. At the time of molding, a small amount of a known additive such as graphite or talc may be added.
  • the dried product of the catalyst precursor or the molded product obtained in this way is calcined to obtain a catalyst.
  • the firing method and firing conditions are not particularly limited, and known methods and conditions can be applied.
  • the optimum conditions for the calcination vary depending on the type of the catalyst raw material to be used, the catalyst composition, and the method for preparing the catalyst precursor. At 500-500 ° C., more preferably at 300-450 ° C., most preferably at 350-400 ° C., preferably at least 0.5 hour, more preferably at 1-500 ° C. Performed for 40 hours.
  • the amount of ammonia adsorbed at o ° c specified in the present invention is 1 OOO / mo 1 Z g—a catalyst higher than the catalyst. May not be obtained.
  • the inert gas refers to a gas that does not decrease the catalytic activity, and examples thereof include nitrogen, carbon dioxide, helium, and argon.
  • a raw material gas containing at least methacrolein and molecular oxygen it is preferable to contact a raw material gas containing at least methacrolein and molecular oxygen with the above-mentioned catalyst of the present invention.
  • the catalyst can be used in both fluidized and fixed beds.
  • the concentration of methacrolein in the raw material gas can be varied in a wide range, but is suitably 1 to 20% by volume, and particularly preferably 3 to 10% by volume.
  • the source gas may contain a small amount of impurities such as lower saturated aldehydes such as formaldehyde diacetaldehyde, but it is preferable that the amount is as small as possible.
  • air air enriched with pure oxygen can be used if necessary.
  • the molecular oxygen concentration in the source gas is preferably from 0.4 to 4 mol, particularly preferably from 0.5 to 3 mol, per mol of methacrolein.
  • the source gas may be diluted by adding an inert gas such as nitrogen or carbon dioxide, and steam may be added to the source gas.
  • the reaction pressure is preferably from normal pressure to several atmospheres.
  • the reaction temperature can be selected in the range of 230 to 450 ° C, but is preferably 250 to 400 ° C.
  • Parts in Examples and Comparative Examples are weights. Means part.
  • the composition ratios of the constituent elements of the catalyst (P, Mo, V, Cu, X component, Y component, and ⁇ component) in the obtained catalyst were obtained from the charged amounts of the raw materials used for preparing the catalyst.
  • the ammonia adsorption amount of the catalyst at 0 ° C was measured by the following method using a BET type adsorption measuring device.
  • ammonia is adsorbed at 0 ° C for 30 minutes, and then the amount of ammonia released from the catalyst when the temperature is raised to 600 ° C is determined by gas chromatography.
  • the amount of ammonia adsorbed at 0 ° C of the catalyst was calculated by dividing the amount of ammonia by the weight of the catalyst.
  • A is the number of moles of supplied methacrolein
  • B is the number of moles of reacted methacrolein
  • C is the number of moles of methacrylic acid generated.
  • This catalyst was filled in a reaction tube, and methacrolein 5%, oxygen 10%, steam 30%, When a source gas of 55% nitrogen (volume / Q) was passed at a reaction temperature of 285 ° C and a contact time of 3.6 seconds, the conversion of methacrolein was 82.9% and the selectivity of methacrylic acid was 84.8%, and the single flow yield of methacrylic acid was 70.3%.
  • a catalyst was prepared in the same manner as in Example 1, except that antimony trioxide was not used, and instead, 0.80 part of silver nitrate and 4.47 parts of a 60% by weight aqueous arsenic acid solution were used. The amount of ammonia adsorbed at 0 ° C of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • Example 4 Same procedure as in Example 1 except that antimony trioxide was not used and instead, zirconium nitrate 12.16 parts, tellurium dioxide 1.51 parts, and potassium nitrate 1.43 parts were used. To prepare a catalyst. The amount of ammonia adsorbed at 0 ° C. on the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • Example 4
  • a catalyst was prepared in the same manner as in Example 1, except that antimony trioxide was not used, and instead, 9.53 parts of iron nitrate and 2.09 parts of tantalum oxide were used. The amount of ammonia adsorbed at 0 ° C of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • a catalyst was prepared in the same manner as in Example 1 except that antimony trioxide was not used, and instead, 0.85 parts of silicon dioxide, 3.26 parts of palladium nitrate, and 2.09 parts of rubidium nitrate were used. Was prepared. The amount of ammonia adsorbed at 0 ° C. of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • Example 6
  • Example 1 No antimony trioxide was used, instead 1.42 parts tin oxide, 0.38 parts titanium dioxide, and 60 weight parts. /.
  • a catalyst was prepared in the same manner as in Example 1, except that 1.12 parts of an arsenic acid aqueous solution was used. The amount of ammonia adsorbed at 0 ° C. of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results. Molybdenum trioxide 100 parts, pure water 400 parts, 85 weight. /. 9.35 parts of phosphoric acid, 3.16 parts of vanadium pentoxide, 3.63 parts of germanium dioxide and 0.46 parts of copper oxide were added and mixed under reflux for 5 hours.
  • Example 7 Same as Example 7 except that germanium dioxide and potassium nitrate were not used, and instead of iron nitrate 11.70 parts, antimony trioxide 4.22 parts, and zinc nitrate 3.44 parts.
  • the catalyst was prepared according to the procedure described above. The amount of ammonia adsorbed at 0 ° C of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • a catalyst was prepared in the same manner as in Comparative Example 1, except that 13.2 parts of ammonium latungstate were used. The amount of ammonia adsorbed at 0 ° C of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • a catalyst was prepared in the same manner as in Comparative Example 1, except that ammonium paramolybdate, copper nitrate, boric acid and cesium nitrate were not used, and instead 7.28 parts of cadmium nitrate was used. The amount of ammonia adsorbed at 0 ° C. on the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • Catalyst was prepared in the same manner as in Comparative Example 1, except that phosphoric acid, copper nitrate, boric acid and cesium nitrate were not used, and instead 4.72 parts of chromium oxide and 3.34 parts of calcium nitrate were used. Was prepared. The amount of ammonia adsorbed at 0 ° C of the obtained catalyst was measured, and the reaction was carried out under the same conditions as in Example 1. Table 1 shows the obtained results.
  • a catalyst was prepared in the same manner as in Example 1 except that the pressed compact was fired at 430 ° C. for 12 hours under flowing air.
  • Table 1 shows the ammonia adsorption amount of this catalyst at 0 ° C and the result of a reaction performed under the same conditions as in Example 1.
  • a catalyst for producing methacrylic acid having a composition represented by the above formula (1) according to the present invention which comprises a catalyst having an amount of adsorbed ammonia at 0 ° C. of at least 1,000 ⁇ 1 / g—catalyst.
  • Methacrylic acid could be produced in high yield by gaseous catalytic oxidation of rhein with molecular oxygen.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un catalyseur destiné à la production à haut rendement d'acide méthacrylique par oxydation catalytique de méthacroléïne avec l'oxygène moléculaire en phase vapeur. L'invention concerne également un procédé permettant la production de ce catalyseur ainsi qu'un procédé permettant la production d'acide méthacrylique au moyen de ce catalyseur. L'invention concerne enfin un procédé d'utilisation du catalyseur pour la production d'acide méthacrylique. Ce catalyseur, qui convient à la production d'acide méthacrylique par oxydation catalytique en phase vapeur de méthacroléïne avec l'oxygène présente une composition représentée par la formule PaMobVcCudXeYfZgOh pour une adsorption de l'ammonium à 0°C d'au moins 1.000 νmol/g de catalyseur
PCT/JP2000/003311 1999-05-27 2000-05-24 Production d'acide methacrylique et catalyseur a cet effet Ceased WO2000072964A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP14831499 1999-05-27
JP11/148314 1999-05-27

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WO2000072964A1 true WO2000072964A1 (fr) 2000-12-07

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005039760A1 (fr) * 2003-10-27 2005-05-06 Mitsubishi Rayon Co., Ltd. Procede de production de catalyseur pour la production d'acide methacrylique, catalyseur pour la production d'acide methacrylique et procede de production d'acide methacrylique
JP2006000814A (ja) * 2004-06-21 2006-01-05 Mitsubishi Rayon Co Ltd パラジウム含有担持触媒、その製造方法、及びそれを用いたα，β−不飽和カルボン酸の製造方法
JP2009050749A (ja) * 2007-08-23 2009-03-12 Mitsubishi Rayon Co Ltd パラジウム含有触媒、その製造方法、およびα，β−不飽和カルボン酸の製造方法
KR20210002576A (ko) * 2018-04-26 2021-01-08 미쯔비시 케미컬 주식회사 메타크릴산 제조용 촉매의 제조 방법, 및 메타크릴산 및 메타크릴산 에스터의 제조 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6176436A (ja) * 1984-09-20 1986-04-18 Mitsubishi Rayon Co Ltd 不飽和カルボン酸の製造法
JPS62175435A (ja) * 1986-01-28 1987-08-01 Mitsubishi Rayon Co Ltd メタクリル酸の製造法
EP0253896A1 (fr) * 1986-01-08 1988-01-27 Mitsubishi Rayon Co., Ltd. Procede de production d'acide methacrylique et catalyseurs utilises dans ce procede
EP0265733A1 (fr) * 1986-10-27 1988-05-04 Mitsubishi Rayon Co., Ltd. Procédé de préparation de l'acide méthacrylique
EP0424900A2 (fr) * 1989-10-25 1991-05-02 Mitsubishi Rayon Co., Ltd. Procédé de préparation des catalyseurs pour la préparation d'acide méthacrylique
JPH05279291A (ja) * 1992-04-02 1993-10-26 Mitsubishi Rayon Co Ltd メタクリル酸の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6176436A (ja) * 1984-09-20 1986-04-18 Mitsubishi Rayon Co Ltd 不飽和カルボン酸の製造法
EP0253896A1 (fr) * 1986-01-08 1988-01-27 Mitsubishi Rayon Co., Ltd. Procede de production d'acide methacrylique et catalyseurs utilises dans ce procede
JPS62175435A (ja) * 1986-01-28 1987-08-01 Mitsubishi Rayon Co Ltd メタクリル酸の製造法
EP0265733A1 (fr) * 1986-10-27 1988-05-04 Mitsubishi Rayon Co., Ltd. Procédé de préparation de l'acide méthacrylique
EP0424900A2 (fr) * 1989-10-25 1991-05-02 Mitsubishi Rayon Co., Ltd. Procédé de préparation des catalyseurs pour la préparation d'acide méthacrylique
JPH05279291A (ja) * 1992-04-02 1993-10-26 Mitsubishi Rayon Co Ltd メタクリル酸の製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005039760A1 (fr) * 2003-10-27 2005-05-06 Mitsubishi Rayon Co., Ltd. Procede de production de catalyseur pour la production d'acide methacrylique, catalyseur pour la production d'acide methacrylique et procede de production d'acide methacrylique
US7662742B2 (en) 2003-10-27 2010-02-16 Mitsubishi Rayon Co., Ltd. Process for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and process for producing methacrylic acid
JP4922614B2 (ja) * 2003-10-27 2012-04-25 三菱レイヨン株式会社 メタクリル酸製造用触媒の製造方法
JP2006000814A (ja) * 2004-06-21 2006-01-05 Mitsubishi Rayon Co Ltd パラジウム含有担持触媒、その製造方法、及びそれを用いたα，β−不飽和カルボン酸の製造方法
JP2009050749A (ja) * 2007-08-23 2009-03-12 Mitsubishi Rayon Co Ltd パラジウム含有触媒、その製造方法、およびα，β−不飽和カルボン酸の製造方法
KR20210002576A (ko) * 2018-04-26 2021-01-08 미쯔비시 케미컬 주식회사 메타크릴산 제조용 촉매의 제조 방법, 및 메타크릴산 및 메타크릴산 에스터의 제조 방법
KR102463952B1 (ko) 2018-04-26 2022-11-04 미쯔비시 케미컬 주식회사 메타크릴산 제조용 촉매의 제조 방법, 및 메타크릴산 및 메타크릴산 에스터의 제조 방법

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