JP5295815B2 - Production catalyst for methacrolein and methacrylic acid - Google Patents

Production catalyst for methacrolein and methacrylic acid Download PDF

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JP5295815B2
JP5295815B2 JP2009034888A JP2009034888A JP5295815B2 JP 5295815 B2 JP5295815 B2 JP 5295815B2 JP 2009034888 A JP2009034888 A JP 2009034888A JP 2009034888 A JP2009034888 A JP 2009034888A JP 5295815 B2 JP5295815 B2 JP 5295815B2
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methacrylic acid
catalyst
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methacrolein
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JP2010188276A (en
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好三郎 野村
修 山西
和也 土本
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住友化学株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Description

The present invention relates to a catalyst for producing methacrolein and methacrylic acid, and more particularly to a catalyst for producing methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene with molecular oxygen.

As a catalyst for producing methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene with molecular oxygen, Japanese Patent Application Laid-Open No. 5-23596 discloses a general formula (1).
Mo 12 Bi b Fe c A d B e O f ··· (1)
[In the formula, Mo represents a molybdenum atom, Bi represents a bismuth atom, Fe represents an iron atom, A represents at least one atom selected from the group consisting of nickel and cobalt, and B represents potassium, rubidium, cesium and thallium. At least one atom selected from the group consisting of: b satisfies 0 <b ≦ 10, c satisfies 0 <c ≦ 10, d satisfies 1 ≦ d ≦ 10, and e satisfies 0 <e ≦ 2 is satisfied, and x represents the number of oxygen atoms determined by the oxidation state of each atom. ]
As a production method thereof, a method of adding an organic substance having a particle diameter of 10 μm or less to the catalyst precursor powder, kneading, molding and firing is disclosed.

By charging such a catalyst into a fixed bed reactor and passing a mixed gas of isobutylene and molecular oxygen through this reactor, isobutylene undergoes gas phase catalytic oxidation with molecular oxygen in the reactor, and methacrolein and methacrylic acid are converted. Can be obtained.

As such a catalyst for producing methacrolein and methacrylic acid, a catalyst capable of producing methacrolein and methacrylic acid from isobutylene with high conversion and high selectivity is required.

JP-A-5-23596

Accordingly, the present inventors have intensively studied to develop a catalyst capable of producing methacrolein and methacrylic acid from isobutylene with high conversion and high selectivity, and as a result, the present invention has been achieved.

That is, the present invention is a catalyst for producing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene with molecular oxygen, which is represented by the above general formula (1) and has a cumulative pore volume of 0.3 cm 3. / g or more, more macroporous volume pore radius 1μm is 0.04cm 3 /g~0.15cm 3 / g, the product of the packing bulk density and specific surface area (X) (Y) (X × Y) is intended to provide a methacrolein and production catalyst of methacrylic acid, which is a 3.3m 2 / cm 3 ~5m 2 / cm 3.

According to the production catalyst of the present invention, methacrolein and methacrylic acid can be produced by gas phase catalytic oxidation of isobutylene with molecular oxygen at high conversion and high selectivity.

The catalyst of the present invention is a catalyst represented by the above general formula (1), and can be produced by, for example, a method of adding an organic powder and water to a catalyst precursor powder, kneading, molding and firing.

The catalyst precursor powder includes at least one atom (A) selected from the group consisting of metal atoms constituting the catalyst represented by the general formula (1), that is, molybdenum atoms, bismuth atoms, iron atoms, nickel and cobalt, It is a precursor powder containing at least one atom (B) selected from the group consisting of potassium, rubidium, cesium and thallium and led to the production catalyst by calcination.

Such catalyst precursor powder includes, for example, an aqueous solution of ammonium paramolybdate, nitrate of at least one atom (A) selected from the group consisting of nickel and cobalt, potassium, rubidium, and bismuth nitrate and ferric nitrate. And an aqueous solution containing nitrate of at least one atom (B) selected from the group consisting of cesium and thallium, and then water is distilled off.

The particle diameter of the catalyst precursor powder is usually 0.1 μm to 50 μm, and the center particle diameter is usually 0.2 μm to 7 μm, preferably 0.3 μm to 3.5 μm.

Examples of the organic powder include polymer compounds, grain powder, wood chips, activated carbon powder, and cellulose powder.
The average particle diameter of the organic powder is 400 μm to 800 μm, preferably 500 μm to 700 μm.
The added amount M 1 (dry mass) of the organic powder is 0.04 to 0.2 times, preferably 0.1 to 0.2 times the amount M 0 (dry mass) of the precursor powder. Mass times.

Organic powder and water, the total amount of organic powder M 1 (dry weight) the value obtained by dividing the true specific gravity (ρ 1) (M 1 / ρ 1) and water amount V 2 (volume) (M 1 / ρ 1 + V 1) and the ratio of the dry weight of the precursor powder (M 0) [(M 1 / ρ 1 + V 1) / M 0 ] is 0.3cm 3 /g~0.6cm 3 / g preferably added so as to 0.2cm 3 /g~0.5cm 3 / g.

Fibers such as ceramic fibers and binders such as methylcellulose may be added to the catalyst precursor powder.

An organic powder and water are added to the catalyst precursor powder and then kneaded, and then the resulting clay-like kneaded product is formed. Examples of the molding method include an extrusion molding method, a tableting molding method, a submerged granulation method, an injection molding method, a rolling granulation method, and a press molding method. The extrusion molding method is preferred. By such a method, it is usually formed into a columnar shape or a ring shape, and the outer diameter is usually 1.5 mm to 10 mm, and the length is usually 1.5 mm to 10 mm. When forming a ring shape, the ratio of the outer diameter (d 1) and the inner diameter (d 2) (d 1 / d 2) is usually 1.1 to 10.

Firing is usually performed in the air. The firing temperature is usually 400 ° C to 700 ° C, preferably 450 ° C to 650 ° C. Thus, by baking, a catalyst can be obtained as a molded body having substantially the same shape as the molded body obtained by molding the kneaded product.

In the catalyst of the present invention, the product (X × Y) of the specific surface area (X) and the packing bulk density (Y) is 3.3 to 5 m 2 / cm 3 . When the firing temperature is increased, the specific surface area (X) is decreased, and when the firing temperature is decreased, the specific surface area (X) is increased. The filling bulk density (Y) can be adjusted by the size and shape of a molded body obtained by molding the catalyst precursor.

The catalyst of the present invention is a catalyst for producing methacrolein and methacrylic acid by vapor-phase catalytic oxidation of isobutylene with molecular oxygen, charged in a fixed bed reactor, and in this fixed bed reactor, By subjecting isobutylene to vapor phase catalytic oxidation with molecular oxygen, methacrolein and methacrylic acid can be produced with high conversion and high selectivity.

The amount of molecular oxygen used is usually 1 to 3 times the mole of isobutylene. The reaction temperature in the catalytic gas phase oxidation is usually 300 ° C. to 400 ° C., and the reaction pressure is atmospheric pressure (about 0.1 MPa (absolute pressure)) to 500 kPa (absolute pressure). Isobutylene and molecular oxygen are usually introduced into the fixed bed reactor at a space velocity SV = 500 / h to 5000 / h. Isobutylene and molecular oxygen may be mixed with other gas components such as nitrogen gas and water vapor and used for the reaction.

Hereinafter, the present invention will be described in more detail, but the present invention is not limited to such examples.

The evaluation method is as follows.
(1) Particle size and center particle size The particle size distribution was determined with a laser scattering particle size distribution analyzer (“Microtrac HRA” manufactured by Reed and Northrup). Further, a cumulative mass% histogram was determined from the particle size distribution, and the central particle size was determined as a cumulative percentage 50% equivalent diameter [D 50 ].
(2) BET specific surface area It was determined by a nitrogen adsorption method using a specific surface area measuring device ["Macsorb Model-1201" manufactured by Mountec Co., Ltd.].
(3) The cumulative pore volume and the macropore volume pore volume measuring device [“MICROERITICS” “Autopore III 9420”] were used to determine the volume by mercury porosimetry.
(4) Filled bulk density A graduated cylinder with an internal volume of 200 mL was filled with 100 g of the catalyst, the apparent volume was measured to determine the density, and the resulting bulk density was obtained.

Example 1
A solution was obtained by dissolving 132.4 parts by mass of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24 · 4H 2 O] in 150 parts by mass of hot water. Cobalt nitrate [Co (NO 3) 2 · 6H 2 O ] 131 parts by weight, ferric nitrate [Fe (NO 3) 3 · 9H 2 O ] 60.6 parts by mass of cesium nitrate [CsNO 3] 5.85 mass Part was dissolved in 60 parts by mass of warm water, and then 29.1 parts by mass of bismuth nitrate [Bi (NO 3 ) 3 .5H 2 O] was dissolved to obtain a solution. While stirring the liquid A, the liquid B was added thereto, and the obtained mixed solution was heat-treated with an air dryer to obtain a catalyst precursor powder. The particle diameter of the catalyst precursor powder was in the range of 0.1 μm to 10 μm, and the center particle diameter was 3 μm.

To 100 parts by mass of the catalyst precursor powder obtained above, 4 parts by mass of walnut shell powder (“# 30” average particle diameter 654 μm, true specific gravity 1.3 g / cm 3 manufactured by Japan Walnut Co., Ltd.), ceramic fiber [Toshiba Monoflux, “RFC400SL”, fiber length 300 μm to 500 μm, fiber diameter 2 μm to 4 μm] 6 parts by mass, methyl cellulose [Shin-Etsu Chemical “SM4000”] 4 parts by mass and ion-exchanged water 42.6 parts by mass are added and mixed. A kneaded product was obtained by kneading with “Miyazaki Tekko Co., Ltd.“ MP-30 ””. This kneaded product was extruded from an extruder and formed into a columnar shape having a diameter of 6 mm and a length of 6 mm to 7 mm. The obtained molded product was dried and then calcined in the hot air circulating furnace at 539 ° C. for 6 hours in the air to obtain a columnar catalyst.

Cumulative pore volume of the catalyst is 0.43 cm 3 / g, more macropore volume pore radius 1μm is 0.11 cm 3 / g, a specific surface area (X) is 4.88m 2 / g, packing bulk density ( Y) was 0.77 g / cm 3 , and the product (X × Y) of specific surface area (X) and packed bulk density (Y) was 3.76 m 2 / cm 3 .

3 cm 3 of the catalyst obtained above was weighed and filled into a glass tube having an inner diameter of 18 mm, and a mixed gas of isobutylene, molecular oxygen, nitrogen and water vapor (molar ratio was 1: 2.2: 6) from one end of the glass. .2: 2) was supplied at a space velocity (SV) of 1750 / h and reacted at a reaction temperature of 370 ° C. to obtain a gas containing methacrolein and methacrylic acid from the other end of the glass tube. The composition of this gas was measured with a gas chromatograph, and the conversion rate (%) and selectivity (%) were determined by the following equations. The conversion rate was 66.7% and the selectivity was 87.1%. .

Conversion (%) = [supplied isobutylene (mol) −unreacted isobutylene (mol)]
÷ [Supplied isobutylene (mol)]
Selectivity (%) = [generated methacrolein (mol) + generated methacrylic acid (mol)]
÷ [supplied isobutylene (mol) -unreacted isobutylene (mol)]

Comparative Example 1
A catalyst was obtained in the same manner as in Example 1 except that the calcination temperature was 553 ° C., and isobutylene and methacrylic acid were obtained. Cumulative pore volume of the catalyst is 0.41 cm 3 / g, more macropore volume pore radius 1μm is 0.11 cm 3 / g, a specific surface area (X) is 3.95m 2 / g, packing bulk density ( Y) was 0.77 g / cm 3 , and the product (X × Y) of the specific surface area (X) and the filling bulk density (Y) was 3.04 m 2 / cm 3 . The conversion of isobutylene and methacrylic acid was 49.4%, and the selectivity was 88.5%.

Comparative Example 2
Walnut shell powder (Nippon Walnut, “F180”, average particle size of 180 μm) was pulverized by a vibration mill to obtain crushed walnut shell powder (true specific gravity of 1.5 g / cm 2 ) having an average particle size of 17.2 μm. . To 100 parts by mass of the catalyst precursor powder obtained in Example 1, 6 parts by mass of the pulverized walnut shell powder obtained above, 6 parts by mass of ceramic fiber [RFC400SL], 4 parts by mass of methylcellulose [SM4000] and 57.6 of ion-exchanged water. Mass parts were added and mixed, and kneaded with a kneader [Miyazaki Tekko "MP-30"] to obtain a kneaded product. A catalyst was obtained in the same manner as in Example 1 except that the kneaded material obtained above was used instead of the kneaded material obtained in Example 1 and the calcination temperature was set to 569 ° C., to obtain methacrolein and methacrylic acid It was. Cumulative pore volume of the catalyst is 0.42 cm 3 / g, more macropore volume pore radius 1μm is 0.01 cm 3 / g, a specific surface area (X) is 3.63m 2 / g, packing bulk density ( Y) was 0.83 g / cm 3 , and the product (X × Y) of specific surface area (X) and packed bulk density (Y) was 3.01 m 2 / cm 3 . The conversion of isobutylene and methacrylic acid was 42.3%, and the selectivity was 88.4%.

Comparative Example 3
To 100 parts by mass of the catalyst precursor powder obtained in Example 1, 6 parts by mass of ceramic fiber [RFC400SL], 4 parts by mass of methylcellulose [SM4000] and 35.7 parts by mass of ion-exchanged water were added and mixed. Kneaded by a company "MP-30"] to obtain a kneaded product. A catalyst was obtained and methacrolein and methacrylic acid were obtained in the same manner as in Example 1 except that the kneaded product obtained above was used instead of the kneaded product obtained in Example 1 and the calcination temperature was 576 ° C. It was. Cumulative pore volume of the catalyst is 0.26 cm 3 / g, more macropore volume pore radius 1μm is 0.02 cm 3 / g, a specific surface area (X) is 2.91m 2 / g, packing bulk density ( Y) was 1.0 g / cm 3 , and the product (X × Y) of the specific surface area (X) and the packing bulk density (Y) was 2.91 m 2 / cm 3 . The conversion of isobutylene and methacrylic acid was 35.3%, and the selectivity was 88.5%.

Claims (3)

  1. A catalyst for producing methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene with molecular oxygen,
    General formula (1)
    Mo 12 Bi b Fe c A d B e O f ··· (1)
    [In the formula, Mo represents a molybdenum atom, Bi represents a bismuth atom, Fe represents an iron atom, A represents at least one atom selected from the group consisting of nickel and cobalt, and B represents potassium, rubidium, cesium and thallium. At least one atom selected from the group consisting of: b satisfies 0 <b ≦ 10, c satisfies 0 <c ≦ 10, d satisfies 1 ≦ d ≦ 10, and e satisfies 0 <e ≦ 2 is satisfied, and x represents the number of oxygen atoms determined by the oxidation state of each atom. ]
    In shown, and the cumulative pore volume of 0.3 cm 3 / g or more, more macroporous volume pore radius 1μm is 0.04cm 3 /g~0.15cm 3 / g, a specific surface area ( X) the filling bulk density (Y) of the product (X × Y) is 3.3m 2 / cm 3 ~5m 2 / cm 3 methacrolein and production catalyst of methacrylic acid, characterized in that.
  2. An organic powder and water having an average particle diameter of 400 μm to 800 μm are added to the catalyst precursor powder represented by the general formula (1), and the addition amount M 1 (dry mass) of the organic powder is the amount M of the precursor powder used. A value (M 1 / ρ 1 ) obtained by dividing the addition amount M 1 (dry mass) of the organic powder by its true specific gravity (ρ 1 ), which is 0.04 times to 0.2 times the 0 (dry mass). And the ratio (M 1 / ρ 1 + V 1 ) / M of the total amount of added water V 2 (volume) (M 1 / ρ 1 + V 1 ) and the dry mass (M 0 ) of the precursor powder 0] added to a 0.3cm 3 /g~0.6cm 3 / g, molding were kneaded, methacrolein and methacrylic acid according to claim 1, characterized in that the calcination of production catalyst Production method.
  3. A process for producing methacrolein and methacrylic acid, characterized in that isobutylene is subjected to gas phase catalytic oxidation with molecular oxygen in a fixed bed reactor packed with the production catalyst according to claim 1.
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WO2019177031A1 (en) * 2018-03-14 2019-09-19 三菱ケミカル株式会社 Catalyst molded body, and method for producing unsaturated aldehyde and unsaturated carboxylic acid using same

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JPS57119837A (en) * 1981-01-16 1982-07-26 Ube Ind Ltd Catalyst for oxidation of olefin
JP2742413B2 (en) * 1987-06-18 1998-04-22 株式会社日本触媒 Excellent production method thereof methacrolein synthesizing catalyst and reproducibility
JP2974826B2 (en) * 1991-07-17 1999-11-10 三菱レイヨン株式会社 Preparation of methacrolein and methacrylic acid production catalyst
DE19855913A1 (en) * 1998-12-03 2000-06-08 Basf Ag Multimetal oxide material for the gas-phase catalytic oxidation of organic compounds
MY139735A (en) * 2003-11-18 2009-10-30 Basf Ag Preparation of acrolein by heterogeneously catalyzed partial gas phase oxidation of propene
CN100546715C (en) * 2004-07-22 2009-10-07 马克斯·普朗克协会弗里茨·哈贝尔研究所;那诺克有限公司;罗伯特·施勒格尔 Metal oxide catalyst and method for the preparation thereof
JP4889083B2 (en) * 2005-09-01 2012-02-29 旭化成ケミカルズ株式会社 Oxide catalyst for producing methacrolein, method for producing the catalyst, and method for producing methacrolein using the catalyst

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