KR101419052B1 - Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid - Google Patents

Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid Download PDF

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KR101419052B1
KR101419052B1 KR1020070096701A KR20070096701A KR101419052B1 KR 101419052 B1 KR101419052 B1 KR 101419052B1 KR 1020070096701 A KR1020070096701 A KR 1020070096701A KR 20070096701 A KR20070096701 A KR 20070096701A KR 101419052 B1 KR101419052 B1 KR 101419052B1
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catalyst
methacrylic acid
mixture
acid
methacrolein
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KR1020070096701A
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Korean (ko)
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KR20080028808A (en
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준야 요시자와
요시히코 오히시
에이이치 시라이시
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스미또모 가가꾸 가부시끼가이샤
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28Regeneration or reactivation
    • B01J27/285Regeneration or reactivation of catalysts comprising compounds of phosphorus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198Vanadium
    • B01J27/199Vanadium with chromium, molybdenum, tungsten or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/48Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • B01J38/66Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1004Surface area
    • B01J35/101410-100 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • 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 bulk chemicals
    • Y02P20/584Recycling of catalysts

Abstract

A catalyst for the production of methacrylic acid comprising a heteropolyacid compound containing phosphorus and molybdenum comprises a step of heat-treating a mixture containing an inactive catalyst, ammonium ion, nitrate ion and water at a temperature of 100 ° C or higher; And then drying and calcining the mixture. The regenerated catalyst has the same catalytic activity as the novel catalyst in the gas-phase catalytic oxidation of methacrolein, isobutylaldehyde, isobutane or isobutyric acid to produce methacrylic acid.
Methacrolein, methacrylic acid

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating a catalyst for the production of methacrylic acid and a method for producing methacrylic acid,

The present invention relates to a method for regenerating a catalyst for producing methacrylic acid. The present invention also relates to a process for producing methacrylic acid using the catalyst regenerated by the regeneration method.

The catalyst for the production of methacrylic acid containing phosphorus and molybdenum-containing heteropolyacid is deteriorated when the catalyst is used for a long time in a gas-phase catalytic oxidation reaction using methacrolein as a raw material since the catalytic activity is reduced due to heat load or the like Are known.

JP-A-61-283352 discloses a method for regenerating an inert catalyst comprising dissolving or suspending an inert catalyst in water to prepare a mixture containing ammonium ions and nitrate ions, and then drying and calcining the mixture Is disclosed.

JP-A-63-130144 discloses a process for the production of a catalyst, which comprises the steps of adding water to an inert catalyst, followed by addition of aqueous ammonia, drying of the mixture at a temperature of 40 to 60 占 폚, Containing heterocyclic compound, an amine or ammonium carbonate, a treatment step of the mixture at a temperature of 40 to 90 DEG C, and a drying and calcination step of the mixture.

JP-A-60-232247 discloses a method comprising a step of dispersing an inactive catalyst in water, a step of adding nitrogen-containing heterocyclic compound and nitric acid thereto, a step of mixing them, and a step of drying and calcining the mixture thereafter have.

JP-A-2001-286762 discloses a method comprising the steps of dispersing an inert catalyst in water, then adding a nitrogen-containing heterocyclic compound and nitric acid thereto, further adding a compound containing a constituent element disappeared from the catalyst, , And then drying and calcining the mixture.

JP-A-2001-286763 discloses the steps of dispersing an inactive catalyst in water, followed by the addition of a nitrogen-containing heterocyclic compound, ammonium nitrate and nitric acid, a mixing step thereof, and a subsequent drying and calcination step Are disclosed.

However, the catalytic activity-recovery effect of the regeneration process disclosed in the prior art is not always sufficient, and the catalytic activity of the regenerated catalyst and the durability of the catalytic activity are not always satisfactory.

An object of the present invention is to provide a regeneration method of a catalyst for the production of methacrylic acid, which can effectively recover the catalytic activity of an inactive catalyst and impart excellent durability to the catalyst.

It is still another object of the present invention to provide a method for producing methacrylic acid with a high conversion and an excellent selectivity using a catalyst regenerated by the regeneration method.

As a result of intensive studies, the present inventors have found that the above object can be achieved by heat-treating a mixture containing an inactive catalyst, an ammonium ion, a nitrate ion and water at a predetermined temperature or higher and then drying and firing the mixture, Thereby completing the invention.

Accordingly, the present invention relates to a method for regenerating a catalyst for the production of methacrylic acid comprising a heteropoly acid compound containing phosphorus and molybdenum, comprising the step of heat-treating a mixture containing an inactive catalyst, ammonium ion, nitrate ion and water at a temperature of 100 캜 or higher And then drying and calcining the mixture.

The present invention also relates to a process for producing methacrylic acid by regenerating a catalyst for the production of methacrylic acid by the regeneration method according to the present invention, and then, in the presence of a regenerated catalyst, a compound selected from the group consisting of methacrolein, isobutylaldehyde, isobutane and isobutyric acid To a vapor-phase catalytic oxidation reaction of the methacrylic acid.

According to the present invention, the activity of the inactive catalyst for methacrylic acid production can be effectively restored, and the durability with good catalytic activity can be restored. Further, methacrylic acid can be produced at a high conversion ratio and a good selectivity using the obtained recycled catalyst.

The catalyst for the production of methacrylic acid, which is regenerated by the process of the present invention, contains a heteropoly acid compound containing phosphorus and molybdenum as essential elements and may contain a free heteropoly acid or a salt of heteropoly acid. In particular, the catalyst preferably comprises an acid salt of a heteropoly acid (i.e., a partially neutralized salt), more preferably an acid salt of a Keggin-type heteropoly acid.

In addition to phosphorus and molybdenum, the catalyst preferably comprises vanadium as an additional element or at least one element (hereinafter sometimes referred to as element X) selected from the group consisting of potassium, rubidium, cesium and thallium, or copper, arsenic, (Hereinafter sometimes referred to as element Y) selected from the group consisting of boron, silver, bismuth, iron, cobalt, lanthanum and cerium. Preferably, the catalyst contains three or less atoms of each of 12 elements of molybdenum, phosphorus, vanadium, element X and element Y, respectively.

If the catalyst for methacrylic acid production is used for the production of methacrylic acid or faces a thermal history, the active site of the catalyst may be decomposed or the specific surface area of the catalyst may be reduced. As a result, the catalytic activity is reduced. In the present invention, an inactive catalyst with reduced catalytic activity is subject to regeneration treatment. By measuring whether or not molybdenum trioxide as a decomposed product of the catalyst is detected by X-ray diffraction (XRD), the decomposition of the active site can be confirmed, and the specific surface area of the catalyst can be measured by evaluating the BET specific surface area.

In the regeneration process, a mixture containing an inactive catalyst, an ammonium ion, a nitrate ion and water is first prepared. There is no limitation on the method of preparing the mixture. For example, after the inactive catalyst is suspended in water, a feed material of ammonium ions and nitrate ions may be added, or an inert catalyst may be suspended in an aqueous solution containing ammonium ions and nitrate ions.

If the inactive catalyst is a shaped catalyst, it can be suspended as it is, or it can be ground and then suspended. When the fiber or the like as the reinforcing material is contained in the shaped catalyst, the strength of the catalyst may be reduced when the fibers are cut or broken. Thus, the shaped catalyst is preferably pulverized without breaking or breaking of the fibers.

Examples of the supply material of ammonium ions include ammonia and ammonium salts such as ammonium nitrate, ammonium carbonate, ammonium hydrogencarbonate and ammonium acetate, preferably ammonia and ammonium nitrate. Examples of feed materials for nitrate ions include nitric acid and nitrates, such as ammonium nitrate, preferably nitric acid and ammonium nitrate. The amount of the feed material is appropriately selected such that the amount of ammonium ion is usually about 0.1 to 15 moles and the amount of nitrate ions is usually about 0.1 to 15 moles, per 12 moles of molybdenum in the mixture.

As a supply source of water, ion exchange water is usually used. The amount of water used is usually 1 to 20 parts by weight per 1 part by weight of molybdenum in the mixture.

In the present invention, the mixture is aged by heat treatment at a temperature of 100 ° C or higher. Through the heat treatment step, the molybdenum trioxide as the decomposed product of the catalyst is converted to a component for reconstituting the catalyst, and then effectively restores the catalytic activity and its durability.

The heat treatment can be usually carried out in an airtight container. The heat treatment can be carried out at normal pressure, under reduced pressure or under pressure.

The heat treatment time is usually 0.1 hour or more, preferably 2 hours or more, more preferably 2 to 10 hours. If the heat treatment time is less than 0.1 hour, the effect of recovering the catalytic activity can not be sufficiently attained. From the viewpoint of productivity, the heat treatment time is preferably 10 hours or less.

In the present invention, after the heat treatment, the mixture is dried and then calcined, whereby a regenerated catalyst can be obtained.

Drying of the mixture can be carried out by any conventional method used in the art, for example, evaporation drying, spray drying, drum drying, flash drying and the like. If necessary, the dry product obtained by the above-mentioned drying method can be preferably molded into the form of a cylinder, a sphere or a ring using a molding aid.

The regenerated catalyst can then be obtained by calcining the dried or molded product. The firing can be carried out in an atmosphere of an oxidizing gas such as oxygen, or in an atmosphere of a non-oxidizing gas such as nitrogen, preferably at a temperature of 300 ° C or higher. It is preferable that the heat treatment (preliminary firing) is carried out by holding the product at a temperature of about 180 to 300 DEG C in an oxidizing gas or a non-oxidizing gas before the firing.

The obtained regenerated catalyst includes a heteropoly acid compound and may include a free heteropoly acid or a salt of heteropoly acid. In particular, the regenerated catalyst preferably comprises an acid salt of heteropoly acid, more preferably an acid salt of keto-type heteropoly acid. More preferably, the structure of the ketene-type heteropoly acid salt is formed at the time of heat treatment (pre-baking).

The regenerated catalyst has substantially the same catalytic activity and durability as that of the fresh catalyst. In the presence of a regenerated catalyst, methacrylic acid can be produced with a high conversion ratio and a good selectivity by subjecting the raw material, for example, methacrolein, to a gas phase catalytic oxidation reaction.

Methacrylic acid is typically prepared by charging the catalyst into a fixed-bed multitubular reactor and feeding a starting gas mixture containing oxygen and oxygen selected from the group consisting of methacrolein, isobutyl aldehyde, isobutane, and isobutyric acid, Reaction systems such as fluidized beds or mobile beds may also be used. As the oxygen source, air is usually used. In addition to oxygen and the feedstock, the starting gas mixture may contain nitrogen, carbon dioxide, carbon monoxide, water vapor, and the like.

For example, when methacrolein is used as a feedstock, the reaction is typically carried out at a concentration of 1 to 10% by volume of methacrolein in the starting gas, a molar ratio of oxygen to methacrolein of 1 to 5, 500 to 5000 h -1 (on a steady state basis), the reaction temperature is 250 to 350 ° C, and the reaction pressure is 0.1 to 0.3 MPa. The starting methacrolein used does not necessarily have to be a purified product of high purity but can be a methacrolein-containing reaction product gas obtained, for example, by gas-phase catalytic oxidation of isobutylene or tert-butyl alcohol.

When isobutane is used as the raw material, the reaction is usually carried out in such a manner that the concentration of isobutane in the starting gas is 1 to 85% by volume, the concentration of water vapor is 3 to 30% by volume, the molar ratio of oxygen to isobutane is 0.05 to 4, The reaction is carried out at a space velocity of 400 to 5000 h -1 (on a steady state basis), at a reaction temperature of 250 to 400 ° C, and at a reaction pressure of 0.1 to 1 MPa. When isobutyric acid or isobutylaldehyde is used as a raw material, substantially the same reaction conditions as those used when methacrolein is used as a raw material are adopted.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the scope of the present invention in any way.

The air used in the examples contained 2% by volume of water (corresponding to the water content of the atmosphere) and the nitrogen used in the examples was substantially anhydrous.

The conversion and selectivity are defined as follows:

Conversion rate (%) =

[(Moles of the reacted methacrolein) / (moles of the supplied methacrolein)] x 100

Selectivity (%) =

[(Number of moles of produced methacrylic acid) / (number of moles of methacrolein reacted)] x 100

Reference Example 1: Preparation of new catalyst and evaluation of new catalyst

Solution A was prepared by dissolving 38.2 kg of cesium nitrate [CsNO 3 ], 27.4 kg of 75 wt% orthophosphoric acid, and 25.2 kg of 70 wt% nitric acid in 224 kg of ion-exchanged water heated to 40 ° C. Separately, 297 kg of ammonium molybdate tetrahydrate [(NH 4 ) 6 Mo 7 O 24 .4H 2 O] was dissolved in 330 kg of ion-exchanged water heated to 40 ° C, and then 8.19 kg of ammonium metavanadate [ NH 4 VO 3 ] was suspended to prepare solution B. The solutions A and B were adjusted to 40 캜. Solution A was added dropwise to solution B with stirring, then the mixture was further stirred in a sealed vessel at 120 캜 for 5.8 hours and then 10.2 kg of antimony trioxide [Sb 2 O 3 ] and 10.2 kg Of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O]. The mixture was then stirred at 120 < 0 > C for 5 hours in a closed vessel. The resulting mixture was dried with a spray drier. 4 parts by weight of ceramic fiber, 13 parts by weight of ammonium nitrate and 9.7 parts by weight of ion-exchanged water were added to 100 parts by weight of the resulting dry powder, and the resulting mixture was kneaded and extruded into a cylinder having a diameter of 5 mm and a height of 6 mm . The molded product was dried at 90 DEG C and 30% relative humidity for 3 hours and then heat treated (pre-calcined) at 220 DEG C for 22 hours in the air stream and then 250 DEG C for 1 hour in the air stream, , Heated to 435 DEG C in a nitrogen stream, and maintained at the same temperature for 3 hours. The product was then cooled to 300 DEG C in a nitrogen stream. After replacing the nitrogen stream with an air stream, the product was heated to 390 占 폚 in the air stream and held at the same temperature for 3 hours. The product was then cooled to 70 DEG C in an air stream and the catalyst was recovered.

The catalyst contained an acid salt of ketene type heteropoly acid containing phosphorus, molybdenum, vanadium, antimony, copper and cesium at an atomic ratio of 1.5, 12, 0.5, 0.5, 0.3 and 1.4, respectively.

[Detection of molybdenum trioxide by XRD evaluation]

The obtained catalyst was analyzed by XRD by the powder method to determine the amount of molybdenum trioxide (MoO 3 ) corresponding to the peak strength at the d-value of 3.38 to 3.41 in the XRD corresponding to the acid salt of ketene type heteropoly acid as the main component The intensity ratio (%) of the peak intensity at the d-value of 3.24 to 3.26 in XRD was calculated. The results are shown in Table 1.

[Evaluation of BET specific surface area]

About 1 g of the obtained catalyst was degassed under vacuum, then dehydrated at 120 占 폚 and the BET specific surface area was evaluated. The results are shown in Table 1.

[Activity test of catalyst]

9 g of the obtained catalyst were charged in a glass micro-reactor having an inner diameter of 15 mm and mixed with 4 volume% methacrolein, 12 volume% molecular oxygen, A starting gas composed of 17 vol.% Water vapor and 67 vol.% Nitrogen was supplied at a space velocity of 670 h - 1 and reacted at a furnace temperature of 280 DEG C (furnace temperature for microreactor heating) The conversion and the selectivity were measured.

Next, to evaluate the durability of the catalytic activity, the catalyst was forced to deteriorate by feeding the starting gas having the same composition as mentioned above at the same space velocity as the above-mentioned and reacting at a temperature of 355 DEG C at the furnace temperature. Thereafter, the starting gas having the same composition as mentioned above was supplied at the same space velocity as the above-mentioned one, reacted at a furnace temperature of 280 DEG C, and the conversion and the selectivity were measured one hour after the initiation of the reaction. Table 1 shows conversion ratios and selectivities before and after the forced deterioration.

Reference Example 2: Recovery and evaluation of inactive catalyst

The novel catalyst prepared in Reference Example 1 was treated in an air stream at 450 캜 for 5 hours to prepare an inactive catalyst. For the inactive catalyst, XRD evaluation, BET specific surface area evaluation and activity test were carried out in the same manner as in Reference Example 1. The results are also shown in Table 1.

Example 1: Evaluation of catalyst regeneration and regeneration catalyst

200 g of the inert catalyst obtained in Reference Example 2 was suspended in 400 g of ion-exchanged water heated to 80 DEG C and then kept for 1 hour. The suspension was cooled to room temperature and then 60.2 g of ammonium nitrate [NH 4 NO 3 ] was added and the mixture was heated to 70 ° C and held at the same temperature for 1 hour. Thereafter, 17.9 g of 25 wt% aqueous ammonia was added. After holding at 70 DEG C for 1 hour, the mixture was heat-treated at 120 DEG C for 5 hours in a closed vessel with stirring. Thereafter, the mixture was dried at 110 DEG C, and 6 parts by weight of ion exchange water was added to 100 parts by weight of the resulting dry product, and the mixture was kneaded and extruded into a cylinder having a diameter of 5 mm and a height of 6 mm. The molded product is heat treated (pre-calcined) at 250 DEG C for one hour in a stream of air at a temperature of 220 DEG C for 22 hours in an air stream, then at 435 DEG C in a nitrogen stream, Hour. In addition, the product was cooled to 300 DEG C in a nitrogen stream. After replacing the nitrogen stream with the air stream, the product was heated to 390 占 폚 in the air stream and held at the same temperature for 3 hours. The reaction mixture was then cooled to 70 DEG C in an air stream and the catalyst was recovered. An XRD evaluation, a BET specific surface area evaluation and an activity test were conducted on the produced regenerated catalyst in the same manner as in Reference Example 1. The results are shown in Table 1.

Comparative Example 1

The same procedure as in Example 1 was repeated except that the mixture was not heat-treated at 120 < 0 > C for 5 hours in a closed vessel. The product was subjected to XRD evaluation, BET specific surface area evaluation and activity test. The results are shown in Table 1.

Reference Example 1 Reference Example 2 Example 1 Comparative Example 1 catalyst new
catalyst
Deteriorated
catalyst
Regenerated catalyst
(Heat treated)
Regenerated catalyst
(Not heat treated)
Molybdenum trioxide
Strength ratio (%)
0 52 0 14
BET specific surface area (m 2 / g) 13 7 11 10
activation
exam
Forced
Before deterioration
Conversion Rate
(%)
99 30 95 91
Selectivity
(%)
70 81 74 75
Forced
After deterioration
Conversion Rate
(%)
87 4 83 64
Selectivity
(%)
84 36 83 83

In contrast to the fresh catalyst in Reference Example 1, the inactive catalyst in Reference Example 2 exhibited an increase in molybdenum trioxide, a decrease in specific surface area, and a significant reduction in the conversion rate, which is the decomposition product of the catalyst. The regenerated catalyst in Example 1, obtained by regenerating the inactive catalyst, showed a recovery of the same level of molybdenum trioxide intensity ratio, specific surface area, and conversion as that in Reference Example 1. On the other hand, in Comparative Example 1 in which the mixture was not heat-treated at 120 ° C for 5 hours, molybdenum trioxide remained, the conversion after forced deterioration was low, and the durability of the catalytic activity was not sufficiently recovered.

Claims (4)

  1. A method for regenerating a catalyst for producing methacrylic acid comprising a heteropoly acid compound containing phosphorus and molybdenum, comprising the steps of:
    Heat treating the mixture containing the inactive catalyst, ammonium ion, nitrate ion and water at a temperature of 100 占 폚 or higher; And then
    Drying and calcining the mixture.
  2. The method according to claim 1, wherein the heat treatment is carried out for at least 2 hours.
  3. 3. The process according to claim 1 or 2, wherein the heteropoly acid compound further comprises vanadium; At least one element selected from the group consisting of potassium, rubidium, cesium and thallium; And at least one element selected from the group consisting of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium.
  4. A process for producing methacrylic acid comprising the steps of:
    Regenerating the catalyst for producing methacrylic acid by the method according to claim 1 or 2; And then
    Catalytic oxidation of at least one compound selected from the group consisting of methacrolein, isobutyl aldehyde, isobutane, and isobutyric acid in the presence of the regenerated catalyst.
KR1020070096701A 2006-09-27 2007-09-21 Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid KR101419052B1 (en)

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JP4957627B2 (en) * 2008-04-09 2012-06-20 住友化学株式会社 Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid
JP5214499B2 (en) * 2009-03-09 2013-06-19 住友化学株式会社 Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid
JP5335490B2 (en) 2009-03-09 2013-11-06 住友化学株式会社 Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid
DE102010010587A1 (en) 2009-03-09 2010-11-18 Sumitomo Chemical Co. Ltd. Reproduction of catalyst for methacrylic acid production consists of heteropolyacid compound involves preparing aqueous slurry, drying to obtain solid heteropolyacid compound, preparing another aqueous slurry, drying and baking
JP4996735B2 (en) * 2010-01-19 2012-08-08 住友化学株式会社 Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid
JP2013000734A (en) 2011-06-22 2013-01-07 Sumitomo Chemical Co Ltd Method for regenerating catalyst for producing methacrylic acid and method for producing methacrylic acid

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