JPH09290162A - Production of oxidation catalyst and production of methacrylic acid - Google Patents

Production of oxidation catalyst and production of methacrylic acid

Info

Publication number
JPH09290162A
JPH09290162A JP8106925A JP10692596A JPH09290162A JP H09290162 A JPH09290162 A JP H09290162A JP 8106925 A JP8106925 A JP 8106925A JP 10692596 A JP10692596 A JP 10692596A JP H09290162 A JPH09290162 A JP H09290162A
Authority
JP
Japan
Prior art keywords
catalyst
solution
oxidation
methacrylic acid
producing
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.)
Pending
Application number
JP8106925A
Other languages
Japanese (ja)
Inventor
Hisao Kinoshita
Yukio Sakai
Nobu Watanabe
久夫 木下
展 渡辺
幸雄 酒井
Original Assignee
Mitsubishi Chem Corp
三菱化学株式会社
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 Chem Corp, 三菱化学株式会社 filed Critical Mitsubishi Chem Corp
Priority to JP8106925A priority Critical patent/JPH09290162A/en
Publication of JPH09290162A publication Critical patent/JPH09290162A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

(57) Abstract: A method for producing a heteropolyacid catalyst having a higher reaction activity and selectivity and a longer catalyst life, which is used for the production of methacrylic acid by vapor phase oxidation of methacrolein, and methacrylic acid by the catalyst. Of manufacturing method of. SOLUTION: In producing an oxidation catalyst containing phosphorus, molybdenum and an alkali metal or thallium, a solution in which all catalyst raw materials are dissolved or suspended in water,
Content of ammonium root is 1 for 12 atoms of molybdenum
Adjust to a range of 7 to 100 mol and adjust its pH to 6.5.
Adjust to the range of -13, and in the presence of the obtained oxidation catalyst, methacrolein is gas-phase oxidized.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an oxidation catalyst and a method for producing methacrylic acid using the catalyst.
More specifically, the present invention relates to a method for producing a heteropolyacid catalyst used for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, t-butanol, isobutane, isobutene, etc., and methacrylic acid using the catalyst. It relates to a method for producing an acid.

[0002]

2. Description of the Related Art It has been known that a heteropolyacid compound having a keguin structure such as 12-molybdophosphoric acid is effective as a catalyst for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein. However, M
Vapor-phase catalytic oxidation of acrolein to acrylic acid with an o-V-based catalyst has an industrial conversion rate of 99% or more and 9% or more.
Compared to the fact that a stable operating record has been achieved for three years or more with a selectivity of 7% or more, it remains at a significantly low level. For this reason, active research and development have been conducted on the catalyst composition, preparation method, drying method, calcination method, catalyst shape, etc., in order to improve reaction activity, methacrylic acid selectivity, catalyst life, or catalyst production stability. , Various proposals have been made so far.

For example, regarding the composition of the catalyst, JP-A-55-
In many patent publications such as Japanese Patent No. 39236, V is essentially essential as a catalyst constituent element, and many elements such as alkali metal, alkaline earth metal, transition metal, and rare earth metal are effective for improving catalyst performance. Is described. JP-A-61-5043, JP-A-61-723
JP-A-3-21346 and JP-A-3-21346 show that a specific Ce compound is effective.
Japanese Patent No. 238051 discloses that a specific Bi raw material is effective.

Japanese Unexamined Patent Publication (Kokai) No. 6-91728 describes that high catalytic performance can be obtained by pre-calcining Sb and Mo, Cu or V among the catalyst components to use as a composite oxide. . Also, a method for preparing the catalyst, for example,
A step of dissolving and mixing and heating the catalyst raw material, specifying the catalyst raw material, controlling the amount of ammonium and nitric acid, etc. (JP-A-61-283352)
JP, JP-A-3-238050, JP, 6-8
Many proposals have been made also in Japanese Patent No. 6932 and Japanese Patent Laid-Open No. 6-86933.

Japanese Unexamined Patent Publication No. 4-7037 and Japanese Unexamined Patent Publication No. 4-1
6242 discloses the pH of a solution prepared by dissolving and mixing catalyst raw materials.
Is kept acidic, and the solution is heated to 85 ° C. or higher to form a Keggin-type heteropoly acid, and then the solution is cooled to 80 ° C. or lower, and then alkali ions and ammonium ions or a base such as pyridine is added, and oxygen is added. A method of firing with a gas having a concentration of 5% or more has been proposed.

Japanese Patent Laid-Open No. 165040/1982 describes that a raw material solution containing ammonium ions is concentrated, dried and baked at 400 to 550 ° C.
The amount of ammonium ions is determined by ammonium paramolybdate used as a raw material and is not intended to adjust the pH of the solution. Japanese Patent Laid-Open No. 6-86932 discloses that ammonium root is 6-1 with respect to 12 mol of molybdenum.
8 mol, nitrate root 0.1 to 5 per 12 mol of molybdenum
It is possible to control the amount of ammonium radicals and nitrate radicals in the solution so that the amount becomes molar and to generate Dawson type heteropolyacid in the solution under special conditions of 110 to 200 ° C. in the autoclave, and calcine in an inert gas atmosphere. Has been described.

JP-A-6-86933 describes that coexistence of sulfate is effective for producing Dawson type heteropolyacid and in this case, autoclave heating is not always necessary. In JP-A-5-140025, ammonium paramolybdate, which is an ammonium salt, is used as a molybdenum raw material. However, when preparing a catalyst, a solution prepared by dissolving and mixing the catalyst raw material was adjusted to pH = 4 by adding acetic acid. ing.

Application of a spray dry method to drying (Japanese Patent Application Laid-Open Nos. 4-182450 and 6-31172) has also been attempted. The calcination of the catalyst also has a great influence on the catalyst performance, and the oxygen concentration and the calcination temperature are controlled (Japanese Patent Laid-Open No. Sho 5
6-161841, JP-A-3-238050), control of ammonia and water vapor (JP-A-58-676)
No. 43) is proposed. On the other hand, addition of pyridine and quinoline for the purpose of controlling the surface area and pores (JP-A-57-171444, JP-B-60-35178, JP-A-60-209258, and JP-B-5-2).
376, JP-A-60-239439, JP-B-1-33097, JP-A-60-232247, JP-A-4-50062), and addition of alcohol / aldehyde / organic acid (JP-A-Hei). No. 6-15178) and the like have been proposed.

[0009]

However, none of the catalysts proposed hitherto has sufficient reaction results, low productivity, large deterioration with time of the catalyst, high reaction temperature, or catalyst preparation methods. It has problems such as lack of reproducibility and cannot be said to have sufficient performance as an industrial catalyst, and further improvement is desired. An object of the present invention is to provide a method for producing a heteropolyacid catalyst having a higher reaction activity and selectivity and a longer catalyst life, which is used for producing methacrylic acid by gas phase oxidation of methacrolein, and a method for producing methacrylic acid by the catalyst. To provide.

[0010]

Means for Solving the Problems The inventors of the present invention have diligently studied a method for producing an oxidation catalyst containing phosphorus, molybdenum and an alkali metal or thallium in order to solve the above-mentioned problems, and as a result, all of the catalyst raw materials have been converted to water. By adjusting the content of ammonium root in the dissolved or suspended catalyst raw material solution to a specific range and adjusting the pH of the solution to be more alkaline than neutral, high reaction activity and selectivity and long catalyst life can be obtained. It was found that a catalyst having the above can be obtained, and the present invention has been completed.

That is, the present invention is: In producing an oxidation catalyst containing phosphorus, molybdenum and an alkali metal or thallium, the solution containing all the catalyst raw materials dissolved or suspended in water has an ammonium root content of 17 to 100 for 12 atoms of molybdenum.
A method for producing an oxidation catalyst, which comprises adjusting the molar range and the pH to a range of 6.5 to 13, and gas phase oxidation of methacrolein in the presence of the oxidation catalyst according to 2.1. The method for producing methacrylic acid is characterized in that Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

(1) Method for Producing Oxidation Catalyst The oxidation catalyst of the present invention is a catalyst containing phosphorus, molybdenum and an alkali metal or thallium, and preferably the general formula (I).

[0013]

Embedded image P a Mo b V c B a d Sb e Cu f X g Y h O i (I)

(Wherein X represents one or more elements selected from the group consisting of K, Rb, Cs and Tl, and Y represents Bi, Mn, Cr, Zr, Co, Ce and Z.
Represents one or more elements selected from the group consisting of n, Fe and Ni, with subscripts a, c, d, e, f, g, h
And i represent atomic ratios of the respective elements when b = 12, a = 0.5-15, c = 0-5, d = 0-5, e = 0.
˜5, f = 0 to 2, g = 0.1 to 3, h = 0 to 2 and i
Is a value determined by the valence and atomic ratio of other elements)).

As metal component raw materials, for molybdenum, ammonium paramolybdate, molybdic acid, molybdenum oxide, etc., and for vanadium, ammonium metavanadate, vanadium oxide, vanadium oxalate, etc.
For phosphorus, orthophosphoric acid, metaphosphoric acid, phosphorus pentoxide, pyrophosphate, ammonium phosphate, etc., for copper, copper nitrate, copper sulfate, cuprous chloride, cupric chloride, etc .; for antimony, antimony oxide, antimony chloride. Compounds such as can be used. Regarding other metals, oxides, hydroxides, nitrates, acetates, which can be converted into oxides by firing,
Compounds such as oxalates, carbonates and chlorides can be used, and among them, nitrates are preferable. Further, a heteropolyacid such as phosphomolybdic acid or ammonium phosphomolybdate can be used as a raw material for molybdenum and phosphorus.

All catalyst raw materials are dissolved or suspended in water. At this time, change the amount of ammonium root in the solution to 1
17 to 100 mol, preferably 17 to 60, per 2 atoms
The pH of the solution is adjusted to be in the range of 6.5 to 13, and the solution is preferably 0.5 to 24 at 40 to 100 ° C.
Time, more preferably 50 to 90 ° C. for 1 to 6 hours,
Warm with stirring. High selectivity may not be obtained at a temperature lower than the above range for a short time, and activity may decrease at a high temperature for a long time. The pH is usually adjusted by adding nitric acid or aqueous ammonia. A carrier component such as silica, diatomaceous earth, or celite may be added to this mixed solution.

The mixed solution containing the catalyst component which has been subjected to the heating treatment is dried by a usual method. Generally 100-25
Evaporate to dryness in a hot air drier kept at 0 ° C. The spray-drying method is an industrially more advantageous method because it is possible to obtain uniform dry particles free from uneven distribution of catalyst components. When it is used as a supported catalyst, the obtained mixed solution is concentrated, if necessary, and then supported on a carrier such as alumina or silicon carbide by an appropriate method.

Prior to calcination, the dried catalyst component is preferably 150 to 350 ° C, more preferably 200 to 300.
Pre-baking is performed by circulating air under the temperature condition of ° C. Optimum conditions vary depending on the catalyst raw material used, catalyst composition, and preparation method, but in general, 300 to 500 ° C. for 1 to 24 hours,
Preferably, the catalyst is activated by firing at 350 to 450 ° C. for 2 to 12 hours. The calcination is preferably carried out under the flow of an inert gas whose oxygen concentration is controlled to 0.1 to 5% by volume, more preferably 0.2 to 2% by volume. If the oxygen concentration is 0.1% by volume or less, in order to sufficiently desorb ammonia, a high temperature is required so that the catalyst itself becomes unstable, or if the treatment is carried out at an appropriate temperature, a remarkably long time is required. There are problems such as need. If the content is 5% by volume or more, some of the ammonia burns on the catalyst, making it difficult to control the calcination, and in some cases, decomposition of the catalyst components may cause a large amount of molybdenum trioxide to be produced, resulting in a significant decrease in catalyst performance. is there.

The precalcined catalyst component is crushed and then tableted. In addition to this, a general molding method such as extrusion molding in a paste form and drying can be arbitrarily selected. The shape of the catalyst is not particularly limited, and the shape of a sphere, a cylinder, a pellet, a ring or the like can be selected optimally in consideration of the type of reactor, conditions and the like. The shape of the ring gives favorable results when used in commonly used multi-tube fixed bed reactors.

In general, preparation of a Keggin-type heteropolyacid such as 12-molybdophosphoric acid requires keeping the pH low in an aqueous solution (MT Heteropolyand.
Isopoly Oxometelates, p1
5) is known. Regarding the pH range in which various heteropolyacids can exist, reported examples (JA Rob va
n Veen et al. CHEM. SOC. DALTO
N. TRANS. , 1986, 1825, L .; Pett
ersson et al. Inorg. Chem. , 1986,
25, 4726), and it is reported that the Keggin-type or Dawson-type heteropolyacid can exist only in a very low pH range. Therefore, conventional solid heteropolyacid catalysts have been prepared (JP-A-4-7037, 4-162).
42), p of a solution in which a catalyst component is dissolved is
It has been generally considered that H is kept at a strong acidity so that the Keggin structure can exist stably, and heated and refluxed for a long time. Recently, it has also been reported that neutral to weakly acidic Dawson type heteropolyacids are produced and rearranged to Keggin type heteropolyacids by firing (JP-A-6-86932 and 6-86933).

However, surprisingly contrary to the conventional wisdom so far, the present inventors have found that the pH of the solution is 6.5 to 13, preferably 6.9 to 12, and the ammonium root is molybdenum 1.
17 to 100 mol, preferably 17 to 6 per 2 atoms
It has been found that higher catalyst performance can be obtained by making 0 mol present. Under these conditions, phosphorus in the solution does not have a Keggin type or Dawson type structure, and
It was confirmed by 31 P-NMR measurement that it existed as a heteropolyacid of 2 Mo 5 O 23 6- or PO 4 3- , and the catalyst component solid matter obtained by drying this solution was amorphous by X-ray diffraction. As a result of infrared absorption and solid state 31 P-NMR measurement, it was revealed that there was no Keggin-type or Dawson-type structure.

The solid of the catalyst component after drying is from 200 to 45.
By firing at a temperature of 0 ° C., an X-ray diffraction pattern basically shows the same pattern as the Keggin-type heteropolyacid ammonium salt. In this process, a solid catalyst component which is amorphous in X-ray diffraction forms a part of the Keggin structure due to a change in the binding state or the elimination of ammonia and the like due to a solid phase reaction. As described above, in the present invention, since the active catalyst structure is formed by the solid-phase reaction, its control is important for expressing good catalytic performance, and after the preliminary calcination, the oxygen concentration is controlled under the controlled conditions. Baking is particularly preferred. Although the reason why the catalyst of the present invention exhibits high performance is not clear, the bonding state of the elements forming the Keggin structure in the catalyst, or the X-ray diffraction amorphous portion not included in the Keggin structure is the pH of the solution. It is assumed that the temperature changes depending on the firing conditions.

(2) Method for producing methacrylic acid The oxidation catalyst produced by the present invention is suitably used for a method for producing methacrylic acid by a gas phase oxidation reaction of methacrolein. In this case, it is preferable to carry out the reaction in the presence of water vapor at a reaction temperature of about 200 to 400 ° C. and a reaction pressure of about 0.5 to 10 atm. As the methacrolein of the reaction raw material, for example, a product gas obtained by catalytically oxidizing isobutene or tertiary butanol for the purpose of producing methacrolein may be used as it is, or
The produced gas may be purified to separate methacrolein from other gases before use.

Air is generally used as the oxygen source for the oxidation, but of course, a mixed gas obtained by diluting oxygen (molecular oxygen) with an inert gas such as carbon dioxide or nitrogen may be used. A mixed gas of water vapor, a reaction raw material, oxygen and the like (hereinafter referred to as a reaction mixed gas) is passed through the catalyst, and the contact time is usually about 1 to 20 seconds. As the composition of the reaction mixed gas, for example, 0.2 to 4 mol of molecular oxygen and 1 to 20 mol of water vapor are used with respect to 1 mol of methacrolein.

In addition, this catalytic oxidation reaction can be carried out with reference to the usual knowledge about methacrolein oxidation unless it goes against the gist of the present invention. The oxidation catalyst obtained in the present invention can also be used for oxidative dehydrogenation of isobutyric acid and production of methacrylic acid by oxidation of isobutyraldehyde. It can also be used when producing methacrylic acid from isobutylene in a single step. In these reactions, the reaction conditions similar to the oxidation of methacrolein can be adopted.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded. The conversion rate, selectivity and yield were determined by the following formulas and displayed on a molar basis.

[0027]

## EQU1 ## Conversion (%) = [(moles of reacted methacrolein) / (moles of methacrolein fed)] × 1
00

[0028]

## EQU2 ## Selectivity (%) = [(number of moles of methacrylic acid formed) / (number of moles of reacted methacrolein)] × 10
0

[0029]

## EQU3 ## Yield (%) = [(moles of methacrylic acid produced) / (moles of methacrolein fed)] × 100

Example 1 (Catalyst preparation) To 600 ml of pure water, 144.96 g of ammonium paramolybdate and 8.00 g of ammonium metavanadate were added and heated to 60 ° C. 85 with stirring
% An aqueous solution containing 15.78 g of phosphoric acid, 6.67 g of cesium nitrate and 3.306 g of copper nitrate trihydrate, and then 9.97 g of antimony trioxide are added, and the temperature is raised to 80 ° C. Here, 28 ml of 25% aqueous ammonia was added dropwise to adjust the pH of the solution to 7, and then the temperature was kept at 80 ° C. for 2 hours. Two
A small amount of white precipitate was deposited during the holding time.

A part of the solution was taken out and dried at 120 ° C. The solid was a pale green color and showed no clear diffraction pattern by X-ray diffraction. The amorphous solid was measured by infrared absorption and 31 P-NM.
The R measurement also did not confirm the Keggin structure or the Dawson structure. The obtained slurry solution was dried and prebaked in an oven maintained at 250 ° C. for 10 hours. The solid after the preliminary calcination was dark green, and a cubic crystal structure similar to 12-molybdophosphoric acid was confirmed by X-ray diffraction. By infrared absorption and solid-state 31 P-NMR measurement, a part of phosphorus contained in the catalyst was confirmed. It turned out to have a Keggin structure. The obtained solid was tablet-molded into a ring having a height of 5 mm, an outer diameter of 3 mm and an inner diameter of 2 mm, and calcined at 400 ° C. for 6 hours under a nitrogen flow containing 0.6% by volume of oxygen to obtain a catalyst. The composition of this catalyst is Mo 12 P 2 V 1 Sb 2 Cu 0.2 Cs in terms of atomic ratio of each component.
It is 0.5 . (However, O, H, N atoms are excluded)

(Catalytic Oxidation Reaction) 30 ml of this catalyst was packed into a stainless steel reaction tube (inner diameter 18 mm) without crushing, and heated through a niter bath to carry out catalytic oxidation of methacrolein. Source gas is methacrolein 5%, oxygen 12%,
It was a mixed gas of 30% steam and 53% nitrogen, and this was reacted under normal pressure at a reaction temperature of 290 ° C. and a space velocity of 1400 / hour. As a result, methacrolein (MACR) conversion rate of 8
8.6%, methacrylic acid (MAA) selectivity 83.5%,
The methacrylic acid (MAA) yield was 74.0%.

Examples 2 to 4 Catalysts were prepared in the same manner as in Example 1 except that the amount of ammonia water shown in Table 1 was added to adjust the pH of the mixed slurry solution in which the catalyst raw materials were dissolved, The reaction was evaluated.
In Examples 2 to 4, unlike the case of Example 1, white precipitation was not observed. Since the catalytic activity increases as the pH of the solution increases, the reaction temperature was set to 280 ° C. in Examples 3 and 4. The results are shown in Table 1.

Comparative Example 1 Catalyst preparation and reaction evaluation were carried out in the same manner as in Example 1 except that the pH of the slurry solution prepared by dissolving and mixing the catalyst raw materials was not adjusted. In Comparative Example 1, a white precipitate was deposited. The results are shown in Table 1. Comparative Examples 2 and 3 pH values shown in Table 1 of slurry solutions obtained by dissolving and mixing catalyst raw materials
The catalyst was prepared and the reaction was evaluated in the same manner as in Example 1 except that the amount of 61% nitric acid aqueous solution shown in Table 1 was added for adjustment. In Comparative Example 2, precipitation of a yellow precipitate was observed.
The results are shown in Table 1.

Examples 5 and 6 Examples except that the pH of the slurry solution in which the catalyst raw materials were dissolved and mixed was adjusted to 8 and the temperature of the solution was 70 ° C. (Example 5) and 90 ° C. (Example 6). A catalyst was prepared in the same manner as in 1, and the reaction was evaluated. The results are shown in Table 1. Example 7, Comparative Example 4 A catalyst was prepared in the same manner as in Example 1 except that the amounts of ammonia water and nitric acid aqueous solution added to the slurry solution in which the catalyst composition and the catalyst raw material were dissolved and mixed were the amounts shown in Table 1, The reaction was evaluated. As shown in the results in Table 1, even if the ammonium ion is sufficient, as shown in Comparative Example 4, high catalytic performance cannot be obtained in the acidic region.

Examples 8 to 9 A catalyst was prepared in the same manner as in Example 2 except that the catalyst composition shown in Table 1 was used, and the reaction was evaluated. Table 1 shows the results. Examples 10 to 13 Catalysts were prepared and reaction evaluations were performed in the same manner as in Example 1 except that the catalyst compositions shown in Table 1 were used. Table 1 shows the results.

[0037]

[Table 1]

[0038]

INDUSTRIAL APPLICABILITY The oxidation catalyst according to the production method of the present invention has higher reaction activity and selectivity and longer catalyst life in the production of methacrylic acid by vapor phase oxidation of methacrolein.

[Procedure amendment]

[Submission date] May 27, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

In general, the preparation of a Keggin-type heteropolyacid such as 12-molybdophosphoric acid requires keeping the pH low in an aqueous solution (MT Pope, Heteropol).
yand Isopoly Oxomelate
s, p15) is known. Regarding the pH range in which various heteropolyacids can exist, there are reported examples (JA Ro.
b van Veen et al. CHEM. SOC. DA
LTON. TRANS. , 1986, 1825, L .; P
ettersson et al. Inorg. Chem. , 19
86, 25, 4726), and it is reported that the Keggin-type or Dawson-type heteropolyacid can exist only in a very low pH range. Therefore, the preparation of a conventional solid heteropolyacid catalyst (Japanese Patent Laid-Open No. 4-7037, 4-
16242), it has been generally considered that the pH of the solution in which the catalyst component is dissolved is kept strongly acidic so that the Keggin structure can exist stably, and the solution is heated under reflux for a long time.
Recently, it has also been reported that neutral to weakly acidic Dawson type heteropolyacids are produced and rearranged to Keggin type heteropolyacids by firing (JP-A-6-86932 and 6-86933).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 57/055 2115-4H C07C 57/055 B // C07B 61/00 300 C07B 61/00 300

Claims (4)

[Claims]
1. When producing an oxidation catalyst containing phosphorus, molybdenum and an alkali metal or thallium, a solution in which all catalyst raw materials are dissolved or suspended in water,
Content of ammonium root is 1 for 12 atoms of molybdenum
Adjust to a range of 7 to 100 mol and adjust its pH to 6.5.
The method for producing an oxidation catalyst is characterized by adjusting to a range of -13.
2. The oxidation catalyst has the general formula (I): P a Mo b V c Ba d Sb e Cu f X g Y h O i (I) (wherein X is K, Rb, Represents one or more elements selected from the group consisting of Cs and Tl, and Y is B
i, Mn, Cr, Zr, Co, Ce, Zn, Fe and N
i represents one or more elements selected from the group consisting of i, and the subscripts a, c, d, e, f, g, h and i are b =
It represents the atomic ratio of each element when 12, and a = 0.1
-5, c = 0-5, d = 0-5, e = 0-5, f = 0
2. g = 0.1 to 3, h = 0 to 2 and i is a value determined by the valence and atomic ratio of other elements)). .
3. A catalyst raw material solution in which all catalyst raw materials are dissolved or suspended in water is dried, and then the dried catalyst raw material is precalcined at 150 to 350 ° C., and then 0.1 to 5% by volume.
The manufacturing method according to claim 1 or 2, wherein the firing is performed at 350 to 450 ° C with the inert gas containing oxygen.
4. A method for producing methacrylic acid, which comprises subjecting methacrolein to gas phase oxidation in the presence of the oxidation catalyst according to any one of claims 1 to 3.
JP8106925A 1996-04-26 1996-04-26 Production of oxidation catalyst and production of methacrylic acid Pending JPH09290162A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8106925A JPH09290162A (en) 1996-04-26 1996-04-26 Production of oxidation catalyst and production of methacrylic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8106925A JPH09290162A (en) 1996-04-26 1996-04-26 Production of oxidation catalyst and production of methacrylic acid

Publications (1)

Publication Number Publication Date
JPH09290162A true JPH09290162A (en) 1997-11-11

Family

ID=14445999

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8106925A Pending JPH09290162A (en) 1996-04-26 1996-04-26 Production of oxidation catalyst and production of methacrylic acid

Country Status (1)

Country Link
JP (1) JPH09290162A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006121100A1 (en) * 2005-05-12 2006-11-16 Nippon Kayaku Kabushiki Kaisha Method for preparing catalyst for production of methacrylic acid
JP2007253033A (en) * 2006-03-22 2007-10-04 Mitsubishi Rayon Co Ltd Catalyst for producing methacrylic acid, its production method, and production method of methacrylic acid
JP2008000681A (en) * 2006-06-22 2008-01-10 Mitsubishi Rayon Co Ltd Manufacturing method of catalyst for manufacturing methacrylic acid
JP2008238098A (en) * 2007-03-28 2008-10-09 Mitsubishi Chemicals Corp Method for preparing composite oxide catalyst
JP2009050770A (en) * 2007-08-24 2009-03-12 Mitsubishi Rayon Co Ltd Method for manufacturing catalyst for producing methacrylic acid and catalyst and method for producing methacrylic acid
JP2011152543A (en) * 2011-04-28 2011-08-11 Nippon Kayaku Co Ltd Method for producing catalyst for producing methacrylic acid
WO2013073691A1 (en) 2011-11-17 2013-05-23 日本化薬株式会社 Catalyst for production of methacrylic acid and method for producing methacrylic acid using same
US8716523B2 (en) 2005-03-29 2014-05-06 Nippon Kayaku Kabushiki Kaisha Catalyst for use in production of methacrylic acid and method for manufacturing the same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8716523B2 (en) 2005-03-29 2014-05-06 Nippon Kayaku Kabushiki Kaisha Catalyst for use in production of methacrylic acid and method for manufacturing the same
US8017547B2 (en) 2005-05-12 2011-09-13 Nippon Kayaku Kabushiki Kaisha Method for manufacturing catalyst for use in production of methacrylic acid
JP2006314923A (en) * 2005-05-12 2006-11-24 Nippon Kayaku Co Ltd Manufacturing method of catalyst for producing methacrylic acid
US8148291B2 (en) 2005-05-12 2012-04-03 Nippon Kayaku Kabushiki Kaisha Method for manufacturing catalyst for use in production of methacrylic acid
WO2006121100A1 (en) * 2005-05-12 2006-11-16 Nippon Kayaku Kabushiki Kaisha Method for preparing catalyst for production of methacrylic acid
JP2007253033A (en) * 2006-03-22 2007-10-04 Mitsubishi Rayon Co Ltd Catalyst for producing methacrylic acid, its production method, and production method of methacrylic acid
JP2008000681A (en) * 2006-06-22 2008-01-10 Mitsubishi Rayon Co Ltd Manufacturing method of catalyst for manufacturing methacrylic acid
JP2008238098A (en) * 2007-03-28 2008-10-09 Mitsubishi Chemicals Corp Method for preparing composite oxide catalyst
JP2009050770A (en) * 2007-08-24 2009-03-12 Mitsubishi Rayon Co Ltd Method for manufacturing catalyst for producing methacrylic acid and catalyst and method for producing methacrylic acid
JP2011152543A (en) * 2011-04-28 2011-08-11 Nippon Kayaku Co Ltd Method for producing catalyst for producing methacrylic acid
WO2013073691A1 (en) 2011-11-17 2013-05-23 日本化薬株式会社 Catalyst for production of methacrylic acid and method for producing methacrylic acid using same
EP2781260A1 (en) * 2011-11-17 2014-09-24 Nippon Kayaku Kabushiki Kaisha Catalyst for production of methacrylic acid and method for producing methacrylic acid using same
JPWO2013073691A1 (en) * 2011-11-17 2015-04-02 日本化薬株式会社 Catalyst for producing methacrylic acid and method for producing methacrylic acid using the same
KR20190003830A (en) 2011-11-17 2019-01-09 닛뽄 가야쿠 가부시키가이샤 Catalyst for production of methacrylic acid and method for producing methacrylic acid using same

Similar Documents

Publication Publication Date Title
US6407280B1 (en) Promoted multi-metal oxide catalyst
DE69725921T2 (en) Catalyst and process for the production of unsaturated aldehydes and acid
EP0450596B1 (en) Process for producing unsaturated aldehydes and unsaturated acids
US6060422A (en) Process for producing acrylic acid
JP2950851B2 (en) Iron / antimony / phosphorus-containing metal oxide catalyst composition and method for producing the same
US4537874A (en) Catalyst for production of unsaturated aldehydes
US5296436A (en) Phosphorous/vanadium oxidation catalyst
KR890000517B1 (en) Catalyst for manufacturing methacrolein
ES2397949T3 (en) Catalyst for amoxidation and preparation and use thereof for the amoxidation of organic compounds
US5446004A (en) Multimetal oxide compositions
US4148757A (en) Process for forming multi-component oxide complex catalysts
US4419270A (en) Oxidation catalyst
JP4642337B2 (en) Process for producing catalysts for the oxidation and ammoxidation of olefins
US5177260A (en) Method for production of acrylic acid
US6624326B2 (en) Method for preparing heteropolyacid catalyst and method for producing methacrylic acid
KR100191368B1 (en) Iron-antimony-molybdenum containing oxide catalyst composition and process for preparing the same
US5618974A (en) Catalyst for production of methacrylic acid and method for production of methacrylic acid by the use of the catalyst
KR100247525B1 (en) Catalyst for production of unsaturated aldehyde and unsaturated carboxylic acid and method for production of unsaturated aldehyde and unsaturated carboxylic acid by the use of the catalyst
KR100284061B1 (en) Method of producing acrylic acid
US7923404B2 (en) Methods for preparing catalysts for methacrolein oxidation
JP3943284B2 (en) Acrylic acid production method
JP2654315B2 (en) Catalyst for producing phthalic anhydride and method for producing phthalic anhydride using the same
US20040116284A1 (en) Preparation of mixed metal oxide catalysts for catalytic oxidation of olefins to unsaturated aldehydes
JP3696239B2 (en) Method for producing catalytically active composite metal oxide material containing elements V and Mo in the form of oxides as basic components
US4224187A (en) Olefin oxidation catalyst and process for its preparation