The present invention production process and the production method of the unsaturated carboxylic acids using a catalyst prepared according to the method of manufacturing a catalyst uh j relates.

[Background Art]

After the step of the unsaturated aldehydes from olefins producing an unsaturated fatty acid corresponds to the oxidation banung typical catalytic vapor phase (cat al yt ic vapor phase ox i dat i on). By partial oxidation of eulre pin oxidizes propylene or isobutylene ten (meth) through an arc the lane (meth) process for producing acrylic acid; Oxidizing the talten naphthyl or ortho- xylene ten process for preparing phthalic anhydride; Benren. The process for producing maleic anhydride by the partial oxidation of butylene or butadiene are typical. In yijeung (meth) acrylic acid paint. Fiber aids. It is used in various fields such as coatings, and moisture absorption of the resin and a high purity (meth) acrylic acid demand surge.

In general, the metal oxide catalyst is co-precipitation reaction method employed in such oxidation banung. A hydrothermal synthesis method. Sol-gel synthesis. It is made of the physical common polymerization method or the like. In the manufacture of the metal oxide catalyst metal precursor is a polyanion. Metal oxide black has pH, concentration of the aqueous solution to precipitate a metallic hydroxide form. Banung temperature. The physical characteristics of the precipitate, and the morphology (morpho l ogy) alters the physical state of the catalyst according to the aging time. Particle size. It affects the crystal structure.

Patent Document 1 discloses a technique for coating the powder on the odd carriers and calcined to produce a catalyst. This technique is the catalyst drying temperature is 300 ° and C, weight ratio of the dried material is there characterized by 5 to 40% by this method of production results in a relatively dry temperature catalyst structure changes increased with the conversion rate and the selectivity to unsaturated aldehyde there was a problem of degradation. Therefore. Unsaturated better

It can implement the conversion rate and selectivity of the aldehyde and the situation is the study of the synthesis method which can easily provide a catalyst urgent.

[Prior art document]

Patent Document 1: Japanese Patent No. 4295521, etc. Messenger No.

[Detailed Description of the Invention]

[SUMMARY]

The present invention provides a process for the preparation of the catalyst.

The invention also provides a process for the production of unsaturated carboxylic acids using a catalyst produced according to the production method.

[Technical Solution]

According to one embodiment of the invention. Preparing a slurry by mixing the metal precursor: drying the slurry in a nor 'to i30 ° c. A grinding and kneading , the method comprising the following forming the first pressure; A first pressure to a molding compound not 'to

130 ° drying in C and pulverized, and then the second pressure molding: and a second pressure: the molding material 300 ° C to about 500 ° . To, and including the step of firing at C ligand is calculated by equation (1) Sublimation to rate of not less than 0 wt% it is provided a method of manufacturing a catalyst represented by the formula (1).

Equation 1

Ligand seunghwaeul (weight = the ligand sublimation amount (kg) / sublimation before ligand amount (kg) * 100

Formula 1

Moi 2 P a A b B c C d D e E f O g

In the formula 1 ,

A is at least one element selected from the group consisting of W, V, Nb and Cr. B, As, B, Sb. Ce, and at least one element from the group consisting of: Suntec Pel and Te, C is Si, Al, Zr, Rh, Cu, Ti, and at least one element selected from the group consisting of Ag, and Sn. D is Na, K. Li, Rb, Cs, Ta, Ca. Mg, and at least one element selected from the group consisting of Sr and Ba, E is one or more elements selected from the group consisting of Fe, Co and Ni.

a, b, c. d, e, f and g represent the atomic ratio of each element. a is from 0.5 to 2, b is 0.01 to 10, c is from 0 to 15. d from 0.01 to 20, e is from 0.01 to 20, f is from 0.01 to 15. g is a value determined by the oxidation state of each atom. Wherein the metal precursor comprises a metal and a ligand, the ligand is NH 3 . NH 2 , ΝΟχ (where X is an integer of 1 to 3), CI. F, Ν. OH, S0 X (where x is 3 or 4). 0, CO, COO. SCN. CN. NCS. 0N0, C n H m 0 x 1 jong or more selected from the group consisting of (where n is from 1 to 20 integer, m is an integer from 1 to 40, X is 1 to 10 integer) and having 1 to 20 alkoxide can.

Preparing a slurry may be prepared from a slurry of metal precursor using a co-precipitation or hydrothermal synthesis method.

In a first step of press-molding the slurry is 110 ° C to 130 ° may be dried for 8 to 20 hours in C. In the second step of the press-molding material in the first press-molding is 110 ° C to 130 ° may be dried for 8 to 20 hours at C,

The manufacturing method may further comprise the step of first coating the press-molded material in an inert carrier, after the step of the second press-molding.

Meanwhile. According to another embodiment of the invention. Method of producing an unsaturated carboxylic acid comprising the step of vapor phase oxidation reaction in which the catalyst is supplied to the unsaturated aldehyde to a fixed half unggi and 240 to 450'C and the temperature of 0.1 to 10 bar produced according to the above method the acid is provided .

In the production method of the unsaturated carboxylic acid groups banung shell-tube heat exchanger may be an expression banung-end. In the production method of the unsaturated carboxylic acid it may in particular be made of methacrylic acid in a high yield by using the meta greater unsaturated aldehyde lane.

【Effects of the Invention】

According to the production process in accordance with one embodiment of the invention it is possible to easily produce a catalyst capable of providing a high conversion rate and selectivity unsaturated carboxylic acid from an unsaturated aldehyde.

[Best mode for practicing the invention;

Process for producing a catalyst according to the specific implementation of the invention below and a method for producing an unsaturated carboxylic acid by using the catalyst prepared by the above method of production, etc.

For a description.

According to one embodiment of the invention, the method comprising: preparing a slurry by mixing a metal precursor; The slurry was 110 ° C to 130 ° dried in C. A step of grinding and kneading, and then forming a first pressure; First pressing the molding material 110 ° C to 130 ° steps to dry in the C and milled, and then forming a second pressure; And a material in which the two press-molding 300 ° C to about 500 ° , and comprising the step of firing in C. Equation

The ligand to the sublimation rate is calculated as less than 1 0% by weight of production method for the catalyst represented by the formula (1) is provided.

Equation 1

Ligand sublimation rate (weight = the ligand sublimation amount (kg.) / Sublimation before ligand amount (kg) «100

[Learning and 1

Mo 12 P a A b B c C d D e E f O g

In the formula 1,

A is W \ V. least one element selected from the group consisting of Nb and Cr,

B, As, B, Sb, Ce. Is at least one element selected from the group consisting of Pd and Te, C is Si, Al, Zr. RlY, Cu. Ti. Is at least one element selected from the group consisting of Ag, and Sn. D is Na, K. Li. Rb. Cs. Ta, Ca, Mg. At least one element selected from the group consisting of Sr and Ba, and. E is one or more elements selected from the group consisting of Fe, Co and Ni,

a, b, c, de f and g represent the atomic ratio of each element, a is 0.5 to 2. b from 0.01 to 10. c is from 0 to 15. (1 0.01 to 20, e is from 0.01 to 20. f is from 0.01 to 15, and. g is a value determined by the oxidation state of each atom. the metal oxide represented by formula 1 has the form of the poly-oxo-metal-rate or by interrogating polyacid. oxidation of the unsaturated aldehyde It may be used to provide high conversion and selectivity unsaturated carboxylic acid.

In preparing the slurry a metal precursor containing the metal and the ligand are required for providing a catalyst of the formula (1) is used. therefore. The metal precursor is the catalysts of Formula 1 , may different types of metal precursors known in the art that the present invention if it comprises a metal ball is required to be used for both.

For example, the metal precursor metal required for providing a catalyst of the formula (1); And ΝΗ 3 , ΝΗ 2 . Ν0χ · (where X is an integer of 1 to 3). CI. F. Ν, OH. S0 X (where X is 3 or 4), 0. CO, COO, SCN. CN, NCS, 0N0. C n H m 0 x (where n is an integer from 1 to 20, I is from 1 to 40 integer, x is an integer from 1 to 10) and at least one ligand is selected from the group consisting of alkoxides having from 1 to 20 carbon atoms It can be included. More specifically. It is as the metal precursor. Ammonium para molybdate ((ΝΗ 4 ) 6 Μο 7 0 24 · 4H 2 0), ammonium paratungstate

((NH 4 ) 10 W 12 0 41 · 5H 2 0). Ammonium metavanadate (NH 4 V0 3 ). Nitrate succession (CsN0 3 ). Copper nitrate (Ci NQs · 3H 2 0), iron nitrate (Fe (N0 3 ) 3 · 9H 2 0), antimony trioxide (Sb 2 0 3 ). Molybdenum trioxide (Mo0 3 ). Pentoxide bar or petting (V 2 0 5 and the like can be given). The metal precursor sheet of each element contained in the catalyst of Formula 1-1 ¾ ever according to the ratio. It can be used as content.

In preparing the slurry to provide P of Formula 1, it may be common to combine with the metal precursor and the phosphoric acid. The content of the phosphoric acid may be appropriately adjusted according to a in formula (I) desired.

In the step of manufacturing a slurry by adding the precursor of the metal traces it can be manufactured in a slurry pohim a catalyst precursor. A method of mixing the metal precursor, for example. Include co-precipitation or hydrothermal synthesis method may be used.

The slurry prepared in the step of preparing the slurry is 1 C to 1301 ' , 115 ° C to 125 ° C, or from about 120 o is dried at a temperature of C. At this time . The drying time may be adjusted about 8 to 20 hours. By drying the slurry under these conditions sublimated more ligands of the metal precursor. It is possible to provide a catalyst that can improve the conversion rate and the selectivity to unsaturated aldehyde. Then, the dried material thus obtained can be pulverized. The pulverization may be performed by various methods known in the art that the present invention; Non-limiting examples. The pulverization vertical cutting machine (Vertical pulverizer). Turbo cutter (Turbo cutter). Turbo grinder (grinder Turbo), rotary cutting mill (Rotary cutter mill). Rattling-stage mill (Cutter mill), disc mill (Disc mill). Piece Crushers (Shred crusher). Crushers (Cnisher). It may be performed using any one selected from the group consisting of crushing equipment chopper (chopper) and source plate type cutter (Disc cutter). next . And kneading the pulverized product. For example. The pulverized product may be kneaded sufficiently so that the comminuted water viscosity increase by using a kneader (kneader).

The first and press-molding step, by press-molding the dough water to prepare a molding material in which the first pressure.

Press-molding process can be carried out according to methods known in the art that the present invention; For example. Press-molding can be carried out by using the extrusion molding apparatus. Further, in the pressure forming step for ease of molding, it may be added in addition to forming an additive. More specifically, as the molding additive polymethacrylate: and / or may be used a solvent such as distilled water or alcohol. Forming additives may be from about 5 to 20 parts by weight to 100 parts by weight of the inland sea dry pulverized.

In the first pressure molding step to the drying pulverized molded spaghetti, cylinders or pressing of a hollow cylindrical form may provide a material of the first press-molding. For example. In the first press-molding step, the dry pressure molding pulverized into spaghetti form may provide a material of the first press-molding.

First pressing the molding material of the first produced through the press-molding step is again 110 ° is dried and pulverized by a C to 130 t, and then forming the second pressure. In the manufacturing method according to an embodiment of the present invention is to provide a catalyst that can improve the conversion and selectivity of unsaturated aldehydes by employing a molding step twice pressure. The second pressure molding step may be carried out as the first, and can proceed as described in the pressurized forming step, the first press-molding step and the second pressure molding step is the same proceeds or or different from each other in the above-described range as a condition . For example. First and drying temperature in the second pressure molding step may be the same adjusted to about 12 (rC. May be first pressed in without using a molding additive shaping the use of only two additives forming the press-molding step.

In the second pressure molding step it may provide a first pressure a dry, crushing the molded material, and then spaghetti, cylinders or hollow second pressure-molded material into a hollow cylindrical shape of the cylindrical form.

Manufacturing method according to one embodiment of the present invention may further comprise the step of first coating the press-molded material in an inert carrier, after the step of the second press-molding. Particular examples of the inert carrier are porous alumino-silicate, silicon carbide. Alumina or silica.

On the other hand, the manufacturing method 300 for a material forming the second pressing ° C to about 500 ° and a step of firing in C. Specifically, the material forming the second pressure is 300 ° C to 450 ° C, 350 ° C to 400 ° C or 360 ° C to 390 ° are fired at C it is possible to provide a catalyst of the formula (1). In this case, the calcination time is not particularly limited. E.g . It may be adjusted to between about 3 to 10 hours.

In the above production method. Ligand to the sublimation rate is calculated by equation (1) is more than 0% by weight, 0.5 parts by weight 1 ¾ above. One . More than 0 wt% or 1. 5% increase may be more than , .

Equation 1

Ligand sublimation rate (increase%) = the amount of sublimation ligand (kg) / sublimation before ligand amount (kg) * 100

Amount of the sublimation former ligand is meant the amount of a ligand comprising a banung solution obtained by dissolving a metal precursor.

Meanwhile, according to another embodiment of the invention. Supplying the unsaturated aldehyde in the half unggi the catalyst fixed according to the above method, and 240 to 45Qt ' temperature and 0.1 to 10 under atmospheric pressure provided a method for producing an unsaturated carboxylic acid comprising the step of gas-phase oxidation reaction of do.

The block saturated carboxylic acid production method, but uses a manufactured according to the manufacturing method of the above-mentioned catalyst the catalyst by oxidizing the unsaturated aldehyde banung according to methods known in the art that the present invention block the saturated carboxylic acid It can provide. Especially. The catalyst is the reaction of meta-size oxide by the lane can be provided with high conversion rate and selectivity of methacrylic acid.

In the production method of the above unsaturated carboxylic acid reactor is a shell-tube heat exchanger may be a group-and-eu formula banung. Specifically. The shell-and-tube heat exchange type and charge the above-described catalyst in a fixed bed of half unggi, an unsaturated aldehyde to the reflecting unggi,

Heunhap the gas containing oxygen, water vapor and an inert gas can be injected. At this time. Unsaturated aldehyde is 1 to 10% by volume relative to the total volume of the total gas heunhap. Oxygen is 1 to 20 vol%, steam is from 10 to 50% by volume, the inert gas may comprise from 20 to 80% by volume. In addition, the gas heunhap is the space velocity of the unsaturated aldehyde from about 30 to 60 hr- 1 may be adjusted so that the.

" Oxidation banung temperature of the unsaturated aldehyde is from about 240 to 450 ° C. About 240 to 340 " . About 240 C, or from about 3 to about 270: may be a coarse ¾. Oxidation reaction pressure is from about 0.1 to 10 bar (atiii). It may be adjusted to about 0.4 to 3 atmospheres, or from 1 to 3 bar. Method for producing the unsaturated carboxylic acid can provide the unsaturated carboxylic acid in high yield using the above catalyst.

Operation of the invention through a specific embodiment of the invention hereinafter. It will be described the effects by nine than ever. but. This is not limited thereto whatsoever any means the scope of the invention as set forth by way of illustration of the invention.

Example 1 Preparation of catalyst

Ammonium para-molybdate in deionized water niL 3000 ((ΝΗ 4 ) 6 Μο: 0 24 · 4Η 2 0) 500 g. Ammonium paratungstate ((NH 4 ) 10 lV 12 04i · 5¾0) 0.62 g, of ammonium metavanadate (NH 4 V0 3 ) 5.52 g, and nitric acid succession (CsN0 3 ) by dissolving 46.0 g to prepare a first banung liquid .

On the other hand, 85% by weight in pure water to 300 niL aqueous phosphoric acid solution 32.65 g, copper nitrate (Cu (N0 3 ) 2 . Eu 3H 2 0) 11.40 g. Iron nitrate (Fe (N0 3 ) 3 · 9H 2 0) was dissolved in 28.60 g was prepared a second solution banung.

The stirring the combined first reaction liquid and the second liquid common banung antimony trioxide (Sb 2 0 3 was added) 6.84 g. Thus obtained and continue stirring the heunhap banung liquid 95t ' was raised to the cooled natural and kept for 3 hours at this temperature.

A slurry containing the catalyst precursor from about 120 ° after drying at C 15 hours was ground to. Then put the dry ground particles in a kneader (kneader) was added to deionized water portion of about 10 parts by weight based on 100 parts by weight of dry pulverized product viscosity

It was kneaded (kneading) until it is fully raised. Then, thus formed pushes the dough material in the form of spaghetti.

A press-molding material at about 120 ° C and dried for about 15 hours. The catalyst precursor dried in the form of spaghetti was pulverized. As a molding additive to the dried pulverized polymethacrylate (PMMA: Average particle diameter: 0.10 ^ ηι) was added to the powder (powder) increased portion 10 for drying the pulverized portion 100 increase and extrusion-molded into a hollow cylindrical shape.

To to the material molded into a cylindrical form Zeng Gong about 5 hours, calcined at about 380 ° C under an air flow to prepare a catalyst of the formula 1-1.

[Chemical Formula 1-1]

Pi .2Mo12W0 ,oiV0.2CLI02Feo .3Sb0.iCsli0

Equation In the above embodiment i 1S ligand sublimation rate is calculated was 1.6% by weight.

Equation 1

Lagan de sublimation rate (increase = the ligand sublimation amount (kg) / sublimation before ligand amount (kg) * 100

Preparation of catalyst: Comparative Example 1

Ammonium para-molybdate in deionized water mL 3000 ((NH 4 ) 6 Mo 7 0 24 . 4H 2 0) 500 g, ammonium paratungstate ((NH 4 ) 10 W 12 0 41 · 5H 2 0) 0.62 g. Ammonium metavanadate (NH 4 V0 3 ) and 5.52 g of cesium nitrate (CsN0 3 was dissolved) 46.0 g to prepare a first solution banung.

On the other hand, 85% increase in the ultra-pure water 300 mL phosphoric acid solution 32.65 g. Copper nitrate (CLI (N0 3 ) 2 · 0 3) 11.40 g, ferric nitrate (Fe (N0 3 ) 3 · 9H 2 0) was dissolved in 28.60 g was prepared a second solution banung.

The stirring a mixture of the reaction liquid and the second liquid banung antimony trioxide (Sb 2 0 3 was added to 6.84). Thus obtained, while stirring continued for heunhap reaction mixture was heated to 95 ° C and kept for 3 hours at this temperature and cool naturally. '

About 12 hours a slurry containing the catalyst precursor from about KX C

After drying it was ground. But then put on the dry ground particles in a kneader (kneader) was added to deionized water portion of about 10 parts by weight based on 100 parts by weight of dry pulverized product dough, the dough in the stop state a sufficient viscosity that occurs. A dough material was molded pressed into spaghetti form.

A press-molding material of about 100 ° at the C and dried for about 12 hours. The catalyst precursor dried in the form of spaghetti was pulverized. As a molding additive to the dried pulverized polymethacrylate (PMMA; average particle diameter: 0.10 / in) and then added in an amount of about 10 parts by weight for a powder (powder) in dry pulverized product 100 parts by weight was extrusion molded into a hollow cylindrical shape.

The material molded into a hollow cylindrical form about 380 under air flow ° to to about 5 hours, firing at C A catalyst was prepared of the formula 1-1.

[Chemical Formula 1-1]

Pi 2Mo12W0 ,oiV0.2C110.2Feo.3Sbo.1Cs 1.0

Ligand sublimation rate, which is calculated by the equation (1) in Comparative Example 1 was 1.0% by weight.

Preparation of Example 2 Catalyst

3000 high-pressure pure water to half unggi niL. A molybdenum oxide (Mo0 3 ) 500 g, 85% phosphoric acid aqueous solution 42.15 g weight. Pentoxide bar or petting (V 2 0 5 was added), and 14.45g. 130t: a first banung solution was stirred for 5 hours were prepared.

Meanwhile . Iron nitrate in pure water to 500 niL (Fe (N0 3 ) 3 9H 2 0) 25.68 g, nitrate seseum (CsN0 3 ) 77.44 g) of copper nitrate (Cu (N0 3 ) 2 ■ 3H 2 0) was dissolved in 15.36 g 2 banung the solution was prepared.

First to stirred a mixture of reaction liquid and the second liquid banung obtain a slurry, and then ammonium nitrate (NH 4 N0 3 ) was added to 190 g, and stirring continued.

Thus the slurry containing the thus obtained catalyst precursor from about 120 ° at C from about 1 ( added after 3 hours drying was pulverized them. Insert the dry ground particles in a kneader (kneader) parts about 10 parts by weight for the pure water to the dried pulverized product 100 parts by weight It was kneaded (kneading) until the viscosity rises sufficiently after. It was then pressure molding the kneaded material in the form of spaghetti.

A press-molding material at about 120 ° C and dried for about 16 hours. The catalyst precursor dried in the form of spaghetti was pulverized. As a molding additive to the dried pulverized polymethacrylate (PMMA; average particle diameter: 0.10) was added in an amount of about 10 parts by weight for a powder (powder) in dry pulverized product 100 parts by weight and extrusion-molded into a cylindrical form Zeng Gong.

The material molded into a hollow cylindrical form about 380 under air flow ° to to about 5 hours, firing at C A catalyst was prepared of the formula 1-2.

[Chemical Formula 1-2]

P1.5MonVo.5C1io.2Feo.2Cs1.25

(When converted to the atomic ratio of Μθ Pl.64Mo to 12 12 V 0 .55Cuo.22Feo.22Cs 1 .36 Im) was ligands sublimation rate of 1.7% by weight, calculated in this example the chamber 2 in the equation (1).

Preparation of catalyst: Comparative Example 2

Ultra-pure water in an autoclave in 3000 niL, molybdenum trioxide (Mo0 3 ) 500 g. 85% by weight aqueous phosphoric acid solution 42.15 g, vanadium pentoxide (V 2 0 5 was added to) 14.45g. 130 ° to C were prepared by first banung solution was stirred for 5 hours di eu,

On the other hand, iron nitrate in pure water mL 500 (Fe (N0 3 ) 3 · 9H 2 0) 25.68 g. Nitrate, cesium (Cs 0 3 ) 77.44 g, copper nitrate (Cu (N0 3 ) 2 ) by dissolving 15.36 g was prepared in the second reaction solution.

To claim 1 banung stirring a mixture of liquid and the second liquid banung obtain a slurry, and then ammonium nitrate (NH 4 N0 3 ) was added to 190 g, and stirring continued.

The slurry containing the thus obtained catalyst precursor was dried at about 100'C about 13 hours was ground to. Put the dried pulverized product in a kneader (kneader), but the dough followed by the addition of ultrapure water portion of about 10 parts by weight based on the dry pulverized product 100 parts by weight. Stop the kneading in a state where sufficient viscosity not occur, and the molding pressure to the dough ingredients in the form of spaghetti.

A press-molding material of about 100 ° at the C and dried at about 13 hours. The catalyst precursor dried in the form of spaghetti was pulverized. As a molding additive to the dried pulverized polymethacrylate (MA: average particle size: 0.10 IM) was added to the powder (powder) increased portion 10 for drying pulverized material to 100 parts by weight and extrusion-molded into a cylindrical form Zeng Gong.

About 380t a material molded into a hollow cylindrical shape under air flow , to about five hours to prepare a catalyst eu firing of formula (I) eu 2.

[Chemical Formula 1-2]

.5M011V0.5CU0.2Fe PI 0 . 2 C Si.25

(When converted to the atomic ratio of Mo to 12 P1.64M012Vo.55Cuo.22Feo.22Cs1.36 Im) ligand sublimation rate calculated in the Comparative Example 2 in the equation (1) was a 1.0% increase.

Test Example: Catalyst Characterization

Examples and by using a stainless banung charge the respective catalysts prepared in the fixed bed according to a comparative example meta greater banung by oxidizing the lane (ethacrolein) to prepare a methacrylic acid (methacrylic acid).

Specifically, methacrolein 4% by volume of a stainless steel semi-unggi charging the catalyst into a fixed bed. Heunhap the gas containing oxygen 10 volume%, water vapor 30% by volume and nitrogen 55% by volume were injected. At this time . Space of the meta crane: rate of 36 hr " 1 ., And the contact time was adjust the infusion rate of heunhap gas ¾ to 4 seconds banung temperature is specifically about 270 greater than about 240 to 3KTC. ° was jokkeol in C. banung pressure was controlled to between about 1 to 3 bar.

To the initial conversion reaction according to the equation 2 to 4. Selecting the calculated degree and yield are summarized in Table 1 below.

And. The reaction time to after the 1000 hours, conversion according to Equation 2 to 4. Selecting and calculating a degree sueul and are summarized in Table 1 below.

Equation (2)

Meta-crane conversion rate (mol%) = [number of moles of the meta banung the crane mole number / supplier of meta crane] X 100

[Equation 3]

Select meth crane also (mol%) = [the number of moles of produced methacrylic acid / banung meth greater the mole number of lanes] X 100

[Equation 4]

Yield (mol = [moles of produced methacrylic acid molar amount / feed of methacrolein;

WE CLAIM

The slurry was 110 ° C to 130 ° comprising: a drying, crushing and mixing in C and then forming the first pressure:

First pressing the molding material 110 ° C to 130 ° drying in C and molding was pulverized, and then the second pressure: and

Second pressing a molding material 300 ° C to about 500 ° , and comprising the step of firing at C,

To process for producing a catalyst represented by the following general formula (1) or more ligands sublimation rate is 0% by weight, which is calculated by Equation 1:

Equation 1

Ligand sublimation rate (% by weight) the amount of sublimation ligand (kg) / sublimation before ligand amount (kg) * 100

Formula 1

Mo 12 P a A b B c C d D e E f O g

In the formula 1 ,

A is at least one element selected from the group consisting of W, V, Nb and Cr. B is As, Sb B., Ce. And at least one element from the group consisting of: Suntec Pel and Te, C is Si / Al. Zr, Rh. Cu. Ti, and one or more elements selected from the group consisting of Ag, and Sn. D is Na. K. Li, Rb, Cs. Ta, Ca. Mg. And at least one element from the group consisting of: Suntec Sr and Ba, E is Fe. Is at least one element selected from the group consisting of Co and Ni,

a, b, cde f and g represent the atomic ratio of each element. a is 0.5 to 2.

b is 0.01 to 10, c is from 0 to 15, d is from 0.01 to 20, e is from 0.01 to 20, f is from 0.01 to 15. g is a value determined by the oxidation state of each atom.

[Claim 2]

According to claim 1. It said metal precursor comprises a metal and a ligand. Ligands ΝΗ 3 . ΝΗ 2 . ΝΟχ (:), where X is an integer of 1 to 3. CI. F, Ν. OH, S0 X (where X is 3 or 4), 0. CO. COO. SCN. CN. NCS, 0N0. C n H m O x (where n is an integer from 1 to 20. Ni is an integer from 1 to 40, X is an integer of 1 to 10) and C 1 at least one selected from the group consisting of alkoxides of 1 to 20, the catalyst the method of manufacture.

[Claim 3]

According to claim 1. Step for preparing the slurry for producing a slurry from a metal precursor using a co-precipitation or hydrothermal synthesis method. Process for producing a catalyst.

[Claim 4]

The method of claim 1 wherein the slurry is 110 ° C to 130 ° drying at C for 8 to 20 hours. Preparation of catalyst. Way .

[5] claims Hing

According to claim 1. The first pressure to the molded material to dry for 1K C to 130'C Ecija 8 to 20 hours. Process for producing a catalyst.

[6.]

The method of claim 1, wherein the method of producing a catalyst comprising a second pressing a molded material after the step of the second press-molding the further step of coating on an inert carrier.

[Claim 7]

Supplying the unsaturated aldehyde in the half unggi the catalyst fixed according to the manufacturing method of claim 1 and 240 to 450 " method for producing an unsaturated carboxylic acid comprising the step of banung phase oxidation at a temperature and 0.1 to 10 atmospheres of an acid.

[8.]

The method of claim 7. The meta crane as the unsaturated aldehyde

Used for producing methacrylic acid. Method for producing an unsaturated carboxylic acid.

[9.]

The method of claim 7. The reactor is a shell-and-tube heat exchanger type unsaturated carboxylic acid used in the method of manufacturing an banung.