WO2019013116A1 - Method for manufacturing catalyst, method for manufacturing unsaturated carboxylic acid, method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid, and method for manufacturing unsaturated carboxylic acid ester - Google Patents

Method for manufacturing catalyst, method for manufacturing unsaturated carboxylic acid, method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid, and method for manufacturing unsaturated carboxylic acid ester Download PDF

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WO2019013116A1
WO2019013116A1 PCT/JP2018/025649 JP2018025649W WO2019013116A1 WO 2019013116 A1 WO2019013116 A1 WO 2019013116A1 JP 2018025649 W JP2018025649 W JP 2018025649W WO 2019013116 A1 WO2019013116 A1 WO 2019013116A1
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Prior art keywords
catalyst
producing
unsaturated carboxylic
carboxylic acid
unsaturated
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PCT/JP2018/025649
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French (fr)
Japanese (ja)
Inventor
充 菅野
拓朗 渡邉
浩一 谷元
正範 新田
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三菱ケミカル株式会社
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Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to MYPI2019007387A priority Critical patent/MY192580A/en
Priority to JP2019529106A priority patent/JP6798617B2/en
Priority to CN201880041543.4A priority patent/CN110809494B/en
Priority to KR1020207003140A priority patent/KR102364540B1/en
Publication of WO2019013116A1 publication Critical patent/WO2019013116A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method of producing a catalyst, a method of producing an unsaturated carboxylic acid, a method of producing an unsaturated aldehyde and an unsaturated carboxylic acid, and a method of producing an unsaturated carboxylic acid ester.
  • the catalyst is generally produced by preparing a raw material liquid such as an aqueous solution or an aqueous slurry containing each element constituting the catalyst, and drying and calcining the raw material liquid.
  • Patent Documents 1 to 3 describe the baking using a gas containing ammonia or water vapor
  • Patent Document 4 describes baking using a non-oxidative gas
  • Patent Document 5 using a gas containing an oxygen-containing organic compound.
  • Patent Document 6 describes about the baking method which consists of several processes which changed the gas to be used, and a calcination temperature.
  • Patent Document 7 describes the gas flow rate to the catalyst precursor.
  • the catalyst produced by the method described in Patent Documents 1 to 7 is a reaction for producing an unsaturated carboxylic acid by vapor phase catalytic oxidation of unsaturated aldehyde with molecular oxygen, or propylene, isobutylene, primary Gas-phase catalytic oxidation of at least one member selected from the group consisting of butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids
  • the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a catalyst capable of producing a target product with high selectivity.
  • a method for producing a catalyst containing at least molybdenum and phosphorus, which is used when producing unsaturated carboxylic acid by vapor phase catalytic oxidation of unsaturated aldehyde with molecular oxygen, which is a catalyst precursor containing a nitrogen-containing component A method for producing a catalyst, comprising the steps of calcining a body by applying pressure above atmospheric pressure.
  • a method of producing a catalyst comprising the steps.
  • the catalyst according to any one of [1] to [3] is calcined under a gas flow of at least one selected from an oxygen-containing gas and an inert gas Method.
  • a method for producing an unsaturated carboxylic acid which comprises producing an unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde with molecular oxygen in the presence of a catalyst produced by the method according to [1].
  • a method for producing an unsaturated carboxylic acid comprising: preparing a catalyst by the method according to [13]; Method. [14] [2] at least one member selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst produced by the method according to [14] [2] A method for producing unsaturated aldehydes and unsaturated carboxylic acids, which comprises the step of vapor phase catalytic oxidation of H 2 O with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids.
  • a catalyst is prepared by the method described in [2], and is selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst
  • a method for producing unsaturated aldehydes and unsaturated carboxylic acids wherein at least one is subjected to gas phase catalytic oxidation with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids.
  • [16] A method for producing an unsaturated carboxylic acid ester, which esterifies the unsaturated carboxylic acid produced by the method according to any one of [12] to [15].
  • the first embodiment of the process for producing a catalyst according to the present invention is a catalyst comprising at least molybdenum and phosphorus, which is used in the vapor phase catalytic oxidation of unsaturated aldehyde with molecular oxygen to produce unsaturated carboxylic acid. It is a manufacturing method. The method includes the steps of calcinating a catalyst precursor containing a nitrogen-containing component by applying a pressure above atmospheric pressure.
  • the second embodiment of the process for producing a catalyst according to the present invention comprises at least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether.
  • This is a method for producing a catalyst containing at least molybdenum and bismuth, which is used in producing gas phase catalytic oxidation with molecular oxygen to produce the corresponding unsaturated aldehyde and unsaturated carboxylic acid.
  • the method includes the steps of calcinating a catalyst precursor containing a nitrogen-containing component by applying a pressure above atmospheric pressure.
  • the pressure at the time of calcination of the catalyst precursor attention is paid to the pressure at the time of calcination of the catalyst precursor, and the desired product is obtained with high selectivity by calcinating the catalyst precursor containing the nitrogen-containing component under a pressure exceeding atmospheric pressure.
  • a producible catalyst can be obtained.
  • the reason is considered as follows. That is, the structure of the catalyst precursor changes in the process of desorption of the nitrogen-containing component during the calcination, and a catalyst active point preferable for the intended reaction is formed. At this time, desorption of the nitrogen-containing component is suppressed by exposing the catalyst precursor to a pressure higher than atmospheric pressure.
  • the process according to the present invention is a catalyst containing at least molybdenum and phosphorus (hereinafter referred to as a catalyst for producing unsaturated carboxylic acid, which is used when producing unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde with molecular oxygen to produce unsaturated carboxylic acid Also used in the manufacture of By carrying out the reaction using the catalyst, unsaturated carboxylic acids can be produced with higher selectivity.
  • the unsaturated aldehyde is preferably acrolein or methacrolein because it can produce acrylic acid or methacrylic acid with higher selectivity.
  • the catalyst contains a heteropoly acid structure, particularly a Keggin-type heteropoly acid structure, because unsaturated carboxylic acid can be produced with higher selectivity.
  • At least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether is subjected to vapor phase catalytic oxidation with molecular oxygen
  • a catalyst containing at least molybdenum and bismuth hereinafter also referred to as a catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid
  • unsaturated aldehydes and unsaturated carboxylic acids can be produced with higher selectivity.
  • the unsaturated aldehyde is preferably acrolein or methacrolein, and the unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid from the viewpoint of selectivity.
  • the composition of the catalyst obtained by the method according to the present invention is not particularly limited, but when the catalyst is the catalyst for producing unsaturated carboxylic acid, from the viewpoint of being able to produce unsaturated carboxylic acid with higher selectivity,
  • the catalyst preferably has a composition represented by the following formula (1).
  • P, Mo, V, Cu and O are element symbols which show phosphorus, molybdenum, vanadium, copper and oxygen, respectively.
  • A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron.
  • E represents at least one element selected from the group consisting of potassium, rubidium, cesium, thallium, magnesium and barium.
  • G is at least one selected from the group consisting of iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum Indicates an element.
  • the catalyst obtained by the method according to the present invention is the catalyst for producing the above-mentioned unsaturated aldehyde and unsaturated carboxylic acid
  • the unsaturated aldehyde and the unsaturated carboxylic acid can be produced at a higher selectivity because
  • the catalyst preferably has a composition represented by the following formula (2).
  • Mo, Bi, Fe, Si and O are element symbols showing molybdenum, bismuth, iron, silicon and oxygen, respectively.
  • X represents at least one element selected from the group consisting of cobalt and nickel.
  • a ′ represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc.
  • E ′ represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium.
  • G ′ represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
  • the method for producing a catalyst according to the present invention is not particularly limited as long as it includes a step of firing a catalyst precursor containing a nitrogen-containing component by applying a pressure exceeding atmospheric pressure (hereinafter also referred to as a firing step).
  • the method comprises the steps of preparing a raw material liquid containing each element constituting the catalyst (hereinafter also referred to as raw material liquid preparation step) and drying the raw material liquid to obtain a catalyst precursor (hereinafter drying step). It is preferable from the viewpoint of obtaining a catalyst capable of producing the target product with higher selectivity, which also includes the calcination step).
  • the method may include a step of forming a catalyst precursor (hereinafter also referred to as a forming step), as necessary, between the drying step and the firing step.
  • the raw material liquid preparation process At a raw material liquid preparation process, the raw material liquid containing each element which comprises a catalyst is prepared.
  • the raw material liquid contains at least molybdenum and phosphorus.
  • the catalyst for producing the unsaturated aldehyde and the unsaturated carboxylic acid the raw material liquid contains at least molybdenum and bismuth.
  • each element which comprise a catalyst when this catalyst is a catalyst for unsaturated carboxylic acid manufacture, it can be set as the element and atomic ratio shown, for example by said Formula (1).
  • the catalyst is a catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid, for example, the element and atomic ratio can be set to the formula (2).
  • the preparation method of the raw material solution is not particularly limited, but a method of preparing a slurry-like raw material solution by charging the raw material of each element into water, heating to 30 to 100 ° C. and stirring is preferable.
  • the amount of water used is preferably 200 to 1000 parts by mass with respect to a total of 100 parts by mass of the raw material of each element.
  • each element The oxide of each element, nitrate, carbonate, ammonium salt etc. can be selected suitably, and can be used.
  • a raw material of molybdenum molybdic acid, molybdenum trioxide, ammonium paramolybdate and the like can be used, and molybdic acid and molybdenum trioxide are preferable.
  • a raw material of phosphorus orthophosphoric acid, phosphorus pentoxide, ammonium phosphate etc. can be used.
  • As a raw material of vanadium, ammonium metavanadate, vanadium pentoxide etc. can be used.
  • copper nitrate, copper sulfate, copper carbonate and the like can be used as a raw material of copper.
  • a raw material of bismuth bismuth nitrate, bismuth oxide, bismuth acetate, bismuth hydroxide and the like can be used. One of these raw materials may be used, or two or more thereof may be used in combination.
  • the raw material liquid preferably contains a nitrogen-containing component.
  • the nitrogen-containing component include ammonium roots, nitrate roots, nitrogen-containing heterocycles and the like, but at least one selected from the group consisting of ammonium roots and nitrate roots, the viewpoint of selectivity of the target product It is preferable from
  • the ammonium root in the present invention is a generic name of ammonia (NH 3 ) which can be ammonium ion (NH 4 + ), and ammonium contained in ammonium-containing compounds such as ammonium salts.
  • ammonium-containing compound examples include ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium vanadate, ammonium salts of elements constituting a catalyst, and the like.
  • the nitrate root in the present invention is a general term for nitrogen oxide ions such as nitrate ion (NO 3 ⁇ ) and nitrite ion (NO 2 ⁇ ).
  • NO 3 ⁇ nitrate ion
  • NO 2 ⁇ nitrite ion
  • the nitrate ion contained in the nitrate of a catalyst structural element is mentioned, for example. One of these may be used, or two or more may be used in combination.
  • the preparation scale of the raw material liquid is not particularly limited, but the lower limit of the amount of the raw material of the main element is preferably 100 g or more, and more preferably 1 kg or more.
  • the upper limit is preferably 10 t or less, more preferably 1 t or less.
  • the drying step the raw material liquid obtained in the raw material liquid preparation step is dried to obtain a catalyst precursor.
  • a drying method of a raw material liquid For example, the evaporation-to-dryness method, spray-drying method, drum drying method, flash drying method etc. are mentioned.
  • the type and type of dryer used for drying the temperature at the time of drying, the atmosphere, and the like.
  • the catalyst precursor obtained preferably has a heteropolyacid structure from the viewpoint of producing unsaturated carboxylic acid with higher selectivity. It is more preferable to include a Keggin type heteropoly acid structure.
  • the amount of the nitrogen-containing component contained in the obtained catalyst precursor is not particularly limited, and can be, for example, 0.5 to 7.0% by mass.
  • the catalyst precursor obtained in the drying step is formed.
  • the molding method There is no particular limitation on the molding method, and known dry and wet molding methods can be applied. For example, tablet molding, press molding, extrusion molding, granulation molding and the like can be mentioned.
  • the shape of the molded article is also not particularly limited, and examples thereof include a cylindrical shape, a ring shape, and a spherical shape. Further, at the time of molding, it is preferable to mold only the catalyst precursor without adding a carrier or the like to the catalyst precursor, but if necessary, known additives such as graphite and talc may be added.
  • the obtained catalyst precursor containing a nitrogen-containing component is calcined by being exposed to a pressure exceeding atmospheric pressure.
  • the pressure to which the catalyst precursor is exposed is preferably 10 kPa (G) or more, more preferably 20 kPa (G) or more, and still more preferably 30 kPa (G) or more.
  • the pressure is preferably 100 kPa (G) or less, more preferably 80 kPa (G) or less, and still more preferably 70 kPa (G) or less.
  • KPa (G) indicates a gauge pressure
  • the atmospheric pressure + gauge pressure is the actual pressure
  • the said pressure be the pressure in the temperature fixed process from temperature rising process of a baking process.
  • the value of the pressure is a value obtained by measuring any one point in the container when firing is performed in a container having no spatial distribution of pressure, and the pressure may be generated when flowing gas in a tubular firing container, etc.
  • the pressure is at the lowest point in the system, such as the pressure at the firing gas outlet.
  • the inside of the system here means the range from the baking gas inlet of a baking container to a baking gas outlet.
  • the method for measuring the pressure in the system is not particularly limited, but can be measured, for example, by providing a pressure gauge upstream of the calcination gas outlet and as close as possible to the calcination gas outlet.
  • the method of increasing the pressure is not particularly limited, but in the case of firing under gas flow as described later, for example, a pipe for the gas outlet is extended, a pressure control valve is provided at the gas outlet This can be achieved by, for example, throttling the valve or connecting the gas outlet to a trap tank filled with water or the like.
  • Oxygen-containing gas such as air, or inert gas
  • the inert gas refers to a gas which does not reduce the catalytic activity, and includes nitrogen, carbon dioxide gas, helium, argon and the like.
  • air, nitrogen, the mixed gas of oxygen and air, or these mixed gas are more preferable, and air is further more preferable.
  • the gas may include water vapor.
  • the content of water vapor is preferably 0.01 to 5% by volume based on the whole gas to be circulated, and more preferably, the lower limit is 0.05% by volume or more and the upper limit is 2% by volume or less.
  • the inside of the firing container may be filled with the atmosphere gas, and then the container may be closed and fired.
  • Gas flow always supplying the atmosphere gas into the firing container
  • baking may be performed below, baking under gas flow is preferable from the viewpoint of catalyst activity.
  • the lower limit of the highest temperature in the firing is preferably 300 ° C. or more, more preferably 320 ° C. or more, still more preferably 350 ° C. or more, and particularly preferably 370 ° C. or more.
  • the upper limit of the maximum temperature is preferably 700 ° C. or less, more preferably 450 ° C. or less, still more preferably 400 ° C. or less, and particularly preferably 390 ° C. or less.
  • the highest temperature means the temperature of the highest temperature portion of the temperature of the inner wall surface of the calcining vessel in contact with the catalyst precursor.
  • a preferable range of the residual amount of the nitrogen-containing component in the obtained catalyst can be, for example, 0.001 to 1 mmol / g per unit mass of catalyst although it depends on the use method of the catalyst.
  • the shape of the firing vessel is not particularly limited, and may be box-shaped or tubular, but it is preferable to use a tubular firing vessel having a cross-sectional area of 2 to 100 cm 2 .
  • the cross-sectional area being 2 cm 2 or more, industrial productivity is improved.
  • temperature control becomes easy and generation
  • the unsaturated aldehyde is gas phase catalytically oxidized with molecular oxygen in the presence of the catalyst produced by the process according to the invention. That is, the method for producing unsaturated carboxylic acid according to the present invention comprises the steps of producing a catalyst by the method according to the present invention, and performing catalytic vapor phase oxidation of unsaturated aldehyde with molecular oxygen in the presence of the catalyst Have.
  • the catalyst produced by the method according to the present invention unsaturated carboxylic acids can be produced with higher selectivity than in the prior art.
  • methacrolein As unsaturated aldehyde, acrolein or methacrolein is preferable, and methacrolein is more preferable.
  • methacrolein is used as the unsaturated aldehyde.
  • methacrolein is gas phase catalytically oxidized by molecular oxygen to obtain methacrylic acid.
  • the concentration of the raw material compound in the raw material gas is not limited and can be set to any concentration, but it is preferably 1 to 20% by volume, the lower limit is 3% by volume or more, and the upper limit is 10% by volume or less.
  • the molecular oxygen concentration in the raw material gas is preferably 0.5 to 4.0 mol with respect to 1 mol of the raw material compound, and the lower limit is particularly preferably 1.0 mol or more and the upper limit is more preferably 3.0 mol or less.
  • an inert gas such as nitrogen or carbon dioxide gas may be added to the source gas for dilution, or steam may be added.
  • the reaction pressure can be set in the range from atmospheric pressure to several hundreds kPa (G).
  • the reaction temperature is preferably 230 to 450 ° C. from the viewpoint of the yield of the desired product, and the lower limit is particularly preferably 250 ° C. or more and the upper limit is more preferably 400 ° C. or less.
  • Method for producing unsaturated aldehyde and unsaturated carboxylic acid At least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst produced by the process according to the invention, by means of molecular oxygen Gas phase catalytic oxidation.
  • the method for producing unsaturated aldehyde and unsaturated carboxylic acid according to the present invention comprises the steps of producing a catalyst by the method according to the present invention, propylene, isobutylene, primary butyl alcohol, Vapor phase catalytic oxidation of at least one member selected from the group consisting of secondary butyl alcohol and methyl tertiary butyl ether with molecular oxygen.
  • a catalyst by the method according to the present invention, unsaturated aldehydes and unsaturated carboxylic acids can be produced with higher selectivity than conventional.
  • the unsaturated aldehyde is preferably acrolein or methacrolein, and more preferably methacrolein.
  • the unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid, and more preferably methacrylic acid.
  • the conditions of the gas phase catalytic oxidation reaction can be the same as the method for producing the unsaturated carboxylic acid.
  • the method for producing an unsaturated carboxylic acid ester according to the present invention esterifies the unsaturated carboxylic acid obtained by the method according to the present invention.
  • Unsaturated carboxylic acid esters can be obtained using unsaturated carboxylic acids obtained by catalytic oxidation.
  • Examples of the alcohol to be reacted with the unsaturated carboxylic acid include methanol, ethanol, isopropanol, n-butanol, isobutanol and the like.
  • Examples of the unsaturated carboxylic acid ester to be obtained include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate.
  • the reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin.
  • the reaction temperature is preferably 50 to 200 ° C.
  • Part in an Example and a comparative example means a mass part.
  • the molar ratio of the catalyst composition was calculated by analyzing the component in which the catalyst was dissolved in aqueous ammonia by ICP emission analysis.
  • F is the number of moles of methacrolein supplied per unit time
  • R is the number of moles of methacrolein reacted in unit time
  • P is the number of moles of methacrylic acid generated per unit time.
  • the selectivity of methacrylic acid changes with the conversion of methacrolein. Therefore, as for the selectivity of methacrylic acid in the gas phase catalytic oxidation reaction using each catalyst, it is preferable to compare the reaction rates of methacrolein with the same value. Therefore, in the following examples and comparative examples, the contact time is changed by appropriately adjusting the amount of the catalyst used for the reaction under a constant reaction gas flow rate, and the reaction rate of methacrolein is equalized to about 40%.
  • Example 1 (1) Raw material liquid preparation process 100 parts of molybdenum trioxide, 4.06 parts of ammonium metavanadate, 6.67 parts of 85 mass% phosphoric acid, 0.84 parts of antimony trioxide and copper nitrate 2.80 to pure water 400 parts I added a department. This was made into a slurry while stirring, and the obtained slurry was heated at 90 ° C. for 3 hours. While maintaining this at 90 ° C., a solution of 11.3 parts of cesium carbonate dissolved in 40.3 parts of pure water was added and held for 30 minutes. Then, a solution of 8.34 parts of ammonium carbonate dissolved in 37.5 parts of pure water was added. Subsequently, the raw material liquid was obtained by hold
  • the obtained raw material solution was heated at 101 ° C. and evaporated to dryness with stirring. Thereafter, the obtained solid was dried at 90 ° C. for 16 hours to obtain a catalyst precursor.
  • the resulting catalyst precursor contained a Keggin-type heteropolyacid structure. Further, the composition except oxygen of the catalyst precursor was Mo 12 V 0.6 P 1.0 Sb 0.1 Cu 0.2 Cs 1.2 (NH 4) 3.0.
  • the obtained catalyst precursor was formed into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm and a length of 5 mm by a tablet forming machine.
  • the molded product of the obtained catalyst precursor is filled in a stainless steel pipe having an inner diameter of 27.5 mm and a length of 6 m, and the catalyst precursor is calcined at 380 ° C. under an air flow of space velocity 370 h ⁇ 1 .
  • the baking gas outlet was connected to an exhaust gas component trap tank filled with water, and the pressure in the main baking step was 64 kPa (G).
  • the holding time at 380 ° C. during firing was 16 hours. In firing, the maximum temperature was 380.degree. From the obtained catalyst, a nitrogen-containing component of 0.001 to 1.0 mmol / g was detected per unit mass of the catalyst.
  • the obtained catalyst was charged in a reaction tube, a reaction gas was introduced, and methacrylic acid was produced by gas phase catalytic oxidation under the following reaction conditions.
  • the results are shown in Table 1.
  • Reaction gas Mixed gas of 4% by volume of methacrolein, 10% by volume of oxygen, 15% by volume of steam and 71% by volume of nitrogen Reaction temperature: 310 ° C.
  • Reaction pressure 101 kPa
  • Contact time 1.8 seconds.
  • Comparative Example 1 By reducing the amount of water in the exhaust gas component trap tank connected to the calcining gas outlet than in Example 1, the pressure in the calcining step was set to 0 kPa (G), and the catalyst precursor was calcined at 380 ° C. for 12 hours A catalyst was produced in the same manner as Example 1 except for the following. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.5 seconds using the obtained catalyst. The results are shown in Table 1.
  • Comparative Example 2 The catalyst was prepared in the same manner as in Example 1 except that the pressure in the calcination step was set to 0 kPa (G) by reducing the amount of water in the exhaust gas component trap tank connected to the calcining gas outlet than in Example 1. Manufactured. In addition, the reaction was performed in the same manner as in Example 1 except that the contact time was changed to 1.2 seconds using the obtained catalyst. The results are shown in Table 1.
  • Example 2 A catalyst was produced in the same manner as in Example 1 except that a pressure control valve was provided at the calcination gas outlet, the pressure in the calcination step was 64 kPa (G), and the catalyst precursor was calcined at 382 ° C. for 16 hours. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.7 seconds using the obtained catalyst. The results are shown in Table 1.
  • Example 3 By reducing the amount of water in the exhaust gas component trap tank connected to the calcining gas outlet than in Example 1, the pressure in the calcining step was 54 kPa (G), and the catalyst precursor was calcined at 382 ° C. for 14 hours A catalyst was produced in the same manner as Example 1 except for the following. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.7 seconds using the obtained catalyst. The results are shown in Table 1.
  • Example 4 A catalyst was produced in the same manner as in Example 2 except that the pressure in the firing step was changed to 10 kPa (G) by the pressure control valve and the catalyst precursor was fired at 380 ° C. for 16 hours. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.4 seconds using the obtained catalyst. The results are shown in Table 1.
  • Example 5 A catalyst was produced in the same manner as in Example 4 except that the pressure in the firing step was changed to 30 kPa (G) by the pressure control valve. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.5 seconds using the obtained catalyst. The results are shown in Table 1.

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Abstract

A catalyst is provided with which a target product can be manufactured with high selectivity. The present invention is a method for manufacturing a catalyst that is used when subjecting unsaturated aldehyde to gas-phase catalytic oxidation using molecular oxygen and manufacturing unsaturated carboxylic acid, the catalyst containing at least molybdenum and phosphorus, wherein the method for manufacturing the catalyst includes a step for exposing a catalyst precursor containing a nitrogen-containing component to a pressure exceeding atmospheric pressure, and firing the catalyst precursor.

Description

触媒の製造方法、不飽和カルボン酸の製造方法、不飽和アルデヒド及び不飽和カルボン酸の製造方法、並びに不飽和カルボン酸エステルの製造方法Method of producing catalyst, method of producing unsaturated carboxylic acid, method of producing unsaturated aldehyde and unsaturated carboxylic acid, and method of producing unsaturated carboxylic acid ester
　本発明は、触媒の製造方法、不飽和カルボン酸の製造方法、不飽和アルデヒド及び不飽和カルボン酸の製造方法、並びに不飽和カルボン酸エステルの製造方法に関する。 The present invention relates to a method of producing a catalyst, a method of producing an unsaturated carboxylic acid, a method of producing an unsaturated aldehyde and an unsaturated carboxylic acid, and a method of producing an unsaturated carboxylic acid ester.
　触媒の製造方法については数多くの検討がなされている。触媒は、一般的には、該触媒を構成する各元素を含む水溶液または水性スラリーなどの原料液を調製し、該原料液を乾燥、焼成することで製造される。 A number of studies have been made on the method of producing the catalyst. The catalyst is generally produced by preparing a raw material liquid such as an aqueous solution or an aqueous slurry containing each element constituting the catalyst, and drying and calcining the raw material liquid.
　前記焼成としては、例えば、特許文献１～３ではアンモニアや水蒸気を含むガスを、特許文献４では非酸化性ガスを、特許文献５では含酸素有機化合物を含むガスを用いた焼成について記載されている。また、特許文献６では用いるガスや焼成温度を変更した複数の工程からなる焼成方法について記載されている。また、特許文献７では触媒前駆体に対するガス流量について記載されている。 For example, Patent Documents 1 to 3 describe the baking using a gas containing ammonia or water vapor, Patent Document 4 describes baking using a non-oxidative gas, and Patent Document 5 using a gas containing an oxygen-containing organic compound. There is. Moreover, in patent document 6, it describes about the baking method which consists of several processes which changed the gas to be used, and a calcination temperature. Patent Document 7 describes the gas flow rate to the catalyst precursor.
特開昭５８－６１８３３号公報JP-A-58-61833 特開昭５８－６７６４３号公報JP-A-58-67643 特開昭５８－７９５４５号公報Japanese Patent Application Laid-Open No. 58-79545 特開昭５９－６６３４９号公報JP-A-59-66349 特開昭５９－６９１４８号公報JP-A-59-69148 特開２０１２－２４５４３２号公報JP 2012-245432 A 特開２００９－２１３９６９号公報JP, 2009-213969, A
　しかしながら、特許文献１～７に記載された方法で製造される触媒は、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する反応、またはプロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する反応に用いた場合、目的生成物の選択率が十分ではないという問題があった。このため、目的生成物をより高い選択率で製造できる触媒の製造方法の開発が望まれている。本発明は前記事情に鑑みてなされたものであり、目的生成物を高い選択率で製造できる触媒を提供することを目的とする。 However, the catalyst produced by the method described in Patent Documents 1 to 7 is a reaction for producing an unsaturated carboxylic acid by vapor phase catalytic oxidation of unsaturated aldehyde with molecular oxygen, or propylene, isobutylene, primary Gas-phase catalytic oxidation of at least one member selected from the group consisting of butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids When used for the reaction, there is a problem that the selectivity of the desired product is not sufficient. For this reason, development of the manufacturing method of the catalyst which can manufacture a target product with higher selectivity is desired. The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a catalyst capable of producing a target product with high selectivity.
　前記課題は、以下の本発明［１］～［１６］によって解決される。 The above problems are solved by the following present inventions [1] to [16].
　［１］不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びリンを含む触媒の製造方法であって、含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程を含む触媒の製造方法。 [1] A method for producing a catalyst containing at least molybdenum and phosphorus, which is used when producing unsaturated carboxylic acid by vapor phase catalytic oxidation of unsaturated aldehyde with molecular oxygen, which is a catalyst precursor containing a nitrogen-containing component A method for producing a catalyst, comprising the steps of calcining a body by applying pressure above atmospheric pressure.
　［２］プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びビスマスを含む触媒の製造方法であって、含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程を含む触媒の製造方法。 [2] At least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether by gas phase catalytic oxidation with molecular oxygen and corresponding A method for producing a catalyst containing at least molybdenum and bismuth, which is used in producing unsaturated aldehyde and unsaturated carboxylic acid, wherein a catalyst precursor containing a nitrogen-containing component is calcined by exposing to pressure exceeding atmospheric pressure. A method of producing a catalyst comprising the steps.
　［３］前記不飽和アルデヒドがアクロレイン又はメタクロレインである［１］または［２］に記載の触媒の製造方法。 [3] The method for producing a catalyst according to [1] or [2], wherein the unsaturated aldehyde is acrolein or methacrolein.
　［４］前記触媒前駆体を焼成する際に、酸素含有ガス及び不活性ガスから選択される少なくとも１種のガス流通下で焼成する［１］から［３］のいずれかに記載の触媒の製造方法。 [4] When calcining the catalyst precursor, the catalyst according to any one of [1] to [3] is calcined under a gas flow of at least one selected from an oxygen-containing gas and an inert gas Method.
　［５］前記圧力が１０ｋＰａ（Ｇ）以上、１００ｋＰａ（Ｇ）以下である［１］から［４］のいずれかに記載の触媒の製造方法。 [5] The method for producing a catalyst according to any one of [1] to [4], wherein the pressure is 10 kPa (G) or more and 100 kPa (G) or less.
　［６］前記圧力が２０ｋＰａ（Ｇ）以上、８０ｋＰａ（Ｇ）以下である［５］に記載の触媒の製造方法。 [6] The method for producing a catalyst according to [5], wherein the pressure is 20 kPa (G) or more and 80 kPa (G) or less.
　［７］前記焼成における温度の最高値が３００℃以上、７００℃以下である［１］から［６］のいずれかに記載の触媒の製造方法。 [7] The method for producing a catalyst according to any one of [1] to [6], wherein the highest temperature in the calcination is 300 ° C. or more and 700 ° C. or less.
　［８］前記焼成における温度の最高値が３５０℃以上、４００℃以下である［７］に記載の触媒の製造方法。 [8] The method for producing a catalyst according to [7], wherein the maximum value of the temperature in the calcination is 350 ° C. or more and 400 ° C. or less.
　［９］前記含窒素成分が、アンモニウム根及び硝酸根からなる群から選択される少なくとも１種である［１］から［８］のいずれかに記載の触媒の製造方法。 [9] The method for producing a catalyst according to any one of [1] to [8], wherein the nitrogen-containing component is at least one selected from the group consisting of ammonium roots and nitrate roots.
　［１０］前記触媒前駆体がヘテロポリ酸構造を含む［１］に記載の触媒の製造方法。 [10] The method for producing a catalyst according to [1], wherein the catalyst precursor contains a heteropoly acid structure.
　［１１］前記ヘテロポリ酸構造がケギン型ヘテロポリ酸構造である［１０］に記載の触媒の製造方法。
　［１２］［１］に記載の方法により製造された触媒の存在下、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する、不飽和カルボン酸の製造方法。 [11] The method for producing a catalyst according to [10], wherein the heteropoly acid structure is a Keggin heteropoly acid structure.
[12] A method for producing an unsaturated carboxylic acid, which comprises producing an unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde with molecular oxygen in the presence of a catalyst produced by the method according to [1].
　［１３］［１］に記載の方法により触媒を製造し、該触媒の存在下、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する、不飽和カルボン酸の製造方法。
　［１４］［２］に記載の方法により製造された触媒の存在下、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する、不飽和アルデヒド及び不飽和カルボン酸の製造方法。 [13] A method for producing an unsaturated carboxylic acid, comprising: preparing a catalyst by the method according to [13]; Method.
[14] [2] at least one member selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst produced by the method according to [14] [2] A method for producing unsaturated aldehydes and unsaturated carboxylic acids, which comprises the step of vapor phase catalytic oxidation of H 2 O with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids.
　［１５］［２］に記載の方法により触媒を製造し、該触媒の存在下、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する、不飽和アルデヒド及び不飽和カルボン酸の製造方法。 [15] A catalyst is prepared by the method described in [2], and is selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst A method for producing unsaturated aldehydes and unsaturated carboxylic acids, wherein at least one is subjected to gas phase catalytic oxidation with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids.
　［１６］［１２］から［１５］のいずれかに記載の方法により製造された不飽和カルボン酸をエステル化する不飽和カルボン酸エステルの製造方法。 [16] A method for producing an unsaturated carboxylic acid ester, which esterifies the unsaturated carboxylic acid produced by the method according to any one of [12] to [15].
　本発明によれば、目的生成物を高い選択率で製造できる触媒を提供することができる。 According to the present invention, it is possible to provide a catalyst capable of producing a target product with high selectivity.
　［触媒の製造方法］
　本発明に係る触媒の製造方法の第一の実施形態は、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びリンを含む触媒の製造方法である。該方法は、含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程を含む。 [Method of producing catalyst]
The first embodiment of the process for producing a catalyst according to the present invention is a catalyst comprising at least molybdenum and phosphorus, which is used in the vapor phase catalytic oxidation of unsaturated aldehyde with molecular oxygen to produce unsaturated carboxylic acid. It is a manufacturing method. The method includes the steps of calcinating a catalyst precursor containing a nitrogen-containing component by applying a pressure above atmospheric pressure.
　また、本発明に係る触媒の製造方法の第二の実施形態は、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びビスマスを含む触媒の製造方法である。該方法は、含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程を含む。 In addition, the second embodiment of the process for producing a catalyst according to the present invention comprises at least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether. This is a method for producing a catalyst containing at least molybdenum and bismuth, which is used in producing gas phase catalytic oxidation with molecular oxygen to produce the corresponding unsaturated aldehyde and unsaturated carboxylic acid. The method includes the steps of calcinating a catalyst precursor containing a nitrogen-containing component by applying a pressure above atmospheric pressure.
　本発明に係る方法では、触媒前駆体の焼成時における圧力に着目し、含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成することで、目的生成物を高い選択率で製造可能な触媒を得ることができる。この理由は以下のように考えられる。すなわち、焼成中に含窒素成分が脱離する過程で触媒前駆体の構造が変化し、目的の反応に好ましい触媒活性点が形成される。この時、触媒前駆体が大気圧よりも高い圧力に曝されることで、含窒素成分の脱離が抑制される。その結果、大気圧以下の圧力下で焼成する場合よりも緩やかな速度で触媒の構造変化が起こり、触媒表面により均質な活性点構造が形成されると推測される。なお従来技術においては、焼成時の圧力の影響については詳しい検討はされていなかった。 In the method according to the present invention, attention is paid to the pressure at the time of calcination of the catalyst precursor, and the desired product is obtained with high selectivity by calcinating the catalyst precursor containing the nitrogen-containing component under a pressure exceeding atmospheric pressure. A producible catalyst can be obtained. The reason is considered as follows. That is, the structure of the catalyst precursor changes in the process of desorption of the nitrogen-containing component during the calcination, and a catalyst active point preferable for the intended reaction is formed. At this time, desorption of the nitrogen-containing component is suppressed by exposing the catalyst precursor to a pressure higher than atmospheric pressure. As a result, it is presumed that the structural change of the catalyst occurs at a slower rate than in the case of calcining under a pressure less than atmospheric pressure, and a homogeneous active point structure is formed by the catalyst surface. In the prior art, the effects of pressure at the time of firing have not been studied in detail.
　本発明に係る方法は、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びリンを含む触媒（以下、不飽和カルボン酸製造用触媒とも示す）の製造に用いられる。該触媒を用いて反応を行うことにより、より高い選択率で不飽和カルボン酸を製造できる。該不飽和アルデヒドはアクロレイン又はメタクロレインであることが、より高い選択率でアクリル酸又はメタクリル酸を製造できるため好ましい。また、該触媒はヘテロポリ酸構造、特にケギン型ヘテロポリ酸構造を含むことが、より高い選択率で不飽和カルボン酸を製造できるため好ましい。 The process according to the present invention is a catalyst containing at least molybdenum and phosphorus (hereinafter referred to as a catalyst for producing unsaturated carboxylic acid, which is used when producing unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde with molecular oxygen to produce unsaturated carboxylic acid Also used in the manufacture of By carrying out the reaction using the catalyst, unsaturated carboxylic acids can be produced with higher selectivity. The unsaturated aldehyde is preferably acrolein or methacrolein because it can produce acrylic acid or methacrylic acid with higher selectivity. In addition, it is preferable that the catalyst contains a heteropoly acid structure, particularly a Keggin-type heteropoly acid structure, because unsaturated carboxylic acid can be produced with higher selectivity.
　また、本発明に係る方法は、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びビスマスを含む触媒（以下、不飽和アルデヒド及び不飽和カルボン酸製造用触媒とも示す）の製造に用いられる。該触媒を用いて反応を行うことにより、より高い選択率で不飽和アルデヒド及び不飽和カルボン酸を製造できる。該不飽和アルデヒドはアクロレイン又はメタクロレイン、該不飽和カルボン酸はアクリル酸又はメタクリル酸であることが、選択率の観点から好ましい。 In the method according to the present invention, at least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether is subjected to vapor phase catalytic oxidation with molecular oxygen Used for producing a catalyst containing at least molybdenum and bismuth (hereinafter also referred to as a catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid) used in producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid. Be By performing the reaction using the catalyst, unsaturated aldehydes and unsaturated carboxylic acids can be produced with higher selectivity. The unsaturated aldehyde is preferably acrolein or methacrolein, and the unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid from the viewpoint of selectivity.
　本発明に係る方法により得られる触媒の組成は特に限定されないが、該触媒が前記不飽和カルボン酸製造用触媒である場合には、不飽和カルボン酸をより高い選択率で製造できる観点から、該触媒は下記式（１）で示される組成を有することが好ましい。 The composition of the catalyst obtained by the method according to the present invention is not particularly limited, but when the catalyst is the catalyst for producing unsaturated carboxylic acid, from the viewpoint of being able to produce unsaturated carboxylic acid with higher selectivity, The catalyst preferably has a composition represented by the following formula (1).
　　Ｐα１Ｍｏα２Ｖα３Ｃｕα４Ａα５Ｅα６Ｇα７Ｏα８　　（１）
　式（１）中、Ｐ、Ｍｏ、Ｖ、Ｃｕ及びＯはそれぞれリン、モリブデン、バナジウム、銅及び酸素を示す元素記号である。Ａはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群から選択される少なくとも１種の元素を示す。Ｅはカリウム、ルビジウム、セシウム、タリウム、マグネシウム及びバリウムからなる群から選択される少なくとも１種の元素を示す。Ｇは鉄、亜鉛、クロム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群から選択される少なくとも１種の元素を示す。α１～α８は各元素の原子比率を表し、α２＝１２のときα１＝０．５～３、α３＝０．０１～３、α４＝０．０１～２、α５＝０～３、好ましくは０．０１～３、α６＝０．０１～３、α７＝０～４であり、α８は前記各元素の原子価を満足するのに必要な酸素の原子比率である。 P α1 Mo α2 V α3 Cu α4 A α5 E α6 G α7 O α8 (1)
In formula (1), P, Mo, V, Cu and O are element symbols which show phosphorus, molybdenum, vanadium, copper and oxygen, respectively. A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. E represents at least one element selected from the group consisting of potassium, rubidium, cesium, thallium, magnesium and barium. G is at least one selected from the group consisting of iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum Indicates an element. α1 to α8 represent atomic ratios of respective elements, and when α2 = 12, α1 = 0.5 to 3, α3 = 0.01 to 3, α4 = 0.01 to 2, α5 = 0 to 3, preferably 0 .01 to 3, .alpha.6 = 0.01 to 3, .alpha.7 = 0 to 4, and .alpha.8 is an atomic ratio of oxygen necessary to satisfy the valences of the respective elements.
　また、本発明に係る方法により得られる触媒が前記不飽和アルデヒド及び不飽和カルボン酸製造用触媒である場合には、不飽和アルデヒド及び不飽和カルボン酸をより高い選択率で製造できる観点から、該触媒は下記式（２）で示される組成を有することが好ましい。 When the catalyst obtained by the method according to the present invention is the catalyst for producing the above-mentioned unsaturated aldehyde and unsaturated carboxylic acid, the unsaturated aldehyde and the unsaturated carboxylic acid can be produced at a higher selectivity because The catalyst preferably has a composition represented by the following formula (2).
　　Ｍｏα９Ｂｉα１０Ｆｅα１１Ｘα１２Ａ’α１３Ｅ’α１４Ｇ’α１５Ｓｉα１６Ｏα１７　　（２）
　式（２）中、Ｍｏ、Ｂｉ、Ｆｅ、Ｓｉ及びＯはそれぞれモリブデン、ビスマス、鉄、ケイ素及び酸素を示す元素記号である。Ｘはコバルト及びニッケルからなる群から選択される少なくとも１種の元素を示す。Ａ’はクロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル及び亜鉛からなる群から選択される少なくとも１種の元素を示す。Ｅ’はリン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン及びチタンからなる群から選択される少なくとも１種の元素を示す。Ｇ’はリチウム、ナトリウム、カリウム、ルビジウム、セシウム及びタリウムからなる群から選択される少なくとも１種の元素を示す。α９～α１７は各元素の原子比率を表し、α９＝１２のときα１０＝０．０１～３、α１１＝０．０１～５、α１２＝１～１２、α１３＝０～８、α１４＝０～５、α１５＝０．００１～２、α１６＝０～２０であり、α１７は前記各元素の原子価を満足するのに必要な酸素の原子比率である。 Mo α9 Bi α10 Fe α11 X α12 A 'α13 E' α14 G 'α15 Si α16 O α17 (2)
In formula (2), Mo, Bi, Fe, Si and O are element symbols showing molybdenum, bismuth, iron, silicon and oxygen, respectively. X represents at least one element selected from the group consisting of cobalt and nickel. A ′ represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc. E ′ represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium. G ′ represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. α9 to α17 represent atomic ratios of respective elements, and when α9 = 12, α10 = 0.01 to 3, α11 = 0.01 to 5, α12 = 1 to 12, α13 = 0 to 8, α14 = 0 to 5 .Alpha.15 = 0.001-2 and .alpha.16 = 0-20, and .alpha.17 is an atomic ratio of oxygen necessary to satisfy the valences of the respective elements.
　本発明に係る触媒の製造方法は、含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程（以下、焼成工程とも示す）を含めば特に限定されない。しかしながら、該方法は、触媒を構成する各元素を含む原料液を調製する工程（以下、原料液調製工程とも示す）と、該原料液を乾燥して触媒前駆体を得る工程（以下、乾燥工程とも示す）と、焼成工程とを含むことが、目的生成物をより高い選択率で製造できる触媒が得られる観点から好ましい。また、該方法は、乾燥工程と焼成工程との間に、必要に応じて、触媒前駆体を成形する工程（以下、成形工程とも示す）を含んでもよい。 The method for producing a catalyst according to the present invention is not particularly limited as long as it includes a step of firing a catalyst precursor containing a nitrogen-containing component by applying a pressure exceeding atmospheric pressure (hereinafter also referred to as a firing step). However, the method comprises the steps of preparing a raw material liquid containing each element constituting the catalyst (hereinafter also referred to as raw material liquid preparation step) and drying the raw material liquid to obtain a catalyst precursor (hereinafter drying step). It is preferable from the viewpoint of obtaining a catalyst capable of producing the target product with higher selectivity, which also includes the calcination step). In addition, the method may include a step of forming a catalyst precursor (hereinafter also referred to as a forming step), as necessary, between the drying step and the firing step.
　（原料液調製工程）
　原料液調製工程では、触媒を構成する各元素を含む原料液を調製する。前記不飽和カルボン酸製造用触媒の製造では、該原料液は少なくともモリブデン及びリンを含む。また、前記不飽和アルデヒド及び不飽和カルボン酸製造用触媒の製造では、該原料液は少なくともモリブデン及びビスマスを含む。該原料液がこれらの元素を含むことで、目的生成物の選択率の高い不飽和カルボン酸製造用触媒、または不飽和アルデヒド及び不飽和カルボン酸製造用触媒を製造することができる。触媒を構成する各元素の種類及び比率については、該触媒が不飽和カルボン酸製造用触媒である場合には、例えば前記式（１）で示される元素及び原子比率とすることができる。また、該触媒が不飽和アルデヒド及び不飽和カルボン酸製造用触媒である場合には、例えば前記式（２）で示される元素及び原子比率とすることができる。 Raw material liquid preparation process
At a raw material liquid preparation process, the raw material liquid containing each element which comprises a catalyst is prepared. In the production of the catalyst for unsaturated carboxylic acid production, the raw material liquid contains at least molybdenum and phosphorus. Further, in the production of the catalyst for producing the unsaturated aldehyde and the unsaturated carboxylic acid, the raw material liquid contains at least molybdenum and bismuth. When the raw material liquid contains these elements, it is possible to produce a catalyst for unsaturated carboxylic acid production with a high selectivity of the desired product, or a catalyst for unsaturated aldehyde and unsaturated carboxylic acid production. About the kind and ratio of each element which comprise a catalyst, when this catalyst is a catalyst for unsaturated carboxylic acid manufacture, it can be set as the element and atomic ratio shown, for example by said Formula (1). When the catalyst is a catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid, for example, the element and atomic ratio can be set to the formula (2).
　原料液の調製方法には特に制限はないが、水に各元素の原料を投入し、３０～１００℃に加熱して撹拌し、スラリー状の原料液を調製する方法が好ましい。水の使用量は、各元素の原料の合計１００質量部に対して、２００～１０００質量部が好ましい。 The preparation method of the raw material solution is not particularly limited, but a method of preparing a slurry-like raw material solution by charging the raw material of each element into water, heating to 30 to 100 ° C. and stirring is preferable. The amount of water used is preferably 200 to 1000 parts by mass with respect to a total of 100 parts by mass of the raw material of each element.
　各元素の原料としては特に限定されず、各元素の酸化物、硝酸塩、炭酸塩、アンモニウム塩等を適宜選択して使用することができる。例えば、モリブデンの原料としては、モリブデン酸、三酸化モリブデン、パラモリブデン酸アンモニウム等が使用でき、モリブデン酸、三酸化モリブデンが好ましい。リンの原料としては、正リン酸、五酸化リン、リン酸アンモニウム等が使用できる。バナジウムの原料としては、メタバナジン酸アンモニウム、五酸化二バナジウム等が使用できる。また、銅の原料としては硝酸銅、硫酸銅、炭酸銅等が使用できる。また、ビスマスの原料としては、硝酸ビスマス、酸化ビスマス、酢酸ビスマス、水酸化ビスマス等が使用できる。これらの原料は一種を用いてもよく、二種以上を併用してもよい。 It does not specifically limit as a raw material of each element, The oxide of each element, nitrate, carbonate, ammonium salt etc. can be selected suitably, and can be used. For example, as a raw material of molybdenum, molybdic acid, molybdenum trioxide, ammonium paramolybdate and the like can be used, and molybdic acid and molybdenum trioxide are preferable. As a raw material of phosphorus, orthophosphoric acid, phosphorus pentoxide, ammonium phosphate etc. can be used. As a raw material of vanadium, ammonium metavanadate, vanadium pentoxide etc. can be used. In addition, copper nitrate, copper sulfate, copper carbonate and the like can be used as a raw material of copper. Further, as a raw material of bismuth, bismuth nitrate, bismuth oxide, bismuth acetate, bismuth hydroxide and the like can be used. One of these raw materials may be used, or two or more thereof may be used in combination.
　本発明に係る方法では、触媒前駆体は含窒素成分を含むため、原料液は含窒素成分を含むことが好ましい。含窒素成分としては、アンモニウム根、硝酸根、含窒素ヘテロ環等が挙げられるが、アンモニウム根及び硝酸根からなる群から選択される少なくとも１種であることが、目的生成物の選択率の観点から好ましい。ここで、本発明におけるアンモニウム根とは、アンモニウムイオン（ＮＨ４ ＋）になり得るアンモニア（ＮＨ３）、及びアンモニウム塩などのアンモニウム含有化合物に含まれるアンモニウムの総称である。アンモニウム含有化合物としては、例えば炭酸アンモニウム、重炭酸アンモニウム、硝酸アンモニウム、酢酸アンモニウム、バナジン酸アンモニウム、触媒構成元素のアンモニウム塩等が挙げられる。また、本発明における硝酸根とは、硝酸イオン（ＮＯ３ －）、亜硝酸イオン（ＮＯ２ －）等の窒素酸化物イオンの総称である。硝酸根としては、例えば触媒構成元素の硝酸塩に含まれる硝酸イオンが挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。なお、前記各元素の原料として各元素のアンモニウム塩や硝酸塩を用いることにより、原料液に含窒素成分が含まれるようにしてもよい。 In the method according to the present invention, since the catalyst precursor contains a nitrogen-containing component, the raw material liquid preferably contains a nitrogen-containing component. Examples of the nitrogen-containing component include ammonium roots, nitrate roots, nitrogen-containing heterocycles and the like, but at least one selected from the group consisting of ammonium roots and nitrate roots, the viewpoint of selectivity of the target product It is preferable from Here, the ammonium root in the present invention is a generic name of ammonia (NH 3 ) which can be ammonium ion (NH 4 + ), and ammonium contained in ammonium-containing compounds such as ammonium salts. Examples of the ammonium-containing compound include ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium vanadate, ammonium salts of elements constituting a catalyst, and the like. Further, the nitrate root in the present invention is a general term for nitrogen oxide ions such as nitrate ion (NO 3 − ) and nitrite ion (NO 2 − ). As a nitrate root, the nitrate ion contained in the nitrate of a catalyst structural element is mentioned, for example. One of these may be used, or two or more may be used in combination. In addition, you may make it a nitrogen-containing component be contained in a raw material liquid by using ammonium salt and nitrate of each element as a raw material of each said element.
　原料液の調製スケールには特に制限はないが、主となる元素の原料の量の下限は１００ｇ以上であることが好ましく、１ｋｇ以上であることがより好ましい。また上限は１０ｔ以下であることが好ましく、１ｔ以下であることがより好ましい。このようなスケールとすることで、良好な原料液を安定に調製できる。 The preparation scale of the raw material liquid is not particularly limited, but the lower limit of the amount of the raw material of the main element is preferably 100 g or more, and more preferably 1 kg or more. The upper limit is preferably 10 t or less, more preferably 1 t or less. By setting such a scale, a good raw material solution can be stably prepared.
　（乾燥工程）
　乾燥工程では、前記原料液調製工程にて得られた原料液を乾燥して触媒前駆体を得る。原料液の乾燥方法には特に制限はないが、例えば蒸発乾固法、噴霧乾燥法、ドラム乾燥法、気流乾燥法等が挙げられる。乾燥に使用する乾燥機の種類、機種、乾燥時の温度、雰囲気等には特に制限はなく、例えば、空気雰囲気下１００～１８０℃で０．１～２０時間乾燥する条件などが挙げられる。乾燥条件を変えることによって、触媒前駆体の流動性、成形性等の物性を制御できるため、目的に応じた条件を設定することが好ましい。 (Drying process)
In the drying step, the raw material liquid obtained in the raw material liquid preparation step is dried to obtain a catalyst precursor. Although there is no restriction | limiting in particular in the drying method of a raw material liquid, For example, the evaporation-to-dryness method, spray-drying method, drum drying method, flash drying method etc. are mentioned. There are no particular restrictions on the type and type of dryer used for drying, the temperature at the time of drying, the atmosphere, and the like. By changing the drying conditions, physical properties such as flowability and moldability of the catalyst precursor can be controlled, so it is preferable to set conditions according to the purpose.
　本発明に係る方法を前記不飽和カルボン酸製造用触媒の製造に用いる場合、得られる触媒前駆体は、より高い選択率で不飽和カルボン酸を製造できる観点から、ヘテロポリ酸構造を含むことが好ましく、ケギン型ヘテロポリ酸構造を含むことがより好ましい。なお、触媒前駆体がヘテロポリ酸構造（ケギン型ヘテロポリ酸構造）を含むか否かは、触媒前駆体を赤外吸収分析で測定することにより確認することができる。例えば触媒前駆体がケギン型ヘテロポリ酸構造を含む場合、得られる赤外吸収スペクトルは、１０６０、９６０、８７０、７８０ｃｍ－１付近に特徴的なピークを有する。 When the method according to the present invention is used for the production of the catalyst for unsaturated carboxylic acid production, the catalyst precursor obtained preferably has a heteropolyacid structure from the viewpoint of producing unsaturated carboxylic acid with higher selectivity. It is more preferable to include a Keggin type heteropoly acid structure. In addition, it can be confirmed by measuring a catalyst precursor by infrared absorption analysis whether the catalyst precursor contains a heteropoly acid structure (Keggin type heteropoly acid structure). For example, when the catalyst precursor contains a Keggin-type heteropolyacid structure, the obtained infrared absorption spectrum has characteristic peaks in the vicinity of 1060, 960, 870, 780 cm -1 .
　得られる触媒前駆体に含まれる含窒素成分の量は特に限定されないが、例えば０．５～７．０質量％であることができる。 The amount of the nitrogen-containing component contained in the obtained catalyst precursor is not particularly limited, and can be, for example, 0.5 to 7.0% by mass.
　（成形工程）
　成形工程では、前記乾燥工程で得られた触媒前駆体を成形する。成形方法には特に制限はなく、公知の乾式及び湿式の成形方法が適用できる。例えば、打錠成形、プレス成形、押出成形、造粒成形等が挙げられる。成形品の形状についても特に限定されず、例えば、円柱状、リング状、球状等の形状が挙げられる。また、成形時には、触媒前駆体に担体等を添加せず、触媒前駆体のみを成形することが好ましいが、必要に応じて、例えばグラファイトやタルクなどの公知の添加剤を加えてもよい。 (Molding process)
In the forming step, the catalyst precursor obtained in the drying step is formed. There is no particular limitation on the molding method, and known dry and wet molding methods can be applied. For example, tablet molding, press molding, extrusion molding, granulation molding and the like can be mentioned. The shape of the molded article is also not particularly limited, and examples thereof include a cylindrical shape, a ring shape, and a spherical shape. Further, at the time of molding, it is preferable to mold only the catalyst precursor without adding a carrier or the like to the catalyst precursor, but if necessary, known additives such as graphite and talc may be added.
　（焼成工程）
　焼成工程では、得られた含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する。該触媒前駆体が曝される圧力は、１０ｋＰａ（Ｇ）以上が好ましく、２０ｋＰａ（Ｇ）以上がより好ましく、３０ｋＰａ（Ｇ）以上がさらに好ましい。また該圧力は、１００ｋＰａ（Ｇ）以下が好ましく、８０ｋＰａ（Ｇ）以下がより好ましく、７０ｋＰａ（Ｇ）以下がさらに好ましい。該圧力が１０ｋＰａ（Ｇ）以上であることにより、含窒素成分の脱離が抑制され、触媒表面により均質な活性点構造が形成される。また、該圧力が１００ｋＰａ（Ｇ）以下であることにより、触媒前駆体からの含窒素成分の脱離が過度に阻害されず、触媒の反応速度低下を抑制できる。なお、「ｋＰａ（Ｇ）」はゲージ圧を示し、大気圧＋ゲージ圧が実際の圧力となる。 (Firing process)
In the calcination step, the obtained catalyst precursor containing a nitrogen-containing component is calcined by being exposed to a pressure exceeding atmospheric pressure. The pressure to which the catalyst precursor is exposed is preferably 10 kPa (G) or more, more preferably 20 kPa (G) or more, and still more preferably 30 kPa (G) or more. The pressure is preferably 100 kPa (G) or less, more preferably 80 kPa (G) or less, and still more preferably 70 kPa (G) or less. By the pressure being 10 kPa (G) or more, desorption of the nitrogen-containing component is suppressed, and a homogeneous active site structure is formed by the catalyst surface. In addition, when the pressure is 100 kPa (G) or less, desorption of the nitrogen-containing component from the catalyst precursor is not excessively inhibited, and a decrease in the reaction rate of the catalyst can be suppressed. "KPa (G)" indicates a gauge pressure, and the atmospheric pressure + gauge pressure is the actual pressure.
　なお、前記圧力とは、焼成工程の昇温過程から温度一定保持過程における圧力とする。また、該圧力の値は、圧力の空間的分布が無い容器内で焼成する場合は、容器内の任意の一点を測定した値であり、管状焼成容器でガスを流通して焼成する場合など圧力の空間的分布がある系では、焼成ガス出口の圧力のように、系内で最も低い部分における値である。また、ここでの系内とは、焼成容器の焼成ガス入口から焼成ガス出口までの範囲を意味する。系内における圧力を測定する方法には特に制限はないが、例えば、焼成ガス出口の上流であって、焼成ガス出口にできる限り近い位置に圧力計を設けることにより測定することができる。また、前記圧力を高くする方法に特に制限はないが、後述するようにガス流通下で焼成を行う場合には、例えばガスの出口の配管を延長する、ガスの出口に圧力制御弁を設けてその弁を絞る、ガスの出口を、水などを充填したトラップ槽に接続する等の方法により達成できる。 In addition, let the said pressure be the pressure in the temperature fixed process from temperature rising process of a baking process. Moreover, the value of the pressure is a value obtained by measuring any one point in the container when firing is performed in a container having no spatial distribution of pressure, and the pressure may be generated when flowing gas in a tubular firing container, etc. In systems where there is a spatial distribution of, the pressure is at the lowest point in the system, such as the pressure at the firing gas outlet. Moreover, the inside of the system here means the range from the baking gas inlet of a baking container to a baking gas outlet. The method for measuring the pressure in the system is not particularly limited, but can be measured, for example, by providing a pressure gauge upstream of the calcination gas outlet and as close as possible to the calcination gas outlet. Further, the method of increasing the pressure is not particularly limited, but in the case of firing under gas flow as described later, for example, a pipe for the gas outlet is extended, a pressure control valve is provided at the gas outlet This can be achieved by, for example, throttling the valve or connecting the gas outlet to a trap tank filled with water or the like.
　触媒前駆体を焼成する際の雰囲気ガスの種類には特に制限はないが、空気等の酸素含有ガスまたは不活性ガスが好ましい。ここで不活性ガスとは触媒活性を低下させないような気体のことを指し、窒素、炭酸ガス、ヘリウム、アルゴン等が挙げられる。前記ガスとしては、空気、窒素、酸素と空気の混合ガス、またはこれらの混合ガスがより好ましく、空気がさらに好ましい。また、前記ガスは水蒸気を含んでもよい。流通させるガス全体に対して水蒸気が０．０１～５体積％含まれることが好ましく、特に、下限は０．０５体積％以上、上限は２体積％以下であることがより好ましい。焼成時の雰囲気ガスの供給の仕方には特に制限はなく、焼成容器内を雰囲気ガスで満たしてから該容器を密閉して焼成してもよく、雰囲気ガスを焼成容器内に常時供給するガス流通下で焼成しても良いが、ガス流通下で焼成することが、触媒活性の観点から好ましい。 Although there is no restriction | limiting in particular in the kind of atmospheric gas at the time of baking a catalyst precursor, Oxygen-containing gas, such as air, or inert gas is preferable. Here, the inert gas refers to a gas which does not reduce the catalytic activity, and includes nitrogen, carbon dioxide gas, helium, argon and the like. As said gas, air, nitrogen, the mixed gas of oxygen and air, or these mixed gas are more preferable, and air is further more preferable. Also, the gas may include water vapor. The content of water vapor is preferably 0.01 to 5% by volume based on the whole gas to be circulated, and more preferably, the lower limit is 0.05% by volume or more and the upper limit is 2% by volume or less. There is no particular limitation on the method of supplying the atmosphere gas at the time of firing, and the inside of the firing container may be filled with the atmosphere gas, and then the container may be closed and fired. Gas flow always supplying the atmosphere gas into the firing container Although baking may be performed below, baking under gas flow is preferable from the viewpoint of catalyst activity.
　前記焼成における温度の最高値の下限は３００℃以上であることが好ましく、３２０℃以上であることがより好ましく、３５０℃以上であることがさらに好ましく、３７０℃以上であることが特に好ましい。また温度の最高値の上限は７００℃以下であることが好ましく、４５０℃以下であることがより好ましく、４００℃以下であることがさらに好ましく、３９０℃以下であることが特に好ましい。焼成温度が３００℃以上であることにより含窒素成分の脱離が促進され、また焼成温度が７００℃以下であることで、触媒の熱分解やシンタリングによる比表面積低下を抑制することができる。ここで、前記温度の最高値とは、触媒前駆体と接する焼成容器の内壁面の温度のうち、最高値となる部分の温度を示すものとする。温度の測定方法は特に制限されないが、熱電対を用いる方法が好ましい。 The lower limit of the highest temperature in the firing is preferably 300 ° C. or more, more preferably 320 ° C. or more, still more preferably 350 ° C. or more, and particularly preferably 370 ° C. or more. The upper limit of the maximum temperature is preferably 700 ° C. or less, more preferably 450 ° C. or less, still more preferably 400 ° C. or less, and particularly preferably 390 ° C. or less. When the calcination temperature is 300 ° C. or more, desorption of the nitrogen-containing component is promoted, and when the calcination temperature is 700 ° C. or less, it is possible to suppress the decrease in specific surface area due to the thermal decomposition or sintering of the catalyst. Here, the highest temperature means the temperature of the highest temperature portion of the temperature of the inner wall surface of the calcining vessel in contact with the catalyst precursor. Although the measuring method in particular of temperature is not restrict | limited, The method of using a thermocouple is preferable.
　得られる触媒中の含窒素成分の残留量の好ましい範囲は、触媒の使用方法などにもよるが、例えば触媒単位質量あたり０．００１～１ｍｍｏｌ／ｇであることができる。 A preferable range of the residual amount of the nitrogen-containing component in the obtained catalyst can be, for example, 0.001 to 1 mmol / g per unit mass of catalyst although it depends on the use method of the catalyst.
　焼成容器の形状は特に制限はなく、箱型でも管状でもよいが、特に断面積が２～１００ｃｍ２である管状焼成容器を用いることが好ましい。該断面積が２ｃｍ２以上であることにより、工業的な生産性が向上する。また、該断面積が１００ｃｍ２以下であることにより、温度制御が容易になり、ホットスポットの発生を抑制できる。 The shape of the firing vessel is not particularly limited, and may be box-shaped or tubular, but it is preferable to use a tubular firing vessel having a cross-sectional area of 2 to 100 cm 2 . By the cross-sectional area being 2 cm 2 or more, industrial productivity is improved. Moreover, temperature control becomes easy and generation | occurrence | production of a hot spot can be suppressed because this cross-sectional area is 100 cm < 2 > or less.
　［不飽和カルボン酸の製造方法］
　本発明に係る方法により製造された触媒の存在下、不飽和アルデヒドを分子状酸素により気相接触酸化する。すなわち、本発明に係る不飽和カルボン酸の製造方法は、本発明に係る方法により触媒を製造する工程と、該触媒の存在下、不飽和アルデヒドを分子状酸素により気相接触酸化する工程とを有する。本発明に係る方法により製造された触媒を使用することで、従来よりも高い選択率で不飽和カルボン酸を製造することができる。不飽和アルデヒドとしてはアクロレイン又はメタクロレインが好ましく、メタクロレインがより好ましい。以下、不飽和アルデヒドとしてメタクロレインを用いる場合について説明する。該方法では、例えば、メタクロレインと分子状酸素を含む原料ガスを触媒に接触させることにより、メタクロレインが分子状酸素により気相接触酸化され、メタクリル酸が得られる。 [Method for producing unsaturated carboxylic acid]
The unsaturated aldehyde is gas phase catalytically oxidized with molecular oxygen in the presence of the catalyst produced by the process according to the invention. That is, the method for producing unsaturated carboxylic acid according to the present invention comprises the steps of producing a catalyst by the method according to the present invention, and performing catalytic vapor phase oxidation of unsaturated aldehyde with molecular oxygen in the presence of the catalyst Have. By using the catalyst produced by the method according to the present invention, unsaturated carboxylic acids can be produced with higher selectivity than in the prior art. As unsaturated aldehyde, acrolein or methacrolein is preferable, and methacrolein is more preferable. Hereinafter, the case where methacrolein is used as the unsaturated aldehyde will be described. In the method, for example, by contacting a catalyst with a raw material gas containing methacrolein and molecular oxygen, methacrolein is gas phase catalytically oxidized by molecular oxygen to obtain methacrylic acid.
　前記原料ガス中の原料化合物濃度には制限はなく、任意の濃度に設定できるが、１～２０容量％が好ましく、下限は３容量％以上、上限は１０容量％以下がより好ましい。原料ガス中の分子状酸素濃度は、原料化合物１ｍｏｌに対して０．５～４．０ｍｏｌが好ましく、特に下限は１．０ｍｏｌ以上、上限は３．０ｍｏｌ以下がより好ましい。また、原料ガスには、希釈のために窒素、炭酸ガス等の不活性ガスを加えてもよく、水蒸気を加えてもよい。反応圧力は、大気圧から数百ｋＰａ（Ｇ）までの範囲内で設定されることができる。反応温度は、目的生成物の収率の観点から、２３０～４５０℃が好ましく、特に下限は２５０℃以上、上限は４００℃以下がより好ましい。 The concentration of the raw material compound in the raw material gas is not limited and can be set to any concentration, but it is preferably 1 to 20% by volume, the lower limit is 3% by volume or more, and the upper limit is 10% by volume or less. The molecular oxygen concentration in the raw material gas is preferably 0.5 to 4.0 mol with respect to 1 mol of the raw material compound, and the lower limit is particularly preferably 1.0 mol or more and the upper limit is more preferably 3.0 mol or less. In addition, an inert gas such as nitrogen or carbon dioxide gas may be added to the source gas for dilution, or steam may be added. The reaction pressure can be set in the range from atmospheric pressure to several hundreds kPa (G). The reaction temperature is preferably 230 to 450 ° C. from the viewpoint of the yield of the desired product, and the lower limit is particularly preferably 250 ° C. or more and the upper limit is more preferably 400 ° C. or less.
　［不飽和アルデヒド及び不飽和カルボン酸の製造方法］
　本発明に係る方法により製造された触媒の存在下、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコールおよびメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化する。すなわち、本発明に係る不飽和アルデヒド及び不飽和カルボン酸の製造方法は、本発明に係る方法により触媒を製造する工程と、該触媒の存在下、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化する工程とを有する。本発明に係る方法により製造された触媒を使用することで、従来よりも高い選択率で不飽和アルデヒド及び不飽和カルボン酸を製造することができる。該不飽和アルデヒドはアクロレイン又はメタクロレインであることが好ましく、メタクロレインであることがより好ましい。該不飽和カルボン酸はアクリル酸又はメタクリル酸であることが好ましく、メタクリル酸であることがより好ましい。気相接触酸化反応の条件は、前記不飽和カルボン酸の製造方法と同様とすることができる。 [Method for producing unsaturated aldehyde and unsaturated carboxylic acid]
At least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst produced by the process according to the invention, by means of molecular oxygen Gas phase catalytic oxidation. That is, the method for producing unsaturated aldehyde and unsaturated carboxylic acid according to the present invention comprises the steps of producing a catalyst by the method according to the present invention, propylene, isobutylene, primary butyl alcohol, Vapor phase catalytic oxidation of at least one member selected from the group consisting of secondary butyl alcohol and methyl tertiary butyl ether with molecular oxygen. By using the catalyst produced by the method according to the present invention, unsaturated aldehydes and unsaturated carboxylic acids can be produced with higher selectivity than conventional. The unsaturated aldehyde is preferably acrolein or methacrolein, and more preferably methacrolein. The unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid, and more preferably methacrylic acid. The conditions of the gas phase catalytic oxidation reaction can be the same as the method for producing the unsaturated carboxylic acid.
　［不飽和カルボン酸エステルの製造方法］
　本発明に係る不飽和カルボン酸エステルの製造方法は、本発明に係る方法により得られる不飽和カルボン酸をエステル化する。該方法によれば、不飽和アルデヒドの気相接触酸化、またはプロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種の気相接触酸化により得られる不飽和カルボン酸を用いて、不飽和カルボン酸エステルを得ることができる。不飽和カルボン酸と反応させるアルコールとしては、メタノール、エタノール、イソプロパノール、ｎ－ブタノール、イソブタノール等が挙げられる。得られる不飽和カルボン酸エステルとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル等が挙げられる。反応は、スルホン酸型カチオン交換樹脂等の酸性触媒の存在下で行うことができる。反応温度は５０～２００℃が好ましい。 [Method for producing unsaturated carboxylic acid ester]
The method for producing an unsaturated carboxylic acid ester according to the present invention esterifies the unsaturated carboxylic acid obtained by the method according to the present invention. According to the method, gas phase catalytic oxidation of unsaturated aldehydes or at least one gas phase selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether Unsaturated carboxylic acid esters can be obtained using unsaturated carboxylic acids obtained by catalytic oxidation. Examples of the alcohol to be reacted with the unsaturated carboxylic acid include methanol, ethanol, isopropanol, n-butanol, isobutanol and the like. Examples of the unsaturated carboxylic acid ester to be obtained include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. The reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50 to 200 ° C.
　以下、実施例及び比較例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例及び比較例中の「部」は質量部を意味する。触媒組成のモル比は、触媒をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって算出した。 Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. "Part" in an Example and a comparative example means a mass part. The molar ratio of the catalyst composition was calculated by analyzing the component in which the catalyst was dissolved in aqueous ammonia by ICP emission analysis.
　メタクリル酸の製造における原料ガス及び生成物の分析は、ガスクロマトグラフィーを用いて行った。ガスクロマトグラフィーの結果から、メタクロレインの反応率及びメタクリル酸の選択率を下記式にて求めた。 The analysis of the source gases and products in the production of methacrylic acid was carried out using gas chromatography. From the results of gas chromatography, the conversion of methacrolein and the selectivity of methacrylic acid were determined by the following formula.
　　メタクロレインの反応率（％）＝（Ｒ／Ｆ）×１００
　　メタクリル酸の選択率（％）　＝（Ｐ／Ｒ）×１００
　式中、Ｆは単位時間に供給したメタクロレインのｍｏｌ数、Ｒは単位時間に反応したメタクロレインのｍｏｌ数、Ｐは単位時間に生成したメタクリル酸のｍｏｌ数である。 Methacrolein reaction rate (%) = (R / F) × 100
Methacrylic acid selectivity (%) = (P / R) × 100
In the formula, F is the number of moles of methacrolein supplied per unit time, R is the number of moles of methacrolein reacted in unit time, and P is the number of moles of methacrylic acid generated per unit time.
　なお、メタクリル酸の選択率はメタクロレインの反応率によって変化する。そのため、各触媒を用いた気相接触酸化反応におけるメタクリル酸の選択率は、メタクロレインの反応率を同じ値に揃えて比較することが好ましい。そのため、以下の実施例及び比較例においては、反応ガス流量一定の下、反応に用いる触媒の量を適宜調整することにより接触時間を変更し、メタクロレインの反応率を４０％程度に揃えた結果を示す。 The selectivity of methacrylic acid changes with the conversion of methacrolein. Therefore, as for the selectivity of methacrylic acid in the gas phase catalytic oxidation reaction using each catalyst, it is preferable to compare the reaction rates of methacrolein with the same value. Therefore, in the following examples and comparative examples, the contact time is changed by appropriately adjusting the amount of the catalyst used for the reaction under a constant reaction gas flow rate, and the reaction rate of methacrolein is equalized to about 40%. Indicates
　［実施例１］
　（１）原料液調製工程
　純水４００部に三酸化モリブテン１００部、メタバナジン酸アンモニウム４．０６部、８５質量％リン酸６．６７部、三酸化二アンチモン０．８４部及び硝酸銅２．８０部を加えた。これを撹拌しながらスラリーとし、得られたスラリーを９０℃で３時間加熱した。これを９０℃に保持した状態で、炭酸セシウム１１．３部を純水４０．３部に溶解した溶液を添加し、３０分保持した。次いで、炭酸アンモニウム８．３４部を純水３７．５部に溶解した溶液を添加した。次いで、９０℃のまま３０分保持することで原料液を得た。 Example 1
(1) Raw material liquid preparation process 100 parts of molybdenum trioxide, 4.06 parts of ammonium metavanadate, 6.67 parts of 85 mass% phosphoric acid, 0.84 parts of antimony trioxide and copper nitrate 2.80 to pure water 400 parts I added a department. This was made into a slurry while stirring, and the obtained slurry was heated at 90 ° C. for 3 hours. While maintaining this at 90 ° C., a solution of 11.3 parts of cesium carbonate dissolved in 40.3 parts of pure water was added and held for 30 minutes. Then, a solution of 8.34 parts of ammonium carbonate dissolved in 37.5 parts of pure water was added. Subsequently, the raw material liquid was obtained by hold | maintaining 90 degreeC for 30 minutes.
　（２）乾燥工程
　得られた原料液を１０１℃で加熱し、撹拌しながら蒸発、乾固した。その後、得られた固形物を９０℃で１６時間乾燥し、触媒前駆体を得た。得られた触媒前駆体はケギン型ヘテロポリ酸構造を含んでいた。また、該触媒前駆体の酸素を除く組成はＭｏ１２Ｖ０．６Ｐ１．０Ｓｂ０．１Ｃｕ０．２Ｃｓ１．２（ＮＨ４）３．０であった。 (2) Drying Step The obtained raw material solution was heated at 101 ° C. and evaporated to dryness with stirring. Thereafter, the obtained solid was dried at 90 ° C. for 16 hours to obtain a catalyst precursor. The resulting catalyst precursor contained a Keggin-type heteropolyacid structure. Further, the composition except oxygen of the catalyst precursor was Mo 12 V 0.6 P 1.0 Sb 0.1 Cu 0.2 Cs 1.2 (NH 4) 3.0.
　（３）成形工程
　得られた触媒前駆体を打錠成形機により、外径５ｍｍ、内径２ｍｍ、長さ５ｍｍのリング状に成形した。 (3) Forming Step The obtained catalyst precursor was formed into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm and a length of 5 mm by a tablet forming machine.
　（４）焼成工程
　得られた触媒前駆体の成形品を内径２７．５ｍｍ、長さ６ｍのステンレスパイプに充填し、空間速度３７０ｈ－１の空気流通下、３８０℃で触媒前駆体を焼成し、触媒を得た。この際、焼成ガス出口を、水を充填した排ガス成分トラップ槽に接続し、本焼成工程における圧力を６４ｋＰａ（Ｇ）とした。また焼成中の３８０℃での保持時間を１６時間とした。焼成において、温度の最高値は３８０℃であった。得られた触媒からは、触媒単位質量あたり０．００１～１．０ｍｍｏｌ／ｇの含窒素成分が検出された。 (4) Firing Step The molded product of the obtained catalyst precursor is filled in a stainless steel pipe having an inner diameter of 27.5 mm and a length of 6 m, and the catalyst precursor is calcined at 380 ° C. under an air flow of space velocity 370 h −1 . I got a catalyst. At this time, the baking gas outlet was connected to an exhaust gas component trap tank filled with water, and the pressure in the main baking step was 64 kPa (G). The holding time at 380 ° C. during firing was 16 hours. In firing, the maximum temperature was 380.degree. From the obtained catalyst, a nitrogen-containing component of 0.001 to 1.0 mmol / g was detected per unit mass of the catalyst.
　得られた触媒を反応管に充填し、反応ガスを導入し、下記反応条件で気相接触酸化によるメタクリル酸の製造を実施した。結果を表１に示す。 The obtained catalyst was charged in a reaction tube, a reaction gas was introduced, and methacrylic acid was produced by gas phase catalytic oxidation under the following reaction conditions. The results are shown in Table 1.
　（反応条件）
　　反応ガス：メタクロレイン４容量％、酸素１０容量％、水蒸気１５容量％及び窒素７１容量％の混合ガス
　　反応温度：３１０℃
　　反応圧力：１０１ｋＰａ（Ｇ）
　　接触時間：１．８秒。 (Reaction conditions)
Reaction gas: Mixed gas of 4% by volume of methacrolein, 10% by volume of oxygen, 15% by volume of steam and 71% by volume of nitrogen Reaction temperature: 310 ° C.
Reaction pressure: 101 kPa (G)
Contact time: 1.8 seconds.
　［比較例１］
　前記焼成ガス出口に接続された前記排ガス成分トラップ槽の水の量を実施例１よりも少なくすることにより、焼成工程における圧力を０ｋＰａ（Ｇ）とし、３８０℃で１２時間触媒前駆体を焼成した以外は、実施例１と同様に触媒を製造した。また、得られた触媒を用い、接触時間を１．５秒に変更した以外は、実施例１と同様の方法で反応を行った。結果を表１に示す。 Comparative Example 1
By reducing the amount of water in the exhaust gas component trap tank connected to the calcining gas outlet than in Example 1, the pressure in the calcining step was set to 0 kPa (G), and the catalyst precursor was calcined at 380 ° C. for 12 hours A catalyst was produced in the same manner as Example 1 except for the following. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.5 seconds using the obtained catalyst. The results are shown in Table 1.
　［比較例２］
　前記焼成ガス出口に接続された前記排ガス成分トラップ槽の水の量を実施例１よりも少なくすることにより、焼成工程における圧力を０ｋＰａ（Ｇ）とした以外は、実施例１と同様に触媒を製造した。また、得られた触媒を用い、接触時間を１．２秒に変更した以外は、実施例１と同様の方法で反応を行った。結果を表１に示す。 Comparative Example 2
The catalyst was prepared in the same manner as in Example 1 except that the pressure in the calcination step was set to 0 kPa (G) by reducing the amount of water in the exhaust gas component trap tank connected to the calcining gas outlet than in Example 1. Manufactured. In addition, the reaction was performed in the same manner as in Example 1 except that the contact time was changed to 1.2 seconds using the obtained catalyst. The results are shown in Table 1.
　［実施例２］
　前記焼成ガス出口に圧力制御弁を設け、焼成工程における圧力を６４ｋＰａ（Ｇ）とし、３８２℃で１６時間触媒前駆体を焼成した以外は、実施例１と同様に触媒を製造した。また、得られた触媒を用い、接触時間を１．７秒に変更した以外は、実施例１と同様の方法で反応を行った。結果を表１に示す。 Example 2
A catalyst was produced in the same manner as in Example 1 except that a pressure control valve was provided at the calcination gas outlet, the pressure in the calcination step was 64 kPa (G), and the catalyst precursor was calcined at 382 ° C. for 16 hours. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.7 seconds using the obtained catalyst. The results are shown in Table 1.
　［実施例３］
　前記焼成ガス出口に接続された前記排ガス成分トラップ槽の水の量を実施例１よりも少なくすることにより、焼成工程における圧力を５４ｋＰａ（Ｇ）とし、３８２℃で１４時間触媒前駆体を焼成した以外は、実施例１と同様に触媒を製造した。また、得られた触媒を用い、接触時間を１．７秒に変更した以外は、実施例１と同様の方法で反応を行った。結果を表１に示す。 [Example 3]
By reducing the amount of water in the exhaust gas component trap tank connected to the calcining gas outlet than in Example 1, the pressure in the calcining step was 54 kPa (G), and the catalyst precursor was calcined at 382 ° C. for 14 hours A catalyst was produced in the same manner as Example 1 except for the following. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.7 seconds using the obtained catalyst. The results are shown in Table 1.
　［実施例４］
　圧力制御弁により焼成工程における圧力を１０ｋＰａ（Ｇ）とし、３８０℃で１６時間触媒前駆体を焼成した以外は、実施例２と同様に触媒を製造した。また、得られた触媒を用い、接触時間を１．４秒に変更した以外は、実施例１と同様の方法で反応を行った。結果を表１に示す。 Example 4
A catalyst was produced in the same manner as in Example 2 except that the pressure in the firing step was changed to 10 kPa (G) by the pressure control valve and the catalyst precursor was fired at 380 ° C. for 16 hours. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.4 seconds using the obtained catalyst. The results are shown in Table 1.
　［実施例５］
　圧力制御弁により焼成工程における圧力を３０ｋＰａ（Ｇ）としたこと以外は、実施例４と同様に触媒を製造した。また、得られた触媒を用い、接触時間を１．５秒に変更した以外は、実施例１と同様の方法で反応を行った。結果を表１に示す。 [Example 5]
A catalyst was produced in the same manner as in Example 4 except that the pressure in the firing step was changed to 30 kPa (G) by the pressure control valve. In addition, the reaction was carried out in the same manner as in Example 1 except that the contact time was changed to 1.5 seconds using the obtained catalyst. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように、本発明に係る方法により触媒を製造した実施例１から５では、比較例１及び２と比較して高い選択率でメタクリル酸を製造することができた。 As shown in Table 1, in Examples 1 to 5 in which the catalyst was produced by the method according to the present invention, methacrylic acid was able to be produced with a high selectivity as compared with Comparative Examples 1 and 2.

Claims (16)

  1. 　不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びリンを含む触媒の製造方法であって、
    　含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程を含む触媒の製造方法。     A method for producing a catalyst containing at least molybdenum and phosphorus, which is used in producing unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde with molecular oxygen,
    A method for producing a catalyst, comprising the step of calcining a catalyst precursor containing a nitrogen-containing component by applying pressure above atmospheric pressure.
  2. 　プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いられる、少なくともモリブデン及びビスマスを含む触媒の製造方法であって、
    　含窒素成分を含む触媒前駆体を、大気圧を超える圧力に曝して焼成する工程を含む触媒の製造方法。     Gas-phase catalytic oxidation of at least one member selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether with molecular oxygen, and the corresponding unsaturated aldehydes And a method for producing a catalyst containing at least molybdenum and bismuth, which is used in producing unsaturated carboxylic acid,
    A method for producing a catalyst, comprising the step of calcining a catalyst precursor containing a nitrogen-containing component by applying pressure above atmospheric pressure.
  3. 　前記不飽和アルデヒドがアクロレイン又はメタクロレインである請求項１または２に記載の触媒の製造方法。 The method for producing a catalyst according to claim 1 or 2, wherein the unsaturated aldehyde is acrolein or methacrolein.
  4. 　前記触媒前駆体を焼成する際に、酸素含有ガス及び不活性ガスから選択される少なくとも１種のガス流通下で焼成する請求項１から３のいずれか１項に記載の触媒の製造方法。 The method for producing a catalyst according to any one of claims 1 to 3, wherein the catalyst precursor is calcined under at least one gas flow selected from an oxygen-containing gas and an inert gas when the catalyst precursor is calcined.
  5. 　前記圧力が１０ｋＰａ（Ｇ）以上、１００ｋＰａ（Ｇ）以下である請求項１から４のいずれか１項に記載の触媒の製造方法。 The method according to any one of claims 1 to 4, wherein the pressure is 10 kPa (G) or more and 100 kPa (G) or less.
  6. 　前記圧力が２０ｋＰａ（Ｇ）以上、８０ｋＰａ（Ｇ）以下である請求項５に記載の触媒の製造方法。 The method for producing a catalyst according to claim 5, wherein the pressure is 20 kPa (G) or more and 80 kPa (G) or less.
  7. 　前記焼成における温度の最高値が３００℃以上、７００℃以下である請求項１から６のいずれか１項に記載の触媒の製造方法。 The method for producing a catalyst according to any one of claims 1 to 6, wherein the maximum value of the temperature in the calcination is 300 ° C or more and 700 ° C or less.
  8. 　前記焼成における温度の最高値が３５０℃以上、４００℃以下である請求項７に記載の触媒の製造方法。 The method for producing a catalyst according to claim 7, wherein the maximum value of the temperature in the calcination is 350 ° C or more and 400 ° C or less.
  9. 　前記含窒素成分が、アンモニウム根及び硝酸根からなる群から選択される少なくとも１種である請求項１から８のいずれか１項に記載の触媒の製造方法。 The method for producing a catalyst according to any one of claims 1 to 8, wherein the nitrogen-containing component is at least one selected from the group consisting of ammonium roots and nitrate roots.
  10. 　前記触媒前駆体がヘテロポリ酸構造を含む請求項１に記載の触媒の製造方法。 The method for producing a catalyst according to claim 1, wherein the catalyst precursor comprises a heteropoly acid structure.
  11. 　前記ヘテロポリ酸構造がケギン型ヘテロポリ酸構造である請求項１０に記載の触媒の製造方法。 The method for producing a catalyst according to claim 10, wherein the heteropoly acid structure is a Keggin heteropoly acid structure.
  12. 　請求項１に記載の方法により製造された触媒の存在下、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する、不飽和カルボン酸の製造方法。 A method for producing an unsaturated carboxylic acid, which comprises subjecting an unsaturated aldehyde to gas phase catalytic oxidation with molecular oxygen in the presence of a catalyst produced by the method according to claim 1 to produce an unsaturated carboxylic acid.
  13. 　請求項１に記載の方法により触媒を製造し、該触媒の存在下、不飽和アルデヒドを分子状酸素により気相接触酸化して不飽和カルボン酸を製造する、不飽和カルボン酸の製造方法。 A method for producing an unsaturated carboxylic acid, comprising producing a catalyst by the method according to claim 1 and catalytically oxidizing the unsaturated aldehyde with molecular oxygen in the presence of the catalyst to produce an unsaturated carboxylic acid.
  14. 　請求項２に記載の方法により製造された触媒の存在下、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する、不飽和アルデヒド及び不飽和カルボン酸の製造方法。 A molecule of at least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst produced by the method according to claim 2 A process for producing unsaturated aldehydes and unsaturated carboxylic acids, which comprises the step of vapor phase catalytic oxidation with oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids.
  15. 　請求項２に記載の方法により触媒を製造し、該触媒の存在下、プロピレン、イソブチレン、第一級ブチルアルコール、第三級ブチルアルコール及びメチル第三級ブチルエーテルからなる群から選択される少なくとも１種を分子状酸素により気相接触酸化して、それぞれに対応する不飽和アルデヒド及び不飽和カルボン酸を製造する、不飽和アルデヒド及び不飽和カルボン酸の製造方法。 A catalyst is produced by the method according to claim 2, and at least one selected from the group consisting of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol and methyl tertiary butyl ether in the presence of the catalyst. A method for producing unsaturated aldehydes and unsaturated carboxylic acids, which comprises the step of vapor phase catalytic oxidation of H 2 O with molecular oxygen to produce corresponding unsaturated aldehydes and unsaturated carboxylic acids.
  16. 　請求項１２から１５のいずれか１項に記載の方法により製造された不飽和カルボン酸をエステル化する不飽和カルボン酸エステルの製造方法。 The manufacturing method of the unsaturated carboxylic acid ester which esterifies the unsaturated carboxylic acid manufactured by the method of any one of Claims 12-15.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2179790A1 (en) * 2008-10-21 2010-04-28 Sued-Chemie AG Bismuth-containing mixed oxide catalysts
WO2012111566A1 (en) * 2011-02-18 2012-08-23 旭化成ケミカルズ株式会社 Burning apparatus, process for producing oxide catalyst, and process for producing unsaturated acid or unsaturated nitrile
JP2014226614A (en) * 2013-05-23 2014-12-08 住友化学株式会社 Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5861833A (en) 1981-10-09 1983-04-13 Mitsubishi Rayon Co Ltd Calcining method of phosphorus and molybdenum type catalyst
JPS5867643A (en) 1981-10-15 1983-04-22 Mitsubishi Rayon Co Ltd Preparation of unsaturated acid
JPS5879545A (en) 1981-11-04 1983-05-13 Mitsubishi Rayon Co Ltd Calcining method for phosphorus-molybdenum catalyst
JPS5966349A (en) 1982-10-05 1984-04-14 Ube Ind Ltd Preparation of catalyst used in manufacture of methacrylic acid
JPS5969148A (en) 1982-10-12 1984-04-19 Ube Ind Ltd Activating method of catalyst for producing methacrylic acid
DE4442346A1 (en) * 1994-11-29 1996-05-30 Basf Ag Process for producing a catalyst consisting of a support body and a catalytically active oxide mass applied to the surface of the support body
IT1290407B1 (en) * 1996-04-29 1998-12-03 Lonza Spa PROCEDURE FOR TRANSFORMING A VANADIUM / PHOSPHORUS MIXED OXIDE-BASED CATALYST PRECURSOR INTO ACTIVE CATALYST
KR100557640B1 (en) * 2004-01-09 2006-03-10 주식회사 엘지화학 Novel Heteropoly Acid Catalyst and Preparing Method Thereof
JP5069152B2 (en) 2008-03-07 2012-11-07 三菱レイヨン株式会社 Unsaturated carboxylic acid synthesis catalyst, method for producing the same, and method for producing unsaturated carboxylic acid using the catalyst
JP5793345B2 (en) 2011-05-25 2015-10-14 住友化学株式会社 Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2179790A1 (en) * 2008-10-21 2010-04-28 Sued-Chemie AG Bismuth-containing mixed oxide catalysts
WO2012111566A1 (en) * 2011-02-18 2012-08-23 旭化成ケミカルズ株式会社 Burning apparatus, process for producing oxide catalyst, and process for producing unsaturated acid or unsaturated nitrile
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