Classifications

• • 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
• • 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
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
  • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • 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 catalyst precursor, a method of producing a catalyst using the precursor, a method of producing methacrylic acid and acrylic acid, and a method of producing methacrylic acid ester and acrylic acid ester.
• the present invention also relates to a precursor of a catalyst used for producing methacrylic acid or acrylic acid by gas phase catalytic oxidation of methacrolein or acrolein using molecular oxygen, and methacrylic acid produced using this precursor.
• the present invention also relates to a method for producing a catalyst for producing acrylic acid, a method for producing methacrylic acid or acrylic acid, and a method for producing methacrylic acid ester or acrylic acid ester.
• a catalyst for producing methacrylic acid a catalyst containing a heteropolyacid such as phosphomolybdic acid, phosphomolybdate or the like or a salt thereof as a main component is known.
• the X-ray-diffraction pattern after baking is prescribed
• patent document 2 it describes about the X-ray-diffraction peak of the raw material for catalyst manufacture, and it is a mixture containing molybdenum and A element (A shows at least 1 sort (s) of elements chosen from the group which consists of phosphorus and arsenic.).
• the precipitate obtained from the solution is subjected to a heat treatment at 250 to 350 ° C. to define an XRD diffraction peak.
• an object of the present invention is to provide a catalyst precursor for producing a catalyst having a higher yield of methacrylic acid and acrylic acid than a conventional catalyst, a method for producing a catalyst from the precursor, and methacrylic acid using the catalyst And acrylic acid, and their esters.
• the present invention is as shown in the following [1] to [8] and [1 '] to [5'].
• a precursor of a catalyst wherein the catalyst comprises methacrylic acid and acrylic acid by vapor phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen
• P a Mo b V c Cu d A e E f G g O h (I) (In formula (I), P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively.
• A is antimony, bismuth, arsenic, germanium, zirconium, tellurium
• silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron
• E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin
• G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium
• [6] The method for producing a catalyst according to [5], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
• [7] A method of producing at least one selected from the group consisting of methacrylic acid and acrylic acid, (1) a step of producing a catalyst by the method according to [5] or [6], and (2) using molecular oxygen in the presence of the catalyst, at least one selected from the group consisting of methacrolein and acrolein Vapor phase catalytic oxidation of one species to produce at least one species selected from the group consisting of methacrylic acid and acrylic acid, Method, including.
• a method for producing at least one selected from the group consisting of methacrylic acid esters and acrylic acid esters (1) a step of producing a catalyst by the method described in [5] or [6], (2) Gas phase catalytic oxidation of at least one member selected from the group consisting of methacrolein and acrolein using molecular oxygen in the presence of the catalyst is selected from the group consisting of methacrylic acid and acrylic acid Manufacturing at least one kind, and (3) esterifying at least one kind selected from the group consisting of the methacrylic acid and the acrylic acid, And how to contain it.
• a precursor of a heteropolyacid salt-containing catalyst which is used in the vapor phase catalytic oxidation of methacrolein with molecular oxygen to produce a catalyst for producing methacrylic acid, which comprises counter cathode Cu—K ⁇ radiation
• Production of methacrylic acid having, in the X-ray diffraction pattern used, peak P1 having 2 ⁇ of 26.16 ° ⁇ 0.06 ° and peak P2 having 2 ⁇ at a higher angle than peak P1 and not exceeding 26.44 ° Catalyst precursor.
• the catalyst precursor for methacrylic acid manufacture which has a composition represented by following formula (I).
• P, Mo, V, Cu and O are element symbols showing phosphorus, molybdenum, vanadium, copper and oxygen respectively.
• A is antimony, bismuth, arsenic, germanium, zirconium, tellurium
• silver E represents at least one element selected from the group consisting of selenium, silicon, tungsten and boron
• E represents iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin
• G is at least one type selected from the group consisting of potassium, rubidium, cesium and thallium
• [4 ′] The method for producing a catalyst for producing methacrylic acid according to [3 ′], wherein the heat treatment temperature in the heat treatment step is 300 to 450 ° C.
• a catalyst for producing methacrylic acid is produced by the method for producing a catalyst for producing methacrylic acid according to [5 '] [3'] or [4 '], and methacrolein is gas phase catalytically oxidized with molecular oxygen in the presence of the catalyst.
• Process for producing methacrylic acid The manufacturing method of the methacrylic acid ester which esterifies the methacrylic acid manufactured by the manufacturing method of methacrylic acid as described in [6 '] [5'].
• the catalyst precursor refers to a catalyst precursor which is composed of a raw material of a catalyst constituent element and which becomes a catalyst by being heat-treated.
• the catalyst produced from the catalyst precursor of the present invention can be used for various oxidation reactions, for example, it is used for the reaction of producing methacrylic acid from methacrolein or acrylic acid from acrolein, and particularly preferably And methacrolein can be used in the reaction for producing methacrylic acid.
• methacrylic acid is manufactured from methacrolein
• these are applicable also when manufacturing acrylic acid from acrolein.
• the catalyst precursor of the present invention contains a heteropoly acid salt, and in the X-ray diffraction pattern (X-ray diffraction line) using counter-cathode Cu-K ⁇ ray, peak P1 having 2 ⁇ of 26.16 ° ⁇ 0.06 ° and , And a peak P2 having a higher angle side than the peak P1 and not greater than 26.44 °.
• the peak at which 2 ⁇ appears around 26 ° in the X-ray diffraction pattern is derived from the (222) plane of the heteropolyacid salt cubic structure.
• the catalyst precursor having two or more peaks in this region has at least two kinds of heteropoly acid salts having different structures or heteropoly acid complex salts (hereinafter collectively referred to as "heteropoly acid (complex) salts").
• heteropoly acid (complex) salts meanss of containing.
• the heteropoly acid complex salt refers to a salt in which heteropoly acid salts having different structures are complexed in a specific ratio.
• the peaks P1 and P2 have a height of 5/100 or more with respect to a diffraction pattern near 25.5 ° derived from ⁇ -alumina shown below.
• the ratio (I1 / I2) of the height I1 of the peak P1 to the height I2 of the peak P2 is preferably 0.05 to 0.92 from the viewpoint of the yield of methacrylic acid.
• the lower limit of I1 / I2 is more preferably 0.1 or more, and the upper limit thereof is more preferably 0.9 or less.
• heteropoly acid (complex) salts having different structures also have different properties and contain heteropoly acid (complex) salts with different properties derived from said peaks P1 and P2 in the X-ray diffraction pattern It is considered that by doing this, an active site structure that is advantageous in the gas phase catalytic oxidation reaction of methacrolein is formed.
• a diffraction pattern originating in the (012) plane of ⁇ -alumina appears around 25.5 °.
• the angle of this diffraction pattern is 25.583 °
• the diffraction pattern appearing from around 26 ° to 26.5 ° is the angle of the diffraction pattern derived from the (222) plane of the heteropoly acid (composite) salt in the catalyst precursor
• 21 Diffraction patterns are also present around 3 to 21.5 °, 23.8 to 24.2 °, and 30.2 to 30.7 °.
• the catalyst precursor of the present invention preferably has a composition represented by the following formula (I) from the viewpoint of methacrylic acid yield.
• the molar ratio of an elemental composition be the value computed by analyzing the component which melt
• P, Mo, V, Cu and O are element symbols showing 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 iron, zinc, chromium, magnesium, calcium
• G is potassium
• It represents at least one element selected from the group consisting of rubidium, cesium and thallium.
• the method for producing the catalyst precursor according to the present invention is not particularly limited, but for example, a step of preparing a dry powder K1 having the peak P1 (hereinafter, also referred to as “dry powder K1 preparation step”); A step of preparing a dry powder K2 having a peak P2 (hereinafter also referred to as “dry powder K2 preparation step”), a step of mixing the dry powder K1 and the dry powder K2 to produce a catalyst precursor (hereinafter, And “a dry powder mixing step”).
• a dry powder K1 having the peak P1 is prepared.
• a catalyst raw material is first mixed, and a heteropoly acid-containing liquid is prepared by heating and stirring.
• the catalyst raw material preferably contains at least phosphorus and molybdenum, and more preferably contains vanadium, copper, the element A, and the element E.
• the raw material compounds of the respective elements are not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxo acids, oxo acid salts, etc. of the respective elements are used singly or in combination of two or more kinds. It can be used.
• a molybdenum raw material ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride and the like can be used.
• phosphates such as orthophosphoric acid, phosphorus pentoxide, or ammonium phosphate, a cesium phosphate, can be used, for example.
• vanadium raw material for example, ammonium vanadate, ammonium metavanadate, vanadium pentoxide, vanadium chloride and the like can be used.
• a copper raw material copper sulfate, copper nitrate, copper acetate, cuprous chloride, cupric chloride etc. can be used, for example. These may use only 1 type and may use 2 or more types together.
• a heteropoly acid containing at least one element of molybdenum, phosphorus, and vanadium may be used as a raw material.
• heteropoly acids include phosphomolybdic acid, phosphovanadomolybdic acid, silicomolybdic acid and the like. These may use only 1 type and may use 2 or more types together.
• Water, ethyl alcohol, acetone or the like can be used as a solvent for dissolving or suspending the raw material compound.
• a solvent for dissolving or suspending the raw material compound One of these may be used, or two or more may be used in combination. Among these, water is preferable as the solvent.
• the temperature at the time of heating and stirring is preferably 50 to 120 ° C.
• the raw material of the element G and the ammonium raw material are added to the prepared heteropolyacid-containing liquid to prepare a heteropolyacid (composite) salt-containing liquid.
• the temperature of the heteropoly acid-containing liquid at the time of addition of the raw material of G element and the ammonium raw material is preferably 70 to 120.degree.
• the element G is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and it is preferable to use cesium from the viewpoint of methacrylic acid yield.
• ammonium 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 raw material include ammonia, ammonium nitrate, ammonium hydrogencarbonate, ammonium carbonate, ammonium acetate, ammonium vanadate and the like, and it is preferable to use ammonium hydrogencarbonate and ammonium carbonate, and it is more preferable to use ammonium carbonate. These may use only 1 type and may use 2 or more types together.
• the lower limit of the value of (Mg1 + Mn1) / Mp1 is preferably 2.8 or more, and more preferably 2.9 or more.
• the upper limit is preferably 4.0 or less, more preferably 3.5 or less.
• the pH of the heteropoly acid (complex) salt-containing solution is preferably 0.1 to 4 from the viewpoint of methacrylic acid yield, and more preferably 0.1 to 2.
• the dried powder K1 is prepared by drying the resulting heteropoly acid (complex) salt-containing solution.
• the drying method in this case is not particularly limited, and for example, evaporation to dryness, spray drying, drum drying, flash drying and the like can be used, and the spray drying is most preferable. It is preferable to carry out drying until the water content of the obtained dry powder K1 becomes 2 wt% or less.
• dry powder K2 preparation process In this step, dry powder K2 having the peak P2 is prepared.
• a heteropolyacid-containing liquid is first prepared by the same method as the dry powder K1 preparing step.
• the raw material of the element G and the ammonium raw material are added to the prepared heteropolyacid-containing liquid to prepare a heteropolyacid (composite) salt-containing liquid.
• the temperature of the heteropoly acid-containing liquid at the time of addition of the raw material of G element and the ammonium raw material is preferably 70 to 120.degree.
• the G element is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, and it is preferable to use cesium from the viewpoint of methacrylic acid yield.
• the prepared heteropoly acid (complex) salt-containing liquid when the smaller one of the number of moles of phosphorus and the number of 1/12 of the number of moles of molybdenum is defined as Mp 2, the number of moles Mg of G element to be added, And when the number Mn2 of moles of ammonium contained in the added ammonium raw material satisfies the following formulas (IV) and (V), a dry powder K2 having a peak P2 can be obtained.
• the lower limit of the value of (Mg 2 + Mn 2) / Mp 2 is preferably 2.8 or more, and more preferably 2.9 or more.
• the upper limit is preferably 4.0 or less, more preferably 3.5 or less.
• the pH of the heteropoly acid (complex) salt-containing solution is preferably 0.1 to 4 from the viewpoint of methacrylic acid yield, and more preferably 0.1 to 2.
• the dried powder K2 is prepared by drying the resulting heteropoly acid (complex) salt-containing solution.
• the drying method in this case is not particularly limited, and for example, evaporation to dryness, spray drying, drum drying, flash drying and the like can be used, and the spray drying is most preferable. It is preferable to carry out drying until the water content of the obtained dry powder K2 becomes 2 wt% or less.
• the dry powder K1 and the dry powder K2 are mixed to prepare a catalyst precursor.
• the mixing method is not particularly limited, but when dry powder K1 and dry powder K2 are dried using a spray drying method, it is only necessary to dry mix dry powder K1 and dry powder K2.
• the dried powder K1 and the dried powder K2 are dried using the evaporation to dryness method or the drum drying method, it is preferable to perform mixing by crushing using a grinder.
• the value of I1 / I2 can be adjusted by the mixing ratio of the dry powders K1 and K2. It is preferable to mix such that the K1 mixing ratio calculated by the following equation is 5 to 95%.
• the lower limit of the K1 mixing ratio is more preferably 10% or more, and the upper limit is more preferably 94% or less.
• K1 mixing ratio mass of dried powder K1 / (mass of dried powder K1 + mass of dried powder K2) ⁇ 100
• the stirring speed at the time of adding the raw material of G element and an ammonium raw material to heteropoly acid containing liquid besides the method of preparing and mixing two types of dry powder as mentioned above, temperature of heteropoly acid containing liquid, G element
• the catalyst precursor having both of the peak P1 and the peak P2 may be prepared in one step by adjusting the addition rates of the raw material and the ammonium raw material.
• the catalyst precursor obtained by the dry powder mixing step may be shaped before the heat treatment step described later.
• the molding method is not particularly limited, and known dry or 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 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, a binder or the like to the catalyst precursor, but if necessary, for example, known additives such as graphite and talc, or known materials derived from organic substances and inorganic substances Binders may be added.
• catalyst precursor obtained in the dry powder mixing step or the molded product of the catalyst precursor obtained in the molding step (hereinafter collectively referred to as “catalyst precursor”) is heat-treated. It is preferable to include a step (hereinafter also referred to as “heat treatment step”).
• the heat treatment process In this step, the catalyst precursor is heat-treated to produce a catalyst.
• the heat treatment step it is possible to obtain a catalyst with less local heat generation under industrial use conditions and high activity per reactor.
• the heat treatment method and conditions are not particularly limited, and known methods and conditions can be applied.
• the heat treatment temperature is preferably 300 to 450 ° C. By setting the heat treatment temperature to 300 ° C. or higher, the ammonium in the catalyst can be removed and the catalyst activity can be made favorable. By setting the heat treatment temperature to 450 ° C. or less, the thermal decomposition of the heteropoly acid is suppressed, and the rapid catalytic activity is achieved. Can be suppressed.
• 0.5 hour or more is preferable and, as for the minimum of heat processing time, 1 hour or more is more preferable.
• the upper limit of heat processing time 40 hours or less are preferable.
• the heat treatment can be performed, for example, in the flow of at least one of air and an inert gas.
• the inert gas indicates a gas which does not reduce the catalytic activity, and examples thereof include nitrogen, carbon dioxide gas, helium, argon and the like. One of these may be used, or two or more may be mixed and used.
• the heat treatment is preferably performed in the flow of an oxygen-containing gas such as air.
• the method for producing methacrylic acid according to the present invention produces methacrylic acid by catalytic oxidation of methacrolein with molecular oxygen in the presence of a catalyst obtained from the catalyst precursor according to the present invention. According to this method, methacrylic acid can be produced in high yield. Methacrylic acid may be produced after a given period of time has elapsed since the catalyst was obtained. Also, the production site of the catalyst and the production site of methacrylic acid may be different.
• methacrylic acid can be produced by contacting a source gas containing methacrolein and molecular oxygen with the catalyst according to the present invention.
• the reaction is preferably carried out in a fixed bed.
• the catalyst may be used as it is without dilution or may be used after diluting it with an inert carrier, or it may be used by laminating a non-diluted layer and a diluted layer to form a plurality of layers.
• the concentration of methacrolein in the raw material gas is not particularly limited, but 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.
• Methacrolein may contain a small amount of impurities such as lower saturated aldehyde which do not substantially affect the reaction.
• the molar ratio of methacrolein to molecular oxygen in the raw material gas is preferably 0.5 to 4.0 mol with respect to 1.0 mol of methacrolein, and the lower limit is 1.0 mol or more and the upper limit is 3.0 mol The following are more preferable. While it is economical to use air as a molecular oxygen source, air enriched with pure oxygen can also be used if desired.
• the source gas may dilute methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide gas. Further, the source gas may contain water vapor.
• methacrylic acid can be obtained with higher selectivity.
• the concentration of water vapor in the raw material gas is preferably 0.1 to 50.0% by volume, and more preferably 1.0 to 40.0% by volume.
• the contact time between the raw material gas and the catalyst is preferably 1.5 to 15.0 seconds, the lower limit is preferably 2.0 seconds or more, and the upper limit is more preferably 5.0 seconds or less.
• the reaction pressure can be set in the range from atmospheric pressure to several hundreds kPa (G). However, (G) means being gauge pressure.
• the reaction temperature is preferably 200 ° C. to 450 ° C., the lower limit is more than 250 ° C., and the upper limit is more preferably 400 ° C. or less.
• the method for producing a methacrylic acid ester according to the present invention can be carried out by esterification of methacrylic acid obtained by the method according to the present invention.
• a methacrylic acid ester can be obtained using methacrylic acid obtained by gas phase catalytic oxidation of methacrolein.
• the alcohol to be reacted with methacrylic acid include methanol, ethanol, isopropanol, n-butanol, isobutanol and the like.
• Examples of the methacrylic acid ester to be obtained include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.
• 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.
• A represents the number of moles of methacrolein supplied
• B represents the number of moles of methacrolein reacted
• C represents the number of moles of methacrylic acid formed.
• Example 1 100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While keeping the temperature at 80 ° C., add 24.14 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then 3.84 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C.
• the resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C. for 16 hours to obtain a dry powder K2a.
• 90 parts of the dry powder K1a and 10 parts of the dry powder K2a were mixed to obtain a catalyst precursor.
• peaks shown in Table 1 were confirmed.
• the catalyst precursor was molded by a tableting machine and placed in a cylindrical quartz glass baking container with an inner diameter of 3 cm. Under air flow, the temperature was raised at 10 ° C./h, and the catalyst was prepared by heat treatment at 380 ° C. for 2 hours.
• the composition of the catalyst excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 1.97 .
• the molar ratio of the elemental composition was calculated by analyzing a component obtained by dissolving the catalyst precursor in aqueous ammonia by ICP emission analysis.
• the catalyst is charged in a reaction tube, and a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of steam and 30% by volume of steam and 55% by volume of nitrogen is used.
• the reaction was done in seconds. The results are shown in Table 1.
• Example 2 100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 30.10 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 1.45 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C., and further dried at 130 ° C.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• Example 3 100 parts of molybdenum trioxide, 6.67 parts of 85 mass% phosphoric acid, 3.36 parts of ammonium metavanadate and 2.10 parts of cupric nitrate were dissolved in 600 parts of pure water. The temperature was raised while stirring, and stirred under reflux at 100 ° C. for 5 hours. While maintaining the temperature at 80 ° C., add 21.56 parts of cesium bicarbonate dissolved in 200 parts of pure water, stir for 15 minutes, and then dissolve 4.88 parts of ammonium bicarbonate dissolved in 200 parts of pure water Was added. The resulting heteropoly acid (composite) salt-containing solution was spray-dried at an outlet temperature of 250 ° C. and further dried at 130 ° C.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• Example 4 Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 6 parts of dry powder K2a was mixed with 94 parts of dry powder K1a to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.04 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-K ⁇ ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• Example 5 Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, the dry powder K1a was mixed with 97 parts of dry powder K2a at a ratio of 3 parts to obtain a catalyst precursor. The composition except hydrogen, nitrogen, and oxygen of the obtained catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.10 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-K ⁇ ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• Example 6 Dry powder K1a and dry powder K2a were obtained in the same manner as in Example 1. Next, 90 parts of dry powder K2a was mixed with 10 parts of dry powder K1a to obtain a catalyst precursor. The composition of the obtained catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.54 . As a result of X-ray diffraction pattern measurement using an anticathode Cu-K ⁇ ray for the catalyst precursor, peaks shown in Table 1 were confirmed.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• Comparative Example 1 A dry powder K1a was obtained by the same method as in Example 1 and used as a catalyst precursor.
• the composition of the catalyst precursor excluding hydrogen, nitrogen and oxygen was P 1 Mo 12 V 0.5 Cu 0.15 Cs 2.15 .
• peaks shown in Table 1 were confirmed.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• Comparative Example 2 A dry powder K2a was obtained by the same method as in Example 1 and used as a catalyst precursor.
• the composition except hydrogen, nitrogen and oxygen of the catalyst precursor was P 1 Mo 12 V 0.5 Cu 0.15 Cs 0.36 .
• peaks shown in Table 1 were confirmed.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.
• the catalyst precursor was shaped and heat-treated in the same manner as in Example 1 to prepare a catalyst. Using this catalyst, methacrylic acid was produced in the same manner as in Example 1. The results are shown in Table 1.

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• 2018
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  • 2018-07-20 WO PCT/JP2018/027205 patent/WO2019026640A1/ja active Application Filing
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  • 2018-07-20 KR KR1020207005090A patent/KR102346234B1/ko active IP Right Grant

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