WO2018051840A1 - Methacrylic acid production catalyst and method for producing same, and method for producing methacrylic acid and methacrylic acid ester - Google Patents
Methacrylic acid production catalyst and method for producing same, and method for producing methacrylic acid and methacrylic acid ester Download PDFInfo
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- WO2018051840A1 WO2018051840A1 PCT/JP2017/031885 JP2017031885W WO2018051840A1 WO 2018051840 A1 WO2018051840 A1 WO 2018051840A1 JP 2017031885 W JP2017031885 W JP 2017031885W WO 2018051840 A1 WO2018051840 A1 WO 2018051840A1
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- 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
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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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- 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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- 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
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- 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
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- 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
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- 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 for producing methacrylic acid, a method for producing the same, and a method for producing methacrylic acid and methacrylic acid esters.
- a heteropolyacid catalyst containing molybdenum element and phosphorus element As a catalyst for producing methacrylic acid used for producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen, a heteropolyacid catalyst containing molybdenum element and phosphorus element is known.
- a heteropolyacid catalyst include a proton type heteropolyacid whose counter cation is a proton, and a heteropoly acid salt in which a part of the proton is substituted with a cation other than a proton.
- the heteropolyacid salt an alkali metal salt whose cation is an alkali metal ion and an ammonium salt whose cation is an ammonium ion are known.
- Proton heteropolyacids are water-soluble, but alkali metal salts of heteropolyacids are generally poorly soluble because of the large cation radii (Non-pat
- Patent Document 1 includes an acid salt of a Keggin type heteropolyacid containing phosphorus and molybdenum, and has a peak intensity of 3.24 to 3.26 ⁇ with respect to a peak intensity of 3.38 to 3.41 ⁇ in X-ray diffraction.
- a catalyst for the production of methacrylic acid is proposed, characterized in that the ratio is from 0.001 to 0.01.
- An object of this invention is to provide the catalyst for methacrylic acid manufacture with a high methacrylic acid yield.
- the present invention includes the following [1] to [11].
- a catalyst for producing methacrylic acid containing a heteropoly acid salt containing at least phosphorus, molybdenum and vanadium which is used when producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen, and having a temperature of 30
- the (222) plane is attributed to the cubic structure of the heteropolyacid salt.
- the ratio (I 1 / I 0 ) of the absolute value of the peak intensity I 1 of the (322) plane due to the cubic structure of the proton type heteropolyacid to the absolute value of the peak intensity I 0 of 0.01 is 0.01 or more and 0.00.
- the catalyst for methacrylic acid production which is 80 or less.
- [4] A method for producing the methacrylic acid production catalyst according to any one of [1] to [3], wherein the heteropoly acid salt-containing liquid i containing at least a phosphorus raw material and an alkali metal ion raw material, and at least a phosphorus raw material And a process for obtaining a catalyst precursor by drying using a heteropoly acid salt-containing liquid ii containing an ammonium ion raw material.
- the method includes the step of mixing the heteropolyacid salt-containing liquid i and the heteropolyacid salt-containing liquid ii to obtain a heteropolyacid salt-containing liquid iii and drying it to obtain a catalyst precursor.
- a dried product of either the heteropolyacid salt-containing liquid i or the heteropolyacid salt-containing liquid ii is mixed with another heteropolyacid salt-containing liquid to obtain a heteropolyacid salt-containing liquid iv, which is dried.
- AMi is the number of moles of alkali metal ions contained in the heteropolyacid-containing liquid i
- Pi is the number of moles of phosphorus contained in the heteropolyacid-containing liquid i
- NH 4 ii is the above-mentioned
- the number of moles of ammonium ions contained in the heteropolyacid-containing liquid ii, and Pii represents the number of moles of phosphorus contained in the heteropolyacid-containing liquid ii, respectively).
- a method for producing methacrylic acid which comprises producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst for producing methacrylic acid according to any one of [1] to [3].
- [11] A method for producing a methacrylic acid ester by producing methacrylic acid by the method described in [9] and esterifying the methacrylic acid.
- a catalyst for producing methacrylic acid having a high yield of methacrylic acid can be provided.
- the catalyst for producing methacrylic acid according to the present invention is a catalyst containing a heteropoly acid salt containing at least phosphorus, molybdenum and vanadium, which is used in producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen. .
- the Cu—K ⁇ ray of the catalyst (hereinafter also referred to as pre-treatment) after being left for 12 hours in an environment maintained at a temperature of 30 ° C. and a humidity of 90% (hereinafter also referred to as pre-treatment) is used.
- the peak intensity I of the (322) plane due to the cubic structure of the proton type heteropolyacid relative to the absolute value of the peak intensity I 0 of the (222) plane due to the cubic structure of the heteropolyacid salt the ratio of the first absolute value (I 1 / I 0) (hereinafter referred to as the peak intensity ratio (I 1 / I 0)) is 0.01 or more 0.80 or less.
- the elemental composition of the catalyst for producing methacrylic acid according to the present invention is not particularly limited as long as it contains at least phosphorus, molybdenum and vanadium, but may further contain other elements besides phosphorus, molybdenum and vanadium. Examples of other elements include copper and cesium. These may further contain one kind or two or more kinds.
- the catalyst for methacrylic acid production according to the present invention preferably has an elemental composition represented by the following formula (4) from the viewpoint of methacrylic acid yield.
- Mo, P, V, Cu and O are element symbols indicating molybdenum, phosphorus, 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 is selected from the group consisting of iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum At least one element is indicated.
- G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
- the elemental composition is a value calculated by analyzing a component in which the catalyst is dissolved in aqueous ammonia by ICP emission spectrometry.
- the peak intensity ratio (I 1 / I 0 ) satisfies the range of 0.01 or more and 0.80 or less.
- the peak intensity ratio (I 1 / I 0 ) is 0.01 or more, the adsorption site of methacrolein on the catalyst surface increases and the catalytic activity is improved.
- the peak intensity ratio (I 1 / I 0 ) is 0.80 or less, the progress of sequential oxidation of methacrylic acid can be suppressed.
- methacrylic acid when the catalyst according to the present invention is used for methacrylic acid production, methacrylic acid can be obtained in high yield. Moreover, it can be expected that a high yield of methacrylic acid can be maintained even when the catalyst is used for a long period of time by having the heteropolyacid salt and the proton type heteropolyacid in a predetermined ratio as in the present invention.
- a pretreatment is performed on the catalyst for producing methacrylic acid.
- the pretreatment is performed by leaving the catalyst at a temperature of 30 ° C. in an environment kept at 90% humidity for 12 hours.
- water molecules are hydrated in the heteropolyacid contained in the catalyst for producing methacrylic acid, and a cubic structure of the proton type heteropolyacid is formed.
- a diffraction pattern was obtained by X-ray diffraction (counter cathode Cu—K ⁇ ray) of the pretreated catalyst that had been subjected to the pretreatment, and the peak intensity I 0 of the (222) plane due to the cubic structure of the heteropolyacid salt was The ratio (I 1 / I 0 ) of the absolute value of the peak intensity I 1 of the (322) plane due to the cubic structure of the proton type heteropolyacid to the absolute value is calculated.
- the peak position does not always match when the polyatom of the heteropolyacid, the heteroatom is substituted with another element, or due to the difference in the number of equivalents of the cation of the heteropolyacid salt, but the surface position can be determined by looking at the peak pattern. Can be confirmed.
- the sum of absolute values of the respective intensities of the (222) plane peaks resulting from the cubic structure of the heteropolyacid salt is I 0 . To do. The same applies to the I 1.
- the X-ray diffraction pattern can be measured with an X-ray structure analyzer (trade name: X′Pert PRO MPD, manufactured by PANalytical).
- the peak intensity ratio (I 1 / I 0 ) is 0.01 or more and 0.80 or less, and from the viewpoint of achieving a higher methacrylic acid yield, the lower limit is preferably 0.05 or more, more preferably 0.40 or more. Preferably, 0.50 or more is more preferable.
- the upper limit is preferably 0.75 or less, more preferably 0.73 or less, and even more preferably 0.70 or less.
- the manufacturing method of the catalyst for methacrylic acid manufacture concerning this invention is not specifically limited, For example, it can manufacture by the following method.
- the method includes a step of dissolving or suspending at least a phosphorus raw material, a molybdenum raw material, and a vanadium raw material in a solvent to prepare a catalyst raw material liquid (hereinafter also referred to as a catalyst raw material liquid preparation step), and a cation raw material in the catalyst raw material liquid.
- a heteropoly acid salt-containing liquid hereinafter also referred to as a cation addition process
- drying the heteropoly acid salt-containing liquid to obtain a catalyst precursor
- a step of producing a catalyst for producing methacrylic acid by heat-treating the precursor hereinafter also referred to as a heat treatment step
- a step of molding the catalyst precursor hereinafter also referred to as a molding step
- the method for producing a methacrylic acid production catalyst according to the present invention comprises a heteropoly acid salt-containing liquid i containing at least a phosphorus raw material and an alkali metal ion raw material, and a heteropoly acid salt containing liquid ii containing at least a phosphorus raw material and an ammonium ion raw material. It is preferable to include a step of using and drying to obtain a catalyst precursor.
- Catalyst raw material preparation process In this step, at least a phosphorus raw material, a molybdenum raw material, and a vanadium raw material are dissolved or suspended in a solvent to prepare a catalyst raw material liquid.
- the raw material compound of each element is not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxoacids, oxoacid salts, and the like of each element are used alone or in combination of two or more. be able to.
- phosphoric acid, phosphorus pentoxide, ammonium phosphate, or the like can be used as the phosphorus raw material.
- molybdenum raw material molybdenum trioxide, ammonium paramolybdate, molybdic acid, molybdenum chloride, or the like can be used.
- vanadium raw material ammonium metavanadate, phosphovanadomolybdic acid, vanadium pentoxide, or the like can be used. These may use 1 type and may use 2 or more types together.
- water As the solvent for dissolving or suspending the raw material compound, water, ethyl alcohol, acetone or the like can be used. These may use 1 type and may use 2 or more types together. Among these, water is preferable as the solvent.
- one type of catalyst raw material liquid may be prepared, or two or more types may be prepared.
- two or more catalyst raw material liquids are prepared and mixed before and after the drying step described later from the viewpoint of easily controlling the peak intensity ratio (I 1 / I 0 ) within the scope of the present invention.
- a cation raw material is added to the catalyst raw material liquid obtained in the catalyst raw material liquid preparation step to obtain a heteropolyacid salt-containing liquid.
- the cation is capable of forming a heteropoly acid salt having a cubic crystal structure, and alkali metal ions such as potassium, rubidium, cesium, and ammonium ions are particularly preferable.
- alkali metal ions such as potassium, rubidium, cesium, and ammonium ions are particularly preferable.
- examples of the cation raw material include alkali metal carbonates, hydrogen carbonates, hydroxides, chloride salts, sulfates, nitrates, and the like.
- examples of the cation raw material include ammonium bicarbonate, ammonium carbonate, ammonium nitrate, and aqueous ammonia. These can use 1 type and can also use 2 or more types together.
- a cation may be contained in the catalyst raw material liquid by using an alkali metal salt or ammonium salt of each element as a raw material for each element.
- a cation raw material it is preferable to use both an alkali metal ion raw material and an ammonium ion raw material from the viewpoint of methacrylic acid yield.
- the catalyst raw material liquid When adding the cation raw material to the catalyst raw material liquid, it is preferable to add the catalyst raw material liquid with stirring.
- the temperature at which the cation raw material is added is preferably 1 to 100 ° C. Then, after adding all or part of the cation raw material, it is preferable to heat and stir at 90 to 150 ° C. for 1 to 10 hours.
- the peak intensity ratio (I 1 / I 0 ) can be adjusted to 0.01 or more and 0.80 or less.
- a cation raw material can be added to at least 1 type of catalyst raw material liquid in this process, and a heteropolyacid salt containing liquid can be prepared.
- the heteropoly acid salt-containing liquid i containing at least a phosphorus raw material and an alkali metal ion raw material and the heteropoly acid salt containing liquid ii containing at least a phosphorus raw material and an ammonium ion raw material results in the peak intensity ratio (I 1 / I 0 ) is preferable from the viewpoint of easy control. Further, it is more preferable that the heteropolyacid salt-containing liquids i and ii satisfy the following formulas (1) to (3) from the viewpoint of easy control of the peak intensity ratio (I 1 / I 0 ).
- AMi is the number of moles of alkali metal ions contained in the heteropolyacid-containing liquid i
- Pi is the number of moles of phosphorus element contained in the heteropolyacid-containing liquid i
- NH 4 ii is the above-mentioned
- the number of moles of ammonium ions contained in the heteropolyacid-containing liquid ii, and Pii respectively represent the number of moles of phosphorus element contained in the heteropolyacid-containing liquid ii.
- AMi / Pi represents the ratio of the number of moles of alkali metal ions to phosphorus element in the heteropolyacid-containing liquid i.
- the lower limit of AMi / Pi is preferably 1.7 or more, and the upper limit is preferably 2.8 or less, the lower limit is 1.9 or more, and the upper limit is more preferably 2.6 or less.
- NH 4 ii / Pii indicates the number of moles of ammonium ions to phosphorus element in the heteropoly acid-containing liquid ii.
- the lower limit of NH 4 ii / Pii is preferably 4.1 or more, and the upper limit is preferably 4.9 or less, the lower limit is 4.2 or more, and the upper limit is more preferably 4.8 or less.
- Pii / Pi represents a mixing ratio of the heteropolyacid-containing liquids i and ii.
- the lower limit of Pii / Pi is preferably 1.1 or more, and the upper limit is preferably 1.9 or less, the lower limit is 1.2 or more, and the upper limit is more preferably 1.8 or less.
- the value of Pii / Pi is increased or decreased within a range where the heteropolyacid salt-containing liquids i and ii satisfy the formulas (1) to (3).
- the heteropolyacid salt-containing liquid obtained in the cation addition step is dried to obtain a catalyst precursor.
- drying method and drying temperature are not particularly limited, and can be appropriately selected depending on the shape and size of the desired dried product.
- Examples of the drying method include a drying method using a box-type dryer, a drum drying method, an airflow drying method, an evaporation to dryness method, and a spray drying method.
- the drying temperature can be, for example, 120 to 500 ° C, the lower limit is preferably 140 ° C or higher, and the upper limit is preferably 400 ° C or lower. Drying can be performed until the heteropolyacid salt-containing liquid is dried.
- the structure of the obtained catalyst precursor can be confirmed by measuring by infrared absorption analysis.
- the catalyst precursor preferably has a Keggin type heteropolyacid structure.
- the obtained infrared absorption spectrum has characteristic peaks around 1060, 960, 870, and 780 cm ⁇ 1 .
- heteropolyacid salt-containing liquids obtained in the cation addition step when there are two or more kinds of heteropolyacid salt-containing liquids obtained in the cation addition step, these can be mixed before and after this step. That is, mixing may be performed in the state of the heteropoly acid salt-containing liquid before drying, or may be performed in the state of the catalyst precursor after drying. Moreover, after drying 1 or more types of heteropolyacid salt containing liquid, what mixed with the other heteropolyacid salt containing liquid may be dried again, and a catalyst precursor may be obtained.
- the peak intensity ratio (I 1 / I 0 ) in the resulting catalyst is within the scope of the present invention. It is preferable to control to methacrylic acid yield.
- a catalyst having a higher methacrylic acid yield can be obtained by mixing two or more kinds of catalyst precursors containing heteropolyacid salts having different atomic ratios.
- a catalyst precursor can be obtained by the drying.
- the catalyst precursor can be obtained by mixing the dried product of the heteropolyacid salt-containing liquid i and the dried product of the heteropolyacid salt-containing liquid ii.
- the heteropolyacid salt-containing liquid i and the heteropolyacid salt-containing liquid ii can be mixed to obtain a heteropolyacid salt-containing liquid iii, which can be dried to obtain a catalyst precursor.
- the dried product of either the heteropolyacid salt-containing liquid i or the heteropolyacid salt-containing liquid ii is mixed with the other heteropolyacid salt-containing liquid to obtain a heteropolyacid salt-containing liquid iv, which is dried.
- a catalyst precursor can be obtained.
- the catalyst precursor obtained by the drying step may be molded.
- the molding method is not particularly limited, and a known dry or wet molding method can be applied.
- tableting molding, press molding, extrusion molding, granulation molding and the like can be mentioned.
- the shape of the molded product is not particularly limited, and examples thereof include a columnar shape, a ring shape, and a spherical shape.
- known additives such as graphite and talc, as well as known from organic and inorganic substances, if necessary.
- a binder may be added.
- a catalyst for methacrylic acid production is produced by heat-treating the catalyst precursor obtained by the drying step or the molded product of the catalyst precursor obtained by the molding step (hereinafter collectively referred to as catalyst precursor).
- the catalyst precursor can be heat-treated under the flow of at least one of air and inert gas.
- the inert gas refers to a gas that does not decrease the catalytic activity, and examples thereof include nitrogen, carbon dioxide, helium, and argon. These may use 1 type and may mix and use 2 or more types.
- the heat treatment is preferably performed under a flow of oxygen-containing gas such as air.
- the shape of the heat treatment container is not particularly limited, it is preferable to use a tubular heat treatment container having a cross-sectional area of 2 square centimeters or more and 100 square centimeters or less.
- the heat treatment temperature is preferably 300 ° C. or higher and 700 ° C. or lower, the lower limit is 320 ° C. or higher, and the upper limit is more preferably 450 ° C. or lower.
- the structure of the resulting catalyst for producing methacrylic acid can be confirmed by measuring by infrared absorption analysis.
- the methacrylic acid production catalyst preferably has a Keggin type heteropolyacid structure.
- the obtained infrared absorption spectrum has characteristic peaks in the vicinity of 1060, 960, 870, and 780 cm ⁇ 1 .
- methacrolein is vapor-phase contact oxidized with molecular oxygen in the presence of the catalyst for methacrylic acid production according to the present invention to produce methacrylic acid. According to this method, methacrylic acid can be produced with a high yield, and a high methacrylic acid yield can be maintained for a long period of time.
- methacrylic acid can be produced by bringing a raw material gas containing methacrolein and molecular oxygen into contact with the methacrylic acid production catalyst according to the present invention. This reaction can be carried out in a fixed bed.
- the catalyst layer may be one layer or two or more layers.
- the catalyst for producing methacrylic acid may contain other additives.
- 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 preferably 3% by volume or more, and the upper limit is more preferably 10% by volume or less.
- the methacrolein may contain a small amount of impurities such as a lower saturated aldehyde that do not substantially affect the present reaction.
- the concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4.0 mol with respect to 1.0 mol of methacrolein, the lower limit is preferably 0.5 mol or more, and the upper limit is more preferably 3.0 mol or less.
- the molecular oxygen source is preferably air from the viewpoint of economy. If necessary, a gas or the like enriched with molecular oxygen by adding pure oxygen to air may be used.
- the raw material gas may be obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the source gas. By performing the reaction in the presence of water vapor, methacrylic acid can be obtained with higher selectivity.
- the concentration of water vapor in the raw material gas is preferably from 0.1 to 50.0% by volume, the lower limit is preferably 1.0% by volume or more, and the upper limit is more preferably 40.0% by volume or less.
- the contact time between the raw material gas and the catalyst for producing methacrylic acid 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 is preferably 0.1 MPa (G) to 1.0 MPa (G). Note that (G) means a gauge pressure.
- the reaction temperature is preferably 200 to 450 ° C, the lower limit is preferably 250 ° C or higher, and the upper limit is more preferably 400 ° C or lower.
- methacrylic acid produced by the method according to the present invention is esterified.
- 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 is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol.
- Examples of the resulting methacrylic acid ester 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.
- Parts in Examples and Comparative Examples means parts by mass.
- the X-ray diffraction pattern was measured with an X-ray structure analyzer (trade name: X'Pert PRO MPD, manufactured by PANalytical).
- the analysis of the raw material gas and the product was performed using gas chromatography. From the results of gas chromatography, the conversion rate of methacrolein, the selectivity of methacrylic acid to be produced, and the yield of methacrylic acid were determined by the following formula.
- Example 1 In 132 parts of pure water, 33 parts of molybdenum trioxide, 2.5 parts of ammonium metavanadate, 2.2 parts of an 85% by mass aqueous phosphoric acid solution, and 2.3 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 8.6 parts of cesium bicarbonate dissolved in 20 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. It was.
- the obtained heteropolyacid salt-containing liquid i-1 was evaporated to dryness to obtain a catalyst precursor A1.
- 54 parts of molybdenum trioxide, 4.1 parts of ammonium metavanadate, 3.6 parts of 85 mass% phosphoric acid aqueous solution, and 3.8 parts of copper (II) nitrate trihydrate were dissolved in 216 parts of pure water. .
- the mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C.
- the obtained heteropolyacid salt-containing liquid ii-1 was evaporated to dryness to obtain a catalyst precursor B1. Next, the catalyst precursors A1 and B1 were mixed to obtain a catalyst precursor.
- the obtained catalyst precursor was molded, and the molded product was put in a cylindrical quartz glass baking container having an inner diameter of 3 cm.
- a catalyst for methacrylic acid production was prepared by heating at 10 ° C./h under air flow and calcining at 380 ° C. for 5 hours. This catalyst for producing methacrylic acid had a Keggin type heteropolyacid structure.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 0.9 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry.
- the obtained catalyst for producing methacrylic acid was filled in a reaction tube, and reacted at a reaction temperature of 300 ° C. through a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen. .
- the product was collected and analyzed by gas chromatography to calculate methacrylic acid yield and the like. The results are shown in Table 1.
- Example 2 A catalyst precursor A1 was obtained in the same manner as in Example 1. On the other hand, in 240 parts of pure water, 60 parts of molybdenum trioxide, 4.6 parts of ammonium metavanadate, 4.0 parts of 85 mass% phosphoric acid aqueous solution, and 4.2 parts of copper (II) nitrate trihydrate were dissolved. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 5.3 parts of ammonium carbonate dissolved in 22.2 parts of pure water was added and stirred for 15 minutes to precipitate the ammonium salt of the heteropolyacid. I let you. The obtained heteropolyacid salt-containing liquid ii-2 was evaporated to dryness to obtain a catalyst precursor B2. Next, the catalyst precursors A1 and B2 were mixed to obtain a catalyst precursor.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- This catalyst for producing methacrylic acid had a Keggin type heteropolyacid structure.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 0.8 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry. Further, a pre-treated catalyst was prepared in the same manner as in Example 1.
- Example 3 In 200 parts of pure water, 50 parts of molybdenum trioxide, 3.8 parts of ammonium metavanadate, 3.3 parts of an 85 mass% phosphoric acid aqueous solution, and 3.5 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 13.0 parts of cesium bicarbonate dissolved in 20 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. Thus, a heteropolyacid salt-containing liquid i-2 was obtained.
- the heteropolyacid salt-containing liquids i-2 and ii-3 are mixed, and the resulting heteropolyacid salt-containing liquid iii-1 is stirred for 15 minutes while being kept at 95 ° C., and then evaporated to dryness to obtain a catalyst precursor.
- a catalyst precursor Got.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- This catalyst for producing methacrylic acid had a Keggin type heteropolyacid structure.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 1.0 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry. Further, a pre-treated catalyst was prepared in the same manner as in Example 1.
- Example 4 In 100 parts of pure water, 25 parts of molybdenum trioxide, 1.9 parts of ammonium metavanadate, 1.7 parts of an 85 mass% phosphoric acid aqueous solution, and 1.8 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 6.5 parts of cesium bicarbonate dissolved in 10 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. It was.
- the obtained heteropolyacid salt-containing liquid i-3 was evaporated to dryness to obtain a catalyst precursor A2.
- a catalyst precursor A2 On the other hand, in 300 parts of pure water, 75 parts of molybdenum trioxide, 5.6 parts of ammonium metavanadate, 5.0 parts of 85 mass% phosphoric acid aqueous solution, and 5.3 parts of copper (II) nitrate trihydrate were dissolved. .
- the mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C.
- the obtained heteropolyacid salt-containing liquid ii-4 was evaporated to dryness to obtain a catalyst precursor B3.
- the catalyst precursors A2 and B3 were mixed to obtain a catalyst precursor.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- This catalyst for producing methacrylic acid had a Keggin type heteropolyacid structure.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 0.6 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry. Further, a pre-treated catalyst was prepared in the same manner as in Example 1.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 2.3 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry.
- a pre-treated catalyst was prepared in the same manner as in Example 1.
- Table 1 The results are shown in Table 1.
- a catalyst precursor A1 was obtained in the same manner as in Example 1. On the other hand, 70 parts of molybdenum trioxide, 5.3 parts of ammonium metavanadate, 4.7 parts of 85 mass% phosphoric acid aqueous solution, and 4.9 parts of copper (II) nitrate trihydrate were dissolved in 280 parts of pure water. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 0.7 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry.
- a pre-treated catalyst was prepared in the same manner as in Example 1.
- the peak intensity ratio I 1 / I 0 was 0.81.
- Table 1 The results are shown in Table 1.
- a catalyst precursor A1 was obtained in the same manner as in Example 1. On the other hand, in 455.2 parts of pure water, 114 parts of molybdenum trioxide, 8.6 parts of ammonium metavanadate, 7.6 parts of 85% by weight aqueous phosphoric acid solution, and 8.0 parts of copper (II) nitrate trihydrate were added. Dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 Cs 0.5 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry.
- a pre-treated catalyst was prepared in the same manner as in Example 1.
- the peak intensity ratio I 1 / I 0 was 2.25.
- Table 1 The results are shown in Table 1.
- the catalyst for methacrylic acid manufacture was manufactured from the catalyst precursor by the method similar to Example 1, and methacrylic acid was manufactured using this catalyst.
- the composition of the catalyst was Mo 12 P 1.0 V 1.1 Cu 0.5 .
- the elemental composition was calculated by analyzing a component in which the catalyst was dissolved in aqueous ammonia by ICP emission spectrometry.
- a pre-treated catalyst was prepared in the same manner as in Example 1.
- I 0 since I 0 was not observed, it was set to 0. Therefore, the peak intensity ratio I 1 / I 0 could not be calculated.
- Table 1 The results are shown in Table 1.
- Example 1 it was confirmed that the peak intensity ratio (I 1 / I 0 ) was within the specified range in the present invention, and the catalyst had a high methacrylic acid yield. Among them, the highest methacrylic acid yield was obtained in Example 2 where the peak intensity ratio (I 1 / I 0 ) was 0.69, and the optimum range for the peak intensity ratio (I 1 / I 0 ) was I found out.
- the catalyst for producing methacrylic acid according to the present invention is industrially useful because it shows a high yield of methacrylic acid when it is used for producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen. .
- the proton type heteropoly acid effectively functions as an active site while maintaining the stability of the heteropoly acid salt, which is high for a long period of time. It can be expected that the yield of methacrylic acid is expressed.
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Abstract
Description
4.0≦NH4ii/Pii≦5.0 (2)
1.0≦Pii/Pi≦2.0 (3)
(式(1)から(3)中、AMiは前記ヘテロポリ酸含有液iに含まれるアルカリ金属イオンのモル数、Piは前記ヘテロポリ酸含有液iに含まれるリンのモル数、NH4iiは前記ヘテロポリ酸含有液iiに含まれるアンモニウムイオンのモル数、Piiは前記ヘテロポリ酸含有液iiに含まれるリンのモル数をそれぞれ示す。)。 1.5 ≦ AMi / Pi ≦ 3.0 (1)
4.0 ≦ NH 4 ii / Pii ≦ 5.0 (2)
1.0 ≦ Pii / Pi ≦ 2.0 (3)
(In the formulas (1) to (3), AMi is the number of moles of alkali metal ions contained in the heteropolyacid-containing liquid i, Pi is the number of moles of phosphorus contained in the heteropolyacid-containing liquid i, and NH 4 ii is the above-mentioned The number of moles of ammonium ions contained in the heteropolyacid-containing liquid ii, and Pii represents the number of moles of phosphorus contained in the heteropolyacid-containing liquid ii, respectively).
本発明に係るメタクリル酸製造用触媒は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられる、少なくともリン、モリブデン及びバナジウムを含むヘテロポリ酸塩を含む触媒である。前記触媒を、温度30℃、湿度90%に保たれた環境下に12時間放置した(以下、前処理とも示す)後の触媒(以下、前処理後触媒とも示す)のCu-Kα線を用いたX線回折パターンにおいて、ヘテロポリ酸塩の立方晶構造に起因する(222)面のピーク強度I0の絶対値に対する、プロトン型ヘテロポリ酸の立方晶構造に起因する(322)面のピーク強度I1の絶対値の比(I1/I0)(以下、ピーク強度比(I1/I0)とも示す)が、0.01以上0.80以下である。 [Catalyst for methacrylic acid production]
The catalyst for producing methacrylic acid according to the present invention is a catalyst containing a heteropoly acid salt containing at least phosphorus, molybdenum and vanadium, which is used in producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen. . The Cu—Kα ray of the catalyst (hereinafter also referred to as pre-treatment) after being left for 12 hours in an environment maintained at a temperature of 30 ° C. and a humidity of 90% (hereinafter also referred to as pre-treatment) is used. In the observed X-ray diffraction pattern, the peak intensity I of the (322) plane due to the cubic structure of the proton type heteropolyacid relative to the absolute value of the peak intensity I 0 of the (222) plane due to the cubic structure of the heteropolyacid salt the ratio of the first absolute value (I 1 / I 0) (hereinafter referred to as the peak intensity ratio (I 1 / I 0)) is 0.01 or more 0.80 or less.
式(4)中、Mo、P、V、CuおよびOはそれぞれモリブデン、リン、バナジウム、銅およ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、タングステンおよ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は鉄、亜鉛、クロム、マグネシウム、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、バリウム、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、セリウムおよ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。Gはリチウム、ナトリウム、カリウム、ルビジウム、セシウムおよ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。a、b、c、d、e、f、gおよびhは各元素の原子比率を表し、a=12の時、b=0.5~3、c=0.01~3、d=0.01~2、e=0.1~3、f=0~3、g=0.01~3であり、h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。なお、前記元素組成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り算出される値である。 Mo a P b V c Cu d A e E f G g O h (4)
In formula (4), Mo, P, V, Cu and O are element symbols indicating molybdenum, phosphorus, 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 is selected from the group consisting of iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum At least one element is indicated. G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a, b, c, d, e, f, g and h represent the atomic ratio of each element. When a = 12, b = 0.5 to 3, c = 0.01 to 3, d = 0. 01 to 2, e = 0.1 to 3, f = 0 to 3, g = 0.01 to 3, and h is an atomic ratio of oxygen necessary to satisfy the valence of each element. The elemental composition is a value calculated by analyzing a component in which the catalyst is dissolved in aqueous ammonia by ICP emission spectrometry.
本発明に係るメタクリル酸製造用触媒の製造方法は特に限定されないが、例えば以下の方法により製造することができる。該方法は、少なくともリン原料、モリブデン原料、およびバナジウム原料を溶媒に溶解または懸濁し、触媒原料液を調製する工程(以下、触媒原料液調製工程とも示す)と、前記触媒原料液にカチオン原料を添加してヘテロポリ酸塩含有液を得る工程(以下、カチオン添加工程とも示す)と、前記ヘテロポリ酸塩含有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、前記触媒前駆体を熱処理してメタクリル酸製造用触媒を製造する工程(以下、熱処理工程とも示す)と、を含む。ここで、熱処理工程の前に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。特に本発明に係るメタクリル酸製造用触媒の製造方法は、少なくともリン原料及びアルカリ金属イオン原料を含むヘテロポリ酸塩含有液iと、少なくともリン原料及びアンモニウムイオン原料を含むヘテロポリ酸塩含有液iiとを用い、乾燥により触媒前駆体を得る工程を含むことが好ましい。 [Method for producing catalyst for producing methacrylic acid]
Although the manufacturing method of the catalyst for methacrylic acid manufacture concerning this invention is not specifically limited, For example, it can manufacture by the following method. The method includes a step of dissolving or suspending at least a phosphorus raw material, a molybdenum raw material, and a vanadium raw material in a solvent to prepare a catalyst raw material liquid (hereinafter also referred to as a catalyst raw material liquid preparation step), and a cation raw material in the catalyst raw material liquid. Adding a heteropoly acid salt-containing liquid (hereinafter also referred to as a cation addition process), drying the heteropoly acid salt-containing liquid to obtain a catalyst precursor (hereinafter also referred to as a drying process), and the catalyst And a step of producing a catalyst for producing methacrylic acid by heat-treating the precursor (hereinafter also referred to as a heat treatment step). Here, a step of molding the catalyst precursor (hereinafter also referred to as a molding step) may be included before the heat treatment step. In particular, the method for producing a methacrylic acid production catalyst according to the present invention comprises a heteropoly acid salt-containing liquid i containing at least a phosphorus raw material and an alkali metal ion raw material, and a heteropoly acid salt containing liquid ii containing at least a phosphorus raw material and an ammonium ion raw material. It is preferable to include a step of using and drying to obtain a catalyst precursor.
本工程では、少なくともリン原料、モリブデン原料、およびバナジウム原料を溶媒に溶解または懸濁し、触媒原料液を調製する。 (Catalyst raw material preparation process)
In this step, at least a phosphorus raw material, a molybdenum raw material, and a vanadium raw material are dissolved or suspended in a solvent to prepare a catalyst raw material liquid.
本工程では、前記触媒原料液調製工程により得られた前記触媒原料液に、カチオン原料を添加してヘテロポリ酸塩含有液を得る。 (Cation addition process)
In this step, a cation raw material is added to the catalyst raw material liquid obtained in the catalyst raw material liquid preparation step to obtain a heteropolyacid salt-containing liquid.
4.0≦NH4ii/Pii≦5.0 (2)
1.0≦Pii/Pi≦2.0 (3)
式(1)から(3)中、AMiは前記ヘテロポリ酸含有液iに含まれるアルカリ金属イオンのモル数、Piは前記ヘテロポリ酸含有液iに含まれるリン元素のモル数、NH4iiは前記ヘテロポリ酸含有液iiに含まれるアンモニウムイオンのモル数、Piiは前記ヘテロポリ酸含有液iiに含まれるリン元素のモル数をそれぞれ示す。前記式(1)において、AMi/Piはヘテロポリ酸含有液iにおけるリン元素に対するアルカリ金属イオンのモル数の比を示す。AMi/Piの下限は1.7以上、上限は2.8以下が好ましく、下限は1.9以上、上限は2.6以下がより好ましい。前記式(2)において、NH4ii/Piiはヘテロポリ酸含有液iiにおけるリン元素に対するアンモニウムイオンのモル数の比を示す。NH4ii/Piiの下限は4.1以上、上限は4.9以下が好ましく、下限は4.2以上、上限は4.8以下がより好ましい。前記式(3)において、Pii/Piはヘテロポリ酸含有液iおよびiiの混合比を示す。Pii/Piの下限は1.1以上、上限は1.9以下が好ましく、下限は1.2以上、上限は1.8以下がより好ましい。 1.5 ≦ AMi / Pi ≦ 3.0 (1)
4.0 ≦ NH 4 ii / Pii ≦ 5.0 (2)
1.0 ≦ Pii / Pi ≦ 2.0 (3)
In formulas (1) to (3), AMi is the number of moles of alkali metal ions contained in the heteropolyacid-containing liquid i, Pi is the number of moles of phosphorus element contained in the heteropolyacid-containing liquid i, and NH 4 ii is the above-mentioned The number of moles of ammonium ions contained in the heteropolyacid-containing liquid ii, and Pii respectively represent the number of moles of phosphorus element contained in the heteropolyacid-containing liquid ii. In the formula (1), AMi / Pi represents the ratio of the number of moles of alkali metal ions to phosphorus element in the heteropolyacid-containing liquid i. The lower limit of AMi / Pi is preferably 1.7 or more, and the upper limit is preferably 2.8 or less, the lower limit is 1.9 or more, and the upper limit is more preferably 2.6 or less. In the formula (2), NH 4 ii / Pii indicates the number of moles of ammonium ions to phosphorus element in the heteropoly acid-containing liquid ii. The lower limit of NH 4 ii / Pii is preferably 4.1 or more, and the upper limit is preferably 4.9 or less, the lower limit is 4.2 or more, and the upper limit is more preferably 4.8 or less. In the formula (3), Pii / Pi represents a mixing ratio of the heteropolyacid-containing liquids i and ii. The lower limit of Pii / Pi is preferably 1.1 or more, and the upper limit is preferably 1.9 or less, the lower limit is 1.2 or more, and the upper limit is more preferably 1.8 or less.
本工程では、前記カチオン添加工程により得られる前記ヘテロポリ酸塩含有液を乾燥して、触媒前駆体を得る。 (Drying process)
In this step, the heteropolyacid salt-containing liquid obtained in the cation addition step is dried to obtain a catalyst precursor.
後述する熱処理工程の前に、前記乾燥工程により得られた触媒前駆体を成形してもよい。成形方法は特に制限されず、公知の乾式又は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。成形品の形状は特に限定されず、例えば、円柱状、リング状、球状等が挙げられる。また、成形時には触媒前駆体に担体やバインダー等を添加せず、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、タルク等の公知の添加剤や有機物、無機物由来の公知のバインダーを添加してもよい。 (Molding process)
Before the heat treatment step described later, the catalyst precursor obtained by the drying step may be molded. The molding method is not particularly limited, and a known dry or wet molding method can be applied. For example, tableting molding, press molding, extrusion molding, granulation molding and the like can be mentioned. The shape of the molded product is not particularly limited, and examples thereof include a columnar shape, a ring shape, and a spherical shape. In addition, it is preferable to form only the catalyst precursor without adding a carrier or a binder to the catalyst precursor at the time of molding. However, known additives such as graphite and talc, as well as known from organic and inorganic substances, if necessary. A binder may be added.
本工程では、前記乾燥工程により得られる触媒前駆体、または前記成形工程により得られる触媒前駆体の成形品(以下、まとめて触媒前駆体と示す)を熱処理してメタクリル酸製造用触媒を製造する。例えば、前記触媒前駆体を空気及び不活性ガスの少なくとも一方の流通下で熱処理することができる。ここで、不活性ガスとは触媒活性を低下させない気体のことを示し、例えば窒素、炭酸ガス、ヘリウム、アルゴン等が挙げられる。これらは一種を用いてもよく、二種以上を混合して使用してもよい。熱処理は、空気等の酸素含有ガス流通下で行われることが好ましい。 (Heat treatment process)
In this step, a catalyst for methacrylic acid production is produced by heat-treating the catalyst precursor obtained by the drying step or the molded product of the catalyst precursor obtained by the molding step (hereinafter collectively referred to as catalyst precursor). . For example, the catalyst precursor can be heat-treated under the flow of at least one of air and inert gas. Here, the inert gas refers to a gas that does not decrease the catalytic activity, and examples thereof include nitrogen, carbon dioxide, helium, and argon. These may use 1 type and may mix and use 2 or more types. The heat treatment is preferably performed under a flow of oxygen-containing gas such as air.
本発明に係るメタクリル酸の製造方法は、本発明に係るメタクリル酸製造用触媒の存在下でメタクロレインを分子状酸素により気相接触酸化して、メタクリル酸を製造する。該方法によれば、高い収率でメタクリル酸を製造することができ、また高いメタクリル酸収率を長期間維持することができる。 [Method for producing methacrylic acid]
In the method for producing methacrylic acid according to the present invention, methacrolein is vapor-phase contact oxidized with molecular oxygen in the presence of the catalyst for methacrylic acid production according to the present invention to produce methacrylic acid. According to this method, methacrylic acid can be produced with a high yield, and a high methacrylic acid yield can be maintained for a long period of time.
本発明に係るメタクリル酸エステルの製造方法は、本発明に係る方法により製造されたメタクリル酸をエステル化する。該方法によれば、メタクロレインの気相接触酸化により得られるメタクリル酸を用いて、メタクリル酸エステルを得ることができる。メタクリル酸と反応させるアルコールとしては特に限定されず、例えばメタノール、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。得られるメタクリル酸エステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタ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 methacrylate ester]
In the method for producing a methacrylic acid ester according to the present invention, methacrylic acid produced by the method according to the present invention is esterified. According to this method, 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 is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the resulting methacrylic acid ester 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.
メタクリル酸選択率(%)=(γ/β)×100
メタクリル酸収率(%)=(γ/α)×100
式中、αは供給したメタクロレイン中の炭素数、βは反応したメタクロレイン中の炭素数、γは生成したメタクリル酸中の炭素数を示す。 Conversion rate of methacrolein (%) = (β / α) × 100
Methacrylic acid selectivity (%) = (γ / β) × 100
Methacrylic acid yield (%) = (γ / α) × 100
In the formula, α represents the number of carbons in the supplied methacrolein, β represents the number of carbons in the reacted methacrolein, and γ represents the number of carbons in the produced methacrylic acid.
純水132部に、三酸化モリブデン33部、メタバナジン酸アンモニウム2.5部、85質量%リン酸水溶液2.2部、および硝酸銅(II)3水和物2.3部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水20部に溶解した重炭酸セシウム8.6部を添加して15分攪拌し、ヘテロポリ酸のセシウム塩を析出させた。得られたヘテロポリ酸塩含有液i-1を蒸発乾固することで、触媒前駆体A1を得た。一方、純水216部に、三酸化モリブデン54部、メタバナジン酸アンモニウム4.1部、85質量%リン酸水溶液3.6部、および硝酸銅(II)3水和物3.8部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水20部に溶解した炭酸アンモニウム4.8部を添加して15分攪拌し、ヘテロポリ酸のアンモニウム塩を析出させた。得られたヘテロポリ酸塩含有液ii-1を蒸発乾固することで、触媒前駆体B1を得た。次に、前記触媒前駆体A1およびB1を混合し、触媒前駆体を得た。 [Example 1]
In 132 parts of pure water, 33 parts of molybdenum trioxide, 2.5 parts of ammonium metavanadate, 2.2 parts of an 85% by mass aqueous phosphoric acid solution, and 2.3 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 8.6 parts of cesium bicarbonate dissolved in 20 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. It was. The obtained heteropolyacid salt-containing liquid i-1 was evaporated to dryness to obtain a catalyst precursor A1. On the other hand, 54 parts of molybdenum trioxide, 4.1 parts of ammonium metavanadate, 3.6 parts of 85 mass% phosphoric acid aqueous solution, and 3.8 parts of copper (II) nitrate trihydrate were dissolved in 216 parts of pure water. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 4.8 parts of ammonium carbonate dissolved in 20 parts of pure water was added and stirred for 15 minutes to precipitate the ammonium salt of the heteropolyacid. . The obtained heteropolyacid salt-containing liquid ii-1 was evaporated to dryness to obtain a catalyst precursor B1. Next, the catalyst precursors A1 and B1 were mixed to obtain a catalyst precursor.
実施例1と同様の方法により触媒前駆体A1を得た。一方、純水240部に、三酸化モリブデン60部、メタバナジン酸アンモニウム4.6部、85質量%リン酸水溶液4.0部、および硝酸銅(II)3水和物4.2部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水22.2部に溶解した炭酸アンモニウム5.3部を添加して15分攪拌し、ヘテロポリ酸のアンモニウム塩を析出させた。得られたヘテロポリ酸塩含有液ii-2を蒸発乾固することで、触媒前駆体B2を得た。次に、前記触媒前駆体A1およびB2を混合し、触媒前駆体を得た。 [Example 2]
A catalyst precursor A1 was obtained in the same manner as in Example 1. On the other hand, in 240 parts of pure water, 60 parts of molybdenum trioxide, 4.6 parts of ammonium metavanadate, 4.0 parts of 85 mass% phosphoric acid aqueous solution, and 4.2 parts of copper (II) nitrate trihydrate were dissolved. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 5.3 parts of ammonium carbonate dissolved in 22.2 parts of pure water was added and stirred for 15 minutes to precipitate the ammonium salt of the heteropolyacid. I let you. The obtained heteropolyacid salt-containing liquid ii-2 was evaporated to dryness to obtain a catalyst precursor B2. Next, the catalyst precursors A1 and B2 were mixed to obtain a catalyst precursor.
純水200部に、三酸化モリブデン50部、メタバナジン酸アンモニウム3.8部、85質量%リン酸水溶液3.3部、および硝酸銅(II)3水和物3.5部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水20部に溶解した重炭酸セシウム13.0部を添加して15分攪拌し、ヘテロポリ酸のセシウム塩を析出させ、ヘテロポリ酸塩含有液i-2を得た。一方、純水280部に、三酸化モリブデン70部、メタバナジン酸アンモニウム5.3部、85質量%リン酸水溶液4.7部、および硝酸銅(II)3水和物4.9部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水20部に溶解した炭酸アンモニウム6.8部を添加して15分攪拌し、ヘテロポリ酸のアンモニウム塩を析出させ、ヘテロポリ酸塩含有液ii-3を得た。前記ヘテロポリ酸塩含有液i-2およびii-3を混合し、得られたヘテロポリ酸塩含有液iii-1を95℃に保ちつつ15分撹拌した後、蒸発乾固することで、触媒前駆体を得た。 [Example 3]
In 200 parts of pure water, 50 parts of molybdenum trioxide, 3.8 parts of ammonium metavanadate, 3.3 parts of an 85 mass% phosphoric acid aqueous solution, and 3.5 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 13.0 parts of cesium bicarbonate dissolved in 20 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. Thus, a heteropolyacid salt-containing liquid i-2 was obtained. On the other hand, 70 parts of molybdenum trioxide, 5.3 parts of ammonium metavanadate, 4.7 parts of 85 mass% phosphoric acid aqueous solution, and 4.9 parts of copper (II) nitrate trihydrate were dissolved in 280 parts of pure water. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 6.8 parts of ammonium carbonate dissolved in 20 parts of pure water was added and stirred for 15 minutes to precipitate the ammonium salt of the heteropolyacid, A heteropolyacid salt-containing liquid ii-3 was obtained. The heteropolyacid salt-containing liquids i-2 and ii-3 are mixed, and the resulting heteropolyacid salt-containing liquid iii-1 is stirred for 15 minutes while being kept at 95 ° C., and then evaporated to dryness to obtain a catalyst precursor. Got.
純水100部に、三酸化モリブデン25部、メタバナジン酸アンモニウム1.9部、85質量%リン酸水溶液1.7部、および硝酸銅(II)3水和物1.8部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水10部に溶解した重炭酸セシウム6.5部を添加して15分攪拌し、ヘテロポリ酸のセシウム塩を析出させた。得られたヘテロポリ酸塩含有液i-3を蒸発乾固することで、触媒前駆体A2を得た。一方、純水300部に、三酸化モリブデン75部、メタバナジン酸アンモニウム5.6部、85質量%リン酸水溶液5.0部、および硝酸銅(II)3水和物5.3部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。得られたヘテロポリ酸塩含有液ii-4を蒸発乾固することで、触媒前駆体B3を得た。次に、前記触媒前駆体A2およびB3を混合し、触媒前駆体を得た。 [Example 4]
In 100 parts of pure water, 25 parts of molybdenum trioxide, 1.9 parts of ammonium metavanadate, 1.7 parts of an 85 mass% phosphoric acid aqueous solution, and 1.8 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 6.5 parts of cesium bicarbonate dissolved in 10 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. It was. The obtained heteropolyacid salt-containing liquid i-3 was evaporated to dryness to obtain a catalyst precursor A2. On the other hand, in 300 parts of pure water, 75 parts of molybdenum trioxide, 5.6 parts of ammonium metavanadate, 5.0 parts of 85 mass% phosphoric acid aqueous solution, and 5.3 parts of copper (II) nitrate trihydrate were dissolved. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. The obtained heteropolyacid salt-containing liquid ii-4 was evaporated to dryness to obtain a catalyst precursor B3. Next, the catalyst precursors A2 and B3 were mixed to obtain a catalyst precursor.
純水400部に、三酸化モリブデン100部、メタバナジン酸アンモニウム7.5部、85質量%リン酸水溶液6.7部、および硝酸銅(II)3水和物7.0部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水40部に溶解した重炭酸セシウム26.0部を添加して15分攪拌し、ヘテロポリ酸のセシウム塩を析出させた。得られたヘテロポリ酸塩含有液i-4を蒸発乾固することで、触媒前駆体を得た。 [Comparative Example 1]
In 400 parts of pure water, 100 parts of molybdenum trioxide, 7.5 parts of ammonium metavanadate, 6.7 parts of 85 mass% phosphoric acid aqueous solution, and 7.0 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 26.0 parts of cesium bicarbonate dissolved in 40 parts of pure water was added and stirred for 15 minutes to precipitate the cesium salt of the heteropolyacid. It was. The obtained heteropolyacid salt-containing liquid i-4 was evaporated to dryness to obtain a catalyst precursor.
実施例1と同様の方法により触媒前駆体A1を得た。一方、純水280部に、三酸化モリブデン70部、メタバナジン酸アンモニウム5.3部、85質量%リン酸水溶液4.7部、および硝酸銅(II)3水和物4.9部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水25.9部に溶解した炭酸アンモニウム6.2部を添加して15分攪拌し、ヘテロポリ酸のアンモニウム塩を析出させた。得られたヘテロポリ酸塩含有液ii-5を蒸発乾固することで、触媒前駆体B4を得た。次に、前記触媒前駆体A1およびB4を混合し、触媒前駆体を得た。 [Comparative Example 2]
A catalyst precursor A1 was obtained in the same manner as in Example 1. On the other hand, 70 parts of molybdenum trioxide, 5.3 parts of ammonium metavanadate, 4.7 parts of 85 mass% phosphoric acid aqueous solution, and 4.9 parts of copper (II) nitrate trihydrate were dissolved in 280 parts of pure water. . The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 6.2 parts of ammonium carbonate dissolved in 25.9 parts of pure water was added and stirred for 15 minutes to precipitate the ammonium salt of the heteropolyacid. I let you. The obtained heteropolyacid salt-containing liquid ii-5 was evaporated to dryness to obtain a catalyst precursor B4. Next, the catalyst precursors A1 and B4 were mixed to obtain a catalyst precursor.
実施例1と同様の方法により触媒前駆体A1を得た。一方、純水455.2部に、三酸化モリブデン114部、メタバナジン酸アンモニウム8.6部、85質量%リン酸水溶液7.6部、および硝酸銅(II)3水和物8.0部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。液温を95℃に保持し、回転翼攪拌機を用いて攪拌しつつ、純水42.1部に溶解した炭酸アンモニウム10.1部を添加して15分攪拌し、ヘテロポリ酸のアンモニウム塩を析出させた。得られたヘテロポリ酸塩含有液ii-6を蒸発乾固することで、触媒前駆体B5を得た。次に、前記触媒前駆体A1およびB5を混合し、触媒前駆体を得た。 [Comparative Example 3]
A catalyst precursor A1 was obtained in the same manner as in Example 1. On the other hand, in 455.2 parts of pure water, 114 parts of molybdenum trioxide, 8.6 parts of ammonium metavanadate, 7.6 parts of 85% by weight aqueous phosphoric acid solution, and 8.0 parts of copper (II) nitrate trihydrate were added. Dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. While maintaining the liquid temperature at 95 ° C. and stirring with a rotary blade stirrer, 10.1 parts of ammonium carbonate dissolved in 42.1 parts of pure water was added and stirred for 15 minutes to precipitate the ammonium salt of the heteropolyacid. I let you. The obtained heteropolyacid salt-containing liquid ii-6 was evaporated to dryness to obtain a catalyst precursor B5. Next, the catalyst precursors A1 and B5 were mixed to obtain a catalyst precursor.
純水400部に、三酸化モリブデン100部、メタバナジン酸アンモニウム7.5部、85質量%リン酸水溶液6.7部、および硝酸銅(II)3水和物7.0部を溶解した。これを攪拌しながら95℃に昇温し、液温を95℃に保ちつつ2時間攪拌した。得られたヘテロポリ酸塩含有液ii-7を蒸発乾固することで、触媒前駆体を得た。 [Comparative Example 4]
In 400 parts of pure water, 100 parts of molybdenum trioxide, 7.5 parts of ammonium metavanadate, 6.7 parts of 85 mass% phosphoric acid aqueous solution, and 7.0 parts of copper (II) nitrate trihydrate were dissolved. The mixture was heated to 95 ° C. while stirring, and stirred for 2 hours while maintaining the liquid temperature at 95 ° C. The obtained heteropolyacid salt-containing liquid ii-7 was evaporated to dryness to obtain a catalyst precursor.
The catalyst for producing methacrylic acid according to the present invention is industrially useful because it shows a high yield of methacrylic acid when it is used for producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen. . In addition, since the crystal structure of the heteropoly acid salt and the proton type heteropoly acid is used as described above, the proton type heteropoly acid effectively functions as an active site while maintaining the stability of the heteropoly acid salt, which is high for a long period of time. It can be expected that the yield of methacrylic acid is expressed.
Claims (11)
- メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられる、少なくともリン、モリブデン及びバナジウムを含むヘテロポリ酸塩を含むメタクリル酸製造用触媒であって、温度30℃、湿度90%に保たれた環境下に12時間放置した前記メタクリル酸製造用触媒のCu-Kα線を用いたX線回折パターンにおいて、ヘテロポリ酸塩の立方晶構造に起因する(222)面のピーク強度I0の絶対値に対する、プロトン型ヘテロポリ酸の立方晶構造に起因する(322)面のピーク強度I1の絶対値の比(I1/I0)が、0.01以上0.80以下である、メタクリル酸製造用触媒。 A catalyst for producing methacrylic acid containing a heteropolyacid salt containing at least phosphorus, molybdenum and vanadium, which is used when producing methacrolein by vapor phase catalytic oxidation of methacrolein with molecular oxygen, temperature 30 ° C., humidity In the X-ray diffraction pattern using the Cu—Kα ray of the catalyst for producing methacrylic acid left for 12 hours in an environment maintained at 90%, the peak intensity of the (222) plane due to the cubic structure of the heteropolyacid salt with respect to the absolute value of I 0, due to the cubic structure of the proton-type heteropoly acid (322) plane ratio of the absolute value of the peak intensity I 1 of (I 1 / I 0) is 0.01 or more 0.80 or less A catalyst for producing methacrylic acid.
- I1/I0が0.05以上0.75以下である請求項1に記載のメタクリル酸製造用触媒。 The catalyst for producing methacrylic acid according to claim 1, wherein I 1 / I 0 is 0.05 or more and 0.75 or less.
- I1/I0が0.40以上0.73以下である請求項2に記載のメタクリル酸製造用触媒。 The catalyst for methacrylic acid production according to claim 2, wherein I 1 / I 0 is 0.40 or more and 0.73 or less.
- 請求項1から3のいずれか1項に記載のメタクリル酸製造用触媒を製造する方法であって、少なくともリン原料及びアルカリ金属イオン原料を含むヘテロポリ酸塩含有液iと、少なくともリン原料及びアンモニウムイオン原料を含むヘテロポリ酸塩含有液iiとを用い、乾燥により触媒前駆体を得る工程を含む、メタクリル酸製造用触媒の製造方法。 A method for producing a catalyst for methacrylic acid production according to any one of claims 1 to 3, wherein at least a phosphorus raw material and a heteropoly acid salt-containing liquid i containing an alkali metal ion raw material, and at least a phosphorus raw material and ammonium ion The manufacturing method of the catalyst for methacrylic acid manufacture including the process of obtaining the catalyst precursor by drying using the heteropolyacid salt containing liquid ii containing a raw material.
- 前記ヘテロポリ酸塩含有液iの乾燥物と前記ヘテロポリ酸塩含有液iiの乾燥物とを混合して触媒前駆体を得る工程を含む、請求項4に記載のメタクリル酸製造用触媒の製造方法。 The method for producing a catalyst for methacrylic acid production according to claim 4, comprising a step of mixing the dried product of the heteropolyacid salt-containing solution i and the dried product of the heteropolyacid salt-containing solution ii to obtain a catalyst precursor.
- 前記ヘテロポリ酸塩含有液iと前記ヘテロポリ酸塩含有液iiとを混合してヘテロポリ酸塩含有液iiiを得、これを乾燥して触媒前駆体を得る工程を含む、請求項4に記載のメタクリル酸製造用触媒の製造方法。 The methacrylic acid of Claim 4 including the process of mixing the said heteropolyacid salt containing liquid i and the said heteropolyacid salt containing liquid ii, obtaining heteropolyacid salt containing liquid iii, and drying this to obtain a catalyst precursor. A method for producing a catalyst for acid production.
- 前記ヘテロポリ酸塩含有液iと前記ヘテロポリ酸塩含有液iiのいずれかの乾燥物をもう一方のヘテロポリ酸塩含有液に混合して、ヘテロポリ酸塩含有液ivを得、これを乾燥して触媒前駆体を得る工程を含む、請求項4に記載のメタクリル酸製造用触媒の製造方法。 One of the heteropolyacid salt-containing liquid i and the heteropolyacid salt-containing liquid ii is mixed with the other heteropolyacid salt-containing liquid to obtain a heteropolyacid salt-containing liquid iv, which is dried to obtain a catalyst. The manufacturing method of the catalyst for methacrylic acid manufacture of Claim 4 including the process of obtaining a precursor.
- 前記ヘテロポリ酸塩含有液iおよびiiが下記式(1)から(3)を満たす、請求項4から7のいずれか1項に記載のメタクリル酸製造用触媒の製造方法。
1.5≦AMi/Pi≦3.0 (1)
4.0≦NH4ii/Pii≦5.0 (2)
1.0≦Pii/Pi≦2.0 (3)
(式(1)から(3)中、AMiは前記ヘテロポリ酸含有液iに含まれるアルカリ金属イオンのモル数、Piは前記ヘテロポリ酸含有液iに含まれるリンのモル数、NH4iiは前記ヘテロポリ酸含有液iiに含まれるアンモニウムイオンのモル数、Piiは前記ヘテロポリ酸含有液iiに含まれるリンのモル数をそれぞれ示す。) The method for producing a catalyst for methacrylic acid production according to any one of claims 4 to 7, wherein the heteropolyacid salt-containing liquids i and ii satisfy the following formulas (1) to (3).
1.5 ≦ AMi / Pi ≦ 3.0 (1)
4.0 ≦ NH 4 ii / Pii ≦ 5.0 (2)
1.0 ≦ Pii / Pi ≦ 2.0 (3)
(In the formulas (1) to (3), AMi is the number of moles of alkali metal ions contained in the heteropolyacid-containing liquid i, Pi is the number of moles of phosphorus contained in the heteropolyacid-containing liquid i, and NH 4 ii is the above-mentioned (The number of moles of ammonium ions contained in the heteropolyacid-containing liquid ii, Pii represents the number of moles of phosphorus contained in the heteropolyacid-containing liquid ii, respectively.) - 請求項1から3のいずれか1項に記載のメタクリル酸製造用触媒の存在下でメタクロレインを分子状酸素により気相接触酸化して、メタクリル酸を製造するメタクリル酸の製造方法。 A method for producing methacrylic acid, wherein methacrylic acid is produced by gas-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst for producing methacrylic acid according to any one of claims 1 to 3.
- 請求項9に記載のメタクリル酸の製造方法により製造されたメタクリル酸をエステル化するメタクリル酸エステルの製造方法。 A method for producing a methacrylic acid ester, wherein the methacrylic acid produced by the method for producing methacrylic acid according to claim 9 is esterified.
- 請求項9に記載の方法によりメタクリル酸を製造し、該メタクリル酸をエステル化するメタクリル酸エステルの製造方法。
The manufacturing method of the methacrylic acid ester which manufactures methacrylic acid by the method of Claim 9, and esterifies this methacrylic acid.
Priority Applications (6)
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JP2017550262A JP6414343B2 (en) | 2016-09-14 | 2017-09-05 | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid and methacrylic acid ester |
CN201780050229.8A CN109641192B (en) | 2016-09-14 | 2017-09-05 | Catalyst for methacrylic acid production, method for producing same, and method for producing methacrylic acid and methacrylic acid ester |
KR1020197010279A KR102216827B1 (en) | 2016-09-14 | 2017-09-05 | Catalyst for producing methacrylic acid and method for producing the same, and method for producing methacrylic acid and methacrylic acid ester |
MYPI2019000714A MY189907A (en) | 2016-09-14 | 2017-09-05 | Catalyst for production of methacrylic acid, method of producing the same, method of producing methacrylic acid, and method of producing methacrylic acid ester |
SG11201900754XA SG11201900754XA (en) | 2016-09-14 | 2017-09-05 | Catalyst for production of methacrylic acid, method of producing the same, method of producing methacrylic acid, and method of producing methacrylic acid ester |
SA519401149A SA519401149B1 (en) | 2016-09-14 | 2019-02-20 | Catalyst for Production of Methacrylic Acid, Method of Producing The Same, Method Of Producing Methacrylic Acid, and Method of Producing Methacrylic Acid Ester |
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KR (1) | KR102216827B1 (en) |
CN (1) | CN109641192B (en) |
MY (1) | MY189907A (en) |
SA (1) | SA519401149B1 (en) |
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Cited By (4)
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WO2019026640A1 (en) * | 2017-07-31 | 2019-02-07 | 三菱ケミカル株式会社 | Catalyst precursor, method for producing catalyst, method for producing methacrylic acid and acrylic acid, and method for producing methacrylic acid ester and acrylic acid ester |
WO2019208715A1 (en) * | 2018-04-26 | 2019-10-31 | 三菱ケミカル株式会社 | Method for producing catalyst for methacrylic-acid production and methods for producing methacrylic acid and methacryic ester |
JP2019188268A (en) * | 2018-04-18 | 2019-10-31 | 三菱ケミカル株式会社 | Manufacturing method of catalyst for manufacturing methacrylic acid, and manufacturing method of methacrylic acid |
JPWO2019187840A1 (en) * | 2018-03-30 | 2020-04-30 | 旭化成株式会社 | Catalyst, catalyst production method, acrylonitrile production method |
Families Citing this family (1)
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CN113893879B (en) * | 2021-11-04 | 2024-02-06 | 淄博市翔力致高新材料有限责任公司 | Heteropoly acid catalyst and preparation method and application thereof |
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Also Published As
Publication number | Publication date |
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SA519401149B1 (en) | 2022-11-14 |
JPWO2018051840A1 (en) | 2018-09-13 |
KR102216827B1 (en) | 2021-02-17 |
KR20190042095A (en) | 2019-04-23 |
CN109641192A (en) | 2019-04-16 |
SG11201900754XA (en) | 2019-02-27 |
MY189907A (en) | 2022-03-21 |
CN109641192B (en) | 2022-05-03 |
JP6414343B2 (en) | 2018-10-31 |
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