WO2022255368A1 - 触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 - Google Patents
触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 Download PDFInfo
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- catalyst
- producing
- carboxylic acid
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- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 11
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- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
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- MIUYJIDYPIERRC-UHFFFAOYSA-J Cl(=O)(=O)(=O)[O-].[Hf+4].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] Chemical group Cl(=O)(=O)(=O)[O-].[Hf+4].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] MIUYJIDYPIERRC-UHFFFAOYSA-J 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical group [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
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- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical group [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
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- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical group CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- MQGNWZLWQBTZJR-UHFFFAOYSA-J zirconium(4+) tetraperchlorate Chemical group [Zr+4].[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O MQGNWZLWQBTZJR-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical group [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical group [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- 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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- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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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
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
Definitions
- the present invention relates to a catalyst, a method for producing a catalyst, and a method for producing an unsaturated carboxylic acid and/or an unsaturated carboxylic acid ester.
- Methyl methacrylate is an extremely useful substance that is used as a raw material for various applications and types of polymers.
- a method for industrially producing methyl methacrylate many methods such as the acetone cyanohydrin method and the direct oxidation method using a C4 raw material have been studied, and in recent years, a production method called the alpha method has attracted attention.
- the alpha process consists of a front-stage reaction for producing methyl propionate using ethylene as a starting material, and a rear-stage reaction for producing methyl methacrylate through an aldol condensation reaction of the obtained methyl propionate.
- improvement of the selectivity of methyl methacrylate in the latter-stage reaction has become an issue, and various catalysts have been investigated.
- Patent Document 1 as a catalyst for the post-reaction in the alpha process, at least one selected from boron, magnesium, aluminum, zirconium and hafnium, containing porous high surface area silica containing 1 to 10% by mass of alkali metal Catalysts containing specific amounts of compounds of one modifier element have been proposed.
- Patent Document 2 proposes a catalyst obtained by supporting at least one modifying metal selected from zirconium or hafnium as one or two metal atoms on a carrier and performing calcination.
- Patent Document 3 at least one modifying metal selected from boron, magnesium, aluminum, zirconium, hafnium, and titanium is supported as one or two metal atoms on a carrier, and a catalytic metal element is further supported and then calcined.
- a catalyst obtained by carrying out is proposed.
- an object of the present invention is to provide a catalyst capable of producing unsaturated carboxylic acid esters and unsaturated carboxylic acids represented by methyl methacrylate with high selectivity.
- the present invention has been made in view of the above circumstances.
- the present inventors have found that the above problem can be solved by using a catalyst that gives a specific value for the peak intensity ratio obtained by Raman spectroscopic analysis, and have accomplished the present invention.
- the gist of the present invention is as follows.
- [11] The catalyst according to [10], wherein in the step (2), the temperature rise rate from when the solid content A reaches 120 ° C. to when it reaches the heat treatment temperature is 10 ° C./min or less.
- Production method. [12]: The method for producing a catalyst according to [10] or [11], wherein in the step (4-1), the solid content C is heat-treated for 15 minutes to 24 hours.
- a method for producing a catalyst having The method for producing a catalyst, wherein in the step (4-2), the temperature rise rate from when the solid content C reaches 120° C. to when it reaches the heat treatment temperature is 10° C./min or less.
- the heating rate from when the solid content C reaches 120° C. to when it reaches the heat treatment temperature is 2 to 8° C./min, [13] or [ 14].
- a step of heat-treating the solid content A to obtain a solid content B (2) a step of heat-treating the solid content A to obtain a solid content B; (3) a step of impregnating the solid content B with a solution or dispersion (liquid B) containing one or more elements Y selected from alkali metal elements to obtain a solid content C; (4-3) A step of heat-treating the solid content C at a heat treatment temperature higher than 450° C. and not higher than 700° C. to obtain a catalyst;
- a method for producing a catalyst having The method for producing a catalyst, wherein in the step (4-3), the temperature rise rate from when the solid content C reaches 120° C. to when it reaches the heat treatment temperature is 10° C./min or less.
- the heating rate from when the solid content C reaches 120° C. to when it reaches the heat treatment temperature is 2 to 8° C./min, [16] or [ 17].
- [21] The method for producing a catalyst according to any one of [10] to [20], wherein the catalyst is a catalyst for producing unsaturated carboxylic acid and/or unsaturated carboxylic acid ester.
- [22] The method for producing a catalyst according to any one of [10] to [21], wherein in the step (1), the element X contains zirconium.
- [23] The method for producing a catalyst according to any one of [10] to [22], wherein in the step (3), the element Y contains cesium.
- [25] Using a catalyst produced by the method for producing a catalyst according to any one of [10] to [23], from a carboxylic acid and/or a carboxylic acid ester and formaldehyde, an unsaturated carboxylic acid and/or an unsaturated A method for producing an unsaturated carboxylic acid and/or an unsaturated carboxylic acid ester, which produces a saturated carboxylic acid ester.
- the present invention it is possible to provide a catalyst that enables the production of the target product, particularly unsaturated carboxylic acid and/or unsaturated carboxylic acid ester, with high selectivity, and a method for producing the catalyst. Moreover, it is possible to provide a method for producing an unsaturated carboxylic acid and/or an unsaturated carboxylic acid ester with high selectivity using the catalyst.
- the peak height ratio I 2 /I 1 obtained by Raman spectroscopic analysis of the catalyst according to the embodiment of the present invention, and methacrylic acid and methacrylic acid when producing methacrylic acid and methyl methacrylate using the catalyst It is a graph which shows the relationship with the selectivity of methyl.
- One embodiment of the present invention comprises one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium, one or more elements Y selected from alkali metal elements, and silica. and, when the maximum peak height at 417 ⁇ 10 cm ⁇ 1 obtained by Raman spectroscopic analysis is I 1 and the maximum peak height at 1050 ⁇ 10 cm ⁇ 1 is I 2 , the peak height The ratio I 2 /I 1 of is 0 to 1.2.
- the shape of the catalyst is not particularly limited, and may be spherical, columnar, ring-shaped, or the like.
- the peak height ratio I 2 /I 1 is 0 to 1.2, the active sites of the side reaction are reduced in the catalyst, and the active sites of the main reaction are moderately highly dispersed. It is believed that product selectivity is improved.
- the upper limit of the value of I 2 /I 1 is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less.
- a catalyst having I 2 /I 1 within the above range can be obtained, for example, by adjusting the heat treatment temperature in the production of the catalyst. In particular, it is preferable to use a method of heat-treating the solid content A and the solid content C under the conditions described in the method for producing the catalyst described later.
- Raman spectroscopic analysis is performed using a laser Raman spectrometer at an excitation wavelength of 488 nm.
- a laser Raman spectrometer for example, a 3D microscopic laser Raman spectrometer Nanofinder (manufactured by Tokyo Instruments) or the like can be used.
- I 2 /I 1 by Raman spectroscopic analysis shall be measured by the following procedure.
- Raman spectroscopic analysis is performed at five points on the cross section of the catalyst divided into two while changing the measurement locations at regular intervals from one end to the other. Subsequently, the obtained Raman spectrum is corrected using a straight line connecting the minimum intensity at 730 ⁇ 2 cm ⁇ 1 and the minimum intensity at 867 ⁇ 2 cm ⁇ 1 as a baseline.
- the length of the perpendicular line from the peak top of the peak at 417 ⁇ 10 cm ⁇ 1 to the baseline is defined as I 1 .
- I 2 be the length of the perpendicular from the top of the peak at 1050 ⁇ 10 cm ⁇ 1 to the straight line drawn between the ends of the peak. The above operation is performed for the 5 analyzed points, and I 1 , I 2 and I 2 /I 1 are calculated as arithmetic mean values.
- the catalyst of this embodiment contains one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium.
- Element X preferably comprises boron or zirconium, more preferably zirconium.
- the element X may be 1 type, and may be 2 or more types.
- the lower limit of the content of the element X is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, relative to the mass of the entire catalyst. More preferably, it is 1% by mass or more, and particularly preferably 1.5% by mass or more.
- the upper limit is preferably 10% by mass or less, more preferably 6% by mass or less, even more preferably 5% by mass or less, and particularly preferably 4% by mass or less.
- the catalyst of the present embodiment contains one or more elements Y selected from alkali metal elements.
- Element Y preferably comprises lithium, sodium, potassium, rubidium or cesium, more preferably potassium, rubidium or cesium, even more preferably cesium.
- the element Y may be 1 type, and may be 2 or more types.
- the lower limit of the content of the element Y is preferably 3% by mass or more, more preferably 4% by mass or more, relative to the mass of the entire catalyst. % by mass or more is more preferable.
- the upper limit is preferably 25% by mass or less, more preferably 18% by mass or less, even more preferably 14% by mass or less, and particularly preferably 12% by mass or less.
- the lower limit of the molar ratio MY/MX is preferably 1.3 or more from the viewpoint of improving the selectivity of the target product. It is more preferably 1.5 or more, still more preferably 1.7 or more, and particularly preferably 1.9 or more.
- the upper limit is preferably 8 or less, more preferably 6 or less, even more preferably 5.5 or less, and particularly preferably 5 or less.
- the contents of element X and element Y can be measured by fluorescent X-ray analysis.
- the molar ratio MY/MX can be calculated from the obtained contents of the element X and the element Y. Fluorescent X-ray analysis is performed under a helium atmosphere using, for example, ZSX Primus IV (manufactured by Rigaku Corporation).
- the catalyst of the present embodiment contains silica.
- silica functions as a carrier.
- the carrier may further contain alumina, zeolite, titania, zirconia, or the like.
- the catalyst of the present embodiment may contain metal elements other than those described above.
- Other metal elements include, for example, iron.
- the upper limit of the content of other metal elements is preferably 1% by mass or less, and 0.5% by mass or less, relative to the total mass of the catalyst. is more preferable, and 0.2% by mass or less is even more preferable.
- the catalyst of the present embodiment may further contain other elements derived from the manufacturing process of the catalyst.
- the lower limit of the BET specific surface area of the catalyst is preferably 50 m 2 /g or more, more preferably 90 m 2 /g or more, and 100 m 2 /g or more. is more preferred.
- the upper limit is preferably 600 m 2 /g or less, more preferably 500 m 2 /g or less, even more preferably 350 m 2 /g or less, and particularly preferably 300 m 2 /g or less.
- the measurement of the BET specific surface area shall be calculated by the BET one-point method using a nitrogen adsorption measuring device.
- the nitrogen adsorption measuring device for example, Macsorb (manufactured by Mountech) can be used.
- a first embodiment of the method for producing a catalyst of the present invention has the following steps. (1) Impregnating a carrier containing silica with a solution or dispersion containing one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium (liquid A) to obtain a solid content Obtaining A. (2) A step of heat-treating the solid content A to obtain a solid content B; (3) A step of obtaining a solid content C by impregnating the solid content B with a solution or dispersion (liquid B) containing one or more elements Y selected from alkali metal elements.
- the solid content A is heat treated at a heat treatment temperature of 150 to 300° C. for 15 minutes to 24 hours.
- step (1) a support containing silica is impregnated with a solution or dispersion (liquid A) containing one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium. , to obtain a solid content A.
- liquid A a solution or dispersion containing one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium.
- Liquid A can be obtained by dissolving or dispersing a compound containing element X in a solvent. At this time, the compound containing the element X may be dissolved or dispersed while stirring the solvent.
- Element X preferably comprises boron or zirconium, more preferably zirconium. In addition, the element X may be 1 type, and may be 2 or more types.
- the compound containing element X is preferably an inorganic salt of element X.
- the compound containing element X is preferably an inorganic salt of element X.
- the inorganic salt is not particularly limited as long as it is an inorganic compound containing no hydrocarbons, and examples thereof include carbonates, nitrates, oxynitrates, sulfates, acetates, ammonium salts, oxides and halides. . These can be used alone or in combination. More specifically, when the element X is boron, boron oxide and the like are included. When the element X is magnesium, magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium acetate and the like can be mentioned.
- the element X is zirconium, zirconium oxynitrate, zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium perchlorate, zirconium acetate and the like can be mentioned, and zirconium oxynitrate is preferably included.
- zirconium oxynitrate is preferably included.
- hafnium, hafnium nitrate, hafnium sulfate, hafnium perchlorate, hafnium acetate and the like are included.
- the element X is titanium, it includes titanium oxide, titanium chloride, titanyl sulfate and the like.
- the lower limit of the content of element X in the resulting catalyst is preferably 0.3% by mass or more, and 0.5% by mass or more, relative to the mass of the entire catalyst. is more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more.
- the upper limit is preferably 10% by mass or less, more preferably 6% by mass or less, even more preferably 5% by mass or less, and particularly preferably 4% by mass or less.
- the content of element X can be adjusted by the amount of element X charged.
- solvent examples include water and organic solvents.
- organic solvent examples include alcohols are preferred, alcohols having 1 to 6 carbon atoms are more preferred, alcohols having 1 to 3 carbon atoms are even more preferred, alcohols having 1 to 2 carbon atoms are particularly preferred, and methanol is most preferred.
- the amount of the compound containing the element X contained in the liquid A is not particularly limited, but from the viewpoint of uniformly dispersing the element X, the lower limit is preferably 2 mmol or more, preferably 5 mmol or more, with respect to 100 mL of the solvent. is more preferable, and 10 mmol or more is even more preferable. From the viewpoint of suppressing reaggregation of the element X, the upper limit is preferably 60 mmol or less, more preferably 50 mmol or less, and even more preferably 40 mmol or less per 100 mL of the solvent.
- the carrier impregnated with liquid A contains silica, and may further contain alumina, zeolite, titania, zirconia, or the like. Silica gel is preferably used as silica.
- the lower limit of the BET specific surface area of the carrier is preferably 50 m 2 /g or more, more preferably 90 m 2 /g or more, and 100 m 2 /g or more, from the viewpoint of improving the selectivity of the target product. is more preferred.
- the upper limit is preferably 600 m 2 /g or less, more preferably 500 m 2 /g or less, even more preferably 350 m 2 /g or less, and particularly preferably 300 m 2 /g or less.
- the method for adjusting the BET specific surface area of the carrier is not particularly limited, but for example, a carrier having pores that provide the desired BET specific surface area can be used.
- the BET specific surface area tends to increase when the pore ratio of the carrier is high, and the BET specific surface area tends to decrease when the pore ratio of the carrier is low.
- the measurement of the BET specific surface area shall be calculated by the BET one-point method using a nitrogen adsorption measuring device.
- the nitrogen adsorption measuring device for example, Macsorb (manufactured by Mountech) can be used.
- the shape of the carrier is not particularly limited, and may be powder, granule, pellet, or tablet.
- the average particle size of the carrier is not particularly limited, but from the viewpoint of suppressing pressure loss in the reaction for producing the target product, the lower limit is preferably 500 ⁇ m or more, more preferably 1 mm or more. More preferably, it is 3 mm or more. From the viewpoint of suppressing the progress of side reactions, the upper limit is preferably 10 mm or less, more preferably 6 mm or less, and even more preferably 5 mm or less.
- the average pore diameter of the carrier is not particularly limited, but from the viewpoint of suppressing the progress of side reactions, the lower limit is preferably 3 nm or more, more preferably 5 nm or more, and further preferably 7 nm or more. preferable. From the viewpoint of maintaining the BET specific surface area, the upper limit is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 50 nm or less.
- the carrier is preferably calcined to remove moisture before being impregnated with the A liquid. Also, the carrier after calcination is preferably stored in a desiccator, dry air, or dry inert gas to keep the moisture removed.
- the method for impregnating the carrier with liquid A is not particularly limited, and any known method can be used. Examples thereof include a pore filling method in which a liquid A is added to the carrier in an amount equal to the pore volume of the carrier, and an immersion method in which the carrier is immersed in the liquid A.
- the time for which the carrier is impregnated with the liquid A is not particularly limited, but from the viewpoint of impregnating the carrier with the element X, the lower limit is preferably 15 minutes or longer, more preferably 1 hour or longer. From the viewpoint of the time required for catalyst production, the upper limit is preferably 50 hours or less, more preferably 30 hours or less, and even more preferably 24 hours or less.
- the amount of liquid A relative to the carrier is not particularly limited, but from the viewpoint of uniformly impregnating the carrier with the element X, the lower limit is preferably 0.9 times or more the pore volume of the carrier. From the viewpoint of reducing the amount of solvent used, the upper limit is preferably 10 times or less, more preferably 5 times or less, and even more preferably 2 times or less the pore volume of the carrier.
- Solid content A is obtained by impregnating the carrier with liquid A.
- Solid content A is preferably obtained by removing the solvent.
- the solvent can be removed by a known method, and examples thereof include a method using a rotary evaporator and a method of separation by filtration.
- Step (2) the solid content A obtained in the step (1) is heat-treated to obtain the solid content B.
- the heat treatment temperature is 150 to 300° C., and the lower limit is preferably 170° C. or higher, more preferably 190° C. or higher.
- the heating rate from when the solid content A reaches 120° C. to when it reaches the heat treatment temperature is preferably 10° C./min or less, more preferably 5° C./min or less. Up to 120° C., the solvent of the solid content A is mainly removed, whereas at temperatures above 120° C., the active site structure of the solid content A changes. It is believed that by setting the heating rate to 120° C. or higher as the above conditions, an active site structure more suitable for production of the target product is formed.
- the heat treatment time is 15 minutes to 24 hours.
- the lower limit of the heat treatment time is preferably 30 minutes or longer, more preferably 1 hour or longer, still more preferably 5 hours or longer, and particularly preferably 10 hours or longer.
- the upper limit is preferably 20 hours or less, more preferably 15 hours or less.
- Step (3) the solid content B obtained in the step (2) is impregnated with a solution or dispersion (liquid B) containing one or more elements Y selected from alkali metal elements to obtain a solid content. get C.
- (B liquid) Liquid B can be obtained by dissolving or dispersing a compound containing element Y in a solvent. At this time, the compound containing the element Y may be dissolved or dispersed while stirring the solvent.
- Element Y preferably comprises lithium, sodium, potassium, rubidium or cesium, more preferably potassium, rubidium or cesium, even more preferably cesium. In addition, the element Y may be 1 type, and may be 2 or more types.
- the compound containing element Y is preferably a salt of element Y. Salts are not particularly limited, and examples thereof include carbonates, nitrates, sulfates, acetates, ammonium salts, oxides, and halides. These can be used alone or in combination.
- the element Y is lithium, lithium carbonate, lithium nitrate, and the like can be mentioned.
- the element Y is sodium, sodium carbonate, sodium nitrate, sodium sulfate and the like are included.
- the element Y is potassium, examples thereof include potassium carbonate, potassium nitrate, potassium sulfate, and the like.
- the element Y is rubidium, rubidium carbonate, rubidium nitrate, rubidium sulfate and the like can be mentioned.
- the element Y is cesium, examples include cesium carbonate, cesium bicarbonate, cesium nitrate, cesium sulfate, and the like.
- the lower limit of the content of the element Y in the resulting catalyst is preferably 3% by mass or more, preferably 4% by mass or more, relative to the mass of the catalyst as a whole. More preferably, it is 6% by mass or more.
- the upper limit is preferably 25% by mass or less, more preferably 18% by mass or less, even more preferably 14% by mass or less, and particularly preferably 12% by mass or less.
- the content of element X can be adjusted by the amount of element X charged.
- the lower limit of the molar ratio MY/MX in the obtained catalyst is 1.3 or more from the viewpoint of improving the selectivity of the target product. It is preferably 1.5 or more, more preferably 1.7 or more, and particularly preferably 1.9 or more.
- the upper limit is preferably 8 or less, more preferably 6 or less, even more preferably 5.5 or less, and particularly preferably 5 or less.
- MY/MX can be adjusted by the charged amount of element Y with respect to element X.
- the same solvent as the above liquid A can be used.
- the amount of the compound containing element Y contained in solution B is not particularly limited, but from the viewpoint of improving the selectivity of the target product, the lower limit is preferably 6 mmol or more, preferably 14 mmol or more, relative to 100 mL of the solvent. is more preferably 25 mmol or more.
- the upper limit is preferably 60 mmol or less, more preferably 50 mmol or less, and even more preferably 40 mmol or less per 100 mL of the solvent.
- the obtained liquid B is at rest before impregnating the solid content B.
- the average particle size of the compound containing the Y element in the liquid B is reduced, and the Y element is appropriately highly dispersed in the resulting catalyst, which tends to improve the selectivity of the target product.
- the lower limit of the standing time of liquid B is 15 minutes or more and the upper limit is 50 hours or less.
- the method for impregnating the solid content B with the liquid B is not particularly limited, and a known method can be used. Examples thereof include a pore filling method in which liquid B is added to solid content B in an amount equal to the pore volume of solid content B, and an immersion method in which solid content B is immersed in liquid B.
- the time for impregnating the solid content B with the liquid B is not particularly limited, but from the viewpoint of impregnating the solid content B with the element Y, the lower limit is preferably 15 minutes or longer, more preferably 1 hour or longer. From the viewpoint of the time required for catalyst production, the upper limit is preferably 50 hours or less, more preferably 30 hours or less, and even more preferably 24 hours or less.
- the amount of liquid B relative to the solid content B is not particularly limited, but from the viewpoint of uniformly impregnating the element Y into the solid content B, the lower limit is preferably 0.9 times or more the pore volume of the solid content B. . From the viewpoint of reducing the amount of solvent used, the upper limit is preferably 10 times or less the pore volume of the solid content B, more preferably 5 times or less.
- the solid content C is obtained by impregnating the solid content B with the liquid B.
- Solid content C is preferably obtained by removing the solvent.
- the solvent can be removed by a known method, and examples thereof include a method using a rotary evaporator and a method of separation by filtration.
- step (4-1) the solid content C obtained in step (3) is heat treated at a heat treatment temperature of 100 to 300° C. to obtain a catalyst.
- the heat treatment can remove the solvent remaining in the solid content C and unnecessary elements other than the element X, the element Y, and silica. Further, by heat-treating under such conditions, the value of the peak height ratio I 2 /I 1 obtained by Raman spectroscopy is within the specified range, and a catalyst with high selectivity for the target product can be obtained. .
- the reason for this is that the heat treatment under the specified conditions in the step (2) and the heat treatment in the step (4-1), the catalyst obtained has an active site structure suitable for producing the target product. This is thought to be due to the formation of That is, the active sites for the side reactions are reduced, and the active site components that cause the main reactions are appropriately dispersed.
- the lower limit of the heat treatment temperature is preferably 110° C. or higher, more preferably 120° C. or higher.
- the upper limit is preferably 250°C or less.
- the lower limit of the heat treatment time is preferably 15 minutes or longer, more preferably 30 minutes or longer, still more preferably 1 hour or longer, particularly preferably 5 hours or longer, and most preferably 10 hours or longer.
- the upper limit is preferably 24 hours or less, more preferably 20 hours or less, and even more preferably 15 hours or less.
- the catalyst can be produced as described above.
- a second embodiment of the method for producing a catalyst of the present invention has the following steps. (1) Impregnating a carrier containing silica with a solution or dispersion containing one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium (liquid A) to obtain a solid content Obtaining A. (2) A step of heat-treating the solid content A to obtain a solid content B; (3) A step of obtaining a solid content C by impregnating the solid content B with a solution or dispersion (liquid B) containing one or more elements Y selected from alkali metal elements.
- step (4-2) A step of heat-treating the solid content C at a heat-treating temperature of 400 to 450° C. to obtain a catalyst. Further, in the second embodiment of the method for producing a catalyst of the present invention, in the step (4-2), the temperature rise rate from when the solid content C reaches 120 ° C. to when it reaches the heat treatment temperature is 10 ° C. / minute or less. Each step will be described in detail below.
- Step (1) and its preferred embodiments are the same as the first embodiment.
- Step (2) the solid content A obtained in the step (1) is heat-treated to obtain the solid content B.
- the heat treatment temperature is preferably 100 to 200°C. Therefore, it is considered that the heat treatment under the conditions of step (4-2) to be described later forms a more suitable active site structure for the production of the target product.
- the lower limit of the heat treatment temperature is more preferably 110°C or higher.
- the upper limit is more preferably 150° C. or lower, more preferably 130° C. or lower.
- the lower limit of the heat treatment time is preferably 15 minutes or longer, more preferably 1 hour or longer, still more preferably 5 hours or longer, and particularly preferably 10 hours or longer.
- the upper limit is preferably 24 hours or less, more preferably 20 hours or less, and even more preferably 15 hours or less.
- Step (3) and its preferred embodiments are the same as the first embodiment.
- step (4-2) the solid content C obtained in step (3) is heat treated at a heat treatment temperature of 400 to 450° C. to obtain a catalyst.
- the heat treatment can remove the solvent remaining in the solid content C and unnecessary elements other than the element X, the element Y, and silica. Further, by heat-treating under such conditions, the value of the peak height ratio I 2 /I 1 obtained by Raman spectroscopy is within the specified range, and a catalyst with high selectivity for the target product can be obtained. .
- the reason for this is thought to be that the heat treatment in step (4-2) forms an active site structure suitable for producing the target product in the resulting catalyst. That is, the active sites for the side reactions are reduced, and the active site components that cause the main reactions are appropriately dispersed.
- the rate of temperature increase from when the solid content C reaches 120° C. to when it reaches the heat treatment temperature is 10° C./min or less. Up to 120° C., the solvent in the solid content C is mainly removed, whereas at temperatures above 120° C., the active site structure of the solid content C changes. It is believed that by setting the heating rate to 120° C. or higher as the above conditions, an active site structure more suitable for production of the target product is formed. More preferably, the lower limit of the heating rate from when the solid content C reaches 120° C. until it reaches the heat treatment temperature is 2° C./min or more, and the upper limit is 8° C./min or less.
- the heat treatment time is preferably 3 hours or longer, more preferably 4 hours or longer, and even more preferably 6 hours or longer.
- the upper limit is preferably 24 hours or less, more preferably 20 hours or less, and even more preferably 15 hours or less.
- the catalyst can be produced as described above.
- a third embodiment of the method for producing a catalyst of the present invention has the following steps. (1) Impregnating a carrier containing silica with a solution or dispersion containing one or more elements X selected from the group consisting of boron, magnesium, aluminum, zirconium, hafnium and titanium (liquid A) to obtain a solid content Obtaining A. (2) A step of heat-treating the solid content A to obtain a solid content B; (3) A step of obtaining a solid content C by impregnating the solid content B with a solution or dispersion (liquid B) containing one or more elements Y selected from alkali metal elements.
- step (4-3) A step of heat-treating the solid content C at a heat-treating temperature higher than 450° C. and not higher than 700° C. to obtain a catalyst. Further, in the third embodiment of the method for producing a catalyst of the present invention, in the step (4-3), the temperature rise rate from when the solid content C reaches 120 ° C. to when it reaches the heat treatment temperature is 10 ° C. / minute or less.
- Step (1)> Step (1) and its preferred embodiments are the same as the first embodiment.
- Step (2)> Step (2) and its preferred embodiments are the same as the second embodiment.
- Step (3)> Step (3) and its preferred embodiments are the same as the first embodiment.
- step (4-3) the solid content C obtained in step (3) is heat-treated at a heat treatment temperature higher than 450° C. and not higher than 700° C. to obtain a catalyst.
- the heat treatment can remove the solvent remaining in the solid content C and unnecessary elements other than the element X, the element Y, and silica. Further, by heat-treating under such conditions, the value of the peak height ratio I 2 /I 1 obtained by Raman spectroscopy is within the specified range, and a catalyst with high selectivity for the target product can be obtained. .
- the reason for this is thought to be that the heat treatment in step (4-3) forms an active site structure suitable for producing the target product in the resulting catalyst. That is, the active sites for the side reactions are reduced, and the active site components that cause the main reactions are appropriately dispersed.
- the lower limit of the heat treatment temperature is preferably 500° C. or higher, more preferably 550° C. or higher, from the viewpoint of improving the selectivity of the target product.
- the upper limit is preferably 650° C. or lower, more preferably 600° C. or lower.
- the rate of temperature increase from when the solid content C reaches 120° C. to when it reaches the heat treatment temperature is 10° C./min or less. Up to 120° C., the solvent in the solid content C is mainly removed, whereas at temperatures above 120° C., the active site structure of the solid content C changes. It is believed that by setting the heating rate to 120° C. or higher as the above conditions, an active site structure more suitable for production of the target product is formed. More preferably, the lower limit of the heating rate from when the solid content C reaches 120° C. until it reaches the heat treatment temperature is 2° C./min or more, and the upper limit is 8° C./min or less.
- the heat treatment time is preferably 15 minutes or longer, more preferably 1 hour or longer, still more preferably 3 hours or longer, particularly preferably 10 hours or longer, and 15 hours, from the viewpoint of reducing the active sites of side reactions in the solid content C.
- the above is most preferred.
- the upper limit is preferably 48 hours or less, more preferably 24 hours or less.
- a catalyst can be produced as described above.
- Method for producing unsaturated carboxylic acid and/or unsaturated carboxylic acid ester By reacting a carboxylic acid and/or a carboxylic acid ester with formaldehyde in the presence of a catalyst according to an embodiment of the invention or a catalyst produced by a process according to an embodiment of the invention, the corresponding unsaturated Carboxylic acids and/or unsaturated carboxylic acid esters can be produced. That is, another embodiment of the present invention is a method for producing unsaturated carboxylic acid and/or unsaturated carboxylic acid ester from carboxylic acid and/or carboxylic acid ester and formaldehyde using the above catalyst. Thereby, unsaturated carboxylic acid and/or unsaturated carboxylic acid ester can be produced with high selectivity.
- the carboxylic acid and/or carboxylic acid ester is preferably a compound represented by the following formula (I).
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
- Methyl propionate is preferable as the compound represented by the above formula (I).
- the catalyst according to this embodiment is particularly effective in a method for producing methacrylic acid and/or methyl methacrylate from methyl propionate and formaldehyde.
- the reaction of a carboxylic acid and/or a carboxylic acid ester with formaldehyde is performed by contacting a reaction raw material containing a carboxylic acid and/or a carboxylic acid ester and formaldehyde with a catalyst to produce an unsaturated carboxylic acid and/or an unsaturated carboxylic acid. to produce esters.
- the molar ratio of formaldehyde to the total number of moles of carboxylic acid and carboxylic acid ester is not particularly limited, but from the viewpoint of improving the selectivity of the target product, it is preferably 0.05 to 20. More preferably, the lower limit is 0.2 or more and the upper limit is 15 or less.
- the above reaction is preferably carried out in the presence of an alcohol.
- the molar ratio of alcohol to the total number of moles of carboxylic acid and/or carboxylic acid ester is not particularly limited, but is preferably 0.05-20. More preferably, the lower limit is 0.1 or more and the upper limit is 10 or less.
- compounds other than the above may be contained within a range that does not significantly impair the effects of the present invention.
- Compounds other than the above include, for example, water.
- the reaction temperature in the above reaction is not particularly limited, but from the viewpoint of improving the selectivity of the target product, the lower limit is preferably 100°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher.
- the upper limit is preferably 400°C or lower, more preferably 370°C or lower, and even more preferably 360°C or lower.
- the contact time between the reaction raw materials and the catalyst is not particularly limited, but from the viewpoint of improving the selectivity of the target product, the lower limit is preferably 0.1 seconds or more, more preferably 1 second or more. Seconds or more are more preferable. From the viewpoint of suppressing the progress of side reactions, the time is preferably 100 seconds or less, more preferably 50 seconds or less, and even more preferably 30 seconds or less.
- the carboxylic acid and/or carboxylic acid ester contained in the reaction raw material can be produced by a known method.
- the carboxylic acid and/or carboxylic acid ester is methyl propionate
- it can be produced by a carbonylation reaction of ethylene.
- the ethylene carbonylation reaction is a method for producing methyl propionate by reacting ethylene with carbon monoxide in the presence of a catalyst that enables ethylene carbonylation.
- the carbonylation reaction of ethylene will be described in detail below.
- the amount of ethylene relative to carbon monoxide is not particularly limited, but the lower limit is preferably 0.01 mol or more, more preferably 0.1 mol or more, per 100 mol of carbon monoxide.
- the upper limit is preferably 100 mol or less, more preferably 10 mol or less.
- the reaction temperature in the carbonylation reaction is not particularly limited, but the lower limit is preferably 20°C or higher, more preferably 40°C or higher, and even more preferably 70°C or higher.
- the upper limit is preferably 250°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower.
- the reaction time is not particularly limited, it is preferably 0.1 to 100 hours.
- the catalyst that enables carbonylation of ethylene is not particularly limited, and known catalysts can be used.
- the catalyst include palladium catalysts having phosphine ligands.
- the palladium catalyst for example, those described in JP-A-10-511034 can be used.
- the palladium catalyst can be produced by a known method.
- the carbonylation reaction is preferably carried out in the presence of an alcohol.
- Alcohols are not particularly limited, and examples thereof include methanol, ethanol, propanol, 2-propanol, 2-butanol and t-butyl alcohol, with methanol and ethanol being preferred.
- alcohol may be used individually by 1 type, and may use 2 or more types together.
- the amount of ethylene relative to alcohol is not particularly limited, but the lower limit is preferably 0.01 mol or more, more preferably 0.1 mol or more, relative to 100 mol of alcohol.
- the upper limit is preferably 100 mol or less, more preferably 10 mol or less.
- carbon monoxide may be supplied together with an inert gas.
- Inert gases include hydrogen, nitrogen, carbon dioxide, argon, and the like.
- Unsaturated carboxylic acid and/or unsaturated carboxylic acid ester can be produced by the above-described method, but the produced unsaturated carboxylic acid and/or unsaturated carboxylic acid ester usually contain impurities. Therefore, in order to remove impurities, it is preferable to purify the obtained unsaturated carboxylic acid and/or unsaturated carboxylic acid ester by a known method such as distillation. The purification conditions may be appropriately adjusted so as to obtain the desired purity of the unsaturated carboxylic acid and/or the unsaturated carboxylic acid ester.
- Heat treatment In this example, the heat treatment of solid content A and solid content C was performed using a muffle furnace.
- product number FUM142PA manufactured by Advantech
- product number DF62 manufactured by Yamato Scientific Co.
- Raman spectrometry The results of Raman spectroscopic measurement of the catalyst were carried out at an excitation wavelength of 488 nm using a 3D microscopic laser Raman spectrometer Nanofinder (manufactured by Tokyo Instruments). I 2 /I 1 was measured by the following procedure. Raman spectroscopic analysis was performed at five points on the cross section of the catalyst divided into two while changing the measurement locations at regular intervals from one end to the other. The obtained Raman spectrum was corrected using a straight line connecting the minimum intensity at 730 ⁇ 2 cm ⁇ 1 and the minimum intensity at 867 ⁇ 2 cm ⁇ 1 as a baseline.
- the length of the perpendicular line from the peak top of the peak at 417 ⁇ 10 cm ⁇ 1 to the baseline was taken as I 1 .
- the length of a perpendicular line from the top of the peak at 1050 ⁇ 10 cm ⁇ 1 to a straight line drawn between both ends of the peak was defined as I 2 .
- I 2 was set to 0 when there was no peak around 1050 ⁇ 10 cm ⁇ 1 .
- the above operation was performed for the 5 points analyzed, and I 1 , I 2 and I 2 /I 1 were calculated as arithmetic mean values.
- the BET specific surface area of the catalyst was calculated by the BET one-point method using a nitrogen adsorption measuring device Macsorb (manufactured by Mountec).
- reaction evaluation The reaction evaluation of the catalyst was carried out using, as an example, the reaction of producing methacrylic acid and/or methyl methacrylate from methyl propionate and formaldehyde.
- the reaction raw materials and reaction products in reaction evaluation were analyzed using gas chromatography (Shimadzu Corporation, GC-2010). From the analysis results, the selectivity of methacrylic acid and methyl methacrylate was calculated by the following formula (II).
- Selectivity (%) of methacrylic acid and methyl methacrylate (number of moles of methacrylic acid and methyl methacrylate produced)/(number of moles of reacted methyl propionate) x 100
- Example 1 4.5 g of zirconium oxynitrate dihydrate (Kishida Chemical, special grade) was dissolved in 135 mL of methanol (Nacalai Tesque, special grade) and allowed to stand for 24 hours to prepare liquid A. 60 g of CARiACT Q-15 (Fuji Silysia Chemical Co., Ltd., particle size: 1.7 to 4 mm, average pore size: 10 nm) was used as a carrier, which was immersed in liquid A and allowed to stand for 3.5 hours. The solvent was then removed using a rotary evaporator to obtain solid content A. The obtained solid content A was heat-treated at a heat treatment temperature of 120° C. for 14 hours to obtain a solid content B.
- CARiACT Q-15 Fruji Silysia Chemical Co., Ltd., particle size: 1.7 to 4 mm, average pore size: 10 nm
- the heating rate of the solid content A was 0.17° C./min.
- 30 g of the obtained solid content B was immersed for 3.5 hours in a liquid B prepared by dissolving 4.9 g of cesium carbonate (Wako Pure Chemical Industries, first grade) in 65 mL of methanol. The solution was then removed by filtration to obtain solid C.
- the obtained solid content C was heat treated at a heat treatment temperature of 500° C. for 3 hours to obtain a catalyst.
- the heating rate of the solid content C was 5° C./min.
- Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst.
- reaction evaluation was performed according to the following procedure.
- About 3 g of the resulting catalyst was charged into the reactor.
- the reaction raw material solution having a molar ratio of 1:1.40:0.19:0.5 of methyl propionate, methanol, formaldehyde and water is evaporated at 300° C. at a flow rate of 0.160 mL/min. and the reactor at 330° C. for 16 hours.
- the reaction raw material liquid having a molar ratio of 1:0.64:0.27:0.01 of methyl propionate, methanol, formaldehyde and water was passed through an evaporator at 300°C, and It was fed to a reactor to produce methacrylic acid and methyl methacrylate.
- Table 1 shows the analysis results of the obtained reaction product.
- FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Examples 2 to 8> A solid content C was obtained in the same manner as in Example 1. The obtained solid content C was heat-treated in the same manner as in Example 1, except that the heat treatment temperature and heat treatment time were changed as shown in Table 1, to obtain a catalyst. Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst. Next, reaction evaluation was performed in the same manner as in Example 1. Table 1 shows the analysis results of the reaction product. FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Example 9 A solid content A was obtained in the same manner as in Example 1.
- the obtained solid content A was heat-treated in the same manner as in Example 1, except that the heat treatment temperature and heat treatment time were changed as shown in Table 1, to obtain a solid content B.
- a solid content C was obtained in the same manner as in Example 1 using the obtained solid content B.
- the obtained solid content C was heat treated at a heat treatment temperature of 120° C. for 14 hours to obtain a catalyst. At this time, the heating rate of the solid content C was 0.17° C./min.
- Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst. Next, reaction evaluation was performed in the same manner as in Example 1. Table 1 shows the analysis results of the reaction product.
- FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Examples 10-11> A solid content A was obtained in the same manner as in Example 1. The obtained solid content A was heat-treated in the same manner as in Example 1, except that the heat treatment temperature and heat treatment time were changed as shown in Table 1, to obtain a solid content B. A solid content C was obtained in the same manner as in Example 1 using the obtained solid content B. The obtained solid content C was heat-treated in the same manner as in Example 9 to obtain a catalyst. Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst. Next, reaction evaluation was performed in the same manner as in Example 1. Table 1 shows the analysis results of the reaction product. FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Example 12 A solid content A was obtained in the same manner as in Example 1. The obtained solid content A was heat-treated at a heat treatment temperature of 200° C. for 14 hours to obtain a solid content B. At this time, the heating rate of the solid content A was 5° C./min. A solid content C was obtained in the same manner as in Example 1 using the obtained solid content B. The obtained solid content C was heat-treated in the same manner as in Example 9 to obtain a catalyst. Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst. Next, reaction evaluation was performed in the same manner as in Example 1. Table 1 shows the analysis results of the reaction product. FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Example 13 A solid content C was obtained in the same manner as in Example 1.
- the obtained solid content C was heat-treated in the same manner as in Example 1, except that the heat treatment temperature and heat treatment time were changed as shown in Table 1, to obtain a catalyst.
- Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst.
- reaction evaluation was performed in the same manner as in Example 1.
- Table 1 shows the analysis results of the reaction product.
- FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Example 1 A solid content C was obtained in the same manner as in Example 1. The obtained solid content C was heat-treated in the same manner as in Example 9 to obtain a catalyst. Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst. Next, reaction evaluation was performed in the same manner as in Example 1. Table 1 shows the analysis results of the reaction product. FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate. ⁇ Comparative Example 2> A solid content C was obtained in the same manner as in Example 1.
- the obtained solid content C was heat-treated in the same manner as in Example 1, except that the heat treatment temperature and heat treatment time were changed as shown in Table 1, to obtain a catalyst.
- Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst.
- reaction evaluation was performed in the same manner as in Example 1.
- Table 1 shows the analysis results of the reaction product.
- FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Example 3 A solid content C was obtained in the same manner as in Example 1. The obtained solid content C was heat treated at a heat treatment temperature of 450° C. for 3 hours to obtain a catalyst. At this time, the heating rate of the solid content C was 25° C./min. Table 1 shows the results of Raman spectroscopic measurement, fluorescent X-ray analysis and BET specific surface area measurement of the catalyst. Next, reaction evaluation was performed in the same manner as in Example 1. Table 1 shows the analysis results of the reaction product. FIG. 1 shows the relationship between the peak height ratio I 2 /I 1 obtained by Raman spectroscopy and the selectivity of methacrylic acid and methyl methacrylate.
- Examples 1 to 13 using catalysts in which the peak height ratio I 2 /I 1 is within the specified range are equivalent to catalysts in which I 2 /I 1 is outside the specified range. It can be seen that the selectivity of methacrylic acid and methyl methacrylate is greatly improved as compared with Comparative Examples 1 to 3 using .
- Examples 1 to 13 using catalysts in which the heat treatment conditions for solid content A and solid content C are within the specified range are comparisons using catalysts in which the heat treatment conditions for solid content A and solid content C are outside the specified range. It can be seen that the selectivity for methacrylic acid and methyl methacrylate is significantly improved compared to Examples 1-3.
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Abstract
Description
すなわち、本発明の課題は、メタクリル酸メチルに代表される不飽和カルボン酸エステルや不飽和カルボン酸を高選択率で製造することができる触媒を提供することである。
[1]:ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xと、アルカリ金属元素から選択される1種以上の元素Yと、シリカと、を含有する触媒であって、
ラマン分光分析により得られる417±10cm-1における最大ピーク高さをI1、1050±10cm-1における最大ピーク高さをI2としたとき、ピーク高さの比I2/I1が0~1.2である触媒。
[2]:前記I2/I1が0~0.5である、[1]に記載の触媒。
[3]:不飽和カルボン酸及び/又は不飽和カルボン酸エステル製造用触媒である、[1]又は[2]に記載の触媒。
[4]:前記元素Xがジルコニウムを含む、[1]~[3]のいずれかに記載の触媒。
[5]:前記元素Xの含有量が、触媒全体の質量に対して0.3~10質量%である、[1]~[4]のいずれかに記載の触媒。
[6]:前記元素Yがセシウムを含む、[1]~[5]のいずれかに記載の触媒。
[7]:前記元素Yの含有量が、触媒全体の質量に対して3~25質量%である、[1]~[6]のいずれかに記載の触媒。
[8]:前記元素Xのモル数をMX、前記元素Yのモル数をMYとしたとき、モル比MY/MXが1.3~8である、[1]~[7]のいずれかに記載の触媒。
[9]:BET比表面積が50~600m2/gである、[1]~[8]のいずれかに記載の触媒。
[10]:(1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程、
(2)前記固形分Aを熱処理して、固形分Bを得る工程、
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程、
(4-1)前記固形分Cを、100~300℃の熱処理温度で熱処理して触媒を得る工程、
を有する触媒の製造方法であって、
前記工程(2)において、前記固形分Aを150~300℃の熱処理温度で15分~24時間熱処理する、触媒の製造方法。
[11]:前記工程(2)において、前記固形分Aが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である、[10]に記載の触媒の製造方法。
[12]:前記工程(4-1)において、前記固形分Cを15分~24時間熱処理する、[10]又は[11]に記載の触媒の製造方法。
[13]:(1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程、
(2)前記固形分Aを熱処理して、固形分Bを得る工程、
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程、
(4-2)前記固形分Cを、400~450℃の熱処理温度で熱処理して触媒を得る工程、
を有する触媒の製造方法であって、
前記工程(4-2)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である、触媒の製造方法。
[14]:前記工程(4-2)において、前記固形分Cを3~24時間熱処理する、[13]に記載の触媒の製造方法。
[15]:前記工程(4-2)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が2~8℃/分である、[13]又は[14]に記載の触媒の製造方法。
[16]:(1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程、
(2)前記固形分Aを熱処理して、固形分Bを得る工程、
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程、
(4-3)前記固形分Cを、450℃より高く700℃以下の熱処理温度で熱処理して触媒を得る工程、
を有する触媒の製造方法であって、
前記工程(4-3)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である、触媒の製造方法。
[17]:前記工程(4-3)において、前記固形分Cを15分~24時間熱処理する、[16]に記載の触媒の製造方法。
[18]:前記工程(4-3)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が2~8℃/分である、[16]又は[17]に記載の触媒の製造方法。
[19]:前記工程(2)において、前記固形分Aを100~200℃の熱処理温度で熱処理する、[13]~[18]のいずれかに記載の触媒の製造方法。
[20]:前記工程(2)において、前記固形分Aを15分~24時間熱処理する、[13]~[19]のいずれかに記載の触媒の製造方法。
[21]:前記触媒が不飽和カルボン酸及び/又は不飽和カルボン酸エステル製造用触媒である、[10]~[20]のいずれかに記載の触媒の製造方法。
[22]:前記工程(1)において、前記元素Xがジルコニウムを含む、[10]~[21]のいずれかに記載の触媒の製造方法。
[23]:前記工程(3)において、前記元素Yがセシウムを含む、[10]~[22]のいずれかに記載の触媒の製造方法。
[24]:[1]~[9]のいずれかに記載の触媒を用いて、カルボン酸及び/又はカルボン酸エステルとホルムアルデヒドから、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する、不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法。
[25]:[10]~[23]のいずれかに記載の触媒の製造方法により製造された触媒を用いて、カルボン酸及び/又はカルボン酸エステルとホルムアルデヒドから、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する、不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載された数値を下限値及び上限値として含む範囲を意味し、「A~B」は、A以上B以下であることを意味する。
本発明の一実施形態は、ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xと、アルカリ金属元素から選択される1種以上の元素Yと、シリカと、を含有する触媒であって、ラマン分光分析により得られる417±10cm-1における最大ピーク高さをI1、1050±10cm-1における最大ピーク高さをI2としたとき、ピーク高さの比I2/I1が0~1.2である。
なお触媒の形状は特段の制限はなく、球状、柱状又はリング形状等が挙げられる。
触媒のラマン分光分析において、417±10cm-1におけるピークは主反応の活性点の構造に由来し、1050±10cm-1におけるピークは副反応の活性点の構造に由来すると推定される。
目的生成物の選択率向上の観点から、I2/I1の値の上限は1以下であることが好ましく、0.5以下であることがより好ましく、0.3以下であることがさらに好ましい。
I2/I1が上記範囲である触媒は、例えば、触媒の製造において熱処理温度を調整することで得ることができる。特に、後述する触媒の製造方法に記載の条件で、固形分A及び固形分Cを熱処理する方法を用いることが好ましい。
2分割した触媒の断面において、端から端まで一定間隔で測定場所を変更しながら、ラマン分光分析を5点実施する。続いて得られたラマンスペクトルに対して、730±2cm-1における最小強度と867±2cm-1における最小強度を結ぶ直線をベースラインとして補正を行う。ベースライン補正後のラマンスペクトルについて、417±10cm-1におけるピークのピークトップから、ベースラインまでの垂線の長さをI1とする。また、1050±10cm-1におけるピークのピークトップから、ピーク両端間で引かれた直線までの垂線の長さをI2とする。分析を実施した5点について以上の操作を行い、算術平均値としてI1、I2及びI2/I1を算出する。
本実施形態の触媒は、ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群からから選択される1種以上の元素Xを含む。元素Xはホウ素又はジルコニウムを含むことが好ましく、ジルコニウムを含むことがより好ましい。なお、元素Xは1種であってもよいし、2種以上であってもよい。
目的生成物の選択率向上の観点から、元素Xの含有量は、触媒全体の質量に対して、下限は0.3質量%以上であることが好ましく、0.5質量%以上であることがより好ましく、1質量%以上であることがさらに好ましく、1.5質量%以上であることが特に好ましい。また上限は10質量%以下であることが好ましく、6質量%以下であることがより好ましく、5質量%以下であることがさらに好ましく、4質量%以下であることが特に好ましい。
目的生成物の選択率向上の観点から、元素Yの含有量は、触媒全体の質量に対して、下限は3質量%以上であることが好ましく、4質量%以上であることがより好ましく、6質量%以上であることがさらに好ましい。また上限は25質量%以下であることが好ましく、18質量%以下であることがより好ましく、14質量%以下であることがさらに好ましく、12質量%以下であることが特に好ましい。
なお、元素X及び元素Yの含有量は、蛍光X線分析により測定できる。また得られた元素X及び元素Yの含有量から、モル比MY/MXを算出できる。蛍光X線分析には、例えばZSX PrimusIV(リガク社製)を用い、ヘリウム雰囲気下において実施する。
また本実施形態の触媒は、触媒の製造工程に由来するその他元素をさらに含んでもよい。
触媒のBET比表面積は、目的生成物の選択率向上の観点から、下限は50m2/g以上であることが好ましく、90m2/g以上であることがより好ましく、100m2/g以上であることがさらに好ましい。また上限は600m2/g以下であることが好ましく、500m2/g以下であることがより好ましく、350m2/g以下であることがさらに好ましく、300m2/g以下であることが特に好ましい。
BET比表面積の測定は、窒素吸着測定装置を用いてBET1点法により算出するものとする。窒素吸着測定装置としては、例えばMacsorb(マウンテック社製)等を用いることができる。
本発明の触媒の製造方法の第一の実施形態は、下記工程を有する。
(1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程。
(2)前記固形分Aを熱処理して、固形分Bを得る工程。
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程。
(4-1)前記固形分Cを、100~300℃の熱処理温度で熱処理して触媒を得る工程。
また本発明の触媒の製造方法の第一の実施形態は、前記工程(2)において、前記固形分Aを150~300℃の熱処理温度で15分~24時間熱処理する。
<工程(1)>
工程(1)では、ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る。
A液は、元素Xを含む化合物を溶媒に溶解又は分散させることで得ることができる。このとき、溶媒を撹拌しながら元素Xを含む化合物を溶解又は分散させてもよい。
元素Xはホウ素又はジルコニウムを含むことが好ましく、ジルコニウムを含むことがより好ましい。なお、元素Xは1種であってもよいし、2種以上であってもよい。
元素Xを含む化合物は、元素Xの無機塩であることが好ましい。元素Xを含む化合物は、元素Xの無機塩であることが好ましい。無機塩としては、炭化水素を含まない無機化合物であれば特段の制限はなく、例えば、炭酸塩、硝酸塩、オキシ硝酸塩、硫酸塩、酢酸塩、アンモニウム塩、酸化物又はハロゲン化物を挙げることができる。これらは単独で、又は組み合わせて使用することができる。より具体的には、元素Xがホウ素の場合、酸化ホウ素等が挙げられる。元素Xがマグネシウムの場合、硝酸マグネシウム、硫酸マグネシウム、炭酸マグネシウム、酢酸マグネシウム等が挙げられる。元素Xがジルコニウムの場合、オキシ硝酸ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、炭酸ジルコニウム、過塩素酸ジルコニウム、酢酸ジルコニウム等が挙げられ、オキシ硝酸ジルコニウムを含むことが好ましい。元素Xがハフニウムの場合、硝酸ハフニウム、硫酸ハフニウム、過塩素酸ハフニウム、酢酸ハフニウム等が挙げられる。元素Xがチタンの場合、酸化チタン、塩化チタン、硫酸チタニル等が挙げられる。
A液を含浸させる担体はシリカを含み、アルミナ、ゼオライト、チタニア又はジルコニア等をさらに含んでもよい。シリカとしては、シリカゲルを用いることが好ましい。
担体のBET比表面積は、目的生成物の選択率向上の観点から、下限は50m2/g以上であることが好ましく、90m2/g以上であることがより好ましく、100m2/g以上であることがさらに好ましい。また上限は600m2/g以下であることが好ましく、500m2/g以下であることがより好ましく、350m2/g以下であることがさらに好ましく、300m2/g以下であることが特に好ましい。
また、担体のBET比表面積を調整する方法は特段の制限はないが、例えば、所望のBET比表面積が得られるような細孔を有する担体を使用することができる。担体が有する細孔割合が多いとBET比表面積は大きくなる傾向があり、担体が有する細孔割合が少ないとBET比表面積は小さくなる傾向がある。
BET比表面積の測定は、窒素吸着測定装置を用いてBET1点法により算出するものとする。窒素吸着測定装置としては、例えばMacsorb(マウンテック社製)等を用いることができる。
担体の平均粒径は特段の制限はないが、目的生成物を製造する反応における圧力損失を抑制する観点から、下限は500μm以上であることが好ましく、1mm以上であることがより好ましく、1.3mm以上であることがさらに好ましい。また副反応の進行を抑制する観点から、上限は10mm以下であることが好ましく、6mm以下であることがより好ましく、5mm以下であることがさらに好ましい。
担体が有する平均細孔径は特段の制限はないが、副反応の進行を抑制する観点から、下限は3nm以上であることが好ましく、5nm以上であることがより好ましく、7nm以上であることがさらに好ましい。またBET比表面積を維持する観点から、上限は200nm以下であることが好ましく、150nm以下であることがより好ましく、100nm以下であることがさらに好ましく、50nm以下であることが特に好ましい。
なお担体は、A液を含浸させる前に焼成して、水分を除去しておくことが好ましい。また焼成後の担体は、デシケーター、乾燥空気、又は乾燥した不活性ガス中で保管し、水分が除去された状態を維持することが好ましい。
A液を担体に含浸させる方法は特段の制限はなく、公知の方法を用いることができる。例えば、担体の細孔容積と等量のA液を担体に添加するポアフィリング法や、担体をA液に浸漬する浸漬法等が挙げられる。
A液を担体に含浸させる時間は特段の制限はないが、元素Xを担体に良好に含浸させる観点から、下限は15分以上が好ましく、1時間以上がより好ましい。また触媒製造に要する時間の観点から、上限は50時間以下が好ましく、30時間以下がより好ましく、24時間以下がさらに好ましい。
工程(2)では、前記工程(1)で得られた固形分Aを熱処理して、固形分Bを得る。
固形分Aが120℃に到達してから熱処理温度に到達するまでの昇温速度は、10℃/分以下であることが好ましく、5℃/分以下であることがより好ましい。温度が120℃までは主に固形分Aの溶媒が除去されるのに対し、120℃以上では固形分Aの活性点構造が変化する。120℃以上の昇温速度を上記の条件とすることにより、目的生成物の製造により好適な活性点構造が形成されると考えられる。
工程(3)では、アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記工程(2)で得られた固形分Bに含浸させて、固形分Cを得る。
B液は、元素Yを含む化合物を溶媒に溶解又は分散させることで得ることができる。このとき、溶媒を撹拌しながら元素Yを含む化合物を溶解又は分散させてもよい。
元素Yはリチウム、ナトリウム、カリウム、ルビジウム又はセシウムを含むことが好ましく、カリウム、ルビジウム又はセシウムを含むことがより好ましく、セシウムを含むことがさらに好ましい。なお、元素Yは1種であってもよいし、2種以上であってもよい。
元素Yを含む化合物は、元素Yの塩であることが好ましい。塩としては、特段の制限はなく、例えば、炭酸塩、硝酸塩、硫酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等を挙げることができる。これらは単独で、又は組み合わせて使用することができる。より具体的には、元素Yがリチウムの場合、炭酸リチウム、硝酸リチウム等が挙げられる。元素Yがナトリウムの場合、炭酸ナトリウム、硝酸ナトリウム、硫酸ナトリウム等が挙げられる。元素Yがカリウムの場合、炭酸カリウム、硝酸カリウム、硫酸カリウム等が挙げられる。元素Yがルビジウムの場合、炭酸ルビジウム、硝酸ルビジウム、硫酸ルビジウム等が挙げられる。元素Yがセシウムの場合、炭酸セシウム、重炭酸セシウム、硝酸セシウム、硫酸セシウム等が挙げられる。
また前記元素Xのモル数をMX、前記元素Yのモル数をMYとしたとき、目的生成物の選択率向上の観点から、得られる触媒におけるモル比MY/MXの下限は1.3以上であることが好ましく、1.5以上であることがより好ましく、1.7以上であることがさらに好ましく、1.9以上であることが特に好ましい。また上限は8以下であることが好ましく、6以下であることがより好ましく、5.5以下であることがさらに好ましく、5以下であることが特に好ましい。MY/MXは、元素Xに対する元素Yの仕込み量により調整できる。
B液を固形分Bに含浸させる方法は特段の制限はなく、公知の方法を用いることができる。例えば、固形分Bの細孔容積と等量のB液を固形分Bに添加するポアフィリング法や、固形分BをB液に浸漬する浸漬法等が挙げられる。
B液を固形分Bに含浸させる時間は特段の制限はないが、元素Yを固形分Bに良好に含浸させる観点から、下限は15分以上が好ましく、1時間以上がより好ましい。また触媒製造に要する時間の観点から、上限は50時間以下が好ましく、30時間以下がより好ましく、24時間以下がさらに好ましい。
工程(4-1)では、前記工程(3)で得られた固形分Cを、100~300℃の熱処理温度で熱処理して触媒を得る。熱処理により固形分Cに残存する溶媒や、元素X、元素Y及びシリカ以外の不要な元素を除去することができる。
またこのような条件で熱処理することにより、ラマン分光測定で得られるピーク高さの比I2/I1の値が規定範囲内であり、目的生成物の選択率が高い触媒を得ることができる。この理由としては、前記工程(2)で規定の条件で熱処理を行い、さらに工程(4-1)で熱処理を行うことで、得られる触媒において、目的生成物の製造に好適な活性点構造が形成されるためと考えられる。すなわち、副反応の活性点が減少するとともに、主反応を生じる活性点成分が適度に高分散化する。
熱処理時間の下限は15分以上が好ましく、30分以上がより好ましく、1時間以上がさらに好ましく、5時間以上が特に好ましく、10時間以上が最も好ましい。また上限は24時間以下が好ましく、20時間以下がより好ましく、15時間以下がさらに好ましい。
以上のようにして、触媒を製造することができる。
本発明の触媒の製造方法の第二の実施形態は、下記工程を有する。
(1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程。
(2)前記固形分Aを熱処理して、固形分Bを得る工程。
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程。
(4-2)前記固形分Cを、400~450℃の熱処理温度で熱処理して触媒を得る工程。
また本発明の触媒の製造方法の第二の実施形態は、前記工程(4-2)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である。
以下、各工程について詳細に説明する。
工程(1)及びその好ましい実施形態は、第一の実施形態と同様である。
工程(2)では、前記工程(1)で得られた固形分Aを熱処理して、固形分Bを得る。
熱処理温度は100~200℃が好ましい。これにより、後述する工程(4-2)の条件で熱処理を行うことにより、目的生成物の製造により好適な活性点構造が形成されると考えられる。熱処理温度の下限は110℃以上がより好ましい。また上限は150℃以下がより好ましく、130℃以下がさらに好ましい。
熱処理時間の下限は15分以上が好ましく、1時間以上がより好ましく、5時間以上がさらに好ましく、10時間以上が特に好ましい。また上限は24時間以下が好ましく、20時間以下がより好ましく、15時間以下がさらに好ましい。
工程(3)及びその好ましい実施形態は、第一の実施形態と同様である。
工程(4-2)では、前記工程(3)で得られた固形分Cを、400~450℃の熱処理温度で熱処理して触媒を得る。熱処理により固形分Cに残存する溶媒や、元素X、元素Y及びシリカ以外の不要な元素を除去することができる。
またこのような条件で熱処理することにより、ラマン分光測定で得られるピーク高さの比I2/I1の値が規定範囲内であり、目的生成物の選択率が高い触媒を得ることができる。この理由としては、工程(4-2)で熱処理を行うことで、得られる触媒において、目的生成物の製造に好適な活性点構造が形成されるためと考えられる。すなわち、副反応の活性点が減少するとともに、主反応を生じる活性点成分が適度に高分散化する。
熱処理時間は、固形分Cにおける副反応の活性点を減少させる観点から、下限は3時間以上が好ましく、4時間以上がより好ましく、6時間以上がさらに好ましい。また上限は24時間以下が好ましく、20時間以下がより好ましく、15時間以下がさらに好ましい。
以上のようにして、触媒を製造することができる。
本発明の触媒の製造方法の第三の実施形態は、下記工程を有する。
(1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程。
(2)前記固形分Aを熱処理して、固形分Bを得る工程。
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程。
(4-3)前記固形分Cを、450℃より高く700℃以下の熱処理温度で熱処理して触媒を得る工程。
また本発明の触媒の製造方法の第三の実施形態は、前記工程(4-3)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である。
<工程(1)>
工程(1)及びその好ましい実施形態は、第一の実施形態と同様である。
<工程(2)>
工程(2)及びその好ましい実施形態は、第二の実施形態と同様である。
<工程(3)>
工程(3)及びその好ましい実施形態は、第一の実施形態と同様である。
工程(4-3)では、前記工程(3)で得られた固形分Cを、450℃より高く700℃以下の熱処理温度で熱処理して触媒を得る。熱処理により固形分Cに残存する溶媒や、元素X、元素Y及びシリカ以外の不要な元素を除去することができる。
またこのような条件で熱処理することにより、ラマン分光測定で得られるピーク高さの比I2/I1の値が規定範囲内であり、目的生成物の選択率が高い触媒を得ることができる。この理由としては、工程(4-3)で熱処理を行うことで、得られる触媒において、目的生成物の製造に好適な活性点構造が形成されるためと考えられる。すなわち、副反応の活性点が減少するとともに、主反応を生じる活性点成分が適度に高分散化する。
固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度は、10℃/分以下である。温度が120℃までは主に固形分Cの溶媒が除去されるのに対し、120℃以上では固形分Cの活性点構造が変化する。120℃以上の昇温速度を上記の条件とすることにより、目的生成物の製造により好適な活性点構造が形成されると考えられる。固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度の下限は2℃/分以上、上限は8℃/分以下がより好ましい。
本発明の一実施形態に係る触媒又は本発明の一実施形態に係る製造方法により製造された触媒の存在下で、カルボン酸及び/又はカルボン酸エステルをホルムアルデヒドと反応させることにより、対応する不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造することができる。すなわち、本発明の別の実施形態は、上記触媒を用いて、カルボン酸及び/又はカルボン酸エステルとホルムアルデヒドから、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する方法である。これにより、高選択率で不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造することができる。
R1-CH2-COOR2・・・式(I)
反応原料において、カルボン酸及びカルボン酸エステルの総モル数に対するホルムアルデヒドのモル比は、特段の制限はないが、目的生成物の選択率向上の観点から、0.05~20であることが好ましい。また下限は0.2以上、上限は15以下であることがより好ましい。
本実施例において、固形分A及び固形分Cの熱処理は、マッフル炉を使用して実施した。マッフル炉としては、製品番号FUM142PA(アドバンテック社製)又は製品番号DF62(ヤマト科学社製)を用いた。
触媒のラマン分光測定結果は、3D顕微レーザーラマン分光装置Nanofinder(東京インスツルメンツ社製)を用い、励起波長488nmで行った。I2/I1は、下記の手順で測定した。
2分割した触媒の断面において、端から端まで一定間隔で測定場所を変更しながら、ラマン分光分析を5点実施した。得られたラマンスペクトルに対して、730±2cm-1における最小強度と867±2cm-1における最小強度を結ぶ直線をベースラインとして補正した。ベースライン補正後のラマンスペクトルについて、417±10cm-1におけるピークのピークトップから、ベースラインまでの垂線の長さをI1とした。また、1050±10cm-1におけるピークのピークトップから、ピーク両端間で引かれた直線までの垂線の長さをI2とした。なお、1050±10cm-1付近にピークが存在しない場合は、I2を0とした。分析を実施した5点について以上の操作を行い、算術平均値としてI1、I2及びI2/I1を算出した。
元素X及び元素Yの含有量は、蛍光X線分析により測定した。また得られた元素X及び元素Yの含有量から、元素Xと元素Yのモル比であるMY/MXを算出した。蛍光X線分析は、ZSX PrimusIV(リガク社製)を用い、ヘリウム雰囲気下において実施した。
触媒のBET比表面積は、窒素吸着測定装置Macsorb(マウンテック社製)を用いてBET1点法により算出した。
触媒の反応評価は、プロピオン酸メチルとホルムアルデヒドからメタクリル酸及び/又はメタクリル酸メチルを製造する反応を例として実施した。反応評価における反応原料及び反応生成物は、ガスクロマトグラフィー(島津製作所、GC-2010)を用いて分析した。分析結果から、メタクリル酸及びメタクリル酸メチルの選択率を下記式(II)により算出した。
メタクリル酸及びメタクリル酸メチルの選択率(%)=(生成したメタクリル酸及びメタクリル酸メチルのモル数)/(反応したプロピオン酸メチルのモル数)×100・・・式(II)
オキシ硝酸ジルコニウム2水和物(キシダ化学、特級)4.5gをメタノール(ナカライテスク、特級)135mLに溶解して24時間静置し、A液を調製した。担体としてCARiACT Q-15(富士シリシア化学(株)、粒径1.7-4mm、平均細孔径10nm)60gを用い、A液を浸漬して3.5時間静置した。次いで、ロータリーエバポレーターを用いて溶媒を除去し、固形分Aを得た。
得られた固形分Aを120℃の熱処理温度で14時間熱処理し、固形分Bを得た。このとき、固形分Aの昇温速度は0.17℃/分であった。
得られた固形分Bのうち30gを、炭酸セシウム(和光純薬、1級)4.9gをメタノール65mLに溶解したB液に3.5時間浸漬した。次いで、濾過により溶液を除去し、固形分Cを得た。
得られた固形分Cを500℃の熱処理温度で3時間熱処理し、触媒を得た。このとき、固形分Cの昇温速度は5℃/分であった。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを、熱処理温度及び熱処理時間を表1に示す通り変更した以外は、実施例1と同様に熱処理し、触媒を得た。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
実施例1と同様の方法により固形分Aを得た。
得られた固形分Aを、熱処理温度及び熱処理時間を表1に示す通り変更した以外は、実施例1と同様に熱処理し、固形分Bを得た。
得られた固形分Bを用い、実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを120℃の熱処理温度で14時間熱処理し、触媒を得た。このとき、固形分Cの昇温速度は0.17℃/分であった。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
実施例1と同様の方法により固形分Aを得た。
得られた固形分Aを、熱処理温度及び熱処理時間を表1に示す通り変更した以外は、実施例1と同様に熱処理し、固形分Bを得た。
得られた固形分Bを用い、実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを、実施例9と同様に熱処理し、触媒を得た。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
実施例1と同様の方法により固形分Aを得た。
得られた固形分Aを200℃の熱処理温度で14時間熱処理し、固形分Bを得た。このとき、固形分Aの昇温速度は5℃/分であった。
得られた固形分Bを用い、実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを、実施例9と同様に熱処理し、触媒を得た。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを、熱処理温度及び熱処理時間を表1に示す通り変更した以外は、実施例1と同様に熱処理し、触媒を得た。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを、実施例9と同様に熱処理し、触媒を得た。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
<比較例2>
実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを、熱処理温度及び熱処理時間を表1に示す通り変更した以外は、実施例1と同様に熱処理し、触媒を得た。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
実施例1と同様の方法により固形分Cを得た。
得られた固形分Cを450℃の熱処理温度で3時間熱処理し、触媒を得た。このとき、固形分Cの昇温速度は25℃/分であった。該触媒のラマン分光測定、蛍光X線分析及びBET比表面積測定の結果を表1に示す。
次に、実施例1と同様に反応評価を行った。反応生成物の分析結果を表1に示す。また、ラマン分光測定により得られたピーク高さの比I2/I1と、メタクリル酸及びメタクリル酸メチルの選択率との関係を図1に示す。
また、固形分A及び固形分Cの熱処理条件が規定範囲内である触媒を使用した実施例1~13は、固形分A及び固形分Cの熱処理条件が規定範囲外である触媒を使用した比較例1~3と比較して、メタクリル酸及びメタクリル酸メチルの選択率が大幅に向上していることが分かる。
Claims (25)
- ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xと、アルカリ金属元素から選択される1種以上の元素Yと、シリカと、を含有する触媒であって、
ラマン分光分析により得られる417±10cm-1における最大ピーク高さをI1、1050±10cm-1における最大ピーク高さをI2としたとき、ピーク高さの比I2/I1が0~1.2である触媒。 - 前記I2/I1が0~0.5である、請求項1に記載の触媒。
- 不飽和カルボン酸及び/又は不飽和カルボン酸エステル製造用触媒である、請求項1又は2に記載の触媒。
- 前記元素Xがジルコニウムを含む、請求項1~3のいずれか1項に記載の触媒。
- 前記元素Xの含有量が、触媒全体の質量に対して0.3~10質量%である、請求項1~4のいずれか1項に記載の触媒。
- 前記元素Yがセシウムを含む、請求項1~5のいずれか1項に記載の触媒。
- 前記元素Yの含有量が、触媒全体の質量に対して3~25質量%である、請求項1~6のいずれか1項に記載の触媒。
- 前記元素Xのモル数をMX、前記元素Yのモル数をMYとしたとき、モル比MY/MXが1.3~8である、請求項1~7のいずれか1項に記載の触媒。
- BET比表面積が50~600m2/gである、請求項1~8のいずれか1項に記載の触媒。
- (1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程、
(2)前記固形分Aを熱処理して、固形分Bを得る工程、
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程、
(4-1)前記固形分Cを、100~300℃の熱処理温度で熱処理して触媒を得る工程、
を有する触媒の製造方法であって、
前記工程(2)において、前記固形分Aを150~300℃の熱処理温度で15分~24時間熱処理する、触媒の製造方法。 - 前記工程(2)において、前記固形分Aが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である、請求項10に記載の触媒の製造方法。
- 前記工程(4-1)において、前記固形分Cを15分~24時間熱処理する、請求項10又は11に記載の触媒の製造方法。
- (1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程、
(2)前記固形分Aを熱処理して、固形分Bを得る工程、
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程、
(4-2)前記固形分Cを、400~450℃の熱処理温度で熱処理して触媒を得る工程、
を有する触媒の製造方法であって、
前記工程(4-2)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である、触媒の製造方法。 - 前記工程(4-2)において、前記固形分Cを3~24時間熱処理する、請求項13に記載の触媒の製造方法。
- 前記工程(4-2)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が2~8℃/分である、請求項13又は14に記載の触媒の製造方法。
- (1)ホウ素、マグネシウム、アルミニウム、ジルコニウム、ハフニウム及びチタンよりなる群から選択される1種以上の元素Xを含む溶液又は分散液(A液)を、シリカを含む担体に含浸させて、固形分Aを得る工程、
(2)前記固形分Aを熱処理して、固形分Bを得る工程、
(3)アルカリ金属元素から選択される1種以上の元素Yを含む溶液又は分散液(B液)を、前記固形分Bに含浸させて、固形分Cを得る工程、
(4-3)前記固形分Cを、450℃より高く700℃以下の熱処理温度で熱処理して触媒を得る工程、
を有する触媒の製造方法であって、
前記工程(4-3)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が10℃/分以下である、触媒の製造方法。 - 前記工程(4-3)において、前記固形分Cを15分~24時間熱処理する、請求項16に記載の触媒の製造方法。
- 前記工程(4-3)において、前記固形分Cが120℃に到達してから熱処理温度に到達するまでの昇温速度が2~8℃/分である、請求項16又は17に記載の触媒の製造方法。
- 前記工程(2)において、前記固形分Aを100~200℃の熱処理温度で熱処理する、請求項13~18のいずれか1項に記載の触媒の製造方法。
- 前記工程(2)において、前記固形分Aを15分~24時間熱処理する、請求項13~19のいずれか1項に記載の触媒の製造方法。
- 前記触媒が不飽和カルボン酸及び/又は不飽和カルボン酸エステル製造用触媒である、請求項10~20のいずれか1項に記載の触媒の製造方法。
- 前記工程(1)において、前記元素Xがジルコニウムを含む、請求項10~21のいずれか1項に記載の触媒の製造方法。
- 前記工程(3)において、前記元素Yがセシウムを含む、請求項10~22のいずれか1項に記載の触媒の製造方法。
- 請求項1~9のいずれか1項に記載の触媒を用いて、カルボン酸及び/又はカルボン酸エステルとホルムアルデヒドから、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する、不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法。
- 請求項10~23のいずれか1項に記載の触媒の製造方法により製造された触媒を用いて、カルボン酸及び/又はカルボン酸エステルとホルムアルデヒドから、不飽和カルボン酸及び/又は不飽和カルボン酸エステルを製造する、不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法。
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CA3222204A CA3222204A1 (en) | 2021-06-01 | 2022-05-31 | Catalyst, method for producing catalyst, and method for producing unsaturated carboxylic acid and/or unsaturated carboxylic acid ester |
KR1020237044744A KR20240013212A (ko) | 2021-06-01 | 2022-05-31 | 촉매, 촉매의 제조 방법, 그리고 불포화 카르복실산 및/또는 불포화 카르복실산 에스테르의 제조 방법 |
BR112023024810A BR112023024810A2 (pt) | 2021-06-01 | 2022-05-31 | Catalisador, método para produção de catalisador, e método para produção de ácido carboxílico insaturado e/ou éster de ácido carboxílico insaturado |
EP22816114.7A EP4353355A1 (en) | 2021-06-01 | 2022-05-31 | Catalyst, method for producing catalyst, and method for producing unsaturated carboxylic acid and/or unsaturated carboxylic acid ester |
CN202280038446.6A CN117396272A (zh) | 2021-06-01 | 2022-05-31 | 催化剂、催化剂的制造方法、以及不饱和羧酸和/或不饱和羧酸酯的制造方法 |
JP2023525862A JPWO2022255368A1 (ja) | 2021-06-01 | 2022-05-31 | |
MX2023014361A MX2023014361A (es) | 2021-06-01 | 2022-05-31 | Catalizador, metodo para producir catalizador, y metodo para producir acido carboxilico insaturado y/o ester de acido carboxilico insaturado. |
US18/524,541 US20240116031A1 (en) | 2021-06-01 | 2023-11-30 | Catalyst, Method for Producing Catalyst, and Method for Producing Unsaturated Carboxylic Acid and/or Unsaturated Carboxylic Acid Ester |
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JP2002511336A (ja) | 1998-04-08 | 2002-04-16 | イネオス アクリリックス ユーケー リミティド | 不飽和酸もしくはそのエステルおよびそのための触媒 |
WO2019053438A1 (en) | 2017-09-13 | 2019-03-21 | Lucite International Uk Limited | PROCESS AND CATALYST FOR PRODUCTION OF CARBOXYLIC ACIDS OR ESTERS WITH ETHYLENE UNSATURATION |
WO2020184616A1 (ja) * | 2019-03-12 | 2020-09-17 | 三菱ケミカル株式会社 | 触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 |
WO2020183193A1 (en) | 2019-03-13 | 2020-09-17 | Lucite International Uk Limited | A process for the production of a catalyst, a catalyst therefrom and a process for production of ethylenically unsaturated carboxylic acids or esters |
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JP2002511336A (ja) | 1998-04-08 | 2002-04-16 | イネオス アクリリックス ユーケー リミティド | 不飽和酸もしくはそのエステルおよびそのための触媒 |
WO2019053438A1 (en) | 2017-09-13 | 2019-03-21 | Lucite International Uk Limited | PROCESS AND CATALYST FOR PRODUCTION OF CARBOXYLIC ACIDS OR ESTERS WITH ETHYLENE UNSATURATION |
JP2020533170A (ja) * | 2017-09-13 | 2020-11-19 | ルーサイト インターナショナル ユーケー リミテッド | エチレン性不飽和カルボン酸又はエステルを製造するための触媒及びプロセス |
WO2020184616A1 (ja) * | 2019-03-12 | 2020-09-17 | 三菱ケミカル株式会社 | 触媒、触媒の製造方法、並びに不飽和カルボン酸及び/又は不飽和カルボン酸エステルの製造方法 |
WO2020183193A1 (en) | 2019-03-13 | 2020-09-17 | Lucite International Uk Limited | A process for the production of a catalyst, a catalyst therefrom and a process for production of ethylenically unsaturated carboxylic acids or esters |
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CN117396272A (zh) | 2024-01-12 |
JPWO2022255368A1 (ja) | 2022-12-08 |
EP4353355A1 (en) | 2024-04-17 |
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