WO2012073584A1 - 不飽和カルボン酸製造用触媒および該触媒を用いる不飽和カルボン酸の製造方法 - Google Patents
不飽和カルボン酸製造用触媒および該触媒を用いる不飽和カルボン酸の製造方法 Download PDFInfo
- Publication number
- WO2012073584A1 WO2012073584A1 PCT/JP2011/071804 JP2011071804W WO2012073584A1 WO 2012073584 A1 WO2012073584 A1 WO 2012073584A1 JP 2011071804 W JP2011071804 W JP 2011071804W WO 2012073584 A1 WO2012073584 A1 WO 2012073584A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- active component
- average fiber
- unsaturated carboxylic
- catalytically active
- Prior art date
Links
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims 3
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- 239000011733 molybdenum Substances 0.000 claims abstract description 7
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- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
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- 239000001301 oxygen Substances 0.000 claims description 11
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
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- 239000010949 copper Substances 0.000 claims description 4
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- 229910052782 aluminium Inorganic materials 0.000 claims description 2
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- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- 239000011574 phosphorus Substances 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 claims description 2
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
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- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
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- 239000000395 magnesium oxide Substances 0.000 description 2
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- 229910052878 cordierite Inorganic materials 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
- B01J27/228—Silicon carbide with phosphorus, arsenic, antimony or bismuth
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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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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- 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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention relates to an unsaturated carboxylic acid production catalyst, and more particularly to a suitable catalyst for producing an unsaturated carboxylic acid by catalytic gas phase oxidation of an unsaturated aldehyde or saturated hydrocarbon in the presence of molecular oxygen.
- the present invention also relates to a method for producing an unsaturated carboxylic acid using this catalyst.
- Unsaturated carboxylic acids such as acrylic acid and methacrylic acid are industrially important as raw materials for various synthetic resins, paints, plasticizers and the like.
- acrylic acid has become increasingly important as a raw material for water-absorbing resins in recent years.
- a method for producing an unsaturated carboxylic acid such as acrylic acid and methacrylic acid for example, in the case of acrylic acid production, first, acrolein is produced by catalytic gas phase oxidation of propylene, and then the contact gas of the obtained acrolein is used. The most common is a two-stage oxidation process consisting of making acrylic acid by phase oxidation.
- methacrolein is first produced by catalytic gas phase oxidation reaction from at least one raw material selected from isobutylene, t-butanol and methyl-t-butyl ether, and then the obtained methacrolein is obtained.
- a two-stage oxidation process is known which consists of further catalytic vapor phase oxidation of lane to produce methacrylic acid.
- Unsaturated aldehydes such as acrolein and methacrolein, or saturated hydrocarbons such as propane are catalytically vapor-oxidized in the presence of molecular oxygen to give the corresponding unsaturated acids such as acrylic acid and methacrylic acid.
- a catalyst used in the method for producing a saturated carboxylic acid a catalyst containing molybdenum and vanadium is widely known.
- the improvement of the mechanical strength required for industrial use as well as the improvement of the yield of the target product is a problem, and the machine can be used without impairing the yield of the target product.
- Many proposals have been made for the purpose of improving the mechanical strength.
- the weight loss rate of the dried product is 5 to 40% by mass (see Japanese Patent Application Laid-Open No. 2004-243213), 0.
- Extruded catalyst containing 5 to 5% by weight of graphite see JP-A-60-150834
- carbon fiber having an average diameter of 1 to 20 ⁇ m, an average length of 10 to 3000 ⁇ m, and a carbon content of 93% or more
- a catalyst containing 0.05 to 10% by weight see JP-A-7-251075), a catalyst obtained by mixing an oxide precursor and an oxide and calcining (see JP-A-2004-351297), etc. Proposed.
- a catalyst for obtaining unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde or saturated hydrocarbon As a catalyst for obtaining unsaturated carboxylic acid by gas phase catalytic oxidation of unsaturated aldehyde or saturated hydrocarbon, a molded catalyst or catalytically active component formed by molding only the catalytically active component into a certain shape is used as an inert carrier.
- a supported catalyst is generally supported. From the viewpoint of reducing the thickness of the catalyst layer and thereby suppressing side reactions due to sequential oxidation of the target product, a supported catalyst is preferred.
- the supported catalyst since the supported catalyst has a form in which the catalytically active component is supported on the inert carrier, the catalytically active component is inactivated by, for example, impact upon dropping the catalyst into the reactor and filling it.
- the mechanical strength of the catalyst is low.
- problems such as an increase in pressure loss due to a catalyst active component peeled off when the catalyst is filled in the reaction tube and a blockage of the reaction tube occur. For this reason, it is desired that the supported catalyst has a higher mechanical strength.
- the catalyst surface is scraped and pulverized by contact between the catalysts generated during canning, transportation, filling, etc. in the catalyst production process or by friction between the catalyst and the wall surface (hereinafter referred to as the catalyst strength).
- the catalyst strength it is also desirable to suppress the “powdering degree”. Suppressing the degree of pulverization is an economic problem that the catalyst powder causes an increase in pressure loss and loss of catalyst components, and a health aspect that the filling worker is exposed to the catalyst powder scattered during the catalyst filling. This is very important in consideration of the above-mentioned problems and environmental problems such as release of such catalyst powder to the atmosphere.
- An object of the present invention is to solve the above-mentioned problems of the prior art, and a supported catalyst suitable for producing an unsaturated carboxylic acid by catalytic gas phase oxidation of an unsaturated aldehyde or saturated hydrocarbon in the presence of molecular oxygen, Specifically, an object of the present invention is to provide a supported catalyst that is excellent in the mechanical strength and degree of pulverization of the catalyst and that can produce the target product in a high yield.
- the inventors of the present invention have described the mechanical strength of a molybdenum-vanadium-based supported catalyst for producing an unsaturated carboxylic acid by catalytic gas phase oxidation of an unsaturated aldehyde or saturated hydrocarbon in the presence of molecular oxygen.
- both mechanical strength and degree of powdering can be improved by including at least two kinds of inorganic fibers having different average fiber diameters together with the catalytically active component. It has been found that a catalyst capable of producing the product in high yield is obtained.
- the present inventors provide a catalyst comprising a catalytically active component containing molybdenum and vanadium as essential components and an inorganic fiber supported on an inert carrier, wherein the inorganic fiber has an average fiber diameter.
- a catalyst containing at least an inorganic fiber having an average fiber diameter of 1.5 to 7 ⁇ m and an inorganic fiber having an average fiber diameter of less than 1.0 ⁇ m is excellent in both mechanical strength and degree of pulverization, and yields a desired product in a high yield. It was found that it can be manufactured by
- the present inventors have further found that the adverse effect on the catalyst performance of the inorganic fiber can be suppressed by setting the total content of the inorganic fiber to 0.5 to 30% by mass with respect to the catalytic active component. .
- a catalyst for producing an unsaturated carboxylic acid by catalytic gas phase oxidation of an unsaturated aldehyde or saturated hydrocarbon in the presence of molecular oxygen which has mechanical strength and powder.
- a supported catalyst which has an excellent degree of conversion and can produce a target product in a high yield.
- the unsaturated carboxylic acid production catalyst of the present invention is a catalyst comprising a catalytically active component containing molybdenum and vanadium as essential components and an inorganic fiber supported on an inert carrier, and the inorganic fiber has an average fiber diameter. It is important to contain at least inorganic fibers having a diameter of less than 1.0 ⁇ m and inorganic fibers having an average fiber diameter of 1.5 to 7 ⁇ m.
- the following general formula (1) Mo 12 V a A b B c C d D e O x (1) (Where Mo is molybdenum, V is vanadium, A is at least one element selected from the group consisting of tungsten and niobium, B is at least selected from chromium, manganese, iron, cobalt, nickel, copper, zinc and bismuth) One element, C is at least one element selected from antimony, tin, tellurium and phosphorus, D is at least one element selected from silicon, aluminum, titanium, cerium and zirconium, and O is oxygen; a, b, c, d, e and x represent atomic ratios of V, A, B, C, D and O, respectively, 0 ⁇ a ⁇ 14, 0 ⁇ b ⁇ 12, 0 ⁇ c ⁇ 6, 0 ⁇ d ⁇ 6 and 0 ⁇ e ⁇ 50, and x is a numerical value determined by the oxidation
- the inorganic fibers having an average fiber diameter of less than 1.0 ⁇ m are particularly preferably those having an average fiber diameter of less than 0.7 ⁇ m, and the inorganic fibers having an average fiber diameter of 1.5 to 7 ⁇ m are preferred. In particular, those having an average fiber diameter of 2 to 5 ⁇ m are preferred.
- An inorganic fiber having an average fiber diameter of less than 1.0 ⁇ m, preferably less than 0.7 ⁇ m, is effective for improving the degree of pulverization mainly by tapping the powder on the catalyst surface from the fineness of the fiber.
- the relatively thick inorganic fibers having an average fiber diameter of 1.5 to 7 ⁇ m, preferably 2 to 5 ⁇ m mainly have mechanical strength such as to keep the support surface and the catalytically active component connected. It is thought that it works effectively for improvement.
- it is important to contain at least two kinds of inorganic fibers having different average fiber diameters. It is difficult to improve both the mechanical strength and the degree of pulverization at the same time with only one of the fibers, and as a result, the mechanical strength or the degree of pulverization that is not improved adversely affects the catalyst performance and the like. .
- the material of the inorganic fiber is not particularly limited, and for example, various whiskers, ceramic fibers, glass fibers, carbon fibers, mineral fibers, metal fibers, and the like can be used.
- the crystal structure may be polycrystalline, monocrystalline or amorphous.
- the two or more kinds of inorganic fibers used may be the same material or different materials, and may be appropriately selected and used as long as the average fiber diameter of the inorganic fibers used satisfies the above-mentioned provisions. be able to.
- the average fiber length of the inorganic fibers is not particularly limited, but considering the dispersibility in the catalyst, it is preferably 1 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m. However, even inorganic fibers having an average fiber length exceeding 1000 ⁇ m can be suitably used by vigorously stirring with a homomixer or the like and cutting so that the average fiber length falls within the above range.
- the content of each of the two or more inorganic fibers is 0.5 to 20 mass with respect to the amount of the catalytically active component in terms of the improvement effect of mechanical strength and / or the degree of pulverization and the catalyst performance, particularly the catalyst life. % Range is preferred.
- the total content of inorganic fibers is preferably in the range of 0.5 to 30% by mass with respect to the amount of the catalytically active component. If the content of the inorganic fiber is less than the above range, the mechanical strength and / or powdering degree is not sufficiently improved, and if it is more than the above range, the amount of the catalytically active component contained in the catalyst is relatively small. Therefore, the catalyst life is shortened.
- the content ratio of the inorganic fiber having an average fiber diameter of less than 1.0 ⁇ m and the inorganic fiber having an average fiber diameter of 1.5 to 7 ⁇ m cannot sufficiently obtain the effect of the other when one of them is extremely large. Then, it is preferably 1: 0.2 to 1: 5 on a mass basis.
- the catalyst of the present invention is supported on an inert carrier except that it must contain at least inorganic fibers having an average fiber diameter of less than 1.0 ⁇ m and inorganic fibers having an average fiber diameter of 1.5 to 7 ⁇ m.
- an inert carrier except that it must contain at least inorganic fibers having an average fiber diameter of less than 1.0 ⁇ m and inorganic fibers having an average fiber diameter of 1.5 to 7 ⁇ m.
- oxides, hydroxides, ammonium salts, nitrates, carbonates, sulfates, organic acid salts, etc. of each component element, or their aqueous solutions, sols, or compounds containing a plurality of elements, etc. For example, by mixing with water, an aqueous solution or aqueous slurry (hereinafter sometimes referred to as “starting raw material mixture”) as a raw material of the catalytically active component represented by the general formula (1) is produced.
- the obtained starting raw material mixture is dried by various methods such as heating and decompression as necessary to produce a catalyst precursor.
- a drying method by heating for example, a method of obtaining a powdery dried product using a spray dryer, a drum dryer or the like, an inert gas such as air or nitrogen using a box-type dryer, a tunnel-type dryer or the like.
- a method in which the solid is further heat-treated as described above.
- a drying method by reduced pressure for example, a method using a vacuum dryer can be employed, and thereby a block or powdery catalyst precursor can be obtained.
- the obtained dried product is sent to the subsequent supporting step through a pulverization step and a classification step for obtaining a powder having an appropriate particle size as necessary.
- the obtained dried product may be once fired and then sent to the supporting step.
- the particle size of the catalyst precursor powder is not particularly limited, but is preferably 500 ⁇ m or less from the viewpoint of excellent supportability.
- the method for adding the inorganic fiber is not particularly limited, and any method can be used as long as the inorganic fiber can be uniformly dispersed in the catalytically active component.
- a method of adding inorganic fibers to the starting raw material mixture of the catalytically active component represented by the general formula (1), or a catalyst precursor obtained after drying or further calcination of the starting raw material mixture of the catalytically active component or The method of adding an inorganic fiber to a baked product can be taken.
- the method of adding and mixing to the starting raw material mixture is preferable from the viewpoint of the dispersibility of the inorganic fibers.
- the inorganic fibers may be added all at once, or may be added separately. For example, a part of the inorganic fibers may be added to the starting material mixture, and the rest may be added to the catalyst precursor obtained by drying or further firing. Also good.
- the supporting method is not particularly limited.
- the starting raw material mixture is evaporated to dryness while heating and stirring on an inert carrier having a fixed shape.
- a method of adhering the catalyst precursor in powder form on an inert carrier as described in JP-A-64-85139, JP-A-8-299797 or JP-A-2004-136267 , Etc. can be employed.
- the inert carrier examples include alumina, silica, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite, and the like.
- alumina silica, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite, and the like.
- the thing of well-known shapes, such as spherical shape, cylindrical shape, and ring shape, can be used.
- a spherical shape it does not need to be a true sphere and may be substantially spherical, and the cross-sectional shape does not have to be a perfect circle in the same way for a cylindrical shape and a ring shape, and may be substantially a circular shape.
- the diameter D and length L are not limited, but both can be set to 1 to 20 mm, preferably 2 to 14 mm, more preferably 2 ⁇ 9 mm.
- the length L is particularly preferably 0.5 to 2.0 times the diameter D, more preferably 0.7 to 1.5 times.
- the amount of the catalytically active component supported on the inert carrier is not particularly limited, but is preferably in the range of 10 to 300% by mass, more preferably in the range of 20 to 200% by mass.
- a molding aid or binder for improving the supporting property, a pore forming agent for forming appropriate pores in the catalyst, and the like can be used.
- Specific examples include organic compounds such as ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, butyl alcohol, phenols, and inorganic compounds such as water, nitric acid, ammonium nitrate, and ammonium carbonate. It is done. These may be used alone or in combination of two or more.
- the carrier obtained in the above-described supporting step is sent to the subsequent drying step and / or firing step.
- the carrier is dried using a generally used box dryer, tunnel dryer, etc., in an inert gas such as air or nitrogen, or a nitrogen oxide or the like.
- the drying temperature is 80 to 300 ° C., preferably 100 to 250 ° C., and the drying time is preferably 1 to 20 hours.
- the firing furnace used in the firing step is not particularly limited, and a generally used box-type firing furnace or tunnel-type firing furnace may be used.
- the firing temperature is 250 to 600 ° C., preferably 300 to 550 ° C., more preferably 350 to 450 ° C., and the firing time is preferably 1 to 20 hours.
- the firing step can be appropriately performed in an air atmosphere, in an air stream, or in an inert gas atmosphere.
- the firing step is usually performed after the drying step, but may be performed without going through the drying step.
- a support prepared using a pre-fired catalytically active component as a catalyst precursor it does not necessarily require a firing step, as long as the molding auxiliary material and binder used in the molding step can be removed, Only the drying step is sufficient.
- the diameter D and length L are not limited, but both are preferably 3 to 15 mm, more preferably. 3 to 10 mm.
- the length L of the pellet catalyst is preferably 0.5 to 2.0 times the diameter D, more preferably 0.7 to 1.5 times.
- the reactor used in the method of the present invention for producing unsaturated carboxylic acid by catalytic gas phase oxidation of unsaturated aldehyde or saturated hydrocarbon-containing gas in the presence of molecular oxygen is not limited as long as it is a fixed bed reactor. However, a fixed bed multi-tubular reactor is particularly preferable.
- the inner diameter of the reaction tube is usually 15 to 50 mm, more preferably 20 to 40 mm, and still more preferably 22 to 38 mm.
- Each reaction tube of the fixed bed multitubular reactor does not necessarily need to be filled with a single catalyst, and can be filled with a plurality of types of catalysts.
- a method of filling a plurality of types of catalysts having different activities so as to form a layer (hereinafter referred to as “reaction zone”) (see JP-A-9-241209 and JP-A-2003-171340), or A method of diluting a part of the catalyst with an inert carrier or the like (see Japanese Patent Application Publication No. 2008-528883) or a method of combining them can be suitably employed.
- the number of reaction zones is appropriately determined depending on the reaction conditions and the scale of the reactor. However, if the number of reaction zones is too large, problems such as complicated packing of the catalyst may occur. 2 to 6 is desirable.
- the reaction conditions in the present invention are not particularly limited, and any conditions generally used for this type of reaction can be used.
- an inert gas for example, nitrogen gas
- the grade of the reaction raw material gas is not particularly limited.
- it contains acrolein-containing gas obtained by dehydration reaction of glycerin or catalytic oxidation reaction of propane and / or propylene, and methacrolein obtained by catalytic oxidation reaction of isobutylene or tertiary butanol. Gas or the like can also be used.
- the extracted catalyst is passed through a sieve whose opening is in the range of 50 to 90%, which is the shorter of the standard value of the catalyst particle size or particle length, and the mass (g) of the catalyst remaining on the sieve is measured.
- an SiC whisker having an average fiber diameter of 0.8 ⁇ m and an average fiber length of 40 ⁇ m in an amount of 15% by mass with respect to the catalytically active component, and an silica-alumina fiber having an average fiber diameter of 2 ⁇ m and an average fiber length of 100 ⁇ m Were added in amounts such that the amount was 15% by mass with respect to the catalytically active component.
- the obtained slurry was dried with a spray dryer and then pulverized to 500 ⁇ m to obtain a dried product.
- Catalyst 1 Mo 12 V 6.0 W 1.8 Cu 3.0 Sb 0.25 Ti 12
- the loading rate was determined by the following formula.
- Support rate (mass%) mass of supported catalyst powder (g) / mass of support used (g) ⁇ 100
- the mechanical strength of the catalyst 1 was measured using a sieve having an opening of 5 mm, and the degree of pulverization was measured using a sieve having an opening of 2 mm. Table 1 shows the mechanical strength and the degree of dusting of the catalyst 1.
- a steel reaction tube having a total length of 3000 mm and an inner diameter of 25 mm and a reactor comprising a shell for covering the same and flowing a heat medium were prepared in the vertical direction.
- the catalyst 1 was dropped from the upper part of the reaction tube and filled so that the layer length was 2800 mm.
- Example 1 A catalyst 2 was obtained in the same manner as in Example 1 except that silica-alumina fibers having an average fiber diameter of 2 ⁇ m and an average fiber length of 100 ⁇ m were not added. The supporting rate of the catalyst 2 and the metal element composition of the catalytically active component excluding oxygen were the same as those of the catalyst 1. Table 1 shows the mechanical strength and degree of pulverization of the catalyst 2. Catalyst 2 was charged into the reactor in the same manner as in Example 1, and an acrolein oxidation reaction was performed under the same conditions. The results are shown in Table 2.
- Example 2 A catalyst 3 was obtained in the same manner as in Example 1 except that no SiC whisker having an average fiber diameter of 0.8 ⁇ m and an average fiber length of 40 ⁇ m was added.
- the supporting rate of the catalyst 3 and the metal element composition of the catalytically active component excluding oxygen were the same as those of the catalyst 1.
- Table 1 shows the mechanical strength and the degree of dusting of the catalyst 3.
- Catalyst 3 was charged into the reactor in the same manner as in Example 1, and acrolein oxidation reaction was performed under the same conditions. The results are shown in Table 2.
- Example 2 In Example 1, instead of using 15% by mass of SiC whisker having an average fiber diameter of 0.8 ⁇ m and an average fiber length of 40 ⁇ m with respect to the catalytically active component, SiC whisker having an average fiber diameter of 0.6 ⁇ m and an average fiber length of 30 ⁇ m is catalytically active.
- Example 2 Silica having an average fiber diameter of 3 ⁇ m and an average fiber length of 150 ⁇ m instead of using 10% by weight of the component and 15% by mass of silica-alumina fiber having an average fiber diameter of 2 ⁇ m and an average fiber length of 100 ⁇ m with respect to the catalytically active component
- a catalyst 4 was obtained in the same manner as in Example 1 except that 10% by mass of alumina fiber was used based on the catalytically active component.
- the supporting rate of the catalyst 4 and the metal element composition of the catalytically active component excluding oxygen were the same as those of the catalyst 1.
- the mechanical strength of the catalyst 4 was measured using a sieve having an opening of 5 mm, and the degree of pulverization was measured using a sieve having an opening of 2 mm.
- Table 1 shows the mechanical strength and the degree of dusting of the catalyst 4.
- Catalyst 4 was charged into the reactor in the same manner as in Example 1, and an acrolein oxidation reaction was performed under the same conditions. The results are
- Example 3 [Catalyst preparation] While heating and stirring 10,000 parts of pure water, 1000 parts of ammonium molybdate, 221 parts of ammonium metavanadate, and 191 parts of ammonium paratungstate were dissolved. Separately, while heating and stirring 1000 parts of pure water, 285 parts of copper nitrate and 69 parts of cobalt nitrate were dissolved. The obtained two aqueous solutions were mixed, and 69 parts of antimony trioxide was added to obtain a starting material mixture. The obtained starting material mixture was dried with a spray dryer and then pulverized to 500 ⁇ m to obtain a dried product.
- SiC whisker having an average fiber diameter of 0.8 ⁇ m and an average fiber length of 40 ⁇ m is added in an amount so as to be 5% by mass with respect to the catalytically active component, and an alumina fiber having an average fiber diameter of 5 ⁇ m and an average fiber length of 200 ⁇ m.
- an alumina fiber having an average fiber diameter of 5 ⁇ m and an average fiber length of 200 ⁇ m was added in an amount of 5% by mass based on the catalytically active component, and mixed with powder to obtain a supporting powder.
- Catalyst 5 Mo 12 V 4.0 W 1.5 Cu 2.5 Co 0.5 Sb 1.0
- the mechanical strength of the catalyst 5 was measured using a sieve having an opening of 5 mm, and the degree of powdering was measured using a sieve having an opening of 2 mm.
- Table 1 shows the mechanical strength and the degree of dusting of the catalyst 5.
- Catalyst 5 was charged into the reactor in the same manner as in Example 1, and an acrolein oxidation reaction was performed under the same conditions. The results are shown in Table 2.
- Example 4 In Example 3, instead of using 5% by mass of the silica-alumina fiber having an average fiber diameter of 5 ⁇ m and an average fiber length of 200 ⁇ m based on the catalytically active component, a silica-alumina fiber having an average fiber diameter of 6 ⁇ m and an average fiber length of 250 ⁇ m is catalytically active.
- a catalyst 6 was obtained in the same manner as in Example 3 except that 5% by mass was used based on the components.
- the supporting rate of the catalyst 6 and the metal element composition of the catalytically active component excluding oxygen were the same as those of the catalyst 5.
- Table 1 shows the mechanical strength and the degree of dusting of the catalyst 6.
- Catalyst 6 was charged into the reactor in the same manner as in Example 1, and an acrolein oxidation reaction was performed under the same conditions. The results are shown in Table 2.
- Example 3 instead of using 5% by mass of an alumina fiber having an average fiber diameter of 5 ⁇ m and an average fiber length of 200 ⁇ m based on the catalytically active component, a glass fiber having an average fiber diameter of 10 ⁇ m and an average fiber length of 300 ⁇ m is used based on the catalytically active component.
- a catalyst 7 was obtained in the same manner as in Example 3 except that 5% by mass was used. The supporting rate of the catalyst 7 and the metal element composition of the catalytically active component excluding oxygen were the same as those of the catalyst 5.
- Table 1 shows the mechanical strength and the degree of dusting of the catalyst 7.
- Catalyst 7 was charged into the reactor in the same manner as in Example 1, and acrolein oxidation reaction was performed under the same conditions. The results are shown in Table 2.
- Example 3 instead of using 5% by mass of an alumina fiber having an average fiber diameter of 5 ⁇ m and an average fiber length of 200 ⁇ m based on the catalytically active component, a glass fiber having an average fiber diameter of 20 ⁇ m and an average fiber length of 500 ⁇ m is used based on the catalytically active component.
- a catalyst 8 was obtained in the same manner as in Example 3 except that 5% by mass was used. The supporting rate of the catalyst 8 and the metal element composition of the catalytically active component excluding oxygen were the same as those of the catalyst 5.
- Table 1 shows the mechanical strength and the degree of dusting of the catalyst 8.
- Catalyst 8 was charged into the reactor in the same manner as in Example 1, and acrolein oxidation reaction was performed under the same conditions. The results are shown in Table 2.
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Abstract
Description
Mo12VaAbBcCdDeOx (1)
(ここで、Moはモリブデン、Vはバナジウム、Aはタングステンおよびニオブからなる群から選ばれる少なくとも1種の元素、Bはクロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛およびビスマスから選ばれる少なくとも1種の元素、Cはアンチモン、スズ、テルルおよびリンから選ばれる少なくとも1種の元素、Dはシリコン、アルミニウム、チタン、セリウムおよびジルコニウムから選ばれる少なくとも1種の元素、そしてOは酸素であり、a、b、c、d、eおよびxはそれぞれV、A、B、C、DおよびOの原子比を表し、0<a≦14、0≦b≦12、0≦c≦6、0≦d≦6および0≦e≦50であり、xは各元素の酸化状態によって定まる数値である。)で表される触媒活性成分が好適である。
転化率[モル%]
=(反応した出発原料のモル数)/(供給した出発原料のモル数)×100
収率[モル%]
=(生成した不飽和カルボン酸のモル数)/(供給した出発原料のモル数)×100
[触媒の機械的強度測定方法]
内径25mm、長さ5000mmのステンレス製反応管を鉛直方向に設置し、該反応管の下端を厚さ1mmのステンレス製受け板で塞ぐ。約50gの触媒を秤量し、該反応管の上端から反応管内に落下させた後、反応管下端のステンレス製受け板を外し、反応管から触媒を静かに抜き出す。抜き出した触媒を、目開きが触媒の粒径あるいは粒長の規格値のうち短いほうの50~90%の範囲である篩にかけ、篩上に残った触媒の質量(g)を計量する。
機械的強度(質量%)=(篩上に残った触媒の質量(g)/反応管上端から落下させた触媒の質量(g))×100
[触媒の粉化度測定方法]
鉛直方向の断面が直径150mmの円であり、水平方向の幅が150mmである円筒ドラム状のステンレス製密閉容器内に触媒を約200gを秤量し入れる。該容器をその水平方向中心軸を中心として150rpmで30分間回転させた後、該容器から触媒を取り出し、目開きが触媒の粒径あるいは粒長の規格値のうち短いほうの10~50%の範囲である篩にかけ、篩状に残った触媒の重量(g)を計量する。
粉化度(質量%)=〔(容器内に入れた触媒の質量(g)-篩上に残った触媒の質量(g))/容器内に入れた触媒の質量(g)〕×100
<実施例1>
[触媒調製]
純水10000部を加熱攪拌しながら、モリブデン酸アンモニウム1000部、メタバナジン酸アンモニウム331部及びパラタングステン酸アンモニウム229部をこれに溶解させた。別に純水1000部を加熱攪拌しながら、硝酸銅342部をこれに溶解させた。得られた2つの水溶液を混合し、三酸化アンチモン17部及び酸化チタン452部を添加することによって、出発原料混合液を得た。これに、平均繊維径0.8μm、平均繊維長40μmのSiCウィスカを触媒活性成分に対して15質量%となるような量で、また、平均繊維径2μm、平均繊維長100μmのシリカ-アルミナ繊維を触媒活性成分に対して15質量%となるような量で、それぞれ添加することによってスラリーを得た。得られたスラリーをスプレードライヤーで乾燥した後、これを500μmに粉砕して乾燥物を得た。皿型転動造粒機の回転皿に平均直径が5.0mmのシリカ-アルミナ担体5000部を投入し、次いで回転皿を回転させた状態で、バインダーとしての10質量%のエチレングリコール水溶液と共に上記乾燥物を徐々に投入することによって担体に担持させた。次いで、得られた担持物を空気雰囲気下に400℃で6時間焼成して触媒1を得た。この触媒1の担持率は約30質量%であり、酸素を除く触媒活性成分の金属元素組成は次の通りであった。
なお、担持率は下記式により求めた。
担持率(質量%)=担持された触媒粉体の質量(g)/用いた担体の質量(g)×100
この触媒1の機械的強度は目開きが5mmの篩いを用い、粉化度は目開きが2mmの篩いを用いて測定した。この触媒1の機械的強度および粉化度を表1に示す。
全長3000mm、内径25mmの鋼鉄製反応管およびこれを覆う、熱媒体を流すための、シェルからなる反応器を鉛直方向に用意した。触媒1を反応管上部から落下させて、層長が2800mmとなるように充填した。
上記触媒1を充填した反応管の下部より、アクロレイン4容量%、酸素4容量%、水蒸気20容量%、及び残部容量%の窒素の混合物である原料ガスを、空間速度2000hr-1(標準状態)で導入することにより、アクロレイン酸化反応を行った。その際、アクロレイン転化率が約98モル%となるように熱媒体温度(反応温度)を調節した。その結果を表2に示す。
実施例1において、平均繊維径2μm、平均繊維長100μmのシリカ-アルミナ繊維を添加しなかったこと以外は、実施例1と同様に調製し、触媒2を得た。この触媒2の担持率、および、酸素を除く触媒活性成分の金属元素組成は触媒1と同じであった。触媒2の機械的強度および粉化度を表1に示す。触媒2を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す。
実施例1において、平均繊維径0.8μm、平均繊維長40μmのSiCウィスカを添加しなかったこと以外は、実施例1と同様に調製し、触媒3を得た。この触媒3の担持率、および、酸素を除く触媒活性成分の金属元素組成は触媒1と同じであった。触媒3の機械的強度および粉化度を表1に示す。触媒3を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す。
実施例1において、平均繊維径0.8μm、平均繊維長40μmのSiCウィスカを触媒活性成分に対して15質量%用いる代わりに、平均繊維径0.6μm、平均繊維長30μmのSiCウィスカを触媒活性成分に対して10質量%用い、かつ、平均繊維径2μm、平均繊維長100μmのシリカ-アルミナ繊維を触媒活性成分に対して15質量%用いる代わりに、平均繊維径3μm、平均繊維長150μmのシリカ-アルミナ繊維を触媒活性成分に対して10質量%用いたこと以外は、実施例1と同様に調製し、触媒4を得た。この触媒4の担持率、および、酸素を除く触媒活性成分の金属元素組成は触媒1と同じであった。触媒4の機械的強度は目開きが5mmの篩いを用い、粉化度は目開きが2mmの篩いを用いて測定した。この触媒4の機械的強度および粉化度を表1に示す。触媒4を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す。
[触媒調製]
純水10000部を加熱攪拌しながら、モリブデン酸アンモニウム1000部、メタバナジン酸アンモニウム221部及びパラタングステン酸アンモニウム191部を溶解させた。別に純水1000部を加熱攪拌しながら、硝酸銅285部及び硝酸コバルト69部を溶解させた。得られた2つの水溶液を混合し、三酸化アンチモン69部を添加することによって、出発原料混合液を得た。得られた出発原料混合液をスプレードライヤーで乾燥した後、これを500μmに粉砕して乾燥物を得た。この乾燥物に平均繊維径0.8μm、平均繊維長40μmのSiCウィスカを触媒活性成分に対して5質量%となるような量で、また、平均繊維径5μm、平均繊維長200μmのアルミナ繊維を触媒活性成分に対して5質量%となるような量で、それぞれ添加し、粉体混合して担持用粉体を得た。皿型転動造粒機の回転皿に平均直径が5.0mmのシリカ-アルミナ担体3500部を投入し、次いで回転皿を回転させた状態で、バインダーとしての10質量%のエチレングリコール水溶液と共に上記担持用粉体を徐々に投入することによって、担体に担持させた。次いで、得られた担持物を空気雰囲気下に400℃で6時間焼成して触媒5を得た。この触媒5の担持率は約30質量%であり、酸素を除く触媒活性成分の金属元素組成は次の通りであった。
触媒5: Mo12V4.0W1.5Cu2.5Co0.5Sb1.0
この触媒5の機械的強度は目開きが5mmの篩いを用い、粉化度は目開きが2mmの篩いを用いて測定した。この触媒5の機械的強度および粉化度を表1に示す。触媒5を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す
<実施例4>
実施例3において、平均繊維径5μm、平均繊維長200μmのシリカ-アルミナ繊維を触媒活性成分に対して5質量%用いる代わりに、平均繊維径6μm、平均繊維長250μmのシリカ-アルミナ繊維を触媒活性成分に対して5質量%用いたこと以外は、実施例3と同様に調製し、触媒6を得た。この触媒6の担持率、および、酸素を除く触媒活性成分の金属元素組成は触媒5と同じであった。触媒6の機械的強度および粉化度を表1に示す。触媒6を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す。
実施例3において、平均繊維径5μm、平均繊維長200μmのアルミナ繊維を触媒活性成分に対して5質量%用いる代わりに、平均繊維径10μm、平均繊維長300μmのガラス繊維を触媒活性成分に対して5質量%用いたこと以外は、実施例3と同様に調製し、触媒7を得た。この触媒7の担持率、および、酸素を除く触媒活性成分の金属元素組成は触媒5と同じであった。触媒7の機械的強度および粉化度を表1に示す。触媒7を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す。
実施例3において、平均繊維径5μm、平均繊維長200μmのアルミナ繊維を触媒活性成分に対して5質量%用いる代わりに、平均繊維径20μm、平均繊維長500μmのガラス繊維を触媒活性成分に対して5質量%用いたこと以外は、実施例3と同様に調製し、触媒8を得た。この触媒8の担持率、および、酸素を除く触媒活性成分の金属元素組成は触媒5と同じであった。触媒8の機械的強度および粉化度を表1に示す。触媒8を実施例1と同様に反応器に充填し、同条件でアクロレイン酸化反応を行った。その結果を表2に示す。
Claims (4)
- モリブデンおよびバナジウムを必須成分として含有する触媒活性成分並びに無機質繊維を不活性担体に担持してなる不飽和カルボン酸製造用触媒であって、前記無機質繊維として、平均繊維径が1.0μm未満である無機質繊維と平均繊維径が1.5~7μmである無機質繊維とを少なくとも含有することを特徴とする触媒。
- 前記無機質繊維の全含有量が、前記触媒活性成分に対して0.5~30質量%である請求項1に記載の触媒。
- 前記触媒活性成分が、下記一般式(1)
Mo12VaAbBcCdDeOx (1)
(ここで、Moはモリブデン、Vはバナジウム、Aはタングステンおよびニオブからなる群から選ばれる少なくとも1種の元素、Bはクロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛およびビスマスから選ばれる少なくとも1種の元素、Cはアンチモン、スズ、テルルおよびリンから選ばれる少なくとも1種の元素、Dはシリコン、アルミニウム、チタン、セリウムおよびジルコニウムから選ばれる少なくとも1種の元素、そしてOは酸素であり、a、b、c、d、eおよびxはそれぞれV、A、B、C、DおよびOの原子比を表し、0<a≦14、0≦b≦12、0≦c≦6、0≦d≦6および0≦e≦50であり、xは各元素の酸化状態によって定まる数値である。)
で表される複合酸化物である請求項1または2に記載の触媒。 - 不飽和アルデヒドまたは飽和炭化水素を分子状酸素の存在下で接触気相酸化して不飽和カルボン酸を製造するにあたり、請求項1~3のいずれか1項に記載の触媒を用いることからなる方法。
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JP2016505377A (ja) * | 2013-05-24 | 2016-02-25 | エルジー・ケム・リミテッド | アクロレインおよびアクリル酸製造用触媒とその製造方法 |
JP2018153777A (ja) * | 2017-03-21 | 2018-10-04 | 株式会社日本触媒 | アクリル酸製造用触媒ならびに該触媒を用いたアクリル酸の製造方法 |
WO2023063349A1 (ja) | 2021-10-14 | 2023-04-20 | 日本化薬株式会社 | 不飽和カルボン酸製造用触媒およびその製造方法、並びに不飽和カルボン酸の製造方法 |
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4911371B1 (ja) | 1970-10-23 | 1974-03-16 | Nippon Catalytic Chem Ind | |
JPS60150834A (ja) | 1984-01-17 | 1985-08-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | メタクリル酸合成用触媒の製造法 |
JPS6485139A (en) | 1987-06-05 | 1989-03-30 | Nippon Catalytic Chem Ind | Catalyst for oxidation of acrolein and manufacture thereof of excellent reproducibility |
JPH07251075A (ja) | 1994-03-15 | 1995-10-03 | Mitsubishi Rayon Co Ltd | 不飽和カルボン酸合成用触媒及びそれを用いた不飽和カルボン酸の製造方法 |
JPH08299797A (ja) | 1995-03-03 | 1996-11-19 | Nippon Kayaku Co Ltd | 触媒及びその製造方法 |
JPH0952053A (ja) * | 1995-08-17 | 1997-02-25 | Sumitomo Chem Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒成形体の製造方法 |
JPH09241209A (ja) | 1996-03-06 | 1997-09-16 | Nippon Shokubai Co Ltd | アクリル酸の製造方法 |
JP2003171340A (ja) | 2001-12-06 | 2003-06-20 | Mitsubishi Chemicals Corp | アクリル酸の製造方法 |
JP2004136267A (ja) | 2002-08-20 | 2004-05-13 | Nippon Shokubai Co Ltd | 触媒の製造方法 |
JP2004243213A (ja) | 2003-02-13 | 2004-09-02 | Nippon Shokubai Co Ltd | アクリル酸製造用触媒およびアクリル酸の製造方法 |
JP2004351297A (ja) | 2003-05-28 | 2004-12-16 | Nippon Shokubai Co Ltd | メタクリル酸製造用触媒、その製造方法およびメタクリル酸の製造方法 |
JP2008528683A (ja) | 2005-02-01 | 2008-07-31 | エルジー・ケム・リミテッド | 不飽和脂肪酸の製造法 |
JP2010201401A (ja) * | 2009-03-06 | 2010-09-16 | Sumitomo Chemical Co Ltd | 押出触媒成形体の製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3892244B2 (ja) * | 2001-03-21 | 2007-03-14 | 株式会社日本触媒 | 不飽和アルデヒドおよび不飽和カルボン酸製造用触媒の製造方法 |
FR2833015B1 (fr) | 2001-11-30 | 2005-01-14 | Rhodia Eng Plastics Srl | Compositions thermoplastiques a proprietes mecaniques ameliorees |
JP3908118B2 (ja) * | 2002-08-08 | 2007-04-25 | 株式会社日本触媒 | アクリル酸の製造方法 |
EP1852406A3 (en) * | 2006-05-01 | 2008-08-06 | Ibiden Co., Ltd. | honeycomb structured body, method for manufacturing honeycomb structured body, honeycomb filter and method for manufacturing honeycomb filter |
WO2008129670A1 (ja) | 2007-04-17 | 2008-10-30 | Ibiden Co., Ltd. | 触媒担持ハニカムおよびその製造方法 |
US20090263303A1 (en) * | 2007-10-16 | 2009-10-22 | Aspen Products Group, Inc. | Purification Device and Method for Purifying a Fluid Stream |
-
2011
- 2011-09-26 JP JP2012546725A patent/JP5628936B2/ja active Active
- 2011-09-26 CN CN201180058222.3A patent/CN103228356B/zh active Active
- 2011-09-26 US US13/990,513 patent/US8940658B2/en active Active
- 2011-09-26 WO PCT/JP2011/071804 patent/WO2012073584A1/ja active Application Filing
- 2011-09-26 EP EP11844503.0A patent/EP2647429B1/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4911371B1 (ja) | 1970-10-23 | 1974-03-16 | Nippon Catalytic Chem Ind | |
JPS60150834A (ja) | 1984-01-17 | 1985-08-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | メタクリル酸合成用触媒の製造法 |
JPS6485139A (en) | 1987-06-05 | 1989-03-30 | Nippon Catalytic Chem Ind | Catalyst for oxidation of acrolein and manufacture thereof of excellent reproducibility |
JPH07251075A (ja) | 1994-03-15 | 1995-10-03 | Mitsubishi Rayon Co Ltd | 不飽和カルボン酸合成用触媒及びそれを用いた不飽和カルボン酸の製造方法 |
JPH08299797A (ja) | 1995-03-03 | 1996-11-19 | Nippon Kayaku Co Ltd | 触媒及びその製造方法 |
JPH0952053A (ja) * | 1995-08-17 | 1997-02-25 | Sumitomo Chem Co Ltd | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒成形体の製造方法 |
JPH09241209A (ja) | 1996-03-06 | 1997-09-16 | Nippon Shokubai Co Ltd | アクリル酸の製造方法 |
JP2003171340A (ja) | 2001-12-06 | 2003-06-20 | Mitsubishi Chemicals Corp | アクリル酸の製造方法 |
JP2004136267A (ja) | 2002-08-20 | 2004-05-13 | Nippon Shokubai Co Ltd | 触媒の製造方法 |
JP2004243213A (ja) | 2003-02-13 | 2004-09-02 | Nippon Shokubai Co Ltd | アクリル酸製造用触媒およびアクリル酸の製造方法 |
JP2004351297A (ja) | 2003-05-28 | 2004-12-16 | Nippon Shokubai Co Ltd | メタクリル酸製造用触媒、その製造方法およびメタクリル酸の製造方法 |
JP2008528683A (ja) | 2005-02-01 | 2008-07-31 | エルジー・ケム・リミテッド | 不飽和脂肪酸の製造法 |
JP2010201401A (ja) * | 2009-03-06 | 2010-09-16 | Sumitomo Chemical Co Ltd | 押出触媒成形体の製造方法 |
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JP2016505377A (ja) * | 2013-05-24 | 2016-02-25 | エルジー・ケム・リミテッド | アクロレインおよびアクリル酸製造用触媒とその製造方法 |
US10857525B2 (en) | 2013-05-24 | 2020-12-08 | Lg Chem, Ltd. | Catalyst for preparing acrolein and acrylic acid, and preparation method thereof |
JP2018153777A (ja) * | 2017-03-21 | 2018-10-04 | 株式会社日本触媒 | アクリル酸製造用触媒ならびに該触媒を用いたアクリル酸の製造方法 |
WO2023063349A1 (ja) | 2021-10-14 | 2023-04-20 | 日本化薬株式会社 | 不飽和カルボン酸製造用触媒およびその製造方法、並びに不飽和カルボン酸の製造方法 |
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CN103228356B (zh) | 2015-09-23 |
US8940658B2 (en) | 2015-01-27 |
CN103228356A (zh) | 2013-07-31 |
JPWO2012073584A1 (ja) | 2014-05-19 |
EP2647429A4 (en) | 2014-08-13 |
EP2647429A1 (en) | 2013-10-09 |
JP5628936B2 (ja) | 2014-11-19 |
US20130253223A1 (en) | 2013-09-26 |
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