WO2016152964A1 - 触媒の製造方法、及び不飽和ニトリルの製造方法 - Google Patents
触媒の製造方法、及び不飽和ニトリルの製造方法 Download PDFInfo
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- WO2016152964A1 WO2016152964A1 PCT/JP2016/059342 JP2016059342W WO2016152964A1 WO 2016152964 A1 WO2016152964 A1 WO 2016152964A1 JP 2016059342 W JP2016059342 W JP 2016059342W WO 2016152964 A1 WO2016152964 A1 WO 2016152964A1
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- WIPO (PCT)
- Prior art keywords
- composite oxide
- catalyst
- drying
- producing
- impregnation
- Prior art date
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/30—Tungsten
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/07—Mononitriles
- C07C255/08—Acrylonitrile; Methacrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a method for producing a catalyst and a method for producing an unsaturated nitrile.
- Patent Document 1 discloses a technique of immersing tungsten and manganese in a Mo—V—Sb—Nb catalyst.
- Patent Document 2 discloses Mo—V—Sb / Te-based catalysts such as tungsten, molybdenum, chromium, zirconium, titanium, niobium, tantalum, vanadium, bismuth, tellurium, palladium, cobalt, nickel, iron, phosphorus, and rare earth elements.
- Patent Document 3 discloses a technique of immersing a solution containing Mo—V—Sb—Nb—W catalyst and tungsten.
- Patent No. 5190994 Japanese Patent No. 3769866 International publication 2011/142178
- the amount of catalyst used for the reaction needs to be at least several hundred kg. Since the amount of the catalyst may be more than several hundred tons, it is necessary to produce a large amount of the catalyst.
- the present invention is a method for producing a catalyst for use in a gas phase catalytic ammoxidation reaction of propane, which can obtain an unsaturated nitrile from propane in a high yield, and can produce a catalyst in a large amount.
- the purpose is to provide.
- the present inventors have found that a specific blending step, a specific first drying step, a specific firing step, a specific impregnation step, and a specific The present invention was completed by finding that it is possible to produce a large amount of a catalyst capable of obtaining an unsaturated nitrile from propane in a high yield by using a method for producing a catalyst having a second drying step. .
- a method for producing a catalyst for use in a gas phase catalytic ammoxidation reaction of propane comprising: A preparation step of dissolving or dispersing the raw material to obtain a raw material preparation liquid; A first drying step of drying the raw material preparation liquid to obtain a dried body; A firing step of firing the dried body to obtain a composite oxide represented by the following formula (1);
- the composite oxide is impregnated with a solution containing at least one specific element selected from the group consisting of tungsten, molybdenum, tellurium, niobium, vanadium, boron, bismuth, manganese, iron, antimony, phosphorus, and rare earth elements, and after the impregnation
- a second drying step of drying the impregnated composite oxide At least one of the impregnation step and the second drying step is performed by stirring the composite oxide or the composite oxide after impregnation while stirring at a stirring power
- a method for producing a catalyst which is a step of impregnating or drying an object.
- Mo 1 V a Nb b A c X d Z e O n (1)
- A represents at least one element selected from the group consisting of Sb and Te
- X represents at least one element selected from the group consisting of W, Bi, Mn
- Z represents at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba.
- A, b, c, d, e, and n are Mo1.
- n is a value determined by the valence of the constituent elements of the composite oxide.
- Pv (kW / m 3 ) P (kW) / V (m 3 ) (2)
- Pv represents the stirring power (kW / m 3 ) per unit complex oxide volume
- P represents the amount of electric power (kW) generated during stirring
- V is charged into the stirring device.
- the volume (m 3 ) of the composite oxide is shown.Pv is 0.001 ⁇ Pv ⁇ 300.)
- the method for producing a catalyst according to [1] wherein the composite oxide is dried at a drying rate of 0.5 mass% / hr or more and 20 mass% / hr or less while flowing.
- an element ratio of the specific element to molybdenum in the composite oxide is 0.0001 or more and 0.50 or less.
- [4] The method for producing a catalyst according to any one of [1] to [3], wherein in the second drying step, the pressure in the apparatus is 20 kPa to 110 kPa in absolute pressure.
- [5] The method for producing a catalyst according to any one of [1] to [4], wherein in the second drying step, the drying time is 0.5 hours or more and 50 hours or less.
- [6] The method for producing a catalyst according to any one of [1] to [5], wherein in the second drying step, the temperature of the composite oxide is 30 ° C. or higher and 650 ° C. or lower.
- the method for producing a catalyst according to the present invention it is possible to produce a large amount of a catalyst capable of obtaining an unsaturated nitrile from propane in a high yield.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with various modifications within the scope of the gist.
- the method for producing a catalyst of this embodiment is a method for producing a catalyst used in a gas phase catalytic ammoxidation reaction of propane, wherein a raw material is dissolved or dispersed to obtain a raw material preparation liquid (hereinafter referred to as “step (1)”.
- a first drying step (hereinafter also referred to as” step (2) ") to dry the raw material preparation liquid to obtain a dried body, and the dried body is baked, and the following formula ( 1), a firing step (hereinafter, also referred to as “step (3)”) for obtaining the composite oxide, and the composite oxide is made of tungsten, molybdenum, tellurium, niobium, vanadium, boron, bismuth, manganese, Impregnation step (hereinafter referred to as “impregnating liquid”) obtained by impregnating a solution containing at least one specific element selected from the group consisting of iron, antimony, phosphorus and rare earth elements (hereinafter also simply referred to as “impregnation liquid”).
- step (5) drying the composite oxide after the impregnation has a second drying step (hereinafter, "step (5)" and also referred to.), The.
- step (5) drying the composite oxide after the impregnation has a second drying step (hereinafter, "step (5)" and also referred to.), The.
- at least one of the impregnation step and the second drying step is performed while stirring with the stirring power per unit composite oxide volume obtained from the following formula (2), while the composite oxide or after the impregnation
- step (5) second drying step
- the “raw material” is not particularly limited as long as it is a compound containing a constituent element of the catalyst. Specifically, the compounds described later can be used.
- A represents at least one element selected from the group consisting of Sb and Te
- X represents at least one element selected from the group consisting of W, Bi, Mn, and Ti
- Z represents at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba.
- n a number determined by the valence of the constituent elements of the composite oxide.
- Pv (kW / m 3 ) P (kW) / V (m 3 ) (2)
- Pv represents the stirring power per unit complex oxide volume (kW / m 3 )
- P represents the amount of electric power (kW) generated during stirring
- V is charged into the stirring device.
- the volume (m 3 ) of the composite oxide is shown. P is 0.001 ⁇ Pv ⁇ 300.
- a indicating the element ratio of V per Mo element is 0.05 ⁇ a ⁇ 1.00, preferably 0.075 ⁇ a ⁇ 0.70, and 0.10 ⁇ It is more preferable that a ⁇ 0.40.
- b indicating the elemental ratio of Nb per Mo element is 0.01 ⁇ b ⁇ 1.00, preferably 0.02 ⁇ b ⁇ 0.70, and 0.03 ⁇ b ⁇ 0. More preferably, it is 40. By being in the above range, more appropriate propane activity can be obtained, and the decomposition of acrylonitrile is further suppressed.
- c representing the element ratio of A per Mo element is 0.01 ⁇ c ⁇ 1.00, preferably 0.03 ⁇ c ⁇ 0.80, and 0.05 ⁇ c ⁇ 0. More preferably, it is 50. By being in the above range, the ammoxidation reaction is more likely to proceed.
- a / c indicating the element ratio of V and A is preferably 0.50 ⁇ (a / c) ⁇ 2.00, and 0.60 ⁇ (a / c) ⁇ 1.80. It is more preferable that 0.70 ⁇ (a / c) ⁇ 1.60. It exists in the tendency which suppresses decomposition
- A represents at least one element selected from the group consisting of Sb and Te.
- d indicating the element ratio of X per Mo1 element is 0.00 ⁇ d ⁇ 1.00, preferably 0.001 ⁇ d ⁇ 0.50, and 0.003 ⁇ d ⁇ 0.40 is more preferable, and 0.005 ⁇ d ⁇ 0.30 is still more preferable.
- X represents at least one element selected from the group consisting of W, Bi, Mn, and Ti. From the viewpoint of industrial long-term use, X preferably represents an element of W, Bi, or Mn. Since there exists a tendency which suppresses decomposition
- e indicating the element ratio of Z per Mo element is 0.00 ⁇ e ⁇ 1.00, preferably 0.0001 ⁇ e ⁇ 0.50, and 0.0005 ⁇ More preferably, e ⁇ 0.30.
- Z represents at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba.
- the carrier on which the catalyst of this embodiment is supported preferably contains silica.
- the catalyst When the catalyst is supported by a support containing silica, the catalyst tends to have high mechanical strength, and thus can be suitably used for a gas phase catalytic ammoxidation reaction using a fluidized bed reactor described later.
- the support contains silica
- the content of silica in the support may be 20% by mass or more and 70% by mass or less in terms of SiO 2 with respect to the total mass (100% by mass) of the catalyst and the support. Preferably, it is 25 mass% or more and 65 mass% or less, More preferably, it is 30 mass% or more and 60 mass% or less.
- the content of silica is preferably 20% by mass or more from the viewpoint of strength and prevention of pulverization.
- silica When the content of silica is 20% by mass or more, there is a tendency that stable operation can be performed when the catalyst is used industrially, the loss of the supported catalyst tends to be small, and this is economically preferable. Moreover, it is preferable that content of a silica is 70 mass% or less from a viewpoint of acquiring sufficient activity and making a required catalyst amount appropriate. In particular, when a catalyst is used in a fluidized bed reaction, when the silica content is 70% by mass or less, the specific gravity of the catalyst tends to be appropriate and a good fluid state tends to be easily formed.
- Step (1) of the present embodiment the raw material is dissolved or dispersed to obtain a raw material preparation liquid.
- the raw material used in that case is not particularly limited as long as the composite oxide having a predetermined composition obtained in step (2) described later can be obtained.
- the raw material for Mo, the raw material for V, and the Nb Examples include raw materials, A raw materials, X raw materials, and Z raw materials.
- the method of dissolving or dispersing the raw material is not limited to the following, but examples include a method of dissolving or dispersing in water and a method of dissolving or dispersing in a solvent, and a method of dissolving or dispersing in water is preferable.
- the raw material preparation liquid is, for example, a Mo raw material, a V raw material, or a Nb raw material, the ratio of which is adjusted to be the composition of the composite oxide represented by the formula (1) obtained in the step (2) described later. , Sb raw material or Te raw material, X raw material, and Z raw material.
- the Mo raw material and V raw material is not particularly limited, respectively, using ammonium heptamolybdate [(NH 4) 6 Mo 7 O 24 ⁇ 4H 2 O] and ammonium metavanadate [NH 4 VO 3] suitably be able to.
- Niobic acid is preferred.
- Niobic acid is represented by Nb 2 O 5 .nH 2 O and is also referred to as niobium hydroxide or niobium oxide hydrate.
- a mixture of niobic acid and dicarboxylic acid having a molar ratio of dicarboxylic acid to niobium (dicarboxylic acid / niobium) of 1.0 or more and 4.0 or less as a raw material of Nb.
- the dicarboxylic acid in this case is not particularly limited, but oxalic acid is preferable.
- Examples of the raw material of A include a raw material of Sb and a raw material of Te.
- the Sb raw material is not particularly limited, antimony trioxide [Sb 2 O 3] are preferred.
- the raw material of Te is not particularly limited, but telluric acid [Te (OH) 6 ] is preferable.
- the raw material for X is not particularly limited as long as it is a substance containing at least one element selected from the group consisting of W, Te, Bi, and Mn. Compounds containing these elements, and metals of these elements are used. Those solubilized with an appropriate reagent can be used. Examples of the compound containing these elements include ammonium salts, nitrates, carboxylates, ammonium carboxylates, peroxocarboxylates, ammonium peroxocarboxylates, ammonium halides, halides containing these elements, Examples include acetylacetonate and alkoxide. Among these, the X raw material is preferably a water-soluble raw material such as nitrate or carboxylate containing these elements, and more preferably ammonium metatungstate.
- the raw material of Z is not particularly limited as long as it is a substance containing at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba, and a compound containing these elements , And those obtained by solubilizing the metals of these elements with an appropriate reagent can be used.
- the compound containing these elements include nitrates (for example, cerium nitrate), carboxylates, carboxylate ammonium salts, peroxocarboxylate salts, ammonium peroxocarboxylate salts, ammonium halide salts containing these elements, Halides, acetylacetonates and alkoxides are mentioned.
- water-soluble raw materials such as nitrates and carboxylates containing these elements are preferable.
- the raw material for silica contained in the carrier is not particularly limited, and silica sol and / or powdered silica can be used for part or all of the silica raw material.
- the powder silica is preferably produced by a high heat method. Powdered silica can be easily added to and mixed with the slurry by being dispersed in water in advance.
- the dispersion method is not particularly limited, and a general homogenizer, homomixer, ultrasonic vibrator, or the like can be dispersed alone or in combination.
- Step (2) First drying step
- the raw material preparation liquid obtained in step (1) described above is dried to obtain a dried body.
- a dried body that becomes a catalyst precursor is obtained.
- the drying method can be performed by a known method, for example, spray drying or evaporation to dryness.
- spray drying it is preferable to obtain a microspherical dry body from the viewpoint of obtaining a favorable fluidity in the reactor.
- spray drying it is preferable to employ spray drying as a drying method.
- the atomization in the spray drying may be any of a centrifugal method, a two-fluid nozzle method, or a high-pressure nozzle method.
- the drying heat source used for spray drying include air heated by steam, an electric heater, or the like.
- the inlet temperature of the dryer of the apparatus used for spray drying is to make the composite oxide particle shape and / or strength obtained in the step (3) described below preferable, and to improve the performance of the obtained composite oxide, etc. From the viewpoint, 150 ° C. or higher and 300 ° C. or lower is preferable.
- the outlet temperature of the dryer is preferably 100 ° C. or higher and 160 ° C. or lower.
- the spraying speed, the feed rate of the raw material mixture, the rotation speed of the atomizer when using the centrifugal method, etc. are adjusted according to the size of the device and the particle size of the dry product obtained is in the preferred range. do it.
- the average particle diameter of the dried product is preferably 5.0 ⁇ m or more and 200 ⁇ m or less, and more preferably 10 ⁇ m or more and 150 ⁇ m or less.
- the average particle size of the dried product was determined by measuring the particle size distribution according to JIS R 1629-1997 “Method for measuring particle size distribution of fine ceramic raw materials by laser diffraction / scattering method” and averaging on a volume basis. It is.
- a part of the dried body is calcined in air at 400 ° C. for 1 hour, and the obtained particles are subjected to a laser diffraction / scattering particle size distribution measuring device (trade name “LS230” manufactured by BECKMAN COULTER). Measured.
- the average particle size is measured after a part of the dried product is “baked in air at 400 ° C. for 1 hour” in order to prevent the dried product from being dissolved in water. That is, “calcination in air at 400 ° C. for 1 hour” is exclusively for measurement, and is not related to the later-described firing step. It may be considered that the particle diameter does not substantially change before and after the firing.
- the measurement of the average particle size is carried out according to a manual attached to a laser diffraction scattering method particle size distribution measuring device (trade name “LS230” manufactured by BECKMAN COULTER).
- the procedure is as follows. First, after background measurement (RunSpeed 60), 0.2 g of particles are weighed into a screw tube of an appropriate size, and 10 cc of water is added. The screw tube is covered (sealed) and shaken well to disperse the particles in water. An ultrasonic wave of 300 W is applied by the apparatus, and the screw tube is sufficiently shaken again.
- the particles dispersed in water are injected into the apparatus main body using a dropper so as to have an appropriate concentration (concentration 10, PIDS60).
- concentration 10, PIDS60 concentration 10, PIDS60.
- concentration display is stabilized, the application of ultrasonic waves is stopped, and after standing for 10 seconds, measurement is started (measurement time 90 seconds).
- the median diameter value of the measurement result is defined as the average particle diameter.
- the catalyst precursor deposition preventing apparatus such as a vibrator for giving vibration to the spray drying apparatus and an air knocker for giving an impact. It is also preferable that spray drying is temporarily stopped at an appropriate frequency and the inside of the apparatus is washed with water or the like. The measurement of the spectrum is preferably performed immediately after the step (2) where unintended heating is likely to occur.
- the operating conditions of the air knocker installed in the drying device can be arbitrarily adjusted according to the size of the device, the wall thickness, or the degree of peeling of the deposits.
- Examples of operating conditions include air knocker impact strength, impact frequency, increase / decrease in the number of air knockers installed, and change of installation position.
- the impact strength of the air knocker is preferably so strong that the wall surface and / or other drying device parts are not deformed or broken even during long-term operation.
- the hitting frequency is preferably once or more per minute, and more preferably once or more per 10 seconds.
- the number and position of air knockers installed increase the number of parts where severe adhesion is observed by internal observation after long-term operation, or move the knocker of the part with little adhesion to the part with strong adhesion. Etc. are preferred.
- Step (3) of this embodiment is a step of firing the dried body obtained in step (2) to obtain a composite oxide represented by the following (1).
- Mo 1 V a Nb b A c X d Z e O n (1)
- A represents at least one element selected from the group consisting of Sb and Te
- X represents at least one element selected from the group consisting of W, Bi, Mn, and Ti
- Z represents at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba.
- n indicates element ratios of each element per Mo element, and 0.01 ⁇ a ⁇ 1.00, 0.01 ⁇ b ⁇ 1.00, 0.01 ⁇ c ⁇ 1.00, 0.00 ⁇ d ⁇ 1.00, 0.00 ⁇ e ⁇ 1.00, and n is a number determined by the valence of the constituent elements of the composite oxide.
- a rotary furnace (rotary kiln) can be used as an apparatus for baking (hereinafter, also referred to as “baking device”).
- the shape of the calciner is not particularly limited, but a tubular shape (firing tube) is preferable from the viewpoint of continuous firing, and a cylindrical shape is particularly preferable.
- the heating method for heating the calciner is preferably an external heating type from the viewpoint of easy adjustment of the calcining temperature so as to have a preferable temperature rising pattern, and an electric furnace can be suitably used.
- the size and material of the firing tube an appropriate one can be selected according to the firing conditions and the firing amount.
- the inner diameter of the firing tube is preferably 70 mm or more and 2000 mm or less, more preferably from the viewpoint of ensuring that the firing temperature distribution in the composite oxide layer is not uneven, and adjusting the firing time and production amount to appropriate values. It is 100 mm or more and 1700 mm or less. Also, the length of the firing tube is such that the residence time of the dried body in the firing tube, that is, the distribution of the firing time is made as narrow as possible, distortion of the firing tube is prevented, the firing time and the production amount are adjusted to appropriate values, etc. From the viewpoint, it is preferably 200 mm or more and 10,000 mm or less, more preferably 800 mm or more and 8000 mm or less.
- the thickness is preferably 2 mm or more, more preferably 4 mm or more, from the viewpoint of having a sufficient thickness that does not damage the fired tube. Further, from the viewpoint that the impact is sufficiently transmitted to the inside of the firing tube, the thickness is preferably 100 mm or less, more preferably 50 mm or less.
- the firing tube is made of powder. It is preferable to have an inclination with respect to the flowing direction and to make the height of the outlet lower than the height of the powder inlet. From the same viewpoint, the inclination angle ⁇ from the horizontal is preferably 0 ° ⁇ ⁇ 80 °, and more preferably 1 ° ⁇ ⁇ ⁇ 40 °.
- the material of the calciner is not particularly limited as long as it is preferably heat-resistant and has a strength that does not break due to impact.
- SUS can be suitably used.
- a weir plate having a hole for the passage of powder in the center is provided perpendicular (or substantially perpendicular) to the flow of the powder, and the firing tube is divided into two or more areas. You can also. By installing the weir plate, it becomes easy to ensure the residence time of the powder in the firing tube.
- the number of weir plates may be one or more.
- the material of the barrier plate is preferably a metal, and the same material as the firing tube can be suitably used. The height of the weir plate can be adjusted according to the residence time to be secured.
- the height of the weir plate is preferably 5.0 mm or more and 50 mm or less, more preferably 10 mm. It is 40 mm or less and more preferably 13 mm or more and 35 mm or less.
- the thickness of the weir plate is not particularly limited and is preferably adjusted according to the size of the firing tube.
- the thickness of the barrier plate is preferably 0.3 mm or more and 30 mm or less, more preferably 0.5 mm or more and 15 mm or less.
- the rotation speed of the firing tube is preferably 0.1 rpm to 30 rpm, more preferably 0.5 rpm to 20 rpm, and still more preferably 1.0 rpm to 10 rpm.
- the heating temperature of the dried body is started from a temperature lower than 400 ° C., It is preferable to raise the temperature continuously or stepwise to a temperature in the range of 550 ° C to 800 ° C.
- the firing atmosphere may be an air atmosphere or an air flow, but from the viewpoint of easy adjustment of the composite oxide to a preferred redox state, at least a part of the dried body is substantially free of oxygen such as nitrogen. It is preferable to calcinate while circulating an inert gas.
- the supply amount of the inert gas is preferably 50 NL / hr or more, more preferably 50 NL / hr or more and 5000 NL / hr or less, per 1 kg of the dried body from the viewpoint of adjusting to a preferable redox state. More preferably, it is 50 NL / hr or more and 3000 NL / hr.
- N liter means a volume (L) measured at standard temperature and pressure conditions, that is, at 0 ° C. and 1 atm.
- the supply amount of the inert gas is preferably 50 NL / hr or more, more preferably 50 NL / hr or more and 5000 N liter / hr from the viewpoint of adjusting to a preferable redox state.
- it is more preferably 50 NL / hr or more and 3000 N liter / hr or less.
- the contact form between the inert gas and the dry body may be a countercurrent contact or a cocurrent contact, but in consideration of the gas components generated from the dry body and air that can be mixed in a trace amount in the dry body, the countercurrent contact is considered. Is preferred.
- the dried product may contain ammonium, organic acid, inorganic acid, etc. in addition to moisture.
- the constituent elements of the composite oxide contained therein are reduced.
- the constituent element of the composite oxide in the dried product has almost the highest oxidation number, in order to bring the reduction rate of the composite oxide into a desired range, only the reduction needs to be performed in the step (3). It is simple.
- the composite oxide obtained in the step (3) is obtained from the group consisting of tungsten, molybdenum, tellurium, niobium, vanadium, boron, bismuth, manganese, iron, antimony, phosphorus, and rare earth elements.
- This is a step of impregnating a solution (impregnation liquid) containing at least one specific element selected from the above to obtain a composite oxide after impregnation (hereinafter also referred to as “impregnated composite oxide”).
- step (4) and the step (5) to be described later is performed while stirring with the stirring power per unit complex oxide volume obtained from the following formula (2), or the above complex oxide or impregnated complex oxidation.
- This is a step of impregnating or drying an object. That is, when the step (5) is not a step that satisfies the requirement, the step (4) is a step that satisfies the requirement.
- filling the said requirement may be sufficient as all of a process (4) and a process (5).
- Pv (kW / m 3 ) P (kW) / V (m 3 ) (2)
- Pv represents the stirring power per unit complex oxide volume (kW / m 3 )
- P represents the amount of electric power (kW) generated during stirring
- V is charged into the stirring device.
- the volume (m 3 ) of the composite oxide is shown.
- Pv is 0.001 ⁇ Pv ⁇ 300.
- the impregnation liquid in the step (4) can be prepared from a specific raw material.
- the impregnating solution is a solution containing at least one specific element selected from the group consisting of tungsten, molybdenum, tellurium, niobium, vanadium, boron, bismuth, manganese, iron, antimony, phosphorus, and rare earth elements. These specific elements are preferably tungsten, niobium, molybdenum, bismuth, manganese, tellurium; rare earth elements cerium and yttrium, and more preferably tungsten, molybdenum, antimony, tellurium, and cerium.
- the type of the specific element is not particularly limited, and it is preferable to appropriately select one or more specific elements.
- the impregnating liquid can be prepared by mixing the following raw materials.
- Tungsten raw materials are not limited to the following, but include, for example, tungsten ammonium salt, nitrate salt, carboxylate salt, carboxylate ammonium salt, peroxocarboxylate salt, peroxocarboxylate ammonium salt, ammonium halide salt, halide Powder raw materials such as acetylacetonate, alkoxide, triphenylated product, polyoxometalate, polyoxometalate ammonium salt, tungsten oxide, ammonium paratungstate, silicotungstic acid, silicotungsto molybdic acid, caivanadotungstic acid, meta Examples thereof include an aqueous solution of ammonium tungstate and a tungsten oxide sol.
- molybdenum raw material examples include, but are not limited to, ammonium heptamolybdate, molybdenum trioxide, phosphomolybdic acid, silicomolybdic acid, and molybdenum pentachloride.
- tellurium raw material examples include, but are not limited to, oxides, hydrides, halides, sulfides, carboxylates, and various complex salts.
- Niobium raw materials include, but are not limited to, niobic acid, niobium inorganic acid salts, and niobium organic acid salts.
- the vanadium raw material is not limited to the following, but examples include ammonium metavanadate, vanadium pentoxide, and vanadium chloride.
- Boron raw materials include, but are not limited to, oxides, sulfides, chlorides, acid salts, perchlorates, carbonates, sulfates, carboxylates, and various complex salts.
- Bismuth raw materials include, but are not limited to, oxides, nitrates, sulfates, halides, chlorides, oxyhalides, triphenylates, bismuth molybdate, and various complex salts.
- Manganese raw materials are not limited to the following, but hydrides, oxides, permanganates, sulfates, nitrates, chlorides, thiocyanates, acetates, phosphates, carbonates, halides, various Examples include complex salts.
- iron raw material examples include, but are not limited to, oxides, sulfides, chlorides, perchlorates, carbonates, sulfates, carboxylates, and various complex salts.
- Antimony raw materials include, but are not limited to, oxides, sulfides, chlorides, nitrates, perchlorates, carbonates, sulfates, carboxylates, tartrate salts, and various complex salts.
- the phosphorus raw material is not limited to the following, but includes oxides, sulfides, chlorides, nitrates, perchlorates, carbonates, sulfates, carboxylates, and various complex salts.
- rare earth materials include cerium materials and yttrium materials.
- the cerium raw material is not particularly limited, and examples thereof include oxides, sulfides, chlorides, nitrates, perchlorates, carbonates, sulfates, carboxylates, and various complex salts.
- These raw materials may be used alone, or a plurality of raw materials may be used in combination.
- an aqueous solution containing a specific element or a compound in which a compound containing a specific element is dispersed in water or a solvent can be used by adjusting the pH as necessary.
- the solvent for dispersing the compound includes water and solvents such as acetone, methanol, ethanol, etc., but water is preferable in view of ease of handling.
- the pH of the impregnating liquid is not particularly limited, but is preferably 0.5 or more and 12.0 or less, more preferably 2.0 or more and 7.0 or less, and 3.0 or more. More preferably, it is 6.0 or less.
- the pH adjuster is not particularly limited, but nitric acid is preferable when adjusting to acidic, and ammonia is preferable when adjusting neutral or basic.
- the content of the specific element in the impregnation liquid is preferably 0.01 mol / kg or more and 2.0 mol / kg or less, more preferably 0.05 mol / kg or more and 1.5 mol / kg or less with respect to the mass of the impregnation liquid, More preferably, it is 0.1 mol / kg or more and 1.0 mol / kg or less.
- the content is 0.01 mol / kg or more, the amount is sufficient to modify the composite oxide, and when the content is 2.0 mol / kg or less, ion exchange due to an excessive specific element is suppressed. There is a tendency to be able to.
- the amount of the impregnation liquid is preferably 0.1 times or more and 3.0 times or less, and 0.3 times or more and 2.5 times or less with respect to the pore volume of the composite oxide. More preferably, it is 0.5 times or more and 2.0 times or less.
- the amount of the impregnating liquid is 0.1 times or more, the specific element tends to be uniformly dispersed in the composite oxide, and when the amount of the impregnating liquid is 3.0 times or less, The metal element in the composite oxide tends to be suppressed from being eluted.
- the amount of the impregnating liquid is preferably 2.0 L or more and 60 L or less, and 6.0 L or more and 50 L or less. More preferably, it is 10 L or more and 40 L or less.
- a gas adsorption method, a mercury intrusion method, or the like As a method for measuring the pore distribution of the catalyst, a gas adsorption method, a mercury intrusion method, or the like is known, but the value varies depending on the measurement method.
- the value of the pore distribution of the catalyst in the present embodiment is obtained by a mercury intrusion method (using Pore Master GT manufactured by QUANTACHROME INSTRUMENTS).
- the mercury intrusion method is a method in which mercury is injected into catalyst particles and the distribution of pore diameter is measured from the relationship between the pressure and the amount of intrusion at this time. An integrated curve of the pore volume with respect to the pore diameter calculated assuming the shape is given.
- a value obtained by first-ordering the pore volume integrated curve with respect to the pore diameter and plotting it against the corresponding pore diameter is usually called a pore distribution.
- a sample (catalyst) of 0.4 to 0.6 g is put in a dilatometer (dilatometer), degassed to 6.67 Pa or less with a vacuum pump, then mercury is injected, and then the dilatometer is placed in an autoclave. It is loaded, the pressure of mercury is gradually increased from normal pressure to 413 MPa, the decrease in mercury liquid level is traced, and the pore distribution is measured from the change in pressure and mercury liquid level (injection amount of mercury into catalyst pores). is there.
- the liquid temperature of the impregnating liquid is not particularly limited, but is preferably 50 ° C. or lower, and more preferably 40 ° C. or lower. By setting the temperature to 50 ° C. or lower, the solvent can be prevented from evaporating during the impregnation, and the dispersibility of the specific element tends to be improved.
- the method of stirring the composite oxide and the impregnating solution is not particularly limited, but the method of dispersing the impregnating solution by adding dropwise to the center of the composite oxide while stirring the composite oxide, and composite oxidation
- the impregnating solution is sprayed and added to the whole without stirring the material, and from the viewpoint of uniformly dispersing the impregnating solution in the composite oxide, the impregnating solution is stirred while stirring the composite oxide.
- a method of spraying the whole is preferred.
- Another method of stirring is to add a small amount of the complex oxide to the impregnating solution, but this reduces uneven dispersion of the impregnating solution in the complex oxide and prevents the complex oxide from adhering to the inner wall of the stirring device. From the viewpoint, a method of adding an impregnating solution to the composite oxide and mixing them is preferable.
- a device for stirring the composite oxide and the impregnating liquid for example, a device in which a rotating shaft and a blade rotating in association therewith are provided in the lower or upper portion of the tank, and the blade is rotated and stirred by a swirling flow, the entire tank
- the apparatus which stirs the whole inside of a tank by rotating is mentioned.
- the former is preferable from the viewpoint that the dispersibility of the impregnating liquid in the composite oxide is good.
- the former may be appropriately selected depending on the wear resistance of the composite oxide, the specific gravity, the specific gravity of the impregnating liquid, and the like.
- the rotor blade is not particularly limited as long as it can uniformly stir the composite oxide, but a propeller type or paddle type can be used.
- the material of the stirring device is not particularly limited, and for example, SUS, glass, ceramic, plastic such as Teflon (registered trademark), and those made of composite materials thereof can be used.
- Composite oxide and the impregnation solution and the stirring power per unit composite oxide volume in mixing (Pv) is, 0.001kW / m 3 or more, preferably 300 kW / m 3 or less, more preferably 0. 005kW / m 3 or more 280kW / m 3 or less, more preferably not more than 0.01 kW / m 3 or more 260kW / m 3. That is, also in the step (4), the stirring power is preferably the stirring power per unit complex oxide volume obtained from the formula (2) described later. Pv can be obtained by dividing the amount of power used (P) of the motor used for stirring by the volume of the complex oxide to be impregnated.
- the amount of power is kept constant and the capacity of the composite oxide is gradually increased.
- the load on the rotor blades increases as the composite oxide capacity increases. Since the amount of electric power is constant despite the increase in load, the rotational speed of the rotor blades decreases as the load increases, and the degree of mixing of the complex oxide decreases.
- the capacity of the composite oxide is gradually reduced in a state where the amount of power is constant, the load on the rotor blades decreases.
- the amount of electric power is adjusted according to the volume of the composite oxide to be within a certain range, so that the mixed state of the composite oxide and the impregnating liquid is improved and the composite oxidation is performed.
- the crack of the object itself can be suppressed.
- the volume of the composite oxide can be obtained by the following equation.
- Composite oxide volume (L) Mixed oxide mass (kg) / bulk specific gravity (kg / L)
- the industrial catalyst needs mass production, and the amount of the composite oxide mixed at a time is preferably at least 10 kg or more, more preferably 30 kg or more, and further preferably 50 kg or more.
- the amount of the composite oxide mixed at a time is preferably at least 10 kg or more, more preferably 30 kg or more, and further preferably 50 kg or more.
- problems such as cracking of the catalyst and deterioration of the dispersibility of the specific element in the composite oxide may occur.
- stirring power obtained from equation (2) above (Pv) the 0.001kW / m 3 or more, by setting the following 300 kW / m 3, prevent cracking catalyst And good dispersibility of the specific element, and a large amount of impregnated catalyst can be produced at one time.
- the catalyst may be produced on a scale exceeding 100 kg, or on a scale exceeding 500 kg or 1000 kg.
- the solvent nonuniformity at the time of impregnation can be eliminated, and the specific element can be uniformly dispersed in the composite oxide.
- the specific element tends to be thick in the portion where the solvent is thick, and the specific element tends to be thin in the portion where the solvent is thin.
- the temperature of the composite oxide is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, and further preferably 40 ° C. or lower.
- the method of adjusting the temperature of the composite oxide is not particularly limited, but the method of adjusting the temperature by making the agitator into a jacket structure and adjusting the temperature by passing cold water through the jacket, and the method of adjusting the temperature by putting room temperature air inside the agitator Is mentioned.
- the stirring time (the time from the start of mixing of the composite oxide and the impregnating liquid to the transition to drying) is preferably within 2 hours, and is preferably within 1.5 hours. More preferred. When the stirring time is within 2 hours, ion exchange between the metal element and the specific element in the composite oxide due to the presence of the composite oxide and the specific element in the liquid phase tends to be suppressed.
- Step (5) of the present embodiment is a step of drying the impregnated complex oxide obtained in step (4) (hereinafter also referred to as “impregnated complex oxide”).
- at least one of the above-described step (4) and step (5) is performed while the composite oxide or the impregnated composite oxidation is performed while stirring at the stirring power per unit composite oxide volume obtained from the following formula (2).
- This is a step of impregnating or drying an object. That is, when the step (4) is not a step that satisfies the requirement, the step (5) is a step that satisfies the requirement.
- filling the said requirement may be sufficient as all of a process (4) and a process (5).
- Pv (kW / m 3 ) P (kW) / V (m 3 ) (2)
- Pv represents the stirring power per unit complex oxide volume (kW / m 3 )
- P represents the amount of electric power (kW) generated during stirring
- V is charged into the stirring device.
- the volume (m 3 ) of the composite oxide is shown.
- Pv is 0.001 ⁇ Pv ⁇ 300.
- the catalyst obtained by drying the impregnated composite oxide obtained in the step (4) is subjected to a gas-phase catalytic ammoxidation reaction of propane, it is more preferable to react with the unsaturated nitrile than to react with the catalyst obtained without impregnation.
- the yield is high.
- the factor that increases the yield is not clear, but it is presumed as follows (however, the factor is not limited to this).
- the composite oxide is a composite that is used for the dehydrogenation reaction of propane by replacing the metal element in the composite oxide with a specific element in the impregnation liquid having a stronger oxygen binding force than the metal element. Lattice oxygen in the oxide becomes difficult to move.
- the substitution reaction between the metal element in the composite oxide and the specific element in the impregnation liquid includes substitution reaction (1) occurring during “impregnation” and substitution with molybdenum occurring during “gas phase ammoxidation reaction”. There appears to be reaction (2). Further, it is considered that the substitution reaction (2) occurring during the gas phase ammoxidation reaction contributes to the complete decomposition of propane.
- the substitution reaction (1) contributes to the improvement of the unsaturated nitrile yield, a difference in the yield of the unsaturated nitrile should be recognized from the initial stage of the reaction. For this reason, it is presumed that the substitution reaction that contributes to the yield improvement of the unsaturated nitrile does not occur at least during the impregnation but occurs during the ammoxidation reaction.
- substitution reaction (1) during the impregnation can be suppressed and the substitution reaction (2) during the ammoxidation reaction can be promoted, it can be considered that the unsaturated nitrile yield is improved. Therefore, as a control method for suppressing the substitution reaction (1) during the impregnation, for example, sufficient agitation in the step (4) and / or the step (5) is performed to suppress solvent unevenness during drying.
- a method of suppressing the presence of a specific element in the impregnating liquid partially at a high concentration and a method of controlling so that the composite oxide and the impregnating liquid do not exist in the liquid phase for a long time is preferable in the case of a large scale in which the substitution reaction (1) during impregnation is likely to occur, the dispersibility of the impregnation liquid is poor, and drying takes time.
- the apparatus for drying the impregnated composite oxide is not particularly limited. For example, after stirring with a stirrer, the temperature of the composite oxide is raised as it is, and after mixing with the stirrer, it is transferred to another drying apparatus. And then drying the composite oxide by raising the temperature of the composite oxide. Since the former can be completed from mixing to drying with one apparatus, there is an advantage that the space for installing the equipment can be reduced. The latter has the advantage that productivity can be improved because mixing and drying can be repeated in separate apparatuses, whereby stirring and drying can be repeated continuously. As a method of flowing the impregnated composite oxide when drying with a stirring device, stirring by a rotary blade is preferable, but it may be made to flow by introducing gas or rotating the entire tank.
- a drying apparatus such as a continuous kiln or a batch-type drying apparatus may be mentioned.
- a drying apparatus such as a continuous kiln has an advantage that productivity can be improved because it can be continuously dried.
- the batch type drying apparatus has an advantage of easy control.
- the material of the apparatus to be dried is not particularly limited. For example, SUS, glass, ceramic, Teflon plastic, or a composite material thereof can be used.
- the drying rate is preferably 0.5% by mass / hr or more and 20% by mass / hr or less, and more preferably 1.0% by mass / hr or more and 15% by mass / hr or less.
- the time when the operation of the apparatus is started is the start of the drying process. Further, the time when the moisture content becomes less than 1.0% by mass is regarded as the end of the drying process, and the time from the start to the end of the drying process is defined as the drying time.
- the determination method of “when the moisture content becomes less than 1.0% by mass” is not particularly limited, but as an example, sampling for measuring the moisture content is performed at least once an hour, and the moisture content is When the content is less than 1.0% by mass, the sampling time can be regarded as “the time when the moisture content is less than 1.0% by mass”. Sampling needs to be performed at least once per hour, but may be performed at arbitrary intervals within one hour.
- drying time under predetermined drying conditions is measured in advance and drying is performed under the same conditions, sampling is not necessary, and it is considered that the drying process has been completed when the previously measured time has elapsed. Also, when the moisture content becomes 0% by mass, the drying process is terminated. It should be noted that after the drying process is completed, it may be further under dry conditions.
- the drying rate is 0.5 mass% / hr or more and 20 mass% / hr or less, whereby the performance of the obtained catalyst is improved and the yield of acrylonitrile is increased. Tend to improve. Although this factor is not clear, it is guessed as follows (however, the factor is not limited to this). When the drying rate is 0.5% by mass / hr or more, the impregnation liquid and the impregnated composite oxide come into contact with each other at a temperature higher than normal temperature, and the performance as a catalyst in the impregnated composite oxide is shortened.
- the performance of the resulting catalyst tends to be improved due to the suppression of elution of the metal element from the active crystal that controls and excessive substitution with the specific element in the impregnating solution.
- the drying rate is 20% by mass / hr or less
- the impregnation liquid that has entered the pores of the impregnated composite oxide comes out on the surface of the composite oxide, and the metal element in the impregnation liquid is impregnated with the impregnation liquid. Due to suppression of non-uniform distribution on the surface of the composite oxide, the performance of the resulting catalyst tends to be improved.
- the impregnated composite oxide is dried while flowing, and thus it is obtained by suppressing unevenness in the dry state of the catalyst, which is likely to be a problem when producing a large amount of catalyst. Catalyst performance tends to improve.
- the drying speed in the range as described above is not particularly limited.
- the temperature of the composite oxide, the pressure in the apparatus hereinafter, also referred to as “tank pressure” or “internal pressure”
- the flow into the apparatus This can be realized by adjusting the drying conditions in step (5) such as the gas flow rate.
- the pressure inside the apparatus is preferably 20 kPa to 110 kPa, more preferably 30 kPa to 110 kPa, in absolute pressure.
- the pressure in the apparatus is in the above range, the drying time can be shortened, and the moisture contained in the pores is prevented from coming out on the surface of the impregnated composite oxide, and the metal element in the impregnating liquid It is inferred that there is a tendency to suppress the uneven distribution.
- the temperature of the composite oxide is preferably 30 ° C. or higher and 650 ° C. or lower, more preferably 40 ° C. or higher and 550 ° C. or lower, further preferably 50 ° C. or higher and 500 ° C. or lower, Preferably they are 60 degreeC or more and 400 degrees C or less.
- the temperature By adjusting the temperature to such a range, it tends to be able to dry quickly and without deteriorating the impregnated composite oxide.
- By setting the temperature to 30 ° C or higher there is a tendency to be able to dry quickly.
- By setting the temperature to 650 ° C or lower deterioration due to peroxidation of the impregnated composite oxide itself and damage to the catalyst due to bumping are prevented.
- the catalyst dried at the temperature exceeding 550 degreeC in order to avoid deterioration by peroxidation, it is preferable to distribute
- the method of adjusting the temperature of the composite oxide is not particularly limited.
- the apparatus used for drying has a jacket structure, and the jacket part is heated through warm water or steam, air heated inside the stirring apparatus, Or the method of heating by putting an inert gas and the method of heating by the frictional heat which generate
- a system in which warm water or steam flows with a jacket structure is preferable.
- the temperature of the composite oxide does not rise above the boiling point of water, but it is better to set the drying conditions to exceed the boiling point of water per unit time. Since the supply of heat increases, it is effective for advancing drying quickly. In addition, since the moisture content is sufficiently reduced just before the end of the drying process, the temperature of the composite oxide can rise above the boiling point of water, so the above-mentioned “temperature of the composite oxide” A more accurate numerical value can be obtained by checking just before the end.
- the temperature rise pattern is not particularly limited, and the temperature may be raised at a constant rate or at an irregular rate. Further, the temperature may be lowered in the middle or kept at a constant temperature. From the viewpoint of drying quickly without degrading the composite oxide, it is preferable to continue supplying heat until the target temperature is reached. Further, when the drying process is finished and the temperature is lowered, the temperature drop pattern is not particularly limited, but it is preferable that the temperature is continuously lowered to around room temperature (for example, 25 ° C.).
- the drying time is preferably 0.5 hours or more and 50 hours or less, more preferably 1.0 hours or more and 48 hours or less, and further preferably 2.0 hours or more and 36 hours or less. is there.
- the drying time is 0.5 hours or longer, a catalyst having a low moisture content and high performance tends to be obtained. This is because when the drying time is 0.5 hour or more, the impregnating liquid that has entered the pores of the impregnating composite oxide suddenly appears on the surface of the impregnating composite oxide, and the metal elements in the impregnating liquid are It is presumed that the performance of the obtained catalyst is improved due to suppression of uneven distribution on the surface of the impregnated composite oxide.
- the drying time in the case of drying with a continuous kiln or the like is preferably 90% by mass or more and 0.5 hours or more and 50 hours or less, more preferably 1. It is 0 hour or more and 48 hours or less, More preferably, it is 2.0 hours or more and 36 hours or less.
- the type of gas flowing into the apparatus is not particularly limited. Is preferred.
- the gas flow rate may be appropriately adjusted while checking the state inside the apparatus.
- stirring power per unit composite oxide volume obtained from (Pv) is, 0.001kW / m 3 or more, preferably 300 kW / m 3 or less, more preferably is less 0.005kW / m 3 or more 280kW / m 3, more preferably not more than 0.01 kW / m 3 or more 260kW / m 3.
- the stirring power can be the stirring power per unit complex oxide volume obtained from the formula (2).
- Pv can be obtained by dividing the amount of power (P) used by the motor drive unit used for stirring by the volume of the complex oxide to be impregnated.
- step (5) By making Pv 0.001 kW / m 3 or more, the stirring in step (5) is sufficiently performed, so that there is no solvent unevenness during drying, and a high yield of unsaturated nitrile can be obtained. It is in the tendency which can be performed, and the crack of a catalyst can be reduced because Pv is 300 kW / m ⁇ 3 > or less.
- the catalyst of this embodiment is obtained by the method for producing a catalyst of this embodiment.
- an unsaturated nitrile can be obtained from propane in a high yield.
- the solvent content of the catalyst is preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.05% by mass or more and 4.0% by mass or less, and further preferably 0.1% by mass or more and 3.0% by mass or less. It is below mass%.
- the solvent content can be determined by the weight reduction rate before and after being placed in an electric furnace at 100 ° C. for 12 hours, but is not limited to this, and any method that can measure the amount of solvent adsorbed on the catalyst may be used. .
- the same method as the abrasion resistance test can be used.
- a SUS tube with a diameter of 2 inches and a length of 1000 mm is installed vertically, a three-hole plate with three holes with a diameter of 1 mm is attached to the bottom, and 50 g of catalyst is placed on the top of the three-hole plate in the SUS tube.
- a 4 inch diameter, 1000 mm long cone was attached to the upper part of the SUS tube, and a mass filter was attached to the upper part of the cone to trap the scattered catalyst.
- the elemental ratio of the specific element to molybdenum of the composite oxide represented by the above formula (1) is preferably 00001 to 0.50.
- the element ratio of the specific element is the element ratio of the specific element impregnated and taken into the composite oxide, and is the element ratio (specific element / Mo) per element of molybdenum in the composite oxide.
- the quantification of the specific element incorporated into the composite oxide by the step (4) can be obtained from the following formula by measuring the composition of the catalyst and the composite oxide by fluorescent X-ray analysis.
- Element ratio of specific elements (specific element composition ratio in catalyst)-(specific element composition ratio in composite oxide)
- the element ratio (specific element / Mo) is preferably 0.0001 or more and 0.5 or less, more preferably 0.0005 or more and 0.3 or less, and further preferably 0.001 or more and 0.1 or less. is there.
- the element ratio (specific element / Mo) is 0.0001 or more, the composite oxide can be sufficiently modified, and the yield tends to be improved when it is subjected to an ammoxidation reaction. Further, when the element ratio (specific element / Mo) is 0.5 or less, ion exchange between an excessive specific element and a metal element in the composite oxide tends to be suppressed.
- the method for producing an unsaturated nitrile according to the present embodiment is a method for producing an unsaturated nitrile by a gas-phase catalytic ammoxidation reaction of propane, the catalyst obtained by the method for producing a catalyst according to the present embodiment, propane, , And a contacting step.
- a method for producing a corresponding unsaturated nitrile by bringing a raw material gas containing propane, ammonia and oxygen into contact with a catalyst contained in a reactor and performing a gas-phase catalytic ammoxidation reaction of propane is described. To do.
- Propane and ammonia are not limited to those having high purity, and propane containing 5.0% by volume or less of impurities such as ethane, ethylene, n-butane, isobutane; 1.0% by volume or less of impurities such as water Ammonia; industrial grade propane gas and ammonia gas can be used.
- the source gas containing oxygen is not particularly limited, and examples thereof include air, air enriched with oxygen, pure oxygen; an inert gas such as helium, argon, carbon dioxide, and nitrogen, or a gas diluted with water vapor. It is done. Among these, when used on an industrial scale, it is preferable to use air for simplicity.
- reaction format examples include a fixed bed, fluidized bed, and moving bed reaction format. From the viewpoint of heat removal from the reactor, a fluidized bed reaction format is preferable.
- the reaction temperature is not particularly limited, but is preferably 350 ° C. or higher and 500 ° C. or lower, and more preferably 380 ° C. or higher and 470 ° C. or lower.
- the reaction temperature is 350 ° C. or higher, the propane ammoxidation reaction tends to proceed at a practical rate, and when it is 500 ° C. or lower, decomposition of the target product tends to be suppressed. It is in.
- the reaction method may be a recycle type in which unreacted raw material gas is collected and re-supplied to the reactor, or a single flow method in which the raw material gas is not recycled may be used, but the preferred composition ratio of the raw material gas varies depending on the reaction method.
- the molar ratio of oxygen to propane is preferably 0.5 or more and 4.5 or less, and 1.0 or more. 4.0 or less is more preferable, and 1.5 or more and 3.5 or less is more preferable.
- the condition for keeping the conversion rate of propane low is preferable in order to increase the selectivity of the corresponding unsaturated nitrile, so the molar ratio (oxygen / propane) is 0.2. It is preferably 3.5 or less, more preferably 0.6 or more and 3.0 or less, and further preferably 1.0 or more and 2.5 or less.
- the composition ratio of the source gas can affect the outlet oxygen concentration, it is preferable to determine the composition ratio in consideration of the fact that the outlet oxygen concentration falls within a desired range in any reaction method. .
- an unsaturated nitrile can be obtained from propane in a high yield, and a catalyst having a small cracking rate can be produced in large quantities.
- AN yield (Evaluation) Yield
- AN yield (shown as “AN yield” in Table 1)
- the number of moles of AN produced was measured by measuring the gas of AN with a known concentration in advance by gas chromatography (GC) and taking a calibration curve, and then quantitatively injecting the gas produced by the ammoxidation reaction into GC. .
- the yield of AN was calculated based on the following formula from the “number of moles of AN produced” obtained by measurement. The results are shown in Table 1.
- AN yield (%) (number of moles of AN produced) / (number of moles of propane supplied) ⁇ 100
- Example 1 (Process (1): Preparation process) 2800 kg of water, ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O] 451.3 kg, ammonium metavanadate [NH 4 VO 3 ] 54.7 kg, antimony trioxide [Sb 2 O 3 ] 78 0.0 kg and 8.9 kg of cerium nitrate hexahydrate [Ce (NO 3 ) 3 .6H 2 O] were added and heated at 95 ° C. for 1 hour with stirring to obtain an aqueous raw material liquid (I).
- a niobium mixed solution was prepared by the following method. Niobic acid 229.5 kg containing 79.8% by mass as Nb 2 O 5 and oxalic acid dihydrate [H 2 C 2 O 4 .2H 2 O] 789.9 kg were mixed in 10 kg of water. The molar ratio of charged oxalic acid / niobium was 5.0, and the concentration of charged niobium was 0.50 (mol-Nb / kg-solution). This solution was heated and stirred at 95 ° C. for 2 hours to obtain a mixed solution in which niobium was dissolved. The mixture was allowed to stand and ice-cooled, and then the solid was separated by suction filtration to obtain a uniform niobium mixture. The molar ratio of oxalic acid / niobium in this niobium mixture was 2.68 according to the following analysis.
- the end point was a point where a faint pale pink color by KMnO 4 lasted for about 30 seconds or more.
- the concentration of oxalic acid was 1.592 (mol-oxalic acid / kg) as a result of calculation according to the following formula from titration. 2KMnO 4 + 3H2SO 4 + 5H 2 C 2 O 4 ⁇ K 2 SO 4 + 2MnSO 4 + 10CO 2 + 8H 2 O
- the obtained niobium mixed liquid was used as a niobium raw material liquid (B 0 ) in the preparation of the following composite oxide.
- aqueous raw material liquid (I) After cooling the obtained aqueous raw material liquid (I) to 70 ° C., 791.1 kg of silica sol containing 34.0% by mass as SiO 2 was added, and hydrogen peroxide containing 30% by mass as H 2 O 2 was added. 90.9 kg of water was added and stirring was continued at 55 ° C. for 30 minutes. Next, aqueous raw material liquid (II), 30.8 kg of 50 mass% ammonium metatungstate aqueous solution as WO 3 , and 1976.3 kg of dispersion liquid in which powder silica is dispersed in water are sequentially added to form an aqueous mixed liquid ( III) was obtained. The aqueous mixed liquid (III) was aged at 50 ° C. for 2 hours and 30 minutes after the addition of the aqueous raw material liquid (II) to obtain a slurry.
- Step (2) First drying step
- the obtained slurry was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder.
- the dryer inlet air temperature was 210 ° C and the outlet air temperature was 120 ° C. The drying operation was repeated several times.
- Impregnation process (Preparation of impregnation solution) Tungsten was selected as a specific element to be impregnated into the composite oxide. 36.9 kg of 50 mass% ammonium metatungstate aqueous solution was added to 162.9 kg of water and mixed to obtain 200 kg as an impregnation liquid. The temperature of the impregnating solution was 25 ° C. and the pH was 4.3.
- a SUS stirrer having a volume of 1500 L was used for mixing the obtained composite oxide and the impregnation liquid.
- the stirring method is a system in which the rotating blades installed in the lower stage of the apparatus are rotated to stir and mix the composite oxide and the impregnating liquid.
- the rotating blades are arranged in two upper and lower inclined paddle type blades. (Rotating blade A) (Refer to Chapter 6 “Agitation / Mixing” in Chapter 7 of the Chemical Engineering Handbook Revised Edition (Maruzen Publishing) for inclined paddles).
- a method of adjusting the temperature by passing cold water, hot water or steam through a jacket provided outside the apparatus was selected.
- the method of adding the impregnating solution was selected by spraying from the upper center of the apparatus.
- 1000 kg (capacity 1000 L) of complex oxide was put in the stirring device, the rotor blades were operated, and the rotational speed was increased until the power consumption of the drive motor for the rotor blades reached 50 kW.
- 200 kg of the impregnating solution was added for 5 minutes, and further stirred for 5 minutes.
- the temperature of the composite oxide was 20 ° C.
- Step (5): Second drying step An apparatus in which the above complex oxide and impregnation liquid were mixed was used as it was, and the power consumption of the drive motor for the rotor blade was the same as that at the time of mixing, and the complex oxide was dried to obtain an impregnation catalyst. Simultaneously with the start of drying, the pressure in the apparatus was adjusted to 50 kPa using a vacuum pump, and warm water was passed through the jacket so that the temperature in the tank during drying was 80 ° C. After 7.0 hours from the start of drying, no steam was generated from the impregnated catalyst, so the hot water flowing in the jacket was switched to cold water to cool the impregnated catalyst.
- Table 1 shows the drying speed, the pressure in the tank, the drying time, and the temperature of the composite oxide.
- the moisture content before the drying treatment was 15.12% by mass from 181.45 kg of water to the total amount of 1200 kg of the composite oxide 1000 kg and the impregnation liquid 200 kg.
- the moisture content after a drying process used the value of the following (physical property 1) moisture content, and drying time was 7.0 hours. From these, the drying rate was 2.1 mass% / hr.
- the cracking rate of the obtained impregnated catalyst was measured as follows. A SUS tube having a diameter of 2 inches and a length of 1000 mm was vertically installed, and a three-hole plate having three holes with a diameter of 1 mm was attached to the bottom, and 50 g of impregnated catalyst was filled therein. Thereafter, a cone having a diameter of 4 inches and a length of 1000 mm was attached to the upper part of the SUS tube, and a filter whose mass was measured in advance was attached to the upper part of the cone in order to trap the impregnated catalyst scattered.
- Example 2 The impregnated catalyst was used under the same conditions as in Example 1 except that the power consumption of the drive motor for the rotor blades was adjusted so that the Pv in the steps (4) and (5) would be the conditions shown in Table 1, respectively.
- the propane ammoxidation reaction was carried out. Each result is shown in Table 1.
- Example 6 Use the equipment used for mixing and drying in steps (4) and (5) instead of the rotary blades in the form of inclined paddle type blades with two blades arranged in two stages (rotary blade B). Except for the above, an impregnated catalyst was produced under the same conditions as in Example 1, and an ammoxidation reaction of propane was performed. Each result is shown in Table 1.
- Example 7 An impregnated catalyst was produced under the same conditions as in Example 1 except that the apparatus used for mixing and drying in steps (4) and (5) was replaced with an apparatus having a rotary blade drive unit at the top of the apparatus. Then, an ammoxidation reaction of propane was performed. Each result is shown in Table 1.
- step (4) antimony was selected as a specific element to be impregnated into the composite oxide, and 29.2 kg of a 30% by mass antimony sol aqueous solution was added to 170.8 kg of water and dispersed to obtain 200 kg as an impregnating liquid.
- the temperature of the impregnating liquid in step (4) was 25 ° C. and the pH was 4.6. Each result is shown in Table 1.
- Example 9 In the step (4), except that cerium was selected as a specific element to be impregnated into the composite oxide, 0.9 kg of 98% by mass of cerium nitrate was mixed in 199.1 kg of water, and 200 kg was obtained as an impregnation solution. An impregnated catalyst was produced under the same conditions as in Example 1, and propane ammoxidation was carried out. In step (4), the temperature of the impregnating liquid was 25 ° C. and the pH was 3.8. Each result is shown in Table 1.
- Example 10 (Example 10) In the step (4), except that tellurium was selected as a specific element to be impregnated in the composite oxide, and mixed with 195.3 kg of water by adding 4.7 kg of 99 mass% telluric acid to obtain 200 kg as an impregnation liquid.
- An impregnated catalyst was produced under the same conditions as in Example 1, and propane ammoxidation was carried out.
- the temperature of the impregnating liquid was 25 ° C. and the pH was 3.7. Each result is shown in Table 1.
- step (4) molybdenum is selected as a specific element to be impregnated into the composite oxide, and 3.5 kg of 99.3% by mass ammonium heptamolybdate is dispersed in 196.5 kg of water, and 220 kg of impregnation liquid is added.
- An impregnated catalyst was produced under the same conditions as in Example 1 except that it was obtained, and propane ammoxidation reaction was carried out.
- the temperature of the impregnating solution in step (4) was 25 ° C. and the pH was 5.5. Each result is shown in Table 1.
- Example 12 to 17 An impregnated catalyst was produced under the same conditions as in Example 1 except that the amount of power used by the drive motor for the rotor blades was adjusted so that only Pv in step (5) would be the conditions shown in Table 1, respectively. The ammoxidation reaction of was carried out. Each result is shown in Table 1.
- Example 18 to 23 An impregnated catalyst was produced under the same conditions as in Example 1 except that the amount of power used by the drive motor for the rotor blades was adjusted so that only Pv in step (4) would be the conditions shown in Table 1, respectively. The ammoxidation reaction of was carried out. Each result is shown in Table 1.
- Example 24 The temperature was adjusted by flowing normal pressure steam through the jacket so that the temperature of the composite oxide during drying in step (5) was 80 ° C., and a portion of the catalyst was extracted after 7.0 hours. Drying continued even after the catalyst was extracted. The moisture content of the catalyst partially extracted after 7.0 hours was 0.23% by mass. After 1.0 hour, the temperature of the composite oxide rose to 100 ° C. due to heat from steam at normal pressure and frictional heat from stirring. The catalyst was sampled and the water content was measured and found to be 0.00% by mass. Thereafter, the impregnation catalyst was cooled by switching the steam flowing in the jacket to cold water, and the impregnation catalyst was prepared under the same conditions as in Example 1 except that the drying time was 8.0 hours in total. The ammoxidation reaction of was carried out. Each result is shown in Table 1.
- Example 25 and 26 (Examples 25 and 26) Implemented except that the pressure in the apparatus in step (5) was adjusted using a vacuum pump so that the absolute pressure was 75 kPa and 101 kPa, and the drying was finished after 14 hours and 20 hours from the start of drying, respectively.
- An impregnated catalyst was produced under the same conditions as in Example 1, and propane ammoxidation was carried out. Each result is shown in Table 1.
- aqueous raw material liquid (I) aqueous raw material liquid (II)
- 29.9 kg of a 50 mass% ammonium metatungstate aqueous solution as WO 3 and 1976.3 kg of a dispersion in which powdered silica is dispersed in water are sequentially added to form an aqueous mixed liquid ( III)
- the aqueous mixed liquid (III) was aged at 50 ° C. for 2 hours and 30 minutes after the addition of the aqueous raw material liquid (II) to obtain a slurry.
- Step (2) First drying step
- the obtained slurry was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder.
- the dryer inlet air temperature was 210 ° C and the outlet air temperature was 120 ° C. The drying operation was repeated several times.
- the impregnated catalyst was produced under the same conditions as in Example 1 except that the operation after step (4) was performed in place of the composite oxide obtained above, and propane ammoxidation reaction was performed. Each result is shown in Table 1.
- Example 28 to 31 The impregnated catalyst was used under the same conditions as in Example 27, except that the amount of power used by the drive motor for the rotor blades was adjusted so that the Pv values in the steps (4) and (5) were as shown in Table 1, respectively.
- the propane ammoxidation reaction was carried out. Each result is shown in Table 1.
- step (4) tungsten was selected as a specific element to be impregnated into the composite oxide, and 0.5 kg of 50 mass% ammonium metatungstate aqueous solution was mixed in 199.5 kg of water to obtain 200 kg as an impregnating liquid.
- the temperature of the impregnating liquid in step (4) was 25 ° C. and the pH was 6.5. Each result is shown in Table 1.
- Example 33 In the step (4), tungsten was selected as a specific element to be impregnated into the composite oxide, and 10.7 kg of a 50 mass% ammonium metatungstate aqueous solution was mixed in 189.3 kg of water to obtain 200 kg as an impregnation liquid.
- An impregnation catalyst was produced under the same conditions as in Example 1 except that the temperature of the impregnation liquid was 25 ° C. and the pH was 4.5, and propane ammoxidation reaction was performed. The temperature of the impregnating liquid in step (4) was 25 ° C. and the pH was 4.5. Each result is shown in Table 1.
- Example 34 In the step (4), the impregnation catalyst was used under the same conditions as in Example 1 except that tungsten was selected as the specific element to be impregnated into the composite oxide and 200.0 kg of 50% by mass aqueous ammonium metatungstate solution was used as the impregnation liquid. And propane ammoxidation was carried out. Each result is shown in Table 1. In step (4), the temperature of the impregnating liquid was 25 ° C. and the pH was 3.35.
- step (4) tungsten is selected as a specific element to be impregnated into the composite oxide, and 37.3 kg of 50 mass% ammonium metatungstate aqueous solution is mixed in 159.7 kg of water, and then 3.0 kg of nitric acid is added.
- An impregnation catalyst was produced under the same conditions as in Example 1 except that 200 kg was obtained as the impregnation liquid, and propane ammoxidation reaction was performed.
- the temperature of the impregnating liquid in step (4) was 25 ° C. and the pH was 0.5. Each result is shown in Table 1.
- step (4) tungsten is selected as a specific element to be impregnated into the composite oxide, and 37.3 kg of 50 mass% ammonium metatungstate aqueous solution is mixed with 161.1 kg of water, and then 1.6 kg of nitric acid is added. 120 kg was obtained as an impregnation liquid.
- the temperature of the impregnating solution was 25 ° C. and the pH was 2.1.
- the impregnation catalyst was prepared and the propane ammoxidation reaction was carried out under the same conditions as in Example 1 except that the above impregnation solution was used. Each result is shown in Table 1.
- step (4) tungsten is selected as a specific element to be impregnated into the composite oxide, and 37.3 kg of 50 mass% ammonium metatungstate aqueous solution is mixed with 161.7 kg of water, and then 1.0 kg of ammonia is added.
- An impregnation catalyst was produced under the same conditions as in Example 1 except that 200 kg was obtained as the impregnation liquid, and propane ammoxidation reaction was performed.
- the temperature of the impregnating liquid was 25 ° C. and the pH was 10.2. Each result is shown in Table 1.
- step (4) tungsten was selected as a specific element to be impregnated into the composite oxide, and 37.1 kg of 50 mass% aqueous ammonium metatungstate solution was mixed in 2.9 kg of water to obtain 40 kg as an impregnation liquid.
- step (4) the temperature of the impregnating solution was 25 ° C. and the pH was 4.3. Each result is shown in Table 1.
- step (4) tungsten was selected as a specific element to be impregnated into the composite oxide, and 37.1 kg of 50 mass% ammonium metatungstate aqueous solution was mixed in 462.9 kg of water to obtain 500 kg as an impregnation liquid.
- the temperature of the impregnating solution was 25 ° C. and the pH was 4.3. Each result is shown in Table 1.
- step (4) tungsten was selected as a specific element to be impregnated into the composite oxide, and 37.1 kg of 50 mass% ammonium metatungstate aqueous solution was mixed in 662.9 kg of water to obtain 700 kg as an impregnation liquid.
- the temperature of the impregnating solution was 25 ° C. and the pH was 4.3. Each result is shown in Table 1.
- step (4) without using the impregnating solution, 1000 kg (volume: 1000 L) of the composite oxide is placed in the stirring device, the rotor blades are operated, and the rotor is driven until the power consumption of the rotor motor is 50 kW. When the number was increased, the rotational speed of the rotary blade was 200 rpm, and then the composite oxide was stirred for 10 minutes. And the catalyst was manufactured on the same conditions as Example 1 except not having performed the process (5), and the ammoxidation reaction of propane was implemented. Each result is shown in Table 1.
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Abstract
Description
[1]
プロパンの気相接触アンモ酸化反応に用いる、触媒の製造方法であって、
原料を溶解又は分散させ、原料調合液を得る調合工程と、
前記原料調合液を乾燥し、乾燥体を得る第一の乾燥工程と、
前記乾燥体を焼成し、下記式(1)で表される複合酸化物を得る焼成工程と、
前記複合酸化物を、タングステン、モリブデン、テルル、ニオブ、バナジウム、ホウ素、ビスマス、マンガン、鉄、アンチモン、リン、希土類元素からなる群より選ばれる少なくとも1つの特定元素を含む溶液に含浸させ、含浸後の複合酸化物を得る含浸工程と、
前記含浸後の複合酸化物を乾燥させる、第二の乾燥工程と、を有し、
前記含浸工程及び前記第二の乾燥工程のいずれか少なくとも一方は、下記式(2)から求められる単位複合酸化物容積あたりの撹拌動力で撹拌しながら、前記複合酸化物又は前記含浸後の複合酸化物を含浸又は乾燥させる工程である、触媒の製造方法。
Mo1VaNbbAcXdZeOn (1)
(式(1)中、Aは、Sb及びTeからなる群より選ばれる少なくとも1種の元素を示し、Xは、W、Bi、Mn、及びTiからなる群より選ばれる少なくとも1種の元素を示し、Zは、La、Ce、Pr、Yb、Y、Sc、Sr、及びBaからなる群より選ばれる少なくとも1種の元素を示す。a、b、c、d、e、及びnは、Mo1元素当たりの各元素の元素比を示し、0.01≦a≦1.00、0.01≦b≦1.00、0.01≦c≦1.00、0.00≦d≦1.00、0.00≦e≦1.00であり、nは、複合酸化物の構成元素の原子価によって決まる値である。)
Pv(kW/m3)=P(kW)/V(m3) (2)
(式(2)中、Pvは、単位複合酸化物容積あたりの撹拌動力(kW/m3)を示し、Pは、撹拌時に発生する電力量(kW)を示し、Vは、撹拌装置に充填する複合酸化物の容積(m3)を示す。Pvは、0.001≦Pv≦300である。)
[2]
前記第二の乾燥工程において、前記複合酸化物を流動させながら、0.5質量%/hr以上20質量%/hr以下の乾燥速度で乾燥させる、[1]に記載の触媒の製造方法。
[3]
前記触媒において、前記複合酸化物中のモリブデンに対する、前記特定元素の元素比が、0.0001以上0.50以下である、[1]又は[2]に記載の触媒の製造方法。
[4]
前記第二の乾燥工程において、装置内の圧力が、絶対圧で、20kPa以上110kPa以下である、[1]~[3]のいずれかに記載の触媒の製造方法。
[5]
前記第二の乾燥工程において、乾燥時間が、0.5時間以上50時間以下である、[1]~[4]のいずれかに記載の触媒の製造方法。
[6]
前記第二の乾燥工程において、前記複合酸化物の温度が、30℃以上650℃以下である、[1]~[5]のいずれかに記載の触媒の製造方法。
[7]
前記含浸工程において、前記複合酸化物の細孔容積に対して、前記特定元素を含む溶液の量が、0.1倍以上3.0倍以下である、[1]~[6]のいずれかに記載の触媒の製造方法。
[8]
プロパンの気相接触アンモ酸化反応により、不飽和ニトリルを製造する方法であって、
[1]~[7]のいずれかに記載の触媒の製造方法により得られた触媒と、プロパンと、を接触させる接触工程を有する、不飽和ニトリルの製造方法。
本実施形態の触媒の製造方法は、プロパンの気相接触アンモ酸化反応に用いる、触媒の製造方法であって、原料を溶解又は分散させ、原料調合液を得る調合工程(以下、「工程(1)」ともいう。)と、当該原料調合液を乾燥し、乾燥体を得る第一の乾燥工程(以下、「工程(2)」ともいう。)と、当該乾燥体を焼成し、下記式(1)で表される複合酸化物を得る焼成工程(以下、「工程(3)」ともいう。)と、当該複合酸化物を、タングステン、モリブデン、テルル、ニオブ、バナジウム、ホウ素、ビスマス、マンガン、鉄、アンチモン、リン、希土類元素からなる群より選ばれる少なくとも1つの特定元素を含む溶液(以下、単に「含浸液」ともいう。)に含浸させ、含浸後の複合酸化物を得る含浸工程(以下、「工程(4)」ともいう。)と、当該含浸後の複合酸化物を乾燥させる、第二の乾燥工程(以下、「工程(5)」ともいう。)と、を有する。また、上記含浸工程及び上記第二の乾燥工程のいずれか少なくとも一方は、下記式(2)から求められる単位複合酸化物容積あたりの撹拌動力で撹拌しながら、上記複合酸化物又は上記含浸後の複合酸化物を含浸又は乾燥させる工程である。ここで「原料」とは、触媒の構成元素を含む化合物であれば特に限定されないが、具体的には、後述する化合物を用いることができる。
Mo1VaNbbAcXdZeOn (1)
式(1)中、Aは、Sb及びTeからなる群より選ばれる少なくとも1種の元素を示し、Xは、W、Bi、Mn、及びTiからなる群より選ばれる少なくとも1種の元素を示し、Zは、La、Ce、Pr、Yb、Y、Sc、Sr、及びBaからなる群より選ばれる少なくとも1種の元素を示す。a、b、c、d、e、及びnは、Mo1元素当たりの各元素の元素比を示し、0.01≦a≦1.00、0.01≦b≦1.00、0.01≦c≦1.00、0.00≦d≦1.00、0.00≦e≦1.00であり、nは、複合酸化物の構成元素の原子価によって決まる数である。
Pv(kW/m3)=P(kW)/V(m3) (2)
式(2)中、Pvは、単位複合酸化物容積あたりの撹拌動力(kW/m3)を示し、Pは、撹拌時に発生する電力量(kW)を示し、Vは、撹拌装置に充填する複合酸化物の容積(m3)を示す。Pは、0.001≦Pv≦300である。
本実施形態の工程(1)は、原料を溶解又は分散させ、原料調合液を得る。その際に用いられる原料としては、後述する工程(2)において得られる所定の組成を有する複合酸化物を得られるものであれば特に限定されないが、例えば、Moの原料、Vの原料、Nbの原料、Aの原料、Xの原料、Zの原料が挙げられる。
本実施形態の工程(2)は、上述した工程(1)で得られた原料調合液を乾燥し、乾燥体を得る。工程(1)を経て得られた原料調合液(例えば、スラリー)を乾燥することによって、触媒前駆体となる乾燥体が得られる。乾燥の方法は、公知の方法で行うことができ、例えば、噴霧乾燥又は蒸発乾固によって行うことができる。気相接触アンモ酸化反応で流動床反応方式を採用する場合、反応器内での流動性を好ましい状態にする等の観点から、微小球状の乾燥体を得ることが好ましい。微小球状の乾燥体を得るためには、乾燥方法として噴霧乾燥を採用するのが好ましい。噴霧乾燥における噴霧化は、遠心方式、二流体ノズル方式、又は高圧ノズル方式のいずれであってもよい。噴霧乾燥に用いる乾燥熱源としては、スチーム、電気ヒーター等によって加熱された空気が挙げられる。噴霧乾燥に用いる装置の乾燥機の入口温度は、後述する工程(3)で得られる複合酸化物粒子形状及び/又は強度を好ましい状態にする、及び得られる複合酸化物の性能を向上させる等の観点から、150℃以上300℃以下が好ましい。また、乾燥機の出口温度は、100℃以上160℃以下が好ましい。
本実施形態の工程(3)は、工程(2)で得られた乾燥体を焼成し、下記(1)で表される複合酸化物を得る工程である。
Mo1VaNbbAcXdZeOn (1)
式(1)中、Aは、Sb及びTeからなる群より選ばれる少なくとも1種の元素を示し、Xは、W、Bi、Mn、及びTiからなる群より選ばれる少なくとも1種の元素を示し、Zは、La、Ce、Pr、Yb、Y、Sc、Sr、及びBaからなる群より選ばれる少なくとも1種の元素を示す。a、b、c、d、e、及びnは、Mo1元素当たりの各元素の元素比を示し、0.01≦a≦1.00、0.01≦b≦1.00、0.01≦c≦1.00、0.00≦d≦1.00、0.00≦e≦1.00であり、nは、複合酸化物の構成元素の原子価によって決まる数である。
本実施形態の工程(4)は、工程(3)で得られた複合酸化物を、タングステン、モリブデン、テルル、ニオブ、バナジウム、ホウ素、ビスマス、マンガン、鉄、アンチモン、リン、希土類元素からなる群より選ばれる少なくとも1つの特定元素を含む溶液(含浸液)に含浸させ、含浸後の複合酸化物(以下、「含浸複合酸化物」ともいう。)を得る工程である。また、工程(4)及び後述する工程(5)のいずれか少なくとも一方は、下記式(2)から求められる単位複合酸化物容積あたりの撹拌動力で撹拌しながら、上記複合酸化物又は含浸複合酸化物を含浸又は乾燥させる工程である。すなわち、工程(5)が当該要件を満たす工程でない場合には、工程(4)が当該要件を満たす工程である。また、工程(4)及び工程(5)のいずれもが、当該要件を満たす工程であってもよい。
Pv(kW/m3)=P(kW)/V(m3) (2)
式(2)中、Pvは、単位複合酸化物容積あたりの撹拌動力(kW/m3)を示し、Pは、撹拌時に発生する電力量(kW)を示し、Vは、撹拌装置に充填する複合酸化物の容積(m3)を示す。Pvは、0.001≦Pv≦300である。さらに、工程(4)における含浸液は、特定の原料から調製することができる。
複合酸化物の容積(L)=複合酸化物の質量(kg)/かさ比重(kg/L)
かさ比重(kg/L)=(複合酸化物充填後の容器質量(kg)-空の容器質量(kg))/容器の容積(L)
本実施形態の工程(5)は、工程(4)で得られた含浸後の複合酸化物(以下、「含浸複合酸化物」ともいう。)を乾燥させる工程である。また、上述した工程(4)及び工程(5)のいずれか少なくとも一方は、下記式(2)から求められる単位複合酸化物容積あたりの撹拌動力で撹拌しながら、上記複合酸化物又は含浸複合酸化物を含浸又は乾燥させる工程である。すなわち、工程(4)が当該要件を満たす工程でない場合には、工程(5)が当該要件を満たす工程である。また、工程(4)及び工程(5)のいずれもが、当該要件を満たす工程であってもよい。
Pv(kW/m3)=P(kW)/V(m3) (2)
式(2)中、Pvは、単位複合酸化物容積あたりの撹拌動力(kW/m3)を示し、Pは、撹拌時に発生する電力量(kW)を示し、Vは、撹拌装置に充填する複合酸化物の容積(m3)を示す。Pvは、0.001≦Pv≦300である。
乾燥速度=(乾燥処理前の含水率-乾燥処理後の含水率)/乾燥時間 (3)
本実施形態の触媒は、本実施形態の触媒の製造方法により得られる。本実施形態の触媒を、プロパンの気相接触アンモ酸化反応に用いることにより、プロパンから不飽和ニトリルを高い収率で得ることができる。
特定元素の元素比=(触媒中の特定元素組成比)-(複合酸化物中の特定元素組成比)
本実施形態の不飽和ニトリルの製造方法は、プロパンの気相接触アンモ酸化反応により、不飽和ニトリルを製造する方法であって、本実施形態の触媒の製造方法により得られた触媒と、プロパンと、を接触させる接触工程を有する。具体例として、反応器に収容した触媒に、プロパン、アンモニア及び酸素を含む原料ガスを接触させて、プロパンの気相接触アンモ酸化反応を行うことにより、対応する不飽和ニトリルを製造する方法について説明する。
実施例と比較例においては、アクリロニトリル(以下、AN)の収率(表1中、「ANの収率」と示す。)は、次の通り求めた。生成したANのモル数は、予め濃度既知のANのガスをガスクロマトグラフィー(GC)にて測定して検量線を採った後に、アンモ酸化反応によって生成したガスをGCに定量注入し、測定した。ANの収率を、測定して得られた「生成したANのモル数」から、下記式に基づいて算出した。結果を表1に示す。
AN収率(%)=(生成したANのモル数)/(供給したプロパンのモル数)×100
(工程(1):調合工程)
水2800kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕451.3kg、メタバナジン酸アンモニウム〔NH4VO3〕54.7kg、三酸化二アンチモン〔Sb2O3〕78.0kg、及び硝酸セリウム6水和物〔Ce(NO3)3・6H2O〕を8.9kg加え、攪拌しながら95℃で1時間加熱して水性原料液(I)を得た。
2KMnO4+3H2SO4+5H2C2O4→K2SO4+2MnSO4+10CO2+8H2O
得られたニオブ混合液は、下記の複合酸化物の調整においてニオブ原料液(B0)として用いた。
得られたスラリーを、遠心式噴霧乾燥器に供給して乾燥し、微小球状の乾燥粉体を得た。乾燥機の入口空気温度は210℃、そして出口空気温度は120℃であった。その乾燥する操作を数回繰り返した。
得られた乾燥粉体を内径500mm、長さ3500mm、肉厚20mmのSUS製円筒状焼成管に充填し、600NL/minの窒素ガス流通下、管を回転させながら、680℃で2時間焼成して複合酸化物を得た。得られた複合酸化物のかさ比重を測定したところは1.00で、細孔容積は0.2cc/gで、触媒組成はMo1.14V0.21Sb0.24Nb0.103W0.03Ce0.009(表中、この触媒組成を「A」と示す)であった。
(含浸液の調合)
複合酸化物に含浸させる特定元素としてタングステンを選択した。水162.9kgに50質量%のメタタングステン酸アンモニウム水溶液37.1kgを入れて混ぜ、含浸液として200kgを得た。含浸液の温度は25℃でpHは4.3であった。
得られた複合酸化物と含浸液との混合には、容積1500LのSUS製撹拌装置を用いた。撹拌方法は装置内の下段に設置された回転翼を回転させて複合酸化物と含浸液とを撹拌混合する方式で、回転翼は羽が4つある傾斜パドル型の翼が上下2段に配置された形(回転翼A)(傾斜パドルについては化学工学便覧改定七版(丸善出版)第6章「撹拌・混合」を参照のこと)で使用した。装置内に充填する複合酸化物の温度調節は装置外側に設けたジャケットに冷水又は温水、蒸気を通して温調する方式を選択した。含浸液の添加手法は装置の中央上部からスプレーで添加する方式を選択した。撹拌装置内に複合酸化物を1000kg(容積1000L)入れて、回転翼を稼働させ、回転翼用の駆動モーターの使用電力量が50kWとなるところまで回転数を上げたところ、回転翼の回転数は200rpmであった。複合酸化物を撹拌しながら、含浸液200kgを5minで添加し、更に5min撹拌を行った。複合酸化物の温度は、20℃であった。
上記の複合酸化物と含浸液とを混合した装置をそのまま用い、回転翼用の駆動モーターの使用電力量は混合時と同じとして、上記の複合酸化物を乾燥し、含浸触媒を得た。乾燥開始と同時に真空ポンプを用いて装置内の圧力を50kPaにし、乾燥時の槽内の温度が80℃になるようにジャケットに温水を流して調整した。乾燥を開始して7.0時間経過後に含浸触媒から水蒸気が発生しなくなったため、ジャケットに流していた温水を冷水に切り替えて含浸触媒の冷却を行った。乾燥速度、槽内圧力、乾燥時間、複合酸化物の温度を表1に示す。乾燥速度は、下記式(3)により求めた。
乾燥速度=(乾燥処理前の含水率-乾燥処理後の含水率)/乾燥時間 (3)
ここで、乾燥処理前の含水率は、複合酸化物1000kgと含浸液200kgとの合計量1200kgに対する水181.45kgから、15.12質量%であった。また、乾燥処理後の含水率は下記の(物性1)含水率の値を用い、乾燥時間は7.0時間であった。これらから、乾燥速度は2.1質量%/hrであった。
得られた含浸触媒の含水率は、次の通り測定した。含浸触媒をSUS容器に100.0045g入れ、100℃の電気炉で12時間乾燥した。乾燥後に電気炉から取り出し、常温まで冷まして含浸触媒の質量を測定したところ、96.3633gであった。乾燥前後の質量減少から求めた含水率を表1に示す。
得られた複合酸化物又は含浸触媒のMoに対する特定元素の元素比は、次の通り測定した。複合酸化物又は含浸触媒の組成分析を行った。組成分析には、蛍光X線分析装置(理学電器社製の商品名「RIX1000」)を使用した。組成分析の結果から求めたW/Mo比を表1に示す。
得られた含浸触媒の割れ率は、次の通り測定した。直径2インチ、長さ1000mmのSUS管を縦に設置し、下部に直径1mmの穴が3つ開いた3穴板を取り付け、その中に含浸触媒を50g充填した。その後、SUS管の上部に、直径4インチ、長さ1000mmのコーンを取り付け、コーンの上部には飛散する含浸触媒をトラップするために予め質量を測定したフィルターを取り付けた。SUS管下部の3穴板よりエアーを700L/minで流し入れ、20時間後にフィルターを取り外してフィルターの質量を測定した。フィルターに回収された含浸触媒の全てが割れた含浸触媒であるとして、含浸触媒50gに対するフィルターに回収された含浸触媒の質量を割れ率(質量%)とした。その結果を表1に示す。
得られた含浸触媒600kgを内径600mmのSUS製流動床反応器に充填した。反応器の触媒充填部底面から、上方30cmの位置に、プロパン、アンモニアを含むガスを供給するノズルを鉛直下向きに設置した。設置位置は反応器の中心、及び反応器の中心を中心とする一辺340mmの正方形の頂点(計5ヶ所)とした。反応器の触媒充填部底面に酸素を含むガスを供給するノズルを鉛直上向きに設置した。設置位置は、プロパン、アンモニアを含むガスを供給するノズルと鉛直方向に重なる位置(5ヶ所)とした。反応器の除熱には定常的に用いる冷却コイル4本、温度微調整用の冷却コイル2本を触媒濃厚層に設置した。触媒温度445℃、反応圧力40kPaで上側のノズルからプロパン、アンモニアを下側のノズルから空気をプロパン:アンモニア:酸素=1:0.93:2.81のモル比で接触時間3.4sec・g/ccとなるよう供給したところ、反応器出口生成ガス中の酸素濃度は3.1%を示した。反応を2週間継続した。2週間継続した後のAN収率を表1に示す。
工程(4)、及び(5)におけるPvをそれぞれ表1に示す条件となるように、回転翼用の駆動モーターの使用電力量を調整したこと以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)、及び(5)における混合、乾燥に用いた装置を、回転翼は羽が2つある傾斜パドル型の翼が上下2段に配置された形(回転翼B)に替えて使用したこと以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)、及び(5)における混合、乾燥に用いた装置を、回転翼の駆動部を装置上部に有する装置に替えて用いたこと以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてアンチモンを選択し、水170.8kgに30質量%のアンチモンゾル水溶液29.2kgを入れて分散させて、含浸液として200kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは4.6であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてセリウムを選択し、水199.1kgに98質量%の硝酸セリウム0.9kgを入れて混ぜ、含浸液として200kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは3.8であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてテルルを選択し、水195.3kgに99質量%のテルル酸4.7kgを入れて混ぜ、含浸液として200kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは3.7であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてモリブデンを選択し、水196.5kgに99.3質量%のヘプタモリブデン酸アンモニウム3.5kgを入れて分散させて、含浸液として220kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは5.5であった。各結果は表1に示す。
工程(5)におけるPvのみをそれぞれ表1に示す条件となるように、回転翼用の駆動モーターの使用電力量を調整したこと以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)におけるPvのみをそれぞれ表1に示す条件となるように、回転翼用の駆動モーターの使用電力量を調整したこと以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(5)における乾燥時の複合酸化物の温度が80℃となるようにジャケットに常圧の蒸気を流して調整し、7.0時間後に一部触媒を抜き出した。触媒を抜き出してからも乾燥は継続した。7.0時間後に一部抜き出した触媒の含水率を測定すると0.23質量%であった。1.0時間後、複合酸化物の温度は常圧の蒸気による熱と撹拌による摩擦熱で100℃まで上昇していた。その触媒をサンプリングし、含水率を測定したところ0.00質量%となっていた。その後、ジャケットに流していた蒸気を冷水に切り替えて含浸触媒の冷却を行い、乾燥時間が合計で8.0時間になったこと以外は、実施例1と同じ条件で含浸触媒を調製し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(5)における装置内の圧力が絶対圧で75kPa、101kPaとなるように真空ポンプを用いて調整し、それぞれ乾燥を開始して14時間、20時間経過後に乾燥を終了したこと以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
(工程1:調合工程)
水2717kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕53.1kg、メタバナジン酸アンモニウム〔NH4VO3〕53.1kg、テルル酸〔Te(OH)6〕119.3kg、及び硝酸セリウム・6水和物〔Ce(NO3)3・6H2O〕8.6kgを加え、攪拌して水性原料液(I)を得た。
得られたスラリーを、遠心式噴霧乾燥器に供給して乾燥し、微小球状の乾燥粉体を得た。乾燥機の入口空気温度は210℃、そして出口空気温度は120℃であった。その乾燥する操作を数回繰り返した。
得られた乾燥粉体を内径500mm、長さ3500mm、肉厚20mmのSUS製円筒状焼成管に充填し、600NL/minの窒素ガス流通下、管を回転させながら、680℃で2時間焼成して複合酸化物を得た。得られた複合酸化物のかさ比重を測定したところは1.00で、細孔容積は0.2cc/gで、触媒組成はMo1.14V0.21Te0.24Nb0.103W0.03Ce0.009(表中、この触媒組成を「B」と示す)であった。
工程(4)、及び(5)におけるPvをそれぞれ表1に示す条件となるように、回転翼用の駆動モーターの使用電力量を調整したこと以外は、実施例27と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水199.5kgに50質量%のメタタングステン酸アンモニウム水溶液0.5kgを入れて混ぜ、含浸液として200kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは6.5であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水189.3kgに50質量%のメタタングステン酸アンモニウム水溶液10.7kgを入れて混ぜ、含浸液として200kgを得た。含浸液の温度は25℃でpHは4.5であった以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは4.5であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、50質量%のメタタングステン酸アンモニウム水溶液200.0kgを含浸液として使用した以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。工程(4)における含浸液の温度は25℃でpHは3.35であった。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水159.7kgに50質量%のメタタングステン酸アンモニウム水溶液37.3kgを入れて混ぜ、その後硝酸を3.0kg入れて含浸液として200kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは0.5であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水161.1kgに50質量%のメタタングステン酸アンモニウム水溶液37.3kgを入れて混ぜ、その後硝酸を1.6kg入れて含浸液として120kgを得た。含浸液の温度は25℃でpHは2.1であった。上述の含浸液を用いたこと以外は、実施例1と同じ条件で含浸触媒の調製、及びプロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水161.7kgに50質量%のメタタングステン酸アンモニウム水溶液37.3kgを入れて混ぜ、その後アンモニアを1.0kg入れて含浸液として200kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは10.2であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水2.9kgに50質量%のメタタングステン酸アンモニウム水溶液37.1kgを入れて混ぜ、含浸液として40kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。工程(4)における含浸液の温度は25℃でpHは4.3であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水462.9kgに50質量%のメタタングステン酸アンモニウム水溶液37.1kgを入れて混ぜ、含浸液として500kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。含浸液の温度は25℃でpHは4.3であった。各結果は表1に示す。
工程(4)において、複合酸化物に含浸させる特定元素としてタングステンを選択し、水662.9kgに50質量%のメタタングステン酸アンモニウム水溶液37.1kgを入れて混ぜ、含浸液として700kgを得た以外は、実施例1と同じ条件で含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。含浸液の温度は25℃でpHは4.3であった。各結果は表1に示す。
工程(4)において、含浸液を用いず、撹拌装置内に複合酸化物を1000kg(容積1000L)入れて回転翼を稼働させ、回転翼用の駆動モーターの使用電力量が50kWとなるところまで回転数を上げたところ、回転翼の回転数は200rpmであり、その後に、複合酸化物を10min撹拌した。そして工程(5)を行わなかったこと以外は、実施例1と同じ条件で触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)、及び(5)におけるPvを0.00077(kW/m3)となるように、回転翼用の駆動モーターの使用電力量を調整した以外は実施例1と同様にして含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
工程(4)、及び(5)におけるPvを333(kW/m3)となるように、回転翼用の駆動モーターの使用電力量を調整した以外は実施例1と同様にして含浸触媒を製造し、プロパンのアンモ酸化反応を実施した。各結果は表1に示す。
Claims (8)
- プロパンの気相接触アンモ酸化反応に用いる、触媒の製造方法であって、
原料を溶解又は分散させ、原料調合液を得る調合工程と、
前記原料調合液を乾燥し、乾燥体を得る第一の乾燥工程と、
前記乾燥体を焼成し、下記式(1)で表される複合酸化物を得る焼成工程と、
前記複合酸化物を、タングステン、モリブデン、テルル、ニオブ、バナジウム、ホウ素、ビスマス、マンガン、鉄、アンチモン、リン、希土類元素からなる群より選ばれる少なくとも1つの特定元素を含む溶液に含浸させ、含浸後の複合酸化物を得る含浸工程と、
前記含浸後の複合酸化物を乾燥させる、第二の乾燥工程と、を有し、
前記含浸工程及び前記第二の乾燥工程のいずれか少なくとも一方は、下記式(2)から求められる単位複合酸化物容積あたりの撹拌動力で撹拌しながら、前記複合酸化物又は前記含浸後の複合酸化物を含浸又は乾燥させる工程である、触媒の製造方法。
Mo1VaNbbAcXdZeOn (1)
(式(1)中、Aは、Sb及びTeからなる群より選ばれる少なくとも1種の元素を示し、Xは、W、Bi、Mn、及びTiからなる群より選ばれる少なくとも1種の元素を示し、Zは、La、Ce、Pr、Yb、Y、Sc、Sr、及びBaからなる群より選ばれる少なくとも1種の元素を示す。a、b、c、d、e、及びnは、Mo1元素当たりの各元素の元素比を示し、0.01≦a≦1.00、0.01≦b≦1.00、0.01≦c≦1.00、0.00≦d≦1.00、0.00≦e≦1.00であり、nは、複合酸化物の構成元素の原子価によって決まる値である。)
Pv(kW/m3)=P(kW)/V(m3) (2)
(式(2)中、Pvは、単位複合酸化物容積あたりの撹拌動力(kW/m3)を示し、Pは、撹拌時に発生する電力量(kW)を示し、Vは、撹拌装置に充填する複合酸化物の容積(m3)を示す。Pvは、0.001≦Pv≦300である。) - 前記第二の乾燥工程において、前記複合酸化物を流動させながら、0.5質量%/hr以上20質量%/hr以下の乾燥速度で乾燥させる、請求項1に記載の触媒の製造方法。
- 前記触媒において、前記複合酸化物中のモリブデンに対する、前記特定元素の元素比が、0.0001以上0.50以下である、請求項1又は2に記載の触媒の製造方法。
- 前記第二の乾燥工程において、装置内の圧力が、絶対圧で、20kPa以上110kPa以下である、請求項1~3のいずれか一項に記載の触媒の製造方法。
- 前記第二の乾燥工程において、乾燥時間が、0.5時間以上50時間以下である、請求項1~4のいずれか一項に記載の触媒の製造方法。
- 前記第二の乾燥工程において、前記複合酸化物の温度が、30℃以上650℃以下である、請求項1~5のいずれか一項に記載の触媒の製造方法。
- 前記含浸工程において、前記複合酸化物の細孔容積に対して、前記特定元素を含む溶液の量が、0.1倍以上3.0倍以下である、請求項1~6のいずれか一項に記載の触媒の製造方法。
- プロパンの気相接触アンモ酸化反応により、不飽和ニトリルを製造する方法であって、
請求項1~7のいずれか一項に記載の触媒の製造方法により得られた触媒と、プロパンと、を接触させる接触工程を有する、不飽和ニトリルの製造方法。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020506862A (ja) * | 2017-01-31 | 2020-03-05 | クラリアント・プロドゥクテ・(ドイチュラント)・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | 大きくされた比表面積およびエタンからエチレンへの酸化的脱水素化に対するより高い活性を有するMoVNbTe触媒の合成 |
JPWO2021172423A1 (ja) * | 2020-02-26 | 2021-09-02 | ||
WO2022070674A1 (ja) * | 2020-09-29 | 2022-04-07 | 昭和電工株式会社 | 酢酸エチル製造用触媒の製造方法 |
Families Citing this family (4)
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EP3653301A4 (en) | 2017-07-14 | 2020-07-15 | Asahi Kasei Kabushiki Kaisha | METHOD FOR PRODUCING CATALYST AND METHOD FOR PRODUCING UNSATURATED NITRILE |
CN108435223B (zh) * | 2018-04-26 | 2020-03-20 | 厦门大学 | 一种磷改性的丙烷氨氧化催化剂及其制备方法和应用 |
KR102473017B1 (ko) * | 2018-07-27 | 2022-12-02 | 주식회사 엘지화학 | 탄소나노튜브의 제조방법 |
CN112354518B (zh) * | 2020-11-16 | 2023-07-25 | 湖南环达环保有限公司 | 一种锌铁复合氧化物负载活性炭脱硫剂的制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07144131A (ja) * | 1993-07-16 | 1995-06-06 | Hoechst Ag | 表面含浸触媒、その製造方法およびそれを酢酸ビニルの製造に用いる方法 |
JPH07185354A (ja) * | 1993-12-27 | 1995-07-25 | Sumitomo Chem Co Ltd | メタクリル酸製造用触媒の製造方法 |
JP2001072641A (ja) * | 1999-09-07 | 2001-03-21 | Mitsubishi Chemicals Corp | 脂肪族アルデヒド酸の製造方法及びその製造用触媒 |
JP3769866B2 (ja) * | 1996-04-18 | 2006-04-26 | 三菱化学株式会社 | 気相接触酸化用触媒の製造方法 |
JP2007117818A (ja) * | 2005-10-26 | 2007-05-17 | Asahi Kasei Chemicals Corp | 酸化物触媒の製造方法 |
JP5190994B2 (ja) * | 2006-03-20 | 2013-04-24 | 旭化成ケミカルズ株式会社 | 酸化又はアンモ酸化用触媒及びその製造方法 |
WO2013172414A1 (ja) * | 2012-05-18 | 2013-11-21 | 日本化薬株式会社 | メタクリル酸製造用触媒、その製造方法及び該触媒を用いるメタクリル酸の製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5190994A (ja) | 1975-02-06 | 1976-08-10 | Suisonoseizohoho | |
RU2455064C1 (ru) * | 2008-06-10 | 2012-07-10 | ЭлДжи КЕМ, ЛТД. | Катализатор для окисления углеводородов при газофазном контакте, способ получения этого катализатора и способ газофазного окисления углеводородов с использованием этого катализатора |
EP2291237A4 (en) * | 2008-06-10 | 2011-12-07 | Lg Chemical Ltd | CATALYST FOR GAS PHASE CONTACTXIDATION OF HYDROCARBON, METHOD OF MANUFACTURING THEREOF AND HYDROCARBON GAS PHASE OXIDATION METHOD USING THEREOF |
JP5249959B2 (ja) | 2010-01-06 | 2013-07-31 | 三菱重工業株式会社 | マルチパス低減装置 |
CN101797510B (zh) * | 2010-04-02 | 2012-07-25 | 华东理工大学 | 含稀土的烷烃氨氧化反应催化剂 |
MY156804A (en) * | 2010-05-13 | 2016-03-31 | Asahi Kasei Chemicals Corp | Mixed catalyst |
JP5866292B2 (ja) * | 2010-11-05 | 2016-02-17 | 旭化成ケミカルズ株式会社 | 酸化物触媒、酸化物触媒の製造方法、不飽和酸の製造方法及び不飽和ニトリルの製造方法 |
CN107008510B (zh) * | 2010-12-17 | 2019-09-10 | 旭化成株式会社 | 催化剂的制造装置及制造方法、以及不饱和酸或不饱和腈的制造方法 |
TWI530321B (zh) * | 2010-12-27 | 2016-04-21 | Asahi Kasei Chemicals Corp | Composite oxide catalyst and its manufacturing method |
-
2016
- 2016-03-24 WO PCT/JP2016/059342 patent/WO2016152964A1/ja active Application Filing
- 2016-03-24 RU RU2017133099A patent/RU2675603C1/ru active
- 2016-03-24 JP JP2017508415A patent/JP6498749B2/ja active Active
- 2016-03-24 EP EP16768867.0A patent/EP3275548B1/en active Active
- 2016-03-24 MY MYPI2017703519A patent/MY186236A/en unknown
- 2016-03-24 KR KR1020177023499A patent/KR102000860B1/ko active IP Right Grant
- 2016-03-24 US US15/561,441 patent/US10807073B2/en active Active
- 2016-03-24 CN CN201680020809.8A patent/CN107427827B/zh active Active
- 2016-03-25 TW TW105109540A patent/TWI597100B/zh active
-
2017
- 2017-09-25 SA SA517390019A patent/SA517390019B1/ar unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07144131A (ja) * | 1993-07-16 | 1995-06-06 | Hoechst Ag | 表面含浸触媒、その製造方法およびそれを酢酸ビニルの製造に用いる方法 |
JPH07185354A (ja) * | 1993-12-27 | 1995-07-25 | Sumitomo Chem Co Ltd | メタクリル酸製造用触媒の製造方法 |
JP3769866B2 (ja) * | 1996-04-18 | 2006-04-26 | 三菱化学株式会社 | 気相接触酸化用触媒の製造方法 |
JP2001072641A (ja) * | 1999-09-07 | 2001-03-21 | Mitsubishi Chemicals Corp | 脂肪族アルデヒド酸の製造方法及びその製造用触媒 |
JP2007117818A (ja) * | 2005-10-26 | 2007-05-17 | Asahi Kasei Chemicals Corp | 酸化物触媒の製造方法 |
JP5190994B2 (ja) * | 2006-03-20 | 2013-04-24 | 旭化成ケミカルズ株式会社 | 酸化又はアンモ酸化用触媒及びその製造方法 |
WO2013172414A1 (ja) * | 2012-05-18 | 2013-11-21 | 日本化薬株式会社 | メタクリル酸製造用触媒、その製造方法及び該触媒を用いるメタクリル酸の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3275548A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020506862A (ja) * | 2017-01-31 | 2020-03-05 | クラリアント・プロドゥクテ・(ドイチュラント)・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | 大きくされた比表面積およびエタンからエチレンへの酸化的脱水素化に対するより高い活性を有するMoVNbTe触媒の合成 |
JPWO2021172423A1 (ja) * | 2020-02-26 | 2021-09-02 | ||
WO2021172423A1 (ja) * | 2020-02-26 | 2021-09-02 | 三菱ケミカル株式会社 | 触媒 |
JP7400940B2 (ja) | 2020-02-26 | 2023-12-19 | 三菱ケミカル株式会社 | 触媒、不飽和アルデヒド及び/又は不飽和カルボン酸を製造する方法、並びに触媒の製造方法 |
WO2022070674A1 (ja) * | 2020-09-29 | 2022-04-07 | 昭和電工株式会社 | 酢酸エチル製造用触媒の製造方法 |
GB2613281A (en) * | 2020-09-29 | 2023-05-31 | Resonac Corp | Method for producing ethyl acetate production catalyst |
JP7396511B2 (ja) | 2020-09-29 | 2023-12-12 | 株式会社レゾナック | 酢酸エチル製造用触媒の製造方法 |
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TW201700171A (zh) | 2017-01-01 |
EP3275548A1 (en) | 2018-01-31 |
KR20170107520A (ko) | 2017-09-25 |
MY186236A (en) | 2021-06-30 |
CN107427827B (zh) | 2021-04-13 |
SA517390019B1 (ar) | 2022-06-12 |
KR102000860B1 (ko) | 2019-07-16 |
CN107427827A (zh) | 2017-12-01 |
RU2675603C1 (ru) | 2018-12-20 |
EP3275548B1 (en) | 2024-03-13 |
JP6498749B2 (ja) | 2019-04-10 |
JPWO2016152964A1 (ja) | 2017-11-02 |
US20180117565A1 (en) | 2018-05-03 |
US10807073B2 (en) | 2020-10-20 |
TWI597100B (zh) | 2017-09-01 |
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