Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8877—Vanadium, tantalum, niobium or polonium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
  • B01J23/8885—Tungsten containing also molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/20—Carbon compounds
  • B01J27/22—Carbides
  • B01J27/224—Silicon carbide
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8871—Rare earth metals or actinides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8876—Arsenic, antimony or bismuth
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • 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
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/084—Decomposition of carbon-containing compounds into carbon

Definitions

• the present invention provides a composite oxide catalyst for producing a corresponding unsaturated carboxylic acid stably over a long period of time and in a high yield by subjecting an unsaturated aldehyde to gas-phase catalytic oxidation with a molecular oxygen-containing gas. And a method for producing the same.
• the production scale for producing acrylic acid by reacting acrolein is usually carried out on a scale of 3 million tons Z years, so that even if the above conversion and selectivity are improved by 0.1%, it is obtained.
• the amount of acrylic acid increases significantly at the level of hundreds and thousands of tons. Therefore, the improvement of the catalyst performance such as the conversion and the selectivity will contribute to the effective use of resources and the rationalization of the process, even if it is a slight improvement.
• Patent Document 1 discloses that Mo Nb V Cu Si
• Y represents at least one element selected from Mg, Ca, Sr, Ba and Zn
• Z represents W, Ce, Sn, Cr, Mn, Fe, Co, Y, Nd, Sm, Ge and 1
• a is 0 ⁇ a ⁇ 12, 0 ⁇ b ⁇ 10, 0 ⁇ c ⁇ 8, 0 ⁇ d ⁇ 1000, 0 ⁇ e ⁇ 1000, 0 ⁇ f ⁇ 2, 0 ⁇ g ⁇ 5, 0 ⁇ h ⁇ 5,
• i is a number determined by the degree of oxidation of each of the above components excluding Si and C
• Patent Document 2 discloses that a catalyst used in the same reaction as that applied to an applicant separate from the present applicant has a formula: Mo V Sb ABC (where A is composed of Nb and Ta Selected
• B is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Cr, W, Mn, Fe, Ru, Co, Ni or P
• C is Ag , Zn, Ti, Sn, Pb, Cu, As or Se.
• Patent Document 1 JP 2003-200055
• Patent Document 2 JP-A-2000-317309
• the present invention provides a method for producing an unsaturated carboxylic acid by subjecting an unsaturated aldehyde to gas-phase catalytic oxidation with a molecular oxygen-containing gas to produce a high conversion of the raw material unsaturated aldehyde and a high unsaturated carboxylic acid.
• a novel method for producing a composite oxide catalyst that provides selectivity and exhibits stable performance over a long period of time.
• the inventor of the present invention has conducted intensive studies to achieve the above object. As a result, a group force consisting of Mo, V, X (Nb and W) which is the same as or similar to Patent Documents 1 and 2 described above was also selected.
• the starting compound of each element is integrated in an aqueous medium in the presence of an organic acid, and the obtained integrated product is dried, molded, and calcined to obtain the catalyst performance. It has also been found that the conversion of unsaturated aldehydes is improved, and in particular, the selectivity of the target unsaturated carboxylic acid is improved.
• Patent Documents 1 and 2 In the production of the composite oxide catalyst of the present invention, means for integrally integrating a source compound of each element in an aqueous medium in the presence of an organic acid is disclosed in Patent Documents 1 and 2. It is different from the usual method as shown.
• the organic acid itself is not used in the production process of the catalyst of Patent Document 1.
• Patent Document 2 uses oxalic acid, which is an organic acid used in the present invention in the catalyst manufacturing process, but has a different composition from the catalyst manufactured by the present invention, which contains Cu as an essential component.
• oxalic acid is used to react with niobic acid to form a complex to dissolve water-insoluble niobic acid. It should not be used to integrate the source compound of each component in an aqueous medium.
• the present invention is characterized by the following points.
• Formula (1) Mo V X Cu Y C SiO (where Mo is molybdenum, V is vanadium, Cu is copper
• C is carbon
• Si is silicon
• O oxygen
• X is at least one element selected from Nb and W
• Y is a group consisting of Sb, Mg, Ca, Sr, Ba and Zn
• At least one element selected from a, b, c, d, e, f and g indicate the atomic ratio of each element, and 0 ⁇ a ⁇ 12, 0 ⁇ b ⁇ 12, 0 ⁇ c ⁇ 12, 0 ⁇ d ⁇ 8, 0 ⁇ e ⁇ 1000, 0 ⁇ f ⁇ 1000, and g is a number determined by the number of oxygen atoms necessary to satisfy the acid state of other elements except Si and c in each of the above components).
• the source compound of each component element is integrated in the presence of an organic acid, and the resulting aqueous solution or dispersion of the integrated product is dried to form a powder.
• a method for producing a composite oxide catalyst comprising: preparing a powder of the above, and firing a molded product obtained by molding the powder.
• the composite oxide catalyst converts the unsaturated aldehyde into a gas phase catalytic acid with a molecular oxygen-containing gas.
• an unsaturated aldehyde is produced by gas phase catalytic oxidation of an unsaturated aldehyde with a molecular oxygen-containing gas to produce an unsaturated carboxylic acid! Accordingly, there is provided a method for producing a composite oxide catalyst which provides a high conversion rate of a raw material unsaturated aldehyde and a high selectivity of an unsaturated carboxylic acid, and shows stable performance over a long period of time.
• the conversion rate of acrolein per catalyst unit is improved, the selectivity of acrylic acid for the catalyst is improved, and the activity of V-complex oxidation for efficiently performing the gas phase catalytic oxidation reaction of acrolein is improved.
• Product catalyst can be manufactured.
• the composite oxide catalyst produced by the present invention is represented by the above formula.
• X, Y, a, b, c, d, e, f, and g are respectively as described above.
• Such a composite oxide catalyst of the present invention is produced by integrating a source compound of each catalyst component constituting the above formula in the presence of an organic acid.
• the term "source compound of each catalyst component” means that the source compound of each catalyst component element is mixed in an aqueous medium system, preferably an aqueous solution or an aqueous dispersion, and optionally mixed. Aging treatment.
• the above-mentioned constant time preferably refers to a range of 1 minute to 24 hours, and the constant temperature preferably ranges from room temperature to 200 ° C.
• the above integration not only the source compound of each element constituting the catalyst but also a carrier material such as alumina, silica, and a heat-resistant oxide may be included as a target of such an integration. it can.
• an organic acid having a property of being easily soluble in water can be used.
• citric acid, oxalic acid and malic acid are preferably at least one selected from the group.
• the amount of the organic acid is preferably 0.001 to 1 mol, more preferably 0.01 to 0.5 mol, per mol of mol.
• the amount of the organic acid is less than 0.001 mol, no improvement in the catalytic performance is observed.On the contrary, when the amount of the organic acid is more than 1 mol, the catalytic performance deteriorates, which is preferable. Absent.
• the source compound of each component of the composite oxide catalyst of the present invention is not particularly limited as long as it is water-soluble or hardly water-soluble, as long as it is a compound that becomes an oxidized product by firing, excluding the silicon carbide compound. Absent. Specific examples of the compound include halides, sulfates, nitrates, ammonium salts, oxides, carboxylate salts, ammonium carboxylate salts, ammonium halide salts, ammonium hydroxide salts, hydrogen acids, and acetyl acetonate of each component. And alkoxides. Specific examples of the raw material compounds of silicon and carbon include green silicon carbide and black silicon carbide, and silicon carbide is preferably a fine powder. As the raw material compound, a compound containing each component alone may be used, or a raw material compound containing two or more components may be used.
• an aqueous solution or aqueous dispersion of the above-mentioned source compound of the catalyst constituent element component is prepared.
• these aqueous solutions or aqueous dispersions are also referred to as slurry solutions.
• the slurry solution can be obtained by uniformly mixing the source compound of each component with water.
• the use ratio of the raw material compound of each component in the slurry solution is determined by the above formula based on the atomic ratio of each catalyst constituent element. May be in the range shown in FIG.
• the organic acid is preferably added at the stage after dissolving Mo and V, even if the organic acid can be added after or during the preparation of the slurry solution.
• the amount of water in the slurry solution is not particularly limited as long as the raw material compounds of the respective components can be completely dissolved or uniformly dispersed. However, the subsequent drying method, drying temperature, and drying are performed. What is necessary is just to determine suitably considering drying conditions, such as time.
• the amount of water is usually 100 to 2,000 parts by weight based on 100 parts by weight of the total amount of the starting material. If the amount of water is less than the above-mentioned predetermined amount, the compound may not be completely dissolved or may not be mixed uniformly. Also, if the amount of water is large, there is a risk that the energy cost during the heat treatment will increase. Through mixing and stirring in the preparation process of the slurry solution, the integration of each element constituting the catalyst proceeds.
• the temperature is preferably room temperature to 200 ° C., particularly preferably 70 to 200 ° C.
• the aging treatment is preferably performed at 100 ° C, preferably for 1 minute to 24 hours, particularly preferably for 30 minutes to 6 hours.
• the aqueous solution or the aqueous dispersion is dried to form a powder.
• the drying is not particularly limited as long as the aqueous solution or the aqueous dispersion can be sufficiently dried and a powder can be obtained, and examples thereof include drum drying, freeze drying, and spray drying.
• Spray drying is a method that can be preferably applied to the present invention because it can be dried to a homogeneous powder state in a short time in an aqueous solution or aqueous dispersion.
• the drying temperature varies depending on the concentration of the slurry solution and the like, and is usually 90 to 200 ° C, preferably 130 to 170 ° C.
• the particle size of the powder obtained by vigorous drying is preferably 10-200 / zm. For this reason, the powder can optionally be dried and then powdered.
• the powder obtained by the drying is molded as follows.
• the molding method is not particularly limited.
• the molding is performed using a binder.
• Preferred binders are selected from silica, graphite and crystalline cellulose as well as group forces.
• the solder can be used in an amount of preferably about 110 to 50 parts by weight based on 100 parts by weight of the powder.
• inorganic fibers such as ceramics fibers and whiskers can be used as a material for improving the mechanical strength of the catalyst particles.
• potassium titanate whiskers and basic magnesium carbonate whiskers Fibers that react with such catalyst components are not preferred. Ceramic fibers are particularly preferred for improving strength.
• the amount of these fibers used is preferably 1 to 30 parts by weight based on 100 parts by weight of the powder.
• the above-mentioned molding aid is usually used by being previously mixed with a powder.
• the powder mixed with a molding aid such as a binder is molded by a method such as (A) tablet molding, (B) extrusion molding, and (C) a spherical or other shape supporting molding method.
• the shape of the molded body is preferably selected to be an appropriate shape such as a sphere, a column, or a ring.
• the molded product thus formed is then calcined to obtain a composite catalyst.
• the sintering temperature can be usually 250-500 ° C, preferably 300-420 ° C, and the sintering time is 150 hours.
• the calcination can be performed in an atmosphere in the presence of an inert gas or molecular oxygen. When the firing temperature is too low, the molybdenum element may be lost due to sublimation if the thermal diffusion of the element is too high.
• the reaction is carried out using a fixed-bed tube reactor. In this case, the reaction can be carried out under a condition generally used for this type of reaction, whether it is a single flow method or a recycling method through a reactor.
• the night bath used in the examples is a salt bath in which a reaction tube is placed in a heat medium which also has a nitrate power of an alkali metal and reacts.
• the heat medium is melted at 200 ° C or higher and used up to 400 ° C. It is possible and has good heat removal efficiency, so it is a reaction bath suitable for an oxidation reaction that generates a large amount of heat.
• the acrolein conversion, acrylic acid selectivity, and acrylic acid yield are defined by the following formulas.
• Akurorein conversion (mol 0/0) 100 X (moles of reacted Akurorein) / (number of moles of the supplied Akurorein)
• Acrylic acid selectivity (mol%) 100 X (number of moles of acrylic acid generated) Z (number of moles of acrolein subjected to transfer)
• Acrylic acid yield (mol 0/0) 100 X (acrylic acid mol number generated) Z (Akurore Inmoru number of supplied)
• a composite metal oxide in which the empirical formula of the constituents excluding oxygen is Mo V Nb Cu Si C
• Example 2 A composite metal oxide in which the empirical formula of the constituents excluding oxygen is Mo V Nb Cu Si C
• the acrolein conversion ratio was 99.0%
• the selectivity for acrylic acid was 97.2%
• the yield of atalylic acid was 96.2%.
• a composite metal whose empirical formula for the components other than oxygen is Mo V Nb W Cu Sb Si C
• An acidified product was prepared as follows.
• the acrolein conversion rate was 99.0%
• the selectivity for acrylic acid was 98.7%
• the yield of atalylic acid was 97.7%.
• a composite metal oxide in which the empirical formula of the constituents excluding oxygen is Mo V Nb Cu Si C
• the catalyst produced by the method of the present invention is used for producing a corresponding unsaturated carboxylic acid in a high yield by subjecting an unsaturated aldehyde to gas-phase catalytic oxidation with a molecular oxygen-containing gas.
• Manufactured unsaturated carboxylic acids such as acrylic acid are widely used as raw materials for various chemicals, monomers for general-purpose resins, monomers for functional resins such as water-absorbing resins, flocculants, thickeners, etc. Used for

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• 2004
  • 2004-09-30 WO PCT/JP2004/014379 patent/WO2005089943A1/ja active Application Filing
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