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
  • B01J23/70—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
• • 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
• • 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
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
  • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
  • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
  • C07C47/22—Acryaldehyde; Methacryaldehyde

Definitions

• the present invention relates to a novel catalyst having high activity and capable of obtaining a target product in a high yield, and particularly when producing an unsaturated aldehyde, an unsaturated carboxylic acid, or a conjugated diene oxidatively, the catalyst activity is improved.
• the present invention relates to a catalyst capable of stably producing a high yield even in a high region.
• by-products may be deposited on the surface of the catalyst or in the gas flow path near the catalyst. These reduce the activity of the catalyst by covering necessary reaction active points on the catalyst surface. Therefore, it is necessary to forcibly increase the activity, and the reaction bath temperature must be increased. As a result, the catalyst is subjected to thermal stress, which causes a reduction in the service life and a further decrease in the selectivity, which leads to a reduction in the yield.
• by-products deposited in the system may cause an increase in the system pressure, which may lower the selectivity and lead to a decrease in yield. In the worst case, a sudden increase in the internal pressure causes an abnormal temperature and a reaction. May run away. In such a case, it is assumed that the operation is stopped for a long time, and that the inside of the system needs to be cleaned and the catalyst needs to be replaced.
• Patent Literature 3 discloses a method of keeping the temperature at a temperature equal to or higher than the boiling point of maleic anhydride in order to prevent clogging of a pipe or the like in the middle part of the first and second stages of the reaction, and devising a very high gas linear velocity.
• Patent Document 4 proposes a method in which the shape of the catalyst used in the subsequent reaction is specified, the porosity between the catalysts is increased, and the clogging of solids from the preceding reactor is suppressed.
• these methods are also not sufficiently satisfactory as industrial methods, and the development of a catalyst that can further improve the yield is desired.
• the process of producing methacrolein and methacrylic acid in order by a two-stage gas-phase catalytic oxidation reaction using isobutylene and t-butyl alcohol as raw materials, and the process of producing methyl methacrylate from methacrylic acid by an esterification reaction is the direct acid method. It is expected to be a highly competitive process because it is safer and has less environmental load compared to other methyl methacrylate production processes, can effectively utilize heat of reaction, and can reduce the price of catalysts.
• isobutylene becomes a poisoning substance in the second-stage reaction in the latter stage, so that the catalytic activity is increased as much as possible. Isobutylene needs to be reduced.
• the reaction bath temperature is increased to increase the isobutylene conversion.
• the methacrolein and / or methacrylic acid yield or selectivity is rapidly increased. Has been found to decrease. That is, it is desired to develop a catalyst having a high yield of methacrolein and / or methacrylic acid even in a region having a high catalytic activity.
• the present invention relates to a method for producing a corresponding unsaturated aldehyde or unsaturated carboxylic acid using propylene, isobutylene, t-butyl alcohol or the like as a raw material, or a gas phase catalytic oxidation method for producing 1,3-butadiene from butenes.
• the present invention proposes a catalyst to be used, which has high selectivity and a high yield of the target product even in a region where the catalytic activity is particularly high.
• the use of the catalyst of the present invention enables long-term operation of the gas phase catalytic oxidation method safely, stably, and at low cost.
• the present inventors have found that a catalyst whose characteristic a, which focuses on the difference between the ionization energies of molybdenum, which is an active site on the catalyst and each element constituting the catalyst, belongs to a specific range greatly contributes to the improvement of the yield. It has been found that when the characteristic b, which focuses on the standard enthalpy of formation of the oxides of the elements constituting the element, also belongs to a specific range, the effect is more remarkably exhibited, and the present invention has been completed. That is, in the characteristic a, the difference in ionization energy affects the acid amount of the catalyst composition, thereby contributing to higher performance of the catalyst. In the characteristic b, the standard enthalpy of formation of the oxide affects the oxidizing power of the catalyst composition. It has been found that it contributes to high performance of the catalyst similarly to the characteristic a.
• the present invention (1) A catalyst in which molybdenum (Mo) is an essential element and the constituent elements in the other catalytically active components satisfy the relationship represented by the following formula (cI): 0.44 ⁇ ⁇ (MoIE ⁇ XIE) ⁇ XC ⁇ ⁇ 1.53 (cI) [In the formula (cI), XIE is the first ionization energy (eV) of each element other than molybdenum, MoIE is the first ionization energy (eV) of molybdenum, and XC is the atomic ratio of the element when molybdenum is 12. When (MoIE-XIE) is smaller than 0, the value is used as 0 for calculation.
• the catalyst of the present invention is very effective for improving the yield in the gas phase catalytic oxidation reaction, particularly in the region where the catalytic activity is high, and uses propylene, isobutylene, t-butyl alcohol or the like as a raw material for the corresponding unsaturated catalyst.
• the catalyst of the present invention is effective for improving the yield even in a region where the catalytic activity is not high, and is also effective in improving the process stability of the partial oxidation reaction accompanied by heat generation such as reduction of ⁇ T (difference between hot spot temperature and reaction bath temperature). It also has the effect of improving the performance.
• [Characteristic a using ionization energy] a ⁇ (MoIE ⁇ XIE) ⁇ XC ⁇ (I)
• the catalyst of the present invention is characterized in that the characteristic a represented by the above formula (I) satisfies 0.44 or more and 1.53 or less for each constituent element of the active component.
• XIE represents the first ionization energy (unit: eV) of each element except molybdenum.
• the first ionization energy is the energy required to remove one electron from a neutral atom.
• bismuth (Bi) is 7.286 eV
• iron (Fe) is 7.902 eV
• cobalt (Co) is 7.881 eV
• nickel (Ni) is 7.640 eV
• zinc (Zn) is 9.394 eV
• sodium (Na) ) Is 5.139 eV
• cesium (Cs) is 3.894 eV
• calcium (Ca) is 6.113 eV
• magnesium (Mg) is 7.647 eV
• aluminum (Al) is 5.986 eV
• silicon (Si) is 8.152 eV.
• MoIE represents the first ionization energy (unit: eV) of molybdenum, specifically, 7.092 eV.
• eV first ionization energy
• XC represents the atomic ratio of the element when molybdenum is set to 12.
• ⁇ in the formula (I) represents the sum of all calculated values of the above elements.
• the characteristic a is the total strength of each constituent element of the catalytically active component which has donated some form of electrons to molybdenum and ionized, and represents a kind of total basicity with respect to molybdenum. If the property a is too high, the acid content will be low, so that the raw materials such as propylene, isobutylene, t-butyl alcohol, etc. will be less likely to be adsorbed, resulting in low activity. It becomes an adsorbed state, and although it is highly active, its selectivity is significantly reduced. That is, it has been found that the yield is reduced if the property a is too high or too low, and it has been clarified by the present inventors that there is an appropriate range.
• ⁇ (MoIE ⁇ XIE) ⁇ XC ⁇ which is the sum of calculated values of all elements in the constituent elements of the catalytically active component, is 0.44 or more and 1.53 or less. When it is within this range, the yield of the gas phase catalytic oxidation reaction is greatly improved.
• the upper limit of the value of ⁇ (MoIE-XIE) ⁇ XC ⁇ is 1.53, but is preferably 1.40, more preferably 1.35, further preferably 1.30, and particularly preferably 1.20. , Most preferably 1.10.
• the lower limit is 0.44, preferably 0.50, more preferably 0.70, even more preferably 0.80, particularly preferably 0.85, and most preferably 0.90.
• the standard enthalpy of formation of an oxide means the heat of reaction that forms the most stable oxide under a standard condition (standard temperature: 298.15 K, standard pressure: 100,000 Pa).
• a standard condition standard temperature: 298.15 K, standard pressure: 100,000 Pa.
• bismuth (Bi) it becomes -573.9 kJ ⁇ mol ⁇ 1 which produces Bi 2 O 3 .
• iron (Fe) it becomes -824.2 kJ ⁇ mol -1 which produces Fe 2 O 3 .
• cobalt (Co) is -237.9 kJ ⁇ mol ⁇ 1
• nickel (Ni) is ⁇ 489.5 kJ ⁇ mol ⁇ 1
• zinc (Zn) is ⁇ 350.5 kJ ⁇ mol ⁇ 1
• sodium ( Na) is ⁇ 414.2 kJ ⁇ mol ⁇ 1
• cesium (Cs) is ⁇ 345.8 kJ ⁇ mol ⁇ 1
• calcium (Ca) is ⁇ 634.9 kJ ⁇ mol ⁇ 1
• magnesium (Mg) is ⁇ 601.6 kJ ⁇ mol ⁇ 1 .
• the oxide of each element is assumed to be in the most stable oxidation state in principle, and a transition metal element having a plurality of valences such as iron is to be considered according to the valence of the raw material at the time of preparing the catalyst.
• XS is a stoichiometric number of each element contained in the oxide.
• bismuth (Bi) is Bi 2 O 3 and thus “2”.
• the case of bismuth (Bi) 573.9kJ ⁇ mol -1 ⁇ 2 286.95kJ ⁇ mol -1.
• XC represents the atomic ratio of the element when molybdenum is 12, as in the case of formula (I).
• ⁇ in the formula (II) represents the sum of all the calculated values of the above elements, as in the case of the formula (I).
• the characteristic b is the sum of the degree of bonding between each constituent element of the catalytically active component and the oxygen atom, and indicates the degree of oxidizing power when the raw material is partially oxidized. If the property b is too high, the oxidizing power becomes high, so that propylene, isobutylene, t-butyl alcohol and the like as raw materials are supplied with an excessive amount of oxygen, and the decomposition and combustion of the raw material significantly reduce the selectivity.
• ⁇ ( ⁇ X ⁇ H ⁇ XS ⁇ XC) ⁇ 10 ⁇ 3 which is the sum of all calculated values of the constituent elements of the catalytically active component, is 0.1 or more and 3.6 or less. When it is within this range, the yield of the gas phase catalytic oxidation reaction is greatly improved.
• the upper limit of the value of ⁇ ( ⁇ X ⁇ H ⁇ XS ⁇ XC) ⁇ 10 ⁇ 3 is 3.6, but is preferably 3.50, more preferably 3.45, still more preferably 3.40, and particularly preferably. It is 3.35, most preferably 3.30.
• the lower limit is 0.10, but is preferably 0.50, more preferably 1.0, even more preferably 1.5, particularly preferably 2.0, and most preferably 2.5.
• the catalyst of the present invention is not particularly limited in terms of composition as long as the above formula (I) satisfies the range of the present invention, but may contain bismuth (Bi), iron (Fe) and cobalt (Co). More preferred. In addition, one of the more preferable embodiments is to further contain nickel (Ni) and cesium (Cs).
• a preferred composition as the catalytically active component of the catalyst of the present invention is represented by the following general formula (III).
• Mo molybdenum, Bi is bismuth, Fe is iron, A is nickel, B is at least one element selected from lithium, sodium, potassium, rubidium, cesium, and thallium, C is boron, phosphorus, chromium, At least one element selected from manganese, zinc, arsenic, niobium, tin, antimony, tellurium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, tungsten, zinc, and lead, and D is from silicon, aluminum, titanium and zirconium At least one element selected, E is at least one element selected from alkaline earth metals, and O is oxygen, and
• a lower limit of b1 in the composition of the above formula (III) 0.3 is preferable, 0.5 is more preferable, and 0.7 is particularly preferable.
• the upper limit of b1 is preferably 8, more preferably 5, and particularly preferably 2.
• the lower limit of c1 in the composition of the above formula (III) is preferably 0.4, more preferably 0.8, and particularly preferably 1.4.
• the upper limit of c1 is preferably 10, more preferably 6, and particularly preferably 3.
• a lower limit of d1 'in the composition of the above formula (III) 1 is preferable, 3 is more preferable, and 5 is particularly preferable.
• the upper limit of d1 ' is preferably 15, more preferably 10, and particularly preferably 8 ,.
• the lower limit of d1 in the composition of the above formula (III) is preferably 0.15, more preferably 0.2, more preferably 0.4, and particularly preferably 0.6.
• the upper limit of d1 is preferably 10, more preferably 6, and particularly preferably 3.
• the lower limit of e1 in the composition of the above formula (III) is preferably 0.1, more preferably 0.2, more preferably 0.3, even more preferably 0.32, and particularly preferably 0.34.
• the upper limit of e1 is preferably 0.8, more preferably 0.6, and particularly preferably 0.5.
• As the upper limit of f1 in the composition of the above formula (III), 6 is preferable, and 3 is more preferable.
• the upper limit of g1 in the composition of the above formula (III) is preferably 20 and more preferably 10.
• As an upper limit of h1 in the composition of the above formula (III), 4 is preferable, and 3 is more preferable.
• the starting material for each element constituting the catalyst of the present invention is not particularly limited.
• molybdenum oxide such as molybdenum trioxide, molybdenum oxide, molybdic acid, ammonium paramolybdate, metamolybdenum may be used as a raw material for the molybdenum component.
• Molybdic acid or a salt thereof such as ammonium acid, a heteropoly acid containing molybdenum such as phosphomolybdic acid or silicomolybdic acid or a salt thereof can be used.
• bismuth salts such as bismuth nitrate, bismuth carbonate, bismuth sulfate, and bismuth acetate, bismuth trioxide, and metal bismuth can be used.
• These raw materials can be used as a solid or as an aqueous solution, a nitric acid solution, or a slurry of a bismuth compound generated from the aqueous solution. It is preferable to use a nitrate, a solution thereof, or a slurry generated from the solution.
• Examples of the raw material of the alkali metal as the component B represented by the general formula (III) include, but are not limited to, hydroxides, chlorides, and carbonates of component elements (lithium, sodium, potassium, rubidium, and cesium). , Sulfates, nitrates, oxides or acetates.
• it is a compound containing cesium, for example, cesium hydroxide, cesium chloride, cesium carbonate, cesium sulfate, cesium oxide, etc., and particularly, cesium nitrate is preferably used.
• the acid amount (H) of the catalyst obtained by the ammonia temperature-programmed desorption method becomes high, and the by-product of the high-boiling compound is produced. Is undesirably increased.
• the atomic ratio of the B component raw material is high, by-products of high boiling compounds are reduced and industrial production can be performed for a long period of time, but the conversion of the raw material decreases, and as a result, a satisfactory yield is obtained. Improvement cannot be expected.
• Starting materials for other component elements include ammonium salts, nitrates, nitrites, carbonates, subcarbonates, acetates, chlorides, inorganic acids, and inorganic acid salts of metal elements generally used in this type of catalyst.
• a heteropoly acid, a salt of a heteropoly acid, a sulfate, a hydroxide, an organic acid salt, an oxide or a mixture thereof, and an ammonium salt and a nitrate are preferably used.
• the compounds containing these active ingredients may be used alone or as a mixture of two or more.
• the slurry liquid can be obtained by uniformly mixing each active ingredient-containing compound and water.
• the amount of water used in the slurry liquid is not particularly limited as long as the whole amount of the compound to be used can be completely dissolved or uniformly mixed.
• the amount of water used may be appropriately determined in consideration of the drying method and the drying conditions. Usually, the amount of water used is 200 parts by mass or more and 2000 parts by mass or less based on 100 parts by mass of the total amount of the compound for slurry preparation. Although the amount of water may be large, too much water has many disadvantages such as an increase in energy cost of the drying step and a case where drying cannot be performed completely.
• a nitrate ion concentration in the slurry liquid immediately before the final drying 8.0 to 50% by mass, preferably 9.0 to 45% by mass, more preferably 10.0% by mass Or more, more preferably 40% by mass or less, most preferably 11.0% by mass or more and 30% by mass or less.
• the ammonium ion concentration in the slurry liquid immediately before drying is 1.0% by mass or more and 10% by mass or less, preferably The content is 1.2% by mass to 8% by mass, more preferably 1.5% by mass to 6% by mass, and most preferably 1.7% by mass to 4% by mass.
• the slurry liquid of the source compound of each of the component elements is obtained by mixing the above source compounds in a batch (a), by mixing them in a batch, and then subjecting them to an aging treatment. It is preferable to prepare by a method of mixing, (d) a method of repeating the mixing and aging treatment stepwise, and a method of combining (a) to (d).
• the above-mentioned aging means that "an industrial raw material or a semi-finished product is processed under specific conditions such as a certain time and a certain temperature to obtain necessary physical properties and chemical properties, increase or progress of a predetermined reaction. Operation ".
• the above-mentioned fixed time refers to a range of 5 minutes to 24 hours
• the fixed temperature refers to a range of room temperature to the boiling point of the aqueous solution or the aqueous dispersion.
• the method of mixing in a stepwise manner is preferable in terms of the activity and yield of the finally obtained catalyst, and more preferable is that the raw materials to be mixed in the mother liquor in a stepwise manner are completely dissolved solutions.
• the most preferable method is a method in which a mixed liquid of an alkali metal solution and a nitrate is mixed with a mother liquor prepared by mixing or slurrying a molybdenum raw material.
• the shape of the stirring blade of the stirrer used when mixing the essential active ingredients is not particularly limited, and propeller blades, turbine blades, paddle blades, inclined paddle blades, screw blades, anchor blades, ribbon blades, large grids Arbitrary stirring blades such as blades may be used in one stage, or the same blade or different blades may be used in two or more stages in the vertical direction. Further, a baffle (baffle) may be provided in the reaction tank as needed.
• the drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness.
• spray drying in which the slurry liquid can be dried into powder or granules in a short time, is particularly preferred in the present invention.
• the drying temperature of the spray drying varies depending on the concentration of the slurry liquid, the liquid sending speed, and the like, but the temperature at the outlet of the dryer is generally 70 ° C or more and 150 ° C or less. Further, it is preferable that the dried slurry liquid obtained at this time is dried so that the average particle diameter thereof is 10 ⁇ m or more and 700 ⁇ m or less.
• the catalyst precursor obtained as described above is preliminarily calcined, molded, and finally calcined, whereby the molded shape can be controlled and maintained, and a catalyst having particularly excellent mechanical strength for industrial use can be obtained. As a result, stable catalytic performance can be exhibited.
• any of a molding method in which the carrier is supported on a carrier such as silica and a non-supporting molding method in which the carrier is not used can be adopted.
• Specific molding methods include, for example, tablet molding, press molding, extrusion molding, and granulation molding.
• As the shape of the molded article for example, a columnar shape, a ring shape, a spherical shape and the like can be appropriately selected in consideration of the operating conditions, but a spherical carrier, particularly a catalyst active component supported on an inert carrier such as silica or alumina.
• a supported catalyst having an average particle size of 3.0 mm to 10.0 mm, preferably 3.0 mm to 8.0 mm is used.
• any of the molding aids, pore-forming agents, and carriers that are added during molding are used as constituent elements of the active ingredient in the present invention. Not taken into account.
• the ratio of the catalyst precursor in the finally obtained molded catalyst depends on the activity of the catalyst.
• the ratio of the catalyst precursor in the above-mentioned molded catalyst is calculated as the loading rate from the following formula based on the charged mass of each raw material.
• Loading ratio (mass%) (mass of pre-fired powder used for molding) / ⁇ (mass of pre-fired powder used for molding) + (mass of carrier used for molding) ⁇ ⁇ 100
• the pre-firing method and pre-firing conditions or the main firing method and main firing conditions are not particularly limited, and known processing methods and conditions can be applied.
• the optimal conditions for the pre-firing and the main firing vary depending on the catalyst raw material used, the catalyst composition, the preparation method, etc., but usually under the flow of an oxygen-containing gas such as air or under the flow of an inert gas, preferably from 200 ° C to 600 ° C, preferably Is performed at a temperature of 300 ° C. to 550 ° C. for 0.5 hour or more, preferably for 1 hour to 40 hours.
• the inert gas refers to a gas that does not decrease the reaction activity of the catalyst, and specific examples include nitrogen, carbon dioxide, helium, and argon.
• the main calcination is an important step in determining the activity of the catalyst in the present invention, but when the activity of the catalyst is low or high, the process parameters of the main calcination step, that is, the oxygen content in the atmosphere, the maximum ultimate temperature, It is known to those skilled in the art to adjust the activity by changing the firing time and the like to obtain the highest yield of the composition, and it is within the scope of the present invention.
• the main firing step is performed after the above-mentioned preliminary firing step, and the highest temperature (main firing temperature) in the main firing step is higher than the highest temperature (pre-firing temperature) in the above-mentioned preliminary firing step. To be high.
• the catalyst of the present invention is preferably used as a catalyst for producing an unsaturated aldehyde compound or an unsaturated carboxylic acid compound, and is preferably used as a catalyst for producing an unsaturated aldehyde compound at the first stage. More preferably, it is particularly preferably used as a catalyst for producing methacrolein from isobutylene.
• the catalyst of the present invention When the catalyst of the present invention is used as a catalyst for producing an unsaturated aldehyde compound, a second-stage oxidation reaction can be performed to obtain an unsaturated carboxylic acid compound.
• the catalyst of the present invention can be used as the second stage catalyst, but is preferably a catalyst represented by the following formula (IV).
• a number, d2 is a positive number of 0 ⁇ d2 ⁇ 3.0
• e2 is a positive number of 0 ⁇ e2 ⁇ 3.0
• f2 is a positive number of 0 ⁇ f2 ⁇ 3.0
• g2 is the valence of each element. It is a value determined by the number.
• a method generally known as a method for preparing this type of catalyst for example, an oxide catalyst, a catalyst having a heteropolyacid or a salt structure thereof, is used.
• a method for preparing this type of catalyst for example, an oxide catalyst, a catalyst having a heteropolyacid or a salt structure thereof, is used.
• Raw materials that can be used in producing the catalyst are not particularly limited, and various materials can be used.
• molybdenum compound ammonium molybdate, molybdic acid, molybdenum oxide and the like can be used
• a vanadium compound ammonium metavanadate, vanadium pentoxide and the like
• a phosphorus compound, phosphoric acid or a salt thereof polymerization Phosphoric acid or a salt thereof can be used
• copper compound copper oxide, copper phosphate, copper sulfate, copper nitrate, copper molybdate, copper metal, etc.
• antimony, arsenic, silver, magnesium, zinc, aluminum, Boron, germanium, tin, lead, titanium, zirconium, chromium, rhenium, bismuth, tungsten, iron, cobalt, nickel, cerium, thorium, potassium and rubidium compounds include nitrates, sulfates, carbonates and phosphates, respectively.
• Organic acid salts, halides, hydroxides, oxidation , Metal or the like can be used.
• the compounds containing these active ingredients may be used alone or as a mixture of two or more.
• the slurry liquid obtained above is dried to obtain a catalytically active component solid.
• the drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness. Among them, spray drying, which can dry the slurry liquid into powder or granules in a short time, is preferred.
• the drying temperature of the spray drying varies depending on the concentration of the slurry liquid, the liquid sending speed, and the like, but the temperature at the outlet of the dryer is generally 70 to 150 ° C. At this time, it is preferable that the dried slurry liquid is dried so that the average particle diameter thereof is 10 to 700 ⁇ m.
• the second-stage catalytically active component solids of the present invention are catalysts having a heteropolyacid structure.
• the catalyst having the heteropolyacid structure has phosphorus banadomolybdic acid as a basic skeleton, and other constituent elements are incorporated into the heteropolyacid structure, thereby contributing to improvement of catalytic activity and selectivity, and thermal stability of the structure. It is thought that it has also contributed to the improvement of performance.
• the catalyst having the heteropolyacid structure is a catalyst having a particularly long life.
• the catalyst having a heteropolyacid structure can be easily prepared by a general method for preparing a heteropolyacid.
• the second-stage catalytically active component solid obtained as described above can be used as it is for a coating mixture, or may be fired to improve moldability.
• the firing method and firing conditions at that time are not particularly limited, and known processing methods and conditions can be applied.
• the optimum conditions for the calcination vary depending on the catalyst raw material, catalyst composition, preparation method and the like to be used, but the calcination temperature is usually 100 to 350 ° C, preferably 150 to 300 ° C, and the calcination time is 1 to 20 hours.
• the firing is usually performed in an air atmosphere, but may be performed in an inert gas atmosphere such as nitrogen, carbon dioxide, helium, and argon, or may be further performed as necessary after firing in an inert gas atmosphere.
• the firing may be performed in an air atmosphere.
• the compound containing an active ingredient when preparing the second-stage slurry does not necessarily need to contain all the active ingredients, and some of the ingredients are used before the following coating step. May be.
• the shape of the catalyst in the second stage of the present invention is not particularly limited, and is used by molding into a column, a tablet, a ring, a sphere or the like in order to reduce the pressure loss of the reaction gas in the oxidation reaction.
• This coating step is preferably a rolling granulation method described below. In this method, for example, in a device having a flat or uneven disk at the bottom of a fixed container, by rotating the disk at high speed, the carrier in the container is vigorously agitated by repetition of rotation and revolving motion.
• the method for adding the binder is as follows: 1) preliminarily mixing with the coating mixture, 2) adding the coating mixture into the fixed container at the same time, and 3) adding the coating mixture into the fixed container. 4) Addition before adding the coating mixture into the fixed container, 5) Separate the coating mixture and the binder, and appropriately combine 2) to 4) to add the entire amount. .
• the addition rate is adjusted using an auto feeder or the like so that the coating mixture does not adhere to the fixed container wall and the coating mixture does not agglomerate and the predetermined amount is supported on the carrier.
• the binder is not particularly limited as long as it is at least one selected from the group consisting of water and organic compounds having a boiling point at 150 ° C. or less at 1 atm or less.
• the binder other than water examples include alcohols such as methanol, ethanol, propanols and butanols, preferably alcohols having 1 to 4 carbon atoms, ethers such as ethyl ether, butyl ether or dioxane, and esters such as ethyl acetate or butyl acetate. And ketones such as acetone and methyl ethyl ketone, and aqueous solutions thereof, and ethanol is particularly preferable.
• ethanol / water 10/0 to 0/10 (mass ratio), preferably 9/1 to 1/9 (mass ratio) by mixing with water.
• the amount of the binder to be used is generally 2 to 60 parts by mass, preferably 10 to 50 parts by mass, per 100 parts by mass of the coating mixture.
• the carrier in the coating include a spherical carrier having a diameter of 1 to 15 mm, preferably 2.5 to 10 mm, such as silicon carbide, alumina, silica alumina, mullite, and alundum. These carriers usually have a porosity of 10 to 70%.
• a molding aid used as necessary silica gel, diatomaceous earth, alumina powder and the like can be mentioned.
• the amount of the molding aid used is usually 1 to 60 parts by mass with respect to 100 parts by mass of the catalytically active component solid.
• inorganic fibers for example, ceramics fibers or whiskers
• the amount of these fibers to be used is generally 1 to 30 parts by mass based on 100 parts by mass of the catalytically active component solid.
• any of the added molding aid, pore-forming agent and carrier regardless of the presence or absence of activity in the sense of converting the raw material to some other product, It shall not be considered as a constituent element of the active ingredient in the present invention.
• the coated catalyst obtained as described above can be directly used as a catalyst in a gas-phase catalytic oxidation reaction, but calcining is preferred because the catalytic activity may be improved.
• the firing method and firing conditions are not particularly limited, and known processing methods and conditions can be applied.
• the optimal conditions for the calcination vary depending on the catalyst raw material, catalyst composition, preparation method and the like used, but the calcination temperature is usually 100 to 450 ° C, preferably 270 to 420 ° C, and the calcination time is 1 to 20 hours.
• the firing is usually performed in an air atmosphere, but may be performed in an inert gas atmosphere such as nitrogen, carbon dioxide, helium, and argon, or may be further performed as necessary after firing in an inert gas atmosphere.
• the firing may be performed in an air atmosphere.
• a carrier By supporting the catalyst used in the present invention on a carrier, favorable effects such as improved heat resistance, improved life, and increased reaction yield can be expected.
• known materials such as alumina, silica, titania, zirconia, niovia, silica alumina, silicon carbide, carbide, and mixtures thereof can be used, and further, the particle size, water absorption, mechanical strength, each crystal phase, etc.
• the crystallinity and the mixing ratio of are not particularly limited, and an appropriate range should be selected in consideration of the final catalyst performance, moldability, production efficiency, and the like.
• the catalyst of the present invention is reacted with propylene, isobutylene, t-butyl alcohol or the like as a raw material to produce the corresponding unsaturated aldehyde or unsaturated carboxylic acid.
• a high yield can be achieved in a region where the catalytic activity is high, and an improvement in the price competitiveness of the product can be expected.
• the catalyst of the present invention is effective for improving the yield even in a region where the catalytic activity is not high, and furthermore, the process stability of the partial oxidation reaction accompanied by heat generation such as reduction of ⁇ T (difference between hot spot temperature and reaction bath temperature). It also has the effect of improving the performance.
• the catalysts of the present invention reduce the by-products that adversely affect the environment and the quality of the final product methyl methacrylate, such as carbon monoxide (CO) and carbon dioxide (CO 2 ), acetaldehyde, acetic acid, acrolein, and formaldehyde. It is also effective.
• the catalyst of the present invention thus obtained is obtained by subjecting at least one raw material selected from, for example, isobutylene and t-butyl alcohol to gas-phase catalytic oxidation using a molecular oxygen-containing gas in the presence of an oxidation catalyst composition.
• a raw material selected from, for example, isobutylene and t-butyl alcohol
• gas-phase catalytic oxidation using a molecular oxygen-containing gas in the presence of an oxidation catalyst composition.
• methacrolein and / or methacrylic acid may be an ordinary single circulation method or a recycling method, and can be carried out under generally used conditions, and is not particularly limited.
• isobutylene as a starting material at room temperature is 1 to 10% by volume, preferably 4 to 9% by volume, more preferably 4 to 7.5% by volume, most preferably 4 to 6% by volume, and molecular oxygen is 3 to 10% by volume.
• 20% by volume, preferably 4 to 18% by volume water vapor is 0 to 60% by volume, preferably 4 to 50% by volume, and inert gas such as carbon dioxide and nitrogen is 20 to 80% by volume, preferably 30 to 60% by volume.
• % Of the mixed gas is introduced into the reaction tube at 250 to 450 ° C. under normal pressure to 10 atm at a space velocity of 300 to 5000 hr -1 to carry out the reaction.
• the isobutylene concentration in the raw material gas is low, the oxygen concentration is high, the steam concentration is high, the space velocity is low, the reaction bath temperature is high, and the reaction tube outlet is further increased.
• the pressure is preferably controlled to be high, but these often have a trade-off relationship with the productivity and / or catalytic performance as an industrial catalyst, and should be provided in an optimum range.
• the region where the catalytic activity is high refers to a reaction bath temperature region where the raw material conversion is high unless otherwise specified, and is synonymous with the region where the raw material conversion is high. More specifically, the region where the catalyst activity is high refers to a region where the raw material conversion is 99.0% or more.
• the reaction bath temperature By increasing the reaction bath temperature, the raw material conversion rate increases, but for example, in the first stage reaction of the direct acid method, it is found that the methacrolein and / or methacrylic acid yield or selectivity sharply decreases.
• high yield means that the total yield of methacrolein and / or methacrylic acid is high in a region where the catalytic activity is high, unless otherwise specified.
• the constituent elements of the catalytically active component refer to all the elements contained in the catalyst raw material solution and the catalyst raw material slurry liquid containing molybdenum as a main component before the drying step in the above catalyst production step, unless otherwise specified.
• raw materials that disappear, sublime, volatilize, and burn at 200 ° C. or less and their constituent elements are not included in the constituent elements of the active component of the catalyst.
• a silicon raw material such as fumed silica added at the time of preparing the raw material slurry liquid is included as a constituent element of the catalytically active component and is considered in the calculations of the formulas (I) and (II).
• ⁇ T is a value obtained by subtracting the reaction bath temperature (BT) from the catalyst hot spot temperature (PT), and indicates a measure of the amount of heat generated at the most exothermic part in the partial oxidation type catalytic reaction involving heat generation.
• BT is the maximum temperature of the temperature distribution in the catalyst packed bed where a thermocouple is installed in the long axis direction in the multitubular reaction tube, and BT is used for cooling the heat generated in the reaction tube. This is the set temperature of the heating medium.
• the number of points for measuring the temperature distribution is not particularly limited.
• the catalyst filling length is equally divided from 10 to 1,000.
• the unsaturated aldehyde and the unsaturated aldehyde compound are organic compounds having at least one double bond and at least one aldehyde in a molecule, for example, acrolein and methacrolein.
• the unsaturated carboxylic acid and the unsaturated carboxylic acid compound are organic compounds having at least one double bond and at least one carboxy group in the molecule, or an ester group thereof, for example, acrylic acid, methacrylic acid, Methyl methacrylate.
• the conjugated diene compound is an organic compound having at least two double bonds in a molecule, for example, 1,3-butadiene and 1,3-pentadiene.
• raw material conversion rate (%) (moles of reacted t-butyl alcohol or isobutylene) / (moles of supplied t-butyl alcohol or isobutylene) ⁇ 100
• Effective yield (%) (total number of moles of generated methacrolein and methacrylic acid) / (number of moles of t-butyl alcohol or isobutylene supplied) ⁇ 100
• CO 2 selectivity (%) (mol number of generated CO 2 ) / (mol number of reacted t-butyl alcohol or isobutylene) ⁇ 100
• Loading ratio (mass%) (mass of pre-fired powder used for molding) / ⁇ (mass of pre-fired powder used for molding) + (mass of carrier used for molding) ⁇ ⁇ 100
• Example 1 (Preparation of catalyst 1) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml of pure water and added to the mother liquor 1. Next, 34 parts by mass of ferric nitrate, 103 parts by mass of cobalt nitrate and 10 parts by mass of nickel nitrate were dissolved in 78 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 2 (Preparation of catalyst 2) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 78 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 3 (Preparation of catalyst 3) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 78 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 4 (Preparation of catalyst 4) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 78 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 5 (Preparation of Catalyst 5) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.9 parts by mass of cesium nitrate was dissolved in 44 ml of pure water and added to the mother liquor 1. Next, 29 parts by mass of ferric nitrate, 95 parts by mass of cobalt nitrate and 2.2 parts by mass of nickel nitrate were dissolved in 67 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• a glycerin solution was used as a binder by a tumbling granulation method with respect to the prefired powder.
• the active carrier was formed into a spherical shape so that the loading ratio was 40% by mass.
• the spherical molded product having a particle size of 4.4 mm thus obtained was calcined at 520 ° C. for 5 hours to obtain Catalyst 5 of the present invention.
• Example 6 (Preparation of catalyst 6) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 0.7 parts by mass of cesium nitrate was dissolved in 8 ml of pure water and added to the mother liquor 1. Next, 29 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 73 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 7 (Preparation of catalyst 7) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 0.6 parts by mass of cesium nitrate was dissolved in 7.0 ml of pure water and added to the mother liquor 1. Next, 29 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 73 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 8 (Preparation of catalyst 8) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 1.4 parts by mass of cesium nitrate was dissolved in 16 ml of pure water and added to the mother liquor 1. Next, 33 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 76 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• the spherical molded product having a particle diameter of 4.4 mm thus obtained was calcined at 520 ° C. for 5 hours to obtain a catalyst 8 of the present invention.
• Example 9 (Preparation of catalyst 9) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 90 parts by mass of cobalt nitrate and 33 parts by mass of nickel nitrate were dissolved in 85 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 10 (Preparation of catalyst 10) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 2.5 parts by mass of cesium nitrate was dissolved in 28 ml of pure water and added to the mother liquor 1. Next, 35 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 77 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• a 33% by mass glycerin solution was used as a binder by a tumbling granulation method in an amount of 33% by mass based on the prefired powder.
• the active carrier was formed into a spherical shape so that the loading ratio was 40% by mass.
• the spherical molded product having a particle size of 4.4 mm thus obtained was calcined at 520 ° C. for 5 hours to obtain a catalyst 10 of the present invention.
• Example 11 (Preparation of catalyst 11) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 1.4 parts by mass of cesium nitrate was dissolved in 16 ml of pure water and added to the mother liquor 1. Next, 33 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 76 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Example 12 (Preparation of catalyst 12) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 0.7 parts by mass of cesium nitrate was dissolved in 8 ml of pure water and added to the mother liquor 1. Next, 29 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 73 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Comparative Example 1 (Preparation of Catalyst 13) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 78 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Comparative Example 2 (Preparation of Catalyst 14) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 0.7 parts by mass of cesium nitrate was dissolved in 8 ml of pure water and added to the mother liquor 1. Next, 29 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 73 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• a 33% by mass glycerin solution was used as a binder by a tumbling granulation method, and 33% by mass of the prefired powder was used.
• the active carrier was formed into a spherical shape so that the loading ratio was 40% by mass.
• the spherical molded product having a particle diameter of 4.4 mm thus obtained was calcined at 520 ° C. for 5 hours to obtain a catalyst 14 for comparison.
• Comparative Example 3 (Preparation of Catalyst 15) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 0.7 parts by mass of cesium nitrate was dissolved in 8 ml of pure water and added to the mother liquor 1. Next, 29 parts by mass of ferric nitrate, 99 parts by mass of cobalt nitrate and 11 parts by mass of nickel nitrate were dissolved in 73 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• Comparative Example 4 (Preparation of Catalyst 16) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C (mother liquor 1). Next, 0.4 parts by mass of cesium nitrate was dissolved in 4 ml of pure water and added to the mother liquor 1. Next, 34 parts by mass of ferric nitrate, 110 parts by mass of cobalt nitrate and 16 parts by mass of nickel nitrate were dissolved in 85 ml of pure water heated to 60 ° C., and added to the mother liquor 1.
• a 33% by mass glycerin solution was used as a binder by a tumbling granulation method in an amount of 33% by mass based on the prefired powder.
• the active carrier was formed into a spherical shape so that the loading ratio was 40% by mass.
• the spherical molded product having a particle diameter of 4.4 mm thus obtained was calcined at 520 ° C. for 5 hours to obtain a catalyst 16 for comparison.
• Table 1 shows the results of Examples, Comparative Examples, corresponding test examples, and reaction bath temperatures, effective yields, and the like at a raw material conversion of 99.0% or more according to Comparative Test Examples.
• Table 1 shows the results of Examples, Comparative Examples, corresponding test examples, and reaction bath temperatures, effective yields, and the like at a raw material conversion of 99.0% or more according to Comparative Test Examples.
• the present invention makes it possible to obtain a highly competitive catalyst particularly in the direct acid method without losing the effective yield even in the region where the catalyst activity is high.
• the catalysts of the present invention have reduced ⁇ T and CO 2 selectivity, which indicates that they are effective in improving process stability and reducing by-products.
• the catalysts of the present invention can provide the target compounds methacrolein and methacrylic acid in higher yields than conventional catalysts even in a region where the catalytic activity is particularly high. .
• Table 2 shows, as a reference example, the results of the reaction bath temperature and effective yield at a raw material conversion rate of 98.0% (interpolated value) using the catalysts of the examples and comparative examples.
• the catalyst of the present invention has a high effective yield even in a region where the catalytic activity is not high.
• the catalyst of the present invention when oxidatively producing an unsaturated aldehyde compound, an unsaturated carboxylic acid compound, or a conjugated diene compound, the desired product can be obtained in a high catalytic activity in a high yield region. It is possible.

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