Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten 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
  • B01J23/002—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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
  • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
• • 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
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
  • B01J27/198—Vanadium
  • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
  • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

• TITLE CATALYST FOR METHACROLEIN OXIDATION AND METHOD FOR
• the present invention relates to a heteropolyacid catalyst including molybdenum (Mo), and phosphorus (P) for use in producing unsaturated acids such as acrylic acid, methacrylic acid or the like in the gas-phase catalytic oxidation of unsaturated aldehydes such as methacrolein, acrolein, or the like or saturated aldehydes such as isobutyraldehyde, where the catalyst components are acidified using an organic acid and method.for making and using same.
• Mo molybdenum
• P phosphorus
• the present invention relates to a heteropolyacid catalyst including molybdenum (Mo) and phosphorus (P) and optionally vanadium (V), bismuth (Bi), and copper (Cu), an optional first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof, and an optional second component selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Zr),
• Mo molyb
• 5,102,847 discloses a catalyst made by using at least one bismuth compound selected from the group consisting of bismuth nitrate and bismuth oxide as a source of bismuth and using nitric acid of more than 1 mole to not more than 5 moles based on 12 moles of molybdenum atoms for dissolving the bismuth compound(s).
• bismuth compound selected from the group consisting of bismuth nitrate and bismuth oxide
• 6,624,326 discloses a process for producing methacrylic acid through vapor phase oxidation or vapor phase oxydehydrogenation of at least one of methacrolein, isobutyl aldehyde and isobutyric acid in the presence of a heteropolyacid catalyst containing a heteropolyacid composed of at least one of molybdophosphoric acid and molybdovanadophosphoric acid or a salt of the heteropolyacid, characterized in that said heteropolyacid catalyst has been prepared by a method comprising preparing an aqueous solution or aqueous dispersion which (1) contains the nitrogen-containing heterocyclic compound, nitrate anions and ammonium ions, (2) the ammonium ion content not exceeding 1.7 moles per mol of the nitrate anion content, and (3) the ammonium ion content not exceeding 10 mols per 12 mols of the molybdenum atom content, by mixing raw materials containing the catalyst-constitu
• IBA means isobutanal sometimes also referred to as isobutyraldehyde.
• MAC methacrolein
• MAA means methacryclic acid.
• T means temperature
• P means pressure
• HC means hydrocarbon
• aldehyde feedstock means a stream including mixtures of isobutanal and methacrolein.
• GC gas chromatography
• FID flame ionization detector of a GC.
• h or hr or hrs means hours.
• mL means milliliter
• min or min. means minutes.
• wt% or wt.% means weight percent.
• vol% or vol.% means volume percent.
• DI water means deionized water.
• pore volume distribution means a desired concentration of small pores, medium pores and large pores.
• small pores means pores having a diameter D less than about 10OA, i.e., D ⁇ 10OA.
• medium pores means pores having a diameter D greater than or equal to about 100 A and less than about 100OA, i.e., IOOA ⁇ D ⁇ 100OA.
• large pore volume means pores having a diameter D greater than or equal to about
• the present invention provides a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo) and phosphorus (P), adapted to gas-phase oxidize unsaturated and/or saturated aldehydes to unsaturated acids, where the catalyst components are acidified with an organic acid.
• Mo molybdenum
• P phosphorus
• the use of an organic acid to acidify the pre-catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• the present invention provides a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo) and phosphorus (P), adapted to gas-phase oxidize unsaturated and/or saturated aldehydes to unsaturated acids, where the catalyst is prepared using an organic acid to acidify the catalyst precursor solution.
• Mo molybdenum
• P phosphorus
• the use of an organic acid to acidify the pre- catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• a majority (>50%) of the pores in the catalyst are medium pores.
• the present invention provides a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo), phosphorus (P) and vanadium (V), adapted to gas- phase oxidize unsaturated and/or saturated aldehydes to unsaturated acids, where the catalyst components are acidified with an organic acid.
• Mo molybdenum
• P phosphorus
• V vanadium
• the use of an organic acid to acidify the pre-catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• the resulting catalyst has a pore size distribution comprising at least 57% medium pores.
• the present invention provides a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo), phosphorus (P), vanadium (V) and bismuth (Bi), adapted to gas-phase oxidize unsaturated and/or saturated aldehydes to unsaturated acids, where the catalyst components are acidified with an organic acid.
• Mo molybdenum
• P phosphorus
• V vanadium
• Bi bismuth
• the use of an organic acid to acidify the pre- catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• the resulting catalyst has a pore size distribution comprising at least 57% medium pores.
• the present invention provides a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo), phosphorus (P), vanadium (V), bismuth (Bi), and a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof, adapted to gas-phase oxidize unsaturated and/or saturated aldehydes to unsaturated acids, where the catalyst components are acidified with an organic acid.
• Mo molybdenum
• P phosphorus
• V vanadium
• Bi bismuth
• K potassium
• Rb rubidium
• Cs cesium
• Tl thallium
• an organic acid to acidify the pre-catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium- containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• the resulting catalyst has a pore size distribution comprising at least 57% medium pores.
• the present invention provides a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo), phosphorus (P), vanadium (V), bismuth (Bi), and a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof, adapted to gas-phase oxidize unsaturated and/or saturated aldehydes to unsaturated acids, where the bismuth component is dissolved in an organic acid solution prior to mixing the bismuth component with a solution of other components and where the unsaturated aldehydes are selected from the group consisting of methacrolein, acrolein, similar unsaturated aldehydes and mixtures or combinations thereof or saturated aldehydes including isobutyraldehyde and where ' the unsaturated acids are selected from the group consisting of acrylic acid, methacrylic acid, similar unsaturated acids, and mixtures or
• an organic acid to acidify the pre-catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• a majority (>50%) of the pores in the catalyst are medium pores.
• the present invention also provides a heteropolyacid catalyst including molybdenum (Mo), phosphorus (P), vanadium (V), bismuth (Bi), and optionally, copper (Cu), a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof, and an optional second component selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Zr), magnesium (Mg),
• Mo
• the use of an organic acid to acidify the pre-catalyst solution, mixture or slurry generally produces a catalyst with a higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• the amount of the ammonium-containing component added to the catalyst preparation is sufficient to produce a catalyst of this invention having a pore size distribution comprising at least 57% medium pores.
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Zr), magnesium (Mg), barium (Ba), lanthanum (La), and mixtures or combinations thereof, a is a number having a value between about 0.5 and about 3.5, b is a number having a value between 0.00 and about 5.0, c is a number having a value between 0.00 and about 1.5, d is a number having a value between 0.00 and about 2.0, e is a number having
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between about 0.01 and about 5.0
• c is a number having a value between 0.00 and about 1.5
• d is a number having a value between 0.00 and about 2.0
• e is a number having a value between 0.00 and about 2.5
• f is a number having a value between 0.00 and about 5.0
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between 0.00 and about 5.0
• c is a number having a value between 0.00 and about L5
• d is a number having a value between about 0.01 and about 2.0
• e is a number having a value between 0.00 and about 2.5
• f is a number having a value between 0.00 and about 5.0
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between about 0.01 and about 5.0
• c is a number having a value between 0.00 and about 1.5
• d is a number having a value between about 0.01 and about 2.0
• e is a number having a value between 0.00 and about 2.5
• f is a number having a value between 0.00 and about 5.0
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between about 0.01 and about 5.0
• c is a number having a value between about 0.01 and about 1.5
• d is a number having a value between about 0.01 and about 2.0
• e is a number having a value between 0.00 and about 2.5
• f is a number having a value between 0.00 and about 5.0
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between about 0.01 and about 5.0
• c is a number having a value between about 0.01 and about 1.5
• d is a number having a value between about 0.01 and about 2.0
• e is a number having a value between about 0.01 and about 2.5
• f is a number having a value between 0.00 and about 5.0
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Zr), magnesium (Mg), barium (Ba), lanthanum (La), and mixtures or combinations thereof, a is a number having a value between about 0.5 and about 3.5, b is a number having a value between about 0.01 and about 5.0, c is a number having a value between about 0.01 and about 1.5, d is a number having a value between about 0.01 and about 2.0, e is a
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula:
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between about 0.1 and about 5.0
• c is a number having a value between about 0.05 and about 1.5
• d is a number having a value between about 0.1 and about 2.0
• e is a number having a value between about 0.2 and about 2.5
• f is a number having a value between about 0.1 and about
• the present invention also provides a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids of the general formula: x
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof, at least two elements Mil selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Zr), magnesium (Mg), barium (Ba), lanthanum (La), and mixtures or combinations thereof, a is a number having a value between about 1.0 and about 2.5, b is a number having a value between about 0.1 and about 2.5
• the present invention provides a method for preparing a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids.
• the references to moles used in describing the preparation of the catalysts of this invention mean relative molar amounts, e.g., if 1 mole of catalyst is being prepared, the catalyst will have moles of components such that the molar ratio of molybdenum to the other components in the catalyst is 12.
• the number of moles of components used during catalyst preparation will be in a molar ratio of 12:a:b:c:d:e:f:g.
• the method includes the step of forming a mixture of 12 moles of molybdenum (1 mole of Mo 12 ), a moles of phosphorus (P), b moles of vanadium (V), c moles of copper (Cu), d moles of bismuth (Bi), e moles of a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof and f moles of a second component selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tant
• the other catalyst components having relative mole amounts b, c, d, e, and f can be added to the catalyst preparation in any order with starting amounts of: 0.01 for b, 0.01 for c, 0.01 for d, 0.01 for e, and 0.01 for f.
• the bismuth is first dissolved in the organic acid and this solution is then added to a solution of the other components.
• the first component is cesium
• the cesium is added to the solution of the other components.
• the pre-catalyst which can be a solution, slurry, dispersion or suspension is then evaporated to form a dried catalytic material, which is then calcined to form a catalyst of this invention.
• the use of an organic acid to acidify the pre- catalyst solution, mixture or slurry generally produces catalyst with higher amount of medium pores, but an optional amount of an ammonium-containing compound can also be added to the catalyst to increase the amount of medium pores formed in the catalyst.
• the amount of an ammonium-containing component is added to the catalyst preparation to produce a pore size distribution comprising at least 50% medium pores, preferably, at least 57% medium pores.
• the present invention also provides a method for preparing preferred novel, highly active and highly selective, heteropolyacid catalysts of Formula (VII) for converting unsaturated and/or saturated aldehydes to unsaturated acids including the steps of forming a first solution including 12 moles of molybdenum (1 mole Of Mo 12 ), a moles of phosphorus (P), b moles of vanadium (V), c moles of copper (Cu), optionally ⁇ moles of bismuth (Bi), e moles of a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof and f moles of a second component selected from the group consisting of antimony (Sb), boron (B), tungsten (
• the present invention provides a method for preparing a novel, highly active and highly selective, heteropolyacid catalyst for converting unsaturated and/or saturated aldehydes to unsaturated acids including the steps of forming a first solution including 12 moles of molybdenum (1 mole OfMo 12 ), a moles of phosphorus (P), b moles of vanadium (V), c moles of copper (Cu), all or some of e moles of a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof and all or some of f moles of a second component selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic
• substantially free of precipitates means that the amount of precipitate present in the solution is less than 5 wt.%, preferably less than 2.5 wt.%, particularly less than 1 wt.% and especially less than 0.5 wt.%, with the ultimate goal being completely solid-free or precipitate-free.
• a bismuth solution including d moles of a bismuth (Bi) component and a sufficient amount of an organic acid to completely dissolve the bismuth component, optionally a remainder of the e moles of the first component and optionally some or all of a remainder of the f moles of the second component is formed, where d is a number having a value between about 0.01 and about 2.0 and the bismuth solution is substantially free of precipitates.
• the bismuth solution is then added to the first solution to form a slurry.
• the slurry is then evaporated to form a dried catalytic material, which is then calcined to form a catalyst of this invention.
• the slurry is heated to about 95 0 C prior to drying and some or all of the remainder of the f moles of second component are added to the heated slurry, where generally the second components added to the heated slurry are second components that require a higher temperature for proper incorporation into the catalyst.
• the resulting composition is then evaporated to form a dried catalytic material, which is then calcined to form a catalyst of this invention. It should be recognized that many of the components can be added to the first solution, the bismuth solution, the slurry or the catalyst before calcining, depending on the specific catalyst being prepared.
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between about 0.1 and about 5.0
• c is a number having a value between about 0.05 and about 1.5
• d is a number having a value between about 0.1 and about 2.0
• e is a number having a value between about 0.2 and about 2.5
• f is a number having a value between about 0.1 and about 5.0
• g is a number having a value representing a sufficient number of oxygen atoms to balance the oxidation state of the catalyst.
• the above method can also be used to prepare preferred catalysts of Formula (IX) where a is a number having a value between about 1.0 and about 2.5, b is a number having a value between about 0.1 and about 2.5, c is a number having a value between about 0.05 and about 0.5, d is a number having a value between about 0.1 and about 1.0, e is a number having a value between about 0.2 and about 2.0, f is a number having a value between about 0.1 and about 2.0, and g moles of oxygen atoms needed to balance the oxidation state of the catalyst.
• the present invention also provides a method for preparing unsaturated acids including the step of contacting an unsaturated and/or saturated aldehyde with a catalyst of this invention to form a corresponding unsaturated acid, where the method is ideally suited for the production of acrylic acid from acrolein or methacrylic acid from methacrolein or both.
• the present invention provides a method for preparing unsaturated acids including the step of contacting an appropriate alkene with a mixed metal oxide catalyst to form a corresponding unsaturated and/or saturated aldehyde and subsequently contacting the unsaturated and/or saturated aldehyde with a catalyst of this invention to form a corresponding unsaturated acid, where the method is ideally suited for the production of acrylic acid and/or methacrylic acid.
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Zr), magnesium (Mg), barium (Ba), lanthanum (La), or mixtures or combinations thereof, a is a number having a value between about 0.5 and about 3.5, b is a number having a value between 0.00 and about 5.0, c is a number having a value between 0.00 and about 1.5, d is a number having a value between 0.00 and about 2.0, e is a number having
• the catalysts of Formula (I) can be prepared by a method where the bismuth component is dissolved in a solution including a sufficient amount of an organic acid to substantially dissolve the bismuth component prior to its addition to a solution containing the other components.
• the catalysts preferably have at least 57% medium pores, which are formed during a controlled calcination process.
• the catalysts of this invention are preferably prepared using water as the solvent, i. e. , the liquid phase is an aqueous liquid phase
• the catalysts of this invention can be made using a mixed aqueous/organic liquid phase, a mixed aqueous/non- aqueous liquid phase, non-aqueous liquid phase or organic liquid phase.
• organic means a carbon-containing
• non-aqueous means a non-aqueous solvent that does not contain carbon.
• the present invention broadly relates a novel, highly active and highly selective, heteropolyacid catalyst including at least molybdenum (Mo), phosphorus (P), optionally vanadium (V), optionally bismuth (Bi), and optionally a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof, adapted to gas-phase oxidize unsaturated aldehydes prepared with an organic acid, especially conjugated unsaturated and/or saturated aldehydes, to unsaturated acids.
• Mo molybdenum
• P phosphorus
• V optionally vanadium
• Bi optionally bismuth
• a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof adapted to gas-phase oxidize unsaturated aldehydes prepared with an organic acid, especially conjugated unsaturated and/or
• the catalysts are especially well suited for oxidatively converting unsaturated and/or saturated aldehydes selected from the group consisting of acrolein, methacrolein, similar unsaturated and/or saturated aldehydes and mixtures or combinations thereof to unsaturated acids selected from the group consisting of acrylic acid, methacrylic acid, similar unsaturated acids, and mixtures or combinations thereof.
• the present invention relates to a heteropolyacid catalyst including molybdenum (Mo), phosphorus (P), optionally vanadium (V), optionally bismuth (Bi), optionally, copper (Cu), optionally a first component selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), or mixtures or combinations thereof, and optionally a second component selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium (Ce), niobium (Nb), indium (In), iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), arsenic (As), silver (Ag), zinc (Zn), lead (Pb), tin (Sn), titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), germanium (Ge), gallium (Ga), zirconium (Mo),
• MI is selected from the group consisting of potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), and mixtures or combinations thereof,
• Mil is selected from the group consisting of antimony (Sb), boron (B), tungsten (W), cerium
• a is a number having a value between about 0.5 and about 3.5
• b is a number having a value between 0.00 and about 5.0
• c is a number having a value between 0.00 and about i.5
• d is a number having a value between 0.00 and about 2.0
• e is a number having a value between 0.00 and about 2.5
• f is a number having a value between 0.0 and about 5.0
• Suitable compounds used for preparation of the catalysts of this invention include, without limitation, metal nitrates, metal carbonates, metal ammonium salts, metal halides, metal oxides, or mixtures or combinations thereof.
• suitable molybdenum components include, without limitation, ammonium paramolybdate, molybdenum trioxide, molybdenum chloride, etc. or mixtures or combinations thereof.
• the preferred molybdenum component is ammonium paramolybdate.
• Suitable vanadium components include, without limitation, ammonium metavanadate, vanadium pentoxide, vanadium chloride, etc. or mixtures or combinations thereof.
• the preferred vanadium component is ammonium metavanadate.
• Suitable phosphorus components include, without limitation, phosphoric acid, ammonium phosphate, etc. or mixtures or combinations thereof.
• the preferred phosphorus component is phosphoric acid.
• Suitable copper components include, without limitation, copper nitrate, copper chloride, etc. or mixtures or combinations thereof.
• the preferred copper component is copper nitrate.
• Suitable bismuth components include, without limitation, bismuth nitrate, bismuth oxide, bismuth acetate, bismuth chloride, etc. or mixtures or combinations thereof.
• the preferred bismuth component is bismuth nitrate.
• Suitable MI components include, without limitation, MI nitrates, MI oxides, MI chlorides, etc. or mixtures or combinations thereof.
• the preferred MI components are MI nitrates and MI oxides or mixtures or combinations thereof.
• Suitable Mil components include, without limitation, Mil nitrates, Mil oxides, Mil chlorides, etc. or mixtures or combinations thereof.
• the preferred Mil components are Mil nitrates and Mil oxides or mixtures or combinations thereof.
• Suitable organic acids for use in the preparation of the catalyst of this invention include, without limitation, any organic acid such as: (1) monocarboxylic acids that are capable of acidifying the preparation to a desired pH value, with or without the addition of a co-acidifying agent such as nitric acid, having between 1 and about 24 carbon atoms, preferably between 1 and about 12 carbon • atoms, and particularly between 1 and about 6 carbon atoms, hydroxylated analogs thereof, or other substituted analogs thereof, provided that the substituent is substantially removed during drying, soaking and/or calcining and causes no adverse effects to the final catalyst; and (2) polycarboxylic acids having between 2 and about 24 carbon atoms, preferably between 2 and about 12 carbon atoms, and particularly between 2 and about 6 carbon atoms, hydroxylated analogs thereof, or other substituted analogs thereof, provided that the substituent is substantially removed during drying, soaking and/or calcining and causes no adverse effects to the final catalyst and is capable of acidifying the preparation to a
• poly means two or more. If bismuth is used in the catalyst preparation, then the bismuth component such as bismuth nitrate or bismuth oxide is dissolved in a solution of the organic acid in the ⁇ presence or absence of water, although in the presence of water is preferred.
• the bismuth component such as bismuth nitrate or bismuth oxide is dissolved in a solution of the organic acid in the ⁇ presence or absence of water, although in the presence of water is preferred.
• organic acids include low to medium molecular weight linear, branched, cyclic-containing or aromatic-containing organic mono acids such as formic acid, acetic acid, propanoic acid, butanoic acid (butyric acid), isobutyric acid, pentanoic acid and its branched analogs, hexanoic acid and its branched analogs, hydroxylated analogs thereof such as ascorbic acid, higher alkanoic acids or their hydroxylated analogs or the like, or mixtures or combinations thereof and linear or branched organic diacids, triacids and polyacids such as citric acid, tartaric acid, or the like and hydroxylated analogs thereof or mixtures or combinations thereof.
• organic mono acids such as formic acid, acetic acid, propanoic acid, butanoic acid (butyric acid), isobutyric acid, pentanoic acid and its branched analogs, hexanoic acid and its branched analogs, hydroxylated analog
• Suitable ammonium-containing compounds for use in this invention include, without limitation, any ammonium compound that undergoes thermal decomposition to volatile components.
• exemplary examples of such ammonium-containing compounds include, without limitation, ammonium hydroxide, ammonium nitrate, ammonium chloride, ammonium bromide, ammonium carbonate, ammonium salts of alkanoic (carboxylic) acids, or mixtures or combinations thereof.
• a mole ratio of the molybdenum-containing compound to the ammonium-containing compound is generally between about 0.5 to about 20.0.
• the mole ratio is between about 2.0 to 15.0, and, particularly, the mole ratio is between about 2.0 to about 10.0.
• the resulting catalysts can be produced with a given pore size distribution comprising small pores, medium pores, and large pores.
• Small pores are pores having a diameter D less than about 10OA, i.e., D ⁇ 10OA.
• Medium pores are pores having a diameter D greater than or equal to about 1 OO ⁇ and less than about 1000 A, i.e., 100 A ⁇ D ⁇ 1000 A.
• Large pores are pores having a diameter D greater than or equal to about lOOOA, i.e., D > 1000 A.
• the catalysts of this invention generally have a pore size distribution comprising between about 0.1% and about 10.0% small pores, between about 55% and about 90% medium pores and the remainder large pores.
• the catalysts of this invention have a pore size distribution comprising between about 0.1% and about 10.0% small pores, between about 55% and about 90% medium pores and the remainder large pores.
• the catalysts of this invention have a pore
• the catalysts of this invention have a pore size distribution comprising between about 1.0% and about 5.0% small pores, at least 57% medium pores and the remainder large pores.
• the catalysts of this invention have a pore size distribution comprising at least 55% medium pores.
• the catalysts of this invention have a pore size distribution comprising between about 55% medium pores and about 90% medium r)ores.
• the catalysts of this invention have a pore size distribution comprising between about 55% medium pores and about 80% medium pores.
• the catalysts of this invention have a pore size distribution comprising between about 57% medium pores and about 80% medium pores. It should be recognized by an ordinary artisan that determining or measuring the pore size or pore size distribution of the catalyst can be based on any standard method such as BET, mercury porosimeter, or similar pore size analyzer.
• the present invention relates to improved catalysts for the oxidation of unsaturated and/or saturated aldehydes, where the catalysts of this invention are prepared from a precursor formulation where a bismuth component is dissolved in a solution including a sufficient amount of an organic acid to substantially dissolve the bismuth component prior to its addition to a solution containing the other components.
• the resulting catalysts can be prepared with an increased amount of medium pores, especially when an ammonium-containing cojnpound is used in the preparation.
• the catalysts of this invention are prepared using a solution of an organic acid to dissolve a bismuth component such as bismuth nitrate (Bi(NO 3 ) 3 ) or other bismuth salts, prior to adding the bismuth component to a solution of the other components and optionally an amount of nitric acid to adjust the pH of the resulting solution to a desired pH value.
• a bismuth component such as bismuth nitrate (Bi(NO 3 ) 3 ) or other bismuth salts
• the bismuth solution is preferably substantially free of precipitates prior to being added to the solution of the other components and upon addition the bismuth solution initiates precipitation.
• Nitric acid referred to here means nitric acid added in producing the catalyst and excludes NO 3 moieties which may be part of the molecular formula for the catalytic components used in preparing the catalysts of this invention.
• the catalysts of this invention are rendered more or less active by a calcination procedure to which they are subjected.
• the general calcination protocol is to calcine a dried catalyst at a temperature and for a time sufficient to obtain a catalyst of a desired activity, generally maximized activity.
• the calcination temperature is above about 35O 0 C and the period of time is between about 2 hours and about 24 hours; however, shorter and longer times can be used.
• the calcination protocol also includes a soak step at a soak temperature and for a soak time sufficient to out gas volatile components and components that form volatile components at high temperature.
• the soak temperature is generally between about 180 0 C and about 250 0 C and the soak period of time is between about 1 hour and about 8 hours; however, shorter and longer times can be used.
• the soak step is designed to allow volatile components and components that form volatile components at high temperature to exit the catalyst gradually and not explosively or so rapidly that the catalyst pore distribution is damaged (collapses or produces too many large pores).
• the protocols include an initial temperature ramp of about 0.25°C/min. to about 0.75 °C/min. for a period of time sufficient to raise the temperature to a desired soak step temperature and a final temperature ramp of about 0.25°C/min. to about 0.75°C/min for a period of time sufficient to raise the temperature to a desired calcination step temperature.
• the ramp rates are generally much higher as is well known in the art of commercial catalyst preparation.
• an ammonium-containing compound is used in conjunction with the organic acid during catalyst preparation to control catalyst pore size distribution, then the components that produce volatile components during drying, soaking and calcining will include nitrates, ammonium salts and the organic acid or its salts.
• the inventors believe that although the amount of nitrate and ammonium ions present in the dried composition is important for producing the desired pore size distribution, the careful control of drying, soaking and calcining conditions is also important in controlling the number of medium pores generated in the final catalyst. If the pre-calcined catalyst is heated too fast, the volatile components have insufficient time to out-gas and the activity of the resulting catalyst is reduced.
• component out gassing can be substantially completed before the catalyst is subjected to its final calcination temperature.
• the catalyst used in the process of the present invention can be used without a carrier, or can be supported on or diluted with an inert carrier.
• Suitable inert carriers include, without limitation, silicates, silicas, aluminates, aluminas, silica-aluminas, silicon carbide, zirconias, titanias, magnesia, similar oxides, other heteropolyacids or mixtures or combinations thereof.
• the catalysts of this invention are ideally suited for producing an unsaturated acid, preferably •a conjugated unsaturated acid such as acrylic acid and/or methacrylic acid by gas-phase catalytic oxidation of a vapor or vapor stream including an unsaturated and/or saturated aldehyde, preferably, a conjugated unsaturated aldehyde such as acrolein and/or methacrolein at a temperature, at a pressure and for a time sufficient to obtain a desired conversion of the unsaturated and/or saturated aldehyde to the corresponding unsaturated acid.
• a conjugated unsaturated acid such as acrylic acid and/or methacrylic acid
• the vapor stream used to contact the catalysts of the present invention generally includes sufficient unsaturated conjugated aldehyde that is converted into an output stream containing commercial quantity of a corresponding unsaturated conjugated acid.
• the vapor stream can have a wide methacrolein concentration range, preferably, the vapor or vapor stream includes from about 1 vol.% to about 20 vol.% of methacrolein, and particularly, the vapor or vapor stream includes from about 2 to about 8 vol.% of methacrolein.
• a methacrolein feed for the preparation of methacrylic acid may also contain large amounts of water and smaller amounts of impurities such as carbon monoxide, carbon dioxide, acetone, acetic acid, acrolein, methacrylic acid, isobutylene and other saturated and unsaturated hydrocarbons, lower saturated aldehydes, etc. , but such impurities have substantially no effect on the conversion of the unsaturated and/or saturated aldehydes to unsaturated acids.
• impurities have substantially no effect on the conversion of the unsaturated and/or saturated aldehydes to unsaturated acids.
• An oxygen concentration in the oxidizing gas used in the conversion of methacrolein to methacrylic acid is set relative to a molar ratio of oxygen to methacrolein.
• the molar ratio has a value between about 0.3 and about 4, preferably, the ratio has a value between about 0.4 and about 2.5.
• the oxidizing gas may be diluted with or contain an inert gas such as nitrogen, steam, carbon dioxide, etc., or mixtures or combinations thereof.
• the oxidation is generally carried out at a reaction pressure between sub-ambient and several atmospheres above ambient, preferably, the pressure is near ambient or as low as practical.
• the oxidation reaction using the catalysts of this invention is generally carried out at an elevated temperature, preferably, at a temperature between about 230 0 C and about 450 0 C, particularly, at a temperature between about 25O 0 C and about 400 0 C and more particularly, at a temperature between about 250 0 C and about 350 0 C.
• the oxidation reaction using the catalysts of this invention can be carried out using a variety of reactor systems including a fixed bed reactor (a reactor having one or more fixed catalyst beds or zones), a fluidized bed reactor (recycling catalyst particles in the reactor are fluidized), a moving bed reactor (catalyst moves in and out of the catalyst zone(s)), a continuous stirred tank reactor or any other reactor system geared for carrying out an oxidizing reaction such as the conversion of unsaturated and/or saturated aldehydes to unsaturated acids.
• a fixed bed reactor a reactor having one or more fixed catalyst beds or zones
• a fluidized bed reactor repeating catalyst particles in the reactor are fluidized
• a moving bed reactor catalyst moves in and out of the catalyst zone(s)
• a continuous stirred tank reactor or any other reactor system geared for carrying out an oxidizing reaction such as the conversion of unsaturated and/or saturated aldehydes to unsaturated acids.
• Example 1 illustrates the preparation of a catalyst of this invention
• Comparative Example 1 illustrates the preparation of a comparative catalyst.
• Examples are also included that analyze the calcination and performance data for the catalysts of this invention and the comparative example reported herein as relative data.
• the activity of the comparative example catalyst was defined as 1.0, so that if a catalyst showed an activity 30% higher than the comparative example catalyst, then this catalyst would have a relative activity of 1.3.
• the relative selectivity of the comparative example was defined as 0.0.
• nitric acid when used that term means about a 70 wt.% aqueous solution of nitric acid. It should be recognized by ordinary artisans that any concentrated nitric acid solution can be used provided that the amount added is adjusted to achieve the desired mole ratio. Also in the following examples, when the term phosphoric acid is used the term means about an 85 wt.% phosphoric acid solution. It should be recognized by ordinary artisans that any concentrated phosphoric acid solution can be used provided that the amount added is adjusted to achieve the desired mole ratio. Also the term acetic acid means glacial acetic acid.
• the MoVCsPCuBi slurry was then heated to 95°C and then 2.56 grams of antimony trioxide and 0.68 grams of boric acid were added to the MoVCsPCuBi slurry to form an MoVCsPCuBiSbB slurry.
• the MoVCsPCuBiSbB slurry was then evaporated at between about 75 and about 100 0 C to form an evaporated mixture.
• the evaporated mixture was then dried at about 130 0 C for about 16 hours and sieved to obtain particles having a size between about 20 and 30 mesh.
• the particles were then heated to a soak temperature of 23O 0 C at a rate of 0.5°C/min and held at the soak temperature for 3 hours in air.
• the particles were then calcined at 370 0 C at a rate of 0.5°C/min. for 5 hours in air to form the catalyst of this invention.
• Example 3 illustrates the preparation of a catalyst of this invention having the following formula Mo 12 P 1-5 V 0-5 Cu 0-1 Bi 0-5 Sb 0-8 Cs 1 0 B 05 O g by the method of Example 1, but order of addition of the bismuth solution and the nitric- acid solution are reversed.
• Example 3 illustrates the preparation of a catalyst of this invention having the following formula Mo 12 P 1-5 V 0-5 Cu 0-1 Bi 0-5 Sb 0-8 Cs 1 0 B 05 O g by the method of Example 1, but order of addition of the bismuth solution and the nitric- acid solution are reversed.
• Example 3 illustrates the preparation of a catalyst of this invention having the following formula Mo 12 P 1-5 V 0-5 Cu 0-1 Bi 0-5 Sb 0-8 Cs 1 0 B 05 O g by the method of Example 1, but order of addition of the bismuth solution and the nitric- acid solution are reversed.
• Example 3 illustrates the preparation of a catalyst of
• Example 4 illustrates the preparation of a catalyst of this invention having the following formula Mo 12 P 1-5 V 0-5 Cu 0-1 Bi 0-5 Sb 0-8 Cs 1-0 B 0-5 O g by the method of Example 1 , but 3.8 grams of nitric acid are used instead of 4.3 grams of nitric acid as in Example 1.
• Example 4
• Example 5 The following example illustrates the preparation of a catalyst of this invention having the following formula Mo 12 P 1-5 V 0-5 Cu 0-2 Bi 015 Sb 048 Cs 1-0 B 015 O g by the method of Example 1 , but the amount of copper nitrate used yielded a final Cu mole amount of 0.2 instead of 0.1 as in Example 1 and the amount of glacial acetic acid used was 2.0 mL instead of 4.0 mL as in Example 1 and the amount of nitric acid used was 3.8 grams instead of 4.3 grams as in Example 1.
• Example 1 illustrates the preparation of a catalyst of this invention having the following formula Mo 12 P 1-5 V 0-5 Cu 0-1 Bi 0-5 Sb 0-5 Cs 1-0 B 0-5 O g by the method of Example 1 , but the amount of antimony oxide used yielded a final Sb mole amount of 0.5 instead of 0.8 as in Example 1 and the amount of nitric acid used was 3.8 grams instead of 4.30 grams as in Example 1.
• the MoVCsPCuBiSbB slurry was then evaporated at between about 75 0 C and about 100 0 C to form an evaporated mixture.
• the evaporated mixture was then dried at about 13O 0 C for about 16 hours and sieved to obtain particles having a size between about 20 and 30 mesh.
• the particles were then heated to a soak temperature of 23O 0 C at a rate of 0.5°C/min and held at the soak temperature for 3 hours in air.
• the particles Vere then heated to a calcination temperature of 370 0 C at a rate of
• the MoVCsPCuBi slurry was then heated to 95 0 C and then 2.56 grams of antimony trioxide and 0.68 grams of boric acid were added to the MoVCsPCuBi slurry to form a MoVCsPCuBiSbB slurry.
• the MoVCsPCuBiSbB slurry was then evaporated at between about 75°C and about 100 0 C to form a evaporated mixture.
• the evaporated mixture was then dried at about 130 0 C for about 16 hours and sieved to obtain particles having a size between about 20 and 30 mesh.
• the particles were then heated to a soak temperature of 23O 0 C at a rate of 0.5°C/min and held at the soak temperature for 3 hours in air.
• the particles were then heated to a calcination temperature of 37O 0 C at a rate of 0.5°C/min. for 5 hours in air to form Comparative Example 1.
• Example 1-7 catalysts were tested under identical flow rate and reaction temperature conditions. The resulting data is tabulated in Table II.
• the error in the relative activity data is about ⁇ 10% and the error in relative selectivity is about ⁇ 1%.
• Example 8-10 catalysts were tested under identical flow rate and reaction temperature conditions. The resulting data is tabulated in Table III. TABLE III Catalytic Performance of Examples 8-10 Catalysts
• the error in the relative activity data is about ⁇ 10% and the error in relative selectivity is about ⁇ 1%.
• catalysts made using glacial acetic acid with or without the use of nitric acid to adjust solution pH have a relative activity between about 1.0 and about 3.0 and a relative selectivity between about -0.5 and about 2.0.

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