EP2435395A2 - Catalyseur et procédé d'oxydation partielle d'hydrocarbures - Google Patents

Catalyseur et procédé d'oxydation partielle d'hydrocarbures

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Publication number
EP2435395A2
EP2435395A2 EP10724375A EP10724375A EP2435395A2 EP 2435395 A2 EP2435395 A2 EP 2435395A2 EP 10724375 A EP10724375 A EP 10724375A EP 10724375 A EP10724375 A EP 10724375A EP 2435395 A2 EP2435395 A2 EP 2435395A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
value
xylene
powder
catalyst according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10724375A
Other languages
German (de)
English (en)
Inventor
Andrey Karpov
Hartmut Hibst
Christine Deissler
Cornelia Katharina Dobner
Frank Rosowski
Nadine Brem
Stephan Schunk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10724375A priority Critical patent/EP2435395A2/fr
Publication of EP2435395A2 publication Critical patent/EP2435395A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a catalyst for the partial oxidation of hydrocarbons in the gas phase, in particular for the partial oxidation of alkylaromatics to aromatic alcohols, aldehydes, carboxylic acids and / or carboxylic anhydrides, and a method using the catalyst.
  • the partial oxidation of hydrocarbons is understood to mean the oxidation of the hydrocarbons to form unsaturated compounds and / or oxygenates.
  • Technically important examples relate, for example, to the partial oxidation of butane to maleic anhydride, of propane or propene to acrolein or acrylic acid, or of alkylaromatics to aromatic carboxylic acids and / or carboxylic anhydrides, such as phthalic anhydride.
  • a mixture of an oxygen-containing gas, for example air, and the hydrocarbon to be oxidized is passed at elevated temperature through a bed of a catalyst.
  • This partial oxidation presumably proceeds according to a combined parallel and subsequent step mechanism.
  • the educt is oxidized on the catalyst surface consecutively via intermediate oxidation products to the final product.
  • the intermediate oxidation product can either be further oxidized or desorbed from the catalytically active surface.
  • a total oxidation takes place, which starts either directly from the starting material or from an intermediate of the selective route.
  • the selective oxidation of a hydrocarbon to a product of value produces many additional reaction products. These can be essentially divided into two subgroups. One group has a lower C / O atomic ratio compared to the desired product. These suboxidation products can be converted into the target product.
  • the second group includes the over-oxidation products and the carbon oxides CO and CO2 (often summarized as CO x ).
  • EP-A 756 894 describes multimetal oxide compositions containing an active phase and a promoter phase. The phases are relative to each other as in a mixture of finely divided active and promoter phase.
  • the active phase comprises molybdenum, vanadium and at least one of the elements tungsten, niobium, tantalum, chromium and cerium;
  • the promoter phase comprises copper and at least one of molybdenum, tungsten, vanadium, niobium and tantalum.
  • the multimetal oxide materials are z. B. used as catalysts for the oxidation of acrolein to acrylic acid.
  • NL 720 99 21 discloses a process for the continuous production of benzaldehyde by oxidation of toluene in the gas phase in the presence of a catalyst comprising molybdenum and at least one other among nickel, cobalt, antimony, bismuth, vanadium, phosphorus, samarium, tantalum, tin and Contains chromium selected element M in the atomic ratio M / Mo of less than 1: 1.
  • EP-A 0 459 729 describes a catalyst for the preparation of substituted benzaldehydes whose catalytically active composition consists of an oxide of the formula VaMobXcYdOe, in which X is Na, K, Rb, Cs or Th and Y is Nb, Ta, P, Sb, Bi, Te, Sn, Pb, B, Cu or Ag.
  • the invention has for its object to find new multimetal oxides as catalysts for the partial oxidation of hydrocarbons, which lead with high selectivity to the desired value products, in particular for the partial oxidation of alkyl aromatics to aromatic alcohols, aldehydes, carboxylic acids and / or carboxylic anhydrides.
  • a catalyst for the partial oxidation of hydrocarbons in the gas phase which contains a multimetal, which consists essentially of a compound of general formula (I)
  • M for at least one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, Al, Ga, In, Si, Sn, Pb, P, Sb, Bi, Y, Ti, Zr , Hf, V, Nb, Ta, Cr, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Au, Zn, Cd, La, Ce, Pr, Nd , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, U, a has a value of 0.5 to 1.5, b has a value of 0.5 to 1.5 has, c has a value of 0.5 to 1, 5, a + b + c has the value 3, d has a value of less than 1, e a number that is characterized by the valency and frequency of the elements other than oxygen determined in formula I, f has a value from 0 to 20,
  • the invention also relates to a process for the partial oxidation of hydrocarbons in which a gaseous stream comprising at least one hydrocarbon and molecular oxygen is passed over a bed of catalyst.
  • the catalysts of the invention are based on a ternary oxide of silver, molybdenum and vanadium.
  • a ternary oxide of silver, molybdenum and vanadium By incorporating atoms M into the structure, the catalytic properties of the multimetal oxide can be modified in terms of its activity and selectivity.
  • a preferably has a value of from 0.7 to 1.3, in particular from 0.8 to 1.2.
  • b preferably has a value of from 0.7 to 1.3, in particular from 0.8 to 1.2.
  • c preferably has a value of 0.7 to 1.3, in particular 0.8 to 1.2.
  • M is at least one selected from Cs, B, Al, Ga, Pb, P, Sb, Bi, Nb, Cr, W, Re, Fe, Co, Cu, Pt, Pd, Zn, La, Ce Element, in particular for at least one element selected from P, Ce, Sb, Bi, Cs, Nb, W, B, Cu, Fe.
  • d has a value of 0 to 0.5, e.g. From 0.001 to 0.2. In other embodiments, d is 0, that is, an element M is absent.
  • the indication of the X-ray diffraction reflexes in this application takes place in the form of the lattice plane spacings d [ ⁇ ] which are independent of the wavelength of the X-radiation used and which can be calculated from the measured diffraction angle by means of the Bragg equation.
  • the complete powder X-ray diffraction pattern of the multimetal oxide of the formula I has, inter alia, the 1 1 diffraction reflexes listed in Table 1. Less intense diffraction reflections of the powder X-ray diagram of the multimetal oxides of the formula I were not taken into account in Table 1.
  • the multimetal oxide is available in several ways. It is z. B. by reacting at least one silver source, at least one molybdenum source, at least one vanadium source and optionally a source of the element M obtained. In general, a thermal treatment follows at a temperature of at least 200 0 C.
  • a source of silver, a molybdenum source, a source of vanadium, and optionally a source of element M are intimately mixed together.
  • the mixing can be done dry, but preferably wet, for example in a solution and / or suspension in a solvent.
  • a solvent can polar organic solvents such as alcohols, polyols, polyethers or amines, e.g. As pyridine, serve is preferably used as the solvent water.
  • the silver source As the silver source, the molybdenum source, the vanadium source and the source of the element M, the elements themselves, oxides or compounds of the elements which are convertible to oxides upon heating, at least when heated in the presence of oxygen, are used.
  • These include hydroxides, oxide hydroxides, polyoxometalates, carboxylates, carbonates and in particular nitrates.
  • Suitable silver sources are, for example, silver powders, silver oxides (such as Ag 2 O), silver nitrate or silver acetate. Preference is given to using silver nitrate or silver acetate.
  • Suitable molybdenum sources are, for example, molybdenum powder, ammonium molybdate or ammonium polymolybdate (for example ammonium dimolybdate, ammonium heptamolybdate, ammonium octamolybdate, ammonium decamolybdate), molybdenum oxides such as MoO 3, MoO 2, molybdenum halides, molybdenum oxyhalides and molybdenum organyls. Because of its general availability and good solubility, preference is given to using ammonium heptamolybdate.
  • suitable vanadium sources are vanadium powder, ammonium monovadate, ammonium polyvanadates (eg ammonium dodanadate), ammonium metavanad, vanadium oxides (such as V2O5, VO2, V2O3 or VO), vanadium halides, vanadium moxyhalides and vanadium organyls.
  • Alternative vanadium sources are sodium ammonium vanadate, potassium metavanadate and potassium orthovanadate. Due to its general availability and good solubility, preference is given to using ammonium metavanate.
  • the element M compounds which are soluble in the solvent used are generally selected. It is possible, for example, to use the carboxylates, in particular the acetates or oxalates, nitrates, oxides, carbonates or halides. Elemental acids or their ammonium salts can be used when M z. B. stands for P. Formulations of nanoparticles of oxides or hydroxides of elements M may also be used. Furthermore, polyanions such as heteropoly acids of Anderson, Dawson or Keggin type or non-Keggin type can be used as sources for the elements M.
  • the amounts of silver source, molybdenum source, vanadium source and source of the element M resulting from a, b, c and d of the formula (I) are mixed for its preparation.
  • Blending of the silver source, molybdenum source, vanadium source and source of element M can generally be carried out at room temperature or at elevated temperature.
  • the reaction is carried out at temperatures of 20 to 375 ° C, preferably at 20 to 100 ° C and particularly preferably at 60 to 100 ° C.
  • the temperature of the reaction is above the temperature of the boiling point of the solvent used, the reaction is expediently carried out under the autogenous pressure of the reaction system in a pressure vessel.
  • the reaction conditions are chosen so that the reaction can be carried out at atmospheric pressure. The duration of this reaction may be a few minutes to several days, depending on the nature of the starting materials reacted and the temperature conditions used.
  • the mixture thus formed can be isolated from the reaction mixture and stored until further use.
  • the isolation can z.
  • Suitable for drying are conventional dryers, such as drum dryers or freeze dryers.
  • the drying of the resulting solution and / or suspension is carried out by spray drying.
  • the spray drying is generally carried out under atmospheric pressure or reduced pressure.
  • the inlet temperature of the drying gas is determined.
  • air is used as the drying gas, but of course other drying gases such as nitrogen or argon can be used.
  • the inlet temperature of the drying gas in the spray dryer is advantageously chosen so that the outlet temperature of the drying gas cooled by evaporation of the solvent does not exceed 200 ° C. for a longer period of time.
  • the starting temperature of the drying gas is adjusted to 50 to 150 ° C, preferably 100 to 140 ° C.
  • the source of the element M can also be added, for example, to a solution of the silver source, molybdenum source and vanadium source to be sprayed or dried.
  • the drying usually gives an amorphous product.
  • thermal treatment includes, preferably under controlled atmosphere.
  • a thermal treatment is static or preferably moved under rotating movements of the furnace chamber.
  • Typical temperature regime for the thermal treatment are in the range of 200 to 800 0 C, preferably from 250 to 500 0 C, particularly preferably from 300 to 400 ° C.
  • the thermal treatment can be carried out under inert (for example nitrogen or noble gases), oxidizing (for example oxygen) or varying atmosphere (initially oxidizing then reducing atmosphere) take place. It is known to the person skilled in the art that mixtures of the gases mentioned can also be used.
  • oxidizing means that in the supplied gas stream after the reaction of all oxidizing and reducing agents contained, oxidizing agent remains in the gas stream, that is, an oxidizing gas stream is fed in gross.
  • reducing means that in the supplied gas stream after the reaction of all oxidizing and reducing agents contained, reducing agent remains in the gas stream, that is to say a reducing gas stream is fed in gross.
  • Inert means in this context that either no oxidizing agent or reducing agent are supplied, or oxidizing and reducing agents in the supplied gas stream are inertly inert, that is, in the supplied gas stream after reaction of all the contained oxidizing and reducing agents, neither oxidizing agent nor reducing agent in Gas flow remains.
  • It may be thermally treated in a stagnant or flowing atmosphere, preferably a treatment is carried out under a flowing gas stream, with a constant supply of fresh gas prior to a gas recycle being preferred.
  • the composition of the atmosphere can be varied as a function of calcination temperature and time.
  • a moving thermal treatment for example by rotary calcination drums, shaking or fluidization, is preferred.
  • a moving thermal treatment for example by rotary calcination drums, shaking or fluidization, is preferred.
  • For the production in the laboratory furnaces are preferred as in FIG. 1 of DE A 10122027.
  • the thermal treatment can also take place under the temperature conditions of the gas phase oxidation in the gas phase oxidation reactor.
  • a so-called precatalyst is introduced into the reactor, which is converted under the temperature conditions of the gas phase oxidation into a catalyst according to the invention.
  • aqueous solutions of inorganic or organic acids and alcoholic solutions (with and without acids) and aqueous hydrogen peroxide solutions are examples of suitable solvents.
  • a source of an element M e.g. B. soaked with a solution of a compound of M and then dried.
  • the multimetal oxide can be used in the form of a full catalyst or in the form of a shell catalyst for the partial oxidation in the gas phase. This can be the Multimetal are applied to an inert support and / or interspersed with an inert support.
  • oxides such as TiO 2, SiO 2, ZrO 2, are added.
  • the powdered multimetal oxide composition is z. B. compressed by tabletting, extrusion or extrusion to a pressure of the desired catalyst geometry.
  • the powdery mixed metal oxide mass optionally aids such.
  • graphite or stearic acid as lubricants and / or molding aids and reinforcing agents such as microfibers of glass, asbestos, silicon carbide or potassium titanate be used.
  • the powdered multimetal oxide composition is applied to preformed inert catalyst supports of suitable geometry.
  • quartz SiO 2
  • porcelain porcelain
  • magnesium oxide tin dioxide
  • silicon carbide silicon carbide
  • rutile alumina
  • Al 2 O 3 aluminum silicate
  • steatite Magnnesium silicate
  • zirconium silicate zirconium silicate
  • cersilicate cersilicate or mixtures of these support materials.
  • Particularly advantageous support materials are steatite and silicon carbide.
  • the carrier material is usually non-porous.
  • non-porous is to be understood in the sense of “non-porous to technically ineffective amounts of pores” because technically unavoidable a small number of pores in the carrier material, which should ideally contain no pores, may be present.
  • the shape of the support material is generally not critical to the coated catalysts of the invention.
  • catalyst supports in the form of spheres, rings, tablets, spirals, tubes, extrudates or chippings can be used.
  • the dimensions of these catalyst supports are the same as the catalyst supports commonly used to prepare shell catalysts for the gas phase partial oxidation of aromatic hydrocarbons.
  • the shell-shaped coating of the inert carrier material known methods are used. For example, a suspension of the active material or a
  • Precursor in a heated coating drum at elevated temperature on the catalyst be sprayed on.
  • fluidised bed coater can also be used.
  • the suspension medium is generally water, preferably binders such as higher alcohols, polyhydric alcohols, e.g. For example, ethylene glycol, 1, 4-butanediol or glycerol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, or cyclic ureas such as N, N '-Dimethylethylenharnstoff or N, N' dimethyl-propyleneurea or (co) polymers, dissolved or advantageous in the form of an aqueous dispersion, wherein in general binder contents of 10 to 20 wt .-%, based on the solids content of the suspension are suitable.
  • Suitable polymeric binders are, for.
  • the layer thickness of the catalyst shell or the sum of the layer thicknesses of the shells containing the catalytically active constituents is generally from 10 to 250 ⁇ m.
  • the catalysts of the invention are used for the partial oxidation of hydrocarbons.
  • the hydrocarbons can be selected from aliphatic hydrocarbons, such as alkanes, in particular C 2 -C 6 -alkanes, cycloalkanes, alkenes, in particular C 5 -C 6 -alkenes, cycloalkenes, alkynes, in particular C 5 -C 6 -alkynes, and cycloalkynes; aromatic hydrocarbons, such as benzene or naphthalene, or in particular alkylaromatics.
  • alkanes in particular C 2 -C 6 -alkanes
  • cycloalkanes alkenes, in particular C 5 -C 6 -alkenes, cycloalkenes, alkynes, in particular C 5 -C 6 -alkynes, and cycloalkynes
  • aromatic hydrocarbons such as benzene or naphthalene, or in particular alkylaromatics.
  • the catalysts according to the invention are used in particular for the partial oxidation of alkylaromatics to aromatic alcohols, aldehydes, carboxylic acids and / or carboxylic anhydrides.
  • Suitable alkylaromatics are compounds having at least one carbocyclic or heterocyclic aromatic ring structure which can be reacted under the conditions of a gas phase senial oxidation to aldehydes, carboxylic acids and / or carboxylic acid anhydrides.
  • Particularly suitable are mono- or polyalkylated aromatics, in particular methylated and / or ethylated aromatics.
  • the aromatic parent compounds may carry substituents which are inert under the conditions of partial oxidation, ie, for. As halogen or the trifluoromethyl, nitro, amino or cyano group. Non-inert substituents also come into consideration when they are in desired under partial oxidation conditions Substituents pass, such as the aminomethyl or the hydroxy methyl group.
  • Preferred aromatic hydrocarbons are toluene, o-xylene, m-xylene, p-xylene and methylpyridines.
  • An embodiment of the process according to the invention relates to the preparation of C8-value products (o-tolualdehyde, o-toluic acid, phthalide, phthalic anhydride) from o-xylene.
  • One embodiment of the process according to the invention relates to the preparation of m-tolualdehyde from m-xylene.
  • An embodiment of the process according to the invention for the partial oxidation relates to the preparation of phthalic anhydride from o-xylene.
  • the catalysts of the invention can be used for this purpose in combination with other, differently active catalysts, for example, vanadium oxide / anatase-based catalysts of the prior art.
  • Further embodiments of the process according to the invention for the partial oxidation relate to the preparation of benzoic acid and / or benzaldehyde from toluene, or of pyridinecarboxylic acids, such as nicotinic acid, from methylpyridines, such as .beta.-picoline.
  • the catalysts according to the invention can be used alone or in combination with other, differently active catalysts, for example catalysts of the prior art based on vanadium oxide / anatase and / or silver vanadates.
  • the different catalysts are generally arranged in separate catalyst beds, which may be arranged in one or more fixed catalyst beds, in the reactor.
  • the catalysts of the invention are suitably filled in the reaction tubes of a tubular reactor, which from the outside, for. B. by means of a molten salt, are thermostated to the reaction temperature.
  • About the thus prepared catalyst pouring the reaction gas at temperatures of generally 250 to 450 0 C, preferably 300 to 420 0 C and more preferably from 320 to 400 0 C and at an overpressure of generally 0.1 to 2.5 bar, preferably from 0.3 to 1, 5 bar at a space velocity of generally 750 to 10,000 Ir 1 , preferably from 1500 to 4000 h- 1 passed .
  • the reaction gas fed to the catalyst is generally obtained by mixing a gas containing molecular oxygen, in addition to oxygen, suitable reaction moderators and / or diluents, such as steam, Lioxide and / or nitrogen, generated with the alkyl aromatic to be oxidized.
  • the molecular oxygen-containing gas generally contains 1 to 100% by volume, preferably 2 to 50% by volume and particularly preferably 4 to 30% by volume of oxygen, 0 to 30% by volume, preferably 0 to 20% by volume.
  • the alkylaromatic compound is reacted on a catalyst whose catalytically active composition contains a multimetal oxide of the formula (I) to give an intermediate reaction mixture and the intermediate reaction mixture or fractions thereof are further reacted on at least one further catalyst ,
  • the alkylaromatic is initially reacted on a bed of the catalyst according to the invention with partial conversion to give a product mixture which may contain the desired oxidation product, suboxidation products thereof and unreacted alkylaromatic.
  • the product mixture can then be further processed by alternatively
  • Fig. 1 shows the X-ray diffractogram of the powder of Example 5B. All X-ray diffractograms were recorded using a diffractometer manufactured by Bruker AXS GmbH, 76187 Düsseldorf Device name: D8 Discover with GADDS (General Area Detector Diffraction System). Cu-K ⁇ radiation (40 kV, 40 mA) was used to record the diffractograms.
  • Solution B was then added to Solution A with stirring. This resulted in a yellow suspension.
  • About a dropping funnel 750 g aqueous NH4 ⁇ H solution (25%) were added dropwise. There was a clear yellow solution.
  • the solution was heated at 80 ° C. for 30 minutes. Subsequently, the solution was spray-dried (spray tower from Niro Inc., Mobile Minor 2000).
  • the carrier was placed in a coating drum with 1, 5 L internal volume. The drum was rotated at 32 revolutions per minute. About 9 g of a mixture of 1, 5 g of glycerol and 7.5 g of water were sprayed onto the carrier via a spray nozzle operated with 150 Nl / h compressed air. At the same time, the powder was introduced into the drum via a vibrating trough. After completion of the coating, the coated carrier body for 5 hours at 100 0 C in a circulating air drying cabinet (Fa. Heraeus) were dried.
  • a circulating air drying cabinet Fe. Heraeus
  • the reactor is heated to 450 0 C (20 ° C / h) and calcined the catalyst for 3 h at 450 0 C under an air atmosphere (100 Nl / h).
  • the tube is cooled to 330 0 C and from top to bottom with 183 Nl / h of air and 55.6 Nl / h of nitrogen and a loading of 48.2 g o-xylene / Nm 3 gas (1, 0 Vol .-% o-xylene) flows through.
  • a C8 product selectivity of 83.3% could be achieved with an o-xylene conversion of 38%.
  • the CO x selectivity was 13.7% (the CO x selectivity corresponds to the proportion of o-xylene converted to combustion products (CO / CO 2), the residual selectivity to 100% corresponds to the proportion of the value product phthalic anhydride, the intermediates o-tolualdehyde, o-toluic acid and phthalide reacted o-xylene and the by-products maleic anhydride, citraconic anhydride and benzoic acid).
  • a powder X-ray diffractogram was measured on the active composition of an expansion sample of the catalyst.
  • the active material of the expansion sample of the catalyst essentially comprises a mixture of AgMoVO 6 and Ag.
  • Example 2 P-doped uncalcined shell catalyst AgMoVP 0 , oo6 ⁇ e
  • the spray powder was prepared analogously to Example 1A.
  • the reactor is heated to 450 0 C (20 ° C / h) and calcined the catalyst for 22.0 h at 450 0 C under an air atmosphere (100 Nl / h).
  • the tube was from above with 183 Nl / h of air and 55.6 Nl / h of nitrogen and a loading of 48.2 g o-xylene / Nm 3 gas (1, 0 vol .-% o -Xylene) flows through.
  • a C 8 product selectivity of 82.0% was achieved with an o-xylene conversion of 43.5%.
  • the CO x selectivity was 15.0% (the CO x selectivity corresponds to the proportion of o-xylene converted to combustion products (CO / CO 2); the residual selectivity to 100% corresponds to the proportion of the desired product phthalic anhydride, the intermediates Tolyl aldehyde, o-toluic acid and phthalide reacted o-xylene and the by-products maleic anhydride, citraconic anhydride and benzoic acid).
  • Example 3 P-doped uncalcined coated catalyst AgM ⁇ o, 9VW 0 , iPo, oo7 ⁇ e
  • the reactor is heated to 450 0 C (20 ° C / h) heated and the catalyst was calcined for 22 h at 450 0 C.
  • the reactor is cooled to 330 ° C. and the catalyst is charged with 0.5% by volume of o-xylene at 15% by volume of oxygen and 4.9% by volume of H 2 O.
  • a C8 product selectivity of 84.2% could be achieved.
  • the CO x selectivity was about 12% (CO x selectivity corresponds to the proportion of o-xylene converted to combustion products (CO, CO 2 ); the residual selectivity to 100% corresponds to the proportion of the desired product phthalic anhydride, the intermediates o-tolualdehyde, o-toluic acid and phthalide reacted o-xylene and the by-products maleic anhydride, citraconic anhydride and benzoic acid).
  • the spray powder was prepared analogously to Example 1A.
  • the resulting spray powder was mixed with 3 wt .-% graphite and mixed in a Rhönrad. Subsequently, the mixture was processed in a compact to tablets 3 mm x 3 mm.
  • Tablets according to Example 4B were calcined in a convection oven (Fa. Heraeus) at 450 0 C for 2 hours in air (300 nL / h). A part of tablets was ground and a powder X-ray diffractogram was taken from the obtained powder. The powder essentially has a pure AgMoVO 6 phase.
  • the tube was flowed through from top to bottom with 358 Nl / h of air with a loading of 48 g o-xylene / Nm 3 gas (1, 0 vol .-% o-xylene).
  • a C 8 product selectivity of 69.4% could be achieved for an o-xylene conversion of 42.7%
  • the CO x selectivity was about 24.0% (the CO x selectivity corresponds to the proportion of o-xylene converted to combustion products (CO, CO 2 ); the residual selectivity to 100% corresponds to the proportion of the desired product phthalic anhydride, the intermediates o-tolualdehyde, o-toluic acid and phthalide reacted o-xylene and the by-products maleic anhydride, citraconic anhydride and benzoic acid).
  • the carrier was placed in a coating drum with 1, 5 L internal volume. The drum was rotated at 32 revolutions per minute. About 12 g of a mixture of 2.3 g of glycerol and 9.7 g of water were sprayed onto the carrier via a spray nozzle operated with 150 Nl / h of compressed air. At the same time, the powder was introduced into the drum via a vibrating trough. After completion of the coating, the coated support bodies were dried for 2.5 hours at 250 ° C. in a circulating air drying cabinet (Heraeus).
  • a powder X-ray diffractogram was measured on the active material of a sample of the catalytic converter, which determines the following interplanar spacings d [ ⁇ ⁇ 0.04] with the relative intensities l re i [%]: 6.06 (17), 4.53 ( 14), 4.05 (25), 3.55 (29), 3.39 (53), 3.32 (57), 3.24 (42), 3.03 (17), 2.88 (31 ), 2.73 (17), 2.67 (16), 2.57 (18), 2.39 (29), 2.36 (100), 2.26 (18), 2.04 (32) , 2,02 (24), 1, 83 (23), 1, 81 (11), 1, 77 (21), 1, 60 (21), 1, 59 (24), 1, 56 (17), 1, 48 (1 1), 1, 44 (39), 1, 42 (14).
  • the active mass of the catalyst modification sample essentially comprises a mixture of AgMoVO 6 , Ag (tab 03-065-2671 of the ICDD PDF 2 file (release 2006)) and V 0 , 95M ⁇ o, 97 ⁇ 5 (file card 01- 077-0649 of the ICDD PDF-2 file (release 2006)).
  • Solution B was then added to Solution A with stirring. This resulted in an ocher yellow suspension and the temperature dropped to 76 ° C.
  • the suspension was heated to 80 0 C and heated at 80 0 C for 30 minutes.
  • the suspension was then spray-dried (spray tower from Niro Inc., Mobile Minor 2000).
  • the coated carrier body for 5 hours at 100 0 C in a circulating air drying cabinet (Fa. Heraeus) were dried and then thermally treated within 2 hours at 500 ° C in a muffle furnace.
  • the weight of the catalytically active composition thus applied was 9.6% by weight, based on the total weight of the finished catalyst.
  • the active material of the catalyst has a pure AgMoVO 6 phase.
  • a powder X-ray diffractogram was measured on the active material of an expansion sample of the catalyst, which had the following interplanar spacings d [ ⁇ ] with the associated relative intensities l rel [%]: 4.53 (17.1), 3.38 (89.8 ), 3.32 (86.2), 3.23 (100), 2.88 (73.4), 2.57 (46.2), 2.39 (63.2), 2.33 (8 , 1), 2.30 (7.5), 2.26 (52.4), 2.22 (9.9), 2.21 (13.7), 2.02 (28.3), 1 , 97 (20,8), 1, 83 (36,9), 1, 81 (16,3), 1, 77 (46,1), 1, 70 (12,4), 1, 68 (4, 4), 1, 66 (6,9), 1, 62 (19,5), 1, 60 (33,4), 1, 59 (40,9), 1, 56 (30,6), 1, 48 (1 1, 1), 1, 45 (13,2), 1, 42 (18,5), 1, 36 (5,2).
  • the active material of the expansion sample of the catalyst essentially has an AgMoVO 6 phase.
  • the calcined powder from Example 6B was compacted by means of a compact (Paul Otto Weber GmbH) and classified to a fraction between 500 and 1000 microns. Catalyst chippings were placed in porcelain dishes on the shaker and with various aqueous metal salt solutions (H 3 BO 3 , LiNO 3 , H 3 PO 4 , Cu (NO 3 ) 2 , Fe (NO 3 ) 3 , Sb (CH 3 COO) 3 , Ce (NO 3 ) 3 , (NH 4 ) NbO (C 2 O 4 ) 2 * x H 2 O, Bi (NO 3 ) 3 , (NH 4 ) 6 H 2 Wi 2 O 40 * x H 2 O) impregnated in different load, dried on a shaker for 30 min in air and then dried for 18 h in a drying oven. The dry active masses were screened to a fraction between 500-1000 microns and tested in the reactor.
  • the catalytic test was carried out on 1 ml of the sample in a 48-fold test reactor according to DE 198 09 477.9.
  • the catalysts were tested at an o-xylene concentration is between 1-3 vol .-%, an oxygen concentration of between 7-17 vol .-%, a water concentration between 5 - 10 vol .-%, a GHSV between 1000-10000 hr 1 tested in a temperature range between 280 - 350 0 C.
  • Tables 2-4 show a section of the tested active masses and the results obtained with respect to CO 2 of the doped and undoped active masses. Table 1. Results of catalyst testing in a single tube reactor

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Abstract

L'invention concerne un catalyseur pour l'oxydation partielle d'hydrocarbures en phase gazeuse. Le catalyseur selon l'invention contient un oxyde multimétallique de formule générale AgaMobVcMdOe * f H2O (I) dans laquelle M représente au moins un élément sélectionné parmi Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, AI, Ga, In, Si, Sn, Pb, P, Sb, Bi, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Au, Zn, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu et U, a vaut 0,5 à 1,5, b vaut 0,5 à 1,5, c vaut 0,5 à 1,5, a+b+c valent 3, d vaut moins de 1, e est un nombre déterminé par la valence et la fréquence des éléments différents de l'oxygène dans la formule (I) et f vaut 0 à 20. L'oxyde multimétallique présente une structure cristalline dont le diffractogramme de rayons X sur poudre est caractérisé par des raies de diffraction à au moins 5 distances interréticulaires sélectionnées parmi d = 4,53, 3,38, 3,32, 3,23, 2,88, 2,57, 2,39, 2,26, 1,83, 1,77 Å (± 0,04 Å).
EP10724375A 2009-05-29 2010-05-28 Catalyseur et procédé d'oxydation partielle d'hydrocarbures Withdrawn EP2435395A2 (fr)

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US8642803B2 (en) 2010-03-03 2014-02-04 Basf Se Preparation of ethylenically unsaturated carboxylic salts by carboxylation of alkenes
US20110230668A1 (en) * 2010-03-19 2011-09-22 Basf Se Catalyst for gas phase oxidations based on low-sulfur and low-calcium titanium dioxide
US8323610B2 (en) 2010-04-12 2012-12-04 Basf Se Catalyst for the oxidation of SO2 to SO3
US8901320B2 (en) 2010-04-13 2014-12-02 Basf Se Process for controlling a gas phase oxidation reactor for preparation of phthalic anhydride
US8859459B2 (en) 2010-06-30 2014-10-14 Basf Se Multilayer catalyst for preparing phthalic anhydride and process for preparing phthalic anhydride
US9212157B2 (en) 2010-07-30 2015-12-15 Basf Se Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride
TWI521028B (zh) 2010-10-05 2016-02-11 巴斯夫歐洲公司 包含特定異聚酸之化學機械研磨組成物
US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
US20140275685A1 (en) * 2013-03-15 2014-09-18 Instituto Mexicano Del Petroleo Multimetallic mixed oxides, its preparation and use for the oxidative dehydrogenation of ethane for producing ethylene
CN105289626B (zh) * 2014-07-24 2017-12-15 中国石油化工股份有限公司 苯乙烯催化剂和苯乙烯的制备方法
US11909046B2 (en) 2017-03-07 2024-02-20 The Research Foundation For The State University Of New York Synthetic methods for crystallite size control of bimetallic polyanionic battery compositions
CN108404944B (zh) * 2018-03-19 2020-08-14 中触媒新材料股份有限公司 一种钒银钼磷酸盐催化剂的合成方法以及催化制备异戊烯醇、异戊烯醛的方法
CN109266398A (zh) * 2018-09-10 2019-01-25 无锡市华易环境科技有限公司 密闭矿热炉冶炼硅锰合金的煤气净化处理方法及净化系统
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