EP2137104A2 - Pyrophosphate de vanadyle polynaire - Google Patents

Pyrophosphate de vanadyle polynaire

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Publication number
EP2137104A2
EP2137104A2 EP08717694A EP08717694A EP2137104A2 EP 2137104 A2 EP2137104 A2 EP 2137104A2 EP 08717694 A EP08717694 A EP 08717694A EP 08717694 A EP08717694 A EP 08717694A EP 2137104 A2 EP2137104 A2 EP 2137104A2
Authority
EP
European Patent Office
Prior art keywords
sub
vanadium
metal
phase
polynary
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.)
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Application number
EP08717694A
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German (de)
English (en)
Inventor
Hartmut Hibst
Robert Glaum
Ernst Benser
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BASF SE
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BASF SE
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Publication date
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Publication of EP2137104A2 publication Critical patent/EP2137104A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/42—Pyrophosphates
    • 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
    • B01J27/186—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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/395—Thickness of the active catalytic layer
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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

Definitions

  • the present invention relates to a polynary vanadyl pyrophosphate, a process for its preparation and its use for heterogeneously catalyzed gas phase oxidations, preferably heterogeneously catalyzed gas phase oxidations of a hydrocarbon having at least four carbon atoms.
  • VPO catalysts Heterogeneous catalysts based on vanadyl pyrophosphate (VO) 2P2 ⁇ 7 (so-called VPO catalysts) are used in the industrial oxidation of n-butane to maleic anhydride as well as in a series of further oxidation reactions of hydrocarbons.
  • VO vanadyl pyrophosphate
  • the vanadyl pyrophosphate catalysts are usually prepared as follows: (1) Synthesis of a vanadyl hydrogen phosphate hemihydrate precursor (VOHPO 4 / 4H 2 O) from a pentavalent vanadium compound (eg, V 2 O 5), a trivalent or trivalent phosphorus Compound (eg ortho and / or pyrophosphoric acid, phosphoric acid ester or phosphorous acid) and a reducing alcohol (eg isobutanol), isolation of the precipitate, drying and optionally shaping (eg tableting) and (2) Preforming of the precursor to vanadyl pyrophosphate ((VO) 2 P2 ⁇ 7 ) by calcination. It is z. For example, see EP-A 0 520 972 and WO 00/72963.
  • the object of the present invention was to provide new polynary vanadyl pyrophosphates.
  • a further object of the present invention was to provide novel polynary vanadyl pyrophosphates with catalytic properties for heterogeneous catalytic gas phase oxidations.
  • Another object of the present invention was to provide new polynary vanadyl pyrophosphates which can be used to modify the catalytic properties of known heterogeneous catalysts based on vanadyl pyrophosphate.
  • M is one or more metals selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In,
  • a has a value of 0.5 to 1.5
  • b has a value of 0 to 0.9
  • c has a value of 1, 5 to 2.5
  • the indication of the X-ray diffraction reflexes in this application takes place in the form of the lattice plane spacings d [A] independent of the wavelength of the X-ray radiation used.
  • the wavelength ⁇ of the X-radiation used for the diffraction and the diffraction angle ⁇ are linked together via the Bragg relationship as follows:
  • d is the respective diffraction reflex associated lattice spacing of the atomic space arrangement.
  • the powder X-ray diffractogram of the polynary vanadyl pyrophosphate of the formula I according to the invention of the formula I is characterized by the diffraction reflexes mentioned above.
  • the diffraction reflections generally have the approximate relative intensities (l re ⁇ [%]) given in Table 1. Further, generally less intense diffraction reflexes of the powder X-ray diffractogram were not taken into account in Table 1.
  • mixtures of the polynary vanadyl pyrophosphates according to the invention with other crystalline compounds have additional diffraction reflexes.
  • Such mixtures of the polynary vanadyl pyrophosphate with other crystalline compounds can be prepared selectively by mixing the polynary Vanadylpyrophosphats invention or can arise in the preparation of polynary Vanadylpyrophosphats invention by incomplete reaction of the starting materials or formation of foreign phases with different crystal structure.
  • the formula I a has a value of 0.8 to 1, 2, in particular about 1.
  • b has a value of 0 to 0.4. In certain embodiments according to the invention, b has the value 0.
  • the formula I c has a value of 1, 8 to 2.2, in particular about 2.
  • M is a metal selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In or combinations of two or more of these metals.
  • M is a metal selected from Cr and Fe.
  • a preferred polynary vanadyl pyrophosphate according to the invention has the following formula:
  • the polynary vanadyl pyrophosphates according to the invention are obtainable in various ways.
  • the polynary vanadyl pyrophosphates according to the invention can be obtained firstly by a solid-state reaction in a closed system.
  • at least two reactants are reacted, which are oxygenated compounds of vanadium, phosphorus compounds of vanadium and mixed oxygen-phosphorus compounds of vanadium, elemental vanadium, oxygen compounds of metal M, phosphorus compounds of metal M and mixed oxygen-phosphorus compounds of metal M and elemental metal M are selected.
  • the reactants are generally selected such that (i) they provide the desired stoichiometry of the elements in formula I, and (ii) the sum of the products of valence times the abundance of non-oxygen elements in the reactants of the sum of the products of Valence times the frequency of elements other than oxygen in Formula I.
  • the starting compounds can be selected so that all the elements other than oxygen have the same value as in Formula I. Alternatively, the starting compounds may be chosen such that some or all of the elements other than oxygen have a valency different from that which occurs in formula I.
  • redox reactions for. As a Synproportionierung, during the solid state reaction, the elements other than oxygen receive the valence, which they have in the formula I.
  • a combination of equivalent amounts of vanadium (III) and vanadium (V) compounds can be used to form tetravalent vanadium in the solid state reaction.
  • the required starting compounds in the form of oxides, phosphates, oxide phosphates, phosphides or the like are either commercially available or known from the literature or can be easily synthesized by the skilled person in analogy to known methods of preparation.
  • the starting materials are intimately mixed, for. B. by fine trituration.
  • the solid state reaction is typically carried out at a temperature of at least 500 ° C, e.g. B. 650 to 1100 0 C, in particular about 800 0 C. Typical reaction times are z. 24 hours to 10 days.
  • Suitable reaction vessels consist for. B. of quartz glass or corundum.
  • a suitable mineralizer such as iodine or PtCb, in the solid-state reaction.
  • polynary vanadyl pyrophosphates according to the invention can be prepared by reacting a) produces a dry mixture of a vanadium source, a source of the metal M and a phosphate source,
  • the intimate mixing of the starting compounds can be carried out in dry or wet form.
  • the starting compounds are expediently used as finely divided powders and subjected to the mixing and optionally compacting the calcination (thermal treatment).
  • the intimate mixing is done in wet form, i. H. in dissolved or suspended form.
  • the starting compounds are mixed together in the form of an aqueous solution (optionally with the concomitant use of complexing agents) and / or suspension.
  • the aqueous solution or suspension is dried and calcined after drying.
  • the drying can be carried out by evaporation in vacuo, by freeze-drying or by conventional evaporation. Preferably, however, the drying process is carried out by spray drying.
  • the outlet temperatures are usually 70 to 150 0 C;
  • the spray drying can be carried out in cocurrent or in countercurrent.
  • Suitable vanadium sources are e.g. Vanadyl sulfate hydrate, vanadyl acetylacetonate, vanadates such as ammonium metavanadate, vanadium oxides such as.
  • vanadates such as ammonium metavanadate
  • vanadium oxides such as.
  • vanadium halides such as vanadium tetrachloride (VCU) and vanadyl halides such.
  • VCU vanadium tetrachloride
  • VOCb Divanadium pentoxide and ammonium vanadate are preferred sources of vanadium.
  • Possible sources of the metal M are all compounds of the elements which are capable of forming oxides and / or hydroxides upon heating (if appropriate in the presence of molecular oxygen, for example in air). Of course, oxides and / or hydroxides of the elemental conformation can also be used as such starting compounds. co-used or exclusively used.
  • the source of the metal M is selected from nitrates, carboxylates, carbonates, bicarbonates, basic carbonates, oxides, hydroxides and metal oxide hydroxides.
  • Suitable phosphate sources are phosphate group-containing compounds or compounds from which phosphate groups are formed by redox reactions and / or upon heating (optionally in the presence of molecular oxygen, eg in air).
  • phosphoric acids in particular orthophosphoric acid, pyro- or metaphosphoric acids, phosphorous acid, hypophosphorous acid, phosphates or hydrogen phosphates, such as diammonium hydrogen phosphate, and elemental phosphorus, such as. B. white phosphorus.
  • the phosphate source is at least partially formed by phosphorous acid or hypophosphorous acid, optionally in combination with orthophosphoric acid.
  • vanadium source or source of the metal M compounds are used, in which the vanadium or the metal M have a higher valence, as they come in the formula I (ie, as the formal valence of V and M, to obtain the Electroneutrality with the O 2 "- and PO 4 3 " anions contained in the formula I is required), it is preferable to provide reduction equivalents to convert the vanadium and / or the metal M into the valence state corresponding to the vanadium and the metal M in the formula I belongs.
  • the reduction equivalents are provided by a reducing agent capable of reducing the superior form of the vanadium and the metal M, respectively.
  • the reduction can be carried out during the preparation of the dry mixture or at the latest when calcining.
  • the preparation of the intimate dry mixture is preferably carried out under an inert gas atmosphere (eg ISb) in order to ensure better control over the oxidation stages.
  • ISb inert gas atmosphere
  • Preferred reducing agents for this purpose are selected from hypophosphorous acid, phosphorous acid, hydrazine (as free base or hydrate or in the form of its salts such as hydrazine dihydrochloride, hydrazine sulfate), hydroxylamine (as free base or in the form of its salts such as hydroxylamine hydrochloride), nitrosylamine, elemental vanadium , elemental phosphorus, borane (also in the form of complex borohydrides such as sodium borohydride) or oxalic acid.
  • Phosphoric acid and / or hypophosphorous acid are preferred reducing agents.
  • reducing agents such as hypophosphorous acid or phosphorous acid
  • elemental vanadium may simultaneously serve as the vanadium source.
  • the dry mixture is thermally treated at temperatures of at least 500 ° C., preferably 700 to 1000 ° C., in particular about 800 ° C.
  • the thermal treatment can be carried out under oxidizing, reducing, as well as under inert atmosphere.
  • As an oxidizing atmosphere z.
  • air with molecular oxygen enriched air or oxygen-depleted air into consideration.
  • the thermal treatment is preferably carried out under an inert atmosphere, ie, for example, under molecular nitrogen and / or noble gas.
  • the thermal treatment is carried out at atmospheric pressure (1 atm).
  • the thermal treatment can also be carried out under vacuum or under pressure.
  • the thermal treatment takes place under a gaseous atmosphere, it can both stand and flow. Preferably, it flows. Overall, the thermal treatment can take up to 24 hours or more.
  • the invention further relates to a gas phase oxidation catalyst which comprises at least one polynary vanadyl pyrophosphate according to the invention.
  • the polynaryanadyl pyrophosphates can be used as such, eg. As a powder, or in the form of moldings are used as heterogeneous catalysts.
  • the shaping is preferably carried out by tableting.
  • a tabletting aid is generally added to the powder and intimately mixed.
  • Tabletting aids are generally catalytically inert and improve the tabletting properties of the powder, for example by increasing the lubricity and flowability.
  • a suitable and preferred Tablettierzkar is called graphite or boron nitride.
  • the added tabletting aids usually remain in the activated catalyst.
  • the powder can also be tabletted and then comminuted to chippings.
  • the shaping of moldings can, for. B. also by applying at least one polynary Vanadylpyrophosphats invention or mixtures containing at least one inventive polynary Vanadylpyrophosphat, carried on a support body.
  • the carrier bodies are preferably chemically inert. That is, they essentially do not interfere with the course of the catalytic gas-phase oxidation catalyzed by the polynary vanadyl pyrophosphates according to the invention.
  • the material used for the support bodies are, in particular, alumina, silica, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide.
  • the surface of the carrier body can be both smooth and rough.
  • the surface of the support body is rough, since an increased surface roughness usually requires an increased adhesive strength of the applied active mass shell.
  • the support material may be porous or non-porous.
  • the carrier material is non-porous, d. H. the total volume of the pores is preferably less than 1 vol.%, Based on the volume of the carrier body.
  • the thickness of the catalytically active layer is usually 10 to 1000 microns, z. B. 50 to 700 microns, 100 to 600 microns or 150 to 400 microns.
  • carrier bodies with any geometric structure come into consideration. Their longest extent is usually 1 to 10 mm.
  • balls or cylinders, in particular hollow cylinders, are used as carrier bodies.
  • the preparation of the shell catalysts can be carried out in the simplest way so that a mass of a polynary vanadyl pyrophosphate of the general formula (I) is formed, converted into a finely divided form and finally applied with the aid of a liquid binder on the surface of the carrier body.
  • the surface of the carrier body is moistened in the simplest way with the liquid binder and attached by contacting with the finely divided mass, a layer of the active composition on the moistened surface.
  • the coated carrier body is dried. Needless to say you can repeat the process to achieve a greater layer thickness.
  • the polynary vanadyl pyrophosphates according to the invention can also be used to modify the catalytic properties, in particular conversion and / or selectivity, of known catalysts, in particular based on vanadyl pyrophosphate.
  • the polynary vanadyl pyrophosphates according to the invention z. B. can be used as a promoter phase in a catalyst based on vanadyl pyrophosphate.
  • the catalyst then comprises a first phase and a second phase in the form of three-dimensionally extended regions, which delimit themselves from their local environment by a different chemical composition.
  • the first phase contains a catalytically active composition based on vanadyl pyrophosphate and the second phase contains at least one polynary vanadyl pyrophosphate according to the invention.
  • finely divided particles of the second phase may be dispersed in the first phase, or
  • the first phase and the second phase may be distributed relative to one another as in a mixture of finely divided first phase and finely divided second phase.
  • the preparation of these two-phase catalysts can, for.
  • Example by preparing a Vanadylhydrogenphosphat hemihydrate precursor (VOHPO 4/4 H2O), this is mixed with preformed particles of the second phase of inventive polynary ren Vanadylpyrophosphat, the resulting mass is deformed and calcined.
  • the vanadyl hydrogenphosphate hemihydrate precursor can be prepared in a manner known per se from a compound of pentavalent vanadium (for example V2O5), a compound with pentavalent or trivalent phosphorus (for example ortho and / or pyrophosphoric acid, phosphoric acid ester or phosphorous acid ) and a reducing alcohol (eg isobutanol) and isolation of the precipitate. It is z. For example, see EP-A 0 520 972 and WO 00/72963.
  • the catalysts according to the invention whose catalytically active composition comprises at least one polynary vanadyl pyrophosphate as defined above, can also be combined with catalysts based on vanadyl pyrophosphate in the form of a structured packing.
  • a gas stream containing a hydrocarbon and molecular oxygen to be oxidized may be passed over a bed of a first gas phase oxidation catalyst upstream in the flow direction of the gas stream and then via one or more downstream beds of a second or further gas phase oxidation catalyst first or second or one of the further beds comprises a catalyst according to the invention.
  • the invention further relates to a process for the partial gas phase oxidation or monoxidation, in which a gas stream containing a hydrocarbon and molecular oxygen is brought into contact with a catalyst according to the invention.
  • the gas stream additionally contains ammonia.
  • ammoxidation is understood as meaning a heterogeneous catalytic process in which methyl-substituted alkenes, arenes and hetarenes are converted into nitriles by reaction with ammonia and oxygen in the presence of transition metal catalysts.
  • the partial gas phase oxidation process in preferred embodiments, is for the production of maleic anhydride, wherein the hydrocarbon employed contains at least four carbon atoms.
  • tube-bundle reactors are generally used.
  • the use of fluidized bed reactors is possible.
  • hydrocarbons are generally aliphatic and aromatic, saturated and unsaturated hydrocarbons having at least four carbon atoms, such as 1, 3-butadiene, 1-butene, cis-2-butene, trans-2-butene, n-butane, C4 mixtures, 1, 3-pentadiene, 1,4-pentadiene, 1-pentene, cis-2-pentene, trans-2-pentene, n-pentane, cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, Cs-mixtures, hexenes, hexanes, xane, cyclohexane and benzene.
  • Preference is given to using 1,3-butadiene, 1-butene, cis-2-butene, trans-2-butene, n-butane, benzene or mixtures thereof.
  • n-butane and n-butane-containing gases and liquids are particularly preferred.
  • the n-butane used can be derived, for example, from natural gas, steam crackers or FCC crackers.
  • the addition of the hydrocarbon is generally quantity controlled, d. H. under constant specification of a defined amount per time unit.
  • the hydrocarbon can be metered in liquid or gaseous form.
  • the dosage in liquid form with subsequent evaporation before entering the reactor.
  • oxygen-containing gases such as air, synthetic air, an oxygen-enriched gas or so-called "pure", d. H. z. B. originating from the air separation oxygen.
  • the oxygen-containing gas is also preferably added in a controlled amount.
  • the gas to be passed through the reactor generally contains a hydrocarbon concentration of 0.5 to 15% by volume and an oxygen concentration of 8 to 25% by volume.
  • the proportion missing to one hundred% by volume consists of further gases such as nitrogen, noble gases, carbon monoxide, carbon dioxide, water vapor, oxygenated hydrocarbons (eg methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetic acid, propanol, propionaldehyde , Propionic acid, acrolein, cetonaldehyde) and mixtures thereof.
  • oxygenated hydrocarbons eg methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetic acid, propanol, propionaldehyde , Propionic acid, acrolein, cetonaldehyde
  • the n-butane content of the total amount of hydrocarbon is preferably more than 90%, and more preferably more than 95%.
  • the gas is preferably fed to the gas in the process according to the invention a volatile phosphorus compound.
  • concentration at the beginning, ie at the reactor inlet at least 0.2 ppm by volume, ie 0.2 10 "6 volume of the volatile phosphorus compounds based on the total volume of gas at the reactor inlet.
  • a content of 0.2 to 20 Volume ppm more preferably from 0.5 to 10 ppm by volume.
  • Volatile phosphorus compounds are to be understood as meaning those phosphorus-containing compounds which are gaseous in the desired concentration under the conditions of use. Suitable volatile phosphorus compounds are, for example, called phosphines and phosphoric acid esters. Particularly preferred are the C 1 to C 4 alkyl phosphoric esters, very particularly preferably trimethyl phosphate, triethyl phosphate and tripropyl phosphate, in particular triethyl phosphate.
  • the process of the invention is generally carried out at a temperature of 300 to 500 0 C. Under the said temperature, the temperature of the catalyst bed located in the reactor is understood, which would be present in the practice of the process in the absence of a chemical reaction.
  • the term means the number average of the temperatures along the reaction zone. In particular, this means that the true, present at the catalyst temperature due to the exothermicity of the oxidation reaction may also be outside the range mentioned.
  • the process according to the invention is preferably carried out at a temperature of from 380 to 460 ° C., more preferably from 380 to 430 ° C.
  • the process according to the invention can be carried out at a pressure below normal pressure (for example up to 0.05 MPa abs) or above normal pressure (for example up to 10 MPa abs). This is to be understood as meaning the pressure present in the reactor unit. Preference is given to a pressure of 0.1 to 1.0 MPa abs, more preferably 0.1 to 0.5 MPa abs.
  • the process according to the invention can be carried out in two preferred process variants, the "straight through” variant and the “recirculation” variant.
  • the "straight pass” maleic anhydride and optionally oxygenated hydrocarbon by-products are removed from the reactor effluent and the remaining gas mixture is discharged and optionally thermally recovered.
  • the “recycling” is also removed from the reactor effluent maleic anhydride and optionally oxygenated hydrocarbon by-products, the remaining gas mixture containing unreacted hydrocarbon, completely or partially recycled to the reactor.
  • Another variant of the "recycling" is the removal of the unreacted hydrocarbon and its return to the reactor.
  • n-butane is used as the starting hydrocarbon and the heterogeneously catalyzed gas-phase oxidation is carried out in the "straight pass" on the catalyst according to the invention.
  • Fig. 1 shows the powder X-ray diffractogram of (VO) Fe 2 (P 2 Oz) 2 ;
  • Figure 2 shows the powder X-ray diffractogram of (VO) Fe2 (P2 ⁇ 7) 2 prepared by an alternative method.
  • the suspension obtained was dried in a spray dryer (Mobile Minor TM 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature:. 330 0 C, outlet temperature: 107 0 C) under nitrogen.
  • the spray powder was calcined for two hours at 800 0 C in nitrogen atmosphere in a rotary quartz tube having an internal volume of 1 L.
  • the resulting powder had a BET specific surface area of 3.5 m 2 / g. From the powder X-ray diffractogram (FIG. 1), the following 2 ⁇ values with the associated intensities I and grid spacing d were determined.
  • the suspension obtained was dried in a spray dryer (Mobile Minor TM 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature: 330 ° C., outlet temperature: 107 ° C.) under nitrogen.
  • the resulting spray powder was calcined in two stages. First, it was calcined at 600 ° C. for two hours in a nitrogen atmosphere in a quartz rotary tube having an inner volume of 1 L. The product was milled in a ball mill for 15 minutes and calcined at 850 ° C. for another two hours in a nitrogen atmosphere.
  • the powder obtained had a BET specific surface area of 1.6 m 2 / g. From the powder X-ray diffractogram (FIG. 2), the following 2 ⁇ values with the associated intensities I and grid spacing d were determined.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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Abstract

L'invention concerne un nouveau pyrophosphate de vanadyle polynaire de formule générale (VO)<SUB>a</SUB>(M<SUB>1-b</SUB>V<SUB>b</SUB>)<SUB>2</SUB>(P<SUB>2</SUB>O<SUB>7</SUB>)<SUB>c</SUB> (I), dans laquelle M représente un ou plusieurs métaux sélectionnés parmi Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga et In, a vaut 0,5 à 1,5, b vaut 0 à 0,9 et c vaut 1,5 à 2,5. Ce nouveau pyrophosphate de vanadyle a une structure cristalline dont le diffractogramme de rayons X sur poudre est caractérisé par des reflets de diffraction définis. Un représentant privilégié en est (VO)Fe<SUB>2</SUB>(P<SUB>2</SUB>O<SUB>7</SUB>)<SUB>2</SUB>. Ces pyrophosphates de vanadyle s'utilisent comme catalyseurs d'oxydation en phase gazeuse, par exemple pour produire de l'anhydride maléique à partir d'un hydrocarbure ayant au moins quatre atomes de carbone.
EP08717694A 2007-03-16 2008-03-12 Pyrophosphate de vanadyle polynaire Withdrawn EP2137104A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007012723A DE102007012723A1 (de) 2007-03-16 2007-03-16 Polynäres Vanadylpyrophosphat
PCT/EP2008/052948 WO2008113730A2 (fr) 2007-03-16 2008-03-12 Pyrophosphate de vanadyle polynaire

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EP2137104A2 true EP2137104A2 (fr) 2009-12-30

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US (1) US20100105927A1 (fr)
EP (1) EP2137104A2 (fr)
JP (1) JP2010524809A (fr)
DE (1) DE102007012723A1 (fr)
WO (1) WO2008113730A2 (fr)

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US8765629B2 (en) 2011-09-16 2014-07-01 Eastman Chemical Company Process for preparing V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids
US9573119B2 (en) 2011-09-16 2017-02-21 Eastman Chemical Company Process for preparing V—Ti—P catalysts for synthesis of 2,3-unsaturated carboxylic acids
US8993801B2 (en) 2011-09-16 2015-03-31 Eastman Chemical Company Process for preparing V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids
US8883672B2 (en) 2011-09-16 2014-11-11 Eastman Chemical Company Process for preparing modified V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids
US8658557B2 (en) * 2011-10-25 2014-02-25 Ineos Usa Llc Catalyst for n-butane oxidation to maleic anhydride
KR101915841B1 (ko) * 2016-05-18 2018-11-06 한국산업기술대학교산학협력단 고 에너지 음극 활물질 및 이를 포함하는 리튬이차전지
DE102017106913A1 (de) 2017-03-30 2018-10-04 Chemische Fabrik Budenheim Kg Verfahren zur Herstellung von elektrisch leitenden Strukturen auf einem Trägermaterial
DE102017106912A1 (de) * 2017-03-30 2018-10-04 Chemische Fabrik Budenheim Kg Verfahren zur Herstellung von Fe(II)P / Fe(II)MetP-Verbindungen
DE102017106911A1 (de) 2017-03-30 2018-10-04 Chemische Fabrik Budenheim Kg Verwendung von kristallwasserfreien Fe(II)-Verbindungen als Strahlungsabsorber
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Also Published As

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US20100105927A1 (en) 2010-04-29
WO2008113730A2 (fr) 2008-09-25
WO2008113730A3 (fr) 2008-12-24
JP2010524809A (ja) 2010-07-22
DE102007012723A1 (de) 2008-09-18

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