WO2020120755A1 - Oxyde mixte comprenant de l'oxygène, du phosphore, du tungstène et au moins un métal issu des groupes 8 à 11 de la classification périodique des éléments - Google Patents

Oxyde mixte comprenant de l'oxygène, du phosphore, du tungstène et au moins un métal issu des groupes 8 à 11 de la classification périodique des éléments Download PDF

Info

Publication number
WO2020120755A1
WO2020120755A1 PCT/EP2019/085132 EP2019085132W WO2020120755A1 WO 2020120755 A1 WO2020120755 A1 WO 2020120755A1 EP 2019085132 W EP2019085132 W EP 2019085132W WO 2020120755 A1 WO2020120755 A1 WO 2020120755A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixed oxide
range
weight
mixture
tungsten
Prior art date
Application number
PCT/EP2019/085132
Other languages
German (de)
English (en)
Inventor
Stephan A Schunk
Sven TITLBACH
Frank Rosowski
Robert Mueller
Christian Schulz
Jingxiu XIE
Sebastian Schaefer
Patricia LOESER
Knut WITTICH
Markus Weber
Robert Glaum
Original Assignee
Basf Se
Technische Universitaet Berlin
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se, Technische Universitaet Berlin filed Critical Basf Se
Publication of WO2020120755A1 publication Critical patent/WO2020120755A1/fr

Links

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
    • 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
    • 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
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—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
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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

  • Mixed oxide comprising oxygen, phosphorus, tungsten and at least one metal from groups 8 to 11 of the periodic table of the elements
  • the present invention relates to a new class of phosphorus, tungsten and metal-containing mixed oxides which contain at least one other metal other than tungsten, platinum group metals being preferred which have catalytically useful properties. Furthermore, the present invention relates to a process for the preparation of these mixed oxides, their use and a process for the catalytic partial oxidation of hydrocarbons using these mixed oxides.
  • Oxygenates are maleic anhydride, acrolein and acrylic acid. These oxygenates are mostly obtained by selective partial oxidation of propane or n-butane, but other organic starting materials are also conceivable for this.
  • Vanadyl pyrophosphate is known from the prior art as a catalyst for the partial oxidation of hydrocarbons, which generally has good selectivity properties and is also very active.
  • tungsten phosphate-based materials of the Re0 3 structure are known, which also include Sc, Ti, V, Cr, Fe, Nb, Mo, In, Sb or mixtures thereof can.
  • example A6 an iron-containing compound was shown which is essentially crystalline.
  • the Re0 3 family of structures are compounds with crystal structures which are derived from the crystal structure of the rhenium (VI) oxide ReÜ 3 .
  • the disclosed tungsten phosphates were prepared wet-chemically by means of solution combustion synthesis and subsequent calcination. Some of the tungsten phosphates shown were tested for their catalytic properties in the conversion of n-butane to maleic anhydride in the temperature range from 375 ° C to 450 ° C. Selectivities in terms of maleic anhydride between 20.6 and 87.4 mol% were achieved.
  • Rhenium trioxide (Re vl 0 3 ) has a characteristic crystal structure, which is also known as
  • This crystal structure is similar to the pervoskite structure, the only difference being the lack of a central atom (calcium in perovskite).
  • Each rhenium atom is octahedrally surrounded by oxygen atoms, while the oxygen atoms are located between two rhenium atoms.
  • Another object was to provide a method for producing such improved mixed oxides. It was one of the tasks of the present
  • mixed oxides which in particular comprise at least one metal selected from Groups 8 to 11 of the Periodic Table of the Elements, tungsten and phosphorus, were shown and examined with regard to their catalytic properties.
  • the mixed oxides according to the invention show a surprisingly high flexibility with regard to their structure and composition.
  • Mixed oxides including vanadium could also be prepared in this way.
  • the mixed oxides according to the invention comprising tungsten, phosphorus and at least one metal selected from groups 8 to 11 of the periodic table of the elements can be prepared by a simple method.
  • the mixed oxides are preferred by means of
  • Solution combustion synthesis which allows a very high but rather uncontrolled energy input into a system. This procedure is characterized by a very short execution time.
  • compositions according to the invention comprising in particular a metal selected from groups 8 to 11 of the Periodic Table of the Elements, tungsten and phosphorus have catalytic properties with regard to the partial oxidation, in particular the selective partial oxidation, of hydrocarbons.
  • Suitable hydrocarbons are, in particular, alkanes and alkenes, such as propane, propene and n-butane, but other hydrocarbons are also conceivable. This is surprising since the person skilled in the art, particularly when using a metal selected from Groups 8 to 11 of the Periodic Table of the Elements, oxidizes the hydrocarbons used to form acetic acid, carbon monoxide and carbon dioxide, i.e. above all total combustion.
  • the mixed oxides according to the invention are surprisingly distinguished by good activity and selectivity with regard to the oxygenates of hydrocarbons.
  • good selectivities with regard to maleic anhydride can be achieved.
  • the mixed oxides according to the invention surprisingly have a comparatively good activity at temperatures in the range from 350 to 450 ° C.
  • a mixed oxide comprising ruthenium, tungsten and phosphorus has excellent properties in the catalytic oxidation of n-butane to maleic anhydride.
  • the mixed oxides according to the invention are preferably produced by means of the solution combustion synthesis.
  • the molar amount of the oxidizing agent HNO3 was measured so that with the preferably used additive glycine as fuel and the more preferably used ammonium - also as fuel - complete combustion to H2O, CO2 and molecular nitrogen can take place.
  • Smaller amounts of nitric acid regularly lead to an incomplete combustion reaction, experience has shown that nitric acid added in excess is already lost during subsequent evaporation, i.e. before the combustion reaction ignites.
  • the present invention thus relates to a mixed oxide comprising oxygen, phosphorus, tungsten and at least one metal M 1 from groups 8 to 11 of the Periodic Table of the Elements, the molar ratio of tungsten to M 1, W: M1, in the range of greater than 0: 1 to less than 6: 1, and
  • the present invention further relates to a shaped body comprising a mixed oxide according to one of the embodiments described herein.
  • the present invention further relates to a method for producing a mixed oxide according to one of the embodiments described herein, comprising
  • Tungsten source a source of M1, a fuel additive and an oxidizer
  • the present invention further relates to a mixed oxide according to one of the embodiments described herein, obtainable or obtained by a process according to one of the embodiments described herein.
  • the present invention further relates to a mixed oxide, obtainable or obtained by a process according to one of the embodiments described herein.
  • Oxidation reaction of one or more hydrocarbons more preferably in a selective partial oxidation reaction of one or more, preferably substituted,
  • Hydrocarbons the hydrocarbons preferably comprising an alkane, an alkene, an aldehyde, a ketone, or an aromatic, are preferred, the hydrocarbons preferably being selected from the group consisting of propanol, isopropanol, propanal, butanol, butanal, benzene, toluene , Xylene, acrolein, methacrolein, ethane, ethene, propane, propene, n-butane, 1-butene, 2-butene, 1, 3-butadiene, isobutane, isobutene, n-pentane, 1-pentene, 2-methyl-but -1-ene, isopentene, 3-methyl-but-1-ene, and mixtures of two or more thereof, more preferably selected from the group consisting of ethane, ethene, propane, propene, n-butane,
  • 1,3-butadiene and mixtures of two or more thereof more preferably selected from the group consisting of propane, propene, n-butane and mixtures of two or more thereof.
  • the present invention further relates to a method for oxidation, preferably for partial oxidation, more preferably for selective partial oxidation of one or more
  • Reaction gas stream comprises one or more hydrocarbons, oxygen (O2), water (H2O) and preferably one or more inert gases;
  • % By weight is more preferably in the range from 11 to 18% by weight, more preferably in the range from 14 to 17% by weight, calculated as the element and based on the weight of the mixed oxide.
  • the content of tungsten in the mixed oxide is in the range from 9 to 20% by weight, more preferably in the range from 12 to 19% by weight, more preferably in the range from 16 to 18% by weight, calculated as the element and based on the weight of the mixed oxide.
  • W molar ratio of tungsten to phosphorus
  • W P
  • this is in the range from 0.2: 1 to 1.4: 1, more preferably in the range from 0.5 to 1.1, more preferably in the range from 0.6: 1 to 1 : 1, more preferably in the range of 0.7: 1 to 0.9: 1.
  • M1 is selected from the group consisting of Ru, Os, Rh, Ir, Pd, Pt, Ag, Au and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Os, Rh, Ir, Pd, Ag and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Rh, Pd, Ag and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Rh , Pd and a mixture of two or more thereof, more preferably from the group consisting of Ru, Pd and a mixture thereof.
  • M1 comprises Ru.
  • the content of M1 in the mixed oxide is in the range from 2.5 to 8.0% by weight, more preferably in the range from 3.0 to 7.4% by weight, more preferably in the range from 3.4 to 4.0% by weight, calculated as element and based on the weight of the mixed oxide.
  • molar ratio of tungsten to M1, W: M1 it is preferred that this is in the range from 0.1: 1 to 5.9: 1, more preferably in the range from 0.5: 1 to 5.5: 1, more preferably in the range from 0.9 : 1 to 4.5: 1, more preferably in the range from 3.75: 1 to 4.25: 1, more preferably in the range from 3.9: 1 to 4.1: 1.
  • the molar ratio of phosphorus to M1, P: M1 is in the range from greater than 0: 1 to less than 5: 1, more preferably in the range from 1: 1 to 20: 1, more preferably in the range from 4: 1 to 11: 1, more preferably in the range from 5: 1 to 10: 1.
  • the mixed oxide consists essentially of oxygen, phosphorus,
  • the mixed oxide is 90 to 100% by weight, more preferably 95 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, from oxygen, phosphorus , Tungsten and M1.
  • the mixed oxide additionally comprises an element M2, different from W and M1, from the metals and semimetals of the periodic table of the elements, more preferably from the metals and semimetals of the groups 3 to 16 of the Periodic Table of the Elements.
  • the mixed oxide comprises an element M2 that is different from W and M1
  • M2 is selected from the group consisting of V, Nb, Ta, Cr, Mo, Sn, Sb, Se, Te and a mixture of two or more thereof, more preferably selected from the group consisting of V, Nb, Cr, Sn, Sb and a mixture of two or more thereof, where M2 more preferably comprises V, and where M2 is more preferably V.
  • the mixed oxide comprises an element M2 which is different from W and M1
  • the content of M2 in the mixed oxide is in the range from 2.0 to 7.0% by weight, more preferably in the range from 2.6 to 6.5% by weight, more preferably in the range from 2.7 to 5.9% by weight, calculated as the element and based on the weight of the mixed oxide.
  • the mixed oxide comprises an element M2 that is different from W and M1
  • the mixed oxide consists essentially of oxygen, phosphorus, tungsten, M1 and M2.
  • the mixed oxide is 90 to 100% by weight, more preferably 95 to 100% by weight, more preferably 98 to 100% by weight, more preferably 99 to 100% by weight, from oxygen, phosphorus , Tungsten, M1 and M2.
  • the mixed oxide according to the present invention is 40 to 100% by weight X-ray amorphous.
  • the mixed oxide is 42 to 99% by weight X-ray amorphous, more preferably 45 to 98% by weight, more preferably 50 to 97% by weight, more preferably 55 to 96% by weight, further preferred 60 to 95% by weight, more preferably 65 to 94% by weight, more preferably 70 to 93
  • the mixed oxide is 1 to 60% by weight crystalline, preferably 2 to 55% by weight, more preferably 3 to 50% by weight preferably 4 to 45% by weight, more preferably 5 to 40% by weight, more preferably 6 to 35% by weight, more preferably 7 to 30% by weight, more preferably 8 to 25% by weight, further preferably 9 to 20% by weight, more preferably 10 to 15% by weight, preferably determined according to Reference Example 1.
  • the mixed oxide comprises a crystalline phase which is structurally analogous to the crystalline phase of ReC> 3.
  • the mixed oxide can further contain two or more crystalline phases.
  • M1 in metallic form is present in the mixed oxide, based on the weight of M1, more preferably less than 1% by weight, more preferably in the range from 0.001 to 1 weight. -%, more preferably in the range of 0.01 to 1% by weight.
  • the mixed oxide be essentially free of molybdenum.
  • the mixed oxide comprises a content of 0 to 0.1% by weight Mo, more preferably 0 to 0.01% by weight Mo, more preferably 0 to 0.001% by weight Mo, calculated as element and based on the weight of the mixed oxide.
  • the mixed oxide comprise vanadium.
  • the mixed oxide may be preferred that the mixed oxide be essentially free of vanadium. It is particularly preferred here that the mixed oxide has a content of 0 to 0.1% by weight V, more preferably 0 to 0.01% by weight V, more preferably 0 to 0.001% by weight V, calculated as an element and based on the weight of the mixed oxide.
  • the mixed oxide described here can be in calcined form or in non-calcined form. It is preferred that the mixed oxide is a calcined mixed oxide. In particular, it is preferred that the mixed oxide is a calcined mixed oxide, the calcination being carried out in a gas atmosphere, preferably comprising, more preferably consisting of air, dry, pure air, nitrogen, argon or a mixture of two or more thereof, the gas atmosphere preferably being one Has temperature in the range of 300 to 800 ° C, more preferably in the range of 350 to 750 ° C.
  • the mixed oxide in particular as a catalyst or as a catalyst component, it is further preferred that the mixed oxide is contained in a shaped body.
  • the present invention therefore further relates to a shaped body comprising a mixed oxide according to one of the embodiments described herein.
  • the present invention further relates to a method for producing a mixed oxide according to one of the embodiments described herein, comprising
  • Tungsten source a source of M1, a fuel additive and an oxidizer
  • the phosphorus source is selected from the group consisting of a phosphoric acid, a salt of a phosphoric acid, an ester of a phosphoric acid and mixtures of two or more thereof, more preferably selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphorus ( V) oxide,
  • Ammonium dihydrogen phosphate diammonium hydrogen phosphate and mixtures of two or more thereof. It is particularly preferred that the phosphorus source comprises orthophosphoric acid, is further preferred.
  • the tungsten source is a tungsten, a paratungstate
  • Metotungstate a poly tungstate or a mixture of two or more thereof.
  • the tungsten source comprises a metatungstate, more preferred.
  • M1 is selected from groups 8 to 11 of the
  • Periodic table of the elements further preferably selected from the group consisting of Ru, Os, Rh, Ir, Pd, Pt, Ag, Au and a mixture of two or more thereof, further preferably selected from the group consisting of Ru, Os, Rh, Ir, Pd, Ag and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Rh, Pd, Ag and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Rh, Pd and a mixture of two or more thereof, more preferably from the group consisting of Ru, Pd and a mixture thereof, M1 more preferably comprising Ru, more preferred.
  • the source of M1 comprises an inorganic, an organic or an organometallic salt.
  • the anion of the salt is a nitrate, a chloride, an oxalate, an acetylacetonate (pentane-2,4-dionato), an acetate, a tartrate, a carbonate, or a mixture of two or more thereof.
  • the salt at a temperature of 25 ° C. and a pressure of 1 bar (abs) is at least 90% by weight in aqueous nitric acid, more preferably in aqueous nitric acid with a concentration in the range from 60 to 70% by weight. % HNO3, is soluble.
  • the molar ratio of tungsten to M1, W: M1, in the mixture according to (i) it is preferred that this is in the range from 2: 1 to 5: 1, more preferably in the range from 2.9: 1 to 4.5: 1 , more preferably in the range from 3.9: 1 to 4.1: 1.
  • the fuel additive is selected from the group consisting of glycine, urea, carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide,
  • Urotropin citric acid, maleic hydrazide, difomylhydrazide and mixtures of two or more thereof. It is particularly preferred that the fuel additive is glycine.
  • the oxidizing agent is selected from the group consisting of H2O2,
  • the molar ratio of the fuel additive to the oxidizing agent it is preferred that this is in the range from 6: 1 to 10: 1, more preferably in the range from 7.5: 1 to 8.5: 1, more preferably in the range from 7.9: 1 to 8.1: 1.
  • the mixture according to (i) can comprise further components, in particular in order to produce a mixed oxide which comprises M2. It is therefore preferred that the mixture according to (i) additionally comprises a suitable source of M2.
  • the mixture according to (i) additionally comprises a source of M2, it is preferred that M2 is selected from the group consisting of V, Nb, Ta, Cr, Mo, Sn, Sb, Se, Te and a mixture of two or more of these, more preferably selected from the group consisting of V, Nb, Cr, Sn, Sb and a mixture of two or more thereof. In particular, it is preferred that M2 comprises V, is further preferred.
  • the mixture according to (i) additionally comprises a source of M2, and wherein M2 comprises V
  • the source of M2 comprises one or more of an orthovanadate, a divanadate, a metavanadate and a polyvanadate.
  • the source of M2 comprises a metavandate, is further preferred.
  • the mixture according to (i) additionally comprises a source of M2, it is preferred that the molar ratio of M2 to M1, M2: M1, in the mixture according to (i) is in the range from 0.5: 1 to 1.5: 1, more preferably in the range from 0.7: 1 to 1.3: 1, more preferably in the range from 0.9: 1 to 1.1: 1.
  • the gas atmosphere in (ii) has a temperature in the range from 60 to 90 ° C., preferably in the range from 70 to 80 ° C. It is further preferred that (iii) solution combustion synthesis
  • the mixture in (iii) is brought to a temperature of at least 375 ° C., more preferably to a temperature in the range from 350 to 450 ° C., more preferably in the range from 390 to 410 ° C.
  • the temperature of the gas atmosphere in (iv) there is no restriction, provided that it is ensured that the material obtained according to (iii) is calcined to obtain the mixed oxide. It is preferred that the gas atmosphere in (iv) has a temperature in the range from 350 to 550 ° C, more preferably in the range from 390 to 510 ° C.
  • the method for producing a mixed oxide according to the present invention can comprise further steps. It is preferred that the method further comprises
  • the method comprises
  • the gas atmosphere in one or more of (ii), (iii), (iv), (v) and (vi) comprise air, ultrapure dry air, nitrogen, argon or a mixture thereof.
  • Oxidation reaction of one or more hydrocarbons more preferably in a selective partial oxidation reaction of one or more, preferably substituted,
  • Hydrocarbons the hydrocarbons preferably comprising an alkane, an alkene, an aldehyde, a ketone, or an aromatic, are preferred, the hydrocarbons preferably being selected from the group consisting of propanol, isopropanol, propanal, butanol, butanal, benzene, toluene , Xylene, acrolein, methacrolein, ethane, ethene, propane, propene, n-butane, 1-butene, 2-butene, 1, 3-butadiene, isobutane, isobutene, n-pentane, 1-pentene, 2-methyl-but -1-ene, isopentene, 3-methyl-but-1-ene, and mixtures of two or more thereof, more preferably selected from the group consisting of ethane, ethene, propane, propene, n-butane,
  • 1,3-butadiene and mixtures of two or more thereof more preferably selected from the group consisting of propane, propene, n-butane and mixtures of two or more thereof.
  • the present invention further relates to a method for oxidation, preferably for partial oxidation, more preferably for selective partial oxidation of one or more
  • Reaction gas stream comprises one or more hydrocarbons, oxygen (O2), water (H2O) and preferably one or more inert gases;
  • reaction zone comprises the mixed oxide arranged in a fixed bed.
  • the reactor comprises two or more reaction zones. It is preferred that two or more reaction zones are arranged parallel to one another.
  • reaction zones are arranged in series.
  • the mixed oxide is contained in a shaped body, for example in a tablet, an extrudate or another suitable shaped body.
  • the mixed oxide, or preferably a shaped body comprising the mixed oxide can be heated in (a). It is preferred that the mixed oxide, or preferably a shaped body comprising the mixed oxide, is heated in (a) to a temperature in the range from 150 to 350 ° C., more preferably to a temperature in the range from 170 to 330 ° C., more preferably to a temperature in the range from 180 to 320 ° C, more preferably to a temperature in the range from 190 to 310 ° C.
  • the mixed oxide preferably a shaped body comprising the mixed oxide
  • Shaped body comprising the mixed oxide, after (a) and before (b) is heated to a temperature in the range from 150 to 350 ° C., more preferably to a temperature in the range from 170 to 330 ° C., more preferably to a temperature in the range from 180 to 320 ° C, more preferably to a temperature in the range from 190 to 310 ° C, and wherein the mixed oxide in (b) is gradually heated to a temperature in the range from 350 to 500 ° C, preferably to a temperature in the range of 370 to 480 ° C, more preferably to a temperature in the range from 380 to 470 ° C, more preferably to a temperature in the range from 390 to 460 ° C.
  • hydrocarbons are selected from the group consisting of propanol, isopropanol, propanal, butanol, butanal, benzene, toluene, xylene, acrolein, methacrolein, ethane, ethene, propane, propene, n-butane, 1-butene, 2-butene, 1, 3-butadiene, isobutane, isobutene, n-pentane, 1-pentene, 2-methyl-but-1-ene, isopentene, 3-methyl-but-1-ene, and mixtures of two or more thereof, more preferably selected from the group consisting of ethane, ethene, propane, propene, n-butane, 1-butene, 2-butene, 1, 3-butadiene, isobutane, isobutene, n-pentane,
  • Hydrocarbons to oxygen (O2) is in the range from 1: 1 to 1:50, preferably in the range from 1: 2 to 1:35, more preferably in the range from 1: 3 to 1:31, more preferably in the range from 1: 4 to 1:20, more preferably in the range from 1: 7 to 1:18, more preferably in the range from 1: 9 to 1:16. It is further preferred that the volume ratio of the one or more hydrocarbons to water (H 2 O) in the reaction gas stream in (b) is in the range from 10: 1 to 1:25, more preferably in the range from 5: 1 to 1: 20, more preferably in the range from 2: 1 to 1:10, more preferably in the range from 1: 1 to 1: 5, more preferably in the range from 1: 2 to 1: 4.
  • reaction gas stream in (b) essentially consists of one or more hydrocarbons, oxygen (O2), water (H2O) and one or more inert gases. It is therefore preferred that from 95 to 100% by volume, preferably from 97 to 100% by volume, more preferably from 98 to 100% by volume, more preferably from 99 to 100% by volume, of the reaction gas stream introduced into the reaction zone (b) from one or several hydrocarbons, oxygen (O2), water (H2O) and one or more
  • reaction gas stream in (b) comprises 0.1 to 5.0% by volume of hydrocarbons, more preferably 0.3 to 3.5% by volume, more preferably 0.5 to 2.5% by volume, more preferably 0.75 to 2.25% by volume, more preferably 0.9 to 2.1% by volume. It is further preferred that the reaction gas stream in (b) comprises 5 to 25% by volume oxygen (O2), more preferably 10 to 25% by volume, more preferably 12 to 23% by volume, more preferably 14 to 21% by volume .
  • O2 oxygen
  • reaction gas stream in (b) comprises 0.1 to 25% by volume of water (H2O), more preferably 0.5 to 20% by volume, more preferably 0.75 to 10% by volume, more preferably 1 to 5% by volume, more preferably 2.5 to 3.5% by volume.
  • H2O water
  • oxidation conditions in the reaction zone comprise a pressure in the range from 0.5 to 5 bar (abs), more preferably in the range from 0.6 to 4 bar (abs), more preferably in the range from 0, 7 to 3.5 bar (abs), more preferably in the range of 0.9 to 3.1 bar (abs). It is further preferred that the oxidation conditions in the reaction zone have a space velocity of the catalyst volume
  • Reaction gas stream based on the volume of the composition provided in (a) in the range from 300 to 100,000 Ir 1 , more preferably in the range from 1,000 to 10,000 ir 1 , more preferably in the range from 1,500 to 6,000 Ir 1 .
  • the inert gases comprise nitrogen (N2), argon or a mixture thereof, preferably the inert gases include nitrogen (N2) and argon, more preferably the inert gases are nitrogen (N2) and argon. It is further preferred that from 95 to 100% by volume, more preferably from 96 to 100% by volume, more preferably from 98 to 100% by volume, more preferably from 99 to 100% by volume of the inert gases from nitrogen (N2) and argon exist. It is further preferred that from 1 to 5% by volume, more preferably from 1.5 to 4.5
  • reaction gas stream comprises propane or propene and the product gas stream comprises acrolein, acrylic acid or a mixture thereof
  • the reaction gas stream comprises n-butane and the
  • Product gas stream includes maleic anhydride. If propane or propene is contained in the reaction gas stream, it is preferred that the reaction gas stream has a content of at least 1.7% by volume of propane or propene. This corresponds to a lean driving style. Alternatively, it is preferred that the reaction gas stream has a content of at most 10.8% by volume of propane or propene. This corresponds to a fat driving style.
  • n-butane is contained in the reaction gas stream, it is preferred that the
  • Reaction gas stream has a content of at least 1.4% by volume of n-butane. This corresponds to a lean driving style. Alternatively, it is preferred that the reaction gas stream has a content of at most 9.4% by volume of n-butane. This corresponds to a fat driving style.
  • the unit bar (abs) refers to a pressure, where 1 bar corresponds to 10 5 Pa and the unit ⁇ refers to a length, where 1 ⁇ corresponds to 10 ⁇ 10 m.
  • the present invention is further characterized by the following embodiments, including the individual and separate combinations of the embodiments indicated by the respective dependencies.
  • each embodiment in this set is explicitly disclosed to the person skilled in the art what means that the wording of this term is to be understood synonymously for the person skilled in the art with “mixed oxide according to one of the embodiments 1, 2, 3 and 4”.
  • mixed oxide comprising oxygen, phosphorus, tungsten, at least one metal M 1 from groups 8 to 11 of the periodic table of the elements,
  • molar ratio of tungsten to M1, W: M1 is in the range from greater than 0: 1 to less than 6: 1,
  • the phosphorus content of the mixed oxide being in the range from 8 to 19% by weight, preferably in the range from 11 to 18% by weight, more preferably in the range from 14 to 17% by weight as an element and based on the weight of the mixed oxide.
  • Tungsten is in the range of 9 to 20% by weight, preferably in the range of 12 to 19% by weight, more preferably in the range of 16 to 18% by weight, calculated as an element and based on the weight of the mixed oxide.
  • the molar ratio of tungsten to phosphorus, W: P being in the range from 0.2: 1 to 1.4: 1, preferably in the range from 0.5 to 1.1, more preferably in the range from 0.6: 1 to 1: 1, more preferably in the range from 0.7: 1 to 0.9: 1.
  • M 1 is selected from the group consisting of Ru, Os, Rh, Ir, Pd, Pt, Ag, Au and a mixture of two or more thereof, preferably selected from the group consisting of Ru, Os, Rh, Ir, Pd, Ag and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Rh, Pd, Ag and a mixture of two or more thereof, more preferably consisting of the group from Ru, Rh, Pd and a mixture of two or more thereof, more preferably from the group consisting of Ru, Pd and a mixture thereof.
  • M 1 comprises Ru, preferably Ru.
  • the M1 content of the mixed oxide being in the range from 2.5 to 8.0% by weight, preferably in the range from 3.0 to 7.4% by weight, more preferably in the range from 3.4 to 4.0% by weight, calculated as an element and based on the weight of the mixed oxide.
  • the molar ratio W: M1 being in the range from 0.1: 1 to 5.9: 1, preferably in the range from 0.5: 1 to 5.5: 1, more preferably in the range from 0.9: 1 to 4.5 : 1, more preferably in the range from 3.75: 1 to 4.25: 1, more preferably in the range from 3.9: 1 to 4.1: 1.
  • Mixed oxide according to one of the embodiments 1 to 9 the mixed oxide consisting of 90 to 100% by weight, preferably 95 to 100% by weight, more preferably 98 to 100% by weight, further preferably 99 to 100% by weight Oxygen, phosphorus, tungsten and M1 exist.
  • Mixed oxide according to one of the embodiments 1 to 10 wherein the mixed oxide is an element M2 different from W and M1 from the metals and semimetals of the
  • Periodic table of the elements comprises, preferably from the metals and semimetals of groups 3 to 16 of the periodic table of the elements.
  • the M2 content of the mixed oxide being in the range from 2.0 to 7.0% by weight, preferably in the range from 2.6 to 6.5
  • % By weight, more preferably in the range from 2.7 to 5.9% by weight, calculated as an element and based on the weight of the mixed oxide.
  • % By weight, preferably determined according to reference example 1.
  • the mixed oxide comprising a content of 0 to 0.1% by weight Mo, preferably from 0 to 0.01% by weight Mo, more preferably from 0 to 0.001% by weight Mo, %, calculated as an element and based on the weight of the mixed oxide.
  • the mixed oxide is calcined, the calcination being carried out in a gas atmosphere, preferably comprising, more preferably consisting of air, dry ultrapure air, nitrogen, argon or a mixture of two or more thereof, wherein the gas atmosphere preferably has a temperature in the range from 300 to 800 ° C, more preferably in the range from 350 to 750 ° C.
  • a gas atmosphere preferably comprising, more preferably consisting of air, dry ultrapure air, nitrogen, argon or a mixture of two or more thereof, wherein the gas atmosphere preferably has a temperature in the range from 300 to 800 ° C, more preferably in the range from 350 to 750 ° C.
  • Shaped body comprising a mixed oxide according to one of the embodiments 1 to 21 and optionally one or more further components, preferably one or more
  • Tungsten source a source of M1, a fuel additive and an oxidizer
  • the phosphorus source is selected from the group consisting of a phosphoric acid, a salt of a phosphoric acid, an ester of a phosphoric acid and mixtures of two or more thereof, preferably selected from the group consisting of orthophosphoric acid, phosphonic acid, Phosphorus (V) oxide, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and mixtures of two or more thereof, the phosphorus source further preferably comprising orthophosphoric acid.
  • the tungsten source comprises a tungsten, a paratungstate, a metatungstate, a poly tungstenate or a mixture of two or more thereof, wherein the tungsten source preferably comprises a metatungstate, more preferably is a tungstenate.
  • M1 is selected from groups 8 to 11 of the periodic table of the elements, preferably selected from the group consisting of Ru, Os, Rh, Ir, Pd, Pt, Ag, Au and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Os, Rh, Ir, Pd, Ag and a mixture of two or more thereof, more preferably selected from the group consisting of Ru, Rh, Pd, Ag and a mixture of two or more thereof, more preferably from the group consisting of Ru, Rh, Pd and a mixture of two or more thereof, more preferably from the group consisting of Ru, Rh, Pd and a mixture thereof, M1 being more preferred Ru includes, is more preferred.
  • the source of M1 comprises an inorganic, an organic or an organometallic salt, the anion of the salt being a nitrate, a chloride, an oxalate, an acetylacetonate (pentane-2,4- dionato), an acetate, a tartrate, a carbonate, or a mixture of two or more thereof, the salt being more preferably at a temperature of 25 ° C. and a pressure of 1 bar (abs) to at least 90% by weight in aqueous nitric acid, preferably in aqueous nitric acid with a concentration in the range from 60 to 70% by weight HN O3, is soluble.
  • the fuel additive is selected from the group consisting of glycine, urea, carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, urotropin, citric acid, maleic hydrazide, difomylhydrazide and Mixtures of two or more thereof, the fuel additive being glycine.
  • the oxidizing agent is selected from the group consisting of H2O2, S, I2, O3, O2, F2, CI2, S2O8, HB1O3, Mn0 2 , KMn0 4 , HN0 3 , NH4NO3, KCIO3, CuO, Mn0 4 , OCh, N0 3 ⁇ , CI0 3- , CI0 2- , Au 3+ , Pt 2+ , Pb 4+ , Br0 3- , Cr0 4 2 , Fe (CN) 6 3 , Co 3 + , Ni 3+ , Fe0 4 2 ⁇ , As0 4 3 ⁇ Cu 2+ , Sn 2+ , Pb 4+ , As 3+ , Bi 3+ and mixtures of two or more thereof, preferably from the group consisting of HNO3, NH 4 Nq3, NO3, the oxidizing agent being more preferably NO3.
  • V consisting of V, Nb, Ta, Cr, Mo, Sn, Sb, Se, Te and a mixture of two or more thereof, more preferably selected from the group consisting of V, Nb, Cr, Sn, Sb and a mixture of two or more thereof, where M2 more preferably comprises V, where M2 is more preferably V.
  • Source of M2 preferably comprises one or more of orthovanadate, divanadate, metavanadate and polyvanadate, the source of M2 preferably comprising metavandate, more preferably metavandate.
  • Method according to one of the embodiments 34 to 36, wherein the molar ratio of M2 to M1, M2: M 1, in the mixture according to (i) is in the range from 0.5: 1 to 1.5: 1, preferably in the range from 0.7: 1 to 1.3: 1, more preferably in the range from 0.9: 1 to 1.1: 1.
  • Solution combustion synthesis includes.
  • Method according to one of the embodiments 24 to 40 the mixture in (iii) being brought to a temperature of at least 375 ° C., preferably to a temperature in the range from 350 to 450 ° C., more preferably in the range from 390 to 410 ° C.
  • (iv) has a temperature in the range of 350 to 550 ° C, preferably in the range of 390 to 510 ° C.
  • a mixed oxide according to one of the embodiments 1 to 22 or 46 to 47 or a shaped body according to embodiment 23 as a catalytically active substance or constituent of a catalyst in a reaction for reacting one or more hydrocarbons, preferably in a catalytic oxidation reaction of one or more hydrocarbons, more preferably in a selective partial one
  • Oxidation reaction of one or more, preferably substituted, hydrocarbons the hydrocarbons preferably comprising an alkane, an alkene, an aldehyde, a ketone, or an aromatic, are preferred, the hydrocarbons preferably being selected from the group consisting of propanol , Isopropanol, propanal,
  • Process for oxidation preferably for partial oxidation, more preferably for selective partial oxidation of one or more hydrocarbons, comprising
  • reaction zone which comprises a mixed oxide according to one of the embodiments 1 to 22 or 46 to 47;
  • reaction gas stream comprising one or more hydrocarbons, oxygen (O2), water (H2O) and preferably one or more inert gases;
  • Product gas stream at least one oxidation product comprising one or more hydrocarbons.
  • Temperature in the range of 170 to 330 ° C more preferably to a temperature in the range of 180 to 320 ° C, more preferably to a temperature in the range of 190 to 310 ° C.
  • the mixed oxide being heated to (a) and before (b) to a temperature in the range from 150 to 350 ° C., preferably to a temperature in the range from 170 to 330 ° C., more preferably to a temperature in the range from 180 to 320 ° C, more preferably to a temperature in the range from 190 to 310 ° C, and wherein the mixed oxide in (b) is gradually heated to a temperature in the range from 350 to 500 ° C , preferably to a temperature in the range from 370 to 480 ° C, more preferably to a temperature in the range from 380 to 470 ° C, more preferably to a temperature in the range from 390 to 460 ° C. 58.
  • the hydrocarbons being selected from the group consisting of propanol, isopropanol, propanal,
  • Method according to one of the embodiments 49 to 58 wherein in the reaction gas stream in (b) the volume ratio of the one or more hydrocarbons to oxygen (O2) is in the range from 1: 1 to 1:50, preferably in the range from 1: 2 to 1:35, more preferably in the range from 1: 3 to 1:31, more preferably in the range from 1: 4 to 1:20, more preferably in the range from 1: 7 to 1:18, more preferably in the range from 1 : 9 to 1:16.
  • the volume ratio of the one or more hydrocarbons to oxygen (O2) is in the range from 1: 1 to 1:50, preferably in the range from 1: 2 to 1:35, more preferably in the range from 1: 3 to 1:31, more preferably in the range from 1: 4 to 1:20, more preferably in the range from 1: 7 to 1:18, more preferably in the range from 1 : 9 to 1:16.
  • Method according to one of the embodiments 49 to 59 wherein in the reaction gas stream in (b) the volume ratio of the one or more hydrocarbons to water (H2O) is in the range from 10: 1 to 1:25, preferably in the range from 5: 1 to 1:20, more preferably in the range from 2: 1 to 1:10, more preferably in the range from 1: 1 to 1: 5, more preferably in the range from 1: 2 to 1: 4.
  • H2O volume ratio of the one or more hydrocarbons to water
  • reaction gas stream introduced into the reaction zone in (b) consists of one or more hydrocarbons, oxygen (O2), water (H2O) and one or more inert gases.
  • reaction gas stream in (b) comprises 0.1 to 5.0% by volume of hydrocarbons, preferably 0.3 to 3.5% by volume, more preferably 0.5 to 2 , 5% by volume, more preferably 0.75 to 2.25% by volume, more preferably 0.9 to 2.1% by volume.
  • reaction gas stream in (b) comprises 5 to 25% by volume oxygen (O2), preferably 10 to 25% by volume, more preferably 12 to 23% by volume, more preferably 14 up to 21% by volume.
  • reaction gas stream in (b) comprises 0.1 to 25% by volume of water (H2O), preferably 0.5 to 20% by volume, more preferably 0.75 to 10% by volume -%, more preferably 1 to 5% by volume, more preferably 2.5 to 3.5% by volume.
  • Oxidation conditions in the reaction zone include a pressure in the range from 0.5 to 5 bar (abs), preferably in the range from 0.6 to 4 bar (abs), more preferably in the range from 0.7 to 3.5 bar (abs) , more preferably in the range from 0.9 to 3.1 bar (abs).
  • Oxidation conditions in the reaction zone are related to catalyst volume
  • Space velocity of the reaction gas stream based on the volume of the composition provided in (a) in the range from 300 to 100,000 fr 1 , preferably in the range from 1,000 to 10,000 Ir 1 , more preferably in the range from 1,500 to 6,000 Ir 1 .
  • the inert gases comprise nitrogen (N 2 ), argon or a mixture thereof, preferably the inert gases comprise nitrogen (N2) and argon, more preferably the inert gases nitrogen (N2) and argon.
  • Method according to one of the embodiments 49 to 67 wherein from 95 to 100% by volume, preferably from 96 to 100% by volume, more preferably from 98 to 100% by volume, further preferably from 99 to 100% by volume of the inert gases consist of nitrogen (N2) and argon.
  • Oxidation conditions are isothermal.
  • reaction gas stream comprises propane or propene and the product gas stream comprises acrolein, acrylic acid or a mixture thereof.
  • reaction gas stream comprises n-butane and the product gas stream comprises maleic anhydride.
  • Reference Example 1 Determination of the X-ray powder diffractogram and the crystallinity
  • Reference example 2 Determination of the element composition using an energy dispersive
  • EDX X-ray spectroscopy
  • Example 1 Production of a mixed oxide according to the invention of the empirical formula
  • Teflon-coated magnetic stirrers evaporated to dryness.
  • the rock residue was divided into six equal portions. Each of the portions was ignited in a flat porcelain bowl (diameter 16 cm) in a preheated laboratory muffle furnace (model L5 / 1 1 temperature controller B170, Nabertherm GmbH, Germany) at 400 ° C and then heated for 10 minutes (solution combustion system).
  • the powders obtained after heating were ground in an agate mortar and combined again.
  • the powder obtained in this way was heated in a silica glass half-ampoule for 2 days at 400 ° C. in a laboratory muffle furnace, ground again in an agate mortar, heated for a further 2 days at 500 ° C. and ground again.
  • the powder then obtained showed a brown color and that shown in Figure 1
  • a Analysis by means of EDX according to reference example 2 showed an oxygen content of 61.62% by weight, of phosphorus of 16.69% by weight, of ruthenium of 3.57% by weight and of tungsten of 12.32% by weight of the powder obtained. %, and vanadium of 5.81% by weight.
  • Example 2 Production of a mixed oxide according to the invention of the empirical formula
  • Teflon-coated magnetic stirrers evaporated to dryness.
  • the rock residue was divided into two equal portions. Each of the portions was ignited in a flat porcelain bowl (diameter 16 cm) in a preheated laboratory muffle furnace (model L5 / 1 1 temperature controller B170, from Nabertherm GmbH, Germany) at 400 ° C. and then heated for 10 min (solution combustion synthesis).
  • the powders obtained after heating were ground in an agate mortar and combined again.
  • the powder thus obtained was in a silica glass half-ampoule 1 d at 400 ° C, 3 d at 500 ° C and 9 d at 600 ° C in
  • Example 3 Preparation of a mixed oxide according to the invention of the empirical formula
  • the mixture was evaporated to dryness on a heating stirrer (magnetic stirrer RH Basic 2, IKA, Germany) at 75 ° C. while stirring with a Teflon-coated magnetic stirrer.
  • the dry residue was divided into three equal portions.
  • Each of the servings was in ignited a flat porcelain bowl (diameter 16 cm) in a preheated laboratory muffle furnace (model L5 / 11 temperature controller B170, Nabertherm GmbH, Germany) at 400 ° C and then heated for 10 min (solution combustion synthesis).
  • the powders obtained after heating were ground in an agate mortar and combined again.
  • the powder thus obtained was heated in a silica glass half-ampoule for 1 day at 500 ° C., 3 days at 600 ° C.
  • Example 4 Preparation of a mixed oxide according to the invention of the empirical formula
  • the mixture was evaporated to dryness on a heating stirrer (magnetic stirrer RH Basic 2, IKA, Germany) at 75 ° C. while stirring with a Teflon-coated magnetic stirrer.
  • the dry residue was divided into three equal portions. Each of the portions was ignited in a flat porcelain bowl (diameter 16 cm) in a preheated laboratory muffle furnace (model L5 / 11 temperature controller B170, from Nabertherm GmbH, Germany) at 400 ° C. and then heated for 10 minutes (solution combustion synthesis).
  • the powders obtained after heating were ground in an agate mortar and combined again. The powder thus obtained was heated in a silica glass half-ampule for 1 day at 500 ° C., 3 days at 600 ° C.
  • Reference example 2 gave an oxygen content of the powder obtained of
  • Example 5 Production of a mixed oxide according to the invention of the empirical formula
  • Teflon-coated magnetic stirrers evaporated to dryness.
  • the rock residue was divided into six equal portions. Each of the portions was ignited in a flat porcelain bowl (diameter 16 cm) in a preheated laboratory muffle furnace (model L5 / 1 1 temperature controller B170, from Nabertherm GmbH, Germany) at 400 ° C. and then heated for 10 min (solution combustion synthesis).
  • the powders obtained after heating were ground in an agate mortar and combined again.
  • the powder obtained in this way was heated in a silica glass half-ampoule for 1 day at 450 ° C. in a laboratory muffle furnace and triturated again.
  • Example 6 Preparation of a mixed oxide according to the invention of the empirical formula
  • Example 5 was repeated, the powders obtained after the solution combustion synthesis, ground in an agate mortar and recombined in one
  • Silica glass ampoules were heated 1 d at 450 ° C, 3 d at 550 ° C and 2 d at 700 ° C in the laboratory muffle furnace.
  • the powder was ground in an agate mortar after each heating step.
  • Analysis by EDX according to Reference Example 2 showed an oxygen content of 62.76% by weight of the powder obtained, of 16.13% by weight of phosphorus, of 3.94% by weight of ruthenium and of 17.17 in tungsten % By weight.
  • Comparative Example 1 Preparation of an empirical mixed oxide not according to the invention
  • Comparative Example 2 Production of an empirical mixed oxide not according to the invention
  • the heating stirrer (magnetic stirrer RH Basic 2, IKA, Germany) was evaporated to dryness at 75 ° C. with stirring using a Teflon-coated magnetic stirrer.
  • the rock residue was divided into three equal portions. Each of the portions was ignited in a flat porcelain bowl (diameter 16 cm) in a preheated laboratory muffle furnace (model L5 / 1 1 temperature controller B170, from Nabertherm GmbH, Germany) at 400 ° C. and then heated for 10 min (solution combustion synthesis).
  • the powders obtained after heating were ground in an agate mortar and combined again.
  • the powder obtained in this way was heated in a silica glass half-ampoule for 2 d at 500 ° C. and 4 d at 600 ° C. in a laboratory muffle furnace.
  • the powder was ground in an agate mortar after each heating step.
  • the powder thus obtained had a brown color and that shown in Figure 8
  • Cn-butane is the concentration of n-butane in the outgoing gas stream
  • Cn-butane, 0 is the concentration of n-butane in the incoming (reaction) gas stream
  • CAr.o is the concentration of
  • Ci is the concentration of the product i, CAr.o the concentration of argon in the incoming (reaction) gas stream, CAr the concentration of argon in the outgoing gas stream, N c, i the number of carbon atoms of the product, Cn-butane the concentration of n- Butane in the outgoing gas stream and c n -butane, o represents the concentration of n-butane in the incoming (reaction) gas stream.
  • the conversion was calculated according to the product-based equation (III):
  • Tables 1 to 8 below show the test results for Examples 1 to 6 and Comparative Examples 1 to 2 for the conversion of n-butane to the individual
  • Figure 1 shows the X-ray powder diffractogram according to Example 1. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 2 shows the X-ray powder diffractogram according to Example 2. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 3 shows the X-ray powder diffractogram according to Example 3. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 4 shows the X-ray powder diffractogram according to Example 4. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 5 shows the X-ray powder diffractogram according to Example 5. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 6 shows the X-ray powder diffractogram according to Example 6. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 7 shows the X-ray powder diffractogram according to comparative example 1. The relative intensity is plotted on the ordinate as a function of the angle 4 theta, which is plotted on the abscissa.
  • Figure 8 shows the X-ray powder diffractogram according to Comparative Example 2. On the
  • the ordinate is the relative intensity as a function of the angle 4 theta, which is plotted on the abscissa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un oxyde mixte comprenant de l'oxygène, du phosphore, du tungstène et au moins un métal (M1) issu des groupes 8 à 11 de la classification périodique des éléments, le rapport molaire tungstène/M1, à savoir W:M1 se situe dans une plage supérieure à 0:1 et inférieure à 6:1, et entre 40 et 100 % en poids de cet oxyde mixte étant amorphe aux rayons X.
PCT/EP2019/085132 2018-12-14 2019-12-13 Oxyde mixte comprenant de l'oxygène, du phosphore, du tungstène et au moins un métal issu des groupes 8 à 11 de la classification périodique des éléments WO2020120755A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18212642.5 2018-12-14
EP18212642 2018-12-14

Publications (1)

Publication Number Publication Date
WO2020120755A1 true WO2020120755A1 (fr) 2020-06-18

Family

ID=65010406

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/085132 WO2020120755A1 (fr) 2018-12-14 2019-12-13 Oxyde mixte comprenant de l'oxygène, du phosphore, du tungstène et au moins un métal issu des groupes 8 à 11 de la classification périodique des éléments

Country Status (1)

Country Link
WO (1) WO2020120755A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US329326A (en) 1885-10-27 Hose-coupling
US20120149919A1 (en) 2009-08-26 2012-06-14 Basf Se Maleic anhydride synthesis catalyst precursor and process for its preparation
US20140179967A1 (en) * 2011-07-26 2014-06-26 Sk Global Chemical Co., Ltd. Method of producing aromatic hydrocarbons from byproducts of aromatic carboxylic acid and/or aromatic carboxylic acid alkylester preparation processes
DE102016007628A1 (de) 2015-06-24 2016-12-29 Basf Se Wolframphosphate der ReO3 - Strukturfamilie
US20180345256A1 (en) * 2015-11-19 2018-12-06 Shell Oil Company Catalyst system and process for the production of glycols

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US329326A (en) 1885-10-27 Hose-coupling
US20120149919A1 (en) 2009-08-26 2012-06-14 Basf Se Maleic anhydride synthesis catalyst precursor and process for its preparation
US20140179967A1 (en) * 2011-07-26 2014-06-26 Sk Global Chemical Co., Ltd. Method of producing aromatic hydrocarbons from byproducts of aromatic carboxylic acid and/or aromatic carboxylic acid alkylester preparation processes
DE102016007628A1 (de) 2015-06-24 2016-12-29 Basf Se Wolframphosphate der ReO3 - Strukturfamilie
US20180345256A1 (en) * 2015-11-19 2018-12-06 Shell Oil Company Catalyst system and process for the production of glycols

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A. WLDR. J. ARNOTTW. J. CROFT: "The reaction of rare earth oxides with a high temperature of rhodium(lll)oxide", INORG. CHEM., vol. 2, no. 5, 1963, pages 972 - 974
HOLLEMANN-WIBERG, LEHRBUCH DER ANORGANISCHEN CHEMIE, 1985, pages 1120
J. SOOSEG. MEYER: "SOS - Programme zur Auswertung von Guinier-Aufnahmen", 1980, UNIVERSITÄT GIESSEN
KENSUKE NISHIKI ET AL: "Preparation and Structural Characterization of Mono-Ru-Substituted [alpha] 2 -Dawson-Type Phosphotungstate with a Carbonyl Ligand and Other Ru(CO)-Substituted Heteropolytungstates : Ru(CO)-Substituted Heteropolytungstates", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY - CHEMISCHE BERICHTE, vol. 2015, no. 16, 1 June 2015 (2015-06-01), DE, pages 2714 - N2723, XP055666687, ISSN: 1434-1948, DOI: 10.1002/ejic.201500226 *

Similar Documents

Publication Publication Date Title
DE3300044C2 (de) Katalysator für die Oxidation von Propylen
DE69636206T2 (de) Verfahren zur Herstellung eines Katalysators
DE69208565T2 (de) Katalysator und Verfahren zur Herstellung von Nitrilen
DE10145958B4 (de) Verfahren zur Herstellung eines Oxidkatalysators für die Oxidation oder Ammonoxidation
DE102011109816B4 (de) Katalysatormaterial für die Oxidation von Kohlenwasserstoffen
DE102011109774B4 (de) Katalysatormaterial für die Oxidation von Kohlenwasserstoffen
DE60018531T2 (de) Oxydkomplex als Katalysator und Verfahren für die Herstellung von Acrylsäure
DE2261907A1 (de) Oxydation von butan zu maleinsaeureanhydrid
DE69918831T2 (de) Verfahren zur regenration von molybden enthaltenden wirbelbett-oxid-katalysatoren
DE2644540B2 (de) Denka, Vanadin, Phosphor, Kupfer, Molybdän und Kobalt enthaltender Katalysator und seine Verwendung
DE60030748T2 (de) Verfahren zur Herstellung von Acrylnitril, gekennzeichnet durch den verwendeten Katalysator
DE2635031C2 (de) Katalysator zur Herstellung einer α,β-ungesättigten aliphatischen Carbonsäure und Verwendung dieses Katalysators
DE102010049824A1 (de) Verfahren zur Herstellung eines Katalysators zur Herstellung von Methacrylsäure und Verfahren zur Herstellung von Methacrylsäure
DE1811062A1 (de) Verfahren zur Herstellung von Acrylnitril
DE102007012724A1 (de) Polynäres Metalloxidphosphat
DE2822757A1 (de) Verfahren zur herstellung von maleinsaeureanhydrid aus 4 kohlenstoffatome enthaltenden kohlenwasserstoffen unter verwendung eines auf hydrothermale weise hergestellten katalysators
WO2005123596A1 (fr) Oxyde polymetallique contenant de l'argent, du vanadium et un element du groupe du phosphore, et son utilisation
DE3111401A1 (de) "stabiler molybdaenkatalysator zur umwandlung von c(pfeil abwaerts)3(pfeil abwaerts)- und c(pfeil abwaerts)4(pfeil abwaerts)-olefinen in ungesaettigte aldehyde und saeuren"
DE3226204A1 (de) Verfahren zur herstellung von antimonhaltigen metalloxidkatalysatoren
DE3047102A1 (de) Verfahren zur herstellung von phenol
WO2020120755A1 (fr) Oxyde mixte comprenant de l'oxygène, du phosphore, du tungstène et au moins un métal issu des groupes 8 à 11 de la classification périodique des éléments
EP1117482A1 (fr) Procede de production de catalyseurs destines a la synthese de l'anhydride de l'acide maleique par oxygenation en phase gazeuse
DE2449387B2 (de) Verfahren zur herstellung eines oxydationskatalysators und dessen verwendung
DE69309106T2 (de) Prozess zur herstellung von (meth)acrylnitril durch ammoxidation
DE102016007628A1 (de) Wolframphosphate der ReO3 - Strukturfamilie

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19816803

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19816803

Country of ref document: EP

Kind code of ref document: A1