EP3576874A1 - Synthesis of a movnbte catalyst having a increased specific surface and higher activity for the oxidative dehydrogenation of ethane to ethylene - Google Patents

Synthesis of a movnbte catalyst having a increased specific surface and higher activity for the oxidative dehydrogenation of ethane to ethylene

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Publication number
EP3576874A1
EP3576874A1 EP18725740.7A EP18725740A EP3576874A1 EP 3576874 A1 EP3576874 A1 EP 3576874A1 EP 18725740 A EP18725740 A EP 18725740A EP 3576874 A1 EP3576874 A1 EP 3576874A1
Authority
EP
European Patent Office
Prior art keywords
mixed oxide
oxide material
mixture
tellurium
catalyst
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.)
Pending
Application number
EP18725740.7A
Other languages
German (de)
French (fr)
Inventor
Gerhard Mestl
Klaus Wanninger
Daniel Melzer
Maria Cruz SANCHEZ-SANCHEZ
Julia Tseglakova
Johannes Lercher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
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Filing date
Publication date
Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP3576874A1 publication Critical patent/EP3576874A1/en
Pending legal-status Critical Current

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    • B01J23/28—Molybdenum
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    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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Definitions

  • the invention relates to a novel mixed oxide material containing molybdenum, vanadium, tellurium and niobium and to the use of the mixed oxide material as a catalyst for the oxidative dehydrogenation of ethane to ethene or the oxidation of propane to acrylic acid and a process for the preparation of the mixed oxide material.
  • MoVNbTe mixed oxides for the oxidation of propane to acrylic acid or for the oxidative dehydrogenation of ethane to ethene are state of the art. More than 200 patents and numerous scientific publications treat catalysts based on MoVNbTe mixed oxides. The promotion of these mixed oxides with other metals of the periodic table is known. The highest acrylic acid yields described above are 60% and that of ethene is about 80%.
  • JP H07-053414 discloses a catalytic process for the production of ethylene by the oxidative hydrogenation of ethane at low temperature, with a high yield and with a high selectivity.
  • This method of producing ethylene by contacting ethane with a molecular oxygen-containing gas in the presence of a catalyst composition at elevated temperature comprises that the catalyst composition contains a mixed metal oxide comprising as essential components molybdenum, vanadium, tellurium and oxygen, and which shows a powder X-ray diffractogram having substantially the following relative peak intensities: 2 ⁇ (+ - 0.4 °), rel. Int: 22.1 ° (100), 28.2 ° (400-3), 36.2 ° (80-3), 45.1 ° (40-3), 50 ° (50-3).
  • MoVNbTe catalysts consist mainly of two orthorhombic phases called "Ml" and "M2" (T. Ushikubo, K. Oshima, A. Kayou, M. Hatano, Studies in Surface Science and Catalysis 112, (1997), 473). The Ml phase seems to play the essential role in the selective oxidation reactions.
  • Ml MoiVo, i 5 Teo, i2Nbo, i280 3, 7 or Mo 7, SVI, 2 Te 0, 937 bi0 2 s, 9
  • M2 * MoiV 0 , 32Teo, 42 bo, o804,6 or M04, 31V1, 3eTei, siNbo, 33O19, si
  • the two main phases can also occur with a slightly different stoichiometry. Both vanadium and molybdenum are in the center of an octahedron of oxygen atoms and therefore partially interchangeable in structure so that the same structure, eg the Ml phase, is also possible with a higher vanadium content.
  • M2 phase is not active for the oxidative dehydrogenation of ethane (See JS Valente et al., ACS Catal.4 (2014), 1292-1301, p.1293 in particular).
  • a catalyst which consists of a very pure Ml phase is desired. It is therefore trying this Crystal phases also clean and produce separately.
  • EP 529853 A2 discloses a catalyst suitable for preparing a nitrile from an alkane, the catalyst having the empirical formula MoVbTe c XxO n , wherein X is at least one of Nb, Ta, W, Ti, Al, Zr, Cr, Mn Fe, Ru, Co, Rh, Ni, Pd, Pt, Sb, Bi, B and Ce, b is 0.01 to 1.0, c is 0.01 to 1.0; x is 0.01 to 1.0; and n is a number satisfying the total metal elements and the catalyst has X-ray diffraction peaks at the following 2 ⁇ angles in its X-ray diffraction pattern: diffraction angle at 2 ⁇ (22.1 ° +/- 0 , 3 °, 28.2 ° +/- 0.3 °, 36.2 ° +/- 0.3 °, 45.2 ° +/- 0.3 °, 50.0 ° +/- 0.3 °).
  • JP H07-232071 discloses a catalytic process for producing a nitrile, at a relatively low temperature and in a high yield, by using an alkane as a raw material and a specific catalyst.
  • the main component of the catalyst is a mixed metal oxide of molybdenum, vanadium, tellurium, oxygen and X (X is one or more elements selected from the group of niobium, tantalum, etc.), wherein the ratio of the main components, ie excluding oxygen, is expressed Formulas I to IV: I) 0.25 ⁇ rMo ⁇ 0.98, II) 0.003 ⁇ rV ⁇ 0.50, III) 0.003 ⁇ rTe ⁇ 0.50, IV) 0 ⁇ rX ⁇ 0.5, (rMo , rV, rTe and rX are respectively the molar parts of molybdenum, vanadium, tellurium and X) and in the XRD, XRD bands of this mixed oxide at the different 29 angles 9.
  • a nitrile can be prepared by reacting an alkane without the presence of a halogenated substance, eg, water, etc. in the reaction system at a low temperature with a high yield.
  • a halogenated substance eg, water, etc.
  • Other successful attempts to produce a pure Ml phase are based on dissolving the M2 phase out of the phase mixture.
  • These experiments are described, for example, in EP 1301457 A2, EP 1558569 A1 or WO 2009106474 A2.
  • AC Sanfiz et al. , Top. Catal. 50 (2008) 19-32 describe hydrothermal syntheses of MoVNbTe oxide. These syntheses are based exclusively on soluble compounds. As a soluble compound of tellurium usually telluric acid Te (OH) 6 is used.
  • tellurium In the most common oxide tellurium compound TeÜ2, tellurium has the oxidation state +4. Unfortunately, tellurium dioxide (TeÜ2) is poorly soluble in water. In telluric acid, however, tellurium has the oxidation state +6. Tellurium must therefore be highly oxidized in the production of telluric acid.
  • the common synthesis is carried out by oxidation of tellurium oxide with hydrogen peroxide, which entails safety problems on a large scale, because hydrogen peroxide can disproportionate in self-decomposition to water and oxygen. Therefore, telluric acid is difficult to produce in large quantities.
  • the Nb component used in the synthesis of MoVNbTe mixed oxides is usually ammonium niobium oxalate. By contrast, niobium oxide is sparingly soluble and is therefore only suitable to a limited extent as starting compound.
  • Watanabe (Applied Catal. A General, 194-195 (2000) 479-485) describes inter alia the hydrothermal synthesis from the less soluble precursors Mo0 3 , V 2 0 5 and Te0 2 .
  • the hydrothermal synthesis gives a ammoxidation catalyst precursor which has twice the activity after calcination compared with a catalyst prepared by the known dry method.
  • the mixed oxides produced by the Solid-state reaction produced show a rather low activity. It has been suggested that the higher activity of the catalyst prepared by the hydrothermal synthesis has to do mainly with the higher surface area.
  • a synthesis of MoVNbTe mixed oxide without the use of telluric acid thus has the potential to be significantly cheaper.
  • WO 2005120702 A1 describes a process for the hydrothermal preparation of multimetal compositions consisting of Mo and V, essentially with the exclusive use of starting materials from the group of oxides, oxide hydrates, oxyacids and hydroxides for the elemental constituents of the oxide multimetal masses, wherein a Subset of the constituent elements contained in the starting materials has an oxidation number below the maximum oxidation number.
  • WO 2013021034 A1 relates to a catalyst material for the oxidation and / or oxidative dehydrogenation of
  • Hydrocarbons in particular for the selective oxidation of propane to acrylic acid, comprising a) molybdenum (Mo), b) vanadium (V), c) niobium (Nb), d) tellurium (Te), e) manganese (Mn) and cobalt in the the molar ratio of at least one element selected from manganese and cobalt to molybdenum in the range 0.01 to 0.2, more preferably 0.02 to 0.15 and most preferably from 0.03: 1 to 0.1: 1 lies.
  • WO 2008068332 A1 relates to novel mesoporous Mischmetalloxid- catalysts and a process for their preparation and their use as a catalyst for the oxidation of hydrocarbons or partially oxidized hydrocarbons.
  • the disclosure relates to mesoporous mixed oxide catalysts containing at least two, preferably at least three different metal species, at least one of which belongs to the group of transition metals, to a process for the preparation of such a catalyst comprising a "neutral templating" preparation step.
  • Calcining step in a substantially oxygen-free atmosphere at a temperature between 300 to 700 ° C and the use of such catalysts as oxidation catalysts for the production of oxidized hydrocarbons and in particular for the selective oxidation or ammoxidation of propane to acrylic acid and acrylonitrile.
  • a preferred catalyst comprises the elements Mo, V, Te and Nb.
  • High-temperature treatment typically above 500 ° C. under inert gas, forms ("activation").
  • activation forms
  • a synthesis method was found for the preparation of a high-purity Ml phase, which dispenses with the final high-temperature treatment.
  • the object of the present invention was therefore to find a mixed oxide material comprising molybdenum, vanadium, tellurium and niobium ("MoVTeNb mixed oxide”) which has the Ml phase and the largest possible specific surface area MoVTeNb mixed oxide to find that as a catalyst material for the oxidation of alkanes has the highest possible activity.
  • MoVTeNb mixed oxide molybdenum, vanadium, tellurium and niobium
  • the object is achieved by a mixed oxide material comprising the elements molybdenum, vanadium, niobium and tellurium, which in the XRD, when using the Cu-K radiation, diffraction peaks h, i, k and 1 whose vertices at the diffraction angles (2 ⁇ ) 26.2 ° ⁇ 0.5 ° (h), 27.0 ° ⁇ 0.5 ° (i), 7.8 ° ⁇ 0.5 ° (k) and 28.0 ° ⁇ 0.5 ° (1 ), characterized in that the mixed oxide material has a pore volume of> 0.1 cm 3 / g.
  • the MoVTeNb mixed oxide of the present invention is produced by a process for producing a mixed oxide material comprising the steps of: a) preparing a mixture of starting compounds containing molybdenum, vanadium, niobium and a tellurium-containing starting compound in which tellurium is in the +4 oxidation state and oxalic acid and at least one further oxo ligand, b) hydrothermal treatment of the mixture of starting compounds at a temperature of 100 to 300 ° C to obtain a product suspension, c) separating and drying the mixed oxide material contained in the product suspension resulting from step b) is.
  • the starting compounds are the molybdenum, vanadium, tellurium and niobium-containing educts of hydrothermal synthesis (Precursor compounds). These each contain one or more of the elements molybdenum, vanadium, tellurium or niobium.
  • the molybdenum-containing starting compound may be e.g. an ammonium heptamolybdate or molybdenum trioxide
  • the vanadium-containing starting compound may be e.g. one
  • the niobium-containing starting compound may be, for example, ammonium niobium oxalate or niobium oxalate or niobium oxide.
  • An advantage of the preparation process according to the invention is that a synthesis of the Ml phase from the insoluble and inexpensive oxides, e.g. M0O3, V2O5, b2Üs and Te Ü2 and a combination of oxalic acid with at least one other oxo ligand succeeds.
  • Other oxo ligands i.e., besides oxalic acid
  • Particularly preferred as another oxo ligand is the use of a mixture of citric acid and glycol.
  • the oxalic acid should preferably be in a mixture of the starting compounds in a Mo / oxalic acid ratio of 1: 0.01 to 1: 1, preferably 1: 0.08 to 1: 0.4, more preferably 1: 0.15 to 1: 0 , 25 present.
  • the at least one further oxo ligand, or all other oxo ligands together, should preferably be more preferably in a mixture of the starting compounds in a Mo / oxo ligand ratio of 1: 0.01 to 1: 1, preferably 1: 0.025 to 1: 0.2 1: 0.05 to 1: 0.1.
  • the synthesis according to the invention surprisingly provides the Ml phase even after the hydrothermal synthesis and the drying, without an energy-intensive high-temperature treatment at a temperature above 400 ° C. being necessary.
  • Crucial to the synthesis of the invention is that in this method, the calcination under nitrogen after the hydrothermal synthesis in contrast to the literature is not required.
  • the preparation process according to the invention allows the synthesis of a MoVNbTe mixed oxide which has the Ml phase. After drying, a MoVNbTe mixed oxide with a pore volume of more than 0.1 cm 3 / g and a high surface area of more than 20 m 2 / g and more preferably of more than 30 m 2 / g.
  • the MoVNbTe mixed oxide according to the invention is therefore particularly suitable as a catalyst material, because for catalytic applications, a high pore volume and a high specific surface area is generally desired.
  • the mixture of starting compounds is preferably in the form of an aqueous suspension and is subsequently treated hydrothermally.
  • hydrothermally refers mainly to the reaction conditions for producing a catalyst ⁇ materials in the presence of water and under elevated temperature and / or elevated pressure, for example in an autoclave.
  • bar of the pressure ranging from 5 to 30, preferably from 10 to 27 bar are exemplary pressure ranges are 11 to 20 bar.
  • step b) gives a product suspension which contains the MoVNbTe mixed oxide as a solid.
  • step c) which is the MoVNbTe mixed oxide according to the invention
  • the drying can be carried out in one step or in two steps in flowing or static air.
  • the first drying step is preferably at 60 to 150 ° C (particularly preferably at 80 to 120 ° C)
  • a second drying step can be carried out at 200 to 400 ° C.
  • step c) of the process of the invention may include one or more of washing, calcining (thermal treatment), and / or milling.
  • the calcination can be carried out at 200 to 500 ° C, preferably 250 ° C to 350 ° C in air.
  • the MoVNbTe mixed oxide according to the invention can be used as
  • Catalyst material for the oxidation and / or oxidative dehydrogenation ("ODH") of hydrocarbons, in particular for the oxidative dehydrogenation of ethane to ethylene can be used.
  • the catalyst or catalyst material is a MoVNbTe mixed oxide prepared by the process of the invention and can be used in a variety of ways in a commercial catalyst. For example, for example, it can be processed by tabletting into catalyst tablets which can then be filled into a reactor.
  • the MoVTeNb composite oxide obtained by the process of the present invention without further calcination, i. immediately after drying, used as a catalyst material.
  • the catalyst material may also be processed into an extrudate (tablets, shaped bodies, honeycomb bodies and the like) together with a suitable binder.
  • a suitable binder Any binder known to those skilled in the art and appearing suitable may be used as the binder.
  • Preferred binders include pseudoboehmite and silicate binders such as colloidal silica or silica sol.
  • the catalyst material can also be processed into a washcoat together with other components, preferably with a binder, more preferably with an organic binder, for example an organic adhesive, polymers, resins or waxes, which can be applied to a metallic or ceramic support. If necessary, additional impregnation steps or calcination steps can take place.
  • a binder more preferably with an organic binder, for example an organic adhesive, polymers, resins or waxes, which can be applied to a metallic or ceramic support. If necessary, additional impregnation steps or calcination steps can take place.
  • the MoVNbTe mixed oxide according to the invention is used in the examples as a catalyst material and therefore partially referred to in the experimental information as a catalyst.
  • FIG. 1 X-ray diffractogram of the catalyst according to the invention from Example 1.
  • FIG. 2 X-ray diffractogram of the comparative catalyst from Comparative Example 1.
  • FIG. 3 X-ray diffractogram of the comparative catalyst from Comparative Example 2, after activation.
  • Figure 4 X-ray diffractogram of the comparative catalyst of Comparative Example 2, before activation.
  • FIG. 5 Pore distribution of the catalyst according to Example 1.
  • FIG. 6 Pore distribution of the catalyst according to Comparative Example 1.
  • FIG. 7 Pore distributions of the catalysts according to Comparative Example 2.
  • FIG. 8 Activity of the catalysts in the ODH reaction of ethane.
  • FIG. 9 Pore distribution of the catalyst according to Example 2.
  • FIG. 10 Activity of the catalyst from Example 2 in the ODH reaction
  • XRD X-ray diffractogram
  • Catalysts are used the following methods:
  • the pore size distribution was determined by means of
  • Nitrogen sorption measurements were performed on a Sorptomatic instrument or a TriStar 3000 instrument at 77K.
  • the X-ray was created by powder X ⁇ diffractometry (XRD) and evaluation by the Scherrerformel.
  • the X-ray tube produced Cu-K radiation.
  • the height of the source-side beam path was adjusted by means of an automatic divergent slit (PDS) such that the sample was irradiated over the entire angular range over a length of 12 mm.
  • PDS automatic divergent slit
  • the width of the detector-side X-ray beam was limited by a fixed aperture to 10 mm. Horizontal divergence was minimized by using a 0.4 rad Soller Slit.
  • the height of the detector-side beam path was adjusted analogously to the source-side beam path by means of an automatic anti-scatter slit (PASS) such that it reflected over the entire angular range over a length of 12 mm on the sample
  • PASS automatic anti-scatter slit
  • samples were prepared, depending on the amount present, either on an amorphous silicon platter or tabletted as flat-bed samples.
  • the teflon cup was sealed and placed in a
  • Loss of activity occurs only in the temperature range above 400 ° C.
  • Example 1 The catalyst described in Example 1 was subjected to thermal treatment (activation) in a tube furnace. For this purpose, 1 g of the dried solid was transferred to a porcelain boat, so that its bottom is covered about 2 mm high with powder.
  • Beakers were each 1.65 L dist. H2O with stirring on a magnetic stirrer with temperature control also heated to 80 ° C. 405.10 g of vanadyl sulfate hydrate (of GfE, V content: 21.2%), 185.59 g of ammonium niobium oxalate (HC Starck Nb content: 20.6%) were then added to each beaker. and 94.14 g of telluric acid (V solution, Te solution and Nb solution) were added and dissolved.
  • Hose pump pumped (pumping time: V solution: 4.5 min at 190 rpm, hose diameter: 8x5 mm, Nb solution: 6 min at 130 rpm hose diameter: 8x5 mm).
  • Precipitation was 90 rpm.
  • the hydrothermal synthesis was carried out in a 40 L autoclave at 175 ° C. for 20 h (heating time: 3 h) with an anchor stirrer at a stirrer speed of 90 rpm. After the synthesis was filtered off with the aid of a vacuum pump with Blauband filter and the filter cake with 5 L dist. Washed H2O.
  • the drying was carried out at 80 ° C in a drying oven for 3 days and then was ground in a hammer mill, with a solids yield of 0.8 kg was obtained.
  • the activation was carried out in a retort at 600 ° C for 2 h in N2 ⁇ flow (heating rate 5 ° C / min N2: 0.5 L / min).
  • the product had a BET surface area of 13 m 2 / g and a pore volume of 0.055 cm 3 / g, with a pore distribution shown in FIG.
  • Comparative Example 3 The catalyst of Comparative Example 2 was used immediately after calcination at 280 ° C for 4 hours. The
  • Example 3 The catalytic activity in the oxidative dehydrogenation ("ODH") of ethane of the catalysts of Example 1 and Comparative Examples 1 and 2 was carried out in a tubular reactor at atmospheric pressure in the temperature range 330 to 420 ° C.
  • ODH oxidative dehydrogenation
  • Catalyst particle size 150-212 pm
  • silicon carbide particle size 150-212 pm
  • the reactor was purged with inert gas prior to the start of the experiment and then heated to 330 ° C. under a helium flow of 50 sccm. After the desired temperature was reached and stable for one hour, was switched to the reaction gas mixture.
  • Comparative Example 2 shows the lowest activity. Comparative Example 1 is made according to the new process of this patent but was still calcined at 600 ° C. The highest catalytic activity is shown by the catalysts according to the invention without
  • Table 1 compares the BET surfaces

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Abstract

The invention relates to a mixed oxide material comprising the elements molybdenum, vanadium, niobium and tellurium, which, when using the Cu-Kα radiation, has diffraction reflections h, i, k and l in the XRD spectrum, said diffraction reflexes having their apex points at the diffraction angles (2⋅) 26.2° ± 0.5° (h), 27.0° ± 0.5° (i), 7.8° ± 0.5° (k) and 28.0° ± 0.5° (l), characterized in that the mixed oxide material has a pore volume of > 0.1 cm3/g. The mixed oxide material according to the invention is produced by a method comprising the steps of: a) producing a mixture of starting compounds containing molybdenum, vanadium, niobium and tellurium dioxide as a tellurium-containing starting compound as well as oxalic acid and a further oxoligand selected from the group consisting of dicarboxylic acids and diols, b) hydrothermally treating the mixture of starting compounds at a temperature of 100 to 300 °C, c) separating and drying the mixed oxide material which is contained in the suspension resulting from step b).

Description

Synthese eines MoVNbTe-Katalysators mit erhöhter spezifischer Oberfläche und höherer Aktivität für die oxidative Dehydrierung von Ethan zu Ethylen Synthesis of a MoVNbTe catalyst with increased specific surface area and higher activity for the oxidative dehydrogenation of ethane to ethylene
Die Erfindung betrifft ein neues Mischoxidmaterial, das Molybdän, Vanadium, Tellur und Niob enthält und die Verwendung des Mischoxidmaterials als Katalysator für die oxidative Dehydrierung von Ethan zu Ethen oder die Oxidation von Propan zu Acrylsäure und ein Verfahren zur Herstellung des Mischoxidmaterials . MoVNbTe-Mischoxide zur Oxidation von Propan zu Acrylsäure oder zur oxidativen Dehydrierung von Ethan zu Ethen sind Stand der Technik. Mehr als 200 Patente und zahlreiche wissenschaftliche Veröffentlichungen behandeln Katalysatoren auf Basis von MoVNbTe-Mischoxiden . Die Promotierung dieser Mischoxide mit anderen Metallen des Periodensystems ist bekannt. Dabei liegen die höchsten vorbeschriebenen Acrylsäure-Ausbeuten bei 60% und die von Ethen bei ca. 80%. The invention relates to a novel mixed oxide material containing molybdenum, vanadium, tellurium and niobium and to the use of the mixed oxide material as a catalyst for the oxidative dehydrogenation of ethane to ethene or the oxidation of propane to acrylic acid and a process for the preparation of the mixed oxide material. MoVNbTe mixed oxides for the oxidation of propane to acrylic acid or for the oxidative dehydrogenation of ethane to ethene are state of the art. More than 200 patents and numerous scientific publications treat catalysts based on MoVNbTe mixed oxides. The promotion of these mixed oxides with other metals of the periodic table is known. The highest acrylic acid yields described above are 60% and that of ethene is about 80%.
Das auf vier Elementen beruhende MoVNbTe-Basissystem für einen Katalysator wurde zuerst von Mitsubishi für die Ammoxidation von Propan zu Acrylnitril (1989, EP 318295 AI) und die Oxidation zu Acrylsäure vorgeschlagen (1994, EP 608838 A2) . In JP H07-053414 (Mitsubishi) wird ein katalytisches Verfahren zur Herstellung von Ethylen durch die oxidative Hydrogenierung von Ethan bei tiefer Temperatur, mit einer hohen Ausbeute und mit einer hohen Selektivität, offenbart. Dieses Verfahren zur Herstellung von Ethylen durch das in Kontakt bringen von Ethan mit einem molekularen Sauerstoff enthaltenden Gas in der Anwesenheit einer Katalysatorzusammensetzung bei erhöhter Temperatur, umfasst, dass die Katalysatorzusammensetzung ein Mischmetalloxid enthält, welches als wesentliche Komponenten Molybdän, Vanadium, Tellur und Sauerstoff aufweist und welches ein Pulver-Röntgendiffraktogramm zeigt, das im Wesentlichen die folgenden relativen Peak-Intensitäten aufweist: 2Θ (+- 0.4°), rel. Int.: 22.1° (100), 28,2° (400-3), 36,2° (80-3), 45.1° (40-3) , 50° (50-3) . MoVNbTe-Katalysatoren bestehen hauptsächlich aus zwei orthorhombischen Phasen, die „Ml" und ,,M2" genannt werden (T. Ushikubo, K. Oshima, A. Kayou, M. Hatano, Studies in Surface Science and Catalysis 112, (1997), 473). Die Ml-Phase scheint bei den selektiven Oxidationsreaktionen die wesentliche Rolle zu spielen. The MoVNbTe base system based on four elements for a catalyst was first proposed by Mitsubishi for the ammoxidation of propane to acrylonitrile (1989, EP 318295 Al) and the oxidation to acrylic acid (1994, EP 608838 A2). JP H07-053414 (Mitsubishi) discloses a catalytic process for the production of ethylene by the oxidative hydrogenation of ethane at low temperature, with a high yield and with a high selectivity. This method of producing ethylene by contacting ethane with a molecular oxygen-containing gas in the presence of a catalyst composition at elevated temperature comprises that the catalyst composition contains a mixed metal oxide comprising as essential components molybdenum, vanadium, tellurium and oxygen, and which shows a powder X-ray diffractogram having substantially the following relative peak intensities: 2Θ (+ - 0.4 °), rel. Int: 22.1 ° (100), 28.2 ° (400-3), 36.2 ° (80-3), 45.1 ° (40-3), 50 ° (50-3). MoVNbTe catalysts consist mainly of two orthorhombic phases called "Ml" and "M2" (T. Ushikubo, K. Oshima, A. Kayou, M. Hatano, Studies in Surface Science and Catalysis 112, (1997), 473). The Ml phase seems to play the essential role in the selective oxidation reactions.
Gemäß P. De Santo et al . , Z. Kristallogr. 219 (2004) 152 können die Hauptphasen Ml und M2 in MoVNbTe-Mischoxiden für die selektive Oxidation beispielsweise mit folgenden Strukturformeln beschrieben werden: Ml: MoiVo,i5Teo,i2Nbo,i2803,7 oder Mo7, sVi, 2Te0, 937 bi02s, 9 According to P. De Santo et al. , Z. Kristallogr. 219 (2004) 152, the main phases Ml and M2 are described in MoVNbTe mixed oxides for the selective oxidation, for example with the following structural formulas: Ml: MoiVo, i 5 Teo, i2Nbo, i280 3, 7 or Mo 7, SVI, 2 Te 0, 937 bi0 2 s, 9
M2 : *MoiV0,32Teo,42 bo,o804,6 oder M04, 31V1, 3eTei, siNbo, 33O19, si M2: * MoiV 0 , 32Teo, 42 bo, o804,6 or M04, 31V1, 3eTei, siNbo, 33O19, si
Die beiden Hauptphasen können auch mit etwas anderer Stöchiometrie auftreten. Sowohl Vanadium, als auch Molybdän sind im Zentrum eines Oktaeders aus Sauerstoffatomen und daher in der Struktur teilweise austauschbar, so dass die gleiche Struktur, z.B. die Ml-Phase, auch mit einem höheren Vanadiumgehalt möglich ist. Eine detaillierte Untersuchung dieser Zusammenhänge findet sich bei P. Botella et al . , Solid State Science 7 (2005) 507-519. Speziell die M2-Phase ist für die oxidative Dehydrierung von Ethan nicht aktiv (Siehe J.S. Valente et al . , ACS Catal. 4(2014), 1292-1301 speziell S.1293) . Für die oxidative Dehydrierung von Ethan ist daher ein Katalysator, der aus einer möglichst reinen Ml-Phase besteht, erwünscht. Es wird daher versucht, diese Kristallphasen auch sauber und getrennt herzustellen. The two main phases can also occur with a slightly different stoichiometry. Both vanadium and molybdenum are in the center of an octahedron of oxygen atoms and therefore partially interchangeable in structure so that the same structure, eg the Ml phase, is also possible with a higher vanadium content. A detailed investigation of these relationships can be found in P. Botella et al. , Solid State Science 7 (2005) 507-519. Specifically, the M2 phase is not active for the oxidative dehydrogenation of ethane (See JS Valente et al., ACS Catal.4 (2014), 1292-1301, p.1293 in particular). For the oxidative dehydrogenation of ethane, therefore, a catalyst which consists of a very pure Ml phase is desired. It is therefore trying this Crystal phases also clean and produce separately.
EP 529853 A2 offenbart einen Katalysator, der zur Herstellung eines Nitrils aus einem Alkan geeignet ist, wobei der Katalysator die empirische Formel MoVbTecXxOn hat, worin X mindestens eines von Nb, Ta, W, Ti, AI, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Sb, Bi, B und Ce ist, b 0,01 bis 1,0 ist, c 0,01 bis 1,0 ist; x 0,01 bis 1,0 ist und n eine Zahl ist, gemäß der die Gesamtwertigkeit der Metallelemente erfüllt ist und der Katalysator Röntgenstrahlbeugungspeaks bei den folgenden 2Θ -Winkeln in seinem Röntgenbeugungsmuster aufweist: Beugungswinkel bei 2Θ (22,1° +/- 0,3°, 28,2° +/- 0,3°, 36,2° +/- 0,3°, 45,2° +/- 0,3°, 50,0° +/- 0,3°). EP 529853 A2 discloses a catalyst suitable for preparing a nitrile from an alkane, the catalyst having the empirical formula MoVbTe c XxO n , wherein X is at least one of Nb, Ta, W, Ti, Al, Zr, Cr, Mn Fe, Ru, Co, Rh, Ni, Pd, Pt, Sb, Bi, B and Ce, b is 0.01 to 1.0, c is 0.01 to 1.0; x is 0.01 to 1.0; and n is a number satisfying the total metal elements and the catalyst has X-ray diffraction peaks at the following 2Θ angles in its X-ray diffraction pattern: diffraction angle at 2Θ (22.1 ° +/- 0 , 3 °, 28.2 ° +/- 0.3 °, 36.2 ° +/- 0.3 °, 45.2 ° +/- 0.3 °, 50.0 ° +/- 0.3 °).
JP H07-232071 offenbart ein katalytisches Verfahren zur Herstellung eines Nitrils, bei einer relativ niedrigen Temperatur und mit einer hohen Ausbeute, unter Verwendung eines Alkans als Rohmaterial und eines bestimmten Katalysators. Die Hauptkomponente des Katalysators ist ein Mischmetalloxid aus Molybdän, Vanadium, Tellur, Sauerstoff und X (X ist eines oder mehrere Elemente ausgewählt aus der Gruppe aus Niob, Tantal etc.), wobei das Verhältnis der Hauptkomponenten, d.h. ausgenommen Sauerstoff, ausgedrückt wird, durch die Formeln I bis IV: I) 0,25 < rMo < 0,98, II) 0,003 < rV < 0,50, III) 0,003 < rTe < 0,50, IV) 0 < rX < 0,5, (rMo, rV, rTe und rX sind jeweils die molaren Teile an Molybdän, Vanadium, Tellur und X) und sich im XRD, XRD-Banden dieses Mischoxides bei den verschiedenen 29-Winkeln 9.0°±0.3°, 22.1°±0.3°, 27.3°±0.3°, 29.2°±0.3° und 35.4°±0.3° zeigen. Demnach kann ein Nitril hergestellt werden, indem ein Alkan ohne die Anwesenheit einer halogenierten Substanz, z.B. mit Wasser etc., im Reaktionssystem, bei einer tiefen Temperatur mit einer hohen Ausbeute umgesetzt wird. Andere erfolgreiche Versuche eine reine Ml-Phase herzustellen, basieren darauf die M2-Phase aus dem Phasengemisch herauszulösen. Diese Versuche sind z.B. in EP 1301457 A2, EP 1558569 AI oder WO 2009106474 A2 beschrieben. A.C. Sanfiz et al . , Top. Catal. 50 (2008) 19-32, beschreiben Hydrothermalsynthesen von MoVNbTe-Oxid . In diesen Synthesen wird ausschließlich von löslichen Verbindungen ausgegangen. Als lösliche Verbindung des Tellurs wird in der Regel Tellursäure Te (OH) 6 eingesetzt. In der gängigsten oxidischen Tellurverbindung TeÜ2 hat Tellur die Oxidationsstufe +4. Leider ist Tellurdioxid (TeÜ2) schlecht wasserlöslich. In der Tellursäure aber hat das Tellur die Oxidationsstufe +6. Tellur muss also bei der Herstellung der Tellursäure hoch oxidiert werden. Die gängige Synthese erfolgt durch Oxidation von Telluroxid mit Wasserstoffperoxid, was im großen Maßstab Sicherheitsprobleme mit sich bringt, denn Wasserstoffperoxid kann in Selbst Zersetzung zu Wasser und Sauerstoff disproportionieren . Deshalb ist Tellursäure nur schwer in großen Mengen herzustellen. Die in der Synthese von MoVNbTe-Mischoxiden eingesetzte Nb- Komponente ist in der Regel Ammoniumnioboxalat . Nioboxid dagegen ist schwerlöslich und eignet sich daher nur bedingt als Ausgangsverbindung. JP H07-232071 discloses a catalytic process for producing a nitrile, at a relatively low temperature and in a high yield, by using an alkane as a raw material and a specific catalyst. The main component of the catalyst is a mixed metal oxide of molybdenum, vanadium, tellurium, oxygen and X (X is one or more elements selected from the group of niobium, tantalum, etc.), wherein the ratio of the main components, ie excluding oxygen, is expressed Formulas I to IV: I) 0.25 <rMo <0.98, II) 0.003 <rV <0.50, III) 0.003 <rTe <0.50, IV) 0 <rX <0.5, (rMo , rV, rTe and rX are respectively the molar parts of molybdenum, vanadium, tellurium and X) and in the XRD, XRD bands of this mixed oxide at the different 29 angles 9.0 ° ± 0.3 °, 22.1 ° ± 0.3 °, 27.3 ° ± 0.3 °, 29.2 ° ± 0.3 ° and 35.4 ° ± 0.3 °. Thus, a nitrile can be prepared by reacting an alkane without the presence of a halogenated substance, eg, water, etc. in the reaction system at a low temperature with a high yield. Other successful attempts to produce a pure Ml phase are based on dissolving the M2 phase out of the phase mixture. These experiments are described, for example, in EP 1301457 A2, EP 1558569 A1 or WO 2009106474 A2. AC Sanfiz et al. , Top. Catal. 50 (2008) 19-32 describe hydrothermal syntheses of MoVNbTe oxide. These syntheses are based exclusively on soluble compounds. As a soluble compound of tellurium usually telluric acid Te (OH) 6 is used. In the most common oxide tellurium compound TeÜ2, tellurium has the oxidation state +4. Unfortunately, tellurium dioxide (TeÜ2) is poorly soluble in water. In telluric acid, however, tellurium has the oxidation state +6. Tellurium must therefore be highly oxidized in the production of telluric acid. The common synthesis is carried out by oxidation of tellurium oxide with hydrogen peroxide, which entails safety problems on a large scale, because hydrogen peroxide can disproportionate in self-decomposition to water and oxygen. Therefore, telluric acid is difficult to produce in large quantities. The Nb component used in the synthesis of MoVNbTe mixed oxides is usually ammonium niobium oxalate. By contrast, niobium oxide is sparingly soluble and is therefore only suitable to a limited extent as starting compound.
Watanabe (Applied Catal. A General, 194-195 (2000) 479-485) beschreibt unter anderem die hydrothermale Synthese aus den wenig löslichen Vorstufen Mo03, V205 und Te02. Die Hydrothermalsynthese ergibt eine Vorstufe für einen Ammoxidations-Katalysator, der im Vergleich zu einem Katalysator, der durch die bekannte trockene Methode hergestellt wird, die doppelt so hohe Aktivität nach der Kalzinierung aufweist. Die Mischoxide, die durch die FestStoffreaktion hergestellt werden, zeigen eine eher geringe Aktivität. Es wurde vorgeschlagen, dass die höhere Aktivität des durch die Hydrothermalsynthese hergestellten Katalysators vor allem mit der höheren Oberfläche zu tun hat. Eine Synthese des MoVNbTe-Mischoxids ohne Einsatz von Tellursäure hat also das Potential deutlich kostengünstiger zu sein . Watanabe (Applied Catal. A General, 194-195 (2000) 479-485) describes inter alia the hydrothermal synthesis from the less soluble precursors Mo0 3 , V 2 0 5 and Te0 2 . The hydrothermal synthesis gives a ammoxidation catalyst precursor which has twice the activity after calcination compared with a catalyst prepared by the known dry method. The mixed oxides produced by the Solid-state reaction produced show a rather low activity. It has been suggested that the higher activity of the catalyst prepared by the hydrothermal synthesis has to do mainly with the higher surface area. A synthesis of MoVNbTe mixed oxide without the use of telluric acid thus has the potential to be significantly cheaper.
WO 2005120702 AI beschreibt ein Verfahren zur hydrothermalen Herstellung von Multimetallmassen, bestehend aus Mo und V, im Wesentlichen unter der ausschließlichen Verwendung von Ausgangsstoffen aus der Gruppe der Oxide, Oxidhydrate, Oxysäuren und Hydroxide für die Element-Bestandteile der oxidischen Multimetall-Massen, wobei eine Teilmenge der in den Ausgangsstoffen enthaltenen Element-Bestandteile eine Oxidationszahl unterhalb der maximalen Oxidationszahl aufweist . WO 2005120702 A1 describes a process for the hydrothermal preparation of multimetal compositions consisting of Mo and V, essentially with the exclusive use of starting materials from the group of oxides, oxide hydrates, oxyacids and hydroxides for the elemental constituents of the oxide multimetal masses, wherein a Subset of the constituent elements contained in the starting materials has an oxidation number below the maximum oxidation number.
WO 2013021034 AI bezieht sich auf ein Katalysatormaterial zur Oxidation und/oder oxidativen Dehydrierung vonWO 2013021034 A1 relates to a catalyst material for the oxidation and / or oxidative dehydrogenation of
Kohlenwasserstoffen, insbesondere zur selektiven Oxidation von Propan zu Acrylsäure, umfassend a) Molybdän (Mo) , b) Vanadium (V) , c) Niob (Nb) , d) Tellur (Te) , e) Mangan (Mn) und Kobalt bei dem das molare Verhältnis mindestens eines Elementes, das ausgewählt ist aus Mangan und Kobalt, zu Molybdän im Bereich 0,01 bis 0,2, bevorzugter 0,02 bis 0,15 und besonders bevorzugt von 0,03:1 bis 0,1:1 liegt. Ferner wird ein Katalysator zur Oxidation und/oder oxidativen Dehydrierung vonHydrocarbons, in particular for the selective oxidation of propane to acrylic acid, comprising a) molybdenum (Mo), b) vanadium (V), c) niobium (Nb), d) tellurium (Te), e) manganese (Mn) and cobalt in the the molar ratio of at least one element selected from manganese and cobalt to molybdenum in the range 0.01 to 0.2, more preferably 0.02 to 0.15 and most preferably from 0.03: 1 to 0.1: 1 lies. Further, a catalyst for the oxidation and / or oxidative dehydrogenation of
Kohlenwasserstoffen, eine Verwendung des Katalysatormaterials oder des Katalysators, ein Verfahren zur Herstellung eines Katalysatormaterials zur Oxidation und/oder oxidativen Dehydrierung von Kohlenwasserstoffen und ein Verfahren zur selektiven Oxidation von Propan zu Acrylsäure angegeben. WO 2008068332 AI betrifft neue mesoporöse Mischmetalloxid- Katalysatoren und ein Verfahren zu deren Herstellung sowie deren Verwendung als Katalysator zur Oxidation von Kohlenwasserstoffen oder partiell oxidierten Kohlenwasserstoffen. Insbesondere bezieht sich die Offenbarung auf mesoporöse Mischoxidkatalysatoren, die mindestens zwei, vorzugsweise mindestens drei verschiedene Metallspezies enthalten, wobei mindestens eine davon zu der Gruppe der Übergangsmetalle gehört, auf ein Verfahren zur Herstellung, eines solchen Katalysators umfassend einen Herstellungsschritt über die „Neutral-Templat"-Route und einenHydrocarbons, a use of the catalyst material or the catalyst, a method for producing a catalyst material for the oxidation and / or oxidative dehydrogenation of hydrocarbons and a method for the selective oxidation of propane to acrylic acid specified. WO 2008068332 A1 relates to novel mesoporous Mischmetalloxid- catalysts and a process for their preparation and their use as a catalyst for the oxidation of hydrocarbons or partially oxidized hydrocarbons. In particular, the disclosure relates to mesoporous mixed oxide catalysts containing at least two, preferably at least three different metal species, at least one of which belongs to the group of transition metals, to a process for the preparation of such a catalyst comprising a "neutral templating" preparation step. Route and one
Kalzinierungsschritt in einer im wesentlichen Sauerstofffreien Atmosphäre bei einer Temperatur zwischen 300 bis 700 °C und auf die Verwendung solcher Katalysatoren als Oxidationskatalysatoren zur Herstellung von oxidierten Kohlenwasserstoffen und insbesondere zur selektiven Oxidation oder Ammoxidation von Propan zu Acrylsäure und Acrylnitril. Ein bevorzugter Katalysator umfasst die Elemente Mo, V, Te und Nb. Den im Stand der Technik beschriebenen Synthesen der Ml-Phase ist gemein, dass nach der Umsetzung der Ausgangsmaterialien sich die Ml-Phase erst im Rahmen einerCalcining step in a substantially oxygen-free atmosphere at a temperature between 300 to 700 ° C and the use of such catalysts as oxidation catalysts for the production of oxidized hydrocarbons and in particular for the selective oxidation or ammoxidation of propane to acrylic acid and acrylonitrile. A preferred catalyst comprises the elements Mo, V, Te and Nb. The synthesis of the Ml phase described in the prior art has in common that after the reaction of the starting materials, the Ml phase only in the context of a
Hochtemperaturbehandlung, typischerweise oberhalb 500 °C unter Inertgas, ausbildet („Aktivierung") . Im Rahmen der vorliegenden Erfindung wurde eine Synthesemethode zur Darstellung einer hochreinen Ml-Phase gefunden, die auf die abschließende Hochtemperaturbehandlung verzichtet. High-temperature treatment, typically above 500 ° C. under inert gas, forms ("activation"). In the context of the present invention, a synthesis method was found for the preparation of a high-purity Ml phase, which dispenses with the final high-temperature treatment.
Aufgabe der vorliegenden Erfindung war es deshalb, ein Mischoxidmaterial enthaltend Molybdän, Vanadium, Tellur und Niob („MoVTeNb-Mischoxid") , das die Ml-Phase und eine möglichst große spezifische Oberfläche aufweist, zu finden. Aufgabe der Erfindung war es weiterhin, ein MoVTeNb-Mischoxid zu finden, das als Katalysatormaterial für die Oxidation von Alkanen eine möglichst hohe Aktivität aufweist. The object of the present invention was therefore to find a mixed oxide material comprising molybdenum, vanadium, tellurium and niobium ("MoVTeNb mixed oxide") which has the Ml phase and the largest possible specific surface area MoVTeNb mixed oxide to find that as a catalyst material for the oxidation of alkanes has the highest possible activity.
Die Aufgabe wird gelöst durch ein Mischoxidmaterial, umfassend die Elemente Molybdän, Vanadium, Niob und Tellur, das im XRD, bei Verwendung der Cu-K -Strahlung, Beugungsreflexe h, i, k und 1 aufweist, deren Scheitelpunkte bei den Beugungswinkeln (2Θ) 26,2° ± 0,5° (h) , 27,0° ± 0,5° (i), 7,8° ± 0,5° (k) und 28,0° ± 0,5° (1) liegen, dadurch gekennzeichnet, dass das Mischoxidmaterial ein Porenvolumen von > 0,1 cm3/g aufweist. The object is achieved by a mixed oxide material comprising the elements molybdenum, vanadium, niobium and tellurium, which in the XRD, when using the Cu-K radiation, diffraction peaks h, i, k and 1 whose vertices at the diffraction angles (2Θ) 26.2 ° ± 0.5 ° (h), 27.0 ° ± 0.5 ° (i), 7.8 ° ± 0.5 ° (k) and 28.0 ° ± 0.5 ° (1 ), characterized in that the mixed oxide material has a pore volume of> 0.1 cm 3 / g.
Das erfindungsgemäße MoVTeNb-Mischoxid wird hergestellt, durch ein Verfahren zur Herstellung eines Mischoxidmaterials umfassend die Schritte: a) Herstellen eines Gemisches aus Ausgangsverbindungen, das Molybdän, Vanadium, Niob und eine Tellur enthaltende Ausgangsverbindung, in der Tellur in der Oxidationsstufe +4 vorliegt, enthält sowie Oxalsäure und mindestens einen weiteren Oxoliganden, b) hydrothermale Behandlung des Gemisches aus Ausgangsverbindungen bei einer Temperatur von 100 bis 300 °C, um eine ProduktSuspension zu erhalten, c) Abtrennen und Trocknen des Mischoxidmaterials, das in der aus Schritt b) resultierenden ProduktSuspension enthalten ist. The MoVTeNb mixed oxide of the present invention is produced by a process for producing a mixed oxide material comprising the steps of: a) preparing a mixture of starting compounds containing molybdenum, vanadium, niobium and a tellurium-containing starting compound in which tellurium is in the +4 oxidation state and oxalic acid and at least one further oxo ligand, b) hydrothermal treatment of the mixture of starting compounds at a temperature of 100 to 300 ° C to obtain a product suspension, c) separating and drying the mixed oxide material contained in the product suspension resulting from step b) is.
Die Ausgangsverbindungen sind die Molybdän, Vanadium, Tellur und Niob enthaltenden Edukte der Hydrothermalsynthese (Vorläuferverbindungen) . Diese enthalten jeweils eines oder mehrere der Elemente Molybdän, Vanadium, Tellur oder Niob. The starting compounds are the molybdenum, vanadium, tellurium and niobium-containing educts of hydrothermal synthesis (Precursor compounds). These each contain one or more of the elements molybdenum, vanadium, tellurium or niobium.
Die Molybdän enthaltende Ausgangsverbindung kann z.B. ein Ammoniumheptamolybdat oder Molybdäntrioxid sein, die Vanadium enthaltende Ausgangsverbindung kann z.B. einThe molybdenum-containing starting compound may be e.g. an ammonium heptamolybdate or molybdenum trioxide, the vanadium-containing starting compound may be e.g. one
Ammoniummetavanadat , Vanadylsulfat oder Vanadiumpentoxid sein, die Niob enthaltende Ausgangsverbindung kann z.B. Ammoniumnioboxalat oder Nioboxalat oder Nioboxid sein. Die Tellur enthaltende Ausgangsverbindung gemäß der Erfindung ist eine, in der Tellur in der Oxidationsstufe +4, d.h. als Tellur ( IV) -Kation vorliegt, wie in Tellurdioxid oder einer Verbindung der Formel Mx n+TeC>3 (mit n = 1 oder 2 und x = 2/n), wobei M ein Alkali- oder Erdalkalimetall ist, wie z.B. Na2 TeC>3. Besonders bevorzugt ist die Tellur enthaltende Ausgangsverbindung Tellurdioxid, das in einem beliebigen Hydratisierungs-Grad vorliegen kann. Ammonium metavanadate, vanadyl sulfate or vanadium pentoxide, the niobium-containing starting compound may be, for example, ammonium niobium oxalate or niobium oxalate or niobium oxide. The tellurium-containing starting compound according to the invention is one in which tellurium is present in the oxidation state +4, ie as tellurium (IV) cation, as in tellurium dioxide or a compound of the formula M x n + TeC> 3 (with n = 1 or 2 and x = 2 / n), where M is an alkali or alkaline earth metal, such as Na 2 TeC> 3. More preferably, the tellurium-containing starting compound is tellurium dioxide, which may be in any degree of hydration.
Ein Vorteil des erfindungsgemäßen Herstellungsverfahrens ist es, dass eine Synthese der Ml-Phase aus den unlöslichen und preisgünstigen Oxiden, z.B. M0O3, V2O5, b2Üs und Te Ü2 und einer Kombination von Oxalsäure mit mindestens einem weiteren Oxoliganden gelingt. Als weitere Oxoliganden (d.h. neben der Oxalsäure) haben sich besonders Dicarbonsäuren und Diole als geeignet herausgestellt sowie organische Verbindungen mit zwei benachbarten Kohlenstoffatomen, die jeweils eine Hydroxy- Gruppe aufweisen. Besonders bevorzugt als weiterer Oxoligand ist die Verwendung eines Gemisches aus Zitronensäure und Glykol . An advantage of the preparation process according to the invention is that a synthesis of the Ml phase from the insoluble and inexpensive oxides, e.g. M0O3, V2O5, b2Üs and Te Ü2 and a combination of oxalic acid with at least one other oxo ligand succeeds. Other oxo ligands (i.e., besides oxalic acid) have been found to be especially dicarboxylic acids and diols, as well as organic compounds having two adjacent carbon atoms each having a hydroxy group. Particularly preferred as another oxo ligand is the use of a mixture of citric acid and glycol.
Die Oxalsäure sollte vorzugsweise im Gemisch der Ausgangsverbindungen in einem Mo/Oxalsäure-Verhältnis von 1:0,01 bis 1:1, bevorzugt 1:0,08 bis 1:0,4, stärker bevorzugt 1:0,15 bis 1:0,25 vorliegen. Der mindestens eine weitere Oxoligand, bzw. alle weiteren Oxoliganden zusammen, sollten vorzugsweise im Gemisch der Ausgangsverbindungen in einem Mo/Oxoliganden-Verhältnis von 1:0,01 bis 1:1, bevorzugt 1:0,025 bis 1:0,2, stärker bevorzugt 1:0,05 bis 1:0,1 vorliegen. The oxalic acid should preferably be in a mixture of the starting compounds in a Mo / oxalic acid ratio of 1: 0.01 to 1: 1, preferably 1: 0.08 to 1: 0.4, more preferably 1: 0.15 to 1: 0 , 25 present. The at least one further oxo ligand, or all other oxo ligands together, should preferably be more preferably in a mixture of the starting compounds in a Mo / oxo ligand ratio of 1: 0.01 to 1: 1, preferably 1: 0.025 to 1: 0.2 1: 0.05 to 1: 0.1.
Die erfindungsgemäße Synthese liefert außerdem überraschenderweise schon nach der hydrothermalen Synthese und der Trocknung die Ml-Phase, ohne dass eine energieintensive Hochtemperaturbehandlung bei einer Temperatur oberhalb 400° C notwendig wäre. Entscheidend bei der erfindungsgemäßen Synthese ist, dass bei diesem Verfahren die Kalzinierung unter Stickstoff nach der hydrothermalen Synthese im Gegensatz zur Literatur nicht erforderlich ist. Surprisingly, the synthesis according to the invention surprisingly provides the Ml phase even after the hydrothermal synthesis and the drying, without an energy-intensive high-temperature treatment at a temperature above 400 ° C. being necessary. Crucial to the synthesis of the invention is that in this method, the calcination under nitrogen after the hydrothermal synthesis in contrast to the literature is not required.
Ein weiterer Vorteil der erfindungsgemäßen Synthese der Ml- Phase ist die hohe Effizienz der Umsetzung der Ausgangsstoffe durch die Hydrothermalsynthese. Sofern sich die Stöchiometrie der Edukte im Bereich Mo/V/Nb/Te = 1:0,22:0,1:0,1 bis 1:0,3:0,17:0,17 bewegt, werden Mo, V, Nb und Te fast vollständig zur Ml-Phase umgesetzt, sodass weniger als 100 ppm aller Metalle in der Mutterlauge verbleiben. Another advantage of the synthesis of the Ml phase according to the invention is the high efficiency of the reaction of the starting materials by the hydrothermal synthesis. If the stoichiometry of the starting materials is in the range Mo / V / Nb / Te = 1: 0.22: 0.1: 0.1 to 1: 0.3: 0.17: 0.17, Mo, V, Nb and Te are almost completely converted to the Ml phase, leaving less than 100 ppm of all metals in the mother liquor.
Die mögliche Stöchiometrie der Ml-Phase ist aus der Literatur hinreichend bekannt und lässt sich durch die Formel Mo!Va bbTecOx mit a = 0,2 bis 0,3, b = 0,1 bis 0,2, c = 0,1 bis 0,25 und x abhängig von der Oxidationsstufe der Metalle (Mo, V, Nb und Te) eine Größe die zum Ladungsausgleich führt. The possible stoichiometry of the Ml phase is well known from the literature and can be described by the formula Mo ! V a b b Te c O x with a = 0.2 to 0.3, b = 0.1 to 0.2, c = 0.1 to 0.25 and x depending on the oxidation state of the metals (Mo, V , Nb and Te) a size that leads to charge balance.
Vorzugsweise sind während der Synthese keine Ammoniumionen anwesend. Das erfindungsgemäße Herstellungsverfahren erlaubt die Synthese eines MoVNbTe-Mischoxids das die Ml-Phase aufweist. Dabei entsteht nach der Trocknung ein MoVNbTe- Mischoxid mit einem Porenvolumen von mehr als 0,1 cm3/g und einer hohen spezifischen Oberfläche von mehr als 20 m2/g und besonders bevorzugt von mehr als 30 m2/g. Das erfindungsgemäße MoVNbTe-Mischoxid ist daher besonders als Katalysatormaterial geeignet, denn für katalytische Anwendungen ist generell ein hohes Porenvolumen und eine hohe spezifische Oberfläche gewünscht . Preferably, no ammonium ions are present during the synthesis. The preparation process according to the invention allows the synthesis of a MoVNbTe mixed oxide which has the Ml phase. After drying, a MoVNbTe mixed oxide with a pore volume of more than 0.1 cm 3 / g and a high surface area of more than 20 m 2 / g and more preferably of more than 30 m 2 / g. The MoVNbTe mixed oxide according to the invention is therefore particularly suitable as a catalyst material, because for catalytic applications, a high pore volume and a high specific surface area is generally desired.
Das Gemisch aus Ausgangsverbindungen liegt vorzugsweise als wässrige Suspension vor und wird anschließend hydrothermal behandelt. Der Begriff „hydrothermal" bezieht sich vorwiegend auf Reaktionsbedingungen zur Herstellung eines Katalysator¬ materials in Gegenwart von Wasser und unter erhöhter Temperatur und/oder erhöhtem Druck, beispielsweise im Autoklaven. Dabei kann der Druck im Bereich von 5 bis 30 bar, bevorzugt von 10 bis 27 bar liegen. Beispielhafte Druckbereiche sind 11 bis 20 bar. The mixture of starting compounds is preferably in the form of an aqueous suspension and is subsequently treated hydrothermally. The term "hydrothermal" refers mainly to the reaction conditions for producing a catalyst ¬ materials in the presence of water and under elevated temperature and / or elevated pressure, for example in an autoclave. In this case, bar of the pressure ranging from 5 to 30, preferably from 10 to 27 bar are exemplary pressure ranges are 11 to 20 bar.
Durch die hydrothermale Behandlung (Schritt b) ) wird eine ProduktSuspension erhalten, die das MoVNbTe-Mischoxid als Feststoff enthält. In dem erfindungsgemäßen Verfahren kann das Abtrennen des Feststoffs der Suspension in Schritt c) , der das erfindungsgemäße MoVNbTe-Mischoxid darstellt, in einen oder mehreren Schritten der Filtration, z.B. durch Abfiltrieren von der Mutterlauge, erfolgen. Das Trocknen kann in einem Schritt durchgeführt werden oder in zwei Schritten in strömender oder statischer Luft. Dabei ist der erste Trocknungsschritt bevorzugt bei 60 bis 150 °C (besonders bevorzugt bei 80 bis 120°C) ein zweiter Trocknungsschritt kann bei 200 bis 400°C durchgeführt werden. Zusätzlich kann Schritt c) des erfindungsgemäßen Verfahrens einen oder mehrere Schritte des Waschens, des Kalzinierens (thermische Behandlung), und/oder des Mahlens beinhalten. Das Kalzinieren kann bei 200 bis 500 °C bevorzugt 250 °C bis 350 °C an Luft erfolgen. Das erfindungsgemäße MoVNbTe-Mischoxid kann alsThe hydrothermal treatment (step b)) gives a product suspension which contains the MoVNbTe mixed oxide as a solid. In the process according to the invention, the separation of the solid from the suspension in step c), which is the MoVNbTe mixed oxide according to the invention, can take place in one or more filtration steps, for example by filtering off the mother liquor. The drying can be carried out in one step or in two steps in flowing or static air. In this case, the first drying step is preferably at 60 to 150 ° C (particularly preferably at 80 to 120 ° C), a second drying step can be carried out at 200 to 400 ° C. Additionally, step c) of the process of the invention may include one or more of washing, calcining (thermal treatment), and / or milling. The calcination can be carried out at 200 to 500 ° C, preferably 250 ° C to 350 ° C in air. The MoVNbTe mixed oxide according to the invention can be used as
Katalysatormaterial zur Oxidation und/oder oxidativen Dehydrierung („ODH") von Kohlenwasserstoffen, insbesondere zur oxidativen Dehydrierung von Ethan zu Ethylen verwendet werden. Catalyst material for the oxidation and / or oxidative dehydrogenation ("ODH") of hydrocarbons, in particular for the oxidative dehydrogenation of ethane to ethylene can be used.
Der Katalysator oder das Katalysatormaterial ist ein MoVNbTe- Mischoxid, das nach dem erfindungsgemäßen Verfahren hergestellt wird und kann auf verschiedene Art in einem kommerziellen Katalysator eingesetzt werden. Z.B. kann es durch Tablettieren zu Katalysatortabletten verarbeitet werden, die dann in einen Reaktor eingefüllt werden können. The catalyst or catalyst material is a MoVNbTe mixed oxide prepared by the process of the invention and can be used in a variety of ways in a commercial catalyst. For example, For example, it can be processed by tabletting into catalyst tablets which can then be filled into a reactor.
Bevorzugterweise wird das MoVTeNb-Mischoxid, das durch das erfindungsgemäße Verfahren erhalten wird, ohne weitere Kalzinierung, d.h. unmittelbar nach der Trocknung, als Katalysatormaterial, eingesetzt. Preferably, the MoVTeNb composite oxide obtained by the process of the present invention, without further calcination, i. immediately after drying, used as a catalyst material.
Das Katalysatormaterial kann auch zusammen mit einem geeigneten Bindemittel zu einem Extrudat (Tabletten, Formkörper, Honigwabenkörper und dergleichen) verarbeitet werden. Als Bindemittel kann jedes dem Fachmann geläufige und geeignet erscheinende Bindemittel verwendet werden. Bevorzugte Bindemittel sind unter anderem Pseudoböhmit sowie silicatische Bindemittel wie kolloidales Siliciumoxid oder Silicasol. The catalyst material may also be processed into an extrudate (tablets, shaped bodies, honeycomb bodies and the like) together with a suitable binder. Any binder known to those skilled in the art and appearing suitable may be used as the binder. Preferred binders include pseudoboehmite and silicate binders such as colloidal silica or silica sol.
Das Katalysatormaterial kann ferner zusammen mit anderen Komponenten, vorzugsweise mit einem Bindemittel, besonders bevorzugt mit einem organischen Bindemittel, beispielsweise einem organischen Kleber, Polymeren, Harzen oder Wachsen, zu einem Washcoat verarbeitet werden, der auf einen metallischen oder keramischen Träger aufgebracht werden kann. Gegebenenfalls können zusätzliche Imprägnierschritte oder Kalzinierschritte erfolgen. Das erfindungsgemäße MoVNbTe-Mischoxid wird in den Beispielen als Katalysatormaterial eingesetzt und bei den experimentellen Angaben daher teilweise als Katalysator bezeichnet. The catalyst material can also be processed into a washcoat together with other components, preferably with a binder, more preferably with an organic binder, for example an organic adhesive, polymers, resins or waxes, which can be applied to a metallic or ceramic support. If necessary, additional impregnation steps or calcination steps can take place. The MoVNbTe mixed oxide according to the invention is used in the examples as a catalyst material and therefore partially referred to in the experimental information as a catalyst.
Figur 1: Röntgendiffraktogramm des erfindungsgemäßen Katalysators aus Beispiel 1. FIG. 1: X-ray diffractogram of the catalyst according to the invention from Example 1.
Figur 2: Röntgendiffraktogramm des Vergleichskatalysators aus Vergleichsbeispiel 1. FIG. 2: X-ray diffractogram of the comparative catalyst from Comparative Example 1.
Figur 3: Röntgendiffraktogramm des Vergleichskatalysators aus Vergleichsbeispiel 2, nach der Aktivierung. FIG. 3: X-ray diffractogram of the comparative catalyst from Comparative Example 2, after activation.
Figur 4: Röntgendiffraktogramm des Vergleichskatalysators aus Vergleichsbeispiel 2, vor der Aktivierung. Figure 4: X-ray diffractogram of the comparative catalyst of Comparative Example 2, before activation.
Figur 5: Porenverteilung des Katalysators nach Beispiel 1. FIG. 5: Pore distribution of the catalyst according to Example 1.
Figur 6: Porenverteilung des Katalysators nach Vergleichsbeispiel 1. FIG. 6: Pore distribution of the catalyst according to Comparative Example 1.
Figur 7: Porenverteilungen der Katalysatoren nach Vergleichsbeispiel 2. FIG. 7: Pore distributions of the catalysts according to Comparative Example 2.
Figur 8: Aktivität der Katalysatoren in der ODH-Reaktion von Ethan . FIG. 8: Activity of the catalysts in the ODH reaction of ethane.
Figur 9: Porenverteilung des Katalysators nach Beispiel 2. FIG. 9: Pore distribution of the catalyst according to Example 2.
Figur 10: Aktivität des Katalysators aus Beispiel 2 in der ODH-Reaktion FIG. 10: Activity of the catalyst from Example 2 in the ODH reaction
Es ist zu erkennen, dass das Röntgendiffraktogramm (XRD) des erfindungsgemäßen Katalysators in Figur 1 die typischen Reflexe der Ml-Phase bei (2Θ=) 26,2° ± 0,5° (h) , 27,0° ± 0,5° (i), 7,8° ± 0,5° (k) und 28,0° ± 0,5° (1) aufweist (bei Verwendung der Cu-K -Strahlung) . Diese sind breiter, als in den durch Aktivierung behandelten Vergleichsbeispielen (Figur 2 und 3) . Die größere Breite erklärt sich dadurch, dass die Kristallitgröße kleiner ist, was mit der größeren spezifischen Oberfläche einhergeht. In Figur 4 ist zu sehen, dass ohne die Aktivierung nur der Reflex bei 22,5°, der den Schichtabstand wiedergibt, klar zu identifizieren ist. Erst nach der Aktivierung (Figur 3) zeigt auch dieser Katalysator die typischen Reflexe der Ml-Phase. It can be seen that the X-ray diffractogram (XRD) of the catalyst according to the invention in FIG. 1 shows the typical reflections of the Ml phase at (2Θ =) 26.2 ° ± 0.5 ° (h), 27.0 ° ± 0.5 ° (i), 7.8 ° ± 0.5 ° (k) and 28.0 ° ± 0.5 ° (1) (using Cu-K radiation). These are wider than in the comparative examples treated by activation (FIGS. 2 and 3). The larger width is explained by the fact that the Crystallite size is smaller, which is associated with the larger specific surface area. In FIG. 4 it can be seen that without the activation only the reflex at 22.5 °, which represents the slice spacing, can be clearly identified. Only after activation (FIG. 3) does this catalyst also show the typical reflexes of the Ml phase.
Charakterisierungsmethoden : Characterization methods:
Zur Bestimmung der Parameter der erfindungsgemäßen For determining the parameters of the invention
Katalysatoren werden die nachstehenden Methoden eingesetzt: Catalysts are used the following methods:
1. BET-Oberfläche : 1. BET surface area:
Die Bestimmung erfolgt nach der BET-Methode gemäß DIN 66131; eine Veröffentlichung der BET-Methode findet sich auch in J. Am. Chem. Soc. 60, 309 (1938) . Die Messungen wurden an einem Sorptomatic 1990 Gerät bei 77 K durchgeführt. Vor der The determination is made according to the BET method according to DIN 66131; a publication of the BET method can also be found in J. Am. Chem. Soc. 60, 309 (1938). The measurements were performed on a Sorptomatic 1990 device at 77K. Before the
Messung wurde die Probe für 2 h bei 523 K evakuiert. Die lineare Regression der Isothermen nach der BET-Methode wurde in einem Druckbereich von p/po = 0,01 - 0,3 (po = 730 Torr) durchgeführt . 2. N2-Porenverteilung Measurement, the sample was evacuated for 2 h at 523 K. The linear regression of the isotherms according to the BET method was carried out in a pressure range of p / po = 0.01-0.3 (po = 730 Torr). 2. N2 pore distribution
Die Porengrößenverteilung wurde mittels  The pore size distribution was determined by means of
StickstoffSorptionsmessungen an einem Sorptomatic Gerät oder einem TriStar 3000 Gerät bei 77 K durchgeführt. Vor der  Nitrogen sorption measurements were performed on a Sorptomatic instrument or a TriStar 3000 instrument at 77K. Before the
Messung wurde die Probe für 2 h bei 523 K evakuiert. Es wurden sowohl Ad- als auch Desorptionsisothermen bestimmt und zur Auswertung nach der Barrett-Joyner-Halenda Methode (BJH) herangezogen. 3. Pulverröntgendiffraktometrie (XRD) Measurement, the sample was evacuated for 2 h at 523 K. Both ad- and desorption isotherms were determined and used for evaluation according to the Barrett-Joyner-Halenda method (BJH). 3. Powder X-ray diffractometry (XRD)
Das Röntgendiffraktogramm wurde durch Pulverröntgen¬ diffraktometrie (XRD) und Auswertung nach der Scherrerformel erstellt. The X-ray was created by powder X ¬ diffractometry (XRD) and evaluation by the Scherrerformel.
Die Diffraktogramme wurden auf einem PANalytical Empyrean, ausgestattet mit einem Medipix PIXcel 3D Detektor, in Θ-Θ Geometrie in einem Winkelbereich von 2Θ = 5 - 70 0 The diffractograms were performed on a PANalytical Empyrean equipped with a Medipix PIXcel 3D detector in Θ-Θ geometry in an angular range of 2Θ = 5 - 70 0
aufgenommen. Die Röntgenröhre erzeugte Cu-K-Strahlung . Die Cu-Kß-Strahlung wurde durch Verwendung eines Ni-Filters im Strahlengang es einfallenden Röntgenstrahls unterdrückt, so dass an der Probe ausschließlich Cu-K -Strahlung mit einer Wellenlänge von 15,4 nm (E = 8,04778 keV) gebeugt wurde. Die Höhe des quellenseitigen Strahlenganges wurde mittels automatischem Divergenzschlitz (programmable diveregence slit - PDS) so angepasst, dass die Probe über den gesamten Winkelbereich auf einer Länge von 12 mm bestrahlt wurde. Die Breite des detektorseitigen Röntgenstrahls wurde durch eine feste Blende auf 10 mm begrenzt. Horizontale Divergenz wurde durch Verwendung eines 0.4 rad Soller Slits minimiert. added. The X-ray tube produced Cu-K radiation. The Cu-Kβ radiation was suppressed by using a Ni filter in the incident X-ray beam path, so that only Cu-K radiation having a wavelength of 15.4 nm (E = 8.04778 keV) was diffracted on the sample. The height of the source-side beam path was adjusted by means of an automatic divergent slit (PDS) such that the sample was irradiated over the entire angular range over a length of 12 mm. The width of the detector-side X-ray beam was limited by a fixed aperture to 10 mm. Horizontal divergence was minimized by using a 0.4 rad Soller Slit.
Die Höhe des detektorseitigen Strahlenganges wurde analog zum quellenseitigen Strahlengang mittels automatischem Anti- brechungsschlit z (programmable anti-scatter slit - PASS) so angepasst, dass über den gesamten Winkelbereich der auf einer Länge von 12 mm auf der Probe reflektierten The height of the detector-side beam path was adjusted analogously to the source-side beam path by means of an automatic anti-scatter slit (PASS) such that it reflected over the entire angular range over a length of 12 mm on the sample
Röntgenstrahl detektiert wurde. X-ray was detected.
Die Proben wurden, je nach vorhandener Menge, entweder auf einem amorphen Siliziumprobenteller oder tablettiert als Flachbettproben präpariert. Ausführungsbeispiele : The samples were prepared, depending on the amount present, either on an amorphous silicon platter or tabletted as flat-bed samples. Exemplary embodiments:
Beispiel 1 : Example 1 :
In einem 100 mL PTFE-Becher wurden 75 mL bidest illiertes Wasser vorgelegt, 177,8 mg Monoethylenglykol zugetropft und anschließend 5397, 9 mg Mo03, 1023, 9 mg V205, 599, 1 mg Te02, 549, 5 mg Nb205«xH20 (Nb = 63, 45 Gew.-%), 540, 9 mg In a 100 mL PTFE beaker, 75 mL bidistilled water were placed, 177.8 mg monoethylene glycol added dropwise and then 5397, 9 mg Mo0 3 , 1023, 9 mg V 2 0 5 , 599, 1 mg Te0 2 , 549, 5 mg Nb 2 0 5 "x H 2 O (Nb = 63, 45 wt%), 540, 9 mg
Zitronensäure und 338,3 mg Oxalsäure aufgeschlämmt . Der Teflonbecher wurde verschlossen und in eine Citric acid and 338.3 mg of oxalic acid slurried. The teflon cup was sealed and placed in a
Edelstahlautoklavenbombe überführt. Diese wurde druckdicht verschlossen und in einem auf 190 °C vorgeheizten Ofen auf eine horizontale drehende Welle gespannt. Nach 48 Stunden wurde die Autoklavenbombe aus dem Ofen entnommen und sofort unter fließendem Wasser abgeschreckt und anschließend in einem Eisbad für 45 Minuten abgekühlt. Die entstandene Produkt Suspension wurde über Filterpapier (Porenweite 3 pm) abfiltriert und der Feststoff mit 200 mL bidest illiertem Wasser gewaschen.  Conveyed stainless steel autoclave bomb. This was pressure-tight and clamped in a preheated to 190 ° C oven on a horizontal rotating shaft. After 48 hours, the autoclave bomb was removed from the oven and immediately quenched under running water and then cooled in an ice bath for 45 minutes. The resulting product suspension was filtered through filter paper (pore size 3 pm) and the solid was washed with 200 ml bidistilled water.
Das so gewonnene Produkt wurde für 16 h in einem The product thus obtained was in a 16 h
Trockenschrank bei 80 °C getrocknet und danach in einem Handmörser zermahlen. Drying oven dried at 80 ° C and then ground in a hand mortar.
Es wurde eine Feststoff-Ausbeute von 6,2 g erreicht. Die BET-Oberfläche des Produkts betrug 83,3 m2/g, das Produkt wies ein Porenvolumen von 0,2 cm3/g und eine Porenverteilung, die in Figur 5 gezeigt wird, auf. Beispiel 2 : A solids yield of 6.2 g was achieved. The BET surface area of the product was 83.3 m 2 / g, the product had a pore volume of 0.2 cm 3 / g and a pore distribution shown in FIG. 5. Example 2:
Die Synthese erfolgte wie unter Beispiel 1 beschrieben, mit der Ausnahme, dass nach 16 h Trocknung bei 80 °C ein The synthesis was carried out as described in Example 1, with the exception that after 16 h drying at 80 ° C a
weiterer Trocknungsschritt für 3 h bei 400 °C erfolgte. Die BET-Oberfläche des Produkts betrug 59,0 m2/g, das Produkt wies ein Porenvolumen von 0,176 cm3/g und eine further drying step for 3 h at 400 ° C. The BET surface area of the product was 59.0 m 2 / g, the product had a pore volume of 0.176 cm 3 / g and a
Porenverteilung, die in Figur 9 gezeigt wird, auf. Pore distribution, which is shown in Figure 9, on.
Aus Figur 10 ist zu erkennen, dass bei 420 °C der From Figure 10 it can be seen that at 420 ° C of
Katalysator mit einer Ethylenbildungsrate von 9xl0~6 mol g_1Kat s_1 etwa die gleiche Aktivität besaß, wie der nur bei 80°C getrocknete Katalysator aus Beispiel 1 (Figur 8) . Der Catalyst having an ethylene formation rate of 9xl0 ~ 6 mol g _1 Kat s _1 about the same activity possessed, as the only dried at 80 ° C catalyst from Example 1 (Figure 8). Of the
Aktivitätsverlust tritt also erst im Temperaturbereich oberhalb von 400°C ein. Loss of activity occurs only in the temperature range above 400 ° C.
Vergleichsbeispiel 1: Comparative Example 1
Der Katalysator, der in Beispiel 1 beschrieben ist, wurde in einem Rohrofen einer thermischen Behandlung (Aktivierung) unterzogen. Dazu wurde 1 g des getrockneten Feststoffes in ein Porzellanschiffchen überführt, so dass dessen Boden ca. 2 mm hoch mit Pulver bedeckt ist. The catalyst described in Example 1 was subjected to thermal treatment (activation) in a tube furnace. For this purpose, 1 g of the dried solid was transferred to a porcelain boat, so that its bottom is covered about 2 mm high with powder.
Die Aktivierung erfolgte bei 600 °C für 2 h (Heizrate The activation took place at 600 ° C. for 2 h (heating rate
10°C/min 2 : 100 mL/min) . Nach dieser Behandlung betrug die BET-Oberfläche 7,3 m2/g, das Produkt wies ein Porenvolumen von 0,013 cm3/g und eine Porenverteilung, die in Figur 6 gezeigt wird, auf. 10 ° C / min 2: 100 mL / min). After this treatment, the BET surface area was 7.3 m 2 / g, the product had a pore volume of 0.013 cm 3 / g and a pore distribution shown in FIG.
Vergleichsbeispiel 2: Comparative Example 2:
Im Autoklaven (40 L) wurden 3,3 L dest. H2O vorgelegt und unter Rühren auf 80 °C erhitzt. Währenddessen wurde 725,58 g Ammoniumheptamolybdat-Tetrahydrat (von HC Starck) In an autoclave (40 L) 3.3 L dist. Submitted H2O and heated to 80 ° C with stirring. Meanwhile, 725.58 g of ammonium heptamolybdate tetrahydrate (from HC Starck) was added.
hineingegeben und gelöst (AHM-Lösung) . In drei 5 L put in and dissolved (AHM solution). In three 5 L
Bechergläsern wurden jeweils 1,65 L dest. H2O unter Rühren auf einem Magnetrührer mit Temperaturregelung ebenfalls auf 80 °C erhitzt. In diese Bechergläser wurden dann jeweils 405,10 g Vanadylsulfathydrat (von GfE, V-Gehalt : 21,2%), 185,59 g Ammoniumnioboxalat (HC Starck- Nb-Gehalt : 20,6%) und 94,14 g Tellursäure (V-Lösung, Te-Lösung und Nb-Lösung) zugegeben und gelöst. Beakers were each 1.65 L dist. H2O with stirring on a magnetic stirrer with temperature control also heated to 80 ° C. 405.10 g of vanadyl sulfate hydrate (of GfE, V content: 21.2%), 185.59 g of ammonium niobium oxalate (HC Starck Nb content: 20.6%) were then added to each beaker. and 94.14 g of telluric acid (V solution, Te solution and Nb solution) were added and dissolved.
Anschließend wurden die V-Lösung, dann die Te-Lösung und zum Schluss die Nb-Lösung in die AHM-Lösung mittels einer Subsequently, the V solution, then the Te solution and finally the Nb solution in the AHM solution by means of a
Schlauchpumpe gepumpt (Pumpzeit: V-Lösung: 4,5 min mit 190 rpm, Schlauchdurchmesser: 8x5 mm, Nb-Lösung: 6 min mit 130 rpm Schlauchdurchmesser: 8x5 mm) . Hose pump pumped (pumping time: V solution: 4.5 min at 190 rpm, hose diameter: 8x5 mm, Nb solution: 6 min at 130 rpm hose diameter: 8x5 mm).
Die entstandene Suspension wurde nun 10 min bei 80 °C weitergerührt. Die Geschwindigkeit des Rührers bei der The resulting suspension was then stirred for a further 10 minutes at 80.degree. The speed of the stirrer at the
Fällung betrug 90 rpm. Precipitation was 90 rpm.
Anschließend wurde mit Stickstoff überlagert, indem im Subsequently, it was overlaid with nitrogen by adding in
Autoklaven mit Stickstoff ein Druck bis ca. 6 bar aufgebaut und das Ablassventil so weit geöffnet wurde, dass der Autoclave with nitrogen pressure up to about 6 bar and the drain valve was opened so far that the
Autoklav unter Druck von N2 durchströmt wird (5 min) . Am Ende wurde der Druck, über das Entlüftungsventil, bis auf 1 bar Restdruck wieder abgelassen. Autoclave is pressurized by N2 (5 min). At the end, the pressure was released via the vent valve, down to 1 bar residual pressure.
Die Hydrothermalsynthese wurde im 40 L Autoklaven bei 175 °C für 20 h (Aufheizzeit: 3 h) mit einem Ankerrührer bei einer Rührergeschwindigkeit von 90 rpm durchgeführt. Nach der Synthese wurde mit Hilfe einer Vakuumpumpe mit Blaubandfilter abfiltriert und der Filterkuchen mit 5 L dest . H2O gewaschen. The hydrothermal synthesis was carried out in a 40 L autoclave at 175 ° C. for 20 h (heating time: 3 h) with an anchor stirrer at a stirrer speed of 90 rpm. After the synthesis was filtered off with the aid of a vacuum pump with Blauband filter and the filter cake with 5 L dist. Washed H2O.
Die Trocknung erfolgte bei 80 °C im Trockenschrank für 3 Tage und anschließend wurde in einer Schlagmühle gemahlen, wobei eine Feststoff-Ausbeute von 0,8 kg erhalten wurde. The drying was carried out at 80 ° C in a drying oven for 3 days and then was ground in a hammer mill, with a solids yield of 0.8 kg was obtained.
Die Kalzinierung erfolgte bei 280 °C für 4 h (Heizrate The calcination was carried out at 280 ° C for 4 h (heating rate
5 °C/min Luft: 1 L/min) . 5 ° C / min air: 1 L / min).
Die Aktivierung erfolgte in einer Retorte bei 600 °C für 2 h im N2~Durchfluss (Heizrate 5°C/min N2 : 0,5 L/min) . Das Produkt wies eine BET-Oberflache von 13 m2/g und ein Porenvolumen von 0,055 cm3/g, mit einer Porenverteilung, die in Figur 7 gezeigt wird, auf. The activation was carried out in a retort at 600 ° C for 2 h in N2 ~ flow (heating rate 5 ° C / min N2: 0.5 L / min). The product had a BET surface area of 13 m 2 / g and a pore volume of 0.055 cm 3 / g, with a pore distribution shown in FIG.
Vergleichsbeispiel 3: Der Katalysator aus Vergleichsbeispiel 2 wurde direkt nach der Kalzinierung bei 280 °C für 4 h verwendet. Die Comparative Example 3: The catalyst of Comparative Example 2 was used immediately after calcination at 280 ° C for 4 hours. The
Aktivierung bei 600°C unter Stickstoff für 2 h wurde nicht durchgeführt . Activation at 600 ° C under nitrogen for 2 h was not performed.
Beispiel 3: Die katalytische Aktivität in der oxidativen Dehydrierung („ODH") von Ethan der Katalysatoren aus Beispiel 1 und den Vergleichsbeispielen 1 und 2 wurde in einem Rohrreaktor bei Atmosphärendruck im Temperaturbereich 330 bis 420 °C Example 3: The catalytic activity in the oxidative dehydrogenation ("ODH") of ethane of the catalysts of Example 1 and Comparative Examples 1 and 2 was carried out in a tubular reactor at atmospheric pressure in the temperature range 330 to 420 ° C.
untersucht. Dazu wurden je 25 mg (Beispiel 1 und examined. For this purpose, 25 mg each (Example 1 and
Vergleichsbeispiel 1) oder 200 mg (Vergleichsbeispiel 2)Comparative Example 1) or 200 mg (Comparative Example 2)
Katalysator (Partikelgröße 150 - 212 pm) mit Silizumcarbid (Partikelgröße 150 - 212 pm) im Massenverhältnis 1 : 5 verdünnt. Unter- und oberhalb des Katalysatorbettes wurde eine Schicht aus jeweils 250 mg Siliziumcarbid der gleichen Partikelgröße eingefüllt und die Enden des Rohrreaktors wurden durch Quarzwollepfropfen verschlossen. Catalyst (particle size 150-212 pm) diluted with silicon carbide (particle size 150-212 pm) in a mass ratio of 1: 5. Below and above the catalyst bed, a layer of each 250 mg of silicon carbide of the same particle size was filled and the ends of the tubular reactor were sealed by Quarzwollepfropfen.
Der Reaktor wurde vor Beginn des Experiments mit Inertgas gespült und anschließend unter einem Heliumfluss von 50 sccm auf 330 °C aufgeheizt. Nachdem die gewünschte Temperatur erreicht wurde und für eine Stunde stabil war, wurde auf das Reaktionsgasgemisch umgeschalten . The reactor was purged with inert gas prior to the start of the experiment and then heated to 330 ° C. under a helium flow of 50 sccm. After the desired temperature was reached and stable for one hour, was switched to the reaction gas mixture.
Die Eingangsgaszusammensetzung war CzHe/Oz/H = 9,1/9,1/81,8 (v/v) bei einem Gesamtvolumenstrom von 50 sccm. The input gas composition was CzHe / Oz / H = 9.1 / 9.1 / 81.8 (v / v) at a total volumetric flow rate of 50 sccm.
Die Analyse des Produktgasstromes wurde in einem The analysis of the product gas stream was in a
Gaschromatographen ausgerüstet mit Haysep N- und Haysep Q- Säulen, einer Molsiebsäule 5A und eir Gas chromatograph equipped with Haysep N and Haysep Q- Columns, a molecular sieve column 5A and eir
Wärmeleitfähigkeitsdetektor bestimmt . Thermal conductivity detector determined.
Die Ethylenbildungsraten unter den oben beschriebenen The ethylene formation rates below those described above
Bedingungen sind in Figur 8 dargestellt. Die Katalysatoraktivität wurde auf die Katalysatormasse normiert, der Katalysator nach dem Stand der Technik aus den löslichen Vorläuferverbindungen (Vergleichsbeispiel 2) zeigt die geringste Aktivität. Vergleichsbeispiel 1 ist nach dem neuen Verfahren dieses Patents hergestellt, wurde aber noch bei 600 °C kalziniert. Die höchste katalytische Aktivität zeigen die erfindungsgemäßen Katalysatoren ohne Conditions are shown in FIG. The catalyst activity was normalized to the catalyst mass, the prior art catalyst from the soluble precursor compounds (Comparative Example 2) shows the lowest activity. Comparative Example 1 is made according to the new process of this patent but was still calcined at 600 ° C. The highest catalytic activity is shown by the catalysts according to the invention without
abschließende Hochtemperaturbehandlung . final high temperature treatment.
Tabelle 1: Table 1:
Tabelle 1 vergleicht die BET-Oberflächen, und die Table 1 compares the BET surfaces, and the
Porenvolumina des erfindungsgemäßen Katalysators mit Pore volumes of the catalyst according to the invention with
Vergleichsbeispielen . Comparative Examples.

Claims

Patentansprüche : Claims:
1. Mischoxidmaterial, umfassend die Elemente Molybdän, 1. mixed oxide material comprising the elements molybdenum,
Vanadium, Niob und Tellur, das im XRD, bei Verwendung der Cu-K -Strahlung, Beugungsreflexe h, i, k und 1 aufweist, deren Scheitelpunkte bei den Beugungswinkeln (2·) 26,2° ± 0,5° (h) , 27,0° ± 0,5° (i), 7,8° ± 0,5° (k) und 28,0° ± 0,5° (1) liegen, dadurch gekennzeichnet, dass das  Vanadium, niobium and tellurium, which in the XRD, when using the Cu-K radiation, has diffraction reflectances h, i, k and 1 whose vertices at the diffraction angles (2 ×) are 26.2 ° ± 0.5 ° (h) , 27.0 ° ± 0.5 ° (i), 7.8 ° ± 0.5 ° (k) and 28.0 ° ± 0.5 ° (1), characterized in that
Mischoxidmaterial ein Porenvolumen von größer 0,1 cm3/g aufweist . Mixed oxide material has a pore volume of greater than 0.1 cm 3 / g.
2. Mischoxidmaterial nach Anspruch 1 dadurch gekennzeichnet, dass es eine BET-Oberflache von mehr als 30 m2/g aufweist. 2. mixed oxide material according to claim 1, characterized in that it has a BET surface area of more than 30 m 2 / g.
3. Mischoxidmaterial nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es ein Volumen der Poren, die kleiner sind als 10 nm, von mehr als 0,2 cm3/g aufweist. 3. Mixed oxide material according to one of the preceding claims, characterized in that it has a volume of pores smaller than 10 nm, of more than 0.2 cm 3 / g.
4. Mischoxidmaterial nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Molverhältnis Mo : Te -S 11 ist und das Molverhältnis Mo:Nb -S 11 ist. 4. mixed oxide material according to any one of the preceding claims, characterized in that the molar ratio Mo: Te -S 11 and the molar ratio Mo: Nb -S 11.
5. Verfahren zur Herstellung eines Mischoxidmaterials nach einem der vorhergehenden Ansprüche, umfassend die 5. A process for producing a mixed oxide material according to any one of the preceding claims, comprising
Schritte :  Steps :
a) Herstellen eines Gemisches aus  a) preparing a mixture of
Ausgangsverbindungen, das Molybdän, Vanadium, Niob und eine Tellur enthaltende Ausgangsverbindung, in der Tellur in der Oxidationsstufe +4 vorliegt, enthält sowie Oxalsäure und mindestens einen weiteren Oxoliganden,  Starting compounds containing molybdenum, vanadium, niobium and a tellurium-containing starting compound in which tellurium is present in the oxidation state +4, and oxalic acid and at least one further oxo ligand,
b) hydrothermale Behandlung des Gemisches aus  b) hydrothermal treatment of the mixture
Ausgangsverbindungen bei einer Temperatur von 100 °C bis 300 °C, um eine ProduktSuspension zu erhalten, Starting compounds at a temperature of 100 ° C to 300 ° C, to a product suspension receive,
c) Abtrennen und Trocknen des Mischoxidmaterials, das in der aus Schritt b) resultierenden  c) separating and drying the mixed oxide material resulting in that resulting from step b)
ProduktSuspension enthalten ist.  Product suspension is included.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Tellur enthaltende Ausgangsverbindung Tellurdioxid oder eine Verbindung der Formel Mx n+TeC>3 mit n = 1 oder 2 und x = 2/n ist, wobei M ein Alkali- oder Erdalkalimetall ist. 6. The method according to claim 5, characterized in that the tellurium-containing starting compound is tellurium dioxide or a compound of the formula M x n + TeC> 3 with n = 1 or 2 and x = 2 / n, where M is an alkali or alkaline earth metal.
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass das Gemisch aus Ausgangsverbindungen als wässrige Suspension vorliegt. 7. The method according to claim 5 or 6, characterized in that the mixture of starting compounds is present as an aqueous suspension.
8. Verfahren nach einem der Ansprüche 5 bis 7, dadurch 8. The method according to any one of claims 5 to 7, characterized
gekennzeichnet, dass das Gemisch aus Ausgangsverbindungen eine Dicarbonsäure, ein Diol, oder eine sonstige  in that the mixture of starting compounds is a dicarboxylic acid, a diol, or another
Verbindung mit zwei Hydroxy-Gruppen in benachbarter  Compound with two hydroxy groups in adjacent
Stellung als weiteren Oxoliganden enthält.  Contains position as another oxo ligand.
9. Verfahren nach einem der Ansprüche 5 bis 8, dadurch 9. The method according to any one of claims 5 to 8, characterized
gekennzeichnet, dass das Gemisch aus Ausgangsverbindungen Molybdäntrioxid enthält.  in that the mixture of starting compounds contains molybdenum trioxide.
10. Verfahren nach einem der Ansprüche 5 bis 9, dadurch 10. The method according to any one of claims 5 to 9, characterized
gekennzeichnet, dass das Gemisch aus Ausgangsverbindungen Vanadiumpentoxid enthält.  characterized in that the mixture of starting compounds contains vanadium pentoxide.
11. Verfahren nach einem der Ansprüche 5 bis 10, dadurch gekennzeichnet, dass das Gemisch aus Ausgangsverbindungen Zitronensäure als weiteren Oxoliganden enthält. 11. The method according to any one of claims 5 to 10, characterized in that the mixture of starting compounds contains citric acid as a further oxo ligand.
12. Verfahren nach einem der Ansprüche 5 bis 11, dadurch gekennzeichnet, dass das Gemisch aus Ausgangsverbindungen Zitronensäure und Glykol als weitere Oxoliganden enthält. 12. The method according to any one of claims 5 to 11, characterized in that the mixture of starting compounds contains citric acid and glycol as further oxo ligands.
13. Verwendung eines Mischoxidmaterials nach Anspruch 1 bis 4 als Katalysatormaterial zur oxidativen Dehydrierung von Ethan zu Ethen. 13. Use of a mixed oxide material according to claim 1 to 4 as a catalyst material for the oxidative dehydrogenation of ethane to ethene.
14. Verwendung eines Mischoxidmaterials nach Anspruch 1 bis 4 als Katalysatormaterial zur Oxidation von Propen zu Acrylsäure . 14. Use of a mixed oxide material according to claim 1 to 4 as a catalyst material for the oxidation of propene to acrylic acid.
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