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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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• 2017
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