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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 molybdenum mixed oxide material as a catalyst for the oxidative dehydrogenation of ethane.
• the invention relates to a MoVNbTe catalyst having reduced content of niobium and tellurium and higher activity for the oxidative dehydrogenation of ethane to ethene or the oxidation of propane to acrylic acid and a process for producing the mixed oxide material.
• MoVNbTe mixed oxides for the oxidation of propane to acrylic acid, for the ammoxidation of propane to acrylonitrile 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%.
• the MoVNbTe base system based on four elements for a catalyst was 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 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 the catalyst composition Contains mixed metal oxide, which contains 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).
• Ml phase seems to play the essential role in the selective oxidation reactions.
• Ml MoiVo, i5Teo, i2Nbo, 128O3, 7 or M07, sVi, 2 Teo, 937 bi028, 9
• M2 * MoiVo, 32Teo, 42 bo, os04,6 or M04, 31V1, 3 eTei, siNbo, 33O19, si
• the two main phases can also occur with a slightly different stoichiometry.
• both vanadium and molybdenum in the center of an octahedron of oxygen atoms and therefore partially interchangeable in the structure, so that the same structure, for example, the Ml phase, even with a higher vanadium content is possible.
• the M2 phase is not active for the oxidative dehydrogenation of ethane. (See JS Valente et al., ACS Catal. 4 (2014), 1292-1301 specifically P.1293).
• EP 529853 A2 discloses a catalyst suitable for the preparation of a nitrile from an alkane, the catalyst having the empirical formula MoVbTe c XxOn 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
• 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.
• the Nb component used in the synthesis of MoVNbTe mixed oxides is usually ammonium niobium oxalate.
• 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 M0O3, V2O5 and TeÜ2.
• the Hydrothermal synthesis provides a precursor to an ammoxidation catalyst which has twice the activity after calcination compared to a catalyst prepared by the known dry method.
• the mixed oxides produced by the solid-state reaction show 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.
• 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.
• Hydrocarbons 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.
• 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 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.
• a synthesis method for the preparation of a high-purity Ml phase was found, which dispenses with the final high-temperature treatment.
• the object of the present invention is to provide a new simplified and efficient synthetic route for the preparation of a mixed oxide material containing molybdenum, vanadium, tellurium and niobium ("MoVTeNb mixed oxide”), which is present in high phase purity as Ml phase.
• MoVTeNb mixed oxide molybdenum, vanadium, tellurium and niobium
• Preparation of a mixed oxide material containing molybdenum, vanadium, tellurium and niobium comprising the steps of: a) preparing a mixture of starting compounds, the molybdenum, vanadium, niobium and a tellurium
• the mixture of starting compounds is preferably in the form of an aqueous suspension and is subsequently treated hydrothermally.
• hydrothermally refers primarily to reaction conditions for the preparation of a
• Catalyst material in the presence of water and at elevated temperature and / or elevated pressure for example in an autoclave.
• the pressure may be in the range from 5 to 30 bar, preferably from 10 to 27 bar. Exemplary pressure ranges are 11 to 20 bar.
• the hydrothermal treatment gives a product suspension which contains the MoVNbTe mixed oxide as a solid.
• 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 ° C to 150 ° C (more preferably at 80 ° C to 120 ° C), a second drying step can be carried out at 200 ° C 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 dried mixture for example, in a flowing or static inert gas atmosphere at about 500 to 700 ° C for activated for at least 1 hour (step d)).
• a flowing or static inert gas atmosphere at about 500 to 700 ° C for activated for at least 1 hour (step d)).
• nitrogen, helium or argon is suitable as the inert gas. It is preferred if the activation takes place in the range of 550 to 650 ° C. For example, activation may be at about 600 ° C for about 2 hours.
• the starting compounds are the molybdenum, vanadium, tellurium and niobium containing reactants of the 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, 2Üs and TeÜ2 be used as starting compounds.
• Other oxo ligands i.e., besides oxalic acid
• 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.
• 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 further oxo ligands together, should preferably be more preferred 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.
• this synthesis provides the Ml phase already after the hydrothermal synthesis and the drying, without the need for a high-temperature treatment at a temperature above 400 ° C.
• the amount of tellurium and niobium used can be significantly reduced and yet the catalytically active Ml phase forms in high phase purity. It has been found that when M0O3, V2O5, b2Üs and TeÜ2 are used with citric acid, glycol and oxalic acid, the hydrothermal crystallization to the Ml phase succeeds without subsequent calcination. Preferably, no ammonium ions are present during the synthesis.
• Manufacturing process allows the synthesis of a MoVTeNb mixed oxide material containing the elements Mo, V, Te and Nb (MoVTeNb mixed oxide) having the Ml phase with only minor amounts of niobium and / or tellurium. It is therefore an object of the present invention to find a MoVTeNb mixed oxide with Ml phase and the lowest possible amount of niobium and tellurium, which can be used as catalyst material and has the highest possible activity for the oxidation of alkanes.
• a mixed oxide material comprising the elements molybdenum, vanadium, niobium and tellurium, which has in the XRD diffraction reflections h, i, k and 1, whose vertices approximately at the diffraction angles (2 x) 26.2 ° ⁇ 0.5 ° (h), 27.0 ° ⁇ 0.5 ° (i), 7.8 ° ⁇ 0.5 ° (k) and 28.0 ° ⁇ 0.5 ° (1), characterized in that has the following stoichiometry:
• b is preferably between 0.001 to 0.8, or between 0.01 and 0.5
• c is preferably between 0.001 to 0.8 or between 0.01 and 0.5.
• the mixed oxide material according to the invention can be used as a catalyst or as a catalyst material for the oxidation and / or oxidative dehydrogenation of hydrocarbons, in particular for the selective oxidation of ethane to ethylene.
• the catalyst material prepared by the process of the present invention can be used in a variety of ways in a commercial catalyst. For example, it can be processed by tabletting into catalyst tablets which can then be filled into a reactor.
• 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.
• 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.
• FIG. 1 X-ray diffractogram of the catalyst from Example 1.
• FIG. 2 X-ray diffractogram of the catalyst from Example 2.
• FIG. 3 X-ray diffractogram of the catalyst from Comparative Example 1.
• FIG. 4 X-ray diffractogram of the catalyst from Comparative Example 2.
• FIG. 5 X-ray diffractogram of the catalyst from Example 4.
• FIG. 6 STEM image of the catalyst from Example 1, in which the crystal structure of the Ml phase can be seen.
• FIG. 7 SEM image of the catalyst from Example 1, in which the needle crystal form of the Ml phase can be seen.
• FIG. 8 N 2 pore distribution of the catalyst from Example 1.
• FIG. 9 N 2 pore distribution of the catalyst from Example 2.
• FIG. 10 N 2 pore distribution of the catalyst from Example 3.
• FIG. 11 Comparison of the catalytic activity of
• FIG. 11 shows that the catalyst according to the invention of Example 1 has a higher activity in the oxidative dehydrogenation of ethane than that of the comparative examples.
• Example 1 is significantly more active with only half as much niobium and tellurium.
• the calcined catalyst according to the invention with only half as much niobium and tellurium from Example 2 is just as active as the treated at the same high temperature catalyst according to the prior art of Comparative Example 1.
• it is much cheaper, because it is less expensive metals niobium and tellurium needed.
• Catalysts are used the following methods:
• Microwave Multiwave GO Microwave Multiwave GO
• Sulfuric acid 1 1 The sample was finely ground in each case before the analysis.
• Step 1 Hold for 10 min. At 100 ° C, 1 min.
• Step 2 Hold for 5 min. At 180 ° C for 20 min.
• Plasma power 1400 watts
• Cooling gas flow 14 1 / min
• Atomizing gas flow 0.8 1 / min
• Mass concentration of scandium is 2 mg / l.
• the X-ray diffractogram was generated by powder X-ray diffractometry (XRD) and evaluation using the Scherrer formula.
• 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 analogous to the source-side beam path by means of automatic anti-scatter slit z (programmable anti-scatter slit - PASS) so adapted to reflect over the entire angular range of a length of 12 mm on the sample
• the samples were prepared, depending on the amount present, either on an amorphous silicon platter or tabletted as flat-bed samples.
• the crystal samples were prepared by microtome technique.
• Acceleration voltage was 2.0 kV and the
• the working distance was mm.
• Example 1 MoV 0 , 3Nbo, osTeo, os
• the resulting product suspension was filtered through filter paper (pore size 3 pm) and the solid was washed with 200 ml bidistilled water.
• Elemental composition of the metals in the product normalized to molybdenum was MoVo, 3oTeo, osNbo, osO x , this corresponds to a mass-based composition of 53.0 wt% Mo, 8.4 wt% V, 2.9 wt% Te and 2.3 wt% Nb. Scanning transmission electron micrographs of the product are shown in FIGS. 6 and 7.
• the BET surface area of the product is 66.4 m 2 / g
• Product has a pore volume of 0.11 cm 3 / g and a
• Example 1 The catalyst described in Example 1 was subjected to a heat treatment in a tube furnace. To this was added 1 g of the dried solid in Transferred porcelain boats, so that its bottom was covered about 2 mm high with powder. Activation took place for 2 h at 600 ° C, at a heating rate of 10 ° C / min in an N2 flow of 100 mL / min.
• the BET surface area of the product was 25.0 m 2 / g, the product had a pore volume of 0.04 cm 3 / g and a pore distribution shown in FIG.
• the XRD of the product is shown in FIG.
• Beakers were each 1.65 L dist. H 2 O 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%) and 94.14 g of telluric acid were then added to each beaker and dissolved (V solution, Nb solution and Te solution). Then the V solution, the Te solution and finally the Nb solution was pumped into the AHM solution by means of a peristaltic pump (pumping time: V solution: 4.5 min at 190 rpm,
• Hose diameter 8x5 mm, Nb solution: 6 min with 130 rpm hose diameter: 8x5 mm). The resulting suspension was stirred for 1 0 min at 8 0 ° C. The speed of the stirrer at the
• Precipitation was 90 rpm. Subsequently, it was overlaid with nitrogen by pressurizing to about 6 bar in the autoclave with nitrogen and the drain valve was opened so far that the autoclave was flowed through under pressure of 2 (5 min). In the end, the pressure was over
• the hydrothermal synthesis was carried out in the 4 0 L autoclave at 175 ° C for 2 0 h. with an anchor stirrer (heating time: 3 h) at a stirrer speed of 90 rpm.
• the activation was carried out in a retort in an N 2 gas atmosphere in the oven at 60 ° C. for 2 h (heating rate 5 ° C./min 2: 0.5 L / min). After this treatment, the BET surface area was 13 m 2 / g. The result was a catalyst with stoichiometry
• the catalyst of Comparative Example 1 was used directly after calcination at 280 ° C for 4 hours.
• Comparative Examples 1 and 2 were tested in a tube reactor at atmospheric pressure in the temperature range 330 ° C to 420 ° C. For this purpose, 25 mg each (Example 1 and
• Comparative Example 1 Comparative Example 1 or 200 mg (Comparative Example 2) catalyst (particle size 150-212 pm) with silicon carbide (particle size 150 to 212 pm) in a mass ratio of 1: 5 diluted. Below and above the catalyst bed, a layer of 250 mg of silicon carbide of the same particle size was filled in and the ends of the tubular reactor were closed by quartz wool grafting.
• 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.
• Example 4 MoV 0 , 3oNb 0 , 03 e 0 , 03
• the resulting product suspension was filtered through filter paper (pore size 3 pm) and the solid was washed with 200 ml bidistilled water.
• Example 5 MoV 0 , 3oNbo, oeTeo, 03
• the resulting product suspension was filtered through filter paper (pore size 3 pm) and the solid was washed with 200 ml bidistilled water.
• the product thus obtained was dried for 16 hours in a drying oven at 80 ° C and then ground in a hand mortar.
• the reactor was purged with inert gas prior to the start of the experiment and then heated to 330 ° C under helium flow of 50 sccm. After the desired temperature was reached and stable for one hour, was switched to the reaction gas mixture.
• Table 1 shows the stoichiometries, and the BET surfaces of the catalysts according to the invention

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