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Definitions

• the invention relates to a method for producing a 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 described above acrylic acid yields are about 60% and that of ethene at about 80%.
• 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) also describes the oxidative dehydrogenation of ethane to ethylene with this type of catalyst.
• MoVNbTe mixed oxides 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.
• M2 * MoiVo, 32 eo, 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 are in the center of an octahedron of oxygen atoms and therefore partially interchangeable in structure so that the same structure, e.g. the Ml phase, even with a higher vanadium content is possible.
• the M2 phase is not active for the oxidative dehydrogenation of ethane (See J. S. Valente et al., ACS Catal.4 (2014), 1292-1301, p1293).
• a catalyst which consists of a very pure Ml phase is desired. It is therefore attempted to produce these crystal phases cleanly and 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 element content 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 Preparation of a nitrile, at a relatively low temperature and with a high yield, 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
• the common synthesis is carried out by oxidation of Tellurium oxide with hydrogen peroxide, which causes 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.
• 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 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 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.
• a synthesis of MoVNbTe mixed oxide without the use of telluric acid has the potential to be significantly cheaper.
• 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. What is desired is a synthesis method that provides a clean Ml phase of a MoVNbTe mixed oxide and with inexpensive starting materials, ie, with simple metal oxides, such as molybdenum trioxide, vanadium pentoxide, niobium pentoxide and tellurium dioxide manages.
• the object of the present invention was therefore to find a simple, scalable, inexpensive and reproducible method, the Ml phase of a MoVNbTe mixed oxide selectively using tellurium dioxide, and otherwise, if possible, using inexpensive metal oxides as starting compounds, in to produce a hydrothermal synthesis.
• the object is achieved by a method for producing a mixed oxide material containing the elements molybdenum, vanadium, niobium and tellurium (“MoVTeNb mixed oxide”), comprising the following steps:
• Starting compounds containing molybdenum, vanadium, niobium and a tellurium-containing starting compound in which tellurium is in the +4 oxidation state contains hydrothermal treatment of the mixture of starting compounds at a temperature of from 100 ° C to 300 ° C, to a product suspension
• the process according to the invention leads to a mixed oxide material which represents a MoVNbTe mixed oxide and which is suitable as a catalyst material.
• the tellurium-containing starting compound has a particle size with a D 90 ⁇ 100 pm, preferably D 90 ⁇ 75 pm, particularly preferably D 90 ⁇ 50 pm.
• the tellurium dioxide used may have a particle size D50 ⁇ 50 pm or ⁇ 35 pm.
• the niobium-containing starting compound which is preferably niobium oxide, likewise has a particle size with a D 90 ⁇ 100 ⁇ m, preferably D 90 ⁇ 75 ⁇ m, particularly preferably D 90 ⁇ 50 ⁇ m.
• the niobium-containing starting compound used which is preferably niobium oxide, have a particle size D50 ⁇ 50 pm or ⁇ 35 pm.
• all starting compounds used may have a particle size with a D 90 ⁇ 100 pm, preferably D 90 ⁇ 75 pm, more preferably D 90 ⁇ 50 pm.
• the Starting compounds have a particle size D50 ⁇ 50 pm or ⁇ 35 pm.
• the starting compounds e.g. Metal oxides used, such as tellurium dioxide
• the particle size D90 is defined as the limit of the particle diameter in the particle size distribution below which 90% of all particles are located.
• the particle size of the meridian, ie the particle size below which half of all particles are in the particle size distribution, is also referred to as particle size D50. It is particularly preferred that the particle size D50 for the tellurium dioxide used as the starting compound is less than 35 ⁇ m.
• the desired particle size D 90 or D 50 of the starting compound can be obtained by starting from a powder having a coarse-grained particle size distribution and mechanically comminuting the particles. This can be done by grinding, with all suitable and familiar to those skilled means can be used, such as hammer mills, planetary mills, mortars, etc.
• the starting compounds are the molybdenum, vanadium, niobium and tellurium-containing educts of the hydrothermal synthesis (precursor compounds). These each contain one or more of the elements molybdenum, vanadium, niobium or tellurium.
• the molybdenum-containing starting compound may be, for example, an ammonium heptamolybdate or molybdenum trioxide
• the vanadium-containing starting compound may be, for example, ammonium metavanadate, vanadyl sulfate or vanadium pentoxide
• the niobium-containing starting compound may be, for example, ammonium niobium oxalate, niobium oxalate or niobium oxide.
• the mixture of starting compounds is preferably present as an aqueous suspension and is treated hydrothermally.
• hydrothermally refers to reaction conditions for the preparation of a catalyst material in the presence of water and under elevated temperature and / or elevated pressure, for example in an autoclave, where the pressure may be in the range from 5 to 30 bar, preferably from 10 to 27 bar Exemplary pressure ranges are 11 to 15 bar, or about 17 bar and 22 to 25 bar.
• step b) gives a product suspension which contains the product as a solid.
• the separation of the solid from the product suspension in step c) 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.
• the first drying step is preferably at 60 to 150 ° C (more preferably at 80 to 120 ° C) and the second drying step at 200 to 350 ° C (more preferably at 220 ° C to 280 ° C) to perform.
• step c) of the process of the invention may include one or more of washing, drying, calcining, 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 is activated, for example, in a flowing or static inert gas atmosphere at about 500 to 700 ° C for at least 1 hour (step d).
• a flowing or static inert gas atmosphere at about 500 to 700 ° C for at least 1 hour.
• nitrogen, helium or argon is suitable as the inert gas. It is preferred if the activation takes place in the range of 550 ° C to 650 ° C. For example, activation may be at about 600 ° C for about 2 hours.
• the obtained MoVNbTe mixed oxide can be used as a catalyst material for the oxidation and / or oxidative dehydrogenation of hydrocarbons, in particular for the selective oxidation of propane to acrylic acid or for the oxidative dehydrogenation of ethane to ethylene. It typically has a BET surface area of 5 to 25 m 2 / g.
• the resulting catalyst material prepared by the process of the present invention 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 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 X-ray diffractogram of the MoVNbTe mixed oxide according to the invention formed by the method according to the invention has the diffraction reflectances h, i, k and 1 whose
• Ri Ph / (Ph + P ⁇ )> 0.3, preferably> 0.35 and more preferably> 0.4; and or
• R2 P ⁇ / (Pi + Pi)> 0.5, preferably> 0.6 and more preferably> 0.63; and or
• R3 Pi / (Pi + Pk) ⁇ 0.8, preferably ⁇ 0.75, especially
• the diffraction reflection i may have the second highest intensity and / or the diffraction reflection h have the third highest intensity.
• the obtained MoVNbTe mixed oxide is used in the examples as a catalyst material and therefore partially referred to in the experimental information as a catalyst.
• FIG. 2 XRD of the MoVNbTe mixed oxide from Example 1.
• FIG. 4 XRD of the MoVNbTe mixed oxide from Comparative Example 1.
• FIG. 5 Particle size distribution of Example 2
• FIG. 6 XRD of the mixed oxide material from Example 2.
• FIG. 7 Comparison of the particle size distribution of the b2Ü used in Example 3 before and after the grinding.
• FIG. 8 XRD of the MoVNbTe mixed oxide from Example 3.
• FIG. 9 XRD of the MoVNbTe mixed oxide from Comparative Example 3.
• 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 reactor was then cooled to room temperature, evacuated, and dipped in a Dewar flask with liquid nitrogen. Nitrogen adsorption was performed at 77 K with an RXM 100 sorption system (Advanced Scientific Design, Inc.).
• the determination of the BET surface area was made with respect to the respective samples of the MoVNbTe mixed oxide on the material dried at 200 ° C in a vacuum.
• the data in the present description regarding the BET surface areas of the MoVNbTe mixed oxide also refer to the BET surface areas of the particular catalyst material used (dried in vacuo at 200 ° C.).
• Powder X-ray diffraction The X-ray was created by powder X ⁇ diffractometry (XRD) and evaluation by the Scherrerformel. The XRD spectra were recorded at 600 ° C in
• Nitrogen activated catalyst materials measured.
• the phase evaluation was done using the Rietveld method with the software Topas
• Beakers were each 1.65 L dist. H2O with stirring on a magnetic stirrer with temperature control also heated to 80 ° C. Into these beakers were then each 405.10 g of vanadyl sulfate hydrate (of GfE, V content: 21.2%) and 185.59 g of ammonium niobium oxalate (HC Starck, Nb content: 20.6%) were added and dissolved (V solution and Nb solution).
• V solution was successively pumped into the AHM solution, then 65.59 g TeÜ2 powder as a solid (TeÜ2 of 5N + particle size distribution see Figure 1) and 1.65 L dist. H2O was added, stirring continued for 1 h at 80 ° C and finally pumped the Nb solution in the AHM solution by means of a peristaltic pump. Pumping time: V solution: 4.5 min at 190 rpm
• the resulting suspension was at 80 ° C for 10 min
• Precipitation was 90 rpm. Subsequently, it was overlaid with nitrogen by passing in
• 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.
• 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 calcination was carried out at 280 ° C for 4 h in the air stream (heating rate 5 ° C / min air: 1 L / min).
• the activation took place in a retort at 600 ° C. for 2 h in the N 2 flow (heating rate 5 ° C./min 2: 0.5 L / min).
• the particle size distribution of the TeÜ2 used was:
• XRD The XRD of the mixed oxide material from Example 1 is shown in FIG. 2 and has the following phase distribution:
• Beakers were each 3.3 L dist. H2O with stirring on a magnetic stirrer with temperature control also heated to 80 ° C. 810.21 g of vanadyl sulfate hydrate (GfE, V content: 21.2%) and 370.59 g were then added to these beakers Ammonium niobium oxalate (HC Starck, Nb content: 20.6%) was added and dissolved (V solution and Nb solution).
• Precipitation was 90 rpm.
• Autoclave was pressurized with N2 (5 min). At the end, the pressure was released via the vent valve, down to 1 bar residual pressure.
• 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.
• 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 0.5 kg was obtained.
• Comparative Example 1 is only about half as large as in the example according to the invention.
• the calcination was carried out at 280 ° C for 4 h in the air stream (heating rate 5 ° C / min air: 1 L / min).
• the XRD of the MoVNbTe mixed oxide of Comparative Example 1 is shown in FIG. 4 and has the following phase distribution:
• Vanadyl sulfate hydrate (GfE, V content: 21.2%) and 185.59 g
• Ammonium niobium oxalate (HC Starck, Nb content: 20.6%) was added and dissolved (V solution and Nb solution).
• TeÜ2 Alpha Aesar from Comparative Example 1
• V solution was successively pumped into the AHM solution, then the Te suspension ground the day before was added, stirring was continued for 1 h at 80 ° C. and finally the Nb solution was pumped into the AHM solution by means of a peristaltic pump. Pumping time: V solution: 5 min at 290 rpm
• Precipitation was 90 rpm.
• the hydrothermal synthesis in the 40 L autoclave was carried out at 175 ° C. for 20 h (heating time: 3 h) with an anchor stirrer at a stirrer speed of 90 rpm.
• the calcination was carried out at 280 ° C for 4 h in the air stream (heating rate 5 ° C / min air: 1 L / min). The activation took place in the retort at 600 ° C. for 2 h in the N 2 stream (heating rate 5 ° C./min 2: 0.5 L / min).
• the XRD of the MoVNbTe mixed oxide from Example 2 is shown in FIG. 6 and has the following phase distribution:
• TeÜ2 Alfa Aesar from Comparative Example 1 in 200 g of dist. H2O slurried and ground in the ball mill (as in Example 2). Subsequently, the portion with 500 ml of dist. Transferred H2O into a beaker. The b2Üs was distilled in 200 g. H2O slurried and ground in the same ball mill. A comparison of particle size distributions before and after milling is shown in FIG.
• a hydrothermal synthesis was carried out in a 40 L autoclave at 190 ° C for 48 h. After the synthesis was filtered by means of a vacuum pump with blue band filter and the
• 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 achieved.
• the calcination was carried out at 280 ° C for 4 h in the air stream (heating rate 5 ° C / min air: 1 L / min).
• the XRD of the MoVNbTe mixed oxide from Example 3 is shown in FIG. 8 and has the following phase distribution:
• Comparative Example 2 First, TeÜ2 (Alfa Aesar from Comparative Example 1) in 200 g of dist. H2O slurried and ground in the ball mill (as in Example 2) and then transferred with water into a beaker so that the volume in the beaker was 1650 ml of water.
• Citric acid 194 g of oxalic acid dihydrate, 19.9 g
• a hydrothermal synthesis was carried out in a 40 L autoclave at 190 ° C / 48 h. After the synthesis was with the help of a vacuum pump with
• 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 achieved.
• the calcination was carried out at 280 ° C for 4 h in the air stream (heating rate 5 ° C / min air: 1 L / min). The activation took place in the retort at 600 ° C. for 2 h in the N 2 stream (heating rate 5 ° C./min 2: 0.5 L / min).
• the XRD of the MoVNbTe mixed oxide from Comparative Example 3 is shown in FIG. 9 and has the following phase distribution:

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