Polynary metal oxide phosphate

INDUSTRIAL APPLICABILITY According to the present invention, a multi-element metal oxide phosphate containing vanadium and optionally at least one other metal, a method for producing the multi-element metal oxide phosphate, and a heterogeneous contact vapor phase oxidation, advantageously. The present invention relates to the use of the multidimensional metal oxide phosphate for heterogeneous catalytic vapor phase oxidation of hydrocarbons having at least 4 carbon atoms.

Vanadyl pyrophosphate (VO)₂P₂O₇Non-homogeneous catalysts based on (so-called VPO catalysts) are used during the industrial oxidation of n-butane to maleic anhydride and during the oxidation reaction of a series of other hydrocarbons.

Vanadyl pyrophosphate catalysts are typically prepared as follows: (1) Vanadyl hydrogen phosphate hemihydrate precursor (VOHPO)₄ 1 / 2H₂O) is a pentavalent vanadium compound (eg V)₂O₅), Phosphorus or trivalent phosphorus compounds (eg, ortho-and / or pyrophosphate, phosphate ester or phosphorous acid) and reducing alcohols (eg, isobutanol) to form a precipitate. Isolated, dried, and optionally molded (eg, tableted), and (2) the precursor was preformed by roasting with vanazyl pyrophosphate ((VO)).₂P₂O₇). See, for example, EP-A0520972 and WO 00/72963.

By using alcohol as a reducing agent, generally several mass% of an organic compound remains in the precursor in an enclosed state, and this organic compound cannot be removed even by careful washing. This organic compound adversely affects the catalytic properties of the catalyst during further catalyst production, especially during calcination. For example, during subsequent calcination, evaporation or thermal decomposition of the encapsulated organic compound occurs under the formation of gaseous components, which can lead to increased pressure inside the crystal and thus decomposition of the catalytic structure. This unfavorable effect is particularly pronounced during roasting under oxidizing conditions, because of the formation of oxidized decomposition products, such as carbon monoxide or carbon dioxide, which results in an essentially larger amount of gas. Is formed. Furthermore, the oxidation of this organic compound locally produces a very large amount of heat, which can lead to thermal damage to the catalyst.

In addition, the encapsulated organic compound has a significant effect on the local oxidation number of vanadium. For example, Kubias et al., In Chemie Ingenieur Technik 72 (3), 2000, pp. 249-251, anaerobic (under non-oxidizing conditions) the vanadyl hydrogen phosphate hemihydrate precursor obtained from an isobutanol solution. It proves the reducing effect of organic carbon during calcination. Anaerobic calcination gives an average oxidation number of 3.1 vanadium in the above examples, whereas aerobic calcination (under oxidative conditions) gives an average oxidation number of about 4 vanadium. ..

Proposals have also been made to add small amounts of divalent, trivalent or tetravalent transition metal oxides, so-called cocatalysts, to vanadyl pyrophosphate to improve catalytic behavior (GJ Hutchings, J. Mater. Chem. 2004, 14, 3385-3395; KV Narayana et al, Z. Anorg. Allg. Chem. 2005, 631, 25-30). Here, the mode of action of the co-catalyst has not been fully clarified at present.

No information has been taught in publications regarding the presence and catalytic behavior of single-phase multidimensional vanadium (IV) phosphates containing divalent, trivalent or tetravalent transition metals different from vanadium. Absent.

Mixed valence vanadium (III, IV) diphosphate, V^III₂(V^IVO) (P₂O₇)₂Has long been known and crystallographically characterized (see JW Johnson et al., Inorg. Chem. 1988, 27, 1646-1648). From BG Golovkin, VL Volkov, Russ. J. Inorg. Chem. 1987, 32, 739-741, diphosphate V as well.₃O₄(P₂O₇) Is known, but the description regarding its characterization is completely missing.

An object of the present invention is to provide a novel multidimensional vanadium oxide phosphate.

Another object of the present invention has been to provide a novel multidimensional vanadium oxide phosphate having catalytic properties for heterogeneous contact vapor phase oxidation.

Another object of the present invention has been to provide a novel multidimensional vanadyl oxide phosphate capable of altering the catalytic properties of known heterogeneous catalysts based on vanadyl pyrophosphate.

Another object of the present invention is to provide a novel method for producing multidimensional vanadium oxide phosphate and a heterogeneous contact gas phase oxidation method.

Accordingly, it has a crystal structure, general formula I M_aV_4-aO_{b b}(PO₄)_c[During the ceremony, M represents one or more metals selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In. a indicates a value from 0 to 2.0, b indicates a value from 2.0 to 4.0, c indicates a value from 2.0 to 4.0] In the multidimensional metal oxide phosphate of the above, the powder X-ray diffraction pattern of the crystal structure has the following lattice spacing d [Å] =<chemistry num="1"><img file="JP2010521402A_D0001.tif" /></chemistry>A metal oxide phosphate was found, which is characterized by diffractive reflections in.

In the present application, X-ray diffraction reflection is expressed in the form of lattice spacing d [Å] regardless of the wavelength of the X-ray used. The wavelength λ of the X-ray used for diffraction and the diffraction angle θ (in the present specification, the peak position of the reflection in the 2θ plot is used as the position of the diffraction reflection) are correlated by the following Bragg's equation. :: 2sinθ = λ / d Here, d is the lattice spacing of the three-dimensional atomic arrangement belonging to each diffraction reflection.

The powder X-ray diffraction pattern of the metal oxide phosphate of formula I according to the present invention is characterized by the above diffraction reflections. Diffractive reflections are generally the approximate relative intensities (I) shown in Table 1._rel[%]) Is shown. Other diffractive reflections of powder X-ray diffraction patterns, which are usually less intense than this, are not considered in Table 1.

Table 1<tables num="1"><img file="JP2010521402A_D0002.tif" /></tables>

However, depending on the crystallinity of the metal oxide phosphate according to the present invention and the texture of the obtained crystal, amplification or attenuation of the intensity of diffraction reflection in the powder X-ray diffraction pattern can occur. Attenuation can occur until the individual diffraction reflections in the powder X-ray diffraction pattern are no longer detectable.

It will be apparent to those skilled in the art that mixtures of metal oxide phosphates according to the present invention with other crystalline compounds have additional diffraction reflections. Mixtures of such metal oxide phosphates with other crystalline compounds can be intentionally produced by mixing metal oxide phosphates according to the invention, or metal oxide phosphates according to the invention. Can result from incomplete reactions of the starting material or the formation of heterogeneous phases with different crystal structures during the production of.

In one advantageous embodiment, in Formula I, a has a value of 0. In another advantageous embodiment, a has a value between 0.8 and 1.2.

Advantageously, in Equation I, b has a value between 2.8 and 3.2.

Advantageously, in Equation I, c has a value between 2.8 and 3.2.

In formula I, M is a metal selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In, or two or more of the metals. Represents a combination. Advantageously M represents a metal selected from Ti, Cr and Fe.

A particularly advantageous metal oxide phosphate according to the invention is the following formula: TiV₃O₃(PO₄)₃ V₄O₃(PO₄)₃ CrV₃O₃(PO₄)₃Or FeV₃O₃(PO₄)₃Have.

The metal oxide phosphate according to the present invention can be obtained in various ways.

The metal oxide phosphate according to the invention, on the one hand, can be obtained by solid reaction in a closed system. For this purpose, vanadium oxygen compounds, vanadium phosphorus compounds, vanadium mixed oxygen phosphorus compounds, element vanadium, metal M oxygen compounds, metal M phosphorus compounds, and metal M mixed oxygen phosphorus compounds, and elements. React at least two reactants selected from metal M.

In this case, the reactants are generally (i) the reactants provide the desired stoichiometry of the elements in formula I, and (ii) the valences of the elements other than oxygen in the reactants are multiplied by a factor. The sum of the products is selected to correspond to the sum of the products of the valences of the elements other than oxygen in Equation I multiplied by a coefficient. The starting compound may be selected such that all elements in the starting compound other than oxygen already have the same valence as the element has in Formula I. Instead, the starting compound is selected such that some or all of the non-oxygen elements in the starting compound have different valences than those elements have in Formula I. May be. By a redox reaction, eg, synproportionation, during a solid reaction, an element other than oxygen obtains the valence that the element has in Formula I. For example, an equivalent combination of vanadium (III) compound and vanadium (V) compound can be used, from which tetravalent vanadium is formed during the solid reaction.

The solid reaction is, for example, the following equations (1) to (3):<chemistry num="2"><img file="JP2010521402A_D0003.tif" /></chemistry>Proceed according to.

The required starting compounds in the form of oxides, phosphates, oxidized phosphates, phosphides, etc. are either commercially available or known in the literature, or are readily available to those skilled in the art similar to known production modalities. Can be synthesized.

The starting material is completely mixed, for example by milling. The solid reaction is typically carried out at a temperature of at least 500 ° C, for example 650 ° C to 1100 ° C, especially about 800 ° C. Typical reaction times are, for example, 24 hours to 10 days. Suitable reaction vessels consist of, for example, quartz glass or corundum.

Suitable mineralizing agents, such as iodine or PtCl, are advantageous during solid reactions to obtain products or single crystals with high crystallinity.₂Can be used together.

Unlike that a) Produce a dry mixture of vanadium source, optionally metal M source and phosphate source, b) Here, in some cases, by preparing a reduction equivalent, the vanadium and / or the metal M is transformed into the valence state of the vanadium and the metal M in Formula I, and c) Calcinate the dry mixture at at least 500 ° C Thereby, the metal oxide phosphate according to the present invention can be produced.

To this end, a suitable source of the elemental components of the metal oxide phosphate produces a dry mixture of fine particles that is as complete as possible in the desired component stoichiometric amount.

Complete mixing of the starting compounds can be done dry or wet.

When done dry, the starting compound is advantageously used as a fine powder and is calcinated (heat treated) after mixing and optionally consolidation.

However, advantageously, complete mixing is done wet, i.e. in dissolved or suspended form. In this case, the starting compounds are usually mixed with each other in the form of an aqueous solution (possibly in combination with a complexing agent) and / or a suspension. Subsequently, the aqueous solution or suspension is dried and then calcinated after drying.

Drying can be done by vacuum evaporation, freeze-drying, or conventional evaporation. However, advantageously the drying process is carried out by spray drying. The outlet temperature is usually 70-150 ° C; spray drying can be done in parallel or countercurrent.

Suitable vanadium sources are, for example, vanadyl sulphate hydrate, vanadyl acetylacetoneate, vanadate, such as ammonium metavanadate, vanadium oxide, for example divanadium pentoxide (V).₂O₅), Vanadium dioxide (VO₂) Or divanadium trioxide (V)₂O₃), Vanadium halides, such as vanadium tetrachloride (VCl)₄) And vanadyl halides, such as VOCl₃Is. Vanadium pentoxide and ammonium vanadate are advantageous sources of vanadium.

As a source for the metal M, compounds of all elements capable of forming oxides and / or hydroxides upon heating (possibly in the presence of molecular oxygen, eg air) are relevant. Of course, as such starting compounds, the elemental oxides and / or hydroxides may already be used in combination, or they may be used exclusively. Oxides, hydroxides and oxide hydroxides of metal M are advantageous sources of metal M.

Suitable phosphate sources are compounds containing phosphate bases or form phosphate bases by a redox reaction and / or upon heating (possibly in the presence of molecular oxygen, eg air). It is a possible compound. This includes phosphoric acid, especially orthophosphoric acid, pyro- or metaphosphoric acid, phosphite, hypophosphoric acid, phosphate or hydrogen phosphate, such as diammonium hydrogen phosphate and elemental phosphorus, such as white phosphorus. Is. Advantageously, the phosphate source is formed, at least in part, from phosphorous acid or hypophosphorous acid, optionally in combination with orthophosphoric acid.

As a source of vanadium or metal M, vanadium or metal M is more than the valence in formula I (ie, O present in formula I).^2-And PO₄^3-If compounds with higher valences (than the formal valences of V and possibly M) required to achieve electrical neutrality with anions are used, by advantageously preparing reduction equivalents. Vanadium and / or metal M must be transformed into the valence state of vanadium and metal M in Formula I.

The reduction equivalent is made from a reducing agent capable of reducing the polyvalent form of vanadium or metal M. The reduction is carried out during the preparation of the dry mixture or at the latest during calcination. Advantageously, the preparation of the completely dry mixture is to ensure improved control over the oxidation number, an inert gas atmosphere (eg N).₂) It is done below.

Advantageous reducing agents for this purpose are hypophosphorous acid, phosphite, hydrazine (as a free base or hydrate, or salts thereof, for example in the form of hydrazine dihydrochloride, hydrazine sulfate), hydroxylamine. From free bases or salts thereof, such as in the form of hydroxylamine hydrochloride, nitrosylamine, element vanadium, element phosphorus, borane (in the form of complex boron hydrides, eg sodium borohydride) or oxalic acid. Be selected. Phosphorous acid and / or hypophosphorous acid are advantageous reducing agents.

Of course, certain reducing agents, such as hypophosphorous acid or phosphorous acid, can be used simultaneously as phosphate sources, or elemental vanadium can be used simultaneously as vanadium sources.

The dry mixture is heat treated at a temperature of at least 500 ° C, preferably 700-1000 ° C, especially about 800 ° C. The heat treatment can be performed in an oxidizing atmosphere, a reducing atmosphere, and further in an inert atmosphere. The oxidizing atmosphere corresponds to, for example, air, molecular oxygen-enriched air, or oxygen-enriched air. However, advantageously the heat treatment is carried out under an inert atmosphere, eg, under molecular nitrogen and / or a rare gas. Heat treatment is usually performed at normal pressure (1 atm). Of course, the heat treatment can also be performed under vacuum or overpressure.

When the heat treatment is performed in a gaseous atmosphere, the atmosphere may be stationary or fluid. Advantageously, the atmosphere is fluid. Overall, the heat treatment can take up to 24 hours or more.

The present invention further relates to a gas phase oxidation catalyst containing at least one multidimensional metal oxide phosphate according to the present invention. The metal oxide phosphate can be used as it is, for example as a powder, or as a heterogeneous catalyst in the form of a molded product.

Advantageously, the molding is done by tableting. For tableting, the powder is generally added with a tableting aid and completely mixed.

Tableting aids are usually catalytically inert and improve the tableting properties of the powder, for example by improving slipperiness and fluidity. Suitable and advantageous tableting aids include graphite or boron nitride. The added tableting aid usually remains in the activated catalyst.

The powder is tableted and subsequently crushed into crushed pieces.

Molding into a molded body may be carried out, for example, by applying to a carrier a mixture containing at least one metal oxide phosphate according to the present invention or at least one metal oxide phosphate according to the present invention. it can.

The carrier is advantageously chemically inert. That is, the carrier essentially does not interfere with the progress of catalytic vapor phase oxidation catalyzed by the metal oxide phosphate according to the invention.

Materials for carriers include, in particular, aluminum oxide, silicon dioxide, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide.

The surface of the carrier may be smooth or rough. It is advantageous for the surface of the carrier to be rough, as the increased surface roughness usually results in increased adhesion of the applied active material shell.

Further, the carrier material may be porous or non-porous. Advantageously the carrier material is non-porous, i.e., the total volume of pores is advantageously less than 1% by volume with respect to the volume of the carrier.

The thickness of the catalytically active layer is usually 10 to 1000 μm, for example 50 to 700 μm, 100 to 600 μm or 150 to 400 μm.

In principle, a carrier having a structure of an arbitrary shape can be mentioned. Its longitudinal extension is usually 1-10 mm. However, advantageously, a sphere or cylinder, especially a hollow cylinder, is used as the carrier.

The production of the shell-type catalyst is extremely simple, in which the metal oxide phosphate material of the general formula (I) is preformed, converted into a fine form, and subsequently applied to the surface of the carrier using a liquid binder. Performed in style. To this end, the surface of the carrier is moistened with a liquid binder in a very simple manner, and contact with the fine metal oxide phosphate material causes a layer of active material to adhere to the moistened surface. Finally, the coated carrier is dried. Not surprisingly, this process is repeated to achieve greater layer thickness.

The metal oxide phosphate according to the invention can also be used to alter catalytic properties, in particular the conversion and / or selectivity of known vanadyl pyrophosphate-based catalysts. For this purpose, the metal oxide phosphate according to the present invention can be used, for example, as a co-catalyst phase in a vanadyl pyrophosphate-based catalyst. In that case, the catalyst advantageously comprises the first phase and the second phase in the form of a three-dimensionally extending range, and the range and the local surroundings of the range are separated by different chemical compositions. In this case, the first phase contains a catalytically active material based on vanadyl pyrophosphate, and the second phase contains at least one multidimensional metal oxide phosphate according to the present invention. In this case, (i) the fine particles of the second phase are dispersed in the first phase, or (ii) the first phase and the second phase are mutually fine-grained first. It is distributed like a mixture of a phase and a finely granular second phase.

The production of the two-phase catalyst described above includes, for example, vanadyl hydrogen phosphate hemihydrate precursor (VOHPO).₄ 1 / 2H₂O) can be produced and this can be done by mixing with the preformed particles of the second phase from the metal oxide phosphate according to the invention, molding and calcining the resulting material. it can. The vanadyl phosphate hemihydrate precursor is a compound of pentavalent vanadium (eg V) by a method known per se.₂O₅), A compound having pentavalent or trivalent phosphorus (eg, ortho-and / or pyrophosphate, phosphate ester or phosphorous acid) and a reducing alcohol (eg, isobutanol) to synthesize a precipitate. It can be obtained by isolation. See, for example, EP-A0520972 and WO 00/72963.

The catalyst according to the invention, wherein the catalytically active material contains at least one metal oxide phosphate as defined above, and a vanadyl pyrophosphate-based catalyst can also be combined in the form of structured packing. For example, a gas stream containing a hydrocarbon and molecular oxygen to be oxidized is subjected to a first gas phase oxidation catalyst layer located upstream in the flow direction of the gas stream, and then a second or other gas phase located downstream. One or more layers of the oxidation catalyst can be conducted, in which case the first layer or the second layer or one of the other layers comprises the catalyst according to the invention.

The present invention further relates to a partial vapor phase oxidation method or an ammoxidation method in which a gas stream containing hydrocarbons and molecular oxygen is brought into contact with the catalyst according to the present invention. In the case of ammoxidation, the gas stream additionally contains ammonia. Ammoxidation is a heterogeneous contact process that, within the scope of the present invention, reacts methyl-substituted alkenes, allenes and hetarene with ammonia and oxygen in the presence of a transition metal catalyst to convert them to nitriles. Is interpreted as.

The partial vapor phase oxidation method is utilized in an advantageous embodiment of the production of maleic anhydride, wherein the hydrocarbon used comprises at least 4 carbon atoms.

The partial vapor phase oxidation method or ammoxidation method according to the present invention is generally used in a tube bundle type reactor. It can also be used in fluidized bed reactors.

Hydrocarbons generally include aliphatic and aromatic, saturated and unsaturated hydrocarbons having at least 4 carbon atoms, such as 1,3-butadiene, 1-butene, cis-2-butene, trans-2-butene. , N-butene, C₄-Mixed, 1,3-pentadiene, 1,4-pentadiene, 1-pentene, cis-2-pentene, trans-2-pentene, n-pentane, cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, C₅-Mixtures, hexene, hexane, cyclohexane and benzene are suitable. 1,3-butadiene, 1-butene, cis-2-butene, trans-2-butene, n-butane, benzene or mixtures thereof are advantageously used.

The use of n-butane and n-butane-containing gases and liquids is particularly advantageous. The n-butane used may be, for example, from a rare gas, from a steam cracker, or from an FCC cracker.

The addition of hydrocarbons is generally carried out under metering, i.e., under a certain standard of a predetermined amount per hour. Hydrocarbons can be supplied in liquid or gaseous form. Liquid supply and subsequent evaporation in front of the reactor inlet are advantageous.

As the oxidant, oxygen-containing gases such as air, synthetic air, oxygen enriched gases or so-called "pure oxygen" (ie, eg, oxygen derived from aerobic decomposition) are used. Oxygen-containing gas is also advantageously added under metering.

The gas conducting the reactor generally has a hydrocarbon concentration of 0.5 to 15% by volume and an oxygen concentration of 8 to 25% by volume. The balance up to 100% by volume is other gases such as nitrogen, rare gas, carbon monoxide, carbon dioxide, water vapor, oxygen-containing hydrocarbons (eg methanol, formaldehyde, formic acid, ethanol, acetylaldehyde, acetic acid, propanol). , Propionaldehyde, propionic acid, acrolein, crotonaldehyde) and mixtures thereof. In the case of selective oxidation of n-butane, the n-butane content with respect to the total amount of hydrocarbons is preferably more than 90%, especially more than 95%.

In order to achieve a long catalyst life and further improvement in conversion, selectivity, yield, catalyst loadability and space-time yield, the method according to the invention favorably supplies the gas with a volatile phosphorus compound. To.

Its concentration is at least 0.2 parts per million at the reactor inlet, i.e. the volume integral of the volatile phosphorus compound relative to the total volume of gas at the reactor inlet 0.2-10.^-6Is. A content of 0.2 to 20 parts per million, particularly preferably 0.5 to 10 parts per million, is advantageous.

Volatile phosphorus compounds are interpreted as all phosphorus-containing compounds that are present in the form of gaseous at the desired concentration under conditions of use. Suitable volatile phosphorus compounds include, for example, phosphine and phosphate esters. C₁-C₄-Alkyl-phosphate esters are particularly advantageous, with trimethyl phosphate, triethyl phosphate and tripropyl phosphate, especially triethyl phosphate.

The method according to the invention is generally carried out at a temperature of 300-500 ° C. The above temperature is interpreted as the temperature of the catalyst layer present in the reactor, which is present in the absence of a chemical reaction during the implementation of the method.

If the temperatures are not exactly equal at all points, the concept means a number mean of temperatures along the reaction region. In particular, this means that the actual temperature on the catalyst can be outside the above range based on the heat generated by the oxidation reaction. Advantageously, the method according to the invention is carried out at a temperature of 380 to 460 ° C, particularly preferably 380 to 430 ° C.

The method according to the invention can be carried out at a pressure below normal pressure (eg, up to 0.05 MPa abs) and above normal pressure (eg, up to 10 MPa abs). The pressure may be interpreted as the pressure in the reactor unit. Pressures of 0.1 to 1.0 MPa abs, especially preferably 0.1 to 0.5 MPa abs, are advantageous.

The method according to the invention can be carried out in two advantageous variants, one with a "straight path" and one with a "return". In the case of a "linear path", maleic anhydride and optionally oxygenated hydrocarbon by-products are removed from the reactor emissions and the residual gas mixture is exhausted and optionally heat is utilized. In the case of "return", the residual gas mixture, which also removes maleic anhydride and optionally oxygenated hydrocarbon by-products from the reaction emissions and contains unreacted hydrocarbons, is completely or partially removed. Return to the reactor. Another variant of "return" is the removal of unreacted hydrocarbons and their return to the reactor.

In a particularly advantageous embodiment for producing maleic anhydride, n-butane is used as the starting hydrocarbon and heterogeneous catalytic vapor phase oxidation is carried out on the catalyst according to the invention in a "linear pathway". ..

The present invention will be described in detail with reference to the accompanying figures and the following examples.

Figure 1 shows the V obtained by the solid reaction.₄O₃(PO₄)₃Shows the Guinier statue of.

Figure 2 shows the CrV obtained by the solid reaction.₃O₃(PO₄)₃Shows the Guinier statue of.

Figure 3 shows the FeV obtained by the solid reaction.₃O₃(PO₄)₃Shows the Guinier statue of.

Figure 4 shows the TiV obtained by the solid reaction.₃O₃(PO₄)₃Shows the Guinier statue of.

Figure 5 shows the V obtained by calcinating a spray-dried precursor in the air.₄O₃(PO₄)₃The powder X-ray diffraction pattern of is shown.

Figure 6 shows FeV obtained by calcinating a spray-dried precursor in the air.₃O₃(PO₄)₃The powder X-ray diffraction pattern of is shown.

Camera FR-552 (Delft, Nonius) used with image plate film (Y. Amemiya, J. Miyahara, NATURE 1988, 336, 89-90) for X-ray diffraction testing by Guinier technology Was (CuK_α1Wire, λ = 1.54051Å, α-quartz monochromator, α-SiO₂, As an internal standard). See K. Maass, R. Glaum, R. Gruehn, Z. anorg. Allg. Chem. 2002, 628, 1663-1672.

All remaining X-ray diffraction tests are CuK as X-rays_αBased on X-ray diffraction pattern obtained using wire (λ = 1.54178Å) (Siemens diffractometer Theta-Theta D-5000: tube voltage: 40kV, tube current: 40mA, aperture V20 (variable), collimator V20 (variable), secondary monochromator aperture (0.1 mm), detector aperture (0.6 mm), measurement interval (2θ): 0.02 [°], measurement time per step: 2.4s, detector: scintillation counter) ..

<figref num="1">V obtained by solid reaction₄O₃(PO₄)₃The figure which shows the Guinje image of.</figref><figref num="2">CrV obtained by solid reaction₃O₃(PO₄)₃The figure which shows the Guinje image of.</figref><figref num="3">FeV obtained by solid reaction₃O₃(PO₄)₃The figure which shows the Guinje image of.</figref><figref num="4">TiV obtained by solid reaction₃O₃(PO₄)₃The figure which shows the Guinje image of.</figref><figref num="5">V obtained by calcinating a spray-dried precursor in the air₄O₃(PO₄)₃The figure which shows the powder X-ray diffraction pattern of.</figref><figref num="6">FeV obtained by calcination of spray-dried precursors in air₃O₃(PO₄)₃The figure which shows the powder X-ray diffraction pattern of.</figref>

A. Production of metal oxide phosphate of formula I Example 1: V by solid reaction₄O₃(PO₄)₃Manufacturing of First, V₂O₅(pa, Merck Eurolap GmbH, Darmstadt, Germany) and V₂O₃(V with hydrogen at 1073K₂O₅[See G. Brauer, A. Simon, Handbuch der Praeparativen Anorganischen Chemie, G. Brauer (Hrsg.), Ferd. Enke Verlag, Stuttgart 1981, p. 1419]) in a closed silica glass ampoule. Then, at T = 1073K, by leveling with the addition of 80 mg of iodine as a mineralizing agent, VO₂Manufactured. As another starting material, VPO₄(R. Glaum, R. Gruehn, Z. Kristallogr. 1992, 198, 41-47) and (VO)₂P₂O₇Was synthesized. VO (HPO)₄) 1 / 2H₂Pyrophosphate was produced by heating O in an argon stream at 1073 K (JW Johnson, DC Johnston, AJ Jacobson, JF Brody, J. A-mer. Chem. Soc. 1984, 106, 8123-8128). .. Vanadyl hemihydrate hydrogen phosphate is previously V in n-butanol.₂O₅And H₃PO₄Precipitated by boiling under reflux (85% pa, Merck Eurolap GmbH, Darmstadt, Germany).

Finally, the title compound is VO₂ 63.9mg, VPO₄ 112.4 mg and (VO)₂P₂O₇ It was obtained by a reaction of 237.0 mg. To this end, the starting material was milled in an agate mortar, compressed into tablets and heated at 1073 K in a closed and degassed silica glass ampoule for 5 days. The use of corundum crucibles avoided the reaction between the tablet and the ampoule wall.

The table below shows the selected unique X-ray diffraction reflections obtained by evaluation of the Guinier image (Fig. 1).

<tables num="2"><img file="JP2010521402A_D0004.tif" /></tables>

Using DTA, the melting point of the title compound was determined to be 1180 K. PtCl as a mineralizing agent₂Add a few mg just below the melting point of the title compound, VO₂, VPO₄And (VO)₂P₂O₇By isothermally heating the starting material mixture from, black equiaxed crystals with edge lengths up to 0.2 mm were formed. Based on the single crystal data, the space groups F2dd (No.43) Z = 24, a = 7.2596 (8) Å, b = 21.786 (2) Å, c = 38.904 (4) Å were found.

Example 2: CrV by solid reaction₃O₃(PO₄)₃Manufacturing of First, the stoichiometric Cr (NO)₃)₃ 9H₂O (Sigma Aldrich Laborchemikalien GmbH, Riedel-de Haen Brand, Seelze, Germany) and NH₄H₂PO₄Evaporate an aqueous solution of (pa, Merck Eurolap GmbH, Darmstadt, Germany) and then remove the dry residue in air at 1273 K, J.-P. Attfield, PD Battle, AK Cheetham, J. Solid State Chem. 1985, Β-CrPO by heating as described in 57, 357-361₄Manufactured.

Then VO₂ 45.8mg, β-CrPO₄ 81.2 mg and (VO)₂P₂O₇ 170 mg was milled in an agate mortar, compressed into tablets, heated in a closed and degassed silica glass ampoule at 753 K for 24 hours, then heated at 1073 K for 5 days.

The table below shows the selected unique X-ray diffraction reflections obtained by evaluation of the Guinier image (Fig. 2).

<tables num="3"><img file="JP2010521402A_D0005.tif" /></tables>

Example 3: FeV by solid reaction₃O₃(PO₄)₃Manufacturing of First, the stoichiometric Fe (NO)₃)₃ 9H₂O (pa, Merck Eurolap GmbH, Darmstadt, Germany) and NH₄H₂PO₄FePO by evaporating an aqueous solution of (pa, Merck Eurolap GmbH, Darmstadt, Germany) and then heating the dry residue in air at 1273 K.₄Manufactured.

Then VO₂ 71.0mg, FePO₄ 132.9 mg and (VO)₂P₂O₇ 263.8 mg was milled in an agate mortar, compressed into tablets, closed and heated in a degassed silica glass ampoule at 753 K for 24 hours, then at 1000 K for 6 days.

The table below shows the selected unique X-ray diffraction reflections obtained by evaluation of the Guinier image (Fig. 3).

<tables num="4"><img file="JP2010521402A_D0006.tif" /></tables>

Example 4: TiV by solid reaction₃O₃(PO₄)₃Manufacturing of First, Ti (HPO₄)₂ H₂TiP is pyrolyzed by gradually raising O to 1073 K and thermally decomposing it.₂O₇Manufactured. Concentrated phosphoric acid (85%, ultra-high) as described in S. Bruque, Miguel AG Aranda, Enrique R. Losilla, Pascual O. -Pastor und P. Maireles- Torres, Inorg. Chem., 1995, 34, 893-899. Purity, TiO in Merck Eurolap GmbH, Darmstadt, Germany)₂Ti (HPO) by hydrolysis of (Industrial, Sigma Aldrich Laborchemikalien GmbH, Riedel-de Haen Brand, Seelze, Germany)₄)₂ H₂Manufactured O.

TiP to produce the title compound₂O₇ 75.9mg, V₂O₃ 52.3mg and VOPO₄ 55.9 mg was placed in a small corundum crucible. PtCl as a mineralizing agent₂ It was dissolved in a degassed ampoule with 25 mg and heated at 753 K for 24 hours and then at 1000 K for 6 days.

The table below shows the selected unique X-ray diffraction reflections obtained by evaluation of the Guinier image (Fig. 4).

<tables num="5"><img file="JP2010521402A_D0007.tif" /></tables>

Example 5: V₄O₃(PO₄)₃Manufacture (catalyst A1) Water 2.5L, V in a glass reactor purged with fluidized nitrogen₂O₅[&gt; 99%, 8 mol, calculated as V] (GfE Umwelttechnik GmbH, Nuremberg, Germany) 727.5 g, H₃PO₄[85%, calculated as 1 mol, P] (Sigma Aldrich, Seelze, Germany) 115.3 g and H₃PO₃[50%, 5 mol, calculated as P] (Sigma Aldrich, Seelze, Germany) 820.0 g was added. The mixture was heated to 90 ° C. under vigorous stirring and stirred at this temperature for 2 hours. Spray dryer (Soborg, Denmark, Mobile Minor, manufactured by Niro A / S) for suspensions produced in this way.^TM 2000, MM, inlet temperature: 330 ° C, outlet temperature: 107 ° C) and dried under nitrogen atmosphere. The obtained solid was baked at 800 ° C. for 2 hours in a quartz rotating tube having an internal volume of 1 L in a nitrogen atmosphere.

The obtained powder is 3.0m²It had a BET specific surface area of / g. A powder X-ray diffraction pattern was obtained from the obtained powder. From this powder X-ray diffraction pattern (Fig. 5), the following 2θ values and the associated intensities I and lattice spacing d were found.

<tables num="6"><img file="JP2010521402A_D0008.tif" /></tables>

Example 6: CrV₃O₃(PO₄)₃Manufacture (catalyst A2) Water 2.5L, V in a glass reactor purged with fluidized nitrogen₂O₅[&gt; 99%, calculated as 3 mol, V] (GfE Umwelttechnik GmbH, Nuremberg, Germany) 272.8g, CrO₃[Calculated as&gt; 99%, 1 mol, Cr] (Sigma Aldrich, Seelze, Germany) 100.0 g and H₃PO₃[50%, 3 mol, calculated as P] (Sigma Aldrich, Seelze, Germany) 492.0 g was added. The mixture was heated to 90 ° C. under vigorous stirring and stirred at this temperature for 2 hours. Spray dryer (Soborg, Denmark, Mobile Minor, manufactured by Niro A / S) for suspensions produced in this way.^TM 2000, MM, inlet temperature: 330 ° C, outlet temperature: 107 ° C) and dried under nitrogen atmosphere. The obtained solid was baked in a nitrogen atmosphere in a quartz rotating tube having an internal volume of 1 L at 775 ° C for 2 hours.

The obtained powder is 1.0m²It had a BET specific surface area of / g. A powder X-ray diffraction pattern was obtained from the obtained powder. From this powder X-ray diffraction pattern, the following 2θ values and the associated intensities I and lattice spacing d were found.

<tables num="7"><img file="JP2010521402A_D0009.tif" /></tables>

Example 7: FeV₃O₃(PO₄)₃Manufacture (catalyst A3) Water 6.0L, V in a glass reactor purged with fluidized nitrogen₂O₅[&gt; 99%, 8.25 mol, calculated as V] (GfE Umwelttechnik GmbH, Nuremberg, Germany) 750.0 g, FeOOH [95%, 2.75 mol, calculated as Fe] (Sicopur^(R) Gelb, BASF, Germany) 257.1g and H₃PO₄[85%, 4.12 mol, calculated as P] (Sigma Aldrich, Seelze, Germany) 475.4 g and H₃PO₃[50%, 4.12 mol, calculated as P] (Sigma Aldrich, Seelze, Germany) 676.2 g was added. The mixture was heated to 90 ° C. under vigorous stirring and stirred at this temperature for 2 hours. Spray dryer (Soborg, Denmark, Mobile Minor, manufactured by Niro A / S) for suspensions produced in this way.^TM 2000, MM, inlet temperature: 330 ° C, outlet temperature: 107 ° C) and dried under nitrogen atmosphere. The obtained solid was baked in a quartz rotating tube having an internal volume of 1 L in a nitrogen atmosphere at 600 ° C. for 2 hours, and then at 800 ° C. for 2 hours.

The obtained powder is 0.7m²It had a BET specific surface area of / g. A powder X-ray diffraction pattern (Fig. 6) was obtained from the obtained powder. From this powder X-ray diffraction pattern, the following 2θ values and the associated intensities I and lattice spacing d were found.

<tables num="8"><img file="JP2010521402A_D0010.tif" /></tables>

B Catalytic testing of catalysts A1, A2 and A3 by selective oxidation of n-butane or 1-butene in the gas phase The catalysts A1, A2 to A3 were compressed with a tablet molding machine into tablets, which were then pulverized into granules (crushed pieces) having a diameter in the range of 1.6 to 2.0 mm.

From the bottom to the top, a reactor consisting of a reaction tube with an inner diameter of 13 mm and a length of 100 cm is filled with a preliminary layer of steatite spheres with a diameter of 2 mm and a reserve layer of 5 cm, and 85 cm of crushed fragments of catalysts A1, A2 to A3. did. During the test for oxidation of 1-butene, the catalyst was mixed with 88% by volume (A1), 75% by volume (A2) to 50% by volume (A3) of the inert material (steatite spheres). The reaction tube was surrounded by an electric heating jacket for temperature control. In addition, the reaction tube contained a thermocouple with a diameter of 3.17 mm for temperature measurement on the catalyst. A gas mixture having a composition of n-butane or 1-butene-air (1% by volume in air) was conducted through the pipes from above to below, respectively. Gas phase oxidation was performed at the temperatures shown in the table below. Immediately after the reactor, the gaseous product was removed and analyzed by gas chromatography. The results obtained are as follows:<tables num="9"><img file="JP2010521402A_D0011.tif" /></tables>

<tables num="10"><img file="JP2010521402A_D0012.tif" /></tables>

Definition: GHSV (Gas Houly Space Velocity) = V_{Inlet gas mixture}/ (V_catalyst T) Conversion rate X = (n_{KW, reactor entrance}-n_{KW, reactor outlet}) / N_{KW, reactor entrance} Selectivity S = n_{MSA, reactor outlet}/ (n_{KW, reactor entrance}-n_{KW, reactor outlet}) Yield Y = X · S n_MSA: Amount of substance of maleic anhydride produced [mol] n_KW: Amount of substance of hydrocarbon at reactor inlet or reactor outlet [mol] V_catalyst: Catalyst layer volume [L] t: Hour unit [h] V_{Inlet gas mixture}Volume of inlet gas mixture normalized to 0 ° C, 0.1013 MPa [NL] (theoretical parameter. If the inlet gas mixture or one component thereof is present in gas phase or solid under these conditions, the provisional gas volume Calculated according to the law of ideal gas)