WO2009106474A2 - Catalyseur à phase enrichie à base de mélange d'oxydes de mo-v-te-nb, et procédé d'élaboration - Google Patents

Catalyseur à phase enrichie à base de mélange d'oxydes de mo-v-te-nb, et procédé d'élaboration Download PDF

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WO2009106474A2
WO2009106474A2 PCT/EP2009/051961 EP2009051961W WO2009106474A2 WO 2009106474 A2 WO2009106474 A2 WO 2009106474A2 EP 2009051961 W EP2009051961 W EP 2009051961W WO 2009106474 A2 WO2009106474 A2 WO 2009106474A2
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phase
metal oxide
catalyst
catalyst material
treatment
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PCT/EP2009/051961
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WO2009106474A3 (fr
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Olaf Timpe
Ayyamperumal Sakthivel
Annette Trunschke
Robert SCHLÖGL
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Olaf Timpe
Ayyamperumal Sakthivel
Annette Trunschke
Schloegl Robert
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Priority to DE112009000404T priority Critical patent/DE112009000404T5/de
Publication of WO2009106474A2 publication Critical patent/WO2009106474A2/fr
Publication of WO2009106474A3 publication Critical patent/WO2009106474A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present: invention concerns a metal oxide catalyst (material) and methods for the preparation thereof, as well as its use in the oxidation of hydrocarbons . More specifically, the present invention relates to a catalyst (material) comprising oxides of Mo, V, Te, and Nb, said catalyst being strongly enriched in ⁇ .1 phase, and its use in the oxidation of hydrocarbons to e.g. unsaturated carboxylic acids such as acrylic acid and methacrylic acid.
  • Multi-metal oxides based on molybdenum, vanadium, tellurium and niobium with a nominal composition of approximately M o l v 0.3 Te 0.23 Nb 0.125 0 X are known from US 5,380,933 and have been reported to achieve outstanding performance as catalyst in the oxidation of alkanes, in particular in the conversion of propane to acrylic acid.
  • such materials normally essentially consist of two orthorhombic phases known as Ml and M2 [T. Ushikubo, K. Oshinxa, A. Kayou and M.
  • Niobium has been postulated to be exclusively located in the centre of a MO7 pentagonal bi-pyramidal unit sharing edges with the surrounding octahedrons [P. DeSanto, et al. ibid.; H. Murayama, et al., ibid.].
  • the (001) planes are congruently stacked along the [001] direction, forming a bronze-like structure similar to the structure of Cs ⁇ _ 7 (Nb2 , 7W2 3)Ol4 (ICSD 67974 [Inorganic Crystal Structure Database, suZ) Düsseldorf, Germany; M. Lundberg and M. Sundberg, Ultramicroscopy 52 (1993) 429]).
  • the M2 phase differs from Ml by the absence of the pentagonal bi- pyramidal unit, and the 7-membered ring [P. DeSanto, et al., ibid.].
  • the formulae of the refined unit cells have been determined to be M07 _ g v l .2 NbTe 0.937°28.9 for M1 and M°4.31 V 1.36 ⁇ e l .81 N ⁇ 0.33 ⁇ 19.81 f° r M2, respectively [P. DeSanto, et al., ibid.].
  • ammonium heptamolybdate, ammonium metavanadate and telluric acid are dissolved in water, followed by the addition of ammonium niobium oxalate to precipitate a slurry, which is then spray-dried.
  • ammonium niobium oxalate is then spray-dried.
  • the final activation of the catalyst is conducted substantially in the absence of oxygen at much higher temperatures of typically 600 to 65O 0 C.
  • This preparation method usually results in catalysts composed of several phases including a mixture of Ml and M2 phase [P. Beato, A, Blume , F. Girgsdi.es, R. E. Jentoft, R.
  • MoVTeNb oxide is hydrothermally synthesized by dissolving (NH4)gM ⁇ 7 ⁇ 24 and telluric acid in water and adding solutions of VOSO4 and niobium oxalate thereto. The resulting slurry is stirred at 8O 0 C before being introduced into an autoclave which is heated at 175 0 C for 48 hours.
  • the catalysts were calcined under nitrogen flow at 500 or 600 0 C for 2 hours prior to catalytic tests. Ueda specifically evaluates the catalytic properties of orthorhombic Mo ⁇ Vg _ 25 Te 0. ll Nb 0.12 0 X and found low conversion and medium selectivity values of 33% C3H8 conversion and 62% acrylic acid selectivity, respectively.
  • the present invention relates to:
  • a metal oxide catalyst material comprising a mixed metal oxide comprising molybdenum (Mo) , vanadium (V) ,
  • Te Tellurium
  • Nb niobium
  • said metal oxide catalyst material has a crystallinity degree of at least 80wt.-% and a content of Ml phase in an amount of at least 85wt.-% based on the entire amount of crystalline metal oxide phase and is obtainable by the above method, and preferably has an average composition which lies within the ranges defined by general formula (I) :
  • x is the molar number of oxygen binding to the metal atoms present in this mixed metal oxide which follows from the relative amount and valence of the metals elements, and 2 is at least one element selected from Ru, Mn, Sc, Ti, Cr, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, Rh, Pd, In, Sb, Ce, Pr, Nd, Te, Sm, Tb, Ta, W, Re, Ir, Pt, Au, Pb, and Bi, as well as
  • a metal oxide catalyst material comprising a mixed oxide comprising molybdenum (Mo) , vanadium (V) , Tellurium (Te) and niobium (Nb) wherein said metal oxide catalyst material has a crystallinity degree of at least 80wt. ⁇ % and comprises Ml phase in an amount of at least 85wt.-% based on the entire amount of crystalline metal oxide catalyst phase and an average composition within the ranges defined by the following formula (II) :
  • a method for producing an oxidized hydrocarbon from a hydrocarbon which comprises subjecting the hydrocarbon to a vapour phase catalytic oxidation reaction in the presence of oxygen and a catalyst comprising a metal oxide catalyst material as defined above, preferably a method wherein the hydrocarbon is an alkane and the oxidized hydrocarbon is an unsaturated carboxylic acid; and
  • a method for increasing the content of Ml phase in a calcined metal oxide catalyst comprising a mixed oxide comprising molybdenum (Mo) , vanadium (V) , Tellurium (Te) and niobium (Nb), which comprises the step of subjecting the calcined metal oxide catalyst to a treatment at a pressure of at least lOMPa and a temperature of at least 400 0 C in the presence of an inert fluid phase, which can be advantageously used in the regeneration of these calcined catalysts.
  • Mo molybdenum
  • V vanadium
  • Te Tellurium
  • Nb niobium
  • Fig. 1 shows a SEM image of a catalyst material sample (MoVTeNbO x ) which was treated according to Example 1 at 500 0 C (773K) in superheated water prior to a final activation treatment .
  • Fig. 2 shows a SEM image of the catalyst material sample according to Fig. 1 after the final activation treatment.
  • Fig. 3 shows XRD patterns [(a) to (c) ] of samples taken at various stages of the preparation of MoVTeNbO x according to example 1 and one Ml reference material [ (d) ] .
  • a-b, a-c, b-d or c-d which can be formed by combining any of the upper limit or the lower limit of this explicitly defined broader quantitative range with the lower limit or the upper limit of any explicitly defined and included (preferred) narrower range .
  • a catalyst precursor mixture comprising at least the four elements molybdenum (Mo) , vanadium (V) , tellurium (Te) and niobium (Nb) and optionally other catalyst metal elements such as Z defined below (in the following also abbreviated as "catalyst metals") is subjected to a calcination treatment in an oxygen-containing atmosphere (air or a synthetic oxygen- containing atmosphere) at a temperature of 150 to 400 0 C to prepare a calcined catalyst precursor.
  • Mo molybdenum
  • V vanadium
  • Te tellurium
  • Nb niobium
  • Z niobium
  • the catalyst precursor mixture to be calcined in the first step of the claimed method can be obtained according to any commonly known process.
  • starting material for the catalyst precursor mixture we understand chemical compounds that comprise catalyst metals and can be converted to metal oxides in the calcination treatment or already contain such oxides (the expression “can be converted” does not exclude that this conversion already takes place at least in part at an earlier point in time, for instance during drying at higher temperature) .
  • the starting material is preferably selected from salts of the catalyst metals, metal-containing acids, in particular oxyacids, metalorganic compounds, organic metal complexes and metal oxides. More preferably it is selected from organic salts and (oxy) acids. It is possible to prepare the catalyst precursor mixture by combining as many metal-containing starting materials as metals are to be included in the final catalyst or by adding at least one starting material that contains more than one of these metals.
  • the catalyst precursor mixture is prepared in a wet mixing method which preferably comprises the steps of
  • salts and/or acids comprising molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb), and optionally at least one further metal to be added to the catalyst such as element Z defined below, in a solvent,
  • Steps (b) , (c) and (d) can be performed subsequently or simultaneously, as in one preferred embodiment of the present invention (spray-drying) .
  • suitable starting materials are typically dissolved or dispersed in predetermined ratios in an appropriate solvent, if required under heating, and combined.
  • the subsequent isolation of a dry catalyst precursor mixture can be effected in an usual manner by e.g. filtration, evaporation to dryness (e.g. rotary evaporation), spray drying, freeze drying, drying at ambient air and/or vacuum drying .
  • Solvents that can be used in the preparation of the catalyst precursor mixture are not specifically limited, and preferred solvents include water, alcohols, preferably methanol, ethanol, propanol and butanol, diois, such as ethylene glycol or propylene glycol, and other polar solvents. Water is more preferred. Further, any suitable mixture of the above solvents can be used.
  • Suitable starting materials metal sources ⁇ for Mo, V, Te and ⁇ SIb oxides are for instance those described in US 5,380,933 (col. 3, line 27 to 57 ⁇ and/or US 6,710,207 (col. 8, lines 12 to 30) r and Include salts and acids (normally oxyacids ⁇ of the desired metal elements.
  • the salts are selected in a manner that after calcining only metals elements and oxygen remain in the calcined catalyst precursor since all other constituents are volatile or rendered volatile by decomposition or oxidation.
  • ammonium salts of the metal element or the corresponding oxyacid
  • organic salts such as oxalates, alkoxides or acetylacetonates
  • organic metal complexes or metalorganic compounds is preferred.
  • the selected salts and acids are preferably soluble or at least dispersible in the selected solvent such as water.
  • the water-solubility of the starting salt or acid is at least 0.1 mol metal per 11 of water at 373K (100 0 C) .
  • Suitable starting salts and acids include for instance ammonium para- or heptamolybdate, molybdenum oxalate, ammonium metavanadate r vanadium oxalate, telluric acid and ammonium niobium oxalate.
  • a solution of the V source e.g. an aqueous ammonium metavanadate solution
  • a solution of the Te source e.g. an aqueous solution of telluric acid
  • a solution of the Mo source e.g. an aqueous solution of ammonium heptamolybdate
  • a Kb source e.g. an aqueous solution of ammonium niobium oxalate
  • the dry catalyst precursor mixture is prepared by spray-drying a clear aqueous solution prepared from molybdenum oxalate, telluric acid, vanadium oxalate and ammonium niobium oxalate. If spray drying is used, drying temperatures in the range of more than 100 to 250 0 C, for instance 150 to 220 0 C are preferred, especially if the catalyst precursor mixture was prepared from aqueous solutions or dispersions.
  • the drying process does not eliminate any remaining moisture in the material to be calcined.
  • the drying process e.g. spray-drying
  • the drying process is terminated if the particles to be calcined do no longer agglomerate. Excessive drying is to be avoided in order to preserve residual moisture, which is believed to be beneficial in transport phenomena. Excessive drying occurs if the dried particles start to dust.
  • the catalyst precursor mixture to be calcined is prepared under so-called “hydrothermal” conditions, that is in the presence of water under elevated temperature and pressure.
  • the starting material for the hydrothermal preparation is preferably selected from the aforementioned catalyst metal-containing compounds, more preferably from inorganic and organic salts and (oxy) acids. Suitable starting salts and acids include for instance ammonium para- or heptamolybdate, molybdenum oxalate, ammonium metavanadate, vanadium oxalate, vanadylsulfate (VOSO4) and hydrates thereof, telluric acid and ammonium niobium oxalate.
  • the hydrothermal preparation comprises the steps of
  • step (c) heating the aqueous mixture at elevated pressure whereby a solid material is formed, (d) collecting and drying rhe solid material formed in step (C) .
  • Step (c) is preferably conducted at a temperature of above 100 0 C up to 25O 0 C, for instance 120 to 200 0 C, preferably 13O 0 C to ISO 0 C at a pressure of more than 0.2 MPa (2 bar) .
  • There is no specific upper pressure limit it is for instance conceivable to work with pressure up to 9MPa.
  • normally pressures of 0.3 to 2MPa, such as 0.4 to 1 MPa are used.
  • the reaction is conducted in a closed reactor, such as an autoclave to make use of the autogeneous pressure generated at higher temperatures by the existing water.
  • the reaction time (at the target temperature) can be varied considerably and may for instance range from 24 to 144 hours, 80 hours to 130 hours being preferred.
  • the reaction is preferably conducted m autoclaves made from a suitable inert material (e.g. Hastelloy C276) or having a suitable inner lining (e.g. Teflon ⁇ .
  • a suitable inert material e.g. Hastelloy C276
  • a suitable inner lining e.g. Teflon ⁇ .
  • the calcination and activation of a catalyst precursor mixture that was hydrothermally prepared under properly selected conditions may lead to Ml rich catalyst materials as shown in comparative example 1.
  • the resulting catalyst materials show an insufficient performance, in particular in terms of propane conversion to acrylic acid.
  • a high performance can only be achieved by an intermediate p/T treatment, i.e. step (ii) of the claimed preparation method as explained in further detail below.
  • the molar ratio of starting materials in terms of metal components is chosen in accordance with the desired final composition of the catalyst under consideration of possible changes as discussed below.
  • the final composition is a mixed metal oxide which comprises the metal oxides of Mo, V, Te and Nb, and optionally oxides of other metal elements, as long as these do not adversely affect the function of the resulting material as a catalyst in the oxidation reactions referred to herein.
  • the final average catalyst composition lies within the ranges defined by general formula ⁇ I) :
  • x is the molar number of oxygen binding to the metal atoms present in this mixed metal oxide which follows from the relative amount and valence of the metal elements, and Z is at least one element selected from Ru, Mn, Sc, Ti, Cr, Fe, Co, Ni, Cu, Zn, Ga, Y, Zr, Rh, Pd, In, Sb, Ce, Pr, Nd, Te, Sm, Tb, Ta, W, Re, Ir, Pt, Au, Pb, and Bi.
  • Average composition means the composition as can be determined with techniques such as XRF particularly suitable for analyzing the bulk elemental composition.
  • XRF particularly suitable for analyzing the bulk elemental composition.
  • the EDX measurements conducted in the experimental section for determining average bulk compositions gave also reliable results .
  • d is 0 in formula (I) .
  • the at least one optional element Z is present (i.e. d > 0), it is preferably at least one element selected from Ru, Mn, Cr, Fe, Co, Ni, Zr, Rh, Pd, In, Sb, Ce, Ta, W, Pt and Bi. More preferred are compounds of formula (I) , wherein Z, if present, is at least one element selected from Cr and Ni.
  • Another preferred embodiment relates to the use of Ru, Cu, Rh, Re and/or Mn as Z element, Ru, Mn and Cu, in particular Ru and Mn being particularly preferred- If element Z is present, the lower limit of d is preferably 0.0005, in particular 0.001.
  • the final average catalyst composition lies within the ranges defined by general formula (II) :
  • the V ratio in the starting material can be lower than specified in formula (I) above, for instance by 2- 20%, 5-15% or 8-13% lower. Accordingly, in the starting material mixture, variable "a" characterizing the V content may be in the order from 0.15 to 0.30. Since the volatility of Te often leads to a Te loss in the final catalyst composition over the starting material mixture, the Te ratio can be higher in the starting material mixture than specified in formula (I) above although this is not preferred.
  • the Te content in the starting material composition is as low as possible to effectively generate Mi phase and the process conditions are optimized to minimize Te loss .
  • the catalyst precursor mixture to be calcined, and thus also the final catalyst material can include a solid, diluent.
  • diluent any inert material can be used that can withstand the conditions of the calcination, the p/T treatment and optionally the activation treatment, does not interact with the metal oxide catalyst material such that the catalytic activity thereof would be impaired, and does not react with the starting materials, intermediates or final products of the oxidation reaction.
  • a solid diluent may be beneficial for various reasons.
  • preferred diluents are characterized by a higher thermal conductivity than the catalytically active metal oxide material. This ensures a better heat transport management and prevents the formation of hot spots during the use of the catalyst, which could lead to undesired side reactions or lowering the catalyst's life.
  • the diluent functions as a separating agent for the catalytically active material and counteracts any sintering processes, which may occur between the grains of catalyst material. Further, the diluent may also improve the surface properties of the catalyst.
  • Suitable diluents may be selected from alumina, zirconium oxide (zirconia) , cerium oxide (CeC ⁇ ), SiC and silica. According to one embodiment, the diluent is treated with a solution containing at least one metal defined in formula (I) prior to its admixture to the catalyst precursor material or a starting material thereof.
  • the optionally pretreated and dried diluent is subjected to the same calcination procedure, as described for the catalyst precursor material, before it is combined with the catalyst starting material.
  • the optionally pretreated diluent preferably undergoes this calcination twice, once prior to mixing with catalyst starting material and a second time together with this catalyst precursor material .
  • the weight ratio of the diluent to the metal oxide catalyst material is not more than 1.5:1 and especially not more than 1:1, e.g. not more than 0.5:1.
  • the diluent can be added at any time prior to the calcination procedure, i.e. it can be mixed with the metal-comprising catalyst starting materials in a dry or a wet state or, if the catalyst precursor mixture is prepared using a solvent, it can be added to the solvent to precipitate the catalyst starting materials on the diluent in the process of preparing the catalyst precursor mixture .
  • the catalyst precursor mixture is then subjected to a calcination in an oxygen-containing atmosphere (step i) at a temperature of 150-400°C, preferably 200-350 0 C, more preferably 250-300 0 C.
  • This procedure is intended to remove volatile constituents and convert catalyst metal elements to their oxides .
  • this calcination reaction is usually conducted at atmospheric pressure. In principle it is, however, also possible to conduct this step under slightly elevated or slightly reduced pressure, for instance within the range of atmospheric pressure + 50% or ⁇ 20%.
  • oxygen- containing atmosphere air or a synthetic oxygen-containing atmosphere can be used. Depending on the other process conditions, oxygen is normally not employed in contents of more than 50 vol.-%. Suitable oxygen volume ratios are for instance 1 to 40 vol.%, 5 to 35 vol.-% or 10 to 30 vol.-%. The remainder is nitrogen as in air or any other inert gas such as Ar or He.
  • any suitable reactor can be used for conducting the calcination.
  • organic metal salts are used as starting material, it is preferred to calcine in a rotating oven which seems to enhance the complete removal of organic constituents.
  • the catalyst precursor mixture is gradually heated from the starting temperature (usually room temperature, that is 2O 0 C) to the final calcination temperature, preferably at a rate of 1 to 20 K/min, in particular 5 to 15 K/min. Calcination is then conducted at the final temperature of 150 to 400 0 C, preferably 200-350 0 C, more preferably 250-300 0 C, preferably over a time period of 20 min to 20 hrs, for instance 30 min to 10 hrs, 1 hr to 5 hrs or 1 hr to 3 hrs.
  • the oxygen-containing atmosphere is preferably moved continuously relative to the catalyst precursor mixture.
  • the expression "moved” relates to embodiments according to which fresh oxygen-containing atmosphere is supplied to replenish possibly consumed and therefore oxygen-depleted atmosphere. Suitable supply rates are for instance in the order of 10 to 100 ml/min, in particular 30 to 70 ml/min, based on a weight of catalyst precursor mixture of 1-50 g.
  • the calcined catalyst material is subjected to a high pressure and high temperature treatment (in the following also referred to as "p/T treatment") at a pressure of at least 10 mPa and a temperature of at least 400 0 C in the presence of an inert fluid phase.
  • p/T treatment a high pressure and high temperature treatment
  • the inventors have surprisingly found that this p/T treatment greatly enhances the formation of Ml phase in the final catalyst material, either during the p/T treatment itself or in a subsequent activation treatment.
  • the pressure and temperature to be used in this treatment there is no specific upper limit regarding the pressure and temperature to be used in this treatment. Accordingly, it is for instance possible to conduct the treatment at pressures of up to 50 MPa or more and temperatures of up to 700 0 C or more. However, very high temperatures and pressures expose the material of the reactor to higher loads. Therefore, it is preferred from an industrial perspective to use the lowest possible temperature and pressure values that are sufficiently effective in forming Ml phase or increasing its content.
  • Further embodiments of the temperature range to be used include 420 to 6G0°C, 440 to 560 0 C and 460 to 540 0 C. According to further embodiments, the pressure can be adjusted within the range of 12 to 40 MPa, 14 to 35 MPa, 15 to 30 MPa and 16 to 25 MPa.
  • the p/T treatment of the present invention is conducted in the presence of an inert fluid phase.
  • This treatment is believed to favor transport reactions thereby triggering dissolution, phase reorganization and recrystallization processes, which enhance the formation of Ml phase.
  • the inert fluid phase may be a vapor, liquid, critical or supercritical phase under the conditions of the p/T treatment.
  • liquid is intended to denote all conditions of pressure and temperature where the phase is not in a vapor state and a critical or supercritical state has not yet been reached.
  • phase-forming compound The compound forming the inert fluid phase (in the following referred to as "phase-forming compound”) should not decompose under the conditions of the p/T treatment. Without wishing to be bound by these mechanistic considerations it would appear that the phase-forming compound might be capable of at least partially dissolving calcined catalyst material thereby enhancing transport and recrystallization processes. Moreover, it seems preferred if the following requirements are fulfilled:
  • the phase-forming compound is a small molecule having preferably a molecular weight of less than 150, more preferably less than 100, in particular less than 80.
  • the phase-forming compound consists of at least two different chemical elements selected from the group consisting of C, S, 0 and H. Compounds containing nitrogen atoms are less preferred.
  • phase-forming compounds are water, CO2 and SO 2 .
  • the p/T treatment of the present invention can be conducted in any apparatus withstanding the required high temperature and pressure conditions. Typically, it is conducted in a tightly sealed autoclave or reactor. To ensure that the pressure loss over the treatment time is as small as possible, specific seal materials, which do not loose their sealing properties under the required pressure and temperature conditions, are preferably used. Copper and silver seals constitute for instance such materials .
  • the p/T treatment of the present invention is preferably conducted over 0.5 to 30 hrs, for instance 1 to 25 hrs, or 2 to 20 hrs.
  • This p/T treatment is normally conducted after air existing in the reactor (e.g. autoclave ⁇ has been replaced by an inert gas such as nitrogen, argon or helium followed by the addition of the phase-forming compound.
  • an inert gas such as nitrogen, argon or helium
  • the metal oxide catalyst material obtained after the p/T treatment may already show a high Ml phase content, such as at least 85wt. ⁇ %, at least 90wt.-% or at least 95wt.-% as well as other characteristics explained later in connection with the claimed metal oxide catalyst. Then, it is not necessary to further enhance the Ml phase content by subjecting the catalyst to the following "activation treatment" .
  • this second thermal treatment (also referred to as “activation treatment”) follows the p/T treatment to further enhance the crystallinity (and thereby also the Ml content), if necessary.
  • the activation treatment proceeds in an inert atmosphere, preferably in nitrogen gas or argon gas, at a temperature of 350-700°C, preferably 550- 68O 0 C, even more preferably 58Q-670°C, in particular 590 to 67O 0 C.
  • the mixed metal oxide (such as Ml phase itself) obtained after the p/T treatment is in a not fully oxidized state (as it contains at least in part molybdenum (Mo) in an oxidation state of less than +VI and at least in part vanadium (V) in an oxidation state less than +V) and complete oxidation to M0O3 or V 2 O 5 , respectively, is to be avoided.
  • Mo molybdenum
  • V vanadium
  • this activation treatment is usually conducted at atmospheric pressure. In principle it is, however, also possible to conduct the treatment under slightly elevated or slightly reduced pressure, for instance within the range of atmospheric pressure + 50% or ⁇ 20%.
  • the treatment time in this step is also not specifically limited, and is preferably 0.5-30 h, more preferably 1-20 h and in particular 1-10 h.
  • the catalyst precursor mixture is gradually heated from the starting temperature ⁇ usually room temperature, that is 20 0 C) to the final activation temperature, preferably at a rate of 0.5 to 5 K/min, in particular 1 to 3 K/min.
  • the present invention also provides a new and superior MoVTeNb mixed oxide catalyst material which shows excellent conversion rates and/or selectivities in the oxidation of hydrocarbons, for instance to unsaturated carboxylic acids.
  • the catalyst material is preferably essentially crystalline which is to be understood as a preferred crystallinity degree of at least 80wt.-%, more preferably at least 85wt.-%, even more preferably at least 90wt.-%, even more preferably at least 95wt.-% based on the total amount of metal oxide catalyst phase (note: of course, neither optionally present diluent nor carrier are considered part of this metal oxide catalyst phase) .
  • the crystallinity can be determined by XRD with an internal standard as explained in the experimental section .
  • the claimed mixed oxide catalyst material is also characterized by a very high content of Ml phase of at least 85wt.-%, preferably at least 90wt.-%, more preferably at least 95wt.-% Ml phase based on the total amount of crystalline metal oxide catalyst phase.
  • the amount of Ml phase in wt.-% can be determined as described in the experimental section.
  • MOg Mo, V
  • NbC>7 pentagonal bipyramidal units sharing edges with surrounding corner- linked MOg octahedrons are believed to allow an unambiguous distinction from M2 phase.
  • background art can be used to define the Ml phase.
  • Ml phase shows a characteristic needle shape with average length values of typically 100 to 400 nm, e.g. 200 to 300 nm, and average diameter values of 50 to 300 nm, e.g. 100 to 250 or 100 to 200 nm. Activation at higher temperatures generally seems to favour the formation of greater average diameters.
  • Morphology studies and shape analysis can be performed using scanning electron microscopy (SEM) . For SEM investigations the samples were deposited on carbon tape without any pre-treatraent. From the SEM images, size distributions of the Ml needles were obtained by measuring the length and diameters of 300 arbitrarily selected Ml needles .
  • a MoVTeNb mixed oxide catalyst material comprising oxides of molybdenum (Mo) , vanadium (V) , tellurium (Te) and niobium (Nb), and optionally further catalyst metals such as element Z defined before, is provided which comprises Ml phase in an amount of at least 85wt.-% r based on the entire amount of crystalline metal oxide catalyst phase, and is obtainable by the above explained preparation method.
  • the average composition of this catalyst material is preferably within the ranges defined by the above general formula (I) f in particular the above formula (II) .
  • the present invention provides a novel catalyst material comprising oxides of molybdenum (Mo) , vanadium (V) , tellurium (Te) and niobium (Nb) and optionally further catalyst metals such as element Z defined before characterized in that it has a Ml phase content of at least 85wt.-% and an average composition that is within the ranges defined by the aforementioned formula (II) .
  • Both the first and the second catalyst material of the invention can be optionally further described by their specific surface.
  • the specific surface area of the catalyst material as measured according to the BET method with nitrogen described in the examples is preferably greater than 5 m ⁇ /g, in particular greater than 6 m ⁇ /g, for instance 6 to 40 m 2 /g, e.g. 7-20 m 2 /g.
  • the first and second catalyst material of the invention preferably show a propane conversion of at least 40%, preferably at least 45%, and/or a selectivity for acrylic acid of at least 65%, preferably at least 70%, under the hydrocarbon oxidation conditions specified in the examples .
  • the catalyst material of the invention can be used as catalyst as obtained after the p/T treatment or, if applicable, the activation treatment, that is as powder.
  • catalyst particles of a definite size are formed from the obtained powdery catalyst material (which may also contain a diluent) .
  • the macroscopic size (average longest diameter) of the individual catalyst particles preferably ranges from 0,5 to 10mm.
  • Catalyst particles of this size can be obtained by processes known in the art, for instance by pressing a dried catalyst starting material, newly crushing the pressed material and carrying out size-selecting steps such as sieving, before conducting the calcination step.
  • the already calcined material is pressed, newly crushed and subjected to size-selecting steps such as sieving.
  • an extrudate may be formed. Pressing and extrusion may be equally conducted with p/T- treated and optionally activated catalyst material.
  • the final catalyst material is coated onto a carrier according to techniques known in the art.
  • This coating of the respective catalyst (precursor) materials can be equally effected at an earlier stage, for instance prior to the calcination treatment, prior to the p/T treatment or prior to the optional activation treatment .
  • the carrier which is preferably inert, can have any shape and surface structure. However, regularly shaped, mechanically stable bodies such as spheres, rings, tube sections, half-rings, saddles, spirals Gr honeycomb carrier bodies or carrier bodies provided with channels such as, for example, fibre mats or ceramic foams are preferred.
  • the size and shape of the carrier bodies is determined, for example, by the dimensions, primarily the internal diameter of the reaction tubes if the catalyst is used in tube or tube-bundle reactors. The diameter of the carrier body should then be between 1/2 and 1/10 of the internal diameter of the reactor. In the case of fluidised bed reactors, the carrier dimensions are determined, for example, by the fluid dynamics In the reactor.
  • Suitable materials are, for example, steatite, duranite, stoneware, porcelain, silicon dioxide, silicates, aluminium oxide, aluminates, silicon carbide or mixtures of these substances. Tube sections, rings or spheres made of ceramic, silicon carbide or carbon are preferably used.
  • the proportion of the layer applied to the carrier is preferably 1 to 30% by weight, particularly preferred 2 to 20% by weight, based on the total mass of the catalyst material (exclusive optionally present diluent) .
  • the thickness of the layer is preferably 5 to 300 ⁇ m, particularly preferred 5 to 10 ⁇ m.
  • the selected carrier is coated with an aqueous slurry of the starting materials for the catalyst precursor material, or a suspension thereof in an organic solvent such as for example toluene, followed by the removal of water or organic solvent and the process steps described in item I (calcination, p/T treatment, optional activation) . If the carrier is coated at a later stage the same technique can be employed under use of an optional heat treatment after the removal of water or organic solvent to fix the catalyst material on the carrier.
  • One further aspect of the present invention relates to a method for oxidizing a hydrocarbon in the presence of oxygen and a catalyst as defined above.
  • this method comprises subjecting a hydrocarbon, in particular an alkane to a vapour phase catalytic oxidation reaction to produce an unsaturated carboxyiic acid.
  • a hydrocarbon in particular an alkane
  • a vapour phase catalytic oxidation reaction to produce an unsaturated carboxyiic acid.
  • This embodiment is preferably applied to Cl to C5 alkanes.
  • propane or isobutane is used as starting alkane, acrylic acid or methacrylic acid will be obtained, respectively, in good yield.
  • the catalyst of the invention can be used under conventional conditions to convert hydrocarbons to unsaturated carboxyiic acids.
  • the reaction is preferably conducted in fixed bed reactors, for instance tubular fixed bed reactors.
  • atmospheric pressure can be used whilst the reaction proceeds similarly under lower or higher pressures.
  • an inert gas e.g. nitrogen
  • steam are admixed to the hydrocarbon (e.g. propane) and oxygen.
  • a standard feed composition is for instance alkane (e.g. propane ⁇ /oxygen/nitrogen/steam of 1/2-2.2/18- 17.8/9 (molar ratio) .
  • Preferred reaction temperatures range from 350 to 45O 0 C.
  • the molar amount of steam (H2O) based on the total molar amount of hydrocarbon, O2, inert gas (e.g. N2) and steam (H2O) can be varied considerably with the catalyst of the invention. Suitable results are achieved with molar amounts of preferably 5-65%, for instance 10-50%.
  • the present inventors have found that Ml-rich catalyst samples are surprisingly stable under conditions of use as described in example 4. After 50 hours essentially no loss of catalytic activity was observed. A phase analysis of catalyst samples used over this period of time did also not reveal any noticeable reduction of Ml phase content. This makes the catalyst of the present invention a particularly attractive choice for industrial methods for the oxidation of hydrocarbons as described hereinbefore wherein the same catalyst batch is used over several months, for instance at least 3 months, at least 6 months, or even at least one year.
  • a saturated or unsaturated hydrocarbon such as C3 to C7 alkane or alkene is oxidized ( "ammoxidation") in the presence of oxygen, ammonia and the catalyst of the invention to the corresponding nitril.
  • Acrylonitrile or methacrylonitrile can be produced in this manner from propane, propylene, isobutane or isobutene, respectively.
  • This embodiment is conducted under conditions usual in the art involving for instance a reaction temperature of 350 to 500 0 C, e.g. 400 to 500 0 C and atmospheric pressure up to 3 atm.
  • oxygen source air is usually employed.
  • the concept underlying the present invention is equally applicable to increase the Ml phase content of calcined MoVTeNb oxide catalyst (material) that has a different history than defined in the claimed preparation method. In this manner it is possible to increase the performance of already calcined catalyst (material) which has for instance undesirably high contents of the amorphous phase or M2 phase.
  • one further aspect of the present invention relates to a method for increasing the content of Ml phase in a calcined metal oxide catalyst material comprising oxides of molybdenum (Mo), vanadium (V), Tellurium (Te) and niobium (Nb) , and optionally at least one further catalyst metal element such as Z defined above, which comprises the step of subjecting the calcined metal oxide catalyst to a treatment at a pressure of at least lOMPa and a temperature of at least 400 0 C in the presence of an inert fluid phase.
  • This treatment can be conducted under the same conditions as set forth in item I for the p/T treatment conducted as second step of claimed preparation method.
  • the p/T-treated catalyst is subjected to an activation treatment in an inert gas atmosphere at a temperature of 350 to 700 0 C, in particular 580-670 0 C.
  • this activation treatment reference is also made to the preparation method of the invention (cf . item I) .
  • the present method is preferably applied to catalysts having an average composition as described in items I and II, for instance catalyst materials of formula (I) or (II) and embodiments thereof.
  • the method can be used to increase the Ml phase content by for instance at least 10wt.-%, at least 20wt. ⁇ %, at least 30wt.-%, at least 40wt.-%, at least 50wt.-%, at least 60wt.- %, at least 70wt.-%, or at least 80wt.-%, depending on the Ml content of the calcined catalyst material to be treated and the target value.
  • the calcined metal oxide catalyst material has a content of less than 70wt.-%, e.g.
  • the calcined catalyst material to be treated is removed from a (usually continuous) process for producing an unsaturated carboxylic acid, which comprises subjecting an alkane to a vapour phase catalytic oxidation reaction in the presence of oxygen and said calcined catalyst (as described in item III), and recycled at least in part to said process after the method of increasing the content of Ml phase has been performed.
  • phase composition of the catalysts was determined by X- ray diffraction performed on laboratory diffractometers, either a STOE STADI P transmission dif fractoraeter equipped with a focusing primary Ge 0 (111) monochromator and a position sensitive detector, using Cu-K(Xi radiation, or a Bruker AXS D8 Advance Bragg-Brentano diffractoraeter equipped with a secondary graphite monochromator and scintillation counter, using Cu-K ⁇ ⁇ 4 .2 radiation.
  • the Ml phase content in (wt.-%) was determined by fitting calculated diffraction patterns to the experimental X-ray diffraction data employing the R.ietveld method (quantitative Rietveld analysis), using the "TOPAS" software (v.3, Bruker AXS) .
  • this analysis yields the mass fractions (weight-%) of those crystalline phases in a phase mixture which have a known crystal structure, the sum of which is defined as 100%. Accordingly, the content of amorphous material can only be determined as explained later.
  • catalysts having a chemical composition as considered in the present invention form as main phases only Ml and M2 and occasionally one or more among five crystalline minority phases, that is (Mo, V, Nb) 5O2 . 4 and VQ _ 95M00.97O5, M0O2 , M0O3 and TeM ⁇ 5 ⁇ 6-
  • the theoretical diffraction patterns of minority phases are taken into account based on the structural information for Mo 5 O 14 (ICSD-27202) and V 0 .95M00.97O5 (ICSD- 39386), MoO 2 (IC ⁇ D-80830) , MoO 3 ( ICSD-35076) , and TeMo 5 O 16 (ICSD-69063) .
  • optional catalyst elements such as Z (in formula I and II) are present (d ⁇ 0.05 based on MojJ they do not alter the diffraction pattern of the crystalline phases to an extent that this needs to be considered within the preciseness of the determination. In the very unlikely case that the crystalline metal oxide phase would contain unknown crystalline material in greater amounts, a crystallographic analysis allows considering its diffraction pattern in the determination of the Ml content.
  • the XRD pattern shows exclusively diffractions signals that can be assigned to Ml phase and is substantially free of other well- defined diffraction peaks.
  • well-defined diffraction peak is to be understood as relating to a diffraction signal having an FWHM (full width at half maximum), i.e. the width of the peak at 50% of its height above the baseline, of at most 3° in 2 theta.
  • the sum of the crystalline phases is
  • Morphology studies and shape analysis can be performed using scanning electron microscopy (SEM) .
  • SEM scanning electron microscopy
  • the samples were deposited on carbon tape without any pre- treatment.
  • a Hitachi S-5200 with a PGT spirit EDX system and a Hitachi S-4800 with an EDAX genesis EDX detector were used.
  • EDX studies in the SEMs were carried out with an accelerated voltage of 10 kV while SEM images were acquired at 2 kV to optimize surface resolution.
  • the dry sample was crushed using a mortar and pestle. The crushed powder was dispersed in dry form on a carbon coated copper grid.
  • a meaningful value can be obtained by averaging the values obtained from 50 EDX measurements .
  • the Quantachrome AUTOSORB software was used to determine the BET surface area of the catalyst of the invention taking into account 5 data points in the linear relative pressure range of the adsorption isotherm (p/po pressure range 0.05 to 0.3) .
  • the amount of sample is around 0.1 g.
  • XRF measurements were carried out on a Sequenz- Rontgenfluoreszenz- ⁇ pektrometersystem S4 PIONEER available from Bruker AXS GmbH, Germany.
  • standard samples can be prepared that are adapted to the sample to be analyzed such as M0O3, V2O5, Te (OH) Q and Nb2 ⁇ 5- If required, other suitable standards can be used as known in the art.
  • VI oxide Molybdenum (VI) oxide (MoO 3 , 99.5 % Fiuka) , telluric acid (Te(OH) 5 , 97.5-102.5 % Aldrich), vanadium(V) oxide (V 2 O 5 , 99.5
  • Distilled water was also utilized for preparation of the aqueous solutions.
  • Mo-V-Te-Nb-O complex oxide catalyst preparation First, the molybdenum (VI) oxide (130 mr ⁇ ol) and oxalic acid dihydrate (158 mmol) were dissolved in distilled water (300 mli) under vigorous stirring at 80 0 C for 30 minutes. Next, the Te containing solution consisted of telluric acid (30 mmol), dissolved in distilled water (30 mL) under continuous stirring at 40 0 C for 15 minutes, was added to the molybdenum containing solution.
  • the V containing solution was prepared by carefully adding oxalic acid dihydrate (56 mmol) to a suspension of the vanadi ⁇ im(V) oxide (19.5 mmol) in distilled water (50 mL) under continuous stirring at 65 0 C for 30 minutes. Then, this solution was added to the Mo/Te one. Afterwards, the Nb containing solution consisted of ammonium niobate(V) oxalate hydrate (16 mmol) dissolved in distilled water (30 mL) under continuous stirring at 40 0 C for 15 minutes was added to the Mo/V/Te containing solution. Finally, the as-derived homogeneous complex solution with nominal molar ratio Mo/V/Te/Nb being 1/0.3/0.23/0.123 was stirred at 40 0 C for a further 30 minutes.
  • the spray- drying procedure was performed in a Btichi 191 Mini Spray Dryer operating with inlet temperature of 150 0 C, outlet temperature of about 110 0 C, aspirator and pump levels of 100 % and 10 %, respectively, and air flow rate of ⁇ 600 mL/min.
  • the resulting powdered product was quickly collected and immediately subjected to a moderate-temperature heat treatment in an atmosphere of air flow (100 mL/min) .
  • the treatment involved a 25 minutes ramping up to 275 0 C and holding at this level for 1 hour.
  • the resulting powder was thoroughly ground in an agate mortar and pestle.
  • Mo-V-Te-Nb-O complex oxide catalyst material was prepared via a p/T-treatment of as-derived precursor in superheated water vapour with following activation in argon.
  • a p/T-treatment of as-derived precursor in superheated water vapour with following activation in argon.
  • 1.6 g of precursor powder and 2.65 mL of distilled water were mixed in a stainless steel vessel (volume - 48 cm 3 ) , the vessel was then capped by a stainless steel cover (copper gasket sets between the vessel and cover) , and placed inside a stainless steel bomb. The bomb was sealed and kept at 500 0 C for 2 hours. Spatula-collected product of the superheated water vapour treatment was then dried at 110 0 C for 2 hours in air.
  • the p/T-treated catalyst material sample displayed a sponge- like morphology as shown in Fig. 1. Its BET surface value was 18 m 2 /g.
  • the resulting powder was thoroughly ground in an agate mortar and pestle and subjected to an activation treatment under heating in an atmosphere of argon flow (100 rrsL/min) .
  • This treatment involved a 40 minutes ramping up to 600 0 C and holding at this level for 2 hours.
  • the as-synthesized catalyst material was thoroughly ground in an agate mortar and pestle and stored in a moisture-free desiccator.
  • the recrystaliization occurring during this activation treatment led to the formation of a virtually phase-pure material containing 95wt.-% Ml, 2wt.-% M2 and 3wt.-% Vg , 95 M00.97O5 as determined by XRD.
  • the activated material displayed the common needle-shaped morphology of Ml phase as shown in Fig. 2.
  • the uppermost XRD pattern stems from a Ml reference material .
  • Fig. 3 thus confirms that the initially amorphous calcined catalyst material (Fig. 3a) undergoes substantial structural rearrangements in the high pressure/temperature ( ⁇ /T) treatment of the present invention. It would appear that under these conditions structural units arrange predominantly along the crystallographic c axis resulting in nano- crystailine Ml as revealed by unisotropic line broadening analysis of simulated Ml patterns (P. D. Santo, D.J. Buttrey, R. K. Grasseli, CG. Lugmair, A. F. Volpe, B. H. Toby, T. Vogt, Z. Cristallogr. 219 (2004 ⁇ 152 ⁇ . However, the material is still X-ray amorphous (see Fig. 3b) . Crystallinity (Fig. 3c) can be achieved in the final activation treatment.
  • Example 1 was repeated except for replacing 2.65 g H2O by 6.57 g solid CO2 (dry ice) and conducting the high pressure and temperature treatment over 15 hrs .
  • the resulting catalyst material had almost the same chemical composition as that of example 1 and very similar properties.
  • Comparative Example 1 hydrogen preparation without subsequent p/T treatment
  • Example 1 The performance of the catalysts according to Example 1 and Comparative Example 1 was evaluated in the following oxidation process.
  • Partial oxidation of propane was carried out in a reactor for parallel catalytic testing with twelve fixed bed quartz tubular reactors (i.d., 4 mm; length, 225 mm), working at atmospheric pressure.
  • the catalyst material was pressed by a hydraulic press (8 ton of force on a round surface of approx. 3cm diameter ⁇ , crushed and sieved manually to particle sizes between 0.24 to 0.45 mm.
  • the feed flow rate was fixed at a gas hourly space velocity (GHSV) of 4800 h "1 (at STP: standard temperature pressure conditions) with a catalytic bed volume of 0.5 ml and the corresponding bed height.
  • GHSV gas hourly space velocity
  • the feed composition was 2.8 vol-% propane, 6.3 vol ⁇ % oxygen, 50.9 vol-% nitrogen and 40 vol-% steam.
  • the reaction was carried out at 673 K (400 0 C) .
  • the products were analyzed by two on-line gas chromatograph systems. At the reactor outlet, the produced gases were analyzed by two GCs and the conversion of propane, the selectivity of acrylic acid and the acrylic acid yield calculated.
  • the first GC was configured with molecular sieve and Porapak columns coupled with a thermal conductivity detector for the analysis of inorganic gases and hydrocarbons (C1-C3) .
  • the second GC was configured with a capillary column (HP-FFAP) coupled with a flame ionization detector for the analysis of oxygenated products .

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Abstract

La présente invention concerne un procédé d'élaboration d'un matériau catalyseur à base d'oxydes de métaux comprenant des oxydes de molybdène (Mo), de vanadium (V), de tellure (Te) et de niobium (Nb). Ce procédé consiste d'abord (i) à prendre un mélange précurseur du catalyseur comprenant du molybdène (Mo), du vanadium (V), du tellure (Te) et du niobium (Nb), et à le calciner sous atmosphère oxygénée à une température de 150 à 400°C de façon à obtenir un matériau catalyseur calciné. Le procédé consiste ensuite (ii) à prendre ce matériau catalyseur calciné et à le soumettre à un traitement à une pression d'au moins 10 MPa à une température d'au moins 400°C en présence d'une phase fluide inerte de façon élaborer un matériau catalyseur comprenant des oxydes de molybdène (Mo), de vanadium (V), de tellure (Te) et de niobium (Nb). Ce procédé donne des matériaux catalyseurs présentant des teneurs très élevées de phase cristallographique MI, offrant une excellente conversion en propane, ainsi que, lors de la conversion du propane, des taux et des coefficients de sélectivité élevés pour l'acide acrylique.
PCT/EP2009/051961 2008-02-25 2009-02-19 Catalyseur à phase enrichie à base de mélange d'oxydes de mo-v-te-nb, et procédé d'élaboration WO2009106474A2 (fr)

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