WO2014062046A1 - Déshydrogénation oxydative de l'éthane en éthylène et préparation d'oxydes mixtes multimétalliques en tant que catalyseurs pour ce procédé - Google Patents

Déshydrogénation oxydative de l'éthane en éthylène et préparation d'oxydes mixtes multimétalliques en tant que catalyseurs pour ce procédé Download PDF

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WO2014062046A1
WO2014062046A1 PCT/MX2013/000121 MX2013000121W WO2014062046A1 WO 2014062046 A1 WO2014062046 A1 WO 2014062046A1 MX 2013000121 W MX2013000121 W MX 2013000121W WO 2014062046 A1 WO2014062046 A1 WO 2014062046A1
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solid
catalyst
mixture
tellurium
grams
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PCT/MX2013/000121
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English (en)
Spanish (es)
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Jaime SÁNCHEZ VALENTE
José Manuel LÓPEZ NIETO
Héctor ARMENDÁRIZ HERRERA
Amada MASSÓ RAMÍREZ
Francisco IVARS BARCELÓ
María de Lourdes Alejandra GUZMÁN CASTILLO
Roberto QUINTANA SOLÓRZANO
Andrea RODRÍGUEZ HERNÁNDEZ
Paz Del Angel Vicente
Etel Maya Flores
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Instituto Mexicano Del Petróleo
Universidad Politécnica De Valencia
Pemex Petroquímica
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Priority claimed from US13/655,620 external-priority patent/US9409156B2/en
Application filed by Instituto Mexicano Del Petróleo, Universidad Politécnica De Valencia, Pemex Petroquímica filed Critical Instituto Mexicano Del Petróleo
Priority to CN201380065588.2A priority Critical patent/CN104968635B/zh
Priority to CA2888633A priority patent/CA2888633C/fr
Priority to JP2015537654A priority patent/JP6125023B2/ja
Publication of WO2014062046A1 publication Critical patent/WO2014062046A1/fr

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
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    • B01J23/24—Chromium, molybdenum or tungsten
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • 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
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • C07C2523/22—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to oxidative dehydrogenation of light paraffins using a catalyst based on mixed multimetallic oxides, tellurium free. Particularly, it relates to the preparation of highly active and selective catalysts for the oxidative dehydrogenation of ethane to produce ethylene at moderate temperatures, ⁇ 500 ° C, without the formation of acetic acid and / or other oxygenated hydrocarbons.
  • the present invention provides catalysts based on mixed oxides, which have a bronze-like orthorhombic structure, referred to as crystalline phase M1, whose diffraction peaks appear at 2 ⁇ equal to 6.6 + 0.4, 7.7 ⁇ 0.4, 9.0 ⁇ 0.4, 22.2 ⁇ 0.4, 26.7 ⁇ 0.4, 26.8 ⁇ 0.4, 27.1 + 0.4; (ICSD 55097) and other crystalline structures that have an important function in obtaining high performance catalysts in the oxidative dehydrogenation of ethane to ethylene.
  • Ethylene is the cornerstone of the petrochemical industry, since; This is the base compound for the production of polymers, ethylbenzene and styrene, among other chemicals of great importance in the modern world.
  • Ethylene is produced from steam cracking (pyrolysis) of saturated hydrocarbon fractions, mainly ethane and propane. Said process is carried out in the presence of superheated steam at temperatures within the range of 800-1000 ° C. The operation under these conditions implies a high energy demand and very high expenses related to the cost and maintenance of the furnaces They provide the heat required for the process.
  • DHO-E oxidative dehydrogenation of ethane
  • the oxidative dehydrogenation of ethane (DHO-E) is an exothermic reaction that is not limited by thermodynamic equilibrium and, therefore, it is possible to obtain the complete conversion of ethane at low reaction temperatures ( ⁇ 500 ° C).
  • the number of side reactions is more limited; Generally, carbon monoxide and carbon dioxide are presented as the main by-products, while coke formation is insignificant.
  • Vanadium-based catalysts supported on conventional materials, were the first catalytic systems used for DHO-E, however, its efficiency in producing ethylene was not very high (Oxidative dehydrogenation of ethane and propane: How far from commercial implementation? Cavani et al., Catalysis Today, 127 (2007) 113). Particularly, at higher ethane conversions, the formation of a significant amount of carbon oxides and acetic acid was observed, to the detriment of ethylene formation.
  • Japanese Patent JP 10143314 issued to Mitsubishi Chemical Industries Ltd. describes a MoVSbX catalytic system (where X corresponds to Ti, Zr, Nb, Ta, Cr, W, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd , Pt, Cu, Ag, Zn, In, Sn, Pb, Bi, Ce and rare earth alkali metals) exhibiting a crystalline structure defined by an X-ray spectrum included in the patent.
  • the catalytic system was used for the selective oxidation of ethane to ethylene, with ethane conversions of up to 90.8% and an ethylene selectivity of 68%.
  • a new catalyst with general formula Mo a V b AIA c X and O z is claimed, where X is at least one of the elements belongs to the group of W and Mn; And it is at least one element selected from the group of Pd, Sb, Ca, P, Ga, Ge, Si, Mg, Nb and K; and "z" is an integer representing the number of oxygen atoms required to satisfy the valence of Mo, V, Al, X and Y.
  • These catalysts were used in the partial oxidation of ethane to produce acetic acid as well as ethylene. .
  • the catalyst composition is represented by the general formula Moi.o aSb b NbcZ d On.
  • Z corresponds to at least one element belonging to the following group W, Cr, Ti, Al, Ta, Zr, Hf, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Zn, B, In, Ge, Sn, Pb, Bi, Y, Ga, rare earth metals and rare earth alkali metals.
  • the solid referred to was used to promote the partial oxidation of propane to acrylic acid, with acetic acid being one of the most important by-products.
  • the claimed catalyst is a solid containing tellurium, of general formula V x MoyNbzTe m Me n Op, where Me is a metal belonging to the group Ta, Ti, W, Hf, Zr and Sb, or a mixture thereof.
  • the metals are deposited on a matrix composed of the oxides of Ti, Zr, Al, Mg, La, Si or mixtures thereof, or even a carbon matrix.
  • Patent application US 2010 / 0256432A1 assigned to Lummus Novolent GMBH / Lummus Technology Inc.
  • US Patent 8,105,971 B2 of Lummus Technology Inc. claim a high performance catalyst for the oxidative dehydrogenation of ethane to ethylene.
  • this catalyst system represented by Moi .29Nbo.i7Sbo.oiTe .OV 0 0 .oi250x
  • ethane conversion reached values of up to 81% with a selectivity to ethylene of 89% when the reaction was conducted at 360 ° C. It is noted that this solid also contains tellurium as an ingredient in the formulation.
  • Figure 7 DRX spectra of the catalyst prepared according to example 23.
  • A Dry solid at 100 ° C
  • B Solid heat treated at 200 ° C in air atmosphere, followed by heat treatment at 600 ° C in flow of nitrogen
  • C Solid heat treated in an air atmosphere at 250 ° C, followed by heat treatment at 600 ° G in nitrogen flow.
  • [*] denotes phase M1, [+] phase M2, and [o] Mo0 3 ;
  • FIG. 8 DRX spectra of the catalyst prepared according to example 24.
  • A Dry solid at 100 ° C
  • B Catalyst after heat treatment at 200 ° C in air atmosphere followed by a second heat treatment at 60 ° C C in nitrogen flow.
  • the symbol [*] denotes phase M1, and [+] phase M2;
  • Figure 9 DRX spectra of the catalyst prepared according to example .25.
  • A Dry solid at 100 ° C
  • B Catalyst after heat treatment at 200 ° C in air atmosphere, followed by a second heat treatment at 600 ° C in nitrogen flow
  • C Heat treated catalyst at 250 ° C in air atmosphere, followed by a second heat treatment at 600 ° C in nitrogen flow
  • D Catalyst heat treated at 280 ° C in air atmosphere, followed by a second heat treatment at 600 ° C in flow of nitrogen
  • [ * ] denotes phase M1, [+] phase 2, and [ ⁇ ] Mo0 3 ;
  • FIG. 10 DRX spectra of the catalyst prepared according to example 27.
  • A Dry solid at 100 ° C
  • B Catalyst after a heat treatment at 200 ° C in an air atmosphere, followed by a second heat treatment at 600 ° C in nitrogen flow
  • C Catalyst heat treated at 250 ° C in air atmosphere, followed by a second heat treatment at 600 ° C in nitrogen flow.
  • [*] denotes phase M1, and [+] the phase the M2, and [ ⁇ ] Mo0 3 ;
  • FIG. 11 Scanning Electron Microscopy images of the catalyst prepared according to Example 8 after drying at 100 ° C. This morphology is representative of the solids prepared with the hydrothermal method described herein;
  • FIG. 13 Scanning Electron Microscopy images of the catalyst prepared according to example 28.
  • (Column A) Images of the dry solid at 100 ° C and
  • (Column B) Images of the catalyst subjected to a heat treatment at 250 ° C in atmosphere of air, followed by a second heat treatment at 600 ° C in nitrogen flow;
  • FIG. 14 Scanning Electron Microscopy images, with elementary chemical analysis within the selected areas (bottom), using the Electronic Dispersive Spectroscopy technique.
  • FIG. 15 (Column A) High Resolution Transmission Electron Microscopy images of the crystals present in the catalyst prepared according to Example 23.
  • Column B Electron nano-diffraction patterns of the selected area (PNDAS), which correspond to the circular area marked on the selected crystal of column A. These images agree with the DRX patterns shown in Figure 7, confirming the presence of several crystalline phases.
  • C Image corresponding to a phase o0 3 crystal, which was confirmed by its electron nanodifraction pattern (side straight).
  • This catalyst was heat treated at 250 ° C in an air atmosphere, followed by a second heat treatment at 600 ° C under nitrogen flow;
  • FIG. 16 Images of the Scanning Electron Microscopy, with elementary chemical analysis (right side) within the selected areas, using the technique of Electronic Dispersive Spectroscopy, of the catalyst prepared according to example 29.
  • the catalyst was subjected to heat treatment at 600 ° C in nitrogen flow;
  • A represents Nb, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, rare earth metals or rare earth alkali metals or mixtures thereof, hei, respectively are included in the range of 0.001 and 4.0; 0 ⁇ j ⁇ 2.0, and the i / h ratio between 0.3 and 10.0, where x represents the number determined by y according with the valence of the other elements present in the multimetallic mixed oxide.
  • the resulting catalyst has an M1 crystalline phase, and one or more additional crystalline phases, which give rise to a very active and selective oxidative dehydrogenation catalyst for the conversion of ethane to ethylene, without the presence of tellurium in the catalyst composition.
  • the catalyst of the formula (I) can be prepared by:
  • the multimetallic mixed solid oxide catalyst of the formula (I) is prepared by a process consisting of forming a mixture, tellurium free, of the metal precursors of molybdenum, vanadium and antimony and from a structure-directing compound selected from the group consisting of primary amines, secondary amines, tertiary amines, ammonia, tetramethylammonium and hydrazine, and subjecting said tellurium-free mixture to hydrothermal treatment to form a solid, wash and dry said solid, and activating the dry solid to form a catalyst having one or more crystalline phases in addition to the crystalline phase M1.
  • Preferred structure directing compounds are methylamine, dimethylamine, trimethylamine, diethylamine, or mixtures thereof.
  • the hydrothermal treatment can be carried out at a temperature between 100-200 ° C for 6-150 hours and the resulting solids are washed and dried at 80-120 ° C, before activation.
  • the preferred hydrothermal treatment is performed at a temperature between 150-180 ° C for 12-48 hours.
  • Activation of dry solids involves a first heat treatment at a temperature in the range of about 150 to about 350 ° C under an oxidizing and / or reducing and / or inert atmosphere for 1 to 5 hours; and subsequently a second heat treatment at a temperature in the range of about 150 to about 700 ° C under an oxidizing or inert atmosphere for 1 to 5 hours.
  • the multimetallic mixed oxide solid catalyst is prepared by a process comprising forming a mixture, tellurium free, of the metal precursors of molybdenum, vanadium and antimony and heat treating said mixture, tellurium free , to form a MoVSb solid, dop the MoVSb solid with a metal cation selected from the group consisting of Nb, Cu, W, Bi, Sn, Ti, Fe, Co, Ni, Cr, Ga, Zr, rare earth elements , alkali or alkaline earth metals, such as salts, oxides, hydroxides, or alkoxides, and thermally activating the MoVSb solid doped with the metal cation to form a catalyst having one or more crystalline phases, in addition to the crystalline phase M1.
  • a metal cation selected from the group consisting of Nb, Cu, W, Bi, Sn, Ti, Fe, Co, Ni, Cr, Ga, Zr, rare earth elements , alkali or alkaline earth metals, such as salts, oxides
  • the doping metal cation is Nb, W, Sn, Cu or K.
  • the MoVSb solid is heated at a temperature in the range of about 150 to about 700 ° C before doping said MoVSb solid and then activate the MoVSb solid doped with the metal cation at a temperature in the range of about 150 to about 700 ° C, under an oxidizing or inert atmosphere for about 1 to 5 hours.
  • the mixed marine oxide has the formula
  • h and i respectively are in the range of 0.001 and 4.0; the ratio i / h between 0.3 and 10.0, and x represents a number determined by y in accordance with the valence of the other elements present in the muitimetál ⁇ co mixed oxide; It is prepared with a process, which comprises, forming a mixture, free of tellurium, of the metal precursors of molybdenum, vanadium and antimony and of a compound director of structure selected from the group consisting of primary amines, secondary amines, tertiary amines, ammonia , tetramethylammonium and hydrazine, and subjecting said telltale free mixture to hydrothermal conditions to form a solid, wash, dry said solid, and thermally activate said dry solid to form a catalyst having one or more crystalline phases in addition of the crystalline phase M1.
  • the preferred compound of preferred structure is methylamine, dimethylamine, trimethylamine, diethylamine, or mixtures thereof.
  • Hydrothermal treatment is carried out at a temperature between 100-200 ° C for 6-150 hours; The resulting solids are washed and dried at 80-120 ° C before activation. Preferably, the hydrothermal treatment. It is performed at a temperature between 150-180 ° C for 12-48 hours.
  • Activation involves a first heat treatment at a temperature in a range of about 150 to about 350 ° C under an oxidizing and / or reducing and / or inert atmosphere for 1 to 5 hours; and a second heat treatment at temperatures ranging from about 150 to about 700 ° C under an oxidizing or inert atmosphere for 1 to 5 hours.
  • the multimetallic mixed oxide having the formula MoV h Sb ⁇ O x (II)
  • hei respectively are in the range of 0.001 and 4.0, the ratio of i / h is between 0.3 and 10.0, and x represents a number determined by and according to the valence of the other elements present in the multimetallic mixed oxide, It prepares by means of a process, which comprises, forming an aqueous solution, free of tellurium, of the metal precursors consisting of molybdenum, vanadium and antimony and of a compound structure director selected from the group consisting of primary amines, secondary amines, tertiary amines , ammonia, tetramethylammonium and hydrazine, and subjecting said tellurium-free mixture to hydrothermal conditions to form a solid, wash and dry said solid, and thermally activate said dry solid to form a catalyst having one or more crystalline phases in addition to the phase Crystalline 1.
  • the preferred compound of preferred structure is methylamine, dimethylamine / na, trimethylamine, diethylamine, or mixtures thereof. Hydrothermal treatment and activation are performed as previously described. In this mode the only metallic precursors mixed with the structure director compound are molybdenum, vanadium and antimony. Therefore, the other metals or metal precursors, such as niobium, are excluded from the solution or mixture, and the base metals of the catalyst are only molybdenum, vanadium and antimony.
  • Another modality involves the formation of a multimetallic mixed oxide that has the formula
  • A represents Nb, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, rare earth metals or rare earth alkali metals or mixtures thereof, hei, respectively are included in the range of 0.001 and 4.0, 0.0001 ⁇ j ⁇ 2.0, the ratio i / h is between 0.3 and 10.0, and x represents a number determined by and according to the valence of the other elements present in the multimetallic mixed oxide, said catalyst has a M1 crystalline phase, and one or more additional crystalline phases; said process comprises, forming a mixture, free of tellurium, of the precursors molybdenum, vanadium and antimony metals and heat treat said tellurium-free mixture to form a MoVSb solid, by doping said MoVSb solid with a doping metal cation represented by A, and thermally activating the MoVSb solid added with the metal cation A to form a catalyst having one or more crystalline phases in addition to the crystalline phase M1.
  • the preferred doping metal cation is Nb, W, Sn, Cu or K.
  • the MoVSb solid is heated to a temperature in the range of about 150 to about 700 ° C before doping said MoVSb solid, and then said solid of MoVSb doped with the metal cation at a temperature in the range of about 150 to about 700 ° C under an oxidizing or inert atmosphere for about 1 to 5 hours.
  • the multimetallic mixed oxide having the formula
  • A represents Nb, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, rare earth metals or rare earth alkali metals or mixtures thereof, hei, respectively are included in the range of 0.001 and 4.0, 0.0001 ⁇ j ⁇ 2.0, the ratio i / h is between 0.3 and 10.0, and x represents a number determined by and according to the valence of the other elements present in the multimetallic mixed oxide, it is prepared with a process that includes the stages,
  • Each of the stages from (a) to (e) is performed without the addition of oxygen or H 2 0 2 .
  • the expression "without adding oxygen” means that neither air, or a gas containing oxygen, is introduced at some stage of the process.
  • no addition of H2O2 means that H2O2 is not added at some stage of the process.
  • no metal cation, other than Mo, V or Sb, is present during catalyst formation, until metal cation A is added, such as Nb.
  • the present invention relates to preparation methods for obtaining multimetallic, oxidized mixed oxide catalysts, its activation process and its use in the partial oxidation of ethane to ethylene.
  • the use of the tellurium-free catalysts of multimetallic mixed oxides of the present invention for the oxidative dehydrogenation of ethane produce a high conversion of ethane and a high selectivity to ethylene, at moderate temperatures ( ⁇ 500 ° C), without formation of oxygenated hydrocarbons, as shown in Figure 18, which corresponds to the catalysts prepared according to example 21.
  • the catalysts of the present invention can be represented by the general formula MoVSbA, where A is one of the following elements: Nb, W, GA, Bl, Sn, Ti, Fe, Co, Cu, Ni, Cr, Zr, metals of rare earths, alkali metals or alkaline metals of rare earths or a mixture thereof. According to another embodiment, the catalyst can be represented by the MoVSb formula.
  • the present invention involves the oxidative dehydrogenation of light paraffins to produce definite, more specifically, a procedure for performing oxidative dehydrogenation of ethane to ethylene by means of a process where ethane is contacted with oxygen or with an oxygen-containing stream, and / or with another oxidizing agent, with a catalyst composed of multimetallic mixed oxides.
  • the catalyst is a solid, tellurium-free, containing Mo, V and Sb, and may optionally include a metal A, the latter selected from the following list: Nb, W, GA, Bi, Sn, Cu, Ti, Fe, Co, Cu, Ni, Cr, Zr, rare earth metals or rare earth alkali metals or mixtures thereof.
  • the catalyst, in the heat treated form is represented by the general formula MoVSbAO corresponding to a solid, in which the metal elements are in combination with oxygen to produce a mixture of metal oxides, with varying oxidation states.
  • molybdenum, vanadium and antimony are present in the form of thermally treated mixed oxide, the catalyst formulation having the formula,
  • hei respectively, are each between 0.001 and 4.0, the ratio of i / h respectively are in the range of 0.3 and 10.0, and x represents a number determined by and according to the valence of the other elements present in the oxide mixed multimetallic.
  • the catalyst is prepared by a process, comprising, forming a mixture, free of tellurium, of the metal precursors of molybdenum, vanadium and antimony in solution with a compound "structure director" selected from the group consisting of amines primary, secondary amines, tertiary amines, ammonia, tetramethylammonium and hydrazine, and subjecting said mixture, tellurium free, to hydrothermal conditions to form a solid.
  • the resulting solid is washed and dried, and then thermally activated, to form a catalyst having one or more crystalline phases in addition to the crystalline phase M1, crystalline phases such as M2 and / or Mo0 3 .
  • the only metals in the catalyst are the basic metals of MoVSb without any additional metal or promoter. Also, after activation and formation of the crystalline phase M1, no further or further treatment is required to provide a very active and selective catalyst.
  • the preferred compound of preferred structure is methylamine, dimethylamine, trimethylamine, diethylamine, or mixtures thereof.
  • the hydrothermal treatment is carried out at temperatures between 100-200 ° C for 6-150 hours and the resulting solids are washed and dried at 80-120 ° C before activation.
  • the hydrothermal treatment is at a temperature between 150-180 ° C for 12-48 hours.
  • Activation involves a first heat treatment at a temperature in the range of about 150 to about 350 ° C, preferably 160 to about 300 ° C, in an oxidizing and / or reducing and / or inert atmosphere for 1 to 5 hours; and a second heat treatment at temperatures ranging from about 150 to about 700 ° C, preferably from 550 to 650 ° C under an oxidizing or inert atmosphere for 1 to 5 hours.
  • the catalyst has the empirical formula:
  • A represents Nb, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, rare earth metals or rare earth alkali metals or mixtures thereof, hei, respectively are included in the range of 0.001 and 4.0, 0.0001 ⁇ j ⁇ 2.0, the ratio of i / h is between 0.3 and 10.0, and x represents a number determined by and according to the valence of the other elements present in the multimetallic mixed oxide, said catalyst has a crystalline phase M1, and one or more additional crystalline phases, said process comprises forming a mixture, tellurium free, of the metal precursors of molybdenum, vanadium and antimony and heat treating said mixture, tellurium free, to form a solid a MoVSb, doping said MoVSb solid with a doping metal cation represented by A, and thermally activate the MoVSb solid doped with the metal cation A to form a catalyst having one or more crystalline phases in addition to the crystalline-MI phase.
  • the preferred doping metal cation is Nb, W, Sn, Cu or K.
  • the MoVSb solid Before doping it, the MoVSb solid is heated to a temperature in the range of about 150 to about 700 ° C and after doping it the MoVSb solid is activated at a temperature in the range of about 150 to about 700 ° C under an oxidizing or inert atmosphere for about 1 to 5 hours. Since “x" depends on the oxidation state of the elements Mo, V, Sb and A, the amount of oxygen in the catalyst represented by "x" depends not only on the chemical composition, but mainly on the activation process used, since that the appropriate combination of oxidizing agents and / or reducing agents allows the oxidation state of the metal atoms to be adapted so that they generate highly active and selective catalysts.
  • A represents Nb, W, GA, B ⁇ , Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, rare earth metals or rare earth alkali metals or mixtures thereof, hei, respectively are comprised in the interval of 0.001 and 4.0, 0.0001 ⁇ j ⁇ 2.0, the ratio of i / h is between 0.3 and 10.0, and x represents a number determined by and according to the valence of the other elements present in the multimetallic mixed oxide, said catalyst having an M1 crystalline phase, and one or more additional crystalline phases, said process comprises the steps,
  • Each of the stages from (a) to (e) is performed without the addition of oxygen or H 2 0 2 .
  • the expression "without the addition of oxygen” means that neither air, or a gas containing oxygen, is introduced at some stage of the process.
  • the expression “without adding H 2 0 2” means that H 2 0 2 is not added at some stage of the process.
  • no metal cation, other than Mo, V or Sb, is present during catalyst formation, until metal cation A, such as Nb, is added.
  • A corresponds to Nb, W, Ga, Bi, Sn, Ti, Fe, Co, Cu, Ni, Cr, Zr, rare earth metals, alkali metals, or rare earth alkali metals, or mixtures thereof.
  • A represents Nb, W, Sn, Cu, K or mixtures thereof.
  • the prepared multimetallic mixed oxides and / or those heat treated activated contain Mo, V and Sb in the form of at least one mixed oxide in the catalyst formulation.
  • the heat treated solid After the heat treatment performed to activate the solids, the heat treated solid exhibits an X-ray pattern with several diffraction lines.
  • the most important diffraction lines present in the activated solid were found at 2 ⁇ equal to 6.6 ⁇ 0.4, 7.7 ⁇ 0.4, 9.0 ⁇ 0.4, 22.2 ⁇ 0.4, 26.7 ⁇ 0.4, 26.8 ⁇ 0.4, 27.1 ⁇ 0.4;
  • Corresponding which correspond to the bronze-like orthorhombic structure referred to as crystalline phase M1 (ICSD 55097).
  • This phase has been repeatedly claimed as the most active for the oxidative dehydrogenation of ethane to ethylene. Therefore, many efforts have been made to produce solids with only the M1 phase.
  • activated solids prepared according to the methods presented in this invention frequently have DRX patterns with additional diffraction lines, which denote the presence of other metal oxides, which are also part of the composition of the multimetallic catalytic system. . It should be noted that these activated solids are remarkably more active and selective in the oxidative dehydrogenation of ethane to ethylene, even compared to those that exhibit only the M1 phase. As can be observed in the DRX patterns shown in Figures 2 to 7, 9, 10 and 17, and in the microscopy images reported in Figures 14 to 16, where the presence of crystalline structures is detected in addition to the M1 phase. The resulting solid is a highly active and selective catalyst for the oxidative dehydrogenation of ethane to ethylene.
  • the catalyst can be supported on a solid, such as silica, silica-gel, amorphous silica, zirconium oxide, silicon carbide, alumina, titanium oxide, cordierite, kaolin, aluminosilicates or a mixture thereof, Figure 16 It is presented as an illustration.
  • the amount of the selected support ranges from 20 to 70% weight, of the total weight of the catalyst.
  • the catalyst can be a self-supporting multimetallic mixed oxide, and / or in strong interaction with the crystalline phase obtained and / or segregated from the metallic elements initially present in the precursor solid, as confirmed in figures, 10 (C) and 14.
  • the segregated metal oxide allows the formation of nanometric-sized crystals of the active phase M1 of the multimetallic oxide, thereby increasing the number of active sites in the catalyst.
  • the segregated phase be the crystalline phase of molybdenum oxide (M0O3) and / or the M2 phase, which facilitates the dispersion of the nanometric crystals of the multimetallic mixed oxide, mainly the M1 phase.
  • the multimetallic mixed oxides catalyst can be prepared by conventional methods from solutions containing the compounds of the various elements, from the solutions of the same pure elements, or from the mixture of both, by adjusting the atomic ratios. desired.
  • the solutions mentioned above are preferably aqueous solutions.
  • the process for preparing the multimetallic mixed oxide catalyst comprises at least the following steps:
  • a first stage in which the different metal precursors are mixed and the pH of the solutions can be adjusted.
  • the second stage involves adjusting the preparation conditions of the metal precursor mixture of the previous stage to produce a solid, either by a hydrothermal process or by a heat treatment process.
  • the third stage involves drying the solid obtained in the second stage.
  • the fourth stage involves the process of heat treatment of the dry solid, to obtain an activated solid, which can be used as a catalyst for the oxidative dehydrogenation of ethane to ethylene.
  • the metal precursors can be: pure metal elements, metal salts, metal oxides, metal hydroxides, metal alkoxides, mineral acids, and / or mixtures thereof.
  • the pH of the mixture of mixed multimetallic oxides of the first stage can be adjusted with organic or inorganic bases or with mineral acids, such as, ammonia, H 2 S0 4 , HN0 3 , HCI or mixture thereof.
  • the mixture is subjected to a hydrothermal treatment, as a second stage, and is maintained between 100-200 ° C for 12-150 hours.
  • the mixture is heat treated at a temperature ranging from 50-100 ° C.
  • the mixture is subjected to an evaporation process to remove water.
  • such incorporated elements include Nb, Cu, W, Bi, Sn, Ti, Fe, Co; Ni, Cr, Ga, Zr, rare earth elements, alkali metal or alkaline earth metal, such as salts, oxides, hydroxides, or alkoxides, pure or as mixtures thereof.
  • the mixture is heat treated at a temperature ranging from 50-100 ° C and subjected to an evaporation process to remove water.
  • the mixed multimetallic oxide mixture prepared in the second stage either by hydrothermal treatment or thermal treatments, is washed or dried at 80-120 ° C, as a third stage.
  • Dry solids, obtained in the third stage, are activated by heat treatments at temperatures ranging from 150-350 ° C in an oxidizing and / or reducing and / or inert atmosphere for 1 to 5 hours; and subsequently heat treated at temperatures ranging from 150 to 700 ° C in oxidizing and / or inert flow, preferably nitrogen, for 1 to 5 hours.
  • the dried solids are activated by heat treatments at temperatures ranging from 150-350 ° C, preferably between 160-300 ° C, in an oxidizing and / or reducing and / or inert atmosphere for 1 to 5 hours; and subsequently treated thermally at temperatures ranging between 150 and 700 ° C, preferably between 550 and 650 ° in oxidizing and / or inert flow, preferably nitrogen, for 1 to 5 hours.
  • a structure directing compound is added to the mixed multimetallic oxide mixture prepared in the first stage
  • such organic species are used as templants, or structure directing agents. or as modifiers of the oxidation state of the metallic elements that form the solid.
  • the mixture is subjected, either to hydrothermal treatment or heat treatment, as a second stage, at a temperature between 100-200 ° C, preferably between 150-180 ° C during 12-48 hours
  • the solid obtained is washed and dried at 80-120 ° C.
  • the organic structure directing compound may be primary amines, secondary amines, tertiary amines, ammonia, tetramethylammonium or hydrazine.
  • the amount of amine that is incorporated into the mixed multimetallic oxide mixture depends on the amount of Mo that the catalyst will contain.
  • the atomic ratio of nitrogen (in the amine) to Mo in the mixed multimetallic oxide mixture is in the range of 0.0001-5.0.
  • hydrazine is added to the mixed multimetallic oxide mixture, as the structure director compound, it will be used in a molar ratio of N 2 H 4 / Mo within the range of 0.001 to 2.0, preferably between 0.01 and 1.0.
  • the metal precursors are molybdenum, vanadium and antimony, which can be added as pure metal elements, or metal salts, or metal oxides, or metal hydroxides, or metal alkoxides or mineral acids or as mixtures of the same. Therefore, sulfates, oxalates, halides or nitrates can be used as metal salts, preferably halides and sulfates.
  • the term "metallic precursor" is proposed to include any form of molybdenum, vanadium and antimony.
  • the molybdenum can be added in the mixing stage preferably in the form of ammonium molybdate, molybdic acid, ammonium hepta-molybdate or molybdenum oxide.
  • Vanadium can also be incorporated during the mixing step, preferably in the form of ammonium anadate, vanadyl sulfate, vanadium oxide, vanadyl oxalate or vanadyl chloride.
  • the antimony in turn, can also be added during the mixing step preferably as antimony oxide, antimony sulfate, antimony oxalate, antimony chloride, antimony bromide, antimony iodide, antimony fluoride or metallic antimony.
  • the antimony may be in the form of Sb (lll), Sb (V) or Sb (0), preferably as a compound of Sb (lll).
  • the doping elements Nb, Cu, W, Bi, Sn, Ti, Fe, Co, Ni, Cr, Ga, Zr, rare earth metals, alkali metals or alkaline metals of rare earths can be added in the form of oxides, hydroxides or alkoxides, pure or as part of a mixture of two or more elements.
  • sulfates, oxalates, halides or metal nitrates, preferably halides and sulfates can be used as a source of metals.
  • Hydrazine in turn, can also be added during the mixing stage or once all the different metal compounds have already been incorporated.
  • the mixing step can be followed by a waiting time in a reactor, either statically or while stirring.
  • the period of time, static or in agitation, can be carried out at atmospheric pressure or under pressure.
  • the formation of the solid precursor of the multimetallic mixed oxide catalyst is carried out, either by hydrothermal process or thermal process.
  • the third stage, for the thermal process can be carried out by conventional methods, that is, evaporation in a furnace, or vacuum drying, or spray drying, and / or a mixture thereof.
  • the temperature and reaction synthesis time have an important effect on the physicochemical properties of the solid. Therefore, the synthesis temperature ranges between 100 and 200 ° C and, preferably between 150 and 180 ° C.
  • the synthesis time is preferably in the range of 6-150 hours, and more specifically, from 12 to 48 hours.
  • the mixture of mixed multimetallic oxides of molybdenum, vanadium and antimony are incorporated, as metal oxides on a support, such as, silica, silica gel, amorphous silica, zirconium oxide , silicon carbide, aluminum oxide, titanium, cordierite, kaolin, aluminosilicates or a mixture thereof.
  • the amount of metal oxides used as a support such as silica, silica gel, amorphous silica, zirconium oxide, silicon carbide, aluminum oxide, titania, cordierite, Kaolin, aluminosilicates, or a mixture thereof, can range from 20 to 70% by weight.
  • an oxidizing agent such as H2O2
  • H2O2 is added to the mixture of mixed multimetallic oxides of molybdenum, vanadium and antimony and the selected support, to adjust the oxidation state of the cations .
  • the final mixture is subjected to heat treatment at a temperature ranging from 50-100 ° C, preferably between 70-90 ° C, and subsequently subjected to an evaporation process to remove water.
  • the solid obtained is washed and dried at 80-120 ° C.
  • Multimetallic mixed oxides activation process The activation process for dry multimetallic mixed oxides is carried out by heat treatments at temperatures ranging from 150-350 ° C, preferably between 160-300 ° C in an oxidizing and / or reducing and / or inert atmosphere for 1 to 5 hours, preferably 2 hours; and subsequently heat treated at temperatures ranging from 150 to 700 ° C, preferably 550 to 65Q ° C in oxidizing and / or inert flow, preferably nitrogen, for 1 to 5 hours, preferably for 2 hours.
  • the oxidizing agents may be oxygen, air, C0 2, nitrous oxide, ozone , or mixtures thereof, preferably oxygen and air.
  • the activation of the dry solids obtained in the third stage can be performed with inert agents that include nitrogen, argon, helium, krypton, neon, xenon or mixtures thereof, preferably nitrogen.
  • the process of activating the dry solids obtained in the third stage can be carried out with reducing agents that include hydrogen, CO, alcohols, H 2 0 2 , light hydrocarbons such as methane, or mixtures thereof.
  • the catalyst prepared in accordance with the process described in the present invention is ready to be used in the oxidative dehydrogenation of ethane to produce ethylene.
  • the oxidative dehydrogenation of ethane to produce ethylene involves contacting ethane, or a mixture of ethane with other light hydrocarbons, with an oxidizing agent and / or an inert agent, using the activated multimetallic mixed oxide solid as catalyst.
  • the raw material for the conversion of ethane, or ethane mixed with other light hydrocarbons, to ethylene preferably it uses light hydrocarbons limited from C1 to C4, in which its content is less than 15% by volume with respect to ethane.
  • Conversion of ethane, or mixed with other light hydrocarbons, ethane to ethylene, using an oxidizing agent may be oxygen, air, C0 2, nitrous oxide, ozone , or mixtures thereof, preferably oxygen and air.
  • Ethane, or ethane mixed with Other light hydrocarbons may include an inert agent, which may be nitrogen, argon, helium, krypton, neon, xenon or mixtures thereof, preferably nitrogen.
  • the oxidative dehydrogenation of ethane to ethylene is carried out in the gas phase, it is carried out in the presence of water vapor.
  • the water content can vary from 0.0001 to 80% molar, preferably between 20 and 60% molar.
  • the catalyst of the present invention exhibits a high conversion of ethane and a high selectivity to ethylene, greater than 92%, at moderate reaction temperatures ⁇ 500 ° C, and at atmospheric pressure, without formation of acetic acid and / or other oxygenated hydrocarbons.
  • the conversion of ethane, or ethane mixed with other light hydrocarbons, to ethylene can be carried out in multitubular fixed bed or fluidized bed reactors at atmospheric pressure (between approximately 0.77 and 1 atmosphere) or under pressure as is conventional, at a reaction temperature from about 250 to 550 ° C, preferably between 300 and 480 ° C, and more preferably within the range of 350-450 ° C.
  • the space-time, corresponding to the ratio of catalyst mass to the inlet molar flow rate of ethane (W / F ° e tano) was in the range of 10 and 800 g ca th (mol) "1. , preferably within the range of 20-600 g ca th (mol) "1 , and more preferably between 30 and 350 g ca th (mol) " 1.
  • the catalysts of the present invention provide a high conversion of ethane, selectivity to ethylene and ethylene production
  • MoVhSb ⁇ AjOx catalysts exhibit an ethane conversion greater than 86% molar and an ethylene selectivity that may be greater than 95% molar, at reaction temperatures ranging from 250 to 550 ° C, and at atmospheric pressure; where space-time, corresponding to the mass ratio of catalyst to the inlet molar flow rate of ethane (W / F ° et anus) was located in the range of 10 and 800 g ca th (mol) "1 .
  • the use of the activated MoV h Sbi catalyst can provide an ethylene selectivity greater than 92%, an ethane conversion greater than 86% with the reaction temperatures ranging from 420 to 540 ° C, under a pressure of operation between 0.8 to 1 atmosphere and the W / F ° et year in the range of 80-160 g ca th (mol) "1 .
  • the use of activated MoV h Sb ⁇ A j catalysts can provide an ethylene selectivity greater than 92%, an ethane conversion greater than 84% and reaction temperatures ranging from 420 to 450 ° C, and an operating pressure between 0.8 to 1 atmosphere, with a W / F ° e tano of 160 g cat h (mol) "1.
  • a catalyst can provide ethylene yield greater than 71%, at reaction temperatures ranging from 420 to 450 ° C , and an operating pressure between 0.8 to 1 atmosphere.
  • the W / F ° e tano was 160 g cat h (mol) "1 .
  • the use of the activated MoV h Sb ⁇ catalyst provides an ethylene selectivity greater than 93%, an ethane conversion greater than 75% at reaction temperatures of 390 to 470 ° C, an operating pressure between 0.8 to 1 atmosphere.
  • the W / F ° et ano was in the range of 80-160 g ca th (mol) "1.
  • such a catalyst can provide an ethylene yield greater than 62%, at reaction temperatures ranging from 390 to 470 ° C, an operating pressure between 0.8 to 1 atmosphere.
  • the / F ° ethane was in the range of 80-160 g cat (mol) "1 .
  • the use of the activated MoV h Sb ⁇ A j catalyst supported on a metal oxide produces an ethylene selectivity greater than 95% and a conversion greater than 71% using reaction temperatures from 430 to 460 ° C, an operating pressure between 0.8 and 1 atmosphere.
  • the W / F ° et ano is in the range of 170-320 g ca th (mol) "1.
  • a MoV h Sb ⁇ A j catalyst supported on a metal oxide can provide an ethylene yield greater than 63%, at temperatures of reaction ranging from 430 to 460 ° C, an operating pressure between 0.8 and 1 atmosphere.
  • the W / F ° ethane was in the range of 170-320 g ca th (mol) "1 .
  • the catalysts of the present invention provide a conversion of ethane greater than 86% molar and a selectivity to ethylene which may be greater than 95% molar, at moderate reaction temperatures ⁇ 500 ° C, and at atmospheric pressure as indicated by the following examples.
  • the ambient temperature is defined herein, as the temperature ranging from 10 to 40 ° C.
  • the results of the catalytic tests, associated with the examples presented here, were obtained at atmospheric pressure, which here is defined as the pressure ranging from 0.77 to 1 atmosphere.
  • Examples 1 to 14 are related to the catalyst prepared by the so-called hydrothermal method.
  • Example 1 11.7 grams of ammonium hepta-molybdate tetrahydrate and 2.7 grams of antimony sulfate are dissolved in 85 grams of distilled water at 80 ° C. At the same time, a solution with 4.0 grams of vanadyl sulfate in 17 grams of distilled water at room temperature is prepared. The second solution is slowly added to the first at room temperature while maintaining constant agitation. Then, the resulting mixture is transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 4 days. The autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 1, with the atomic ratio M01.oVo.3eSbo.15.
  • this is catalytically tested in a fixed bed quartz reactor, using, as feed, a gaseous mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 1 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 2 10.7 grams of ammonium hepta-molybdate tetrahydrate and 3.3 grams of antimony bromide are dissolved in 78 grams of distilled water at 80 ° C.
  • a solution is prepared with 3.6 grams of vanadyl sulfate in 15 grams of distilled water at room temperature.
  • the second solution is slowly added to the first at room temperature while maintaining constant agitation.
  • the resulting mixture is transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave.
  • the autoclave is maintained, without stirring, at 175 ° C for 4 days.
  • the autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 2, with the atomic ratio Moi .o 0 .36Sb 0 .i5-
  • it is catalytically tested in a fixed-bed quartz reactor, using as a feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 1 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 3 12.3 grams of ammonium hepta-molybdate tetrahydrate and 2.4 grams of antimony chloride are dissolved in 90 grams of distilled water at 80 ° C.
  • a solution is prepared with 4.1 grams of vanadyl sulfate in 17 grams of distilled water at room temperature.
  • the second solution is slowly added to the first at room temperature while maintaining constant agitation.
  • the resulting mixture is transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 4 days. The autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 3, with the atomic ratio M01. Vo.3eS o.15.
  • this is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 1 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • the autoclave is maintained, without stirring, at 175 ° C for 4 days.
  • the autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid dries at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 4, with the atomic ratio M01 0 or 36Sbo.15.
  • this is catalytically tested in a fixed bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 1 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 5 18.1 grams of ammonium hepta-molybdate tetrahydrate and 4.1 grams of antimony sulfate are dissolved in 132 grams of distilled water at 80 ° C and then this solution is acidified with 8.5 ml of H 2 S0 4 1M (pH 2.0). In parallel, another solution is prepared with 6.0 grams of vanadyl sulfate in 25 grams of distilled water at room temperature. The second solution is slowly added to the first at room temperature while maintaining constant agitation. The resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave.
  • the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water.
  • the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours in the nitrogen flow.
  • the solid resulting from this example is called catalyst 5, with the atomic ratio M01 0Vo.36Sbo.15.
  • this is catalytically tested in a fixed-bed quartz reactor, using as feed, a gaseous mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Example 6 8.9 grams of ammonium hepta-molybdate tetrahydrate and 2.7 grams of antimony bromide are dissolved in 141 grams of distilled water at 80 ° C. In parallel, a solution is prepared with 3.0 grams of vanadyl sulfate in 13 grams of distilled water at room temperature. The second solution is slowly added to the first at room temperature while maintaining constant agitation. The resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave.
  • the autoclave is maintained, without stirring, at 175 ° C for 4 days.
  • the autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water.
  • the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 6, with the atomic ratio MoL0 0.36Sb0.15.
  • this is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Example 7 17.1 grams of tetrahydrated ammonium hepta molybdate and 5.3 grams of antimony bromide are Dissolve in 125 grams of distilled water at 80 ° C.
  • a solution is prepared with 5.7 grams of vanadyl sulfate in 24 grams of distilled water at room temperature.
  • the second solution is slowly added to the first at room temperature while maintaining constant agitation.
  • the resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave.
  • the autoclave is maintained, without stirring, at 175 ° C for 2 days.
  • the autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 7, with the atomic ratio oi. 0 O.36S 0 .i5-
  • it is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gaseous mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7 / 84.
  • Table 1 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 8 10.8 grams of ammonium hepta-molybdate tetrahydrate and 3.3 grams of antimony bromide are dissolved in 79 grams of distilled water at 80 ° C.
  • a solution is prepared with 3.6 grams of vanadyl sulfate in 15 grams of distilled water at room temperature.
  • the second solution is slowly added to the first at room temperature while maintaining constant agitation.
  • the resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 1 day. The autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 8 with the atomic ratio oi.oV 0 .36Sb 0 .i5-
  • the X-ray diffraction spectra of the catalyst, (A) dry at 100 ° C and (B) heat treated at 600 ° C in nitrogen flow, are shown in Figure 1.
  • Example 9 17.5 grams of ammonium hepta-molybdate tetrahydrate and 5.4 grams of antimony bromide are dissolved in 127 grams of distilled water at 80 ° C. At the same time, a solution with 5.8 grams of vanadyl sulfate in 25 grams of distilled water at room temperature is prepared. The second solution is slowly added to the first at room temperature while maintaining constant stirring and then 0.2 grams of acidic potassium carbonate are incorporated into the new solution. The resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 4 days.
  • the autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid resulting from this example is called catalyst 9 with the atomic ratio 01 or o.36Sbo.15Ko 02-
  • it is catalytically tested in a fixed-bed quartz reactor, using, as feed, a compound gaseous mixture by ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • the results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 10 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 10 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow. Separately, 0.01 grams of acidic potassium carbonate are dissolved in 3.1 grams of water at room temperature to produce a solution, which is added to 7.8 g of the solid obtained previously. The suspension resulting from the previous step is filtered and the solid obtained is washed with distilled water, dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow. This heat treated sample is called catalyst 10 with the atomic ratio oi .o o.36Sbo.15 o.002.
  • this is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • the results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 11 18.1 grams of ammonium hepta molybdate tetrahydrate and 5.5 grams of antimony bromide are dissolved in 132 grams of distilled water at 80 ° C. In parallel, a solution with 6.0 grams of vanadyl sulfate in 13 grams of distilled water at room temperature. The second solution is slowly added to the first at room temperature while maintaining constant agitation. The resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 4 days. The autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow. Separately, 0.02 grams of copper (II) sulfate are dissolved in 3.1 grams of water at room temperature to produce a solution which is added to 7.8 grams of the solid obtained previously. The suspension resulting from the previous step is filtered and the solid obtained is washed with distilled water, dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • This heat-treated sample is called catalyst 11, with the atomic ratio of 1.0V0.36S 0.15Cu0.003-
  • catalyst 11 is catalytically tested in a fixed bed quartz reactor made, using, as feed, a mixture gas composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 1 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 12 18.1 grams of ammonium hepta-molybdate tetrahydrate and 5.5 grams of antimony bromide are dissolved in 132 grams of distilled water at 80 ° C. In parallel, a solution with 6.0 grams of vanadyl sulfate in 13 grams of distilled water at room temperature is prepared. The second solution is slowly added to the first at room temperature while maintaining constant agitation. The resulting mixture is then transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 4 days. The autoclave is subsequently cooled to room temperature.
  • the contents of the autoclave are filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow. Separately, 0.02 grams of niobium oxalate are dissolved in 3.1 grams of water at room temperature to produce a solution, which is added to 7.8 g of the solid obtained previously. The suspension resulting from the previous step is filtered and the solid obtained is washed with distilled water, dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • This heat treated sample is called catalyst 12 with the atomic ratio M01 0 o.36S o.15N o.003 ⁇
  • it is catalytically tested in a fixed-bed quartz reactor, using, as a feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio) of 9/7/84.
  • the results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 1.
  • Example 13 18.1 grams of ammonium hepta-molybdate tetrahydrate and 5.5 grams of antimony bromide are dissolved in 132 grams of distilled water at 80 ° C. In parallel, a solution with 6.0 grams of vanadyl sulfate in 13 grams of distilled water at room temperature is prepared. The second solution is slowly added to the first at room temperature while maintaining constant agitation. Then the resulting mixture is transferred to a stainless steel autoclave coated with Teflon. Nitrogen is bubbled for 5 minutes in the mixture to remove the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 4 days. The autoclave is subsequently cooled to room temperature.
  • He Autoclave content is filtered and then the solid fraction is recovered and washed with distilled water. Subsequently, the solid is dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow. Separately, 0.03 grams of ammonium metatungstate is dissolved in 3.1 grams of water at room temperature to produce a solution, which is added to 7.8 g of the solid obtained previously. The suspension resulting from the previous step is filtered and the solid obtained is washed with distilled water, dried at 100 ° C and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • This heat-treated sample is called catalyst 13 with the atomic ratio o1.0 0.36S 0.15W0.002 ⁇
  • it is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • the results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time are shown in Table 1.
  • the catalysts of Examples 10-14 have the crystalline phases M1, M2 and o0 3 .
  • Examples 15 to 22 correspond to the preparation of the catalysts by means of the method called heat treatment.
  • Example 15 3.6 grams of ammonium hepta-molybdate tetrahydrate and 0.9 grams of antimony sulfate are dissolved in 63 grams of distilled water at 80 ° C while maintaining continuous stirring for approximately 1 hour.
  • the resulting mixture is stirred for several minutes (solution A).
  • 0.5 grams of niobium oxalate are dissolved in 18 grams of distilled water at 80 ° C (solution B). Subsequently, solution B is slowly added to solution A at room temperature while maintaining continuous stirring.
  • the water in the new solution is removed by evaporation by applying vacuum at 50 ° C in a rotary evaporator.
  • the resulting solid is dried at 100 ° C, then treated thermally at 280 ° C in nitrogen flow and finally heat treated at 600 ° C for 2 hours in nitrogen flow.
  • the solid sample produced in this example is called a catalyst
  • the water in the new solution is removed by evaporation by applying vacuum at 50 ° C in a rotary evaporator.
  • the resulting solid is dried at 100 ° C, then heat treated at 280 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid sample produced in this example is called a catalyst
  • the resulting solid is dried at 100 ° C, then heat treated at 280 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid sample produced in this example is called catalyst 17 with the atomic ratio M01..oVo.27Sbo.i6N bo.06-
  • it is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 2 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 2.
  • the solid sample produced in this example is called catalyst 18 with the atomic ratio M01.oV 0 .24Sb 0 .i 6 o.o6-
  • the X-ray diffraction pattern of the heat treated catalyst at 280 ° C in an air atmosphere and then heat treated at 600 ° C under nitrogen flow, is shown in Figure 2.
  • it is catalytically tested in a fixed bed quartz reactor, using, as feed, a gaseous mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/83.
  • Table 2 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 2.
  • the water in the new solution is removed by evaporation by applying vacuum at 50 ° C in a rotary evaporator.
  • the resulting solid is dried at 100 ° G, and then heat treated at 280 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid sample produced in this example is denominated catalyst 19 with the atomic ratio Mo1.0 0.2 Sb0.i6Nb0.06 ⁇
  • the X-ray diffraction pattern of the catalyst heat treated at 280 ° C in air atmosphere and then heat treated at 600 ° C in nitrogen flow, is shown in Figure 3.
  • this is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gaseous mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84 .
  • the results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 2.
  • Solution B is slowly added to solution A at room temperature while maintaining continuous stirring.
  • the water in the new solution is removed by evaporation by applying vacuum at 60 ° C in a rotary evaporator.
  • the resulting solid is dried at 100 ° C, then heat treated at 280 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid sample produced in this example is called catalyst 20 with the atomic ratio oLo o.25S o.i6 o.06
  • the X-ray diffraction pattern of the catalyst heat treated at 280 ° C in an air atmosphere and then heat treated at 600 ° C in nitrogen flow is shown in Figure 4.
  • the water in the new solution is removed by evaporation by applying vacuum at 60 ° C in a rotary evaporator.
  • the resulting solid is dried at 100 ° C, then heat treated at 300 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid sample produced in this example is called catalyst 21 with the atomic ratio M01.o o.25Sbo.i6Nbo.06 ⁇
  • the X-ray diffraction pattern of the catalyst heat treated at 300 ° C in an air atmosphere and then heat treated at 600 ° C in nitrogen flow is shown in Figure 5.
  • Example 22 7.0 grams of ammonium hepta-molybdate tetrahydrate are dissolved in 40 grams of distilled water at room temperature applying continuous stirring and then 0.99 grams of antimony trioxide and 0.80 grams of a 50% by weight hydrogen peroxide solution are added. The resulting mixture is kept under stirring at 80 ° C for 1 hour until complete dissolution of the antimony trioxide to produce solution A.
  • 1.4 grams of ammonium metavanadate are dissolved in 40 grams of distilled water at 80 ° C (solution B).
  • 1.28 grams of niobium oxalate are dissolved in 20 grams of distilled water at 80 ° C producing solution C.
  • Example 23 6.9 grams of molybdic acid, 2.27 grams of methylamine hydrochloride (CH 3 NH 2 HCI) together with 1.58 grams of antimony sulfate are dissolved in 85 grams of distilled water at 80 ° C.
  • a second solution is prepared containing 2.29 grams of vanadyl sulfate in 17 grams of water at room temperature. The second solution is slowly added to the first at room temperature while stirring. The resulting mixture is further stirred for 30 minutes and subsequently transferred to a stainless steel autoclave coated with Teflon. The mixture is bubbled with nitrogen for 5 minutes to displace the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature, and its contents are filtered.
  • the solid fraction is recovered and then washed with distilled water.
  • the solid is subsequently dried at 100 ° C, then heat treated at 250 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the heat treated sample is called catalyst 23 with the atomic ratio Mo 1 0 Vo.38Sb 0.16-
  • the X-ray diffraction patterns of the catalyst, (A) dry at 100 ° C, (B) heat treated in an air atmosphere at 200 ° C and then heat treated at 600 ° C in nitrogen flow and (C) heat treated in an air atmosphere at 250 ° C and then heat treated at 600 ° C in nitrogen flow, are shown in Figure 7.
  • Example 24 6.9 grams of molybdic acid, 2.73 grams of dimethylamine hydrochloride (CH 3 NHCH 3 HCI) together with 1.58 grams of antimony sulfate are dissolved in 85 grams of distilled water at 80 ° C.
  • a second solution is prepared containing 2.29 grams of vanadyl sulfate in 17 grams of water at room temperature. The second solution is slowly added to the first at room temperature under stirring. The resulting mixture is further stirred for 30 minutes and subsequently transferred to a stainless steel autoclave coated with Teflon. The mixture is bubbled with nitrogen for 5 minutes to displace the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature, and its contents are filtered.
  • the solid fraction is recovered and then washed with distilled water.
  • the solid is subsequently dried at 100 ° C, then heat treated at 200 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the heat treated sample is called catalyst 24 with the atomic ratio Mo-i .oVo.38Sbo, 16 .
  • X-ray diffraction patterns of the catalyst, (A) dry at 100 ° C, (B) heat treated in an air atmosphere at 200 ° C and then heat treated at 600 ° C under nitrogen flow, are shown in the figure 8.
  • Example 25 6.9 grams of molybdic acid, 2.73 grams of ethylamine hydrochloride (CH3CH2NHHCI) and 1.58 grams of antimony sulfate are dissolved in 85 grams of distilled water at 80 ° C.
  • a second solution is prepared containing 2.29 grams of vanadyl sulfate in 17 grams of water at room temperature. The second solution is slowly added to the first at room temperature while stirring. The resulting mixture is further stirred for 30 minutes and subsequently transferred to a stainless steel autoclave coated with Teflon. The mixture is bubbled with nitrogen for 5 minutes to displace the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature, and its contents are filtered.
  • the solid fraction is recovered and then washed with distilled water.
  • the solid is subsequently dried at 100 ° C, then heat treated at 250 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the heat treated sample is called catalyst 25 with the Moi atomic ratio . oVo.38Sbo.i6N.
  • Example 26 6.9 grams of molybdic acid, 2.73 grams of ethylamine hydrochloride (CH 3 CH 2 NHHCI) together with 1.58 grams of antimony sulfate are dissolved in 85 grams of distilled water at 80 ° C.
  • a second solution is prepared containing 2.29 grams of vanadyl sulfate in 17 grams of water at room temperature. The second solution is slowly added to the first at room temperature while stirring. The resulting mixture is further stirred for 30 minutes and subsequently transferred to a stainless steel autoclave coated with Teflon. The mixture is bubbled with nitrogen for 5 minutes to displace the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature, and its contents are filtered.
  • the solid fraction is recovered and then washed with distilled water.
  • the solid is subsequently dried at 100 ° C, then heat treated at 200 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the heat-treated sample is called catalyst 26 with the atomic ratio Moi.oV 0 .3 8 Sbo 16-
  • it is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 3 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 3.
  • Example 27 6.9 grams of molybdic acid, 3.18 grams of trimethylamine hydrochloride [(CH 3 ) 3 NHCI] together with 1.58 grams of antimony sulfate are dissolved in 85 ml of distilled water at 80 ° C.
  • a second solution is prepared containing 2.29 grams of vanadyl sulfate in 17 grams of water at room temperature. The second solution is slowly added to the first at room temperature while stirring. The resulting mixture is further stirred for 30 minutes and subsequently transferred to a stainless steel autoclave coated with Teflon. The mixture is bubbled with nitrogen for 5 minutes to displace the air contained within the autoclave. Then, the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature, and its contents are filtered.
  • the solid fraction is recovered and then washed with distilled water.
  • the solid is subsequently dried at 100 ° C, then heat treated at 200 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the heat treated sample is called catalyst 27 with the Moi atomic ratio o.38Sbo.i6-
  • the X-ray diffraction patterns of the catalyst, (A) dry at 100 ° C, (B) heat treated in an air atmosphere at 200 ° C and then heat treated at 600 ° C in nitrogen flow, (C) heat treated in an air atmosphere at 250 ° C and then heat treated at 600 ° C in nitrogen flow, are shown in Figure 10.
  • Example 28 6.9 grams of molybdic acid, 3.18 grams of trimethylamine hydrochloride [(CH 3 ) 3 NHCI] together with 1.58 grams of antimony sulfate are dissolved in 85 ml of distilled water at 80 ° C.
  • a second solution is prepared containing 2.29 grams of vanadyl sulfate in 17 grams of water at room temperature. The second solution is slowly added to the first at room temperature under stirring. The resulting mixture is further stirred for 30 minutes and, subsequently, it is transferred to a stainless steel autoclave coated with Teflon. The mixture is bubbled with nitrogen for 5 minutes to displace the air contained within the autoclave.
  • the autoclave is maintained, without stirring, at 175 ° C for 1 day.
  • the autoclave is subsequently cooled to room temperature, and its contents are filtered.
  • the solid fraction is recovered and then washed with distilled water.
  • the solid is subsequently dried at 100 ° C, then heat treated at 250 ° C in an air atmosphere and finally heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the heat treated sample is called catalyst 28 with the atomic ratio Moi, oV 0 .38Sbo.i6- images Scanning Electron Microscopy, reflect) catalyst (Column A) dry at 100 ° C and (Column B) heat treated under an air atmosphere at 250 ° C and then heat treated at 600 ° C under nitrogen flow, they are shown in Figure 13.
  • column B in addition to the Scanning Electron Microscopy images of the catalyst, is shown Elemental chemical analysis, of the selected areas, by the technique of Electronic Dispersive Spectroscopy (bottom), of the catalyst heat treated in an air atmosphere at 250 ° C and then heat treated at 600 ° C in nitrogen flow.
  • this is catalytically tested in a fixed-bed quartz reactor, using, as feed, a gas mixture composed of ethane / oxygen / nitrogen with a nominal molar ratio of 9/7/84.
  • Table 3 The results of the catalytic activity test with the corresponding operating conditions, in terms of temperature and space-time, are shown in Table 3.
  • the following example corresponds to the preparation of the supported catalysts by the so-called heat treatment method.
  • Example 29 8.0 grams of ammonium hepta-molybdate tetrahydrate, 1.2189 grams of ammonium metavanadate and 1,734 grams of antimony oxide (Sb 2 0 3 ) are dissolved in 32 grams of water at 100 ° C, the mixture was kept under stirring for 2 hours, then the solution was cooled to 50 Q C. Subsequently, 7.96 grams of silica gel were added, with a pore size of 60 ⁇ and a surface area 500 m 2 / g, stirring for 30 minutes. Finally, 8 grams of dilute H 2 0 2 (5% by weight) were added and stirred for 1 hour (solution A).
  • a solution is prepared with 1.88 grams of niobium oxalate in 5 grams of water at 60 ° C while stirring; Then the solution was cooled to room temperature. This last solution is slowly added to solution A at room temperature while maintaining constant agitation. The water in the new solution is removed by evaporation. The resulting solid is dried at 100 ° C, and then heat treated at 600 ° C for 2 hours under nitrogen flow.
  • the solid sample produced in this example is composed of 40% by weight of Si0 2 and 60% by weight of the active phase with the atomic ratio o1 0 o.23S o.26 bo.09, the sample is called catalyst 29.
  • Tables 1 to 3 show the results of the catalytic behavior of mixed multimetallic oxides, which were prepared by various methodologies and with varied chemical compositions. Only the most important parameters were included. Table 1. Catalytic behavior, with the corresponding operating conditions, of DHO-E on oV h Sb ⁇ A j catalysts, prepared by the method called hydrothermal.
  • Example 1 540 80 70 70 49
  • Example 14 420 160 69 91 63 Table 2. Catalytic behavior, with the corresponding operating conditions, of the DHO-E on the MoV h Sb ⁇ A j catalysts, prepared by the so-called heat treatment method.
  • Example 20 440 70 30 93 28

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Abstract

La déshydrogénation oxydative de parafines légères, telles que l'éthane, à des températures modérées (<500°C) pour produire de l'éthylène sans formation de produits secondaires tels que l'acide acétique et/ou d'autres hydrocarbures oxygénés est obtenue au moyen de catalyseurs multimétalliques exempts de tellure et comprenant la phase orthorhombique M1 et d'autres structures cristallines ayant un rôle important dans l'obtention des catalyseurs à haut rendement pour la déshydrogénation oxydative de l'éthane en éthylène. De tels catalyseurs sont préparés selon des procédés thermiques et hydrothermiques.
PCT/MX2013/000121 2012-10-19 2013-10-04 Déshydrogénation oxydative de l'éthane en éthylène et préparation d'oxydes mixtes multimétalliques en tant que catalyseurs pour ce procédé WO2014062046A1 (fr)

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CA2888633A CA2888633C (fr) 2012-10-19 2013-10-04 Deshydrogenation oxydative de l'ethane en ethylene et preparation d'oxydes mixtes multimetalliques en tant que catalyseurs pour ce procede
JP2015537654A JP6125023B2 (ja) 2012-10-19 2013-10-04 エチレンへのエタンの酸化脱水素及びこのようなプロセスのための触媒としての多金属混合酸化物の調製

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US13/655,620 US9409156B2 (en) 2012-10-19 2012-10-19 Oxidative dehydrogenation of ethane to ethylene and preparation of multimetallic mixed oxide catalyst for such process
MX2013006308A MX345578B (es) 2012-10-19 2013-06-05 Procedimiento para la preparacion de oxidos mixtos multimetalicos y su uso como catalizadores de alto desempeño en la deshidrogenacion oxidativa de etano para la produccion de etileno, sin formacion de acido acetico u otros hidrocarburos oxigenados.
MXMX/A/2013/006308 2013-06-05
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994580A (en) * 1996-10-21 1999-11-30 Toagosei Co., Ltd. Process for producing acrylic acid

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994580A (en) * 1996-10-21 1999-11-30 Toagosei Co., Ltd. Process for producing acrylic acid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
IVARS, F. ET AL.: "Selective oxidation of propane over alkali-doped Mo-V-Sb-0 catalysts.", CATALYSIS TODAY, vol. 141, no. 3, 2009, pages 294 - 299 *
NOVAKOVA, EKATERINA K. ET AL.: "Propane Oxidation on Mo-V-Sb-Nb Mixed-Oxide Catalysts: 1. Kinetic and Mechanistic Studies.", JOURNAL OF CATALYSIS, vol. 211, no. 1, 2002, pages 226 - 234 *
SAFONOVA, OLGA V. ET AL.: "Mechanism of the oxidation-reduction of the MoVSbNbO catalyst: In operando X-ray absorption spectroscopy and electrical conductivity measurements.", THE JOURNAL OF PHYSICAL CHEMISTRY B, vol. 110, no. 47, 2006, pages 23962 - 23967 *

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