CN101878194A - Process for the ammoxidation or oxidation of propane and isobutane - Google Patents

Process for the ammoxidation or oxidation of propane and isobutane Download PDF

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CN101878194A
CN101878194A CN2008801183712A CN200880118371A CN101878194A CN 101878194 A CN101878194 A CN 101878194A CN 2008801183712 A CN2008801183712 A CN 2008801183712A CN 200880118371 A CN200880118371 A CN 200880118371A CN 101878194 A CN101878194 A CN 101878194A
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compound
oxide
catalyst
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mixture
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克里斯托斯·帕帕里佐斯
迈克尔·J·西利
小詹姆斯·F·布拉兹迪尔
巴豪焦·钱德拉·苏特拉达尔
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Ineos USA LLC
BP Corp North America Inc
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BP Corp North America Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for the ammoxidation or oxidation of a saturated or unsaturated or mixture of saturated and unsaturated hydrocarbon, the process including the steps of combining a performance modifier, a fresh mixed oxide catalyst, or a used mixed oxide catalyst and a fresh and used mixed oxide catalyst to form a catalyst mixture, and contacting the hydrocarbon with an oxygen-containing gas, or an oxygen-containing gas and ammonia, in the presence of the catalyst mixture. The performance modifier may include a compound selected from the group consisting of aluminum compounds, antimony compounds, arsenic compounds, boron compounds, cerium compounds, germanium compounds, lithium compounds, molybdenum compounds, neodymium compounds, niobium compounds, phosphorus compounds, selenium compounds, tantalum compounds, tellurium compounds, titanium compounds, tungsten compounds, vanadium compounds, zirconium compounds and mixtures thereof.

Description

The ammonia oxidation of propane and Trimethylmethane or method for oxidation
Technical field
The present invention generally relates to the ammonia oxidation of stable hydrocarbon or unsaturated hydrocarbons or oxidation to generate the method for unsaturated nitrile or unsaturated organic acid.The present invention be more particularly directed to the propane flammable gas inversion of phases becomes vinyl cyanide to become methacrylonitrile (by ammonia oxidation) or propane flammable gas inversion of phases to become vinylformic acid to become the method for methacrylic acid (by oxidation) with the Trimethylmethane gas phase conversion with the Trimethylmethane gas phase conversion.
Background technology
Mixed metal oxide catalyst has been used to propane and has changed into vinyl cyanide and be used for Trimethylmethane and change into methacrylonitrile (passing through oxidative ammonolysis) and/or be used for propane and change into vinylformic acid (passing through oxidizing reaction).In this field, comprise numerous patent and patent application, comprise, for example people's such as Ushikubo United States Patent (USP) 5,750,760, people's such as Komada United States Patent (USP) 6,036,880, people's such as Komada United States Patent (USP) 6,043,186, people's such as Hinago United States Patent (USP) 6,143,916, people's such as Inoue United States Patent (USP) 6,514,902, people's such as Komada U.S. Patent application US 2003/0088118, the PCT patent application WO 2004/108278 of people's such as Gaffney U.S. Patent application 2004/0063990 and Asahi Kasei Kabushiki Kaisha.
Be incorporated in the oxidation of propane usefulness mixed metal oxide catalyst that comprises Mo-V-O by the oxide compound of initial stage impregnating metal isopropoxide solution oxide compound promotor such as niobium, tellurium and antimony.Described catalyzer drying and calcination then through dipping.
Mixed metal oxide catalyst carries out surface modification and it is reported the catalyst performance with improvement by the vapour deposition of tellurium.When after modification, handling, can be observed further improvement with oxygen.
Tellurium compound and optional molybdenum compound are added in the compound oxides catalyzer that comprises molybdenum, tellurium, vanadium and niobium as catalyst activator.Described catalyst activator in the near future is added in the reactor so that keep catalyst activity in normal operation.
Tellurium compound and/or molybdenum compound property compound as a supplement are added in the used catalyst that comprises molybdenum, vanadium, niobium and antimony.In general, knownly in comprising the reactor of catalyzer of molybdenum, employing adds molybdenum compound.
Although comprise molybdenum, vanadium, antimony and other and be effective to propane and change into vinyl cyanide and be used for Trimethylmethane and change into methacrylonitrile (passing through oxidative ammonolysis) and/or be used for propane and change into vinylformic acid and be used for existing improvement of catalyst field that Trimethylmethane changes into the component of methacrylic acid (passing through oxidizing reaction) relating to, described catalyzer needed further improvement before commericially feasible.Usually, the catalyst system that is used for this reaction known in the art generally suffers the low yield problem of desired product.
Wish the method for the useful products of the higher yield of generation.Also wish under reaction conditions, to have the stability of improvement and/or the catalyzer that in reactor, has the heatproof degree fluctuation of improvement.
Summary of the invention
In one embodiment, the invention provides the ammonia oxidation of mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbons or oxidation to generate the method for unsaturated nitrile or unsaturated organic acid, described method comprises: catalyst mixture is provided, it comprises fresh mixed metal oxide catalyst, exhausted mixed metal oxide catalyst and performance modifier, described fresh mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, described exhausted mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, described performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, molybdenum compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; And make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbons in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.In certain embodiments, described catalyst mixture comprises two or more property modification immunomodulator compounds.
The present invention comprises that also the ammonia oxidation of mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbons is to generate the method for unsaturated nitrile, described method comprises: catalyst mixture is provided, and it comprises: be selected from following performance modifier: aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; Fresh mixed metal oxide catalyst; With the exhausted mixed metal oxide catalyst; Wherein said fresh catalyzer and described used catalyst are independently of one another by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo; With make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon in the presence of described catalyst mixture, contact ammonia and oxygen-containing gas with the mixture of unsaturated hydrocarbon.
In one embodiment, the invention provides the ammonia oxidation of mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbons or oxidation to generate the method for unsaturated nitrile or unsaturated organic acid, described method comprises: catalyst mixture is provided, it comprises the physical mixture of mixed metal oxide catalyst and performance modifier, wherein said mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, and wherein said performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.
The present invention comprises that also the ammonia oxidation of mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon or oxidation are to generate the method for unsaturated nitrile or unsaturated organic acid, described method comprises: catalyst composition and performance modifier are merged to form catalyst mixture, and wherein said catalyst composition comprises the mixed oxide by following empirical formula definition: Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo, and wherein said performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.
In one embodiment, the ammonia oxidation of mixture that the present invention relates to stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon is to generate the method for unsaturated nitrile, described method comprises: catalyst composition and performance modifier are merged to form catalyst mixture, and wherein said catalyst composition comprises the mixed oxide by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo, and wherein said performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon in the presence of described catalyst mixture, contact ammonia and oxygen-containing gas with the mixture of unsaturated hydrocarbon.
Detailed Description Of The Invention
The present invention generally relates to stable hydrocarbon or unsaturated hydrocarbons (ammonia) method for oxidation and can be used for the catalyst composition of described method.This method is effective to propane ammoxidation and generates vinyl cyanide and be used for the Trimethylmethane ammonia oxidation and generate methacrylonitrile and/or be used for propane and change into vinylformic acid and be used for Trimethylmethane and change into methacrylic acid (passing through oxidizing reaction).
In one or more embodiments, the method of the ammonia oxidation of the mixture of unsaturated nitrile by comprising stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon prepares, and may further comprise the steps: performance modifier, fresh mixed oxide catalyst composition and exhausted mixed oxide catalyst composition are merged with the formation catalyst mixture, and make described hydrocarbon contact ammonia and oxygen-containing gas in the presence of described catalyst mixture.
The invention provides the ammonia oxidation of mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon or oxidation to generate the method for unsaturated nitrile or unsaturated organic acid, described method comprises: catalyst mixture is provided, it comprises fresh mixed metal oxide catalyst, exhausted mixed metal oxide catalyst and performance modifier, described fresh mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, described exhausted mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, described performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.
As embodiment, described catalyst modifier is selected from aluminum nitrate, aluminum oxide, weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13, arsenic oxide arsenoxide (III), arsenic oxide arsenoxide (V), arsenic acid, boron oxide, boric acid, ceric ammonium nitrate, cerous acetate, Sedemesis (III) hydrate, cerium oxide (IV), germanium oxide (IV), Lithium Oxide 98min, lithium hydroxide, lithium acetate, lithium nitrate, lithium tartrate, Niobium ammonium oxalate, niobium oxalate, niobium oxides, Vanadium Pentoxide in FLAKES, ammonium phosphate, tin anhydride, tantalum oxide (V), telluric acid, tellurium dioxide, tellurium trioxide, rutile titanium dioxide (TiO 2), anatase type titanium dioxide (TiO 2), titanium isopropoxide, TiO (oxalate), tungstic oxide, oxalic acid vanadyl, vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), Zircosol ZN, zirconium white and composition thereof.
As further embodiment, described catalyst mixture comprises the performance modifier/mole Mo at least about 0.01 mole in the total amount of fresh mixed metal oxide catalyst and exhausted mixed metal oxide catalyst.In another embodiment, the present invention includes fresh mixed oxide catalyst and performance modifier are merged by wet impregnation.As one aspect of the present invention, use non-hydrothermal solution synthetic method to prepare described fresh mixed oxide catalyst and described exhausted mixed oxide catalyst one or both of.In addition, the present invention can comprise described fresh mixed oxide catalyst, described exhausted mixed oxide catalyst and described performance modifier physical mixed; The wherein said step that provides further comprises described fresh mixed oxide catalyst composition and the premixed step of described performance modifier.In addition, the present invention can comprise the step of heating or the described catalyst mixture of calcination.
In one embodiment, described fresh catalyst composition comprises the mixed oxide by following empirical formula definition: Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo.
In one embodiment, described used catalyst composition comprises the mixed oxide by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo.
The present invention also provides the ammonia oxidation of mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon or oxidation to generate the method for unsaturated nitrile or unsaturated organic acid, described method comprises: with dry blending metal oxide catalyst and performance modifier physical mixed to form catalyst mixture, wherein said mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, and wherein said performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.
Performance modifier of the present invention is selected from aluminum nitrate, aluminum oxide, weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13, arsenic oxide arsenoxide (III), arsenic oxide arsenoxide (V), arsenic acid, boron oxide, boric acid, ceric ammonium nitrate, cerous acetate, Sedemesis (III) hydrate, cerium oxide (IV), germanium oxide (IV), Lithium Oxide 98min, lithium hydroxide, lithium acetate, lithium nitrate, lithium tartrate, Neodymium trichloride (III), Neodymium trioxide (III), isopropoxy neodymium (III), neodymium acetate (III) hydrate, Niobium ammonium oxalate, niobium oxalate, niobium oxides, Vanadium Pentoxide in FLAKES, ammonium phosphate, tin anhydride, tantalum oxide (V), rutile titanium dioxide (TiO 2), anatase type titanium dioxide (TiO 2), titanium isopropoxide, TiO (oxalate), tungstic oxide, oxalic acid vanadyl, vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), Zircosol ZN, zirconium white and composition thereof.
As an embodiment, described mixed metal oxide catalyst further comprises at least a following element that is selected from: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tungsten, titanium, tin, germanium, zirconium, lithium and hafnium.In described mixed metal oxide catalyst and the described performance modifier one or more comprise the carrier that is selected from silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide or its mixture.In addition, described catalyst mixture also comprises the performance modifier/mole Mo at least about 0.01 mole in described mixed metal oxide catalyst.In one aspect of the invention, described physical mixed step comprises the mixed metal oxide catalyst through calcination is mixed with performance modifier.
In one embodiment, described mixed metal oxide catalyst comprises the mixed oxide by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo.
As an embodiment of the ammonia oxidation of the mixture of described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon, wherein said contact procedure comprises makes described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon contact ammonia and oxygen-containing gas with the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture.
One aspect of the present invention provides the dry blending metal oxide catalyst by non-hydrothermal solution synthetic method preparation.
In addition, one embodiment of the invention provide the physical mixed step, comprise with without calcination or mix with performance modifier forming mixture through the dry blending metal oxide catalyst of part calcination, and comprise the step of the described mixture of calcination in addition.
Performance modifier
Can be before in being incorporated into reactor with described performance modifier and described catalyst mix.In one or more embodiments, described performance modifier is to be selected from the following compound or the mixture of this compound: aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, molybdenum compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound and zirconium compounds.In one or more embodiments, described performance modifier can be supported on the inert support that includes but not limited to silicon-dioxide, titanium dioxide, zirconium white or its mixture.
The example of aluminum compound comprises aluminum nitrate and aluminum oxide (Al 2O 3).The example of antimony compounds comprises weisspiessglanz, antimony oxalate and antimony tartrate.Specific examples comprises weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III) and weisspiessglanz (V), antimony tetroxide (Sb 2O 4) and Sb 6O 13The example of arsenic compound comprises arsenic oxide arsenoxide (III), arsenic oxide arsenoxide (V) and arsenic acid.The example of boron compound comprises boron oxide and boric acid.
The example of cerium compound comprises ceric ammonium nitrate, cerous acetate, Sedemesis (III) hydrate and cerium oxide (IV).The example of germanium compound comprises germanium oxide (IV).The example of lithium compound comprises lithium hydroxide, Lithium Oxide 98min, lithium nitrate, lithium acetate and lithium tartrate.
The example of molybdenum compound comprises molybdenum oxide (VI) (MoO 3), Ammonium Heptamolybdate and molybdic acid.The example of neodymium compound comprises Neodymium trichloride (III), Neodymium trioxide (III), isopropoxy neodymium (III) and neodymium acetate (III) hydrate.The example of niobium compound comprises Niobium ammonium oxalate, niobium oxalate and niobium oxides.
The example of phosphorus compound comprises Vanadium Pentoxide in FLAKES and ammonium phosphate.The example of selenium compound comprises tin anhydride.The example of tantalum compound comprises tantalum oxide (V).The example of tellurium compound comprises telluric acid, tellurium dioxide and tellurium trioxide.
The example of titanium compound comprises rutile-type and/or anatase type titanium dioxide (TiO 2), titanium isopropoxide and TiO (oxalate).Titanium dioxide is as Degussa P-25, and Tronox A-K-1 and Tronox 8602 (being called A-K-350 in the past) are obtained.The example of tungsten compound comprises tungstic oxide, wolframic acid and ammonium tungstate.The example of vanadium compound comprises the oxalic acid vanadyl, vanadium oxide (III), vanadium oxide (IV), ammonium meta-vanadate and vanadium oxide (V).The example of zirconium compounds comprises Zircosol ZN and zirconium white (ZrO 2).
In one or more embodiments, use two or more property modification immunomodulator compounds.Described modifier compound can side by side or according to the order of sequence be joined in the described catalyst mixture.Described modifier compound can be incorporated into by premix or join respectively in the described catalyst mixture.
In one embodiment, described performance modifier be can with the mixed oxide catalyst physical mixed to improve the solid of catalyst performance.Described performance modifier can comprise that before being used for method of the present invention for example, process is ground, sieves and/or compressed through Overheating Treatment or mechanical treatment.
In other embodiment, described performance modifier can be merged in solution or slurry, is used for described performance modifier dipping mixed oxide catalyst composition.
The amount that is added into the performance modifier in the described catalyst mixture is not particularly limited.In one embodiment, the amount of performance modifier can be used in the total amount of fresh mixed oxide catalyst and exhausted mixed oxide catalyst with respect to the mole number of the described performance modifier of every mole of molybdenum and represents.In one or more embodiments, described catalyst mixture comprises the performance modifier/mole molybdenum at least about 0.01 mole.In these or other embodiment, described catalyst mixture comprises up to about 1.0 moles performance modifier/mole molybdenum in the total amount of fresh mixed oxide catalyst and exhausted mixed oxide catalyst.In one embodiment, described catalyst mixture comprises about 0.01 to about 1.0 moles performance modifier/mole molybdenum.In another embodiment, described catalyst mixture comprises about 0.011 to about 0.5 mole performance modifier/mole molybdenum in the total amount of fresh mixed oxide catalyst and exhausted mixed oxide catalyst, comprise about 0.012 to about 0.2 mole performance modifier/mole molybdenum in another embodiment.
In addition, performance modifier further comprises molybdenum compound.Described performance modifier can comprise weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13, germanium oxide (IV), telluric acid, lithium hydroxide or cerium oxide (IV) or its mixture.
In one embodiment, described performance modifier comprises weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13Or its mixture.In addition, described performance modifier can further comprise tellurium compound.
As an embodiment, described performance modifier, described fresh mixed metal oxide and in the described exhausted mixed metal oxide catalyst one or more comprise the carrier that is selected from silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide or its mixture.
The mixed oxide catalyst composition
The method of improvement of the present invention also is applicable to many fresh and ammonia oxidation of exhausted mixed oxide and oxidation catalyst compositions.The catalyzer that term used herein is fresh is meant and is not exposed to the catalyzer that reactor content flows down.Used catalyst used herein is meant and is exposed to the catalyzer that reactor content flows down.In certain embodiments, described fresh have identical initial composition with used catalyst, and in other embodiment, described fresh different with initial composition used catalyst.Described mixed oxide catalyst composition of Miao Shuing and preparation thereof are applicable to fresh and used catalyst composition of the present invention hereinafter.
In one embodiment, described mixed oxide catalyst composition comprises molybdenum, vanadium, niobium, and comprises in antimony and the tellurium one or both.In one or more embodiments, described mixed oxide catalyst further comprises at least a following element that is selected from: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.In certain embodiments, described catalyst composition can comprise at least a element that is selected from tungsten, tellurium, titanium, tin, germanium, zirconium and hafnium.Used herein " at least a being selected from ... element " or " at least a being selected from ... lanthanon " in its scope, comprise two or more the cited elements or the mixture of lanthanon respectively.
In one embodiment, describedly fresh comprise molybdenum, vanadium, antimony and niobium with exhausted mixed oxide catalyst one or both of, and can be independently by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, and Ti, Sn, Ge, Zr, Hf, Li and composition thereof,
L is selected from La, Ce, and Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof,
0.1≤a≤1.0，
0.01≤b≤1.0，
0.001≤c≤0.25，
0≤d≤0.6，
0≤e≤1; With
N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is that one or more other elements in described mixed oxide can be lower than the oxidation state existence of its highest oxidation state and the mol ratio that a, b, c, d and e represent corresponding element and one mole of Mo.
In one or more embodiments, wherein said catalyst composition is used in the method for ammoxidation, and X can be selected from W, Te, Ti, Ge, Sn, Zr, Hf, Li and composition thereof.In other embodiment, X can be selected from W, Te, Ti, Sn, Zr, Hf, Li and composition thereof.In other embodiment of the described catalyst composition of being described by above-mentioned empirical formula, X is one of W, Te, Ti, Li or Sn.In other embodiment of the described catalyst composition of being described by above-mentioned empirical formula, X is W.
In one or more embodiments, when described catalyst composition is used in the method for ammoxidation, L can be selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.In other embodiment of the described catalyst composition of being described by above-mentioned empirical formula, L is Pr, and L is Nd, and L is Sm, and L is Eu, and L is Gd, and L is Tb, and L is Dy, and L is Ho, and L is Er, and L is Tm, and L is that Yb and L are Lu.In other embodiment of the described catalyst composition of being described by above-mentioned empirical formula, L is one of Nd, Ce or Pr.
In other embodiment of the described catalyst composition of describing by above-mentioned empirical formula, a, b, c and d are positioned at following scope: 0.1≤a independently of one another, 0.2＜a, a＜0.3, a＜0.4, a＜0.8, a≤1.0,0.01≤b, 0.05＜b, 0.1＜b, b＜0.3, b＜0.6, b≤1.0,0.001≤c, 0.01＜c, 0.02＜c, 0.03＜c, 0.04＜c, c＜0.05, c＜0.1, c＜0.15, c＜0.2, c≤0.25,0≤d, 0.001＜d, 0.002＜d, 0.003＜d, 0.004＜d, d＜0.006, d＜0.01, d＜0.02, d＜0.05, d＜0.1, d≤0.2,0≤e, 0.001＜e, e＜0.006, e＜0.01, e＜0.02, e＜0.04, e＜0.1, e≤1.
Described catalyzer of the present invention can be made as (that is, described catalyzer can comprise carrier or can be body catalyst) of being carried or not carried.Appropriate carriers is a silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide or its mixture.Yet when zirconium white or titanium dioxide during as solid support material, the ratio of molybdenum and zirconium or titanium increases and surpasses the value shown in the following formula so, thereby makes that Mo and the ratio of Zr or Ti are about 1: 1 to 1: 10.Carrier causes harder and more attrition resistant catalyzer generally as the tackiness agent of described catalyzer.Yet for commercial applications, the suitable blend of active phase (being the mixture of aforesaid catalysed oxidation thing) and described carrier helps catalyzer to obtain acceptable activity and hardness (resistance to abrasion).Say that directly any increase of the amount of active phase reduces the hardness of described catalyzer.Described carrier accounts for described by 10 to 90 weight % of bearing catalyst.Usually, described carrier accounts for described by 40 to 60 weight % of bearing catalyst.In one embodiment of the invention, described carrier can account for described by the about 10 weight % of being low to moderate of bearing catalyst.In one embodiment of the invention, described carrier can account for described by the about 30 weight % of being low to moderate of bearing catalyst.In another embodiment of the invention, described carrier can account for the about 70 weight % of described as many as by bearing catalyst.
The mixed metal oxide catalyst preparation
The method of the described catalyzer that preparation the present invention is used is not crucial.Can use any method known in the art, such as, but not limited to hydrothermal solution synthetic method and non-hydrothermal solution synthetic method.
In one or more embodiments, described mixed metal oxide catalyst can be by hydrothermal solution synthetic method preparation as herein described.The hydrothermal solution synthetic method is disclosed in people's such as Gaffney U.S. Patent application 2003/0004379, people's " " New Synthesis Route forMo-V-Nb-Te mixed oxides catalyst for propane ammoxidation such as Watanabe "; AppliedCatalysis A:General; 194-195; people such as pp.479-485 (2000) and Ueda; " Selective Oxidation of Light Alkanes over hydrothermally synthesizedMo-V-M-O (M=Al, Ga, Bi, Sb and Te) oxide catalysts. "; Applied CatalysisA:General; 200; pp.135-145, it is incorporated herein by reference.
Usually, catalyst composition as herein described can be by the preparation of hydrothermal solution synthetic method, in the method, come source compound (promptly, comprise and/or provide one or more to be used for the compound of the metal of described mixed metal oxide catalyst composition) mix to form reaction medium and this reaction medium is reacted in sealed reaction vessel under high pressure and high temperature at aqueous solution, last the time that is enough to form described mixed metal oxide.In one embodiment, described hydrothermal solution is synthetic to be continued to be enough to make any organic compound of existing in the reaction medium (for example, the solvent that uses) or comes time of any organic compound complete reaction that source compound is added into the described mixed metal oxide component that described catalyst composition is provided any in the described catalyzer of preparation.
Describedly come source compound in sealed reaction vessel, under greater than 100 ℃ temperature and pressure, to react greater than environmental stress.In one embodiment, described come source compound in described sealed reaction vessel under at least about 125 ℃ of temperature, in another embodiment under at least about 150 ℃ temperature and in another embodiment, under at least about 175 ℃ temperature, react.In one embodiment, described come source compound in described sealed reaction vessel under at least about the pressure of 25psig and in another embodiment under at least about the pressure of 50psig and in another embodiment, under pressure, react at least about 100psig.In one or more embodiments, describedly come source compound in described sealed reaction vessel, under pressure, to react up to about 300psig.This sealed reaction vessel can be equipped with pressure control device, described container is excessively pressurizeed and/or is used to regulate described reaction pressure avoiding.
Describedly come the source compound can be by such rules reaction, these rules comprise comes source compound to mix during reactions steps with described.Described specific mixers system is not crucial, and can comprise for example during reaction by the described component of any effective means mixing (for example stir or stir).This method comprises the content that for example stirs described reaction vessel, and for example, the reaction vessel that comprises described component by jolting, rolling or vibration carries out.This method for example also comprise by use the agitation elements in described reaction vessel at least in part and combine with this agitation elements or and the stirring that provided of described reaction vessel bonded motivating force between described agitation elements and described reaction vessel, to provide relative movement.Described agitation elements can be a drive-type and/or axle support type agitation elements.Described motivating force can directly be incorporated into described agitation elements or can be incorporated into described agitation elements (for example closing by magnetic knot) indirectly.With the reacting phase ratio of unmixed, described mixing generally is enough to make between the component of reaction medium effectively reaction takes place, and is enough to form more the reaction medium of homogeneous (for example, and cause the more mixed metal oxide precursors of homogeneous).This can cause beginning the more efficient consumption of material and cause the more mixed metal oxide product of homogeneous.Cause also that at the described reaction medium of mixing during the reactions steps described mixed metal oxide product forms in solution, but not on the side of described reaction vessel, form.This makes by carrying out reclaiming more rapidly of described mixed metal oxide product such as centrifugal, decant or filtering technology and separate, and has been avoided reclaim the needs of most of product from the side of described reaction vessel.More advantageously be, in solution, have described mixed metal oxide form and allow on all surface of described particle, to carry out particle growth, but not carry out particle growth at limited exposed surface when described reactor wall outwards takes place in growth.
Generally wish in described reaction vessel, to keep certain headspace.If the amount of headspace can be decided according to Vessel Design or reaction mixture used agitation type when stirring.Overhead stirring reaction container for example can adopt 50% headspace.Usually, described headspace is full of ambient air, and it provides a certain amount of oxygen to reaction.Yet described headspace as known in the art, can be filled with other gas so that reactant such as O to be provided 2Or inert atmosphere such as Ar or N 2The amount of headspace with and interior gas decide according to required reaction, this is known in the art.
Describedly come source compound can be in sealed reaction vessel reacting under about 4 the initial pH at the most.In the hydrothermal solution building-up process, the pH of reaction mixture can change, thereby makes the final pH of described reaction mixture may be higher or lower than described initial pH.In one or more embodiments, describedly come source compound in described sealed reaction vessel, reacting under about 3.5 the pH at the most.In some embodiments, described component can be in described sealed reaction vessel at the most about 3.0, at the most about 2.5, at the most about 2.0, at the most about 1.5 or about at the most pH of 1.0, at the most about 0.5 or about at the most 0 under react.In one or more embodiments, described pH can be 0.5 to about 4, and in other embodiment, described pH can be about 0 to about 4, and in other embodiment, described pH can be about 0.5 to about 3.5.In some embodiments, described pH is about 0.7 to about 3.3, in certain embodiments, is about 1 to about 3.Described pH can regulate by adding acid or alkali in described reaction mixture.
Described come source compound can be in sealed reaction vessel above-mentioned reaction conditions (comprising for example aforesaid temperature of reaction, reaction pressure, pH, stirring or the like) down reaction be enough to form for some time of described mixed metal oxide.In one or more embodiments, so the described mixed metal oxide that forms comprises the sosoloid that contains required element as discussed above, and its at least a portion comprises the essential crystalline structure that is used for active and selectivity propane or oxidation of isobutane and/or ammoxidation catalyst.The accurate period in described reaction times is not strict crucial, and for example can comprise at least about three hours, at least about six hours, at least about 12 hours, at least about 18 hours, at least about twenty four hours, at least about 30 hours, at least about 36 hours, at least about 42 hours, at least about 48 hours, at least about 54 hours, at least six ten hours, at least about 66 hours at least about 72 hours.Reaction period even can surpass three days, for example comprise at least about four days, at least about five days, at least about six days, at least about seven days, at least about two weeks, at least about three weeks or at least about one month.
Comprise and provide some aqueous solutions that come source compound (also being called " source " herein) to can be used as described metal-salt of described catalyzer used metal component in synthetic to be provided for described reaction vessel.Some come source compound to can be used as solid or are provided for described reaction vessel as comprising the slurry that is dispersed in the solid particulate in the aqueous medium.Some come source compound to can be used as solid or are provided for described reaction vessel as comprising the slurry that is dispersed in the solid particulate in non-aqueous solvent or other non-aqueous media.
The source examples for compounds that is used for synthetic catalyzer as herein described comprise following those.The example in lithium source comprises lithium hydroxide, Lithium Oxide 98min, lithium acetate, lithium tartrate and lithium nitrate.The example in vanadium source comprises vanadylic sulfate, ammonium meta-vanadate and vanadium oxide (V).The example in antimony source comprises weisspiessglanz (III), antimony acetate (III), antimony oxalate (III), weisspiessglanz (V), antimony trisulfate (III) and antimony tartrate (III).The example in niobium source comprises niobium oxalate, Niobium ammonium oxalate, niobium oxides, ethanol niobium and niobic acid.
The tungsten source comprises ammonium metawolframate, wolframic acid and tungstic oxide.The tellurium source comprises telluric acid, tellurium dioxide, tellurium trioxide, organic tellurium compound such as methyl tellurium phenol and dimethyl tellurium phenol.
The titanium source comprises rutile-type and/or anatase type titanium dioxide (TiO 2), titanium isopropoxide, TiO (oxalate), TiO (acetylacetonate) 2With the titan-alkoxide mixture, such as Tyzor 131.Titanium dioxide is as Degussa P-25, and Tronox A-K-1 and Tronox 8602 (being called A-K-350 in the past) are obtained.The tin source comprises tin acetate (II).The germanium source comprises germanium oxide (IV).The zirconium source comprises Zircosol ZN and zirconium white (IV).The hafnium source can comprise hafnium chloride (IV) and hafnia (IV).
The lanthanum source comprises Lanthanum trichloride (III), lanthanum trioxide (III) and lanthanum acetate (III) hydrate.The cerium source comprises Cerium II Chloride (III), cerium oxide (III), isopropoxy cerium (III) and cerous acetate (III) hydrate.Praseodymium source comprise praseodymium chloride (III), Praseodymium trioxide (III, IV), isopropoxy praseodymium (III) and acetate praseodymium (III) hydrate.The neodymium source comprises Neodymium trichloride (III), Neodymium trioxide (III), isopropoxy neodymium (III) and neodymium acetate (III) hydrate.The samarium source can comprise samarium trichloride (III), Samarium trioxide (III), isopropoxy samarium (III) and acetate samarium (III) hydrate.The europium source can comprise Europium trichloride (III), europium sesquioxide (III) and acetate europium (III) hydrate.The gadolinium source can comprise Gadolinium trichloride (III), gadolinium sesquioxide (III) and gadolinium (III) hydrate.The terbium source comprises terbium chloride (III), terbium sesquioxide (III) and acetate terbium (III) hydrate.The dysprosium source can comprise Dysprosium trichloride (III), dysprosium oxide (III), isopropoxy dysprosium (III) and acetate dysprosium (III) hydrate.The holmium source can comprise Holmium trichloride (III), Holmium trioxide (III) and acetate holmium (III) hydrate.The erbium source can comprise Erbium trichloride (III), Erbium trioxide (III), isopropoxy erbium (III) and acetate erbium (III) hydrate.The thulium source can comprise thulium chloride (III), trioxide (III) and acetate thulium (III) hydrate.The ytterbium source can comprise Ytterbium trichloride (III), ytterbium oxide (III), isopropoxy ytterbium (III) and ytterbium acetate (III) hydrate.The lutetium source can comprise lutecium chloride (III), lutecium oxide (III) and acetate lutetium (III) hydrate.The nitrate of above-named metal also can be used as to come source compound.
The amount of aqueous solvent can be different owing to being merged with the difference of the solubleness of coming source compound that forms specific mixed metal oxide in described reaction medium.The amount of aqueous solvent should be enough to obtain the slurry (solid that can be stirred and mixtures of liquids) of described reactant at least.In the hydrothermal solution of mixed metal oxide is synthetic, generally stay a certain amount of headspace at described reaction vessel.
According to described reactions steps, the other step of described method for preparing catalyst can comprise treatment step, comprise that for example cooling comprises the reaction medium (for example being cooled to about ambient temperature) of described mixed metal oxide, from described liquid, separate comprise described mixed metal oxide solid particulate (for example, by the centrifugal and/or described supernatant liquor of decant, perhaps, by filtering), (for example wash separated solid particulate, use distilled water or deionized water), carry out separating step and washing step one or many repeatedly, and carry out last separating step.In one embodiment, the treating step comprises dry described reaction medium, such as by rotary evaporation, spraying drying, lyophilize or the method for similarly removing liquid.
After described treatment step, can with through the washing and isolating mixed metal oxide drying.Dry described mixed metal oxide can be in envrionment conditions (for example, under about 25 ℃ temperature, at barometric point) under carry out, and/or for example carrying out in about 40 ℃ of baking ovens in about 150 ℃ temperature range, and in one or more embodiments, arrived about 15 hours time of drying in about five hours in about 120 ℃ of processes, and in one or more embodiments, dry about 12 hours.Dry can under controlled or not controlled atmosphere, carrying out, and described dry atmosphere can be rare gas element, oxidizing gas, reducing gas or air.
In one or more embodiments of the present invention, described mixed metal oxide catalyst can be by non-hydrothermal solution synthetic method preparation as herein described.The synthetic US patent application 2006/0235238 that also is disclosed in SatoruKomada and Sadao Shoji of non-hydrothermal solution, and among the WO 2006/019078 of Kato Takakai and Fukushima Satoshi, it is incorporated herein by reference.
A kind of non-hydrothermal solution method can usually followingly be described.Come source compound, vanadium to come source compound, antimony to come source compound, optional other to come source compound, hydrogen peroxide and carrier colloidal sol such as silicon dioxide gel to prepare first aqueous solution/slurry by merging molybdenum under heating and agitation condition.Come source compound, optional dicarboxylic acid and optional other to come source compound to prepare second aqueous solution/slurry by merging niobium under heating and agitation condition.Described first and second aqueous solutions/slurry is merged to form the 3rd aqueous solution/slurry.The solid that can remove precipitation and/or suspend, and with described aqueous mixture drying to form the dry blending metal oxide catalyst.Can adopt multiple treatment step and drying and/or method for calcinating.
In one embodiment, non-hydrothermal solution method can followingly more accurately be described, and wherein first aqueous solution/slurry is expressed as (A), and second aqueous solution/slurry is expressed as (B).Ammonium Heptamolybdate, ammonium meta-vanadate and antimonous oxide are added to the water, then the mixture heating up that generates are arrived at least 50 ℃ temperature, thereby obtain aqueous mixture (A).Preferred heating is stirred at the same time under the condition of described mixture and is carried out.Advantageously, described aqueous mixture is heated to about 70 ℃ of temperature to the normal boiling point scope of described mixture.Described heating can have under the condition that the equipment of reflux exchanger refluxes in use to be carried out.Under the reflux situation, described boiling point is generally about 101 ℃ to 102 ℃.It is about more than 0.5 hour that high temperature can keep.When Heating temperature is about 80 ℃ to about 100 ℃, be generally described heat-up time about 1 to about 5 hours.When Heating temperature low relatively (for example, being lower than about 50 ℃), need longer described heat-up time.
Randomly, the colloidal sol of hydrogen peroxide and/or solid support material such as silicon dioxide gel can be added into after aforesaid heating in the described aqueous mixture (A).When hydrogen peroxide being joined described aqueous mixture (A), the amount of described hydrogen peroxide can be and makes hydrogen peroxide and mol ratio (H in the antimony compounds of antimony 2O 2/ Sb mol ratio) is about 0.01 to about 20, in one embodiment,, in another embodiment, is about 1 to about 2.5 for about 0.5 to about 3.After adding hydrogen peroxide, aqueous mixture (A) can be at about 30 ℃ of stir abouts 30 minutes to about 2 hours under about 70 ℃ temperature.
In one or more embodiments, aqueous solution/slurry (B) thus can come source compound, optional dicarboxylic acid and/or other to come source compound to form the initial aqueous solution that contains niobium or have the aqueous mixture that contains niobium that wherein is suspended with a part of described niobium compound to prepare by under heating and agitation condition, merging water, niobium.Described initial aqueous solution that contains niobium or the aqueous mixture that contains niobium can be cooled then, thereby if add dicarboxylic acid, its part is precipitable.Can from the initial aqueous solution that contains niobium, remove sedimentary dicarboxylic acid after the cooling step, or from the described aqueous mixture that contains niobium, remove the niobium compound of sedimentary dicarboxylic acid and suspension, thereby obtain to contain the waterborne liquid (B) of niobium.
In one embodiment, waterborne liquid (B) can be by being added to the water niobium compound (for example niobic acid), and it is obtained then the mixture heating up that generates to be arrived about 100 ℃ temperature to about 50 ℃.When niobic acid is a described niobium when coming source compound, also can add dicarboxylic acid.The dissolving of described niobium compound can be promoted by adding a spot of ammoniacal liquor.
The example of suitable dicarboxylic acid comprises oxalic acid.In one embodiment, niobic acid and oxalic acid are added to the water,, thereby obtain waterborne liquid (B) then by mixture heating up and stirring with described generation.Usually, described dicarboxylic acid and described mol ratio in the described niobium compound of niobium are about 1 to 4, in one embodiment, are about 2 to about 4.
In other embodiment, described niobium comes source compound to comprise oxalic acid hydrogen niobium or Niobium ammonium oxalate.When using oxalic acid hydrogen niobium or Niobium ammonium oxalate, do not require described dicarboxylic acid as described niobium compound.
Usually, described niobium come source compound can solid, mixture or be added into as the form of the dispersion in suitable medium.When niobic acid when the described niobium compound, in the time of can polluting the acidic impurities of described niobic acid in order to remove during described niobic acid generates, described niobic acid is with preceding available ammonia soln and/or water washing.Using freshly prepd niobium also is favourable as described niobium compound.Yet, because prolonged preservation etc. and the niobium compound of sex change slightly (sex change of for example dewatering) can be used.
Described niobium compound (in niobium) in one or more embodiments, is maintained at about 0.2 in described initial aqueous solution that contains niobium or the concentration in the aqueous mixture in the scope of about 0.8 mole of/kilogram described solution or mixture.Described dicarboxylic acid is in one or more embodiments, so that dicarboxylic acid and mol ratio in the niobium compound of niobium are about 2 to about 6 amount use.When using excessive described dicarboxylic acid, a large amount of described niobium compounds can be dissolved in the described dicarboxylic acid aqueous solution; Yet the amount of sedimentary described dicarboxylic acid can become too big when the initial aqueous solution that contains niobium that obtained of cooling or mixture, thereby the availability of described dicarboxylic acid is reduced.On the other hand, when using described dicarboxylic acid in shortage, a large amount of described niobium compounds can keep insoluble in described aqueous solution or mixture or keep suspending, thereby can be removed from described aqueous mixture subsequently, thereby the availability of described niobium compound is reduced.
Can use any suitable method of cooling.For example, can simply carry out described cooling by means of ice bath.
Described sedimentary dicarboxylic acid (or described sedimentary dicarboxylic acid and dispersive niobium compound) remove can be by ordinary method for example by decant or filtration and easily carry out.
When the mol ratio of the described dicarboxylic acid/niobium of the aqueous solution that contains niobium that obtains is positioned at about 2 to about 6 scope in addition the time, described niobium compound or dicarboxylic acid can be joined in the described waterborne liquid (B), thereby make the mol ratio of described dicarboxylic acid/niobium of described solution fall in the above-mentioned scope.Yet, usually, this operation is unnecessary because have can be by the concentration of suitably controlling described niobium compound, described dicarboxylic acid and described niobium compound at about 2 the waterborne liquids (B) of described dicarboxylic acid/niobium mol ratio in about 4 scopes ratio and the above-mentioned initial aqueous solution that contains niobium or the cooling temperature of aqueous mixture prepare.
Described waterborne liquid (B) can further comprise one or more other components.In one or more embodiments, waterborne liquid (B) can further comprise hydrogen peroxide (H 2O 2).In these or other embodiment, waterborne liquid (B) can further comprise one or more in antimony compounds (for example antimonous oxide), titanium compound (for example titanium dioxide, it can be the mixture of rutile titanium dioxide and anatase titanium dioxide) and the cerium compound (for example cerous acetate).In one embodiment, the amount of described hydrogen peroxide is to make hydrogen peroxide and mol ratio (H in the niobium compound of niobium 2O 2/ Nb mol ratio) be about 0.5 to about 20, and be about 1 to about 20 in another embodiment.In certain embodiments, antimony compounds mixes with described waterborne liquid of at least a portion (B) and described hydrogen peroxide, thereby making to be no more than approximately 5 in the described antimony compounds of antimony and mol ratio (Sb/Nb mol ratio) in the described niobium compound of niobium, and is about 0.01 to about 2 in one embodiment.
Aqueous mixture (A) and waterborne liquid (B) can be suitable ratio be mixed together to form aqueous solution/slurry.(a) will decide according to the required composition of described catalyzer with ratio (b).Solid amount in the described aqueous mixture is generally more than about 10 weight %.In one embodiment, total weight based on described mixture, solid amount in the described aqueous mixture is about 10 to 60 weight %, be about 15 to 55 weight % in another embodiment, and in another embodiment, the solid amount in the described mixture is about 20 to about 50 weight %.
In one or more embodiments, when wishing the silicon-dioxide bearing catalyst, preparation aqueous solution/slurry is to comprise silicon-dioxide source (being silica sol or pyrogenic silica).The amount in silicon-dioxide source can suitably be regulated according to the amount of described silica supports required in the catalyzer that will obtain.
But described aqueous solution/slurry drying is to remove liquid portion.Drying can be undertaken by ordinary method such as spraying drying or evaporation drying.Spraying drying is particularly useful, because obtained thin, globular, drying solid.Described spraying drying can be undertaken by centrifugal.
But described aqueous solution/slurry drying is to remove described liquid portion.Dry can being undertaken by ordinary method such as spraying drying or evaporation drying.Spraying drying is particularly useful, because obtain thin, globular, drying solid.Described spraying drying can by centrifugal, carry out by two-phase flow nozzle method or by the high pressure spray nozzle method.As the exsiccant heating source, the preferred use by heated air such as steam, electricradiators.If it is favourable to about 300 ℃ that the inlet of described spray-dryer is about 150 ℃ to the temperature of its dryer part.
At this moment, no matter the material of drying forms by hydrothermal solution method or non-hydrothermal solution method, can be called as the dry blending metal oxide catalyst.Can understand, term " is done " and " drying " is meant the solid of having removed most of liquid from it, although can keep some moisture.Therefore, unless otherwise stated, term " is done " and " drying " should be understood to mean dry in fact.For the purpose of this specification sheets, term " dry blending metal oxide catalyst " continues to be meant that this dry blending metal oxide catalyst can experience optional other processing this material of (comprising calcining as mentioned below and grinding).In addition, term " dry blending metal oxide catalyst " can refer to the catalyzer that used in reactor.Therefore, the dry blending metal oxide catalyst can grind through calcination or without calcining, and crushing becomes bead, extrudes or other form or shape, and can be fresh catalyzer or used catalyst.
As indicated above, described dry blending metal oxide catalyst can experience other processing.This processing can comprise the calcining of for example carrying out (for example being included in the thermal treatment under oxidation or the reductive condition) under multiple processing atmosphere.Described dry blending metal oxide can pass through crushing off and on or grind before this processing and/or during this processing.In one embodiment, for example, described dry blending metal oxide can be randomly through crushing, and then through calcination.
Described calcining can be carried out in inert atmosphere, reducing atmosphere or oxidizing atmosphere.In one embodiment, at least a portion calcining is carried out under inert gas atmosphere (for example at inert gas flow), carries out under the nitrogen such as oxygen-free gas in fact.In one or more embodiments, described calcination condition comprises that about 200 ℃ are arrived about 700 ℃ temperature, in other embodiment, comprises that about 400 ℃ are arrived about 650 ℃ temperature.
In one or more embodiments, the Heating temperature of dry blending metal oxide catalyst is continuously or off and on from being elevated to about 550 ℃ to about 700 ℃ less than about 400 ℃.In certain embodiments, can adopt multistep to calcine suddenly.In these embodiments, described dry blending metal oxide catalyst can be calcined through part under at least about 200 ℃ relative low temperature in temperature range mentioned above, calcines through part under at least about one or more comparatively high tempss of 400 ℃ then.
The mixed metal oxide of treated (for example through calcination) can experience further mechanical treatment, and for example comprising grinds, sieves and compress described mixed metal oxide forms the final form that it uses in the methods of the invention.
In other embodiment, described catalyzer can be shaped as its final form before any calcining or other thermal treatment.For example, in the preparation fixed bed catalyst, described catalyst precursor slurry is generally by at high temperature being heated, and be shaped before calcining then (for example extrude, become bead etc.) becomes required fixed bed catalyst size and structure.Similarly, in the preparation fluid catalyst, described catalyst precursor slurry can be by spraying drying to obtain to have in about 10 the microspherical catalyst particles of particle diameter in about 200 micrometer ranges, calcining then.Those skilled in the art will appreciate that the variant of aforesaid method.
Calcining can adopt rotary kiln, fluidized-bed kiln or the like to carry out.In one or more embodiments, calcining is carried out under unstable state, and has avoided unstable incinerating problem (deterioration and/or destruction or the crack that cause the described character of the catalyzer that obtains).
Thereby condition(s) of calcination can make the described catalyzer that forms have about 5m through chosen in advance 2/ g is to 35m 2The specific surface area of/g.Thereby described condition(s) of calcination can advantageously make the catalyzer that generates comprise one or more crystal phases through chosen in advance.
Form the method for physical mixture.
Described catalyst mixture can merge described fresh catalyzer, used catalyst composition and performance modifier by certain combination of physical mixed, wet impregnation or these technology and prepare.But one or more described component pre-mixings.Order of addition(of ingredients) is not crucial.In one embodiment, but described performance modifier and fresh catalyzer pre-mixing, and mix with described used catalyst then.Described performance modifier can be heated in a plurality of stages of the described fresh catalyst composition of preparation.Yet, in certain embodiments, when described properties-correcting agent is added in the described fresh catalyst composition of final form, visible improved performance.
In one embodiment, but described performance modifier and used catalyst pre-mixing, and then with described fresh catalyst mix.In one embodiment, described performance modifier is a solid, and can be by levigate before described properties-correcting agent and described catalyst composition are merged.In another embodiment, described performance modifier has thicker size of particles,, is in the rank of the size of particles of described catalyzer that is.
In one or more embodiments, described performance modifier can be added in described exhausted and fresh catalyst composition one or both of by wet impregnation.In one embodiment, performance modifier, fresh mixed oxide catalyst and the described physical mixture of exhausted mixed oxide catalyst can experience thermal treatment or calcining.
In certain embodiments, when using two or more property modification immunomodulator compounds, described property modification immunomodulator compounds can be joined in the described catalyst mixture respectively, perhaps by pre-mixing to form the properties-correcting agent mixture.Described properties-correcting agent mixture can mix with the mixed oxide catalyst composition by physical mixed or dipping then.
Propane and Trimethylmethane are via the conversion of ammonia oxidation and oxidizing reaction
The invention provides propane and be converted into the method that vinyl cyanide and Trimethylmethane are converted into methacrylonitrile.Described method comprises processability properties-correcting agent as mentioned above, fresh mixed oxide catalyst composition and the mixture of exhausted mixed oxide catalyst composition, and make described catalyst mixture under the existence of oxygen (for example comprising in the streams of oxygen-containing gas being provided in the reaction zone, such as and generally be air) and ammonia, contact propane or Trimethylmethane under the reaction conditions that effectively forms vinyl cyanide or methacrylonitrile.For this reaction, described streams comprises propane or Trimethylmethane, oxygen-containing gas such as air and ammonia.In one or more embodiments, the mol ratio of propane or Trimethylmethane and oxygen is about 0.125 to about 5, is about 0.25 to about 4.5 and is about 0.35 to about 4 in another embodiment in another embodiment.In one or more embodiments, the mol ratio of propane or Trimethylmethane and ammonia is about 0.3 to about 4 and is about 0.5 to about 3 in another embodiment.Described streams also can comprise one or more other material components, comprises vinyl cyanide or methacrylonitrile product (for example, derive from recycle stream or derive from the previous stage of staged reactor), and/or steam.For example, the total amount that described streams can comprise with respect to described logistics is the other material components of about 5 weight % to about 30 weight %, or is the other material components of about 5 moles of % to about 30 moles of % with respect to the amount of propane in the described streams or Trimethylmethane.In one embodiment, as herein described to be used for the method that propane ammoxidation becomes vinyl cyanide be one-through process, that is, it is recovered in nothing but operates under the recirculation of unreacted material material.
By one or more above-mentioned catalyzer are provided in the vapor phase stream reactor, and make described catalyzer (for example comprise in the streams of oxygen-containing gas and be provided this reaction zone effectively forming under acrylic acid reaction conditions at oxygen, such as and generally be air) have contact propane down, also propane can be converted into vinylformic acid and Trimethylmethane can be converted into methacrylic acid.The described material materials flow that is used for this reaction preferably comprises about 0.15 to about propane of 5, preferred about 0.25 to about 2 or the Trimethylmethane ratio with oxygen.Described streams also can comprise one or more other material components, comprises acrylic or methacrylic acid product (for example, derive from recycle stream or derive from the previous stage of staged reactor), and/or steam.For example, the total amount that described streams can comprise with respect to described logistics is the other material components of about 5 weight % to about 30 weight %, or is the other material components of about 5 moles of % to about 30 moles of % with respect to the amount of propane in the described streams or Trimethylmethane.
The particular design of vapor phase stream reactor is not strict crucial.Therefore, described vapor phase stream reactor can be fixed-bed reactor, the reactor of fluidized-bed reactor or other type.Described reactor can be a single reaction vessel, perhaps can be a reactor in multistage reactor system.In one or more embodiments, described reactor comprises the one or more opening for feeds that are used for reactant feed stream is supplied to the reaction zone of described reactor, comprise the reaction zone of described catalyst mixture, and the outlet that is used to discharge reaction product and unreacted reactant.
Described reaction conditions can be converted into propane vinyl cyanide or vinylformic acid respectively or be used for described Trimethylmethane is converted into methacrylonitrile or methacrylic acid being used for effectively through control, or described Trimethylmethane is converted into methacrylonitrile.Usually, reaction conditions comprises that about 300 ℃ are arrived about 550 ℃ of temperature, about in one embodiment 325 ℃ to about 500 ℃, about in some embodiments 350 ℃ to about 450 ℃ and about in other embodiments 430 ℃ to about 520 ℃.The pressure of described reaction zone can arrive about 100psig and arrive about 50psig for about 0psig in some embodiments for about 0psig in one embodiment through controlling to reach about 0psig to about 200psig.
Usually, the streams that comprises propane or iso-butylene can be about 0.02 to about 5 so that weight hourly space velocity (WHSV) to be provided through control through the flow velocity of the reaction zone of described vapor phase stream reactor, in some embodiments is about 0.05 to about 1, be about 0.1 to about 0.5 in other embodiments, under each situation, for example, with propane or Trimethylmethane gram number/catalyzer gram number/hour expression.
If wish, can be according to methods known in the art with the vinyl cyanide and/or acrylic or methacrylic nitrile and/or methacrylic acid product and other by product and/or the unreacted reactants separate that generate.By product in ammonia oxidation can comprise CO x(carbonic acid gas+carbon monoxide), prussic acid (HCN) and acetonitrile or methyl-cyanide (CH 3CN).The effluent of described reactor also can comprise unreacted oxygen (O 2), ammonia (NH 3), nitrogen (N 2), helium (He) and the catalyst fines of being carried secretly.
Embodiment
For the present invention is described, prepared the sample of multiple catalyst mixture, under similar reaction conditions, estimate then.Following composition is that nominal is formed, and calculates based on the total metal that adds in the preparation of described catalyst mixture.Because some metals are possible loss or possibility incomplete reaction in Preparation of Catalyst, the true composition of therefore final catalyst mixture may be different slightly with described nominal composition as follows.
Live catalyst can be produced with its final form according to method as herein described.The described live catalyst of a part and used catalyst and catalyst modifier merge, and use mechanical mixer to mix under dry state.
At diameter is evaluate catalysts in 1 inch the 40cc fluidized-bed reactor.Described reactor loads about 20 to about 45g pelleted catalyst or catalyst mixture.Propane is fed in the described reactor to the speed of about 0.15WWH (that is, the weight of the weight/catalyzer of propane/hour) with about 0.04.Usually, ammonia so that being about 1 to about 1.5 speed, the ratio of described ammonia and propane is fed to described reactor.Pressure in the described reactor is maintained at about 2 to about 15psig.Temperature of reaction is about 420 about 460 ℃.
Comparative example 1: prepared the catalyzer with following nominal composition: MoV 0.21Sb 0.24Nb 0.09O x, and comprise the silica supports of 45 weight %.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 1.
Embodiment 1-1: with the used catalyst of comparative example 1 with the ratio of 2/3 used catalyst and 1/3 live catalyst with have nominal and form MoV 0.21Sb 0.24Nb 0.09O xLive catalyst merge, and with amount and the Sb of 0.1 mole of Sb/ mole Mo in the described base catalyst composition 2O 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 1.
Comparative example 2: prepared and have the catalyzer that the nominal identical with comparative example 1 formed.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 1.
Embodiment 2-1: with the used catalyst of comparative example 2 with the ratio of 2/3 used catalyst and 1/3 live catalyst with have nominal and form MoV 0.21Sb 0.24Nb 0.09O xLive catalyst merge, and with amount and the MoO of 0.02 mole of Mo/ mole Mo in the described base catalyst composition 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 1.
Embodiment 2-2: with the used catalyst of comparative example 2-1 with the ratio of 2/3 used catalyst and 1/3 live catalyst with have nominal and form MoV 0.21Sb 0.24Nb 0.09O xLive catalyst merge, and with amount and the Sb of 0.1 mole of Sb/ mole Mo in the described base catalyst composition 2O 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 1.
Table 1
Figure GPA00001142602900291
Comparative example 3: prepared the catalyzer with following nominal composition: MoV 0.21Sb 0.24Nb 0.09O x, and comprise the silica supports of 45 weight %.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-1: with the catalyzer of comparative example 3 and the Sb that with respect to every mole of Mo in the described base catalyst composition is 0.05 mole 2O 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-2: with the catalyzer of comparative example 3 and the Sb that with respect to every mole of Mo in the described base catalyst composition is 0.1 mole 2O 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.His result is as shown in table 2.
Embodiment 3-3: with the catalyzer of comparative example 3 and the Sb that with respect to every mole of Mo in the described base catalyst composition is 0.2 mole 2O 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-4: with the catalyzer of comparative example 3 and the TiO that with respect to every mole of Mo in the described base catalyst composition is 0.02 mole 2Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-5: with the catalyzer of comparative example 3 and the H that with respect to every mole of Mo in the described base catalyst composition is 0.02 mole 6TeO 6Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-6: the Sb that with catalyzer and relative every mole of Mo of comparative example 3 is 0.1 mole 2O 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Catalyst performance was summarised in the table 2 after the time expand of normal operation.
Embodiment 3-7: with the catalyzer of comparative example 3 and the H that with respect to every mole of Mo in the described base catalyst composition is 0.05 mole 3BO 3Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-8: with the catalyzer of comparative example 3 and the Sb that with respect to every mole of Mo is 0.1 mole 2O 4Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described the results are shown in the table 2.
Embodiment 3-9: with the catalyzer of comparative example 3 and the (NH that with respect to every mole of Mo is 0.05 mole 4) 2HPO 4Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Embodiment 3-10: the catalyzer of comparative example 3 is merged with the LiOH that with respect to every mole of Mo in the described base catalyst composition is 0.04 mole.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 2.
Table 2
Comparative example 4: prepared the catalyzer with following nominal composition: MoV 0.3Sb 0.2Nb 0.08Ti 0.1Ce 0.005O x, and comprise the silica supports of 45 weight %.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 3.
Embodiment 4-1: with the catalyzer of comparative example 4 and the GeO that with respect to every mole of Mo in the described base catalyst composition is 0.025 mole 2Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 3.
Embodiment 4-2: with the catalyzer of comparative example 4 and the GeO that with respect to every mole of Mo in the described base catalyst composition is 0.025 mole 2Merge.Described catalyzer is estimated in the 40cc fluidized-bed reactor.Described result is as shown in table 3.
Table 3
The embodiment numbering ??WWH Pressure p sig Temperature ℃ Propane transforms % Vinyl cyanide is selected % Acrylonitrile yield % HCN yield % Acetonitrile yield % Vinylformic acid yield % ??CO 2Yield % CO yield % The hours of normal operation
Comparative example 4 ??0.060 ??10 ??440 ??84.3 ??44.9 ??37.8 ??5.7 ??2.7 ??1.1 ??20.6 ??15.2 ??17
Embodiment 4-1 ??0.060 ??10 ??440 ??83.4 ??48.9 ??40.8 ??5.1 ??3.4 ??2.3 ??16.6 ??13.8 ??17
??0.060 ??10 ??440 ??83.3 ??48.8 ??40.7 ??5.2 ??3.3 ??1.9 ??16.9 ??14.0 ??19
Embodiment 4-2 ??0.060 ??10 ??440 ??82.5 ??49.2 ??40.5 ??5.1 ??3.4 ??2.2 ??15.5 ??14.1 ??17
Although description above and above-mentioned embodiment are typical, obviously can carry out many changes, modification and variant according to this description by those skilled in the art for practice of the present invention.Therefore, all these changes, modification and variants are covered by purport of claims and wide region.

Claims (25)

1. the ammonia oxidation of the mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon or oxidation are to generate the method for unsaturated nitrile or unsaturated organic acid, and described method comprises:
Catalyst mixture is provided, and it comprises
Fresh mixed metal oxide catalyst, it comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium,
The exhausted mixed metal oxide catalyst, its comprise molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium and
Performance modifier, it is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With
Make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.
2. the process of claim 1 wherein that described catalyst modifier is selected from aluminum nitrate, aluminum oxide, weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13, arsenic oxide arsenoxide (III), arsenic oxide arsenoxide (V), arsenic acid, boron oxide, boric acid, ceric ammonium nitrate, cerous acetate, Sedemesis (III) hydrate, cerium oxide (IV), germanium oxide (IV), Lithium Oxide 98min, lithium hydroxide, lithium acetate, lithium nitrate, lithium tartrate, Niobium ammonium oxalate, niobium oxalate, niobium oxides, Vanadium Pentoxide in FLAKES, ammonium phosphate, tin anhydride, tantalum oxide (V), telluric acid, tellurium dioxide, tellurium trioxide, rutile titanium dioxide (TiO 2), anatase type titanium dioxide (TiO 2), titanium isopropoxide, TiO (oxalate), tungstic oxide, oxalic acid vanadyl, vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), Zircosol ZN, zirconium white and composition thereof.
3. the process of claim 1 wherein that described performance modifier, described fresh mixed metal oxide catalyst and in the described exhausted mixed metal oxide catalyst one or more comprise the carrier that is selected from silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide or its mixture.
4. the process of claim 1 wherein that described catalyst mixture comprises the performance modifier/mole Mo at least about 0.01 mole in the total amount of fresh mixed metal oxide catalyst and exhausted mixed metal oxide catalyst.
5. the process of claim 1 wherein that described performance modifier further comprises molybdenum compound.
6. the process of claim 1 wherein and use non-hydrothermal solution synthetic method to prepare described fresh mixed oxide catalyst and described exhausted mixed oxide catalyst one or both of.
7. the process of claim 1 wherein that described fresh catalyst composition comprises the mixed oxide by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, S n, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo.
8. the process of claim 1 wherein that described used catalyst composition comprises the mixed oxide by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo.
9. the process of claim 1 wherein that described performance modifier comprises weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13, germanium oxide (IV), telluric acid, lithium hydroxide or cerium oxide (IV) or its mixture.
10. the process of claim 1 wherein that the described step that provides comprises described fresh mixed oxide catalyst, described exhausted mixed oxide catalyst and described performance modifier physical mixed.
11. the method for claim 10, the wherein said step that provides further comprises described fresh mixed oxide catalyst composition and the premixed step of described performance modifier.
12. the process of claim 1 wherein that the described step that provides comprises by wet impregnation fresh mixed oxide catalyst and performance modifier merging.
13. the process of claim 1 wherein that the described step that provides further comprises the heating or the step of the described catalyst mixture of calcination.
14. the ammonia oxidation of the mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon or oxidation are to generate the method for unsaturated nitrile or unsaturated organic acid, described method comprises:
With dry blending metal oxide catalyst and performance modifier physical mixed to form catalyst mixture, wherein said mixed metal oxide catalyst comprises molybdenum, vanadium, niobium and at least a element that is selected from antimony and tellurium, and wherein said performance modifier is selected from aluminum compound, antimony compounds, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, phosphorus compound, selenium compound, tantalum compound, titanium compound, tungsten compound, vanadium compound, zirconium compounds and composition thereof; With
Make described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture, contact oxygen-containing gas or contact oxygen-containing gas and ammonia.
15. the method for claim 14, wherein said performance modifier is selected from aluminum nitrate, aluminum oxide, weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13, arsenic oxide arsenoxide (III), arsenic oxide arsenoxide (V), arsenic acid, boron oxide, boric acid, ceric ammonium nitrate, cerous acetate, Sedemesis (III) hydrate, cerium oxide (IV), germanium oxide (IV), Lithium Oxide 98min, lithium hydroxide, lithium acetate, lithium nitrate, lithium tartrate, Neodymium trichloride (III), Neodymium trioxide (III), isopropoxy neodymium (III), neodymium acetate (III) hydrate, Niobium ammonium oxalate, niobium oxalate, niobium oxides, Vanadium Pentoxide in FLAKES, ammonium phosphate, tin anhydride, tantalum oxide (V), rutile titanium dioxide (TiO 2), anatase type titanium dioxide (TiO 2), titanium isopropoxide, TiO (oxalate), tungstic oxide, oxalic acid vanadyl, vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), Zircosol ZN, zirconium white and composition thereof.
16. the method for claim 14, wherein said mixed metal oxide catalyst further comprise at least a following element that is selected from: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tungsten, titanium, tin, germanium, zirconium, lithium and hafnium.
17. the method for claim 14, one or more in wherein said mixed metal oxide catalyst and the described performance modifier comprise the carrier that is selected from silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide or its mixture.
18. the method for claim 14, wherein said catalyst mixture comprise the performance modifier/mole Mo at least about 0.01 mole in described mixed metal oxide catalyst.
19. the method for claim 14, wherein said physical mixed step comprise the mixed metal oxide catalyst through calcination is mixed with performance modifier.
20. the method for claim 14, wherein said mixed metal oxide catalyst comprise the mixed oxide by following empirical formula definition:
Mo 1V aSb bNb cX dL eO n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and composition thereof; L is selected from Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and composition thereof; 0.1≤a≤1.0,0.01≤b≤1.0,0.001≤c≤0.25,0≤d≤0.6,0≤e≤1; N is that the valency that satisfies whole other elements that exist in the described mixed oxide requires required oxygen atomicity, precondition is the oxidation state existence that one or more other elements in described mixed oxide can be lower than its highest oxidation state, and a, b, c, d and e represent the mol ratio of corresponding element and one mole of Mo.
21. the method for claim 14, wherein said performance modifier comprise weisspiessglanz (III), antimony oxalate (III), antimony tartrate (III), weisspiessglanz (V), antimony tetroxide, Sb 6O 13Or its mixture.
22. the method for claim 14, wherein said performance modifier further comprises tellurium compound.
23. the method for claim 14, be used for the ammonia oxidation of the mixture of stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon and unsaturated hydrocarbon, wherein said contact procedure comprises makes described stable hydrocarbon or unsaturated hydrocarbons or stable hydrocarbon contact ammonia and oxygen-containing gas with the mixture of unsaturated hydrocarbon in the presence of described catalyst mixture.
24. the method for claim 14, wherein said dry blending metal oxide catalyst prepares by non-hydrothermal solution synthetic method.
25. the method for claim 14, wherein said physical mixed step comprise with without calcination or mix with performance modifier forming mixture through the dry blending metal oxide catalyst of part calcination, and comprise the step of the described mixture of calcination in addition.
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