JP5450426B2 - Ammoxidation or oxidation method of propane and isobutane - Google Patents

Description

  The present invention generally relates to a process for ammoxidation or oxidation of saturated or unsaturated hydrocarbons to produce unsaturated nitriles or unsaturated organic acids. More particularly, the present invention relates to the gas phase conversion of propane to acrylonitrile and isobutane to methacrylonitrile (by ammoxidation), or the gas phase conversion of propane to acrylic acid and isobutane to methacrylic acid (by oxidation). Regarding the method.

Mixed metal oxide catalysts are used to convert propane to acrylonitrile and isobutane to methacrylonitrile (by ammoxidation) and / or propane to acrylic acid (by oxidation). I came. There are a number of patents and patent applications known in the art, such as U.S. Patent No. 5,750,760 granted to Ushikubo et al., U.S. Patent No. 6,036,880 granted to Komada et al. No. 6,043,186, U.S. Patent No. 6,143,916 granted to Ninako et al., U.S. Patent No. 6,514,902 granted to Inoue et al., U.S. Patent Application 2003 / 0088118A1 by Komada et al., U.S. Patent Application 2004 / 0063990A1 by Gaffney et al. PCT patent application WO2004 / 108278A1 by the company.
Mo-VO-containing mixed metal oxide catalysts for propane oxidation are mixed with oxide promoters such as niobium oxide, tellurium oxide and antimony oxide by incipient impregnation of metal isopropoxide solution. After impregnation, the catalyst is dried and calcined.
It has been reported that the catalyst performance is improved by performing surface modification by vapor-depositing tellurium on a mixed metal oxide catalyst. Furthermore, improvement was observed by post-reformation treatment using oxygen.

To the composite oxide catalyst containing molybdenum, tellurium, vanadium and niobium, a tellurium compound and optionally a molybdenum compound are added as a catalyst activator. This catalyst activator is charged into the reactor after some time after preparation (on-stream) to maintain catalyst activity.
Tellurium compounds and / or molybdenum compounds are added as compensative compounds after the use of catalysts containing molybdenum, vanadium, niobium and antimony. More generally, it is known to add a molybdenum compound to a reactor using a molybdenum-containing catalyst.
Molybdenum, vanadium, antimony and propane effective for the conversion of propane to acrylonitrile and isobutane to methacrylonitrile (by ammoxidation) and / or the conversion of propane to acrylic acid and isobutane to methacrylic acid (by oxidation) While technologies related to catalysts containing other components have progressed, further improvements are needed for the catalysts to survive in the market. In general, conventional catalyst systems used for such reactions have the problem of generally low yields of desired products.
It is desirable to have a method that can prepare useful products in higher yields. In addition, a catalyst that exhibits improved stability under reaction conditions and / or improved temperature resistance change in the reaction apparatus is desired.

  One embodiment of the present invention is to ammoxidize or oxidize saturated hydrocarbons, unsaturated hydrocarbons, or a mixture of saturated and unsaturated hydrocarbons to produce unsaturated nitriles or unsaturated organic acids. A process comprising the steps of: using an unused mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium; and molybdenum and vanadium. Used mixed metal oxide catalyst containing at least one component selected from the group consisting of niobium, antimony and tellurium, an aluminum compound, an antimony compound, an arsenic compound, a boron compound, a cerium compound, a germanium compound, Lithium compound, molybdenum compound, neodymium compound, niobium compound, phosphorus compound, selenization And a catalyst mixture comprising a performance modifier selected from the group consisting of a tantalum compound, a tellurium compound, a titanium compound, a tungsten compound, a vanadium compound, a zirconium compound, and a mixture thereof. A saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon is brought into contact with an oxygen-containing gas or an oxygen-containing gas and ammonia. In certain embodiments, the catalyst mixture includes two or more performance modifier compounds.

The present invention also includes a method of ammoxidizing a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon to produce an unsaturated nitrile, which includes an aluminum compound, an antimony Compounds, arsenic compounds, boron compounds, cerium compounds, germanium compounds, lithium compounds, neodymium compounds, niobium compounds, phosphorus compounds, selenium compounds, tantalum compounds, tellurium compounds, titanium compounds, tungsten compounds, vanadium compounds, zirconium compounds and mixtures thereof Providing a catalyst mixture comprising a performance modifier selected from the group consisting of: an unused mixed metal oxide catalyst; and a used mixed metal oxide catalyst, wherein the unused And the spent catalyst are each independently of the formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof, L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof, 0.1 ≦ a ≦ 1.0, 0.01 ≦ b ≦ 1.0, 0.001 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 1 and n are the number of oxygen atoms necessary to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in an oxidation state lower than the oxidation state; Contacting the saturated hydrocarbon, unsaturated hydrocarbon, or a mixture of saturated and unsaturated hydrocarbons with ammonia and oxygen-containing gas in the presence of the catalyst mixture.
One embodiment of the present invention provides a method for ammoxidation or oxidation of saturated or unsaturated hydrocarbons or a mixture of saturated and unsaturated hydrocarbons to produce unsaturated nitriles or unsaturated organic acids. The method includes a mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium, an aluminum compound, an antimony compound, an arsenic compound, a boron compound, and cerium. Performance adjustment selected from the group consisting of compounds, germanium compounds, lithium compounds, neodymium compounds, niobium compounds, phosphorus compounds, selenium compounds, tantalum compounds, tellurium compounds, titanium compounds, tungsten compounds, vanadium compounds, zirconium compounds and mixtures thereof Contains a physical mixture with the agent Providing medium mixture, and a step of contacting in the presence of a saturated or unsaturated hydrocarbon mixtures or saturated and unsaturated hydrocarbons, oxygen-containing gas or an oxygen-containing gas and ammonia of the catalyst mixture.

The present invention also includes a method of ammoxidation or oxidation of a saturated or unsaturated hydrocarbon or a mixture of saturated and unsaturated hydrocarbons to produce an unsaturated nitrile or an unsaturated organic acid, the method comprising: Following formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof, L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof, 0.1 ≦ a ≦ 1.0, 0.01 ≦ b ≦ 1.0, 0.001 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 1 and n are the number of oxygen atoms necessary to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in an oxidation state lower than the oxidation state) Catalyst composition containing, aluminum compound, antimony compound, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium A catalyst mixture is formed by mixing a performance modifier selected from the group consisting of bu compound, phosphorus compound, selenium compound, tantalum compound, tellurium compound, titanium compound, tungsten compound, vanadium compound, zirconium compound and mixtures thereof. And contacting a saturated or unsaturated hydrocarbon or a mixture of saturated and unsaturated hydrocarbons with oxygen-containing gas or oxygen-containing gas and ammonia in the presence of the catalyst mixture.

One embodiment of the present invention relates to a process for ammoxidation of a saturated or unsaturated hydrocarbon or a mixture of saturated and unsaturated hydrocarbons to produce an unsaturated nitrile, wherein the process comprises the following formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof; L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu, and mixtures 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 the number of oxygen atoms required to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are less than their highest oxidation state. A, b, c, d and e represent the molar ratios of the respective elements corresponding to 1 mol of Mo, provided that the catalyst can be present in a lower oxidation state. Composition, aluminum compound, antimony compound, arsenic compound, boron compound, cerium compound, germanium compound, lithium compound, neodymium compound, niobium compound, Mixing a performance compound selected from the group consisting of a phosphorus compound, a selenium compound, a tantalum compound, a tellurium compound, a titanium compound, a tungsten compound, a vanadium compound, a zirconium compound, and a mixture thereof to form a catalyst mixture; Contacting a saturated or unsaturated hydrocarbon or a mixture of saturated and unsaturated hydrocarbons with ammonia and an oxygen-containing gas in the presence of the catalyst mixture.

The present invention relates to a process for (ammo) oxidation of saturated or unsaturated hydrocarbons and a catalyst composition which can be used in the process. This method is effective for ammoxidation of propane to acrylonitrile and isobutane to methacrylonitrile and / or conversion of propane to acrylic acid and isobutane to methacrylic acid (by oxidation reaction).
In one or more embodiments, a method comprising ammoxidation of a saturated or unsaturated hydrocarbon or a mixture of saturated and unsaturated hydrocarbons, comprising the use of a performance modifier and an unused composite oxide catalyst composition The unsaturated nitrile is prepared by a method comprising mixing a spent composite oxide catalyst composition to form a catalyst mixture and contacting the hydrocarbon with ammonia and an oxygen-containing gas in the presence of the catalyst mixture.
The present invention provides a method for producing an unsaturated nitrile or an unsaturated organic acid by ammoxidation or oxidation of a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon. And the method includes the use of an unused mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium, molybdenum, vanadium, niobium, antimony and A spent mixed metal oxide catalyst containing at least one component selected from the group consisting of tellurium, an aluminum compound, an antimony compound, an arsenic compound, a boron compound, a cerium compound, a germanium compound, a lithium compound, a neodymium compound, Niobium compounds, phosphorus compounds, selenium compounds, tantalum compounds, tellurium compounds A catalyst mixture comprising a titanium compound, a tungsten compound, a vanadium compound, a zirconium compound, and a mixture thereof, and a saturated hydrocarbon, an unsaturated hydrocarbon in the presence of the catalyst mixture. Or a step of contacting a mixture of saturated hydrocarbon and unsaturated hydrocarbon with oxygen-containing gas or oxygen-containing gas and ammonia.

As an embodiment, the catalyst regulator is aluminum nitrate, alumina, antimony (III) oxide, antimony (III) oxalate, antimony (III) tartrate, antimony (V), antimony tetroxide, Sb ₆ O ₁₃ , arsenic oxide (III), arsenic oxide (V), arsenic acid, boron oxide, boric acid, cerium ammonium nitrate, cerium acetate, cerium oxalate (III) hydrate, cerium oxide (IV), germanium (IV) oxide, lithium oxide, Lithium hydroxide, lithium acetate, lithium nitrate, lithium tartrate, ammonium niobium oxalate, niobium oxalate niobium oxide, phosphorus pentoxide, ammonium phosphate, selenium dioxide, tantalum oxide (V), telluric acid, tellurium dioxide, tellurium trioxide , rutile titanium dioxide (TiO _2), anatase titanium dioxide (TiO _2), titanium isopropoxide, TiO (oxalate), trioxide tungsten Emissions, vanadyl oxalate, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V), is selected from zirconyl nitrate, the group consisting of zirconia, and mixtures thereof.
In one embodiment, the catalyst mixture includes at least 0.01 moles of performance modifier per mole of molybdenum in the total amount of unused and spent mixed metal oxide catalyst. Another embodiment of the present invention comprises the step of mixing the unused mixed metal oxide catalyst and the performance modifier by wet impregnation. As an aspect of the present invention, either or both of the unused composite oxide catalyst and the used composite oxide catalyst are prepared using a method that is not hydrothermal synthesis. Furthermore, the present invention may have a step of physically mixing the unused composite oxide catalyst, the used composite oxide catalyst, and the performance modifier, and this step may be performed by using the unused composite oxide catalyst. The method further includes a step of premixing the composition and the performance modifier. Furthermore, this invention can have the process of heating or baking the said catalyst mixture.

In one embodiment, the unused catalyst composition has the formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof; L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu, and mixtures 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 the number of oxygen atoms required to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are less than their highest oxidation state. A, b, c, d, and e represent a molar ratio of each element corresponding to 1 mol of Mo, provided that the oxide can exist in a lower oxidation state.
In one embodiment, the spent catalyst composition has the following formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof; L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu, and mixtures 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 the number of oxygen atoms required to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are less than their highest oxidation state. A, b, c, d, and e represent a molar ratio of each element corresponding to 1 mol of Mo, provided that the oxide can exist in a lower oxidation state.

The present invention also provides a method for producing an unsaturated nitrile or an unsaturated organic acid by ammoxidizing or oxidizing a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon. The method includes a dry mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium, an aluminum compound, an antimony compound, an arsenic compound, Performance selected from the group consisting of boron compounds, cerium compounds, germanium compounds, lithium compounds, neodymium compounds, niobium compounds, phosphorus compounds, selenium compounds, tantalum compounds, titanium compounds, tungsten compounds, vanadium compounds, zirconium compounds and mixtures thereof. Catalyst mixing by physically mixing the regulator Forming a have the presence of the catalyst mixture, saturated hydrocarbons, unsaturated hydrocarbons, or a mixture of saturated hydrocarbons and unsaturated hydrocarbons, the step of contacting an oxygen-containing gas or oxygen-containing gas and ammonia.
The performance regulator of the present invention includes aluminum nitrate, alumina, antimony (III) oxide, antimony (III) oxalate, antimony (III) tartrate, antimony (V), antimony tetraoxide, Sb ₆ O ₁₃ , arsenic oxide ( III), arsenic oxide (V), arsenic acid, boron oxide, boric acid, cerium ammonium nitrate, cerium acetate, cerium oxalate (III) hydrate, cerium oxide (IV), germanium (IV) oxide, lithium oxide, water Lithium oxide, lithium acetate, lithium nitrate, lithium tartrate, neodymium (III) chloride, neodymium (III) oxide, neodymium (III) isopropoxide, neodymium (III) acetate hydrate, ammonium niobium oxalate, niobium oxalate oxidation niobium, phosphorus pentoxide, ammonium phosphate, selenium dioxide, tantalum oxide (V), rutile titanium dioxide (TiO _2), anatase titanium dioxide (TiO _2), titanium isopropoxide Selected from the group consisting of oxide, TiO (oxalate), tungsten trioxide, vanadyl oxalate, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, zirconyl nitrate, zirconia and mixtures thereof .

In one embodiment, the mixed metal oxide catalyst is lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tungsten, titanium, tin, germanium. And at least one element selected from the group consisting of zirconium, lithium and hafnium. One or more of the mixed metal oxide catalyst and performance modifier has a support selected from the group consisting of silica, alumina, zirconia, titania or mixtures thereof. Also, at least about 0.01 mole of performance modifier is included in the catalyst mixture per mole of molybdenum in the mixed metal oxide catalyst. As one aspect of the present invention, the physical mixing step includes a step of mixing the calcined mixed metal oxide catalyst and the performance modifier.
In one embodiment, the mixed metal oxide catalyst has the formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof, L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof, 0.1 ≦ a ≦ 1.0, 0.01 ≦ b ≦ 1.0, 0.001 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 1 and n are the number of oxygen atoms necessary to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in an oxidation state lower than the oxidation state) including.
In one embodiment, the ammoxidation of a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of saturated and unsaturated hydrocarbons is conducted in the contacting step with a saturated hydrocarbon, an unsaturated hydrocarbon, or a saturated hydrocarbon. Contacting the mixture of hydrogen and unsaturated hydrocarbon with ammonia and oxygen-containing gas in the presence of the catalyst mixture.
One aspect of the present invention is that the dry mixed metal oxide catalyst is prepared by methods other than hydrothermal synthesis.
Furthermore, one of the embodiments of the present invention includes a physical mixing step, which comprises mixing a non-calcined or partially calcined dry mixed metal oxide catalyst and a performance modifier to form a mixture; And a step of firing the mixture.

Performance modifier The performance modifier may be mixed with the catalyst prior to introducing the catalyst into the reactor. In one or more embodiments, 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, A compound or a mixture of compounds selected from the group consisting of titanium compounds, tungsten compounds, vanadium compounds and zirconium compounds. In one or more embodiments, the performance modifier may be supported on an inert carrier, which includes but is not limited to silica, titania, zirconia, or mixtures thereof. .
Examples of aluminum compounds include aluminum nitrate and alumina (Al ₂ O ₃ ). Examples of the antimony compound include antimony oxide, antimony oxalate, and antimony tartrate. Specific examples include antimony (III) oxide, antimony (III) oxalate, antimony (III) tartrate and antimony (V), antimony tetraoxide (Sb ₂ O ₄ ) and Sb ₆ O ₁₃ . Examples of arsenic compounds include arsenic oxide (III), arsenic oxide (V), and arsenic acid. Examples of boron compounds include boron oxide and boric acid.
Examples of cerium compounds include cerium ammonium nitrate, cerium acetate, cerium (III) oxalate hydrate, and cerium (IV) oxide. Examples of germanium compounds include germanium (IV) oxide. Examples of the lithium compound include lithium hydroxide, lithium oxide, lithium nitrate, lithium acetate, and lithium tartrate.

Examples of molybdenum compounds include molybdenum oxide (VI) (MoO ₃ ), ammonium heptamolybdate and molybdic acid. Examples of neodymium compounds include neodymium (III) chloride, neodymium (III) oxide, neodymium (III) isopropoxide, and neodymium (III) acetate hydrate. Examples of niobium compounds include ammonium niobium oxalate, niobium oxalate and niobium oxide.
Examples of phosphorus compounds include phosphorus pentoxide and ammonium phosphate. Examples of selenium compounds include selenium dioxide. An example of the tantalum compound is tantalum oxide (V). Examples of tellurium compounds include telluric acid, tellurium dioxide, and tellurium trioxide.
Examples of the titanium compound include rutile type and / or anatase type titanium dioxide (TiO ₂ ), titanium isopropoxide, and TiO (oxalate). Titanium dioxide is available as Degussa P-25, Tronox AK-1 and Tronox 8602 (previously referred to as AK-350). Examples of the tungsten compound include tungsten trioxide, tungstic acid, and ammonium tungstate. Examples of vanadium compounds include vanadyl oxalate, vanadium oxide (III), vanadium oxide (IV), ammonium metavanadate, and vanadium oxide (V). Examples of zirconium compounds include zirconyl nitrate and zirconia (ZrO ₂ ).

In one or more embodiments, two or more performance modifier compounds are used. These performance modifier compounds can be added to the catalyst mixture simultaneously or sequentially. The performance modifier compounds may be premixed or added individually to the catalyst mixture.
According to one embodiment, the performance modifier is a solid that is physically mixed with the composite oxide catalyst to improve catalyst performance. The performance modifier may be subjected to heat treatment or mechanical treatment such as pulverization, sieving and / or pressing before being used in the method of the present invention.
In another embodiment, the performance modifier may be introduced into a solution or slurry that can be used to impregnate the composite oxide catalyst composition with the performance modifier.
The amount of the performance modifier added to the catalyst mixture is not particularly limited. According to one embodiment, the amount of performance modifier can be expressed in moles of performance modifier per mole of molybdenum in the total amount of unused and used mixed metal oxide catalyst. In one or more embodiments, the catalyst mixture contains at least 0.01 moles of performance modifier per mole of molybdenum. In these or other embodiments, up to approximately 1.0 mole of performance modifier is included in the catalyst mixture per mole of molybdenum in the total amount of unused and spent mixed metal oxide catalyst. In one embodiment, from about 0.01 mole to about 1.0 mole of performance modifier is included in the catalyst mixture per mole of molybdenum. In another embodiment, from about 0.011 mole to about 0.5 mole, and in another embodiment from about 0.012 mole to about 0.2 mole, per mole of molybdenum in the total amount of unused and spent composite oxide catalyst. Is included in the catalyst mixture.
The performance regulator further contains a molybdenum compound. Performance regulators include antimony (III) oxide, antimony (III) oxalate, antimony (III) tartrate, antimony (V), antimony tetraoxide, Sb ₆ O ₁₃ , germanium (IV) oxide, telluric acid, water Lithium oxide, cerium (IV) oxide or mixtures thereof may be included.
In one embodiment, the performance modifier comprises antimony (III) oxide, antimony (III) oxalate, antimony (III) tartrate, antimony (V), antimony tetroxide, Sb ₆ O ₁₃ or a mixture thereof. Including. Further, the performance modifier may further contain a tellurium compound.
In one embodiment, the group consisting of the performance modifier, the unused mixed metal oxide catalyst and the used mixed metal oxide catalyst is composed of silica, alumina, zirconia, titania or a mixture thereof. Having a carrier selected from

Composite Oxide Catalyst Composition The superior method of the present invention applies to many unused and used composite oxide catalyst compositions for ammoxidation and oxidation. As used herein, an unused catalyst refers to a catalyst that has not been deposited in the reactor feedstream. As used herein, spent catalyst refers to the catalyst that is carried in the feed stream of the reactor. Depending on the embodiment, the initial composition of the unused catalyst and the used catalyst may be the same, and the initial composition of the unused catalyst and the used catalyst may be different. The description of the composite oxide catalyst composition described below and the description of its preparation apply to both the unused catalyst and the used catalyst composition of the present invention.
In one embodiment, the composite oxide catalyst composition includes molybdenum, vanadium, niobium, and / or one of antimony and tellurium. In one or more embodiments, the composite oxide catalyst is selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. And further comprising at least one element. In some embodiments, the catalyst mixture may include at least one element selected from the group consisting of tungsten, tellurium, titanium, tin, germanium, zirconium and hafnium. As used herein, “at least one element selected from the group” or “at least one lanthanide selected from the group” means an element or lanthanum listed within the scope of the present specification. A mixture of two or more series elements is included.

In one embodiment, one or both of the unused composite oxide catalyst and the used composite oxide catalyst contain molybdenum, vanadium, antimony, and niobium, and can be respectively defined by the following formulae.
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof;
L is selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and mixtures 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 the number of oxygen atoms necessary to satisfy the valence condition of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are in their highest oxidation state. A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in a lower oxidation state. )
In one or more embodiments in which the catalyst composition is used for ammoxidation, X is selected from the group consisting of W, Te, Ti, Ge, Sn, Zr, Hf, Li, and mixtures thereof. Good. In other embodiments, X may be selected from the group consisting of W, Te, Ti, Sn, Zr, Hf, Li, and mixtures thereof. In another embodiment of the catalyst composition described in the above formula, X is one of W, Te, Ti, Li or Sn. In another embodiment of the catalyst composition described in the above formula, X is W.

In one or more embodiments where the catalyst composition is used for ammoxidation, L consists of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. It may be selected from a group. In another embodiment of the catalyst composition described above, L is Pr, L is Nd, L is Sm, L is Eu, L is Gd, L is Tb, L is Dy, L is Ho, and L is Er. , L is Tm, L is Yb, and L is Lu. In another embodiment of the catalyst composition described in the above formula, L is any one of Nd, Ce or Pr.
In another embodiment of the catalyst composition described in the above formula, a, b, c and d are independently in the following ranges. 0.1 ≤ a, 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 <0.002, 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.
The catalyst of the present invention may or may not be a supported catalyst (ie, the catalyst may have a support or may be a bulk catalyst). Suitable carriers are silica, alumina, zirconia, titania or mixtures thereof. However, when zirconia or titania is used as the support, the ratio of molybdenum to zirconium or titanium is greater than the value shown in the above formula. For example, the ratio of Mo: Zr or Ti is approximately 1: 1 to 1:10. In general, the carrier serves as a binder for the catalyst, resulting in a more robust and less wearable catalyst. For business use, the active phase (that is, the above-mentioned catalyst oxide complex) and the support are appropriately combined to help to obtain the activity and hardness (abrasion resistance) acceptable as a catalyst. As the amount of active phase increases, the hardness of the catalyst decreases. The support is 10 to 90% by mass of the supported catalyst. In many cases, the support is 40-60% by weight of the supported catalyst. One embodiment of the present invention may be a carrier as small as about 10% by weight of the supported catalyst. One embodiment of the present invention may be as small as about 30% by weight of the supported catalyst. In another embodiment of the present invention, the support may be about 70% by weight of the supported catalyst.

Preparation of Mixed Metal Oxide Catalyst The method for producing the catalyst used in the present invention is not critical. Any method known in the art, such as a hydrothermal synthesis method or a method that is not a hydrothermal synthesis method, can be used, but is not limited to these methods.
In one or more embodiments, the mixed metal oxide catalyst can be prepared by the hydrothermal synthesis method described herein. Hydrothermal synthesis is described in US patent application 2003/0004379 to Gaffney et al., “New Synthesis Route for Mo-V-Nb-Te mixed oxides catalyst for propane ammoxidation. Novel synthesis method of composite oxide catalyst) "Watanabe et al., Applied Catalysis A: General, 194-195, 479-485 (2000), and" Selective Oxidation of Light Alkanes over hydrothermally synthesized Mo-VMO (M = Al, (Ga, Bi, Sb and Te) oxide catalysts (selective oxidation of light alkanes with hydrothermally synthesized Mo-VMO (M = Al, Ga, Bi, Sb and Te) oxide catalysts) "Ueda et al., Applied Catalysis A: General, 200, pages 135-145, which are incorporated herein by reference.
In general, the catalyst compositions described herein can be prepared by hydrothermal synthesis, which contains and / or provides a source compound (ie, one or more metals of a mixed metal oxide catalyst composition). Compound) in an aqueous solution to form a reaction medium, and this reaction medium is reacted in a sealed reactor for a time sufficient to increase pressure and temperature to form a mixed metal oxide. In one embodiment, the hydrothermal synthesis is continued for a sufficient period of time, the organic compound present in the reaction medium, such as the solvent used in the catalyst preparation or the added organic compound, and the catalyst composition. The source compound supplying the mixed metal oxide component is completely reacted.
The source compound is reacted in a sealed reactor at a temperature higher than 100 ° C. and higher than ambient pressure. In one embodiment, the reaction of the source compound in a closed reactor is conducted at a temperature of at least about 125 ° C, in another embodiment at least about 150 ° C, and in yet another embodiment at least about 175 ° C. According to one embodiment, the reaction of the source compound in a closed reactor is performed at a pressure of at least about 25 psig, in another embodiment at least about 50 psig, and in yet another embodiment at least about 100 psig. In one or more embodiments, the source compound is reacted in a closed reactor under a pressure up to about 300 psig. A pressure controller may be attached to the closed reactor to prevent excessive pressure on the reactor and / or to adjust the reaction pressure.

  The source compound may be reacted by a protocol that includes mixing the source compound during the reaction step. The detailed mixing mechanism is not particularly important and includes, for example, mixing (eg, stirring) the components during the reaction in any effective manner. Examples of such a method include stirring the contents of the reactor by shaking, tumbling, or vibrating the reactor containing the reaction components. Further, stirring is performed using a stirring member at least a part of which is located in the reactor, and a driving force connected to the stirring member or the reactor for imparting a relative motion between the stirring member and the reactor. As an example. Examples of the stirring member include a shaft driving type and / or a shaft supporting type stirring member. The driving force may be directly connected to the stirring member or indirectly connected (for example, via magnetic coupling). In general, sufficient mixing allows for an efficient reaction between the components of the reaction medium, resulting in a more uniform reaction medium (resulting in a more uniform mixed metal oxide compared to reactions without mixing). Precursor) is formed. As a result, the starting material is consumed more efficiently and the product mixed metal oxide is more uniform. Further, by mixing the reaction medium during the reaction step, the product mixed metal oxide can be formed in a solution form rather than on the side surface of the reaction vessel. This makes it possible to more easily collect and separate mixed metal oxides produced by centrifugation, decantation, or filtration, and eliminates the need to collect most of the product from the side of the reaction vessel. Even more advantageous is that when particle growth occurs from the reactor wall, it is limited to the growth of the exposed surface of the particle, but by forming the mixed metal oxide in solution, it can be applied to all surfaces of the particle. Particle growth is expected.

Usually, it is desirable to secure an empty space in the reaction vessel. The amount of head clearance can be determined by the design of the container or the stirring method used when stirring the reaction mixture. For example, an overhead stirring reaction vessel should have an upper head clearance of 50%. In general, since the head space is filled with ambient air, a considerable amount of oxygen is supplied to the reaction system. Alternatively, as is well known, the head space can be filled with another gas such as O ₂ or an inert gas such as Ar or N ₂ supplied to the reactant. The amount of head space and the gas contained therein is determined by the desired reaction, as is known in the art.
The reaction of the source compound in a sealed reactor can be performed at an initial pH value of approximately 4 or less. The pH of the reaction mixture changes in the course of hydrothermal synthesis, and may be lowered if the final pH value of the reaction mixture becomes higher than the initial pH value. According to one or more embodiments, the source compound is reacted in a sealed reaction vessel at approximately pH 3.5 or lower. The components can also be reacted in a closed reaction vessel with a pH value of about 3.0 or less, about 2.5 or less, about 2.0 or less, about 1.5 or less, about 1.0 or less, about 0.5 or less, or about 0 or less. In one or more embodiments, the pH value is from about 0.5 to about 4, in other embodiments from about 0 to about 4, and in yet another embodiment from about 0.5 to about 3.5. In some embodiments, the pH value is from about 0.7 to about 3.3, or even from about 1 to about 3. This pH value can be adjusted by adding acid or base to the reaction mixture.

The source compound should have sufficient time to form the mixed metal oxide in the sealed reaction vessel under the above reaction conditions (for example, as described above including reaction temperature, reaction pressure, pH value, stirring, etc.). To react. According to one or more embodiments, the mixed metal oxide thus formed contains a solid solution containing the necessary elements as described above, at least partly of which is an effective and selective oxidation of propane or isobutane and The crystal structure required for the ammoxidation catalyst is included. The exact reaction time is not narrowly limited, for example, at least about 3 hours, at least about 6 hours, at least about 12 hours, at least about 18 hours, at least about 24 hours, at least about 30 hours, at least about 36 hours, at least about 42 hours. Time, at least about 48 hours, at least about 54 hours, at least about 60 hours, at least about 66 hours, at least about 72 hours. The reaction time can be longer than 3 days, for example at least about 4 days, at least about 5 days, at least about 6 days, at least about 7 days, at least about 2 weeks, at least about 3 weeks, or at least about 1 month. There is also.
The source compound containing and supplying the metal component used in the synthesis of the catalyst (sometimes referred to herein as “source”) may be prepared in the reaction vessel as an aqueous solution of a metal salt. Depending on the source compound, the reaction vessel may be prepared as a solid or as a slurry containing solid particles dispersed in an aqueous medium. Some source compounds can be prepared in the reaction vessel as a solid or as a slurry containing solid particles dispersed in a non-aqueous solvent or other non-aqueous medium.
Examples of source compounds for synthesizing the catalysts described herein include the following. Examples of the lithium source compound include lithium hydroxide, lithium oxide, lithium acetate, lithium tartrate, and lithium nitrate. Examples of the vanadium source compound include vanadyl sulfate, ammonium metavanadate, vanadium oxide (V), and the like. Examples of antimony source compounds include antimony (III) oxide, antimony (III) acetate, antimony (III) oxalate, antimony (V), antimony (III) sulfate, and antimony (III) tartrate. . Examples of niobium source compounds include niobium oxalate, ammonium niobium oxalate, niobium oxide, niobium ethoxide, niobic acid, and the like.

Examples of the tungsten source include ammonium metatungstate, tungstic acid, and tungsten trioxide. Examples of tellurium sources include telluric acid, tellurium dioxide, tellurium trioxide, organic tellurium compounds such as methyl tellurol and dimethyl tellurol.
Titanium sources include rutile and / or anatase titanium dioxide (TiO ₂ ), titanium isopropoxide, TiO (oxalate), TiO (acetylacetonate) ₂ , and titanium alkoxide complexes such as Tyzor 131. Can be mentioned. Titanium dioxide is available as Degussa P-25, Tronox AK-1 and Tronox 8602 (previously referred to as AK-350). Examples of tin source compounds include tin (II) acetate. Examples of the germanium source compound include germanium (IV) oxide. Zirconium sources include zirconyl nitrate and zirconium (IV) oxide. Examples of the source of hafnium include hafnium chloride (IV) and hafnium oxide (IV).

  Examples of the lanthanum source include lanthanum chloride (III), lanthanum oxide (III), and lanthanum acetate (III) hydrate. Examples of the cerium source include cerium (III) chloride, cerium (III) oxide, cerium (III) isopropoxide, and cerium (III) acetate hydrate. Examples of the praseodymium source include praseodymium (III) chloride, praseodymium oxide (III, IV), praseodymium (III) isopropoxide, praseodymium (III) acetate hydrate, and the like. Examples of the neodymium source include neodymium chloride (III), neodymium (III) oxide, neodymium (III) isopropoxide, and neodymium (III) acetate hydrate. Examples of the samarium source include samarium (III) chloride, samarium (III) oxide, samarium (III) isopropoxide, samarium (III) acetate hydrate, and the like. Examples of europium sources include europium (III) chloride, europium (III) oxide, and europium (III) acetate hydrate. Examples of the gadolinium source include gadolinium (III) chloride, gadolinium (III) oxide, and gadolinium (III) acetate hydrate. Examples of the terbium source include terbium (III) chloride, terbium (III) oxide, and terbium acetate (III) hydrate. Examples of the dysprosium source include dysprosium (III) chloride, dysprosium (III) oxide, dysprosium (III) isopropoxide, dysprosium (III) acetate hydrate, and the like. Examples of the holmium source include holmium (III) chloride, holmium (III) oxide, and holmium (III) acetate hydrate. Examples of the erbium source include erbium (III) chloride, erbium (III) oxide, erbium (III) isopropoxide, erbium acetate (III) hydrate and the like. Examples of thulium sources include thulium (III) chloride, thulium (III) oxide, thulium acetate (III) hydrate and the like. Examples of the source of ytterbium include ytterbium chloride (III), ytterbium oxide (III), ytterbium (III) isopropoxide, ytterbium acetate (III) hydrate, and the like. Examples of the source of lutetium include lutetium chloride (III), lutetium oxide (III), and lutetium acetate (III) hydrate. The metal nitrates listed above can also be used as source compounds.

The amount of aqueous solvent in the reaction medium depends on the solubility of the source compound mixed to form the individual mixed metal oxides. The amount of aqueous solvent should be at least sufficient to make a slurry of the reactants (stirrable with a mixture of solid and liquid). In general, the hydrothermal synthesis of mixed metal oxides leaves the top free space in the reaction vessel.
Subsequent to the reaction step, there may be a work-up step as a further step of the catalyst preparation method, for example, a step of cooling the reaction medium containing the mixed metal oxide (eg, cooling to about ambient temperature). ), Separating the solid particulate matter containing mixed metal oxides from the liquid (eg, by centrifuging and / or decanting or filtering the supernatant), washing the separated solid particulate matter (eg, distillation) Water or deionized water), a step of repeating the separation step and the washing step one or more times, a step of performing a final separation step, and the like. According to one embodiment, the work-up process includes drying the reaction medium, such as by rotary evaporation, spray drying, lyophilization, or similar methods to remove liquids.
After completion of the work-up process, the mixed and separated mixed metal oxide may be dried. Drying of the mixed metal oxide is under ambient conditions (eg, temperature about 25 ° C., atmospheric pressure) and / or in an oven at a temperature in the range of, for example, about 40 to about 150 ° C., in another embodiment at about 120 ° C. About 5 to about 15 hours, and in some embodiments about 12 hours of drying time. Drying may be performed with or without adjusting the atmosphere, and the drying atmosphere may be an inert gas, an oxidizing gas, a reducing gas, or air.

In one or more of the embodiments, the mixed metal oxide catalyst can be prepared by methods other than the hydrothermal synthesis method described herein. Methods other than hydrothermal synthesis are also disclosed in US Patent Application 2006/0235238 by Satoru Komada and Sadao Shoji, Takaaki Kato and Satoshi Fukushima, which are included in the description of this application by reference. To do.
One method other than hydrothermal synthesis is generally as follows. A first aqueous solution / slurry is prepared by mixing a carrier sol such as a molybdenum source compound, a vanadium source compound, an antimony source compound, optionally another source compound, hydrogen peroxide, and a silica sol with heating and stirring. A niobium source compound, any dicarboxylic acid, and any other source compound are mixed with heating and stirring to prepare a second aqueous solution / slurry. The first and second aqueous solution / slurry are mixed to form a third aqueous solution / slurry. The precipitate and / or precipitated solid is removed and the aqueous mixture is dried to form a dry mixed metal oxide catalyst. Various work-up steps and various drying and / or firing methods can be used.
According to one embodiment, one of the methods other than hydrothermal synthesis is more specifically as follows: the first aqueous solution / slurry is (A) and the second aqueous solution / slurry is (B ). Ammonium heptamolybdate, ammonium metavanadate, and antimony trioxide are added to water and the mixture is heated to at least 50 ° C. to obtain an aqueous mixture (A). It is preferred to heat the mixture with stirring. It is preferred to heat the aqueous mixture to a temperature in the range of about 70 ° C. to the normal boiling point of the aqueous mixture. Heating may be performed under reflux using an apparatus having a reflux condenser. When heated under reflux, this boiling point is usually about 101-102 ° C. Keep the heated temperature for about 0.5 hours. When the heating temperature is about 80 to about 100 ° C., the heating time is usually about 1 to about 5 hours. If the heating temperature is relatively low (eg, below about 50 ° C.), a longer heating time is required.

Optionally, a sol of hydrogen peroxide and / or carrier material (such as silica sol) may be added to the aqueous mixture (A) after the heating. When hydrogen peroxide is added to the aqueous mixture (A), the molar ratio of hydrogen peroxide: antimony compound expressed as antimony (H ₂ O ₂ / Sb molar ratio) is from about 0.01 to about 20, in yet another embodiment The amount of hydrogen peroxide may be about 0.5 to about 3, and in another embodiment about 1 to about 2.5. After the hydrogen peroxide addition, the aqueous mixture (A) may be stirred at about 30 to about 70 ° C. for about 30 minutes to about 2 hours.
In one or more embodiments, the preparation of the aqueous solution / slurry (B) is by mixing water and the niobium source compound, any dicarboxylic acid and / or other source compound with heating and stirring, whereby: A preliminary niobium-containing aqueous solution or a niobium-containing aqueous mixture in which a part of the niobium compound is suspended is obtained. Thereafter, the preliminary niobium-containing aqueous solution or niobium-containing aqueous mixture is cooled. If dicarboxylic acid is added, a part of the aqueous solution may be precipitated. The cooling step may be performed after removing the precipitated dicarboxylic acid from the preliminary niobium-containing aqueous solution, or after removing the precipitated dicarboxylic acid and the suspended niobium compound from the niobium-containing aqueous mixture. Thereby, a niobium containing aqueous liquid (B) is obtained.
In certain embodiments, an aqueous liquid (B) is obtained by adding a niobium compound (eg, niobic acid) to water and heating the resulting mixture to a temperature in the range of about 50 to about 100 ° C. When niobic acid is a niobium source compound, dicarboxylic acid may also be added. The addition of a small amount of aqueous ammonia can promote the dissolution of the niobium compound.

An example of a suitable dicarboxylic acid is oxalic acid. In one embodiment, niobic acid and oxalic acid are added to water and the resulting mixture is heated and stirred to obtain an aqueous liquid (B). Generally, the molar ratio of dicarboxylic acid: niobium compound represented by niobium ranges from about 1 to about 4, and in some embodiments from about 2 to about 4.
According to another embodiment, the niobium source compound includes niobium hydrogen oxalate or ammonium niobium oxalate. When either niobium hydrogen oxalate or ammonium niobium oxalate is used as the niobium compound, no dicarboxylic acid is required.
In general, the niobium source compound can be added in the form of a solid or a mixture or dispersion in a suitable medium. When niobic acid is used as a niobium compound, niobic acid may be washed with an aqueous ammonia solution and / or water before use for the purpose of removing acidic impurities that may contaminate niobic acid during production. As the niobium compound, it is preferable to use a newly prepared niobium compound. However, it is also possible to use niobium compounds that have been slightly modified (for example, by dehydration) due to long-term storage or the like.
The concentration of the niobium compound (expressed as niobium) in the preliminary niobium-containing aqueous solution or mixture is maintained from about 0.2 to about 0.8 mol / kg per kg of solution or mixture in one or more embodiments. In one or more embodiments, the dicarboxylic acid is used in an amount such that the molar ratio of dicarboxylic acid: niobium compound represented by niobium is from about 2 to about 6. When the dicarboxylic acid is used in excess, a large amount of the niobium compound can be dissolved in the dicarboxylic acid aqueous solution, but when the obtained preliminary niobium-containing aqueous solution or mixture is cooled, the amount of the precipitated dicarboxylic acid may be excessively increased. The utilization rate of dicarboxylic acid is reduced. On the other hand, if the amount of dicarboxylic acid used is insufficient, a large amount of niobium compound may remain suspended without being dissolved in the aqueous solution or mixture, and may subsequently be removed from the aqueous mixture. Cause a decline.

Any suitable method may be used for cooling. For example, it can be simply cooled in an ice bath.
The precipitated dicarboxylic acid (or the precipitated dicarboxylic acid and the dispersed niobium compound) can be easily removed by a conventional method such as decantation or filtration.
When the dicarboxylic acid: niobium molar ratio of the resulting niobium-containing aqueous solution is not in the range of about 2 to about 6, either the niobium compound or the dicarboxylic acid is added to the aqueous liquid (B) to add the dicarboxylic acid: niobium mole of the solution. Ensure that the ratio is within the above range. However, the molar ratio of dicarboxylic acid: niobium is usually from about 2 to about by appropriately adjusting the concentration of niobium compound, the ratio of dicarboxylic acid: niobium compound, and the cooling temperature of the above preliminary niobium-containing aqueous solution or aqueous mixture. Since the aqueous liquid (B) in the range of 4 can be prepared, the treatment as described above is unnecessary.
The aqueous liquid (B) may further contain an additional component. In one or more embodiments, the aqueous liquid (B) may further comprise hydrogen peroxide (H ₂ O ₂ )). In these or other embodiments, the aqueous liquid (B) comprises one or more antimony compounds (eg, antimony trioxide), titanium compounds (eg, titanium dioxide (a mixture of rutile and anatase types). And may further comprise a cerium compound (eg, cerium acetate) According to one embodiment, the amount of hydrogen peroxide is a molar ratio of niobium compound expressed as hydrogen peroxide: niobium (H ₂ O ₂ / Nb) is from about 0.5 to about 20, and in another embodiment from about 1 to about 20. In a specific embodiment, the antimony compound represented by antimony: of the niobium compound represented by niobium In some embodiments, the antimony compound is combined with at least a portion of the aqueous liquid (B) so that the molar ratio (Sb / Nb molar ratio) is not greater than about 5, in some embodiments, from about 0.01 to about 2. It is mixed with hydrogen peroxide.

Aqueous mixture (A) and aqueous liquid (B) are mixed together in an appropriate ratio to form an aqueous solution / slurry. The ratio (a) :( b) depends on the desired composition of the catalyst. The amount of solids in the aqueous mixture is usually above about 10% by weight. In one embodiment, based on the total weight of the mixture, the amount of solids in the aqueous mixture is about 10-60% by weight, in another embodiment about 15-55% by weight, according to yet another embodiment. And the amount of solids in the mixture is from about 20 to about 50% by weight.
In one or more embodiments, the silica-supported catalyst, if desired, is prepared such that the aqueous solution / slurry includes a silica source compound (ie, silica sol or fumed silica). The amount of the silica source compound may be appropriately adjusted according to the desired amount of the silica carrier in the obtained catalyst.
The aqueous solution / slurry can be dried to remove the liquid portion. Drying can be performed by conventional methods such as spray drying or evaporation drying. Spray drying is particularly useful because a fine spherical dry solid is obtained. Spray drying can be performed by centrifugation.
The aqueous solution / slurry can be dried to remove the liquid portion. Drying can be performed by conventional methods such as spray drying or evaporation drying. Spray drying is particularly useful because a fine spherical dry solid is obtained. Spray drying can be performed by centrifugation, a two-phase flow nozzle method or a high pressure nozzle method. As a heat source for drying, air heated with steam, an electric heater or the like is preferably used. The temperature at the inlet of the spray dryer is preferably about 150 to about 300 ° C.

Regardless of whether it is formed by the hydrothermal method, what is dried at this point is called a dry mixed metal oxide catalyst. The terms “dry” and “dry” are taken to describe the state of the solid with some of the water removed, although some moisture may remain. Thus, unless stated otherwise, the terms “dry” and “dry” are to be interpreted as substantially dry. For the purposes of this specification, the term “dry mixed metal oxide catalyst” refers to this material while the dry mixed metal oxide catalyst is subjected to any further processing, including calcination and grinding described below. It keeps pointing. Furthermore, the term “dry mixed metal oxide catalyst” will refer to the catalyst used in the reactor. Therefore, the dry mixed metal oxide catalyst may not be calcined, may be pulverized, coarsely crushed, pelletized, extruded, or may be molded, shaped, and unused catalyst. It may be a used catalyst.
The dry mixed metal oxide catalyst may be further processed as previously described herein. Examples of such treatment include firing (including heat treatment under oxidizing conditions or reducing conditions) performed under various treatment atmospheres. Prior to such treatment and / or during such treatment, the dry mixed metal oxide may be crushed or ground intermittently. According to one embodiment, for example, the dry mixed metal oxide may be crushed and then fired.
Firing can be performed in an inert atmosphere, a reducing atmosphere, or an oxidizing atmosphere. In one embodiment, at least a portion of the firing is performed in an inert gas atmosphere such as nitrogen gas that is substantially free of oxygen (eg, under an inert gas stream). In one or more embodiments, the firing conditions include a temperature of about 200 to about 700 ° C., and in other embodiments about 400 to about 650 ° C.

In one or more embodiments, the heating temperature of the dry mixed metal oxide catalyst is continuously or intermittently increased from less than about 400 ° C. to about 550 ° C. and from about 550 ° C. to about 700 ° C. In some embodiments, multi-stage firing may be used. In this embodiment, the dry mixed metal oxide catalyst is partially calcined at a relatively low temperature of at least about 200 ° C. and then calcined by raising it to a higher temperature (at least about 400 ° C.) one or more times within the above range. May be.
The treated (eg, calcined) mixed metal oxide may be further mechanically processed, for example, by pulverizing, sieving, and pressurizing to use the mixed metal oxide in the method of the present invention. It may be in the form.
In other embodiments, the catalyst may be formed into a final form prior to calcination or other heat treatment. For example, in the preparation of a fixed bed catalyst, the catalyst precursor slurry is generally heated and dried at a high temperature, and then formed into a desired fixed bed catalyst size and shape (for example, extrusion, pellet molding, etc.), and thereafter Firing is performed. Similarly, in the preparation of a fluidized bed catalyst, the catalyst precursor slurry is spray-dried to form fine spheroid catalyst particles having a particle size of about 10 to about 200 micrometers, and then calcined. Variations on the method will be apparent to those skilled in the art.
Firing can be performed using a rotary furnace, a fluidized bed kiln or the like. According to one or more embodiments, the non-stationary calcination prevents non-uniform calcination (degradation of physical properties and / or breakage or cracking of the resulting catalyst).
The calcination conditions are set in advance so that the specific surface area of the formed catalyst is about 5 to about 35 m ² / g. It is preferable to set the firing conditions in advance so that the obtained catalyst has one or more crystal phases.

Method of forming a physical mixture
The catalyst mixture is prepared by mixing the unused catalyst composition, the spent catalyst composition and the performance modifier by physical mixing, wet impregnation or a combination of these techniques. One or more components may be premixed. The order of addition is not important. In some embodiments, the performance modifier and the unused catalyst are premixed and then mixed with the spent catalyst. Performance modifiers may be added at various stages in the process of preparing the unused catalyst composition. However, according to certain embodiments, an improvement in performance is seen when a performance modifier is added to the final form of the unused catalyst composition.
According to one embodiment, the performance modifier and the spent catalyst may be premixed and then mixed with the unused catalyst. According to one embodiment, the performance modifier is solid and the performance modifier may be micronized prior to mixing the performance modifier and the catalyst composition. In another embodiment, the performance modifier particle size is coarser, about the catalyst particle size.
In one or more embodiments, a performance modifier may be added by wet impregnation to either or both of the used catalyst composition and the unused catalyst composition. In some embodiments, the physical mixture of the performance modifier, the unused composite oxide catalyst, and the composite oxide catalyst used may be heat treated or calcined.
According to certain embodiments, when two or more performance modifier compounds are used, the performance modifier compounds may be added separately to the catalyst mixture or premixed to form the modifier mixture. This modifier mixture may be mixed with the composite oxide catalyst composition by physical mixing or impregnation.

The present invention provides a method for converting propane to acrylonitrile and a method for converting isobutane to methacrylonitrile. The method comprises the steps of preparing a mixture of a performance modifier, an unused composite oxide catalyst composition and a used composite oxide catalyst composition as described hereinbefore, and acrylonitrile or methacrylonitrile. Under the reaction conditions effective to form a catalyst mixture in the presence of propane or isobutane and oxygen (eg, typically fed into a reaction zone of a feed stream containing an oxygen-containing gas such as air) and the presence of ammonia A step of contacting below is included. This reaction includes propane or isobutane, an oxygen-containing gas such as air, and ammonia in the feed stream. In one or more embodiments, the propane or isobutane: oxygen molar ratio is from about 0.125 to about 5, in another embodiment from about 0.25 to about 4.5, and in yet another embodiment from about 0.35 to about 4. According to one or more embodiments, the molar ratio of propane or isobutane: ammonia is about 0.3 to about 4, and in another embodiment about 0.5 to about 3. The feed stream can include one or more additional feed components including acrylonitrile or methacrylonitrile product (eg, from a recycle stream or from the front of a multi-stage reactor) and / or steam. For example, the feed stream contains from about 5 to about 30% by weight of the additional feed component in a mass ratio relative to the total feed stream, or from about 5 to about 30% in a molar ratio to the amount of propane or isobutane in the feed stream. May be. According to one embodiment, the propane to acrylonitrile ammoxidation process described herein is a once-through process that operates without recycling the unreacted feed after recovery.

Also, the conversion of propane to acrylic acid and isobutane to methacrylic acid also provides one or more of the above catalysts to a gas-phase flow reactor, which provides effective reaction conditions for the formation of acrylic acid. And by contacting the catalyst with propane in the presence of oxygen (eg, typically fed into a reaction zone of a feed stream containing an oxygen-containing gas such as air). The feed stream for this reaction preferably contains from about 0.15 to about 5, more preferably from about 0.25 to about 2, propane or isobutane: oxygen. Further, the feed stream can include one or more additional feed components including acrylic acid or methacrylic acid product (eg, from a recycle stream or from the front stage of a multi-stage reactor) and / or steam. For example, the feed stream contains from about 5 to about 30% by weight of the additional feed components in a mass ratio relative to the total feed stream, or from about 5 to about 30% by mole ratio to the amount of propane or isobutane in the feed stream May be.
The specific design of the gas phase flow reactor is not limited. That is, the gas phase flow reactor may be a fixed bed reactor, a fluidized bed reactor, or another type of reactor. The reactor may be a single reaction vessel or a multi-stage reaction vessel. In one or more embodiments, the reactor includes one or more feed inlets for supplying a reactant feed stream to the reaction zone of the reaction vessel, a reaction zone having a catalyst mixture, and unreacted reaction products. And an outlet for discharging the reactants present.

The reaction conditions are adjusted so as to be effective for conversion from propane to acrylonitrile or acrylic acid, or from isobutane to methacrylonitrile or methacrylic acid, or from isobutane to methacrylonitrile. That's fine. Generally, the reaction conditions include a temperature of about 300 to about 550 ° C, in some embodiments about 325 to about 500 ° C, in another embodiment about 350 to about 450 ° C, and in yet another embodiment about 430 to about 520 ° C. It is. The pressure in the reaction zone may be adjusted to a range from about 0 to about 200 psig, in some embodiments from about 0 to about 100 psig, and in yet another embodiment from about 0 to about 50 psig.
Typically, the flow rate of the propane or isobutene-containing feed stream passing through the reaction zone of the gas phase flow reactor is, for example, expressed as about 0.02 to about 5, expressed as gram weight of propane or isobutane relative to gram weight of catalyst per hour, In some embodiments, the weight hourly space velocity (WHSV) may range from about 0.05 to about 1 and in other embodiments from about 0.1 to about 0.5.
The resulting acrylonitrile and / or acrylic acid or methacrylonitrile and / or methacrylic acid product should be isolated from other by-products and / or unreacted products by methods known in the art, if desired. Can do. By-products in ammoxidation include CO _x (carbon dioxide + carbon monoxide), hydrogen cyanide (HCN) and acetonitrile or methyl cyanide (CH ₃ CN). The effluent of the reactor contains unreacted oxygen (O ₂ ), ammonia (NH ₃ ), nitrogen (N ₂ ), helium (He) and entrained catalyst particles.

Specific Embodiments For purposes of illustrating the present invention, various catalyst mixture samples were prepared and then evaluated under similar reaction conditions. The compositions listed below are display compositions based on all metals added in the preparation of the catalyst mixture. Since some metals are lost during catalyst preparation or do not react completely, the actual composition of the final catalyst mixture may be slightly different from the indicated composition shown below.
The unused catalyst was prepared in the final form by the method described herein. A portion of the unused catalyst was combined with the spent catalyst and catalyst modifier and mixed dry using a mechanical mixer.
The catalyst was evaluated in a fluidized bed reactor with a 1 inch diameter (2.54 cm) capacity and 40 cc capacity. The reactor was charged with about 20 to about 45 g of granular catalyst or catalyst mixture. Propane was fed into the reactor at a flow rate between about 0.04 and about 0.15 WWH (ie, propane mass / catalyst mass / hour). Ammonia was fed to the reactor at a flow rate such that the ammonia: propane ratio was about 1 to about 1.5. The pressure in the reactor was maintained at about 2 to about 15 psig. The reaction temperature was in the range of about 420 to about 460 ° C.
Comparative Example 1 A catalyst having a display composition of MoV _0.21 Sb _0.24 Nb _0.09 O _x and containing 45% by mass of a silica support was prepared. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 1.
Example 1-1: The spent catalyst of Comparative Example 1 and an unused catalyst having the indicated composition MoV _0.21 Sb _0.24 Nb _0.09 O _x were mixed in a ratio of 2/3: 1/3, and further a basic catalyst composition It was mixed Sb ₂ O ₃ with respect to 1 mol of molybdenum in the object as antimony (Sb) is 0.1 mole. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 1.
Comparative Example 2: A catalyst having the same display composition as Comparative Example 1 was prepared. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 1.
Example 2-1: The used catalyst of Comparative Example 2 and an unused catalyst having the indicated composition MoV _0.21 Sb _0.24 Nb _0.09 O _x were mixed in a ratio of 2/3: 1/3, and further a basic catalyst MoO ₃ was mixed so that molybdenum (Mo) was 0.02 mol per 1 mol of molybdenum in the composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 1.
Example 2-2: The spent catalyst of Example 2-1 and an unused catalyst with the indicated composition MoV _0.21 Sb _0.24 Nb _0.09 O _x were mixed in a ratio of 2/3: 1/3, Sb ₂ O ₃ was mixed so that Sb was 0.1 mol per 1 mol of molybdenum in the resulting catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 1.

Comparative Example 3 A catalyst having a display composition of MoV _0.21 Sb _0.24 Nb _0.09 O _x and containing 45% by mass of a silica support was prepared. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-1: The catalyst of Comparative Example 3 and 0.05 mol of Sb ₂ O ₃ were mixed with 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-2: The catalyst of Comparative Example 3 and 0.1 mol of Sb ₂ O ₃ were mixed with 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-3: The catalyst of Comparative Example ₃ was mixed with 0.2 mol of Sb ₂ O ₃ with respect to 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-4: The catalyst of Comparative Example 3 was mixed with 0.02 mol of TiO ₂ with respect to 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-5: The catalyst of Comparative Example 3 was mixed with 0.02 mol of H ₆ TeO ₆ with respect to 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-6: The catalyst of Comparative Example ₃ was mixed with 0.1 mol of Sb ₂ O ₃ with respect to 1 mol of molybdenum. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The catalyst performance after a long production time is summarized in Table 2.
Example 3-7: The catalyst of Comparative Example ₃ was mixed with 0.05 mol of H ₃ BO ₃ with respect to 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-8: The catalyst of Comparative Example 3 was mixed with 0.1 mol of Sb ₂ O ₄ with respect to 1 mol of molybdenum. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-9: The catalyst of Comparative Example 3 and 0.05 mol of (NH ₄ ) ₂ HPO ₄ were mixed with 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.
Example 3-10: The catalyst of Comparative Example 3 was mixed with 0.04 mol of LiOH with respect to 1 mol of molybdenum. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 2.

Comparative Example 4: A catalyst having a display composition of MoV _0.3 Sb _0.2 Nb _0.08 Ti _0.1 Ce _0.005 O _x and containing 45% by mass of a silica support was prepared. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 3.
Example 4-1: The catalyst of Comparative Example 4 was mixed with 0.025 mol of GeO ₂ with respect to 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 3.
Example 4-2: The catalyst of Comparative Example 4 was mixed with 0.025 mol of CeO ₂ with respect to 1 mol of molybdenum in the basic catalyst composition. The catalyst was evaluated in a fluidized bed reactor with a capacity of 40 cc. The results are shown in Table 3.

  While the above description and embodiments are representative for practicing the invention, various alternatives, modifications, and variations will become apparent to those skilled in the art in view of this specification. Accordingly, such alternatives, modifications, and variations are intended to fall within the scope of the appended claims.

Claims (17)

A method of ammoxidizing or oxidizing a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon to produce an unsaturated nitrile or an unsaturated organic acid,
The method
An unused mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium;
A spent mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium;
A performance regulator selected from the group consisting of antimony (III) oxide, antimony (III) oxalate, antimony (III) tartrate, antimony (V), antimony tetroxide, Sb ₆ O ₁₃ and mixtures thereof. Providing a catalyst mixture;
Contacting the saturated hydrocarbon, unsaturated hydrocarbon, or mixture of saturated hydrocarbon and unsaturated hydrocarbon with oxygen-containing gas or oxygen-containing gas and ammonia in the presence of the catalyst mixture.   One or more of the performance modifier, the unused mixed metal oxide catalyst and the used mixed metal oxide catalyst are selected from the group consisting of silica, alumina, zirconia, titania or mixtures thereof. The method of claim 1, comprising a carrier.   The method of claim 1, wherein the catalyst mixture comprises at least 0.01 mole of the performance modifier per mole of molybdenum in the total amount of the unused mixed metal oxide catalyst and the spent mixed metal oxide catalyst. .   The method according to claim 1, wherein one or both of the unused mixed metal oxide catalyst and the used mixed metal oxide catalyst are prepared by a method other than hydrothermal synthesis. The unused catalyst composition has the following formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof, L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof, 0.1 ≦ a ≦ 1.0, 0.01 ≦ b ≦ 1.0, 0.001 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 1 and n are the number of oxygen atoms necessary to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in an oxidation state lower than the oxidation state) The method of claim 1 comprising: The used catalyst composition has the following formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof, L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof, 0.1 ≦ a ≦ 1.0, 0.01 ≦ b ≦ 1.0, 0.001 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 1 and n are the number of oxygen atoms necessary to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in an oxidation state lower than the oxidation state) The method of claim 1 comprising:   The method of claim 1, wherein the providing step comprises physically mixing the unused composite oxide catalyst, the used composite oxide catalyst, and the performance modifier. The method of claim 7 , wherein the providing step further comprises premixing the unused composite oxide catalyst and the performance modifier.   The method according to claim 1, wherein the providing step includes a step of mixing an unused composite oxide catalyst and a performance modifier by wet impregnation. A method of ammoxidation or oxidation of a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon to produce an unsaturated nitrile or an unsaturated organic acid, the method comprising:
A dry mixed metal oxide catalyst containing molybdenum, vanadium, niobium, and at least one component selected from the group consisting of antimony and tellurium, antimony oxide (III), antimony oxalate (III), antimony tartrate (III ), Antimony oxide (V), antimony tetroxide, Sb ₆ O ₁₃ and a performance modifier selected from the group consisting of these and physically mixing to form a catalyst mixture;
Contacting the saturated hydrocarbon, unsaturated hydrocarbon, or mixture of saturated and unsaturated hydrocarbons with oxygen-containing gas or oxygen-containing gas and ammonia in the presence of the catalyst mixture. The mixed metal oxide catalyst is made of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tungsten, titanium, tin, germanium, zirconium, lithium and hafnium. The method of claim 10 , further comprising at least one element selected from the group consisting of: The method of claim 10 , wherein one or more of the mixed metal oxide catalyst and the performance modifier comprises a support selected from the group consisting of silica, alumina, zirconia, titania or mixtures thereof. The method of claim 10 , wherein the catalyst mixture comprises at least 0.01 moles of performance modifier per mole of molybdenum in the mixed metal oxide catalyst. The method of claim 10 , wherein the physical mixing step comprises mixing a calcined mixed metal oxide catalyst and a performance modifier. The mixed metal oxide catalyst has the following formula:
_{Mo 1 V a Sb b Nb c} X d L e O n
Wherein X is selected from the group consisting of W, Te, Ti, Sn, Ge, Zr, Hf, Li and mixtures thereof, L is Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Selected from the group consisting of Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof, 0.1 ≦ a ≦ 1.0, 0.01 ≦ b ≦ 1.0, 0.001 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 1 and n are the number of oxygen atoms necessary to satisfy the valence of all other elements present in the composite oxide, but one or more of the other elements in the composite oxide are A, b, c, d and e represent the molar ratio of each element corresponding to 1 mol of Mo, provided that it can exist in an oxidation state lower than the oxidation state) The method of claim 10 comprising: The ammoxidation of a saturated hydrocarbon, an unsaturated hydrocarbon, or a mixture of a saturated hydrocarbon and an unsaturated hydrocarbon is carried out when the contacting step is the saturated hydrocarbon, the unsaturated hydrocarbon, or the saturated hydrocarbon and the unsaturated hydrocarbon. 11. The method of claim 10 , comprising contacting a mixture with hydrogen with ammonia and an oxygen containing gas in the presence of the catalyst mixture. The method of claim 10 , wherein the dry mixed metal oxide catalyst is prepared by other than a hydrothermal synthesis method.