WO2010077451A1 - Highly stable and refractory materials used as catalyst supports - Google Patents

Highly stable and refractory materials used as catalyst supports Download PDF

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WO2010077451A1
WO2010077451A1 PCT/US2009/064508 US2009064508W WO2010077451A1 WO 2010077451 A1 WO2010077451 A1 WO 2010077451A1 US 2009064508 W US2009064508 W US 2009064508W WO 2010077451 A1 WO2010077451 A1 WO 2010077451A1
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catalytic
catalytic process
metal
metal oxides
felt
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Manuela Serban
Alakananda Bhattacharyya
Kurt M. Vanden Bussche
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Honeywell UOP LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the support used to disperse the active catalytic phase is a critical element for the overall success of the catalytic system.
  • Supports anchor the catalyst materials and the distribution of the catalyst active sites depends on the physical properties of the supports. Overall performance and the life of a catalyst system often depend on the nature and composition of the supports. In particular, for high temperature applications under corrosive environments, the catalytic system has to be thermally stable and resistant to repeated temperature cycling as well as inert to chemical attack by the reaction media.
  • This invention discloses processes for the use of a highly porous, stable and refractory class of materials, namely (metal) oxide felts, such as, Zr ⁇ 2, Ce2 ⁇ 3, Ce ⁇ 2, Y2O3, Ti ⁇ 2, Hf ⁇ 2, AI2O3, M>2 ⁇ 5, La2U3, Sn ⁇ O ⁇ ⁇ Yb2U3, and the like and their combinations used as catalytic supports for different varied applications.
  • metal oxide felts such as, Zr ⁇ 2, Ce2 ⁇ 3, Ce ⁇ 2, Y2O3, Ti ⁇ 2, Hf ⁇ 2, AI2O3, M>2 ⁇ 5, La2U3, Sn ⁇ O ⁇ ⁇ Yb2U3, and the like and their combinations used as catalytic supports for different varied applications.
  • Two major physical properties of a catalyst support are surface area and pore volume.
  • the stacking property of the felt materials is changed drastically; from the natural gravity based stacking of traditional catalysts packed in a fixed bed reactor that creates a certain void space, to a flexible, controlled, fabricated stacking for the felt materials. This may allow effective interaction of the feed with the catalyst.
  • the flexibility of the felt openings is significantly different than the rigid porous structure of a traditional catalyst, fact that could offer unique properties to the felt catalyst.
  • the felt material is used as an absorbent in which the physical dimension of the phases generated during absorption and regeneration are very different, e.g., oxide and sulfide phases
  • the flexible felt porous structure could allow repeated cycling between smaller and bulkier phases without weakening the support porous structure.
  • the potential applications for these felt materials used as catalytic supports may be in the areas of low, medium or high temperature catalytic processes, under an oxidizing or reducing environment, under highly acidic or basic conditions, in gas, liquid, or mixed phases.
  • the support is a highly porous, stable and refractory ceramic textile composed entirely of inorganic fibers.
  • zirconia felts are composed of 100%, 4-6 micron diameter 10% yttria-stabilized zirconia fibers which are mechanically interlocked to give a light weight, very flexible and porous media.
  • the zirconia felts can be used in extremely corrosive environments, they are stable in strong oxidizing or reducing conditions, and are not reactive to alkali vapors or salts. They undergo no phase transition on temperature cycling and are capable of use at temperatures in excess of 1500 0 C. Similarly, ceria felts have high surface area, high temperature stability and excellent thermal shock resistance. Some properties of the zirconia and ceria felts are given in the following Table.
  • the metal oxide felt material comprises layers having a thickness from 0.25 to 6.35 mm.
  • the metal oxide felt material has a bulk porosity from 50 to 100% and preferably from 88 to 96%.
  • the metal oxide felt material has a bulk density of 128 to 1073 grams/liter and a melting point between 1500° and 5000 0 C.
  • the catalytic active phase supported on the above porous felts for any given catalytic application could be any metals, mixed metals, i.e., Pt, Pd, Rh, Ag, metal oxides or mixed metal oxides of Zn, Fe, Ni, Co, Cu, Ce, Ba, Ca, Mo, Mn, Mg, Ti, V, W and their mixtures dispersed on the above oxide felts using any of the methods known in the art, i.e., wet impregnation and subsequent calcination and/or reduction, metal vapor deposition and subsequent metal oxidation.
  • This class of highly porous, stable and refractory materials can be used as catalytic supports for any given catalytic application at low, medium or high temperature, under an oxidizing or reducing environment, under highly acidic or basic conditions in gas, liquid, or mixed phases.
  • some examples of such applications and their corresponding catalysts include the following catalytic materials.
  • Noble metals i.e., palladium, ruthenium, rhodium, osmium, iridium, and platinum and selected promoters and stabilizers, can be supported on these felt supports for the dehydrogenation of light paraffins, i.e., ethane, propane, butane, to their corresponding olefins.
  • concentration of noble metal will range from 0.01 to 2 wt-% and the promoter from 0.1 to 4 wt-%.
  • the reaction temperatures can range from 400° to 800 0 C at pressures less than 2 atmospheres.
  • Noble metals i.e., palladium, ruthenium, rhodium, osmium, iridium and platinum and selected promoters such as copper, silver, gold, zinc, cadmium and mercury and stabilizers, supported on these felt supports can be used for the selective hydrogenation of dienes (acetylene or propadiene) to their corresponding olefins (ethylene or propylene).
  • concentration of noble metal will range from 0.01 to 2 wt-% and the promoter from 0.01 to 4 wt-%.
  • the reaction temperatures can range from 0° to 100 0 C at pressures greater than 2 atmospheres.
  • Noble metals i.e., palladium, ruthenium, rhodium, osmium, iridium and platinum and selected promoters and stabilizers, i.e., rhenium, ruthenium, tin, iron, silver, cobalt, manganese, and molybdenum supported on these felt supports can be used for the hydrogenation of monocarboxylic, dicarboxylic, or multicarboxylic acids.
  • these reactions include the hydrogenation of maleic acid to produce tetrahydrofuran and 1, 4, buthanediol and mixtures thereof.
  • the Noble metal is present in concentrations of 0.05 to 5 wt-% and the promoter present from 1 to 10 wt-%.
  • the reaction temperatures can range from 50° to 300 0 C at pressures from 20 to 400 atmospheres.
  • Redox mixed metal oxides such as molybdenum, vanadium, antimony, bismuth and the like on stable and inert felts as described above can be used for the oxidation of hydrocarbons. For example, the oxidation or ammoxidation of butane to produce acrylic acid and acrylonitrile, respectively, may be performed.
  • the total metals ranges from 10 to 60 wt-%.
  • the reaction temperatures can range from 200° to 600 0 C at pressures from 1 to 4 atmospheres.
  • Silver and selected promoters like alkali or alkaline earth chloride salts supported on these felts can be used for the epoxidation of light olefins.
  • oxidation of ethylene to ethylene oxide may range from 3 to 25 wt-%.
  • the reaction temperatures can range from 150° to 250 0 C at pressures from 7 to 33 atmospheres.
  • Metal or metal oxides of Mg, Ce or any other metal oxides with favorable thermodynamics for the metal sulfate phase formation in an oxidizing environment supported on these felt supports can be used for the removal of S-compounds from any gas stream containing S-compounds, e.g., removal of SO x from oxidizing FCC flue gases.
  • 10 to 100% of metal oxides are converted to metal sulfates.
  • the total metals can range from 10 to 60 wt-%.
  • the reaction temperatures may range from 250° to 95O 0 C at pressures from 1 to 100 atmospheres. An example of how to make use of this invention is provided below.
  • a manganese oxide supported on yttria stabilized zirconia felt was prepared via the wet impregnation technique and calcined at 800 0 C under air.
  • the Mn loading was 22 wt-%.
  • the Mn oxide supported on yttria stabilized zirconia felt catalyst showed characteristic lines at 23.2 ⁇ 0.5 deg. 2-theta, 28.942 ⁇ 0.5 deg. 2-theta, 30.220 ⁇ 0.5 deg. 2-theta, 33.039 ⁇ 0.5 deg. 2-theta, 35.060 ⁇ 0.5 deg. 2-theta, 38.303 ⁇ 0.5 deg. 2-theta, 45.243 ⁇ 0.5 deg.
  • High resolution Scanning Electron Microscopy (SEM) image reveals that the metal oxide coats the fibers of the zirconia felt uniformly and a Backscattered Electron image of a cross-section of the metal oxide on the felt material mounted on a resin indicates that the metal oxide layer is very porous.
  • This material was used as a sulfur scavenger from a fuel gas simulating an air-blown gasifier containing 1.35% H2S + 13.3% H 2 + 13.14% CO + 13.5% CO 2 + 59% N 2 .
  • the sulfidation step was done at 75O 0 C and 1600 h ⁇ l space velocity. Under these reducing conditions, the active oxide phase for the sulfidation reaction is Mn(II)O.
  • the regeneration was performed in- situ with lean air (2%O 2 in N 2 ) at 800 0 C and 1600 h ⁇ l space velocity.
  • the Mn-zirconia felt sorbent can easily be cycled between the oxide and sulfide phases with 100% S uptake.
  • the zirconia felt structure remained intact and the only manganese phase detected was MnS with no MnO left behind.
  • the XRD spectra of the five times oxidized material indicates that the sulfided Mn was completely oxidized to Mn 2 O ⁇ (which is further fully reduced to Mn(II)O in the presence of the reducing fuel gas during the sulfidation cycle).
  • the metal oxide supported on this felt material has more sulfur absorbing capacity than metal on traditional bulk zirconia, freshly precipitated or amorphous.

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Abstract

This invention involves highly porous, stable metal oxide felt materials that are used as catalytic supports for a number of different applications including dehydrogenation of light paraffins to olefins, selective hydrogenation of dienes to olefins, hydrogenation of carboxylic acids, oxidation or ammoxidation reactions, epoxidation of light olefins and removal of sulfur compounds from gas streams.

Description

HIGHLY STABLE AND REFRACTORY MATERIALS USED AS CATALYST SUPPORTS
BACKGROUND OF THE INVENTION
[0001] For any heterogeneous catalytic applications, the support used to disperse the active catalytic phase is a critical element for the overall success of the catalytic system.
Supports anchor the catalyst materials and the distribution of the catalyst active sites depends on the physical properties of the supports. Overall performance and the life of a catalyst system often depend on the nature and composition of the supports. In particular, for high temperature applications under corrosive environments, the catalytic system has to be thermally stable and resistant to repeated temperature cycling as well as inert to chemical attack by the reaction media.
SUMMARY OF THE INVENTION
[0002] This invention discloses processes for the use of a highly porous, stable and refractory class of materials, namely (metal) oxide felts, such as, Zrθ2, Ce2θ3, Ceθ2, Y2O3, Tiθ2, Hfθ2, AI2O3, M>2θ5, La2U3, Sn^Oβ^ Yb2U3, and the like and their combinations used as catalytic supports for different varied applications. Two major physical properties of a catalyst support are surface area and pore volume. Although these properties are not changed in the felt materials, the stacking property of the felt materials is changed drastically; from the natural gravity based stacking of traditional catalysts packed in a fixed bed reactor that creates a certain void space, to a flexible, controlled, fabricated stacking for the felt materials. This may allow effective interaction of the feed with the catalyst. Also, the flexibility of the felt openings is significantly different than the rigid porous structure of a traditional catalyst, fact that could offer unique properties to the felt catalyst. For example, if the felt material is used as an absorbent in which the physical dimension of the phases generated during absorption and regeneration are very different, e.g., oxide and sulfide phases, the flexible felt porous structure could allow repeated cycling between smaller and bulkier phases without weakening the support porous structure. DETAILED DESCRIPTION OF THE INVENTION
[0003] The potential applications for these felt materials used as catalytic supports may be in the areas of low, medium or high temperature catalytic processes, under an oxidizing or reducing environment, under highly acidic or basic conditions, in gas, liquid, or mixed phases. What makes this invention unique is the support used to disperse the active catalytic phase. The support is a highly porous, stable and refractory ceramic textile composed entirely of inorganic fibers. For example, zirconia felts are composed of 100%, 4-6 micron diameter 10% yttria-stabilized zirconia fibers which are mechanically interlocked to give a light weight, very flexible and porous media. The zirconia felts can be used in extremely corrosive environments, they are stable in strong oxidizing or reducing conditions, and are not reactive to alkali vapors or salts. They undergo no phase transition on temperature cycling and are capable of use at temperatures in excess of 15000C. Similarly, ceria felts have high surface area, high temperature stability and excellent thermal shock resistance. Some properties of the zirconia and ceria felts are given in the following Table. In addition to zirconia and ceria, it is possible to fabricate other refractory (metal) oxide felts, such as Y2O3, Tiθ2, Hfθ2, AI2O3, Nb2θ5, La2θ3, Yb2U3, and mixed oxide felts like Al2θ3-Siθ2, Hfθ2-Ceθ2, Sm2θ3-Ceθ2, Yb2θ3-Ceθ2- The metal oxide felt material comprises layers having a thickness from 0.25 to 6.35 mm. The metal oxide felt material has a bulk porosity from 50 to 100% and preferably from 88 to 96%. The metal oxide felt material has a bulk density of 128 to 1073 grams/liter and a melting point between 1500° and 50000C.
TABLE
Figure imgf000003_0001
[0004] The catalytic active phase supported on the above porous felts for any given catalytic application could be any metals, mixed metals, i.e., Pt, Pd, Rh, Ag, metal oxides or mixed metal oxides of Zn, Fe, Ni, Co, Cu, Ce, Ba, Ca, Mo, Mn, Mg, Ti, V, W and their mixtures dispersed on the above oxide felts using any of the methods known in the art, i.e., wet impregnation and subsequent calcination and/or reduction, metal vapor deposition and subsequent metal oxidation.
[0005] This class of highly porous, stable and refractory materials can be used as catalytic supports for any given catalytic application at low, medium or high temperature, under an oxidizing or reducing environment, under highly acidic or basic conditions in gas, liquid, or mixed phases. Without wanting to be exclusive, some examples of such applications and their corresponding catalysts include the following catalytic materials.
[0006] Noble metals, i.e., palladium, ruthenium, rhodium, osmium, iridium, and platinum and selected promoters and stabilizers, can be supported on these felt supports for the dehydrogenation of light paraffins, i.e., ethane, propane, butane, to their corresponding olefins. Generally, the concentration of noble metal will range from 0.01 to 2 wt-% and the promoter from 0.1 to 4 wt-%. The reaction temperatures can range from 400° to 8000C at pressures less than 2 atmospheres.
[0007] Noble metals, i.e., palladium, ruthenium, rhodium, osmium, iridium and platinum and selected promoters such as copper, silver, gold, zinc, cadmium and mercury and stabilizers, supported on these felt supports can be used for the selective hydrogenation of dienes (acetylene or propadiene) to their corresponding olefins (ethylene or propylene). The concentration of noble metal will range from 0.01 to 2 wt-% and the promoter from 0.01 to 4 wt-%. The reaction temperatures can range from 0° to 1000C at pressures greater than 2 atmospheres. [0008] Noble metals, i.e., palladium, ruthenium, rhodium, osmium, iridium and platinum and selected promoters and stabilizers, i.e., rhenium, ruthenium, tin, iron, silver, cobalt, manganese, and molybdenum supported on these felt supports can be used for the hydrogenation of monocarboxylic, dicarboxylic, or multicarboxylic acids. For example, these reactions include the hydrogenation of maleic acid to produce tetrahydrofuran and 1, 4, buthanediol and mixtures thereof. The Noble metal is present in concentrations of 0.05 to 5 wt-% and the promoter present from 1 to 10 wt-%. The reaction temperatures can range from 50° to 3000C at pressures from 20 to 400 atmospheres. [0009] Redox mixed metal oxides such as molybdenum, vanadium, antimony, bismuth and the like on stable and inert felts as described above can be used for the oxidation of hydrocarbons. For example, the oxidation or ammoxidation of butane to produce acrylic acid and acrylonitrile, respectively, may be performed. The total metals ranges from 10 to 60 wt-%. The reaction temperatures can range from 200° to 6000C at pressures from 1 to 4 atmospheres.
[0010] Silver and selected promoters like alkali or alkaline earth chloride salts supported on these felts can be used for the epoxidation of light olefins. For example, oxidation of ethylene to ethylene oxide. The metal concentration of silver may range from 3 to 25 wt-%. The reaction temperatures can range from 150° to 2500C at pressures from 7 to 33 atmospheres.
[0011] Metal or metal oxides of manganese, zinc, iron, copper, nickel or any other metal oxides with favorable thermodynamics for the metal sulfide phase formation in a reducing environment supported on these felt supports for the removal of S-compounds from any gas stream containing S-compounds, e.g., removal of H2S and COS compounds from a reducing fuel gas originating from a coal gasifier. In these reactions, 10 to 100% of the metal oxide is converted to metal sulfide. Metal or metal oxides of Mg, Ce or any other metal oxides with favorable thermodynamics for the metal sulfate phase formation in an oxidizing environment supported on these felt supports can be used for the removal of S-compounds from any gas stream containing S-compounds, e.g., removal of SOx from oxidizing FCC flue gases. In these reactions, 10 to 100% of metal oxides are converted to metal sulfates. The total metals can range from 10 to 60 wt-%. The reaction temperatures may range from 250° to 95O0C at pressures from 1 to 100 atmospheres. An example of how to make use of this invention is provided below. [0012] A manganese oxide supported on yttria stabilized zirconia felt was prepared via the wet impregnation technique and calcined at 8000C under air. The Mn loading was 22 wt-%. The Mn oxide supported on yttria stabilized zirconia felt catalyst showed characteristic lines at 23.2 ± 0.5 deg. 2-theta, 28.942 ± 0.5 deg. 2-theta, 30.220 ± 0.5 deg. 2-theta, 33.039 ± 0.5 deg. 2-theta, 35.060 ± 0.5 deg. 2-theta, 38.303 ± 0.5 deg. 2-theta, 45.243 ± 0.5 deg. 2- theta, 49.441 ± 0.5 deg. 2-theta, 50.318 ± 0.5 deg. 2-theta, 55.261 ± 0.5 deg. 2-theta, 57.024 ± 0.5 deg. 2-theta, 59.779 ± 0.5 deg. 2-theta, 62.779 ± 0.5 deg. 2-theta, 65.841 ± 0.5 deg. 2-theta, under X-Ray Diffraction. High resolution Scanning Electron Microscopy (SEM) image reveals that the metal oxide coats the fibers of the zirconia felt uniformly and a Backscattered Electron image of a cross-section of the metal oxide on the felt material mounted on a resin indicates that the metal oxide layer is very porous. This material was used as a sulfur scavenger from a fuel gas simulating an air-blown gasifier containing 1.35% H2S + 13.3% H2 + 13.14% CO + 13.5% CO2 + 59% N2. The sulfidation step was done at 75O0C and 1600 h~l space velocity. Under these reducing conditions, the active oxide phase for the sulfidation reaction is Mn(II)O. The regeneration was performed in- situ with lean air (2%O2 in N2) at 8000C and 1600 h~l space velocity. The Mn-zirconia felt sorbent can easily be cycled between the oxide and sulfide phases with 100% S uptake. [0013] After the six cycles test, the zirconia felt structure remained intact and the only manganese phase detected was MnS with no MnO left behind. The XRD spectra of the five times oxidized material indicates that the sulfided Mn was completely oxidized to Mn2Oβ (which is further fully reduced to Mn(II)O in the presence of the reducing fuel gas during the sulfidation cycle). The metal oxide supported on this felt material has more sulfur absorbing capacity than metal on traditional bulk zirconia, freshly precipitated or amorphous.

Claims

CLAIMS:
1. A catalytic process comprising contacting a feed with a composite material comprising a support structure and a catalytic material deposited on said support structure, wherein said support structure comprises a metal oxide felt material and said catalytic material is selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides, mixed metal sulfides.
2. The catalytic process of claim 1 wherein said metal oxide felt material is selected from the group consisting of ZrC>2, CeC>2, Ce2C>3 TiC>2, Nb2U5, Y2O3, B2O3, HfC>2, AI2O3, Al2θ3-Siθ2, Hfθ2-Ceθ2, Yb2θ3-CeC>2, Sm2θ3-Ceθ2, and mixtures and solid solutions thereof.
3. The catalytic process of claim 1 wherein said catalytic material is selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides, mixed metal sulfides.
4. The catalytic process of claim 1 wherein said catalytic material comprises a noble metal and promoters and stabilizers thereof.
5. The catalytic process of claim 1 wherein said catalytic process is a dehydrogenation or hydrogenation reaction.
6. The catalytic process of claim 5 wherein said dehydrogenation converts light paraffins to corresponding light olefins.
7. The catalytic process of claim 5 wherein said hydrogenation reaction converts dienes to a corresponding olefin.
8. The catalytic process of claim 5 wherein said feed for said hydrogenation reaction is a monocarboxylic acid, dicarboxylic acid, multicarboxylic acid or mixtures thereof.
9. The catalytic process of claim 1 wherein said catalytic process is an oxidation of hydrocarbons and said catalyst material comprises one or more metal oxides.
10. The catalytic process of claim 1 wherein said feed comprises one or more light olefins and said catalytic process comprises reacting said one or more light olefins with a catalytic material for in an epoxidation reaction.
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