WO2002016026A2 - Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof - Google Patents

Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof Download PDF

Info

Publication number
WO2002016026A2
WO2002016026A2 PCT/US2001/026737 US0126737W WO0216026A2 WO 2002016026 A2 WO2002016026 A2 WO 2002016026A2 US 0126737 W US0126737 W US 0126737W WO 0216026 A2 WO0216026 A2 WO 0216026A2
Authority
WO
WIPO (PCT)
Prior art keywords
adsorbent
catalyst
agent
catalyst compound
binder
Prior art date
Application number
PCT/US2001/026737
Other languages
French (fr)
Other versions
WO2002016026A3 (en
Inventor
Svetlana Iretskaya
Bryan E. Kepner
Eric A. Mintz
Mark B. Mitchell
Original Assignee
Apyron Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Apyron Technologies, Inc. filed Critical Apyron Technologies, Inc.
Priority to AU2001286831A priority Critical patent/AU2001286831A1/en
Publication of WO2002016026A2 publication Critical patent/WO2002016026A2/en
Publication of WO2002016026A3 publication Critical patent/WO2002016026A3/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • 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
    • B01D53/8609—Sulfur oxides
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0288—Halides of compounds other than those provided for in B01J20/046
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3265—Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • 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

Definitions

  • This invention relates generally to methods for producing adsorbent and/or catalyst compositions that have been promoted with halide ions.
  • the invention further relates to the adsorbent and/or catalyst compositions produced by the methods of the invention.
  • the invention relates methods for reducing or eliminating a nitrogen oxide compound or a sulfur oxide compound from an environment using the adsorbent and/or catalyst compositions of the invention. Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
  • Figure 1 shows sulfur dioxide uptake by 7% CuO/Al 2 0 3 prepared by different acids.
  • Figure 2 shows sulfur dioxide uptake by 7% CuO/Al 2 0 3 .
  • Figure 3 shows NH 3 /NO inlet ratio vs. temperature using 5% CuO/Al 2 0 3 catalyst.
  • Figure 4 shows NH 3 /NO inlet ratio vs. temperature using 5% CuO/Al 2 0 3 catalyst post- treated with HO.
  • Figure 5 shows NH 3 /NO inlet ratio vs. temperature using 5% CuO/Al 2 0 3 catalyst po st- treated with HO and S 0 2 .
  • Figure 6 shows sulfur dioxide uptake by CuO on Si0 2 and Zr0 2 /Al 2 0 3 .
  • Figure 7 shows NH 3 /NO range for SCR using 5% CuO/Al 2 0 3 catalyst post-treated with HC1 and (NH 4 ) 2 S0 4 .
  • Figure 8 shows J H 3 /NO range for SCR using 5% CuO/Al 2 0 3 catalyst post-treated with HO and S0 2 .
  • Figure 9 shows NH 3 /NO range for SCR using A1 2 0 3 impregnated with
  • Figure 10 shows NH 3 /NO range for SCR using A1 2 0 3 impregnated with Cu(N0 3 ) 2 , calcined (5% CuO), and post-treated with NH 4 C1 and S0 2 .
  • Figure 11 shows NH 3 /NO range for SCR using Ml-monolith coated with 5% CuO/Al 2 0 3 , and post-treated with chloride and S0 2 .
  • ppm refers to parts per million.
  • cc refers to cubic centimeter.
  • composition is a system that is prepared from and is composed of two or more different components.
  • this invention in one embodiment, relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • step (a) admixing a support with (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture; (b) heating the mixture produced in step (a) at from 20 to 1,800 °C to produce a heated rnixture;
  • step (c) contacting the heated mixture produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst compound and/or precursor/support composition;
  • step (d) • heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group I compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • step (c) contacting the dried mixture produced in step (b) with a halide agent to produce a halide adsorbent and/or catalyst compound and/or precursor/support composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group II compositions.”
  • the invention farther relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group III compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) admixing components comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a mixture to produce a binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the binder/support system produced in step (d) with a halide agent to produce a halide/binder/support system;
  • step (f) heating the composition produced in step (e) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group IN compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) mixing components comprising
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group N compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group NI compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • compositions produced in step (b) heating the composition produced in step (a) at from 20 to 1,800 °C.
  • the compositions produced by this process are referred to herein as "Group Nil compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • step (b) heating the mixture produced in step (a) at from 20 to 1,800 °C to produce a heated mixture
  • step (c) contacting the heated mixture produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst/support composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group NIII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • step (b) drying the mixture to produce a dried mixture;
  • step (c) contacting the dried mixture produced in step (b) with a halide agent to produce a halide/ adsorbent and/or catalyst compound or precursor/support composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group IX compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group X compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (b) removing a sufficient amount of water from the mixture to cross-link the binder with itself and/or the support to produce a binder/support system; (c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the binder/support system produced in step (d) with a halide agent to produce a halide/binder/support system;
  • step (f) heating the composition produced in step (e) at from 20 to 1,800 °C;
  • step (g) contacting the heated composition produced in step (f) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XI compositions.”
  • the invention fuither relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XIII compositions.”
  • the invention further relates to a process for producing an adsorbent and/or catalyst compound, comprising:
  • step (b) heating the composition produced in step (a) from 20 to 1,800 °C;
  • compositions produced by this process are referred to herein as "Group XIV compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) heating the composition produced in step (b) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group XV compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) admixing components comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • compositions produced by this process are referred to herein as "Group XVI compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group XVII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800° C;
  • step (e) contacting the heated composition produced in step (d) with a halide agent to produce a halide/binder/support system;
  • step (f) heating the composition produced in step (e) at from 20 to 1,800° C.
  • compositions produced by this process are referred to herein as "Group XVIII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (b) removing a sufficient amount of water from the mixture to cross-link components i and/or ii to produce an adsorbent and/or catalyst and binder system; (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system; and
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group XIX compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C.
  • compositions produced by this process are referred to herein as "Group XX compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition; (d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XXI compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C; (e) contacting the heated composition produced in step (d) with a halide agent to produce a halide/binder/support system;
  • step (f) heating the composition produced in step (e) at from 20 to 1,800 °C;
  • step (g) contacting the heated composition produced in step (f) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XXII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XXIII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XXIV compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • compositions produced by this process are referred to herein as "Group XXV compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800° C;
  • step (e) contacting the heated composition produced in step (d) with an oxoanion agent.
  • compositions produced by this process are referred to herein as "Group XXVI compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • compositions produced by this process are referred to herein as "Group XXVII compositions.”
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (d) heating the composition produced in step (c) at from 20 to 1,800 °C;
  • compositions produced by this process are referred to herein as "Group XXVIII compositions.”
  • the invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • step (b) contacting the mixture produced in step (a) with a hahde agent to produce a halide/adsorbent and/or catalyst/support composition;
  • step (c) contacting the composition produced in step (b) with an oxoanion agent
  • step (a), (b), and/or (c) is heated at from 20°C to 1,800 °C.
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
  • step (b) contacting the mixture produced in step (a) with a hahde agent to produce a halide/adsorbent and/or catalyst/support composition; and (c) contacting the composition produced in step (b) with an oxoanion agent,
  • step (a), (b), and/or (c) is heated at from 20 °C to 1,800 °C.
  • the invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system; wherein the product produced in step (a), (b), and/or (c) is heated at from 20 °C to 1,800 °C.
  • the invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (b) and/or (c) wherein the product produced in step (b) and/or (c) is heated at from 20 °C to 1,800 °C.
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system;
  • step (b) and/or (c) wherein the product produced in step (b) and/or (c) is heated at from 20 °C to 1,800 °C.
  • the invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • admixing components comprising: (i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
  • the invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • the invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
  • a binder comprising a colloidal metal oxide or colloidal metalloid oxide
  • step (c) heating the product produced in step (b) from 20 °C to 1,800 °C.
  • the invention further relates to the compositions produced by the processes of the present invention.
  • the invention further relates to an adsorbent and/or catalyst and binder system comprising (1) a binder that has been cross.-linked with itself and/or at least one type of an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor and (2) at least one hahde ion.
  • the invention further relates to an adsorbent and/or catalyst and binder system comprising (1) a binder that has been cross-linked with itself and/or at least one type of an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor; (2) at least one hahde ion; and (3) at least one oxoanion.
  • the invention further relates to an adsorbent and/or catalyst system comprising a support, an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor, and a hahde ion.
  • the invention further relates to an adsorbent and/or catalyst system comprising a support, an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor, a hahde ion, and an oxoanion.
  • the invention further relates to a monohth comprising one or more compositions of the invention.
  • any metal oxide known in the art can be used as the support in the present invention.
  • metal oxides include, but are not Bit ted to, oxide complexes, such as transition metal oxides, lanthanide oxides, as well as oxides of Group IIA (Mg, Ca, Sr, Ba), Group IIIA (B, Al, Ga, In, TI), Group IVA (Si, Ge, Sn, Pb), and Group VA (As, Sb, Bi).
  • the metal oxide comprises an oxide of aluminum, cerium, cobalt, chromium, hafnium, nickel, titanium, copper, vanadium, sihcon, manganese, iron, zinc, zkconium, magnesium, thorium, ura um, or a combination thereof.
  • any oxidation state of the metal oxide may be useful for the present invention.
  • the metal oxide can be a mixture of at least two metal oxide particles having the same metal with varying stoichiometry and oxidation states.
  • the metal oxide comprises A1 2 0 3 , Ga ⁇ , Ti0 2 , CuO, Cu j O, V 2 0 5 , Si0 2 , Mn0 2 , Mn 2 0 3 , Mn 3 0 4 , ZnO, MgO, Th0 2 , Zr0 2 , Fe 2 0 3 , Fe 3 0 4 , or zeohte.
  • the support is aluminum oxide, sihcon dioxide, zkconium dioxide, titanium dioxide, or an oxide of magnesium, more preferably duminum oxide.
  • the sihcon dioxide is diatomite or diatomaceous earth.
  • the support is particle disclosed in U.S. Patent No. 5,948,726, which is incorporated by reference in its entkety.
  • the support comprises a ceramic, for example, a ceramic monolith.
  • the metal oxide further comprises a second type of an oxide of aluminum, cerium, cobalt, cjhromium, hafnium, nickel, titanium, copper, vanadium, sihcon, manganese, on, zinc, zkconium, magnesium, thorium, uranium, or a combination thereof.
  • the metal oxide further comprises a second type of particles of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, sihcon dioxide, manganese dioxide, kon oxide, zinc oxide, or zeohte.
  • Typical zeohtes used in the present invention include "Y" type, "beta " type, mordenite, and ZsM5.
  • the support comprises aluminum oxide, sihcon dioxide, or an oxide of magnesium, preferably aluminum oxide.
  • the metal oxide itself comprises an adsorbent and/or catalyst compound.
  • the metal oxide acts as an adsorbent, the metal oxide can adsorb a large amount of contaminant from the envkonment.
  • the metal oxide is an adsorbent, the sulfur oxide or nitrogen oxide is chemically bonded to and very tightly retained in the metal oxide.
  • the metal oxide when the metal oxide comprises an adsorbent and/or catalyst compound, the metal oxide can be regenerated using techniques known in the art.
  • the support comprises a metal oxide, the metal oxide absorbs the contaminant from the envkonment.
  • the metal oxide When the metal oxide behaves as a catalyst, the metal oxide can catalyticahy decompose or remediate oxides of nitrogen.
  • any of the compositions of the present invention is performed.
  • the timing and number heating steps will vary depending upon the particular composition. In general, any of the heating steps are from 20 °C to 1,800 °C.
  • the support is heated from 20 to 1,800 °C prior to admixing the support with the adsorbent and/or catalyst compound or adsorbent and/or catalyst precursor.
  • the lower limit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C
  • the upper limit of the heating temperature is 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower hmit can be used with any upper limit.
  • the temperature is from 100 °C to 1,000 °C, 200 °C to 900 °C, 300 °C to 800 °C, or 400 °C to 700 °C.
  • the metal oxide comprises calcined or sintered alirminum oxide that was produced by calcining or sintering the precursor to the aluminum oxide at a particle temperature of from 200 °C to 1,800 °C.
  • the precursor to the calcined or sintered aluminum oxide can include but is not limited to boehmite, bauxite, pseudo-boehmite, scale, Al(OH) 3 , and alumina hydrates.
  • the metal oxide is acid treated prior to admixing with the adsorbent and/or catalyst compound or precursor.
  • AH of the metal oxides disclosed above can be acid treated.
  • the acid activation or enhancement treatment process disclosed in U.S. Patent No. 5,985,790, and international pubhcationno. WO 97/47380 entitled "Acid Contacted Enhanced Adsorbent Particle and/or Catalyst and Binder System," which are herein incorporated by this reference in thek entkety, can be used in the present invention to prepare the acid treated metal oxide.
  • the acid that can be used in this invention can be any acid or mixture of acids that can promote the formation of hydroxyl groups onto the surface of the pores of the metal oxide.
  • acids include, but are not limited to, nitric acid, sulfuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid, and mixtures thereof.
  • the acid is diluted with water to prevent dissolution of the metal oxide.
  • only a dilute solution of the acid is requked to achieve maximum or saturated loading of the hydroxyl groups on the metal oxide.
  • a 0.5 wt. % (0.09 N; pH of about 2.9) and even a 0.1 wt. % (0.02 N; pH of about 3.25) acetic acid solution has been found effective.
  • a wide range of concentrations of acid can be used in this invention from very dilute to very concentrated depending on the hazards involved and the economics of production.
  • the acid contacting is more than a surface wash but less than an etching.
  • the acid is of an upper strength equivalent to a 0.5 N (normahty) aqueous solution of acetic acid.
  • the acid concentration is from 0.0001 N to 2 N.
  • the upper strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N or 0.001 N aqueous acetic acid solution. Any lower limit can be used with any upper hmit.
  • the lower strength of the acid should be that which provides more than a surface washing but imparts enhanced adsorbent effects to the metal oxide.
  • the lower strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N, 0.001 N, 0.0005 N, or 0.0001 N aqueous acetic acid solution.
  • the acid concentration range is from 0.0001 N to 0.25 N, 0.0005 N to 0.09, 0.005 N to 0.075 N, or 0.01 N to 0.05 N.
  • the acid preferably has some water present to provide OH " and/or H + ions, which bond with the metal oxide.
  • the water is preferably distilled water to minimize the amount of impurities contacting the metal oxide during acid treatment.
  • the acid enhanced metal oxide is made by the following process.
  • the metal oxide can be contacted with the acid by various means, including the metal oxide being dipped in, extensively washing with, or submerged in the acid.
  • the length of time the metal oxide is be contacted with the acid varies according to the ability of the particular metal oxide to generate hydroxyl groups on the surface and pores of the particle.
  • the time can be as low as 30 seconds, a few (three) minutes, at least 15 minutes, at least one hour, at least 6 hours, at least 12 hours, or at least one day, to achieve adequate adsorption results and/or to preferably assure saturation.
  • the tkne must be sufficient to at least increase the number of hydroxyl groups on the metal oxide.
  • the metal oxide is submerged in the acid, and saturation is typically complete when there is complete coverage of the metal oxide pores with the acid solution.
  • the contacting should be substantial enough to provide penetration of the acid throughout the pores of the metal oxide thereby increasing the number of hydroxyl groups on the pore surface of the particle. Mere washing the outside surface of the metal oxide to remove impurities is not sufficient to provide adequate penetration of the acid into and throughout the pores of the metal oxide.
  • the acid contacted metal oxide is then optionaUy rinsed, preferably with water. Rinsing of the acid contacted metal oxide does not reduce the enhanced adsorptive capability of the particle. When rinsed, the metal oxide is preferably rinsed with distilled water to minimize impurity contact.
  • the acid treated metal oxide is dried by a low to moderate heat treatment to remove excess hquid, such as acid or water, from the rinsing. Typically, the drying is from about 50 °C to about 200 °C. Drying of the metal oxide also reduces the transfer cost of the particle. In one embodiment, the acid treated metal oxide is not calcined or recalcined after acid treatment.
  • the support prior to admixing the support with the adsorbent and/or catalyst compound and/or the adsorbent and/or catalyst precursor, is a metal oxide that is (1) calcined at a particle temperature of from 200 to 700 C C, and (2) contacted with a dilute acid, wherein the acid contacting is more than a surface wash but less than an etching, wherein the resultant acid treated metal oxide is not subsequently calcined.
  • the acid treated metal oxide is aluminum oxide.
  • the invention contemplates the use of any prior art adsorbent and/or catalyst compound or composite composition of two or more types of adsorbent and/or catalyst compounds as the adsorbent and/or catalyst compound.
  • An "adsorbent and/or catalyst compound” is any compound that can adsorb and/or catalytically degrade sulfur oxide(s) or nitrogen oxide(s). Depending upon the selection of the compound or precursor, the compound or precursor can behave as an adsorbent, a catalyst, or a combination thereof.
  • the adsorbent and/or catalyst compound may also catalytically convert the sulfur oxide(s) and nitrogen oxide(s) to another form or compound.
  • the adsorbent and/or catalyst compound comprises an oxide compound.
  • the compound in one embodiment comprises a metal or metalloid oxide particle.
  • oxide complexes such as transition metal oxides, lanthanide oxides, thorium oxide, as well as oxides of Group IIA (Mg, Ca, Sr, Ba), Group IIIA (B, Al, Ga, In, TI), Group INA (Si, Ge, Sn, Pb), and Group NA (As, Sb, Bi).
  • the compound comprises an oxide of aluminum, cerium, hafnium, titanium, copper, chromium, vanadium, sihcon, manganese, kon, zinc, zkconium, tungsten, rhenium, arsenic, magnesium, thorium, uranium, silver, cadimium, tin, lead, antimony, ruthenium, osmium, cobalt or nickel or zeohte.
  • any oxidation state of the oxide complexes may be useful for the present invention.
  • the oxide can be a mixture of at least two metal oxide compounds having the same metal with varying stoichiometry and oxidation states.
  • the adsorbent and/or catalyst compound or precursor comprises A1 2 0 3 , N 2 O 5 , Si0 2 , Mn0 2 , Mn 2 0 3 , Mn 3 0 4 , ZnO, W0 2 , WO 3 , Re 2 O 7 , As 2 0 3 , As 2 0 5 , MgO, Th0 2 , Ag 2 O, AgO, CdO, Sn0 2 , PbO, FeO, Fe 2 0 3 , Fe 3 O 4 , Ru 2 0 3 , RuO, Os0 4 , Sb 2 O 3 , CoO, Co 2 0 3 , ⁇ iO or zeohte.
  • the adsorbent and/or catalyst compound further comprises a second type of adsorbent and/or catalyst compound of an oxide of aluminum, cerium, hafnium, titanium, copper, chromium, vanadium, sihcon, manganese, kon, zinc, zkconium, tungsten, rhenium, arsenic, magnesium, thorium, uranium, silver, cadimium, tin, lead, antimony, ruthenium, osmium, cobalt or nickel or zeohte, activated carbon, including coal and coconut carbon, peat, zinc or tin.
  • a second type of adsorbent and/or catalyst compound of an oxide of aluminum, cerium, hafnium, titanium, copper, chromium, vanadium, sihcon, manganese, kon, zinc, zkconium, tungsten, rhenium, arsenic, magnesium, thorium, uranium, silver, cadimium,
  • the adsorbent and/or catalyst compound further comprises a second type of adsorbent and/or catalyst compound of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, sihcon dioxide, manganese dioxide, kon oxide, zinc oxide, zeohte, activated carbon, peat, zinc or tin particle.
  • Typical zeohtes used in the present invention include "Y" type, "beta " type, mordenite, and ZsM5.
  • the adsorbent and/or catalyst compound or precursor comprises aluminum oxide that was produced by calcining the precursor to the calcined aluminum oxide at a particle temperature of from 300 ° C to 700 ° C.
  • the precursor to calcined alummum oxide can include but is not limited to boehmite, bauxite, pseudo-boehmite, scale, Al(OH) 3 and alumina hydrates. In the case of other metal oxide complexes, these complexes can also be calcined or uncalcined.
  • the adsorbent and/or catalyst compound is a vanadium compound, a titanium compound, a zinc compound, or a copper compound.
  • the adsorbent and/or catalyst compound is an alkoxide, nitrate, carbonate, sulfate, acetate, aceto acetate, gluconate, benzoate, or carboxylate of vanadium, titanium, zinc, or copper.
  • the adsorbent and/or catalyst compound is a copper compound.
  • copper compounds include, but are not limited to Cu(N0 3 ) 2 , Cu(N0 3 ) 2 • XH 2 0, CuC0 3 , CuS0 4 , CuO, C , Cu(OAc) 2 , copper aceto acetonate, copper oxalate, copper gluconate, a copper benzoate, a copper carboxylate, or a combination thereof.
  • the adsorbent and/or catalyst compound is CuO.
  • the adsorbent and/or catalyst compound and the metal oxide are not the same compound.
  • the metal oxide and the adsorbent and/or catalyst compound are the same compound.
  • the metal oxide support can be calcined or sintered aluminum oxide, and the adsorbent and/or catalyst particle can be acid treated aluminum, oxide that has not been calcined or sintered.
  • an "adsorbent and/or catalyst precursor” is a compound that can be converted to an adsorbent and/or catalyst compound. The steps requked to convert the precursor to the compound will vary depending upon the precursor selected. For example, an adsorbent and/or catalyst precursor, such as CuCl 2 , can be subjected to a hydrolysis step followed by exposure to heat to remove water to produce CuO. In one embodiment, heating the adsorbent and/or catalyst precursor can convert the precursor to the corresponding adsorbent and/or catalyst compound.
  • adsorbent and/or catalyst precursors include, but are not hmited to, a vanadium hahde compound, a titanium halide compound, a zinc hahde compound, or a copper hahde compound.
  • Hahde is defined as fluoride, chloride, bromide, or iodide.
  • the adsorbent and/or catalyst precursor is a copper compound that can be converted to a copper oxide.
  • the adsorbent and/or catalyst precursor is a copper hahde compound, preferably CuCl 2 , CuBr 2 , Cul 2 , or Cul.
  • the adsorbent and/or catalyst precursor is Cu(N0 3 ) 2 , copper sulfate, copper oxalate, copper acetate, copper oxide, a copper alkoxide, or a copper carboxylate.
  • the adsorbent and/or catalyst precursor can be used in combination with an adsorbent and/or catalyst compound.
  • the support and the adsorbent and/or catalyst compound and/or the adsorbent and/or catalyst precursor can be admixed using a variety of techniques known in the art.
  • an acidic solvent is used to admix the components.
  • the support and the adsorbent and/or catalyst compound or precursor are admixed in the presence of a solvent. Many solvents can be used to admix the support and the adsorbent and/or catalyst compound or precursor.
  • the solvent used to admix the support and the adsorbent and/or catalyst compound or precursor comprises water, acidic water, basic water, an alcohol, a ketone, an ester, an ether, an aldehyde, a polyol, or a combination thereof.
  • the support and the adsorbent and/or catalyst compound or precursor can be admixed in dry form, and the dry mixture is optionally contacted with a solvent. After the admixing step, the mixture is composed of an intimate mixture of the support and the adsorbent and/or catalyst compound or precursor.
  • the resultant composition is heated from 20 to 1,800 °C.
  • the lower jjmit of the heating temperature is 20, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C
  • the upper limit of the heating temperature is 300, 400, 500, 600, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower limit can be used with any upper limit.
  • the temperature is from 100 °C to 1,000 °C, 200 °C to 900 °C, 300 °C to 800 °C, or 400 °C to 700 °C.
  • the heated composition is allowed to cool to room temperature prior to conducting any additional steps (e.g., reduction, oxidation, or contacting with the hahde agent and/or oxoanion agent).
  • a second heating step can be performed after the composition is contacted with the hahde agent and/or the oxoanion agent.
  • the resultant composition is dried from 20 to 100 °C, 20 to 50 °C, 20 to 30 °C, and preferably at 25 °C in order to remove any residual solvent that may be present in the admixture.
  • the drying step is performed by allowing the composition to stand at ambient temperature for a sufficient time so that the majority of the solvent has evaporated.
  • the dried mixture then can either be subjected to additional steps (e.g., reduction, oxidation, or contacting with the hahde agent and/or oxoanion agent), or the dried mixture can be heated at from 80 to 1,800 °C then subsequently subjected to additional steps.
  • the amount of the adsorbent and/or catalyst compound or precursor that can be admixed with the support can vary depending upon the adsorbent and/or catalyst compound or precursor and the support that are selected and the apphcation of the resulting composition.
  • the support is from 0.1 to 99.9 % by weight and the adsorbent and/or catalyst compound and/or precursor is from 0.1 to 99.9 % by weight, wherein the sum of the adsorbent and/or catalyst compound and/or precursor and the support is 100 %.
  • the support is from 5 to 95 %, 10 to 90 %, 20 to 80 %, or 30 to 70 % by weight
  • adsorbent and/or catalyst compound and/or precursor is from 5 to 95 %, 10 to 90 %, 20 to 80 %, or 30 to 70 % by weight, wherein the sum of the adsorbent and/or catalyst compound and/or precursor and the support is 100 %.
  • the composition can include other components, such as additives and fillers.
  • any of the adsorbent and/or catalyst compositions of the present invention can optionaUy be contacted with a reducing agent prior to contacting the composition with the hahde agent and/or oxoanion agent to reduce at least some of the adsorbent and/or catalyst compound or precursor present in the composition.
  • the phrase "at least some" when referring to the amount of the adsorbent and/or catalyst compound or precursor that is reduced or oxidized is defined as greater than 0 % to a maximum of 100 % reduction or oxidation of the adsorbent and/or catalyst compound or precursor.
  • the lower lknit of reduction or oxidation is 1, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, or 80% and the upper hmit 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 95, or 100%. Any lower limit can be used with any upper limit.
  • the % reduction or oxidation is from 1 to 100 %, 5 to 95 %, 10 to 90 %, 20 to 80 %, 30 to 70 %, or 40 to 60 %. AdditionaUy, the support and/or binder may also be reduced depending upon the type of support, binder, and reducing agent that are used.
  • the majority of reducing agents known in the art can be used in the present invention.
  • the selection of the reducing agent varies depending upon the redox potential of the adsorbent and/or catalyst compound or precursor, support, and/or the binder that are used.
  • the support is a metal oxide
  • the reducing agent comprises a reducing sugar or an antioxidant. Any reducing sugar known in the art can be used in the present invention as a reducing agent.
  • reducing agents include, but are not Iknited to, glucose, fructose, formaldehyde, hydrazine, sodium dithionate, sodium bisulfite, ascorbic acid (vitamin C), vitamin E, carbon monoxide, hydrogen, methanol, or ethanol.
  • any of the compositions of the present invention that contain at least some reduced adsorbent and/or catalyst compound or precursor can optionaUy be oxidized so that at least some of the reduced adsorbent and/or catalyst compound or precursor is oxidized.
  • the reduced adsorbent and/or catalyst compound or precursor can be oxidized to a variety of oxidation states.
  • the selection of the particular oxidizing agent depends upon the reduced adsorbent and/or catalyst compound or precursor, the support, and/or the binder. By using redox potentials as described above, it is possible to selectively oxidize at least some of the adsorbent and/or catalyst compound or precursor and not the support or the binder.
  • some of the support can be oxidized as weU.
  • An advantage of the oxidation step is that when the reduced adsorbent and/or catalyst compound or precursor is an elemental metal that is incorporated throughout the support and/or the binder, and the elemental metal is oxidized to the corresponding metal oxide, the resultant oxidized composition has coUoidal metal oxide incorporated or impregnated throughout the support.
  • Another advantage of the oxidation step is that it is possible to produce a composition that has elemental metal and the corresponding metal oxide dispersed throughout the support and/or the binder, which is difficult to reproduce using prior art techniques.
  • oxidizing agents include, but are not limited to, oxygen, oxone ® , ozone, peroxymono sulfate, hydrogen peroxide, C10 2 , 00 3 " , ak, or a combination thereof.
  • the composition containing at least some of the reduced adsorbent and/or catalyst compound or precursor can be heated in ak at from 80 to 1,500 °C in order to oxidize at least some of the reduced adsorbent and/or catalyst compound or precursor.
  • the lower limit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900 °C
  • the upper limit is 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, or 1,500 °C. Any lower hmit can be used with any upper lknit.
  • the temperature is from 100 °C to 1,500 °C, 200 °C to 1,300 °C, 300 °C to 1,100 °C, or 400 °C to 900 °C.
  • compositions of the present invention containing the adsorbent and/or catalyst compound or precursor can be contacted with the reducing agent or oxidizing agent using techniques known in the art.
  • the composition containing the support and the adsorbent and/or catalyst compound or precursor is contacted with an aqueous solution of the reducing agent or the oxidizing agent.
  • the amount of reducing agent or oxidizing agent that is used can vary, and wiU depend on the amount of the adsorbent and/or catalyst compound or precursor that is present in the composition as weU as the desked degree of reduction or oxidation of the adsorbent and/or catalyst compound.
  • the resultant, reduced composition is contacted with an oxidizing agent.
  • the composition can be contacted with a reducing agent or oxidizing agent at from 0 to 100 °C.
  • the mixing time can be as short as the time it takes the reducing or oxidizing agent to contact the composition.
  • binders disclosed in U.S. Patent No. 5,948,726, and international pubhcationno. WO 97/47380 entitled “Acid Contacted Enhanced Adsorbent Particle and/or Catalyst and Binder System,” which are herein incorporated by this reference in thek entkety, are useful as the cross-linkable binders of the present invention.
  • the binder of the present invention comprises an oxide particle that is capable of reacting, preferably cross-linking, with (1) itself; (2) the support, and/or (3) the adsorbent and/or catalyst compound or precursor.
  • the binder when the support is a metal oxide, the binder cross-links with the metal oxide upon drying by forming chemical bonds with itself and the metal oxide. Under acidic conditions, the binder has a large number of surface hydroxyl groups.
  • the binder which is designated as B-OH, cross-hnks with itself upon the loss of water to generate B-O-B.
  • the binder B-OH can also cross-link with a metal oxide complex (M-O) or metal hydroxyl complex (M-OH) to produce B-O-M.
  • CoUoidal metal or metaUoid oxide i. e. , coUoidal metal oxide or coUoidal metaUoid oxide binder
  • a particle comprising a metal or metaUoid mixed hydroxide, hydroxide oxide, or oxide particle, such that the weight loss from the coUoidal metal or metaUoid oxide binder due to loss of water upon ignition is from 1 to 100%, 5 to 99%, 10 to 98%, or 50 to 95% of the theoretical water weight loss on going from the pure metal or metaUoid hydroxide to the corresponding pure metal or metaUoid oxide.
  • the loss of water on going from the pure metal or metaUoid hydroxide to the corresponding pure metal or metaUoid oxide is defined as 100% of the water weight loss.
  • the weight loss refers to loss of water based on the initial weight of water (not the total initial binder weight).
  • the binder system involves the use of a binder in combination with a support and an adsorbent and/or catalyst compound or precursor with few or no surface hydroxyl groups, such that the support and/or the adsorbent and/or catalyst compound or precursor does not cross-link or only nominaUy cross-links with the binder.
  • a binder in combination with a support and an adsorbent and/or catalyst compound or precursor with few or no surface hydroxyl groups, such that the support and/or the adsorbent and/or catalyst compound or precursor does not cross-link or only nominaUy cross-links with the binder.
  • particles that possess only nominal amounts or that do not posses surface hydroxyl groups include particles of metals or non-metals, such as, but not limited to zinc or carbon, respectively.
  • the binder cross-links with itself in a manner described above to form a three dimensional network or matrix that physicaUy entraps or holds the support and the adsorbent and/or catalyst compound or precursor without cross-linking or cross-hhking only to a very smaU degree with the support and/or the adsorbent and/or catalyst compound or precursor.
  • Binders that can be used in the present invention are coUoidal metal or metaUoid oxide complexes.
  • CoUoidal as used herein is defined as an oxide group that has a substantial number of hydroxyl groups that can form a dispersion in aqueous media. This is to be distinguished from the other use of the term coUoid as used in regard to a size of less than 1 ⁇
  • the binders herein are typically smaU in size, e.g. less than 150 ⁇ m, but they do not have to be aU less than 1 ⁇ m. TypicaUy, the binder is un-calcined to maxknize the hydroxyl group avaUability.
  • binders include but are not limited to any metal or metaUoid oxide complex that has a substantial number of hydroxyl groups that can form a dispersion in aqueous media.
  • the binder is coUoidal aluininuin oxide, coUoidal silicon dioxide, coUoidal kon oxide, or a mixture thereof, preferably coUoidal aluminum oxide or coUoidal sihcon dioxide.
  • CoUoidal aluminum, oxide can be a powder, sol, gel or aqueous dispersion.
  • CoUoidal aluminum oxide may be further stabilized with an acid, preferably nitric acid, and even more preferably 3 to 4% nitric acid.
  • coUoidal metal or metaUoid oxide ie., coUoidal metal oxide or coUoidal metaUoid oxide binder
  • coUoidal metal or metaUoid oxide binder also refers to a particle that is capable of forming a gel in water. If the coUoidal metal or metaUoid oxide binder does not form a gel in water, then the binder does not possess a sufficient number surface hydroxyl groups to crosslink with itself, the support, and/or the adsorbent and/or catalyst compound. Prior art coUoidal particles (ie, particle size less than 1 ⁇ m) generaUy do not form gels in water.
  • the binder is from 1% to 99.9% by weight of the mixture, preferably from 10% to 35% by weight.
  • the binder wUl be referred to as "coUoidal" to distinguish it from the metal oxides that can be used as the support material or the adsorbent and/or catalyst material, as the composition types can be the same, e.g. they can aU contain aluminum oxides.
  • the coUoidal aluminum, oxide is un-calcined with a sufficient number of hydroxyl groups such that the total particle weight loss (as distinguished from just water weight loss discussed above) upon ignition is between from 5% to 34%, more preferably from 20% to 31%.
  • the coUoidal aluminum oxide size is preferably from 5 nm to 400 ⁇ m, preferably at least 30 wt% is less than 25 ⁇ m and 95 wt% is less than 100 ⁇ m.
  • the coUoidal sihcon dioxide is un-calcined with a sufficient number of hydroxyl groups such that the total particle weight loss upon ignition is between from 5% to 37%, more preferably from 20% to 31 %.
  • the coUoidal sihcon dioxide size is preferably from 5 nm to 250 ⁇ m, preferably at least 30 wt% is less than 25 ⁇ m and 95 wt% is less than 100 ⁇ m.
  • An acid facilitates the cross-linking of the binder with (1) itself; (2) the support; (3) and/or the adsorbent and/or catalyst compound or precursor.
  • the addition of an acid to the binder facilitates or enables the reaction (ie., cross- linking) between the binder with itself and the different components.
  • a strong or dUute acid can be used.
  • the acid is dUuted with water to prevent dissolution of the particle and/or for cost effectiveness.
  • the acid treatment is preferably of a concentration (e.g., normahty or molarity), acid type, temperature and length of time to cross-link the binder with itself , the support, and/or the adsorbent and/or catalyst compound or precursor.
  • the acid comprises nitric acid, suUuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid or mixtures thereof, preferably acetic acid or nitric acid.
  • the concentration of the acid is from 0.15 N to 8.5 N, preferably from 0.5 N to 1.7 N.
  • the volume of dkute acid used must be high enough so that the compositions of the present invention can be used as is or further processed, such as extruded or peUetized.
  • a base facilitates the cross-linking of the binder with (1) itself; (2) the support; (3) and/or the adsorbent and/or catalyst compound or precursor.
  • Any of the supports and adsorbent and/or catalyst compounds or precursors described above can be used in this embodiment of the invention.
  • the base that can be used in this invention can be any base or mixture of bases that can promote the formation of hydroxyl groups onto the surface of the support and/or the adsorbent and/or catalyst compound or precursor.
  • any base known in the art can be used to prepare the binder system
  • useful bases include, but are not limited to, LiOH, NaOH, KOH, RbOH, CsOH, Be(OH) 2 , Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , Bronsted bases, or Lewis bases such as, ammonia or pyridine in water.
  • the concentration of the base wiU vary depending upon the selection of the support, the binder, and/or the adsorbent and/or catalyst compound or precursor. In one embodiment, the concentration is from 0.1 to 0.5 N.
  • the metal oxide is base treated prior to admixing the adsorbent and/or catalyst compound or precursor. AU of the metal oxides described above can be base treated.
  • the base is of an upper strength equivalent to a 0.5 N (normahty) aqueous solution.
  • the base concentration is from 0.0001 N to 2 N.
  • the upper strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N or 0.001 N aqueous solution. Any lower lknit can be used with any upper limit.
  • the lower strength of the base should be that which provides more than a surface washing but imparts enhanced adsorbent effects to the metal oxide.
  • the lower strength of the base is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N, 0.001 N, 0.0005 N, or 0.0001 N aqueous solution, hi one embodknent, the base concentration range is from 0.0001 N to 0.25 N, 0.0005 N to 0.09, 0.005 N to 0.075 N, or 0.01 N to 0.05 N.
  • the invention relates to a composition for binding adsorbent and/or catalytic particles to produce an agglomerated particle produced by the process comprising
  • the binder comprises coUoidal aluminum oxide or coUoidal silicon dioxide. Techniques commonly used in the art can be employed to remove the water to promote cross-lMdng.
  • the water is removed by azeotropic distillation. For example, the water is removed by placing the particles in a solvent such benzene, toluene, or m-xylene and carrying out an azeotropic distillation using a Dean Stark trap to remove the water to cross-link the binder.
  • the resultant binder when water is removed from the binder, the resultant binder is highly hydroxylated, which provides a particle with a very high density of Br ⁇ nsted acid sites.
  • This binder can serve as starting materials in the production of agglomerated adsorbent and/or catalyst systems. By increasing the number of Br ⁇ nsted acid sites, it is possible to increase the overaU adsorbent and/or catalytic properties of the agglomerated particle.
  • water can be used to prepare the binder syste
  • the support and/or the adsorbent and/or catalyst compound or precursor are pretreated with an acid or a base to produce surface hydroxyl groups
  • water can be used to facilitate cross-linking between the binder and the support and/or the adsorbent and/or catalyst precursor.
  • any of the particles disclosed in U.S. Patent No. 5,985,790, and international publication no. WO 97/47380 can be used in this embodiment of the invention.
  • Any of the acid-treated or base- treated supports and adsorbent and/or catalyst compounds or precursors described above can be used in this embodiment of the invention.
  • the cross- linking temperature as used herein is the temperature at which the binder cross- hnks with itself, the support, and/or the adsorbent and/or catalyst compound or precursor at an acceptable rate.
  • the cross-linking temperature is from 25 °C to 600 °C.
  • the cross- linking temperature for certain binders is at room temperature although the rate of cross-linking at this temperature is slow.
  • the cross- linking temperature is from 50 °C, 70 °C, 110 °C, or 150 °C to 200 °C, 250 °C, 300 °C, 350 °C, 400 °C, 500 °C, or 600 °C, preferably 150 °C to 300 °C, even more preferably about 250 °C.
  • the cross-linking temperature is from 75 °C to 150 °C. The cross-linking process can take place in open ak, under an inert atmosphere or under reduced pressure.
  • the binder/adsorbent and/or catalyst composition is heated from 20 to 1,800 °C in order to vary the surface area and pore volume of the composition.
  • the lower limit of the heating temperature is 80, 100, 150, 20, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900 °C
  • the upper hmit is 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, or 1,800 °C. Any lower limit can be used with any upper limit.
  • the temperature is from 100 °C to 1,800 °C, 200 °C to 1,500 °C, 300 °C to 1,200 °C, or 400 °C to 900 °C.
  • the binder/adsorbent and/or catalyst composition is calcined. In another embodiment, the binder/adsorbent and/or catalyst composition is sintered.
  • the binder/adsorbent and/or catalyst composition of the present invention can be prepared by a variety of techniques.
  • the (1) binder; (2) the support; and (3) the adsorbent and/or catalyst particle are pre- mixed in dry form
  • the coUoidal binder can be added or prepared in situ.
  • alum could be added as a dry powder and converted to coUoidal aluminum oxide in situ.
  • Other aluminum based compounds can be used for the in situ process, such as aluminum chloride, aluminum secondary butoxide, and the like.
  • an acid, base, or water is added to the mixture, and the mixture is stirred or agitated, typicaUy from 1 minute to 2 hours, preferably from 10 minutes to 40 minutes, until the material has a homogeneous "clay" like texture.
  • the mixture is then ready for cross-linking or can be first fed through an extruder and then cut or chopped into a final shape. After the final shape is made, the mixture is transferred to a drying oven where it is dried from 15 minutes to 4 hours, preferably from 30 minutes to 2 hours.
  • the binder and support is admixed with an acid, base, or water, and the resultant mixture is crosslinked to produce a binder/support system, then the binder/support system is subsequently admixed with the adsorbent and/or catalyst compound or precursor.
  • any support described above can be used in combination with the binder and the adsorbent and/or catalyst compound or precursor.
  • the support comprises aluminum oxide, sihcon dioxide, or an oxide of magnesium, preferably aluminum oxide.
  • the metal oxide when the support is a metal oxide, the metal oxide is (1) calcined at a particle temperature of from 200 to 700 °C, and (2) contacted with a dUute acid.
  • the acid treated metal oxide is aluminum oxide.
  • any of the adsorbent and/or catalyst compounds or precursors previously disclosed can be used to prepare the binder/adsorbent and/or catalyst composition.
  • a binder of the present invention can be combined with any composition of the invention to produce a binder/adsorbent and/or catalyst composition.
  • compositions can be
  • the binder/adsorbent and/or catalyst composition can be optionaUy contacted with a (1) reducing agent; or (2) a reducing agent foUowed by an oxidizing agent using the techniques and reagents described above prior to contacting the composition with the hahde agent and/or oxoanion agent.
  • the reduced composition can be heated in ak at from 80 to 120 °C in order to oxidize at least some of the reduced adsorbent and/or catalyst compound or precursor.
  • the binder is coUoidal aluminum oxide
  • the support is aluminum oxide
  • the adsorbent and/or catalyst compound is a copper compound, preferably CuO or Cu ⁇ O.
  • compositions of the present invention can be admixed with a second adsorbent and/or catalyst compound or precursor to produce a new composition contakiing two or more adsorbent and/or catalyst compounds an or precursors prior to contacting with the hahde agent and/or oxoanion agent.
  • the second adsorbent and/or catalyst compound or precursor can be any of the adsorbent and/or catalyst compounds or precursors previously disclosed.
  • the resultant composition can be optionaUy contacted with (1) a reducing agent to reduce at least some of the second adsorbent and/or catalyst compound; or (2) a reducing agent to reduce at least some of the additional adsorbent and/or catalyst compound or precursor foUowed by oxidizing the resultant composition prior to contacting the composition with the hahde agent and/or oxoanion agent.
  • the binder/adsorbent and/or catalyst composition can be admixed with one or more additional adsorbent and/or catalyst compounds and/or precursors to produce a second binder/adsorbent and/or catalyst composition, foUowed by optionaUy contacting the second binder/adsorbent and/or catalyst composition with (1) a reducing agent to reduce at least some of the additional adsorbent and/or catalyst compound and/or precursor; or (2) a reducing agent to reduce at least some of the additional adsorbent and/or catalyst compound and/or precursor foUowed by oxidizing some at least some of the reduced adsorbent and/or catalyst compound or precursor.
  • the binder/adsorbent and/or catalyst composition is (I) contacted with (1) a reducing agent to reduce at least some of the adsorbent and/or catalyst compound or precursor; or (2) a reducing agent to reduce at least some of the adsorbent and/or catalyst compound or precursor foUowed by oxidizing at least some of the reduced adsorbent and/or catalyst compound or precursor to produce a reduced and/or oxidized binder/adsorbent and/or catalyst composition, and (II) admixing two or more adsorbent and/or catalyst compounds and/or precursors with the reduced and/or oxidized binder/adsorbent and/or catalyst composition.
  • compositions of the present invention can vary greatly depending on the end use. hi one embodiment, the compositions of the present invention can be extruded to a particular shape and size using techniques known in the art.
  • hahde agent is defined as any compound that is a source of fluoride ions, chloride ions, bromide ions, or iodide ions when the hahde agent is admixed with a solvent.
  • a solvent any solvent that partiaUy or completely dissolves the hahde agent is suitable in the invention.
  • the solvent is water.
  • the hahde agent is a chloride compound, a bromide compound, or an iodide compound.
  • the chloride compound is any salt or acid that contains a chloride ion.
  • chloride agents include, but are not limited to, HO, Lid, NaCI, KCl, RbO, CsCl, BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , A1C1 3 , or NH 4 C1, quaternary alkyl ammonium chloride, a chloride salt of a group I, II or III metal, a chloride salt of a transition metal, or a combination thereof.
  • the hahde agent is aqueous or gaseous HO.
  • the adsorbent and/or catalyst compound or precursor can be contacted with the hahde agent using techniques known in the art to produce a hahde adsorbent and/or catalyst compound or precursor.
  • a 'hahde adsorbent and/or catalyst compound or precursor" and a "chloride adsorbent and/or catalyst compound or precursor” is defined herein as any adsorbent and/or catalyst compound or precursor that has been contacted or treated with a hahde agent or a chloride agent, respectively.
  • the contacting step typicaUy involves admixing a homogeneous solution or a suspension of the hahde agent with the adsorbent and/or catalyst composition to produce the halide/adsorbent and/or catalyst composition.
  • the adsorbent and/or catalyst composition can be in dry form or it can be a homogeneous or heterogeneous solution when it is contacted with the hahde agent. In one embodiment, the adsorbent and/or catalyst composition is in dry form when it is contacted with the hahde agent.
  • the halide/adsorbent and/or catalyst composition can be prepared in situ by admixing (1) the adsorbent and/or catalyst compound or precursor; (2) the support and/or the binder; and (3) HO (aqueous or gaseous) or NH 4 C1. After the halide/adsorbent and/or catalyst composition is prepared in situ, it can be optionaUy contacted with additional hahde agent.
  • the amount of hahde agent and the duration of the contacting step wiU vary depending upon the selection of the hahde agent and the adsorbent and/or catalyst composition as weU as the end use of the halide/adsorbent and/or catalyst composition.
  • the ratio of (the amount metal ion, in moles, contained in the adsorbent and/or catalyst composition)/(the amount of hahde ions, in moles, used to treat the adsorbent and/or catalyst composition) is from 0.5 to 50, 0.5 to 40, 0.5 to 30, 0.5 to 20 0.5 to 10, 0.5 to 1.
  • the hahde ion may not be present in the halide/adsorbent and/or catalyst composition after contacting the adsorbent and/or catalyst compound or precursor with the hahde agent and/or heating the resultant hahde adsorbent and/or catalyst compound or precursor.
  • the haUde agent is a chloride agent
  • HO can be removed during the heating step.
  • the particle After contacting the particle with the hahde agent, the particle is dried and optionaUy calcined at a temperature from 20 to 1,800 °C.
  • the lower hmit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C
  • the upper hmit of the heating temperature is 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower limit can be used with any upper limit.
  • the temperature is from 100 °C to 1,800 °C, 200 °C to 1,500 °C, 300 °C to 1,200 °C, or 400 °C to 900 °C.
  • the chloride/adsorbent and/or catalyst composition is prepared by an in situ process comprising admixing coUoidal aluminum oxide, aluminum oxide, and CuO with HO.
  • the halide/adsorbent and/or catalyst composition can be contacted with an oxoanion agent to produce an oxo/adsorbent and/or catalyst compound or precursor.
  • An "oxo/adsorbent and/or catalyst compound or precursor” is defined herein as any halide/adsorbent and/or catalyst compound or precursor that has been contacted or treated with an oxoanion agent.
  • the "oxoanion agent” is any compound or group of compounds that can incorporate an oxoanion into the binder, support, and/or adsorbent and/or catalyst compound or precursor.
  • An oxoacid or the salt thereof can be used as the oxoanion agent.
  • oxoanions useful in the present invention are disclosed in "Advanced Inorganic Chemistry" by F. A. Cotton and G.
  • oxoanion also includes isopoly and heteropoly anions.
  • the counterion of the oxoanion can be any cation known in the art.
  • the oxoanion agent is a sulfating agent.
  • a sulfating agent is any compound or group of compounds that can incorporate SO 4 "2 or SO 3 "2 ions into the binder, support, and/or adsorbent and/or catalyst compound or precursor.
  • any salt or acid that contains S0 4 "2 ions can be used.
  • the si ⁇ fating agent can be partially or completely soluble in a solvent, preferably water.
  • the sulfating agent is a group I metal sulfate, a group II metal sulfate, a group III metal sulfate, or a mixture thereof.
  • the sulfating agent is H 2 S0 4 or (NH 4 ) 2 S0 4 .
  • the compositions of the invention can be contacted with (1) S0 2 and O 2 or (2) SO 2 in ak to incorporate SO 4 "2 ions into the composition.
  • the chloride/adsorbent and/or catalyst composition can be contacted with a stream of S0 2 and 0 2 in an inert gas such as nitrogen or hehum, or a reactive gas such as ak, vehicle exhaust, or power plant emissions, to sulfate the halide/adsorbent and/or catalyst composition.
  • the amount of oxoanion agent and the duration of the contacting step wUl vary depending upon the oxoanion agent and the binder, support, and/or adsorbent and/or catalyst compound or precursor selected as weU as the end use of the composition.
  • the ratio of (the amount metal ion, in moles, contained in the adsorbent and/or catalyst composition)/(the amount of sulfate or oxoanion, in moles, used to treat the adsorbent and/or catalyst composition) is from 0.5 to 50, 0.5 to 40, 0.5 to 30, 0.5 to 20 0.5 to 10, 0.5 to 1.
  • the chloride/adsorbent and/or catalyst composition is produced by admixing coUoidal aluminum oxide, aluminum oxide, and CuO with HO, and the resultant chloride/adsorbent and/or catalyst composition is contacted with S0 2 and 0 2 in hehu
  • the chloride/adsorbent and/or catalyst composition is produced by adrnixing coUoidal duminum oxide, aluminum oxide, and CuO with HO, and the chloride/adsorbent and/or catalyst composition is contacted with (NH 4 ) 2 S0 4 .
  • the invention further relates to a method for reducing or eliminating the amount of nitrogen oxide(s) or sulfur oxide(s) from an envkonment, comprising contacting the envkonment with a chloride/adsorbent and/or catalyst composition.
  • the invention further relates to a monolith comprising any of the adsorbent and/or catalyst compositions of the invention.
  • Any monohth known in the art can be used in the invention.
  • the monoliths disclosed in U.S. Patent nos. 5,395,600; 5,445,786; 6,037,307; 4,199,477; and 4,564,608, which are incorporated by reference in thek entkety, are useful in the invention.
  • the monohth is made from a ceramic material, cordierite, or metal.
  • the compositions of the invention can be apphed to the monohth using techniques known in the art. In one embodiment the compositions of this invention is wet milled for sufficient time to achieve an average particle size of less than 10 microns.
  • compositions of this invention are subjected to dry or wet grinding to give particles between 0.1 and 100 microns. In another embodiment the compositions of this invention are subjected to dry or wet grinding to give particles between 2 and 15 microns. In another embodknent a slurry of compositions of this invention are baU milled to a particle size range in witch 90 % of the particles were less than 10 microns. In one embodiment, the dispersed composition can be apphed to the monohth by coating the monohth with the composition or by dipping the monohth in the composition.
  • the adsorbent and/or catalyst composition can be spray-dried onto the monohth
  • the resultant monohth can be dried by heating and further heated at a temperature from 80 to 1,800 °C.
  • the lower limit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C
  • the upper limit of the heating temperature is 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower limit can be used with any upper limit.
  • the temperature is from 100 °C to 1,800 °C, 200 °C to 1,500 °C, 300 °C to 1,200 °C, or 400 °C to 900 °C.
  • the monohth can optionaUy be contacted with additional adsorbent and/or catalyst composition foUowed by drying and heating.
  • the invention further relates to a method for removing or eliminating
  • the invention further relates to a method for removing or eliminating SO 2 and/or S0 3 from an envkonment, comprising
  • the invention further relates to a method for removing or eliminating S0 2 and/or SO 3 from an envkonment, comprising contacting the envkonment in the presence of ak or oxygen with an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention from 100 °C to 600 °C.
  • the invention further relates to a method for removing or ejjminating
  • the invention further relates to a method for removing or eliminating nitrogen oxide(s) from an envkonment, comprising contacting an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention with the envkonment in the presence of a reducing gas from 125 °C to 1,000 °C.
  • Nitrogen oxides and sulfur oxides are generaUy represented in the art by the formulas NOx and SOx, respectively.
  • nitrogen oxides include, but are not limited to, NO, N0 2 , N 2 0 4 , N 2 0 5 , and N 2 0.
  • sulfur oxides include, but are not limited to, S0 2 , S0 3 , and SCO.
  • the envkonment can be any gas or liquid stream that contains a sulfur oxide and/or a nitrogen oxide.
  • the envkonment is a gas or hquid stream, preferably a gas stream.
  • a halide/adsorbent and/or catalyst composition can be used to remove sulfur oxides from a gas strea
  • the halide/adsorbent and/or catalyst composition is placed in a device and heated from 100 °C to 800 °C, 100 °C to 600 °C, and preferably 200 °C to 400 °C to remove water.
  • the lower limit is 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C
  • the upper limit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 700 °C, or 800 °C.
  • the temperature is from 150 °C to 800 °C, 200 °C to 700 °C, or 300 °C to 600 °C.
  • the halide/adsorbent and/or catalyst composition can optionaUy be heated in the presence of a halide/adsorbent and/or catalyst composition reducing agent to reduce the adsorbent and/or catalyst compound or precursor to produce a reduced halide/adsorbent and/or catalyst composition.
  • the temperature at which reduction is performed is from 100 °C to 600 °C.
  • halide/adsorbent and/or catalyst composition reducing agents useful in the present invention include, but are not limited to, hydrogen, carbon monoxide, diesel fuel, refinery off gas, kerosene, olefins, paraffins, and hydrocarbons such as methane, ethane, propane, or isobutane, with methane as the preferred reducing agent.
  • the reduced halide/adsorbent and/or catalyst composition can then be optionaUy oxidized with a gas stream containing ak or oxygen.
  • the halide/adsorbent and/or catalyst composition is then exposed to a gas stream containing the sulfur oxide from 100 °C to 600 °C.
  • the lower limit is 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C
  • the upper hmit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, or 550 °C.
  • the sulfur oxide is S0 2 . Any lower hmit can be used with any upper limit.
  • the temperature is from 100 °C to 550 °C, 200 °C to 450 °C, or 250 °C to 400 °C.
  • the adsorbent and/or catalyst composition can be regenerated.
  • regeneration can be accomphshed by exposing the adsorbent and/or catalyst composition with the any of the reducing gases disclosed above from 100 °C to 800 °C, preferably 200 °C to 600 °C.
  • the lower limit is 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C
  • the upper hmit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 700 °C, or 800 °C.
  • the temperature is from 150 °C to 800 °C, 200 °C to 700 °C, or 300 °C to 600 °C.
  • the reducing agent is in an inert gas such as nitrogen or hehum, and is passed through the adsorbent and/or catalyst composition.
  • the reducing gas is methane. After regeneration, the adsorbent and/or catalyst composition can subsequently be exposed to the envkonment containing the sulfur oxide.
  • an oxoanion adsorbent and/or catalyst composition preferably a sulfated/adsorbent and/or catalyst composition
  • the sulfated/adsorbent and/or catalyst composition is placed in a device and heated from 100 °C to 800 °C, preferably 200 °C to 600 °C, to remove adsorbed contaminants from the composition.
  • the sulfated/adsorbent and/or catalyst composition is then is exposed to a gas stream containing one or more nitrogen oxide compounds from 125 °C to 1,000 °C, preferably from 125 °C to 500 °C.
  • the lower limit is 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C
  • the upper limit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 700 °C, 800 °C, or 900 °C. Any lower hmit can be used with any upper limit.
  • the temperature is from 150 °C to 900 °C, 200 °C to 800 °C, 300 °C to 700 °C, or 400 °C to 600 °C.
  • a reducing agent that can reduce the oxide(s) of nitrogen in the presence of the oxoanion/adsorbent and/or catalyst composition.
  • oxoanion/adsorbent and/or catalyst composition reducing agents useful in the present invention include, but are not limited to, ammonia, hydrogen, carbon monoxide, diesel fuel, refinery off gas, kerosene, olefins, paraffins, urea, cyanuric acid, ammonium sulfate, organic amines, alcohols such as methanol, ethanol, or propanol, hydrocarbons such as methane, ethane, propane, or isobutane, partiaUy combusted hydrocarbons, or exhaust gas.
  • the oxoanion/adsorbent and/or catalyst composition reducing agent is ammonia.
  • the halide/adsorbent and/or catalyst compositions or the oxoanion/adsorbent and/or catalyst compositions of the invention are used in a monohth or a series of monoliths to remove sulfur oxides and nitrogen oxides from an envkonment.
  • the monohth(s) containing the adsorbent and/or catalyst composition can be exposed to any envkonment that contains a sulfur oxide or nitrogen oxide, including, but not limited to, automobfle and power plant emissions.
  • the adsorbent and/or catalyst compositions remove sulfur dioxide compounds from an envkonment at a faster rate and lower temperatures when compared to prior art compositions. Not wishing to be bound by theory, it is believed that the presence of the haUde ions in the halide/adsorbent and/or catalyst composition are responsible for the lower temperatures requked for removing the sulfur oxide compounds from the envkonment. It is also beheved that the treatment of the adsorbent and/or catalyst compositions with a hahde agent leads to a redispersion of the metal or metal oxide on the support surface. In addition, hahde treatment of the adsorbent and/or catalyst compositions can change the Lewis acidity of the adsorbent and/or catalyst compositions.
  • the change in dispersion and Lewis acidity can enhance the reactivity of the adsorbent and/or catalyst compositions. It is advantageous to reduce the reaction temperature, because it aUows less-capital intensive equipment to be used. Lower reaction temperatures also lead to lower energy costs and, thus, lower operating costs.
  • contacting the adsorbent and/or catalyst compositions with an oxoanion agent further modifies the Lewis acidity of the adsorbent and/or catalyst compositions and, thus, further enhances the activity of the adsorbent and/or catalyst compositions.
  • an oxoanion agent in the case of nitrogen oxide removal, the present invention permits a wider range of operating temperatures and reducing gas/nitrogen oxide ratios when compared to prior art compositions.
  • compositions comprising copper oxide and a binder systems as set forth in Table 1 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726.
  • alumina refers to almninurn oxide.
  • Alumina (Compalox C) coUoidal alumina (Condea P2), copper oxide (Fisher), were combined in a mixing vessel, the amount of each component varied as indicated in Table 1.
  • the “dry” components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomphshed, a solution of 7 % acetic acid in distiUed water was added to the mixture.
  • the amount of the acid solution compared to the other components varied between 45 and 55 wt. % of the total dry mixture weight. This solution was added to the dry materials and mixed until the material agglomerated with a pan agglomerator. The agglomerated peUets were transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the sample had been calcined they were analyzed for copper content. The copper content as weight % Cu and CuO is reported in Table 1.
  • compositions comprising copper oxide and a binder systems as set forth in Table 2 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726.
  • Alumina Very GH
  • coUoidal alumina Condea P2
  • copper oxide Fisher
  • the "dry" components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomphshed, a solution of 7 % nitric acid in distilled water was added to the mixture. The amount of the acid solution compared to the other components varied between 70 and 75 wt. % of the total dry mixture weight.
  • This solution (approximately 70-75 mL) was added to the dry materials and mixed until the material had a homogenous "modeling clay" like consistency. The material was then extruded with a hand held press. The extruded media were transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the sample had been calcined they were analyzed for copper content. The copper content as weight % Cu and CuO is reported in Table 2.
  • compositions comprising copper oxide and a binder systems as set forth in Table 3 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726.
  • Alumina Very GH
  • coUoidal alumina Condea P2
  • copper oxide Fisher
  • the extruded media was transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the sample had been calcined they were analyzed for copper content.
  • the copper content as weight % Cu and CuO is reported in Table 3.
  • the copper oxide-alumina composite particle material 7HC1 (Table 3, Example 3), 7.9 % CuO (244.8 mg), was placed in a platinum mesh holder in a Cahn TG 151 thermogravimetric analyzer.
  • the reactor was assembled and then purged with hehum for 20 minutes at 10 psi.
  • the purge gas (hehum), furnace gas (nitrogen), and reaction gas flows were set to 200 cc, 200 cc and 180 cc per minute, respectively.
  • the sample was heated to 500° C under a flow of nitrogen and methane for 15 minutes to remove water and other unwanted adsorbates and reduce the copper oxide.
  • the weight of the sample dropped to 221.1 mg.
  • the sample was then cooled to 150 °C under a nitrogen flow.
  • the sample weight increased to 222.45 mg.
  • the sample was exposed to a stream of 2,000 ppm of sulfur dioxide and 2 % oxygen, balance nitrogen. The sample was treated with the stream for 30 min at 150 °C, during which time the sample weight increased to 233.8 mg.
  • the reactor was then purged with nitrogen for 10 minutes at 150 °C.
  • the adsorbent was then regenerated by heating it to 500 °C for 15 minutes in a methane stream The methane stream was then replaced with a nitrogen stream and the sample was cooled to 150 °C. At this point the sample was ready for the next adsorption/desorption cycle. Four additional adsorption deso tion cycles were performed.
  • the copper oxide-alumina composite particle material, lOHO (Table 3, Example 3) 10.75 % CuO (247.2 mg), was placed in a platinum holder in a Cahn TG 151 thermo gravimetric analyzer and adsorption/desorption cycles were carried out as described in Example 4. The results of these cycles are given in Table 5.
  • Example 6 - SO, adsorption on CuO/ALOc coparticle 13HC1 The copper oxide- alumina composite particle material 13 HO (Table 3,
  • Example 3 13.25 % CuO (248.2 mg) was placed in a platinum holder in a Cahn TG 151 theimo gravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 6.
  • the copper oxide-alumina composite particle 7HOAc (Table 1, Example 1) 7.6 % CuO (254.5 mg) was placed in a platinum holder in a Cahn TG 151 thermogravimetric and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 7.
  • Figure 1 is a plot of the weight % S0 2 uptake vs. time for the thkd adsorption cycle (sohd line with diamonds).
  • the copper oxide-alumina composite particle 13 HOAc (Example 1, Table 1) 13.75 % CuO (251.2 mg) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 8.
  • the copper oxide- dumina composite particle 7HN0 3 (Table 2, Example 2) 7.9 % CuO (250.40 mg) was placed in a platinum holder in a Calm TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 9.
  • Example 10- HCl treatment of co-particles 7HOAc and 13HOAc Samples of copper oxide-alumina composite particles 7HOAc and
  • Example 12 SO, adsorption on CnO/ALO,, HOAc coparticles treated with HCl
  • FIG. 1 is a plot of the weight % S0 2 uptake vs. time for the thkd adso ⁇ tion cycle (dashed line with diamonds).
  • Example 18 Impregnation of alumina with CuO, or Cu(NO «), Granular alumina, 1/16 inch, diameter, was treated with a CuCl 2 or
  • Example 21 - SO adsorption on alumina impregnated with sodium chloride
  • Granular alumina 1/16 inch diameter was treated with 0.53g of NaCI solution prepared from 1.4 g NaCI and 3.6g H 2 0, for approximately 1 min and then calcined at 400 °C for 1 hour to give a sample identified as NaCl-1.
  • a 258.9 mg sample was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adso ⁇ tion/deso ⁇ tion cycles carried out as described in Example 4. The results of these cycles are given in Table 21.
  • compositions comprising copper oxide and a binder system as set forth in Table 23 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726.
  • Alumina Very GH
  • coUoidal alumina Condea P2
  • copper oxide Fisher
  • the "dry" components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomplished, a solution of 7 % acetic acid in distiUed water was added to the mixture. The amount of the acid solution compared to the other components varied between 80 and 82 wt. % of the total dry mixture weight.
  • Example 24 Selective Catalytic reduction of NO with ammonia over CuO/Al,O memo prepared with HOAc (5 % CuO).
  • the flow gas was prepared by blending different gaseous reactants: He or O 2 /He, NH 3 /He, NO/He.
  • Premixed certified gases 1% NO in He, 1% NH 3 in He, and 3% 0 2 in He
  • Three mass flow controUers (Teledyne Hastings Mass Flow controUer HFC 202) were used to control the flow rates of the individual reactant gas mixtures.
  • the sample was heated to 400° C under hehum flow (0.5 SLPM) for approximately 2 hours to remove adsorbed contaminants from the sample.
  • the sample was then cooled to 350 °C whUe under a hehum flow.
  • the sample was exposed to a stream nitric oxide, ammonia and oxygen in hehum Flow rate of the oxygen/hehum gas mixture was set at 0.5 SLPM.
  • Flow rates of the nitric oxide/hehum and ammonia/heUum were adjusted to have the reactant gas composition as foUows: 670 ppm NO, 720 ppm NH 3 .
  • Products were continuously analyzed with a Nicolet Magna IR 560 FT-IR spectrometer.
  • Outlet concentrations of NO, N0 2 , N 2 O, NH 3 , and H 2 0 were measured using a long path-length infrared gas ceU, using cahbrated infrared analysis software QASOFT'96. After equUibiium was reached at 325° C the date was recorded. The ammonia inlet concentration was increased to examine its influence on degree of NO conversion. Table 24 gives gas outlet concentrations at four different ammonia concentrations at 325° C. Table 24
  • Example 26-S elective catalytic reduction of NO with ammonia over CuO/Al,O « coparticle prepared with HOAc (5 % CuO) and post-treated with HCl.
  • Table 30 gives gas outlet concentrations at four different ammonia inlet concentrations and temperatures.
  • Example 31 Selective catalytic reduction of NO with ammonia over CuO/Al,O ⁇ coparticle prepared with HCl (5 % CuO) and post-treated with SO,
  • Example 29 A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid prepared as described in Example 24 was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 29 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 32 gives the minimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH 3 :NO ratio that gives 5 ppm or less NH 3 shp at selected temperatures. Figure 3 plots the 90 % NO conversion and the 5 % ammonia shp NH 3 :NO ratios as a function of temperature.
  • Example 33 Selective catalytic reduction of NO with ammonia over CuO/Al,O, coparticle prepared with HOAc (5 % CuO) post treated with HCl
  • Example 10 A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid and post treated with HCl as described in Example 10 (HOAc-HCl-7) was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 33 gives the mmimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maxknum NH 3 :NO ratio that gives 5 ppm or less NH 3 shp at selected temperatures.
  • Figure 4 plots the 90 % NO conversion and the 5 % ammonia shp NH 3 :NO ratios as a function of temperature.
  • Example 34 Selective catalytic reduction of NO with ammonia over CuO/Al,Oc coparticle prepared with HCl (5 % CuO) post treated with SO,
  • Example 29 A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared with HCl as binding acid and post treated with S0 2 as described in Example 29 was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 34 gives the minimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH 3 :NO ratio that gives 5 ppm or less NH 3 shp at selected temperatures.
  • Figure 5 plots the 90 and 100 % NO conversion and the 5 and 0 % ammonia shp NH 3 :NO ratios as a function of temperature.
  • Example 35 Preparation of co-particles using SiO,. MgQ. TiO,. and ZrO,/Al,O as supports for copper oxide
  • Example Si0 2 - 1 Copper nitrate impregnated sihca 7% CuO (253.96 mg) prepared as described in Example 35 (sample Si0 2 - 1) was placed in a platinum holder in a Calm TG 151 thermogravknetric analyzer and adso ⁇ tion/deso ⁇ tion cycles carried out as described in Example 4. The results of these cycles are given in Table 36.
  • Figure 6 is a plot of the weight % S0 2 uptake vs. time for the thkd adso ⁇ tion cycle (dashed line with filled ckcles).
  • Example 37 - SO adsorption on magnesium oxide impregnated with copper nitrate Copper nitrate impregnated magnesium oxide 7% CuO (257.34 mg) prepared as described in Example 35 (sample MgO - 1) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer as and adso ⁇ tion/deso ⁇ tion cycles carried out as described in Example 4. The results of these cycles are given in Table 37. Table 37
  • Example 38 Copper nitrate impregnated titanium oxide 5.7% CuO (255.46 mg) prepared as described in Example 38 (sample Ti0 2 - 1) was placed in a platinum holder in a Cahn TG 151 thermo gravknetric analyzer and adso ⁇ tion/deso ⁇ tion cycles carried out as described in Example 4. The results of these cycles are given in Table 38.
  • the sulfur dioxide/oxygen mixture used in that experiment had the foUowing concentration: 1% S0 2 , 6% 0 2 , balance - hehum.
  • Table 39 is a plot of the weight % S0 2 uptake vs. time for the thkd adso ⁇ tion cycle (sohd line with filled diamonds). Table 39
  • Example 40 Post-treating of co-particles prepared in Example 35 with NH.C1 solution
  • Co-particles, prepared as described in Example 35 were post-treated by ammonium chloride solutions as described in Table 40 at room temperature for approximately 1 min and then calcined at 400 °C for 1 hour. Table 40
  • Example 42 - SO adsorption on magnesium oxide impregnated with copper nitrate and post-treated by ammonium chloride
  • Example MgO -l-O Copper nitrate impregnated magnesium oxide 7% CuO (261.55 mg) prepared as described in Example 35 and post-treated as described in Example 40 (sample MgO -l-O) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adso ⁇ tion/deso ⁇ tion cycles were carried out as described in Example 4. The results of these cycles are given in Table 42.
  • Example Ti0 2 -l-O Copper nitrate impregnated titanium oxide 5.7% CuO (259.0 mg) prepared as described in Example 35 and post- treated as described in Example 40 (sample Ti0 2 -l-O) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adso ⁇ tion/deso ⁇ tion cycles were carried out as described in Example 4. The results of these cycles are given in Table 43.
  • Example Zr0 2 /Al 2 0 3 -l-O Copper nitrate impregnated zkco um-aluminum oxide 7% CuO (257.47 mg) prepared as described in Example 35 and post-treated as described in Example 40 (sample Zr0 2 /Al 2 0 3 -l-O) was placed in a platinum holder in a Cahn TG 151 thermogravknetric analyzer and adso ⁇ tion/deso ⁇ tion cycles were carried out as described in Example 4.
  • Sulfur dioxide/oxygen mixture used in that experiment had the foUowing concentration: 1% S0 2 , 6% 0 2 , balance - hehum. The results of these cycles are given in Table 44.
  • Figure 6 is a plot of the weight % S0 2 uptake vs. time for the thkd adso ⁇ tion cycle (sohd line with fiUed diamonds). Table 44
  • the co-particles were calcined at 400 ° C for 1 hour.
  • Example 46 Selective catalytic reduction of NO with ammonia over CuO/Al,O, co-particle 5HC1 post-treated with (NH,),SO,
  • Example 45 A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared as described in Example 45 was placed in a fixed-bed quartz tube reactor. The sample was prepared and selective catalytic reduction experiment was carried out as described in Example 24.
  • Table 46 gives the minimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH 3 :NO ratio that gives 5 ppm or less NH 3 shp at selected temperatures.
  • Figure 7 gives a plot of the 90 % NO conversion and 5 % ammonia shp NH 3 :NO ratios as a function of temperature.
  • Example 47 Selective catalytic reduction of NO with ammonia over CuO/ALO co-particle post treated with HCl and sulfated on a monolith
  • a ceramic monohth (1 inch long, 3 A inches OD, 400 ceUs per square inch) was coated with a finely ground sample of copper oxide-alumina composite particles, 5 % CuO prepared with HOAc as binding acid as described in Example 23 and post-treated with HCl as described in Example 10 (sample # HOAc-HCl-7) and sulfated as described in Example 29 with S0 2 and 0 2 in He.
  • the catalyst loading was 1.84 g after several apphcation/drying cycles.
  • the monohth was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24.
  • Table 47 gives the minimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH 3 : NO ratio that gives 5 ppm or less NH 3 shp at selected temperatures.
  • Figure 8 gives a plot of the 90 % NO conversion and 5 % ammonia shp NH 3 :NO ratios as a function of temperature.
  • Example 48 Selective catalytic reduction of NO with ammonia over alumina impregnated with Cu(NO,,)neig calcined, and post-treated with sulfur dioxide
  • Example 49 A sample of copper nitrate impregnated and calcined alumina, sample CuN03-2-O (5.00 g, approximately 10 cc) prepared as described in Example 49, and post- treated with S0 2 as described in Example 29 was placed in a fixed- bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and 5 % ammonia shp ratio as a function of temperature were mapped. Table 50 gives the minimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH 3 :NO ratio that gives 5 ppm or less NH 3 shp at selected temperatures.
  • Figure 10 plots the 90 % NO conversion ration and the 5 % ammonia shp ratio as a function temperature.
  • Powdered vanadium oxide supported on titanium oxide, anatase type was prepared as described in US Patent No. 5,696,046 to Ikeyama et al.
  • the vanadium oxide/titanium oxide catalysts was apphed as a wash-coat on to a ceramic monohth (1 inch long, 3 A inches OD, 400 ceUs per square inch).
  • a catalyst loading of 2.0 g was achieved after several appUcation/drying cycles.
  • the monohth was placed in a fixed-bed quartz tube reactor and the sample was prepared and selective catalytic reduction was carried out as described in Example 24.
  • Table 51 gives the minimum NH 3 :NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH 3 :NO ratio that gives 5 ppm or less NH 3 shp at a selected temperatures in the range 200-450° C.
  • Figure 11 gives a plot of the 90 % NO conversion and 5 % ammonia shp as a function temperature for this vanadium oxide/titanium oxide catalyst (sohd lines). For comparison, this figure include a plot of the 90 % NO conversion and 5 % ammonia shp as a function temperature for a monohth coated with CuO/Al 2 0 3 and post-treated with HCl and sulfur dioxide (Example 47 - dashed lines).

Abstract

This invention relates generally to methods for producing adsorbent and/or catalyst compositions that have been promoted with halide ions. The invention further relates to the adsorbent and/or catalyst compositions produced by the methods of the invention. Finally, the invention relates methods for reducing or eliminating a nitrogen oxide compound or a sulfur oxide compound from an environment using the adsorbent and/or catalyst compositions of the invention.

Description

ADSORBENT AND/OR CATALYST COMPOUNDS PROMOTED WITH HALIDE IONS AND METHODS OF MAKING AND USING THEREOF
SUMMARY OF THE INVENTION
This invention relates generally to methods for producing adsorbent and/or catalyst compositions that have been promoted with halide ions. The invention further relates to the adsorbent and/or catalyst compositions produced by the methods of the invention. Finally, the invention relates methods for reducing or eliminating a nitrogen oxide compound or a sulfur oxide compound from an environment using the adsorbent and/or catalyst compositions of the invention. Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 shows sulfur dioxide uptake by 7% CuO/Al203 prepared by different acids.
Figure 2 shows sulfur dioxide uptake by 7% CuO/Al203.
Figure 3 shows NH3/NO inlet ratio vs. temperature using 5% CuO/Al203 catalyst.
Figure 4 shows NH3/NO inlet ratio vs. temperature using 5% CuO/Al203 catalyst post- treated with HO.
Figure 5 shows NH3/NO inlet ratio vs. temperature using 5% CuO/Al203 catalyst po st- treated with HO and S 02. Figure 6 shows sulfur dioxide uptake by CuO on Si02 and Zr02/Al203.
Figure 7 shows NH3/NO range for SCR using 5% CuO/Al203 catalyst post-treated with HC1 and (NH4)2S04.
Figure 8 shows J H3/NO range for SCR using 5% CuO/Al203 catalyst post-treated with HO and S02.
Figure 9 shows NH3/NO range for SCR using A1203 impregnated with
Cu(N03)2, calcined (5% CuO), and post-treated with S02.
Figure 10 shows NH3/NO range for SCR using A1203 impregnated with Cu(N03)2, calcined (5% CuO), and post-treated with NH4C1 and S02.
Figure 11 shows NH3/NO range for SCR using Ml-monolith coated with 5% CuO/Al203, and post-treated with chloride and S02.
DESCRIPTION OF THE INVENTION
The present invention may be understood by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.
Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. In this specification, reference will be made to a number of terms which shall be defined to have the following meanings:
The singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise.
The term "ppm" refers to parts per million.
The term "cc" refers to cubic centimeter.
The term "mL" refers to illiliter.
The term "psi" refers to pounds per square inch.
"Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
The term "composition" as used herein is a system that is prepared from and is composed of two or more different components.
In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one embodiment, relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) admixing a support with (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture; (b) heating the mixture produced in step (a) at from 20 to 1,800 °C to produce a heated rnixture;
(c) contacting the heated mixture produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst compound and/or precursor/support composition; and
(d) • heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group I compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) admixing a support with (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture;
(b) drying the mixture to produce a dried mixture;
(c) contacting the dried mixture produced in step (b) with a halide agent to produce a halide adsorbent and/or catalyst compound and/or precursor/support composition; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group II compositions."
The invention farther relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) adrj ixing components comprising:
(i) a support;
(ii) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(ϋi) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a mixture; and
(iv) an acid;
(b) removing a sufficient amount of water to cross-link the binder with itself, the support, and/or the adsorbent and/or catalyst compound and/or adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group III compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) admixing components comprising:
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ϋ) a support, and
(iii) an acid,
(b) removing a sufficient amount of water from the mixture to cross-link the binder with itself and/or the support to produce a binder/support system;
(c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a mixture to produce a binder/adsorbent and/or catalyst composition;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C;
(e) contacting the binder/support system produced in step (d) with a halide agent to produce a halide/binder/support system; and
(f) heating the composition produced in step (e) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group IN compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor catalyst compound and/or an adsorbent and/or catalyst precursor, and
(iii) an acid,
(b) removing a sufficient amount of water from the mixture to cross-link components i and/or ii to produce an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group N compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor that does not cross-link with the binder, and
(iii) an acid,
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group NI compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) contacting a composition comprising copper oxide and aluminum oxide with a halide agent to produce a halide/copper oxide/aluxninum. oxide composition, and
(b) heating the composition produced in step (a) at from 20 to 1,800 °C. The compositions produced by this process are referred to herein as "Group Nil compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture;
(b) heating the mixture produced in step (a) at from 20 to 1,800 °C to produce a heated mixture;
(c) contacting the heated mixture produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst/support composition;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group NIII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) admixing a support and (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture;
(b) drying the mixture to produce a dried mixture; (c) contacting the dried mixture produced in step (b) with a halide agent to produce a halide/ adsorbent and/or catalyst compound or precursor/support composition;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group IX compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a support;
(ii) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(iii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor;
(iv) an acid;
(b) removing a sufficient amount of water to cross-link the binder with itself, the support, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group X compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) a support, and
(iii) an acid,
(b) removing a sufficient amount of water from the mixture to cross-link the binder with itself and/or the support to produce a binder/support system; (c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C;
(e) contacting the binder/support system produced in step (d) with a halide agent to produce a halide/binder/support system;
(f) heating the composition produced in step (e) at from 20 to 1,800 °C; and
(g) contacting the heated composition produced in step (f) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XI compositions."
The invention fuither relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor, and
(iii) an acid, (b) removing a sufficient amount of water from the mixture to cross-link components i and/or ii to produce an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor that does not cross-link with the binder, and
(iii) an acid, (b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XIII compositions."
The invention further relates to a process for producing an adsorbent and/or catalyst compound, comprising:
(a) contacting a composition comprising copper oxide and alrrrnina particle with a halide agent to produce a halide/copper oxide/aluminum oxide composition;
(b) heating the composition produced in step (a) from 20 to 1,800 °C; and
(c) contacting the heated composition produced in step (b) with an oxoanion agent. The compositions produced by this process are referred to herein as "Group XIV compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) adrmxing components comprising:
(i) a support;
(ii) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(iii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(iv) HC1 or NH4C1;
(b) removing a sufficient amount of water to cross-link the binder with itself, the support, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition; and
(c) heating the composition produced in step (b) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group XV compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) admixing components comprising:
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(iii) a base; and
(b) removing a sufficient amount of water to cross-link the binder with itself, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition.
The compositions produced by this process are referred to herein as "Group XVI compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(iii) a base; (b) removing a sufficient amount of water to cross-link the binder with itself, the support, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group XVII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) a support, and
(iii) a base,
(b) removing a sufficient amount of water from the mixture to cross-link the binder with itself and/or the support to produce a binder/support system;
(c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(d) heating the composition produced in step (c) at from 20 to 1,800° C;
(e) contacting the heated composition produced in step (d) with a halide agent to produce a halide/binder/support system; and
(f) heating the composition produced in step (e) at from 20 to 1,800° C.
The compositions produced by this process are referred to herein as "Group XVIII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor, and
(hi) a base,
(b) removing a sufficient amount of water from the mixture to cross-link components i and/or ii to produce an adsorbent and/or catalyst and binder system; (c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group XIX compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor that does not cross-link with the binder, and
(hi) a base,
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system; and
(d) heating the composition produced in step (c) at from 20 to 1,800 °C.
The compositions produced by this process are referred to herein as "Group XX compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a support;
(ii) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(iii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(iv) a base;
(b) removing a sufficient amount of water to cross-link the binder with itself, the support, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(c) contacting the binder/adsorbent and/or catalyst composition produced in step (b) with a halide agent to produce a halide/binder/adsorbent and/or catalyst composition; (d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XXI compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) a support, and
(iii) a base,
(b) removing a sufficient amount of water from the mixture to cross-link the binder with itself and/or the support to produce a binder/support system;
(c) admixing the binder/support system produced in step (b) with (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; (e) contacting the heated composition produced in step (d) with a halide agent to produce a halide/binder/support system;
(f) heating the composition produced in step (e) at from 20 to 1,800 °C; and
(g) contacting the heated composition produced in step (f) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XXII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor, and
(hi) a base,
(b) removing a sufficient amount of water from the mixture to cross-link components i and/or ii to produce an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XXIII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor that does not cross-link with the binder, and
(iii) a base,
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XXIV compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a calcined, metal oxide particle that was produced by calcining the particle temperature of from 300 °C to 700° C, then treating the calcined particle with an acid for a sufficient time to increase the adsorbent properties of the particle, and
(iii) water,
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder syste
The compositions produced by this process are referred to herein as "Group XXV compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a calcined, metal oxide particle that was produced by calcining the particle temperature of from 300 °C to 700° C, then treating the calcined particle with an acid for a sufficient time to increase the adsorbent properties of the particle, and
(iii) water,
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system;
(d) heating the composition produced in step (c) at from 20 to 1,800° C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent.
The compositions produced by this process are referred to herein as "Group XXVI compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a particle that has been pretreated with a base, and
(iii) water, and
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system The compositions produced by this process are referred to herein as "Group XXVII compositions."
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a particle that has been pretreated with a base, and
(hi) water,
(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catalyst and binder system;
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a halide agent to produce a halide/adsorbent and/or catalyst and binder system;
(d) heating the composition produced in step (c) at from 20 to 1,800 °C; and
(e) contacting the heated composition produced in step (d) with an oxoanion agent. The compositions produced by this process are referred to herein as "Group XXVIII compositions."
The invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) admixing a support with (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture;
(b) contacting the mixture produced in step (a) with a hahde agent to produce a halide/adsorbent and/or catalyst/support composition; and
(c) contacting the composition produced in step (b) with an oxoanion agent,
wherein the product produced in step (a), (b), and/or (c) is heated at from 20°C to 1,800 °C.
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) admixing a support with a copper compound to produce a mixture;
(b) contacting the mixture produced in step (a) with a hahde agent to produce a halide/adsorbent and/or catalyst/support composition; and (c) contacting the composition produced in step (b) with an oxoanion agent,
wherein the product produced in step (a), (b), and/or (c) is heated at from 20 °C to 1,800 °C.
The invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor and/or an adsorbent and/or catalyst precursor,
(iii) a support; and
(iv) an acid,
(b) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (ii) and/or (iii); and
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system; wherein the product produced in step (a), (b), and/or (c) is heated at from 20 °C to 1,800 °C.
The invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising colloidal aluminum oxide or colloidal sihcon dioxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor and/or an adsorbent and/or catalyst precursor comprising a copper compound;
(hi) a support comprising aluminum oxide; and
(iv) an acid,
(b) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (ii) and/or (iii);and
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system;
wherein the product produced in step (b) and/or (c) is heated at from 20 °C to 1,800 °C. The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor and/or an adsorbent and/or catalyst precursor,
(hi) a support; and
(iv) abase,
(b) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (ii) and/or (hi); and
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a halide/adsorbent and/or catalyst and binder system;
wherein the product produced in step (b) and/or (c) is heated at from 20 °C to 1,800 °C.
The invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising: (i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(hi) a base; and
(a) removing a sufficient amount of water to cross-link the binder with itself and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition.
The invention further relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a calcined, metal oxide particle that was produced by calcining the particle temperature of from 300 °C to 700° C, then treating the calcined particle with an acid for a sufficient time to increase the adsorbent properties of the particle, and (hi) water, and
(b) removing a sufficient amount of water to cross-link the binder with itself and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition.
The invention also relates to a process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a support;
(ii) a binder comprising a colloidal metal oxide or colloidal metalloid oxide;
(hi) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(iv) HC1 or NH4C1;
(b) removing a sufficient amount of water to cross- nk the binder with itself, the support, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition; and
(c) heating the product produced in step (b) from 20 °C to 1,800 °C. The invention further relates to the compositions produced by the processes of the present invention.
The invention further relates to an adsorbent and/or catalyst and binder system comprising (1) a binder that has been cross.-linked with itself and/or at least one type of an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor and (2) at least one hahde ion.
The invention further relates to an adsorbent and/or catalyst and binder system comprising (1) a binder that has been cross-linked with itself and/or at least one type of an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor; (2) at least one hahde ion; and (3) at least one oxoanion.
The invention further relates to an adsorbent and/or catalyst system comprising a support, an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor, and a hahde ion.
The invention further relates to an adsorbent and/or catalyst system comprising a support, an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor, a hahde ion, and an oxoanion.
The invention further relates to a monohth comprising one or more compositions of the invention.
Any metal oxide known in the art can be used as the support in the present invention. Examples of such metal oxides include, but are not Ihr ted to, oxide complexes, such as transition metal oxides, lanthanide oxides, as well as oxides of Group IIA (Mg, Ca, Sr, Ba), Group IIIA (B, Al, Ga, In, TI), Group IVA (Si, Ge, Sn, Pb), and Group VA (As, Sb, Bi). In another embodiment, the metal oxide comprises an oxide of aluminum, cerium, cobalt, chromium, hafnium, nickel, titanium, copper, vanadium, sihcon, manganese, iron, zinc, zkconium, magnesium, thorium, ura um, or a combination thereof. Typically, any oxidation state of the metal oxide may be useful for the present invention. The metal oxide can be a mixture of at least two metal oxide particles having the same metal with varying stoichiometry and oxidation states. In one embodiment, the metal oxide comprises A1203, Ga^, Ti02, CuO, CujO, V205, Si02, Mn02, Mn203, Mn304, ZnO, MgO, Th02, Zr02, Fe203, Fe304, or zeohte. In a preferred embodiment, the support is aluminum oxide, sihcon dioxide, zkconium dioxide, titanium dioxide, or an oxide of magnesium, more preferably duminum oxide. In one embodiment, when the support is sihcon dioxide, the sihcon dioxide is diatomite or diatomaceous earth. In another embodiment, the support is particle disclosed in U.S. Patent No. 5,948,726, which is incorporated by reference in its entkety.
In another embodiment, the support comprises a ceramic, for example, a ceramic monolith.
In a further embodiment, the metal oxide further comprises a second type of an oxide of aluminum, cerium, cobalt, cjhromium, hafnium, nickel, titanium, copper, vanadium, sihcon, manganese, on, zinc, zkconium, magnesium, thorium, uranium, or a combination thereof. In another embodiment, the metal oxide further comprises a second type of particles of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, sihcon dioxide, manganese dioxide, kon oxide, zinc oxide, or zeohte. Typical zeohtes used in the present invention include "Y" type, "beta " type, mordenite, and ZsM5. In one embodiment, the support comprises aluminum oxide, sihcon dioxide, or an oxide of magnesium, preferably aluminum oxide. In another embodiment, the metal oxide itself comprises an adsorbent and/or catalyst compound. When the metal oxide acts as an adsorbent, the metal oxide can adsorb a large amount of contaminant from the envkonment. When the metal oxide is an adsorbent, the sulfur oxide or nitrogen oxide is chemically bonded to and very tightly retained in the metal oxide. In one embodiment, when the metal oxide comprises an adsorbent and/or catalyst compound, the metal oxide can be regenerated using techniques known in the art. In another embodiment, when the support comprises a metal oxide, the metal oxide absorbs the contaminant from the envkonment.
When the metal oxide behaves as a catalyst, the metal oxide can catalyticahy decompose or remediate oxides of nitrogen.
During the preparation of any of the compositions of the present invention, one or more heating steps is performed. The timing and number heating steps will vary depending upon the particular composition. In general, any of the heating steps are from 20 °C to 1,800 °C.
In one embodiment, the support is heated from 20 to 1,800 °C prior to admixing the support with the adsorbent and/or catalyst compound or adsorbent and/or catalyst precursor. In various embodiments, the lower limit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C, and the upper limit of the heating temperature is 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower hmit can be used with any upper limit. In one embodiment, the temperature is from 100 °C to 1,000 °C, 200 °C to 900 °C, 300 °C to 800 °C, or 400 °C to 700 °C. In one embodiment, when the support is a metal oxide, the metal oxide comprises calcined or sintered alirminum oxide that was produced by calcining or sintering the precursor to the aluminum oxide at a particle temperature of from 200 °C to 1,800 °C. The precursor to the calcined or sintered aluminum oxide can include but is not limited to boehmite, bauxite, pseudo-boehmite, scale, Al(OH)3, and alumina hydrates.
In another embodiment, the metal oxide is acid treated prior to admixing with the adsorbent and/or catalyst compound or precursor. AH of the metal oxides disclosed above can be acid treated. The acid activation or enhancement treatment process disclosed in U.S. Patent No. 5,985,790, and international pubhcationno. WO 97/47380 entitled "Acid Contacted Enhanced Adsorbent Particle and/or Catalyst and Binder System," which are herein incorporated by this reference in thek entkety, can be used in the present invention to prepare the acid treated metal oxide.
The acid that can be used in this invention can be any acid or mixture of acids that can promote the formation of hydroxyl groups onto the surface of the pores of the metal oxide. Examples of such acids include, but are not limited to, nitric acid, sulfuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid, and mixtures thereof.
In one embodiment, the acid is diluted with water to prevent dissolution of the metal oxide. In one embodiment, only a dilute solution of the acid is requked to achieve maximum or saturated loading of the hydroxyl groups on the metal oxide. For example, a 0.5 wt. % (0.09 N; pH of about 2.9) and even a 0.1 wt. % (0.02 N; pH of about 3.25) acetic acid solution has been found effective. However, a wide range of concentrations of acid can be used in this invention from very dilute to very concentrated depending on the hazards involved and the economics of production.
In one embodiment, the acid contacting is more than a surface wash but less than an etching. In one embodiment, the acid is of an upper strength equivalent to a 0.5 N (normahty) aqueous solution of acetic acid. In another embodiment, the acid concentration is from 0.0001 N to 2 N. In other embodiments, the upper strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N or 0.001 N aqueous acetic acid solution. Any lower limit can be used with any upper hmit. The lower strength of the acid should be that which provides more than a surface washing but imparts enhanced adsorbent effects to the metal oxide. In particular embodiments, the lower strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N, 0.001 N, 0.0005 N, or 0.0001 N aqueous acetic acid solution. In one embodiment, the acid concentration range is from 0.0001 N to 0.25 N, 0.0005 N to 0.09, 0.005 N to 0.075 N, or 0.01 N to 0.05 N.
Additionally, the acid preferably has some water present to provide OH" and/or H+ ions, which bond with the metal oxide. When the acid is diluted with water, the water is preferably distilled water to minimize the amount of impurities contacting the metal oxide during acid treatment.
Typically, the acid enhanced metal oxide is made by the following process. The metal oxide can be contacted with the acid by various means, including the metal oxide being dipped in, extensively washing with, or submerged in the acid. The length of time the metal oxide is be contacted with the acid varies according to the ability of the particular metal oxide to generate hydroxyl groups on the surface and pores of the particle. The time can be as low as 30 seconds, a few (three) minutes, at least 15 minutes, at least one hour, at least 6 hours, at least 12 hours, or at least one day, to achieve adequate adsorption results and/or to preferably assure saturation. The tkne must be sufficient to at least increase the number of hydroxyl groups on the metal oxide. In one embodiment, the metal oxide is submerged in the acid, and saturation is typically complete when there is complete coverage of the metal oxide pores with the acid solution. The contacting should be substantial enough to provide penetration of the acid throughout the pores of the metal oxide thereby increasing the number of hydroxyl groups on the pore surface of the particle. Mere washing the outside surface of the metal oxide to remove impurities is not sufficient to provide adequate penetration of the acid into and throughout the pores of the metal oxide.
The acid contacted metal oxide is then optionaUy rinsed, preferably with water. Rinsing of the acid contacted metal oxide does not reduce the enhanced adsorptive capability of the particle. When rinsed, the metal oxide is preferably rinsed with distilled water to minimize impurity contact.
Optionally, the acid treated metal oxide is dried by a low to moderate heat treatment to remove excess hquid, such as acid or water, from the rinsing. Typically, the drying is from about 50 °C to about 200 °C. Drying of the metal oxide also reduces the transfer cost of the particle. In one embodiment, the acid treated metal oxide is not calcined or recalcined after acid treatment.
hi one embodiment, prior to admixing the support with the adsorbent and/or catalyst compound and/or the adsorbent and/or catalyst precursor, the support is a metal oxide that is (1) calcined at a particle temperature of from 200 to 700 CC, and (2) contacted with a dilute acid, wherein the acid contacting is more than a surface wash but less than an etching, wherein the resultant acid treated metal oxide is not subsequently calcined. Preferably, the acid treated metal oxide is aluminum oxide.
The invention contemplates the use of any prior art adsorbent and/or catalyst compound or composite composition of two or more types of adsorbent and/or catalyst compounds as the adsorbent and/or catalyst compound. An "adsorbent and/or catalyst compound" is any compound that can adsorb and/or catalytically degrade sulfur oxide(s) or nitrogen oxide(s). Depending upon the selection of the compound or precursor, the compound or precursor can behave as an adsorbent, a catalyst, or a combination thereof. The adsorbent and/or catalyst compound may also catalytically convert the sulfur oxide(s) and nitrogen oxide(s) to another form or compound.
In a preferred embodiment, the adsorbent and/or catalyst compound comprises an oxide compound. The compound in one embodiment comprises a metal or metalloid oxide particle. Examples of such compounds include, but are not limited to, oxide complexes, such as transition metal oxides, lanthanide oxides, thorium oxide, as well as oxides of Group IIA (Mg, Ca, Sr, Ba), Group IIIA (B, Al, Ga, In, TI), Group INA (Si, Ge, Sn, Pb), and Group NA (As, Sb, Bi). In another embodiment, the compound comprises an oxide of aluminum, cerium, hafnium, titanium, copper, chromium, vanadium, sihcon, manganese, kon, zinc, zkconium, tungsten, rhenium, arsenic, magnesium, thorium, uranium, silver, cadimium, tin, lead, antimony, ruthenium, osmium, cobalt or nickel or zeohte. Typically, any oxidation state of the oxide complexes may be useful for the present invention. The oxide can be a mixture of at least two metal oxide compounds having the same metal with varying stoichiometry and oxidation states. In one embodiment, the adsorbent and/or catalyst compound or precursor comprises A1203,
Figure imgf000041_0001
N2O5, Si02, Mn02, Mn203, Mn304, ZnO, W02, WO3, Re2O7, As203, As205, MgO, Th02, Ag2O, AgO, CdO, Sn02, PbO, FeO, Fe203, Fe3O4, Ru203, RuO, Os04, Sb2O3, CoO, Co203, ΝiO or zeohte.
In a further embodiment, the adsorbent and/or catalyst compound further comprises a second type of adsorbent and/or catalyst compound of an oxide of aluminum, cerium, hafnium, titanium, copper, chromium, vanadium, sihcon, manganese, kon, zinc, zkconium, tungsten, rhenium, arsenic, magnesium, thorium, uranium, silver, cadimium, tin, lead, antimony, ruthenium, osmium, cobalt or nickel or zeohte, activated carbon, including coal and coconut carbon, peat, zinc or tin. In another embodiment, the adsorbent and/or catalyst compound further comprises a second type of adsorbent and/or catalyst compound of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, sihcon dioxide, manganese dioxide, kon oxide, zinc oxide, zeohte, activated carbon, peat, zinc or tin particle. Typical zeohtes used in the present invention include "Y" type, "beta " type, mordenite, and ZsM5. In one embodiment, the adsorbent and/or catalyst compound or precursor comprises aluminum oxide that was produced by calcining the precursor to the calcined aluminum oxide at a particle temperature of from 300 ° C to 700 ° C. The precursor to calcined alummum oxide can include but is not limited to boehmite, bauxite, pseudo-boehmite, scale, Al(OH)3 and alumina hydrates. In the case of other metal oxide complexes, these complexes can also be calcined or uncalcined.
In one embodiment, the adsorbent and/or catalyst compound is a vanadium compound, a titanium compound, a zinc compound, or a copper compound. In one embodiment, the adsorbent and/or catalyst compound is an alkoxide, nitrate, carbonate, sulfate, acetate, aceto acetate, gluconate, benzoate, or carboxylate of vanadium, titanium, zinc, or copper. In a preferred embodiment, the adsorbent and/or catalyst compound is a copper compound. Examples of copper compounds include, but are not limited to Cu(N03)2, Cu(N03)2 • XH20, CuC03, CuS04, CuO, C , Cu(OAc)2, copper aceto acetonate, copper oxalate, copper gluconate, a copper benzoate, a copper carboxylate, or a combination thereof. In a preferred embodknent, the adsorbent and/or catalyst compound is CuO.
In one embodiment, when the support is a metal oxide, the adsorbent and/or catalyst compound and the metal oxide are not the same compound. In another embodiment, when the support is a metal oxide, the metal oxide and the adsorbent and/or catalyst compound are the same compound. For example, the metal oxide support can be calcined or sintered aluminum oxide, and the adsorbent and/or catalyst particle can be acid treated aluminum, oxide that has not been calcined or sintered.
An "adsorbent and/or catalyst precursor" is a compound that can be converted to an adsorbent and/or catalyst compound. The steps requked to convert the precursor to the compound will vary depending upon the precursor selected. For example, an adsorbent and/or catalyst precursor, such as CuCl2, can be subjected to a hydrolysis step followed by exposure to heat to remove water to produce CuO. In one embodiment, heating the adsorbent and/or catalyst precursor can convert the precursor to the corresponding adsorbent and/or catalyst compound. Examples of adsorbent and/or catalyst precursors include, but are not hmited to, a vanadium hahde compound, a titanium halide compound, a zinc hahde compound, or a copper hahde compound. Hahde is defined as fluoride, chloride, bromide, or iodide. In one embodiment, the adsorbent and/or catalyst precursor is a copper compound that can be converted to a copper oxide. In one embodiment, the adsorbent and/or catalyst precursor is a copper hahde compound, preferably CuCl2, CuBr2, Cul2, or Cul. In another embodiment, the adsorbent and/or catalyst precursor is Cu(N03)2, copper sulfate, copper oxalate, copper acetate, copper oxide, a copper alkoxide, or a copper carboxylate. In another embodknent, the adsorbent and/or catalyst precursor can be used in combination with an adsorbent and/or catalyst compound.
The support and the adsorbent and/or catalyst compound and/or the adsorbent and/or catalyst precursor can be admixed using a variety of techniques known in the art. In one embodiment, when the support comprises a metal oxide, and the adsorbent and/or catalyst compound comprises a metal oxide or an elemental metal, then an acidic solvent is used to admix the components. In another embodiment, the support and the adsorbent and/or catalyst compound or precursor are admixed in the presence of a solvent. Many solvents can be used to admix the support and the adsorbent and/or catalyst compound or precursor. In one embodknent, the solvent used to admix the support and the adsorbent and/or catalyst compound or precursor comprises water, acidic water, basic water, an alcohol, a ketone, an ester, an ether, an aldehyde, a polyol, or a combination thereof. Alternatively, the support and the adsorbent and/or catalyst compound or precursor can be admixed in dry form, and the dry mixture is optionally contacted with a solvent. After the admixing step, the mixture is composed of an intimate mixture of the support and the adsorbent and/or catalyst compound or precursor.
In one embodiment, once the support and the adsorbent and/or catalyst compound and/or precursor have been admixed, the resultant composition is heated from 20 to 1,800 °C. The lower jjmit of the heating temperature is 20, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C, and the upper limit of the heating temperature is 300, 400, 500, 600, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower limit can be used with any upper limit. In one embodiment, the temperature is from 100 °C to 1,000 °C, 200 °C to 900 °C, 300 °C to 800 °C, or 400 °C to 700 °C. Generally, after the heating step is performed, the heated composition is allowed to cool to room temperature prior to conducting any additional steps (e.g., reduction, oxidation, or contacting with the hahde agent and/or oxoanion agent). In another embodiment, a second heating step can be performed after the composition is contacted with the hahde agent and/or the oxoanion agent.
In one embodiment, once the support and the adsorbent and/or catalyst compound and/or precursor have been admixed, the resultant composition is dried from 20 to 100 °C, 20 to 50 °C, 20 to 30 °C, and preferably at 25 °C in order to remove any residual solvent that may be present in the admixture. Generally, the drying step is performed by allowing the composition to stand at ambient temperature for a sufficient time so that the majority of the solvent has evaporated. The dried mixture then can either be subjected to additional steps (e.g., reduction, oxidation, or contacting with the hahde agent and/or oxoanion agent), or the dried mixture can be heated at from 80 to 1,800 °C then subsequently subjected to additional steps.
The amount of the adsorbent and/or catalyst compound or precursor that can be admixed with the support can vary depending upon the adsorbent and/or catalyst compound or precursor and the support that are selected and the apphcation of the resulting composition. In one embodiment, the support is from 0.1 to 99.9 % by weight and the adsorbent and/or catalyst compound and/or precursor is from 0.1 to 99.9 % by weight, wherein the sum of the adsorbent and/or catalyst compound and/or precursor and the support is 100 %. In another embodiment, the support is from 5 to 95 %, 10 to 90 %, 20 to 80 %, or 30 to 70 % by weight, and adsorbent and/or catalyst compound and/or precursor is from 5 to 95 %, 10 to 90 %, 20 to 80 %, or 30 to 70 % by weight, wherein the sum of the adsorbent and/or catalyst compound and/or precursor and the support is 100 %. Although the sum of the support and the adsorbent and/or catalyst compound and/or precursor is 100 %, the composition can include other components, such as additives and fillers.
In one embodiment, any of the adsorbent and/or catalyst compositions of the present invention can optionaUy be contacted with a reducing agent prior to contacting the composition with the hahde agent and/or oxoanion agent to reduce at least some of the adsorbent and/or catalyst compound or precursor present in the composition. The phrase "at least some" when referring to the amount of the adsorbent and/or catalyst compound or precursor that is reduced or oxidized is defined as greater than 0 % to a maximum of 100 % reduction or oxidation of the adsorbent and/or catalyst compound or precursor. In various embodiments, the lower lknit of reduction or oxidation is 1, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, or 80% and the upper hmit 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 95, or 100%. Any lower limit can be used with any upper limit. In one embodiment, the % reduction or oxidation is from 1 to 100 %, 5 to 95 %, 10 to 90 %, 20 to 80 %, 30 to 70 %, or 40 to 60 %. AdditionaUy, the support and/or binder may also be reduced depending upon the type of support, binder, and reducing agent that are used.
The majority of reducing agents known in the art can be used in the present invention. The selection of the reducing agent varies depending upon the redox potential of the adsorbent and/or catalyst compound or precursor, support, and/or the binder that are used. For example, when the support is a metal oxide, it is possible to selectively reduce the adsorbent and/or catalyst compound or precursor without reducing the metal oxide by knowing the reduction potential of the metal oxide and the adsorbent and/or catalyst compound or precursor and the redox potential of the reducing agent. In one embodiment, the reducing agent comprises a reducing sugar or an antioxidant. Any reducing sugar known in the art can be used in the present invention as a reducing agent. Examples of reducing agents include, but are not Iknited to, glucose, fructose, formaldehyde, hydrazine, sodium dithionate, sodium bisulfite, ascorbic acid (vitamin C), vitamin E, carbon monoxide, hydrogen, methanol, or ethanol.
In another embodknent, any of the compositions of the present invention that contain at least some reduced adsorbent and/or catalyst compound or precursor can optionaUy be oxidized so that at least some of the reduced adsorbent and/or catalyst compound or precursor is oxidized. When the reduced adsorbent and/or catalyst compound or precursor is oxidized, it can be oxidized to a variety of oxidation states. The selection of the particular oxidizing agent depends upon the reduced adsorbent and/or catalyst compound or precursor, the support, and/or the binder. By using redox potentials as described above, it is possible to selectively oxidize at least some of the adsorbent and/or catalyst compound or precursor and not the support or the binder. Additionally, some of the support can be oxidized as weU. An advantage of the oxidation step is that when the reduced adsorbent and/or catalyst compound or precursor is an elemental metal that is incorporated throughout the support and/or the binder, and the elemental metal is oxidized to the corresponding metal oxide, the resultant oxidized composition has coUoidal metal oxide incorporated or impregnated throughout the support. Another advantage of the oxidation step is that it is possible to produce a composition that has elemental metal and the corresponding metal oxide dispersed throughout the support and/or the binder, which is difficult to reproduce using prior art techniques.
The majority of oxidizing agents known in the art can be used in the present invention. Examples of oxidizing agents include, but are not limited to, oxygen, oxone®, ozone, peroxymono sulfate, hydrogen peroxide, C102, 003 ", ak, or a combination thereof.
In another embodiment, the composition containing at least some of the reduced adsorbent and/or catalyst compound or precursor can be heated in ak at from 80 to 1,500 °C in order to oxidize at least some of the reduced adsorbent and/or catalyst compound or precursor. The lower limit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900 °C, and the upper limit is 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, or 1,500 °C. Any lower hmit can be used with any upper lknit. In one embodiment, the temperature is from 100 °C to 1,500 °C, 200 °C to 1,300 °C, 300 °C to 1,100 °C, or 400 °C to 900 °C.
Any of the compositions of the present invention containing the adsorbent and/or catalyst compound or precursor can be contacted with the reducing agent or oxidizing agent using techniques known in the art. hi one embodiment, the composition containing the support and the adsorbent and/or catalyst compound or precursor is contacted with an aqueous solution of the reducing agent or the oxidizing agent. The amount of reducing agent or oxidizing agent that is used can vary, and wiU depend on the amount of the adsorbent and/or catalyst compound or precursor that is present in the composition as weU as the desked degree of reduction or oxidation of the adsorbent and/or catalyst compound. In one embodiment, once the composition containing the adsorbent and/or catalyst compound or precursor has been contacted with the reducing agent, the resultant, reduced composition is contacted with an oxidizing agent. In one embodiment, the composition can be contacted with a reducing agent or oxidizing agent at from 0 to 100 °C. In one embodiment, the mixing time can be as short as the time it takes the reducing or oxidizing agent to contact the composition.
The binders disclosed in U.S. Patent No. 5,948,726, and international pubhcationno. WO 97/47380 entitled "Acid Contacted Enhanced Adsorbent Particle and/or Catalyst and Binder System," which are herein incorporated by this reference in thek entkety, are useful as the cross-linkable binders of the present invention.
The binder of the present invention comprises an oxide particle that is capable of reacting, preferably cross-linking, with (1) itself; (2) the support, and/or (3) the adsorbent and/or catalyst compound or precursor. In one embodiment, when the support is a metal oxide, the binder cross-links with the metal oxide upon drying by forming chemical bonds with itself and the metal oxide. Under acidic conditions, the binder has a large number of surface hydroxyl groups. In one embodiment, the binder, which is designated as B-OH, cross-hnks with itself upon the loss of water to generate B-O-B. In addition to cross-linking with itself, the binder B-OH can also cross-link with a metal oxide complex (M-O) or metal hydroxyl complex (M-OH) to produce B-O-M.
"CoUoidal metal or metaUoid oxide (i. e. , coUoidal metal oxide or coUoidal metaUoid oxide) binder" as defined herein means a particle comprising a metal or metaUoid mixed hydroxide, hydroxide oxide, or oxide particle, such that the weight loss from the coUoidal metal or metaUoid oxide binder due to loss of water upon ignition is from 1 to 100%, 5 to 99%, 10 to 98%, or 50 to 95% of the theoretical water weight loss on going from the pure metal or metaUoid hydroxide to the corresponding pure metal or metaUoid oxide. The loss of water on going from the pure metal or metaUoid hydroxide to the corresponding pure metal or metaUoid oxide (e.g., the conversion of n M(OH)x to IVL m and y H20 or more specificaUy from 2 Al(OH)3 to Al2O3 and 3 H20) is defined as 100% of the water weight loss. Thus, the weight loss refers to loss of water based on the initial weight of water (not the total initial binder weight). There is a continuum of metal or metaUoid hydroxides, hydroxide oxides, and oxides in a typical commercial product, such that, loss or removal of water from the metal or metaUoid hydroxides produces the corresponding hydroxide oxides which upon further loss or removal of water give the corresponding metal or metaUoid oxides. Through tins continuum the loss or removal of water produces M-O-M bonds, where M is a metal or metaUoid. The particles of this continuum, except for the pure metal or metaUoid oxides, are suitable to serve as coUoidal metal or coUoidal oxide binders in this invention.
In another embodiment, the binder system involves the use of a binder in combination with a support and an adsorbent and/or catalyst compound or precursor with few or no surface hydroxyl groups, such that the support and/or the adsorbent and/or catalyst compound or precursor does not cross-link or only nominaUy cross-links with the binder. Examples of particles that possess only nominal amounts or that do not posses surface hydroxyl groups include particles of metals or non-metals, such as, but not limited to zinc or carbon, respectively. In this embodiment, the binder cross-links with itself in a manner described above to form a three dimensional network or matrix that physicaUy entraps or holds the support and the adsorbent and/or catalyst compound or precursor without cross-linking or cross-hhking only to a very smaU degree with the support and/or the adsorbent and/or catalyst compound or precursor.
Binders that can be used in the present invention are coUoidal metal or metaUoid oxide complexes. CoUoidal as used herein is defined as an oxide group that has a substantial number of hydroxyl groups that can form a dispersion in aqueous media. This is to be distinguished from the other use of the term coUoid as used in regard to a size of less than 1 μ The binders herein are typically smaU in size, e.g. less than 150 μm, but they do not have to be aU less than 1 μm. TypicaUy, the binder is un-calcined to maxknize the hydroxyl group avaUability. Moreover, they must have a substantial number of hydroxyl groups that can form a dispersion in aqueous media, which is not always true of coUoid particles merely defined as being less than 1 μm. Examples of binders include but are not limited to any metal or metaUoid oxide complex that has a substantial number of hydroxyl groups that can form a dispersion in aqueous media. In one embodiment, the binder is coUoidal aluininuin oxide, coUoidal silicon dioxide, coUoidal kon oxide, or a mixture thereof, preferably coUoidal aluminum oxide or coUoidal sihcon dioxide. CoUoidal aluminum, oxide can be a powder, sol, gel or aqueous dispersion. CoUoidal aluminum oxide may be further stabilized with an acid, preferably nitric acid, and even more preferably 3 to 4% nitric acid.
The phrase "coUoidal metal or metaUoid oxide (ie., coUoidal metal oxide or coUoidal metaUoid oxide) binder" also refers to a particle that is capable of forming a gel in water. If the coUoidal metal or metaUoid oxide binder does not form a gel in water, then the binder does not possess a sufficient number surface hydroxyl groups to crosslink with itself, the support, and/or the adsorbent and/or catalyst compound. Prior art coUoidal particles (ie, particle size less than 1 μm) generaUy do not form gels in water.
In one embodiment, the binder is from 1% to 99.9% by weight of the mixture, preferably from 10% to 35% by weight. As used herein, the binder wUl be referred to as "coUoidal" to distinguish it from the metal oxides that can be used as the support material or the adsorbent and/or catalyst material, as the composition types can be the same, e.g. they can aU contain aluminum oxides.
In a preferred embodiment, the coUoidal aluminum, oxide is un-calcined with a sufficient number of hydroxyl groups such that the total particle weight loss (as distinguished from just water weight loss discussed above) upon ignition is between from 5% to 34%, more preferably from 20% to 31%. The coUoidal aluminum oxide size is preferably from 5 nm to 400 μm, preferably at least 30 wt% is less than 25 μm and 95 wt% is less than 100 μm.
In another embodiment, the coUoidal sihcon dioxide is un-calcined with a sufficient number of hydroxyl groups such that the total particle weight loss upon ignition is between from 5% to 37%, more preferably from 20% to 31 %. The coUoidal sihcon dioxide size is preferably from 5 nm to 250 μm, preferably at least 30 wt% is less than 25 μm and 95 wt% is less than 100 μm.
An acid facilitates the cross-linking of the binder with (1) itself; (2) the support; (3) and/or the adsorbent and/or catalyst compound or precursor. The addition of an acid to the binder facilitates or enables the reaction (ie., cross- linking) between the binder with itself and the different components. A strong or dUute acid can be used. In one embodiment, the acid is dUuted with water to prevent dissolution of the particle and/or for cost effectiveness. The acid treatment is preferably of a concentration (e.g., normahty or molarity), acid type, temperature and length of time to cross-link the binder with itself , the support, and/or the adsorbent and/or catalyst compound or precursor.
In one embodiment, the acid comprises nitric acid, suUuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid or mixtures thereof, preferably acetic acid or nitric acid. In another embodiment, the concentration of the acid is from 0.15 N to 8.5 N, preferably from 0.5 N to 1.7 N. The volume of dkute acid used must be high enough so that the compositions of the present invention can be used as is or further processed, such as extruded or peUetized.
In another embodiment, a base facilitates the cross-linking of the binder with (1) itself; (2) the support; (3) and/or the adsorbent and/or catalyst compound or precursor. Any of the supports and adsorbent and/or catalyst compounds or precursors described above can be used in this embodiment of the invention. The base that can be used in this invention can be any base or mixture of bases that can promote the formation of hydroxyl groups onto the surface of the support and/or the adsorbent and/or catalyst compound or precursor. Any base known in the art can be used to prepare the binder system Examples of useful bases include, but are not limited to, LiOH, NaOH, KOH, RbOH, CsOH, Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2, Bronsted bases, or Lewis bases such as, ammonia or pyridine in water. The concentration of the base wiU vary depending upon the selection of the support, the binder, and/or the adsorbent and/or catalyst compound or precursor. In one embodiment, the concentration is from 0.1 to 0.5 N.
In another embodiment, the metal oxide is base treated prior to admixing the adsorbent and/or catalyst compound or precursor. AU of the metal oxides described above can be base treated. In another embodiment, the base is of an upper strength equivalent to a 0.5 N (normahty) aqueous solution. In another embodiment, the base concentration is from 0.0001 N to 2 N. In other embodiments, the upper strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N or 0.001 N aqueous solution. Any lower lknit can be used with any upper limit. The lower strength of the base should be that which provides more than a surface washing but imparts enhanced adsorbent effects to the metal oxide. In particular embodiments, the lower strength of the base is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N, 0.001 N, 0.0005 N, or 0.0001 N aqueous solution, hi one embodknent, the base concentration range is from 0.0001 N to 0.25 N, 0.0005 N to 0.09, 0.005 N to 0.075 N, or 0.01 N to 0.05 N.
In a further embodiment, the invention relates to a composition for binding adsorbent and/or catalytic particles to produce an agglomerated particle produced by the process comprising
(i) mixing components comprising
(a) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide, and
(b) abase, and
(k) removing a sufficient amount of water from the mixture to cross-link the binder to itself, thereby producing a composition for binding adsorbent and/or catalytic particles.
Any of the binders and bases disclosed above can be used in this embodiment of the invention. In one embodiment, the binder comprises coUoidal aluminum oxide or coUoidal silicon dioxide. Techniques commonly used in the art can be employed to remove the water to promote cross-lMdng. In one embodiment, the water is removed by azeotropic distillation. For example, the water is removed by placing the particles in a solvent such benzene, toluene, or m-xylene and carrying out an azeotropic distillation using a Dean Stark trap to remove the water to cross-link the binder. Not wishing to be bound by theory, when water is removed from the binder, the resultant binder is highly hydroxylated, which provides a particle with a very high density of Brønsted acid sites. This binder can serve as starting materials in the production of agglomerated adsorbent and/or catalyst systems. By increasing the number of Brønsted acid sites, it is possible to increase the overaU adsorbent and/or catalytic properties of the agglomerated particle.
In another embodiment, water can be used to prepare the binder syste In one embodiment, when the support and/or the adsorbent and/or catalyst compound or precursor are pretreated with an acid or a base to produce surface hydroxyl groups, then water can be used to facilitate cross-linking between the binder and the support and/or the adsorbent and/or catalyst precursor. For example, any of the particles disclosed in U.S. Patent No. 5,985,790, and international publication no. WO 97/47380 can be used in this embodiment of the invention. Any of the acid-treated or base- treated supports and adsorbent and/or catalyst compounds or precursors described above can be used in this embodiment of the invention.
In order to ensure efficient cross-Unking, water is preferably removed from the resulting binder/adsorbent and/or catalyst composition. This is typicaUy performed by using a drying agent or heating the syste The cross- linking temperature as used herein is the temperature at which the binder cross- hnks with itself, the support, and/or the adsorbent and/or catalyst compound or precursor at an acceptable rate. In one embodiment, the cross-linking temperature is from 25 °C to 600 °C. Thus, in one embodiment, the cross- linking temperature for certain binders is at room temperature although the rate of cross-linking at this temperature is slow. In various embodiments, the cross- linking temperature is from 50 °C, 70 °C, 110 °C, or 150 °C to 200 °C, 250 °C, 300 °C, 350 °C, 400 °C, 500 °C, or 600 °C, preferably 150 °C to 300 °C, even more preferably about 250 °C. In one embodiment, when the binder is coUoidal aluminum oxide or coUoidal sihcon dioxide, the cross-linking temperature is from 75 °C to 150 °C. The cross-linking process can take place in open ak, under an inert atmosphere or under reduced pressure.
In another embodknent, after the cross-linking step, the binder/adsorbent and/or catalyst composition is heated from 20 to 1,800 °C in order to vary the surface area and pore volume of the composition. The lower limit of the heating temperature is 80, 100, 150, 20, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900 °C, and the upper hmit is 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, or 1,800 °C. Any lower limit can be used with any upper limit. In one embodiment, the temperature is from 100 °C to 1,800 °C, 200 °C to 1,500 °C, 300 °C to 1,200 °C, or 400 °C to 900 °C. In one embodiment, the binder/adsorbent and/or catalyst composition is calcined. In another embodiment, the binder/adsorbent and/or catalyst composition is sintered.
The binder/adsorbent and/or catalyst composition of the present invention can be prepared by a variety of techniques. In one embodiment, the (1) binder; (2) the support; and (3) the adsorbent and/or catalyst particle are pre- mixed in dry form The coUoidal binder can be added or prepared in situ. For example, alum could be added as a dry powder and converted to coUoidal aluminum oxide in situ. Other aluminum based compounds can be used for the in situ process, such as aluminum chloride, aluminum secondary butoxide, and the like. Depending upon the adsorbent and/or catalyst compound or precursor and the support that are selected, an acid, base, or water is added to the mixture, and the mixture is stirred or agitated, typicaUy from 1 minute to 2 hours, preferably from 10 minutes to 40 minutes, until the material has a homogeneous "clay" like texture. The mixture is then ready for cross-linking or can be first fed through an extruder and then cut or chopped into a final shape. After the final shape is made, the mixture is transferred to a drying oven where it is dried from 15 minutes to 4 hours, preferably from 30 minutes to 2 hours. In another embodiment, the binder and support is admixed with an acid, base, or water, and the resultant mixture is crosslinked to produce a binder/support system, then the binder/support system is subsequently admixed with the adsorbent and/or catalyst compound or precursor.
Any support described above can be used in combination with the binder and the adsorbent and/or catalyst compound or precursor. In one embodknent, the support comprises aluminum oxide, sihcon dioxide, or an oxide of magnesium, preferably aluminum oxide. In another embodknent, when the support is a metal oxide, the metal oxide is (1) calcined at a particle temperature of from 200 to 700 °C, and (2) contacted with a dUute acid. In a preferred embodiment, the acid treated metal oxide is aluminum oxide.
Any of the adsorbent and/or catalyst compounds or precursors previously disclosed can be used to prepare the binder/adsorbent and/or catalyst composition.
In one embodiment, a binder of the present invention can be combined with any composition of the invention to produce a binder/adsorbent and/or catalyst composition. In one embodiment, compositions can be
(i) admixed with a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide and an acid to produce a mixture, and (ii) removing a sufficient amount of water from the mixture to cross-link the binder with itself and/or the composition to produce a binder/adsorbent and/or catalyst composition.
In one embodiment, once the binder/adsorbent and/or catalyst composition is produced, it can be optionaUy contacted with a (1) reducing agent; or (2) a reducing agent foUowed by an oxidizing agent using the techniques and reagents described above prior to contacting the composition with the hahde agent and/or oxoanion agent. Alternatively, after the binder/adsorbent and/or catalyst composition has been contacted with a reducing agent, the reduced composition can be heated in ak at from 80 to 120 °C in order to oxidize at least some of the reduced adsorbent and/or catalyst compound or precursor.
In one embodiment, the binder is coUoidal aluminum oxide, the support is aluminum oxide, and the adsorbent and/or catalyst compound is a copper compound, preferably CuO or Cu^O.
Any of the compositions of the present invention can be admixed with a second adsorbent and/or catalyst compound or precursor to produce a new composition contakiing two or more adsorbent and/or catalyst compounds an or precursors prior to contacting with the hahde agent and/or oxoanion agent. The second adsorbent and/or catalyst compound or precursor can be any of the adsorbent and/or catalyst compounds or precursors previously disclosed. Once the composition contakiing two or more adsorbent and/or catalyst compounds and/or precursors has been produced, the resultant composition can be optionaUy contacted with (1) a reducing agent to reduce at least some of the second adsorbent and/or catalyst compound; or (2) a reducing agent to reduce at least some of the additional adsorbent and/or catalyst compound or precursor foUowed by oxidizing the resultant composition prior to contacting the composition with the hahde agent and/or oxoanion agent.
In one embodiment, the binder/adsorbent and/or catalyst composition can be admixed with one or more additional adsorbent and/or catalyst compounds and/or precursors to produce a second binder/adsorbent and/or catalyst composition, foUowed by optionaUy contacting the second binder/adsorbent and/or catalyst composition with (1) a reducing agent to reduce at least some of the additional adsorbent and/or catalyst compound and/or precursor; or (2) a reducing agent to reduce at least some of the additional adsorbent and/or catalyst compound and/or precursor foUowed by oxidizing some at least some of the reduced adsorbent and/or catalyst compound or precursor. Alternatively, the binder/adsorbent and/or catalyst composition is (I) contacted with (1) a reducing agent to reduce at least some of the adsorbent and/or catalyst compound or precursor; or (2) a reducing agent to reduce at least some of the adsorbent and/or catalyst compound or precursor foUowed by oxidizing at least some of the reduced adsorbent and/or catalyst compound or precursor to produce a reduced and/or oxidized binder/adsorbent and/or catalyst composition, and (II) admixing two or more adsorbent and/or catalyst compounds and/or precursors with the reduced and/or oxidized binder/adsorbent and/or catalyst composition.
The size and shape of the particles present in the composition can vary greatly depending on the end use. hi one embodiment, the compositions of the present invention can be extruded to a particular shape and size using techniques known in the art.
Any of the compositions described above can be contacted with a hahde agent. A "hahde agent" is defined as any compound that is a source of fluoride ions, chloride ions, bromide ions, or iodide ions when the hahde agent is admixed with a solvent. GeneraUy, any solvent that partiaUy or completely dissolves the hahde agent is suitable in the invention. In one embodiment, the solvent is water. In one embodiment, the hahde agent is a chloride compound, a bromide compound, or an iodide compound. In one embodiment, the chloride compound is any salt or acid that contains a chloride ion. Examples of useful chloride agents include, but are not limited to, HO, Lid, NaCI, KCl, RbO, CsCl, BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, A1C13, or NH4C1, quaternary alkyl ammonium chloride, a chloride salt of a group I, II or III metal, a chloride salt of a transition metal, or a combination thereof. In one embodiment, the hahde agent is aqueous or gaseous HO.
The adsorbent and/or catalyst compound or precursor can be contacted with the hahde agent using techniques known in the art to produce a hahde adsorbent and/or catalyst compound or precursor. A 'hahde adsorbent and/or catalyst compound or precursor" and a "chloride adsorbent and/or catalyst compound or precursor" is defined herein as any adsorbent and/or catalyst compound or precursor that has been contacted or treated with a hahde agent or a chloride agent, respectively. The contacting step typicaUy involves admixing a homogeneous solution or a suspension of the hahde agent with the adsorbent and/or catalyst composition to produce the halide/adsorbent and/or catalyst composition. In one embodiment, the adsorbent and/or catalyst composition can be in dry form or it can be a homogeneous or heterogeneous solution when it is contacted with the hahde agent. In one embodiment, the adsorbent and/or catalyst composition is in dry form when it is contacted with the hahde agent. In another embodiment, the halide/adsorbent and/or catalyst composition can be prepared in situ by admixing (1) the adsorbent and/or catalyst compound or precursor; (2) the support and/or the binder; and (3) HO (aqueous or gaseous) or NH4C1. After the halide/adsorbent and/or catalyst composition is prepared in situ, it can be optionaUy contacted with additional hahde agent. The amount of hahde agent and the duration of the contacting step wiU vary depending upon the selection of the hahde agent and the adsorbent and/or catalyst composition as weU as the end use of the halide/adsorbent and/or catalyst composition. In one embodiment, the ratio of (the amount metal ion, in moles, contained in the adsorbent and/or catalyst composition)/(the amount of hahde ions, in moles, used to treat the adsorbent and/or catalyst composition) is from 0.5 to 50, 0.5 to 40, 0.5 to 30, 0.5 to 20 0.5 to 10, 0.5 to 1. In another embodiment, the hahde ion may not be present in the halide/adsorbent and/or catalyst composition after contacting the adsorbent and/or catalyst compound or precursor with the hahde agent and/or heating the resultant hahde adsorbent and/or catalyst compound or precursor. For example, if the haUde agent is a chloride agent, then HO can be removed during the heating step.
After contacting the particle with the hahde agent, the particle is dried and optionaUy calcined at a temperature from 20 to 1,800 °C. In various embodiments, the lower hmit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C, and the upper hmit of the heating temperature is 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower limit can be used with any upper limit. In one embodiment, the temperature is from 100 °C to 1,800 °C, 200 °C to 1,500 °C, 300 °C to 1,200 °C, or 400 °C to 900 °C.
In one embodiment, the chloride/adsorbent and/or catalyst composition is prepared by an in situ process comprising admixing coUoidal aluminum oxide, aluminum oxide, and CuO with HO.
In another embodiment, after the contacting step with the hahde agent, the halide/adsorbent and/or catalyst composition can be contacted with an oxoanion agent to produce an oxo/adsorbent and/or catalyst compound or precursor. An "oxo/adsorbent and/or catalyst compound or precursor" is defined herein as any halide/adsorbent and/or catalyst compound or precursor that has been contacted or treated with an oxoanion agent. The "oxoanion agent" is any compound or group of compounds that can incorporate an oxoanion into the binder, support, and/or adsorbent and/or catalyst compound or precursor. An oxoacid or the salt thereof can be used as the oxoanion agent. In one embodiment, the oxoacid has the general formula HπXOm, where n = 1-3, m = 1- 4, and X is any of the non-metallic elements, preferably S, P, As, Sb, and more preferably S and P. Examples of oxoanions useful in the present invention are disclosed in "Advanced Inorganic Chemistry" by F. A. Cotton and G.
Wilkinson, Fifth ed., m WUey & Sons, 1988, pages 104-106, 481-489, which is herein incorporated by reference in its entkety. The term "oxoanion" also includes isopoly and heteropoly anions. The isopoly and heteropoly anions disclosed in "Advanced Inorganic Chemistry" by F. A. Cotton and G. Wilkinson, Fifth ed. , John WUey & Sons, 1988, pages 811-819, which is also incorporated by reference in its entkety, are useful in the present invention. The counterion of the oxoanion can be any cation known in the art.
In one embodiment, the oxoanion agent is a sulfating agent. A sulfating agent is any compound or group of compounds that can incorporate SO4 "2 or SO3 "2 ions into the binder, support, and/or adsorbent and/or catalyst compound or precursor. In one embodiment, any salt or acid that contains S04 "2 ions can be used. In this embodiment, the siύfating agent can be partially or completely soluble in a solvent, preferably water. In one embodiment, the sulfating agent is a group I metal sulfate, a group II metal sulfate, a group III metal sulfate, or a mixture thereof. In one embodiment, the sulfating agent is H2S04 or (NH4)2S04. In another embodiment, the compositions of the invention can be contacted with (1) S02 and O2 or (2) SO2 in ak to incorporate SO4 "2 ions into the composition. For example, the chloride/adsorbent and/or catalyst composition can be contacted with a stream of S02 and 02 in an inert gas such as nitrogen or hehum, or a reactive gas such as ak, vehicle exhaust, or power plant emissions, to sulfate the halide/adsorbent and/or catalyst composition.
The amount of oxoanion agent and the duration of the contacting step wUl vary depending upon the oxoanion agent and the binder, support, and/or adsorbent and/or catalyst compound or precursor selected as weU as the end use of the composition. In one embodiment, the ratio of (the amount metal ion, in moles, contained in the adsorbent and/or catalyst composition)/(the amount of sulfate or oxoanion, in moles, used to treat the adsorbent and/or catalyst composition) is from 0.5 to 50, 0.5 to 40, 0.5 to 30, 0.5 to 20 0.5 to 10, 0.5 to 1.
In one embodiment, the chloride/adsorbent and/or catalyst composition is produced by admixing coUoidal aluminum oxide, aluminum oxide, and CuO with HO, and the resultant chloride/adsorbent and/or catalyst composition is contacted with S02 and 02 in hehu In another embodiment, the chloride/adsorbent and/or catalyst composition is produced by adrnixing coUoidal duminum oxide, aluminum oxide, and CuO with HO, and the chloride/adsorbent and/or catalyst composition is contacted with (NH4)2S04.
The invention further relates to a method for reducing or eliminating the amount of nitrogen oxide(s) or sulfur oxide(s) from an envkonment, comprising contacting the envkonment with a chloride/adsorbent and/or catalyst composition.
The invention further relates to a monolith comprising any of the adsorbent and/or catalyst compositions of the invention. Any monohth known in the art can be used in the invention. The monoliths disclosed in U.S. Patent nos. 5,395,600; 5,445,786; 6,037,307; 4,199,477; and 4,564,608, which are incorporated by reference in thek entkety, are useful in the invention. TypicaUy, the monohth is made from a ceramic material, cordierite, or metal. The compositions of the invention can be apphed to the monohth using techniques known in the art. In one embodiment the compositions of this invention is wet milled for sufficient time to achieve an average particle size of less than 10 microns. In another embodiment the compositions of this invention are subjected to dry or wet grinding to give particles between 0.1 and 100 microns. In another embodiment the compositions of this invention are subjected to dry or wet grinding to give particles between 2 and 15 microns. In another embodknent a slurry of compositions of this invention are baU milled to a particle size range in witch 90 % of the particles were less than 10 microns. In one embodiment, the dispersed composition can be apphed to the monohth by coating the monohth with the composition or by dipping the monohth in the composition. Alternatively, the adsorbent and/or catalyst composition can be spray-dried onto the monohth Once the monohth has been contacted with the composition, the resultant monohth can be dried by heating and further heated at a temperature from 80 to 1,800 °C. In various embodiments, the lower limit of the heating temperature is 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 °C, and the upper limit of the heating temperature is 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, or 1,700 °C. Any lower limit can be used with any upper limit. In one embodiment, the temperature is from 100 °C to 1,800 °C, 200 °C to 1,500 °C, 300 °C to 1,200 °C, or 400 °C to 900 °C. The monohth can optionaUy be contacted with additional adsorbent and/or catalyst composition foUowed by drying and heating.
The invention further relates to a method for removing or eliminating
SO2 and/or SO3 from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention at from 100 °C to 600 °C. The invention further relates to a method for removing or eliminating SO2 and/or S03 from an envkonment, comprising
(a) reducing an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention with a reducing gas to produce a reduced composition;
(b) oxidizing the reduced composition of (a) with a gas stream comprising ak or oxygen to produce an oxidized composition; and
(c) contacting the envkonment comprising S02 and/or S03 with the oxidized composition produced in (b) at from 100 °C to 600 °C.
The invention further relates to a method for removing or eliminating S02 and/or SO3 from an envkonment, comprising contacting the envkonment in the presence of ak or oxygen with an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention from 100 °C to 600 °C.
The invention further relates to a method for removing or ejjminating
SO2 and/or SO3 from an envkonment, comprising
(a) reducing an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention with a reducing gas to produce a reduced composition, and
(b) contacting the reduced composition with the envkonment in the presence of ak or oxygen from 100 °C to 600° C. The invention further relates to a method for removing or eliminating nitrogen oxide(s) from an envkonment, comprising contacting an adsorbent and/or catalyst composition comprising one or more of the compositions of the invention with the envkonment in the presence of a reducing gas from 125 °C to 1,000 °C.
Nitrogen oxides and sulfur oxides are generaUy represented in the art by the formulas NOx and SOx, respectively. Examples of nitrogen oxides include, but are not limited to, NO, N02, N204, N205, and N20. Examples of sulfur oxides include, but are not limited to, S02, S03, and SCO.
The envkonment can be any gas or liquid stream that contains a sulfur oxide and/or a nitrogen oxide. In one embodiment, the envkonment is a gas or hquid stream, preferably a gas stream.
In one embodiment, a halide/adsorbent and/or catalyst composition can be used to remove sulfur oxides from a gas strea In this embodiment, the halide/adsorbent and/or catalyst composition is placed in a device and heated from 100 °C to 800 °C, 100 °C to 600 °C, and preferably 200 °C to 400 °C to remove water. In one embodiment, the lower limit is 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C, and the upper limit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 700 °C, or 800 °C. Any lower hmit can be used with any upper limit. In one embodiment, the temperature is from 150 °C to 800 °C, 200 °C to 700 °C, or 300 °C to 600 °C. The halide/adsorbent and/or catalyst composition can optionaUy be heated in the presence of a halide/adsorbent and/or catalyst composition reducing agent to reduce the adsorbent and/or catalyst compound or precursor to produce a reduced halide/adsorbent and/or catalyst composition. The temperature at which reduction is performed is from 100 °C to 600 °C. Examples of halide/adsorbent and/or catalyst composition reducing agents useful in the present invention include, but are not limited to, hydrogen, carbon monoxide, diesel fuel, refinery off gas, kerosene, olefins, paraffins, and hydrocarbons such as methane, ethane, propane, or isobutane, with methane as the preferred reducing agent. The reduced halide/adsorbent and/or catalyst composition can then be optionaUy oxidized with a gas stream containing ak or oxygen.
In one embodiment, the halide/adsorbent and/or catalyst composition is then exposed to a gas stream containing the sulfur oxide from 100 °C to 600 °C. In one embodiment, the lower limit is 100 °C, 125 °C, 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C, and the upper hmit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, or 550 °C. hi one embodiment, the sulfur oxide is S02. Any lower hmit can be used with any upper limit. In one embodiment, the temperature is from 100 °C to 550 °C, 200 °C to 450 °C, or 250 °C to 400 °C.
After the adsorbent and/or catalyst composition has been exposed to the sulfur oxide compound, the adsorbent and/or catalyst composition can be regenerated. In one embodiment, regeneration can be accomphshed by exposing the adsorbent and/or catalyst composition with the any of the reducing gases disclosed above from 100 °C to 800 °C, preferably 200 °C to 600 °C. In one embodiment, the lower limit is 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C, and the upper hmit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 700 °C, or 800 °C. Any lower limit can be used with any upper limit, hi one embodiment, the temperature is from 150 °C to 800 °C, 200 °C to 700 °C, or 300 °C to 600 °C. hi one embodiment, the reducing agent is in an inert gas such as nitrogen or hehum, and is passed through the adsorbent and/or catalyst composition. In one embodiment, the reducing gas is methane. After regeneration, the adsorbent and/or catalyst composition can subsequently be exposed to the envkonment containing the sulfur oxide. In another embodiment, an oxoanion adsorbent and/or catalyst composition, preferably a sulfated/adsorbent and/or catalyst composition, can be used to remove nitrogen oxides from a gas strea In this embodiment, the sulfated/adsorbent and/or catalyst composition is placed in a device and heated from 100 °C to 800 °C, preferably 200 °C to 600 °C, to remove adsorbed contaminants from the composition. The sulfated/adsorbent and/or catalyst composition is then is exposed to a gas stream containing one or more nitrogen oxide compounds from 125 °C to 1,000 °C, preferably from 125 °C to 500 °C. In one embodknent, the lower limit is 150 °C, 175 °C, 200 °C, 250 °C, 300 °C, or 350 °C, and the upper limit is 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 700 °C, 800 °C, or 900 °C. Any lower hmit can be used with any upper limit. In one embodiment, the temperature is from 150 °C to 900 °C, 200 °C to 800 °C, 300 °C to 700 °C, or 400 °C to 600 °C. In addition, present in the stream is a reducing agent that can reduce the oxide(s) of nitrogen in the presence of the oxoanion/adsorbent and/or catalyst composition. Examples of oxoanion/adsorbent and/or catalyst composition reducing agents useful in the present invention include, but are not limited to, ammonia, hydrogen, carbon monoxide, diesel fuel, refinery off gas, kerosene, olefins, paraffins, urea, cyanuric acid, ammonium sulfate, organic amines, alcohols such as methanol, ethanol, or propanol, hydrocarbons such as methane, ethane, propane, or isobutane, partiaUy combusted hydrocarbons, or exhaust gas. In a preferred embodiment, the oxoanion/adsorbent and/or catalyst composition reducing agent is ammonia.
In one embodiment, the halide/adsorbent and/or catalyst compositions or the oxoanion/adsorbent and/or catalyst compositions of the invention are used in a monohth or a series of monoliths to remove sulfur oxides and nitrogen oxides from an envkonment. The monohth(s) containing the adsorbent and/or catalyst composition can be exposed to any envkonment that contains a sulfur oxide or nitrogen oxide, including, but not limited to, automobfle and power plant emissions.
The adsorbent and/or catalyst compositions remove sulfur dioxide compounds from an envkonment at a faster rate and lower temperatures when compared to prior art compositions. Not wishing to be bound by theory, it is believed that the presence of the haUde ions in the halide/adsorbent and/or catalyst composition are responsible for the lower temperatures requked for removing the sulfur oxide compounds from the envkonment. It is also beheved that the treatment of the adsorbent and/or catalyst compositions with a hahde agent leads to a redispersion of the metal or metal oxide on the support surface. In addition, hahde treatment of the adsorbent and/or catalyst compositions can change the Lewis acidity of the adsorbent and/or catalyst compositions. The change in dispersion and Lewis acidity can enhance the reactivity of the adsorbent and/or catalyst compositions. It is advantageous to reduce the reaction temperature, because it aUows less-capital intensive equipment to be used. Lower reaction temperatures also lead to lower energy costs and, thus, lower operating costs.
It is also beheved that contacting the adsorbent and/or catalyst compositions with an oxoanion agent further modifies the Lewis acidity of the adsorbent and/or catalyst compositions and, thus, further enhances the activity of the adsorbent and/or catalyst compositions. In the case of nitrogen oxide removal, the present invention permits a wider range of operating temperatures and reducing gas/nitrogen oxide ratios when compared to prior art compositions.
FinaUy, it is beheved that treatment of the adsorbent and/or catalyst compositions with a hahde agent and/or a polyoxanion agent permits the resultant composition to selectively poison undeskable adsorbent and/or catalyst sites that lead to undeskable competing reactions. EXPERIMENTAL
The foUowing examples are put forth so as to provide those of ordinary skiU in the art with a complete disclosure and description of how the compositions claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as thek invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by volume, temperature is in °C or is at ambient temperature and pressure is at or near atmospheric.
Example 1
Various compositions comprising copper oxide and a binder systems as set forth in Table 1 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726. Throughout the examples, the term "alumina" refers to almninurn oxide. Alumina (Compalox C), coUoidal alumina (Condea P2), copper oxide (Fisher), were combined in a mixing vessel, the amount of each component varied as indicated in Table 1. The "dry" components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomphshed, a solution of 7 % acetic acid in distiUed water was added to the mixture. The amount of the acid solution compared to the other components varied between 45 and 55 wt. % of the total dry mixture weight. This solution was added to the dry materials and mixed until the material agglomerated with a pan agglomerator. The agglomerated peUets were transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the sample had been calcined they were analyzed for copper content. The copper content as weight % Cu and CuO is reported in Table 1.
Table 1
Figure imgf000070_0001
Example 2
Various compositions comprising copper oxide and a binder systems as set forth in Table 2 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726. Alumina (Versal GH), coUoidal alumina (Condea P2), copper oxide (Fisher), were combined in a mixing vessel, the amount of each component varied as indicated in Table 2. The "dry" components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomphshed, a solution of 7 % nitric acid in distilled water was added to the mixture. The amount of the acid solution compared to the other components varied between 70 and 75 wt. % of the total dry mixture weight. This solution (approximately 70-75 mL) was added to the dry materials and mixed until the material had a homogenous "modeling clay" like consistency. The material was then extruded with a hand held press. The extruded media were transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the sample had been calcined they were analyzed for copper content. The copper content as weight % Cu and CuO is reported in Table 2.
Table 2
Figure imgf000071_0001
Example 3
Various compositions comprising copper oxide and a binder systems as set forth in Table 3 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726. Alumina (Versal GH), coUoidal alumina (Condea P2), copper oxide (Fisher), were combined in a mixing vessel, the amount of each component varied as indicated in Table 3. The "dry" components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomphshed, a solution of 7 % hydrochloric acid in distiUed water was added to the mixture for samples 7HC1, lOHQ, and 13 HO, 5 % hydrochloric acid in distiUed water was added to the mixture for sample 5 HO. The amount of the acid solution compared to the other components varied between 70 and 75 wt. % of the total dry mixture weight. This solution (approximately 70-75 mL) was added to the dry materials and mixed until the material had a homogenous "modeling clay" like consistency. The material was then extruded with a hand held press. The extruded media was transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the sample had been calcined they were analyzed for copper content. The copper content as weight % Cu and CuO is reported in Table 3.
Table 3
Figure imgf000072_0001
Example 4 - SO, adsorption on CuO/A O, copar icle 7HC1
The copper oxide-alumina composite particle material, 7HC1 (Table 3, Example 3), 7.9 % CuO (244.8 mg), was placed in a platinum mesh holder in a Cahn TG 151 thermogravimetric analyzer. The reactor was assembled and then purged with hehum for 20 minutes at 10 psi. The purge gas (hehum), furnace gas (nitrogen), and reaction gas flows were set to 200 cc, 200 cc and 180 cc per minute, respectively. The sample was heated to 500° C under a flow of nitrogen and methane for 15 minutes to remove water and other unwanted adsorbates and reduce the copper oxide. The weight of the sample dropped to 221.1 mg. The sample was then cooled to 150 °C under a nitrogen flow. The sample weight increased to 222.45 mg. At 150 °C the sample was exposed to a stream of 2,000 ppm of sulfur dioxide and 2 % oxygen, balance nitrogen. The sample was treated with the stream for 30 min at 150 °C, during which time the sample weight increased to 233.8 mg. The reactor was then purged with nitrogen for 10 minutes at 150 °C. The adsorbent was then regenerated by heating it to 500 °C for 15 minutes in a methane stream The methane stream was then replaced with a nitrogen stream and the sample was cooled to 150 °C. At this point the sample was ready for the next adsorption/desorption cycle. Four additional adsorption deso tion cycles were performed. The percent weight gain relative to that of the reduced sample prior to adsorption and the corresponding calculated weight gain due to S02 for each cycle is given in Table 4. Figure 1 is a plot of the weight % SO2 uptake vs. time for the thkd adsorption cycle (dashed line with filled ckcles).
Table 4
Figure imgf000073_0001
Example 5 - SO, adsorption on CnO/ALO, coparticle 10HC1
The copper oxide-alumina composite particle material, lOHO (Table 3, Example 3) 10.75 % CuO (247.2 mg), was placed in a platinum holder in a Cahn TG 151 thermo gravimetric analyzer and adsorption/desorption cycles were carried out as described in Example 4. The results of these cycles are given in Table 5.
Table 5
Figure imgf000074_0001
Example 6 - SO, adsorption on CuO/ALOc coparticle 13HC1 The copper oxide- alumina composite particle material 13 HO (Table 3,
Example 3) 13.25 % CuO (248.2 mg) was placed in a platinum holder in a Cahn TG 151 theimo gravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 6.
Table 6
Figure imgf000074_0002
Example 7 - SO, adsorption on CuO/ALO, coparticle prepared with 7HOAc
The copper oxide-alumina composite particle 7HOAc (Table 1, Example 1) 7.6 % CuO (254.5 mg) was placed in a platinum holder in a Cahn TG 151 thermogravimetric and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 7. Figure 1 is a plot of the weight % S02 uptake vs. time for the thkd adsorption cycle (sohd line with diamonds).
Table 7
Figure imgf000075_0001
Example 8
SO, adsorption on CuO/Al,O? coparticle prepared with 13HOAc.
The copper oxide-alumina composite particle 13 HOAc (Example 1, Table 1) 13.75 % CuO (251.2 mg) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 8.
Table 8
Figure imgf000075_0002
Example 9 - SO, adsorption on CnO/Al,O coparticle 7HNO<.
The copper oxide- dumina composite particle 7HN03 (Table 2, Example 2) 7.9 % CuO (250.40 mg) was placed in a platinum holder in a Calm TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 9.
Table 9
Figure imgf000076_0001
Example 10- HCl treatment of co-particles 7HOAc and 13HOAc Samples of copper oxide-alumina composite particles 7HOAc and
13HOAc (Table 1, Example 1) were treated at room temperature for approximately 1 min with 0.6 g of an HCl solution prepared as described in Table 10, the co -particle was then calcined at 400 °C for 1 hour.
Table 10
Figure imgf000076_0002
Example 11 - SO, adsorption on CnO/Al,O, HOAc coparticles treated with HCl
Sample HOAc-HCl-1 (Table 10, Example 10), 251.0 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 11.
Table 11
Figure imgf000077_0001
Example 12 - SO, adsorption on CnO/ALO,, HOAc coparticles treated with HCl
Sample HOAc-HCl-2 (Table 10, Example 10), 251.7 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 12.
Table 12
Figure imgf000077_0002
Example 13 - SO, adsorption on CuO/Al,O, HOAc coparticles treated with HCl
Sample HOAc-HCl-3 (Table 10, Example 10), 252.9 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsorption desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 13.
Table 13
Figure imgf000078_0001
Example 14 - SO, adsorption on CnO/ALO^ HOAc coparticles treated with HCl
Sample HOAc-HCl-4 (Table 10, Example 10), 252.3 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsorption/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 14.
Table 14
Figure imgf000078_0002
Example 15 - SO, adsorption on CuO/Al,O« HOAc coparticles treated with HCl
Sample HOAc-HCl-5 (Table 10, Example 10), 252.4 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desorption cycles carried out as described in Example 4. The results of these cycles are given in Table 15. Figure 1 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (sohd line with open ckcles).
Table 15
Figure imgf000079_0001
Example 16 - SO, adsorption on CnO/ALO HOAc coparticles treated with HCl
Sample HOAc-HCl-6 (Table 10, Example 10), 250.9 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 16.
Table 16
Figure imgf000079_0002
Example 17 - SO, adsorption on alumina
A sample of dumina granules, 256.4 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 17. Figure 2 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (dashed line with diamonds).
Table 17
Figure imgf000080_0001
Example 18 - Impregnation of alumina with CuO, or Cu(NO«), Granular alumina, 1/16 inch, diameter, was treated with a CuCl2 or
Cu(N03)2 solution as described in Table 18 at room temperature for approximately 1 min and than calcined at 450° C for 1 hour.
Table 18
Figure imgf000080_0002
Example 19 - SO, adsorption on alumina impregnated with CuO,
The copper chloride knpregnated alumina sample CuCl2-l (Table 18, Example 18), 239.4 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric and adsoφtion/desoφtion cycles were carried out as described in Example 4. The results of these cycles are given in Table 19.
Table 19
Figure imgf000081_0001
Example 20 - SO, adsorption on co-alumina impregnated with Cuf O ),
A copper nitrate impregnated/calcined alumina sample CuN03-l (Table 18, Example 18), 248.7 mg, was placed in a platinum holder in a Cahn TG 151 thermogravimetric and adsoφtion/desoφtion cycles were carried out as described in Example 4. The results of these cycles are given in Table 20. Figure 2 is a plot of the weight % S02 uptake vs. tkne for the thkd adsoφtion cycle (sohd line with filled ckcles).
Table 20
Figure imgf000081_0002
Example 21 - SO, adsorption on alumina impregnated with sodium chloride
Granular alumina, 1/16 inch diameter was treated with 0.53g of NaCI solution prepared from 1.4 g NaCI and 3.6g H20, for approximately 1 min and then calcined at 400 °C for 1 hour to give a sample identified as NaCl-1. A 258.9 mg sample was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 21.
Table 21
Figure imgf000082_0001
Example 22 - SO, adsorption on CuO/ALO^ prepared impregnating alumina with CufNO?), and post-treated bv NaCI
Sample CuN03-l, 1.0 g (Table 18, Example 18) was treated at room temperature for approximately one minute with 0.53 g of a sodium chloride solution prepared from 0.19 g of NaCI dissolved in 4.8 g water, and then calcined at 400 °C for 1 hour to give sample # CuNO3-l-Cl. A 246.3 mg sample of CuN03-l-0 was placed in a platinum holder in a Calm TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 22. Figure 2 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (sohd line with filled ckcles). Table 22
Figure imgf000082_0002
Example 23
Various compositions comprising copper oxide and a binder system as set forth in Table 23 were prepared in accordance with the foUowing general procedure disclosed in U.S. Patent No. 5,948,726. Alumina (Versal GH), coUoidal alumina (Condea P2), copper oxide (Fisher), were combined in a mixing vessel, the amount of each component varied as indicated in Table 23. The "dry" components were pre-mixed to ensure a homogenous mixture of aU of the components. After this was accomplished, a solution of 7 % acetic acid in distiUed water was added to the mixture. The amount of the acid solution compared to the other components varied between 80 and 82 wt. % of the total dry mixture weight. This solution was added to the dry materials and mixed until the material agglomerated. The agglomerated media were transferred to a drying oven at 200 to 300 °F and then calcined for one hour at 400 °C. After the samples were calcined they were analyzed for copper content. The copper content as weight % Cu and CuO is reported in Table 23.
Table 23
Figure imgf000083_0001
Example 24 Selective Catalytic reduction of NO with ammonia over CuO/Al,O„ coparticle prepared with HOAc (5 % CuO).
Copper oxide-alumina composite particle 5 % CuO (5.00 m, approximately 10 mL) prepared with HOAc as binding acid, prepared as described in Example 23, was placed in a fixed-bed quartz tube reactor. The flow gas was prepared by blending different gaseous reactants: He or O2/He, NH3/He, NO/He. Premixed certified gases (1% NO in He, 1% NH3 in He, and 3% 02 in He) were suppUed by Matheson. Three mass flow controUers (Teledyne Hastings Mass Flow controUer HFC 202) were used to control the flow rates of the individual reactant gas mixtures. The sample was heated to 400° C under hehum flow (0.5 SLPM) for approximately 2 hours to remove adsorbed contaminants from the sample. The sample was then cooled to 350 °C whUe under a hehum flow. At 350 °C the sample was exposed to a stream nitric oxide, ammonia and oxygen in hehum Flow rate of the oxygen/hehum gas mixture was set at 0.5 SLPM. Flow rates of the nitric oxide/hehum and ammonia/heUum were adjusted to have the reactant gas composition as foUows: 670 ppm NO, 720 ppm NH3. Products were continuously analyzed with a Nicolet Magna IR 560 FT-IR spectrometer. Outlet concentrations of NO, N02, N2O, NH3, and H20 were measured using a long path-length infrared gas ceU, using cahbrated infrared analysis software QASOFT'96. After equUibiium was reached at 325° C the date was recorded. The ammonia inlet concentration was increased to examine its influence on degree of NO conversion. Table 24 gives gas outlet concentrations at four different ammonia concentrations at 325° C. Table 24
Figure imgf000084_0001
Example 25-Selective catalytic reduction of NO with ammonia over CuO/Al,O coparticle prepared with HCl (5 % CuO .
Copper oxide-alumina composite particle 5 % CuO (5.00 g, approximately 10 mL) prepared with HCl as binding acid, prepared as described in Example 3 (elemental analysis indicated that the sample was 3.74 % Copper and 1.67 % chloride), was placed in a fixed-bed quartz tube reactor. The sample was prepared and selective catalytic reduction experiment was carried out as described in example 24. Table 25 gives the gas outlet concentrations at four different ammonia concentrations at 325 °C.
Table 25
Figure imgf000085_0001
Example 26-S elective catalytic reduction of NO with ammonia over CuO/Al,O« coparticle prepared with HOAc (5 % CuO) and post-treated with HCl.
Copper oxide-dumina composite particle 5 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid, prepared as described in Example 23 and post-treated with HCl to give sample HOAc-HCl-7 as described in Example 10, was placed in a fixed-bed quartz tube reactor. The sample was prepared and selective catalytic reduction experiment was carried out as described in example 24. Table 26 gives the gas outlet concentrations at four different ammonia concentrations at 325 °C.
Table 26
Figure imgf000086_0001
Example 27-Selective catalytic reduction of NO with ammonia over CuO/A O^ coparticle prepared with HOAc (3 % CuO).
A sample of copper oxide-dumina composite particles 3 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid, prepared as described in Example 23, was placed in a fixed-bed quartz tube reactor. The sample was prepared and selective catalytic reduction experiment was carried out as described in example 24. Table 27 gives the gas outlet concentrations at two different ammonia concentrations at 325 °C.
Table 27
Figure imgf000087_0001
Example 28-Selective catalytic reduction of NO with ammonia over CuO/Al,O« coparticle prepared with HOAc (3 % CuO) and post-treated with HCl.
A sample of copper oxide-alumina composite particles 3 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid, prepared as described in Example 23 and post- treated with HCl to give sample HOAc-HO- 8, as described in Example 10, was placed in a fixed-bed quartz tube reactor. The sample was prepared and selective catalytic reduction experiment was carried out as described in example 24. Table 28 gives the gas outlet concentrations at two different ammonia concentrations at 325 °C.
Table 28
Figure imgf000088_0001
Example 29 - Preparation of co-particles by using SO, as post-treating agent
Two samples of copper oxide-alumina composite particle 5 % CuO were used for post- treatment by sulfur dioxide: One prepared with HOAc as binding acid prepared as described in Example 23 (5-125); and another prepared with HO as binding acid prepared as described in Example 3 (5HC1). Samples, 5.00 g, of each material were exposed to a flowing gas mixture containing 740 ppm of S02, balance He, at a flow rate of approximately 0.5 SLPM at 325 °C for 40 minutes. A summary of those post- treatments is shown in the Table 29. Table 29
Figure imgf000089_0001
Example 30 - Selective catalytic reduction of NO with ammonia over
CuO/ALO coparticle prepared with HOAc (5 % CuO) and post-treated with SO,
Copper oxide-alumina composite particle 5 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid prepared as described in Example 29, was placed in a fixed-bed quartz tube reactor and the selective catalytic reduction experiment was carried out as described in example 24. Table 30 gives gas outlet concentrations at four different ammonia inlet concentrations and temperatures. Table 30
Figure imgf000089_0002
Example 31 ■ Selective catalytic reduction of NO with ammonia over CuO/Al,O< coparticle prepared with HCl (5 % CuO) and post-treated with SO,
Copper oxide-alumina composite particle 5 % CuO (5.00 g, approximately 10 mL) prepared with HCl as binding acid prepared as described in Example 3 (elemental analysis indicated that the sample was 3.74% Cu and 1.67% chloride) and post- treated with S02 as described in Example 29, was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24. Table 31 gives gas outlet concentrations at four different ammonia inlet concentrations and temperatures. Elemental analysis of the recovered catalyst indicated 0.73% chloride and 0.48% sulfur.
Table 31
Figure imgf000090_0001
Example 32
Selective catalytic reduction of NO with ammonia over CuO/Al,O, coparticle prepared with HOAc (5 % CuO)
A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid prepared as described in Example 24 was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 29 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 32 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3:NO ratio that gives 5 ppm or less NH3 shp at selected temperatures. Figure 3 plots the 90 % NO conversion and the 5 % ammonia shp NH3:NO ratios as a function of temperature.
Table 32
Figure imgf000091_0001
Example 33- Selective catalytic reduction of NO with ammonia over CuO/Al,O, coparticle prepared with HOAc (5 % CuO) post treated with HCl
A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared with HOAc as binding acid and post treated with HCl as described in Example 10 (HOAc-HCl-7) was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 33 gives the mmimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maxknum NH3:NO ratio that gives 5 ppm or less NH3 shp at selected temperatures. Figure 4 plots the 90 % NO conversion and the 5 % ammonia shp NH3:NO ratios as a function of temperature.
Table 33
Figure imgf000092_0001
Example 34 - Selective catalytic reduction of NO with ammonia over CuO/Al,Oc coparticle prepared with HCl (5 % CuO) post treated with SO,
A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared with HCl as binding acid and post treated with S02 as described in Example 29 was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 34 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3:NO ratio that gives 5 ppm or less NH3 shp at selected temperatures. Figure 5 plots the 90 and 100 % NO conversion and the 5 and 0 % ammonia shp NH3:NO ratios as a function of temperature.
Table 34
Figure imgf000093_0001
Example 35 - Preparation of co-particles using SiO,. MgQ. TiO,. and ZrO,/Al,O as supports for copper oxide
Various metal oxides supports, were treated with Cu(N03)23H20 solutions as described in Table 35 at room temperature for approximately 1 min and than calcined at 450 °C for 1 hour.
Table 35
Figure imgf000094_0001
Example 36 - SO, adsorption on silica impregnated with copper nitrate
Copper nitrate impregnated sihca 7% CuO (253.96 mg) prepared as described in Example 35 (sample Si02 - 1) was placed in a platinum holder in a Calm TG 151 thermogravknetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 36. Figure 6 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (dashed line with filled ckcles).
Table 36
Figure imgf000094_0002
Example 37 - SO, adsorption on magnesium oxide impregnated with copper nitrate Copper nitrate impregnated magnesium oxide 7% CuO (257.34 mg) prepared as described in Example 35 (sample MgO - 1) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer as and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 37. Table 37
Figure imgf000095_0001
Example 38 - SO, adsorption on titanium oxide impregnated with copper nitrate
Copper nitrate impregnated titanium oxide 5.7% CuO (255.46 mg) prepared as described in Example 38 (sample Ti02 - 1) was placed in a platinum holder in a Cahn TG 151 thermo gravknetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The results of these cycles are given in Table 38.
Table 38
Figure imgf000095_0002
Example 39 - SO, adsorption on zirconi n-aluminum oxides impregnated with copper nitrate Copper nitrate impregnated zkconium- aluminum oxide 7% CuO (253.65 mg) prepared as described in Example 38 (sample Zr02/Al203-1) was placed in a platinum holder in a Cahn TG 151 theimo gravimetric analyzer and adsoφtion/desoφtion cycles carried out as described in Example 4. The sulfur dioxide/oxygen mixture used in that experiment had the foUowing concentration: 1% S02, 6% 02, balance - hehum. The results of these cycles are given in Table 39. Figure 6 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (sohd line with filled diamonds). Table 39
Figure imgf000096_0001
Example 40 - Post-treating of co-particles prepared in Example 35 with NH.C1 solution
Co-particles, prepared as described in Example 35 were post-treated by ammonium chloride solutions as described in Table 40 at room temperature for approximately 1 min and then calcined at 400 °C for 1 hour. Table 40
Figure imgf000096_0002
Example 41 - SO, adsorption on silica impregnated with copper nitrate and post-treated by ammonium chloride
Copper nitrate impregnated sUica 7% CuO (256.29 mg ) prepared as described in Example 35 and post-treated as described in Example 40 (sample Si02-l-O) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles were carried out as described in Example 4. The results of these cycles are given in Table 41. Figure 6 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (dashed line with open ckcles).
Table 41
Figure imgf000097_0001
Example 42 - SO, adsorption on magnesium oxide impregnated with copper nitrate and post-treated by ammonium chloride
Copper nitrate impregnated magnesium oxide 7% CuO (261.55 mg) prepared as described in Example 35 and post-treated as described in Example 40 (sample MgO -l-O) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles were carried out as described in Example 4. The results of these cycles are given in Table 42.
Table 42
Figure imgf000097_0002
Example 43 - SO, adsorption on titanium oxide impregnated with copper nitrate and post-treated by ammonium chloride
Copper nitrate impregnated titanium oxide 5.7% CuO (259.0 mg) prepared as described in Example 35 and post- treated as described in Example 40 (sample Ti02-l-O) was placed in a platinum holder in a Cahn TG 151 thermogravimetric analyzer and adsoφtion/desoφtion cycles were carried out as described in Example 4. The results of these cycles are given in Table 43.
Table 43
Figure imgf000098_0001
Example 44 - SO, adsorption on zirconium-aluminum oxides impregnated with copper nitrate and post-treated by ammonium chloride
Copper nitrate impregnated zkco um-aluminum oxide 7% CuO (257.47 mg) prepared as described in Example 35 and post-treated as described in Example 40 (sample Zr02/Al203-l-O) was placed in a platinum holder in a Cahn TG 151 thermogravknetric analyzer and adsoφtion/desoφtion cycles were carried out as described in Example 4. Sulfur dioxide/oxygen mixture used in that experiment had the foUowing concentration: 1% S02, 6% 02, balance - hehum. The results of these cycles are given in Table 44. Figure 6 is a plot of the weight % S02 uptake vs. time for the thkd adsoφtion cycle (sohd line with fiUed diamonds). Table 44
Figure imgf000098_0002
Example 45 - Treatment of co-particle 5HC1 with (NH,),SO,
A sample of composite particle 5HO prepared as described in Example 3, 10 g, was treated at room temperature for approximately 1 min with 10 g of an (NH4)2S04 solution prepared form 0.0412 g of (NH4)2S04 in 9.96 g of de- ionized water. The co-particles were calcined at 400 ° C for 1 hour.
Example 46 - Selective catalytic reduction of NO with ammonia over CuO/Al,O, co-particle 5HC1 post-treated with (NH,),SO,
A sample of copper oxide-alumina composite particles 5 % CuO (5.00 g, approximately 10 mL) prepared as described in Example 45 was placed in a fixed-bed quartz tube reactor. The sample was prepared and selective catalytic reduction experiment was carried out as described in Example 24. Table 46 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3:NO ratio that gives 5 ppm or less NH3 shp at selected temperatures. Figure 7 gives a plot of the 90 % NO conversion and 5 % ammonia shp NH3:NO ratios as a function of temperature.
Table 46
Figure imgf000099_0001
Example 47 - Selective catalytic reduction of NO with ammonia over CuO/ALO co-particle post treated with HCl and sulfated on a monolith
A ceramic monohth (1 inch long, 3A inches OD, 400 ceUs per square inch) was coated with a finely ground sample of copper oxide-alumina composite particles, 5 % CuO prepared with HOAc as binding acid as described in Example 23 and post-treated with HCl as described in Example 10 (sample # HOAc-HCl-7) and sulfated as described in Example 29 with S02 and 02 in He. The catalyst loading was 1.84 g after several apphcation/drying cycles. The monohth was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24. Table 47 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3: NO ratio that gives 5 ppm or less NH3 shp at selected temperatures. Figure 8 gives a plot of the 90 % NO conversion and 5 % ammonia shp NH3:NO ratios as a function of temperature.
Table 47
Figure imgf000100_0001
Example 48 - Selective catalytic reduction of NO with ammonia over alumina impregnated with Cu(NO,,)„ calcined, and post-treated with sulfur dioxide
The copper nitrate impregnated and calcined alumina sample CuN03-2 (5.00 g, approximately 10 mL) prepared as described in Example 18 and post- treated with S02 as described in Example 29 was placed in a fixed-bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and the 5 % ammonia shp ratio as a function of temperature were mapped. Table 48 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3:NO ratio that gives 5 ppm or less NH3 shp at a selected temperatures. Figure 9 plots the 90 % NO conversion ration and 5 % ammonia shp ratio as a function of temperature.
Table 48
Figure imgf000101_0001
Example 49 - Treatment of sample # CuNO^-2 with ammomum chloride
A sample of material CuN03-2 (Table 18, Example 18), 5.0 g, was treated at room temperature for approximately one minute with 2.65 g of ammonium chloride solution prepared from 0.253 g of NH4C1 dissolved in 9.75 g water, and then calcined at 400 C for 1 hour to give sample CuN03-2-O Example 50 - Selective catalytic reduction of NO with ammonia over alumina impregnated with Cu(NOc),, calcined, and post-treated with N E C1 and sulfur dioxide
A sample of copper nitrate impregnated and calcined alumina, sample CuN03-2-O (5.00 g, approximately 10 cc) prepared as described in Example 49, and post- treated with S02 as described in Example 29 was placed in a fixed- bed quartz tube reactor. The sample was prepared and the selective catalytic reduction experiment was carried out as described in Example 24 with the exception that the 90 % NO conversion ratio and 5 % ammonia shp ratio as a function of temperature were mapped. Table 50 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3:NO ratio that gives 5 ppm or less NH3 shp at selected temperatures. Figure 10 plots the 90 % NO conversion ration and the 5 % ammonia shp ratio as a function temperature.
Table 50
Figure imgf000102_0001
Example 51-Selective catalytic reduction of NO with ammonia over vanadium-titanium catalyst
Powdered vanadium oxide supported on titanium oxide, anatase type, was prepared as described in US Patent No. 5,696,046 to Ikeyama et al. The vanadium oxide/titanium oxide catalysts was apphed as a wash-coat on to a ceramic monohth (1 inch long, 3A inches OD, 400 ceUs per square inch). A catalyst loading of 2.0 g was achieved after several appUcation/drying cycles. The monohth was placed in a fixed-bed quartz tube reactor and the sample was prepared and selective catalytic reduction was carried out as described in Example 24. Table 51 gives the minimum NH3:NO ratio necessary to give 90 % or greater NO conversion, and the maximum NH3:NO ratio that gives 5 ppm or less NH3 shp at a selected temperatures in the range 200-450° C. Figure 11 gives a plot of the 90 % NO conversion and 5 % ammonia shp as a function temperature for this vanadium oxide/titanium oxide catalyst (sohd lines). For comparison, this figure include a plot of the 90 % NO conversion and 5 % ammonia shp as a function temperature for a monohth coated with CuO/Al203 and post-treated with HCl and sulfur dioxide (Example 47 - dashed lines).
Table 51
Figure imgf000103_0001
Throughout this apphcation, various pubhcations are referenced. The disclosures of these pubhcations in thek entketies are hereby incoφorated by reference into this apphcation in order to more fuUy describe the state of the art to which this invention pertains.
It wUl be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spkit of the invention. Other embodiments of the invention wUl be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only.

Claims

What is claimed:
2. A process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(b) admixing a support with (i) an adsorbent and/or catalyst compound and/or (h) an adsorbent and/or catalyst precursor to produce a mixture;
(c) contacting the mixture produced in step (a) with a hahde agent to produce a halide/adsorbent and/or catalyst/support composition; and
(d) contacting the composition produced in step (b) with an oxoanion agent,
wherein the product produced in step (a), (b), and/or (c) is heated at from 20°C to 1,800 °C.
2. The process of claim 1, wherein the support comprises a metal oxide.
3. The process of claim 1, wherein the support comprises a metal oxide, and the metal oxide comprises A1203,
Figure imgf000105_0001
Ti02, CuO, CujO, V205, Si02, Mn02, Mn203, Mn304, ZnO, MgO, Zr02, Th02, Fe203, Fe304, or combination thereof.
4. The process of claim 1, wherein the support comprises a binder system produced by the steps comprising
(I) mixing components comprising (a) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide,
(b) an oxide adsorbent and/or catalyst particle, and
(c) an acid, and
(II) removing a sufficient amount of water from the mixture to crosslink the binder with itself and/or the oxide adsorbent and/or catalyst particle.
5. The process of claim 1 , wherein the support comprises a zeohte.
6. The process of claim 1, wherein the support comprises a ceramic, cordierite, metal, or a combination thereof.
7. The process of claim 1, wherein the support comprises a ceramic monohth.
8. The process of claim 1 , wherein the adsorbent and/or catalyst compound or adsorbent and/or catalyst precursor comprises JA1203, GajOg, Ti02, CuO, CuA V205, Si02, Mn02, Mn203, Mn304, ZnO, W02, W03, Re207, As203, As205, MgO, Th02, Ag20, AgO, CdO, Sn02, PbO, FeO, Fe203, Fe304, Rn s, RuO, Os04, Sb203, CoO, Co203, NiO, zeohte, or a combination thereof.
9. The process of claim 1, wherein the adsorbent and/or catalyst compound or adsorbent and/or catalyst precursor comprises a copper compound, and the copper compound comprises Cu(N03)2, Cu(N03)2-XH20, CuC03, CuS04, CuCl2, CuBr2, Cul2, Cul, CuO, C jO, Cu(OAc)2, copper aceto acetonate, copper gluconate, copper benzonate, copper oxalate, or a combination thereof.
10. The process of claim 1, wherein the hahde agent comprises a chloride compound, a bromide compound, an iodide compound, or a mixture thereof.
11. The process of claim 1, wherein the hahde agent comprises HCl, LiQ, NaCI, KCl, RbCl, CsCl, BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, A1C13, NH4C1, quaternary alkyl ammonium chloride, a chloride salt of a group I, II or III metal, a chloride salt of a transition metal, or a combination thereof.
12. The process of claim 1, wherein the oxoanion agent is an oxoacid or the salt thereof, wherein the oxoacid has the formula HπXOm, wherein n is from 1 to 3, m is from 1 to 4, and X is a non-metallic element.
13. The process of claim 1, wherein the oxoanion agent is a sulfating agent.
14. The process of claim 13, wherein the sulfating agent comprises (i) S02 and 02 at from 100°C to 800°C or (h) S02 and ak at from 100 °C to 800 °C.
15. The process of claim 13, wherein the sulfating agent comprises ammonium sulfate, a group I metal sulfate, a group II metal sulfate, a group III metal sulfate, or a mixture thereof.
16. The process of claim 1, wherein after step (a) a heating step is performed.
17. The process of claim 1, wherein after step (b) a heating step is performed.
18. The process of claim 1, wherein a heating step is performed after steps (a), (b), and (c).
19. A process for producing a composition containing an adsorbent and/or catalyst compound, comprising:
(a) admixing a support with a copper compound to produce a mixture;
(b) contacting the mixture produced in step (a) with a hahde agent to produce a hahde/adsorbent and/or catalyst/support composition; and
(c) contacting the composition produced in step (b) with an oxoanion agent,
wherein the product produced in step (a), (b), and/or (c) is heated at from 20 °C to 1,800 °C.
20. The process of claim 19, wherein the support comprises a metal oxide.
21. The process of claim 19, wherein the support comprises a metal oxide, and the metal oxide comprises A1203, Ga^, Ti02, CuO, Cu^O, V205, Si02, Mn02, Mn203, Mn304, ZnO, MgO, Zr02, Th02, Fe203, Fe304, or combination thereof.
22. The process of claim 19, wherein the support comprises a binder system produced by the steps comprising
(I) mixing components comprising
(a) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide,
(b) an oxide adsorbent and/or catalyst particle, and
(c) an acid, and
(II) removing a sufficient amount of water from the mixture to crosslink the binder with itself and/or the oxide adsorbent and/or catalyst particle.
23. The process of claim 19, wherein the support comprises a zeohte.
24. The process of clakn 19, wherein the support comprises a ceramic, cordierite, metal, or a combination thereof.
25. The process of claim 19, wherein the support comprises a ceramic monohth.
26. The process of claim 19, wherein the copper compound comprises Cu(N03)2, Cu(N03)2-XH20, CuC03, CuS04, CuCl2, CuBr2, Cul2, Cul, CuO, CUjO, Cu(OAc)2, copper aceto acetonate, copper gluconate, copper benzonate, copper oxalate, or a combination thereof.
27. The process of claim 19, wherem the hahde agent comprises a chloride compound, a bromide compound, an iodide compound, or a mixture thereof.
28. The process of claim 19, wherein the hahde agent comprises HCl, LiQ, NaCI, KCl, RbCl, CsCl, BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, A1C13, NH4Q, quaternary alkyl ammomum chloride, a chloride salt of a group I, II or III metal, a chloride salt of a transition metal, or a combination thereof.
29. The process of claim 19, wherein the oxoanion agent is an oxoacid or the salt thereof, wherein the oxoacid has the formula BLXOm, wherein n is from 1 to 3, m is from 1 to 4, and X is a non-metallic element.
30. The process of claim 19, wherein the oxoanion agent is a sulfating agent.
31. The process of claim 30, wherein the sulfating agent comprises (i) S02 and 02 at from 100 °C to 800 °C or (h) S02 and ak at from 100 °C to 800 °C.
32. The process of claim 30, wherein the sulfating agent comprises ammonium sulfate, a group I metal sulfate, a group II metal sulfate, a group III metal sulfate, or a mixture thereof.
33. The process of claim 19, wherein after step (a) a heating step is performed.
34. The process of claim 19, wherein after step (b) a heating step is performed.
35. The process of claim 19, wherem a heatmg step is perlormed after steps (a), (b), and (c).
36. The process of claim 19, wherein the support is aluminum oxide, the adsorbent and/or catalyst compound or precursor is Cu(N03)2-XH20, the hahde agent is NH4C1, and the oxoanion agent is S02in ak or oxygen.
37. The adsorbent and/or catalyst compound produced by the process of claim 1.
38. The adsorbent and/or catalyst compound produced by the process of claim 19.
39. The adsorbent and/or catalyst compound produced by the process of claim 36.
40. A method for reducing or eliminating the amount of sulfur oxide from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst compound produced by the steps comprising:
(a) admixing a support with (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture; and
(b) contacting the mixture produced in step (a) with a hahde agent to produce a halide/adsorbent and/or catalyst/support composition,
wherein the mixture produced in steps (a) and/or (b) is heated at from 20 °C to 1,800 °C. ill
41. The method of claim 40, further comprising alter step (b), contactmg the halide/adsorbent and/or catalyst/support composition with an oxoanion agent.
42. The method of claim 40, wherein the sulfur oxide comprises S02, SOs, SCO, or combination thereof.
43. The method of claim 40, wherein the support is aluminum oxide, the adsorbent and/or catalyst compound is Cu(N03)2»XH20, and the hahde agent is NH4C1.
44. The method of claim 43, wherein after the contacting step (b), regenerating the halide/adsorbent and/or catalyst/support composition comprising contacting the hahde/adsorbent and/or catalyst/support composition with a reducing agent and then an oxidizing agent.
45. The method of claim 40, wherein after the contacting step (b), regenerating the hahde/adsorbent and/or catalyst/support composition comprising contacting the hahde/adsorbent and/or catalyst/support composition with a reducing agent and then an oxidizing agent.
46. A method for reducing or ejhminating the amount of nitrogen oxide from an envkonment, comprising (I) contacting the envkonment with an adsorbent and/or catalyst compound produced by the steps comprising:
(a) admixing a support with (i) an adsorbent and/or catalyst compound and/or (ii) an adsorbent and/or catalyst precursor to produce a mixture; and (b) contacting the mixture produced m step (a) witri a halide agent to produce a hahde/adsorbent and/or catalyst/support composition,
wherein the mixture produced in steps (a) and/or (b) is heated at from 20 °C to 1,800 °C,
(II) in the presence of a reducing gas.
47. The method of claim 46, further comprising after step (b), contacting the hahde/adsorbent and/or catalyst/support composition with an oxoanion agent.
48. The method of claim 46, wherein the nitrogen oxide comprises NO, N02, N204, N205, N20, or combination thereof.
49. The method of claim 46, wherein the reducing gas comprises ammonia, hydrogen, carbon monoxide, diesel fuel, refinery gas, kerosene, an olefin, a paraffin, urea, cyanuric acid, ammonium sulfate, an organic amine, an alcohol, a hydrocarbon, a partiaUy combusted hydrocarbon, exhaust gas, or a mixture thereof.
50. The method of claim 49, wherein the hydrocarbon comprises methane, ethane, propane, isobutane, or a mixture thereof.
51. The method of claim 46, wherein the support is duminum oxide, the adsorbent and/or catalyst compound or precursor is Cu(N03)2-XH20, the hahde agent is NH4C1, the oxoanion agent is S02in ak or oxygen, and the reducing gas is NH3.
52. A process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor and/or an adsorbent and/or catalyst precursor,
(hi) a support; and
(iv) an acid,
(b) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (ii) and/or (hi); and
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a hahde/adsorbent and/or catalyst and binder system;
wherein the product produced in step (a), (b), and/or (c) is heated at from 20 °C to 1,800 °C.
53. The process of claim 52, further comprising after step (c) admixing the hahde/adsorbent and/or catalyst and binder system with an oxoanion agent.
54. The process of claim 53, wherem the oxo nion agent is an oxoacid or the salt thereof, wherein the oxoacid has the formula FLXOm, wherein n is from 1 to 3, m is from 1 to 4, and X is a non-metaUic element.
55. The process of claim 53, wherein the oxoanion agent is a sulfating agent.
56. The process of claim 55, wherein the sulfating agent comprises (i) S02 and 02 or (h) S02 and ak.
57. The process of claim 55, wherein the sulfating agent comprises ammonium sulfate, a group I metal sulfate, a group II metal sulfate, a group III metal sulfate, or a mixture thereof.
58. The process of claim 52, wherein after step (a) a heating step is performed.
59. The process of claim 52, wherein after step (b) a heating step is performed.
60. The process of claim 52, wherein a heating step is performed after steps (a), (b), and (c).
61. The process of claim 52, wherein the support comprises a metal oxide.
62. The process of claim 52, wherein the support comprises a zeohte.
63. The process of claim 52, wherein the support comprises a ceramic.
64. The process of claim 52, wherein the support comprises a ceramic monohth
65. The process of claim 52, wherein the support comprises a metal oxide, and the metal oxide comprises A1203, Ga^, Ti02, CuO, C^O, V205, Si02, Mn02, Mn203, Mn304, ZnO, MgO, Th02, Zr02, Fe203, Fe304or combination thereof.
66. The process of claim 52, wherein the binder comprises coUoidal aluminum oxide or coUoidal silicon dioxide.
67. The process of claim 52, wherein the adsorbent and/or catalyst compound or adsorbent and/or catalyst precursor comprises A1203, GaA, Ti02, CuO, Cu^O, V205, Si02, Mn02, Mn203, Mn304, ZnO, W02, W03, Re207, As203, As205, MgO, Th02, Ag20, AgO, CdO, Sn02, PbO, FeO, Fe203, Fe304, Ru^, RuO, Os04, Sb203, CoO, Co203, NiO, zeohte, or a combination thereof.
68. The process of claim 52, wherein the adsorbent and/or catalyst compound or adsorbent and/or catalyst precursor comprises a copper compound, and the copper compound comprises Cu(N03)2, Cu(N03)2- XH20, CuC03, CuS04, CuCl2, CuBr2, Cul2, Cul, CuO, Cu20, Cu(OAc)2, copper aceto acetonate, copper gluconate, copper benzonate, copper oxalate, or a combination thereof.
69. The process of claim 52, wherein the hahde agent comprises a chloride compound, a bromide compound, an iodide compound, or a mixture thereof.
70. The process of claim 52, wherein the hahde agent comprises HCl, LiCl, NaCI, KCl, RbCl, CsCl, BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, A1C13, NH4C1, quaternary ammonium chloride, a chloride salt of a group I, II or III metal, a chloride salt of a transition metal, or a combination thereof.
71. The process of claim 52, wherein the acid comprises hydrochloric acid, nitric acid, acetic acid ammonium chloride, or a combination thereof.
72. A process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising coUoidal aluminum oxide or coUoidal silicon dioxide,
(h) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor and/or an adsorbent and/or catalyst precursor comprising a copper compound;
(hi) a support comprising aluminum oxide; and
(iv) an acid,
(b) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (h) and/or (ih);and
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a hahde/adsorbent and/or catalyst and binder system; wherein the product produced m step (b) and/or (c) is heated at from 20 °C to 1,800 °C.
73. The method of claim 72, further comprising after step (c), contacting the hahde/adsorbent and/or catalyst/support composition with an oxoanion agent.
74. A process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor and/or an adsorbent and/or catalyst precursor,
(hi) a support; and
(iv) a base,
(b) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (ii) and/or (hi); and
(c) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a hahde/adsorbent and/or catalyst and binder system; wherein the product produced m step (b) and/or (c) is heated at from 20 °C to 1,800 °C.
75. The method of claim 74, further comprising after step (c), contacting the hahde/adsorbent and/or catalyst/support composition with an oxoanion agent.
76. A process for producing a composition containing an adsorbent and/or. catalyst compound comprising:
(a) mixing components comprising
(i) a binder comprising a coUoidal metal oxide or coUoidal metalloid oxide,
(h) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a calcined, metal oxide particle that was produced by calcining the particle temperature of from 300 °C to 700° C, then treating the calcined particle with an acid for a sufficient time to increase the adsorbent properties of the particle;
(hi) water,
(a) removing a sufficient amount of water from the mixture to crosslink the binder with itself or with component (ii);
(b) contacting the adsorbent and/or catalyst and binder system produced in step (b) with a hahde agent to produce a hahde/adsorbent and/or catalyst and binder system; wherein the product produced in step (b) and/or (c) is heated at from 20 °C to 1,800 °C.
77. The method of claim 76, further comprising after step (b), contacting the hahde/adsorbent and/or catalyst/support composition with an oxoanion agent.
78. A process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a support;
(ii) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide;
(hi) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(iv) HCl or NH4C1;
(b) removing a sufficient amount of water to cross-link the binder with itself, the support, and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition; and
(c) heating the product produced in step (b) from 20 °C to 1,800 °C.
79. The method of claim 78, lurtrier compnsmg alter step (c), contactmg trie hahde/adsorbent and/or catalyst/support composition with an oxoanion agent.
80. The adsorbent and/or catalyst compound produced by the process of claim 52.
81. The adsorbent and/or catalyst compound produced by the process of claim 72.
82. The adsorbent and/or catalyst compound produced by the process of claim 74.
83. The adsorbent and/or catalyst compound produced by the process of claim 76.
84. The adsorbent and/or catalyst compound produced by the process of claim 78.
85. A method for reducing or eliminating the amount of sulfur oxide from an envkonment, comprising contacting the envkonment with the adsorbent and/or catalyst compound produced by process of claim 52.
86.. The method of claim 85, wherein after the contacting step, regenerating the adsorbent and/or catalyst compound comprising contacting the adsorbent and/or catalyst compound with a reducing agent and then an oxidizing agent.
87. A method for reducing or ehmmatmg the amount ot sulfur oxide from an envkonment, comprising contacting the envkonment with the adsorbent and/or catalyst compound produced by process of claim 72.
88. The method of claim 87, wherein after the contacting step, regenerating the adsorbent and/or catalyst compound comprising contacting the adsorbent and/or catalyst compound with a reducing agent and then an oxidizing agent.
89. A method for reducing or eliminating the amount of sulfur oxide from an envkonment, comprising contacting the envkonment with the adsorbent and/or catalyst compound produced by process of claim 74.
90. The method of claim 89, wherein after the contacting step, regenerating the adsorbent and/or catalyst compound comprising contacting the adsorbent and/or catalyst compound with a reducing agent and then an oxidizing agent.
91. A method for reducing or eliminating the amount of sulfur oxide from an envkonment, comprising contacting the envkonment with the adsorbent and/or catalyst compound produced by process of claim 76.
92. The method of claim 91 , wherein after the contacting step, regenerating the adsorbent and/or catalyst compound comprising contacting the adsorbent and/or catalyst compound with a reducing agent and then an oxidizing agent.
93. A method for reducing or eliminating the amount of sulfur oxide from an envkonment, comprising contacting the envkonment with the adsorbent and/or catalyst compound produced by process of claim 78.
94. The method of claim 93, wherein after the contacting step, regenerating the adsorbent and/or catalyst compound comprising contacting the adsorbent and/or catalyst compound with a reducing agent and then an oxidizing agent.
95. A method for reducing or eliminating the amount of nitrogen oxide from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst compound produced by the process in claim 52 in the presence of a reducing agent.
96. A method for reducing or eliminating the amount of nitrogen oxide from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst compound produced by the process in claim 72 in the presence of a reducing agent.
97. A method for reducing or ehminating the amount of nitrogen oxide from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst compound produced by the process in claim 74 in the presence of a reducing agent.
98. A method for reducing or eliminating the amount of nitrogen oxide from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst compound produced by the process in claim 76 in the presence of a reducing agent.
99. A method for reducing or eliminating the amount of nitrogen oxide from an envkonment, comprising contacting the envkonment with an adsorbent and/or catalyst compound produced by the process in claim 78 in the presence of a reducing agent.
100. An adsorbent and/or catalyst and bmder system compnsmg (1) a bmder that has been cross-hhked with itself and/or at least one type of an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor and (2) at least one hahde ion.
101. An adsorbent and/or catalyst and binder system comprising (1) a binder that has been cross-linked with itself and/or at least one type of an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor; (2) at least one hahde ion; and (3) at least one oxoanion.
102. An adsorbent and/or catalyst system comprising a support, an adsorbent and/or catalyst compound and/or an adsorbent and/or catalyst precursor, a hahde ion, and an oxoanion.
103. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 1.
104. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 19.
105. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 36.
106. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 52.
107. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 72.
108. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 74.
109. A monohth compriskig the adsorbent and/or catalyst compound produced by the process of claim 76.
110. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 78.
111. A process for producing a composition containing an adsorbent and/or catalyst compound comprising:
(a) admixing components comprising:
(i) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide;
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor; and
(hi) a base; and
(a) removing a sufficient amount of water to cross-link the binder with itself and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition.
112. A process for producing a composition containing an adsorbent and/or catalyst compound comprising: (a) mixing components comprising
(i) a binder comprising a coUoidal metal oxide or coUoidal metaUoid oxide,
(ii) (1) an adsorbent and/or catalyst compound and/or (2) an adsorbent and/or catalyst precursor comprising a calcined, metal oxide particle that was produced by calcining the particle temperature of from 300 °C to 700° C, then treating the calcined particle with an acid for a sufficient time to increase the adsorbent properties of the particle, and
(hi) water, and
(b) removing a sufficient amount of water to cross-link the binder with itself and/or the adsorbent and/or catalyst compound or the adsorbent and/or catalyst precursor to produce a binder/adsorbent and/or catalyst composition.
113. The adsorbent and/or catalyst compound produced by the process of claim 111.
114. The adsorbent and/or catalyst compound produced by the process of claim 112.
115. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 111. A monohth comprising the adsorbent and/or catalyst compound produced by the process of claim 112.
PCT/US2001/026737 2000-08-25 2001-08-27 Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof WO2002016026A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001286831A AU2001286831A1 (en) 2000-08-25 2001-08-27 Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US22780600P 2000-08-25 2000-08-25
US60/227,806 2000-08-25
US71554200A 2000-11-17 2000-11-17
US09/715,542 2000-11-17

Publications (2)

Publication Number Publication Date
WO2002016026A2 true WO2002016026A2 (en) 2002-02-28
WO2002016026A3 WO2002016026A3 (en) 2004-02-26

Family

ID=26921778

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/026737 WO2002016026A2 (en) 2000-08-25 2001-08-27 Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof

Country Status (2)

Country Link
AU (1) AU2001286831A1 (en)
WO (1) WO2002016026A2 (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1754050A2 (en) * 2004-05-26 2007-02-21 Ceramatec, Inc. NOx GAS SENSOR METHOD AND DEVICE
WO2008037255A1 (en) * 2006-09-25 2008-04-03 Technical University Of Denmark Alkali resistant catalyst
CN102728300A (en) * 2012-06-18 2012-10-17 中国科学院生态环境研究中心 MnO2-doped composite magnetic nanometer adsorbent, its preparation method and its application
CN103285803A (en) * 2013-07-03 2013-09-11 西北师范大学 Method of preparing porous CdO absorbent through thermal decomposition and application of porous CdO absorbent in wastewater treatment
WO2013149241A1 (en) * 2012-03-30 2013-10-03 Fuel Tech, Inc. Dry processes, apparatus, compositions and systems for reducing sulfur oxides and hci
CN103599751A (en) * 2013-10-25 2014-02-26 浙江大学 Preparation method of thiol-functionalized magnetic silica nano-material
CN104437514A (en) * 2014-12-28 2015-03-25 桂林理工大学 Visible light responded photocatalyst Co3ZnFeSbO8 and preparation method thereof
CN104624203A (en) * 2015-01-31 2015-05-20 大连理工大学 Pb modified Co oxide matrix N2O decomposition catalyst as well as preparation method and application of catalyst
US9289721B2 (en) 2013-02-27 2016-03-22 Fuel Tech, Inc. Process and apparatus for improving the operation of wet scrubbers
CN105688821A (en) * 2016-01-22 2016-06-22 昆明理工大学 Preparation method and application of modified superparamagnetic Fe3O4 nanoparticle
US9393518B2 (en) 2013-02-27 2016-07-19 Fuel Tech, Inc. Processes, apparatus, compositions and systems for reducing emissions of HCI and/or sulfur oxides
US9399597B2 (en) 2013-04-01 2016-07-26 Fuel Tech, Inc. Ash compositions recovered from coal combustion gases having reduced emissions of HCI and/or mercury
CN105964282A (en) * 2016-06-23 2016-09-28 淮北师范大学 Method for preparing CuI-Fe3O4 magnetic nanocomposite through one-pot ball-milling solid phase method
CN106140205A (en) * 2016-06-23 2016-11-23 淮北师范大学 The method that one pot of ball milling solid phase method prepares CuI stannic oxide/graphene nano composite
CN106390910A (en) * 2016-12-02 2017-02-15 中国工程物理研究院核物理与化学研究所 Preparation method of bifunctional Ag20/niobate composite adsorption material and application thereof
CN106823772A (en) * 2017-04-12 2017-06-13 湖南云平环保科技有限公司 Desulfuration in furnace synergist and desulfurizing agent
US9718025B2 (en) 2013-04-01 2017-08-01 Fuel Tech, Inc. Reducing hydrochloric acid in cement kilns
US9802154B2 (en) 2012-03-30 2017-10-31 Fuel Tech, Inc. Process for sulfur dioxide, hydrochloric acid and mercury mediation
CN108993501A (en) * 2018-08-09 2018-12-14 苏州汉力新材料有限公司 A kind of silver-silver oxide-zinc oxide photocatalysis material preparation method
CN109675582A (en) * 2018-12-25 2019-04-26 西安近代化学研究所 A kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof
US20190184369A1 (en) * 2017-12-20 2019-06-20 Uop Llc Enhancement of reduction resistance for manganese oxide adsorbents
CN110385141A (en) * 2018-04-20 2019-10-29 武汉大学 A kind of composite catalyst and preparation method thereof for the direct preparing aromatic hydrocarbon of synthesis gas
CN110841699A (en) * 2019-10-22 2020-02-28 中国石油天然气股份有限公司 Photocatalyst for improving volatile organic compound treatment efficiency and preparation method thereof
CN110935422A (en) * 2019-12-18 2020-03-31 华能山东发电有限公司 Process for enriching heavy metals in desulfurization wastewater based on high-stability adsorbent
CN112467270A (en) * 2020-11-03 2021-03-09 浙江锋锂新能源科技有限公司 Composite air suction element, preparation method thereof and flatulence-preventing self-repairing soft-package lithium battery
CN112452328A (en) * 2020-11-06 2021-03-09 上海簇睿低碳能源技术有限公司 NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103578594B (en) * 2013-10-30 2016-06-29 清华大学 A kind of use nanometer Fe3O4-CeO2The method of radionuclide removed by material
CN110616456B (en) * 2019-10-23 2021-05-04 南京大学 Preparation method of high-quality kappa-phase gallium oxide epitaxial film

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1089716A (en) * 1964-09-14 1967-11-08 Shell Internationale Res Matts Process for the removal of sulphur dioxide from gas mixtures and redox catalysts for use in this process
US3663453A (en) * 1970-04-20 1972-05-16 Phillips Petroleum Co Skeletal isomerization of olefins over halogen-containing zirconia catalyst
US3957952A (en) * 1973-03-19 1976-05-18 Shell Oil Company High capacity sulfur oxide-acceptors and their preparation
US4521530A (en) * 1983-06-15 1985-06-04 Teledyne Industries, Inc., Teledyne Water Pik Catalyst of palladium, copper and nickel on a substrate
WO1991018667A1 (en) * 1990-06-08 1991-12-12 Michigan State University PROCESS USING SORBENTS FOR THE REMOVAL OF SOx FROM FLUE GAS AND OTHER GAS STREAMS
US5948726A (en) * 1994-12-07 1999-09-07 Project Earth Industries, Inc. Adsorbent and/or catalyst and binder system and method of making therefor
US6037307A (en) * 1998-07-10 2000-03-14 Goal Line Environmental Technologies Llc Catalyst/sorber for treating sulfur compound containing effluent
US6096936A (en) * 1998-08-14 2000-08-01 Idemitsu Kosan Co., Ltd. L-type zeolite catalyst
US6224840B1 (en) * 1997-09-04 2001-05-01 Korea Advanced Institute Of Science And Technology γ-Al2O3 sorbent impregnated with alkali salt and CuO

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1089716A (en) * 1964-09-14 1967-11-08 Shell Internationale Res Matts Process for the removal of sulphur dioxide from gas mixtures and redox catalysts for use in this process
US3663453A (en) * 1970-04-20 1972-05-16 Phillips Petroleum Co Skeletal isomerization of olefins over halogen-containing zirconia catalyst
US3957952A (en) * 1973-03-19 1976-05-18 Shell Oil Company High capacity sulfur oxide-acceptors and their preparation
US4521530A (en) * 1983-06-15 1985-06-04 Teledyne Industries, Inc., Teledyne Water Pik Catalyst of palladium, copper and nickel on a substrate
WO1991018667A1 (en) * 1990-06-08 1991-12-12 Michigan State University PROCESS USING SORBENTS FOR THE REMOVAL OF SOx FROM FLUE GAS AND OTHER GAS STREAMS
US5948726A (en) * 1994-12-07 1999-09-07 Project Earth Industries, Inc. Adsorbent and/or catalyst and binder system and method of making therefor
US6224840B1 (en) * 1997-09-04 2001-05-01 Korea Advanced Institute Of Science And Technology γ-Al2O3 sorbent impregnated with alkali salt and CuO
US6037307A (en) * 1998-07-10 2000-03-14 Goal Line Environmental Technologies Llc Catalyst/sorber for treating sulfur compound containing effluent
US6096936A (en) * 1998-08-14 2000-08-01 Idemitsu Kosan Co., Ltd. L-type zeolite catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SANG MUN JEONG: "Enhancement of the SO2 sorption capacity of CuO/y-Al2O3 sorbent by an alkali-salt promoter" INDUSTRIAL AND ENGINEERING CHEMISTRY RESEARCH, vol. 36, no. 12, December 1997 (1997-12), pages 5425-5431, XP002255406 Washington, DC, USA *

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1754050A2 (en) * 2004-05-26 2007-02-21 Ceramatec, Inc. NOx GAS SENSOR METHOD AND DEVICE
EP1754050A4 (en) * 2004-05-26 2011-05-18 Emisense Technologies Llc NOx GAS SENSOR METHOD AND DEVICE
WO2008037255A1 (en) * 2006-09-25 2008-04-03 Technical University Of Denmark Alkali resistant catalyst
EP1923135A1 (en) * 2006-09-25 2008-05-21 Technical University of Denmark Alkali resistent SCR catalysts
US7993617B2 (en) 2006-09-25 2011-08-09 Technical University Of Denmark Alkali resistant catalyst
AU2007302446B2 (en) * 2006-09-25 2012-02-16 Technical University Of Denmark Alkali resistant catalyst
US8916120B2 (en) 2012-03-30 2014-12-23 Fuel Tech, Inc. Dry processes, apparatus, compositions and systems for reducing sulfur oxides and HCI
WO2013149241A1 (en) * 2012-03-30 2013-10-03 Fuel Tech, Inc. Dry processes, apparatus, compositions and systems for reducing sulfur oxides and hci
US9802154B2 (en) 2012-03-30 2017-10-31 Fuel Tech, Inc. Process for sulfur dioxide, hydrochloric acid and mercury mediation
CN102728300A (en) * 2012-06-18 2012-10-17 中国科学院生态环境研究中心 MnO2-doped composite magnetic nanometer adsorbent, its preparation method and its application
CN102728300B (en) * 2012-06-18 2016-04-13 中国科学院生态环境研究中心 Compound magnetic nano adsorber of a kind of dopping manganese dioxide and preparation method thereof, application
US9289721B2 (en) 2013-02-27 2016-03-22 Fuel Tech, Inc. Process and apparatus for improving the operation of wet scrubbers
US9393518B2 (en) 2013-02-27 2016-07-19 Fuel Tech, Inc. Processes, apparatus, compositions and systems for reducing emissions of HCI and/or sulfur oxides
US9399597B2 (en) 2013-04-01 2016-07-26 Fuel Tech, Inc. Ash compositions recovered from coal combustion gases having reduced emissions of HCI and/or mercury
US9718025B2 (en) 2013-04-01 2017-08-01 Fuel Tech, Inc. Reducing hydrochloric acid in cement kilns
CN103285803A (en) * 2013-07-03 2013-09-11 西北师范大学 Method of preparing porous CdO absorbent through thermal decomposition and application of porous CdO absorbent in wastewater treatment
CN103599751A (en) * 2013-10-25 2014-02-26 浙江大学 Preparation method of thiol-functionalized magnetic silica nano-material
CN104437514A (en) * 2014-12-28 2015-03-25 桂林理工大学 Visible light responded photocatalyst Co3ZnFeSbO8 and preparation method thereof
CN104624203A (en) * 2015-01-31 2015-05-20 大连理工大学 Pb modified Co oxide matrix N2O decomposition catalyst as well as preparation method and application of catalyst
CN105688821A (en) * 2016-01-22 2016-06-22 昆明理工大学 Preparation method and application of modified superparamagnetic Fe3O4 nanoparticle
CN105688821B (en) * 2016-01-22 2018-04-06 昆明理工大学 A kind of preparation method and application of modified super-paramagnetic ferriferrous oxide nano particulate
CN106140205A (en) * 2016-06-23 2016-11-23 淮北师范大学 The method that one pot of ball milling solid phase method prepares CuI stannic oxide/graphene nano composite
CN105964282A (en) * 2016-06-23 2016-09-28 淮北师范大学 Method for preparing CuI-Fe3O4 magnetic nanocomposite through one-pot ball-milling solid phase method
CN106390910A (en) * 2016-12-02 2017-02-15 中国工程物理研究院核物理与化学研究所 Preparation method of bifunctional Ag20/niobate composite adsorption material and application thereof
CN106390910B (en) * 2016-12-02 2018-08-31 中国工程物理研究院核物理与化学研究所 A kind of preparation method and applications of difunctional Ag2O/ niobic acids composite adsorbing material
CN106823772A (en) * 2017-04-12 2017-06-13 湖南云平环保科技有限公司 Desulfuration in furnace synergist and desulfurizing agent
US11000821B2 (en) * 2017-12-20 2021-05-11 Uop Llc Enhancement of reduction resistance for manganese oxide adsorbents
US20190184369A1 (en) * 2017-12-20 2019-06-20 Uop Llc Enhancement of reduction resistance for manganese oxide adsorbents
WO2019126405A1 (en) 2017-12-20 2019-06-27 Uop Llc Enhancement of reduction resistance for manganese oxide adsorbents
US11938459B2 (en) 2017-12-20 2024-03-26 Uop Llc Enhancement of reduction resistance for manganese oxide adsorbents
EP3727676A4 (en) * 2017-12-20 2021-08-25 Uop Llc Enhancement of reduction resistance for manganese oxide adsorbents
CN110385141B (en) * 2018-04-20 2021-05-04 武汉大学 Composite catalyst for directly preparing aromatic hydrocarbon from synthesis gas and preparation method thereof
CN110385141A (en) * 2018-04-20 2019-10-29 武汉大学 A kind of composite catalyst and preparation method thereof for the direct preparing aromatic hydrocarbon of synthesis gas
CN108993501A (en) * 2018-08-09 2018-12-14 苏州汉力新材料有限公司 A kind of silver-silver oxide-zinc oxide photocatalysis material preparation method
CN109675582A (en) * 2018-12-25 2019-04-26 西安近代化学研究所 A kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof
CN110841699B (en) * 2019-10-22 2022-11-01 中国石油天然气股份有限公司 Photocatalyst for improving volatile organic compound treatment efficiency and preparation method thereof
CN110841699A (en) * 2019-10-22 2020-02-28 中国石油天然气股份有限公司 Photocatalyst for improving volatile organic compound treatment efficiency and preparation method thereof
CN110935422A (en) * 2019-12-18 2020-03-31 华能山东发电有限公司 Process for enriching heavy metals in desulfurization wastewater based on high-stability adsorbent
CN110935422B (en) * 2019-12-18 2022-03-29 华能山东发电有限公司 Process for enriching heavy metals in desulfurization wastewater based on high-stability adsorbent
CN112467270A (en) * 2020-11-03 2021-03-09 浙江锋锂新能源科技有限公司 Composite air suction element, preparation method thereof and flatulence-preventing self-repairing soft-package lithium battery
CN112452328A (en) * 2020-11-06 2021-03-09 上海簇睿低碳能源技术有限公司 NiO@SiO2Preparation method of @ CoAl-LDH multistage core-shell catalyst

Also Published As

Publication number Publication date
WO2002016026A3 (en) 2004-02-26
AU2001286831A1 (en) 2002-03-04

Similar Documents

Publication Publication Date Title
WO2002016026A2 (en) Adsorbent and/or catalyst compounds promoted with halide ions and methods of making and using thereof
AU728032B2 (en) Acid contacted enhanced adsorbent and/or catalyst and binder system
US6342191B1 (en) Anchored catalyst system and method of making and using thereof
US5948726A (en) Adsorbent and/or catalyst and binder system and method of making therefor
Tang et al. Complete oxidation of formaldehyde over Ag/MnOx–CeO2 catalysts
US7329359B2 (en) Application of catalysts for destruction of organic compounds in liquid media
EP1870158B1 (en) Transition metal-substituted hydrotalcite catalyst for removing nitrogen oxides from the exhaust gas of diesel engine by storage-reduction.
KR102580600B1 (en) Cerium- and zirconium-based mixed oxides
US20090221418A1 (en) Method for production of highly-active metal/metal oxide catalysts
EP2081681B1 (en) Process for preparing a sulfur tolerant alumina catalyst support
EP1832345A1 (en) Catalyst for exhaust gas purification
KR20010023631A (en) SOx ADDITIVE SYSTEMS BASED UPON USE OF MULTIPLE PARTICLE SPECIES
JP2007534477A (en) Catalyst for simultaneously removing carbon monoxide and hydrocarbons from oxygen-rich exhaust gas, and method for producing the same
CA2426315A1 (en) Catalyst for destruction of co, voc, and halogenated organic emissions
CN110678262A (en) Exhaust gas purifying oxidation catalyst structure, method for producing same, exhaust gas treatment device for automobile, catalyst molded body, and gas purifying method
EP0714693A1 (en) Exhaust gas cleaner and method for cleaning exhaust gas
Hou et al. The promotion effect of tungsten on monolith Pt/Ce 0.65 Zr 0.35 O 2 catalysts for the catalytic oxidation of toluene
US5795553A (en) Nitrogen oxide adsorbing material
CN109590021B (en) Sandwich-structured ammonia leakage catalyst and preparation method and application thereof
WO2002040149A2 (en) Acid contacted enhanced adsorbent particle, binder and oxide adsorbent and/or oxide catalyst system, and method of making and using therefor
JP2007252989A (en) Catalyst for carbon monoxide methanation and methanation method of carbon monoxide using the catalyst
Picasso et al. Preparation by co-precipitation of Ce–Mn based catalysts for combustion of n-hexane
JPH06315634A (en) Catalytic structure for nitrogen oxide catalytic reduction
US20010009884A1 (en) Adsorbent and/or catalyst and binder system and method of making and using therefor
CN1055957C (en) Hydrocarbon dearsoniumizer, its prepn. method and use in dearsoniumizing hydrocarbon

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)