WO2015195819A1 - Molecular sieve catalyst compositions, catalytic composites, systems, and methods - Google Patents

Molecular sieve catalyst compositions, catalytic composites, systems, and methods Download PDF

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Publication number
WO2015195819A1
WO2015195819A1 PCT/US2015/036255 US2015036255W WO2015195819A1 WO 2015195819 A1 WO2015195819 A1 WO 2015195819A1 US 2015036255 W US2015036255 W US 2015036255W WO 2015195819 A1 WO2015195819 A1 WO 2015195819A1
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WIPO (PCT)
Prior art keywords
scr catalyst
catalyst
molecular sieve
alumina
ammonia
Prior art date
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Ceased
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PCT/US2015/036255
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English (en)
French (fr)
Inventor
Xiaofan Yang
John K. Hochmuth
Wen-Mei Xue
Xiaoming Wang
Matthew Tyler Caudle
Ahmad Moini
Dustin O. HOLLOBAUGH
Qi Fu
Michael Breen
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BASF Corp
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BASF Corp
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Publication date
Priority claimed from US14/687,097 external-priority patent/US9889437B2/en
Priority to JP2016573737A priority Critical patent/JP6615794B2/ja
Priority to EP15808974.8A priority patent/EP3157671A4/en
Priority to CA2952437A priority patent/CA2952437C/en
Priority to RU2017101429A priority patent/RU2727801C2/ru
Priority to CN201580043934.6A priority patent/CN106660021B/zh
Application filed by BASF Corp filed Critical BASF Corp
Priority to MX2016016920A priority patent/MX2016016920A/es
Priority to BR112016029733A priority patent/BR112016029733B8/pt
Priority to KR1020177001106A priority patent/KR102436905B1/ko
Publication of WO2015195819A1 publication Critical patent/WO2015195819A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Definitions

  • Catalysts employed in the SCR process ideally should be able to retain good catalytic activity over the wide range of temperature conditions of use, for example, 200 °C to 600 °C or higher, under hydrothermal conditions. Hydrothermal conditions are often encountered in practice, such as during the regeneration of a soot filter, a component of the exhaust gas treatment system used for the removal of particles.
  • zeolite having these properties is chabazite (CHA), which is a small pore zeolite with 8 member-ring pore openings (-3.8 Angstroms) accessible through its 3 -dimensional porosity.
  • CHA chabazite
  • a cage like structure results from the connection of double six-ring building units by 4 rings.
  • Metal-promoted zeolite catalysts including, among others, iron-promoted and copper-promoted zeolite catalysts, for the selective catalytic reduction of nitrogen oxides with ammonia are known.
  • Iron-promoted zeolite beta has been an effective commercial catalyst for the selective reduction of nitrogen oxides with ammonia.
  • hydrothermal conditions for example exhibited during the regeneration of a soot filter with temperatures locally exceeding 700 °C, the activity of many metal-promoted zeolites begins to decline. This decline is often attributed to dealumination of the zeolite and the consequent loss of metal-containing active centers within the zeolite.
  • a first aspect of the invention is directed to a selective catalytic reduction (SCR) material.
  • a selective catalytic reduction material comprises a spherical particle including an agglomeration of crystals of a molecular sieve, wherein the spherical particle has a median particle size in the range of about 0.5 to about 5 microns.
  • the SCR catalyst material of the first through third embodiments is modified, wherein the molecular sieve has a structure type selected from AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT, and SAV.
  • the SCR catalyst material of the first through fourth embodiments is modified, wherein the molecular sieve has a structure type selected from AEI, CHA, and AFX.
  • the SCR catalyst material of the first through fifth embodiments wherein the molecular sieve has the CHA structure type.
  • the SCR catalyst material of the first through sixth embodiments is modified, wherein the molecular sieve having the CHA structure type is selected from an aluminosilicate zeolite, a borosilicate, a gallosilicate, a SAPO, an A1PO, a MeAPSO, and a MeAPO.
  • the SCR catalyst material of the first through eighth embodiments is modified, wherein the molecular sieve is selected from SSZ-13 and SSZ-62.
  • the SCR catalyst material of the first through ninth embodiments is modified, wherein the molecular sieve is promoted with a metal selected from Cu, Fe, Co, Ni, La, Ce, Mn, V, Ag, and combinations thereof.
  • the SCR catalyst material of the first through tenth embodiments is modified, wherein the molecular sieve is promoted with a metal selected from Cu, Fe, and combinations thereof.
  • the SCR catalyst material of the first through eleventh embodiments is modified, wherein the SCR catalyst material is effective to catalyze the selective catalytic reduction of nitrogen oxides in the presence of a reductant at temperatures between 200 °C and 600 °C.
  • the SCR catalyst material of the tenth and eleventh embodiments is modified, wherein the metal is present in an amount in the range of about 0.1 to about 10 wt. % on an oxide basis.
  • the SCR catalyst material of the first through fifteenth embodiments is modified, wherein the crystals have a crystal size in the range of about 1 to about 250 nm.
  • the SCR catalyst material of the first through sixteenth embodiments is modified, wherein the crystals have a crystal size in the range of about 100 to about 250 nm.
  • the SCR catalyst material of the first through seventeenth embodiments is modified, wherein the SCR catalyst material is in the form of a washcoat.
  • the SCR catalyst material of the eighteenth embodiment is modified, wherein the washcoat is a layer deposited on a substrate.
  • the SCR catalyst material of nineteenth embodiment is modified, wherein the substrate comprises a filter.
  • the SCR catalyst material of the twentieth embodiment is modified, wherein the filter is a wall flow filter.
  • the SCR catalyst material of the twentieth embodiment is modified, wherein the filter is a flow through filter.
  • the SCR catalyst material of the first through twenty-second embodiments is modified, wherein at least 80% of the spherical particles have a median particle size in the range of 0.5 to 2.5 microns.
  • the SCR catalyst material of the first through twenty-third embodiments is modified, wherein the molecular sieve comprises a zeolitic framework material of silicon and aluminum atoms, wherein a fraction of the silicon atoms are isomorphously substituted with a tetravalent metal.
  • the SCR catalyst material of the twenty-fourth embodiment is modified, wherein the molecular sieve is promoted with a metal selected from Cu, Fe, Co, Ni, La, Ce, Mn, V, Ag, and combinations thereof.
  • the SCR catalyst material of the twenty-twenty fourth and twenty-fifth embodiments is modified, wherein the tetravelent metal comprises a tetravalent transition metal.
  • the SCR catalyst material of the twenty-fourth through twenty-sixth embodiments is modified, wherein the tetravalent transition metal is selected from the group consisting of Ti, Zr, Hf, Ge, and combinations thereof.
  • the SCR catalyst material of the twenty-fourth through twenty-seventh embodiments is modified, wherein the tetravalent transition metal comprises Ti.
  • a second aspect of the invention is directed to a method for selectively reducing nitrogen oxide (NO x ).
  • the method for selectively reducing nitrogen oxide (NO x ) comprises contacting an exhaust gas stream containing NO x with a SCR catalyst material comprising a spherical particle including an agglomeration of crystals of a molecular sieve, wherein the spherical particle has a median particle size in the range of about 0.5 to about 5 microns.
  • the method for selectively reducing nitrogen oxide (NO x ) comprises contacting an exhaust gas stream containing NO x with the SCR catalyst material of the first through twenty-eighth embodiments.
  • a third aspect of the invention is direct to a system for treating exhaust gas from a lean burn engine containing NO x .
  • the system for treating exhaust gas from a lean burn engine containing NO x comprises the SCR catalyst material of the first through twenty-eighth embodiments and at least one other exhaust gas treatment component.
  • a thirty-first embodiment pertains to a SCR catalyst comprising a zeolitic framework material of silicon and aluminum atoms, wherein a fraction of the silicon atoms are isomorphously substituted with a tetravalent metal and the catalyst is promoted with a metal selected from Cu, Fe, Co, Ni, La, Ce, Mn, V, Ag, and combinations thereof.
  • the SCR catalyst of the thirty-first embodiment is modified, wherein the tetravalent metal comprises a tetravalent transition metal.
  • the SCR catalyst of the thirty-first and thirty-second embodiments is modified, wherein the tetravalent transition metal is selected from the group consisting of Ti, Zr, Hf, Ge, and combinations thereof.
  • the SCR catalyst of the thirty-first through thirty- fourth embodiments is modified, wherein the silica to alumina ratio is in the range of 1 to 300.
  • the SCR catalyst of the thirty-first through thirty-fifth embodiments is modified, wherein the silica to alumina ratio is in the range of 1 to 50.
  • the SCR catalyst of the thirty-first through thirty- sixth embodiments is modified, wherein the tetravalent metal to alumina ratio is in the range of 0.0001 to 1000.
  • the SCR catalyst of the thirty-first through thirty- seventh embodiments is modified, wherein the tetravalent metal to alumina ratio is in the range of 0.01 to 10.
  • the SCR catalyst of the thirty-first through thirty- eighth embodiments is modified, wherein the tetravalent metal to alumina ratio is in the range of 0.01 to 2.
  • the SCR catalyst of the thirty- first through thirty-ninth embodiments is modified, wherein the silica to tetravalent metal ratio is in the range of 1 to 100.
  • the SCR catalyst of the thirty-first through a fourtieth embodiment is modified, wherein the silica to tetravalent metal ratio is in the range of 5 to 20.
  • the SCR catalyst of the thirty-first through forty-first embodiments if modified, wherein the zeolitic framework material comprises ring sizes no larger than 12.
  • the SCR catalyst of the thirty-first through forty- second embodiments is modified, wherein the zeolitic framework material comprises a d6r unit.
  • the SCR catalyst of the thirty-first through forty-third embodiments is modified, wherein the zeolitic framework material is selected from AEI, AFT, AFX, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, WEN, and combinations thereof.
  • the zeolitic framework material is selected from AEI, AFT, AFX, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, WEN, and combinations thereof.
  • the SCR catalyst of the thirty-first through forty-fourth embodiments is modified, wherein the zeolitic framework material is selected from AEI, CHA, AFX, ERI, KFI, LEV, and combinations thereof.
  • the SCR catalyst of the thirty-first through forty-fifth embodiments is modified, wherein the zeolitic framework material is selected from AEI, CHA, and AFX.
  • the SCR catalyst of the thirty-first through forty- sixth embodiments is modified, wherein the zeolitic framework material is CHA.
  • the SCR catalyst of the thirty-first through forty- seventh embodiments is modified, wherein the catalyst is promoted with Cu, Fe, and combinations thereof.
  • the SCR catalyst of the thirty-first through forty- eighth embodiments is modified, wherein the catalyst is effective to promote the formation of NO + .
  • the SCR catalyst of the thirty-first through forty-ninth embodiments is modified with the proviso that the zeolitic framework excludes phosphorous atoms.
  • Embodiments of a further aspect of the invention are directed to an exhaust gas treatment system.
  • an exhaust gas treatment system comprises an exhaust gas stream containing ammonia and a catalyst in accordance with the thirty-first through fiftieth embodiments.
  • a fifty-third embodiment is provided directed to use of the catalyst of any of the first through fiftieth embodiments as a catalyst for the selective catalytic reduction of NO x in the presence of ammonia.
  • a fifty-fourth embodiment pertains to SCR catalyst composite comprising a SCR catalyst material that promotes the reaction of ammonia with nitrogen oxides to form nitrogen and H 2 0 selectively over a temperature range of 150 °C to 600 °C; and an ammonia storage material comprising a transition metal having an oxidation state of IV, the SCR catalyst material effective to store ammonia at 400° C and above with a minimum NH3 storage of 0.1 g/L at 400 °C.
  • the SCR catalyst composite of the fifty-fourth embodiment is modified, wherein the transition metal is selected from the group consisting of Ti, Ce, Zr, Hf, Ge, and combinations thereof.
  • the SCR catalyst composite the fifty-fourth and fifty- fifth embodiments is modified, wherein the SCR catalyst material is isomorphously substituted with the ammonia storage material.
  • the SCR catalyst composite of the fifty-fourth and fifty-fifth embodiments is modified, wherein the ammonia storage material is dispersed in the SCR catalyst material.
  • the SCR catalyst composite of the fifty-fourth and fifty-fifth embodiments is modified, wherein the ammonia storage material is dispersed as a layer on the SCR catalyst material.
  • the SCR catalyst composite of the fifty-fourth and fifty-fifth embodiments is modified, wherein the ammonia storage material and the SCR catalyst material are arranged in a zoned configuration.
  • the SCR catalyst composite of the fifty-ninth embodiment is modified, wherein the ammonia storage material is upstream of the SCR catalyst material.
  • the SCR catalyst composite of the fifty-fourth and fifty-fifth embodiments is modified, wherein the SCR catalyst material is ion-exchanged with the ammonia storage material.
  • the SCR catalyst composite of the fifty- fourth through sixty-first embodiments is modified, wherein the SCR catalyst material is disposed on a filter.
  • the SCR catalyst composite of the sixty-second embodiment is modified, wherein the filter is a wall flow filter.
  • the SCR catalyst composite of the sixty-second embodiment is modified, wherein the filter is a flow through filter.
  • FIG. 4B shows a cutaway view of a section of a wall flow filter substrate
  • FIG. 6 is a SEM image showing crystal morphology of a catalyst material according to the Comparative Example
  • FIG. 7 is a bar graph comparing NO x conversion for catalysts according to the Examples.
  • FIG. 8 is a bar graph comparing N 2 0 make for catalysts according to the Examples.
  • FIG. 9 is a graph comparing NO x conversion for catalysts according to the Examples.
  • FIG. 10 is a graph comparing N2O make for catalysts according to the Examples.
  • FIG. 11 is a bar graph comparing NO x conversion at 20 ppm NH3 slip for catalysts according to the Examples;
  • FIG. 12 is an ATR analysis for catalysts according to the Examples.
  • FIG. 13 is a FTIR analysis for catalysts according to the Examples.
  • FIG. 14 is a FTIR analysis for catalysts according to the Examples.
  • FIG. 15 is a scanning electron microscope image of material according to the Examples.
  • FIG. 16 compares NO x conversion for catalysts according to the Examples
  • FIG. 17 compares NO x conversion for catalysts according to the Examples;
  • FIGS. 18A and 18B are scanning electron microscope images of material of materials according to the Examples;
  • FIG. 19 is a washcoat porosity measurement for catalysts according to the Examples.
  • FIG. 20 compares NH 3 absorption for catalysts according to the Examples
  • FIG. 21 compares NH 3 absorption for catalysts according to the Examples.
  • FIG. 22 compares NH 3 absorption for catalysts according to the Examples
  • FIG. 23 compares NH 3 absorption for catalysts according to the Examples.
  • SCR selective catalytic reduction
  • NO x reduction technologies for light and heavy-duty vehicles.
  • Selective catalytic reduction (SCR) of NO x using urea is an effective and dominant emission control technology for NO x control.
  • an SCR catalyst that has improved performance compared to the current Cu-SSZ-13 based benchmark technology is necessary.
  • an SCR catalyst material having improved NOx conversion efficiency and lower N 2 0 make relative to the current Cu-SSZ-13 based benchmark technologies.
  • the SCR catalyst material effectively promotes the reaction of ammonia with nitrogen oxides to form nitrogen and H 2 0 selectively over a temperature range of 200 to 600 °C.
  • Embodiments of the invention are directed to a selective catalytic reduction material comprising a spherical particle including an agglomeration of crystals of a molecular sieve. It was surprisingly found that spherical particles having an agglomeration of crystals of a molecular sieve are particularly suitable in exhaust gas purification catalyst components, in particular as SCR catalyst materials.
  • a catalytic article or “catalyst composite” refers to an element that is used to promote a desired reaction.
  • a catalytic article or catalyst composite may comprise a washcoat containing a catalytic species, e.g. a catalyst composition, on a substrate.
  • SCR selective catalytic reduction
  • FTIR Fourier transform infrared spectroscopy, which is a technique used to obtain an infrared spectrum of absorption, emission, photoconductivity or Raman scattering of a solid, liquid, or gas.
  • ATR refers to attenuated total reflectance, which is a sampling technique used in conjunction with infrared spectroscopy, particularly FTIR, which enables samples to be examined directly in the solid or liquid state without further preparation.
  • a selective catalytic reduction catalyst material comprises a spherical particle including an agglomeration of crystals of a molecular sieve, wherein the spherical particle has a median particle size in the range of about 0.5 to about 5 microns.
  • molecular sieve refers to framework materials such as zeolites and other framework materials (e.g. isomorphously substituted materials), which may in particulate form in combination with one or more promoter metals be used as catalysts.
  • Molecular sieves are materials based on an extensive three-dimensional network of oxygen ions containing generally tetrahedral type sites and having a substantially uniform pore distribution, with the average pore size being no larger than 20 A. The pore sizes are defined by the ring size.
  • zeolite refers to a specific example of a molecular sieve, including silicon and aluminum atoms.
  • the molecular sieves by their structure type, it is intended to include the structure type and any and all isotypic framework materials such as SAPO, ALPO and MeAPO materials having the same structure type as the zeolite materials.
  • aluminosilicate zeolite structure type limits the material to molecular sieves that do not include phosphorus or other metals substituted in the framework.
  • aluminosilicate zeolite excludes aluminophosphate materials such as SAPO, ALPO, and MeAPO materials, and the broader term "zeolite” is intended to include aluminosilicates and aluminophosphates.
  • Zeolites are crystalline materials having rather uniform pore sizes which, depending upon the type of zeolite and the type and amount of cations included in the zeolite lattice, range from about 3 to 10 Angstroms in diameter. Zeolites generally comprise silica to alumina (SAR) molar ratios of 2 or greater.
  • aluminophosphates refers to another specific example of a molecular sieve, including aluminum and phosphate atoms. Aluminophosphates are crystalline materials having rather uniform pore sizes.
  • molecular sieves e.g. zeolite
  • zeolite are defined as aluminosilicates with open 3 -dimensional framework structures composed of corner-sharing T0 4 tetrahedra, where T is Al or Si, or optionally P.
  • Cations that balance the charge of the anionic framework are loosely associated with the framework oxygens, and the remaining pore volume is filled with water molecules.
  • the non-framework cations are generally exchangeable, and the water molecules removable.
  • the molecular sieve can be isomorphously substituted.
  • zeolitic framework and “zeolitic framework material” refer to a specific example of a molecular sieve, further including silicon and aluminum atoms.
  • the molecular sieve comprises a zeolitic framework material of silicon (Si) and aluminum (Al) ions, wherein a fraction of the silicon atoms are isomorphously substituted with a tetravalent metal.
  • the framework does not include phosphorous (P) atoms.
  • isomorphously substituted and “isomorphous substitution” refer to the substitution of one element for another in a mineral without a significant change in the crystal structure. Elements that can substitute for each other generally have similar ionic radii and valence state. In one or more embodiments, a fraction of the silicon atoms are isomorphously substituted with a tetravalent metal. In other words, a fraction of the silicon atoms in the zeolitic framework material are being replaced with a tetravalent metal. Such isomorophous substitution does not significantly alter the crystal structure of the zeolitic framework material.
  • tetravalent metal refers to a metal having a state with four electrons available for covalent chemical bonding in its valence (outermost electron shell). Tetravalent metals include germanium (Ge) and those transition metals located in Group 4 of the periodic table, titanium (Ti), zirconium (Zr), and hafnium (Hf). In one or more embodiments, the tetravalent metal is selected from Ti, Zr, Hf, Ge, and combinations thereof. In specific embodiments, the tetravalent metal comprises Ti.
  • a fraction of the silicon atoms are isomorphously substituted with a transition metal having an oxidation state of IV.
  • a transition metal having an oxidation state of IV can either be in oxide form, or intrinsically embedded in the SCR catalyst material.
  • transition metal having an oxidation state of IV refers to a metal having a state with four electrons available for covalent chemical bonding in its valence (outermost electron shell).
  • Transition metals having an oxidation state of IV include germanium (Ge), cerium (Ce), and those transition metals located in Group 4 of the periodic table, titanium (Ti), zirconium (Zr), and hafnium (Hf).
  • the transition metal having an oxidation state of IV is selected from Ti, Ce, Zr, Hf, Ge, and combinations thereof.
  • the transition metal having an oxidation state of IV comprises Ti.
  • the zeolitic framework material comprises MO4/S1O4/AIO4 tetrahedra (where M is a tetravalent metal) and is linked by common oxygen atoms to form a three-dimensional network.
  • the isomorphously substituted tetravalent metals are embedded into the zeolitic framework material as a tetrahedral atom (M0 4 ).
  • the isomorphously substituted tetrahedron units together with the silicon and aluminum tetrahedron units then form the framework of the zeolitic material.
  • the tetravalent metal comprises titanium
  • the zeolitic framework material includes Ti04/Si04/A104 tetrahedra.
  • the catalyst comprises a zeolitic framework of silicon and aluminum atoms, wherein a fraction of the silicon atoms are isomorphously substituted with titanium.
  • the isomorphously substituted zeolitic framework material of one or more embodiments is differentiated mainly according to the geometry of the voids which are formed by the rigid network of the M04/(Si04)/A104 tetrahedra (where M is a tetravalent metal).
  • the molecular sieve comprises S1O4/AIO4 tetrahedra and is linked by common oxygen atoms to form a three-dimensional network.
  • the molecular sieve comprises S1O4/AIO4/PO4 tetrahedra.
  • the molecular sieve of one or more embodiments is differentiated mainly according to the geometry of the voids which are formed by the rigid network of the (Si04)/A10 4 , or S1O4/AIO4/PO4, tetrahedra.
  • the entrances to the voids are formed from 6, 8, 10, or 12 ring atoms with respect to the atoms which form the entrance opening.
  • the molecular sieve comprises ring sizes of no larger than 12, including 6, 8, 10, and 12.
  • the molecular sieve can be based on the framework topology by which the structures are identified.
  • any structure type of zeolite can be used, such as structure types of ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, SCO, CFI, SGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EON, EPI, ERI, ESV, ETR, EUO, FAU, FER, FRA, GIS
  • the molecular sieve comprises an 8-ring small pore aluminosilicate zeolite.
  • small pore refers to pore openings which are smaller than about 5 Angstroms, for example on the order of ⁇ 3.8 Angstroms.
  • the phrase "8-ring" zeolites refers to zeolites having 8-ring pore openings and double-six ring secondary building units and having a cage like structure resulting from the connection of double six -ring building units by 4 rings.
  • Zeolites are comprised of secondary building units (SBU) and composite building units (CBU), and appear in many different framework structures. Secondary building units contain up to 16 tetrahedral atoms and are non-chiral.
  • Composite building units are not required to be achiral, and cannot necessarily be used to build the entire framework.
  • a group of zeolites have a single 4-ring (s4r) composite building unit in their framework structure.
  • the "4" denotes the positions of tetrahedral silicon and aluminum atoms, and the oxygen atoms are located in between tetrahedral atoms.
  • Other composite building units include, for example, a single 6-ring (s6r) unit, a double 4-ring (d4r) unit, and a double 6-ring (d6r) unit.
  • the d4r unit is created by joining two s4r units.
  • the d6r unit is created by joining two s6r units.
  • Zeolitic structure types that have a d6r secondary building unit include AEI, AFT, AFX, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, and WEN.
  • the tetravalent metal comprises titanium
  • the titania to alumina ratio is in the range of 0.0001 to 10000, including 0.0001 to 10000, 0.001 to 1000, and 0.01 to 10.
  • the titania to alumina ratio is in the range of 0.01 to 10, including 0.01 to 10, 0.01 : to 5, 0.01 to 2, and 0.01 to 1.
  • the titania to alumina ratio is in the range of 0.01 to 2.
  • promoted refers to a component that is intentionally added to the molecular sieve, as opposed to impurities inherent in the molecular sieve.
  • a promoter is intentionally added to enhance activity of a catalyst compared to a catalyst that does not have promoter intentionally added.
  • a suitable metal is exchanged into the molecular sieve.
  • the molecular sieve is promoted with a metal selected from Cu, Fe, Co, Ni, La, Ce, Mn, V, Ag, and combinations thereof. In specific embodiments, the molecular sieve is promoted with Cu, Fe, and combinations thereof.
  • the promoter metal content of the molecular sieve, calculated as the oxide is, in one or more embodiments, at least about 0.1 wt.%, reported on a volatile-free basis.
  • the promoter metal comprises Cu, and the Cu content, calculated as CuO is in the range of up to about 10 wt.%, including 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, and 0.1 wt.%, in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the Cu content, calculated as CuO is in the range of about 2 to about 5 wt.%.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the molecular sieve having this specific combination of SAR and Cu content has a median particle size in the range of about 0.5 to about 5 microns, and more specifically, about 1.2 to about 3.5 microns, and the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm.
  • the Cu content may be in the range of 0.1-10 wt.%, or 0.5 to 8 wt.%, or 0.8 to 6 wt.%, or 1 to 4 wt.%, or even 2-3 wt.% in each case based on the total weight of the calcined molecular sieve reported on a volatile free oxide basis.
  • the promoter metal can be ion exchanged into the isomorphously substituted molecular sieve.
  • copper is ion exchanged into the isomorphously substituted molecular sieve. The metal can be exchanged after the preparation or manufacture of the isomorphously substituted molecular sieve.
  • the spherical particle has a median particle size in the range of about 0.5 to about 5 microns, including 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4, 4.24, 4.5, 4.75, and 5 microns.
  • the particle size of the spherical particle can be measured by a microscope, and more particularly a scanning electron microscope (SEM).
  • the spherical particle has a median particle size in the range of about 1.0 to about 5 microns, including a range of about 1.2 to about 3.5 microns.
  • the term "median particle size" refers to the median cross-sectional diameter of the spherical particles. In one or more embodiments, at least 80% of the spherical particles have a median particle size in the range of 0.5 to 2.5 microns.
  • the individual crystals of molecular sieve have a crystal size in the range of about 1 to about 250 nm, including 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, and 250 nm.
  • the crystal size of the individual crystals of molecular sieve can be measured by a microscope, and more particularly a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the individual crystals of a molecular sieve have a crystal size in the range of about 100 to about 250 nm, or about 100 to about 200 nm.
  • the individual crystals of molecular sieve may be cubic, spherical, platelet, needle-like, isometric, octahedral, tetragonal, hexagonal, orthorhombic, trigonal, and the like, or any combination thereof.
  • the catalyst material has a monodispersed snowball structure.
  • a monodispersed snowball refers to an arrangement or collection of a number of individual molecular sieve crystals into a substantially spherical mass.
  • the term "monodispersed” means that the individual molecular sieve crystals are uniform and approximately the same size, having a crystal size in the range of about 1 to about 250 nanometers.
  • the monodispersed snowball is similar to individual snow particles forming a snowball.
  • the catalyst material has a spherical snowball structure, wherein at least 80% of the spherical particle has a median particle size in the range of 0.5 to 2.5 microns.
  • the individual crystals of molecular sieve form a microagglomerate, which then forms a macro agglomerated snowball structure.
  • the microagglomerates have a size in the range of less than 1.0 micron, including less than 0.9, less than 0.8, less than 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.3, less than 0.2, and less than 0.1 micron
  • the macroagglomerate spherical snowball has a particle size in the range of about 0.5 to about 5 microns, including about 1.2 to about 3.5 microns.
  • the size of the microagglomerates can be measured by a microscope, and more particularly a scanning electron microscope (SEM).
  • the monodispersed snowball structure of one or more embodiments may be more readily understood by the schematic in FIG. 1.
  • FIG. 1 an exemplary embodiment of a catalyst material is shown.
  • the catalyst material comprises a spherical particle 10 including an agglomeration of crystals 20.
  • the spherical particle 10 has a particle size, S p , of about 0.5 to about 5 microns, including about 1.2 to about 3.5 microns.
  • the individual crystals 20 of a molecular sieve have a crystal size S c in the range of about 1 to about 250 nanometers, including about 100 to 250 nm, or 100 to 200 nm.
  • the individual crystals 20 of molecular sieve form a microagglomerate 30, which then forms the macroagglomerated snowball structure 10.
  • the microagglomerate 30 has a size S m in the range of less than 1.0 micron and greater than 0 microns.
  • the spherical particles of the crystals of molecular sieve are significantly different in structure than molecular sieves having the CHA structure which do not have an agglomerated snowball structure.
  • the powder or sprayed material can be shaped without any other compounds, e.g. by suitable compacting, to obtain moldings of a desired geometry, e.g. tablets, cylinders, spheres, or the like.
  • Embodiments of the invention are directed to a catalyst composite comprising a SCR catalyst material and an ammonia storage material comprising a transition metal having an oxidation state of IV.
  • the SCR catalyst composite is effective to store ammonia at 400 °C and above with a minimum NH 3 storage of 0.1 g/L at 400 °C.
  • the SCR catalyst material promotes the reaction of ammonia with nitrogen oxides to form nitrogen and H 2 0 selectively over a temperature range of 150 °C to 600 °C
  • the ammonia storage material is effective to store ammonia at 400° C and above with a minimum NH 3 storage of 0.1 g/L at 400 °C. It was surprisingly found that the catalyst composites are particularly suitable in exhaust gas purification catalyst components, in particular as SCR catalysts.
  • the SCR catalyst material and the ammonia storage material are arranged in a zoned configuration. In one or more embodiments, the SCR catalyst material and the ammonia storage material are arranged in a laterally zoned configuration, with the ammonia storage material upstream from the SCR catalyst material.
  • the term "laterally zoned" refers to the location of the SCR catalyst material and the ammonia storage material relative to one another. Lateral means side-by-side such that the SCR catalyst material and the ammonia storage material are located one beside the other with the ammonia storage material upstream of the SCR catalyst material.
  • the SCR catalyst material is ion-exchanged with the ammonia storage material.
  • the length of the ammonia storage material 210 is denoted as first zone 210a in FIG. 2.
  • the ammonia storage material 210 comprises a transition metal having an oxidation state of IV.
  • the SCR catalyst material 220 extends from the outlet end 250 of the substrate 230 through less than the entire axial length L of the substrate 230.
  • the length of the SCR catalyst material 220 is denoted as the second zone 220a in FIG. 2.
  • the SCR catalyst material 220 promotes the reaction of ammonia with nitrogen oxides to form nitrogen and H 2 0 selectively over a temperature range of 150 °C to 600 °C, and the ammonia storage material 210 is effective to store ammonia at 400° C and above with a minimum NH 3 storage of 0.00001 g/L.
  • the substrates 112 and 113 generally comprise a plurality of channels 114 of a honeycomb substrate, of which only one channel is shown in cross-section for clarity.
  • the ammonia storage material 118 extends from the inlet end 122a of the substrate 112 through the entire axial length LI of the substrate 112 to the outlet end 124a.
  • the length of the ammonia storage material 118 is denoted as first zone 118a in FIG. 3.
  • the ammonia storage material 118 comprises a transition metal having an oxidation state of IV.
  • the SCR catalyst material 120 extends from the outlet end 124b of the substrate 113 through the entire axial length L2 of the substrate 113 to the inlet end 122b.
  • the SCR catalyst material 120 defines a second zone 120a.
  • the length of the SCR catalyst material is denoted as the second zone 20b in FIG. 3.
  • the SCR catalyst material 120 promotes the reaction of ammonia with nitrogen oxides to form nitrogen and H 2 0 selectively over a temperature range of 150 °C to 600 °C, and the ammonia storage material 118 is effective to store ammonia at 400° C and above with a minimum NH 3 storage of 0.00001 g/L.
  • the length of the zones 118a and 120a can be varied as described with respect to FIG. 2.
  • wall flow filter substrates are composed of ceramic- like materials such as cordierite, a-alumina, silicon carbide, silicon nitride, zirconia, mullite, spodumene, alumina-silica-magnesia or zirconium silicate, or of porous, refractory metal.
  • wall flow substrates are formed of ceramic fiber composite materials.
  • wall flow substrates are formed from cordierite and silicon carbide. Such materials are able to withstand the environment, particularly high temperatures, encountered in treating the exhaust streams.
  • Typical wall flow filters in commercial use are formed with lower wall porosities, e.g., from about 35% to 50%, than the wall flow filters utilized in the invention.
  • the pore size distribution of commercial wall flow filters is typically very broad with a mean pore size smaller than 17 microns.
  • the substrates are immersed vertically in a portion of the catalyst slurry such that the top of the substrate is located just above the surface of the slurry. In this manner slurry contacts the inlet face of each honeycomb wall, but is prevented from contacting the outlet face of each wall.
  • the sample is left in the slurry for about 30 seconds.
  • the substrate is removed from the slurry, and excess slurry is removed from the wall flow substrate first by allowing it to drain from the channels, then by blowing with compressed air (against the direction of slurry penetration ), and then by pulling a vacuum from the direction of slurry penetration.
  • the catalyst slurry permeates the walls of the substrate, yet the pores are not occluded to the extent that undue back pressure will build up in the finished substrate.
  • permeate when used to describe the dispersion of the catalyst slurry on the substrate, means that the catalyst composition is dispersed throughout the wall of the substrate.
  • the coated substrates are dried typically at about 100 °C and calcined at a higher temperature (e.g., 300 to 450 °C). After calcining, the catalyst loading can be determined through calculation of the coated and uncoated weights of the substrate. As will be apparent to those of skill in the art, the catalyst loading can be modified by altering the solids content of the coating slurry. Alternatively, repeated immersions of the substrate in the coating slurry can be conducted, followed by removal of the excess slurry as described above.
  • the ammonia storage material of the SCR catalyst composite is dispersed within the SCR catalyst material.
  • the SCR catalyst material comprises a molecular sieve having a framework of silicon (Si) and aluminum (Al) ions, and, optionally phosphorus (P) ions, wherein a fraction of the silicon atoms are isomorphously substituted with the ammonia storage material which comprises a transition metal having an oxidation state of IV.
  • an ammonia oxidation (AMOx) catalyst may be provided downstream of the SCR catalyst composite to remove any slipped ammonia from the exhaust gas treatment system.
  • the AMOx catalyst may comprise a platinum group metal such as platinum, palladium, rhodium, or combinations thereof.
  • AMOx and/or SCR catalyst material(s) can be coated on the flow through or wall- flow filter. If a wall flow substrate is utilized, the resulting system will be able to remove particulate matter along with gaseous pollutants.
  • the wall-flow filter substrate can be made from materials commonly known in the art, such as cordierite, aluminum titanate or silicon carbide. It will be understood that the loading of the catalytic composition on a wall flow substrate will depend on substrate properties such as porosity and wall thickness, and typically will be lower than loading on a flow through substrate.
  • the SCR catalyst material comprises a molecular sieve which comprises S1O4/AIO4 tetrahedra.
  • the SCR catalyst material is isomorphously substituted with the ammonia storage material.
  • the SCR catalyst material comprises MO4/S1O4/AIO4 tetrahedra (where M is a transition metal having an oxidation state of IV) and is linked by common oxygen atoms to form a three-dimensional network.
  • MO4/S1O4/AIO4 tetrahedra where M is a transition metal having an oxidation state of IV
  • the isomorphously substituted transition metal having an oxidation state of IV is embedded into the molecular sieve as a tetrahedral atom (MO4).
  • the isomorphously substituted tetrahedron units together with the silicon and aluminum tetrahedron units then form the framework of the molecular sieve.
  • the transition metal having an oxidation state of IV comprises titanium
  • the SCR catalyst material then includes TiCVSiCVAlC ⁇ tetrahedra.
  • the SCR catalyst material comprises a molecular sieve which comprises S1O4/AIO4/PO4 tetrahedra.
  • the SCR catalyst material is isomorphously substituted with the ammonia storage material.
  • the SCR catalyst material comprises MO4/S1O4/AIO4/PO4 tetrahedra (where M is a transition metal having an oxidation state of IV) and is linked by common oxygen atoms to form a three- dimensional network.
  • the isomorphously substituted transition metal having an oxidation state of rV is embedded into the molecular sieve as a tetrahedral atom (MO4).
  • the isomorphously substituted tetrahedron units together with the silicon, aluminum, and phosphorus tetrahedron units then form the framework of the molecular sieve.
  • the transition metal having an oxidation state of IV comprises titanium
  • the SCR catalyst material then includes TiCVSiCVAlCVPC tetrahedra.
  • the isomorphously substituted molecular sieve of one or more embodiments is differentiated mainly according to the geometry of the voids which are formed by the rigid network of the M04/(Si04)/A104 tetrahedra (where M is a transition metal having an oxidation state of IV).
  • the molecular material has a structure type selected from the group consisting of MFI, BEA, CHA, AEI, AFX, ERI, KFI, LEV, and combinations thereof.
  • the molecular sieve has a structure type selected from CHA, AEI, and AFX.
  • the molecular sieve comprises SSZ-13, SSZ-39, or SAPO-34.
  • the molecular sieve is an aluminosilicate zeolite type and has the AEI structure type, for example, SSZ-39.
  • the molecular sieves by their structure type, it is intended to include the structure type and any and all isotypic framework materials such as SAPO, A1PO and MeAPO materials having the same structure type.
  • the ratio of silica to alumina of a molecular sieve can vary over a wide range.
  • the molecular sieve has a silica to alumina molar ratio (SAR) in the range of 2 to 300, including 5 to 250; 5 to 200; 5 to 100; and 5 to 50.
  • the molecular sieve has a silica to alumina molar ratio (SAR) in the range of 10 to 200, 10 to 100, 10 to 75, 10 to 60, and 10 to 50; 15 to 100, 15 to 75, 15 to 60, and 15 to 50; 20 to 100, 20 to 75, 20 to 60, and 20 to 50.
  • the ratio of transition metal having an oxidation state of IV to alumina can vary over a very wide range.
  • the transition metal having an oxidation state of IV to alumina ratio is in the range of 0.001 to 10000, including 0.001 : 10000, 0.001 to 1000, 0.01 to 10.
  • the transition metal having an oxidation state of IV to alumina ratio is in the range of 0.01 to 10, including 0.01 to 10, 0.01 : to 5, 0.01 to 2, and 0.01 to 1.
  • the transition metal having an oxidation state of IV to alumina ratio is in the range of 0.01 to 2.
  • the ratio of silica to transition metal having an oxidation state of IV can vary over a wide range. It is noted that this ratio is an atomic ratio, not a molar ratio. In one or more embodiments, the silica to transition metal having an oxidation state of IV ratio is in the range of 1 to 100, including 1 to 50, 1 to 30, 1 to 25, 1 to 20, 5 to 20, and 10 to 20. In specific embodiments, the silica to transition metal having an oxidation state of IV ratio is about 15. In one or more embodiments, the transition metal having an oxidation state of IV comprises titanium, and the silica to titania ratio is in the range of 1 to 100, including 1 to 50, 1 to 30, 1 to 25, 1 to 20, 5 to 20, and 10 to 20. In specific embodiments, the silica to titania ratio is about 15.
  • a suitable metal is exchanged into the SCR catalyst material.
  • the SCR catalyst material is promoted with a metal selected from Cu, Fe, Co, Ni, La, Ce, Mn, V, Ag, and combinations thereof.
  • the SCR catalyst material is promoted with Cu, Fe, and combinations thereof.
  • the promoter metal content of the SCR catalyst material, calculated as the oxide, is, in one or more embodiments, at least about 0.1 wt%, reported on a volatile-free basis.
  • the promoter metal comprises Cu, and the Cu content, calculated as CuO is in the range of up to about 10 wt%, including 9, 8, 7, 6, 5, 4, 3, 2,and 1 wt %, in each case based on the total weight of the calcined SCR catalyst material reported on a volatile free basis.
  • the Cu content, calculated as CuO is in the range of about 2 to about 5 wt%.
  • the SCR catalyst material comprises a mixed oxide.
  • the term "mixed oxide” refers to an oxide that contains cations of more than one chemical element or cations of a single element in several states of oxidation.
  • the mixed oxide is selected from Fe/titania (e.g. FeTi0 3 ), Fe/alumina (e.g. FeAl 2 0 3 ), Mg/titania (e.g. MgTi0 3 ), Mg/alumina (e.g. MgAl 2 0 3 ), Mn/alumina, Mn/titania (e.g. MnO x /Ti0 2 ) (e.g.
  • the mixed oxide comprises vanadia/titania.
  • the vanadia/titania oxide can be activated or stabilized with tungsten (e.g. WO3) to provide V2O5/T1O2/ WO3.
  • the SCR catalyst material comprises titania on to which vanadia has been dispersed.
  • the vanadia can be dispersed at concentrations ranging from 1 to 10 wt%, including 1, 2, 3, 4, 5, 6, 7, 8, 9, 10wt%.
  • the vanadia is activated or stabilized by tungsten (W0 3 ).
  • the tungsten can be dispersed at concentrations ranging from 0.5 to 10 wt%, including 1, 2, 3, 3. 4, 5, 6, 7, 8, 9, and 10 wt%. All percentages are on an oxide basis.
  • the SCR catalyst material comprises a refractory metal oxide support material.
  • the terms "refractory metal oxide support” and “support” refer to the underlying high surface area material upon which additional chemical compounds or elements are carried.
  • the support particles have pores larger than 20 A and a wide pore distribution.
  • metal oxide supports exclude molecular sieves, specifically, zeolites.
  • high surface area refractory metal oxide supports can be utilized, e.g., alumina support materials, also referred to as "gamma alumina” or “activated alumina,” which typically exhibit a BET surface area in excess of 60 square meters per gram (“m 2 /g"), often up to about 200 m 2 /g or higher.
  • gamma alumina gamma alumina
  • activated alumina is usually a mixture of the gamma and delta phases of alumina, but may also contain substantial amounts of eta, kappa and theta alumina phases.
  • the selective catalytic reduction material comprising a spherical particle including an agglomeration of crystals of a molecular sieve exhibits an aged NOx conversion at 200 °C of at least 50% measured at a gas hourly space velocity of 80000 h "1 .
  • the material exhibits an aged NO x conversion at 450 °C of at least 70% measured at a gas hourly space velocity of 80000 h "1 .
  • the catalyst material is effective to lower N2O make.
  • the SCR catalyst composite comprises a SCR catalyst material and an ammonia storage material comprising a transition metal having an oxidation state of IV
  • the SCR catalyst material promotes the reaction of ammonia with nitrogen oxides to form nitrogen and H2O selectively over a temperature range of 150 °C to 600°C
  • the ammonia storage material is effective to store ammonia at temperatures of about 400 °C and above with a minimum ammonia storage of 0.00001 g/L.
  • the oxygen content of the exhaust gas stream is from 0 to 30% and the water content is from 1 to 20%.
  • the SCR catalyst composite according to one or more embodiments adsorbs NH3 even in the presence of H2O.
  • the SCR catalyst composites of one or more embodiments show more pronounced high temperature ammonia storage capacity than reference SCR catalyst materials and catalyst composites.
  • the catalyst materials can be applied to a substrate as a washcoat.
  • substrate refers to the monolithic material onto which the catalyst is placed, typically in the form of a washcoat.
  • a washcoat is formed by preparing a slurry containing a specified solids content (e.g., 30-90% by weight) of catalyst in a liquid vehicle, which is then coated onto a substrate and dried to provide a washcoat layer.
  • the substrate is a ceramic or metal having a honeycomb structure.
  • Any suitable substrate may be employed, such as a monolithic substrate of the type having fine, parallel gas flow passages extending there through from an inlet or an outlet face of the substrate such that passages are open to fluid flow there through.
  • the passages which are essentially straight paths from their fluid inlet to their fluid outlet, are defined by walls on which the catalytic material is coated as a washcoat so that the gases flowing through the passages contact the catalytic material.
  • the flow passages of the monolithic substrate are thin-walled channels, which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc.
  • the ceramic substrate may be made of any suitable refractory material, e.g. cordierite, cordierite-a-alumina, silicon nitride, zircon mullite, spodumene, alumina-silica- magnesia, zircon silicate, sillimanite, a magnesium silicate, zircon, petalite, a-alumina, an aluminosilicate and the like.
  • suitable refractory material e.g. cordierite, cordierite-a-alumina, silicon nitride, zircon mullite, spodumene, alumina-silica- magnesia, zircon silicate, sillimanite, a magnesium silicate, zircon, petalite, a-alumina, an aluminosilicate and the like.
  • the substrates useful for the catalyst of embodiments of the present invention may also be metallic in nature and be composed of one or more metals or metal alloys.
  • the metallic substrates may be employed in various shapes such as pellets, corrugated sheet or monolithic form.
  • Specific examples of metallic substrates include the heat-resistant, base- metal alloys, especially those in which iron is a substantial or major component.
  • Such alloys may contain one or more of nickel, chromium, and aluminum, and the total of these metals may advantageously comprise at least about 15 wt. % of the alloy, for instance, about 10 to 25 wt. % chromium, about 1 to 8 wt. % of aluminum, and about 0 to 20 wt. % of nickel.
  • a molecular sieve having the CHA structure may be prepared according to various techniques known in the art, for example United States Patent Nos. 4,544,538 (Zones) and
  • the obtained alkali metal zeolite is NH 4 -exchanged to form NH 4 -
  • the NH 4 - ion exchange can be carried out according to various techniques known in the art, for example Bleken, F.; Bjorgen, M.; Palumbo, L.; Bordiga, S.; Svelle, S.; Gebrud,
  • a molecular sieve having a snowball-type morphology water can be prepared from adamantyltrimethylammonium hydroxide (ADAOH), aqueous sodium hydroxide, aluminum isopropoxide powder, and colloidal silica.
  • ADAOH adamantyltrimethylammonium hydroxide
  • aqueous sodium hydroxide aluminum isopropoxide powder
  • colloidal silica colloidal silica
  • the catalyst material comprises a zeolitic framework material of silicon and aluminum atoms, wherein a fraction of the silicon atoms are isomorphously substituted with a tetravalent metal.
  • the H-form can be prepared by calcination of the ammonia form, which is obtained through double NH4NO3 exchanges with the sodium form.
  • the Ti level is unchanged/stable through the NH4NO3 exchange processes.
  • the copper promoted isomorphously substituted zeolitic framework can be prepared by ion exchange using the H-form and Cu(OAc)2 to achieve the desired amount of promoter metal.
  • the SCR catalyst composite comprises an SCR catalyst material having a zeolitic framework material of silicon and aluminum atoms, wherein a fraction of the silicon atoms are isomorphously substituted with the transition metal having an oxidation state of IV of the ammonia storage material.
  • the sodium form of the isomorphously substituted molecular sieve can be prepared from a 0.03Al 2 O3:SiO2:0.07TiO2:0.06Na2O:0.08ATMAOH:2.33H 2 O gel composition through autoclave hydrothermal synthesis. The product is recovered by filtration, and the template is removed by calcination. The final crystalline material can be characterized by x-ray diffraction studies.
  • An additional aspect of the invention is directed to a method of catalyzing a chemical reaction wherein the spherical particle including an agglomeration of crystals of a molecular sieve according to embodiments of the invention is employed as catalytically active material.
  • a further aspect of the invention is directed to a method of catalyzing a chemical reaction wherein the SCR catalyst composite that comprises an SCR catalyst material and an ammonia storage material comprising a transition metal having an oxidation state of IV according to embodiments of the invention is employed as catalytically active material.
  • One or more embodiments provide a method of selectively reducing nitrogen oxides (NOx).
  • the method comprises contacting an exhaust gas stream containing NO x with the catalyst materials or the catalyst composites of one or more embodiments.
  • the selective reduction of nitrogen oxides wherein the selective catalytic reduction catalyst material comprises a spherical particle including an agglomeration of crystals of a molecular sieve, wherein the spherical particle has a median particle size in the range of about 0.5 to about 5 microns, of embodiments of the invention is employed as catalytically active material is carried out in the presence of ammonia or urea.
  • urea is the reducing agent of choice for mobile SCR systems.
  • the SCR system is integrated in the exhaust gas treatment system of a vehicle and, also typically, contains the following main components: selective catalytic reduction material comprising a spherical particle including an agglomeration of crystals of a molecular sieve, wherein the spherical particle has a median particle size in the range of about 0.5 to about 5 microns according to embodiments of the invention; a urea storage tank; a urea pump; a urea dosing system; a urea injector/nozzle; and a respective control unit.
  • gas stream broadly refers to any combination of flowing gas that may contain solid or liquid particulate matter.
  • gaseous stream or “exhaust gas stream” means a stream of gaseous constituents, such as the exhaust of a lean burn engine, which may contain entrained non-gaseous components such as liquid droplets, solid particulates, and the like.
  • the exhaust gas stream of a lean burn engine typically further comprises combustion products, products of incomplete combustion, oxides of nitrogen, combustible and/or carbonaceous particulate matter (soot), and un-reacted oxygen and nitrogen.
  • a further aspect of the invention is directed to an exhaust gas treatment system.
  • the exhaust gas treatment system comprises an exhaust gas stream optionally containing a reductant like ammonia, urea, and/or hydrocarbon, and in specific embodiments, ammonia and/or urea, and a selective catalytic reduction material comprising a spherical particle including an agglomeration of crystals of a molecular sieve, wherein the spherical particle has a median particle size in the range of about 0.5 to about 5 microns.
  • the catalyst material is effective for destroying at least a portion of the ammonia in the exhaust gas stream.
  • the obtained CuCHA catalyst comprised CuO at a range of about 3 to 3.5% by weight, as determined by ICP analysis.
  • a CuCHA slurry was prepared to 40% target solids. The slurry was milled and a binder of zirconium acetate in dilute acetic acid (containing 30% Zr0 2 ) was added into the slurry with agitation.
  • the slurry was coated onto l"Dx3"L cellular ceramic cores, having a cell density of 400 cpsi (cells per square inch) and a wall thickness of 6.5 mil.
  • the coated cores were dried at 110 °C for 3 hours and calcined at about 400 °C for 1 hour.
  • the coating process was repeated once to obtain a target washcoat loading of in the range of 2-3 g/in 3 .
  • the as-synthesized snowball material (Example 2) has a characteristic secondary structure of spheres with a diameter size of 1-2 ⁇ , as identified by SEM analysis (secondary electron imaging) at a scale of 5000x.
  • the individual crystals of molecular sieve have a crystal size in the range of about 100 to 200 nm.
  • the slurry was milled and a binder of zirconium acetate in dilute acetic acid (containing 30%
  • Example 3 The Example 3 slurries were then coated onto a substrate to a washcoat loading of
  • Nitrogen oxides selective catalytic reduction (SCR) efficiency and selectivity of a fresh catalyst core was measured by adding a feed gas mixture of 500 ppm of NO, 500 ppm of
  • Figure 9 is a graph showing the NO x conversion (%) versus temperature (°C) for the catalyst of Example 1 (comparative) versus the inventive catalyst of Example 3, having 3.2% CuO.
  • Figure 10 is a graph showing the N 2 0 make (ppm) versus temperature (°C) for the catalyst of Example 1 (comparative) versus the inventive catalyst of Example 3, having 3.2% CuO.
  • An isomorphously substituted zeolitic material (Na-[Ti]CHA) was prepared from an 0.03Al2O3:SiO 2 :0.07TiO2:0.06Na2O:0.08ATMAOH:2.33H 2 O gel composition through autoclave hydrothermal synthesis at 155 °C for 5 days. The product was recovered by filtration, and the template was removed by calcination at 600 °C for 5 hours. The final crystalline material had an x-ray powder diffraction pattern indicating > 90% CHA phase and a silica/alumina ratio (SAR) of 25 by XRF.
  • SAR silica/alumina ratio
  • a copper promoted isomorphously substituted zeolitic material (Cu2.72-[Ti]CHA) was prepared by ion exchange at 50 °C (2 hrs.) using the material of Example 8 (H-[Ti]CHA) and Cu(OAc) 2 (0.06 M), showing a Cu content of 2.72% (ICP).
  • a copper promoted isomorphously substituted zeolitic material (Cu3.64-[Ti]CHA) was prepared by ion exchange at 50 °C (2 hrs.) using the material of Example 9 (H-[Ti]CHA) and Cu(OAc) 2 (0.125 M), showing a Cu content of 3.64% (ICP)
  • a standard copper promoted zeolitic material (Cu3.84-CHA) was prepared according to the process provided in U.S. 8404203B2, with comparable Cu content (3.84%) to Example 10. This material is provided as the reference for aging benchmarking.
  • Example 10 The material of Example 10 (Cu-[Ti]CHA) was washcoated on a flow-through ceramic substrate at a loading of 2.1 g/in 3 .
  • the typical SCR testing condition includes simulated diesel exhaust gas (500 ppm NO, 500 ppm N3 ⁇ 4, 10% 0 2 , 5% H 2 0, and balance N 2 ) and temperature points from 200 °C to 600 °C. Conversion of NO and NH3 at various temperatures are monitored by FTIR. An aging condition of 750 °C exposure to 10% H2O for 5 hrs. is adopted if desired to evaluate long term hydrothermal durability.
  • a copper promoted isomorphously substituted zeolitic material (Cu-[Ti]AEI) is prepared by ion exchange at 50 °C (2 hrs.) using the material of Example 22 (H-[Ti]AEI) and Cu(OAc) 2 (0.06 M).
  • An isomorphously substituted zeolitic material (Na-[Ti]AFX) is prepared analogously to the material of Example 7. The product is recovered by filtration, and the template is removed by calcination at 600 °C for 5 hours.
  • An isomorphously substituted zeolitic material (H-[Ti]AFX) is prepared by 500 °C calcination (4 hrs.) of NH 4 -[Ti]AFX, which is obtained through double NH NO3 (2.4 M) exchanges with the material of Example 24 (Na-[Ti]AFX).
  • a copper promoted isomorphously substituted zeolitic material (Cu-[Ti]AFX) is prepared by ion exchange at 50 °C (2 hrs.) using the material of Example 25 (H-[Ti]AFX) and Cu(OAc) 2 (0.06 M).
  • An isomorphously substituted zeolitic material (Na-[Ti]CHA) was prepared from an 0.03Al2O3:SiO 2 :0.07TiO2:0.06Na2O:0.08ATMAOH:2.33H 2 O gel composition through autoclave hydrothermal synthesis at 155°C for 5 days. The product was recovered by filtration, and the template was removed by calcination at 600 °C for 5 hours. The final crystalline material had an X-ray powder diffraction pattern indicating > 90% CHA phase and a SAR of 25 by XRF. Other SAR, e.g., 20, can also be obtained by proper adjustment of Si/Al ratio in the starting gel.
  • An isomorphously substituted zeolitic material (H-[Ti]CHA) was prepared by 500 °C calcination (4 hrs) of NH 4 -[Ti]CHA, which was obtained through double NH 4 N0 3 (2.4 M) exchanges with the material of Example 27 (Na-[Ti]CHA). The Ti level was unchanged through the NH4NO3 exchange processes, 4.3% vs. 4.5%.
  • the zeolitic material H-CHA was prepared according to the process of Example 28 and 29, but without Ti addition to the initial synthesis sol gel for zeolite hydrothermal crystallization.
  • a copper promoted isomorphously substituted zeolitic material (Cu-[Ti]CHA (SAR 20)) was prepared by ion exchange at 50 °C (2 hrs) using the material of Example 29 (H- [TiJCHA) and Cu(OAc) 2 . Variation of Cu concentration in the exchange process produced a series of copper zeolite, e.g., Cu2.46-[Ti]CHA (Example 31a), Cu3.03-[Ti]CHA (Example 31b), Cu3.64-[Ti]CHA (Example 31c), and Cu3.78-[Ti]CHA (Example 3 Id) (numbers after Cu denote Cu percentage).
  • a Fe-CHA (Fe: 2.5%) was synthesized similarly as Cu-CHA but using Fe(N0 3 )3 in the solution exchange, and was selected as a comparative sample.
  • a copper promoted isomorphously substituted zeolitic material (Cu-[Ti]AEI) is prepared by ion exchange at 50 °C (2 hrs) using the material of Example 42 (H-[Ti]AEI) and Cu(OAc) 2 (0.06 M).

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WO2020222105A3 (en) * 2019-04-27 2020-12-10 Sud Chemie India Pvt. Ltd. Methods of preparation of metal exchanged zeolites
US11219886B2 (en) * 2018-05-25 2022-01-11 Basf Se Rare earth element containing aluminum-rich zeolitic material
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BR112016029733A2 (pt) 2017-08-22
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KR102436905B1 (ko) 2022-08-29
CN106660022A (zh) 2017-05-10
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