• 专利附录
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    • 专利摘要:
    hydrothermally stable low temperature nox reduction nh3-scr catalyst composition and catalytic converter a catalyst composition includes a heterobimetallic zeolite characterized by a chabazite structure charged with copper ions and at least one trivalent metal ion other than al3 +. the catalyst composition decreases nox emissions from diesel discharge and is suitable for operation in a catalytic converter.
    公开号:BR112014020419B1
    申请号:R112014020419
    申请日:2013-02-22
    公开日:2020-05-05
    发明作者:K Narula Chaitanya；Yang Xiaofan
    申请人:Ut Battelle Llc；
    IPC主号:
    专利说明:

    "COMPOSITION OF NH3-SCR CATALYST FOR REDUCING NOX LOW TEMPERATURE HYDROTERMICALLY STABLE AND CATALYTIC CONVERTER"
    CROSS REFERENCE TO RELATED ORDERS [001] This order claims the priority benefit of U.S. Order No. 13 / 404,071, filed on February 24, 2012 which is hereby incorporated by reference in its entirety. Specifically referenced is US Patent Application No. 12 / 855,794 filed on August 13, 2010, Publication No. 20120039759 published on February 16, 2012, entitled “Zeolite-Based SCR Catalysts ant Their Use in Diesel Engine Emission Treatment” by Chaitanya K. Narula and Xiaofan Yang, the complete description of which is hereby incorporated by reference.
    DECLARATION CONSIDERING FEDERATELY SPONSORED RESEARCH [002] The United States Government has rights in this invention under contract no. DE-AC05-00OR22725 between the United States Department of Energy and UT-Battelle, LLC.
    BACKGROUND OF THE INVENTION [003] Diesel engines are known to be significantly more efficient fuels than their gasoline counterparts. Therefore, the introduction of a diesel engine in on-road and off-road systems (for example, industrial or domestic equipment, such as heavy machinery and lawn mowers) is highly desirable. In addition, gasoline engines, operating in an oxygen-rich environment (insufficient gasoline engines) are also more fuel efficient than the stoichiometric engines currently used.
    [004] The high fuel efficiency of insufficient diesel and gasoline engines results in an oxygen-rich (ie insufficient) discharge
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    2/22 that mainly contains NOx gases. Although NOx gases can be effectively removed from poor oxygen discharges, when produced in gasoline engine emissions, the removal of NOx gases in insufficient gasoline / diesel engine emissions remains a significant challenge. In particular, the standard three-way catalyst works well for gasoline engines, however, it does not know the regulatory requirements of EPA when used for diesel engines.
    [005] To meet EPA regulatory requirements for diesel engines, extensive efforts are underway to find catalysts that can effectively treat NOx in the oxygen-rich emissions emitted by diesel engines. The main approach to reducing NOx in diesel emissions is selective catalytic reduction (SCR). In SCR, ammonium or urea is often used as a reducing agent. The best NH3-SCR catalysts known for reducing NOx under the insufficient environment of diesel engine emissions are Cu-ZSM-5 and Fe-ZSM-5. These have been shown to work effectively only within reduced temperature ranges. Cu-ZSM-5 generally exhibits better NOx reduction activity at lower temperatures while Fe-ZSM-5 exhibits better activity at higher temperatures. Thus, a combination of Cu-ZSM-5 and Fe-ZSM-5 zeolites (that is, as a heterogeneous mixture) was used in an effort to treat NOx effectively within an extended temperature range. The latest generation NH3-SCR catalyst is based on Cu-SSZ-13 and is now commercially available.
    [006] Although Cu / Fe mixtures provide an improvement in the emissions process than diesel-powered passenger vehicles, Cu / Fe mixtures are significantly inadequate at low temperatures. In particular, the catalysts currently employed do not reduce NOx emissions
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    3/22 effectively at low temperatures, such as 150 - 200 ° C, which is more critical in off-road diesel engines than in passenger vehicles. In addition, the Cu / Fe mixture can only be adequately efficient within separate reduced temperature ranges, for example, a high and a low temperature range. However, particularly for off-road diesel engines that can operate over a wide range of temperatures, there would be a significant benefit in a catalyst that can operate effectively over a wide range of temperatures (for example, from 150 ° C to 650 ° Ç). If a gasoline engine is operated in an insufficient mode, not much NOx is produced at low temperature. However, the catalyst described in this invention is suitable for use with gasoline engines that operate in an insufficient way as well as diesel engines used for transportation (cars, trucks, railroad machines, ships, etc.)
    BRIEF SUMMARY OF THE INVENTION [007] According to the examples of the present invention, the foregoing and other objects are obtained by a catalyst composition that includes a heterobimetallic zeolite characterized by a chabazite structure charged with copper ions and at least one ion of trivalent metal other than Al 3+ . The catalyst composition reduces NOx emissions in diesel discharge and is suitable for operation in a catalytic converter.
    BRIEF DESCRIPTION OF THE DRAWINGS [008] Fig. 1 is a graph showing the comparative performance of CuFeSSZ-13 and Cu-SSZ-13 catalysts according to the examples of the present invention.
    [009] Fig. 2 is a graph showing the comparative performance of CuFeSSZ-13 and aged CuFe-SSZ-13 catalysts according to the examples of the present invention.
    [010] For a better understanding of the present invention, together with
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    4/22 others and additional objects, advantages and capabilities thereof, reference is made to the following description and appended claims with respect to the drawings described above.
    DETAILED DESCRIPTION OF THE INVENTION [011] The present invention is directed to a catalyst to mitigate (i.e., remove or reduce) NOx emissions from hydrocarbons (e.g., discharge of diesel, gasoline and / or kerosene). The catalyst includes a new class of heterobimetallic zeolites based on the chabazite structure, such as CuFeSSZ-13, for example. The new zeolites described here overcome the hydrothermal durability issues of all known NH3-SCR catalysts for NOx reduction while preserving their high NOx reduction capacity at low temperatures.
    [012] A zeolite considered here can be any of the porous aluminosilicate structures known in the art that are stable under high temperature conditions, that is, at least 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, and higher temperatures up to, for example, 500 ° C, 550 ° C, 600 ° C, 650 ° C, 700 ° C, 750 ° C, 800 ° C, 850 ° C, or 900 ° C. In particular examples of the present invention, zeolite is stable from at least 100 ° C and up to 700 ° C. Typically, the zeolite is ordered to have a crystalline or partially crystalline structure. The zeolite can generally be described as a three-dimensional structure containing units of silicate (SiO2 or SiO4) and aluminate (Al2O3 or AlO4) that are interconnected (that is, cross-linked) by the division of oxygen atoms.
    [013] The zeolite can be microporous (ie, pore size less than 2 pm), mesoporous (ie, pore size within 2-50 pm, or sub-range at that point), or a combination of them. In several examples of the present invention, the zeolite material is completely or substantially microporous. Being completely or substantially microporous, the pore volume due
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    5/22 to micropores can be, for example, 100%, or at least 95%, 96%, 97%, 98%, 99%, or 99.5%, with the remaining pore volume being due to the mesopores, or in some examples of the present invention, macropores (pore size greater than 50 pm). In other examples of the present invention, the zeolite material is completely or substantially mesoporous. Being completely or substantially mesoporous, the pore volume due to the mesopores can be, for example, 100%, or at least 95%, 96%, 97%, 98%, 99%, or 99.5%, with the volume of remainder being due to micropores, or in some examples of the present invention, macropores. In yet other examples of the present invention, the zeolite material contains an abundance of micropores and mesopores. Containing an abundance of micropores and mesopores, the pore volume due to the mesopores can be, for example, up to, at least, or precisely 50%, 60%, 70%, 80%, or 90%, with the balance of the volume of pore being due to mesopores, or vice versa.
    [014] The various forms of zeolite are generally known through their respective abbreviations such as, for example, ABW, ACO, AEI, AEN, AFG, AFN, AFT, AFX, APC, APD, ATN, ATT, ATV, AWO, AWW , BCT, BIK, BOF, BRE, CAS, CDO, CHA, DFT, DOH, EAB, EPI, ERI, ESV, FAR, FRA, GIS, GIU, IHW, ITE, ITW, JBW, JRY, KFI, LAU, LEV , LIO, LOS, LTA, LTN, MAR, MON, MTF, MWW, NAT, NSI, OWE, PAU, PHI, RHO, RTE, RTH, RWR, SAS, SAT, SAV, SBN, SIV, SOD, STI, STT , THO, TOL, UEI, UFI, or ZON. Some particular examples of zeolites include the zeolite chabazite class (for example, SSZ-13, SSZ-62, Phi, SAPO-34, LZ-218 and Linde D). The compositions, structures, and properties of chabazite zeolites are well known in the art, and have been described in detail, as found in, for example, US Patents 4,544,538, 6,709,644, 4,124,686, 4,333,859, and 2,950 .952, the contents of which are incorporated herein by reference in their entirety.
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    6/22 [015] The zeolite can have any suitable silica-to-aluminum ratio (ie SiO2 / Al2O3 or Si / Al). For example, in several examples of the present invention, the zeolite can have a Si / Al ratio of precisely at least less than, or up to 1,2, 3, 4, 5, 6, 7, 8, 9, 10 , 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 150, or 200, or a Si / Al ratio within a range linked by any two of the preceding values. In particular examples of the present invention, zeolite has a Si / Al ratio of 1 to 45.
    [016] In particular examples of the present invention, the zeolite is SSZ-13 which belongs to the ABC-6 family of zeolites, all of which are also considered here. In particular examples of the present invention, the SSZ-13 zeolite is represented by the formula RNaNabAl2.4Si33.6O 2 «wH2O (1.4 <a <27) (0.7 <b <4.3) (1 <w <7), where RN is N, N, N-1-trimethyladamantammonium.
    [017] Typically, zeolite contains a number of cationic species. As is well known in the art, the amount of cationic species is generally proportional to the amount of aluminum in the zeolite. This is because the replacement of silicon atoms with lower valiant aluminum atoms requires the presence of counter-cations to establish a charge balance. Some examples of cationic species include hydrogen ions (H + ), alkali metal ions, alkaline earth metal ions, and main group metal ions. Some examples of alkali metal ions that can be included in zeolite include lithium (Li +), sodium (Na +), potassium (K +), rubidium (Rb +), and cesium (Cs +). Some examples of alkaline earth metal ions that can be included in zeolite include (Be 2+ ), magnesium (Mg 2+ ), calcium (Ca 2+ ), strontium (Sr 2+ ), and barium (Ba 2+ ). Some examples of main group metal ions that can be included in zeolite include boron (B 3+ ), gallium (Ga 3+ ), indium (In 3+ ), and arsenic (As 3+ ). In some examples of the present invention, a combination of cationic species is included.
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    7/22
    Cationic species can be in a trace amount (for example, no more than 0.01 or 0.001%), or alternatively, in a significant amount (for example, above 0.01%, and even, for example, 0.1, 0.5, 1, 2, 3, 4, or 5% by weight of zeolite).
    [018] The zeolite described above is charged with an amount of copper ions. Copper ions can be cuprous (Cu +) or cupric (Cu 2+ ) in nature. The copper loading can be any suitable amount. In different examples of the present invention, the copper loading is precisely at least less than, or even, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05% , 0.06%, 0.07%, 0.08%, 0.09%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% , 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5 %, or a copper load within a range linked by any two of the preceding values, where the load is expressed as the amount of metal by weight of the zeolite. In particular examples of the present invention, the copper loading is any value up to 2.5%.
    [019] In addition to copper ions, the zeolite catalyst of the present invention also includes at least one trivalent metal ion. When used here, the term trivalent metal ion is defined as a trivalent metal ion other than aluminum (Al 3+ ). Without wishing to be bound by any theory, it is believed that the trivalent metal is incorporated into the zeolite material. In this way, it is believed that the embedded trivalent metal ion is attached in the zeolite to an appropriate number of oxygen atoms, that is, as a metal oxide unit in close proximity (for example, within contact or electronic communication) to copper ions. The close proximity between the trivalent metal ions and copper ions is believed to cause a combined effect different from the cumulative effect of these ions when they are not in such close proximity. The effect mainly considered here is the effect on the resulting catalyst's ability to process NOx gases (ie, the
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    8/22 NOx conversion capacity of the catalyst).
    [020] In some examples of the present invention, only one type of trivalent metal ion apart from aluminum is incorporated into the zeolite. In other examples of the present invention, at least two types of trivalent metal ions apart from aluminum are incorporated into the zeolite. In still other examples of the present invention, at least three types of trivalent metal ions apart from aluminum are incorporated into the zeolite. In yet other examples of the present invention, precisely two or precisely three types of trivalent metal ions apart from aluminum are incorporated into the zeolite.
    [021] Each of the trivalent metal ions can be included in any suitable amount, such as precisely at least less than, or even, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, or an amount within a range linked by any two of the preceding values. In particular examples of the present invention, each of the trivalent metal ions can be included in an amount of, precisely, at least less than, or up to 2.5%. In examples of the present invention where more than one type of trivalent metal ion is included, the loading of each metal can be selected independently from any of the above exemplary amounts or ranges. In other examples of the present invention, the total amount of the trivalent metal ions other than aluminum conforms to any of the exemplary values provided above.
    [022] In a first set of examples of the present invention, at least one trivalent metal ion is selected from trivalent transition metal ions. The one or more transition metals can be selected from any or a select portion of the following types of transition metals: elements from Groups IIIB (group Sc), IVB (group Ti), VB (group V), VIB (group Cr),
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    9/22
    VIIB (group Mn), VIIIB (groups Fe and Co) of the Periodic Table of the Elements. Some examples of trivalent transition metal ions include Sc 3+ , Y3 +, V3 +, Nb 3+ , Cr 3+ , Fe 3+ , and Co 3+ . In other examples of the present invention, the trivalent metal ion excludes all transition metal ions, or alternatively, excludes any, two or more specific classes or examples of transition metal ions provided above. In particular examples of the present invention, trivalent transition metal ions include Sc 3+ , or Fe 3+ , or a combination thereof.
    [023] In a second set of examples of the present invention, at least one trivalent metal ion is selected from trivalent main group metal ions. The one or more main group metals can be selected from any or a select portion of Group IIIA (group B) and / or VA (group N) elements in the Periodic Table, different from aluminum. Some examples of trivalent main group metal ions include Ga 3+ , In 3+ , As 3+ , Sb 3+ , and Bi 3+ . In other examples of the present invention, the trivalent metal ion excludes all main group metal ions other than aluminum, or alternatively excludes any one, two or more specific classes or examples of main group metal ions provided above. In particular examples of the present invention, trivalent main group metal ions include at least In 3+ .
    [024] In a third set of examples of the present invention, at least one trivalent metal ion is selected from trivalent lanthanide metal ions. Some examples of trivalent lanthanide metal ions considered here include La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3 + , Er 3+ , Tm 3+ , Yb 3+ , and Lu 3+ . In particular examples of the present invention, the trivalent lanthanide metal ion is selected from one or a combination of La 3+ , Ce 3+ , Pr 3+ , and Nd 3+ . In other particular examples of the present invention, the trivalent lanthanide metal ion is or includes La 3+ .
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    10/22 [025] In a fourth set of examples of the present invention, at least two trivalent metal ions are selected from trivalent transition metal ions. Some combinations of trivalent transition metal ions considered here include Sc 3+ in combination with one or more other trivalent transition metal ions, or Fe 3+ in combination with one or more other trivalent transition metal ions, or Y 3 + in combination with one or more other trivalent transition metal ions.
    [026] In a fifth set of examples of the present invention, at least two trivalent metal ions are selected from trivalent main group metal ions. Some combinations of trivalent main group metal ions considered here include In 3+ in combination with one or more other trivalent main group metal ions, or Ga 3+ in combination with one or more other trivalent main group metal ions, or As 3+ in combination with one or more other trivalent main group metal ions.
    [027] In a sixth set of examples of the present invention, at least two trivalent metal ions are selected from trivalent lanthanide metal ions. Some combinations of trivalent lanthanide metal ions considered here include La 3+ in combination with one or more other trivalent lanthanide metal ions, or Ce 3+ in combination with one or more other trivalent lanthanide metal ions, or Pr 3 + in combination with one or more other trivalent lanthanide metal ions, or Nd 3+ in combination with one or more other trivalent lanthanide metal ions.
    [028] In a seventh set of examples of the present invention, at least one trivalent metal ion is a trivalent transition metal ion and at least one trivalent metal ion is a trivalent lanthanide metal ion. For example, in particular examples of the present invention, at least one trivalent metal ion is selected from Sc 3+ , Fe 3+ , and / or Y 3+ , and another trivalent metal ion is
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    11/22 selected from La 3+ , Ce 3+ , Pr 3+ , and / or Nd 3+ .
    [029] In an eighth set of examples of the present invention, at least one trivalent metal ion is a trivalent transition metal ion and at least one trivalent metal ion is a trivalent main group metal ion. For example, in particular examples of the present invention, at least one trivalent metal ion is selected from Sc 3+ , Fe 3+ , and / or Y 3+ , and another trivalent metal ion is selected from In 3 + , Ga 3+ , and / or In 3+ .
    [030] In a ninth set of examples of the present invention, at least one trivalent metal ion is a trivalent main group metal ion and at least one trivalent metal ion is a trivalent lanthanide metal ion. For example, in particular examples of the present invention, at least one trivalent metal ion is selected from Sc 3+ , Fe 3+ , and / or Y 3+ , and another trivalent metal ion is selected from La 3 + , Ce 3+ , Pr 3+ , and / or Nd 3+ .
    [031] In a tenth set of examples of the present invention, at least three trivalent metal ions in the zeolite are included. The at least three trivalent metal ions can be selected from trivalent transition metal ions, trivalent main group metal ions, and / or trivalent lanthanide metal ions.
    [032] In particular examples of the present invention, one, two, three, or more trivalent metal ions are selected from Sc 3+ , Fe 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , In 3+ , and / or Ga 3+ . In more particular examples of the present invention, one, two, three, or more trivalent metal ions are selected from Sc 3+ , Fe 3+ , La 3+ , and / or In 3+ .
    [033] The zeolite catalyst described above is not typically covered with a layer or film containing metal. However, the present invention also finds the zeolite catalyst described above coated with a film or layer containing metal as long as the film or layer does not prevent
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    12/22 substantially the catalyst will function effectively as a NOx reduction catalyst as intended herein. Being coated, the film or layer resides on the surface of the zeolite. In some examples of the present invention, the surface of the zeolite refers only to the outer surface (i.e., as defined by the outer contour area of the zeolite catalyst), while in other examples of the present invention, the surface of the zeolite refers to a or includes internal surfaces of the zeolite, such as the surfaces within the pores or channels of the zeolite. The metal-containing film or layer can serve, for example, to adjust the physical characteristics of the catalyst, the catalytic efficiency, or catalytic selectivity. Some examples of metal-containing surfaces include the oxides and / or sulphides of alkali metals, alkaline earth metals, divalent or main group transition metals (eg, Zn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Pd 2+ , Pt 2+ , Sn 2+ , or Pb 2+ ), tetravalent transition metals (eg Ti 4+ , Zr 4+ , Rh 4+ , Ir 4+ , Mn 4+ , Ge 4+ , Sn 4+ , and Te 4+ ), pentavalent or main group transition metals (for example, Nb 5+ , Ta 5+ , and Sb 5+ ), and hexavalent transition metals (for example, Cr 6+ , Mo 6+ , and W 6+ ). In other examples of the present invention, one or more specific classes or types of any of the foregoing additional metal ions are (are) excluded from the zeolite catalyst.
    [034] The catalyst described here can be synthesized by any suitable method known in the art. The method considered here should incorporate the metal ions (ie, copper and one or more trivalent metal ions) homogeneously in the zeolite. The resulting metal-loaded catalyst contains a homogeneous distribution of metal ions at a molecular level, that is, the catalyst does not contain macroscopic regions that contain only one type of metal ion, as would be obtained by grinding and mixing two sources of zeolite that each contains a different metal ion.
    [035] In particular examples of the present invention, the catalyst described
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    13/22 here, the zeolite is first prepared by saturating the metals to be charged. The impregnation step can be achieved, for example, by treating the zeolite with one or more solutions that contain the metals to be charged. When treating the zeolite with the solution containing metal, the solution containing metal is contacted with the zeolite such that the solution is absorbed into the zeolite, preferably in the entire volume of the zeolite.
    [036] In one embodiment, the impregnation step is achieved by treating the zeolite with a solution that contains all the metals to be loaded. In another embodiment, the impregnation step is achieved by treating the zeolite with two or more solutions, in which the different solutions contain different metals or combinations of metals. Each treatment of the zeolite with an impregnation solution corresponds to a separate impregnation step. Typically, when more than one impregnation step is employed, a drying and / or thermal treatment step is employed between the impregnation steps.
    [037] The metal impregnation solution contains at least one or more metal ions to be (be) loaded into the zeolite, as well as a liquid vehicle to distribute the metal ions in the zeolite. Metal ions are usually in the form of metal salts. Preferably, the metal salts are completely dissolved in the liquid vehicle. The metal salt contains one or more metal ions in ionic association with one or more counterions. Any one or more of the metal ions described above can serve as the metal ion portion. The counter-anion can be selected from, for example, halides (F - , Cl - , Br - , or I - ), carboxylates (eg, formate, acetate, propionate, or butyrate), sulfate, nitrate, phosphate , chlorate, bromate, iodate, hydroxide, β-diketonate (for example, acetylacetonate), and dicarboxylates (for example, oxalate, malonate, or succinate). In some examples of the present invention, the counter-anion may contain one or more metals, including one or more metals to be (are) loaded into the zeolite. Some examples of such contra
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    14/22 anions include titanate, zirconate, vanadate, niobate, tantalate, chromate, molybdate, tungstate, arsenate, antimonate, stannate and tellurate. In other examples of the present invention, one or more specific classes or types of any of the preceding counter-anions are (are) excluded from the impregnation solution (or alternatively, are excluded from being incorporated ( s) in the zeolite).
    [038] In particular examples of the present invention, the catalyst is prepared by forming a sludge containing zeolite powder and the metals to be incorporated. The resulting sludge is dried and set on fire to form a powder. The powder is then combined with organic and / or inorganic binders and mixed wet to form a paste. The resulting paste can be formed in any desired shape, for example, by extrusion into stick, honeycomb, or pinwheel structures. The extruded structures are then dried and set on fire to form the final catalyst. In other examples of the present invention, the zeolite powder, metals, and binders are all combined together to form a paste, which is then extruded and fired.
    [039] After impregnating the zeolite, the metal-loaded zeolite is typically dried and / or subjected to a heat treatment step (for example, a burning or calcination step). The functions of the heat treatment step to permanently incorporate the saturated metals in the zeolite, for example, forming metal oxide bonds within the zeolite material. In different examples of the present invention, the heat treatment step can be conducted at a temperature of at least 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C, 650 ° C, 700 ° C, 750 ° C, or 800 ° C, or within a range at that point, for a period of time, for example, 15 minutes, 30 minutes, 1 hour, 2 hours, 6 hours, 12 hours, 24 hours, 30 hours, 36 hours, or 48 hours, or within a range at that point. In particular examples of the present invention, the heat treatment step is carried out at a
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    15/22 temperature of at least 500 ° C over a period of time of at least two hours. In some examples of the present invention, the heat treatment step includes a step of increasing the temperature from a lower temperature to a higher temperature, and / or from a higher temperature to a lower temperature. For example, the heat treatment step may include an increase stage from 100 ° C to 700 ° C, or vice versa, at a rate of 1.2, 5, or 10 ° C / min.
    [040] Generally, one or more heat treatment steps are conducted under normal atmospheric pressure. However, in some examples of the present invention, a high pressure (for example, above 1 atm and up to 2, 5, or 10 atm) is employed, while in other examples of the present invention, a reduced pressure (for example, below 1, 0., 5, or 0.2 atm) is employed. In addition, although heat treatment steps are generally conducted below a normal air atmosphere, in some examples of the present invention, a high oxygen, reduced oxygen, or inert atmosphere is used. Some gases that can be included in the process atmosphere include, for example, oxygen, nitrogen, helium, argon, carbon dioxide, and mixtures thereof.
    [041] Generally, the zeolite catalyst described here is in the form of a powder. In a first set of examples of the present invention, at least a portion, or all, of the particles of the powder are smaller than one micron (i.e., nanotechnology particles). Nano-size particles can have a particle size precisely of at least up to, or less than, for example, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 , 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, or 950 nanometers (nm), or a particle size within a bounded range for any two of the preceding values. In a second set of examples of the present invention, at least a portion, or all, of the powder particles have a size at or above 1 micron in the
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    16/22 size. Micron-size particles can have a particle size precisely of at least up to, or less than, for example, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 , or 100 microns (pm), or a particle size within a range linked by any two of the preceding values. In some examples of the present invention, crystals or simple grains of the catalyst correspond to any of the sizes provided above, while in other examples of the present invention, crystals or grains of the catalyst are agglomerated to provide crystallites or agglomerated grains having any of the above exemplary dimensions.
    [042] In other examples of the present invention, the zeolite catalyst can be in the form of a film, a coating, or a multiplicity of films or coatings. The thickness of the coatings or multiplicity of coatings can be, for example, 1, 2, 5, 10, 50, or 100 microns, or a strip at that point, or up to 100 microns in thickness. In still other examples of the present invention, the zeolite catalyst is in the form of a solid of non-particulate (i.e., continuous) volume. In still other examples of the present invention, the zeolite catalyst can be fibrous or in the form of a mesh.
    [043] The catalyst can also be mixed with or attached to a support material suitable for operation in a catalytic converter. The support material can be a powder (for example, having any of the above particle sizes), granular (for example, 0.5 mm or larger particle size), a bulk material, such as a honeycomb monolith full flow type, one plate or multi-plate structure, or corrugated metal sheets. If a honeycomb structure is used, the honeycomb structure can contain any suitable cell density. For example, the honeycomb structure may contain 100, 200, 300, 400, 500, 600, 700, 800, or 900 cells / in 2 (or 62-140 cells / cm 2 ) or greater. The support material is generally constructed in a
    Petition 870190086569, of 9/3/2019, p. 25/52
    17/22 refractory composition, such as those containing cordierite, mullite, aluminum (for example, α-, γ-, or θ-alumina), or zirconia, or a combination thereof. Honeycomb structure, in particular, is described in detail in, for example, U.S. Patents 5,314,665, 7,442,425, and 7,438,868, the contents of which are hereby incorporated by reference in their entirety. When corrugated or other types of metal sheets are used, they can be layered on top of each other with catalyst material supported on the sheets such that the passages remain which allow the discharge gas to flow between the sheets. The layered sheets can also be formed in a structure, such as a cylinder, by airing the sheets.
    [044] The catalyst described here preferably exhibits a NOx conversion temperature profile that is improved over that of Cu-SSZ-13, as described in U.S. Patent 7,601,662.
    [045] In a first set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at 150 ° C. When used herein, the phrase NOx conversion high at 150 ° C is defined as a NOx conversion of at least or above 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85 % at 150 ° C.
    [046] In a second set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at 200 ° C. When used herein, the phrase NOx conversion high at 200 ° C is defined as a NOx conversion of at least or above 80%, 85%, or 90% at 200 ° C.
    [047] In a third set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at a temperature in the range of 250 ° C to 450 ° C. When used herein, the phrase high NOx conversion at 250-450 ° C is defined as a NOx conversion of at least or above 60%, 65%, 70%, 75%, 80%, 85%, or 90% at a temperature of 250 ° C,
    Petition 870190086569, of 9/3/2019, p. 26/52
    18/22
    300 ° C, 350 ° C, 400 ° C, or 450 ° C, at a temperature in the range of 250 ° C to 450 ° C, or temperatures that vary within the range.
    [048] In a fourth set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at a temperature in the range of 500 ° C to 525 ° C. When used herein, the phrase NOx conversion high at 500-525 ° C is defined as a NOx conversion of at least or above 60%, 65%, 70%, 75%, 80%, or 85% at a temperature in the range of 500 ° C to 525 ° C, or temperatures that vary within the range.
    [049] In a fifth set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at a temperature of 550 ° C. When used here, the phrase high NOx conversion at 550 ° C is defined as a NOx conversion of at least or above 60%, 65%, 70%, 75%, or 80% at a temperature of 550 ° C.
    [050] In a sixth set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at a temperature in the range of 600 ° C to 650 ° C. When used herein, the phrase NOx conversion high at 600-650 ° C is defined as a NOx conversion of at least or above 60%, 65%, 70%, 75%, or 80% at a temperature in the 600 ° C to 650 ° C, or temperatures that vary within the range.
    [051] In a seventh set of examples of the present invention, the catalyst described here preferably exhibits a high NOx conversion at 150 ° C while also exhibiting a high NOx conversion at 200 ° C, and / or a high NOx conversion at 250-450 ° C, and / or a high NOx conversion at 500-525 ° C, and / or a high NOx conversion at 550 ° C, and / or a high NOx conversion at 600-650 ° C.
    [052] In some examples, the invention is directed to a catalytic converter which contains the above metal-loaded zeolite catalyst as a catalyst. The catalyst is typically arranged in an element of
    Petition 870190086569, of 9/3/2019, p. 27/52
    19/22 refractory support, such as corrugated metal sheets or a honeycomb structure, as described above. The catalytic converter can be any of the catalytic converters known in the art, and particularly, those catalytic converters particularly adapted for the processing of diesel fuel discharge. The construction and operation of such catalytic converters are well known in the art, as described in detail in, for example, US Patents 7,691,340, 7,678,348, 7,575,727, 7,442,425, 7,438,868, 7,412,824, 7,288 .230, 6,919,052, and 5,314,665, the contents of which are incorporated herein by reference in their entirety.
    [053] As basic elements, the catalytic converter typically contains the catalyst arranged in a support element such that the passages are made available for the discharge to pass through them, and the supported catalyst included in a metal cover. The metal cover is generally connected with one or more inlets (i.e., tubes) to transfer the exhaust gases to the supported catalyst. The metal cover may also include one or more gaskets.
    [054] In particular examples of the present invention, the catalytic converter is connected with an ammonium source for the ammonia to mix within the discharge gas stream. As is well known in the art, ammonia works as a reducer in selective catalytic reduction (SCR) processes. Ammonia can be in any suitable form, such as anhydrous ammonia, aqueous ammonia, urea, ammonium carbonate, ammonium formate, or ammonium carbamate. In some examples of the present invention, the ammonia source is supplied continuously in the discharge stream before and / or during the time that the discharge stream reaches the catalyst. In other examples of the present invention, ammonia is supplied intermittently. In other examples of the present invention, the ammonia source is supplied before the discharge stream reaches the catalyst. In this way, the ammonia source is first absorbed into the catalyst before reacting with the
    Petition 870190086569, of 9/3/2019, p. 28/52
    20/22 discharge current. Generally, an ammonia storage tank is used to contain the ammonia source.
    [055] In the design of an SCR system, numerous other elements can be interconnected with the catalytic converter and the ammonia source. For example, a vaporizer can be included between the ammonia source and the catalytic converter to convert (i.e., decompose) the ammonia source into ammonia gas. A mixer can also be incorporated between the ammonia source and the catalytic converter (or between the vaporizer and the catalytic converter) to mix the ammonia with the discharge stream. Other elements, such as heaters, pumps, and fans, can be included to improve the system. The SCR system can be integrated into any system that makes use of an insufficiently burning engine, particularly those engines that use diesel fuel. The SCR system can be integrated, for example, into the engine system of a passenger vehicle, truck, utility boiler, industrial boiler, solid waste boiler (ie, when used in the municipal waste process), vessel, locomotive , tunnel drilling machine, submarine, construction equipment, gas turbine, nuclear power plant, airplane, lawn mower, or chainsaw.
    [056] Examples have been mentioned below for the purpose of illustration and to describe certain specific examples of the present invention. However, the scope of this invention should not be limited in any way by the examples mentioned here.
    EXAMPLE I [057] H-SSZ-13 was prepared according to U.S. Patent 4,544,538. CuSSZ-13 was synthesized as follows: a sample of 2,664 g of Cu (OAc) 2.H2O was dissolved in 600 ml of deionized water (0.022M), followed by the addition of H-SSZ13 (10.00 g). The slurry was stirred for 2 hours at 50 ° C. The blue solid was collected through filtration after cooling, washed with deionized water, and
    Petition 870190086569, of 9/3/2019, p. 29/52
    21/22 calcined in air at 500 ° C (10 ° C / min) for 4 hours to provide Cu-SSZ-13. Elemental analysis: Cu 3.46, Al 4.05%.
    [058] CuFe-SSZ-13 was obtained by the following procedure: 10 g of Cu-SSZ13 were suspended in a water solution of 50 ml of 0.015M Fe (NO3) 3, degassed with N2, and the stirring continued for 2 hours at 80 ° C. The yellow solid was obtained after filtration, and the filtrate was clear and colorless. The product was then calcined in air at 500 ° C (2 ° C / min) for 2 hours to produce pale yellow CuFe-SSZ-13. Elemental analysis: Cu 2.71%, Fe 0.357%, Al 3.86%.
    [059] CuFe-SSZ-13 can also be prepared by an incipient moisture method. In this method, 10 g of Cu-SSZ-13 were ground with 0.3 g of Fe (NO3) 3.9H2O and only enough water was added to cover the surface of Cu-SSZ-13. The color of Cu-SSZ-13 slowly changed from green to yellow. The sample was allowed to dry in air and then calcined in air at 500 ° C (2C / min) for 4 hours to produce pale yellow CuFe-SSZ-13.
    EXAMPLE II [060] Cu-SSZ-13 and CuFe-SSZ-13 catalyst powders were tested comparatively. The catalyst powders were mixed with equal amounts (by weight) of inert cordierite and transferred to a bench reactor. A degreening was done in a flow of 8.5% O2, 8% CO2, and 7.25% H2O with N2 in equilibrium at a temperature of 600 ° C (inlet gas temperature) and a space velocity of 50,000 h -1 for two hours. The NOx conversion efficiency experiments employed simulated a diesel discharge containing 8.5% O2, 8% CO2, 7.25% H2O, 250 ppm NO2, 250 ppm NO, 500 ppm NH3, and N2 as equilibrium at a spatial speed of 50,000 h -1 and evaluated in the temperature range of 150 ° C to 650 ° C. The results are shown in Fig. 1. The CuFe-SSZ-13 catalyst clearly shows better performance in the range of 150-650 ° C. The difference in NOx conversion performance is especially
    Petition 870190086569, of 9/3/2019, p. 30/52
    22/22 notable at 150 ° C where Cu-SSZ-13 converts ~ 40% NOx whereas CuFeSSZ-13 converts ~ 75% NOx under test conditions.
    EXAMPLE III [061] Accelerated aging was performed on the CuFeSSZ-13 catalyst powder using an aging protocol that exposes the catalyst to a temperature of 675 ° C for 50 hours under an air flow containing 10% water. Test results are shown in Fig. 2.
    [062] The CuFe-SSZ-13 catalyst demonstrates high hydrothermal durability and has high NOx conversion performance in the range of 150-650 ° C. The NOx reduction at 150 ° C is ~ 65%, which is better than fresh Cu-SSZ-13 as shown in Fig. 1.
    [063] While it was shown and described what are currently considered to be examples of the invention, it will be obvious to those skilled in the art that various changes and modifications can be prepared in this without departing from the scope of the inventions defined by the attached claims.
    权利要求:
    Claims (35)
    [1]
    1. Catalyst composition CHARACTERIZED by the fact that it comprises a heterobimetallic zeolite defined by a chabazite structure charged with copper ions and at least one trivalent metal ion other than Al 3+ , in which said copper ions are present in said catalyst in a charge amount greater than 1% by weight and said at least one trivalent metal ion is present in said catalyst in a charge amount of less than 1% by weight and wherein the charge amounts of said copper and trivalent metal ions are effective in achieving a conversion of NOx at 150 ° C of at least 50%.
    [2]
    2. Catalyst composition according to claim 1, CHARACTERIZED by the fact that said at least one trivalent metal ion comprises a trivalent transition metal ion.
    [3]
    3. Catalyst composition according to claim 2, CHARACTERIZED by the fact that said at least one trivalent transition metal ion is selected from the group consisting of Sc 3+ , Y 3+ , V 3+ , Nb 3+ , Cr 3+ , Fe 3+ , and Co 3+ .
    [4]
    4. Catalyst composition according to claim 1, CHARACTERIZED by the fact that said at least one trivalent metal ion comprises a metal ion of the trivalent main group.
    [5]
    5. Catalyst composition according to claim 4, CHARACTERIZED by the fact that said metal ion from the main trivalent group is selected from the group consisting of Ga 3+ , In 3+ , As 3+ , Sb 3+ , and Bi 3+ .
    [6]
    6. Catalyst composition according to claim 1, CHARACTERIZED by the fact that said at least one trivalent metal ion is selected from the group consisting of Fe 3+ , In 3+ , Sc 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , and Lu 3+ .
    Petition 870190086569, of 9/3/2019, p. 32/52
    2/5
    [7]
    7. Catalyst composition according to claim 1, characterized by the fact that said at least one trivalent metal ion comprises a combination of at least two trivalent metal ions.
    [8]
    Catalyst composition according to claim 7,
    CHARACTERIZED by the fact that said at least two trivalent metal ions comprise trivalent transition metal ions.
    [9]
    Catalyst composition according to claim 7,
    CHARACTERIZED by the fact that at least one trivalent metal ion comprises a trivalent transition metal ion and at least one other trivalent metal ion comprises a trivalent lanthanide metal ion.
    [10]
    10. Catalyst composition according to claim 7, CHARACTERIZED by the fact that at least one trivalent metal ion comprises a trivalent transition metal ion and in which at least one other trivalent metal ion comprises a metal ion of the trivalent main group.
    [11]
    Catalyst composition according to claim 7, CHARACTERIZED by the fact that at least one trivalent metal ion comprises a metal ion of the trivalent main group and in which at least one other trivalent metal ion comprises a metal ion of trivalent lanthanide.
    [12]
    12. Catalyst composition according to claim 1,
    CHARACTERIZED by the fact that said zeolite comprises CuFe-SSZ-13.
    [13]
    Catalyst composition according to claim 1,
    CHARACTERIZED by the fact that said catalyst exhibits a conversion of NOx at 150 ° C of at least 60%.
    [14]
    14. Catalyst composition according to claim 13, CHARACTERIZED by the fact that said catalyst also exhibits a conversion of NOx at 200 ° C of at least 85%.
    Petition 870190086569, of 9/3/2019, p. 33/52
    3/5
    [15]
    15. Catalyst composition according to claim 13, CHARACTERIZED by the fact that said catalyst also exhibits a conversion of NOx at 600 ° C of at least 65%.
    [16]
    16. Catalyst composition according to claim 1, CHARACTERIZED by the fact that said copper ions are present in said catalyst in a loading amount of at least 1.5% by weight and said trivalent metal ion is present in said catalyst in a loading amount of at least 1%.
    [17]
    17. Catalyst composition according to claim 1, CHARACTERIZED by the fact that said copper ions are present in said catalyst in a loading amount of at least 2% by weight and said trivalent metal ion is present in said catalyst in a loading amount of at least 1%.
    [18]
    18. Catalyst composition according to claim 1, CHARACTERIZED by the fact that said trivalent metal ion is the Fe (III) ion.
    [19]
    19. Catalytic converter CHARACTERIZED by the fact that it comprises a catalyst loaded on a refractory substrate, said catalyst comprising a heterobimetallic zeolite defined by a chabazite structure charged with copper ions and at least one trivalent metal ion other than Al 3+ , wherein said copper ions are present in said catalyst in a charge amount greater than 1% by weight and wherein said at least one trivalent metal ion is present in said catalyst in a charge amount of less than 1 % by weight, and in which the loading amounts of said copper and trivalent metal ions are effective to achieve a conversion of NOx at 150 ° C of at least 50%.
    [20]
    20. Catalytic converter, according to claim 19, CHARACTERIZED by the fact that said at least one metal ion
    Petition 870190086569, of 9/3/2019, p. 34/52
    4/5 trivalent comprises a trivalent transition metal ion.
    [21]
    21. Catalytic converter according to claim 20, CHARACTERIZED by the fact that said trivalent transition metal ion is selected from the group consisting of Sc 3+ , Y 3+ , V 3+ , Nb 3+ , Cr 3+ , Fe 3+ and Co 3+ .
    [22]
    22. Catalytic converter according to claim 19, CHARACTERIZED by the fact that said at least one trivalent metal ion comprises a metal ion of the trivalent main group.
    [23]
    23. Catalytic converter according to claim 22, CHARACTERIZED by the fact that said metal ion of the main trivalent group is selected from the group consisting of Ga 3+ , In 3+ , As 3+ , Sb 3+ and Bi 3+ .
    [24]
    24. Catalytic converter according to claim 19, CHARACTERIZED by the fact that said at least one trivalent metal ion is selected from the group consisting of Fe 3+ , In 3+ , Sc 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ and Lu 3 + .
    [25]
    25. Catalytic converter according to claim 19, CHARACTERIZED by the fact that said at least one trivalent metal ion comprises a combination of at least two trivalent metal ions.
    [26]
    26. Catalytic converter according to claim 25, CHARACTERIZED by the fact that said at least two trivalent metal ions comprise trivalent transition metal ions.
    [27]
    27. Catalytic converter according to claim 25, CHARACTERIZED by the fact that at least one trivalent metal ion comprises a trivalent transition metal ion and in which at least one other trivalent metal ion comprises a lanthanide metal ion trivalent.
    [28]
    28. Catalytic converter according to claim 25, CHARACTERIZED by the fact that at least one trivalent metal ion
    Petition 870190086569, of 9/3/2019, p. 35/52
    5/5 comprises a trivalent transition metal ion and at least one other trivalent metal ion comprises a metal ion of the trivalent main group.
    [29]
    29. Catalytic converter according to claim 25, CHARACTERIZED by the fact that at least one trivalent metal ion comprises a metal ion of the trivalent main group and in which at least one other trivalent metal ion comprises a metal ion of trivalent lanthanide.
    [30]
    30. Catalytic converter, according to claim 19, CHARACTERIZED by the fact that said zeolite comprises CuFe-SSZ-13.
    [31]
    31. Catalytic converter according to claim 19, CHARACTERIZED by the fact that said catalyst exhibits a conversion of NOx at 150 ° C of at least 60%.
    [32]
    32. Catalytic converter according to claim 31, CHARACTERIZED by the fact that said catalyst exhibits a conversion of NOx at 200 ° C of at least 85%.
    [33]
    33. Catalytic converter according to claim 31,
    CHARACTERIZED by the fact that said catalyst exhibits a conversion of
    NOx at 600 ° C of at least 65%.
    [34]
    34. Catalytic converter according to claim 19,
    CHARACTERIZED by the fact that the said refractory substrate is defined by a structure selected from the group consisting of a stick structure, a honeycomb structure, and a paper pinwheel structure.
    [35]
    35. Catalytic converter, according to claim 19, CHARACTERIZED by the fact that said trivalent metal ion is the Fe (III) ion.
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B06T| Formal requirements before examination|
    2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2019-12-03| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.21 NA RPI NO 2550 DE 19/11/2019 POR TER SIDO INDEVIDA. |
    2020-03-17| B09A| Decision: intention to grant|
    2020-05-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/404,071|US8987162B2|2010-08-13|2012-02-24|Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst|
    PCT/US2013/027206|WO2013126619A1|2012-02-24|2013-02-22|Hydrothermally stable, low-temperature nox reduction nh3-scr catalyst|
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