Strengthening the introduction of extraskeletal metals into aluminosilicate zeolites

Abstract

To provide a simplified preparation process of a metal-containing aluminosilicate zeolite.SOLUTION: A process involves the steps of: (a) forming a reactant mixture A containing (i) an aqueous slurry of an aluminosilicate zeolite in the H+-form and (ii) a metal-containing compound or free metal, where the mixture A does not contain ammonia, ammonium hydroxide or an ammonium salt, and where the aluminosilicate zeolite is AEI; and (b) reacting the metal-containing compound or free metal with the aluminosilicate zeolite in the H+-form in the reactant mixture A to form a product mixture B containing an extra-framework metal-containing aluminosilicate zeolite. The metal includes one or more of Cu, Mn, Ni and Pd. The step of reacting the metal-containing compound or free metal with the aluminosilicate zeolite in the H+-form is performed in single exchange. After forming the mixture B, the extra-framework metal-containing aluminosilicate zeolite is not separated from the mixture after the reaction.SELECTED DRAWING: Figure 1

Description

[Technical Field] 【0001】 This invention provides a single step for converting metal ions to H + This invention relates to a process for producing an extraskeletal metal-containing aluminosilicate zeolite by ion exchange with a specific type of aluminosilicate zeolite, and the resulting reaction mixture can be used to form a wash coat. Unlike conventional ion exchange methods, this method separates the reaction mixture from the formed metal-containing aluminosilicate and washes the metal-containing aluminosilicate with water in a series of repeated steps to remove impurities from the metal-containing aluminosilicate. [Background technology] 【0002】 Aluminosilicate zeolites are crystalline aluminosilicate materials that have fairly uniform pore sizes, generally ranging in diameter from about 3 to 10 angstroms, depending on the type of zeolite, the position of the cations, the type of cations, and the number of cations contained in the zeolite. 【0003】 The use of synthetic zeolites to facilitate specific reactions, such as the selective catalytic reduction (SCR) of nitrogen oxides with reducing agents such as ammonia, urea, and / or hydrocarbons in the presence of oxygen, is well known in the art. 【0004】 The process for synthesizing zeolites may vary depending on the zeolite's skeletal structure. Zeolites are typically synthesized using a structure-directing agent (also called a template or organic template) along with silica and alumina sources. The structure-directing agent is an organic compound, such as tetraethylammonium hydroxide (TEAOH), or an inorganic cation, such as Na. + Or K + It can be of this type. During crystallization, tetrahedral silica-alumina units are organized around a structure-directing agent (SDA) to form the desired framework, and the SDA is often contained within the pore structure of the zeolite crystal. 【0005】 It has been found that the catalytic activity of aluminosilicate zeolites can be improved by introducing extra-framework metals into the aluminosilicate zeolites. The researchers have described various methods for introducing various metals into a number of molecular sieves. 【0006】 Dedecek et al. (Microporous and Mesoporous Materials 32 (1999) 63-74) investigated the direct exchange of copper into Na + , Ca 2+ , Cs + , and Ba 2+ -type chabazite. By a single exchange process, materials with a Cu / Al ratio of 0.01-0.28 were produced. In examples where two ion exchanges were carried out, materials with Cu / Al ratios of 0.34, 0.38, and 0.32 were produced. 【0007】 International Publication No. 2008 / 077590 describes a process for directly metal-exchanging iron, copper and / or silver into the Na + -type of zeolites having an MFI or BEA structure, and the metal exchange is carried out by suspending the zeolite in an aqueous solution containing metal ions and ammonium ions. 【0008】 International Publication No. 2008 / 106519 (U.S. Patent No. 7,601,622) discloses a catalyst comprising a zeolite having a CHA crystal structure prepared via copper that exchanges NH4 + -type CHA with copper sulfate or copper acetate. The processes of ion exchange, filtration, washing, and drying were carried out at least twice (repeated at least once). In some examples, multiple ion exchange, filtration, washing, and drying steps were used, and these steps were carried out up to 5 times. In some examples, the coated slurry containing the calcined CuCHA catalyst was treated with additional copper sulfate to increase the total concentration of CuO. In one example, a CuCHA catalyst containing 1.94% CuO was prepared by a single ion exchange, but the details of the exchange were not provided. 【0009】 International Publication No. 2008 / 132452 discloses various small-pore NH4+ Disclosed is that zeolites (SAPO-34, SSZ-13, Sigma-1, ZSM-34, ZSM-5) and beta (large-pore zeolite) can be ion-exchanged with transition metals. It has been disclosed that by repeating this procedure, a desired metal loading higher than that obtained by single ion-exchange can be achieved. According to the examples, multiple aqueous ion-exchanges may be required to achieve a desired loading of 3 wt% Cu. 【0010】 In U.S. Patent No. 2011 / 0165052, a method for preparing CuCHA by ion-exchanging copper into Na + type or NH4 type CHA is disclosed. 【0011】 In U.S. Patent No. 2017 / 0095804, a method for preparing a metal-exchanged zeolite is disclosed by preparing (a) one or more microporous zeotype materials showing an ion-exchange capacity and (b) a dry mixture of one or more metal compounds, and heating the mixture to a temperature lower than 300 °C for a time sufficient to initiate and carry out solid ion-exchange between the ions of the metal compound and the ions of the zeolite material in a gas atmosphere containing ammonia. Also disclosed are the advantages of using solid ion-exchange over the conventional method of contacting the zeolite with a solution of the desired metal ions. 【0012】 U.S. Patent No. 8,795,626 relates to chabazite-type zeolites having copper and an alkaline earth metal supported thereon. In one example, using conventional ion-exchange, Cu is exchanged into H + type zeolite, and after the reaction, the solid is separated from the liquid, washed, dried, and then the alkaline earth metal is exchanged into CuCHA. 【0013】 Unfortunately, achieving the desired metal loading may involve inefficient and wasteful procedures. There is a continuing desire to simplify the process for preparing metal-containing aluminosilicates, because this process involves many processing steps that add capital and operating costs to the manufacturing process. [Overview of the Initiative] 【0014】 The preparation process for exoskeleton-containing aluminosilicate zeolites is (a)(i)H + A step of forming a reaction mixture A comprising (ii) an aqueous slurry of aluminosilicate zeolite of type and (ii) a metal-containing compound or a free metal, wherein the mixture does not contain ammonia, ammonium hydroxide, or an ammonium salt, and a step of releasing the metal or free metal from the metal-containing compound into the reaction mixture A. + A step of reacting a type of aluminosilicate zeolite to form a product mixture B containing an extraskeletal metal aluminosilicate zeolite, wherein the metal is H + The process of reacting the aluminosilicate zeolite of a specific type is carried out in a single exchange, and after forming product mixture B, the extraskeletal metal-containing aluminosilicate zeolite is not separated from product mixture B, and the process includes these steps. 【0015】 A process for preparing a wash coat containing an exoskeleton metal-containing aluminosilicate zeolite comprises (a) preparing a product mixture B containing an exoskeleton metal-containing aluminosilicate zeolite according to the process described herein, and (b) combining the product mixture B, i.e., the reaction mixture containing the exoskeleton metal-containing aluminosilicate zeolite, with a binder, a rheological modifier, or a mixture of a binder and a rheological modifier to form a wash coat mixture C. 【0016】 From the standpoint of efficiency, minimizing waste flow, and reducing the number of required processes, the method described herein offers several advantages over current state-of-the-art technologies. This allows for improved throughput of articles manufactured using exoskeleton metal-containing aluminosilicate zeolite while reducing energy consumption. The resulting mixture B, containing the metal incorporated into the aluminosilicate zeolite, can be used directly in forming a wash coat without requiring (a) the removal of water and undesirable reaction products from the resulting mixture B, (b) washing or further processing the exoskeleton metal-containing aluminosilicate zeolite, and / or (c) calcining the metal incorporated into the aluminosilicate zeolite. 【0017】 This simplifies the overall process, eliminating the need to wash the reaction mixture to remove metals not incorporated into the aluminosilicate zeolite, and thus eliminating the need to remove water, resulting in increased productivity and savings in both energy and materials. It also eliminates the need for two calcination steps: one when producing the exosilicate metal-containing aluminosilicate zeolite, and another after applying a wash coat to the substrate. The method described herein makes it possible to eliminate the calcination step when producing the exosilicate metal-containing aluminosilicate zeolite. This reduces capital expenditures on separate drying and calcination equipment and saves operational capital by reducing inventory in the process. [Brief explanation of the drawing] 【0018】 [Figure 1] The steady-state NOx conversion rate and N2O concentration are shown based on samples prepared by the method described herein after mild hydrothermal aging (620°C / 100h / 10%H2O). [Figure 2] The steady-state NOx conversion rate is shown based on samples prepared by the method described herein after moderate hydrothermal aging (750°C / 80h / 10%H2O). [Figure 3]The steady-state NOx conversion rate is shown based on samples prepared by the method described herein after severe hydrothermal aging (900°C / 4h / 4.5%H2O). [Modes for carrying out the invention] 【0019】 As used herein, the singular forms "a," "an," and "the" refer to multiple objects unless the context clearly indicates otherwise. For example, a reference to "a catalyst" includes a mixture of two or more catalysts. 【0020】 The term "approximately" means roughly and refers to a range of the value to which the term relates, which is optionally ±25%, preferably ±10%, more preferably ±5%, or most preferably ±1%. 【0021】 When one or more ranges are specified for various numerical elements, the values ​​will be included in one or more ranges unless otherwise specified. 【0022】 As used herein, the term “metal” refers to copper, iron, manganese, nickel, and / or palladium that are replaced by or located on aluminosilicate zeolite. As used herein, the term “metal-containing compound or free metal” refers to a metal, oxide, or free metal that is a cation in a salt of a metal. Where a metal exists as a cation, it may exist in solution in the form of a salt containing the metal as a cation together with anions. 【0023】 The term “H + "Type" aluminosilicate zeolites refer to aluminosilicate zeolites that have a skeletal charge substantially equilibrated by protons. In this type, aluminosilicate zeolites generally have H at the exchange site. + It contains a mixture of alkali and / or alkaline earth cations. + Type aluminosilicate zeolite is H +In the type, the values ​​can be ≥90%, ≥95%, ≥96%, ≥97%, ≥98%, or ≥99%. + The amount of aluminosilicate zeolite of a particular type may vary depending on the specific aluminosilicate zeolite batch and the method used to form the aluminosilicate zeolite. 【0024】 The term "extra-skeleton metal-containing aluminosilicate zeolite" refers to aluminosilicate zeolite in which the metal is present on the surface and / or inside the cage and / or pores of the aluminosilicate zeolite. It does not refer to aluminosilicate in which the metal is present within the aluminosilicate skeleton. 【0025】 Pores are openings that extend from one side of a crystal to the other, but are not linear. A cage is a polyhedral pore, and its windows, the faces of the polyhedral pore, are too narrow for molecules larger than water to enter. This means that the maximum size of the cage window is a six-membered ring. 【0026】 When the metal is a salt cation, the term "react" refers to the ion exchange of the metal with the zeolite. When the metal is a metal oxide or free metal, the term "react" refers to the movement of the metal oxide or free metal onto and / or into the zeolite. 【0027】 When the metal is a salt cation, the term “product mixture C” refers to the mixture formed after metal exchange occurs with the aluminosilicate zeolite, resulting in the formation of “extra-skeleton metal-containing aluminosilicate zeolite.” This metal exchange can be ion exchange. The reaction mixture includes “extra-skeleton metal-containing aluminosilicate zeolite,” all reaction products present in the mixture, and water. When the metal is a free metal or metal oxide, the term “product mixture C” refers to the mixture formed after the metal or metal oxide migrates to an external position within the aluminosilicate zeolite. 【0028】 The term "calcination" means heating a material in air, oxygen, or an inert atmosphere. This definition is consistent with the IUPAC definition of calcination. (IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Created by ADMcNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML online revised version: http: / / goldbook.iupac.org (2006-), created by M.Nic, J.Jirat, B.Kosata, updated by A.Jenkins. ISBN 0-9678550-9-8. doi:10.1351 / goldbook.) Calcination is performed to decompose metal salts, promote the exchange of metal ions in the catalyst, and adhere the catalyst to the substrate. The temperature used for firing varies depending on the components of the material being fired, and is generally about 400°C to about 900°C for about 0.25 to 8 hours. In some cases, firing can be carried out at temperatures up to about 1200°C. In applications involving the processes described herein, firing is generally carried out at temperatures of about 400°C to about 700°C for about 0.25 to 8 hours, preferably at temperatures of about 400°C to about 650°C for about 0.25 to 4 hours. 【0029】 The term "wash coat" refers to the carrier of the catalytic material used to disperse the material over a large portion of the surface of a substrate. The catalytic material is suspended in the wash coat before it is applied to the substrate. 【0030】 The term "comprising" is synonymous with "including," "containing," or "characterized by," and is comprehensive or open-ended, not excluding any additional unlisted elements or methods. 【0031】 As used herein, the term “essentially consisting of” limits the scope of a feature to a particular material, process, and any other material or process, such as trace impurities that do not substantially affect the fundamental properties of that feature. The expression “essentially consisting of” encompasses the expression “consisting of.” 【0032】 The term "consists of" excludes any elements, processes, or components not explicitly stated in the claims. 【0033】 This specification describes a process for preparing exoskeleton metal-containing aluminosilicate zeolites. The process for producing the exoskeleton metal-containing aluminosilicate zeolites described herein can be carried out using either a batch tank or a continuous process manufacturing method. The exoskeleton metal-containing aluminosilicate zeolites obtained or obtainable by the process of the present invention can be processed and used as described in the literature for other exoskeleton metal-containing aluminosilicate zeolites. The exoskeleton metal-containing aluminosilicate zeolites in their as-prepared state can also be directly incorporated into a wash coat as part of a process for forming an exoskeleton metal-containing aluminosilicate zeolite and then a wash coat applied to a substrate. 【0034】 1. Process for incorporating metals into the external framework of aluminosilicate zeolite. The process for preparing an aluminosilicate zeolite containing extraskeletal metals is as follows: (a)(i)H + A step of forming a reaction mixture A comprising (ii) an aqueous slurry of aluminosilicate zeolite of type and (ii) a metal-containing compound or a free metal, wherein the mixture does not contain ammonia, ammonium hydroxide, or an ammonium salt. (b) Metal reacts with H in mixture A + The process includes reacting a type of aluminosilicate zeolite to form a reaction mixture B, i.e., a reaction mixture containing an extraskeletal metal-containing aluminosilicate zeolite, The metal contains one or more of copper, iron, manganese, nickel, and palladium, and the metal is H + The reaction step with the aluminosilicate zeolite is carried out in a single exchange, and after forming product mixture B, the exoskeleton metal-containing aluminosilicate zeolite is not separated from product mixture B. 【0035】 Process (a) (i)H + A reaction mixture A is formed comprising (ii) an aqueous slurry of aluminosilicate zeolite of type and (ii) a metal-containing compound or a free metal, wherein the mixture does not contain ammonia, ammonium hydroxide, or ammonium salts. 【0036】 As used herein, the term aluminosilicate zeolite encompasses aluminosilicate zeolites having any one of the skeletal structures listed in the zeolite structure database published by the International Zeolite Association (IZA). Zeolites have a three-dimensional framework of interconnected tetrahedrons containing aluminum, silicon, and oxygen atoms, where all four oxygen atoms located at the corners of each tetrahedron are shared with adjacent tetrahedron crystals. Non-oxygen atoms within the tetrahedrons are called T atoms. 【0037】 Aluminosilicate zeolites can be small-pore, medium-pore, or large-pore aluminosilicate zeolites, or a combination thereof. Small-pore aluminosilicate zeolites typically have pores defined by rings of 8 or fewer T atoms and an average pore diameter of less than approximately 0.5 nm (5 Å). Medium-pore aluminosilicate zeolites typically have pores defined by rings of 10 T atoms and an average pore diameter of approximately 0.5–0.6 nm (5–6 Å), while large-pore materials have pores defined by rings of 12 or more T atoms and a pore diameter greater than 0.6 nm (6 Å). 【0038】 The small-pore aluminosilicate zeolite can be selected from the group of skeletal types consisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, KFI, LEV, LTA, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SFW, SIV, THO, TSC, UEI, UFI, VNI, YUG, and ZON, as well as mixtures thereof and / or intergrowth. Preferably, the small-pore aluminosilicate zeolite is selected from the group of skeletal types consisting of AEI, AFT, AFX, CHA, DDR, ERI, KFI, LEV, LTA, SFW, and RHO. 【0039】 The medium-pore aluminosilicate zeolite can be selected from the group of skeletal types consisting of AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB, NAT, NES, OBW, PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, SVR, SZR, TER, TON, TUN, UOS, VSV, WEI, and WEN, as well as mixtures thereof and / or Intergrowth. Preferably, the medium-pore aluminosilicate zeolite is selected from the group of skeletal types consisting of FER, MEL, MFI, STI, and STT. 【0040】 Large-pore aluminosilicate zeolites can be selected from the group of skeleton types consisting of AFI, AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV, IWW, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS, STO, SSF, SSY, USI, UWY, and VET, as well as mixtures thereof and / or intergrowth. Preferably, the large-pore molecular sieve is selected from the group of skeletal types consisting of AFI, BEA, GME, MAZ, MOR, and OFF. 【0041】 Aluminosilicate zeolite is preferably AEI, AFT, AFX, BEA * , CHA, DDR, ERI, FAU, FER, GME, HEU, ITE, KFI, LEV, LTA, MFI, MWW, RHO, RTH, SFW, * The framework includes SFV, STT, SZR, and UFI, as well as skeletal types selected from the group consisting of intergrowths and mixtures thereof. 【0042】 Aluminosilicate zeolites may have a silica / alumina molar ratio (SAR) defined as SiO2 / Al2O3, which is 5 to 50, preferably 8 to 40, more preferably 10 to 35, and even more preferably 13 to 25. 【0043】 Aluminosilicate zeolites can have the same particle size distribution as the metal-containing aluminosilicate zeolites outside the formed framework. Alternatively, aluminosilicate zeolites can have a particle size distribution that can be processed by jet milling, wet milling, or steam-assisted jet milling, etc., so that the metal-containing aluminosilicate zeolites have the desired particle size distribution. Wet milling can be carried out in a recirculation chamber mill or a basket-type immersion mill. Both wet mills use beads as an abrasion medium. Jet milling utilizes a high-speed jet of compressed air to cause abrasion by colliding particles with each other. 【0044】 Aluminosilicate zeolite can be treated before use in step (a) to alter one or more of its properties. For example, the treatment can alter the particle size or particle size distribution of the aluminosilicate zeolite. The acidity of the aluminosilicate zeolite can be altered by washing it with, for example, acid or EDTA. The aluminosilicate zeolite can be subjected to other forms of dealuminization, including hydrothermal treatment. 【0045】 H + Aluminosilicate zeolite of a specific type Step (a) includes H + A type of aluminosilicate zeolite is required. The applicants have identified H + We discovered that the use of type NH3 aluminosilicate zeolite enables the use of single-skeleton extrametal exchange and achieves a higher level of metal absorption than the use of NH3 type aluminosilicate zeolite. This is shown in Examples 1 and 2 below. 【0046】 Reaction mixture A contains 5% to 50%, preferably 10% to 45%, more preferably 20% to 45%, of H + It may contain aluminosilicate zeolite of a specific type. Reaction mixture A may be a slurry or suspension, preferably a slurry. 【0047】 metal The metal may include one or more of copper, iron, manganese, nickel, and palladium, preferably one or more of copper, manganese, nickel, and palladium. 【0048】 The metals may include combinations of iron with one or more of the following: copper, manganese, nickel, and palladium. 【0049】 The amount of metal supported in the metal-containing aluminosilicate zeolite outside the skeleton may be 0.1% to 10% by weight, preferably 0.1% to 7% by weight, and more preferably 0.1% to 5% by weight, relative to the amount of aluminosilicate zeolite. 【0050】 Metal salts Step (a) may use one or more salts of metals. The metal salts require metal cations and anions. 【0051】 Various salts of metals, or mixtures of salts, can be used. Preferably, the metal salts do not form complexes with other materials during metal exchange. Preferably, at least one of the metal salts is soluble in acidic aqueous solutions (pH ≤ 5). A combination of soluble and non-acidic water-soluble (pH ≥ 7) metal salts can be used. The metal salts may preferably contain one or more of the following anions: acetates, bromides, carbonates, chlorides, citrates, fluorides, formates, hydroxides, iodides, nitrates, oxalates, phosphates, and sulfates, or combinations thereof. 【0052】 One or more salts of a metal can consist of two salts, and the anions of these salts can be selected from acetates, formates, and hydroxides. 【0053】 The metal salt may be soluble in water, or it may be a physical mixture of the metal salt, such as a slurry or suspension. 【0054】 Metal concentration in reaction mixture A Metal-containing compounds or free metals may be present in solutions, slurries, or suspensions having a concentration of metal that achieves the desired loading amount of metal in aluminosilicate zeolite through a single ion exchange. If the metal-containing compound is water-soluble, the desired loading amount may be based on the absorption rate of the metal, determined by the difference between the concentration of metal in the supernatant sample derived from product mixture B, i.e., the reaction mixture after the exchange reaction, and the concentration of metal in the supernatant sample derived from reaction mixture A before the reaction occurred. A supernatant sample for analysis can be obtained by separating the solid from the liquid by centrifugation of a portion of reaction mixture A and product mixture B. The difference in the amounts of metal in reaction mixture A and product mixture B corresponds to the amount of metal exchanged on the external zonal framework of the zeolite. If the metal is a free metal, or in the form of a metal-containing compound that is not water-soluble but present in the slurry or suspension, samples of reaction mixture A and product mixture B may need to be analyzed in a way that solubilizes the metal without removing it from the external zonal framework of the zeolite. 【0055】 The metal-containing compound may be present in a solution, suspension, or slurry, depending on its water solubility and concentration. The concentration of the metal needs to be at a level that achieves the desired amount of metal supported in the aluminosilicate zeolite in a single step. The concentration of the metal in the solution can vary over a wide range depending on the solubility of the metal-containing compound in water, the presence of other water-soluble materials, and the concentration of the extraskeletal metal-containing aluminosilicate zeolite required for washcoat mixture C (used as a washcoat or to form a washcoat). The concentration of the metal-containing compound in water at the temperature for forming reaction mixture A, or at the reaction temperature for forming product mixture B, i.e., the reaction solution, may be in the range of 0.1 to 2.5 moles, preferably 0.5 to 2 moles, more preferably 0.1 to 1 mole, and even more preferably 0.2 to 0.5 moles. 【0056】 The metal-containing compound or metal may be present in a solution, suspension, or slurry, depending on the water solubility and concentration of the metal-containing compound or metal. The concentration of the metal needs to be at a level that achieves the desired amount of metal supported in the aluminosilicate zeolite in a single step. The concentration of the metal in the solution can vary over a wide range depending on the solubility of the metal-containing compound in water, the presence of other water-soluble materials, and the concentration of the extraskeletal metal-containing aluminosilicate zeolite required for washcoat mixture C (used as a washcoat or to form a washcoat). At the temperature for forming reaction mixture A, or at the reaction temperature for forming product mixture B, i.e., the reaction solution, the concentration of the metal-containing compound or metal in reaction mixture A may be in the range of 0.01 to 2.5 moles, preferably 0.05 to 2 moles, more preferably 0.05 to 1 mole, and even more preferably 0.075 to 0.5 moles. 【0057】 Step (a) requires that reaction mixture A does not contain ammonia, ammonium hydroxide, or an ammonium salt. By using ammonia, ammonium hydroxide, or an ammonium salt, an ammonium complex may be formed with the metal. With some metals, the complex may increase the metal concentration in the solution. If the pore size of the aluminosilicate zeolite is sufficiently large, the exchange of metal can be improved. However, in the case of small-pore aluminosilicate zeolites, the exchange may be hindered by the large radius of the complex. If the metal complex is too large, the concentration of the metal in the solution will increase. If the formation of the complex is more thermodynamically stable, the concentration of the metal in the solution will increase. 【0058】 This can also be seen as relating to reverse exchange and competition between ammonium and the desired metal cation. The presence of the ammonia complex allows for a change in the amount of metal exchanged, with the metal being replaced by aluminosilicate zeolite. 【0059】 In the initial part of the process, whether in batch or continuous mode, the aluminosilicate zeolite is dispersed in or mixed with a solution, slurry, or suspension of a metal-containing compound or free metal containing water. 【0060】 In batch processes, aluminosilicate zeolite can be dispersed in or mixed with a metal-containing compound or a solution, slurry, or suspension containing free metals, preferably as a dry powder / crystal or slurry. 【0061】 In continuous processes, this dispersion or mixing can be performed using an in-line continuous mixing system. Examples of such mixers include the Silverson in-line LS series mixer, Admix Fastfeed in-line mixer, Ystral Conti TDS mixer, IKA MHD 2000 in-line mixer, and Arde Barinco Dispershear. Preferably, the metal-containing compound is in a solution that can be precisely injected into the mixer, preferably using a rotor-stator pump, and the zeolite powder can be precisely injected into the mixer, preferably using a loss-in-weight powder feeder system. This ensures that the solid concentration and metal ion concentration of the output slurry from the mixer are controlled. If the salt is in slurry or suspension form, it can preferably be precisely injected into the mixer, preferably using a rotor-stator pump, and the zeolite powder can be precisely injected into the mixer, preferably using a loss-in-weight powder feeder system. This ensures that the (a) solid concentration and (b) metal ion concentration of the output slurry from the mixer are controlled. 【0062】 H + A mixture is formed of a type of aluminosilicate zeolite and a solution, slurry, or suspension of a metal-containing compound or free metal of the metal incorporated into the aluminosilicate zeolite. 【0063】 H +Aluminosilicate zeolite of type H, metal-containing compound or free metal and water may be added together in any order. + Aluminosilicate zeolite can be added as a powder or a mixture with water, as a slurry or suspension, or as a solution / mixture, preferably an aqueous solution / mixture of a metal salt, a metal-containing compound, or a combination of free metals. 【0064】 Aqueous solutions, slurries, or suspensions of metal-containing compounds or free metals may be at temperatures between 10°C and 90°C in which metal exchange reactions occur. 【0065】 Alternatively, a solution, slurry, or suspension of a metal-containing compound or free metal, preferably an aqueous solution, is placed in water with H + Type aluminosilicate zeolite or solid H + It can be added to a mixture of type aluminosilicate zeolites. Depending on the metal-containing compound or free metal and zeolite, the solution, slurry or suspension of the metal-containing compound or free metal is cooled at room temperature (about 30°C) to about 10°C, below room temperature (about 30°C), or heated from room temperature (about 30°C) to about 90°C, preferably about 50 to about 75°C, and more preferably about 55 to about 70°C, and then H + Aluminosilicate zeolite can be added to a solution, slurry, or suspension of a metal-containing compound or free metal, or H + It can be added to type aluminosilicate zeolite. 【0066】 Reaction mixture A has a pH that depends on the concentration of aluminosilicate zeolite, a metal-containing compound or free metal, and the concentrations of the aluminosilicate zeolite and the metal-containing compound or free metal. 【0067】 The step of forming reaction mixture A may further include adjusting the pH of reaction mixture A by adding a base. The base is an inorganic base, preferably a metal hydroxide, or an organic base, preferably an alkyl ammonia hydroxide, the alkyl ammonia hydroxide containing 4 to 16 carbon atoms. 【0068】 The pH of reaction mixture A can be adjusted to make it more basic, thereby increasing the amount of metal loaded onto the zeolite in the metal exchange in step b). The step of adjusting the pH of reaction mixture A may include supplying a base such that the concentration of hydroxide ions in the solution is equal to or greater than the concentration of the metal in the solution. 【0069】 The step of adjusting the pH of reaction mixture A may include adding a sufficient amount of base to remove the amount of free metal in the solution to less than 10% of the total metal, preferably less than 5%, and more preferably less than 1%. 【0070】 Step (b) React the metal with H in mixture A + It is reacted with a type of aluminosilicate zeolite to form a product mixture B containing an aluminosilicate zeolite containing an extraskeletal metal. 【0071】 In the second part of the process, an ion exchange reaction is used to incorporate the metal into the aluminosilicate zeolite, forming an extra-skeletal metal-containing aluminosilicate zeolite. 【0072】 Metal reacts with H in mixture A + The step of reacting a type of aluminosilicate zeolite to form a product mixture B containing an extraskeletal metal-containing aluminosilicate zeolite includes mixing reaction mixture A at a temperature and time sufficient to obtain a desired amount of metal loading on the aluminosilicate zeolite. 【0073】 mixture The reaction mixture A, slurry, or suspension can be properly mixed to form a product mixture B with good mixing, thereby preventing solid precipitation. Those skilled in the art will recognize the apparatus and techniques that can be used to obtain such a mixture. 【0074】 Reaction temperature The step of reacting reaction mixture A to form an extraskeletal metal-containing aluminosilicate zeolite may include cooling or heating the reaction mixture to a temperature of 10°C to 90°C, preferably 20°C to 85°C, more preferably 25°C to 75°C, and most preferably 30°C to 75°C. If the metal-containing compound in reaction mixture A contains copper acetate, reaction mixture A needs to be heated to a temperature of 40°C to 85°C, more preferably 55°C to 75°C. 【0075】 The step of reacting reaction mixture A to form an aluminosilicate zeolite containing an extra-skeletal metal may include mixing reaction mixture A at a temperature that does not require heating, such as ambient temperature. Depending on the circumstances, the reaction may be carried out at a temperature that requires cooling, such as 10-12°C. The step of reacting reaction mixture A to form an aluminosilicate zeolite containing an extra-skeletal metal can be carried out at ambient temperature or a temperature that requires cooling. 【0076】 Time for metal exchange or reaction The length of time required to form a mixture containing metal-containing aluminosilicate zeolite depends on one or more of the following: aluminosilicate zeolite, SAR of aluminosilicate zeolite, type of aluminosilicate zeolite, particle size of aluminosilicate zeolite, desired metal load, metal salt, temperature at which reaction mixture A is heated, and concentration of reactants. 【0077】 The reaction time for the exchange of the metal to an extra-skeletal position within the aluminosilicate zeolite during contact with a metal-containing compound or a solution, slurry, or suspension of a free metal can be about 1 minute to about 24 hours, preferably about 5 minutes to about 18 hours, more preferably about 15 minutes to about 12 hours, about 10 minutes to about 5 hours, about 10 minutes to about 3 hours, or about 10 minutes to about 1 hour. 【0078】 pH: Use of basic additives The pH of reaction mixture A may be in the range of about 4 to about 7, preferably in the range of about 5 to about 7, and more preferably in the range of about 5 to about 6. 【0079】 Depending on the starting materials used, it may be necessary to adjust the pH of the slurry or suspension so that the pH of reaction mixture A has the above-mentioned value. The pH can be adjusted to the above-mentioned value using a base, which is an inorganic base, preferably a metal hydroxide, or an organic base, preferably an alkyl ammonia hydroxide, where the alkyl ammonia hydroxide contains 4 to 16 carbon atoms. Preferably, the base is an alkylammonium hydroxide. 【0080】 Absorption rate The absorption rate is a measure of the amount of metal transferred from a metal-containing compound or free metal to the aluminosilicate zeolite as an extra-skeletal metal. The absorption rate is defined as the number of moles of metal in or on the aluminosilicate zeolite / the number of moles of metal in the starting solution × 100. The absorption rate is the total amount of metal exchanged for and adsorbed onto the aluminosilicate zeolite. The absorption rate can range from about 80% to about 98%, depending on the source of the aluminosilicate zeolite used, the reaction temperature, and the reaction time. The metal absorption rate can be at least about 80%, preferably at least about 85%, more preferably at least about 90%, and most preferably at least about 92%. 【0081】 Cooling of the resulting mixture B If the reaction is carried out at room temperature (maximum 40°C), cooling of the product mixture B after metal exchange is not required. 【0082】 If the reaction is carried out at a temperature higher than room temperature (above 40°C), the resulting mixture B must be cooled to room temperature (up to 40°C) or further processed for other uses before producing a wash coat using a mixture of exoskeleton metal-containing aluminosilicate zeolites. 【0083】 In a batch process, reaction mixture A is mixed at a non-heating temperature, or at the temperature described above, until the desired amount of metal absorption by the zeolite is reached. 【0084】 In a continuous process, the output slurry from the first part of the continuous process can be continuously supplied to a thermally controlled mixer reactor system to carry out the ion exchange reaction. Typical mixer reactors that can be used for this purpose are tubular reactors, continuous agitated flow reactors, or baffle reactors, such as vibrating baffle reactors, spinning disk reactors, or spinning cone reactors. These reactors may have different types of mixer interiors, selected and optimized according to the mixing operation required herein. Typically, a thermally controlled system in a pipe of a desired length containing static mixing elements can be used in operation, provided that the slurry has a residence time in the reactor to ensure that the ion exchange reaction is complete, which can be confirmed by analysis. The reaction mixture A, i.e., the output slurry from the first part of the continuous process, can be pumped through the pipe at a controlled, desired rate to complete the reaction within the length of the pipe. The static mixing elements in the pipe ensure thorough mixing of the slurry and prevent the sedimentation of zeolite and any other insoluble components. The temperature of the outside of the piping can be controlled by an external heating system to ensure sufficient heat transfer throughout the entire piping system and to allow the slurry in the reactor to reach the set temperature required for the desired ion exchange. At the ends of the piping, the slurry can be cooled by cooling the outer surface of the piping. 【0085】 If the resulting mixture B (containing an extra-skeletal metal-containing aluminosilicate zeolite) is heated, the process may further include the step of cooling the mixture formed in step (b) to room temperature. 【0086】 Extra-skeletal metal-containing aluminosilicate zeolite The extraskeletal metal-containing aluminosilicate zeolite obtained / can be obtained by the above process may have the following composition. 【0087】 Metal ions vs. metal oxides The extraskeletal metal-containing aluminosilicate zeolite obtained / can be obtained by the above process may have a weight ratio of replaced metal to metal oxide, measured after calcining the aluminosilicate zeolite in air at 450°C for 1 hour, of ≥1, ≥2, ≥3, ≥4, ≥5, ≥6, ≥7, ≥8, ≥8.5, or ≥9. 【0088】 Weight percentage of metal The target loading amount of metal in the metal-containing aluminosilicate zeolite obtained / obtainable by the above process, calculated as a metal oxide, may be ≤10 wt%, ≤9 wt%, ≤8 wt%, ≤7 wt%, ≤6 wt%, ≤5 wt%, ≤4 wt%, or ≤3 wt%, depending on the metal and the aluminosilicate zeolite. The metal oxide may be MO, M2O, or M, depending on the metal. x O y It can be of the form of. For example, if the metal is copper, the metal oxide is CuO. If the metal is iron, the metal oxide is Fe2O3. Those skilled in the art will recognize that the target load depends on the intended use of the aluminosilicate zeolite, the metal, and the extraskeletal metal-containing aluminosilicate zeolite. For example, using metal-containing aluminosilicate zeolite, NO x When treating exhaust gas containing a mixture of NO and N2O, the target amount of metal supported on aluminosilicate zeolite is NO x And, in order to target the reduction of N2O, different metal loading amounts can be selected, so NO in exhaust gas xAnd it may vary depending on the concentration of N2O. 【0089】 Free metal In addition to the metals that are exchanged to increase the concentration of metals associated with the exchange sites in the structure of the aluminosilicate zeolite, non-exchanged metals, generally in the form of metal oxides or hydroxides, known as free metals, may be present on the surface of the aluminosilicate zeolite. In some aspects of the present invention, free metals are not present on the aluminosilicate zeolite. 【0090】 Metal / Al The atomic ratio of the metal to aluminum in the metal-containing aluminosilicate zeolite obtained / can be obtained by the above process may be about 0.05 to 1.4, preferably about 0.25 to about 0.7. 【0091】 The exoskeleton metal-containing aluminosilicate zeolite can be dried and / or treated and used as is known in compositions and processes known to be used with exoskeleton metal-containing aluminosilicates. 【0092】 The above process eliminates many of the post-treatment processes required when conventional ion exchange methods are used. After the formation of the exoskeleton metal-containing aluminosilicate zeolite, the aluminosilicate zeolite can be treated using methods known to those skilled in the art to obtain purified aluminosilicate zeolite, preferably in solid form. Preferably, the resulting mixture B containing the aluminosilicate zeolite can be used directly without isolation or purification to form a wash coat that can be applied to a substrate used to purify exhaust gases from an engine. There is no need to separate the exoskeleton metal-containing aluminosilicate zeolite from the mother liquor resulting from the metal incorporation. 【0093】 2. Formation of a wash coat containing a generated mixture B, which includes an extraskeletal metal-containing aluminosilicate zeolite. The process for preparing a wash coat containing an extraskeletal metal-containing aluminosilicate zeolite is as follows: (a) A step of preparing a product mixture B containing the above-mentioned metal-containing aluminosilicate zeolite outside the skeleton, (b) The process includes the step of combining the resulting mixture B with a binder, a rheological modifier, or a mixture of a binder and a rheological modifier to form a wash coat mixture C, i.e., a wash coat. 【0094】 Wash coat mixture C comprises a product mixture B containing an exoskeleton metal-containing aluminosilicate zeolite, and one or more of a binder and a rheology modifier. The wash coat can be formed using three different processes that use the same materials. In the first process, the binder and the exoskeleton metal-containing aluminosilicate zeolite are combined, and then the rheology modifier is added. In the second process, the rheology modifier and the exoskeleton metal-containing aluminosilicate zeolite are combined, and then the binder is added. In the third process, the binder and rheology modifier are combined with the exoskeleton metal-containing aluminosilicate zeolite, and the binder and rheology modifier may be added simultaneously as a mixture or as two separate materials. 【0095】 In each of these processes, when combining two materials, the order in which they are combined is not limited. For example, product mixture B can be combined with the binder mixture / solution by adding product mixture B to the binder mixture / solution, or by adding the binder mixture / solution to product mixture B. The binder can be added as a powder or aqueous slurry. 【0096】 Binder A binder, also known as a binding agent, is a material used to hold or attract other materials in a wash coat together and to the substrate to which it is applied. 【0097】 The binder may include alumina, aluminum hydroxide, TiO2, SiO2, ZrO2, CeZrO2, SnO2, aluminophosphates, non-zeolite aluminosilicates, silica-alumina, clay, or mixtures thereof. 【0098】 The binder can be added in powder form or in slurry to a mixture containing an extraskeletal metal-containing aluminosilicate zeolite, i.e., product mixture B, or to a mixture containing product mixture B and a rheology modifier, to form wash coat mixture C, i.e., wash coat. 【0099】 The binder can be added to the wash coat mixture C in an amount of 1 to 20% of the total solids, preferably 1 to 15%, and more preferably 1 to 10% of the total solids. 【0100】 The binder can be added in an amount of 1 to 10% by weight, preferably 1 to 5% by weight, of the product mixture B, i.e., the reaction mixture. 【0101】 Rheological modifier Rheology modifiers may include polysaccharides, starch, cellulose, alginates, cellulose (i.e., cellulosic substances), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, and ethylhydroxyethylcellulose, as well as mixtures thereof. 【0102】 Rheological modifiers may include clays such as laponite, kaolin, bentonite, or organic clay. 【0103】 The rheological modifier may include at least one polysaccharide selected from the group consisting of galactomannan gum, xanthan gum, curdlan, schizophyllan, scleroglucan, deutan gum, welan gum, and mixtures of two or more of these. In embodiments where the washcoat requires low pH and high temperature stability, the rheological modifier preferably includes scleroglucan and / or schizophyllan, with scleroglucan being particularly preferred. 【0104】 Polysaccharide rheological modifiers may be starch, cellulose, or alginates, or may be derived from starch, cellulose (i.e., cellulosic substances), or alginates. However, these rheological modifiers do not share all the properties of scleroglucan, welan gum, and deutan gum. For example, hydroxyethylcellulose may decompose when heated, even at neutral or basic pH levels. 【0105】 Cellulose-based rheological modifiers can be selected from the group consisting of carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, and ethylhydroxyethylcellulose. 【0106】 The polysaccharide rheological modifier may also be an associative rheological modifier, and examples of such cellulosic substances include hydrophobic modified hydroxyethylcellulose or hydrophobic modified ethyl hydroxyethylcellulose. 【0107】 According to the present invention, it is possible to use a single rheological modifier as defined herein, a mixture thereof, or two or more thereof. For example, in one embodiment, at least one rheological modifier may be a mixture of guar gum and xanthan gum. 【0108】 A rheological modifier, either in powder form or as a slurry with water, can be added to the resulting mixture B or a mixture containing the resulting mixture B and a binder to form a wash coat mixture C. 【0109】 The rheological modifier can be added in an amount of 0.05 to 10% of the total solids, preferably 0.05 to 5%, and more preferably 0.05 to 3% of the total solids. 【0110】 The rheological modifier can be added to the resulting mixture B in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and contains an extraskeletal metal-containing aluminosilicate zeolite. 【0111】 Process for forming wash coat mixture C Washcoat mixture C comprises (a) a product mixture B containing an extraskeletal metal-containing aluminosilicate zeolite, and (b) a mixture of one or more of a binder and a rheology control agent. 【0112】 If the washcoat mixture C contains (i) a product mixture B and (ii) a binder or rheological modifier, the binder or rheological modifier can be added directly to the product mixture B, or the product mixture B can be added directly to the binder or rheological modifier. Preferably, the binder or rheological modifier exists as a solution, slurry, or suspension. 【0113】 If washcoat mixture C contains (i) a product mixture B and (ii) a binder and a rheological modifier, the washcoat can be formed using three different processes that use the same materials. In the first process, the binder and product mixture B are combined, and then the rheological modifier is added. In the second process, the rheological modifier and product mixture B are combined, and then the binder is added. In the third process, the binder and rheological modifier are combined with product mixture B, and the binder and rheological modifier can be added simultaneously as a mixture or as two separate materials. In each of these processes, when combining two materials, the order in which they are combined is not specified. For example, product mixture B can be combined with a binder mixture / solution by adding product mixture B to a binder mixture / solution, or by adding a binder mixture / solution to product mixture B. The binder or rheological modifier can be added to product mixture B as a solution, slurry, or suspension. Alternatively, product mixture B can be added to a solution, slurry, or suspension of the binder or rheological modifier. These processes provide the flexibility required by those skilled in the art. 【0114】 In each of these three processes, the extraskeletal metal-containing aluminosilicate zeolite is provided as a cooled or unheated product mixture B, i.e., the product mixture obtained from the reaction, and when the mixture formed after the reaction is used directly to create a wash coat, the metal can be incorporated into the extraskeletal position of the aluminosilicate zeolite from a metal-containing compound or free metal. Alternatively, the concentration of the extraskeletal metal-containing aluminosilicate zeolite in the mixture can be changed by processing the product mixture B formed after the reaction to incorporate the metal from a metal-containing compound or free metal into the extraskeletal position of the aluminosilicate zeolite, thereby changing the amount of water in the mixture. Generally, changing the amount of water is done to obtain a solid material or a more concentrated solution. 【0115】 In each of these three processes, the pH of one or more solutions, slurries, or suspensions containing the exoskeleton metal-containing aluminosilicate zeolite, a binder, and a rheological modifier can be adjusted by adding a base. The base is an inorganic base, preferably a metal hydroxide, or an organic base, preferably an alkyl ammonia hydroxide, where the alkyl ammonia hydroxide contains 4 to 16 carbon atoms. Preferably, the base is an alkylammonium hydroxide. The allylammonium hydroxide may be at least one of tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), and tetrabutylammonium hydroxide (TBAOH). Unlike steps a) and b) involved in the formation of the exoskeleton metal-containing aluminosilicate zeolite, the base may contain ammonia or ammonium ions. In one embodiment, washcoat mixture C does not contain ammonia or ammonium ions. 【0116】 The process may further include a step of adjusting the pH of washcoat mixture C by adding a base. The amount of base added may be based on the amount of metal in the solution. - The concentration of the added OH- to free metal may be higher than the concentration of the free metal in the solution, but the ratio of added OH- to free metal must be 2:1 or less. The base can be added to one or more of the product mixture B, the binder, the rheological modifier, or a combination of two or more of these. The base can be added after or simultaneously with the addition of the binder or rheological modifier. When the binder and rheological modifier are added in separate input streams, the base can be added in either these input streams or the separate input stream. 【0117】 When a continuous process is used to form the resulting mixture B, i.e., the reaction mixture, the resulting mixture B can be combined with one or more of the binder and rheology control agents. This can be done either in batch or continuous process using mixing techniques known in the art. 【0118】 A wash coat comprising, or essentially consisting of, the generated mixture B and one or more of a binder and a rheological modifier can be applied to a substrate using procedures well known to those skilled in the art. Preferably, the method used to apply the wash coat to the substrate is selected from the methods described in International Publication No. 9947260, No. 2011080525, or No. 2014195685, which are incorporated by reference. 【0119】 The substrate, ceramic, or metal monolith may be a low-porous or high-porous filter. The substrate may be a low-porous or high-porous flow-through or wall-flow filter. Preferably, the filter is a wall-flow filter. Preferably, the filter has high porosity. The term “high-porous substrate” refers to a substrate having a porosity of about 40 to about 80%. A high-porous substrate may preferably have a porosity of at least about 45%, more preferably at least about 50%. A high-porous substrate may preferably have a porosity of less than about 75%, more preferably less than about 70%. As used herein, the term porosity preferably refers to total porosity as measured by mercury porosimetry. Porosity is measured on an uncoated substrate. 【0120】 This method may further include the step of drying and firing a substrate containing a wash coat containing the generated mixture B. 【0121】 The firing of wash-coated substrates can be carried out at temperatures ranging up to approximately 850°C. The firing can be carried out in stages at a continuous temperature. The term "staged at a continuous temperature" means that the wash-coated substrate to be fired is heated to a specific temperature, held at this temperature for a specific time, heated from this temperature to at least one further temperature, and held at that temperature for a specific time. For example, staged firing is described in International Publication 2009 / 141324 (also published as U.S. Patent No. 8,715,618), which is incorporated by reference. 【0122】 The firing may be affected by any of the following preferred atmospheres, such as air, oxygen-deficient dilute air, oxygen, nitrogen, water vapor, synthetic air, or carbon dioxide. Preferably, the firing is carried out in air. The firing can be carried out in a dual manner, namely a first firing in an oxygen-reducing or oxygen-free atmosphere, and a second firing in air, an oxygen-enriched atmosphere, or a pure oxygen atmosphere. The humidity of the atmosphere can be controlled. 【0123】 One of the main advantages of using the process described herein is the reduction in energy consumption, which is due to the fact that only one firing is required on the wash-coated substrate. Other methods currently in use require at least two firings, namely one firing of the metal-containing aluminosilicate zeolite and another firing of the wash-coated support. These energy savings can be significant, especially considering the temperatures and the length of time the materials are fired. 【0124】 When using conventional ion exchange methods, other energy savings can be found by directly using the metal-containing aluminosilicate zeolite outside the framework in the wash coat, instead of having to wash the metal-containing aluminosilicate zeolite. In addition, when using the method described herein, the energy required to isolate the metal-containing aluminosilicate zeolite by currently used methods is not necessary. 【0125】 Product-by-process The present invention also relates to extraskeletal metal-containing aluminosilicate zeolites that can be obtained or are obtained by the process described above. 【0126】 The following examples further illustrate the process and materials of the present invention. [Examples] 【0127】 The applicants said, H + We discovered that using aluminosilicate zeolite of type 1 allows for single-step extraskeletal metal exchange, resulting in a higher metal load compared to using NH4-type aluminosilicate zeolite. This is shown in Example 1 below. 【0128】 Example 1 Copper is used in commercially available NH4 + Replace with CHA type, NH4 + CHA of the specified type can be treated with acid to obtain H in situ + Convert to type CHA and use commercially available H + A sample of type CHA was evaluated by determining the copper absorption rate from a copper acetate solution at 65°C to obtain a copper zeolite containing 2.4% by weight of copper. The solid content was approximately 38%. 【0129】 The same method as above was used, except that the initial concentration of copper in the solution was 3.3%. 【0130】 [Table 1] The SAR values ​​in the above samples were determined before calcination and before subsequent ion exchange. + When the H type was used, the Cu absorption rate decreased slightly (2-3%). When the ammonia type was used, the Cu absorption rate increased slightly (5%). + The NH4 type yielded more consistent results. 【0131】 Example 2 - Cu salt vs. Cu salt mixture Copper is used in H at SAR22 using a single copper salt or a blend of copper salts. + The copper content of each copper salt was determined by the proportion of the total copper metal that could be exchanged. Copper acetate was used as the primary copper source and blended with copper carbonate or copper hydroxide as the secondary source. + The CHA and Cu salts of the specified type were added to deionized water, and the system was heated to 65°C while mixing. The reaction mixture was held at 65°C for 5 hours, then cooled to room temperature, and samples for analysis were taken. 【0132】 The table below shows the copper absorption rates of copper-aluminosilicate zeolites produced using the above procedure with various copper salt blends. Both copper carbonate and copper hydroxide showed improved copper absorption rates when copper acetate was added compared to copper acetate alone. 【0133】 [Table 2] 【0134】 Example 3 Similar to Example 2, the temperature was 70°C, and the percentage of copper from copper hydroxide varied from 0 to 66.7%, except that AEI with a SAR of 20 and a copper content of 3.75% was used instead of CHA. 【0135】 The table below shows the copper absorption rates for various ratios of copper acetate blended with copper hydroxide. As the proportion of copper hydroxide increases, the copper absorption rate improves compared to copper acetate alone, even beyond a 50:50 ratio. 【0136】 [Table 3] 【0137】 Example 4 Using a single manganese salt, different amounts of manganese in SAR10 are H +The use of AFX type was investigated at 50 and 80°C. The solid was added to deionized water, and the system was heated to 80°C while mixing. The temperature was maintained for 2 hours, at which point it was cooled to room temperature, and samples for analysis were taken. 【0138】 The table below shows the manganese absorption rates for different temperature and weight percentage combinations. Reaction temperature is important because, when the metal is manganese, higher temperatures improve manganese absorption. Excess manganese in solution reduces absorption compared to lower weight percentages. 【0139】 [Table 4] 【0140】 Example 5 CuCHA samples with Cu loadings of 2.4% Cu (low loading) and 3.3% Cu (high loading). The samples were aged under the following tested conditions, and the resulting NOx conversion rates at various temperatures were determined. Before aging Medium: 750℃ / 80h / 10%H2O Severe: 900℃ / 4h / 4.5%H2O Mild: 620℃ / 100h / 10%H2O 【0141】 When evaluated before aging (not shown), the NOx conversion rate based on a low-supported sample at 200°C was 50,000 h -1 The space velocity was higher than 90%, and the NH3 to NOx ratio was 1, suggesting appropriate Cu exchange for the SCR reaction. After mild (620°C / 100h / 10%H2O, Figure 1) and moderate (750°C / 80h / 10%H2O, Figure 2) hydrothermal aging, the steady-state NOx conversion rate using the low-supported sample was similar to that of the high-supported sample. However, N2O formation based on the low-concentration sample was higher than 350°C. Following heavy hydrothermal aging (900°C / 4h / 4.5%H2O, Figure 3), the low-supported catalyst showed significant deactivation compared to the high-supported sample. Furthermore, the disclosure of the present invention may include the following embodiments. (Aspect 1) A process for preparing an aluminosilicate zeolite containing an extraskeletal metal, (a)(i)H + A step of forming a reaction mixture A comprising (ii) an aqueous slurry of aluminosilicate zeolite of type and (ii) a metal-containing compound or a free metal, wherein the mixture does not contain ammonia, ammonium hydroxide, or an ammonium salt. (b) The metal in the H + The process includes reacting a type aluminosilicate zeolite to form a product mixture B containing the metal-containing aluminosilicate zeolite outside the framework, The aforementioned metal includes one or more of copper, manganese, nickel, and palladium, and the aforementioned metal is H + The step of reacting the aluminosilicate zeolite of a certain type is carried out in a single exchange, and after forming product mixture B, the extraskeletal metal-containing aluminosilicate zeolite is not separated from the mixture after the reaction. (Aspect 2) The process according to embodiment 1, wherein the metal-containing compound or free metal of reaction mixture A further comprises an iron salt. (Aspect 3) The process according to embodiment 1 or 2, wherein the reaction mixture A has a pH, and the step of forming the reaction mixture A further comprises adjusting the pH of the reaction mixture A by adding a base. (Aspect 4) The process according to embodiment 3, wherein the base is an inorganic base, preferably a metal hydroxide, or an organic base, preferably an alkyl ammonia hydroxide, and the alkyl ammonia hydroxide contains 4 to 16 carbon atoms. (Appendix 5) The process according to any one of embodiments 1 to 4, further comprising adjusting the pH of the product mixture B by adding a base in order to increase the amount of extraskeletal metal present in the extraskeletal metal-containing aluminosilicate zeolite. (Aspect 6) The process according to any one of embodiments 1 to 5, wherein the reaction mixture A constitutes 5% to 50% by weight, preferably 10% to 45% by weight, and more preferably 15% to 40% by weight of the extraskeletal metal-containing aluminosilicate zeolite. (Aspect 7) The process according to any one of embodiments 1 to 6, wherein the step of reacting the reaction mixture A to form the metal-containing aluminosilicate zeolite outside the skeleton comprises mixing the reaction mixture at ambient temperature or a temperature requiring cooling. (Pattern 8) The process according to any one of embodiments 1 to 7, wherein the step of reacting reaction mixture A to form the metal-containing aluminosilicate zeolite outside the skeleton includes reacting reaction mixture A at a temperature of 10 to 30°C. (Aspect 9) The process according to any one of embodiments 1 to 6, wherein the step of reacting the reaction mixture A to form the extraskeletal metal-containing aluminosilicate zeolite includes heating the reaction mixture A to a temperature of 30°C to 90°C, preferably 40°C to 85°C, and more preferably 55°C to 75°C. (Aspect 10) The process according to any one of embodiments 1 to 9, wherein if the metal-containing compound or free metal contains copper acetate, the reaction mixture A is heated to 40°C to 85°C, more preferably 55°C to 75°C. (Aspect 11) A process described in any one of embodiments 1 to 6 and 10, (c) A process further comprising the step of cooling the mixture formed in step (b) to room temperature. (Aspect 12) The process according to any one of embodiments 1 to 11, wherein the aluminosilicate zeolite is treated before step a, and the treatment changes one or more of the particle size of the aluminosilicate zeolite, the particle size distribution of the aluminosilicate zeolite, the acidity of the aluminosilicate zeolite, or the amount of dealuminization. (Aspect 13) A process for preparing a wash coat containing an extraskeletal metal-containing aluminosilicate zeolite, (a) A step of preparing a product mixture B containing the metal-containing aluminosilicate zeolite outside the skeleton, (b) A process comprising the step of combining the resulting mixture B with a binder, a rheological modifier, or a mixture of a binder and a rheological modifier to form a wash coat mixture C. (Aspect 14) The process according to embodiment 13, wherein the wash coat mixture C has a pH, and the process further comprises the step of adjusting the pH of the wash coat mixture C by adding a base. (Aspect 15) The process according to embodiment 14, wherein the step of adjusting the pH of the wash coat mixture C is performed after or simultaneously with the addition of the binder, the rheological modifier, or a combination of the binder and the rheological modifier.

Claims

[Claim 1] A process for preparing an aluminosilicate zeolite containing an extraskeletal metal, (a)(i)H ＋ A step of forming a reaction mixture A comprising (ii) an aqueous slurry of aluminosilicate zeolite of type A and a metal-containing compound or free metal, wherein the reaction mixture A does not contain ammonia, ammonium hydroxide, or ammonium salt, and the aluminosilicate zeolite is AEI, (b) The metal-containing compound or free metal in the reaction mixture A H ＋ The process includes reacting a type aluminosilicate zeolite to form a product mixture B containing the metal-containing aluminosilicate zeolite outside the skeleton, The metal in the metal-containing compound or free metal comprises one or more of copper, manganese, nickel, and palladium, and the metal-containing compound or free metal is H ＋ The step of reacting the aluminosilicate zeolite of a certain type is carried out in a single exchange, and after forming the product mixture B, the extraskeletal metal-containing aluminosilicate zeolite is not separated from the product mixture B after the reaction. [Claim 2] The process according to claim 1, wherein the metal-containing compound or free metal of reaction mixture A further comprises an iron salt. [Claim 3] The process according to claim 1 or 2, wherein the reaction mixture A has a pH, and the step of forming the reaction mixture A further comprises adjusting the pH of the reaction mixture A by adding a base. [Claim 4] The process according to claim 3, wherein the base is an inorganic base or an organic base. [Claim 5] The process according to any one of claims 1 to 4, further comprising adjusting the pH of the product mixture B by adding a base in order to increase the amount of extraskeletal metal present in the extraskeletal metal-containing aluminosilicate zeolite. [Claim 6] The reaction mixture A contains 5% to 50% by weight of the H ＋ The process according to any one of claims 1 to 5, comprising a type aluminosilicate zeolite. [Claim 7] The process according to any one of claims 1 to 6, wherein the step of reacting the reaction mixture A to form the extraskeletal metal-containing aluminosilicate zeolite comprises mixing the reaction mixture A at 10 to 90°C. [Claim 8] The process according to any one of claims 1 to 7, wherein the step of reacting reaction mixture A to form the extraskeletal metal-containing aluminosilicate zeolite comprises reacting reaction mixture A at a temperature of 10 to 30°C. [Claim 9] The process according to any one of claims 1 to 6, wherein the step of reacting the reaction mixture A to form the extraskeletal metal-containing aluminosilicate zeolite includes heating the reaction mixture A to a temperature of 30°C to 90°C. [Claim 10] The process according to any one of claims 1 to 7, wherein if the metal-containing compound or free metal contains copper acetate, the reaction mixture A is heated to 40°C to 85°C. [Claim 11] A process according to any one of claims 1 to 6 and 10, (c) A process further comprising the step of cooling the resulting mixture B formed in step (b) to room temperature. [Claim 12] The process according to any one of claims 1 to 11, wherein the aluminosilicate zeolite is treated before step a, and the treatment changes one or more of the particle size of the aluminosilicate zeolite, the particle size distribution of the aluminosilicate zeolite, the acidity of the aluminosilicate zeolite, or the amount of dealuminization. [Claim 13] A process for preparing a wash coat containing an extraskeletal metal-containing aluminosilicate zeolite, (a)(i)H ＋ A step of forming a reaction mixture A comprising (ii) an aqueous slurry of aluminosilicate zeolite of type A and a metal-containing compound or free metal, wherein the reaction mixture A does not contain ammonia, ammonium hydroxide, or ammonium salt, and the aluminosilicate zeolite is AEI, (b) The metal-containing compound or free metal in the reaction mixture A H ＋ A step of reacting with a type aluminosilicate zeolite to form a product mixture B containing the metal-containing aluminosilicate zeolite outside the framework, (c) A step of forming a wash coat mixture C by combining the generated mixture B with a binder, a rheological modifier, or a mixture of a binder and a rheological modifier. Includes, The metal in the metal-containing compound or free metal comprises one or more of copper, manganese, nickel, and palladium, and the metal-containing compound or free metal is H ＋ The step of reacting the aluminosilicate zeolite of the type is carried out in a single exchange, and after forming the product mixture B, the metal-containing aluminosilicate zeolite is not separated from the product mixture B after the reaction. process. [Claim 14] The process according to claim 13, wherein the wash coat mixture C has a pH, and the process further comprises the step of adjusting the pH of the wash coat mixture C by adding a base. [Claim 15] The process according to claim 14, wherein the step of adjusting the pH of the wash coat mixture C is performed after or simultaneously with the addition of the binder, the rheological modifier, or a combination of the binder and the rheological modifier. [Claim 16] The process according to claim 14 or 15, further comprising the step of applying the washcoat mixture C onto a substrate to form a coated substrate.

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