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EP3962644A2 - Procédé de préparation de zéolites échangées par un métal - Google Patents

Procédé de préparation de zéolites échangées par un métal

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Publication number
EP3962644A2
EP3962644A2 EP20799297.5A EP20799297A EP3962644A2 EP 3962644 A2 EP3962644 A2 EP 3962644A2 EP 20799297 A EP20799297 A EP 20799297A EP 3962644 A2 EP3962644 A2 EP 3962644A2
Authority
EP
European Patent Office
Prior art keywords
zeolite
metal
exchanged
copper
reaction medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20799297.5A
Other languages
German (de)
English (en)
Inventor
Arshia Altaf Lalljee
Vasudev Nagesh SHETTI
Arun Gurudath Basrur
Rajeshkumar Manubhai PATEL
Vijay Sopan Narkhede
Dhananjay Prabhakar SABDE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie India Pvt Ltd
Original Assignee
Sued Chemie India Pvt Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sued Chemie India Pvt Ltd filed Critical Sued Chemie India Pvt Ltd
Publication of EP3962644A2 publication Critical patent/EP3962644A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/723—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7215—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment

Definitions

  • Embodiments of this invention relate to novel methods of preparation of metal exchanged aluminosiliicate and silicoaluminophosphate zeolites for use as catalysts for the treatment of exhaust gases.
  • T h Si, Al, P, Ti, Ge, Sn etc.
  • the first synthetic zeolite was described by Barrer in 1948. [Barrer, J. Chem. Soc. 127 (1948)]. Since this discovery, more than 200 new zeolitic structures have been discovered, all of them containing different pore architectures (http://www.iza-online.org/). Indeed, zeolites can be classified depending on the size of their pores, whose ring openings are defined by a number of T h atoms.
  • small pore zeolites show openings with 8- T h atoms
  • medium pore zeolites present openings with 10- T h atoms
  • large pore zeolites have openings with 12- T h atoms
  • extra-large pore zeolites present openings with more than 12- T h atoms.
  • zeolite with specific physico-chemical properties for a particular chemical process will directly depend on the nature of reactants and products involved in the process (such as size, shape, hydrophobicity, etc.), and also on the reaction conditions.
  • reactants and products such as size, shape, hydrophobicity, etc.
  • the nature of the reactants and products will affect to the diffusion of those molecules within the pores and cavities of the zeolite, and consequently, the selection of the zeolite with the adequate pore topology for the chemicals involved in the reaction will be essential.
  • the zeolite must be stable, both structurally and chemically, on the required reaction conditions.
  • Patent 7,601,662 (2009); Moliner, et al. PCT/EP2012/057795; Korhonen, et al, Chem. Commun., 2011, 47, 800].
  • This higher hydrothermal stability can be explained by the coordination of copper atoms to the double six- membered rings units (D6R) present in the large cavities of these small-pore zeolites, as suggested Fickel and Lobo [J. Phys. Chem. C, 2010, 114, 1633].
  • metal exchanged zeolites are prepared by ion-exchange techniques using zeolite and metal ions.
  • the current invention directly uses the metal to be exchanged as its elemental form. It is less expensive than the corresponding salts of the metal. It uses demineralized water as the medium for liquid ion exchange without adding any acid or alkali to the medium. The residual liquid after ion exchange does not require any further treatment nor is any gaseous pollutant evolved. Carbon dioxide which is a greenhouse gas is used along with water in this invention. Thus, the method of the current invention addresses the problems existing with prior art methods.
  • Inorganic salts or organometallic compounds of the metal to be exchanged are used as reactants.
  • Media used for the exchange in liquid state are either acidic or basic in nature.
  • the filtrate after exchanging the metal with ion exchange sites still contains significant amount of residual metal ions and other chemicals which can pose hazard to the environment. It can be recycled for a limited number of times. Its disposal requires treatment which not only adds to cost but also to the effluent load.
  • the use of the above metal salts or organometallic compounds as precursors of the metal to be exchanged with the ion exchange sites of the zeolite also adds to cost. Specialized equipment is required for methods such as CVD or sublimation ⁇
  • AEI, AFX, CHA, KFI, LTA, IMF, ITH, MEF, MFI, SZR, TUN, *BEA, BEC, FAU, FER, MOR, FEV zeolite or zeotype materials are claimed microporous materials.
  • Zeolite or zeotype materials from the group consisting of ZSM-5, zeolite Y, beta zeolite, SSZ-13, SSZ-39, SSZ-62, Chabazite, and SAPO-34, SAPO-44, Ferrierite, TNU-9 are claimed. H or NH4 forms of the zeolites or zeotypes are claimed. Presence of an organic structure directing agent in these microporous materials is also claimed.
  • Metals to be exchanged are selected from the group Fe, Co, Cu.
  • Metal compounds which are precursors of these metals include oxides, nitrates, phosphates, sulfates, oxalates, acetates or combination thereof.
  • US patent 9889437 assigned to BASF claims a SCR catalyst comprising a zeolite with framework of Si and A1 atoms, wherein a fraction of the silicon atoms is isomorphously substituted with Ti.
  • Zeolitic frameworks selected from CHA, AFX, and AEI are claimed. Promoters are disclosed as Cu and Fe or their combination and these are incorporated by ion-exchange into the zeolite.
  • the zeolite used is an aluminosilicate in which Ti is isomorphously substituted. Use of these materials for treating exhaust gases is claimed.
  • Articles wherein the substrate is ceramic or metal having honeycomb structure catalytic coating of the materials disclosed in this patent are claimed.
  • Crystal structure is claimed as SSZ-13 in a dependent claim.
  • RM of Cu are either soluble or insoluble materials such as nitrates, sulfates, acetates, chlorides, complex salts, oxides, and composite oxides which include copper.
  • the catalyst composition contains ion and non-exchanged Cu.
  • Non exchanged Cu salt is left on the zeolite. Examples are provided which use aq Cu sulfate ion pH adj to 3.5 with HN03, at 80°C, lh, exchanged solid filtered and washed / not washed to retain free Cu.
  • Incipient wetness method using aqueous solution of copper sulfate is also provided in examples;
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • Dependent claims describe the weight of water used to prepare the copper solution to weight of the zeolite used for copper exchange step in the range 2-80; reaction temperature of exchange step as 10-100C;
  • Source of copper is claimed as copper acetate or an ammoniacal solution of copper ions; cone of Cu 0.075-0.3 molar, Cu acetate or ammoniacal solution of Cu ions is claimed as source of Cu;
  • Sodium content of the copper exchanged CHA zeolite is claimed to be ⁇ 2500 ppm.
  • the weight ratio of exchanged Cu to Cu oxide is claimed to be at least about 1.
  • the SAR range of the CHA zeolite is claimed from 15 to 40 and Copper: aluminum atomic ratio 0.25 to 0.50. Characteristics of this catalyst using TPR; UV-VIS; Diffuse reflectance FTIR are claimed.
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst in this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • the copper is exchanged into sodium or ammonium form of CHA, and the copper containing zeolite contains weight ratio of exchanged Cu: Cu oxide at least about 1 as per dependent claims.
  • the SAR range of the CHA zeolite is claimed from 15 to 40 and Copper: aluminum atomic ratio 0.25 to 0.50.
  • US 8535629 assigned to Johnson Matthey Public Ltd Co claims a catalyst composition comprising zeolite material having mean crystal size 0.5 pm, CHA framework, SAR 10-25; an extraframework promoter metal disposed in said zeolite as free and/or exchanged metal, wherein the extraframework metal is selected from Cu or Fe or mixtures, M:A1 0.10 - 0.24 based on framework Al.
  • Dependent claims describe the zeolite as SSZ-13 isotype, mean crystal size 1-5 pm, promoter metal Cu wherein majority of said Cu is exchanged Cu.
  • a dependent claim describes the source of Cu as an aqueous solution comprising Cu and ammonia. Another dependent claims that no Cu source is employed after crystallization of the zeolite. Thus, Cu is incorporated into the zeolite product during crystallization of the zeolite (direct synthesis). Further the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • the alkali earth metal is disclosed as from the group (Ca, Mg. Ba). Ratios of Cmalkali earth metal and alkali earth metakAl are claimed in dependent claims.
  • the copper and alkali earth metals are claimed to occupy ion exchange sites of the zeolite.
  • the raw materials used for supporting copper and the alkali earth metal may be copper and the alkali earth metal, or a nitrate, sulfate, acetate, chloride, complex salt, oxide or composite oxide or the like containing both metals. Either soluble or insoluble materials can be used as these raw materials. Aq.
  • Cu acetate is used in examples cited in this patent.
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • the copper salt solution is a compound selected from among copper(II) sulfate, copper(II) nitrate, copper(II) acetate and copper(II) acetylacetonate dissolved in water and/or a polar solvent selected from the group consisting of acetylacetone, short-chain alcohols having up to three carbon atoms, acetonitrile, acetone, dimethyl sulfoxide (DMSO), methyl ethyl ketone and mixtures thereof.
  • a polar solvent selected from the group consisting of acetylacetone, short-chain alcohols having up to three carbon atoms, acetonitrile, acetone, dimethyl sulfoxide (DMSO), methyl ethyl ketone and mixtures thereof.
  • US 8865120 assigned to Umicore claims a process for the production of metal doped Zeolites or Zeotypes comprising the steps of: i) providing a dry intimate mixture of a Zeolite or Zeotype with one or more precursor compound or compounds comprising a complex formed out of a transition metal and a ligand, which has a structure of formula I: ML.sup.
  • M is a metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, and Ce; and L.sup.l is carbonyl, amine, alkyl, alkoxy, alkene, arene, phosphine or other neutral coordinating ligand; m is a number ranging from 0 to 6; n is a number equal to the valence of M; and L.sup.2 is a diketonate, ketoiminato or related member of this homologous series like a ligand of formula II: ##STR00002## wherein: R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl and substituted acyl; and ii) calcining the mixture without reduced pressure at a temperature and a time sufficient to mobilise and decompose
  • a dependent claim cites that the aqueous solution which is used for crystallization is free of alkali and alkaline earth metals. Ion exchange with Cu using its acetate as the source is disclosed in examples.
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • US 8906329 assigned to JM PLC claims a catalyst composition
  • a catalyst composition comprising a. a zeolite material having a CHA crystal structure and a silica to alumina mole ratio (SAR) of about 10 to about 25; and b. a non-aluminum base metal (M), wherein said zeolite material contains said base metal in a base metal to aluminum ratio (M:A1) of about 0.10 to about 0.24.
  • M:A1 base metal to aluminum ratio
  • independent claims disclose that the zeolite has a mean crystal size of about 1 to 5 microns, SAR of 10 to 20, non-phosphorus CHA structure, base metal M which is selected from the group consisting of Cr, Ce, Mn, Fe, Co, Ni and Cu.
  • Methods to incorporate M are cited as blending or ion-exchange in the body of this patent.
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • US 8987162 assigned to UT-Battelle, LLC claims a catalyst composition comprising a heterobimetallic zeolite characterized by a chabazite structure loaded with copper ions and iron(III) ions, wherein said copper ions are present in said catalyst in a loading amount of above 1 wt % and said iron(III) ions are present in said catalyst in a loading amount of less than 1 wt %, and said copper and iron loading amounts are effective to achieve a NO.sub.x conversion at 150.degree. C. of at least 50% in the presence of an ammonia reductant.
  • the iron (III) ions are in combination with at least one other trivalent metal ion which is a transition metal or lanthanide trivalent ion.
  • the zeolite comprises CuFe-SSZ-13.
  • the Cu component of the catalyst is described as Cul+ or Cu2+ ions with Cu loading up to 2.5 wt%.
  • Metal impregnation using solutions is described as the method for incorporating the metal into the zeolite.
  • the metal ions are generally in the form of metal salts.
  • the metal salts are completely dissolved in the liquid carrier.
  • the metal salt contains one or more metal ions in ionic association with one or more counter anions.
  • the counter-anion can be selected from, for example, halides (F.sup.-, Cl.sup.-, Br.sup.-, or I.sup.-), carboxylates (e.g., formate, acetate, propionate, or butyrate), sulfate, nitrate, phosphate, chlorate, bromate, iodate, hydroxide, .beta.-diketonate (e.g., acetylacetonate), and dicarboxylates (e.g., oxalate, malonate, or succinate).
  • halides F.sup.-, Cl.sup.-, Br.sup.-, or I.sup.-
  • carboxylates e.g., formate, acetate, propionate, or butyrate
  • sulfate e.g., formate, acetate, propionate, or butyrate
  • sulfate nit
  • the counter-anion may contain one or more metals, including one or more metals to be loaded into the zeolite.
  • Some examples of such counter-anions include titanate, zirconate, vanadate, niobate, tantalate, chromate, molybdate, tungstate, arsenate, antimonate, stannate, and tellurate.
  • one or more classes or specific types of any of the foregoing counter-anions are excluded from the impregnating solution (or alternatively, excluded from being incorporated into the zeolite).
  • the catalyst is prepared by forming a slurry containing zeolite powder and the metals to be incorporated.
  • the resulting slurry is dried and fired to form a powder.
  • the powder is then combined with organic and/or inorganic binders and wet- mixed to form a paste.
  • the resulting paste can be formed into any desired shape, e.g., by extrusion into rod, honeycomb, or pinwheel structures.
  • the extruded structures are then dried and fired to form the final catalyst.
  • the zeolite powder, metals, and binders are all combined together to form a paste, which is then extruded and fired.
  • the use of the metal in its elemental form or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent.
  • Iron promoted SSZ-13 is disclosed in dependent claim.
  • the catalyst contains ion- exchanged copper and non-exchanged copper. Use of copper sulphate solution for incorporating the Cu into the zeolite is disclosed in examples.
  • US 9302256 assigned to BASF claims a selective catalytic reduction catalyst comprising an 8-ring small pore molecular sieve promoted with greater than 5 wt. % iron so that the catalyst is effective to catalyze the selective catalytic reduction of nitrogen oxides in the presence of a reductant, wherein the 8-ring small pore molecular sieve has a silica to alumina ratio in the range of 10 and 100.
  • the catalyst wherein the iron-promoted 8-ring small pore molecular sieve is selected from the group consisting of iron-promoted zeolite having a structure type selected from AEI, AFT, AFX, CHA, EAB, ERI, KFI, LEV, SAS, SAT, and SAV.
  • Another claim covers iron promoted SSZ-13. Ion exchange or inclusion into the colloid used for crystallizing the zeolite are described in the body of the patent as methods of metal incorporation.
  • US 9656253 assigned to IBIDEN Co. claims a zeolite comprising: a CHA structure; a Si0.sub.2/Al.sub.20.sub.3 composition ratio less than about 15; an average particle size from about 0.1 pm to 0.46 pm; and Cu supported on the zeolite.
  • PXRD specifics of the zeolite are claimed.
  • Cu content 3.5-6.0 wt% by mass of zeolite is claimed.
  • Cu ion exchange is carried out by immersing the zeolite in an aqueous solution of one selected from copper acetate, copper nitrate, copper sulfate, and copper chloride. Preferred among these is an aqueous solution of copper acetate.
  • Cu copper is supported on the zeolite by performing ion exchange with an aqueous solution of copper acetate (II) having a copper concentration of 0.1 to 2.5% by mass and a solution temperature of room temperature to 50.degree. C. under atmospheric pressure.
  • II copper acetate
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • the SAR of CHA is disclosed as 5-100, Cu 0.05-15 wt%. Specific methods of incorporating Cu into the CHA zeolite are not disclosed in this patent.
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • US 10202284 assigned to IBIDEN Co claims a method for producing zeolite having a CHA structure in which Cu is carried, the method comprising: mixing a powder of the zeolite having the CHA structure and a powder of Cu salt, which is at least one salt selected from the group including copper sulfate, copper nitrate, copper acetate, and copper chloride, with each other to produce powder mixture; and heating the powder mixture under atmospheric pressure.
  • independent claims disclose the water content of the powder mix ⁇ 30 wt%, heating temperature 250-800C, source of Cu salt is copper nitrate, atmosphere during heating step is oxidizing atmosphere, Cu/Al 0.2-0.5 molar, SAR pf CHA ⁇ 15, average particle size of the CHA zeolite is 0.5 pm or less.
  • Other sources of the Cu salt used are cited in body of this patent as preferably at least one salt selected from the group consisting of copper sulfate, copper nitrate, copper acetate, and copper chloride. The patent cites that these Cu salts are low in cost, and can further lower the cost in the method for producing the zeolite.
  • US 8906329 assigned to JMPL Co claims a catalyst composition
  • a catalyst composition comprising a. a zeolite material having a CHA crystal structure and a silica to alumina mole ratio (SAR) of about 10 to about 25; and b. a non-aluminum base metal (M), wherein said zeolite material contains said base metal in a base metal to aluminum ratio (M:A1) of about 0.10 to about 0.24.
  • SAR silica to alumina mole ratio
  • M non-aluminum base metal
  • a chabazite is immersed in a solution containing copper nitrate for a time sufficient to allow incorporation of the catalytically active copper cations into the molecular sieve structure by ion exchange. Un-exchanged copper ions are precipitated out. Depending on the application, a portion of the un-exchanged ions can remain in the molecular sieve material as free copper. The metal-exchanged molecular sieve may then be washed, dried and calcined.
  • the metal content of the catalytic material by weight preferably comprises from about 0.1 to about 10 percent by weight, more preferably from about 0.5 to about 10 percent by weight, for example about 1 to about 5 percent by weight or about 2 to about 3 percent by weight, based on the weight of the zeolite.
  • the use of the metal in its elemental form or a metal formate salt solution or soluble compound of alkyl ammonium hydroxide of the metal as a precursor of the metal to be exchanged is neither claimed nor disclosed in the method used to prepare the catalyst of this patent. Neither is use of a gaseous reaction medium during incorporation of the metal into the zeolite claimed or disclosed in this patent.
  • Figure 1 shows the Temperature programmed Reduction pattern of Cu-SSZ-13 catalyst of Example 1 which is prepared as per the method of the current invention. Two major peaks are observed, one at about 170°C and the other at about 410°C.
  • Figure 2 shows Diffuse Reflectance UV-VIS spectrum of Cu-SSZ-13 catalyst of Example 1 which is prepared by the method of the current invention. It shows a strong peak at about 220 nm.
  • FIG. 3 shows catalytic performance results for SCR of catalysts of Examples 1 and 3 which are prepared as per the method of the current invention. Details of the test are provided in Example 12. As seen from Figure 3 the catalyst samples prepared by the method of the current invention show good SCR activity over a wide range of temperature ranging from 180°C to 510°C.
  • Method comprising combination of elemental source of the metal to be ion exchanged, gaseous reaction medium comprising at least carbon dioxide and a liquid reaction medium comprising water or organic solvents.
  • gaseous reaction medium comprising at least carbon dioxide
  • a liquid reaction medium comprising water or organic solvents.
  • Steps in preparation of the metal exchanged zeolite as per the above-mentioned method are provided below.
  • the crystalline zeolite or a mixture of crystalline zeolites used for ion exchange may be in their alkali form, ammonium form or proton form. Using alkali form is advantageous because it saves costs incurred on ion exchange to ammonium or proton form.
  • the alkali form may be either or both of sodium and potassium.
  • the liquid reaction medium of the method comprises demineralized water. It is taken in a vessel such as an autoclave in sufficient quantity to form a slurry of the zeolites when they are added to it.
  • the metal to be ion exchanged with the zeolite such as for example copper, is added in its elemental (metallic) form to the demineralized water (liquid reaction medium).
  • the zeolite or a mixture of zeolites is added to the above mixture. And the mixture is stirred/agitated.
  • the pH of the liquid reaction medium is close to neutral. It typically ranges 7 ⁇ 1.
  • the weight ratio of liquid reaction medium to the zeolite ranges from 200 to 2.
  • a gaseous reaction medium such as atmospheric air or carbon dioxide is then added to the vessel. Where added carbon dioxide is used, the ratio of metal to carbon dioxide in the reaction medium ranges from 0.5 to 0.001 molar ratio.
  • the ratio of carbon dioxide to hydrogen in the reaction medium ranges from 3: 1 to 100:0 molar ratio
  • the above mixture is heated to temperature 15 to 200°C. From an energy cost perspective, it is advantageous to carry out the method at lower temperature such as ambient temperature.
  • the pressure of the ion exchange step ranges from 0.1 to 50 bar g. This pressure comprises both the pressure due to the gaseous reaction medium which is added to the vessel as well as autogenous pressure arising from vapor pressure of the liquid medium depending on the temperature of the process.
  • the duration of the ion exchange step for completion of the ion exchange step typically ranges from 0.1 to 48h.
  • the temperature of the water used for washing ranges from 5 to 98°C. The washing step can be avoided and it results in cost savings.
  • the ion exchanged zeolite is recovered by filtration.
  • the ion exchanged zeolite with or without washing is dried at 90 to 150°C and calcined in a gaseous medium comprising a mixture of nitrogen and oxygen.
  • step 15 Repeating the steps 2 to 14 above with the ion exchanged zeolite from step 14 instead of a sample of fresh zeolite in step 4, until the desired extent of metal exchange is achieved on the zeolite.
  • the ion exchanged zeolites prepared as per the above method are active for the selective reduction of NOx in the temperature range 150-750°C. They show good hydrothermal stability up to 750°C. Hydrothermal aging is carried out for 16h at 750°C in a stream of air containing 10 mol% water, gas hourly space velocity 900 h 1 . Decrease in activity of the aged catalyst is less than 5% relative to the fresh catalyst prior to aging.
  • the liquid reaction medium can also be reused.
  • the method of preparation of metal exchanged zeolite materials or their mixtures involves the process of carrying out the ion exchange step in the presence of both a liquid reaction medium and a gaseous reaction medium and wherein the precursor of the metal to be exchanged is preferably in the form of the elemental metal itself.
  • the elemental metal which is used for exchanging with ion exchange site of the zeolite can be in any shape, size or form.
  • this metal can be in the form of a fine powder or regular or irregularly shaped granules or extrusions or filings or ingots or any other shape and size.
  • the liquid reaction medium is a single liquid substance or mixtures of liquid substances which are polar by chemical nature.
  • the liquid reaction medium is preferably water.
  • the metal in its elemental form is one or more of Copper, Iron, Manganese or Cobalt.
  • the unreacted metal if any remaining behind after the ion exchange step and the liquid reaction medium are recovered and reused.
  • the gaseous reaction medium is carbon dioxide.
  • the gaseous reaction medium can be a mixture of carbon dioxide with air or oxygen or nitrogen or hydrogen or argon or helium. Atmospheric air alone also suffices as the gaseous reaction medium.
  • Source of carbon dioxide can also be flue gas from combustion of fossil or renewable fuels/materials. Carbon dioxide is a greenhouse gas and its utilization for useful purposes is desirable from an environmental standpoint.
  • the zeolite is selected from the group having framework CHA, MFI, BEA, AEI (SSZ-39), AFX (SSZ-16/SAPO-56), KFI(ZK-5), LTA (Type A), intergrowth zeolite with AFX/CHA structure, CHA/AEI intergrowth structure, SSZ-52, SSZ- 27, SSZ-28, SSZ-98, SSZ-99, SSZ-104, , ITQ3, SSZ-105,
  • the CHA includes both
  • zeolites aluminosilicate and silicoaluminophosphate materials.
  • Silica alumina molar ratios of the zeolites ranging from about 6 to 200. Crystal size of the zeolites range from 0.02 to 10 pm and particle size of the zeolite in powder form range from 1 to 200 pm.
  • the zeolites may be in any size shape or form such as powder, extrude or beads, trilobes, quadralobes, computer designed shape, tablets or rings etc. Alkali contents of the zeolites are typically less than or equal to about 5000 ppm.
  • Method Variant 1 Using a soluble compound of alkyl ammonium hydroxide of the metal to be ion exchanged as the precursor of the metal which is to be ion exchanged:
  • copper metal is reacted with water solution of Alkyl ammonium hydroxide to prepare soluble copper compound.
  • the soluble copper compound is then reacted with zeolite to form corresponding Cu-Zeolite.
  • the subject soluble copper compound i.e. Copper Alkyl Ammonium Hydroxide solution is prepared by reacting Copper metal with Alkyl ammonium hydroxides using the following molar composition relative to one mole of copper metal: 0.1 to 10 moles of Alkyl Ammonium hydroxide; 2 to 200 moles of Water.
  • Cu metal is reacted with water solution of Alkyl Ammonium Hydroxides (Quaternary Alkyl Ammonium Hydroxide) 2.
  • Alkyl Ammonium Hydroxides Quaternary Alkyl Ammonium Hydroxide
  • the mixture obtained is then subjected to thermal or hydrothermal synthesis at a temperature range of 50 to 150 degree Celsius at atmospheric or autogenous pressure from 0-30 bar g in an autoclave for 20 minutes to 180 minutes
  • Zeolite is added to the soluble Cu solution and the solution is reacted (ion exchanged) with Zeolite to prepare Cu-Zeolite.
  • the zeolite after copper loading is separated by filtration and subjected to drying and calcination or the zeolite after copper loading is spray dried to obtain Cu-Zeolite powder, which is subjected to drying and calcination.
  • Alkyl Ammonium Hydroxides may be Tetra Methyl Ammonium Hydroxide or Tetra Ethyl Ammonium Hydroxide or Tetra Propyl Ammonium Hydroxide or Tetra butyl Ammonium Hydroxide or combinations thereof.
  • Method VII.Method Variant 2 Using a solution of the formate salt of the metal to be ion exchanged as the precursor of the metal which is to be ion exchanged:
  • copper metal is reacted with aqueous solution of formic acid at elevated temperature (about 90°C with stirring) to form a solution of copper formate.
  • the solution is evaporated to dryness and then redissolved a number of times till pH of the aqueous solution reaches at least 6.0. It is finally evaporated to dryness.
  • An aqueous solution of this solid is used for ion exchange with the zeolite at elevated temperature such as 60°C for 5h. This is followed by washing to remove excess free copper salt which is not bound to the zeolite. This is followed by drying and calcination.
  • the zeolite used for ion exchange may be in its alkali form, ammonium form or proton form. Using alkali form is advantageous because it saves costs incurred on ion exchange to ammonium or proton form.
  • the metal to be exchanged such as for example copper
  • formic acid is reacted with formic acid at elevated temperature to form a solution of the metal formate.
  • the zeolite is added to the above mixture. And the mixture is stirred/agitated.
  • the weight ratio of liquid reaction medium to the zeolite ranges from 200 to 2.
  • the duration of the ion exchange step ranges from 0.1 to 48h.
  • the ion exchanged zeolite is washed after the ion exchange step.
  • the temperature of the water used for washing ranges from 20 to 70°C.
  • the ion exchanged zeolite is then dried at 90 to 150°C and calcined in a gaseous medium comprising a mixture of nitrogen and oxygen.
  • the copper exchanged CHA zeolite exhibits temperature programmed desorption peaks in the temperature range 150-300°C and 450-600°C and UV-VIS signal in the range 190-300 nm.
  • the ion exchanged zeolite is active for the selective reduction of NO x in the temperature range 150-750°C. It shows good hydrothermal stability up to 750°C.
  • the slurry was filtered, dried in air 120°C and calcined at 550°C.
  • the product was a greenish blue colored powder of Copper containing SSZ-13.
  • Powder X-ray diffraction pattern was characteristic of SSZ-13.
  • Chemical analysis of the sample confirmed the presence of 3.5 wt% copper in the ion exchanged SSZ-13 zeolite.
  • Two major reduction peaks were found in H2-TPR at 170°C and 410°C (Fig. 1) and a prominent absorption band at 220 nm in DRUV-Visible spectrum (Fig. 2).
  • Filtrate contained 0.9 ppm Copper.
  • the concentration of dissolved copper remaining behind in the solution after its use for ion exchange is shown in (Table 1). As seen from the Table, the concentration is very low. It is largely less than 1 ppm which is desirable from effluent quality standpoint as well as from loss of valuable metal standpoint.
  • Table 1 Copper content present in Copper loaded zeolite samples (Cu wt% in final sample) and dissolved Cu content present in mother liquor after filtration
  • the slurry was filtered, thoroughly washed with deionized water, dried in air 120°C and calcined at 550°C.
  • the product was a greenish blue colored powder of Copper containing SSZ-13. Powder X-ray diffraction pattern was characteristic of SSZ-13. Chemical analysis of the sample confirmed the presence of 3.5 wt% copper in the ion exchanged SSZ-13 zeolite. Two major reduction peaks were found in H2- TPR at 170°C and 400°C and a prominent absorption band at 220 nm in DRUV-Visible spectrum.
  • the slurry was filtered, dried in air 120°C and calcined at 550°C.
  • the product was a mildly greenish blue colored powder of Copper containing SSZ-13.
  • Powder X-ray diffraction pattern was characteristic of SSZ-13.
  • Chemical analysis of the sample confirmed the presence of 2.7 wt% copper in the ion exchanged SSZ-13 zeolite. Two major reduction peaks were found in H2-TPR at 170°C and 400°C and a prominent absorption band at 220 nm in DRUV-Visible spectrum.
  • Powder X-ray diffraction pattern was characteristic of SSZ-13. Chemical analysis of the sample confirmed the presence of 2.5 wt% copper in the ion exchanged SSZ-13 zeolite. Two major reduction peaks were found in H2-TPR at 170°C and 400°C and a prominent absorption band at 220 nm in DRUV- Visible spectrum.
  • the product was a mildly greenish blue colored powder of Copper containing ZSM-5. Powder X-ray diffraction pattern was characteristic of ZSM-5 structure. Chemical analysis of the sample confirmed the presence of 1.7 wt% copper in the ion exchanged ZSM-5 zeolite.
  • the slurry was filtered, dried in air 120°C and calcined at 550°C.
  • the product was a mildly greenish blue colored powder of Copper containing Beta zeolite. Powder X-ray diffraction pattern was characteristic of BEA structure. Chemical analysis of the sample confirmed the presence of 2.1 wt% copper in the ion exchanged Beta zeolite.
  • the product was a mildly greenish blue colored powder of Copper containing SAPO-34. Powder X-ray diffraction pattern was characteristic of SAPO-34 zeolite. Chemical analysis of the sample confirmed the presence of 1.4 wt% copper in the ion exchanged SAPO-34 zeolite.
  • the slurry was filtered, dried in air 120°C and calcined at 550°C.
  • the product was a greenish blue colored powder of Copper containing SSZ-13.
  • Powder X-ray diffraction pattern was characteristic of SSZ-13.
  • Chemical analysis of the sample confirmed the presence of 2.5 wt% copper in the ion exchanged SSZ-13 zeolite.
  • Three major reduction peaks were found in H2-TPR at 200, 300 and 410°C. A prominent absorption band at 220 nm along with shoulder at 280 nm in DRUV-Visible spectrum was observed.
  • the ion exchanged powder was filtered and washed with equal amount of water, dried at 120°C and calcined at 550°C.
  • the calcined powder was further subjected to a second exchange by repeating the exchange procedure.
  • the final powder is greenish blue colored Copper containing SSZ-13 powder.
  • Powder X-ray diffraction pattern was characteristic of SSZ-13.
  • Chemical analysis of the sample confirmed the presence of 2.0 wt% copper in the ion exchanged SSZ-13 zeolite.
  • Three reduction peaks were found in H2-TPR at 200, 300 and 650°C. Two prominent absorption bands were observed at 220 and 280 nm in DRUV- Visible spectrum.
  • Comparative Example 1 Synthesis of Copper exchanged SSZ-13 using copper acetate as per prior art: 30 g CU(CH 3 C00) 2 H 2 0 is dissolved in 1L deionized water to which 100 g H-SSZ-13 Zeolite powder was added. The slurry was stirred in a R.B flask equipped with condenser at 60 °C for 4-5 hours. The slurry is then filtered and washed with 1L of deionized water. The solid was dried at 120°C and subsequently calcined at 550 °C. This exchange process was repeated using the calcined powder. Chemical analysis of the sample confirmed the presence of 3.2 wt% Copper in the ion exchanged SSZ-13 powder. Two reduction peaks were found in H2-TPR at 170 and 420 °C. A major absorption band at 220 nm was observed in DRUV-Visible spectrum.
  • Coating of copper containing microporous solid on honeycomb type substrate 100 g of the calcined zeolitic material containing Cu obtained according to example 1 was mixed with both 145 ml of deionized water and 32.66 g Bindizil 2034 DI binder.
  • the slurry was coated onto 1 " outer diameter x 3" length cylindrical cellular ceramic core having a cell density of 400 cpsi (cells per square inch) and a wall thickness of 6.5 mm.
  • the coated cores were dried at 110° C for 3 hours and calcined at 550°C for 1 hour.
  • the coating process was repeated once to obtain a target washcoat loading of 110 g/1.
  • the washcoat loading is defined as the dry weight gain on the honeycomb with respect to the volume.
  • Nitrogen oxides selective catalytic reduction (SCR) efficiency of a fresh catalyst core were measured by adding a feed gas mixture of 500 ppm of NO, 550 ppm of NH3, 10% 02, 5% H20, 5%C02, balanced with N2 to a steady state reactor containing a l " outer diameter x 3" length catalyst core.
  • the washcoated honeycomb substrate was placed inside a reactor tube heated by an electrical furnace.
  • the gases NO, NH3, 02, N2, C02 and H20 were preheated in a preheater furnace before entering the reactor.

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Abstract

L'invention concerne des procédés de préparation de zéolites échangées par un métal au moyen d'un échange d'ions de métaux tels que le cuivre, le fer ou le manganèse avec des aluminosilicates et des silicoaluminophosphates tels que CHA, MFI, BEA et des structures de zéolite à petits pores. Le procédé utilise une combinaison d'un milieu réactionnel liquide avec un milieu réactionnel gazeux, le métal à échanger étant de préférence sous forme métallique élémentaire et le milieu réactionnel gazeux comprend au moins du dioxyde de carbone. Ces zéolites échangées par un métal sont utiles en tant que catalyseurs pour la réduction d'oxydes d'azote à partir de flux gazeux par réduction catalytique sélective avec de l'ammoniac ou de l'urée.
EP20799297.5A 2019-04-27 2020-04-27 Procédé de préparation de zéolites échangées par un métal Withdrawn EP3962644A2 (fr)

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CN112844467B (zh) * 2021-02-18 2023-03-14 齐齐哈尔大学 一种脱硝催化剂及其制备方法和应用
CN116832854B (zh) * 2023-06-16 2025-09-19 山东大学 磷-镓改性铜基分子筛废气净化功能材料及其制备方法与应用

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EP2689846A1 (fr) * 2007-08-13 2014-01-29 PQ Corporation Réduction catalytique selective des oxydes d'azote avec des zéolites d'aluminosilicate contenant du fer
US8293199B2 (en) * 2009-12-18 2012-10-23 Basf Corporation Process for preparation of copper containing molecular sieves with the CHA structure, catalysts, systems and methods
US8293198B2 (en) * 2009-12-18 2012-10-23 Basf Corporation Process of direct copper exchange into Na+-form of chabazite molecular sieve, and catalysts, systems and methods
EP2463028A1 (fr) * 2010-12-11 2012-06-13 Umicore Ag & Co. Kg Procédé de production de zéolites et zéotypes dopés en métal et application associée à l'élimination catalytique d'oxydes d'azote
EP2465606A1 (fr) * 2010-12-16 2012-06-20 Umicore Ag & Co. Kg Catalyseur à base de zéolite doté d'une activité catalytique améliorée et destiné à la réduction d'oxydes d'azote
CA2945010C (fr) * 2014-04-07 2020-07-21 Haldor Topsoe A/S Procede de production de zeolites a echange de metal par echange d'ions a l'etat solide a basses temperatures
WO2015154829A1 (fr) * 2014-04-07 2015-10-15 Haldor Topsøe A/S Procédé de production de matériaux microporeux ayant subi un échange de métaux par échange d'ions à l'état solide
CN106660022B (zh) * 2014-06-18 2020-09-22 巴斯夫公司 分子筛催化剂组合物、催化剂复合材料、体系和方法
CN105251528A (zh) * 2015-09-14 2016-01-20 天津大学 以四乙基氢氧化铵与铜氨络合物混合作为模板剂一步合成Cu-CHA催化剂的方法

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