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WO2017210812A1 - Zéolite de terre rare et son procédé de préparation - Google Patents

Zéolite de terre rare et son procédé de préparation Download PDF

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WO2017210812A1
WO2017210812A1 PCT/CN2016/084906 CN2016084906W WO2017210812A1 WO 2017210812 A1 WO2017210812 A1 WO 2017210812A1 CN 2016084906 W CN2016084906 W CN 2016084906W WO 2017210812 A1 WO2017210812 A1 WO 2017210812A1
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rare earth
zeolite
anyone
process according
earth zeolite
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Lin FANG
Floryan De Campo
Peng Wu
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East China Normal University
Rhodia Operations SAS
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East China Normal University
Rhodia Operations SAS
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    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof

Definitions

  • the present invention relates to a novel rare earth zeolite with a particular morphology and its method for preparation thereof.
  • rare earth zeolite catalyst in various chemical reactions, including cracking, hydrocracking, dewaxing and various acid-catalyzed reactions like alkylation and acylation.
  • These rare earth zeolites are usually obtained by post-treatment of an existing crystalline zeolite structure, such as by ion-exchanging with the alkaline metal ions in the zeolite, as described in US 3173854; or by impregnating a zeolite in a lanthanum-containing solution and then drying the resulted mixture, as described in US 4622308; or alternatively, by forming an extruded honeycomb catalyst body from a mixture of zeolite, rare earth oxide and a suitable binder material, as described in US 20120058034.
  • the rare earth zeolite obtained by the conventional ion exchange or impregnation post-treatment may exhibit undesired instability in chemical reactions, as the rare earth elements therein can be removed by further exchanging with a more readily exchangeable cation in the reaction medium, or aggregated on the external surfaces of the zeolite.
  • the process for forming an extruded zeolite-rare earth composite structure has the obvious disadvantages of high equipment requirements and complicated operation.
  • these post-treatment methods share a common difficulty to incorporate lanthanides into the existing metallosilicate zeolite framework, as lanthanides generally have much larger radii than Si 4+ ions.
  • the extra-framework lanthanide oxides/ions thus formed in the post-treated zeolites inevitably, narrow the zeolite micropores and block the access of reactants to the active catalytic sites in zeolite micro-channels.
  • CN 1151885 C discloses an amine template-free method to synthesize a rare earth-containing mordenite zeolite, by vigorously mixing sodium silicate, an aluminium source, an inorganic acid, an inorganic base with a rare earth compound and a fluoride as a crystallizing agent, and subsequently using hydrothermal crystallization to treat the mixture for a few days, then washing and drying the resultant solid to obtain a rare earth-containing mordenite with high Si/Al ratio.
  • the framework-substituted Ln ions showed a catalytic promotion effect while that is unobserved from extra-framework ones in the impregnated or ion-exchanged Ln-containing MCM-22 zeolites.
  • Mordenite is an aluminosilicate zeolite with an natural composition of Na 8 [Al 8 Si 40 O 96 ] 3 ⁇ nH 2 O, and it is known that the Si/Al ratio of the synthetic mordenite varies from 5 to 10 depending on the chemical composition of the reactant mixture without using an organic structure directing agent (OSDA) under hydrothermal condition.
  • OSDA organic structure directing agent
  • the acid modulation of mordenite is usually realized by dealumination or using dual structure directing agent (Hydrothermal synthesis of high-silica mordenite by dual-templating method, Microporous and Mesoporous Materials 145 (2011) 80–86) .
  • dual structure directing agent Hydrothermal deactivation of the zeolite, and the latter applies complicated synthesis protocol and relatively expensive template.
  • cerium impregnation of zeolites is one of the methods for deactivation of the external surface for non-selective reactions (e.g. isomerisation of products) at the external acid sites.
  • Tert-Butylation of toluene over mordenite and cerium-modified mordenite catalysts Applied Catalysis A: General 299 (2006) 122–130.
  • Selective deactivation of acid sites on the external surface Applied Catalysis A: General 131 (1995) 15-32.
  • both abovementioned one-pot methods are not ideal, since they either rely on fluoride compounds, which are objectionable environmental pollutants, or necessarily require an expensive silica source (TEOS) that is viable in acidic medium, which is over–costly for industrial application standard.
  • TEOS silica source
  • the present invention relates to a novel rare earth zeolite, a process for preparing the novel rare earth zeolite while obviating the prior art drawbacks discussed above.
  • Fig. 1A is a scanning electron micrograph (SEM) of a pristine zeolite, illustrating its typical morphology.
  • Fig. 1B is a scanning electron micrograph (SEM) of a cerium oxide-containing zeolite produced in accordance with the invention, which illustrates the characteristic morphology of the inventive rare earth zeolite.
  • Figs. 2A-C are three transmission electron micrographs (TEM) of a same cerium oxide-containing zeolite produced in accordance with the invention, at different magnifications.
  • Fig. 2A clearly illustrates the characteristic “nanoflower-like” structure of the inventive rare earth zeolite produced by the one-pot manufacture method of the present invention.
  • Fig. 2B is an enlargement view of cerium oxide nanoparticles embedded in crystal body of Fig. 2A
  • Fig. 2C is an enlargement view of elongated crystals of Fig. 2A.
  • the present invention relates to a novel rare earth zeolite, notably mordenite zeolite and a process for preparing the novel rare earth zeolite.
  • the present invention also concerns compositions comprising the novel rare earth zeolite and use of the novel rare earth zeolite as catalyst.
  • any particular upper concentration can be associated with any particular lower concentration.
  • specific surface area is understood to mean the BET specific surface area determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 laid down from the Brunauer-Emmett-Teller method described in the periodical “The Journal of the American Chemical Society, 60, 309 (1938) ” . Specific surface areas are expressed for a designated calcination temperature and time.
  • a rare earth element (REE) or rare earth metal (REM) is one of a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides, as well as scandium and yttrium.
  • Rare earth elements are cerium (Ce) , dysprosium (Dy) , erbium (Er) , europium (Eu) , gadolinium (Gd) , holmium (Ho) , lanthanum (La) , lutetium (Lu) , neodymium (Nd) , praseodymium (Pr) , promethium (Pm) , samarium (Sm) , scandium (Sc) , terbium (Tb) , thulium (Tm) , ytterbium (Yb) and yttrium (Y) .
  • a rare earth zeolite comprising a zeolite framework structure and at least one rare earth species, wherein the rare earth species is embedded in the zeolite framework structure.
  • Zeolite-type framework structures are based on fully cross-linked tetrahedra containing Si, Al, P and occasionally other atoms. These are generally called T-atoms.
  • the bridges are invariably formed by oxygen atoms.
  • the framework is normally three-dimensional of tetrahedrally coordinated T-atoms with cavities or channels with the smallest opening larger than six T-atoms.
  • T-atom may be Si, Al, P, As, Ga, Ge, B, Be, etc.
  • rare earth zeolite refers to a zeolite which contains rare earth metal in elemental form, rare earth metal salt or rare earth metal oxide.
  • rare earth species refers to rare earth metal in any form, in particular
  • the rare earth species of present invention are embedded in zeolite framework structures instead of being aggregated on the external surfaces or supported in the channels.
  • the framework structures of zeolite are formed by a growth surrounding the rare earth metal oxide.
  • the rare earth metal oxide which has the basic property, may be “free” enough to act as an acid modifier and therefore decreases the acidity of zeolite that is caused by the low Si/Al ratio.
  • the rare earth zeolite of present invention has a core crystal and a plurality of elongated crystals extended radially from the core crystal.
  • Said core crystal is the main body of rare earth zeolite.
  • elongated crystals observed to take the form of nano-sheets have advantageously length comprised between 0.001 ⁇ m and 10 ⁇ m, preferably between 0.01 ⁇ m and 2 ⁇ m, more preferably between 0.05 ⁇ m and 0.5 ⁇ m; besides, they have width advantageously comprised between 0.0005 ⁇ m and 5 ⁇ m, preferably between 0.005 ⁇ m and 1 ⁇ m, more preferably between 0.01 ⁇ m and 0.5 ⁇ m.
  • the elongated crystals observed to take the form of nano-sheets have advantageously number average length comprised between 0.01 ⁇ m and 5 ⁇ m, preferably between 0.05 ⁇ m and 0.5 ⁇ m; besides, they have number average width advantageously comprised between 0.001 ⁇ m and 0.5 ⁇ m, preferably between 0.01 ⁇ m and 0.1 ⁇ m.
  • the length orwidth could be measured by TEM coupled with image analysis.
  • the length is the longest cord in the direction nano-sheets perpendicularly growing from the core crystal.
  • the width of nano-sheets is the longest cord in the direction perpendicular to the length.
  • rare earth metal oxide particles surrounded by framework are embedded in crystal body of zeolite as demonstrated by Fig. 2B. Therefore, stability of this novel rare earth zeolite is much better than those produced by conventional ion exchange or impregnation post-treatment.
  • the rare earth zeolite of present invention may contain more “free” rare earth metal oxide nanoparticles than mordenite zeolite produced by method of CN1151885 C. The “free” rare earth metal oxide nanoparticles can not only adjust the acidity, but also be directly used as a catalyst.
  • the rare earth zeolites of the present invention are found to possess a good combination of the favourable properties of the pure zeolite and rare earth elements.
  • the rare earth zeolites of the present invention exhibit superior.
  • the rare earth zeolite of present invention may have a formula as follows:
  • REO 2/m represents a rare earth metal oxide
  • RE is a rare earth metal
  • M is alkali metal
  • m is rare earth metal ion valence.
  • the rare earth metal oxide in the rare earth zeolite may be selected from oxides of cerium, lanthanum, praseodymium, and neodymium. Among them, particularly preferred example is cerium oxide.
  • the rare earth metal oxide may be in the form of monomer or clusterwhen being embedded in the framework structures.
  • the rare earth metal oxide is in the form of cluster.
  • the weight ratio of rare earth metal oxide embedded in the framework structures of zeolite may be comprised between 1%and 100%, preferably 20%and 90%, more preferably 30%and 60%based on total weight contained in zeolite.
  • the zeolite of the present invention could have a fairly high specific surface area comprised between 300-700 m 2 /g, as determined by Brunauer-Emmett-Teller (BET) isotherm measurement.
  • BET Brunauer-Emmett-Teller
  • This invention concerns a process for preparing rare earth zeolite, comprising:
  • step (v) subjecting gel of step (iv) to a hydrothermal treatment to obtain a rare earth zeolite.
  • the rare earth zeolite obtained by the process is identical to the rare earth zeolite above mentioned.
  • the source of aluminium used may be any of those in commercial use, including but not limited to aluminium metal, hydrated alumina, or a water-soluble aluminium salt such as aluminium sulphate.
  • the rare earth metal may be preferably selected from a group consisting of cerium, lanthanum, praseodymium, and neodymium. Among these, cerium, lanthanum is more preferable.
  • the rare earth metal salt may be selected from a group consisting of nitrate, chloride, acetate, acetylacetonate.
  • the pH of the acidic solution (A) may be adjusted by use of an inorganic acid, an organic acid or a salt thereof and is preferably comprised between 0.5 and 5.
  • the source of silica used may be any of those in commercial use, including but not limited to silica power, asilicate such as an alkali metal silicate or an aqueous colloidal suspension of silica.
  • the pH of the basic solution (B) may be adjusted by the addition of any suitable base, e.g. sodium hydroxide and alkali metal bicarbonate and is preferably comprised between 8 and 14.
  • any suitable base e.g. sodium hydroxide and alkali metal bicarbonate and is preferably comprised between 8 and 14.
  • the basic solution (C) comprises at least one inorganic or organic alkali metal salt. Among them, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate are more preferable.
  • the pH of the basic solution (C) may be comprised between 8 and 14.
  • step (i) , step (ii) , step (iii) of the invented process may be reversed, or performed simultaneously.
  • an organic template agent is optionally added and mixed into the solution.
  • Template agent is species added to synthesis media to aid/guide in the organization of the building blocks that form the framework.
  • the organic template agent is preferably a glycol, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol and the like, or members of the group consisting of triethanolamine, sulfolane, tetraethylene pentamine and diethylglycol dibenzoate.
  • glycol such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol and the like, or members of the group consisting of triethanolamine, sulfolane, tetraethylene pentamine and diethylglycol dibenzoate.
  • glycol refers to an organic compound comprising two or more hydroxyl groups.
  • step (iv) it is preferable to gradually and simultaneously add the acidic solution (A) and the basic solution (B) to basic solution (C) .
  • the flow rate ratio of acidic solution (A) to basic solution (B) may be comprised between 5: 1 and 1: 5 when adding them to basic solution (C) .
  • step (iv) the mixture is preferably stirred during the entire period of time to facilitate a good mixing of all ingredients.
  • step (iv) the pH of the mixed solution is preferably kept between 9 and 11.
  • the pH of the reaction medium may be adjusted by the addition of any suitable base or acid.
  • step (v) the gel is subject to a hydrothermal treatment, which is advantageously carried out at a temperature in a range of from 100°C to 200°C and preferably from 140°C to 180°C, for a time within the range of from 10 to 100 hours and advantageously from 5 to 50 hours.
  • step (v) may be further subjected to a calcination treatment, which is usually carried out in a temperature of from 300°C to 1000°C, preferably from 400°C to 700°C, and more preferably from 500°C to 600°C.
  • the calcination treatment may be performed for a period of from 1 hour to 15 hours and advantageously from 2 hours to 10 hours.
  • rare earth metal salt transfers to rare earth metal oxide
  • source of aluminium finally transfers to aluminium oxide
  • silica is obtained from the source of silica after abovementioned process.
  • the person of ordinary skill in the art can easily calculate the amount of raw materials based on the expected precursors in reaction mixture.
  • the preferable ratio of precursors may have a formula as follows:
  • REO 2/m represents a rare earth metal oxide
  • RE is a rare earth metal
  • M is alkali metal
  • m is rare earth metal ion valence.
  • the invention as so concerns a rare earth zeolite susceptible to be obtained by the process as mentioned above.
  • the rare earth zeolites of the present invention are useful as catalyst or catalyst supports in a large number of reactions, including but not limited to cracking, hydrocracking, dewaxing, alkylation, acylation and dehydration. If desired, catalytically active metals may be further deposited onto the rare earth zeolite of the present invention, by impregnation, ion exchange or other loading approaches known in the art.
  • the present invention pertains to a catalyst composition comprising at least 25%by weight of the rare earth zeolite of present invention.
  • the rare earth zeolite of present invention may be used in the form of powders, including powders consisting wholly or in part of single crystals, or instead be incorporated in shaped agglomerates, such as tablets, extrudates or spheres, which may be obtained by combining the rare earth zeolite with a binder material that is substantially inert under the conditions of the applied catalytic reaction.
  • binder material any suitable material may be used, for example, silica, metal oxides, or clays, such as montmorillonite, bentonite and kaolin clays, the clays optionally being calcined or chemically modified prior to use.
  • the rare earth zeolite may be present in amount from about 30 to about 99%by weight, preferably from 50 to 90%by weight.
  • Yet another embodiment of the invention is a dehydration process comprising contacting an organic compound with a catalyst at dehydration conditions to give a dehydrated product, the catalyst comprising at least one rare earth zeolite comprising a zeolite framework structure and at least one rare earth species, wherein rare earth species are embedded in zeolite framework structure.
  • the dehydration process may be carried out by any conventionally known process, which comprises contacting an organic compound with a rare earth zeolite catalyst of present invention at dehydration reaction conditions to give a dehydrated product.
  • said organic compound may be an alcohol, of which the dehydrated product is the corresponding olefin.
  • said organic compound is selected from alcohols having 2 to 10 carbons.
  • Particular alcohol reactants of interest in the dehydration process include butanol, phenylethanol, and 1, 3-butanediol, among which 1, 3-butanediol is further preferred.
  • the dehydration process of the present invention may be performed in a fixed bed reactor, a moving bed reactor or a fluidized bed reactor. A continuous process is most efficiently carried out in a fixed bed reactor.
  • the dehydration process temperature can range from 250°C to 500°C, preferably from 280°C to 400°C, and more preferably from 330°C to 380°C.
  • the dehydration process can be performed at any pressure but mostly using moderate pressure for operational convenience.
  • the absolute pressure of the reactor ranges from 0.05 MPa to 3 MPa, advantageously from 0.1 MPa to 2 MPa, and more advantageously from 0.5 MPa to 1.5 MPa.
  • acatalyst comprising the rare earth zeolite of present invention is charged to the reactor and activated or dried at a temperature of at least 200°C, under vacuum or dry, inert gas. Subsequently, the temperature and pressure of the reactor are adjusted to the desired dehydration conditions and a reactant flow containing at least an alcohol is introduced, to contact with the activated catalyst in the reactor. The reactor effluent containing the dehydrated olefin product is collected.
  • a crystalline cerium oxide-containing zeolite of present invention was prepared by the following procedure. First prepared are three solutions labelled as A, B and C, respectively.
  • Solution A was prepared by dissolving 0.525 g Ce (NO 3 ) 3 ⁇ 6H 2 O and 1.82 g Al (NO 3 ) 3 ⁇ 9H 2 O in 30 ml aqueous solution of H 2 SO 4 , which has a pH of 1.85.
  • Solution B was prepared by mixing 3.50 g of sodium silicate with 40 g of deionized water, which has a pH of 10.28.
  • Solution C was prepared by dissolving 5.3 g of Na 2 CO 3 in 34 g of deionized water, which has a pH of 12.
  • solution A and solution B were dropwisely added in solution C with a flow rate ratio of2: 1, in a 150 mL Teflon reactor and the thus formed gel was vigorously stirred therein, for 2 hours.
  • the gel was sealed in a Teflon beaker and heated in an autoclave at 180°C for 20 hours.
  • the resultant solid product was filtrated and washed with deionized water and then subjected to a calcination treatment at 450°C in air for 2 hours, giving the final product of cerium oxide-containing zeolite.
  • the final product showed the following analysis:
  • element contents were provided on a Vario EI elemental analyzer. Inductively coupled plasma atomic emission spectrometry (ICP-AES) was employed to determine the Ce, Si, Al, Na contents in the products, which were dissolved in 30 wt%HF acid. )
  • the morphology of the final cerium oxide-containing zeolite product, a formed “nanoflower-shaped” zeolite was studied by Scanning Electron Microscopy (SEM) (Fig. 1B) which is markedly different from the smooth brick-shaped morphology of a pristine zeolite (Fig. 1A) .
  • SEM Scanning Electron Microscopy
  • TEM transmission electron micrographs
  • the crystal cell parameter is analyzed by XRD.
  • XRD PowderX-ray Diffraction
  • the diffraction pattern was collected in the 2 ⁇ range of 5-50°at a scan speed of 4°/min and a scan step of 0.01°.
  • the phase identification was made by comparison to the Joint Committee on Powder Diffraction Standard (JCPDSs) .
  • JCPDSs Joint Committee on Powder Diffraction Standard
  • the average crystallite size was calculated using the width at half-height of the most intense peaks of diffraction pattern and well-known Debye-Scherrer equation. It is worthy to note that the calculated crystallinity is relative crystallinity. It is estimated by the intensity of the major peaks.
  • Pristine zeolite was prepared by the following procedure. First prepared are three solutions labelled as A, B and C, respectively.
  • Solution A was prepared by dissolving 2.27 g Al (NO 3 ) 3 ⁇ 9H 2 O in 30 ml aqueous solution of H 2 SO 4 , which has a pH of 1.25.
  • Solution B was prepared by mixing 3.50 g of sodium silicate with 40 g of deionized water, which has a pH of 10.32
  • Solution C was prepared by dissolving 5.3 g of Na 2 CO 3 in 34 g of deionized water.
  • solution A and solution B were dropwisely added in solution C with a flow rate ratio of 2: 1, in a150 mL Teflon reactor and the thus formed gel was vigorously stirred therein, for 2 hours.
  • the gel was sealed in a Teflon beaker and heated in an autoclave at 180°C for 20 hours.
  • the resultant solid product was filtrated and washed with deionized water, and then subjected to a calcination treatment at 450°C in airfor 2 hours, giving the final product of zeolite.
  • Post-synthesized cerium oxide-containing zeolite was prepared by the following procedure using incipient wetness method.
  • a solution was prepared by dissolving 0.1520 g Ce (NO 3 ) 3 ⁇ 6H 2 O in 1.5 ml aqueous solution. 1 g pure zeolite was added in the solution and the mixture was vigorously stirred at room temperature for 2 h and then it was dried at 80 °C for overnight and followed calcination at 450°C for 2 h to obtain the final product cerium oxide-containing zeolite.
  • This comparative example is performed in the same way of Example 2 in he presence of different catalyst. It shows catalyst of the rare earth zeolite of present invention has better catalytic activity.
  • This comparative example is performed in the same way of Example 2 in the presence of different catalyst. It shows catalyst of the rare earth zeolite of present invention has better catalytic activity.

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Abstract

La présente invention porte sur une zéolite de terre rare présentant une morphologie particulière et sur son procédé de préparation, l'espèce de métal de terre rare étant incorporée dans une structure à armature de zéolite.
PCT/CN2016/084906 2016-06-06 2016-06-06 Zéolite de terre rare et son procédé de préparation Ceased WO2017210812A1 (fr)

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