• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    BETA ZEOLIT CONTAINING IRON AND ORGANIC FREE AND METHOD OF SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES IN EXHAUST GAS. A Beta Zeolite containing metal and free of organics is described with a silica to alumina (SAR) ratio ranging from 5 to 20, and a metal content of at least 0.5% by weight. Also described is a method of producing the aforementioned Beta zeolite without an organic structure steering agent (SDA). The metal, which may comprise Fe or Cu, can be discovered in an amount ranging from 1 to 10% by weight. Also described is a method of selective catalytic reduction of nitrogen oxides in exhaust gases using the described zeolite.
    公开号:BR112012029648B1
    申请号:R112012029648-5
    申请日:2011-05-18
    公开日:2020-12-22
    发明作者:Hong-Xin Li；William E. Cormier；Bjorn Moden
    申请人:Pq Corporation；
    IPC主号:
    专利说明:

    [001] This application claims the benefit of domestic priority for U.S. Provisional Patent Application No. 61 / 347,210, filed on May 21, 2010, which is incorporated herein in its entirety as a reference.
    [002] The present description refers to a Beta containing metal zeolite and methods of producing it. The present description also refers to methods of using such zeolites, including for selective catalytic reduction (SCR) of nitrogen oxides (NOx) in exhaust gases.
    [003] Nitric oxides (NOx) have long been known as polluting gases, mainly for the reason of their corrosive action. In fact, they are the main cause of acid rain. The main contributor to NOx pollution is its emission in the exhaust gases of diesel cars and stationary sources such as coal-fired power plants and turbines. To avoid these harmful emissions, SCER is employed and involves the use of zeolitic catalysts to convert NOx into nitrogen and water.
    [004] The following patents describe the use of zeolites or similar catalytic materials, and are incorporated herein by reference. U.S. Patent No. 4,952,385, U.S. Patent No. 4,961,917, U.S. Patent No. 5,451,387, U.S. Patent No. 6,689,709, U.S. Patent No. 7,118,722, U.S. Patent No. 6,890,501.
    [005] In general, the synthesis of zeolites, particularly Beta zeolite, occurs in the presence of organic models, which are known in the art as structure directing agents (SDAs). A common SDA that is typically used to synthesize Beta zeolite is tetraethylammonium hydroxide (TEAOH). However, the disadvantages associated with the use of such SDAs, including increased material cost, increased processing steps, and adverse effect on the environment, make it desirable to develop a process for synthesizing zeolites, such as Beta zeolite, without the use of organic SDAs .
    [006] The synthesis of organic free Beta zeolite has been known in the technique. See, for example, B. Xie, J. Song, L. Ren, Y. Ji, J. Li, F.-S. Xiao, Chemistry of Materials, 2008, 20, 4533, and G. Majano, L. Delmotte, V. Valtchev, S. Mintova, Chemistry of Materials, 2009, 21, 4184, which are incorporated here in their entirety as reference. None of these references, however, describes the claimed method of producing a Beta zeolite containing metal, and certainly not a Beta zeolite used for selective catalytic reduction of NOx. Thus, there is a need to synthesize an organic zeolite Beta free, it also includes a metal and allows the selective catalytic reduction of NOx in the exhaust gases. As a result, the finished Beta-Fe product is superior to any Fe-zeolite described in Fe dispersion and selective catalytic reduction activity. RESUME
    [007] Thus, a Beta zeolite containing deorganic free metal with a silica to alumina (SAR) ratio ranging from 5 to 20, and a method of producing it, is described. The Beta zeolite described here is synthesized without any direct use of an organic structure directing agent (SDA). Thus, the resulting Beta zeolite has no organic model material in its crystalline structure at any point during processing excluding any residual quantity resulting from the base materials. In one embodiment, the Beta zeolite production method according to the present description uses silica of more than 30 percent of the synthesis mixture, such as a silica use of more than 40 percent, or even more than 50 percent cent.
    [008] In the embodiment, the metal comprises iron (Fe) or copper (Cu) in an amount of at least 0.5% by weight, such as an amount ranging from 1-10% by weight.
    [009] In one embodiment, the Beta zeolite containing metal described here shows a conversion of NOx of at least 40% at 200 ° C after being vaporized at 700 ° C for 16 hours in 10% steam with the balance being air.
    [0010] A method of selective catalytic reduction of nitrogen oxides in exhaust gases using the Beta zeolite described here is also described. In one embodiment, the method comprises contacting the exhaust gases at least partially with a Beta zeolite containing a metal with SAR ranging from 5 to 20 and a metal such as iron or copper in an amount of at least 0.5% by weight - only, such as 1-10% by weight. Brief Description of Drawings
    [0011] The attached figures are incorporated into this specification and form part of it.
    [0012] Figure 1 is a graph showing the conversion of NO in Beta-Fe materials vaporized at 700 ° C for 16 hours into 10% steam and the balance being air, in a sample according to the present description and in a comparative sample.
    [0013] Figure 2 is an x-ray diffraction pattern from Example 1.
    [0014] Figure 3 is an x-ray diffraction pattern from Example 3.
    [0015] Figure 4 is an x-ray diffraction pattern from Example 4.
    [0016] Figure 5 is a scanning electron microscope image of the material in Example 1.
    [0017] Figure 6 is a scanning electron microscope image of the material in Example 3.
    [0018] Figure 7 is a scanning electron microscope image of the material in Example 4.
    [0019] Figure 8 is a graph showing the NH3-SCR activity of Fe dezeolite Beta exchanged and samples of mordenite [Vaporization: 700 ° C for 16 hours at 10% steam / air, SCR: 500 ppm, NO: 500 ppm, NH3, 5% O2, balance: inert gases, SV: 60000 h-1].
    [0020] Figure 9 is a graph showing the NH3-SCR activity of Example 4 exchanged with various amounts of Fe [Vaporization: 700 ° C for 16 hours at 10% steam / air, SCR: 500 ppm, NO: 500 ppm, NH3 , 5% O2, balance: inert gases, SV: 60000 h-1].
    [0021] Figure 10 is a graph showing the NH3-SCR activity of Beta zeolite with freshly exchanged Fe, mordenite, and Y samples [SCR: 500 ppm, NO: 500 ppm, NH3, 5% O2, balance: inert gases, SV : 60000 h-1].
    [0022] Figure 11 is a graph showing the NH3-SCR activity of newly vaporized Beta-Cu [Vaporization: 700 ° C for 16 hours at 10% steam / air, SCR: 500 ppm, NO: 500 ppm, NH3, 5% O2, balance: inert gases, SV: 60000 h-1].
    [0023] Figure 12 is a graph showing UV data from Beta zeolite samples with exchanged Fe that were treated under the following conditions before recording the spectrum: Vaporization: 700 ° C for 16 hours in 10% steam / air, in situ dehydration to 400 ° C, followed by cooling to room temperature.
    [0024] Figure 13 is a graph showing UV data from Example4 exchanged with various amounts of Fe. Before recording the spectrum, the material was treated as follows: Vaporization: 700 ° C for 16 hours in 10% steam / air, in situ dehydration up to 400 ° C, followed by cooling to room temperature. DETAILED DESCRIPTION OF THE INVENTION Definitions
    [0025] "Organic free" refers to a method of producing Beta olive oil without the direct use of organic models, such as the organic structure directing agent (SDA) during synthesis. However, it is appreciated that when a base material is used, such as pure Beta zeolite, the base material may have been produced with or without an SDA. Thus, the term refers to the fact that the resulting Beta product was never in direct contact with an organic structure directing agent (SDA) during any stage of processing, but the base material may have been produced using a SDA, providing at most a residual or secondary contact with the pore structure. In one embodiment, the resulting Beta zeolite, even if exposed to residual or secondary contact with an SDA, would not need one or two post-synthesis steps to open the porous volume of the crystalline structures.
    [0026] "Use of silica" refers to the efficiency in which silica is used in the synthesis of Beta zeolite. The use of silica can be calculated by dividing the silica to alumina ratio (SAR) of the product by the SAR of the synthesis mixture, excluding the base material.
    [0027] "Hydrothermally stable" means having the ability to retain a certain percentage of the initial surface area and / or microporous volume after exposure to an elevated temperature and / or humidity conditions (compared to room temperature) for a certain period of time.
    [0028] "Initial surface area" means the surface area of the newly produced crystalline material before being exposed to any condition of aging.
    [0029] "Initial micropore volume" means the micro-pore volume of the newly produced crystalline material before being exposed to any aging condition.
    [0030] "Direct synthesis" (or any of its versions) refers to a method that does not require a metallic doping process after the zeolite has been formed, such as a subsequent ion exchange or impregnation method.
    [0031] "Ion exchange" refers to exchanging non-structural ionic elements and / or molecules contained in zeolitic materials for other elements and / or molecules, such as metals. In general, almost every conceivable element can be used in the ion exchange step, including at least one element selected from the following group: Cu, Fe, Co, Cr, N i, V and Nb, preferably Cu and Fe.
    [0032] "Defined by the Structure Commission of the International Zeo-lite Association" means the structures included, but not limited to, structures described in the "Atlas of Zeolite Frameworks Types", ed. Baericher and others, Sixth Revised Edition (Elsevier 2007), which is incorporated here in its entirety as a reference.
    [0033] "Selective Catalytic Reduction" or "SCR" refers to the reduction of NOx (typically without ammonia) in the presence of oxygen to form nitrogen and H2O.
    [0034] "Exhaust gas" refers to any waste gas formed in an industrial process or operation and by internal combustion engines, such as by any motor vehicle.
    [0035] The unique pore structure associated with crystalline microporous aluminosilicates, such as zeolites, has led to its successful use in a wide variety of applications, including as catalysts, absorbents, and ion exchangers. In particular, the combination of this unique three-dimensional 12-ring system, and its high thermal stability, made Beta zeolite one of the most important industrial zeolites. Traditionally, this zeolite was prepared from precursor materials containing organic structure governing agents (SDAs). The SDAs typically used to prepare Beta zeolite (such as TEAOH and dibenzyl dimethylammonium hydroxide) are not only expensive, but are inevitably wrapped in the zeolitic structure, so that a removal step, for example, heat treatment, is necessary for its removal. In addition, when organic SDAs are used to prepare Beta zeolite, typically high silica products are obtained. For example, a typical SAR of synthetic Beta zeolite is above 20, often above 40.
    [0036] In accordance with the present invention, it has been discovered that Beta umzeolite containing metal can be produced without the use of an organic structure directing agent (SDA). By avoiding the use of an organic model, the resulting Beta zeolite does not have undesirable organic materials in the crystalline material. As a result, one or more post-synthesis treatments such as calcination are unnecessary to remove SDAs from the crystallized material.
    [0037] Thus, a Beta zeolite containing metal that has not come into contact with an organic structure governing agent (SDA) and a method of producing it is described. In one embodiment, the Beta zeolite has a SAR ranging from 5 to 20. preferably not more than 12, such as a range from 5 to 11.
    [0038] In one embodiment, the Beta zeolite described here has crystal grains greater than 0.1 micron, as well as crystal sizes ranging from 0.2 to 5 microns;
    [0039] In one embodiment, the metal portion of the Betac zeolite comprises copper or iron, which can be introduced into the Be zeolite in various ways, such as by liquid phase, or exchange of solid ions, or impregnation, or incorporated by direct synthesis. In a modality, the metallic portion of the Beta zeolite comprises iron in an amount ranging from 1.0 to 10.0% by weight of the total weight of the material, with at least 60% of the iron present as isolated cations in the locations exchange.
    [0040] In another embodiment, the metallic portion of the Betacompreende zeolite covers in an amount ranging from 1.0 to 10.0% by weight of the total weight of the material.
    [0041] The source of iron is typically one, iron salt and is chosen from ferric nitrate, ferric chloride, ferrous chloride, and ferrous sulfate.
    [0042] The copper source is typically chosen from cupric acetate, cupric chloride, cupric hydroxide, cupric nitrate, and cupric sulfate.
    [0043] A method of producing a zeoliteBeta containing metal is also described. Generally, the present method is aimed at producing a Beta zeolite containing metal by initially making an aqueous solution comprising NaOH and an alumina source. Non-limiting examples of alumina sources that can be used in the present description include sodium aluminate, aluminum hydroxide, alumina, aluminum nitrate, and aluminum sulfate.
    [0044] Next, a source of silica is added to the solution and mixed. The silica source can comprise a silica gel or silica sol, which is typically added under vigorous stirring conditions. Non-limiting examples of other sources of silica that can be used include known silicates, such as silica gel, sodium silicate and sodium metasilicate, as well as colloidal silica, precipitated silica, silica-alumina, etc.
    [0045] Next, a source of Beta zeolite is added, typically in an amount ranging from about 1 to 15% by weight, such as 10% by weight, in relation to the silica content of the mixture. The Beta zeolite source is a commercially available Beta. In a modality, The Beta zeolite source are crystals comprising a zeolite material having a Beta structure. Although the mixture can be prepared by any known means, in one embodiment, the mixture is used by moving or stirring. After mixing for about 30 minutes, a gel is formed. The mixing time can be up to 24 hours, or even up to 48 hours.
    [0046] Next, the gel is heated to form a product. The duration of the crystallization step varies depending on the desired parameters for the final product, such as crystal size and purity. The synthesis is interrupted when the pure Beta zeolite is formed. In one embodiment, the crystallization step comprises heating the gel in an autoclave to a temperature ranging from 100 to 200 ° C, such as 125 ° C, for a time varying from 24 to 200 hours, such as 40 to 150 hours, or even 50 to 125 hours.
    [0047] It is important in the commercial production of zeolite to use raw materials efficiently. In the synthesis of Beta zeolite without SDA, the use of silica is of the utmost importance since it is the largest component by weight in the synthesis mixture. In the synthesis of commercial zeolite, the use of silica must be greater than 30%, such as greater than 40%, or even greater than 50%. The use of silica can be calculated by dividing the silica to aluminum ratio (SAR) of the product by the SAR of the synthesis mixture excluding the base material.
    [0048] Next, the crystallized material is optionally treated by at least one process chosen between separation, washing and drying. The separation of the crystallized product occurs using well-known techniques, such as nitration, ultrafiltration, diafiltration, centrifugation and / or decantation methods, where the filtration methods may involve suction and / or pressure filtration steps.
    [0049] After the filtration, washing and drying procedures, the crystallized product presents a pure Beta zeolite phase.
    [0050] Regarding the optional washing steps, suitable agents that can be used include water, alcohols such as methanol, ethanol or propanol or mixtures thereof. Typically, the isolated and purified zeolite material is washed until the effluent pH is in the range of 6 to 8.
    [0051] The method may comprise an additional step of removing any residual sodium from the product. This is typically done through an ion exchange process with known or similar salts, including ammonium salts of Cl, SO4, NO3. In one embodiment, residual sodium is removed by mixing the product in a solution of a desired salt, such as NH4NO3, for example by mixing the solid at least once with the NH4NO3 solution (3.6M).
    [0052] In one embodiment, the product can also be subjected to an ion exchange and / or an impregnation step to increase the amount of metal and add at least one additional metal.
    [0053] In addition to the production method of the invention and the zeoliteBeta of the invention, a method of using the Beta zeolite described in the invention is described. For example, an exhaust gas typical of a diesel engine contains about 2 to 15% by volume of oxygen and about 20 to 500 parts per million by volume of nitrogen oxides (usually comprising a mixture of NO and NO2). The reduction of nitrogen oxides with ammonia to form nitrogen and H2O, can be catalyzed by zeolites promoted with metal, so the process is often referred to as "selective" catalytic reduction (SCR) of nitrogen oxides.
    [0054] Thus, a method of selective catalytic reduction of nitrogen oxides in the exhaust gas is also described. In a modality, the method comprises:
    [0055] contact at least partially exhaust gases with a product comprising a Beta zeolite containing metal with SAR between 5 and 20, where the Beta zeolite is made without organic structure directing agent (SDA) and the metal comprises iron and / or copper in an amount of at least 1.0% by weight, such as an amount ranging from 1-10% by weight.
    [0056] It is appreciated that the contact step can be performed in the presence of ammonia, urea or an ammonia-generating compound. Non-limiting examples of ammonia-generating compounds include ammonium carbamate, ammonium formate, ammonium carbonate, and metal-amine complexes. It is appreciated that any compound that is capable of generating ammonia can be used in the contact step described here. In this modality, the contact step is typically performed in the presence of a hydrocarbon compound.
    [0057] In one embodiment, the product described here may be in the form of a body in the form of a tube or honeycomb; a tight bed; microspheres; or structural parts. The cramped bed can comprise balls, pebbles, pellets, tablets, extrudates, other particles and their combinations. The structural parts can be in the form of sheets or tubes. In addition, the gutter or honeycomb body or structural part can be formed by extruding a mixture comprising Beta zeolite.
    [0058] In one embodiment, the Beta zeolite containing metal described here exhibits a NOx conversion of at least 40% at 200 ° C for selective catalytic reduction, with an ammonia-generating compound after exposure to 700 ° C for 16 hours in the presence of up to 10% by volume of water vapor.
    [0059] Thus, in one embodiment, a SCR method of nitrogen oxides in exhaust gases is also described which comprises contacting at least partially an exhaust gas with the Beta zeolite described here. To reduce nitrogen oxide emissions, in various exhaust gases, ammonia is typically added to the gas stream containing nitrogen oxides. In one embodiment of the present invention, ammonia is used to allow the gas stream, when contacted with the Beta zeolite of the present invention at elevated temperatures, to catalyze the reduction of nitrogen oxides.
    [0060] In one embodiment, a urea solution can be used to supply ammonia to the gas stream. This is particularly true when used in automotive exhaust treatment applications and fixed NOx reduction applications.
    [0061] Non-limiting examples of the types of exhaust gases that can be treated with the described zeolites include automotive spills for both on-road and off-road vehicles, including diesel engines. In addition, leakage from fixed sources, such as power plants, stationary diesel engines, and coal-fired plants can be treated. Thus, exhaust emission treatment methods are also described, such as automotive exhaust or stationary sources.
    [0062] The Beta zeolite of the present invention can be supplied in the form of a fine powder that is mixed with or coated with a suitable refractory binder, such as alumina, bentonite, silica, or silica-alumina, and formed into a mixture that is deposited on a suitable refractory substrate. In one embodiment, the carrier substrate may have a "honeycomb" structure. Such carriers are well known in the art as having many parallel and thin passages of gas flow extending there. Non-limiting examples of the material used to produce the honeycomb structure include cordierite, mullite, silicon carbide, alumina, titanium, zirconia, silica, alumina-silica, alumina-zirconia, stainless steel, Fe-Cr-Al alloy and their combinations.
    [0063] In another embodiment, Beta zeolite can be supplied discreetly (as opposed to a coating on a substrate). Non-limiting examples of such forms include pellets, tablets or particles of any other suitable form, for use in a tight bed, for example. Beta zeolite according to the present invention can also be formed into shaped parts such as plates, tubes, or the like.
    [0064] In addition to the subject discussed above, the present description a number of other exemplary characteristics such as those which will be explained hereinafter. It should be understood that both the previous description and the following description are only exemplary. EXAMPLES Example 1. Synthesis of organic free Beta (SAR = 10.3) and subsequent exchange of Fe to produce Beta-Fe (4.0% by weight, SAR = 10.3)
    [0065] Water, NaOH (50%), and sodium aluminate (23.5% Al2O3.19.6% Na2O) were mixed. Silica gel (PQ Corporation) was added to the solution and mixed vigorously for 1 hour. Finally, a Beta zeolite commercially available (Zeolyst International) in an amount of 5% in relation to the silica content of the mixture were added to the mixture and stirred for 30 minutes. The gel had the following molar composition: 15.0 SiO2: 1.0 Al2O3: 3.8 Na2O: 259 H2O
    [0066] The gel was loaded in a Parr 45 mL pump and heated under static conditions at 125 ° C for 120 hours. After cooling, the product was recovered by filtration and washing. The product's x-ray diffraction pattern showed a pure Beta zeolite phase.
    [0067] To remove residual sodium, the solid was mixed in a 3.6 M NH4NO3 solution and stirred at 90 ° C for 2 hours. This NH4NO3 exchange process was repeated twice. After filtration, washing and drying, the final product had a silicate-alumina ratio (SAR) of 10.3. The BET surface area of the product was 665 m2 / g and the micropore volume was 0.23 cc / g.
    [0068] The sample then exchanged ions with a solution of FeSO4 at 70 ° C for 2 hours. After filtration, washing and drying, the Fe-Beta product contained 4.0% Fe by weight.
    [0069] After spraying at 700 ° C for 16 hours in 10% steam / air, the BET surface area of the material was 461 m2 / g and the volume of the micro-pore was 0.15 cc / g. Example 2. (Comparative): Beta-Fe (1.0 wt% Fe, SAR = 25) by aqueous ion exchange
    [0070] Zeolyst commercial Zeolite Beta (CP 814E, SAR = 25) ionized with FeCl2 solution at 80 ° C for 2 hours. After filtration, washing and drying, the Beta-Fe product had 1.0 wt% Fe, the BET surface area was 693 m2 / g and a micropore volume of 0.19 cc / g.
    [0071] After spraying at 700 ° C for 18 hours at 10% va-per-air, the surface area of the material was 590 m2 / g and the volume of the micropore was 0.16 cc / g. Example 3. Synthesis of organic free Beta
    [0072] Water, NaOH (50%), and sodium aluminate (23.5% Al2O3) were mixed. Silica gel (PQ Corporation) was added to the solution and mixed vigorously for 1 hour. Finally, a Beta zeolite made available commercially (Zeolyst International) in an amount of 10% by weight in relation to the silica content of the mixture were added to the mixture and stirred for 24 hours. The gel had the following molar composition. 32.8 SiO2: 1.0 Al2O3: 9.2 Na2O: 794 H2O
    [0073] The gel was loaded into a 2 liter Parr autoclave and heated to 125 ° C for 47 hours under static conditions. After cooling, the product was recovered by filtration and washing. The product's x-ray diffraction pattern showed pure Beta zeolite phase.
    [0074] To remove residual sodium, the solid was mixed in a solution of 3.6M NH4NO3 and mixed at 90 ° C for 2 hours. This NH4NO3 exchange process was repeated twice. The properties of the material after filtration, washing, and drying are listed in Table 1.
    [0075] The sample then had ions exchanged with a Fe2SO4 solution at 70 ° C for 2 hours, followed by filtration, washing and drying. Fe content, surface area and micropore volume are listed in Table 2. Example 4. Synthesis of organic free Beta
    [0076] Water, NaOH (50%) and sodium aluminate (23.5% Al2O3) were mixed. Silica gel (PQ Corporation) was added to the solution and mixed vigorously for 1 hour. Finally, a Beta zeolite made available commercially (Zeolyst International) in the amount of 10% by weight in relation to the silica content of the mixture were added to the mixture and mixed for 24 hours. The gel had the following molar composition: 22.0 SiO2: 1.0 Al2O3: 6.2 Na2O: 337 H2O
    [0077] The gel was loaded into a 2 liter Parr autoclave and heated to 125 ° C for 52 hours while stirring at 100 rpm. After cooling, the product was recovered by filtration and washing. The product's x-ray diffraction pattern showed pure Beta zeolite phase.
    [0078] To remove residual sodium, the solid was mixed in a 3.6M NH4NO3 solution and stirred at 90 ° C for 2 hours. This NH4NO3 exchange process was repeated twice. The properties of the material after filtering, washing and drying are listed in Table 1.
    [0079] The sample then exchanged ions with a solution of FeSO4 at 70 ° C for 2 hours, followed by filtration, washing and drying. Fe content, surface area, and micropore volume are listed in Table 2.
    [0080] The NH4 Beta exchanged from this example also exchanged ions to obtain different Fe charges using FeSO4 solutions at 20 ° C for 2 hours, followed by filtration, washing and drying.
    [0081] The NH4 Beta exchanged from this example also had it loaded with copper nitrate to obtain a sample containing 4.8% Cu. Table 1. Properties of organic free Beta samples with exchanged NH4
    Table 2. Properties of Beta samples with Fe recently changed and after vaporization at 700 ° C for 16 hours in 10% water / air.
    Example 5. (Comparative) - Fe-mordenite (1.5% by weight, SAR = 14) by aqueous ion exchange
    [0082] Zeolyst commercial bitolite (SAR = 14) had ions exchanged with a solution of FeSO4 at 70 ° C for 2 hours. After filtration, washing and drying, the product Fe-mordenita had 1.5% by weight of Fe, a surface area of 522 m2 / g and a microporous volume of 0.19 cc / g.
    [0083] After spraying at 700 ° C for 16 hours in 10% steam / air, the surface area of the material was 460 m2 / g and the micropore volume was 0.15 cc / g. Example 6 (Comparative). Fe-Y (1.5% by weight, SARE = 5.5) by aqueous ion exchange
    [0084] Zeolyst commercial Zeolite Y (CBV 500, SAR = 5.5) had Fetrocado. After filtration, washing and drying, the Fe-Y product had 1.5 wt% Fe, a BET surface area of 759 m2 / g and a microporous volume of 0.27 cc / g. NH3-SCR of NO with ferroaluminosilicate zeolites
    [0085] Beta-Fe activities for NO conversion using NH3 as a reducer were evaluated in a flow-type reactor. Samples of zeolite powder were pressed and sieved to 35/70 mesh and loaded into a quartz tube reactor. The gas stream contained 500 ppm NO, 500 ppm NH3, 5% O2 and the balance being N2. The hourly space velocity for all reactions was 60,000 h-1. The reactor temperature was increased and the NO conversion was determined with an infrared analyzer at each temperature range. Figure 1 compares SCR of N O with NH3 in Beta-Fe samples vaporized at 700 ° C for 16 hours in 10% H2O / air. FT-UV spectroscopy of zeolites containing Fe
    [0086] UV spectra were collected at room temperature from 200 to 400 nm in Fe samples vaporized after evacuation in situ at 400 ° C, and are shown in Figures 12 and 13. The spectra were rolled out to 5 Gaussian peaks centered on 192, 209 , 228, 266 and 308 nm (variation of +/- 10 nm for each peak) with an adjusted precision of R2> 0.99. Peak areas as well as percentages of peak areas are shown in Table 3. Peaks centered below 300 nm are associated with isolated Fe species, while peaks above 300 nm are associated with oligomeric Fe species. Materials with Fe exchanged from various Fe-based Fe-Beta produced in example 4 have more than 80% Fe as isolated Fe sites, while Comparative Example 2 has 73% isolated sites. Table 3. Integration of peaks of the UV data in Figure 13

    [0087] The NH3-SCR activity correlates well with the depic area of the UV peaks centered at 209 and 228 nm, that is, the larger those peak areas, the more active the material is. For example, Beta in example 4 with 1.0% Fe has peak areas of 40 and 47 units of area (units KM per nm) at 209 and 228 nm respectively, and one, the conversion of 38% NOx at 200 ° C. Beta in example 4 with 1.7% Fe has peak areas of 55 and 73 KM units per nm at 209m and 228 nm respectively, and a 55% NOx conversion. Beta zeolite in example 4 with 2.0% Fe has peak areas of 87 and 101 KM units per nm at 209 and 228 nm respectively, and a NOx conversion of 84%. The increase in NOx conversion occurs simultaneously with the increase in peak areas at 209 and 228 nm, suggesting that these bands are associated with the active sites for NH4-SCR in these materials.
    [0088] Unless otherwise stated, all numbers expressing amounts of ingredients, reaction conditions, etc. used in the specification and in the claims are to be understood as being modified in all instances by the term "about". Consequently, unless otherwise indicated, the numerical parameters adjusted in the specification and in the appended claims are approximations that may vary depending on the desired properties that are sought in the present invention.
    [0089] Other embodiments of the invention will be apparent to those who are skilled in the art from considering the specification and practice of the invention described herein. It is intended that the specification and examples are considered only as examples, with the true scope and spirit of the invention being indicated by the following claims.
    权利要求:
    Claims (19)
    [0001]
    1. Beta zeolite containing iron and free of organics, characterized by the fact that it presents the molar ratio between silica and alumina (SAR) ranging from 5 to 20, in which said iron is in an amount in the range of 2.0 at 10% by weight and at least 60% of said iron is present as an isolated cation at the cation exchange sites, and in which said Beta zeolite shows a conversion of NOx of at least 40% at 200 ° C for reduction selective catalytic with an ammonia-generating compound after exposure to 700 ° C for 16 h in the presence of up to 10% by volume of water vapor.
    [0002]
    2. Beta zeolite containing iron and free of organics according to claim 1, characterized by the fact that if said Beta zeolite contains any organic structure directing agent (SDA) within the pore structure, it originated from the material base during synthesis.
    [0003]
    3. Beta zeolite containing iron according to claim 1, characterized by the fact that the referred SAR ranges from 5 to 11.
    [0004]
    Beta zeolite containing iron according to claim 1, characterized by the fact that said iron is introduced by solid or liquid ion exchange, impregnation, or incorporated by direct synthesis.
    [0005]
    5. Beta zeolite containing iron according to claim 1, characterized by the fact that said iron is present in an amount in the range of 3.0 to 8.0% by weight.
    [0006]
    6. Beta zeolite containing iron, free of organics, according to claim 1, characterized by the fact that it presents a conversion of NOx of at least 60% at 200 ° C, for selective catalytic reduction with an ammonia-generating compound after exposure to 700 ° C for 16 hours in the presence of up to 10% by volume of water.
    [0007]
    7. Method of selective catalytic reduction of oxides of nitrogen in exhaust gas, characterized by the fact that it comprises: contact, at least partially, said exhaust gases with an article comprising a Beta zeolite containing iron and free of organic products, in which said iron is present in an amount in the range of 2.0 to 10% by weight and at least 60% of said iron is present as an isolated cation in cation exchange sites, in which said Beta zeolite presents a conversion of NOx of at least 40% at 200 ° C for selective catalytic reduction with an ammonia-generating compound after exposure to 700 ° C for 16 h in the presence of up to 10% by volume of water vapor, and in which the aforementioned beta zeolite containing iron and free of organics, has a molar ratio between silica and alumina (SAR) in the range of 5 to 20.
    [0008]
    8. Method according to claim 7, characterized by the fact that said Beta zeolite has SAR in the range of 5 to 11.
    [0009]
    9. Method according to claim 7, characterized by the fact that if said Beta zeolite contains any organic structure directing agent (SDA) within the pore structure, it originated from the seed material during synthesis.
    [0010]
    10. Method according to claim 7, characterized by the fact that said contact step is carried out in the presence of ammonia, urea or an ammonia-generating compound.
    [0011]
    11. Method according to claim 7, characterized by the fact that said contact step is carried out in the presence of hydrocarbon compound.
    [0012]
    12. Method according to claim 7, characterized by the fact that said iron is introduced by solid or liquid ion exchange, impregnation or incorporated by direct synthesis.
    [0013]
    Method according to claim 7, characterized in that said iron comprises an amount in the range of 3.0 to 8.0% by weight of the total weight of said material.
    [0014]
    14. Method according to claim 7, characterized by the fact that said Beta zeolite has a crystal size greater than 0.1 micrometer.
    [0015]
    15. Method according to claim 7, characterized by the fact that said Beta zeolite has a crystal size in the range of 0.2 to 5 micrometers.
    [0016]
    16. Method according to claim 7, characterized by the fact that said article is in the form of a gutter or honeycomb body; a packed bed; microspheres; or structural parts.
    [0017]
    17. Method according to claim 16, characterized by the fact that said packed bed comprises balls, axes, pellets, tablets, extrudates, other particles, or combinations thereof.
    [0018]
    18. Method according to claim 16, characterized by the fact that said structural parts are in the form of plates or tubes.
    [0019]
    19. Method according to claim 16, characterized by the fact that the trough or honeycomb body or structural part is formed by extruding a mixture including Beta zeolite.
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    同族专利:
    公开号 | 公开日
    EP2571604B1|2014-04-16|
    US20190054420A1|2019-02-21|
    KR101852143B1|2018-04-25|
    JP5797749B2|2015-10-21|
    EP2571604A2|2013-03-27|
    ES2465617T3|2014-06-06|
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    JP2017109924A|2017-06-22|
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    DK2571604T3|2014-05-12|
    JP6231525B2|2017-11-15|
    MX2012013535A|2013-04-03|
    CA2800393A1|2011-11-24|
    RU2012155698A|2014-06-27|
    JP2013526406A|2013-06-24|
    BR112012029648A2|2016-08-02|
    ZA201309393B|2014-08-27|
    JP2015205277A|2015-11-19|
    KR20130109980A|2013-10-08|
    MX343465B|2016-11-07|
    CN105312081B|2020-09-15|
    PL2571604T3|2014-09-30|
    JP6397064B2|2018-09-26|
    US20110286914A1|2011-11-24|
    RU2641771C1|2018-01-22|
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    优先权:
    申请号 | 申请日 | 专利标题
    US34721010P| true| 2010-05-21|2010-05-21|
    US61/347,210|2010-05-21|
    PCT/US2011/036997|WO2011146615A2|2010-05-21|2011-05-18|Novel metal-containing zeolite beta for nox reduction and methods of making the same|
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