process for preparing a copper-containing molecular sieve with the structure of chabazite (cha), cop

专利摘要:
process for preparing a copper-containing molecular sieve with the structure of chabazite (cha), copper-containing molecular sieve, catalyst, catalyst use, exhaust gas treatment system, and method for selectively reducing nitrogen oxides in ~ ~. processes are disclosed for preparing copper-containing molecular sieves with the cha structure, where copper is exchanged to the chabazite form using a liquid copper solution, where the copper concentration is in a range. from about 0.001 to about 0.4 molar. Molecular sieves with the structure of tea, catalysts incorporating molecular sieves and methods for their use are also described.
公开号:BR112012014791B1
申请号:R112012014791-9
申请日:2010-12-17
公开日:2018-12-18
发明作者:Tilman Beutel；Martin Dieterle；Ulrich Müller；Ivor Bull；Ahmad Moini；Michael Breen；Barbara Slawski；Saeed Alerasool；Wenyong Lin；Xinsheng Liu
申请人:Basf Corporation；
IPC主号:

专利说明:

"PROCESS FOR PREPARING A SCREENING MOLECULAR CONTAINING COPPER WITH chabazite STRUCTURE (CHA) SCREENING MOLECULAR CONTAINING COPPER, CATALYST, CATALYST OF USE, TREATMENT SYSTEM EXHAUST GAS, AND, METHOD TO REDUCE SELECTIVELY OXIDES OF NITROGEN IN _X "
Background [1] The modalities of the present invention relate to a process for the preparation of molecular sieves containing copper with the CHA structure, having a molar ratio of silica to alumina greater than about 10, in which copper is exchanged for the Na ⁺ form of Chabazite, using a liquid copper solution, in which the copper concentration is in a range of about 0.001 to about 0.4 molar. In addition, this invention relates to molecular sieves containing copper with the CHA structure, obtainable or obtained through the process described above, and to catalysts, systems and methods.
[2] Both synthetic and natural zeolites and their use in promoting certain reactions, which include selective catalytic reduction (SCR) of nitrogen oxides with a reducing agent such that ammonia, urea and / or hydrocarbon, in the presence oxygen, are well known in the art. Zeolites are crystalline aluminosilicate materials having reasonably uniform pore sizes that, depending on the type of zeolite and the type and quantity of cations included in the zeolite lattice, have a range of about 3 to 10 Angstroms in diameter. Chabazite (CHA) is a small pore zeolite with 8-membered ring openings (-3.8 Angstroms), accessible through its three-dimensional porosity (as defined by the International Zeolite Association). A cage-like structure results from the connection of building units of six double rings by 4 rings.
[3] X-ray diffraction studies for and locations of
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2 / 4Ί cations in Chabazite identified seven cation sites being coordinated with the structure's oxygen, labeled A, B, C, D, F, H, and I. They are located in the center of a double six-membered ring, at or near the center of six-membered rings in the Chabazite cage, and at, around the eight-membered ring in the Chabazite cage and the F, H and I sites are located around the eight-membered ring in the Chabazita cage (see Mortier, WJ "Compilation of Extra Framework Sites in Zeolites", Butterworth Scientific Limited, 1982, pll and Pluth, JJ Smith, JV Mortier, WJ Mat. Res. Bull., 12 (1977), 1001).
[4] The catalysts employed in the SCR process should ideally be able to retain good catalytic activity in a wide range of temperature conditions of use, for example, from 200 ° C to 600 °, or higher under hydrothermal conditions. Hydrothermal conditions are often encountered in practice, such that during the regeneration of a soot filter, a component of the exhaust gas treatment system, used for particulate removal.
[5] Metal-promoted zeolite catalysts including, but not limited to, iron-promoted and copper-promoted zeolite catalysts for the selective catalytic reduction of nitrogen oxides with ammonia are known.
[6] Beta zeolite promoted with iron (US 4,961,917) has been an effective commercial catalyst for the selective reduction of nitrogen oxides with ammonia.
[7] Unfortunately, it has been found that, under severe hydrothermal conditions, for example, those that are exhibited during the regeneration of a soot filter with temperatures exceeding 700 ° C locally, the activity of many zeolites promoted with metal begins to decline. The decline is often attributed to the de-alumination of the zeolite and the consequent loss of active centers containing metal within the zeolite.
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3>! ΑΊ [8] Ο Chabazite-containing metal preparation process, as known in the art, can be divided into four sub-stages: i) crystallization of the organic template containing Na-Chabazite, ii) calcination of Na-Chabazite, iii) exchanging NH4 to form NH ₄ -Chabazite, and iv) exchanging NH ₄ -Chabazite with metal to form metal-Chabazite. The NH4 exchange stage aims to remove alkali metals (for example, Na) that are detrimental to the hydrothermal stability of the final catalyst.
[9] The typical Na2Ü level of Na-Chabazite is between 6000 and 8000 ppm. Sodium is known to be able to degrade the structure of zeolite under hydrothermal curing conditions, through the formation of Na ₄ SiO ₄ and Na ₂ Al ₂ O ₄ and the concomitant de-alumination of the zeolite. In order to keep the Na2Ü content low, an exchange of NH4 with, for example, NH4NO3 is carried out in a third stage.
[10] Dedecek et al. describe in “Microporous and Mesoporous Materials” 32 (1999) 63-74 a direct copper exchange to a form of Na ⁺ , Ca ⁺ , Cs ⁺ , Ba ²⁺ of Chabazite. An aqueous solution of copper acetate is used, with copper concentrations ranging between 0.20 and 7.6% by weight, which is between 0.001 and 0.1 molar. The liquid to solid ratio ranges from 20 to 110. The silica to alumina ratio is between 5 and 8. In all direct exchanges (ie copper in the Na form of zeolite) of natural chabazite, the total alkali metal content of molecular sieves containing copper with the CHA structure is greater than about 4.6% by weight (expressed as metallic oxide). In addition, in the direct exchange of synthetic Na-Chabazite, the sodium content is greater than about 0.97%, by weight, of Na2Ü when the exchange stage is used, or about 0.73% , by weight, of Na2O, when two exchange stages are used.
[11] WO 2008/77590 describes a process of exchange with direct metal to the Na ⁺ form of a zeolite material, in which the exchange with metal is carried out by suspending a zeolite material in a suspension
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4/47 aqueous, which comprises metal ions and ammonium ions. As specific non-limiting examples of metal, iron, silver and copper ions are described. The use of double ammonium salt is used in specific modalities. In the examples, BEA was used as the zeolite material and iron and ammonium (II) sulfate hexahydrate as the source of iron, having a concentration of about 0.025 and 0.09 molar. Catalytic data have not been exposed.
[12] The technical challenge of the direct copper exchange process is to replace Na ⁺ ions with Cu ²⁺ ions and reach target loads of both metals to simultaneously satisfy catalytic performance and stability requires the SCR process. Both excess CuO and residual Na ₂ O are assumed to have a detrimental effect on the performance of the catalyst after curing.
[13] WO 2008/106519 discloses a catalyst comprising: a zeolite having the crystal structure of CHA and a molar ratio of silica to alumina of more than 15 and an atomic ratio of copper to aluminum exceeding 0.25. The catalyst is prepared by exchanging CHA copper in an NPLC form with copper sulfate or copper acetate. The copper concentration of the aqueous copper sulfate ion exchange stage ranges from 0.025 to 1 molar, where multiple copper ion exchange stages are required to obtain the target copper charges. The resulting catalyst from copper sulfate ion exchange exhibits a 45 to 59% NOx conversion at 200 ° C and ~ 82% at 450 ° C. Free work needs to be added in order to improve performance at 200 ° C after curing. The exchange of 0.4 M copper acetate results in a material with a conversion of NOx after curing from 70 to 88% at 200 and 450 ° C, respectively. In WO 2008/106519, a large excess of copper is used, so that a CuO charge of about 3% by weight is achieved; the yield of the typical Cu exchange using copper sulfate is only about 4%. For copper acetate, the Cu exchange yield is between 24 and 31%.
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5/47 [14] US 2008/0241060 and WO 2008/134252 state that the zeolite material can be loaded with iron and / or copper, while iron and / or copper are introduced into the microporous crystalline material through ion exchange in solid or aqueous state, or incorporated through direct synthesis (during zeolite synthesis), whereas direct synthesis does not require a metal doping process after the zeolite has been formed. In the US 2008/0241060 examples, NH4NO3 was used for the removal of residual sodium, but copper ion exchange is not described. Example 2 of WO 2008/132452 mentions that an ammonium exchange was performed prior to the aqueous copper exchange, using copper nitrate. It is mentioned that multiple aqueous ion exchanges were carried out, so that 3% by weight of Cu was achieved. No details were provided regarding the reaction conditions.
[15] There is a continuing desire to simplify the process of preparing molecular sieves containing copper with the CHA structure and this process contains many stages of processing, adding capital and operating cost to the manufacturing process.
Summary [16] In one or more modalities, an SCR catalyst, based on molecular sieves provided here, exhibits a NO _X conversion activity comparable to state-of-the-art catalysts, obtained through a synthesis in several stages (exchange of covers NH ₄ -Chabazite). In general, catalysts are provided, which exhibit both good NOx conversion activity at low temperature (NO _X conversion> 50% at 200 ° C) and good NOx conversion activity at high temperature (NO conversion _X > 70% at 450 ° C). NO _X activity is measured under constant state conditions, under conditions of maximum NH3 suspension in a gas mixture of 500 ppm NO, 500 ppm NH3, 10% O ₂ , 5% H2O, N2 equilibrium, in a spatial velocity based on volume
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6/47 of 80,000 h ¹ .
[17] One or more embodiments of the invention provide a new process that saves time and costs for the preparation of a Chabazite containing Cu. Still other embodiments of the invention provide a process, which exhibits a high use of copper. The high conversion rate also provides advantages in the control of tailings water, beneficial to the environment.
[18] Thus, the modalities of the present invention refer to a process for the preparation of molecular sieves containing copper with the CHA structure, having a silica to alumina ratio of more than about 10, in which copper it is switched to the Na ⁺ form of Chabazite, using a liquid copper solution, where the copper concentration is in the range of about 0.001 to about 4.
[19] In specific embodiments, direct copper exchange eliminates conventional NH4 ion exchange, which is applied to Na-Chabazite, in order to eliminate residual Na. In addition, some Chabazite materials contain other alkali metal cations, which are detrimental to the stability of the catalyst, such as potassium. Sodium and potassium are used frequently in the crystallization of Chabazite. Direct exchange can eliminate residual alkali metals.
[20] In a first embodiment, a process for the preparation of a molecular sieve containing copper, with the CHA structure, having a molar ratio of silica to alumina of more than about 10, in which copper is exchanged to form Chabazite Na ⁺ , using a liquid copper solution, where the copper concentration is in the range of about 0.001 to about 0.4 molar. In a second embodiment, the process of the first embodiment is modified in such a way that the ratio of liquid to solid is defined as the weight of water used to prepare the Cu solution in relation to the weight of the starting zeolite used in the copper exchange is in a range of about 2 to about 80. A third modality involves
Petition 870180056807, of 06/29/2018, p. 16/60 / 47 a modification of the first and second modalities, in such a way that the reaction temperature of the copper exchange stage is in a range of about 10 to about 100 ° C. A fourth modality involves a modification of any of the first to third modalities, in which copper acetate or an ammoniacal solution of copper ions is used as the source of copper. According to a fifth embodiment, any of the first to fourth embodiments can be modified so that the copper concentration is in the range of about 0.075 to about 0.3 molar. In a sixth embodiment, any of the first to fifth embodiments can be modified in such a way that the molecular sieve has a sodium content of less than about 2500 ppm.
[21] A seventh modality refers to the molecular sieve containing copper with the CHA structure, produced through the process of any of the modalities, according to the first to sixth modalities.
[22] An eighth modality refers to the molecular sieve containing copper, with the CHA structure, in which the molecular sieve containing copper with the CHA structure shows at least two signals in a TPR spectrum of H ₂ where the maximum of the signal I is in a range from about 25 to about 400 ° C and the maximum signal II is in a range from about 475 ° C to about 800 ° C. A ninth modality refers to a molecular sieve containing copper, with the CHA structure of the eighth modality, in which the molecular sieves containing copper with the CHA structure have a wavelength of half-height-half-width of UV-VIS in a range of about 15 to about 35 nm. A ninth modality refers to a molecular sieve containing copper from the eighth and ninth modalities, in which the molecular sieve has a ratio, by weight, of copper exchanged to copper oxide of at least about 1. In an eleventh modality, eighth, ninth and tenth modality is included
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8/47 the characteristic that molecular sieves containing copper with the CHA structure show at least one peak in a diffuse reflectance FT-IR spectroscopy method at about 1948 cm ¹ .
[23] A twelfth modality refers to a molecular sieve containing copper with the CHA structure, having a molar ratio of silica to alumina of more than 10, and a copper content, calculated as CuO, of at least 1 , 5% by weight, based on the total weight of the calcined zeolite, where the atomic ratio of copper to sodium is more than 0.5 and up to 200, and the weight ratio of copper switched to oxide of copper is at least about 1.
[24] A thirteenth modality refers to a catalyst containing a molecular sieve containing copper, with the CHA structure of any of the seventh, eighth through twelfth modalities.
[25] A fourteenth modality refers to the use of a catalyst containing a molecular sieve containing copper, with the CHA structure of the thirteenth modality, as a catalyst for the selective reduction of NO _X nitrogen oxides; for the oxidation of NH ₃ ; for the decomposition of N2O; for soot oxidation; for emission control in Advanced Emission Systems; as an additive in fluid catalytic cracking processes; as a catalyst in organic conversion reactions; or as a catalyst in “stationary source” processes.
[26] A fifteenth modality consists of an exhaust gas treatment system, comprising an exhaust gas stream containing ammonia and / or urea and at least one catalyst containing a molecular sieve containing copper with the CHA structure accordingly. with the thirteenth modality.
[27] A method for selectively reducing NO _X nitrogen oxides, in which a gas stream containing NO _X nitrogen oxides is
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9/47 contacted with molecular sieves containing copper with the CHA structure of any of the seventh or eighth to the twelfth modalities.
Brief Description of the Drawings:
[28] Figure 1 is a graph of H ₂ -TPR for examples # 2 to # 4;
[29] Figure 2 is a UV-VIS spectrum for examples # 2 to # 4; and [30] Figure 3 is a graph, which shows the relationship between the half height and half width of the UV band and the conversion of NOx at 450 ° C.
Detailed Description [31] As used in this report and in the appended claims, the singular forms “one” and “o” include plural referents, unless the context clearly indicates otherwise. Thus, for example, the reference to "a catalyst" includes a mixture of two or more catalysts, and the like.
[32] As used in this report and in the attached claims, the term "Chabazite Na ⁺ form" refers to the calcined form of this zeolite, without any ion exchange. In this form, the zeolite generally contains a mixture of the Na + and H + cations at the exchange sites. The fraction of sites occupied by Na + cations varies, depending on the specific zeolite batch and formulation.
[33] A molecular sieve can be zeolitic — zeolites— or non-zeolitic, and the zeolitic and non-zeolitic molecular sieves have the chabazite crystal structure, which is also referred to here as the CHA structure by the Intemational Zeolite Association. The zeolitic chabazite includes a naturally occurring tectosilicate mineral from a group of zeolites with the approximate formula:
(Ca, Na ₂ , K ₂ , Mg) AI2S14O12 χ 6H2O (for example, calcium silicate and hydrated aluminum). Three synthetic forms of zeolitic chabazite are
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10/47 described in “Zeolite Molecular Sieves”, by D. W. Breck, published in 1973 by John Wiley & Sons, which is incorporated by reference. The three synthetic forms reported by Breck are Zeolite K-G, described in J. Chem. Soc., P. 2822 (1956), Barrer et al .; Zeolite D, described in British Patent No. 868,846 (1961); and Zeolite R, described in U.S. Patent No. 3,030,181, which are incorporated by reference. The synthesis of another synthetic form of zeolitic chabazite, SSZ-13, is described in U.S. Pat. U. S. No. 4,544,538, which is incorporated by reference. The synthesis of a synthetic form of a non-zeolytic molecular sieve having the chabazite crystal structure, silicoaluminophosphate 34 (SAPO-34) is described in U.S. Patent No. 7,264,789, which is incorporated herein by reference. A method of producing yet another synthetic non-zeolytic molecular sieve having the chabazite structure, SAPO-44, is described in U.S. Patent No. 6,162,415, which is incorporated herein by reference.
[34] The synthesis of Na ⁺ zeolites having the CHA structure can be performed according to various techniques in the art. For example, in a synthesis of SSZ-13, a silica source, an alumina source, and an organic targeting agent are mixed under alkaline conditions. Typical silica sources include various types of fumigated silica, precipitated silica, and colloidal silica, as well as silicon alkoxides. Typical sources of alumina include bohemites, pseudo-bohemites, aluminum hydroxides, aluminum salts, such as aluminum sulfate or sodium aluminate, and aluminum alkoxides. Typically, sodium hydroxide is added to the reaction mixture. A typical targeting agent for synthesis is trimethyl ammonium adamantyl hydroxide, although other quaternary amines and / or ammonium salts can be substituted or added to the last targeting agent. The reaction mixture is heated in a vessel under pressure, with stirring, in order to provide the crystalline SSZ-13 product. Typical reaction temperatures are in the range of 100 and 200 ° C, in
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11/47 specific modes between 135 and 170 ° C. The reaction time periods are between 1 hour and 30 days, and in specific modalities between 10 hours and 3 days.
[35] At the conclusion of the reaction, the pH is optionally adjusted to between 6 and 10, and in specific modalities to between 7 and 7.5, and the product is filtered and washed with water. Any acid can be used to adjust the pH, and in specific modalities nitric acid is used. Alternatively, the product can be centrifuged. Organic additives can be used to assist in handling and isolating the solid product. Spray drying is an optional stage in product processing. The solid product is heat treated in air or nitrogen. Alternatively, each gas treatment can be applied in several sequences, or mixtures of gases can be applied. Typical calcination temperatures are in the range of 400 ° C to 850 ° C.
TEA:
[36] In specific embodiments, molecular sieves containing copper with the CHA structure include all aluminosilicate, borosilicate, galossilicate, MeAPSO, and MeAPO compositions. These include, but are not limited to, SSZ-13, SSZ-62, natural chabazite, KG zeolite, Linde D, Linde R, LZ-218, LZ-235, LZ-236 K-14, SAPO-34, SAPO-44 , SAPO- 47, ZYT-6, CuSAPO-34, CuSAPO-44, and CuSAPO-47. Even more preferably, the material should have an aluminosilicate composition, such as SSZ-13 and SSZ-62.
Concentration:
[37] The copper concentration of the liquid copper solution, used in copper ion exchange in specific modalities, is in a range of about 0.01 to about 0.35 molar, and in even more specific modalities in a range from about 0.05 to about 0.3 molar, and in even more specific modalities in a range from about 0.075 to about
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12/47
0.3 molar, and in even more specific modalities in a range from about 0.1 to about 0.3 molar, and in even more specific modalities in a range from about 0.1 to about about 0.25 molar and in even more specific embodiments in a range of from about 0.125 to about 0.25 molar.
Solid-liquid ratio:
[38] The solid-liquid ratio, which is defined here as the weight of water and copper salt used to prepare the Cu solution in relation to the dry weight of the starting zeolite used in the copper exchange stage, is, in specific modalities, in a range from about 0.1 to about 800, more specifically in a range from about 2 to about 80, even more specifically in a range from about 2 to about 15, even more specifically in a range of from about 2 to about 10, and even more specifically in a range of from about 4 to about 10 8.
Combination: concentration-ratio solid: liquid:
[39] According to a preferred embodiment of the embodiments of the present invention, the concentration of the copper solution used in the copper ion exchange stage is in the range of from 0.05 to about 0.3, and the ratio from solid to liquid, which is defined here as the weight of water and copper salt used to prepare the Cu solution in relation to the weight of the starting zeolite, is in a range of from about 2 to about 10 In more specific modalities, the concentration of the copper solution, used in copper ion exchange, is, in specific modalities, in a range from 0.1 to about 0.25, and the ratio of solid to liquid is in a range from about 4 to about 8.
Reaction temperature:
[40] The reaction temperature of the copper exchange stage is, in specific modalities, in a range of about 15 to about 100 ° C, and of
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13/47 an even more specific mode in a range of about 20 to about 60 ° C. In the case where ammoniacal solutions of copper ions are used as a source of copper, the reaction temperature is, in specific modalities, in a range of about 20 to about 35 ° C, and even more specifically in a range of about 20 to about 25 ° C.
Order of addition of reagents:
[41] The zeolite reagents, the source of copper to water can be added in any order. In specific modalities, the zeolite is added to a previously prepared solution of salt or copper complex, which can be at room temperature or previously heated to the ion exchange temperature. In even more specific embodiments, the previously prepared solution of salt or copper complex is heated to a temperature of about 20 to about 90 ° C, even more specifically from about 40 to about 75 ° C, and in even more specific embodiments of about 55 to about 65 ° C, before adding the zeolite.
Reaction time:
[42] The reaction time period of the ion exchange stage according to some modalities is in a range of about 1 minute to about 24 hours, in even more specific modalities, in a range of about 30 minutes to about 8 hours, and in even more specific modalities in a range from about 1 minute to about 10 hours, and in even more specific modalities from about 10 minutes to about 5 hours, and in even more specific modalities in a range from about 10 minutes to about 3 hours, and in even more specific modalities from about 30 minutes to about 1 hour.
Reaction Conditions:
[43] The aqueous solution in specific embodiments is suitably stirred. In general, the agitation speed is decreased as the size of the reactor increases.
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14/47 pH: use of acid additives [44] In specific embodiments, the pH of the ion exchange stage is in the range of about 1 to about 6, more specifically in the range of about 2 to about 6, and even more specifically in a range of about 3 to about 5.5. In the case where an ammoniacal solution of copper ions is used as the copper source, the pH of the ion exchange stage is in a range of about 5 to about 14, and in even more specific modalities in a range of about from 6 to about 12, and in even more specific modalities in a range of about 8 to about 11.
[45] Depending on the starting materials used, it may be necessary to adjust the pH of the aqueous solution, so that the pH has the values described above. In specific modalities, the pH is adjusted to the values described above, using acetic acid or ammonia, which can be added as an aqueous solution.
Copper species:
[46] In general, all sources of Cu salts can be used. For example, copper (II) oxide, copper acetate, copper nitrate, copper chloride, copper fluoride, copper sulfate, copper carbonate, copper oxalate, and ammonia solutions of copper ions, for example amine and copper carbonate, can be mentioned. In specific embodiments, an aqueous solution of at least one salt or Cu oxide is employed. Copper oxide and Cu salts, for example, copper acetate, copper fluoride, copper chloride and ammonia solutions of copper ions are preferred. In even more specific modalities, copper acetate and / or ammoniacal solutions of copper ions are used, for example, amine and copper carbonate. The use of a mixture of two or more sources suitable for Cu can be mentioned.
Ammonia solutions of copper ions:
[47] Panias et al. (Oryktos Ploutos (2000), 116, 47-56) report the
Petition 870180056807, of 06/29/2018, p. 24/60! ΑΠ speciation of divalent copper ions in ammoniacal solutions. The amino complexes of divalent copper Cu (NH ₃ ) _n ²⁺ are, in practice, the predominant forms, in which copper is found in acidic or strongly alkaline ammoniacal solutions. The Cu (NH3) 4 ²⁺ ion is the most important ion in the Cu ²⁺ -NH3-H2O system. It presents a region of broad stability, which varies from weakly acidic solutions, with a pH of 5, to a strongly alkaline solution, with a pH of 14. The divalent copper hydroxyl complexes are satisfied with the Cu ²⁺ -NH system ₃ -H2O only in very strongly alkaline solutions with a pH greater than 12 and in diluted ammoniacal solutions, with a total ammonia concentration below 0.1 M. In ammoniacal solutions, copper is found in the form of Cu ² ions ⁺ free only in highly acidic aqueous solutions.
Cu: Al in the copper suspension for the copper exchange stage:
[48] Using copper acetate, the molar ratio of Cu to Al in the copper suspension for the copper exchange stage in specific modalities is in the range of about 0.25 to about 2, and in even more modalities specific in a range from about 0.5 to 1.5 and in even more specific modalities in a range from about 0.5 to 1.5, and in even more specific modalities in a range of about 0.5 to about 1.2. Using ammonia solutions of copper ions, the Cu to Al ratio in specific modalities is in the range of about 0.001 to about 1, in even more specific modalities in the range of about 0.25 to about 0.8 , and in even more specific modalities in a range from about 0.25 to about 0.6, and in even more specific modalities in a range from about 0.25 to about 0.5. The suspension consists of a zeolite dispersed in a copper solution.
Yield:
[49] Percentage yield is defined as the number of moles of Cu in the zeolite / number of moles of Cu in the starting solution x 100. In
Petition 870180056807, of 06/29/2018, p. 25/60 6! ΑΠ specific modalities, the yield of the copper exchange stage is at least about 30%, in specific modalities of at least about 35%, in even more specific modalities of at least about 40% , in even more specific modalities of at least about 60%, and in even more specific modalities of at least 80%, and in even more specific modalities of at least 90%, and in even more specific modalities of at least about 95 %.
Repeating the ion exchange:
[50] The copper exchange stage can be repeated for 0-10 times, and in specific modalities 0-2 times. In even more specific modalities, the copper exchange stage is conducted only once, and is not repeated.
After treatment:
[51] After the copper exchange stage, the exchange suspension containing the molecular sieve containing copper with the CHA structure is suitably separated from the mother liquor. Prior to separation, the temperature of the mother liquor can suitably be lowered to a desired value, using an adequate cooling rate.
[52] This separation can be carried out by all suitable methods, known to those skilled in the art, for example, by means of decantation, filtration, ultrafiltration, diafiltration or centrifugation or, for example, by spray drying and granulation methods by spray.
[53] The Chabazite molecular sieve can be washed at least once with a suitable washing agent. It is possible to use identical or different washing agents, or mixtures of washing agents, in the case of at least two of the washing stages.
[54] The washing agents used can be, for example, water, alcohols, such as, for example, methanol, ethanol or propanol, or mixtures of
Petition 870180056807, of 06/29/2018, p. 26/60 / 47 two or more of them. For example, mixtures of two or more alcohols, such as, for example, methanol and ethanol or methanol and propanol or ethanol and propanol or methanol and ethanol and propanol, or mixtures of water and at least one alcohol, such as, for example , water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol, can be mentioned as mixtures.
[55] The wash water temperature of the wash stage in specific modes is in a range of about 10 to about 100 ° C, in even more specific modes in a range of from about 15 to about 60 ° C, and in even more specific modalities in a range of about 20 to about 35 ° C, and in even more specific modalities in a range of from about 20 to about 25 ° C.
[56] After separation and optionally washing, molecular sieves containing copper with the CHA structure can be dried. Drying temperatures and drying duration can be carried out using techniques known to those skilled in the art. The drying temperature in specific modalities is in a range from about room temperature to about 200 ° C and the drying duration, in specific modalities, is in a range from about 0.1 to about 48 hours.
[57] After separation, optionally washing and drying, molecular sieves containing copper with the CHA structure can be calcined in at least one additional stage.
[58] The calcination of the Chabazite molecular sieve, in specific modalities, is carried out at a temperature in the range of up to about 750 ° C. According to an alternative, if the calcination is carried out under static conditions, such as, for example, in a muffle furnace, temperatures of up to about 500 to about 850 ° C are preferred. In
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18/47 even more specific modalities are used from 500 to 800 ° C, and in even more specific modalities from 500 to 750 ° C. According to yet another alternative, if the calcination is carried out under dynamic conditions, such as, for example, in a rotary calciner, temperatures of up to about 500 to 750 ° C are preferred.
[59] The calcination can also be carried out, gradually, at successive temperatures. The term "gradually at successive temperatures", as used in the context of modalities of the invention, designates calcination, in which the zeolite to be calcined is heated to a certain temperature, maintained at this temperature for a certain period of time and heated from of this temperature to at least one additional temperature and kept there, in shifts, for a certain period of time. As an example, a gradual calcination is described in the international patent application having the application number PCT / EP2009 / 056036, PCT / EP 2009/056036 incorporated as reference.
[60] Calcination can be carried out in any suitable atmosphere, such as, for example, in air, poor air depleted of oxygen, oxygen, nitrogen, water vapor, synthetic air, carbon dioxide. The calcination is, in specific modalities, carried out under air. It may also be conceivable that the calcination is carried out in a double mode, that is, in a mode comprising a first calcination in an oxygen-reduced or oxygen-free atmosphere, said mode comprising a second calcination in an atmosphere of pure or enriched oxygen in oxygen.
[61] According to a specific modality, a first stage of calcination is carried out in an atmosphere comprising from about 5 to about 15% air and from about 80 to about 95% nitrogen, while the second stage calcination is carried out in an atmosphere comprising about 100% air.
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Process by Process:
[62] The modalities of the present invention also refer to molecular sieves containing copper with the CHA structure, having the Chabazite crystal structure, obtainable or obtained through the process described above.
Product:
[63] The modalities of the present invention also refer to molecular sieves containing copper, with the CHA structure as such, or obtained / obtainable through the process described above from modalities of the present invention, having a molar ratio of silica to alumina of more than than 10, and a copper content, calculated as CuO, of at least 1.5% by weight, reported on a volatile substance-free base, where the molecular sieves containing copper with the CHA structure have at least two signals in H2 TPR spectra, while the maximum signal I is in a range of 25 to 400 ° C and the maximum signal II is in a range of 475 ° C to about 800 ° C, measured after calcination of the zeolite at 500 ° C in air for 30 minutes.
[64] Signal I can be correlated to two reactions: i) Cu ²⁺ + V2
H2 = Cu ⁺ + H ⁺ and ii) CuO + H2 = Cu + H2O and the signal II can be correlated to a reaction iii) Cu ⁺ + V2 H2 = Cu + H ⁺ , while the maximum of the signal II is in a range from about 475 ° C to about 800 ° C.
[65] In specific modalities, the maximum signal II is in a range from about 480 ° C to about 800 ° C, in even more specific modalities in a range from about 490 ° C to about 800 ° C, and in even more specific modalities in a range of about 550 ° C to about 800 ° C.
[66] The use of this technique for the evaluation of metal-containing zeolites has been demonstrated in the literature. For example, Yan and colleagues
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20/47 report on the properties of Cu-ZSM-5 in the Journal of Catalysis, 161, 43-54 (1996).
Cu ²⁺ versus CuO:
[67] In specific embodiments, molecular sieves containing copper calcined with the CHA structure, as such, or obtained / obtained through the above described method of the present invention have a ratio, by weight, of copper switched to copper oxide at least about 1, measured after calcination of the zeolite at 450 ° C, in air, for 1 hour. In specific embodiments, the weight ratio of copper switched to copper oxide is at least about 1.5. In even more specific modalities, the ratio of copper exchanged to copper oxide is at least about 2.
[68] In specific modalities, the exchanged copper is located in the active sites called C and H sites. Thus, molecular sieves containing copper with the CHA structure, in specific modalities, exhibit a peak at about 1948 cm ¹ (site C) and optionally at about 1929 cm ¹ (H site), measured by diffuse reflectance FT-IR spectroscopy (DRIFT) methods.
[69] The use of the FTIR technique has been demonstrated in the literature, for example, in Giamello et al., J.Catal. 136, 510-520 (1992).
UV-VIS of copper-containing molecular sieves with the CHA structure [70] In specific embodiments, the copper-containing molecular sieves calcined with the CHA structure, as such, or obtained / obtainable through the above described process of the invention's modalities, have a half-height and half-width UV-VIS wavelength in a range of about 5 to about 35 nm, in more specific modalities in a range of about 10 to 30 nm, and in even more specific modalities in a range from about 15 to about 25 nm, measured after the
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21/47 calcination of the zeolite at 450 ° C, in air, for 1 hour.
[71] The use of the UV-VIS technique has been demonstrated in the literature, for example in J. Catai. 220, 500-512 (2003).
Copper weight%:
[72] The Cu content of the molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through the process described above from modalities of the present invention, calculated as CuO, in specific modalities, is at least about 1.5% by weight, and in even more specific modalities of at least about 2% by weight, and in even more specific modalities of at least about 2.5% by weight, reported on a substance-free basis volatile. In even more specific modalities, the Cu content of the Chabazite molecular sieve, calculated as CuO, is in a range of up to about 5% by weight, in more specific modalities of up to about 4% by weight, and in even more specific modalities of up to about 3.5% by weight, in each case on a basis free from volatile substances. Thus, in specific modalities, the Cu content ranges of the Chabazite molecular sieve, calculated as CuO, are from about 2 to about 5% by weight, in even more specific modalities from about from 2 to about 4%, by weight, and in even more specific modalities from about 2.5 to about 3.5%, by weight, and in even more specific modalities from about 2.75 to about 3 , 25%, by weight, in each case, reported on a volatile substance-free basis. All weight% values are reported on a volatile substance-free basis.
Free copper:
[73] In addition to copper, which is exchanged in order to increase the level of copper associated with the sites exchanged in the zeolite structure, unchanged copper, in the form of salt, may be present in the molecular sieve with the CHA, the so-called free copper. However, in
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22/47 specific modalities, there is no free copper present in the Chabazite molecular sieve.
Silica / Alumina:
[74] In specific embodiments, molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through the process described above from embodiments of the present invention, have a molar ratio of silica to alumina of more than about 15, even more specifically of more than about 20. In specific embodiments, the copper-containing Chabazite has a molar ratio of silica to alumina in a range of about 20 to about 256, and in even more specific modalities in a range from about 25 to about 40.
Cu / Al:
[75] In specific embodiments, the atomic ratio of copper to aluminum of molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through the above described method of embodiments of the present invention exceeds 0.25. In even more specific embodiments, the copper to aluminum ratio is from about 0.25 to about 1, and in even more specific embodiments from about 0.25 to about 0.5. In even more specific embodiments, the copper to aluminum ratio is about 0.3 to about 0.4.
SCR activity:
[76] In specific embodiments, molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through the described method of embodiments of the present invention exhibit a cured NOx conversion at 200 ° C of at least 50 %, measured at a space velocity based on the hourly gas volume of 80000 h ¹ under steady state conditions, under conditions of maximum NH ₃ suspension, in a gas mixture of 500 ppm NO, 500 ppm NH ₃ , 10% O2. 5% H2O, and N2 balance. In specific modalities, molecular sieves containing
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23/47 copper with the CHA structure exhibits a cured NOx conversion, at 450 ° C, of at least [77] 70%, measured at a special hourly speed of 80,000 h ¹ . In even more specific modalities, the conversion of cured NOx, at 200 ° C, is at least 55% and, at 450 ° C, at least 75%, and in even more specific modalities, the conversion of cured NOx, at 200 ° C, is at least 60% and, at 450 ° C, at least 80%, measured at an hourly, gaseous spatial speed of 80000 h ¹ . Typical conditions for this hydrothermal cure are: the copper-containing catalyst is placed in a tube oven, in a gas stream containing 10% H ₂ O, 10% O ₂ , N ₂ equilibrium, at a spatial speed based on volume from 8,000 to 12,500 h ¹ , for 24 hours at 750 ° C or from 1 to 6 hours at 850 ° C.
[78] The measurement of SCR activity has been demonstrated in the literature, for example, in WO 2008/106519.
Sodium content:
[79] In specific embodiments, molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through the process described above from embodiments of the present invention, have a sodium content (reported as Na ₂ O on a base free of volatile substances) of less than 2% by weight reported on a volatile substance-free basis. In more specific modalities, the sodium content is below 1%, by weight, and in even more specific modalities below 2500 ppm, in even more specific modalities below 2000 ppm, and in more specific modalities below 1000 ppm and in even more specific embodiments below 500 ppm, and even more preferably below 100 ppm.
Na: Al:
[80] In specific embodiments, molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through
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24/47 above described methods of the present invention, have a sodium to aluminum ratio of less than 0.7. In even more specific modalities, the ratio of sodium to aluminum atomic is less than 0.35, in even more specific modalities of less than 0.007, and in even more specific modalities of 0.03 and in even more specific modalities of less than 0.02.
Na: Cu:
[81] In specific embodiments, molecular sieves containing copper with the CHA structure, as such, or obtained / obtainable through the process described above from embodiments of the present invention, have an atomic copper to sodium ratio of more than 0.5 . In more specific modalities, the ratio of copper to atomic sodium is more than 1, in even more specific modalities of more than 10, and in even more specific modalities of more than 50.
Chabazite with high Na:
[82] The modalities of the invention also refer to molecular sieves containing copper, with the CHA structure, as such, or obtained / obtainable through the processes described above. In one or more embodiments, molecular sieves containing copper have a molar ratio of silica to alumina of more than 10, and a copper content, calculated as CuO, of at least 1.5% by weight, reported on a base free of volatile substances, where the atomic ratio of copper to sodium is more than 0.5 and up to 200, and the ratio of copper switched to copper oxide is at least about 1.
Additional metal:
[83] Molecular sieves containing copper having the CHA structure, as such, or obtained / obtainable through the above-described process of embodiments of the present invention may still contain one or more transition metals. In specific modalities, the Chabazite molecular sieve
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25/47 may contain transition metals capable of oxidizing NO to NO2 and / or storing NH ₃ . The transition metal is, in specific modalities, selected from the group, which consists of Fe, Co, Ni, Zn, Y, Ce, Zr and V. In general, all sources suitable for Fe, Co, Ni , Zn, Y, Ce, Zr and V can be used. For example, nitrate, oxalate, sulfate, acetate, carbonate, hydroxide, acetyl acetonate, oxide, hydrate, and / or salts, such as chloride, bromide and iodide, can be mentioned.
[84] In addition, molecular sieves containing copper with the CHA structure may contain one or more lanthanides. In a specific embodiment, a source of lanthanide is, among others, lanthanum nitrate.
[85] In addition, molecular sieves containing copper with the CHA structure may contain one or more precious metals (for example, Pd, Pt).
BET:
[86] In specific embodiments, molecular sieves containing copper with the CHA structure, as such or obtained / obtainable through the process described above from embodiments of the invention, exhibit a BET surface area, determined according to DIN 66131, of at at least about 400 m ² / g, more specific modalities of at least about 550 m ² / g, and in even more specific modalities of about 650 m ² / g. In specific modalities, the molecular sieve with the Chabazite structure exhibits a BET surface area in a range from about 400 to about 750 m ² / g, and in more specific modalities from about 500 to about 750 m ² / g, and in even more specific modalities from about 600 to 750 m ² / g.
Average crystallite length:
[87] In specific modalities, the crystallites of the molecular sieves containing copper calcined with the CHA structure, as such,
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26/47 or obtained / obtainable through the process described above of modalities of the present invention, present an average length in a range from 10 nanometers to 100 micrometers, in more specific modalities in a range from 50 nanometers to 5 micrometers, and in even more specific modalities in a range of 50 nanometers to 500 nanometers, as determined by SEM.
TOC:
[88] In specific embodiments, molecular sieves containing copper calcined with the CHA structure, as such, or obtained / obtainable through the process described above from embodiments of the present invention, have a TOC (total organic carbon) content of 0, 1% by weight or less based on the total weight of the Chabazite molecular sieve.
Thermal stability:
[89] In specific embodiments, molecular sieves containing copper calcined with the CHA structure, as such, or obtained / obtainable through the process described above from the modalities of the present invention, have a thermal stability, determined through differential thermal analysis or differential scanning calorimetry in a range from about 900 to about 1400 ° C, and in specific modalities in a range from about 1100 to about 1400 ° C, and in even more specific modalities in a range from about 1150 to about 1400 ° C. For example, the measurement of thermal stability is described in PCT / EP 2009/056036, on page 38.
Form:
[90] The Chabazite molecular sieve according to the modalities of the present invention can be provided in the form of a powder or a pulverized material, obtained from the separation techniques described above, for example, decantation, filtration, centrifugation, or spraying.
Petition 870180056807, of 06/29/2018, p. 36/60 / 47 [91] In general, the powdered or pulverized material can be formed without any other compounds, for example through adequate compaction, so that molds of a desired geometry are obtained, for example, tablets, cylinders, spheres, or the like.
[92] As an example, powdered or powdered material is mixed with or coated by means of suitable modifiers, well known in the art. For example, modifiers such as silica, alumina, zeolites or refractory binders (for example, a zirconium precursor) can be used. The powder or the pulverized material, optionally after mixing or coating by means of suitable modifiers, can be formed into a suspension, for example with water, which is deposited on a refractory vehicle (for example, WO 2008/106519 ).
[93] The Chabazite molecular sieve of the modalities of the invention can also be provided in the form of extrudates, pellets, tablets or particles of any suitable form, for use as a compacted bed of a particulate catalyst, or as molded parts, such as than plates, saddles, tubes or the like.
Catalyst:
[94] Thus, the modalities of the invention refer to a catalyst containing a molecular sieve containing copper with the CHA structure, obtainable or obtained by means of the above described process, disposed on a substrate.
[95] The substrate can be any of those materials typically used for the preparation of catalysts and will normally comprise a ceramic or metallic honeycomb structure. Any suitable substrate can be used, such that a monolithic substrate, of the type that has parallel, thin gas flow passages, extending
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28/47 therethrough, from an entrance face or an exit face of the substrate, in such a way that the passages are open to the flow of fluid through them (hereinafter referred to as alveolar throughflow substrates) . The substrate can also be a wall flow filter substrate, in which the channels are alternately blocked, allowing a gas stream to be introduced into the channels from one direction (inlet direction), to flow through the channel walls. and leaving from the channels from another direction (exit direction). In addition, suitable vehicles / substrates, as well as suitable coating processes, are described in the international patent application having application number PCT / EP2009 / 056036 and WO 2008/106519, PCT / EP 2009/056036 and WO 2008 / 106519, which are incorporated by reference.
SCR / Exhaust gas treatment system:
[96] In general, molecular sieves containing copper with the CHA structure described above can be used as a molecular sieve, adsorbent, catalyst, catalyst support or as a binder thereof. In particular, its use as a catalyst is preferred.
[97] Furthermore, the modalities of the invention relate to a method of catalyzing a chemical reaction, in which molecular sieves containing copper with the CHA structure according to the modalities of the invention are employed as a catalytically active material.
[98] Among others, the said catalyst can be used as a catalyst for the selective reduction (SCR) of nitrogen oxides (NO _X ); for the oxidation of NH3, in particular for the oxidation of an NH3 suspension in diesel systems; for the decomposition of N2O; for soot oxidation; for emission control in Emission Systems
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29! 47
Advanced, such as in Homogeneous Load Compression Ignition engines (HCC1); as an additive in fluid catalytic cracking (FCC) processes; as a catalyst in organic conversion reactions; or as a catalyst in “stationary source” processes. For applications in oxidation reactions, in specific embodiments, an additional precious metal component is added to the copper chabazite (eg, Pd, Pt).
[99] Thus, the modalities of the invention also refer to a method to selectively reduce nitrogen oxides (NO _X ) by contacting a stream containing NO _X with a catalyst containing molecular sieves containing copper with the CHA structure according to the modalities of the invention, under suitable reduction conditions; to an NH ₃ oxidation method, in particular oxidation of NH ₃ suspension in diesel systems, by contacting a chain containing NH ₃ with a catalyst containing the molecular sieves containing copper with the CHA structure according to with the modalities of the invention, under suitable oxidation conditions; a method of decomposing N ₂ O by contacting a stream containing N ₂ O with a catalyst containing molecular sieves containing copper with the CHA structure according to the modalities of the invention, under suitable composition conditions; to a method to control emissions in Advanced Emission Systems, such as in Homogeneous Charge Compression Ignition (HCC1) engines, through contact with an emission current with a catalyst with molecular sieves containing copper with the CHA structure according to the modalities of the invention, under suitable conditions; to a FCC fluid catalytic cracking process, in which molecular sieves containing copper with the CHA structure according to the modalities of the invention are employed as an additive; to a method for converting an organic compound
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30/47 by contacting said compound with a catalyst containing the molecular sieves containing copper with the CHA structure according to the modalities of the invention, under suitable conversion conditions; to a "stationary source" process, in which a catalyst containing the molecular sieves containing copper with the CHA structure according to the modalities of the invention is employed.
[100] In particular, the selective reduction of nitrogen oxides, in which the Chabazite molecular sieves according to the modalities of the invention are used as a catalytically active material, is carried out in the presence of ammonia or urea. Although ammonia is the reducing agent of choice for stationary power plants, urea is the reducing agent of choice for mobile SCR systems. Typically, the SCR system is integrated into the exhaust gas treatment system of a vehicle and, moreover, in a typical way, it contains the following main components: SCR catalyst containing the molecular sieves with the structure CHA according to the modalities of the invention; a urea storage tank; a urea pump; a urea dosing system; a urea injector / nozzle; and a respective control unit.
NO _X reduction method:
[101] In this way, the modalities of the invention also refer to a method for the selective reduction of nitrogen oxides (NO _X ), in which a gas stream containing nitrogen oxides (NO _X ), for example, a nitrogen gas exhaust formed in an industrial process or operation, and in specific modalities also containing ammonia and / or urea, is contacted with the Chabazite molecular sieves according to the modalities of the invention.
[102] The term nitrogen oxides, NO _X , as used in the context of the modalities of the invention, means nitrogen oxides,
Petition 870180056807, of 06/29/2018, p. 40/60 / 47 a special mode the dinitrogen oxide (N2O), nitrogen monoxide (NO), dinitrogen trioxide (N2O3), nitrogen dioxide (NO2), dinitrogen tetroxide (N2O4), dinitrogen pentoxide (N2O5) , nitrogen peroxide (NO3).
[103] Nitrogen oxides, which are reduced using a catalyst containing Chabazite molecular sieves according to the modalities of the invention or Chabazite molecular sieves, obtainable or obtained according to the modalities of the invention, can be obtained through any process, for example, like a stream of waste water. Among others, the waste gas streams, as obtained in the processes for the production of adipic acid, nitric acid, hydroxylamine derivatives, caprolactam, glyoxal, methyl-glyoxal, glyoxylic acid or in processes for burning nitrogenous materials, can be mentioned.
[104] In particularly specific embodiments, a catalyst containing the Chabazite molecular sieves according to the modalities of the invention or the Chabazite molecular sieves, obtainable or obtained according to the modalities of the invention, is used for the removal of nitrogen oxides (NO _X ) from exhaust gases from internal combustion engines, in particular diesel engines, which operate in combustion conditions with air in excess of that required for stoichiometric combustion, that is, poor.
[105] Thus, the modalities of the invention also refer to a method for the removal of nitrogen oxides (NO _X ) from exhaust gases from internal combustion engines, in particular diesel engines, which operate under conditions combustion with air in excess of that required for stoichiometric combustion, that is, in poor conditions, in which a catalyst containing Chabazite molecular sieves according to the modalities of the invention or Chabazite molecular sieves, obtainable or obtained according to the modalities of the invention, is
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32/47 used as a catalytically active material.
Exhaust gas treatment system:
[106] The modalities of the invention refer to an exhaust gas treatment system, which comprises an exhaust gas stream optionally containing an ammonia, urea and / or hydrocarbon reducing agent, and in specific modalities, ammonia and / or urea, and a catalyst containing a molecular sieve containing copper with the CHA structure, obtainable or obtained through the process described above, arranged on a substrate, a soot filter and a diesel oxidation catalyst.
[107] The soot filter, catalyzed or non-catalyzed, can be upstream or downstream of said catalyst. The diesel oxidation catalyst in specific embodiments is located upstream of said catalyst. In specific embodiments, said diesel oxidation catalyst and said soot catalyst filter are upstream of said catalyst.
[108] In specific modalities, the exhaust is transported from the diesel engine to a downstream position in the exhaust system, and in more specific modalities, containing NO _X , where a reducing agent is added and the exhaust current with the reducing agent added, being transported to said catalyst.
[109] For example, a catalyzed soot filter, a diesel oxidation catalyst, and a reducing agent are described in WO 2008/106519, which is incorporated by reference.
[110] The following examples should further illustrate the process and modalities materials of the present invention.
Examples
H2-TPR spectra [111] Programmed Temperature Reduction (TPR) measurements
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33/47 were performed on a Micromeritics Autochem 2910 Analyzer with a TCD detector. Pretreatment was carried out at 4% 02 / He from room temperature to 500 ° C, at 20 ° C / minute, and with a retention period of 20 minutes. The sample was then cooled to room temperature. This was followed by a helium purge for 10 minutes. TPR was performed in 0.5% H2 / N2 from room temperature to 900 ° C, at 10 ° C / minute and for a period of retention. A liquid argon trap was used during the reduction.
UV-VIS [112] The samples were ground manually using a mortar and pestle before compaction of the sample inside a 0.2 cm quartz cuvette. The diffuse reflectance UV-VIS spectra expressed through F (R) were collected using a diffuse reflectance connection with a BaSO4 coated integration sphere inside a Cary 300 UV-VIS spectrometer. The following instrument parameter settings have been used:
Scan rate = 300 nm
SBW (resolution) = 2.0 nm
Beam mode = double reverse
Exchange of UV-Vis = 350 nm
Reference line correction mode Signal for noise correction mode Comparative Examples:
1. Comparative Example 1:
[113] Example 1 of WO 2008/106519 describes the multi-stage synthesis of CuSSZ-13 through two exchanges of 1 M copper sulfate in the NH4 form of SSZ-13. The pH was adjusted to 7.5 by the addition of nitric acid, in order to allow an improved filtration. The details regarding the important synthesis conditions and the properties of the
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3ΑΙ4Ί material are found in Tables 1 and 2.
2. Comparative Example 2:
[114] Example 18 of WO 2008/106519 describes the multistage synthesis of CuSSZ-13 through a switch from copper acetate to the NH4 form of SSZ-13. Details of important synthesis conditions and material properties are found in Tables 1 and 2.
3. Comparative Example 3:
[115] Comparative Example 2 was also performed using the same batch of Na-SSZ-13 described below in Example 1 B (32 SiO2: Al ₂ O3, and 0.71% by weight of Na2O in a base free of volatile substances), which was used for all other inventive examples. First, the ammonium exchange was performed in a way to remove the sodium, before the exchange with 0.4 M copper acetate described in Example 18 to WO 2008/106519 was repeated. The final composition was 3.58 wt.% CuO, less than 100 ppm Na2O and 32.6 S1O2: AI2O3. Details on important synthesis conditions and material properties are found in Table 1.
4. Comparative Example 4:
[116] Example 19 of WO 2008/106519 was also performed using the same batch of Na-SSZ-13 described below in Example 1 B (32 S1O2: AI2O3, and 0.71%, by weight, of Na2O on a base free of volatile substances, which was used for all examples according to the invention First, an ammonium exchange was performed before the 0.3 M copper acetate exchange described in Example 18 of WO 2008/106519 was repeated. The final composition was 3.31% by weight of CuO, less than 100 ppm of Na2O and 32.6 of SiO2: A12O3.The details of the synthesis conditions and material properties are found in Table 1.
Inventive Examples:
Example 1- Na-SSZ13 starting material
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Example ΙΑ - Na-SSZ13 starting material (1) [117] SSZ-13 was crystallized, as described in US 4,544,538 using trimethyl adamantyl ammonium hydroxide as the template and sodium hydroxide as an additional source of OH. The pH was adjusted to 7.5, the material was recovered by filtration and dried before calcination at 600 ° C, in order to produce the Na form of SSZ-13.
[118] Chemical analysis showed that the material had 31.8 S1O2: AI2O3, and 0.62% by weight of Na2O in a base free of volatile substances. XRD indicated that pure SSZ-13 had been obtained. The BET surface of the calcined material, determined according to DIN 66131, was 663 m ² / g.
Example 1 B- Na-SSZ13 starting material (2) [119] SSZ-13 was synthesized as described in Example 1 A. Chemical analysis showed that the material had 32.3 S1O2: AI2O3, and 0.71 % by weight of Na2Ü on a base free from volatile substances. XRD indicated that pure SSZ-13 had been obtained. The BET surface of the calcined material, determined according to DIN 66131, was 613 m ² / g. The water content of the powder was ~ 4.8% by weight.
2. Exchange of Direct Copper Acetate as Na
2.1.1. Reagents and suspension preparation (Examples 2-6) [120] The following starting materials were used:
Copper Acetate Monohydrate
Deionized water
Sodium Chabazite of Example IA
2.1.2. Ion exchange and chemical analysis conditions (Examples # 2- # 5) [121] The Table lists the important synthesis parameters for ion exchange in Examples 2 to 5. Typically, 200 g of Na-CHA (Example 1 A) were immersed in 800 ml of the respective acetate solution
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36/47 copper at room temperature (room temp.) And stirred in a 1 L jacketed glass reactor. The volume of the exchange suspension was kept constant at a liquid: solid ratio of 4: 1, which is defined above. An exception was Example 5, in which Cu: Al was adjusted by reducing the amount of solid added to 125 g (5, 33 liquid: solid). After 30 minutes, the temperature of the water jacket was increased to 60 ° C, using a circulating heating bath. The temperature inside the exchange vessel was measured independently, with a thermometer, and is typically 57-58 ° C. The exchange suspension was maintained for 3 hours at this temperature, and then filtered hot (without additional cooling) through a 33 cm diameter Buchner funnel using a Whatmann paper filter (> 25 pm filtration). The filtrate was collected and its pH was measured after cooling to room temperature. The filter cake was then washed with batches of deionized water, until the conductivity of the washing water reached 200 pScm ¹ . All samples of the filter cake were washed with washing water at room temperature.
[122] The CuO, Na ₂ O and A1 ₂ O ₃ contents of the Cu-CHA filter cake samples were analyzed using ICP analysis. The SiO ₂ content was calculated from the difference. All values are reported on a volatile substance-free basis. Table 1 also summarizes the load of CuO and Na ₂ O.
2.2.1. Preparation of reagents and suspension (Example 6) [123] The following starting materials were used:
Copper acetate monohydrate
Deionized water
Copper chabazite of Example 1 B
2.2.2. Ion exchange and chemical analysis conditions (Example 6) [124] Table 1 also lists the synthesis parameters
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37/47 important for ion exchange in the preparation of Example 6. A copper acetate solution was prepared by dissolving 57.5 g of copper acetate monohydrate in 2822.5 g of deionized water in a glass reactor. 4 liters jacketed. This solution was heated to 60 ° C, before adding 360 g of Na-CHA (Example 1 B). 150 g of deionized water was used to wash the reactor walls, in order to ensure that all the zeolite was in solution. The volume of the exchange suspension was kept constant at a liquid: solid ratio of 8: 1. The temperature of 60 ° C was maintained for 8 hours, during which time the pH was in the range of 4.75 to 4.5. After 8 hours of ion exchange, the suspension was filtered hot through a 33 cm Buechner funnel, using Whatman 541 filter paper (> 25 pm filtration). The filter cake was then washed with deionized water, until the conductivity of the washing water reached 200 pScm ¹ . The sample was washed with washing water at room temperature. The resulting powder was then dried in an oven at 120 ° C for 16 hours.
[125] The CuO, Na2Ü and AI2O contents of the Cu-CHA filter cake samples were analyzed using ICP analysis. All values are reported on a volatile substance-free basis. Table 1 also summarizes the load of CuO and Na2O. It had a water content of ~ 15.8% by weight.
Table 1: Copper acetate exchange conditions, yield and chemical analysis for the direct exchange of NaCHA. Additional details of comparative examples from the multistage exchange of NH4CHA.
Example 2 3 4 5 6 Copper exchange stages 1 1 1 1 1 Copper concentration (mol / 1) 0.3 0.2 0.13 0.13 0.1 Cu: Al (molar ratio) 1.2 0.8 0.5 0.8 0.86 CuO in zeolite (% by weight) 3.66 2.79 2.33 2.92 3.57 Na2O in zeolite (ppm) 54 287 816 136 321 CU Yield (%) 40 45 60 46 56 Example Comp. 1 Comp. 2 Comp. 3 Comp 4 Comp. 2 Copper exchange stages 2 1 1 1 1 Copper concentration (mol / 1) 1* 0.4 0.4 0.3 0.4 Cu: Al (molar ratio) 4 * 1.6 1.73 1.3 1.6 CuO in zeolite (% by weight) 2.41 3.06 3.58 3.31 3.06
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Example Comp. 1 Comp. 2 Comp. 3 Comp 4 Comp. 2 Na2O in zeolite (ppm) <100 <100 <100 <100 <100 Cu yield (%) 3.8 24 28 35 24
* 2 Exchanges were performed using these conditions. The yield is calculated for Cu after 2 changes.
3. Preparation of catalyst, cure in core-reactor tests
3.1. Catalyst Coating (Catalyst Examples # 2 - # 5) [126] For the preparation of coated monolithic test grades, the filter cake, produced as described as Examples 2 to 5 (45% water content measured after calcination at 600 ° C in air for 1 hour) was produced in a suspension of 38-45% solid containing, through the addition of deionized water. The Cu-CHA suspension was then ground in a ceramic ball mill to a particle size of D90 of less than 10 pm (for example, from 4 to 10 pm) measured with a Sympatec particle size analyzer, using dispersion front laser. No acid or binder was added to the suspension in order to test the intrinsic activity of the catalyst. The ground suspension was coated on a ceramic monolith (NGK) 1 "in diameter and 2" in length, having a cell density of 400 cpsi and a wall thickness of 6 mil. The target dryness gain was 2.3 g / in ³ , which corresponds to the active catalyst load in WO 2008 / 106519. Typically, two to three coatings were required for the objective to be achieved, the content of solids of the additional coatings having been adjusted, in order to satisfy the objective increase in dryness gain. After each coating, the core was dried for 3 hours, at 90 ° C, in air. The last drying stage was followed by calcination, for 1 hour, at 450 ° C, in air, in a muffle funnel.
3.2. Healing and Catalytic Tests (Catalyst Examples # 2- # 5) [127] The cores were hydrothermally cured in a tube oven, in a gas stream containing 10% H2), 10% O2, N2 balance,
Petition 870180056807, of 06/29/2018, p. 48/60
39/47 at a space speed of 8,000 h ¹ at 200 ° C, 250 ° C, 300 ° C, and 450 ° C. As the activity is usually above 90% at 250 ° C and 300 ° C, only the conversion of NOx at low temperature at 200 ° C and at high temperature at 450 ° C was discussed.
[128] DeNO _x activity was measured under steady state conditions under conditions of maximum NH ₃ suspension in a laboratory reactor, in a gas mixture of 500 ppm NO, 500 ppm NH ₃ , 10% O ₂ , 5% H2O, N2 equilibrium, at a spatial speed based on the volume of 80,000 h ¹ at 200 ° C, 250 ° C, 300 ° C, and 450 ° C. As the activity is usually above 90% at 250 ° C and 300 ° C, only the NOx conversion activity at low temperature at 200 ° C and at high temperature at 450 ° C will be discussed.
[129] Table 2 contains DeNOx activity after curing at 200 and 450 ° C, from the core based catalytic test reactor described in this section.
Table 2: DeNOx activity of the coated catalyst at 200 and 450 ° C after hydrothermal curing.
Example Catalyst2 Catalyst3 Catalyst4 Catalyst5 Catalyst comp 1 Catalyst comp 2 Conversion of NOx cured at 200 ° C (%) 61 55 53 63 45 70 Conversion of NOx cured at 450 ° C (%) 68 77 81 83 82 88
4. Catalyst preparation, curing in tests in the extruded reactor.
4.1. Preparation of the Catalyst (Example of catalyst # 6, comparative examples # 3 and # 4).
[130] The powders obtained from comparative examples 3 and 4 and example 6, were first prepared as an extrudate, prior to testing. A typical preparation would involve adding 18 g of water and 20 g of dry powder to a Stephan-Werke GmbH mixer (model No.: 0ZDe042 / 4s), at a mixing rate of 80 revolutions per minute. This was mixed
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40/47 until it became homogeneous, which took about 10 minutes. Then, 0.5 g of polyethylene oxide (PEO) was added and mixed until homogeneous, which took 2 minutes. 2.5% by weight of PEO was added to the mixture as a binder. Then, 2 g of water was added slowly and the paste was mixed for about 5 minutes, so that it became homogeneous. This paste was then pressed in a hand-produced press with an extinction hole 2 mm in diameter and 10 cm in length. The resulting quench was then dried at 120 ° C for about 5 hours and calcined at 540 ° C for 5 hours. The extrudate was then sized in the form of pellets and sieved in such a way that a pellet size of 0.5 to 1 mm was separated. This fraction of size was used for testing in the reactor. The used sieves were obtained from the Retsch Company (500 pm sieve (S / N 04025277) and a 1 mm sieve (S / N 04009529), both having a diameter of 200 mm and a height of 25 mm). The resulting catalyst retains the exemplary name of this powder form, that is, catalyst example 6 was produced from example 6.
4.2. Curing and Catalytic Tests (Catalyst Example # 6, Comparative Examples # 3 and # 4) [131] The curing reactor was composed of a steel tube 1 mm thick (class 1.4841 from Buhlmann Group) with diameters of 500 mm high and 18 mm internal diameter. A nickel blanket oven was used to heat the reactor to the target reaction temperature, which was monitored through an internal thermal pair at the sample site. The steam was prepared by heating controlled amounts of water to 150 ° C, using a steel pre-vaporizer, before mixing with the remaining gases in a static mixer. The gases, along with the steam, were then passed through a preheater, in order to allow the target temperature to be reached.
Petition 870180056807, of 06/29/2018, p. 50/60
41/47 [132] The extrudates, formed as described in section 4.1, were cured hydrothermally in a tube oven, in a gas stream containing 10% H2O, 10% O2, N2 equilibrium, at a space velocity of 12. 500 h ' ¹ , for 6 hours at 850 ° C. These catalysts are now described as being in the cured state. The resulting catalyst retains the exemplary name of its powder form, ie, catalyst example 3 was produced from example 3.
[133] The cured catalyst samples were evaluated for selective catalytic reduction of NO _X activity in the following catalyst setting:
[134] The reactor was composed of a steel tube 1 mm thick (class 1.4541 from Buhlmann Group), with diameters 500 mm high and 18 mm internal diameter. A furnace based on a copper blanket was used to heat the reactor to the target reaction temperature, which was monitored through an internal thermal pair, at the sample location.
[135] 5 ml (~ 1.8 g) of the sample was loaded into the reactor and fixed with a plug of silica wool at each end of the sample. The height of the sample was controlled by filling the volume of the empty reactor with an inert silica-based material (Ceramtek AG-products # 1.080001.01.00.00; 0.5 to 1 mm - 45 g at the bottom and 108 g at the bottom top of the sample).
[136] An inlet gas mixture was formed containing 500 ppm NO, 500 ppm NH ₃ , 10% O2, 5% steam, and He balance. Steam was prepared by heating controlled amounts of water to 150 ° C using a steel pre-vaporizer (Buhlmann class 1.4541, and dimensions were 6 mm in diameter and 900 mm in length), before mixing with the remaining gases in a static mixer. This gas mixture was then passed through a preheater set at 250 ° C and a static mixer, before being introduced into the SCR reactor, described in the previous paragraph.
Petition 870180056807, of 06/29/2018, p. 51/60
42! 47 [137] DeNO _x activity was measured under constant state conditions by measuring the concentrations of NO _X , NH ₃ and N2O at the output using an FTIR spectrometer. The samples were tested at reaction temperatures of 200 and 450 ° C. In addition, they were tested at an hourly gaseous space velocity based on the volume of 80,000 h ¹ . The NO conversion was then calculated as (NO input concentration (ppm) - NO output concentration (ppm) / NO input concentration (ppm)) * 100. N2O production was also recorded as the concentration in ppm.
[138] Table 3 contains the DeNOx activity after curing at 200 and 450 ° C of the catalyst of Example 6 and the catalyst of comparative examples 3 and 4, as measured in this reactor based on the extrudate.
Table 3: DeNOx activity of the extrudate catalyst at 200 and 450 ° C after hydrothermal curing.
Example Catalyst 6 Catalyst Comp. 3 Catalyst Comp. 4 Conversion of NO cured at 200 ° C (%) 74 65 72 Conversion of NO cured at 450 ° C (%) 74 69 76
5. Additional characterization
5.1. Programmed Temperature Reduction (H2-TPR) [139] In order to characterize the Cu state, H2-
TPR were taken from examples # 2 to # 4, as described above. Figure 1 and Table 4 show the hydrogen consumption measured as a function of temperature for examples # 2, # 3, and # 4 (effect of the CuO charge). There are two main reduction signals: a low temperature I signal, around 190 ° C and a high temperature signal II. The consumption of H2 in these samples corresponds to a complete reduction from Cu ²⁺ to Cu °. The signals I and II of hydrogen consumption may be interpreted as a reduction in two stages of cupric ions to Cu metal, signal I corresponding to the reduction of Cu ²⁺ to Cu ⁺ ions (reaction 1), and signal II to the reduction of Cu ⁺ ions to Cu ° metal (reaction 3). Signal I may also contain contributions from CuO, which is reduced by one stage at about 200 ° C
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43/47 at 220 ° C for Cu metal (reaction 2).
Signal I: l) Cu ²⁺ + ^x / ₂ H ₂ = Cu ⁺ + H ⁺
2) CuO + H ₂ = Cu + H ₂ O
Signal II: 3) Cu ⁺ + ^x / ₂ H ₂ = Cu + H ⁺
Table 4: H ₂ -TPR of Examples # 2 to # 4
Examples Maximum signal Π, H ₂ -TPR (° C) #2 490 # 3 550 # 4 590
5.2. Characterization by UV-vis spectroscopy [140] Figure 2 and Table 5 show UV-vis spectra from examples # 2 to # 4 after curing for 6 hours at 850 ° C. All spectra have the common characteristic of a main charge transfer range (CT) around 205- 210 nm. This range can be attributed to an electronic transition from oxygen binders to divalent copper ions. Table 5: UV-vis spectra of Examples # 2 to # 4
Examples Wavelength at half height and half width (nm) #2 34 # 3 28 # 4 26
[141] Figure 3 shows a relationship between the half height and half width of the UV band and the conversion of NOx at 450 ° C.
6. Examples 7 and 8 - Adjustment of the Direct Copper Acetate Exchange pH of the Na form
6.1. Reagents and suspension preparation
Copper acetate monohydrate
Acetic Acid
Deionized water
Sodium chabazite of Example 1 A
6.2. Ion exchange conditions and chemical analysis [142] Table 6 lists the important synthesis parameters for ion exchange. All process stages for these samples are as described in example 2.1.2. Example 7 has no addition of acetic acid to the
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ΔΑΙΔΠ exchange suspension, while Example 8 has an additional amount of acetic acid added to adjust the pH. The pH of the solution was adjusted from 5.2 to 4.7, before adding Na-CHA.
[143] The CuO, Na2O and AI2O3 contents of the Cu-CHA filter cake samples were determined as described in 2.1.2.
Table 6: Copper acetate exchange condition, yield and chemical analysis for the direct exchange of NaCHA with pH adjustment using acetic acid.
Example 7 8 Copper Concentration (mol / 1) 0.2 0.2 Cu: Al (molar ratio) 1.2 1.2 Concentration of Acetic Acid (mol / 1) 0 0.07 pH of the copper solution 5.2 4.7 CuO in zeolite (% by weight) 3.26 2.75 Na2O in zeolite (ppm) 110 189 Cu Yield (%) 35 29
6.3. Catalyst coating [144] The coated catalyst was prepared as described in Example 3.1.
6.4. Curing and Catalytic Tests [145] Curing and the catalytic testing protocol are described in Example 3.2 (core based reactor). Table 7 contains DeNOx activity after curing at 200 and 450 ° C.
Table 7: DeNOx activity of the coated catalyst at 200 and 450 ° C after hydrothermal curing
Example Catalyst 7 Catalyst 8 Conversion of NOx cured at 200 ° C (%) 57 62 Conversion of NOx cured at 450 ° (%) 73 80
7. Direct exchange of Na form with copper ammonia solution.
7. 1. Example 9- Direct exchange at 60 ° C of Na form with ammonia copper solution.
7.1.1. Reagents and suspension preparation [146] The following starting materials were used:
Aqueous solution of Cu (NH3) 4 (14.6% by weight of Cu)
Deionized water
Petition 870180056807, of 06/29/2018, p. 54/60! 4Ί
Sodium Chabazite of Example 1B
7.1.2. Ion exchange conditions and chemical analysis [147] 360 g of Na-CHA were immersed in 2880 ml of 0.05 M copper tetraamine solution at 60 ° C and stirred in a 4 L jacketed glass reactor. The volume of the exchange suspension was kept constant at a liquid: solid ratio of 8: 1. The pH value was 12. The exchange suspension was maintained for 8 hours at this temperature, and then filtered hot through a 33 cm diameter Buechner funnel using Whatmann 541 filter paper (> 25 pm filtration). The filter cake was then washed until the conductivity of the wash water reached 200 pScm ¹ . The sample was then washed with washing water at room temperature.
[148] Chemical analysis indicated 3.19% by weight of CuO and 1884 ppm of Na2O, reported on a volatile substance-free basis. The SiO2: A12O3 ratio of the product was 32.3.
[149] Cu yield was 100%.
7.2. Example 10 - Direct exchange at room temperature of the Na form with ammoniacal copper solution.
7.2.1. Reagents and preparation of the suspension [150] The following starting materials were used: Aqueous solution of Cu (NH3) 4 (14.6% by weight of Cu) Deionized Water
Sodium chabazite of Example 1B
7.2.2. Ion exchange conditions and chemical analysis [151] 360 g of Na-CHA were immersed in 2880 ml of copper tetraamine solution at room temperature (~ 25 ° C) and stirred in a 4 L jacketed glass reactor. The pH of the copper tetraamine solution, before adding the zeolite, was measured as 10.5. The volume of the exchange suspension was kept constant at an 8: 1 liquid: sodium ratio. The suspension of
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The exchange was maintained for 6 hours at this temperature (the pH at the end of the reaction was 8.6), and then filtered hot through a 33 cm diameter Buechner funnel using Whatmann 541 filter paper (filtration> 25 pm). The filter cake was then washed until the conductivity of the wash water reached 200 pScm ¹ . The sample was washed with washing water at room temperature.
[152] Chemical analysis indicated 3.15% by weight of CuO and 1393 ppm of Na2Ü, reported on a volatile substance-free basis. This example indicates the advantage of lower temperatures for improved Na removal. The product's S1O2: AIO3 ratio was 31.3.
[153] Cu yield was 99%.
7.3. Preparation of the Catalyst (Examples 9 and 10) [154] The extrudate-based catalyst was prepared as described in Example 4.1.
7.2. Curing and Catalytic Tests [155] Curing and the catalytic testing protocol are described in Example 4.2 (extrudate based reactor). Table 8 contains DeNOx activity after curing at 200 and 450 ° C. Comparative examples are shown in Table 3.
Table 8: DeNOx activity of the coated catalyst at 200 and 450 ° C, after hydrothermal curing.
Example 9 10 Conversion of NOx cured at 200 ° C (%) 53 67 Conversion of NOx cured at 450 ° C (%) 65 73
8. Cu: Al, Na: Al and Cu: Na ratios.
[156] Table 9 contains the Cu: Al, Na: Al and Cu: Na ratios for all Chabazite molecular sieves mentioned in the examples described above.
Table 9: Cu: Al, Na: Al and Cu: Na ratios
Example Cu: Al Na: Al Cu: Na Comparative, e.g. 1 0.3 ND AT Comparative, e.g. 2 0.38 0 240 Comparative, e.g. 3 0.48 ND AT
Petition 870180056807, of 06/29/2018, p. 56/60 / 47
Comparative, e.g. 4 0.44 ND AT Example # 2 0.48 0 240 Example # 3 0.37 0.01 37 Example # 4 0.3 0.03 11 Example # 5 0.38 0.01 76 Example # 6 0.46 0.01 43 Example # 7 0.43 0 108 Example # 8 0.36 0.01 60 Example # 9 0.43 0.07 7 Example # 10 0.41 0.05 9
ND = not exposed, N / A = not applicable
Petition 870180056807, of 06/29/2018, p. 57/60

权利要求:
Claims (10)
[1]
1. Process for the preparation of a molecular sieve containing copper with the Chabazite (CHA) structure having a molar ratio of silica to alumina of more than 10, characterized by the fact that copper is switched to the Na ⁺ form of Chabazite , using a liquid copper solution, where the copper concentration is in the range of 0.001 to 0.4 molar, where the molecular sieve has a sodium content of less than 2500 ppm.
[2]
2. Process according to claim 1, characterized by the fact that the ratio of liquid to solid, which is defined as the weight of water used to prepare the Cu solution in relation to the weight of the starting zeolite used in the exchange stage copper is in a range of 2 to 80.
[3]
Process according to claim 1 or 2, characterized by the fact that the reaction temperature of the copper exchange stage is in the range of 10 to 100 ° C.
[4]
Process according to any one of claims 1 to 3, characterized by the fact that copper acetate or an ammoniacal solution of copper ions is used as the source of copper.
[5]
Process according to any one of claims 1 to 4, characterized by the fact that the copper concentration is in the range of 0.075 to 0.3 molar.
[6]
6. Molecular sieve containing copper with the CHA structure, characterized by the fact that it is produced through the process as defined in any one of claims 1 to 5.
[7]
7. Catalyst, characterized by the fact that it contains a molecular sieve containing copper with the CHA structure as defined in claim 6 disposed on a substrate.
[8]
8. Use of the catalyst containing molecular sieves containing
Petition 870180056807, of 06/29/2018, p. 58/60
2/2 copper with the CHA structure as defined in claim 7, characterized by the fact that it is as a catalyst for the selective reduction of nitrogen oxides NO _X ; for the oxidation of NH ₃ ; for the decomposition of N2O; for soot oxidation; for emission control in Advanced Emission Systems; as an additive in fluid catalytic cracking processes; as a catalyst in organic conversion reactions; or as a catalyst in “stationary source” processes.
[9]
9. Exhaust gas treatment system, characterized by the fact that it comprises an exhaust gas stream containing ammonia and / or urea and at least one catalyst containing molecular sieves containing copper with the CHA structure as defined in claim 7.
[10]
10. Method for selectively reducing nitrogen oxides NO _X , characterized by the fact that a gas stream containing NO _X nitrogen oxides is brought into contact with the molecular sieves containing copper with the CHA structure as defined in claim 6.

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法律状态:
2018-04-03| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2018-10-09| B09A| Decision: intention to grant|

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2018-12-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US28770409P| true| 2009-12-18|2009-12-18|

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US61/287,704|2009-12-18|

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PCT/EP2010/070094|WO2011073398A2|2009-12-18|2010-12-17|Process of direct copper exchange into na+-form of chabazite molecular sieve, and catalysts, systems and methods|

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