Process for the production of zeolites and zeotypes donated with metals.

专利摘要:
The process for producing metal-doped zeolites and zeotypes The present invention relates to a process for producing ion-exchange zeolites and zeotypes (metal-doped 5-metal doped). In particular, the method applied uses a sublimation step to incorporate the ion into the channels of the zeolitic material. Accordingly, according to this dry procedure no solvent is involved which prevents certain drawbacks connected with the wet exchange processes known in the state of the art.
公开号:BR112013014529B1
申请号:R112013014529-3
申请日:2011-12-08
公开日:2019-05-14
发明作者:Fei Wen；Barry W. L. Southward；Liesbet Jongen；Alexander Hofmann；Daniel Herein
申请人:Umicore Ag & Co. Kg；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for PROCESS FOR THE PRODUCTION OF ZEOLITES AND ZEOTYPES DOPED WITH METALS.
The present invention relates to a process for the production of zeolites and zeotypes doped with metals. In particular, the applied method uses a sublimation step to introduce the metal into the channels / cages of zeolitic material. Thus, according to this dry procedure, no solvent is involved which prevents certain inconveniences connected with wet exchange, impregnation or other metal addition processes known in the art.
Metal-doped zeolites or zeotypes and their use, in particular in the catalytic conversion of nitrogen oxides, for example, waste or exhaust gases, are known in the prior art. Metal doped zeolites and zeotypes are doped with at least 15 a catalytically active metal component. The catalytically active metal component is typically a transition metal, in particular a catalytically active metal such as copper or iron, etc. These metal doped zeolites and zeotypes are used in particular both in pure form and as constituents of coatings in 20 catalyst structures.
The metal addition / exchange process is the key step in converting 'white' zeolite to zeotype in the active form of a catalyst required, for example, to facilitate the selective catalytic reduction (SCR) of nitric oxide and ( NO and NO2, respectively, hereafter 25 oxides of nitrogen or NOx) with urea / NH3 (or a similar N-based reducer) in the exhaust train of a vehicle. Thus, the production of zeolites and zeotypes doped with metals / with metal exchange is an area of considerable academic and commercial interest, as witnessed by the extensive body of patents and open literature that focuses on this object. The 30 various methods for producing metal doped zeolites can be grouped into several classes.
First, it is the 'true' ion exchange that involves the
Petition 870190007236, of 23/01/2019, p. 7/17
2/41 treatment of zeolite / zeotype of alkali metal, alkaline earth metal or ammonium by a buffer solution of the appropriate metal, potentially at elevated temperatures, in order to exchange the cation (Na ⁺ , K ⁺ , NH ₄ ⁺ , etc. ) by the desired metal. This method is exemplified by US patents 4,961,917, US 6,221,324, US 7,049,261, US 7,601,662, WO 2008/132452 A2, US Patent Application 2002/0016252 A1, Iwamoto et al. J Phys Chem 95 (9) (1991) pages 3727-3730, Kapteijn et al. J Catai 167 (1997) pages 256-265, Kieger et al. J Catai 183 (1999) pages 267-280, Dedececk et al. J. Catai 200 (2001) pages 160-170, Groothaert et al. Phys Chem Chem Phys 5 (2003) pages 2135-2144, Moretti et al. J Catai 232 (2005) pages 476-487, Park et al. J. Catai 240 (2006) pages 47-57, Berthomieu et al. J Phys Chem B 110 (2006) pages 16413-16421, Bludsky et al. Phys Chem Chem Phys 8 (2006), pages 5535-5542, Brandenberger et al. Cat Rev 50 (4) (2008) pages 492-531 and Sjoval et al. J Phys Chem C 113 (2009) pages 1392-1405, among others.
Second, the doping of the metal can be achieved by impregnating water or using a proton paste or zeolite / ammonium zeotype impregnation by the appropriate precursor, followed by high temperature calcination. This process is also sometimes referred to as ion exchange, but this is not correct in the strictest sense because the exchange occurs only during calcination after decomposition of the precursor which results in the formation of mobile ions. Thus, this process may be less efficient than 'true' ion exchange and may result in a 'induction' phase in performance due to experimentation with the material for an insufficient time at temperatures to provide effective replacement of the structure's protons by metal ions. Examples of such an approach can be found in U.S. patents 5,908,806, U.S. 5,116,586, U.S. 5,270,024, U.S. 5,271,913, U.S. 5,516,497, U.S. 5,776,423, Lee et al. App Cat B Env 5 (1994) pages 7-21 and Sueto et al. J. Chem. Soc. Faraday Trans. 93 (4) 1997 pages 659-664.
The metal species can also be introduced directly into the layout structure using the synthetic method, for example, as
3/41 in the synthesis of Cu-ALPO-34 (Me-ALPO = metal doped aluminum phosphate), Cu-APSO-34 (Me-APSO = metal doped silicon-aluminum phosphate) and Me-ALPO systems and Related Me-APSO reported in EP patent 1,142,833 B1, Frache et al. CatToday 75 (2002) pages 359 -365 and Palella et al. J Catai 217 (2003) pages 100-106.
Alternatively, it is possible to introduce the metal into the zeolite / zeotype through solid state ion exchange (SSIE). Here, the doping of the metal is obtained by the reaction, at 400-800 ° C depending on the specific precursor, between an intimate mixture of zeolite / zeotype and an appropriate volatile precursor at high temperature, for example, fluoride, metal chloride, etc. This method is exemplified by and, described in more detail in U.S. patents 5,434,114, U.S. 5,545,784, Beyer et al. Zeolites 8 (1988) pages 79-81, Weckhuysen et al. J Catai 175 (1988) pages 338-346, and Brandenberger et al. Cat Rev 50 (4) (2008) pages 492-531.
Metal modification can also be achieved through chemical vapor deposition (CVD). Here, the zeolite is 'degassed' at 500 ° C + under reduced pressure to remove adsorbates, for example, water, before its exposure, at room temperature, to the saturated vapor of the volatile metal precursor, again typically volatile halides or fluorocarbon metal salts. This approach is the basis of US patent 6,043,177, Chen and Sachtler Cat Today 42 (1998) pages 73-83 and Kuroda et al. Chem Comm 22 (1997) pages 2241-2242. An additional and somewhat related method for metal doping is described in patent application WO 2008/009453 A2 (or in EP 0 955 080 B1) in which the 'degassed' zeolite / ammonium zeotype has been 'intimately ground' with catalytically active metal it is calcined at 400-600 ° C for 10 to 16 hours under reduced pressure in the presence of a nitrogen-containing compound, for example, an ammonium salt. It is claimed that, since doping occurs as part of a solid state ion exchange reaction under a protective atmosphere, for example, under NH ₃ or N ₂ , that the anaerobic conditions during calcination provide a zeolite doped with relatively stable metal for a long time. Similarly, provisions are claimed in the US patent
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2010075834, which presents a method for the production of ion exchange zeolites, which comprises:
i) the provision of a dry mixture of:
a) a zeolite, and
b) a catalytically active metal compound, ii) intimate grinding of the mixture, iii) heating the mixture in a reactor to a defined temperature, iv) maintaining the mixture at the defined temperature, and
v) cooling to room temperature and obtaining the metal doped zeolite.
This process is characterized by the fact that the internal pressure in the reactor during heating is maintained in the range of 0-200 mbar. According to this teaching, the catalytically active metal is preferably selected from the group consisting of Cu, Co, Rh, Pd, Ir, Pt, Ru, Fe, Ni, V. The catalytically active metal is used in the form of a salt , for example, a nitrate, a sulfate, a sulfite, a hydroxide, a nitrite, etc., or in the form of a complex compound.
However, despite this considerable body of work, to date, there are still pending challenges with regard to obtaining a simple, robust and economical process for the production of zeolites / zeotypes containing metals. Thus, although formal ion exchange is highly effective for the production of active catalysts with high metal dispersion, there are multiple steps involved in the process, some of which are slow and costly to perform commercially and certainly may require several cycles to obtain the ideal metal content, for example, US patent 6,221,324 describes the production of a Na-Y Faujasite with Cu / Ca exchange within each successive ion exchange step (for Ca and then Cu) that requires stirring of the paste / suspension of salt and zeolite for 24 hours. Likewise, U.S. patent 7,049,261 discloses a recipe for the production of 2.9% by weight of Cu-ZSM5 catalyst that involves a triple repetition of an exchange step with agitation
5/41 for 24 hours, followed by filtration, washing and drying at 110 ° C for 12 hours. Finally, the material is calcined for 5 hours at 500 ° C, resulting in a total synthesis time of almost 5 days. It should also be noted that the ion exchange of zeolites can present problems, since certain species, for example, iron salts, form larger hydration covers, which makes it difficult or even prevents a migration of the iron species to the zeolite . A final issue is that the ion exchange generates an extensive residual current that potentially contains a mixture of alkali or alkaline earth metals, ammonium hydroxide and nitrates produced during repeated washing steps, which in itself requires expensive treatment before it can be released safely into the environment.
Some of these issues are facilitated by the use of the impregnation / calcination process, however, as indicated, materials produced in this way may exhibit new underperformance due to decreased efficiency in the initial ion exchange. In addition, industrial scale application requires that this process must be carried out through a paste-based precipitation in which the precursor, for example, Cu (NO3) 2 * 3H ₂ O (or a solution thereof) is mixed with a paste containing the white zeolite / zeotype. However, the dissolution of the precursor results in the generation of an acidic charge in the paste which in turn needs the addition of a basic compound (ie, pH> 7) to neutralize the acid before chemical damage can occur to the zeolite / zeotype, as well as starting the precipitation of the soluble metal species, as highlighted above. However, care must be taken in selecting the base used in order to limit the complexation of the metal ion by the base because this should decrease the ion's ability to participate in the pore / channel structure of the arrangement. In addition, the base itself can attack / damage the zeolitic material, causing another problem in the conventional wet process. In an attempt to solve these problems, organic bases such as, for example, tetraethyl ammonium hydroxide (TEAH), can be used, for example, in US patent 5,908,806. However, during calcination, this organic species may undergo incomplete combustion and then decompose into
6/41 an environment with limited O2 to produce harmful by-products which, in turn, limits yield and requires additional processing steps during calcination. On a commercial scale this should have a cost impact (additional scrubbers and / or slower calcination process with reduced volume of the part on the belt to minimize harmful emissions). In addition, it is also known that zeolites or zeotypes doped with metal produced by impregnation / calcination can suffer from limitations in durability. Specifically, they are subjected to structural collapse and deactivation at T> 800 ° C, caused by the destabilization of the structure by the acid - base chemistry of the paste. This additional instability represents a problem for the commercial implementation of SCR technology, since these high temperatures can be obtained during regeneration with a diesel filter.
A final problem is generated during ion exchange and impregnation processes when catalytically active components are introduced into zeolites or zeotypes that can have different stable oxidation states, for example, iron, vanadium or copper. Thus, during an aqueous ion exchange, the catalytically active species can also be further oxidized until a more thermodynamically stable, but less catalytically effective oxidation state is achieved.
The use of doped zeotypes in the structure produced by direct synthesis eliminates the above problems. However, it has been found that such materials have problems with hydrothermal durability as reflected in decreased crystallinity and surface area after aging, as well as decreased Cu activity in the structure versus Cu in conventional ion exchange positions ( Frache et al. Cat Today 75 (2002) pages 359 -365 and Palella et al. J Catai 217 (2003) pages 100-106). In addition, the increased complexity of the synthesis presents problems in reproducibility in terms of the concentration and the location of dopant within the structure, and both factors affect the performance of the catalyst.
The problems for SSIE, CVD and related methods are quite similar and can be summarized in this way. First, all of these methods are associated with the release of harmful by-products, and in some cases corrosive and / or toxic, for example, HF, HCI, etc. Due to the fact that this release occurs at 400-800 ° C, potentially in the presence of residual moisture, an environment harmful to humans and the integrity of the structure of the arrangement is created. Second, the required temperatures can exceed the thermal durability of the structure, and, to a minimum, will result in sintering (crystal growth), which can adversely affect subsequent catalytic performance due to increases in average free diffusion passes . Third, there is extensive residual contamination of zeolite / zeotype with alkali metals or other metals. This contamination comes from the super-exchange of metal to the weak acid centers associated with defects in the structure. It can be removed by washing, but only with the resulting exposure of the sample to alkaline materials, for example, NaOH, which can result in more attack on the structure. In addition, the requirement for reduced pressures before and / or during metal doping presents technical and cost problems to be scaled. Finally, the processes as described above can lead to disadvantageous non-uniform metal distribution. Finally, in the case of iron doped zeolites, the catalytically active species of Fe ²⁺ can also be oxidized to inactivate Fe ³⁺ at high temperatures.
As indicated, a key application of zeolites / zeotypes doped with metals is the remediation of NOx through Selective Catalytic Reduction (SCR) by using a reducer containing N. Nitrogen oxides are well known and the toxic by-products of combustion engines generation, fossil fuel electricity generation and industrial processes. NO is formed through reactions of free radicals in the combustion process (see Y.B. Zeldovich (Acta Physico-chem. USSR, 21 (1946) 577), that is:
N ₂ + O'ANO + N '(1)
Ν '+ O ₂ -> NO + 0' (2)
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Ο NOx is toxic to living beings (PE Morrow J. Toxicol Environ Health 13 (2-3), (1984), 205-27), and contributes to several sources of pollution, for example, acid rain, photochemical pollution and ozone, all of which have been correlated to adverse impacts on human health (MV Twigg, Applied Catalysis B, vol. 70, (2007), 2). Thus, strict legislative limits have been introduced to regulate their issuance, for example, Euro 5 and Euro 6 [Regulation (EC) no. 715/2007 of the European Parliament, June 20, 2007, Official Journal of the European Union L 171/1, Twigg, Applied Catalysis B, vol. 70, (2007), pages 2-25 and R. M. Heck, R. J. Farrauto Applied Catalysis A vol. 211, (2001), pages 443 457 and references therein].
NOx control for stoichiometric gasoline engines is provided by the three-way catalytic converter (for example, see SAE 2005-01-1111). However, the three-way conversion is only effective for stoichiometric fuel reasons and not for diesel or another fuel-poor combustion cycle, that is, oxygen-rich, that is, direct injection of poor gasoline. As such, the advantages of diesel engines with regard to durability, high torque at low rpm and greater fuel economy / lower CO ₂ and HC emissions also pose a challenge to achieve the NOx objectives. urea / NH _{3 has} been developed in this way as one of a range of exhaust aftertreatment technologies to satisfy this requirement.
SCR chemistry comprises a complex set of decomposition (3 - for urea loading) and reduction reactions - oxidation (49) with various intermediates that form the basis for academic and practical study, for example, Fritz and Pitchon App Cat B 13 (1997) 1-25, Kondratenko et al. App Cat B 84 (2008) 497-504, Brüggemann and Keil J. Phys. Chem. C (2009), 113, 13930, SAE 2008-01-1184, SAE 2008-01-1323, etc. These reactions are summarized in equations 3-9. Equations 4-6 detail the desired SCR chemicals. However, competitive processes can occur, for example, parasitic oxidation of NH ₃ (7-9). This can result in the formation of N ₂ and H ₂ O, in the generation of N ₂ O, a powerful greenhouse gas (about 300 stronger than CO ₂ ), or even additional NOx.
9/41 (3) (NH ₂ ) CO + 4H ₂ O 2NH ₃ + 6CO ₂ (4) 4NO + 4NH ₃ + O ₂ 4N ₂ + 6H ₂ O (5) 3NO ₂ + 4NH ₃ (7/2) N ₂ + 6H ₂ O (6) NO + NO ₂ + 2NH ₃ 2N ₂ + 3H ₂ O (7) 4NH ₃ + 3O ₂ 2N ₂ + 6H ₂ O (8) 4NH ₃ + 5O ₂ -> 4NO + 6H ₂ O (9) 2NH ₃ + 2O ₂ -> N ₂ O + 3H ₂ O hydrolysis of urea
Standard SCR / 'slow' only SCR of NO ₂
SCR 'rapid' oxidation of parasitic NH ₃ to N ₂ oxidation of parasitic NH ₃ to NO oxidation of parasitic NH ₃ to N ₂ O
The main reaction is represented in equation (4). However, under practical conditions it has been shown that the reaction of 50:50 mixtures of NO / NO ₂ results in the highest rate of NOx conversion (6) (ESJ Lox
Handbook of Heterogeneous Catalysis, 1st edition, pages 2274-2345 and references therein). However, although the reaction between NH ₃ and NO _{2 is known to} occur (5), it is not kinetically dominant. Thus, as the NO ₂ concentration increases above about 50%, there is a concomitant decrease in catalyst activity and rate (Grossale et al. J. Catai, 256 (2008) 312-322).
Thus, what is required in the state of the art is a technology to provide highly active and selective metal doped / metal exchange SCR catalysts with improved hydrothermal durability and reduced cost. This must be achieved by developing a synthetic method for the production of zeolites and zeotypes that contain metals. This method should provide benefits of greater simplicity and robust production, reduced waste generation, high metal dispersion and reduced processing cost. In addition, it must provide these improvements while providing materials that retain a wide operating range, tolerance to high NO ₂ levels and high resistance to HC and SOx poisons in the exhaust stream to satisfy the requirements of modern control architectures emission of multiple bricks.
The aim of the present invention is the development of a method for the production of zeolites and zeotypes doped with metals / with metal exchange that provides advantageous materials for NOx SCR, in particular in exhausting lean motor vehicles. In addition, the present invention encompasses a process that is advantageous over prior art processes, from an ecological and economic perspective.
These and other known objectives of the elements versed in the technique are achieved with the application of a process for the production of zeolites or zeotypes doped with metals, which comprises the steps of:
i) provision of a dry intimate mixture of a zeolite or a zeotype with a precursor compound comprising a complex formed by a transition metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, and Ce is a binder, in which the complex decomposes to result in the metal or metal ion at temperatures between 100 ° C and 500 ° C; and ii) calcination of the mixture at a temperature and for a time sufficient to initiate a solid-state sublimation of the metal or metal ion; and iii) obtaining the zeolite or zeotype doped with metal, in a very favorable and non-obvious way. On the day that the present invention was elaborated, it could not have been predicted by the element skilled in the art that the durability of the material and its catalytic properties are enhanced to such an extent in comparison to those of the prior art that less material according to the invention causes an effect comparable or the same amount of material serves for superior results which in turn leads to reduced costs when produced on a commercial scale.
The person skilled in the art is aware that zeolites and zeotypes can enter the field when referring to appropriate disposal structures that allow NOx reduction. For this purpose reference is made to the definitions and citations in the literature above. For the process of the present invention, however, certain zeolites and zeotypes are considered to be preferred. These are selected from the group consisting of one or a mixture of the Faujasita type, Pentasil type, zeolite or Chabazite zeotype, for example, SAPO-34 or other '8 ring' structures of the CHA type structure and related structure types, for example example, A11 / 41
El, AFT, AFX, DDR, ERI, ITE, ITW, KFI, LEV, LTA, PAU, RHO, and UFI. The most preferred are those selected from the group consisting of the Pentasil type, SAPO-34, especially ZSM5 and β zeolite, and Chabazite type structure. The most preferred of all are Chabazite / SAPO-34 and zeolite β.
It has been proven that transition metals that readily undergo oxidation and reduction reactions can serve as prominent metals in order to reduce nitrogen oxides according to the SCR process. Favorable metals that exhibit such behavior are those selected from the group consisting of metals defined as transition metals, that is, the 38 elements in groups 3 to 12 of the Periodic Table of the Elements. Of these, the metals according to the invention are those selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag and Ce. The most preferred are the metals selected from the group of Fe, Cu and Ce. The most preferred of all are metals such as Cu and Fe in this regard.
In order to allow the metal to enter the structure of the original zeolite or zeotype structure, a metal precursor with modest volatility and an appropriate decomposition temperature is required, for example, the complex is decomposing to result in the metal or the metal ion at temperatures between 100 ° C and 500 ° C, preferably from 200 ° C to 450 ° C, which can have a structure of formula I:
ML ¹ mL ² n (I) where:
M is a metal chosen from the group mentioned above.
L ¹ can be carbonyl, amine, alkyl, alkoxy, alkene, arene, phosphine or another neutral coordinating ligand, m can be a number ranging from 0 to 6, n can be a number equal to the valence of M, and L ² advantageously includes a diketonate, a ketoiminate or a related member of that homologous series as a linker of formula II:
R1
12/41 in which:
R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl and substituted acyl.
Precursor compounds comprising a complex formed of a metal and a binder comprising a diketonate structure are known to the skilled person. Further details regarding these compounds and their production can be found at: Fernelius and Bryant Inorg Synth 5 (1957) 130-131, Hammond et al. Inorg Chem 2 (1963) 73-76, W02004 / 056737 A1 and references therein. Other binders in complex form that encompass a diketonate structure are also known in the prior art, as exemplified in Finn et al. J Chem Soc (1938) 1254, Van Uitert et al. J Am Chem Soc 75 (1953) 2736-2738, and David et al. J Mol Struct 563-564 (2001) 573-578. Preferable structures of these types of binders can be those selected from the group consisting of R1 and R2 in formula II as alkyls. Most preferably, these linkers are selected from the group consisting of R1 and R2 as methyl or tert-butyl; the most preferred of all is acetylacetonate acac, R1 and R2 in II are methyl groups).
When low-valence metal compounds are employed, carbonyl complexes which are preferably stable at room temperature with carbon monoxide as a binder are preferred, considering their volatility and moderate decomposition temperatures. The syntheses of such compounds are well known and generally carried out by reducing a metal salt in the presence of CO. More details about these compounds and their preparation can be found at: Abel Quart Rev 17 (1963) 133-159, Hieber Adv Organomet Chem 8 (1970) 128, Abel and Stone Quart Rev 24 (1970) 498-552, and Werner Angew Chem Int Ed 29 (1990) 1077.
The mixture of zeolites / zeotypes and precursor compound must subsequently be heated in order to mobilize the complexed metal to diffuse into the pores and channels of the structure. To allow this, care must be taken to balance the temperature sufficiently to allow for
13/41 composition of the precursor compound to initiate and facilitate diffusion while ensuring that the temperature is not too high to cause the degradation of the structure or excessive sintering of the zeolite / zeotype crystals. Thus, this calcination occurs preferably at temperatures above 200 ° C. In a preferred embodiment the mixture is calcined at a temperature of 200 - 500 ° C. More preferably, a temperature between 350 and 450 ° C is applied. It must be emphasized that this process is not dependent on reduced pressure or specific reaction gases and can be carried out under a static or fluent gas, for example, air or an inert gas such as N ₂ or a reducing atmosphere comprising, for example, about 0.5% to 4% H ₂ without compromising the performance of the final catalyst.
In addition, it should be noted that the duration of the calcination or heating procedure must occur within an appropriate range. The high temperature exposure of the mixture can typically last up to 12 hours. Preferably, the heat treatment comprises a time of about 1 to 5 hours. Most preferably, the mixture is exposed to high temperature treatment as described above. Advantageously, the mixture is exposed to temperatures of about 350 - 450 ° C for 1 to 5 hours. Most preferably, the process is carried out at about 350 ° C for a period of 90 to 150 minutes.
In order to ensure that the catalytically required concentration of the sublime metal diffuses into the pores, cages and channels of the zeolite and the zeotype, specific relationships of both ingredients must be present in the mixture. Thus, it is preferable that the mixture comprises the material of the structure and the precursor compound in such a way that the decomposition of the precursor results in a metal concentration within the zeolite / zeotype of about 0.01% by weight of metal at about 10% by weight of metal, preferably 0.1 - 7.5% by weight. Most preferably, the concentration of the metal within the zeolite / zeotype should be in the range of about 1 to 4% by weight. Most preferably, the concentration of the metal within the zeolite / zeotype should be about 1.5 to about 2.5% by weight. Must be
14/41 observed at this point that this metal load is somewhat lower than that described in the prior art, in which larger metal loads and in fact the requirement for 'excess' metal is described, as this protects zeolite against hydrothermal aging (WO2010-054034 or W02008-106519 A1).
A second embodiment of the present invention relates to a material or mixture of materials produced according to the process of the invention, in which the material or mixture of materials when applied to a support as indicated below catalyzes the reduction of oxides of nitrogen by reacting with a reducing agent containing nitrogen at a temperature as low as 100 ° C. The term catalyzes the reduction of nitrogen oxides through reaction with a reducing agent containing nitrogen at a temperature as low as 100 ° C has to be understood in the sense that the reduction occurs at 100 ° C to some extent. Preferably, the reactivity at 100 ° C compared to the maximum reactivity of the material or mixture of materials is> 0.2%, more preferably> 0.5% and even more preferably> 1%.
In a further aspect, the present invention relates to a catalyst comprising the material or mixture of materials obtained according to a process of the present invention, wherein the catalyst comprises an inert refractory binder selected from the group consisting of alumina, titania, non-zeolitic silica-alumina, silica, zirconia and mixtures thereof coated in a flow through ceramic monolith, metal substrate foam or on a wall flow filter substrate. Preferably, the catalyst described above is produced in a manner in which the material or mixture of materials described above and the binder are coated in different zones in a flow through a ceramic monolith, metal substrate foam or on a wall flow filter substrate.
In a still further aspect, the present invention relates to a monolith catalyst formed by extruding the material or mixing materials according to a process of the present invention.
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A different embodiment of the present invention relates to the use of a catalyst or a monolith catalyst as shown above for the selective catalytic reduction of nitrogen oxides. Advantageously, the use of such a catalyst or monolith catalyst is handled in a way, in which the nitrogen-containing reduct source is introduced to obtain an effective NH ₃ : NOx ratio (ratio a) at the catalyst inlet from 0.5 to 2. In addition, the use of a catalyst or monolith catalyst as described above occurs preferably when the NO: NO ₂ ratio recorded at the entrance of the catalyst is 1: 0 to 1: 3 by volume, preferably from 1: 0.8 to 1: 1.2, and more preferably about 1: 1.
Typically, the material or mixture of materials produced in accordance with the process of the invention is presented as a catalytic device comprising a wrapper arranged around a substrate with an SCR catalyst comprising the material or mixture of materials and which is arranged on the substrate. In addition, the method for treating the exhaust gas from a lean gasoline burn or a compression ignition exhaust or a lean fossil fuel combustion exhaust stream may comprise the introduction of said exhaust stream to such SCR catalyst ; and the reduction in N ₂ of the NOx component of said exhaust current.
The material or mixture of materials can be included in the formulation by combining alumina, silica or another suitable binder and optionally with other catalyst materials, for example, Ce-based oxygen storage component to form a mixture, drying (active or passively), and optionally the calcination of the mixture. More specifically, a paste can be formed by combining the material of the invention with alumina or silica and water, and optionally pH control agents, for example, inorganic or organic acids or bases and / or other components. This paste can then be coated by washing over an appropriate substrate. The wash coated product can be dried and heat treated to fix the wash coating on the substrate.
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This paste produced from the above process can be dried and heat treated, for example, at temperatures from about 350 ° C to about 1,000 ° C, or more specifically from about 400 ° C to about 600 ° C, to form the final catalyst formulation. Alternatively, or in addition, the paste can be coated by washing over the substrate and then heat treated as described above, to adjust the surface area and crystalline nature of the support.
The obtained catalyst comprises a zeolite / zeotype metal exchanged for the sublimation method presented here. The catalyst can also comprise an inert refractory binder. The supported catalyst can subsequently be arranged on a substrate. The substrate can comprise any material designed for use in the desired environment. Possible materials include cordierite, silicon carbide, metal, metal oxides (eg, alumina, and others), glass and others, and mixtures that comprise at least one of the above materials. These materials can be in the form of packaging material, extrudates, sheets, preform, mat, fibrous material, monoliths, for example, a honeycomb structure, and still others, wall flow monoliths (with capacity for filtration of diesel particles), other porous structures, for example, porous glasses, sponges, foams, and others (depending on the particular device), and combinations that comprise at least one of the above materials and shapes, for example, metal sheets, sponges open pore alumina, and porous ultra-low expansion glass. In addition, these substrates can be coated with oxides and / or hexa-aluminates, such as a stainless steel sheet coated with a hexa-aluminate scale. Alternatively, the cation-doped lattice material can be extruded, with suitable binders and fibers, such as a monolith or a monolithic wall flow structure.
Although the substrate can have any size or geometry, the size and geometry are preferably chosen to optimize the geometric area in the design parameters of the exhaust emission control device provided. Typically, the substrate has a geometry of
17/41 hive, with combs through channels with any shape of multiple sides or rounded, with substantially square, triangular, pentagonal, hexagonal, heptagonal, or octagonal or similar geometries preferred due to the ease of manufacture and increased surface area.
Once the supported catalytic material is in the substrate, the substrate can be arranged in a wrapper to form the converter. The enclosure can have any design and comprise any material suitable for the application. Suitable materials may comprise metals, alloys, and the like, such as ferritic stainless steels (including stainless steels, for example, from 400-Series such as SS-409, SS-439 and SS-441), and other alloys (for example, example, those containing nickel, chromium, aluminum, yttrium and others, to allow greater stability and / or resistance to corrosion at operating temperatures or under oxidation or reduction atmospheres).
In addition, similar materials such as the casing, end cone (s), end plate (s), exhaust manifold cover (s), and so on, can be concentric fitted at one or both ends and be fixed to the enclosure to provide a gas-tight seal. These components can be formed separately (for example, molded or the like), or they can be formed integrally with the enclosure when using methods such as, for example, a rotation formation, or the like.
A retaining material can be arranged between the housing and the substrate. The retention material, which can be in the form of a mat, particulates, or the like, can be an intumescent material, for example, a material that comprises a vermiculite component, that is, a component that expands with application heat, a non-swelling material, or a combination thereof. Such materials may comprise ceramic fibers, for example, ceramic fibers and other materials such as organic and inorganic binders and the like, or combinations comprising at least one of the above materials.
In this way, the monolith coated with the doped catalyst
18/41 with metal / with metal exchange is incorporated into the exhaust flow of the lean fuel engine. This provides a means for treating said exhaust stream to decrease NOx concentrations by passing said exhaust stream over the aforementioned SCR catalyst under conditions of liquid oxidation in the presence of urea or ammonia injected into the exhaust, or another N-containing reducer to facilitate catalytic conversion into environmentally benign nitrogen gas.
Figure 1 shows the data for the gas model test of two reference samples of 3% Cu-SAPO34, where A and B are prepared by the conventional impregnation method as described in the examples.
Figure 2 illustrates the model gas performance test data from the reference samples, A and B, after a 2-hour aging cycle performed at 780 ° C in the air.
Figure 3 illustrates the activity of A and B after a 2-hour aging cycle at 900 ° C in the air.
Figure 4a compares the Programmed H ₂ Temperature Reduction (TPR) characteristics of fresh 3% Cu-SAPO34 samples.
Figure 4b shows the TPR of H ₂ from the 3% CuSAPO34 samples after aging at 780 ° C in the air.
Figure 5a contrasts the fresh XRD patterns of the 3% Cu-SAPO34 variants.
Figure 5b summarizes the XRD of the samples in Figure 5a, for example, aging at 780 ° C in the air.
Figure 5c records the XRD patterns of the samples in Figure 5a, for example, aging at 900 ° C in the air.
Figure 6a shows the conversion of fresh NO from 3% Cu-SAPO34 variants prepared using the Cu precursors and the methods detailed in Table 2.
Figure 6b summarizes the conversion of fresh NH ₃ to the 3% Cu-SAPO34 samples prepared using precursors and methods
19/41 detailed in Table 2.
Figure 7a shows NO conversions. of the materials recorded in Figure 6a after a 12-hour aging cycle at 780 ° C in the air.
Figure 7b illustrates the NH ₃ conversions of the materials recorded in Figure 6b after a 12-hour aging cycle at 780 ° C in the air.
Figure 8a records the NO conversions of the materials recorded in Figure 6a after an aging cycle that comprises 2 hours at 900 ° C in the air.
Figure 8b is a summary of the activity of the NH ₃ conversions of the materials recorded in Figure 6b after a 2-hour aging cycle at 900 ° C in the air.
Figure 9 compares and contrasts the activity of two fresh 3% samples of Cu-SAPO34 prepared by a standard (A) versus the sublimation method that employs the Cu precursor (acac) ₂ (F).
Figure 10 compares the activity of the 3% CuSAPO34 samples prepared by the standard (A) versus the sublimation method (F), after aging at 780 ° C for 2 (A) or 12 (F) hours, respectively.
Figure 11 contrasts the activity of 3% CuSAPO34 samples prepared by a standard (A) versus the sublimation method, as described in Table 2 (F) after aging at 900 ° C for 2 hours.
Figure 12a shows the impact of the Cu charge on the conversion of fresh NO from a series of Cu-SAPO34 samples produced by sublimation at 500 ° C into N ₂ .
Figure 12b highlights the effect of the Cu charge on the conversion of fresh NH ₃ from a series of Cu-SAPO34 samples produced by the sublimation method at 500 ° C into N ₂ .
Figure 13a records the conversion of NO, for example, from Figure 12a after an aging cycle comprising 2 hours at
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780 ° C in the air.
Figure 13b illustrates the conversion of NH ₃ from the samples, for example, Figure 12b after an aging cycle comprising 2 hours at 780 ° C in air.
Figure 14a shows the NO conversion of the samples, for example, Figure 12a after an aging cycle in which the sample is exposed to air at 900 ° C for 2 hours.
Figure 14b summarizes the NH ₃ conversion of the samples, for example, Figure 12b after an aging cycle at 900 ° C for 2 hours in the air.
Figure 15 shows the fresh activity for the 2% samples of Cu-SAPO34 prepared by variant forms of the sublimation method in which the impact mixing method was examined.
Figure 16 summarizes the performance of the samples, for example, Figure 12 after catalyst aging at 780 ° C in air for 2 hours.
Figure 17 illustrates the performance of the samples, for example, Figure 12 after aging the catalyst at 900 ° C in air for 2 hours.
Figure 18 examines the effect of the Cu charge on the conversion of fresh NO from a series of Cu-SAPO34 samples produced by sublimation at 350 ° C in the air.
Figure 19 reports the performance of the samples, for example, Figure 18 after aging for 2 hours at 780 ° C in the air.
Figure 20 is a summary of the samples, for example, Figure 18 after aging for 2 hours in the air at 900 ° C.
Figure 21 shows the performance of the samples, for example, Figure 18 after catalyst aging at 950 ° C in air for 2 hours.
Figure 22 records the conversion data for the samples, for example, Figure 18 after a hydrothermal aging cycle comprising 16 hours at 750 ° C in a mixture of air and 10% steam.
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Figure 23 shows the performance data for the samples, for example, from Figure 18 after a hydrothermal aging cycle that comprises 4 hours at 900 ° C in a mixture of air and 10% steam.
Figure 24 compares the conversion data of non-sintered NO to 2.5% by weight of samples of Fe ZSM5 and zeolite β, prepared by wet impregnation or using the sublimation method.
Figure 25 summarizes the conversion data for non-sintered NO to 2 and 4% by weight of ZSM5 or Cu doped zeolite β.
Sample Key:
A: addition of the 3% solution of Cu-SAPO34 ex Cu (NO3) 2 to a well mixed SAPO34 paste.
B: addition of 3% Cu-SAPO34 ex Cu (NO3) 2 crystal to the poorly mixed SAPO34 paste.
C: physical mixture of 3% Cu-SAPO34 ex
D: calcined physical mixture of 3% Cu-SAPO34
E: aqueous ion exchange of 3% Cu-SAPO34 ex
F: sublimation of 3% Cu-SAPO34 ex of copper acetylacetonate
G: sublimation of 3% Cu-SAPO34 ex of copper oxalate (CUC2O4)
H: sublimation of 3% Cu-SAPO34 ex of copper acetate (Cu (CH ₃ COO) ₂ )
I: sublimation of 2% Cu-SAPO34 ex with mixing when using an ink stirrer (see main text)
J: sublimation of 2% Cu-SAPO34 ex with mixing when using a coffee grinder (see main text)
K: sublimation of 2% Cu-SAPO34 ex with mixing when using an overhead stirrer (see main text)
The following dataset includes a diverse range of preparation examples using different metal fillers, metal precursors and process variations as an illustration of the flexibility of the metal doping method and its application to SCR. The comparison
22/41 straight versus conventional synthesis methods (ion exchange and impregnation / paste law) is done to illustrate the performance benefits and durability of the new method. The data series in this case is an example set of a much larger body of work and refers to the measurements of catalytic performance. These measurements were made when using a conventional plug-flow model gas reactor. In these measurements, the gas streams, simulating the flared lean exhaust gas, were passed over and through the interleaved particles of test samples under varying temperature conditions, and the sample's effectiveness in reducing NOx was determined by means of a FTIR (Fourier Transformation Infrared) spectrometer online. Table 1 details the complete experimental parameters used to generate the data included here.
Table 1: Model gas test conditions
Component / Parameter Concentration / Adjustment NH ₃ 450 ppm AT THE 500 ppm H ₂ O 3% the ₂ 5% Temperature Ramp 500 to 85 ° C to -2 ° C / min Sample mass 200 mg Sample particle size 500 - 700 pm GHSV 100,000 h ' ¹
Figures 1-3 summarize the performance data for two comparative reference samples of 3% Cu-SAPO34, A and B, produced by a conventional paste impregnation / calcination method (see examples). These data reflect the inherent problems of this approach and its dependence on mixing for the synthesis of 'good' materials. Thus, sample B exhibits decreased fresh activity, in terms of the activation of NH ₃ and the subsequent reduction of NOx. Sample A, produced with a 'good' mix, is better with about 20% higher NOx conversion during the 'light-off (T <200 ° C), and intermediate temperature ranges (200 <T <300 ° Ç). However, at no point does the conversion
23/41 NO of one sample or another is close to the theoretical maximum of 90% in the feed ratio, or to 0.9. In fact, the maximum conversion for sample A peaks at about 80% between 210 <T <270 ° C. This decreased NOx conversion is consistent with an NH ₃ conversion limited to only about 90% in the same temperature range, implying a limitation of the inherent activity for this sample. This limited NH ₃ conversion is focused on the high temperature window (T> 300 ° C) for both samples. However, in no case does the increased NH ₃ conversion correspond to an improvement in NOx conversion, and especially in the case of sample A there is instead a decrease in N ₂ , that is, an increase in N2, that is, an increase in NO and N ₂ O, consistent with the increased rates of parasitic oxidation of NH ₃ (see introduction reactions 7 9). After aging for 2 hours in air at 780 ° C, sample A shows small losses in activity at lower temperatures (<200 ° C), but improvements in both conversions of NO and NH ₃ at all other temperatures, consistent with a moderate induction effect. On the other hand, with sample B at low low temperature, the conversions of NO and peak NH ₃ are about 20% more altar with the sample now showing a better efficiency for the use of NH ₃ in SCR versus fresh state. Such effects are archetypal of the phenomenon of induction. These data are consistent with the TPR data shown in Figures 4a and 4b. Here, sample A exhibits a bimodal reduction response, a peak at about 250 ° C, consistent with the reduction of dispersed CuO and a second peak at about 475 ° C, indicative of a more difficult to reduce CuO-based species , typical of stabilized / ion-exchange metal oxide in zeolite. In comparison, sample B exhibits a greater redox characteristic due to the dispersed CuO and a lower performance at high temperature, at about 425 ° C, indicative of the species with structure change. After aging at 780 ° C / in air, both samples show a more similar bimodal response. This is consistent with the high temperature migration of Cu to the ion exchange sites. However, such Cu migration can also cause the formation of the bulky CuO species (Tenorite), which is a catalyst for
24/41 oxidation of active NH ₃ at higher temperatures. Thus, it is not surprising that at a T> 400 ° C the conversion of NO from sample B exhibits a marked decrease in the selectivity of N ₂ due to the greater formation of NO and NO ₂ , again consistent with the oxidation of NH ₃ increased parasitic. The non-selective oxidation highlighted for sample B is also consistent with the TPR in Figure 4b, in which an additional peak at about 275 ° C is noted, consistent with the reduction of bulky CuO. With more aging, for 2 hours at 900 ° C in the air, the differences between the two compositionally equivalent materials are even more evident. In this way, sample B is completely deactivated and exhibits only residual parasitic NH ₃ oxidation at a T> 300 ° C. On the other hand, sample A retains some SCR function, although suppressed, with a peak NO conversion of about 35%. Such catastrophic deactivation is of interest, since the indicated peak temperatures can approach or even exceed 900 ° C, for example, during a catalyzed filter regeneration - especially if the engine falls into the idle intermediate cycle. The reasons for this catastrophic deactivation are clear from the XRD analysis (Figures 5a-5c). Both fresh samples show reflections consistent with the paternal SAPO-34 structure. There is no evidence of CuO other than X-rays or other phases that result from the destruction of SAPO-34 during pulp processing. This is not the case after aging the air at 780 ° C where sample B, produced with a 'poor' mixture, shows clear reflections at about 21 ° and 35 ° consistent with the presence of Cristobalite, a mineral phase at SiO ₂ base. This phase can only be produced through the loss of Si from SAPO-34, that is, the impregnation / calcination of the paste results in a premature structural collapse of the structure. This collapse is apparent for both samples after aging at 900 ° C in the air (Figure 5c). The collapse is again more intense for sample B, since minor reflections consistent with the residual SAPO-34 phase are evident for sample A 'well' mixed. These issues are reflected in Table 3 which summarizes the fresh and aged surface area (BET). Here, sample B presents
25/41 a decreased fresh BET and evidence of the surface area / structural collapse after aging at 780 ° C. Thus, from these data it can be seen that the conventional synthesis method exhibits serious deficiencies with respect to performance and durability.
In order to eliminate these deficiencies, a series of additional comparative references and Cu-SAPO34 test powders were produced, as detailed in Table 2 and described in the examples.
Table 2: Sublimation Synthesis Precursor Experiments:
Note - Samples C, D, E can be considered as additional comparative references.
Sample % by weight of Cu Precursor / method Ç 3 Intimate physical mixture of CuO and SA-PO34 without calcination D 3 Intimate physical mixture of CuO and SAPO34 calcined for 2 h at 500 ° C in the air AND 3 Ion exchange using Cu acetate followed by calcination for 2 h at 350 ° C in air F 3 Intimate physical mixture of Cu (Acac) ₂ with calcination for 2 h at 350 ° C in the air G 3 Intimate physical mixture of Cu oxalate with calcination for 2 h at 50 ° C in air H 3 Intimate physical mixture of Cu acetate with calcination for 2 h at 350 ° C in air
Table 3: Analysis of the surface area of fresh and aged 3% Cu-SAPO34 samples
Sample Fresh BET (m ² / g) BET ex 780'C (m ² / g) THE 619 563 B 572 511 F 612 600
Their SCR efficacies have been examined, resulting in
26/41 results in 6a-8b. The activity of these samples is quite diverse. Fresh E, F and H samples indicate high conversions of both NO and NH ₃ , whereas C, D and G do not, and in fact at T> 350 ° C exhibit an increasing propensity for non-selective NH oxidation ₃ with the concomitant production of NOx, and thus apparent negative conversions of NO. After aging at 780 ° C (12 hours / air) samples E, F and H exhibit equal or worse performance, that is, no induction effect or premature collapse, whereas samples C, D and G exhibit significant performance gains, especially samples D and G, reflecting an especially strong induction effect. Further aging at 900 ° C results in decreased conversion of NO and NH ₃ for all samples. However, it must be emphasized that the loss of performance is a fraction of that exhibited by samples A and B produced by the conventional process. In this way, peak NO conversions vary from about 40 to about 70%, that is, up to twice that observed for the best reference powder. From these data, it is apparent that the decomposition / sublimation of Cu (acac) ₂ provides an ideal fresh and aged performance without a period of induction or premature deactivation. Sample D (CuO mixed with SAPO34) also indicates high activity, but this is only after aging, again consistent with sample B. On the other hand, the fresh performance of sample E (ion exchange) is competitive with sublimation method, reflecting an initially ideal interaction between Cu and the structure. However, this sample exhibits a poor aging response consistent with sintering the free Cu species to form bulky CuO resulting in extensive parasitic oxidation of NH ₃ to NO, with an initial temperature of about 250 ° C. Similarly, sample H, produced by sublimation of copper acetate, exhibits good fresh activity, but again the aging stability of the powder was insufficient to merit further examination.
The benefits of the sublimation method versus the impregnation / calcination of the paste are highlighted in Figures 9-11. Here, sample F exhibits a higher fresh activity for the conversion of NO and NH ₃ .
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It provides a significant improvement in light-off performance with an NO conversion about 25% higher than the reference at 165 ° C. Similarly, the performance in the intermediate temperature range is 5-10% higher, whereas at a T> 350 ° C the conversion of NO is equal. These benefits are replicated after the aging cycle at 780 ° C. In fact, despite the more intense aging of sample F (12 hours versus 2) it retains a higher light-off value and an intermediate NH ₃ temperature and conversion range. The enhanced durability of the sublimation sample is also highlighted in Figure 11. Thus, after the air aging cycle at 900 ° C, the paste impregnation / calcination sample was subjected to catastrophic deactivation with a peak NO conversion around 35% versus> 70% for the ex sublimation sample. These performance benefits are reflected in the redox characteristics of sample F (Figures 4a / b). In this way, the fresh sample F exhibits a preferred bimodal redox response with the high temperature (500 ° C) redox peak attributed to copper with stabilized structure. The comparison between the fresh and aging data at 780 ° C does not show any shift in the temperature of that peak, unlike samples A and B. This indicates that the sublimation synthesis provides for the appropriate distribution of Cu in this preferred site directly in the fresh condition whereas conventional synthesis requires additional high-temperature treatment (induction) i.e. SSIE, to achieve that preferred most active state. XRD measurements (Figures 5a 5c) are correlated with performance and TPR data. The fresh sample F only shows reflections due to SAPO34, although the crystallinity of this sample is higher than those of samples A and B (stronger and more acute reflections). After the sample F at 780 ° C maintains a high degree of crystalline response, with only small traces of Cristobalite present (bounce at 21.5 °). An additional aging at 900 ° C results, however, in the collapse of SAPO34 with only the trace reflections evident in a pattern that consists mainly of Cristobalite. This collapse is attributed to the destabilization of the long-range order of SAPO34 due to the high copper content, since, based on measurements of
28/41 activity, sufficient active sites are retained to provide catalytic function. Other deactivation trends are seen in the surface area data (Table 3). Fresh samples A and F exhibit comparable fresh BET, about 40 m ² / g greater than sample B, consistent with the outlined questions. However, after aging at 780 ° C while sample F shows only a minor loss of BET, both samples A and B exhibit significant decreases, consistent with the destabilization of the structure that is matched by the sample preparation method, or that is, the sublimation method allows the doping of Cu with a reduced penalty in relation to the stability of the structure at higher temperatures.
The efficiency of the metal exchange achieved by the sublimation method also offers the possibility to decrease levels of metal dopant to improve durability at high temperature, without any penalty in relation to the catalytic function. This possibility is illustrated in Figures 12a to 14b. Here, the effectiveness of Cu charges ranging from 1% by weight to 3% by weight is compared to an aging function. The samples were prepared as outlined in the examples and in all cases the intimate mixture of the precursors was calcined in a fluent N2 atmosphere. Traces of fresh NOx conversion show an evident benefit for Cu loads> 2% by weight, with a peak NOx conversion of about 85%. Similarly, an almost quantitative NH ₃ conversion for these samples is recorded for all temperatures> 200 ° C. The decreased activity of NOx conversion at low low temperature of 1 and 1.5% copper is attributed to lower rates of conversion of NH ₃ , whose floor is around 88% and about 72% for samples of 1 , 5 and 1% copper, respectively. After aging at 780 ° C, there is almost no change in the performance of the most loaded Cu samples with the peak NOx conversion still close to the theoretical maximum value to that determined. On the other hand, samples of 1 and 1.5% Cu show significant improvements in performance and now achieve a Nox conversion response of 62% and 78%. This improvement is attributed to an effect of mobility
29/41 of copper (induction). After the cycle in the air at 900 ° C, it is noticed that the performance rating changes. In this way, the sample of 3% by weight of Cu exhibits a reduced conversion of NH ₃ / NOx, due to the high temperature reactions inherent between Cu and the structure. Thus, after this cycle of more intense aging, the ideal performance is obtained at 2 or 2.5% copper with the 1.5% Cu sample now also offering competitive performance. However, the key messages in this case are that the new synthesis method provides enhanced activity and durability at a decreased Cu load and effective materials can be produced by fluent N ₂ calcination.
The benefits such as the superior performance in the decreased metal load were confirmed by the elemental analysis of samples selected from the data above. Thus, from table 4 it can be seen that high performance is obtained at Cu levels lower than 15 applied typically in the prior art. For example, WO2010-054034 or W02008-106519A1.
Table 4: ICP analysis of X% Cu-SAPO34 samples
2.5 Cu ex Acac 2 Cu ex Acac 1.5 Cu ex Acac % by weight of Al 20.40 20.40 20.60 % by weight of Si 4.16 4.16 4.21 % by weight of P 20.10 20.00 20.10 % by weight of Cu 2.27 1.83 1.37 Al Moles 0.7561 0.7561 0.7635 Moles of Si 0.1481 0.1481 0.1499 Moles of P 0.6490 0.6458 0.6490 Cu Moles 0.0357 0.0288 0.0216 Cu: AI 0.0472 0.0381 0.0282 AI: Cu 21.1646 26.2533 35.4121 Su: Si 0.2412 0.1945 0.1439 Si: Cu 4.1454 5.1421 6.9512
As highlighted above, a special benefit of sublimation is the robustness of the synthesis method. This is reflected in Figures 15-17 where
30/41 the impact of using different mixing devices to produce the homogeneous mixture of salt - structure was investigated. These data confirm the high activity of samples doped with 2% Cu produced by three different mixing devices, in all cases a higher conversion of NH ₃ and NOx versus conventional samples at 3%. In addition, the activities of the three samples are within the experimental error for the fresh aging cycles, ex 780 ° C, ex 900 ° C. Again, the peak NOx conversion after the most intense cycle at 900 ° C is about 80%, a significant improvement over conventional references. Thus, it is apparent that a range of mixing devices can be employed in the process without having an adverse effect on the final catalyst.
An additional demonstration of the robustness of the preparation method and the superior thermal durability of the samples produced by the sublimation method is exemplified in Figures 18-21. All samples in this case were produced as detailed in the examples with final calcination in static air. The data is not surprising; all samples exhibit activity and stability trends almost identical to that seen in 12a - 14b. In this way, fresh NOx conversions exceed 85% and the samples indicate a wide window of high activity with low oxidation of parasitic NH ₃ / NOx formation. Performance after aging at 780 ° C exhibits little to no change, except the improvements seen for samples doped with 1 and 1.5% Cu seen in Figures 12a / 13a. Figure 20 confirms the deficiency of the 3% Cu sample after aging in air at 900 ° C, which shows the onset of solid state reactions between the copper dopant and the structure. These trends are even more apparent after aging at 900 ° C in the air, with both 3 and 2.5% Cu samples showing almost complete deactivation. On the other hand, the 1.5% Cu sample still has a high activity with a peak NOx conversion close to 80%. These data suggest that the flexibility of the sublimation method may offer the opportunity to adapt levels of metal dopant, as required in the application, for example, the use of a zeotype with a lower Cu content in
31/41 an SDPF (particulate filter coated by SCR wash), both as a homogeneous wash coating and as a zone in DPF. The use of a zone of a material with a lower Cu load with increased durability and high activity after the intense aging of filter regeneration is especially interesting in relation to peak DPF temperatures during regeneration.
Other examples of durability, in this example in the presence of air and steam (10%) at 750 and 900 ° C, can be found in Figures 22 and 23. Here, the comparison is made between samples calcined in air and in N ₂ to a varied Cu content. After aging for 16 h at 750 ° C air + 10% steam, all samples retain excellent activity with peak NOx conversions of around 80%. No difference is seen between samples calcined in the air versus N ₂ to 2 or 2.5% copper and there is only a small performance penalty observed for the sample loaded with 1.5% Cu. This is not the case after aging for 4 h at 900 ° C in air / steam. Here, both 2.5% Cu samples exhibit almost identical performance and catastrophic deactivation. Similarly, the activity of the 2% Cu samples is comparable, but very poor. On the other hand, the 1.5% Cu sample retains an acceptable performance with a peak NOx conversion of about 57% after this inhospitable aging. It should be emphasized that these data also reflect fundamental instability due to high-temperature solid-state reactions between Cu and the zeotype structure rather than a weakness in the new synthetic method, for example, as in Figures 3 and 11. Consistent with this hypothesis, better activity is retained at a lower copper load, also consistent with Figures 14a / b and 20.
The application of the sublimation method for the introduction of other types of metal and with other structures of the arrangement is shown in Figures 24 and 25, respectively. Thus, in Figure 24 the activity of zeolites promoted with non-sintered iron (2.5% by weight of Fe), specifically ZSM5 (SAR 23) and β (SAR 38), prepared by the conventional impregnation or sublimation method. Here, although all
32/41 samples exhibit an activity for the SCR process, requiring higher temperatures than observed for Cu-based samples consistent with the prior art, for example, W02008 / 132452 A2, it is apparent that for a given layout structure the activity is significantly higher for samples prepared by the sublimation method than that obtained by the conventional impregnation process, further confirmation of the benefits of the new method. In addition, the sublimation method can also be advantageously applied for the preparation of other zeolite systems promoted with standard copper. This is reflected in Figure 25, in which the non-sintered activity of 2 and 4% by weight of ZSM5 and β samples promoted with copper, prepared by Cu (acac) ₂ sublimation, following the standard method, is reported. Again, all samples exhibit high activity and achieve a stoichiometric, or almost stoichiometric, NO conversion, with NH ₃ available in the supply current.
The present invention relates to the development and use of an improved method for the production of zeolites / zeotypes doped with metals / with metal exchange and its application to the remediation of NOx of internal combustion engines through the process of selective catalytic reduction ( SCR) when using a reducer containing post-injected N. The method is also characterized by the fact that it uses a dry process, that is, non-aqueous (or based on another solvent) in which the metal ions are introduced into the material of the structure by a sublimation / decomposition of an appropriate metal precursor. , for example, diketonate, specific carbonyl complexes or the like as part of an intimate mixture of a precursor compound and zeolites / zeotypes. The process is also characterized by its robust nature that does not require a specific reactive gas environment and reduced pressure. It provides the formation of the desired metal doped structure material, which is also part of the present invention, without the generation of significant harmful or toxic waste by-products.
Benefits and features include:
a) Simplicity: the process involves mixing two
33/41 dry powders followed by high temperature treatment. There is no need for complex mixing units or paste handling systems. The dry process eliminates any requirement for filtering, washing or drying the paste. In addition, the process is insensitive to the atmosphere or pressure of the reactor used during calcination. This is an advantage over the prior art, since neither a protective nor reducing gas has to be applied.
b) Cost: material savings come from the simplicity of the synthesis without resorting to the equipment and process described in a). More savings come from removing the pH monitoring equipment from the paste and temperature, etc.
c) Time: the production of the final powder can be completed in as little as 2 hours, contrary to the multi-day requirements of the conventional wet change or the requirements of many hours of impregnation / calcination of the paste (mixing time to ensure homogeneity, the limit contribution of the exotherm of the wetting of zeolite / zeotype in the paste chemistry, etc.).
d) Decreased environmental impact: unlike the prior art processes, the present process limits the generation of secondary products to the stoichiometric amounts of CO ₂ from the decomposition of the precursor binders. There is no generation of extensive aqueous waste streams, such as with ion exchange, nor the generation of potentially toxic emissions, for example, HF or HCI gas as seen for SSIE or compounds containing N (organic amines or nitrogen oxides) ) as observed for the paste impregnation / calcination method (combustion of NH ₃ or organo-nitrogen bases used to control the pH of the paste / metal precipitation). In addition, due to the stoichiometric nature of the preparation, there is no excess material or additional chemical product required for the production of the catalyst, reducing the environmental impact to a minimum.
e) More robust and more flexible method for the introduction of dopant: the dopant's objective requires a simple calculation for ignition loss
34/41 tion of precursor materials. The absence of any chemical species or additional processes decreases any stacked tolerances to the absolute minimum.
f) Performance benefits: in contrast to the conventional paste impregnation / calcination process, the sublimation method introduces the metal directly into the specific active exchange center of the zeolite / zeotype. In this way, no induction period is observed. In addition, due to the increased efficiency of metal doping by the sublimation method, there is no need to 'overload' the zeolite / zeotype to obtain the 'complete' metal doping required for optimal performance. This provides an improvement in the selectivity of the catalyst, that is, a reduced oxidation of parasitic NH ₃ , as may result from the formation of a catalytically active phase, for example, CuO (Tenorite), distinct or detectable by the X-ray diffraction method conventional. Second, improved durability / stability in aging of the metal-containing frame material is achieved, since the decreased metal charge limits the high-temperature (> 750 ° C) solid-state reactions between the dopant and the structure, a primary cause of phase collapse and the formation of new catalytically inactive phases during / after aging. Finally, the dry sublimation process eliminates the need for pH modifiers or pulp rheology, for example, HNO ₃ or TEAH. The use of both classes of these modifiers, acidic or basic, is problematic, since both species can react with the zeolite or the zeotype and extract the atoms from the structure, thereby destabilizing the structure. Such damages are not detectable in fresh powders, but are known to cause adverse consequences for high temperature durability.
Definitions:
It should also be noted that the terms first, second and others in this case do not denote any order of importance, but are used instead to distinguish one element from another, and the terms one and one in this case do not denote a limitation of amount,
35/41 but, instead, denote the presence of at least one of the items mentioned. In addition, all of the ranges presented here are, for example, inclusive and combinable ranges, for example, ranges of up to about 50 weight percent (% by weight), with about 5 weight percent to about 20 weight percent desired, and about 10% by weight to about 15% by weight most desired are inclusive of extreme points and all intermediate values of the ranges, for example, about 5% by weight to about 25% by weight, about from 5% by weight to about 15% by weight, etc.
Zeolite: Zeolites are microporous crystalline aluminosilicate materials characterized by well-ordered 3-D structures with uniform 3 to 10 A pore / channel / cage structures (depending on the type of structure) and the ability to be subjected to ion exchange to allow the dispersion of catalytically active cations throughout the structure.
Zeotype: Zeotypes are structural isotypes / isomorphs of zeolites, but instead of an array structure derived from bonded silica and alumina tetrahedra, they are based, for example, on: alumina-phosphate (ALPO), silica-alumina-dosphate ( SAPO), metal-alumina-phosphate (Me-ALPO) or metal-silica-alumina-phosphate (MeAPSO).
The zeolitic material is a material based on the structural formalisms of zeolites or zeotypes.
Structured ligands with diketonate: They involve a ligand, that is, an ion or a molecule that binds to a central metal-atom that forms a coordination complex that has two sets of chemical functionality that exhibit Ceto-Enol forms. Here, the Keto forms, ie Ketone / Aldehyde (carbonyl or hydrocarbon containing C = O) - Enol (unsaturated alcohol, ie C = C-C = C-OH) are derived from organic chemistry. A key feature of Ceto - Enol systems is that they exhibit a property known as tautomerism, which refers to a chemical balance between a Ceto and an Enol form that involves the interconversion of the two forms through the transfer of protons and the change of electrons in Link.
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The catalyst and process described above and other characteristics will be appreciated and understood by the elements skilled in the art from the following detailed description, the drawings, and the attached claims.
EXAMPLES
Comparative Reference Sample A: 150 g of SAPO34 of the H + form were added, with constant stirring, to 480 ml of deionized water to produce the paste with a solids content of 24%. This addition results in an exotherm within the paste, requiring care to be taken during this step. The paste was stirred continuously for a minimum of 30 minutes to allow the exotherm to dissipate the Zeotype wetting. Then, 17.1 g of Cu (NO ₃ ) ₃ .3H2O crystals were dissolved under vigorous stirring in 30 g of deionized water. The solution produced in this way was added in drops to the vortex of the paste for 15 minutes. In order to facilitate the alkaline precipitation (pH> 7) of copper, the resulting paste, with a pH of about 4, was treated in drops by the addition of 48 g of a solution of tetraethyl ammonium hydroxide (35% by weight) of TEAH), following the method of the US patent 5,908,806 to reach an extreme point pH of 7-8. The sample was stirred for another 60 minutes before drying for 20 hours at 65 ° C in air and then was calcined for 2 hours at 500 ° C in air. The resulting powder was mixed as per Table 1 and tested without further modification.
Comparative reference sample B. 150 g of SAPO34 of the H + form were added, with constant stirring, to 240 ml of deionized water to produce a paste (38.5% solids). Since this addition resulted in a significant exotherm, care was taken during this step and the paste was stirred continuously for a minimum of 30 minutes to dissipate that exotherm. Then, 17.1 g of Cu (NO ₃ ) ₃ .3H ₂ O crystals were added to the paste vortex for 1 minute to produce a paste with a pH of 4. Again, precipitation was obtained by adding in drops of 48 g of a solution of tetraethyl ammonium hydroxide (35% by weight of TEAH), to reach an end point pH of the
37/41
7-8. The paste produced by this addition was extremely viscous and difficult to mix. The sample was stirred for another 60 minutes before drying for 20 hours at 65 ° C in the air and then was calcined for 2 hours at 500 ° C in the air. The resulting powder was mixed as listed in Table 1 and tested without further modification.
Preparation procedure for about 100 q of 3% by weight of Cu powder SAPO34 by sublimation / solid mixing (sample F):
12.2 g of copper acetylacetonate (24.4% by weight of Cu, ex Alrdich) were blended with 100 g of SAPO34 in a sealable plastic bottle of 250 ml capacity. Then, 10 g of Y-stabilized ZrO ₂ granules (diameter 5 mm) were added. The flask was sealed and fixed to a paint mixer (Olbrich Model RM 500, 0.55 KW) and homogenized by vibration for 5 minutes. The flask was then released from the paint mixer and the mixture passed through a large sieve to remove the granules. Finally, the mixed powders were transferred to a calcination vessel and heated in static air (or alternatively in flowing N ₂ ) at 350 ° C (at a ramp rate of 5 ° C / min) and for a period of 2 hours. produce the active catalyst powder, which was mixed and tested as per Table 1.
Preparation procedure for 3% by weight of Cu in SAPQ34 powders by means of solid mixing when using CuO as precursor to Cu (sample C): This material was prepared following the method described above, except for the fact that the mixture comprised 0.194 g of CuO (which is 79.88% by weight of Cu) and 5 g of H-SAPO34 and the material was calcined after the intimate mixture was produced.
Preparation procedure for 3% by weight of Cu in SAPO powders34 by means of solid mixing and calcination when using CuO as precursor of Cu (sample D): This material was prepared following the method described above, except for the fact that the mixture comprised 0.194 g of CuO (which is 79.88% by weight of Cu) and 5 g of H-SAPO34. After mixing, the bottle was then released from the paint mixer and the mixture and grinding medium passed through a large sieve to remove the granules.
38/41 them. Finally, the mixed powders were transferred to a calcination vessel and heated in static air at 350 ° C (at a ramp rate of 5 ° C / min) and for a period of 2 hours to produce the active catalyst powder.
Comparative Reference E: Ex-aqueous ion exchange of 3% Cu-SAPO34: 150 g of SAPO34 of the H + form were added, under constant stirring, to 200 ml (ie, 200 g) of deionized water to produce the paste with a 42.8% solid content. Specific care was taken again during this step to limit the exotherm generated by wetting the powder. The paste was then stirred continuously for a minimum of 30 minutes to allow the exotherm to dissipate. Then, 14.0 g of Cu II acetate (which is 32% by weight of Cu) were dissolved under vigorous stirring in 400 g of deionized water. The solution was produced in this way by adding drops to the vortex of the zeotype paste for 15 minutes. The obtained mixture was stirred overnight before drying for 10 hours at 110 ° C in the air and then calcined for 2 hours at 500 ° C in the air. The resulting powder was mixed as indicated in Table 1 and tested without further modification.
Preparation procedure for about 100 q of 3% by weight of Cu in SAPO34 powders by means of solid mixing / sublimation when using copper oxalate as a precursor of Cu (comparative reference sample G): Prepared by following the described method above, except that the mixture comprised 7.5 g of Cu II oxalate (which is 39.8% by weight of CU) and 100 g of H-SAPO34.
Preparation procedure for about 100 q of 3% by weight of Cu in SAPO34 powders by means of solid mixing / sublimation when using copper acetate as precursor of Cu (comparative reference sample H): Prepared by following the described method above, except that the mixture comprised 9.3 g of Cu II acetate (which is 32% by weight of Cu) and 100 g of H-SAPO34.
Preparation procedure for about 100 q of 2.5% by weight of Cu in SAPO34 powders when using copper acetylacetonate as a precursor by means of solid mixing / sublimation: Prepared at
39/41 follow the method described above, except that the mixture comprised 10.1 g of Cu II acetylacetonate and 100 g of H-SAPO34.
Preparation procedure for about 100 g of 2% by weight of Cu in SAPO34 powders when using copper acetylacetonate as a precursor by means of solid mixing / sublimation: Prepared by following the method described above, except for the fact that the mixture comprised 8.07 g of Cu II acetylacetonate and 100 g of H-SAPO34.
Preparation procedure for about 100 g of 1.5% by weight of Cu in SAPO34 powders when using copper acetylacetonate as a precursor by means of solid mixing / sublimation: Prepared by following the method described above, except for the fact that the The mixture comprised 6.0 g of Cu II acetylacetonate and 100 g of H-SAPO34.
Preparation procedure for about 100 q of 1% by weight of Cu in SAPO34 powders when using copper acetylacetonate as a precursor by means of solid mixing / sublimation: Prepared by following the method described above, except for the fact that the mixture comprised 4.0 g of Cu II acetylacetonate and 100 g of H-SAPO34.
Preparation procedure for about 100 q of 2 wt% Cu in SAPO34 powders when using copper acetylacetonate as a precursor by means of solid mixing / sublimation when using a coffee grinder as a mixing device (sample J): This material was prepared as described above, except that the mixture was finely homogenized using a sealable coffee grinder device (IKA, model: M20 Universal Mill) for 5 minutes before calcination.
Preparation procedure for about 100 q of 2% by weight of Cu in SAPO34 powders when using copper acetylacetonate as a precursor by means of solid mixing / sublimation when using an overhead stirring unit as a mixing device (sample K): This material was prepared as described above, except that the mixture was finely homogenized in an open bowl using an aerial shear mixing device (HiTEC-Zang, model: MiscoPakt @ 40/41 mini-35) for 5 minutes before calcination.
Preparation procedure for about 120 q of 2.5 wt% Fe powder in ZSM5 by solid mixing / sublimation using iron acetylacetonate as a precursor to Fe: Prepared by following the method described above for Cu / SAPO34 , except that the mixture comprised 15.8 g of Fe III acetylacetonate and 109 g of ZSM5.
Preparation procedure for about 120 q of 2.5 wt% Fe in zeolite powder β by means of solid mixing / sublimation when using iron acetylacetonate as a precursor of Fe: Prepared by following the method described above for Cu / SAPO34, except for the fact that the mixture comprised 15.8 g of Fe III acetylacetonate and 114 g of β zeolite.
Preparation procedure for the comparative reference sample Fe (NO ₃ ) ₃ Zsm5-NH ₄ ⁺ (2.5% by weight of Fe): 218 g of ZSM5 in NH4 ⁺ form were added, with constant stirring, to 800 ml of deionized water, to produce the paste with a solids content of 20%. The paste was stirred continuously for a minimum of 60 minutes to allow the exotherm to dissipate from the zeotype wetting. Then, 36.2 g of Fe (NO3) ₃ .3H ₂ O crystals were dissolved under vigorous stirring in 100 g of deionized water. The solution produced in this way was added in drops to the vortex of the paste for 15 minutes and was also kept stirring for 24 h. Then, the paste was dried for 24 hours at 65 ° C in the air and then was calcined for 2 hours at 500 ° C in the air. The resulting powder was mixed as per Table 1 and tested without further modification.
Comparative reference sample of Fe (NO3) 3 Zeolite β (2.5% by weight of Fe): Prepared by following the method described above, except that the NH ₄ ^{+ form} of zeolite β was used.
Preparation procedure for about 120 q of 2 wt% Cu in ZSM5 powders by means of solid mixing / sublimation when using copper acetylacetonate as Cu precursor: Prepared by following the method described above for Cu / SAPO34, except because the mixture comprised 8.25 g of Cu II acetylacetonate and 115 g of ZSM5.
41/41
Preparation procedure for about 120 g of 2 wt% Cu in zeolite powder β by means of solid mixing / sublimation when using copper acetylacetonate as a precursor to Cu: Prepared by following the method described above for Cu / SAPO34, except for the fact that the mixture comprised 8.25 g of Cu II acetylacetonate and 115 g of β zeolite.

权利要求:
Claims (7)
[1]
1. Process for the production of zeolites or zeotypes doped with metals, characterized by the fact that it comprises the steps of:
i) Provision of a dry intimate mixture of a zeolite or a zeotype with one or more precursor compounds or compounds comprising a complex formed by a transition metal and a binder, which has a structure of formula I:
ML ¹ mL ² n (I) in which it is a metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag and Ce; and
L ¹ is carbonyl, amine, alkyl, alkoxy, alkene, arene, phosphine or other neutral coordinating binder;
m is a number that ranges from 0 to 6;
n is a number equal to the valence of M; and
L ² is a diketonate, ketoiminate or a related member of this homologous series as a ligand of formula II:
O O where:
R1 and R2 are independently alkyl; and ii) calcination of the mixture without reduced pressure at a temperature and for a time sufficient to mobilize and decompose the precursor compound; and iii) obtaining the zeolite or the metal doped zeotype.
[2]
2. Process according to claim 1, characterized by the fact that the zeolites or zeotypes are selected from the group consisting of one or a mixture of the Faujasita type, Pentasil type, zeolite or Chabazite zeotype, for example, SAPO-34 or other '8 ring' structures of the CHA type structure and related structure types, for example, AEI, AFT, AFX, DDR, ERI, ITE, ITW, KFI, LEV, LTA, PAU, RHO, and UFI.
[3]
3. Process according to claim 1 or 2,
Petition 870190007236, of 23/01/2019, p. 8/17
2/2 characterized by the fact that the metal is selected from the group of Fe, Cu, Co, Ag and Ce.
[4]
4. Process according to any one of claims 1 to
3, characterized by the fact that the complex ligand is selected and from one or a mixture of the group comprising a diketonate structure and carbonyl species.
[5]
Process according to any one of claims 1 to
4, characterized by the fact that the mixture is calcined at a temperature of> 200 ° C - 650 ° C.
[6]
6. Process according to any one of claims 1 to
5, characterized by the fact that the mixture is calcined at a temperature of about 350 - 450 ° C for 1 - 5 hours.
[7]
Process according to any one of claims 1 to
6, characterized by the fact that the mixture comprises the zeolite or zeotype material and the precursor compound to provide a subsequent metal dopant charge of about 0.01% by weight of metal to about 10% by weight of metal.

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同族专利:

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公开号 | 公开日

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KR101950670B1|2019-02-21|

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EP2648845A1|2013-10-16|

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BR112013014529A2|2016-09-20|

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RU2013131779A|2015-01-20|

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US8865120B2|2014-10-21|

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EP2463028A1|2012-06-13|

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US20130251611A1|2013-09-26|

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法律状态:
2018-10-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-03-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-05-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/12/2011, OBSERVADAS AS CONDICOES LEGAIS |

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2020-12-22| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

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2021-04-13| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2607 DE 22-12-2020 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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EP10015547.2|2010-12-11|

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EP10015547A|EP2463028A1|2010-12-11|2010-12-11|Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides|

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PCT/EP2011/072190|WO2012076648A1|2010-12-11|2011-12-08|Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic remediation of nitrogen oxides|

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