ORGANOTEMPLATE-FREE SYNTHETIC PROCESS FOR THE PRODUCTION OF A ZEOLYTIC MATERIAL, SYNTHETIC ORGANOTEM

专利摘要:
organo-template-free synthetic process for the production of a zeolitic material organo-template-free zeolitic material and the use thereof The present invention relates to an organo-template-free synthetic process for the production of a zeolitic material having a frame structure of the cha type comprising y02, x 203, and optionally comprising z205, wherein said process comprises the steps of: (1) providing a mixture comprising one or more sources o for y02, one or more sources for x 203, and seed crystals, having a cha frame structure, in which the cha frame structure of the seed crystals comprises y02, x 203, and optionally comprises z205; and (2) crystallize the mixture obtained in step (1); where y is a tetravalent element, x is a trivalent element and z is a pentavalent element, where, optionally, one or more sources for z205 are additionally provided in step (1), and where the cha frame structure of the crystals seed does not contain z205, the seed crystals then have a y02: x 203 molar ratio of 5 or greater than 5.
公开号:BR112014011308B1
申请号:R112014011308-4
申请日:2012-11-09
公开日:2021-04-13
发明作者:Stefan Maurer；Hanpeng Jin；Jeff Yang；Ulrich Müller
申请人:Basf Se；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a zeolytic material free of synthetic organotemplate with a frame structure of the CHA type and to a process for the production of said material that does not involve the use of an organotemplate. In addition, the present invention relates to the use of a zeolitic material free of zeolitic organotemplate having a CHA type frame structure. INTRODUCTION
[002] Molecular sieves are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, frame-type zeolites and other micro-porous crystalline molecular sieves, for which a structure has been established, are assigned a three-letter code and are described in the Atlas of Zeolite Framework Types, 5th edition, Elsevier, London , England (2001).
[003] Among these zeolitic materials, Chazabite is a well-studied example, in which it is the classic representative of the class of zeolitic materials, having a CHA frame structure. In addition to aluminum silicates such as Chazabite, the class of zeolitic materials, having a CHA frame structure comprises a large number of compounds additionally comprising phosphorus in the frame structure are known which are accordingly referred to as silicoaluminophosphates (SAPO). In addition to said compounds, additionally molecular sieves of the CHA structure type are known which contain aluminum and phosphorus in their frame, still contain little or no silica and are accordingly referred to as aluminophosphates (APO). Zeolitic materials belonging to the molecular sieve class, having the CHA-type frame structure are used in a variety of applications and in particular serve as heterogeneous catalysts in a wide range of reactions such as methanol, olefin catalysis and selective catalytic reduction of NOx nitrogen oxides, to name a few of the most important applications. CHA frame type zeolitic materials are characterized by pore / channel systems (8MR) of three-dimensional 8-membered rings containing double-membered six-membered rings (D6R) and chains.
[004] US 7,067,108 B2 discloses Chazabite frame type zeolites. Zeolites are prepared using a specific seeding material, namely a crystalline material having a frame type other than Chazabite frame type, such as AEI type, LEV type or OFF type, in addition to N, N, N- hydroxide trimethyl-1-adamantilammon used as the frame steering agent.
[005] US 6,974,889 B1, on the other hand, discloses a process for the manufacture of a crystalline molecular sieve, such as zeolites of structure type CHA or LEV, contained phosphorus in its frame, in which tetratiammonium hydroxide is used as the agent of modeling, and in which a colloidal crystalline molecular sieve is used as seed material. In particular, this document teaches the use of seed crystals, having the type of structure LEV, OFF, or CHA, in which said seed crystals must be as small as possible to control the particle size of the product, as well as to accelerate its formation . Specifically, the SAPO-34 synthesis is disclosed in said document, using colloidal solutions of Chazabite crystals.
[006] Although some progress has been made regarding the costs of the organotemplate used in the synthesis of CHA-type zeolites, as well as with regard to the duration of the synthetic process, the biggest disadvantage remains with respect to the necessary use of a structure direction which must be removed subsequently. In this event, the organotemplates are contained in the pore structure of the resulting zeolite, in such a way that it can first be effectively used in an application only after its removal. In addition, the organotemplate can generally only be removed by a calcination process or the like, in such a way that recycling of the organotemplate is not possible. Another disadvantage refers to the decomposition of the organic template material during hydrothermal synthesis, which not only makes it necessary to use reaction vessels, exhibiting high pressure resistance, but also limits the possibility of recycling materials used in the synthesis due to the presence waste from organic decomposition products. As a result of these restrictions, the known procedures for producing CHA-type zeolite materials are highly costly, making these zeolites unattractive for a variety of applications.
[007] Additionally, the necessary removal of the organotemplate by calcination at high temperatures, usually at 450 to 930 ° C or even higher, is not only disadvantageous due to the destruction of expensive organic template, but also results in excess energy consumption and produces harmful gases and other unwanted waste products. In addition, the severe heat treatment ultimately limits the types of architectures which can be provided according to known production methods. In particular, although ion exchange methods for extracting the organotemplate from Zeolitic material have been developed as an environmentally friendly alternative to calcination to remove the organic template, only a part of the organic templates can be successfully recycled, the rest also strongly interacting with the zeolite frame for complete removal. Accordingly, the synthesis of zeolite materials of the CHA type which are devoid of an organotemplate continues to be effectively limited to those materials capable of withstanding the harsh conditions necessary for the complete removal of the organotemplates necessarily used in the synthesis thereof. As a result, the severe heat treatment ultimately limits production to thermally stabilize CHA-type zeolite materials, especially for those which exhibit a high SiO2: Al2O3 molar ratio.
[008] In Hasegawa et al., Journal of Membrane Science 2010, 347, 193-196, a process for the preparation of a layer of Chabazite-type zeolite in a porous tube α-Al2O3 is disclosed in which said synthesis is achieved by use of crystals, having the CHA frame structure in combination with the use of strontium as the structural steering agent in the sown synthesis, in which the inter Zeolitic transformation crystals of type Y zeolite into type CHA zeolite were obtained. Li et al. in Microporous and Mesoporous Materials 2011, 143, 270-276, on the other hand, also refers to the synthesis of Chabazite-type zeolite layers in porous α-Al2O3 substrates using CHA seeding materials obtained from Y-type zeolite inter-transformation in CHA-type zeolite, in which, however, unlike Hasegawa et al., potassium is used as a structural steering agent in the synthetic process. Said processes are, however, highly limited by the fact that the Zeolitic material of the CHA type used as the seeding agent is specifically obtained from inter Zeolitic transformation, as a result of which the zeolitic materials of the CHA type which can be obtained by such processes are also very limited. In particular, the proportions of Si Al available for materials of said sowing materials obtained from inter Zeolitic transformation are highly limited, so that only materials having very low proportions of Si Al can be used. Thus, the sowing material employed in Hasegawa et al. exhibits a SiO2: Al2O3 molar ratio of only 4.8 to obtain a product having a SiO2: Al2O3 molar ratio of 6.4. Li et al, on the other hand, only allows the production of zeolitic materials, having the CHA-type frame structure with a SiO2: Al2O3 molar ratio of 5.72.
[009] Consequently, there is still a considerable need for an organotemplate-free production process of a Zeolitic material having a CHA-type frame structure which can provide a large number of different zeolitic materials, having a wide range of physical and chemical properties. chemical, which are reflected in particular by SiO2: Al2O3 molar proportions in said materials. In addition, there is a particular need for the provision of an organotemplate-free synthetic process which is truly template-free and not linked to the specific use of other ions as structural steering agents which are again highly limiting with respect to the range of different zeolitic materials which can be produced and the specific respective chemical and physical properties which can be obtained.
[010] Furthermore, in addition to the considerable restrictions of the processes known in the prior art, there is also a considerable need for a cost efficient process which provides a microcrystalline product, the processes known respectively by Hasegawa and Li et al, involving the use of bulky support materials and excessive amounts of seeding material compared to the actual amount of zeolite obtained. In addition, the products in Hasegawa and Li et al. they can only be obtained in the form of membrane layers, supported by bulky support materials respectively consisting of a specific zeolite seeding material provided on a solid support.
[011] Accordingly, there is also a need for an organotemplate-free synthetic process which can provide a microcrystalline Zeolitic material, having the CHA-type frame structure. DETAILED DESCRIPTION
[012] It was, therefore, an object of the present invention to provide a process for the organotemplate-free synthesis of a Zeolitic material having a CHA-type frame structure adapted to a wide range of zeolitic materials and seeding products, in particular with regard to concerns SiO2: Al2O3 molar ratios which can be obtained.
[013] It was an object of the present invention to provide a process for the organotemplate-free synthesis of a Zeolitic material having CHA-type frame structure adapted to a wide range of zeolitic materials and seeding products which can be conducted under mild conditions and non-destructive towards zeolite architecture In particular, it was also an object to provide a process for the production of such materials which do not involve a high temperature calcination treatment or other treatments normally used for the removal of organotemplates present in the structure of frame.
[014] An additional object of the present invention was to provide a cost effective and improved process for the production of organolemplate-free Zeolitic materials having a CHA-type frame structure adapted to a wide range of zeolitic materials and seeding products in particular with respect in time for crystallization, energy consumption and environmental pollution.
[015] In addition, it was also an object of the present invention to provide a wide range of Zeolitic materials free of organotemplate having CHA-like frame structure which has an intact architecture as directly obtained from the crystallization process.
[016] Thus, it was discovered that, according to the present invention, a wide range of different Zeolitic material, having a CHA-like frame structure can be obtained without using an organotemplate in their synthesis, particularly with regard to with respect to SiO2: molar proportions of Al2O3 which can be achieved in the CHA frame structure. In particular, it was found that when using seed crystals of a Zeolitic material having a CHA-like frame structure in an organotemplate-free synthetic process, in which said seed crystals exhibit in particular intermediate to high SiO2: molar ratios of AlO3, a wide variety of zeolitic materials free of organotemplate having a CHA type frame structure can be directly obtained which do not require the time and cost intensive procedures required for the removal of organotemplates normally used in their production. Thus, a synthetic one-pot procedure is provided to directly obtain a wide range of zeolitic materials free of organotemplate having a CHA-type frame structure, in which the porosity of said Zeolitic material is given directly and must not first be provided by a or more post-synthetic treatments to remove structure, targeting crystallized frame agents, where the structure steering agents are typically organotemplates.
[017] In addition to these considerable advantages, it was found that according to the inventive process, new zeolitic materials, having a CHA-type frame structure can be obtained exhibiting unprecedented properties, which can be used advantageously in current and future applications. In particular, CHA-like structures are accessible from which their chemical composition and / or physical properties cannot be obtained by organotemplate-mediated synthesis. According to the present invention, such frames include in particular CHA-type frames with intermediate and high Si content not achieved by known synthetic methodologies. Such new frameworks accessible by free organotemplate synthesis are of considerable interest, particularly in catalytic applications or elsewhere for the capture of organic molecules, as well as in absorption applications due to the intermediate lowering density of acid sites and in particular the functionalities aluminum which can be reached in it.
[018] In addition, due to the absence of organic materials in the reaction mixture, which are prone to decomposition, low pressure devices can be used in the inventive process, in which the materials used in it can be easily recycled due to the absence of waste of organic products.
[019] Thus, in view of the numerous considerable advantages mentioned above, a highly efficient process is provided for the production of a wide variety of zeolitic materials having a CHA-type frame structure preferably exhibiting intermediate and high SiO2: molar ratios of Al2O3 , in which said process involves considerably lower costs than methodologies mediated by organotemplate. It is not only due to the possibility of using simpler devices, in particular with regard to the amount of pressure that they must withstand in summary. Much more, the new process does not require organotemplates, which are by far the most expensive components in synthetic methodologies mediated by organotemplate, in particular due to the fact that expensive organotemplates cannot be effectively recycled, but are preferably destroyed in the course of to provide the organotemplate-free product. Accordingly, the present invention provides a process with highly reduced costs in view of the cheap raw materials, the simplest apparatus which can be used and the highly reduced amount of product residues, thus providing a highly effective production process .
[020] Therefore, the present invention relates to an organotemplate-free synthetic process for the production of a Zeolitic material having a CHA-type frame structure comprising YO2, X2O3, and optionally comprising Z2O5, wherein said process comprises the steps of: (1) providing a mixture comprising one or more sources for YO2, one or more sources for X2O3 and seed crystals having a CHA frame structure, wherein the CHA frame structure of the seed crystals comprises YO2, X2O3 and optionally comprises Z2O5 ; and (2) crystallize the mixture obtained in step (1); where Y is a tetravalent element, X is a trivalent element and Z is a pentavalent element, where, optionally, one or more sources for Z2O5 are additionally provided in step (1) and where the CHA frame structure of the crystals seed does not contain Z2O5, the seed crystals then have a YO2: XO23 molar ratio of 5 or greater than 5, where YO2: X2O3 molar ratio preferably ranges from 5 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 20 to 50, more preferably from 25 to 40, most preferably from 28 and 35 and even more preferably from 29 to 33.
[021] According to the inventive process, at no time does the mixture provided in step (1) and crystallize in step (2) contain more than an impurity of an organic structure steering agent, specifically used in the synthesis of zeolitic materials , having a CHA-like frame structure, in particular specific tetra alkyl ammonium compounds, dialkyl amines, heterocyclic amines and combinations of two or more of the same. More preferably, one or more structural steering agents comprise one or more compounds selected from the group consisting of tetra (C1 - C5) alkyl ammonium compounds, di (C1 - C5) alkyl amines, oxygen containing 5 to heteroxycline amines 8 ring members and combinations of two or more of the same, more preferably from the group consisting of tetra (C2 - C4) alkyl ammonium compounds, di (C2 - C4) alkyl amines, oxygen containing 5 to 7 ring member heteroxycylic amines and combinations of two or more of the same, more preferably of the group consisting of tetra alkyl ammonium (C2 - C3) compounds, di (C2 - C3) alkyl amines, oxygen containing 5 or 6 membered heteroxycyclic amines and combinations of two or more of them, and / or organotemplates such as any suitable N-alkyl-3-quinuclidinol compound, N, N, N-trialkyl-exoaminonorbornane compound, N, N, N-trimethyl-1-adamantylamonium compound, N, N , composed of N-trimethyl-2-adamantylamon io, N, N, N-trimethylcyclohexylammonium compound, N, N-dimethyl-3,3-dimethylpiperidinium compound, N, N-methylethyl-3,3-dimethylpiperidinium compound, N, N-dimethyl-2-methylpiperidinium compound, compound 1,3,3,6,6-pentamethyl-6-azonium-bicyclo (3.2.1) octane, N, N-dimethylcyclohexylamine compound or any appropriate N, N, N-trimethylbenzylammonium compound, including combinations of two or more of the same . Such impurity can, for example, be caused by organic structure steering agents still present in seed crystals used in the inventive process. Organotemplates contained in seed crystal material however, may not participate in the crystallization process since they are trapped within the seed crystal frame and, therefore, may not act on structural steering agents within the scope of the present invention.
[022] Within the scope of the present invention, a "organotemplate-free" synthetic process refers to a synthetic process, in which the materials used therein are substantially free of organotemplate materials, in which "substantially" used in the present invention with respect to refers to the amount of one or more organotemplates contained in one or more materials used in a synthetic process indicates an amount of 0.1% by weight or less than one or more organotemplates, preferably 0.05% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less and even more preferably 0.0001% by weight or less of the same. Said amounts of one or more organotemplates, if they present any of the materials used in the synthetic process, they can also be indicated as "impurities" or "traces" within the scope of the present invention. In addition, it is noted that the terms "organotemplate" and "organic structure steering agent" are used interchangeably in the present application.
[023] The term "organotemplate", as used in this application designates any conceivable organic material which is suitable for synthesis by means of a template of a zeolite material, preferably a zeolite material having a CHA-type frame structure, and even more preferably, which is suitable for the synthesis of Chazabite. Such organotemplates, for example, include any suitable tetra alkyl ammonium compound, dialkyl amine, heterocyclic amine, N-alkyl-3-quinuclidinol compound, N, N, N-trialkyl-exoaminonorbornane compound, N, N, compound of N-trimethyl-1-adamantylammonium, N, N, compound N-trimethyl-2-adamantylammonium, N, N, compound N-trimethylcyclohexylammonium, N, compound N-dimethyl-3,3-dimethylpiperidinium, N, compound N-methylethyl- 3,3-dimethylpiperidinium, N, compound N-dimethyl-2-methylpiperidinium, compound 1,3,3,6,6-pentamethyl-6-azonium-bicyclo (3.2.1) octane, N, compound N-dimethylcyclohexylamine and any appropriate N, N, N-trimethylbenzylammonium compound.
[024] Furthermore, within the scope of the present invention, YO2, X2O3, and optionally Z2O5 are composed in the CHA-type frame structure as structural building elements, rather than non-structural elements which may be present in the pores and cavities formed by the frame structure and typical for zeolitic materials in general.
[025] According to the present invention, a Zeolitic material having a CHA-type frame structure is crystallized in step (2), wherein said material comprises YO2. In principle, Y represents any conceivable tetravalent element, Y representing one or more tetravalent elements. Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr and Ge and combinations thereof. More preferably, Y represents Si, Ti or Zr or any combination of said tetravalent elements, even more preferably for Si, and / or Sn. According to the present invention, it is particularly preferred that Y represents Si.
[026] According to the inventive process, one or more sources for YO2 are provided in step (1), in which said one or more sources can be provided in any conceivable form, provided that a Zeolitic material having a frame structure of the CHA type comprising YO2 and X2O3 can be crystallized in step (2). Preferably, YO2 is provided as and / or as a compound which includes YO2 as a chemical part and / or as a compound which (in part or entirely) is chemically transformed into YO2 during the inventive process. In preferred embodiments of the present invention, where Y represents Si or a combination of Si with one or more additionally tetravalent elements, the source for SiO2 preferably provided in step (1) can also be any conceivable source. Thus, by way of example, any type of silica and / or silicate can be used, in which preferably one or more sources for YO2 comprise one or more silicate. As said one or more silicates, any conceivable silicate or combination of silicates can be used in which it is preferred that said one or more silicates comprise one or more alkali metal silicates, the alkali metal, preferably being selected from the group consisting of Li , Na, K, Rb and Cs. According to particularly preferred embodiments, one or more silicates comprise one or more sodium and / or one or more potassium silicates, wherein even more preferably one or more silicates comprise one or more sodium silicates.
[027] Within the scope of the present invention, the term "silicate" as a preferred source for YO2 generally refers to any conceivable silicates, provided that an organotemplate-free zeolitic material having a CHA-like frame structure can be crystallized in step (2) the inventive process. According to a particularly preferred scope of the present invention, the term "silicate" refers to the anion [SiO3] 2- comprised in the particularly preferred silicate compounds comprised in one or more sources for YO2.
[028] Thus, according to the present invention it is preferred that one or more sources for YO2 comprise one or more silicates, preferably one or more alkali metal silicates, wherein the alkali metal is preferably selected from the group consisting of Li, Na , K, Rb and Cs, where more preferably the alkali metal is Na and / or K, and where even more preferably the alkali metal is Na.
[029] According to particularly preferred embodiments of the present invention in which one or more sources for YO2 provided in step (1) comprises one or more silicates, it is further preferred that said one or more silicates make up a glass of water. In principle, any type of water glass or combinations thereof can be used in the present invention as the one or more sources for YO2 provided that a Zeolitic material having a CHA-like frame structure can be obtained, in which preferably sodium silicate and / or potassium is used as a glass of water, more preferably sodium silicate.
[030] Thus, according to particularly preferred embodiments of the present invention, the mixture provided in step (1) comprises a glass of water, preferably potassium silicate and / or, and even more preferably sodium silicate.
[031] According to said preferred embodiments of the present invention in which one or more sources for YO2 comprises one or more silicates, it is further preferred that one or more silicas are added to the mixture provided in step (1), in addition to one or more silicates. In principle, any possible source of silica can be employed, provided that a Zeolitic material having the CHA-type frame structure can be crystallized in step (2). Thus, by way of example, any type of silica can be used as pyrogenic silica, silica hydrolates, reactive amorphous silicas, silica gel, silicic acid, colloidal silica, pyrogenic silica, silicic acid esters, tetra alkoxy silanes or mixtures of hair at least two of these compounds, in which more preferably one or more silica hydrosols and / or one or more colloidal silicas are used and even more preferably one or more colloidal silicas.
[032] Thus, according to particular embodiments of the present invention which are still additionally preferred, the mixture provided in step (1) of the inventive process additionally comprises one or more silicas in addition to one or more silicates, preferably one or more hydrosols silicas and / or colloidal silicas, and even more preferably one or more colloidal silicas in addition to one or more silicates.
[033] According to the present invention, X2O3 is comprised of Zeolitic material having a CHA-like frame structure which is crystallized in step (2). In principle, X provided in step (1) in one or more sources for X2O3 represents any conceivable trivalent element, X represents one or more trivalent elements. Preferred trivalent elements according to the present invention include Al, B, em and Ga and combinations thereof. More preferably, X represents Al, B, or In, or any combination of said trivalent elements, even more preferably Al and / or B. According to the present invention, it is particularly preferred that X represents Al.
[034] In the process of the present invention, one or more sources for X2O3 provided in step (1) can be provided in any conceivable form, provided that a Zeolitic material having a CHA-like frame structure is crystallized in step (2). Preferably, X2O3 is provided as and / or as a compound which comprises X2O3 as a chemical part and / or as a compound which (in part or entirely) is chemically transformed to X2O3 during the inventive process.
[035] In more preferred embodiments of the present invention, where X represents Al or a combination of Al with one or more additionally trivalent elements, the source for Al2O3 provided in step (1) can be any conceivable source. Any type of alumina and aluminates, aluminum salts such as, for example, alkali metal aluminates, aluminum alcoholates, such as, for example, aluminum triisopropylates or hydrated alumina, such as, for example, alumina or mixtures thereof. Preferably, the source for Al2O3 comprises at least one compound selected from the group consisting of alumina and aluminates, preferably aluminates, more preferably alkali metal aluminates, where even more preferably, the alkali metal of the aluminate comprises one or more of the alkali metals M Among the preferred alkali metal aluminates, at least one source preferably comprises potassium and / or sodium aluminate, more preferably sodium aluminate. In particularly preferred embodiments of the present invention, the source for Al2O3 is sodium aluminate.
[036] Thus, according to preferred modalities of the inventive process, one or more sources for X2O3 comprises one or more aluminate salts, preferably one or more alkali metal aluminates, in which the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs, where more preferably the alkali metal is Na and / or K, and where even more preferably the alkali metal is Na.
[037] According to particularly preferred modalities of the inventive process, the mixture according to step (1) comprises one or more silicates as a source for YO2 and one or more aluminates as a source for X2O3, more preferably one or more metal silicates alkali and one or more alkali metal aluminates, more preferably a sodium and / or potassium silicate and a sodium and / or potassium aluminate, more preferably a sodium silicate and sodium aluminate, where even more preferably the one or more sources for YO2 comprises a glass of sodium water (Na2SiO3) and the one or more sources for X2O3 comprises sodium aluminate. According to alternatively particularly preferred embodiments of the present invention, the mixture according to step (1) comprises one or more silicas in addition to one or more silicates as a source for YO2 and one or more aluminates as a source for X2O3, more preferably one or more more colloidal silicas in addition to one or more alkali metal silicates and one or more alkali metal aluminates, more preferably one or more colloidal silicas in addition to a sodium and / or aluminum silicate and potassium and / or sodium aluminate, more preferably one or more colloidal silicas in addition to a sodium silicate and sodium aluminate, in which even more preferably the one or more sources for YO2 comprises one or more colloidal silicas in addition to a glass of sodium water (Na2SiO3) and one or more sources for X2O3 comprise sodium aluminate.
[038] According to the inventive process, the mixture provided and step (1) optionally comprises one or more sources for Z2O5, where Z represents any conceivable pentavalent element, Z represents one or more pentavalent elements. Preferably, Z2O5 is provided as and / or as a compound which comprises Z2O5 as a chemical part and / or as a compound which (in part or entirely) is chemically converted to Z2O5 during the inventive process. In principle, any conceivable source can be provided as one or more sources for Z2O5 provided that in step (2) of the inventive process, a Zeolitic material having a CHA-like frame structure is crystallized. Preferred pentavalent Z elements according to the present invention include P, As, Sb, Bi, V, Nb, Ta and combinations of two or more of the same. More preferably, Z represents P, As, V and combinations of two or more of the same, wherein even more preferably Z comprises P or As. According to particularly preferred embodiments, Z comprises P, where it is particularly preferred that Z represents P.
[039] According to the inventive process, the mixture provided in step (1) comprises seed crystals, having a CHA-type frame structure, in which the CHA-type frame structure of the seed crystals comprises YO2 and X2O3 and in which if the CHA frame structure of the seed crystals does not contain Z2O5, said seed crystals then exhibit a YO2: X2O3 molar ratio of 5 or greater than 5. Thus, it was found that seed crystals having a CHA type frame structure comprising YO2 and X2O3, where YO2: molar ratio of X2O3 is 5 or greater than 5, an organotemplate-free synthetic process can be provided to obtain a Zeolitic material of the CHA type having a structure comprising YO2 and X2O3, in particularly in instances where the CHA frame structure of the seed crystals does not contain Z2O5. In particular, in opposition to the state of the art mentioned in the introductory section of the present application and which employs specific seed crystals obtained from inter Zeolitic transformation, said seed crystals, being, therefore, restricted to particular YO2: molar proportions X2O3 due to the method of its In production, the process of the present invention allows the use of seed crystals exhibiting intermediate and high YO2: X2O3 molar ratios. Within the context of the present invention, intermediate and high YO2: molar ratios of X2O3 generally refer to molar ratios having a value of 5 or greater than 5 and in particular YO2: molar ratios of X2O3 according to particular and preferred modalities of the present invention. Thus, in accordance with the present invention, the YO2: X2O3 molar ratio of the seed crystals having a CHA-type frame structure provided in step (1) of the inventive process can exhibit any conceivable YO2: molar proportion of X2O3 provided that said value it is 5 or a value greater than 5, and that a Zeolitic material having a CHA-type frame structure can be crystallized in step (2) of the inventive process. Thus, by way of example, the seed crystals provided in step (1) of the inventive process can exhibit a YO2: molar ratio of X2O3 in the range of anywhere from 5 to 200 where it is preferable that the molar ratio exhibited by the seed crystals is comprised in the range of 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 20 to 50, more preferably from 25 to 40 and even more, preferably from 28 to 35. From according to particularly preferred embodiments of the present invention, the YO2: X2O3 molar ratio of the seed crystals is in the range of 29 to 33.
[040] In accordance with the present invention, the seed crystals, having a CHA-type frame structure provided in step (1) of the inventive process, may optionally comprise Z2O5. In said instances, the seed crystals, having a CHA-type frame structure provided in step (1) of the inventive process, exhibits a molar ratio of YO2: nX2O3: pZ2O5, more specifically, according to said optional modalities of the present invention in that the CHA-type frame structure of the seed crystals additionally comprise Z2O5, said crystals are not necessarily characterized by a YO2: molar ratio of X2O3 but rather by a molar ratio of YO2: nX2O3: pZ2O5 where the value for the ratio (1 + 2p) :( np) is characteristic for the CHA type frame structure of said seed crystals.
[041] Thus, according to said modalities of the present invention in which the CHA-type frame structure of the seed crystals additionally comprises Z2O5, there is no particular restriction on YO2: molar ratio of X2O3 to which the seed crystals additionally comprising Z2O5 can display. Thus, considering the value for the ratio (1 + 2p) :( n-p), this ratio can have any suitable value, provided that an organolemplate-free Zeolitic material can be crystallized in step (2). Thus, by way of example, the value for the ratio (1 + 2p) :( n- p) can be 1 or greater than 1, where it is preferable that said value be 2 or greater than 2, more preferably 3 or greater than 3 and even more preferably 5 or greater than 5. Thus, according to preferred embodiments of the inventive process, the value for the proportion (1 + 2p) :( np) of seed crystals additionally comprising Z2O5 can vary anywhere from 1 to 500, more preferably from 2 to 400, more preferably from 3 to 300, more preferably from 5 to 200, more preferably from 6 to 150, more preferably from 8 to 100, most preferably from 12 to 70, most preferably from 20 to 50 , more preferably from 25 to 40 and even more, preferably between 28 and 35. And even more, preferably from 29 to 33. According to particularly preferred modalities of the inventive process, the value for the ratio (1 + 2p) :( np ) in relation to the molar ratio of YO2: nX2O3: pZ2O5 of the crystals seed is comprised in the range of 29 to 33.
[042] Thus, according to preferred modalities of the inventive process, the CHA frame structure of the seed crystals additionally comprises Z2O5 in addition to YO2 and X2O3, the seed crystals have a YO2: nX2O3: pZ2O5 molar ratio, where the value for the ratio (1 + 2p): (np) is 5 or greater than 5, where the value for the ratio (1 + 2p): (np) preferably ranges from 5 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 20 to 50, more preferably from 25 to 40, most preferably from 28 to 35 and even more preferably from 29 to 33.
[043] Regarding the composition of the seed crystals having a CHA frame structure, there is no particular restriction on their composition, provided that they comprise YO2 and X2O3, where Y is a tetravalent element and X is a trivalent element, and provided that they are suitable for crystallizing an organotemplate-free zeolitic material having a CHA-type frame structure in step (2) of the inventive process. As defined above with respect to the inventive process, YO2 and X2O3 comprise in the structure of the seed crystals having a CHA frame structure not contained therein as structure-building elements, rather than non-structural elements which may be present in the pores and / or cavities formed by the CHA frame structure and typical for zeolitic materials in general.
[044] In principle, seed crystals having a CHA frame structure can comprise any conceivable tetravalent element Y, where Y represents one or more tetravalent elements. Preferred tetravalent elements comprised in the seed crystals according to the present invention include Si, Sn, Ti, Zr and Ge and combinations of two or more of the same. More preferably, Y represents Si, Ti or Zr or any combination of said tetravalent elements, even more preferably for Si, and / or Sn. According to the present invention, it is particularly preferred that Y represents Si.
[045] According to the present invention it is further preferred that both said one or more sources for YO2 and the seed crystals, having a CHA frame structure provided in step (1) comprise the same or more tetravalent elements, where more preferably Y comprised in one or more sources for YO2 and Y comprised in the seed crystals, having a CHA frame structure represent the same or more tetravalent elements according to particular and preferred embodiments of the present invention.
[046] In addition, seed crystals having a CHA frame structure can comprise any suitable trivalent element X, where again X represents one or more trivalent elements. Preferred trivalent elements according to the present invention include Al, B, em and Ga and combinations thereof. More preferably, X comprises Al or Ga, where more preferably X comprises Al, and where even more preferably X is Al.
[047] As for one or more tetravalent Y elements, it is further preferred according to the inventive process that both said one or more sources for X2O3 and the seed crystals having a CHA frame structure provided in step (1) comprise the same one or more trivalent elements X, where even more preferably X comprised in one or more sources for X2O3 and X comprised in the seed crystals, having a CHA frame structure represents the same or more tetravalent elements according to particular and preferred embodiments of the present invention .
[048] Finally, with respect to the use of seed crystals, optionally comprising Z2O5 in the inventive process, the CHA frame structure can accordingly comprise any suitable pentavalent element Z, where Z represents any of the various pentavalent elements. Preferred pentavalent elements according to the present invention include P, As, Sb, Bi, V, Nb, Ta and combinations of two or more of the same. More preferably Z is comprised of one or more pentavalent elements selected from the group consisting of P, As, V and combinations of two or more of the same, where more preferably Z comprises P or As, preferably P, and where even more preferably Z is P
[049] According to particularly preferred embodiments, both said one or more sources for YO2 and said one or more sources for X2O3, as well as the seed crystals, having a CHA frame structure provided in step (1) comprise the same one or more tetravalent elements Y in addition to the same one or more trivalent elements X, wherein even more preferably Y comprised in one or more sources for YO2 and Y comprised in the seed crystals, as well as X comprised in one or more sources for X2O3 and X comprised in the crystals seed represent the same one or more tetravalent elements and the same one or more trivalent elements, respectively, according to particular and preferred embodiments of the present invention.
[050] According to the present invention, there is no particular restriction with respect to the quantity of one or more sources for YO2 and one or more sources for X2O3 provided in the mixture in step (1) of the inventive process provided that a material can Zeolithic having CHA frame structure comprising YO2 and X2O3 can be crystallized in step (2). Thus, in principle, any conceivable YO2: X2O3 molar ratio can be provided in the mixture provided in step (1), where, for example, said molar ratio can vary anywhere from 1 to 200. According to the present However, it is preferred that the YO2: molar ratio of O X23 of the mixture provided in step (1) is comprised in the range of 2 to 150 and more preferably of 5 to 100, more preferably of 10 to 70, more preferably of 15 to 50 and even more, preferably from 20 to 45. According to particularly preferred embodiments of the present invention, the molar ratio of YO2: X2O3 of the mixture provided in step (1) ranges from 25 to 42.
[051] Therefore, it is preferred according to the present invention that the YO2: X2O3 molar ratio of the mixture provided in step (1), ranges from 1 to 200, preferably from 2 to 150, more preferably from 5 to 100, more preferably from 10 to 70, more preferably from 15 to 50, more preferably from 20 to 45, and most preferably from 25 to 42.
[052] In the process of the present invention, the mixture provided in step (1) preferably comprises one or more alkali metals M. In general, said one or more alkali metals M can be provided with any suitable compounds or compounds comprising one or more metals alkali M, wherein preferably one or more alkali metals M are provided as one or more alkali metal salts. According to particularly preferred embodiments thereof, one or more alkali metals M are provided as one or more alkali metal compounds being one or more sources for YO2 and / or one or more sources for X2O3, even more preferably as a or more alkali metal compounds being the respective sources for YO2 and X2O3. According to said particularly preferred embodiments, one or more alkali metal compounds used as sources for YO2 and / or X2O3 preferably comprises one or more alkali metal salts used as one or more sources for YO2 and / or X2O3 wherein according to a particularly preferred embodiment one or more alkali metal salts are used as one or more sources for YO2 and / or X2O3 and preferably as one or more sources for YO2 and X2O3.
[053] With respect to one or more alkali metals M preferably comprised in the mixture provided in step (1) of the inventive process, any alkali metal M or combination of alkali metals M can be used, wherein, preferably one or more alkali metals M they are selected from the group consisting of Li, Na, K, Rb and Cs and combinations of two or more of the same, most preferably from the group consisting of Li, ND, Rb, Cs and combinations of two or more of the same. According to particularly preferred embodiments, one or more alkali metals M comprise Li and / or ND and Na, wherein even more preferably one or more alkali metal is Li and / or Na and, preferably, Na.
[054] Regarding the preferred modalities of the inventive process, in which one or more alkali metals M are provided in step (1), there is no particular restriction according to the present invention as to the quantity of one or more alkali metals M, which can be provided therein, provided that a Zeolitic material having a frame structure of the CHA type is crystallized in step (2). Thus, by way of example, the M2O: molar proportion of YO2 of the mixture provided in step (1) according to said preferred modalities can vary anywhere from 0.01 to 5, where preferably said proportion varies from 0.05 to 2, more preferably from 0.1 to 1.5, more preferably from 0.15 to 1 and even more, preferably from 0.2 to 0.5. According to particularly preferred embodiments, the molar ratio of M2O: YO2 of the mixture provided in step (1) ranges from 0.25 to 0.35.
[055] In addition, according to preferred modalities of the inventive process, in which the mixture provided in step (1) comprises one or more alkali metals M, there is also no particular restriction with respect to M2O: X2O3 molar ratio of the mixture , again provided that a Zeolitic material having a frame structure of the CHA type is crystallized in step (2). The same applies accordingly for YO2: X2O3: Molar proportions of M2O3 of said preferred mixtures comprising one or more alkali metals M. Thus, by way of example, YO2: X2O3: Molar proportions of M2O3 of said preferred mixtures may vary by anywhere from (5-100): 1: (0.5-50), where, preferably the molar proportions are in the range from (10-70): 1: (1 - 30), preferably from to from (15 - 50): 1: (1 - 20), preferably from (20 - 45): 1: (4-15). According to particularly preferred embodiments, the molar ratio of YO2: X2O3: M2O3 of the mixture provided in step (1) varies from (25-42): 1: (5 - 14).
[056] According to alternatively preferred modalities of the inventive process, in which the mixture provided in step (1) comprises one or more alkali metals M, said mixture does not contain potassium and / or does not contain strontium. According to the present invention, a mixture defined as not containing potassium and / or strontium relates to a mixture in which the amount of potassium and / or strontium contained therein is 0.001% by weight or less of potassium and / or strontium, preferably 0.0005% by weight or less, more preferably 0.00001% by weight or less, more preferably 0.000005% by weight or less, and even more preferably 0.000001% by weight or less thereof. Said amounts of potassium and / or strontium, if all present in the mixture provided in step (1), can also be denoted as "impurities" or "traces" within the context of the present invention. According to particularly preferred embodiments of the present invention, the mixture provided in step (1) does not contain potassium.
[057] Thus, according to the preferred embodiments of the present invention, the mixture provided in step (1) does not contain any K and / or Sr, preferably no K.
[058] According to the present invention, there is no particular restriction as to the CHA-like frame structure exhibited by the seed crystals provided that said seed crystals exhibit a typical X-ray diffraction pattern of a particular CHA frame structure in with respect to the reflections and their positions of degree 2 θ in relation to each other. Thus, in principle, provided that the diffraction pattern is typical of a CHA-type frame structure, there is no particular restriction with respect to the actual position of the reflections measured as angle 2 θ, nor with respect to the intensities of the individual reflections in relation to each other. According to the preferred modalities of the present invention, however, the first reflection in the seed crystal x-ray diffraction pattern, that is, the reflection, having the smallest angle value 2 θ, is the reflection having the highest intensity among all measured reflections , that is, the reflection, measured at the 2 θ smallest diffraction angle, has an intensity of 100%. In addition, when using Cu K (alpha 1) radiation, it is more preferred that the diffraction angle 2 θ having an intensity of 100% is comprised in the range of 5 to 15 ° 2 θ in which more preferably, this more intense reflection is comprised in the range of 8 to 12 ° 2 θ, more preferably from 9 to 10.5 ° 2 θ, more preferably from 9.2 to 10 ° 2 θ, more preferably from 9.5 to 9.7 ° 2 θ and still more, preferably from 9.55 to 9.65 ° 2 θ. According to particularly preferred embodiments of the present invention, the most intense reflection in the diffraction pattern of the seed crystals having a CHA-like frame structure when using CU K (alpha 1) radiation is comprised in the range of 9.58 to 9.62 ° 2 θ.
[059] In accordance with the process of the present invention, seed crystals are provided in step (1), wherein said seed crystals comprise a Zeolitic material having a CHA-like frame structure. In general, said seed crystals can comprise any Zeolitic material having a CHA-like frame structure, provided that if the CHA frame structure of the seed crystals does not contain Z2O5, the frame structure has a YO2: X2O3 molar ratio of 5 or greater than 5 provided that a Zeolitic material having a frame structure of the CHA type is crystallized in step (2). Preferably, the Zeolitic material having a CHA-like frame structure comprised in the seed crystals is a Zeolitic material obtained according to the inventive process and in particular according to any of the particular or preferred embodiments of the same described in the present application. More preferably, the Zeolitic material having a CHA-like frame structure comprised in the seed crystals is the same as the Zeolitic material having a CHA-like frame structure which then crystallizes in step (2). Particularly preferred according to the present invention are seed crystals comprising one or more zeolites selected from the group consisting of (Ni (deta) 2) -UT-6, Chabazite, | Li-Na | [Al-Si-O] -CHA, DAF-5, Chabazite-Na, Chabazite-K LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO- 34, SAPO-47, SSZ-13, SSZ -62, UiO-21, Willhendersonite, ZK-14, ZYT-6 and combinations of two or more of the same, preferably from the group consisting of Chabazite, | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, Chabazite-K, SAPO-34, SAPO-47, SSZ-13, SSZ-62 and combinations of two or more of the same, more preferably from the group consisting of Chabazite , | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, more preferably from the group consisting of Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, in which even more preferably the seed crystals having a CHA frame structure comprise Chabazite-Na and / or SAPO-34 and preferably Chabazite-Na. According to additionally preferred embodiments of the present invention, the seed crystals provided in step (1) comprise one or more of the particular and preferred zeolites mentioned above, wherein said one or more zeolites have been obtained according to the inventive process.
[060] According to the inventive process, any suitable amount of seed crystals can be provided in the mixture according to step (1), provided that a Zeolitic material having a CHA-like frame structure is crystallized in step (2). However, it has been found that a Zeolitic material having a CHA-like frame structure can be crystallized in step (2) using a low amount of seed crystals in the mixture according to step (1). In particular, as compared to Hasegawa and Li et al. discussed in the introductory part of the present application, where large amounts of seed crystal material is required to obtain a zeolite membrane, it is possible according to the present invention to produce a greater amount of Zeolitic material with a frame structure of the type CHA compared to the amount of seed crystals provided in the mixture according to step (1). Thus, by way of example, an amount of seed crystals can be provided in a mixture according to step (1) ranging anywhere from 0.05 to 50% by weight based on 100% by weight of YO2 in one or more sources for YO2 provided in step (1) to obtain a Zeolitic material having a CHA type frame structure in step (2). According to the present invention it is however preferred that an amount of 0.1 to 30% by weight of seed crystals is used, more preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight and still more preferably 5 to 12% by weight. According to a particularly preferred embodiment of the present invention, the amount of seed crystals in the mixture according to step (1) varies from 9 to 11% by weight based on 100% by weight of YO2 in one or more YO2 sources.
[061] In accordance with additional embodiments of the present invention, which are still additionally preferred, it is possible to use even smaller amounts of seed crystals in the mixture according to step (1), so that an amount of seed crystals is preferably provided in the mixture according to step (1) ranging from 0.05 to 30% by weight based on 100% by weight of YO2 in one or more sources for YO2e more, preferably from 0.1 to 15% by weight , more preferably from 0.5 to 10% by weight, more preferably from 1 to 8% by weight and even more, preferably from 3 to 6% by weight. According to said particularly preferred embodiment, it is particularly preferred to provide an amount of seed crystals in the mixture according to step (1) in the range of 4 to 5.5% by weight based on 100% by weight of YO2 in one or more sources of YO2.
[062] According to the present invention, the mixture according to step (1) of the inventive process preferably additionally comprises one or more solvents. In this regard, any conceivable solvents can be used in any suitable amount, provided that a Zeolitic material having a CHA-type frame structure comprising YO2, X2O3, and optionally, comprising Z2O5 can be obtained from the crystallization in step (2). Thus, by way of example, one or more solvents may be chosen from water, organic solvents and mixtures thereof, preferably from the group consisting of distilled water, alcohols and mixtures thereof. Most preferably from the group consisting of distilled water, methanol, ethanol, propanol and mixtures thereof. According to particularly preferred embodiments of the present invention, only water and preferably only distilled water is contained in the mixture according to step (1) as the solvent.
[063] Therefore, according to preferred modalities of the inventive process, the mixture according to step (1) comprises one or more solvents, in which said one or more solvents, preferably comprises water, more preferably distilled water.
[064] Regarding one or more solvents, which are preferably provided in the mixture according to step (1), any suitable amount can be used. Therefore, with respect to preferred modalities in which water and preferably distilled water is included in the mixture according to step (1) as the solvent, and in which even more preferably only distilled water is contained in the mixture, H2O. Molar proportion of YO2 of the mixture provided in step (1) can vary anywhere from 1 to 150. According to said preferred modalities, however, it is preferable that the molar ratio of H2O: YO2 varies from 3 to 100, more preferably from 5 to 50, more preferably from 10 to 30 and even more, preferably from 15 to 25. According to particularly preferred embodiments of the present invention, wherein the mixture according to step (1) comprises water as a solvent and even more preferably in which distilled water is the only solvent present in said mixture, it is preferred that the H2O: molar proportion of YO2 of the mixture according to step (1) varies from 16 to 19.
[065] In preferred embodiments of the process of the present invention, the mixture according to step (1) additionally comprises one or more sources of one or more elements suitable for isomorphic substitution at least a part of the atoms of Y and / or atoms of X in the CHA-type frame structure. In general, any conceivable elements can be used provided that they can effectively be replaced in the CHA-type frame structure via isomorphic substitution. In preferred embodiments one or more elements are preferably selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, Be, and mixtures of two or more of the same, plus preferably in which one or more elements are selected from the group consisting of B, Fe, Ti, Sn, Zr, Cu, and mixtures of two or more of the same, in which even more preferably one or more elements is Fe and / or Cu, preferably Cu.
[066] Therefore, the present invention therefore also provides a synthetic pot procedure for the preparation of an organotemplate-free Zeolitic material having a CHA-type frame structure, preferably an organotemplate-free zeolitic material which is isomorphically substituted, where isomorphic substitution is not achieved by conventional processes, involving post-synthetic treatment of an existing frame, in which frame elements are treated so that they can be replaced with other atoms that are then contained in the frame structure resulting. In particular, according to the inventive process, it is not necessary to remove existing frame atoms to produce an isomorphically substituted frame structure.
[067] In general, according to step (1) of the inventive process, the molar ratio of YO2 to the element or the sum of one or more elements suitable for isomorphic substitution can have any conceivable value, where the molar ratio preferably varies from 5 to 200, more preferably from 10 to 100, more preferably from 20 to 70, and even more, preferably from 25 to 50.
[068] In general, and (2) according to the inventive process can be carried out in any conceivable manner, provided that a Zeolitic material having a CHA-type frame structure is crystallized from the mixture according to step (1) . The mixture can be crystallized in any type of container, in which a stirring medium is preferably employed, preferably by rotating and / or stirring the container and more preferably by stirring the mixture.
[069] According to the inventive process, the mixture is preferably heated during at least part of the crystallization process in step (2). In general, the mixture can be heated to any conceivable crystallization temperature, provided that a Zeolitic material having a CHA-like frame structure is crystallized from the mixture. Preferably, the mixture is heated in step (2) to a crystallization temperature ranging from 80 to 200 ° C, more preferably from 90 to 180 ° C, more preferably from 100 to 160 ° C, more preferably from 110 to 140 ° C and even more preferably from 115 to 130 ° C.
[070] In preferred embodiments of the present invention, the mixture according to step (1) is subjected in step (2) to a pressure which is raised with respect to normal pressure. The term "normal pressure", as used in the context of the present invention refers to a pressure of 101,325 Pa in the ideal case. However, this pressure may vary within limits known to the person skilled in the art. For example, this pressure can be in the range of 95,000 to 106,000 or from 96,000 to 105,000 or from 97,000 to 104,000 or from 98,000 to 103,000 or from 99,000 to 102,000 Pa.
[071] In preferred embodiments of the inventive process, in which a solvent is present in the mixture according to step (1), in addition it is preferred that heating in step (2) is conducted under solvothermal conditions, meaning that the mixture is crystallized under autogenous solvent pressure which is used, for example, by conducting heating in an autoclave or other suitable crystallization vessel to generate solvothermal conditions. In particularly preferred embodiments in which the solvent comprises water, preferably distilled water, heating in step (2) accordingly is conducted preferably under hydrothermal conditions.
[072] The apparatus which can be used in the present invention for crystallization is not particularly restricted, provided that the desired parameters for the crystallization process can be carried out, in particular with regard to the preferred modalities which require particular crystallization conditions. In the preferred modalities conducted under solvothermal conditions, any type of autoclave or digestion container can be used.
[073] In general, the duration of the crystallization process in step (2) of the inventive process is not particularly limited. In preferred modalities involving heating the mixture according to step (1) involves, said crystallization process is conducted for a period ranging from 5 to 200h, more preferably from 20 to 160h, more preferably from 60 to 140h, and even more preferably from 100 to 130h
[074] According to the preferred embodiments of the present invention, in which the mixture is heated in step (2), said heating can be conducted during the entire crystallization process or during only one or more parts of it, provided that a Zeolitic material having the CHA type frame structure is crystallized. Preferably, heating is conducted for the duration of the crystallization.
[075] In general, the process of the present invention may optionally comprise additional steps for the chemical and / or additionally physical and / or work-up transformation of the Zeolitic material having a CHA type frame structure crystallized in step (2) mixture provided in step (1). The crystallized material for example may be subject to any isolation sequence and / or washing procedures, in which the Zeolitic material obtained from crystallization in step (2) is preferably subjected to at least one insulation and at least one washing procedure .
[076] Isolation of the crystallized product can be achieved by any conceivable means. Preferably, isolation of the crystallized product can be achieved by means of filtration, ultra filtration, diafiltration, centrifugation and / or decantation methods, in which filtration methods may involve suction and / or pressure filtration steps.
[077] With respect to one or more optional washing procedures, any conceivable solvent can be used. They are washing agents which can be used, for example, water, alcohols, such as methanol, ethanol or propanol or mixtures of two or more of the same. Examples of mixtures are mixtures of two or more alcohols, such as 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 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. Water or a mixture of water and at least one alcohol, preferably water and ethanol, is preferred, distilled water being very particularly preferred as the sole washing agent.
[078] Preferably, the separated Zeolitic material is washed until the pH of the washing agent, preferably the washing water, is in the range of 6 to 8, preferably of 6.5 to 7.5, as determined through an electrode standard glass.
[079] In addition, the inventive process may optionally comprise one or more drying steps. In general, all conceivable means of drying can be used. Drying procedures preferably include heating and / or vacuum application for Zeolitic material having a CHA-type frame structure. In predicted embodiments of the present invention, one or more drying steps may involve spray drying, preferably spray granulation of the Zeolitic material.
[080] In embodiments which comprise at least one drying step, the drying temperatures are preferably in the range of 25 ° C to 150 ° C, more preferably from 60 to 140 ° C, more preferably from 70 to 130 ° C and furthermore, preferably in the range of 75 to 125 ° C. The drying times are preferably in the range of 2 to 60 h, more preferably in the range of 6 to 48 hours, more preferably from 12 to 36 h and even more, preferably from 18 to 30 h.
[081] According to the inventive process, the Zeolitic material crystallized in step (2), optionally, can be submitted to at least one step of an ion exchange procedure, in which the term "ion exchange", according to The present invention generally refers to unclassed ionic elements and / or molecules contained in the Zeolitic material. Preferably, the unframed ionic element comprises one or more of one or more alkali metals M preferably comprised in the Zeolitic material having a CHA-like frame structure, more preferably Na and / or K and even more preferably Na.
[082] In general, any conceivable ion exchange procedure with all possible ionic elements and / or molecules can be conducted on the Zeolitic material, with the exception of the organic structure directing agents specifically used in the synthesis of zeolitic materials, having a frame structure of the type CHA, in particular specific alkylammonium tetra compounds, dialkyl amines, heterocyclic amines, including combinations of two or more of them, and / or related to organotemplates such as any suitable N-alkyl-3-quinuclidinol compound, N, N compound, N-trialkyl-exoaminonorbornane, composed of N, N, N-trimethyl-1-adamantylamonium, composed of N, N, N-trimethyl-2-adamantylamonium, N, N, N-trimethylcyclohexylammonium compound, composed of N, N- dimethyl-3,3-dimethylpiperidinium, composed of N, N-methylethyl-3,3-dimethylpiperidinium, composed of N, composed of N-dimethyl-2-methylpiperidinium, composed of 1,3,3,6,6-pentamethyl- 6-azonium-bicycles (3.2.1) octane, composed of N, N-dimet ilcyclohexylamine or any appropriate compound of N, N, N-trimethylbenzylammonium, including combinations of two or more of the same. Preferably, as ionic elements at least one cation and / or cationic element is employed which is preferably selected from the group consisting of H +, NH4 +, Sr, Zr, Cr, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more of them, most preferably from the group consisting of H +, NH4 +, Sr, Cr, Fe, Co, Ni, Cu, and mixtures of two or more of and even more preferably from the group consisting of H +, NH4 +, Fe, Cu, and mixtures of two or more of them. Preferably, the Zeolitic material is first ionically exchanged with H + and / or NH4 + and more, preferably with NH4 +, before being subjected to additionally an ion exchange procedure, more preferably before being subjected to ion exchange with at least one cation and / or cationic element selected from the group consisting of Sr, Zr, Cr, Fe, CoNi, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au and mixtures of two or more, more preferably from the group consisting of Sr, Cr, Fe, Co, Ni, Cu and mixtures of two or more of the same, in which even more preferably at least one cation and / or cationic element comprises or preferably consists of Cu and / or Fe and preferably Cu .
[083] In general, the optional washing and / or isolation and / or ion exchange procedures comprised in the inventive process can be conducted in any conceivably order and repeated as often as desired.
[084] Therefore, according to preferred embodiments of the present invention, the organotemplate-free synthetic process for the production of a Zeolitic material having a CHA-type frame structure additionally comprises one or more of the following steps of (3), isolating the Zeolitic material having a CHA type frame structure, preferably by filtration, and / or (4) washing the Zeolitic material having a CHA type frame structure, and / or (5) drying the Zeolitic material having a frame structure of the CHA type, and / or (6) subjecting the Zeolitic material having a CHA type frame structure to an ion exchange procedure, in which steps (3) and / or (4) and / or (5) and / or (6) can be conducted in any order, and in which one or more of said steps is preferably repeated one or more times.
[085] Furthermore, according to particularly preferred modalities of the inventive process including at least one step (6) of subjecting the Zeolitic material having a CHA-like frame structure to an ion exchange procedure, it is additionally preferable that at least a step (6) to at least one non-framed ionic element contained in the zeolitic material having a CHA type frame is exchanged by means of ions, preferably at least one cation and / or cationic element, in which at least one cation and / or cationic element is preferably selected from the group consisting of H +, NH4 +, Sr, Zr, Cr, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more of the same, more preferably from the group consisting of H +, NH4 +, Sr, Cr, Fe, Co, Ni, Cu, and mixtures of two or more of the same, more preferably from the group consisting of H +, NH4 +, Fe, Cu, and mixtures of two or more of the same, in which even more preferably at least one cation and / or cationic element is Cu and / or Fe and preferably Cu, wherein said at least one non-ionic frame element is preferably one or more alkali metals, more preferably Na and / or K and even more preferably Na.
[086] According to an additional modality of the inventive process, the crystallized Zeolitic material in step (2) is directly subjected to at least one drying step, preferably spray granulation and or spray drying, without isolation, washing or drying of the Zeolitic material in advance. Directly, by submitting the mixture obtained from step (2) of the inventive process to a spray drying or granulation stage, spraying has the advantage that isolation and drying are performed in a single stage. Consequently, in accordance with this embodiment of the present invention, an even more preferred process is provided in which not only avoid removal of organotemplate compounds, but also the number of post-synthesis examination steps is minimized, as a result of which organotemplate-free zeolitic material having a CHA-like frame structure can be obtained from a highly simplified process.
[087] According to an additional embodiment of the present invention, the Zeolitic material obtained from crystallization in step (2) is subjected to at least one insulating step before being subjected to at least one ion exchange procedure, preferably at least an insulating step followed by at least one washing step and much more preferably at least one isolating step followed by at least one washing step followed by at least one drying step.
[088] In the process of the present invention, it is preferred that a calcination step is not employed. In general, a calcination step involves heating the crystallized Zeolitic material according to step (2) above a temperature of 500 ° C. More preferably, a process according to the present invention for the production of a Zeolitic material having a CHA type frame structure which does not comprise a calcination step refers to processes, wherein the Zeolitic material crystallized according to step (2) is not subjected in a subsequent step to a temperature above 450 ° C, more preferably 350 ° C, more preferably 300 ° C, more preferably at 250 ° C, more preferably at 200 ° C and even more preferably at 150 ° C. According to the present invention it is particularly preferred that after the completion of step (2) of the inventive process, in which the crystallized Zeolitic material is at room temperature, said material is subsequently not subject to any heating process normally or properly carried out for removing organotemplates form a Zeolitic material having a CHA-type frame structure. Within the scope of the present invention, a Zeolithic material that is "non-calcined" is one that has not been subjected to any of the aforementioned calcination procedures.
[089] In general, the Zeolitic material having a CHA frame structure Obtained according to the inventive process can be any conceivable CHA frame zeolite comprising YO2, X2O3, and optionally comprising Z2O5, where Y is a tetravalent element, X is a trivalent element, and Z is a pentavalent element.
[090] Furthermore, the present invention relates to a synthetic zeolitic material of free organotemplate having a CHA type frame structure which is also obtained by the process according to the present invention or by any conceivable process which leads to a Zeolitic material having a CHA-like frame structure as can be obtained according to the inventive process. According to particularly preferred embodiments, the organotemplate-free synthetic Zeolitic material having a CHA-type frame structure is a non-calcined Zeolitic material which is also obtained by the process according to the present invention or by any conceivable process which leads to a Zeolitic material having a CHA-like frame structure as can be obtained according to the inventive process. Within the scope of the present invention, a material which is designated as a "synthetic" material does not mean that the material designated as such may not occur naturally in nature. In particular, a "synthetic" material only indicates that it is artificial, but it does not exclude that the material as such can occur naturally. Therefore, by way of example, the present invention also relates to a synthetic Chazabite. In this regard, it is further noted that, within the scope of the present invention, the term "organotemplate-free Zeolitic material" is synonymous with "organotemplate-free Zeolitic synthetic material".
[091] Therefore, the present invention also relates to an organotemplate-free synthetic zeolitic material having a CHA-type frame structure which is obtained and / or obtainable according to the inventive process and in particular according to the modalities or preferential arrangements described in this application.
[092] In addition, the present invention also relates to an organotemplate-free Zeolitic synthetic zeolitic material, as such, having a CHA-like frame structure comprising YO2, X2O3, and optionally, comprising Z2O5, wherein said Zeolitic material is non-calcined and in which if the CHA frame structure does not contain Z2O5, then the CHA frame structure has a YO2: X2O3 molar ratio of 7 or greater than 7. Thus, it was discovered that as opposed to the state of the art discussed in the introductory part of the application, an organotemplate-free synthetic zeolitic material having a CHA-type frame structure comprising YO2 and X2O3 can be obtained according to the present invention in which the YO2: X2O3 molar ratio can exhibit high and intermediate values of 7 or greater than 7. In addition, it has been found that a free zeolitic synthetic organotemplate material having a CHA-like frame structure can be provided other than very restricted and compact structures. currently provided for in the technique made possible by the use of specific inter-zeolitic transformations.
[093] According to preferred embodiments of the present invention in which the CHA frame structure does not contain Z2O5, the YO2: X2O3 molar ratio of the CHA frame structure ranges from 7 to 200, preferably from 7.5 to 100, plus preferably from 5 to 50, more preferably from 8.5 to 30, more preferably from 9 to 20, and even more preferably from 9.3 to 17. According to particularly preferred embodiments of the present invention, however, YO2: molar ratio of X2O3 of the CHA frame structure ranges from 9.5 to 15.
[094] According to specific modalities of the present invention in which the structure of the CHA frame of the zeolitic synthetic material free of the zeolitic organotemplate additionally comprises Z2O5 in addition to YO2 and X2O3, there is, in general, no particular restriction on YO2: molar ratios of X2O3 exhibited by such materials, so that the YO2: molar ratio of X2O3 in such inventive materials can have any conceivable value. According to particular embodiments of the present invention in which the CHA-type frame structure additionally comprises Z2O5 in addition to YO2 and X2O3, the CHA-type frame structure then has a molar ratio of YO2: nX2O3: pZ2O5, where the value for the ratio (1 + 2p) :( np) can have any conceivable value. Thus, by way of example, the value for the ratio (1 + 2p) :( np) can be 1 or greater than 1, where it is preferred that said value be 2 or greater than 2, more preferably 3 or greater than 3 and even more preferably 5 or greater than 5, and even more preferably 7 or more than 7. Thus, according to preferred embodiments of the inventive process, the value for the proportion (1 + 2p) :( np) of seed crystals additionally comprising Z2O5 can range anywhere from 1 to 500, more preferably from 2 to 400, more preferably from 3 to 300, more preferably from 5 to 250, more preferably from 7 to 200, more preferably from 7.5 to 100, most preferably from 8 to 50, more preferably from 8.5 to 30, more preferably from 9 to 20 and even more, preferably between 9.3 to 17 and even more, preferably from 9.5 to 15. According to an alternatively preferred modality, where the CHA frame structure comprises Z2O5, the value for proposing it tion (1 + 2p) :( n- p) is in the range from.
[095] Within the scope of the present invention, unless otherwise specified, the term "organotemplate-free Zeolitic material" as used to refer to organotemplate-free Zeolitic material in accordance with preferred embodiments of the present invention designates both the organotemplate-free zeolitic material having a CHA-type frame structure which is obtained and / or obtainable according to the inventive process, as well as the organotemplate-free zeolitic material as such, having a CHA-type frame structure comprising YO2 , X2O3, and optionally comprising Z2O5, where Y is a tetravalent element, X is a trivalent element and Z is a pentavalent element, where if the CHA frame structure does not contain Z2O5, the CHA frame structure then has a YO2: X2O3 molar ratio of 7 or greater than 7, and in which said Zeolitic material is preferably uncalcined.
[096] According to the present invention, there is no particular restriction on the CHA-type frame structure exhibited by the inventive materials provided that the organotemplate-free zeolitic material having a CHA-type frame structure exhibits a typical diffraction pattern of x-rays of a CHA frame structure in particular with respect to reflections and their positions of degree 2 θ with respect to each other. Thus, in principle, provided that the diffraction pattern is typical of a CHA-type frame structure, there is no particular restriction with respect to the actual position of the reflections measured as angle 2 θ, nor with respect to the intensities of the individual reflections in relation to each other. According to the preferred embodiments of the present invention, however, the first reflection in the x-ray diffraction pattern of the zeolitic material having a CHA-type frame structure, that is, the reflection, having the smallest angle value 2 θ is the reflection having the highest intensity among all measured reflections, that is, the reflection measured at the 2 θ lowest diffraction angle has an intensity of 100%. In addition, when using Cu K (alpha 1) radiation, it is more preferred that the diffraction angle 2 θ having an intensity of 100% is comprised in the range of 5 to 15 ° 2 θ in which more preferably, this more intense reflection is comprised in the range of 8 to 12 ° 2 θ, more preferably from 9 to 10.5 ° 2 θ, more preferably from 9.2 to 10 ° 2 θ, more preferably from 9.5 to 9.7 ° 2 θ and still more, preferably from 9.55 to 9.65 ° 2 θ. According to particularly preferred embodiments of the present invention, the most intense reflection on the diffraction pattern of organotemplate-free zeolitic material having a CHA-type frame structure when using Cu K (alpha 1) radiation is comprised in the range of 9.58 to 9.62 ° 2 θ.
[097] Therefore, according to the preferred embodiments of the present invention, the CHA frame structure of the inventive zeolitic material exhibits an X-ray diffraction pattern in which the most intense reflection, having an intensity of 100% has an angle of 2θ diffraction in the range of 5 to 15, preferably from 8 to 12, more preferably from 9 to 10.5, more preferably from 9.2 to 10, more preferably from 9.5 to 9.7, most preferably from 9.55 at 9.65 and even more preferably from 9.58 to 9.62, where the diffraction angle 2θ is obtained using Cu K (alpha 1) radiation.
[098] Regarding the 29Si MAS NMR of the inventive Zeolitic material, there is no particular restriction on the number and / or ppm values and / or respective relative intensities of the signals displayed in the NMR spectrum. According to preferred embodiments of the present invention, the 29Si MAS NMR comprises a first peak (P1), in the range of -96 to -98.8 ppm, a second peak (P2), in the range of -102 to -104 , 5 ppm and a third peak (P3), in the range of -109 to -111 ppm, in which the integration of the first, second and third peaks in the 29Si MAS NMR of the Zeolitic material offers a proportion of integration values P1: P2 : P3 of (0.35 - 0.55): 1: (0.1 - 1.8). In particular, the -109 ppm signal of the 29 Si MAS NMR corresponds to structures Q4, where the respective signals in ppm of -103 and -98 are assigned to structures Q3, or Q4.
[099] According to particularly preferred modalities, the first peak (P1) in the 29Si MAS NMR of the inventive Zeolitic material is comprised in the range of -96.5 to -98.5 ppm, more preferably from -96.8 to -98 , 2 ppm more preferably from -97 to -98 ppm and even more preferably from -97.2 to -97.8 ppm. However, it is particularly preferred according to the present invention that the first peak (P1) in the 29Si MAS NMR is in the range of -97.4 to -97.6 ppm. In addition, the second peak (P2) in the 29Si MAS NMR of the inventive Zeolitic material is preferably comprised in the range of -102.5 to -104 ppm, more preferably from -102.8 to -103.7 ppm and even more, preferably from -103 to -103.5 ppm, in which, according to particularly preferred modalities, the second peak (P2) is in the range of -103.2 to -103.4 ppm Finally, it is additionally preferable that the third peak (P3) ) in the 29Si MAS NMR of the inventive Zeolitic material is comprised in the range from -108.5 to -110.5 ppm, more preferably from -109 to-110 ppm, more preferably from -109.1 to -109.7 ppm and even more, preferably from -109.2 to -109.6 ppm. According to the particularly preferred modalities, however, third peak (P3) in the 29Si MAS NMR is in the range of -109.3 to -109.5 ppm.
[100] Furthermore, as for the integration of the first, second and third peaks no29 Si MAS NMR of the Zeolitic material offering a proportion of the integration values P1: P2: P3, according to particularly preferred modalities, this proportion varies preferably from (0.4 - 0.5): 1: (0.25 - 1.5), more preferably (0.42 - 0.49): 1: (0.4 - 1.2), more preferably (0.43 - 0.48): 1: (0.5 - 0.9), more preferably (0.435 - 0.475): 1: (0.55 - 0.7) and even more preferably (0, 45 - 0.47): 1: (0.6 - 0.65). According to particularly preferred embodiments of the present invention, the proportion of the integration values P1: P2: P3 varies from (0.455-0.465): 1: (0.62 - 0.64).
[101] Regarding the 27Al MAS NMR spectrum of inventive zeolitic materials having the CHA-type frame structure, again, there is no particular restriction on the number and / or respective ppm values and / or respective signal intensities which may be included in the NMR spectrum. According to preferred embodiments of the present invention, however, the 27Al MAS NMR spectrum of the inventive materials comprises a peak (P '1) in the range of -54.5 to -57.5 ppm. More specifically, the signal at about 55 ppm in the 27Al MAS NMR spectrum corresponds to tetrahedrally coordinated Al sites. According to the present invention, it is additionally preferred that the peak (P'1) in the 27Si MAS NMR spectrum of the inventive Zeolitic material is in the range of from -55 to -57 ppm, more preferably from -55 to -56 .8 ppm, more preferably from -55.7 to -56.5 ppm and even more, preferably from -55.9 to -56.3 ppm. According to particularly preferred modalities, the peak (P'1) in the 27Al MAS NMR spectrum of the inventive Zeolitic materials is in the range of -56 to -56.2 ppm.
[102] There is no specific restriction according to the present invention as to the standard used in the 29Si and 27Al MAS NMR experiments to obtain the respective values for the chemical change in ppm in the 29 Si and 27Al MAS NMR spectrum according to particular modalities and preferred embodiments of the present invention, in which an external standard is used, preferably. According to particularly preferred modalities, the external standard used in the 29 Si MAS NMR experiment is the polymer Q8M8, in which the resonance of the trimethylsilyl M group is 12.5 ppm. Regarding the 27Al MAS NMR experiment, on the other hand, a 1 M aqueous solution of AlCl3 is used as an external reference zero. Thus, according to the present invention, the chemical displacement values in ppm defined in the present application concerning the 29Si and 27Al MAS NMR spectrum of the inventive zeolitic materials having a CHA-type frame structure are preferably based on the use of the polymer Q8M8 as a external secondary standard in the 29 Si MAS NMR experiment, in which the resonance of the trimethylsilyl M group is set at 12.5 ppm as well as on the use of a 1 M aqueous solution of AlCl3 as an external reference zero in the 27Al MAS NMR experiment , respectively.
[103] According to the present invention the organotemplate-free zeolitic material having a CHA-type frame structure comprises YO2. In principle, Y represents any conceivable tetravalent element, Y representing one or more tetravalent elements. Preferred tetravalent elements according to the present invention include Si, Sn, Ti, Zr and Ge and combinations thereof. More preferably, Y represents Si, Ti or Zr or any combination of said tetravalent elements, even more preferably for Si, and / or Sn. According to the present invention, it is particularly preferred that Y represents Si.
[104] In addition, the organotemplate-free zeolitic material having a CHA-like frame structure comprises X2O3. Again, in principle, X represents any conceivable trivalent element, X represents one or more trivalent elements. Preferred trivalent elements according to the present invention include Al, B, em and Ga and combinations thereof. More preferably, X represents Al, B, or In, or any combination of said trivalent elements, even more preferably Al and / or B. According to the present invention, it is particularly preferred that X represents Al.
[105] Finally, according to the present invention, the organotemplate-free zeolitic material having a CHA-type frame structure optionally comprises Z2O5, where Z represents any conceivable pentavalent element, Z represents one or more pentavalent elements. Preferred pentavalent Z elements according to the present invention include P, As, Sb, Bi, V, Nb, Ta and combinations of two or more of the same. More preferably, Z represents P, As, V and combinations of two or more of the same, wherein even more preferably Z comprises P or As. According to particularly preferred embodiments, Z comprises P, where it is particularly preferred that Z represents P.
[106] Within the scope of the present invention, an "organotemplate-free" zeolitic material refers to a zeolitic material, which is substantially free of organotemplate materials, where "substantially" as employed in the present invention concerns the amount of one or more organotemplates contained in the zeolitic material indicates an amount of 0.1% by weight or less than one or more organotemplates, preferably 0.05% by weight or less, more preferably 0.001% by weight or less, more preferably 0, 0005% by weight or less and even more preferably 0.0001% by weight or less of the same. Said amounts of one or more organotemplates, if all present in the zeolitic material, can also be indicated as "impurities" or "traces" within the scope of the present invention. Therefore, according to the present invention, the zeolitic material contains no more than an impurity of an organic structure steering agent specifically used in the synthesis of zeolitic materials, having a CHA-like frame structure, in particular specific tetraalkylammonium salts and / or related organotemplate such as for example any suitable alkylammonium tetra compound, dialkyl amines, heterocyclic amines, including combinations of two or more of them, and / or related to organotemplates such as any suitable N-alkyl-3-quinuclidinol compound, N, N, N-trialkyl-exoaminonorbornane compound, N, N, N-trimethyl-1-adamantylamonium compound, N, N, N-trimethyl-2-adamantylamonium compound, N, N, N-trimethylcyclohexylammonium compound, N, N-dimethyl-3,3-dimethylpiperidinium compound, N, N-methylethyl-3,3-dimethylpiperidinium compound, N compound, N-dimethyl-2-methylpiperidinium compound, 1,3,3 compound, 6,6-pentamethyl-6-azonium-bicycles (3.2 .1) octane, compound of N, N-dimethylcyclohexylamine or any appropriate compound of N, N, N-trimethylbenzylammonium. Such an impurity can, for example, be caused by organic structure steering agents, still present in seed crystals used in the inventive process or in any other process by which the Zeolitic material according to the present invention can be obtained.
[107] According to the present invention, the organotemplate-free synthetic zeolitic material having a CHA-type frame is preferably uncalcined, in which, with the exception of the conditions under which it is crystallized, the Zeolitic material has a frame structure of the CHA type according to the present invention has not been subjected to a heating process normally or properly conducted to remove organotemplates from a Zeolitic material having a CHA type frame structure.
[108] In accordance with the present invention, inventive zeolitic materials having a CHA-type frame structure may contain extra framework ions, wherein said ions preferably contain one or more metals, more preferably one or more alkali metal M. according to preferred modalities containing one or more alkali metals M, it is additionally preferred that said one or more metals are selected from the group consisting of Li, Na, K, Rb and Cs and combinations of two or more of the same, in that most preferably M is Na and / or K, and even more preferably M is Na.
[109] In addition, according to preferred embodiments of the present invention, where the zeolitic material free of the zeolitic organotemplate comprises one or more alkali metals M as non-framed elements, the M: X2O3 molar ratio preferably ranges from 0.05 to 10, more preferably from 0.1 to 7, more preferably from 0.5 to 5, more preferably from 1 to 3.5, most preferably from 1.5 to 3 and even more preferably from 1.8 to 2.8 .
[110] According to the present invention, it is additionally preferred that when the zeolitic material free of the zeolitic organotemplate comprises one or more alkali metals M as unframed elements. There is no particular restriction according to the present invention as to the particular amount of alkali metal M which can be contained as an element not framed in the Zeolitic material. Thus, in principle, the M: X2O3 molar ratio can have any conceivable value. Accordingly by way of example, the M: molar ratio of X2O3 can vary anywhere from 0.05 to 10, where it is preferred that the M: molar ratio of X2O3 ranges from 0.1 to 7, preferably from 0.5 to 5, more preferably from 1 to 3.5, more preferably from 1.5 to 3, more preferably from 1.8 to 2.8.
[111] According to preferred modalities, at least a part of the alkali metals M optionally present in the Zeolitic material having a CHA-type frame structure are replaced by one or more cation and / or cationic element. In general, any cation and / or cationic element can replace alkali metals M, where cations and / or cationic elements are preferred which are suitable for ion exchange in Zeolitic material, with the exception of organic structure steering agents specifically used in synthesis of zeolitic materials, having a CHA-like frame structure, in particular specific tetra alkylammonium compounds, dialkyl amines, heterocyclic amines, including combinations of two or more of them, and / or related to organotemplates such as any N-alkyl compound -3-quinuclidinol suitable, Compound of N, N, N-trialkyl-exoaminonorbornane, compound of N, N, N-trimethyl-1-adamantylamonium, compound of N, N, N-trimethyl-2-adamantylamonium, N, N, Trimethylcyclohexylammonium N-compound, N, N-dimethyl-3,3-dimethylpiperidinium compound, N, N-methylethyl-3,3-dimethylpiperidinium compound, N compound, N-dimethyl-2-methylpiperidinium compound, composed of 1,3,3,6,6-pentame tyl-6-azonium-bicyclo (3.2.1) octane, composed of N, N-dimethylcyclohexylamine or any appropriate compound of N, N, N-trimethylbenzylammonium.
[112] Preferably, one or more cations and / or cationic element is selected from the group consisting of H +, NH4 +, Sr, Zr, Cr, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more of the same, more preferably from the group consisting of H +, NH4 +, Sr, Cr, Fe, Co, Ni, Cu, and mixtures of two or more of the same, more preferably from the group consisting of H +, NH4 +, Fe, Cu, and mixtures of two or more of them, and even more preferably in which at least a part of the alkali metal atoms M is replaced by Fe and / or Cu, preferably by Cu.
[113] In accordance with preferred embodiments of the present invention, at least a part of the Y atoms in the CHA-type frame are replaced isomorphically by one or more elements. In general, Y can be isomorphically replaced by any suitable elements, where one or more elements are preferably selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, Be, and mixtures of two or more of the same, more preferably in which one or more elements are selected from the group consisting of B, Fe, Ti, Sn, Zr, Cu, and mixtures of two or more of the same, in which even more preferably one or more elements is Fe and / or Cu, preferably Cu.
[114] In general, there is no particular restriction according to the present invention as to the part of Y atoms, which can be isomorphically substituted within the CHA type framework of the preferred organotemplate-free zeolitic material. According to preferred embodiments, the molar ratio of YO2 to one or more element ranges from 5 to 100, preferably from 10 to 80, more preferably from 20 to 60 and even more preferably from 25 to 50.
[115] Therefore, as described above, the organotemplate-free zeolitic material according to the present invention may comprise one or more of any zeolites having a CHA-type frame structure, provided that said frame structure comprises YO2 and X2O3, and that if the CHA frame does not contain Z2O5, then the CHA frame structure has a YO2: X2O3 molar ratio of 7 or greater than 7. According to the modalities of the present invention, the organotemplate-free zeolitic material comprises one or more zeolites selected from the group consisting of (Ni (deta) 2) -UT-6, Chabazite, | Li-Na | [Al-Si-O] -CHA, DAF-5, Chabazite-Na, Chabazite-K LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO-34, SAPO-47, SSZ-13, SSZ -62, UiO- 21, Willhndersonite, ZK-14, ZYT-6 and combinations of two or more of the same, preferably from the group consisting of Chabazite, | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, Chabazite-K, SAPO-34, SAPO-47, SSZ-13, SSZ-62 and combinations of two or more of the same, more preferably from the group consisting of Chabazite , | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, more preferably from the group consisting of Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, in which even more preferably the seed crystals having a CHA frame structure comprise Chabazite-Na and / or SAPO-34 and preferably Chabazite-Na.
[116] Depending on the specific needs of your application, the Zeolithic material of the present invention can be used as such, as in the form of a powder, a spray powder or a spray granulate obtained from the separation techniques described above, by decantation, filtration, centrifugation or spraying.
[117] In many industrial applications, it is often desired by the user not to use the Zeolitic material as a powder or pulverized material, that is, the Zeolitic material obtained by separating the material from its mother liquor, optionally including washing and drying and calcination subsequent, but a Zeolitic material which is further processed to give molds. Such molds are required particularly in many industrial processes, for example, in many processes in which the Zeolitic material of the present invention is employed as a catalyst or absorbent.
[118] Therefore, the present invention also relates to a mold comprising the inventive Zeolitic material.
[119] In general, the powder or pulverized material can be formed without any other compounds, for example, by the appropriate compaction to obtain molds of a desired geometry, for example, inserts, cylinders, spheres or the like.
[120] Preferably, the powder or pulverized material is mixed with or coated with a suitable refractory binder. In general, suitable binders are all compounds which give them adhesion and / or cohesion between the particles of zeolitic material to be bonded which go beyond the physisorption which can be present without a binder. Examples of such binders are metal oxides, such as, for example, SiO2, Al2O3, TiO2, ZrO2 or MgO or clays or mixtures of two or more of these compounds. Naturally occurring clays that can be used include the Montmorillonite and kaolin family, which families include subentonites and kaolin commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is kaolinite, halosite, diquite, nacrite or anauxite. Such clays can be used in the raw state, as originally extracted or initially subjected to calcination, acid treatment or chemical modification. In addition, the Zeolitic material according to the present invention can be composed of a porous matrix material such as silica-alumina, silica-magnesia, zirconia-silica, silica-thorium, silica-beryllium and silica-titanium, as well as ternary compositions such as silica-alumina-thorium, silica-alumina-zirconia, silica-alumina-magnesia and zirconia-silica-magnesia.
[121] The Zeolitic material of the present invention can also be provided in the form of extrudates, pellets, tablets or particles of any other suitable form, for use as a packaged bed of particle catalyst, or in the form of parts such as plates, saddles, tubes or the like.
[122] Also, preferably, the powder or the pulverized material, optionally, after mixing or coating with a suitable refractory binder as described above, is formed into a paste, for example, with water, which is deposited on a suitable refractory carrier. . The paste can also comprise other compounds, for example, stabilizers, defoamers, promoters or the like. Typically, the carrier comprises a member, often referred to as a "honeycomb" carrier, comprising one or more refractory bodies having a plurality of fine gas, parallel gas flow passage extending through there. Such carriers are well known in the art and can be made of any suitable material such as cordierite or the like.
[123] In general, the Zeolitic material described above can be used as a molecular sieve, absorbent, catalyst, catalyst support or binder. For example, Zeolitic material can be used as a molecular sieve for dry or liquid gases, for selective molecular separation, for example, for the separation of hydrocarbons or amines; as an ion exchanger; as a chemical carrier; as an absorbent, in particular as an absorbent for the separation of hydrocarbons or amines; or as a catalyst. Most preferably, the Zeolitic material according to the present invention is used as a catalyst and / or as a catalyst support.
[124] According to a preferred embodiment of the present invention, the Zeolitic material of the invention is used in a catalytic process, preferably as a catalyst and / or catalyst support and most preferably as a catalyst. In general, the Zeolitic material of the invention can be used as a catalyst and / or catalyst support in any conceivable catalytic process, in which processes involving the conversion of at least one organic compound is preferred, more preferably of organic compounds, comprising at least a bond of carbon - carbon and / or carbon - oxygen and / or carbon - nitrogen, more preferably organic compounds, comprising at least one oxygen bond of carbon - carbon and / or carbon-oxygen and even more, preferably of organic compounds, comprising at least one carbon-carbon bond. In preferred embodiments of the present invention, the Zeolitic material is used as a catalyst and / or as a catalyst support in a fluid catalytic cracking (FCC) process.
[125] Furthermore, it is preferred according to the present invention, that the Zeolitic material is used as a catalyst for the production of light olefins from non-petroleum raw material by converting oxygenated compounds, such as lower alcohols (methanol, ethanol ), ethers (dimethyl ether, methyl ethyl ether), esters (dimethyl carbonate, methyl metanoate) and the like for olefins and especially in the conversion of lower alcohols to light olefins. According to particularly preferred embodiments, the Zeolitic material of the present invention is used in the conversion of methanol to olefins (MTO)
[126] According to an additional embodiment of the present invention, the Zeolitic material of the invention is used, preferably, in a catalytic process that involves the conversion of at least one compound comprising at least one nitrogen-oxygen bond. Particularly preferred according to the present invention is the use of Zeolitic material as a catalyst and / or catalyst support in a selective catalytic reduction (SCR) process for the selective reduction of NOx nitrogen oxides; for the oxidation of NH3, in particular for the slip oxidation of NH3 in diesel systems; for the decomposition of N2O. The term nitrogen oxides NOx, as used in the context of the present invention means nitrogen oxides, especially dinitrogen oxide (N2O), nitrogen monoxide (NO), dinitrogen trioxide (N2O3), nitrogen dioxide (NO2), dinitrogen tetroxide (N2O4), dinitrogen pentoxide (N2O5), nitrogen peroxide (NO3). According to particularly preferred embodiments of the present invention, the Zeolitic material used in a catalytic process that involves at least one compound comprising at least one nitrogen-oxygen bond comprises Cu and / or Fe and most preferably Cu.
[127] Therefore, the present invention also relates to a method for selectively reducing NOx nitrogen oxides by contacting a NOx containing stream with a catalyst containing the Zeolitic material according to the present invention under suitable reduction conditions; for an NH3 oxidation method, in particular NH3 oxidation slips in diesel systems, a NH3-containing stream comes in contact with a catalyst containing the Zeolitic material according to the present invention under suitable oxidizing conditions; for an N2O decomposition method by contacting a flow containing N2O with a catalyst containing the Zeolitic material according to the present invention under suitable decomposition conditions; for a method of controlling emissions in advanced emission systems, such as homogeneous charge compression ignition engines (HCCl) by contacting an emissions stream with a catalyst containing the Zeolitic material according to the present invention under suitable conditions; for an FCC fluid catalytic cracking process in which the Zeolitic material according to the present invention is employed as an additive; for a method of converting an organic compound by contacting said compound with a catalyst containing the Zeolitic material according to the present invention under suitable conditions of conversion; for a "fixed source" process in which a catalyst containing the Zeolitic material according to the present invention is employed.
[128] Therefore, the present invention also relates to a method for selectively reducing NOx nitrogen oxides, in which a gas stream containing NOX nitrogen oxides, preferably also containing ammonium and / urea, is in contact with the zeolitic material according to the present invention or the Zeolitic material can be obtained or obtained according to the present invention, preferably in the form of a molded catalyst, even more preferably as a molded catalyst in which the Zeolitic material is deposited in a refractory support carrier even more suitable, preferably on a "honeycomb" carrier.
[129] The nitrogen oxides which are reduced using a catalyst containing the Zeolitic material according to the present invention or the Zeolitic material which can be obtained or obtained according to the present invention can be obtained by any process, for example, as a stream of gas waste. Among others, gas residue streams obtained in 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.
[130] More preferably, the zeolitic material according to the present invention also or the Zeolitic material which can be obtained or obtained according to the present invention, is used as a molded catalyst, even more preferably as a molded catalyst in which the material Zeolitic is deposited in a refractory support carrier suitable, even more, preferably in a "honeycomb" carrier, for the selective reduction of NOx nitrogen oxides, for example for the selective catalytic reduction of nitrogen oxides. In particular, the selective reduction of nitrogen oxides, in which the Zeolitic material according to the present invention is employed as a catalytically active material is carried out in the presence of ammonia or urea. While 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 engine and vehicle design and also typically contains the following main components: SCR catalyst containing the Zeolitic material according to the present invention; a urea storage tank; a urea pump; an urea metering system; a urea nozzle / injector; and a respective control unit.
[131] Furthermore, it is preferred according to the present invention that the Zeolitic material is used as a molecular trap for organic compounds. In general, any type of organic compound can be trapped in the Zeolitic material, where it is preferred that the compound be reversibly trapped, such that it can later be released from the Zeolitic material, preferably in which the organic compound is released - preferably without conversion - by an increase in temperature and / or a decrease in pressure. In addition, it is preferable that the Zeolitic material is used to trap organic compounds whose dimensions allow them to penetrate the micro-porous system of the molecular structure. In accordance with still further embodiments of the present invention, it is preferred that the trapped compounds are released upon at least partial conversion to a chemical derivative and / or to a decomposition product thereof, preferably to a thermal decomposition product thereof.
[132] When preparing specific catalytic compositions or compositions for different purposes, it is also conceivable to mix the Zeolitic material according to the present invention with at least one other catalytically active material or one being active with respect to its designated purpose. It is also possible to mix at least two different inventive materials which may differ in their YO2: molar ratio of X2O3, or as the case may be in their YO2: X2O3: molar ratio of Z2O5 when two or more different materials contain Z2O5, Z , preferably being phosphorus, in which the two different inventive materials are even more preferably in their SiO2: Al2O3 and / or SiO2: Al2O3: molar proportion of P2O5, and / or in the presence or absence of one or more additional metals such as one or more transition metals and / or specific amounts of an additional metal such as a transition metal, wherein according to particularly preferred embodiments, that or more transition metal comprises Cu and / or Fe, more preferably Cu. It is also possible to mix at least two different inventive materials with at least one other catalytically active material or one material being active with respect to its designated purpose.
[133] Also, the catalyst can be discarded on a substrate. The substrate can be any of those materials typically used for preparing catalysts and generally comprises ceramic or honeycomb. Any suitable substrate can be employed, such as a monolithic substrate of the type that has thin, parallel gas flow passages extending there through an inlet or an outlet face of the substrate, such that passages are opened for the flow of fluid there through (referred to as honeycomb flow through substrates). The passages, which are essentially narrow paths from your fluid inlet to your fluid outlet, are defined by the walls on which the catalytic material is laid out as a washable coating so that gases flowing through the passages come into contact with the material. catalytic. The flow passages of the monolithic substrate are thin-walled channels, which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures can contain about 60 to about 400 or more gas inlet openings (i.e., cells) per square inch (2.54 x 2.54 cm) in cross section.
[134] The substrate can also be a wall-flow filter substrate, where the channels are alternately blocked, allowing a gaseous stream to enter the channels in one direction (inlet direction), to flow through the channel walls and outlet channels from the other direction (exit direction). The catalyst composition can be coated on the flow or wall-flow filter. If a wall flow substrate is used, the resulting system will be able to remove particles together with polluting gases. The wall-flow filter substrate can be made from materials commonly known in the art, such as cordierite, aluminum titanate or silicon carbide. It will be understood that the loading of the catalytic composition onto a wall flow substrate will depend on substrate properties, such as porosity and wall thickness, and will typically be less than the load on a flow through substrate.
[135] The ceramic substrate can be made of any suitable refractory material, for example, cordierite, cordierite-alumina, silicon nitride, zircon mullite, spodumene, silica alumina magnesia, zirconium silicate, silimanite, a magnesium silicate , zircon, Petalite, alpha-alumina, an aluminum silicate and the like.
[136] Substrates useful for the catalysts of modalities of the present invention can also be metallic in nature and be composed of one or more metals or metal alloys. Metallic substrates can be used in various formats such as corrugated sheets or monolithic form. Suitable metal supports include heat-resistant metals and metal alloys such as titanium and stainless steel, as well as other alloys in which iron is a substantial or major component. Such alloys can contain one or more of nickel, chromium and / or aluminum, and the total amount of these metals can advantageously include at least 15% by weight.% Of the alloy, for example, 10-25% by weight.% Chromium, 3- 8% by weight.% Aluminum and up to 20% by weight.% Nickel. The alloys can also contain small amounts or traces of one or more metals such as copper, manganese, vanadium, titanium and the like. The metal surface or substrates can be oxidized at high temperatures, for example, 1000 ° C or higher, to improve the corrosion resistance of the alloys, forming an oxide layer on the surface of the substrates. Such high temperature-induced oxidation can improve the adhesion of the refractory metal oxide support and catalytically promote metallic components for the substrate.
[137] In alternative embodiments, Zeolitic material according to the present invention can be deposited on an open cell foam substrate. Such substrates are well known in the art and are typically formed of refractory metal or ceramic materials.
[138] Especially preferable is the use of a catalyst containing the Zeolitic material according to the present invention or the Zeolitic material which can be obtained or obtained according to the present invention for removing Nox nitrogen oxides from exhaust gases from engines internal combustion, in particular diesel engines, which operate under combustion conditions with air higher than that required for stoichiometric combustion, that is, to lean.
[139] Therefore, the present invention also relates to a method for the removal of NOx nitrogen oxides from the exhaust gases of internal combustion engines, in particular diesel engines, which operate under combustion conditions with higher air a required for stoichiometric combustion, that is, under inclined conditions, in which a catalyst containing the Zeolitic material according to the present invention or the Zeolitic material which can be obtained or obtained according to the present invention is employed as a catalytically active material.
[140] The present invention, therefore, relates to the use of the Zeolitic material of the invention, in particular in the field of field and / or catalysis and / or in the treatment of exhaust gases, where the treatment of exhaust gases said comprises of industrial and automotive exhaust gas. For these and other applications, the Zeolitic material of the present invention can by way of example be used as a molecular sieve, catalyst, and / or catalyst support.
[141] In embodiments of the present invention, therefore, it relates to the use of the Zeolithic material of the invention, in either catalysis and / or in the treatment of exhaust gases, the zeolitic material used in the treatment of exhaust gases said comprises treatment of exhaust gas. industrial and automotive exhaust. In a particularly preferred embodiment, the Zeolitic material used in the treatment of exhaust gases is composed in a hydrocarbon trap.
[142] Therefore, the present invention relates more to the use of a Zeolitic material in accordance with the present invention and in particular according to respective preferred and particularly preferred modalities, as defined in the present application, as a molecular sieve, as an adsorbent, for ion exchange, as a catalyst and / or as a support catalyst, preferably as a catalyst for selective catalytic reduction (SCR) of NOx nitrogen oxides; for the oxidation of NH3, in particular for the slip oxidation of NH de3 in diesel systems; for the decomposition of N2O; as an additive in catalytic fluid cracking (FCC) processes; and / or as a catalyst in organic conversion reactions, preferably in the conversion of alcohols to olefins and more, preferably in methanol for olefin catalysis (MTO). In accordance with the present invention it is however particularly preferred that the Zeolitic organotemplate-free material having a CHA-like frame structure is used as a catalyst for the selective catalytic reduction (SCR) of NOx nitrogen oxides. DESCRIPTION OF THE FIGURES
[143] In the respective 29Si and 27Al NMR spectra shown in the figures, ppm values are plotted along the abscissa, where the exact ppm values are indicated above the respective peaks. In addition, the integrals for the relative peak intensity are indicated below the respective peaks.
[144] X-ray diffraction patterns (XRD) shown in the figures, respectively, were measured using alpha-1Cu K radiation. In the respective diffractograms, the angle theta diffraction in ° is shown along the abscissa and the intensities are plotted along the ordinate.
[145] Figure 1A shows the X-ray diffraction pattern of sodium Chazabite seed crystals obtained by hydrothermal synthesis in example 1. As a reference, the diffractogram additionally includes a line pattern which is typical for the frame structure of the type TEA.
[146] Figure 1B shows the 29Si MAS NMR spectrum obtained for those of sodium Chazabite seed crystals obtained by hydrothermal synthesis in example 1.
[147] Figure 1C shows the 27Si MAS NMR spectrum obtained for those of sodium Chazabite seed crystals obtained by hydrothermal synthesis in example 1.
[148] Figure 1D shows the x-ray diffraction pattern of the Zeolitic material having a CHA-type frame structure obtained from targeted seed synthesis in Example 1.
[149] Figure 1E shows the Zeolitic material obtained from targeted seed synthesis in example 1 as obtained using scanning electron microscopy.
[150] Figure 1F shows the 29Si MAS NMR spectrum obtained for the zeolitic material having a CHA-like frame structure obtained from targeted seed synthesis in example 1.
[151] Figure 1C shows the 27Si MAS NMR spectrum of the Zeolitic material having a CHA-like frame structure obtained from targeted seed synthesis in Example 1.
[152] Figure 2A shows the x-ray diffraction pattern of the Zeolitic material having a CHA-type frame structure obtained from targeted seed synthesis in Example 1.
[153] Figure 2B shows the 29Si MAS NMR spectrum obtained for the zeolitic material having a CHA-like frame structure obtained from targeted seed synthesis in example 1.
[154] Figure 2C shows the 27Si MAS NMR spectrum obtained for the zeolitic material having a CHA-like frame structure obtained from targeted seed synthesis in example 2.
[155] Figures 3 shows the X-ray diffraction pattern of the H form of the Zeolitic material having a CHA-type frame structure obtained from targeted seed synthesis after ion exchange in Example3.
[156] Figures 4-7 shows the x-ray diffraction patterns of Zeolithic materials having a CHA-type frame structure obtained from targeted seed synthesis in Examples 4-7, respectively. EXAMPLES
[157] In the following examples, 29Si and 27Al solid-state NMR experiments were conducted on an Avance 300 spectrometer equipped with a wide-bore magnet (Bruker Biospin, Germany).
[158] For 29Si NMR solid state, samples were packaged in 7 mm rotors and measured under magic angle rotation at 5 kHz at room temperature. 29Si spectra were recorded using direct polarization with a 90 ° pulse, the acquisition of a 25 ms signal under heteronuclear dissociation of high-power protons and a recycling delay of 120 s. Spectra were referenced with the polymer Q8M8 as an external secondary standard, defining the resonance of the trimethylsilyl M group at 12.5 ppm. The spectra were processed with Bruker Topspin (Bruker Biospin, Germany).
[159] For 27Si NMR solid state, samples were packaged in 4 mm rotors and measured under magic angle rotation at 10 kHz at room temperature. 27Si spectra were recorded using direct polarization with a 15 ° pulse, a 20 ms signal acquisition and a 0.25 s recycle. Spectra were referenced with 1 mol / L of AlCl3 ^ 6H2O solution as a zero reference. The spectra were processed with Bruker Topspin (Bruker Biospin, Germany). EXAMPLE 1: PREPARATION OF CHAZABITE SEED CRYSTALS
[160] 16.5 kg of an aqueous solution of 1-adamantyltrimethyl ammonium hydroxide (13.4% by weight) and 570 g of sodium hydroxide were placed in a 60 l autoclave while stirring. After 30 min, 1,786 kg of aluminum triisopropanolate were added to them and the resulting mixture stirred for 1 h, after which 21.4 kg of LUDOX® AS40 (Aldrich) were added to the mixture which was then stirred an additional 30 minutes, thus providing a synthesis gel exhibiting a SiO2: Al2O3: Na2O: H2O: 33: 1: 1,63: 341: 2,35 molar ratio of ammonium 1-adamantyl trimethyl. The autoclave was then sealed closed and the synthesis mixture heated to 160 ° C using a heating inclination of 70 ° C / h after which the temperature was maintained for 30 h. After cooling to room temperature, the resulting suspension was neutralized to pH = 7 using nitric acid (10%), after which the resulting precipitate was filtered and washed with distilled water for washing water electroneutrality having a conductivity of less than 10 mS . The resulting filter cake was then impregnated with distilled water to support a solution with 10% by weight of solids. The paste was then spray dried at a temperature of 290 ° C, after which the resulting solid was heated to 600 ° C using a slope of 2 ° C / min and kept at that temperature for 5 h, thus providing 3 , 85 kg of crystalline sodium Chazabite as a white microcrystalline powder.
[161] Elemental analysis: Si: 37 g / 100 g Al: 2.2 g / 100 g Na: 1.1 g / 100 g
[162] Therefore, according to the elementary analysis, the SiO2: Al2O3 ratio of the product is approximately 32.4: 1.
[163] In Figure 1A, the XRD of the sodium Chazabite seed material is displayed, showing the diffraction pattern characteristic of the CHA-type zeolite frame structure.
[164] In figure 1B, the 29 Si MAS NMR of sodium Chazabite obtained from the template synthesis procedure is shown. As can be extracted from the NMR spectrum shown in figure 1B, three main peaks are observed at -99.0 ppm (P1), -103.8 ppm (P2) and -109.7 ppm (P3), respectively, in that the relative intensity of the peaks sustain a P1: P2: P3 ratio of 0.1296: 0.2994: 0.5710. In particular, the -109 ppm signal of the 29 Si MAS NMR corresponds to structures Q4, where the respective signals in ppm of -103 and -98 are assigned to structures Q3, or Q4.
[165] In Figure 1, the 27Al MAS NMR spectrum of the sodium Chazabite product is displayed revealing a peak at -54.2 ppm corresponding to the tetrahedrally coordinated Al sites of the Chazabite material obtained from template synthesis. SYNTHESIS OF SEED DIRECTION OF A CHA TYPE ZEOLIT
[166] 85.83 g of distilled water were placed in a 250 ml autoclave to which 2.38 g of NaAlO 2 and 3.04 g of sodium Chazabite seed crystals were added with stirring. 97.34 g of a glass solution of aqueous sodium water (34%; Woellner) was then added slowly. Finally, 11.51 g of LUDOX® AS40 (40% by weight of SiO2) was added and the resulting suspension further stirred for 2 min, thus providing a synthesis gel exhibiting a SiO2: Al2O3: Na2O: molar H2O ratio of 40 : 1: 11,5: 705. The resulting synthesis gel was then crystallized in the autoclave at 120 ° C, where it was kept for 120 h. After allowing to cool to room temperature, the suspension was filtered off and the filter cake washed three times with distilled water. The washed filter cake was then dried at 120 ° C for 25 hrs to provide 12.5 g of a Zeolitic material having the CHA frame structure as a white, microcrystalline powder.
[167] Elemental analysis: Si: 35 g / 100 g Al: 4.6 g / 100 g Na: 5.3 g / 100 g
[168] Therefore, according to the elementary analysis, the SiO2: Al2O3: Na2O ratio of the product is approximately 14.6: 1: 1.35.
[169] In Figure 1D, the XRD of the crystalline product obtained according to the organotemplate-free synthesis is shown, revealing a characteristic diffraction pattern of a CHA-type frame structure. Figure 1E shows a SEM image of the crystalline product.
[170] Thus, a Zeolitic material having the CHA-like frame structure can effectively be obtained using sodium Chazabite seed crystals obtained from synthesis using an organotemplate as a structural steering agent. In particular, a Chabazite-type Zeolitic material can be obtained, exhibiting an intermediate SiO2: molar Al2O3 ratio of about 15. Furthermore, said material can be obtained in relatively high purity, the remaining solid isolated from the reaction product, in largely attributed to silica and / or amorphous silicate.
[171] In Figure 1F, the 29 Si MAS NMR of the crystalline product obtained from the synthetic procedure is shown. As can be extracted from the NMR spectrum shown in figure 1F, three main peaks are observed at -98.1 ppm (P1), -103.3 ppm (P2) and -109.3 ppm (P3), respectively, in that the relative intensity of the peaks provide a P1: P2: P3 ratio of 0.2137: 0.4112: 0.3171. In particular, the -109 ppm signal of the 29 Si MAS NMR corresponds to structures Q4, where the respective signals in ppm of -103 and -98 are assigned to structures Q3, or Q4.
[172] In Figure 1G, the 27Al MAS NMR spectrum of the crystalline product is displayed revealing a peak at -55.9 ppm corresponding to tetrahedrally coordinated Al sites of the material obtained from organotemplate-free synthesis. The lowest peak -10.5 ppm is attributed to octahedrally coordinated aluminum of products and side impurities contained in the sample.
[173] Thus, when comparing the 29Si and 27Al MAS NMR spectra in figures 1B and 1C for Chazabite obtained from template synthesis with the corresponding spectra in figures 1F and 1G obtained for the present Zeolitic material having a CHA type frame structure as obtained from organotemplate-free synthesis, there are differences with respect to the ppm values at which corresponding peaks are observed. Considerable differences are observed with respect to the relative intensities of the peaks in the 29Si MAS NMR spectra. Taken together, it reflects a clearly different distribution of the Al- and Si- sites in the CHA frame structure obtained from organotemplate-free synthesis, so that the products can also be distinguished from materials obtained from template synthesis. In particular, this applies to calcined products as well, so that the inventive products can be clearly distinguished from zeolitic materials having the CHA-type frame structure obtained from template synthesis not only being the fact that the inventive products but also directly obtained from synthesis does not contain an organotemplate. Much more inventive materials can be distinguished from the former by a first single-frame CHA type architecture, particularly with regard to the distribution of Si and Al sites, thus providing new materials with unprecedented physical and chemical properties . EXAMPLE 2
[174] 81.28 g of distilled water was placed in a 250 ml autoclave after which 2.38 g of NaAlO2 and 3.04 g of sodium Chazabite seed crystals obtained from example 1 were added under stirring. Subsequently, 115.4 g of an aqueous sodium glass cup solution (34%; Woellner) was added slowly, after which the suspension was stirred an additional 2 min, thus providing a synthesis gel exhibiting a SiO2 : Al2O3: Na2O: molar H2O ratio of 40: 1: 13,4: 705. The autoclave was sealed then sealed closed and the synthesis mixture crystallized at 120 ° C at 120 h. After allowing to cool to room temperature, the resulting suspension was filtered off and the filter cake washed three times with distilled water. The washed filter cake was then dried at 120 ° C for 24 h to provide 10.4 g of Chazabite as a white, microcrystalline powder.
[175] Elemental analysis: Si: 28.7 g / 100 g Al: 5.6 g / 100 g Na: 4.4 g / 100 g
[176] Therefore, according to the elementary analysis, the SiO2: Al2O3: molar Na2O ratio of the product is approximately 9.8: 1: 0.92.
[177] Figure 2A shows the XRD of the crystalline product obtained from the organotemplate-free synthesis which exhibits a diffraction pattern characteristic of zeolitic materials having a CHA-like frame structure.
[178] Thus, as can be taken from the results of example 2, the use of a glass of sodium water alone as the source for SiO2 in the formed Chazabite material leads to a considerably higher crystallinity of the resulting product. However, it is evident from the x-ray diffraction pattern of the material obtained in example 2 that the resulting product contains slightly higher levels of crystalline impurities provisionally attributed to Mordenite.
[179] In figure 1B, the 29 Si MAS NMR of the crystalline product obtained from the synthetic procedure is shown. As can be extracted from the NMR spectrum shown in figure 2B, three main peaks are observed at -97.5 ppm (P1), -103.8 ppm (P2) and -109.4 ppm (P3), respectively, in that the relative intensity of the peaks sustain a P1: P2: P3 ratio of 0.2157: 0.4690: 0.2964.
[180] In Figure 2C, the 27Al MAS NMR spectrum of the crystalline product is displayed revealing a peak at -56.1 ppm corresponding to tetrahedrally coordinated Al sites of the material obtained from organotemplate-free synthesis.
[181] Thus, referring to the results shown and discussed in example1, the distinguishing characteristics of the zeolitic materials obtained according to the inventive process is also clearly evident when comparing the spectra obtained from 29Si and 27Al MAS NMR with the respective spectra of the samples Sodium Chazabite obtained from template synthesis shown in figures 1B and 1C, respectively. EXAMPLE 3 ION EXCHANGE OF ORGANOTEMPLATE-FREE ZEOLYTIC MATERIAL
[182] 7.44 g of the Chazabite material of example 1 was mixed with 7.44 g of the Chazabite material of example 2, thus forming a 1: 1 mixture. 14.88 g of ammonium nitrate were dissolved in 59.52 g of distilled water placed in a 250 ml flask, after which the Chazabite material mixture was added to the solution and the resulting mixture was then heated to 90 ° C for 2 h. After allowing to cool to room temperature, the solid material was filtered off and washed with distilled water until the wash water was free of nitrate. The filter cake was then dried at 120 ° C for 16 h after which it was then calcined by heating to 600 ° C using a slope of 1 ° C / min and keeping the material at this temperature for 5 h. The ion exchange procedure was then repeated once afterwards which yielded 12.11 g of a microcrystalline solid.
[183] Elemental analysis: Si: 37 g / 100 g Al: 6 g / 100 g Na: 0.04 g / 100 g
[184] Therefore, according to the elementary analysis, the SiO2: molar Al2O3 ratio of the product is approximately 11.9.
[185] Figure 3 shows the XRD of the H-form of the crystalline product obtained from ion exchange, where the diffraction pattern occurs, which maintains the CHA-type frame structure of the Zeolitic material. EXAMPLE 4
[186] 87.71 g of distilled water were placed in a 250 ml autoclave after which 3.57 g of NaAlO2 and 3.04 g of sodium Chazabite seed crystals obtained from example 1 were added under stirring. Subsequently, 91.12 g of sodium beaker solution (34% by weight) was added slowly to them. Finally, 15.7 g of LUDOX AS40 (40% by weight SiO2) were added, after which the solution was stirred for an additional 2 min, thus providing a synthesis gel exhibiting a SiO2: Al2O3: Na2O: ratio molar H2O of 27: 1: 7,7: 470. The autoclave was then sealed closed and the synthesis mixture heated to 120 ° C for 120 h for crystallization. After allowing to cool to room temperature, the solid product was filtered off and the filter cake washed three times with distilled water. The filter cake was then dried at 120 ° C for 24 h to obtain 15 g of organotemplate-free Chazabite.
[187] Figure 4 shows the XRD of the crystalline product obtained from the organotemplate-free synthesis in which the diffraction pattern is characteristic for the zeolitic material having a CHA-like frame structure. EXAMPLE 5
[188] The synthesis procedure of example 4, was repeated, in which the synthesis mixture was heated for 144 h at 120 ° C, thus providing 16.2 g of organotemplate-free Chazabite.
[189] Figure 5 shows the XRD of the crystalline product obtained from said example, in which it is evident that compared to example 4, in addition to obtaining a higher yield, the amount of minor crystalline impurities is reduced compared to the product obtained for example 4 of which XRD is shown in Figure 4. EXAMPLE 6
[190] 89.61 g of distilled water were placed in a 250 ml autoclave to which 4.77 g of NaAlO2 and 3.05 g of sodium Chazabite seed crystals as obtained from example 1 were then added and the mixture agitated. Subsequently, 84.87 g of a solution of a glass of aqueous sodium water (34% by weight) was added slowly, after which 19.9 g of LUDOX AS40 (40% by weight SiO2) was stirred in, and then the which the mixture was stirred an additional 2 min, thus providing a synthesis gel having a SiO2: Al2O3: Na2O: molar ratio of H2O of 20: 1: 5.8: 353. The resulting mixture was then heated in the autoclave under hydrothermal conditions at 120 ° C for 120 h. After allowing to cool to room temperature, the resulting suspension was filtered off and the filter cake washed three times with distilled water. The filter cake was dried at 120 ° C for 24 h, thus providing 19.6 g of Chazabite.
[191] Figure 6 shows the XRD of the crystalline product obtained from the organotemplate-free synthesis. In particular, in addition to exhibiting a standard diffraction characteristic for zeolitic materials, having the CHA-type frame structure, a certain amount of crystalline impurities can be noted which exceeds the amount of such impurities in the product obtained from examples 1, 2, 4 and 5, respectively. Thus, it is evident that synthesis gels employing a low SiO2: molar ratio of Al2O3 provides a product of slightly lower purity, in which, however, the predominant product obtained is the organotemplate-free material, having the CHA-type frame structure in in accordance with the present invention. EXAMPLE 7
[192] Example procedure 6 was repeated in which the synthesis gel was crystallized for 144 h at 120 ° C instead of 120 h of, thus obtaining 21.4 g of an organotemplate-free Chazabite containing solid product.
[193] Figure 7 shows the XRD of the crystalline product obtained from the organotemplate-free synthesis in which the diffraction pattern characteristic of the zeolitic material having a CHA-like frame structure remains the dominant characteristic. However, it is evident that a greater amount of amorphous product is produced compared to the product obtained from the example procedure 6. On the other hand, it appears that, compared to the Chazabite product obtained from example 6, the product of the present procedure provides less crystalline impurities which, in particular, are provisionally attributed to Mordenite by-product.
[194] Accordingly, a comparison of the examples can be taken, a constant reduction of SiO2: molar proportion of Al2O3 in the respective synthesis gels appears to be responsible for an increase in amorphous and / or crystalline by-products present in the reaction product. However, as in particular they can be taken from the x-ray diffraction patterns obtained for the respective crystallization products, the organotemplate-free zeolitic material, having the CHA-type frame structure according to the present invention remains the product predominant in all the synthetic procedures shown above. Consequently, the present invention provides a highly efficient and versatile method for the production of a highly profitable and organotemplate-free zeolitic material having the CHA-type frame structure which, as shown in the 29Si and 27Al spectroscopy MAS NMR results can be clearly distinguished from materials obtained according to a methodology that involves the use of organotemplates as structural steering agents as shown above to obtain the sodium Chazabite seed crystal material. DOCUMENTS CITED IN STATE OF TECHNIQUE
[195] US 7,067,108 B2.
[196] US 6,974,889 B1.
[197] Hasegawa et al., Journal of Membrane Science 2010, 347, 193-196.
[198] Li et al., Microporous and Mesoporous Materials 2011, 143, 270-276.

权利要求:
Claims (42)
[0001]
1. ORGANOTEMPLATE-FREE SYNTHETIC PROCESS FOR THE PRODUCTION OF A ZEOLYTIC MATERIAL having a CHA-type frame structure comprising YO2, X2O3, and optionally comprising Z2O5, characterized by said process comprising the steps of: (1) providing a mixture comprising one or more sources for YO2, one or more sources for X2O3, and seed crystals, having a CHA frame structure, in which the CHA frame structure of the seed crystals comprises YO2, X2O3, and optionally comprises Z2O5; and (2) crystallize the mixture obtained in step (1); where Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of the same, X is selected from the group consisting of Al, B, In, Ga and combinations of two or more of the same, and Z is selected from the group consisting of P, As, V and combinations of two or more of the same, where, optionally, one or more sources for Z2O5 are additionally provided in step (1) , and where the CHA frame structure of the seed crystals does not contain Z2O5, the seed crystals then have a molar ratio of YO2: X2O3 of 5 or greater than 5; wherein the mixture is heated in step (2) to a crystallization temperature ranging from 80 to 200 ° C; wherein the crystallization process in step (2) is conducted for a period ranging from 5 to 200 h; wherein the mixture provided in step (1) does not contain K.
[0002]
2. PROCESS, according to claim 1, characterized by the CHA frame structure of the seed crystals additionally comprising Z2O5 in addition to YO2 and X2O3, the seed crystals having a molar ratio YO2: nX2O3: pZ2O5, where the value for the ratio (1 + 2p) :( np) is 5 or greater than 5, where the value for the ratio (1 + 2p) :( np) preferably ranges from 5 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 20 to 50, more preferably from 25 to 40, more preferably from 28 to 35 and even more preferably from 29 to 33.
[0003]
PROCESS according to any one of claims 1 to 2, characterized in that the molar ratio YO2: X2O3 of the mixture provided in step (1) varies from 1 to 200, preferably from 2 to 150, more preferably from 5 to 100, more preferably from 10 to 70, more preferably from 15 to 50, more preferably from 20 to 45, and most preferably from 25 to 42.
[0004]
PROCESS according to any one of claims 1 to 3, characterized in that the mixture provided in step (1) comprises one or more alkali metals M, wherein one or more alkali metals M are preferably selected from the group consisting of Li, Na , K, Rb and Cs, more preferably from the group consisting of Li, Na, Rb and Cs, where more preferably the one or more alkali metals are Li and / or Na, and preferably Na.
[0005]
PROCESS according to claim 4, characterized in that the molar ratio M2O: YO2 in the mixture according to step (1) varies from 0.01 to 5, preferably from 0.05 to 2, more preferably from 0.1 to 1.5, more preferably from 0.15 to 1, more preferably from 0.2 to 0.5 and even more preferably from 0.25 to 0.35.
[0006]
6. PROCESS according to any one of claims 4 to 5, characterized by the molar proportions YO2: X2O3: M2O in the mixture according to step (1) vary from (5-100): 1: (0.5 - 50 ), preferably (10-70): 1: (1-30), preferably (15-50): 1: (2-20), preferably (20-45): 1: (4-15), and preferably (25-42): 1: (5-14).
[0007]
PROCESS according to any one of claims 1 to 6, characterized in that the mixture provided in step (1) contains no K and no Mr.
[0008]
PROCESS according to any one of claims 1 to 7, characterized in that the seed crystals having a CHA frame structure exhibit an X-ray diffraction pattern, in which the most intense reflection having an intensity of 100% has an angle of 2θ diffraction in the range of 5 to 15, preferably from 8 to 12, more preferably from 9 to 10.5, more preferably from 9.2 to 10, more preferably from 9.5 to 9.7, more preferably from 9, 55 to 9.65 and even more preferably from 9.58 to 9.62, where the diffraction angle 2θ is obtained using Cu K (alpha 1) radiation.
[0009]
PROCESS according to any one of claims 1 to 8, characterized in that Y is comprised in the seed crystals and / or, preferably, and where Y preferably provided in step (1) in one or more sources for YO2, is / they are independently of each other selected from the group consisting of Si, Sn, Ti, Zr, Ge and mixtures of two or more of the same, Y preferably being Si.
[0010]
PROCESS according to any one of claims 1 to 9, characterized in that one or more sources for YO2 comprise one or more silicates, preferably one or more alkali metal silicates, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs, where more preferably the alkali metal is Na and / or K, and where even more preferably the alkali metal is Na.
[0011]
PROCESS according to claim 10, characterized by the mixture provided in step (1) preferably additionally comprising one or more silicas in addition to one or more silicates, preferably one or more silica hydrosols and / or one or more colloidal silicas, and even more preferably one or more colloidal silicas in addition to one or more silicates.
[0012]
PROCESS according to any one of claims 10 to 11, characterized in that the mixture provided in step (1) comprises a glass of water, preferably sodium and / or potassium silicate, more preferably sodium silicate.
[0013]
13. PROCESS according to any one of claims 1 to 12, characterized in that X is comprised in the seed crystals and / or, preferably, and, where X provided in step (1), in one or more sources for X2O3 is / are , independently of each other, selected from the group comprising Al, B, In, Ga, and mixtures of two or more of the same, X preferably being Al and / or B, and most preferably being Al.
[0014]
PROCESS according to any one of claims 1 to 13, characterized in that one or more sources for X2O3 comprise one or more aluminate salts, preferably one or more alkali metal aluminates, wherein the alkali metal is preferably selected from the group which consists of Li, Na, K, Rb and Cs, where more preferably the alkali metal is Na and / or K, and where even more preferably the alkali metal is Na.
[0015]
PROCESS according to any one of claims 1 to 14, characterized in that Z is optionally comprised in the seed crystals and / or, preferably and, where Z in one or more sources for Z2O5, optionally additionally provided in step (1) is / are independently of each other selected from the group consisting of P, As, V, and combinations of two or more of the same, where more preferably Z comprises P or As, preferably P, and where most preferably Z is P.
[0016]
16. PROCESS according to any one of claims 1 to 15, characterized in that one or more sources for Z2O5 comprise one or more phosphates and / or one or more oxides and / or one or more phosphorus acids, preferably one or more acids phosphoric acid, more preferably phosphoric acid, and where, even more preferably the source for Z2O5 is phosphoric acid.
[0017]
17. PROCESS according to any one of claims 1 to 16, characterized in that the seed crystals having a CHA frame structure comprise one or more zeolites selected from the group consisting of (Ni (deta) 2) - UT - 6, Chabazite, | Li-Na | [Al-Si-O] -CHA, DAF-5, Chabazite-Na, Chabazite-K, LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO-34, SAPO-47, SSZ-13, SSZ-62, UiO-21, Willhendersonite, ZK-14, ZYT-6 and combinations of two or more of them, preferably from the group consisting of Chabazite, | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, Chabazite-K, SAPO-34, SAPO-47, SSZ-13, SSZ-62 and combinations of two or more of the same, more preferably of the group consisting of Chabazite , | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, more preferably the group consisting of Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, wherein even more preferably the seed crystals, having a CHA frame structure comprising Chabazite-Na and / or SAPO-34 and preferably Chabazite-Na.
[0018]
18. PROCESS according to any one of claims 1 to 17, characterized in that the amount of seed crystals in the mixture according to step (1) varies from 0.05 to 50% by weight based on 100% by weight of YO2 in one or more sources for YO2, preferably from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, more preferably from 1 to 15% by weight, more preferably from 5 to 12% by weight and even more, preferably from 9 to 11% by weight.
[0019]
19. PROCESS according to any one of claims 1 to 18, characterized in that the mixture provided in step (1) additionally comprises one or more solvents, wherein said one or more solvents, preferably comprises water, more preferably distilled water.
[0020]
20. PROCESS according to any one of claims 1 to 19, characterized in that the molar ratio of H2O: YO2 of the mixture according to step (1) varies from 1 to 150, preferably from 3 to 100, more preferably from 5 to 50 most preferably from 10 to 30, more preferably from 15 to 25 and even more preferably from 16 to 19.
[0021]
21. PROCESS according to any one of claims 1 to 20, characterized in that the mixture provided in step (1) comprises one or more sources of one or more elements suitable for isomorphic substitution at least a part of the atoms of Y and / or X atoms in the CHA-type frame structure, where one or more elements are preferably selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, Be, and mixtures of two or more of the same, more preferably in which one or more elements are selected from the group consisting of B, Fe, Ti, Sn, Zr, Cu, and mixtures of two or more of the same, in which even more preferably one or more elements is Fe and / or Cu, preferably Cu.
[0022]
22. PROCESS according to claim 21, characterized in that the molar ratio of YO2 to one or more elements suitable for isomorphic substitution varies from 5 to 200, preferably from 10 to 100, more preferably from 20 to 70 and even more preferably from 25 to 50.
[0023]
23. PROCESS according to any one of claims 1 to 22, characterized by the crystallization provided in step (2) involves heating the mixture from 90 to 180 ° C, more preferably from 100 to 160 ° C, more preferably from 110 to 140 ° C and even more preferably 115 to 130 ° C.
[0024]
24. PROCESS according to any one of claims 1 to 23, characterized in that the crystallization provided in step (2) is conducted under solvothermal conditions, preferably under hydrothermal conditions.
[0025]
25. PROCESS according to any one of claims 1 to 24, characterized by the crystallization provided in step (2) involves heating the mixture from 20 to 160h, more preferably from 60 to 140h, and even more preferably from 100 to 130h.
[0026]
26. PROCESS according to any one of claims 1 to 25, characterized in that it additionally comprises one or more of the following steps of (3) isolating the zeolitic material having a CHA-type frame structure, preferably by filtration, and / or ( 4) washing the zeolitic material having a CHA type frame structure, and / or (5) drying the zeolitic material having a CHA type frame structure, and / or (6) submitting the zeolitic material having a CHA type frame structure. CHA type to an ion exchange process, in which steps (3) and / or (4) and / or (5) and / or (6) can be carried out in any order, and in which one or more of said steps it is preferably repeated one or more times.
[0027]
27. PROCESS according to any one of claims 1 to 26, characterized in that, in at least one step (6), at least one element of non-ionic structure contained in the zeolitic material having a CHA type frame is ionically exchanged, preferably against at least one cation and / or cationic element, wherein at least one cation and / or cationic element is preferably selected from the group consisting of H +, NH4 +, Sr, Zr, Cr, Fe, Co, Ni, Cu, Zn, Ru , Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more of the same, more preferably of the group consisting of H +, NH4 +, Sr, Cr, Fe, Co, Ni, Cu, and mixtures of two or more of the same, more preferably of the group consisting of H +, NH4 +, Fe, Cu, and mixtures of two or more of the same, wherein even more preferably at least one cation and / or cationic element is Cu and / or Fe and preferably Cu, wherein said at least one non-ionic frame element is preferably one or more alkali metals, more preferably Na and / or K and even more preferably Na.
[0028]
28. PROCESS according to any one of claims 1 to 27, characterized in that the organotemplate-free synthesis does not comprise a calcination step.
[0029]
29. A process according to any one of claims 1 to 28, characterized in that the seed crystals comprise a zeolitic material having a CHA-like frame structure as synthesized in the process according to any one of claims 1 to 28.
[0030]
30. SYNTHETIC ORGANOTEMPLATE-FREE ZEOLYTIC MATERIAL, which has a CHA-type frame structure obtained by the process, as defined in any one of claims 1 to 29, wherein said zeolitic material is non-calcined, characterized by: Y ser Si, and where the 29Si MAS NMR of the zeolitic material comprises: a first peak (P1) in the range of -96 to -98.8 ppm, a second peak (P2) in the range of -102 to -104.5 ppm and a third peak (P3) in the range of -109 to -111 ppm, where the integration of the first, second and third peaks in the 29Si MAS NMR of the zeolitic material offers a proportion of integration values P1: P2: P3 that varies from (0, 35 - 0.55): 1: (0.1 - 1.8).
[0031]
31. ZEOLYTIC MATERIAL according to claim 30, characterized in that, if the CHA frame structure does not contain Z2O5, the CHA frame structure will then have a molar ratio YO2: X2O3 of 7 or greater than 7, where the structure of The CHA frame exhibits an X-ray diffraction pattern in which the most intense reflection, having an intensity of 100%, has a 2θ diffraction angle in the range of 5 to 15, preferably from 8 to 12, more preferably from 9 to 10 , 5, more preferably from 9.2 to 10, more preferably from 9.5 to 9.7, more preferably from 9.55 to 9.65 and even more preferably from 9.58 to 9.62, where the Difference angle 2θ is obtained using Cu K radiation (alpha 1).
[0032]
32. ZEOLYTIC MATERIAL according to any one of claims 30 to 31, characterized in that X is selected from the group consisting of Al, B, In, Ga and mixtures of two or more of the same, X preferably being Al and / or B and more preferably Al.
[0033]
33. ZEOLYTIC MATERIAL according to any of claims 30 to 32, characterized in that, if the CHA frame structure additionally comprises Z2O5 in addition to YO2 and X2O3, the CHA frame structure will then have a molar ratio of YO2: nX2O3: pZ2O5 , where the value for the ratio (1 + 2p) :( np) is 7 or greater than 7, where the value for the ratio (1 + 2p): (np) preferably ranges from 7 to 200, more preferably from 7.5 to 100, more preferably from 8 to 50, more preferably from 8.5 to 30, more preferably from 9 to 20, more preferably from 9.3 to 17, and even more preferably from 9.5 to 15.
[0034]
34. ZEOLYTIC MATERIAL according to any one of claims 30 to 33, characterized in that Z is selected from the group consisting of P, As, V, and combinations of two or more of the same, wherein more preferably Z comprises P or As , preferably P, and where even more preferably Z is P.
[0035]
35. ZEOLYTIC MATERIAL according to any one of claims 30 to 34, characterized in that Y comprises Si, and wherein the 29Si MAS NMR of the zeolitic material comprises: a first peak (P1) in the range of -96 to -98.8 ppm, preferably from -96.5 to -98.5 ppm, more preferably from -96.8 to -98.2 ppm, more preferably from -97 to -98 ppm, more preferably from -97.2 to -97, 8 ppm and even more preferably from -97.4 to -97.6 ppm; a second peak (P2) in the range from -102 to -104.5 ppm, preferably from -102.5 to -104 ppm, more preferably from -102.8 to -103.7 ppm, more preferably from -103 to - 103.5 ppm and even more, preferably from -103.2 to -103.4 ppm; a third peak (P3) in the range from -109 to -111 ppm, preferably from -108.5 to -110.5 ppm, more preferably from -109 to -110 ppm, more preferably from -109.1 to -109, 7 ppm, more preferably from -109.2 to -109.6 ppm and even more preferably from -109.3 to -109.5 ppm; where the integration of the first, second and third peaks in the 29Si MAS NMR of the zeolitic material offers a proportion of the integration values P1: P2: P3 ranging from (0.35 - 0.55): 1: (0.1 - 1 , 8), preferably (0.4 - 0.5): 1: (0.25 - 1.5), more preferably (0.42 - 0.49): 1: (0.4 - 1, 2), more preferably (0.43 - 0.48): 1: (0.5 - 0.9), more preferably (0.435 - 0.475): 1: (0.55 - 0.7), more preferably (0.45 - 0.47): 1: (0.6 - 0.65) and even more preferably (0.455 - 0.465): 1: (0.62 - 0.64).
[0036]
36. ZEOLYTIC MATERIAL according to any one of claims 30 to 35, characterized in that X comprises Al, and wherein the 27Al MAS NMR of the zeolitic material comprises a peak (P'1) in the range of -54.5 to -57 .5 ppm, preferably from -55 to -57 ppm, more preferably from -55.5 to -56.8 ppm, more preferably from -55.7 to -56.5 ppm, more preferably from -55.9 to -56.3 ppm, more preferably from -56 to -56.2 ppm.
[0037]
37. ZEOLYTIC MATERIAL according to any one of claims 30 to 36, characterized in that the CHA frame comprises one or more alkali metals M as extra ions framework, wherein one or more alkali metals M are preferably selected from the group consisting of Li, Na , K, Rb and Cs, where more preferably M is Na and / or K, and where even more preferably M is Na.
[0038]
38. ZEOLYTIC MATERIAL, according to claim 37, characterized in that the molar proportion of alkali metal M: X2O3 varies from 0.05 to 10, preferably from 0.1 to 7, more preferably from 0.5 to 5, more preferably from 1 to 3.5, more preferably 1.5 to 3 and even more preferably 1.8 to 2.8.
[0039]
39. ZEOLYTIC MATERIAL according to any one of claims 37 to 38, characterized in that at least a part of the alkali metal atoms M is replaced by one or more cations and / or cationic element, in which one or more cations and / or cationic element is preferably selected from the group consisting of H +, NH4 +, Sr, Zr, Cr, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and mixtures of two or more of the same, more preferably of the group consisting of H +, NH4 +, Sr, Cr, Fe, Co, Ni, Cu, and mixtures of two or more of the same, more preferably of the group consisting of H +, NH4 +, Fe, Cu, and mixtures of two or more of the same, and even more preferably wherein at least a part of the alkali metal atoms M is replaced by Fe and / or Cu, preferably by Cu.
[0040]
40. ZEOLYTIC MATERIAL according to any one of claims 30 to 39, characterized in that at least a part of the Y atoms and / or X atoms in the CHA-type frame structure is isomorphically replaced by one or more elements, wherein one or more elements are preferably selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, Be, and mixtures of two or more of the same, more preferably in which one or more elements are selected from the group consisting of B, Fe, Ti, Sn, Zr, Cu, and mixtures of two or more of the same, wherein even more preferably one or more elements is Fe and / or Cu, preferably Cu.
[0041]
41. ZEOLYTIC MATERIAL according to any one of claims 30 to 40, characterized in that the zeolitic material comprises one or more zeolites selected from the group consisting of (Ni (deta) 2) -UT-6, Chabazite, | Li-Na | [Al-Si-O] -CHA, DAF-5, Chabazite-Na, Chabazite-K, LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO-34, SAPO-47, SSZ-13, SSZ-62, UiO-21, Willhendersonite, ZK-14, ZYT-6 and combinations of two or more of them, preferably from the group consisting of Chabazite, | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, Chabazite-K, SAPO-34, SAPO-47, SSZ-13, SSZ-62 and combinations of two or more of the same, more preferably of the group consisting of Chabazite , | Li-Na | [Al-Si-O] -CHA, Chabazite-Na, SAPO-34, SSZ-13, and combinations of two or more of the same, more preferably of the group consisting of Chabazite-Na, SAPO-34, SSZ-13 and combinations of two or more of the same, wherein even more preferably the seed crystals having a CHA frame structure comprise Chabazite-Na and / or SAPO-34 and preferably Chabazite-Na.
[0042]
42. USE OF A SYNTHETIC FREE ORGANOTEMPLATE ZEOLYTIC MATERIAL, which has a CHA frame structure, as defined in any of claims 30 to 41, characterized by being as a molecular sieve, as an adsorbent, by ion exchange, as a catalyst and / or as a catalyst support.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-04-13| 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 09/11/2012, 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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EP11188857.4|2011-11-11|

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EP11188857|2011-11-11|

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PCT/IB2012/056292|WO2013068976A1|2011-11-11|2012-11-09|Organotemplate-free synthetic process for the production of a zeolitic material of the cha-type structure|

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