KR20160106635A - Bimetal-exchanged zeolite beta from organotemplate-free synthesis and use thereof in the selective catalytic reduction of nox - Google Patents

Abstract

The present invention relates to a process for the preparation of a zeolite material having a BEA-type framework structure comprising YO ₂ and X ₂ O ₃ , comprising the steps of: (1) mixing a mixture comprising at least one source of YO ₂ and at least one source of X ₂ O ₃ Lt; / RTI > (2) crystallizing the mixture obtained in step (1); (3) performing an ion-exchange procedure with copper for the zeolite material having the BEA-type framework structure obtained in step (2); And (4) performing an ion exchange procedure with Fe for the Cu ion-exchanged zeolite material obtained in step (3), wherein Y is a tetravalent element, X is a trivalent element, Wherein the mixture provided in step (1) and crystallized in step (2) further comprises a column comprising at least one zeolite material having a BEA-type framework structure, wherein step (2) ) Does not contain an organic template as a structure-directing agent, and also relates to a process for the treatment of NO _x by the zeolite material itself with a BEA backbone structure, and in particular by selective catalytic reduction (SCR) ≪ / RTI >

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bimetallic-exchanged zeolite beta and a use thereof in selective catalytic reduction of NOx by synthesis without organic template. ≪ Desc / Clms Page number 1 >

The present invention is directed to a method of making such materials that does not involve the use of zeolite materials and organotemplates having a BEA-type framework structure comprising ion-exchanged forms of copper and iron. The present invention also relates to the use of zeolite materials having a BEA-type framework structure comprising ion-exchanged forms of copper and iron, as catalysts for particularly selective catalytic reduction (SCR) in the contact process, by selective catalytic reduction (SCR) using the present invention relates to a process for treating NO _x.

The zeolite beta is one of the most outstanding and widely studied zeolite materials with a BEA-type framework. The zeolite beta contains SiO ₂ and Al ₂ O ₃ in the framework and is characterized by a three-dimensional 12-member ring (12MR) pore / channel system. The zeolite is believed to be an important microporous catalyst that has been widely used in the petroleum refining and fine chemical industry. The synthesis of zeolite beta was first described in U.S. Patent No. 3,308,069, where tetraethylammonium cations are used as structure directing agents. In addition to improving the known manufacturing procedures, it is also possible to use dibenzyl-1,4-diazabicyclo [2,2,2] octane in U.S. Patent No. 4,554,145 and other structures such as dibenzylmethylammonium in U.S. Patent No. 4,642,226 Despite considerable efforts to find alternative routes to it, including the use of derivatizing agents, conventional zeolite beta manufacturing processes typically rely on the use of organic template compounds. For example, U.S. Pat. No. 5,139,759 discloses that if the organic template compound is not present in the synthesis procedure of the zeolite beta, the ZSM-5 product is instead produced.

Recently, it has been found that zeolite beta and related materials can be prepared without organic templates. Xiao et al. Have shown that the synthesis of zeolite beta can be successfully accomplished by using zeolite beta clusters without an organic template in the synthesis mixture [Chemistry of Materials, 2008, 20 , pp. 4533-4535] and supported information. WO 2010/146156 A discloses an organic templateless synthesis of a zeolite material with a BEA-type framework structure, in particular an organic templateless synthesis of zeolite beta. Majano et al. Have reported that an Al-rich zeolite beta material with a Si / Al ratio as low as 3.9 can be obtained from a reaction using seeding in the absence of an organic template [Chemistry of Materials, 2009, 21 , pp. 4184-4191. In addition to the considerable advantage that there is no need to use costly organic templates that require subsequent removal from the microporous framework by calcination, the synthesis method without the new organic template also has an unprecedentedly low Al / Si ratio Thereby making it possible to produce a rich zeolite beta.

It is well known in the art that both synthetic zeolite and natural zeolite can be used as catalysts for a variety of chemical reactions, including selective catalytic reduction (SCR) of nitrogen oxides using ammonia in the presence of oxygen. More specifically, in the so-called SCR process, the reaction of forming nitrogen and H ₂ O by reducing nitrogen oxides using ammonia is selectively enhanced by the catalyst, while the oxidation of ammonia by an undesired reaction, such as oxygen, Reactions that form undesirable by-products such as ₂ O should be avoided. The catalyst used in the SCR process should ideally be capable of retaining excellent catalytic activity under hydrothermal conditions and also in the presence of sulfur compounds over a wide range of temperatures, such as 200 DEG C to 600 DEG C or more. High temperature and hydrothermal conditions are commonly encountered in practical situations, such as during the regeneration of catalytic char filters, which are components necessary for removal of char particles in an exhaust gas treatment system.

In particular, Fe- and Cu-promoted zeolite catalysts have been found to be effective for selective catalytic reduction of nitrogen oxides using ammonia. However, these two types of zeolites are known to have certain limitations in terms of catalytic activity. See, for example, Metkar et al., Applied catalysis B: Environmental, 2012, 111-112 , pp. 67-80], Cu-exchanged zeolites are more effective at low temperatures (i.e. below 350 ° C), while Fe-exchanged zeolites are more effective at higher temperatures (ie above 400 ° C). In the light of these different preferred operating temperatures of Cu-exchanged zeolites and Fe-exchanged zeolites, significant efforts have been made to obtain an improved "all-around" zeolite catalyst which is active over a relatively wide temperature range. Metca et al. Studied the catalytic performance of a mixture of Cu-exchanged zeolite and Fe-exchanged zeolite. However, the mixture exhibited NO _x conversions similar to the average of the performance of the individual zeolites. Furthermore, Yang et al. (Journal of Physical Chemistry, 2012, 116 , pp. 23322-23331] studied bimetallic zeolite beta produced by continuous ion-exchange of copper and iron into commercially available zeolites, a product of Zeolyst International. However, such bimetallic zeolite beta does not exhibit improved NO _x conversion efficiency at low temperatures of 150 ° C as compared to Cu-exchanged zeolite beta. It is also observed that the catalytic activity of the bimetallic zeolite beta at temperatures higher than 300 ° C is reduced much more rapidly than Cu-exchanged zeolites (see FIG. 4 of Yang et al.).

On the other hand, recently, WO 2013/118063 A1 discloses Fe-containing zeolite beta and Cu-containing zeolite beta prepared by synthesis without organic template, and their use in selective catalytic reduction of NO _x . The zeolite beta exhibits a higher catalytic activity than the corresponding zeolite obtained by synthesis with a template. In addition, the Cu-exchanged and Fe-exchanged samples of the zeolite beta from the synthesis without organic template show continuous catalyst performance after severe use conditions simulated by a hydrothermal process, respectively.

Therefore, there is still a challenge to provide improved zeolite catalysts that can exhibit high activity over a wide temperature range for SCR applications. In particular, high activity at a low temperature of about 200 DEG C is very necessary for practical use of the SCR catalyst. There is also a need to provide improved catalysts that combine the advantages of Fe-exchanged zeolites and Cu-exchanged zeolites in SCR reactions. On the other hand, high sulfur resistance is also required, particularly in high sulfur content, especially in reactant gases, as is the case in Asia, particularly in China and India.

Although significant advances have been made in recent years with regard to the synthesis of new zeolite materials having a BEA-type framework structure, there remains a significant need to provide new zeolite materials with improved characteristics. This applies in particular to the many contact applications in which they are currently used, in particular in the context of SCR.

It is therefore an object of the present invention to provide an improved zeolite material, in particular an improved zeolite catalyst. More particularly, the present invention relates to a process for the conversion of nitrogen oxides into reducing agents, in particular in selective catalytic reduction (SCR), for the conversion of nitrogen oxides into compounds which are not harmful to the environment, such as nitrogen and oxygen, It is an object of the present invention to provide a zeolite catalyst exhibiting high catalytic activity and high sulfur resistance.

It is therefore surprising that zeolite materials which are continuously ion-exchanged with copper and iron can be obtained (in this case, the zeolite material having a BEA-type framework structure can be obtained from a synthesis without an organic template and the Cu-exchange precedes the Fe- ) Exhibit improved performance as SCR catalysts as compared to Cu-exchanged zeolites or Fe-exchanged zeolites. This result shows that conventional bimetallic-exchanged zeolite materials known in the art having BEA-type frameworks obtained from the synthesis mediated by organic templates, wherein the corresponding bimetallic-exchanged zeolites are SCR Which does not exhibit improved catalyst performance compared to single-metal-exchanged zeolites in the reaction).

In particular, as demonstrated in the experimental part, the bimetallic-exchanged (i.e., Cu / Fe-exchanged) zeolite material of the present invention having a BEA-type framework structure obtainable from synthesis without organic template is Cu- Zeolite and Fe-exchanged zeolite, both at low temperature and at high temperature. Thus, the Cu / Fe-exchanged zeolite from the synthesis without organic template has unexpectedly surpassed the beneficial effect of the two single-metal-exchanged zeolites in the desired operating temperature range, Zeolite appears to be superior to mechanical mixtures of the two single-metal-exchanged zeolites in the SCR reaction.

It has furthermore surprisingly been found that the order of ion-exchange with copper and iron during the preparation of the zeolite material has an essential effect on the resulting product, since the Cu / Fe-exchanged zeolite beta of the present invention has an iron And exhibit higher catalytic activity, especially in the higher temperature range than the exchanged Fe / Cu-exchanged zeolite beta.

Finally, very unexpectedly, it is believed that the Cu / Fe-exchanged zeolites of the present invention exhibit improved sulfur resistance in the catalytic reaction, and even more surprisingly, the Cu / Fe-exchanged zeolites of the present invention can be effectively regenerated .

Figure 1 shows the NO conversion efficiencies of Examples 4, 5 and 8-10 in the SCR reaction. In this figure, the reaction temperature is plotted along the abscissa, and the NO conversion efficiency is plotted along the ordinate.
Figure 2 shows the NO conversion efficiencies of Examples 7, 11 and 12 in the SCR reaction. In this figure, the reaction temperature is plotted along the abscissa, and the NO conversion efficiency is plotted along the ordinate.
Figure 3 shows the NO conversion efficiencies of Examples 4, 5 and 7 in the SCR reaction. In this figure, the reaction time is plotted along the abscissa and the NO conversion efficiency is plotted along the ordinate.
4 shows the TG and DTG curves of Example 4. Fig. In this figure, the temperatures are plotted along the abscissa while the sample mass and mass loss rates are plotted along the left and right ordinate, respectively.
5 shows the TG and DTG curves of Example 5. Fig. In this figure, the temperatures are plotted along the abscissa while the sample mass and mass loss rates are plotted along the left and right ordinate, respectively.
6 shows the TG and DTG curves of Example 7. Fig. In this figure, the temperatures are plotted along the abscissa while the sample mass and mass loss rates are plotted along the left and right ordinate, respectively.
Figure 7 shows the time-dependent NO conversion efficiency of the regenerated catalyst and the fresh catalyst of Example 7; In this figure, the reaction time is plotted along the abscissa and the NO conversion efficiency is plotted along the ordinate.

The present invention therefore relates to a process for the preparation of zeolite materials having a BEA-type skeleton structure comprising YO ₂ and X ₂ O ₃ , said process comprising the steps of: (1) contacting one or more sources of YO ₂ and one of X ₂ O ₃ Preparing a mixture comprising the above sources; (2) crystallizing the mixture obtained in step (1); (3) performing an ion-exchange procedure with copper for the zeolite material having the BEA-type framework structure obtained in step (2); And (4) performing an ion-exchange procedure with iron for the Cu-exchanged zeolite material obtained in step (3), wherein Y is a tetravalent element and X is a trivalent element Wherein the mixture provided in step (1) and crystallized in step (2) further comprises a column comprising at least one zeolite material having a BEA-type framework structure, wherein the step provided in step (1) 2) does not contain an organic template as a structure-directing agent.

According to the present invention, there is no particular limitation as to the number and / or type of zeolite material obtained in step (2) of the method of the present invention, if it has BEA skeleton structure and includes YO ₂ and X ₂ O ₃ . Thus, for example, the zeolite material can be selected from the group consisting of zeolite beta, [B-Si-O] -BEA, [Ga-Si-O] -BEA, [Ti- At least one zeolite having a BEA backbone structure selected from the group consisting of zeolite, tschernichite, and pure silica beta, wherein preferably the zeolite material obtained in step (2) comprises zeolite beta , And even more preferably the BEA-type framework structure is zeolite beta.

According to the process of the present invention, the mixture provided in step (1) and crystallized in step (2) is an organic structure directing agent which is used in particular for the synthesis of zeolite materials having a BEA- Tetraalkylammonium salts such as ammonium and / or dibenzylmethylammonium salts and / or related organic templates, and dibenzyl-1,4-diazabicyclo [2,2,2] octane. Such impurities may be caused, for example, by organic structure derivatives still present in the seeds used in the process of the present invention. However, the organic template contained in the seed material may not participate in the crystallization process because it is trapped in the capillary skeleton, and therefore may not act as a structure directing agent within the meaning of the present invention.

In addition, YO ₂ and X ₂ O ₃ are included in the BEA-type framework structure as a structure-forming element as opposed to non-skeletal elements that are formed by the skeleton structure and can typically be present in typical voids and steels in zeolite materials .

According to the present invention, a zeolite material having a BEA-type framework structure is obtained in step (2). The material comprises YO ₂ , where Y represents any recognizable tetravalent element and Y represents one or several 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 the above tetravalent elements, more preferably Si and / or Sn. According to the present invention, it is particularly preferable that Y represents Si.

Furthermore, according to the process of the present invention, a zeolite material having a skeleton structure containing BEA- YO ₂ if this can be crystallized in step (2), YO ₂ will be provided in step (1) in any perceptible form of . Preferably, YO ₂ is provided as such and / or as a compound comprising YO ₂ as a chemical moiety and / or as a compound chemically modified (partially or completely) with YO ₂ during the process of the present invention. In a preferred embodiment of the present invention wherein Y represents Si, or a combination of Si and one or more other quatemary elements, the source of SiO ₂ provided in step (1) may be any recognizable source. Thus, for example, all types of silica and silicates, preferably fumed silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesqui-silicate or disilicate, Colloidal silica, pyrogenic silica, silicate ester, tetraalkoxysilane, or a mixture of two or more of these compounds.

In a preferred embodiment of the process of the present invention wherein the mixture according to step (1) comprises at least one source of SiO ₂ , said source preferably comprises at least one compound selected from the group consisting of silica and / or silicate, Comprises at least one silicate and at least one silica. Of the preferred silicates, alkali metal silicates are particularly preferred and the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs, more preferably the alkali metal is Na and / or K, The alkali metal is Na. According to a particularly preferred embodiment, the at least one source of SiO ₂ contained in the mixture provided in step (1) comprises water glass, preferably sodium and / or potassium water glass, more preferably sodium water glass. According to this embodiment, it is also preferred that at least one source of SiO ₂ comprises sodium silicate and / or potassium silicate, even more preferably sodium silicate, and in a particularly preferred embodiment of the present invention the source of SiO ₂ is sodium silicate to be.

Among the preferred silica which may be included in one or more of the source of YO ₂ in step (1), which are any one of silica, preferably fumed silica, silica-dihydro-sol, reactive amorphous solid silicas, silica gel, silicic acid, colloidal silica, Mars Silica, silicic acid ester, tetraalkoxysilane, or a mixture of two or more of these compounds. In particular, according to a preferred embodiment, one or more sources of SiO ₂ is at least one silica selected from fumed silica, silica-dihydro-sol, reactive amorphous solid silicas, silica gel, colloidal silica, chemical conversion of silica or the group consisting of a mixture of two or more of these compounds . However, it is preferred according to the invention that the at least one silica comprises at least one silica hydrosol and / or at least one colloidal silica, even more preferably at least one colloidal silica.

It is therefore preferred according to the invention that the at least one source of YO ₂ provided in step (1) comprises at least one silicate and / or silica, preferably at least one silicate and at least one silica, Preferably comprises at least one alkali metal silicate and the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs, more preferably the alkali metal is Na and / or K, The alkali metal is Na, more preferably the at least one silicate comprises water glass, more preferably sodium silicate and / or potassium silicate, more preferably sodium silicate, and the at least one silica preferably comprises at least one silica Hydrogels and / or one or more colloidal silicas, It comprises at least one colloidal silica.

Therefore, a silicate, preferably comprising at least one alkali metal silicate and alkali metal one at least one source of the YO ₂ or more that is provided in step (1) preferably from the group consisting of Li, Na, K, Rb and Cs And more preferably the embodiment of the present invention is preferred in which the alkali metal is Na and / or K, and even more preferably the alkali metal is Na. In addition, according to certain preferred embodiments described above, one or more sources of YO ₂ additionally comprise one or more silicates in addition to one or more silicas, preferably one or more silica hydrogels and / or one or more colloidal silicas, even more preferably one or more It is further preferred to further include at least one colloidal silica in addition to the silicate. Alternatively, or additionally, it is further preferred according to the invention that the at least one silicate provided in step (1) comprises water glass, preferably sodium silicate and / or potassium silicate, even more preferably sodium silicate.

Also with respect to the zeolite material having a BEA-type framework structure obtained in step (2) comprising X ₂ O ₃ , X may represent any recognizable trivalent element, and X may represent one or several 3 Represents an element. Preferred trivalent elements in accordance with the present invention include Al, B, In and Ga, and a combination thereof. More preferably, Y represents Al, B or In, or any combination of the above trivalent elements, and more preferably Al and / or B. According to the present invention, it is particularly preferable that X represents Al.

For example, where boron is incorporated, for example, glass boron and / or borate and / or boric acid esters such as triethyl borate or trimethyl borate may be used as the starting material.

With respect to one or more sources of X ₂ O ₃ provided in step (1), if a zeolite material having a BEA-type framework structure comprising X ₂ O ₃ can be crystallized in step (2), X ₂ O ₃ There is no particular limitation. Preferably, X ₂ O ₃ is itself and / or chemically modified with X ₂ O ₃ as a compound comprising X ₂ O ₃ as a chemical moiety and / or during the process of the present invention (partially or completely) ≪ / RTI >

In a more preferred embodiment of the present invention wherein X represents a combination of Al or Al and one or more other trivalent elements, the source of Al ₂ O ₃ provided in step (1) may be any recognizable source. Any type of alumina and aluminate, such as, for example, alkali metal aluminates, aluminum salts; Aluminum alcoholates such as aluminum triisopropylate; Or hydrated alumina such as, for example, alumina trihydrate; Or a mixture thereof. Preferably, the source of Al ₂ O ₃ comprises at least one compound selected from the group consisting of alumina and aluminates, preferably aluminates, more preferably alkali metal aluminates, wherein the alkali metals are selected from the group consisting of Li, Na, K, Rb and Cs, more preferably the alkali metal is Na and / or K, and even more preferably the alkali metal is Na. Among the preferred alkali metal aluminates, the at least one source preferably comprises sodium aluminate and / or potassium aluminate, more preferably sodium aluminate. In a particularly preferred embodiment of the present invention, the source of Al ₂ O ₃ is sodium aluminate.

If the zeolite material without an organic template having a BEA-type framework structure containing both YO ₂ and X ₂ O ₃ can be crystallized in step (2), the YO ₂ and X ₂ O ₃ provided in step (1) The amount of each of the one or more sources is not limited according to the present invention. Thus, for a, YO ₂ in the mixture according to step (1): X ₂ O ₃ molar ratio is from 1 to be 200 days and, preferably, a mixture of YO _2: X ₂ O ₃ molar ratio is from 5 to 100, more preferably Is from 10 to 50, more preferably from 15 to 40, even more preferably from 20 to 30, still more preferably from 23 to 25. [ According to a particularly preferred embodiment of the present invention, YO ₂ in the mixture provided in step (1) is X ₂ O ₃ molar ratio is from 23.5 to 24.

In a further preferred embodiment of the invention, the zeolite material obtained in step (2) of the process of the present invention comprises at least one alkali metal M, wherein M is Li, Na, K, Cs, ≪ / RTI > According to a particularly preferred embodiment, the at least one alkali metal M is selected from the group consisting of Li, Na, K and combinations of two or more thereof, more preferably the alkali metal M is Na and / or K, Na. In a particularly preferred embodiment of the process of the present invention, the alkali metal is contained in one or more sources of the YO ₂ and / or X ₂ O ₃ , partially or completely provided in step (1), and preferably all of the alkali metals .

Generally, if the zeolite material having a BEA-type framework structure is crystallized in step (2). The alkali metal M can be contained in the mixture according to step (1) of the process of the present invention in any appreciable amount. Thus, by way of example, the M: YO ₂ molar ratio of the mixture provided in step (1) may be 0.05 to 5, preferably the mixture provided in step (1) and crystallized in step (2) It represents the YO ₂ molar ratio and more preferably from 0.3 to 1, more preferably from 0.4 to 0.8, more preferably 0.45 to 0.7, even more preferably of 0.5 to 0.65 M. According to a particularly preferred embodiment, the molar ratio of M: YO ₂ in the mixture according to step (1) is 0.55 to 0.6.

Therefore, in general, if the zeolite material without an organic template having a BEA-type framework structure can be crystallized in step (2), one or more sources of YO ₂ , one or more sources of X ₂ O ₃ , Any appreciable amount of one or more alkali metal M optionally included in the mixture provided in the process of the invention can be used in the process of the present invention. Thus, by way of example, the molar ratio of YO ₂ : X ₂ O ₃ : M in the mixture according to step (1) may be (1 to 200): 1: (0.5 to 100). However, YO ₂ provided and indicates the mixture to be crystallized in step (2) in step (1): X ₂ O _3: M molar ratio of (5-100): 1: (5 to 75), more preferably (10 (11 to 20): 1: (8 to 50), more preferably (15 to 40): 1: (23 to 25): 1: (12 to 15) is preferable according to the present invention. According to a particularly preferred embodiment, the molar ratio of YO ₂ : X ₂ O ₃ : M of the mixture provided in step (1) and crystallized in step (2) is (23.5-24): 1: (13-14).

According to the method of the present invention, a seed crystal is provided in step (1), wherein said seed crystal comprises a zeolite material having a BEA-type framework structure. Generally, if the zeolite material having a BEA-type framework structure is crystallized in step (2), the clay can comprise any zeolite material having a BEA-type framework structure. Preferably, the zeolite material having the BEA-type framework structure included in the seed crystal is a zeolite material obtained according to the method of the present invention. More preferably, the zeolite material having the BEA-type framework structure contained in the seed crystal is the same as the zeolite material having the BEA-type framework structure crystallized in step (2). Particularly preferred is a zeolite beta, more preferably a zeolite beta containing zeolite beta obtained according to the process of the invention. In a particularly preferred embodiment, the seed crystal is a zeolite beta crystal, preferably a zeolite beta crystal obtained according to the method of the present invention.

According to the process of the present invention, if a zeolite material having a BEA-type framework structure is crystallized in step (2), any suitable amount of seed may be provided to the mixture according to step (1). In general, the amount of the seed crystal contained in the mixture according to step (1) on the basis of the YO ₂ 100% by weight of at least one source of the YO ₂ 0.1 to 30% by weight, preferably at this stage, 0.5 to seed crystal of 20% by weight (2). ≪ / RTI > More preferably, the amount of the seed crystal contained in the mixture according to step (1) is 1 to 10 wt%, more preferably 1.5 to 5 wt%, and still more preferably 2 to 4 wt%. According to a particularly preferred embodiment, the amount of seeding provided in the mixture according to step (1) is from 2.5 to 3.5% by weight.

In step (1) according to the invention, the mixture can be prepared by any perceptible means, preferably by agitation, preferably by stirring.

According to the invention, the mixture according to step (1) of the process according to the invention preferably further comprises at least one solvent. In this regard, if from the crystallization in step (2) to obtain a zeolite substance having a skeleton structure containing BEA- YO ₂ and X ₂ O _3, it can be any perceivable solvent in any suitable amount of have. Thus, for example, water, organic solvents and mixtures thereof, preferably from the group consisting of deionized water, alcohols and mixtures thereof, more preferably from the group consisting of deionized water, methanol, ethanol, propanol and mixtures thereof One or more solvents can be selected. According to a particularly preferred embodiment of the present invention, only water, preferably deionized water, is contained as a solvent in the mixture according to step (1).

With respect to the amount of at least one solvent preferably provided in the mixture according to step (1) of the method of the present invention, the zeolite material without an organic template having a BEA-type skeleton structure again comprising YO ₂ and X ₂ O ₃ If it can be crystallized in step (2), no special restrictions apply. Thus, by way of example, according to a particularly preferred embodiment of the present invention wherein the solvent comprises water, the H ₂ O: YO ₂ molar ratio of the mixture may be from 5 to 100, and preferably the H ₂ O: YO ₂ molar ratio is from 10 To 50, more preferably from 13 to 30, still more preferably from 15 to 20. [ According to a particularly preferred embodiment of the present invention, the H ₂ O: YO ₂ molar ratio of the mixture provided in step (1) of the process of the invention and crystallized in step (2) is from 17 to 18.

Generally, if the zeolite material having the BEA-type framework structure is crystallized from the mixture according to step (1), step (2) according to the method of the present invention can be carried out in any perceptible manner. The mixture can be crystallized in any type of vessel, preferably by means of rotation and / or stirring of the vessel, more preferably by agitation of the mixture.

According to the process of the invention, the mixture is preferably heated during at least part of the crystallization process of step (2). Generally, if the zeolite material having a BEA-type framework structure is crystallized from the mixture, the mixture can be heated to any appreciable crystallization temperature. Preferably, the mixture is heated to a crystallization temperature of 80 to 200 DEG C, more preferably 90 to 180 DEG C, more preferably 100 to 160 DEG C, more preferably 110 to 140 DEG C, even more preferably 115 to 130 DEG C Heat it.

The desired heating can be carried out in step (2) of the process of the invention in any perceptible manner suitable for the crystallization of the zeolite material with the BEA-type framework structure. In general, heating can be performed at one crystallization temperature, or the heating is changed between different temperatures. Preferably, a heat ramp is used to reach the crystallization temperature, wherein the heating rate is preferably 10 to 100 占 폚 / hour, more preferably 20 to 70 占 폚 / hour, More preferably 30 to 50 占 폚 / hour, still more preferably 35 to 45 占 폚 / hour.

In a preferred embodiment of the present invention, the mixture according to step (1) is subjected to a pressure higher than the normal pressure in step (2). The term "normal pressure" used in the context of the present invention relates to a pressure of 101,325 Pa in an ideal case. However, this pressure can vary within the boundaries known to those skilled in the art. By way of example, this pressure may be 95,000 to 106,000 Pa, or 96,000 to 105,000 Pa, or 97,000 to 104,000 Pa, or 98,000 to 103,000 Pa, or 99,000 to 102,000 Pa.

In a preferred embodiment of the process according to the invention in which the solvent is present in the mixture according to step (1), heating in step (2) is carried out under solvent thermal conditions (for example an autoclave suitable for generating solvent thermal conditions or It is meant to crystallize the mixture under an autogenous pressure of the solvent used, by performing heating in another crystallization vessel). In a particularly preferred embodiment wherein the solvent comprises or consists of water, preferably deionized water, the heating in step (2) is preferably carried out under hydrothermal conditions.

The apparatus that can be used in the present invention for crystallization is not particularly limited, as long as preferable parameters for the crystallization process can be realized particularly in connection with preferred embodiments requiring specific crystallization conditions. In a preferred embodiment carried out under solvent thermal conditions, any type of autoclave or decomposition vessel may be used.

In general, the time of the crystallization step in step (2) of the method of the present invention is not particularly limited. In a preferred embodiment involving the heating of the mixture according to step (1), the heating time is from 5 to 160 hours, more preferably from 10 to 140 hours, more preferably from 20 to 120 hours, even more preferably from 40 to 100 hours The crystallization process is preferably performed for 60 to 80 hours.

According to a preferred embodiment of the present invention in which the mixture is heated in step (2), if the zeolite material having the BEA-type framework structure is crystallized, the heating can be performed only during the entire crystallization process or during a portion thereof. Preferably, heating is performed for the entire crystallization time.

Generally, the process of the present invention optionally further comprises post-treatment and / or further physical and / or chemical modification of the zeolite material having a BEA-type framework structure crystallized in step (2) from the mixture provided in step (1) Lt; / RTI > For example, any number and sequence of isolating and / or washing and / or drying procedures can be carried out on the crystallized material, and the zeolite material obtained from the crystallization in step (2) More preferably one or more isolation and one or more washing procedures, even more preferably one or more isolation, one or more washing, and one or more drying procedures.

With regard to the preferred embodiment of the present invention which performs one or more isolation procedures for the zeolite material without the organic template crystallized in step (2), it is possible to achieve said isolation of the product crystallized by any recognizable means have. Preferably, isolation of the product crystallized by filtration, ultrafiltration, diafiltration, centrifugation and / or decantation is effected, wherein the filtration method comprises an inhalation and / or pressure filtration step can do.

With respect to one or more optional cleansing procedures, any recognizable solvent may be used. The detergent that may be used is, for example, water, an alcohol (e.g., methanol, ethanol or propanol), or a mixture of two or more thereof. Examples of mixtures are mixtures of two or more alcohols (e.g., methanol and ethanol, or methanol and propanol, or ethanol and propanol, or methanol and ethanol and propanol), or mixtures of water and one or more alcohols 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 methanol and propanol). Mixtures of water or water and one or more alcohols (preferably water and ethanol) are preferred, and deionized water is very particularly preferred as the sole detergent.

Preferably, the separated zeolite material is washed until the pH of the detergent, preferably the wash water, is determined through a standard glass electrode of from 6 to 8, preferably from 6.5 to 7.5.

In addition, in connection with one or more optional drying steps, any perceptible drying means may in principle be employed. However, the drying procedure preferably involves applying a vacuum to the zeolite material having a heating and / or BEA-type framework structure. In another preferred embodiment of the present invention, the one or more drying steps may comprise spray drying, preferably spray granulation of the zeolite material crystallized in step (2) of the method of the present invention.

In embodiments involving one or more drying steps, the drying temperature is preferably from 25 to 150 DEG C, more preferably from 60 to 140 DEG C, more preferably from 70 to 130 DEG C, even more preferably from 75 to 125 DEG C to be. The drying time is preferably 2 to 60 hours, more preferably 6 to 48 hours, still more preferably 12 to 24 hours.

In general, the optional cleaning and / or drying procedures included in the method of the present invention can be repeated as often as desired in any recognizable sequence.

Therefore, in accordance with the method of the present invention, before step (3) after step (2), the method comprises the steps of (i) subjecting the zeolite material having the BEA-type framework structure obtained in step (2) Isolating; And (ii) optionally, washing the zeolite material having the BEA-type framework structure obtained in step (2); And / or (iii) optionally, drying the zeolite material having the BEA-type framework structure obtained in step (2), wherein step (i) and / Or (ii) and / or (iii) can be carried out in any order, and one or more of the steps are preferably repeated one or more times.

Preferably, the process of the present invention comprises at least one step (i) of isolating the crystallized zeolite material according to step (2) more preferably by filtration. According to the process of the invention it is also preferred to carry out at least one drying step (iii) for the zeolite material after at least one isolation step (i), more preferably for at least one drying step for the zeolite Perform at least one washing step (ii). In a particularly preferred embodiment, at least one isolation step (i) is performed on the zeolite material crystallized according to step (2), followed by one or more washing steps (ii), followed by one or more drying steps iii).

According to another embodiment of the method of the invention, which is otherwise preferred, the zeolite material crystallized in step (2) is subjected to one or more drying steps, preferably one or more spray drying or spray granulation steps, It is particularly preferred to carry out the one or more spray drying or spray granulation steps without preliminary isolation or washing. Performing a direct spray drying or spray granulation step on the mixture obtained from step (2) of the method of the present invention has the advantage of performing isolation and drying in a single step. As a result, according to this embodiment of the present invention, a more preferred method of avoiding the removal of organic template compounds as well as minimizing the number of post-synthesis post-treatment steps is provided, resulting in a BEA-type framework structure Lt; RTI ID = 0.0 > zeolite < / RTI >

According to the method of the present invention, the ion exchange procedure of step (3) and step (4) is successively performed on the zeolite material crystallized in step (2). The term "ion-exchange" in the present invention generally refers to the exchange of non-skeletal ionic elements of a zeolitic material with other ionic elements, wherein the non-skeletal ionic element is a zeolite Lt; / RTI > In connection with the ion-exchange procedure, there is no particular limitation as to whether or not the above step is repeated and the number of times the step is repeated, not only for the specific impregnation method to be applied.

According to the process of the present invention, a solvent or solvent mixture is preferably used to dissolve the metal (i.e., copper or iron) compound for the ion-exchange procedure. If the metal compound can be solvated in a solvent, there is no particular limitation on the type of solvent that can be used. Thus, by way of example, the solvent or solvent mixture is preferably a mixture of water, methanol, ethanol, propanol, butanol, pentanol, acetone, benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane, And more preferably an inorganic solvent and / or an organic solvent selected from the group consisting of water, ethanol, propanol, benzene, toluene, and combinations of two or more thereof. Even more preferably, the solvent or solvent mixture used to dissolve the copper or iron compound for the ion-exchange procedure is water or toluene, preferably water.

With respect to the amount of solvent or solvent mixture preferably used in the ion-exchange procedure according to step (3) and step (4), if copper and iron can again be effectively exchanged as non-framework elements of the zeolite material, There is no particular restriction according to the method. Thus, for example, an excess of solvent or solvent mixture can be used in the ion-exchange procedure, wherein the solvated metal (i.e., copper in step (3) and iron in step (4) And conversely the ions contained in the zeolite material exchanged with copper or iron can be suitably solvated into the solvent or solvent mixture and thus escape from the porous system of the zeolite material. Alternatively, however, the solubilized copper or iron in the solvent or solvent mixture may be slightly exceeded by the porous volume of the zeolitic material to enter the porous system of the zeolitic material by capillary action according to the incipient wetness impregnation technique Ion exchange can be achieved using a solvent or solvent mixture approximately equivalent to or slightly less than the volume of the solvent. According to certain embodiments of the present invention utilizing this ion-exchange technique, the ion-exchange process is directly carried out in the porous system of the zeolite material without any ions necessarily leaving the zeolite material with an excess of solvent.

With regard to the ion-exchange procedure of the present invention, there is no limitation as to how the metal copper or iron is introduced into the exchangeable sites of the zeolite material. By way of example, the copper or iron compound may be dissolved in a solvent or solvent mixture to form copper or iron ions, which may then diffuse into the exchangeable sites of the zeolite material. Alternatively, the copper or iron compound may be dissolved in a solvent or solvent mixture and then impregnated with the zeolite material by an initial wetting method, and the impregnated zeolite material is calcined such that the metal copper or iron migrates into the exchangeable portion of the zeolite material Where calcination preferably decomposes the copper or iron compound to produce their ionic form and then convert them to a counterion for the zeolite framework structure and more preferably to a non-copper and / or zeolite framework for the zeolite framework structure, Can be ion-exchanged for non-ferrous ions.

With respect to the amount of solvent used in the procedures of step (3) and / or step (4), it is contemplated that any suitable amount of solvent may be added to the zeolite framework, There are no special restrictions that can be applied accordingly. Thus, for example, a liquid to solid weight ratio of from 0.1 to 20 can be used. However, in accordance with the present invention, the liquid to solid weight ratio of the solvent or solvent mixture to the zeolite material is from 1 to 15, more preferably from 2 to 12, more preferably from 3 to 10, and even more preferably from 4 to 9 , And still more preferably from 5 to 8 carbon atoms. According to the invention, it is particularly preferred that the liquid to solid weight ratio used in the ion-exchange procedure of step (3) and / or step (4) is from 6 to 7.

However, in accordance with the present invention, the amount of solvent used in the ion-exchange procedure of step (3) and / or step (4) of the method of the present invention is such that the ion- It is also preferred to select such that the volume is below the volume of solvent that can be absorbed by the microvoids of the framework. According to the present invention it is particularly preferred that the ion-exchange at one or more of step (3) and step (4) be performed by an initial wetting technique, more preferably at least step (4) , And even more preferably only the ion-exchange in step (4) is carried out by an initial wetting technique. In particular, if step (4) is performed using an initial wetting technique, without being bound by any particular theory, if the ion-exchanged copper is replaced with iron in step (3) and then an excess of solvent is used in the ion- Avoid leaving the zeolite by excess solvent as is observed. This is particularly advantageous for embodiments in which ion exchange in step (4) is carried out using non-polar and / or aprotic solvents such as benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane and combinations of two or more thereof . Thus, according to the present invention there is provided a process for the preparation of compounds of the formula I from the group consisting of benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane and combinations of two or more thereof, more preferably benzene, toluene, hexane, heptane, (4) is particularly preferably carried out using a solvent or mixture of solvents selected from the group consisting of toluene, toluene, -Substance, and even more preferably toluene is used as the solvent for the ion-exchange in step (4). It is therefore possible to select from the group consisting of benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane and combinations of two or more thereof, more preferably selected from the group consisting of benzene, toluene, hexane, heptane and combinations of two or more thereof It is also particularly preferred in accordance with the invention to carry out the ion-exchange in step (4) using an initial wetting technique using a solvent or solvent mixture which is more preferably using a solvent mixture comprising toluene Ion-exchange is carried out in step (4) through initial wetting, and more preferably toluene is used as the solvent.

According to the invention, the amount of copper ion-exchanged into the zeolite obtained in step (3) is preferably from 0.1 to 25% by weight, calculated as CuO. As a result, the type of Cu-exchange procedure used in step (3) is suitably selected with particular reference to the type and / or amount of solvent or solvent mixture that is preferably used herein and is included within the scope of the present invention When necessary to achieve copper loading in the ion-exchanged material, it is repeated one or more times. However, according to the present invention, the total amount of copper in the ion-exchanged material obtained in step (3) is 0.2 to 20% by weight, more preferably 0.5 to 15% by weight, more preferably 0.8 to 10% More preferably from 1 to 8.0% by weight, still more preferably from 1.2 to 7.0% by weight, still more preferably from 1.5 to 6.0% by weight, still more preferably from 2.5 to 5.5% by weight. According to a particularly preferred embodiment of the present invention, the total amount of copper in the zeolite material is 3.0 to 4.0 wt%.

According to the invention, the amount of iron ion-exchanged in the zeolite material obtained in step (4) is preferably from 0.1 to 25% by weight, calculated as Fe ₂ O ₃ . As a result, the type of Fe-exchange procedure used in step (4) is also suitably selected with reference to the type and / or quantity of the solvent or solvent mixture preferably used particularly herein, ≪ / RTI > is repeated one or more times as needed to achieve iron loading in the ion-exchanged material. However, according to the present invention, the total amount of iron calculated as Fe ₂ O ₃ in the ion-exchanged material obtained in step (4) is 0.2 to 15% by weight, more preferably 0.3 to 10% by weight, Is preferably 0.5 to 7.5% by weight, more preferably 0.7 to 5.0% by weight, still more preferably 0.8 to 4.0% by weight, still more preferably 1.0 to 3.5% by weight. According to a particularly preferred embodiment of the invention, the total amount of iron in the zeolite material is from 2.0 to 3.1% by weight.

In accordance with a preferred embodiment of the present invention, the solvent or solvent mixture is preferably used in an ion-exchange procedure wherein the solubility of the metal (i.e., copper or iron) compound in the solvent or solvent mixture is such that the solubility of the metal The concentration of the compound is suitable to obtain a zeolite material having a loading of the corresponding metal according to certain and / or preferred embodiments of the present invention. In the case of using such a solution, after the ion exchange process of not more than 5 times using each metal (copper or iron), preferably not more than 4 times, more preferably not more than 3 times, more preferably not more than 2 times , Even more preferably after a single ion-exchange procedure using such a solution, metal loading of the zeolite material with the BEA-type framework structure is achieved.

With respect to the copper compound used in the Cu-exchange in step (3) of the method of the present invention, it is preferred that the at least one copper-containing compound is selected from any suitable copper, preferably copper (I) and / -Containing compound can be used. The at least one copper-containing compound is preferably a copper (II) compound, more preferably a copper (II) salt. By way of example, the at least one copper-containing compound may be selected from the group consisting of copper (II) halide, preferably copper (II) chloride and / or copper (II) bromide, more preferably copper (II) chloride, Copper (II), Hydrogen Phosphate (II), Hydrogen Phosphate (II), Copper Phosphate (II), Copper (II) (II) acetate, copper (II) acetate, copper (II) citrate, copper (II) malonate, copper (II) oxalate, copper (II) tartrate and mixtures of two or more thereof (II) chloride, preferably copper chloride (II), copper sulfate (II), copper nitrate (II), acetic acid Copper (II), and mixtures of two or more thereof. According to a particularly preferred embodiment of the present invention, the copper compound used in the Cu-exchange in step (3) comprises copper (II) acetate, more preferably the copper compound is copper (II) acetate.

For the iron compound used in the Fe-exchange in step (4) of the process of the present invention, any suitable iron-containing compound may be used. The at least one iron-containing compound used in step (4) is preferably selected from the group consisting of iron (II) and iron (III) salts, iron complexes and combinations of two or more thereof. More preferably, the iron-containing compound is selected from the group consisting of iron sulfate, iron sulfite, ferrous sulfate, iron chloride, iron bromide, iron iodide, iron fluoride, iron perchlorate, iron nitrate, iron nitrite, iron phosphate, More preferably from the group consisting of iron, iron oxide, iron oxide, iron carbonate, iron hydrogen carbonate, iron acetate, iron citrate, iron malonic acid, iron oxalate, iron tartrate, hexacyano iron salt, ferrocene, ferrocenium salt, Iron sulfate, iron chloride, iron nitrate, ferrocene, and combinations of two or more thereof. According to a particularly preferred embodiment of the present invention, the iron-containing compound used for Fe-exchange in step (4) comprises iron sulfate and / or ferrocene, more preferably ferrocene is used as the iron compound in step (4) do.

According to certain embodiments of the present invention, the zeolite material obtained in step (2) of the process of the present invention optionally comprises H ⁺ and / or NH ₄ ⁺ before ion-exchange with copper in step (3) And / or may be ion-exchanged with NH ₄ ⁺ and / or optionally calcined. According to a preferred embodiment of the present invention, the zeolite material obtained in step (2) is first ion-exchanged with NH ₄ ⁺ before Cu-exchange in step (3). In this connection, any perceptible ion-exchange procedure, such as treating the zeolite material with a solution of the ammonium salt, can be accomplished by exchanging the ionic non-skeletal element contained in the zeolite material obtained in step (2) with NH ₄ ⁺ . According to this preferred embodiment, the calcination of the ion-exchanged zeolite material with NH ₄ ⁺ before ion-exchange with copper so that copper is ion-exchanged with respect to NH ₄ ⁺ present as a counter ion to the zeolite skeleton It is also preferred.

Therefore, the ion-exchange of the zeolite material having a BEA-type skeleton structure in step (3) is carried out in the same manner as the ion-exchange non-skeleton element contained in the zeolite material having the BEA-type skeleton structure obtained in step (2) to one or more of the H ⁺ and / or NH ₄ ^+, preferably exchanging with NH ₄ ^+; And (3b) carrying out an ion-exchange procedure with copper for the zeolite material having the BEA-type framework structure obtained in step (3a).

According to certain embodiments of the present invention, the Cu-exchanged zeolite material obtained in step (3) is calcined prior to the Fe-exchange procedure in step (4). If the resulting material can be ion-exchanged with further iron to obtain a Cu / Fe-exchanged material, the calcination can be carried out at any suitable temperature for any appreciable time, Preferably 0.1 to 25% by weight, calculated as CuO, and the iron loading is preferably 0.1 to 25% by weight, calculated as Fe ₂ O ₃ . For example, the calcination temperature may be 300 to 850 占 폚, preferably 350 to 750 占 폚, more preferably 400 to 650 占 폚, still more preferably 425 to 600 占 폚, still more preferably 450 to 550 占 폚. According to a particularly preferred embodiment of the present invention, the zeolite material obtained in step (3) is calcined at 475 to 525 캜 before the Fe-exchange in step (4). Further, with respect to the time of the calcination procedure optionally used before the Fe-exchange in the step (4), it is preferably 0.1 to 24 hours, preferably 0.5 to 18 hours, more preferably 1 to 12 hours, 2 to 10 hours, more preferably 2.5 to 7 hours. According to a particularly preferred embodiment, the calcination procedure is carried out for 3 to 5 hours before the Fe-exchange.

According to the present invention, a calcination step may further be carried out on the zeolite material obtained in step (4) of the method of the present invention. For example, the calcining temperature used in step (4) is in the range of 300 to 850 캜, preferably 350 to 750 캜, more preferably 400 to 650 캜, more preferably 425 to 600 캜, 550 < 0 > C. According to the present invention, it is particularly preferred to calcine the zeolite material obtained in step (4) at 475 to 525 占 폚. In addition, the preferred calcination time for the zeolite material obtained from the ion-exchange in step (4) is 0.1 to 24 hours, more preferably 0.2 to 12 hours, more preferably 0.5 to 5 hours, Can be calcined for 1 to 3 hours. According to a particularly preferred embodiment, the calcination procedure of the zeolite material obtained in step (4) is carried out for 1.5 to 2.5 hours.

It is, however, also possible according to the invention to carry out ion-exchange with iron in step (4) so that the actual ion-exchange takes place only during or mainly during this calcination of the zeolite material after loading with one or more iron- desirable. This applies in particular to embodiments in which one or more iron compounds contain at least one iron complex which does not react directly with the zeolite material in contact therewith.

Therefore, the Fe-exchange procedure in step (4) according to the present invention comprises: (4a) tethering the Cu-exchanged zeolite material obtained in step (3) with one or more iron- 4b) It is particularly preferred to include calcining the zeolite material obtained in step (4a).

Thus, in accordance with the present invention, it is particularly preferred to impregnate the zeolite material obtained in step (3) with at least one iron-containing compound in step (4a), and preferably one or more of the iron- , More preferably selected from the group consisting of iron citrate, iron malonic acid, iron oxalate, iron tartrate, hexacyano iron salt, ferrocene, ferrocenium salt and combinations of two or more thereof, It is particularly preferable that the iron-containing compound is a ferrocene-containing compound, and the ferrocene is particularly preferably used as the iron-containing compound in the step (4a). It is also possible to use a solvent selected from the group consisting of non-polar and / or aprotic solvents such as benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane and combinations of two or more thereof in step (4a) It is particularly preferred to impregnate one or more iron-containing compounds, more preferably the impregnation is carried out in step (4a) using a solvent mixture comprising toluene, and still more preferably the toluene is impregnated in step (4a) Is used as a solvent. Therefore, one selected from the group consisting of iron complexes, more preferably one selected from the group consisting of iron citrate, iron malonic acid, iron oxalate, iron tartrate, hexacyano iron salt, ferrocene, ferrocenium salt and combinations of two or more thereof Or a non-polar and / or aprotic solvent such as benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane, and combinations of two or more thereof It is particularly preferred to carry out the impregnation in step (4a), and it is particularly preferred to carry out the impregnation with a solvent mixture comprising toluene, wherein the at least one iron-containing compound comprises ferrocene, Impregnation in step (4a) was carried out using ferrocene as the iron-containing compound and toluene as the solvent The.

With respect to the amount of solvent used in the preferred impregnation procedure of step (4a), generally in the process of the present invention, any suitable amount of solvent is used herein, as defined in certain preferred embodiments of the process of the invention herein No special restrictions apply. However, in accordance with the present invention, it is preferred to carry out the impregnation in step (4a) so that the impregnation is preferably carried out according to the initial wetting technique, such that the amount of solvent is less than the volume of solvent which can be absorbed by the micropores of the zeolite framework desirable.

As described above, it has been found that according to the process of the present invention it is possible to provide a zeolite material which exhibits unexpected improved properties, particularly in relation to catalytic activity. More particularly, surprisingly, according to the process of the present invention, zeolite materials having a BEA-type framework structure continuously exchanged with copper and iron which exhibit high catalytic activity over a wide temperature range in SCR applications can be provided.

The invention therefore also relates to zeolite materials having a BEA-type framework structure obtainable and / or obtainable according to certain preferred embodiments of the process of the invention as defined herein. Within the meaning of the present invention, the term "obtainable" refers to any perception that results in a zeolite material having a BEA-type framework structure, such as may be obtained by the process according to the invention, Refers to any zeolite material having a BEA-type framework structure obtained by a possible method.

Accordingly, the present invention also relates to a zeolite material itself having a BEA-type framework structure having an X-ray diffraction pattern comprising at least the following reflectivity, wherein 100% is the intensity of the maximum peak in the X- Wherein the BEA-type framework structure comprises YO ₂ and X ₂ O ₃ , Y is a tetravalent element, X is a trivalent element, the zeolite material contains copper and iron in ion-exchanged form, The ion exchange with copper is carried out before ion exchange with iron:

Preferably, the zeolite material with a BEA-type framework structure according to the invention has an X-ray diffraction pattern comprising at least the following reflectivities, wherein 100% relates to the intensity of the maximum peak in X-ray diffraction:

More preferably, the zeolite material of the present invention having a BEA-type framework structure exhibiting a powder rotation pattern according to the present invention can be prepared by the process according to the invention, or a BEA-type skeleton, Lt; RTI ID = 0.0 > zeolite < / RTI >

According to the present invention, in a zeolite material having a BEA-type framework structure, Y represents any recognizable tetravalent element, and Y represents one or several 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 these tetravalent elements, more preferably Si and / or Sn. According to the present invention, it is particularly preferable that Y represents Si.

In addition, with respect to X ₂ O ₃ , which is additionally included in the skeleton of the zeolite material having a BEA structure, X may represent any recognizable trivalent element and X represents one or several trivalent elements. Preferred trivalent elements according to the present invention include Al, B, In and Ga, and combinations thereof. More preferably, Y represents Al, B or In, or any combination of the above trivalent elements, and more preferably Al and / or B. According to the present invention, it is particularly preferable that X represents Al.

According to the invention, YO ₂ represents the zeolite material of the present invention having a BEA--like skeleton structure: there is no particular limitation with respect to the X ₂ O ₃ mole ratio. Therefore, in principle, the zeolite material of the present invention may have any appreciable YO ₂ : X ₂ O ₃ molar ratio. Thus, by way of example, the zeolite material having a BEA-type framework structure may have a YO ₂ : X ₂ O ₃ molar ratio of 2 to 100, preferably a YO ₂ : X ₂ O ₃ molar ratio of 4 to 70, More preferably 5 to 50, still more preferably 6 to 30, still more preferably 7 to 20, still more preferably 8 to 15, still more preferably 9 to 13. According to a particularly preferred embodiment, the zeolite material of the present invention having a BEA-type framework structure has a YO ₂ : X ₂ O ₃ molar ratio of 10 to 11.

According to the present invention, there is no particular limitation on the loading of copper in the zeolite material. Thus, by way of example, the copper loading is from 0.1 to 25% by weight, preferably from 0.2 to 20% by weight, more preferably from 0.5 to 15% by weight, more preferably from 0.8 to 0.8% by weight, calculated as CuO, based on the total weight of the zeolite material To 10% by weight, more preferably 1.0 to 8.0% by weight, still more preferably 1.2 to 7.0% by weight, still more preferably 1.5 to 6.0% by weight, still more preferably 2.5 to 5.5% by weight. According to a particularly preferred embodiment, the zeolite material of the present invention has a copper loading of 3.0 to 4.0 wt%.

In addition, according to the present invention, there is no particular limitation on the iron loading of the zeolite material. Therefore, again, for example, the iron loading is 0.1 to 25% by weight, preferably 0.2 to 15% by weight, more preferably 0.3 to 10% by weight, calculated as Fe ₂ O ₃ based on the total weight of the zeolite material, More preferably from 0.5 to 7.5% by weight, still more preferably from 0.7 to 5.0% by weight, still more preferably from 0.8 to 4.0% by weight, still more preferably from 1.0 to 3.5% by weight. According to certain preferred embodiments, the zeolite material of the present invention has an iron loading of 2.0 to 3.1 wt%.

According to the present invention, there is also no particular limitation on the molar ratio of Cu: X ₂ O _{3 in} the zeolite material. The Cu: X ₂ O ₃ molar ratio of the zeolite material is 0.01 to 2.4, preferably 0.02 to 1.9, more preferably 0.05 to 1.45, even more preferably 0.08 to 0.8, still more preferably 0.1 to 0.7, 0.14 to 0.6, more preferably 0.2 to 0.5. Even more preferably, the molar ratio of Cu: X ₂ O _{3 in the} zeolite material is 0.3 to 0.4.

Further, according to the present invention, the molar ratio of Fe: X ₂ O _{3 in} the zeolite material is not particularly limited. The molar ratio of Fe: X ₂ O ₃ of the zeolite material is 0.01 to 2.4, preferably 0.02 to 1.4, more preferably 0.03 to 1.0, further preferably 0.05 to 0.7, still more preferably 0.07 to 0.5, May be 0.08 to 0.4, more preferably 0.1 to 0.35. Even more preferably, the molar ratio of Fe: X ₂ O _{3 in} the zeolite material is from 0.25 to 0.30.

Depending on the specific needs of its use, the materials of the present invention according to certain preferred embodiments of the present invention may be used in the form of powders, spray powders or sprayed microparticles obtained from the above described separation techniques, such as sloping, filtering, centrifuging or spraying It can be used by itself.

In many industrial applications, the zeolite material is used by the user as a means of separating the zeolite material from the powdered or atomized material, i.e., from the mother liquor (optionally including washing and drying) and the zeolite material obtained by subsequent calcination It is often desired to use zeolite materials that are further processed to provide molded articles without use. Such molded articles are particularly required in many industrial processes, for example in a number of processes in which the zeolite material of the present invention is used as a catalyst or adsorbent.

Thus, the present invention also relates to a molded article comprising the copper and iron ion-exchanged zeolite material of the present invention having a BEA-type framework structure.

Generally, a powder or sprayed material can be molded, for example, without any other compound by suitable compression, to obtain a molded article of the desired geometric shape (e.g., tablet, cylinder, sphere, etc.).

Preferably, the powder or sprayed material is mixed with a suitable refractory binder or coated with a suitable refractory binder. In general, suitable binders are all compounds that impart adhesion and / or aggregation between zeolite material particles that must be bonded in excess of the physical adsorption that may be present without the binder. Examples of such binders are, for example _{SiO 2, Al 2 O 3,} TiO 2, ZrO ₂ or a mixture of metal oxide, MgO, or viscosity, or two or more of these compounds such as The naturally occurring clays that may be used include montmorillonite and kaolin series, which include suet bentonite, and Dixie, McNamee, which is a major mineral component, such as halloysite, kaolinite, dickite, , Georgia and Florida clays, and the like. These clays may be used as originally mined raw materials, or may first be subjected to calcination, acid treatment or chemical modification. The zeolite material according to the present invention can also be used in the production of silica-alumina, silica-magnesia, silica-zirconia, silica-tori, silica- beryllium and silica- -Magnesia and silica-magnesia-zirconia. ≪ / RTI >

Also preferably, after being coated with a suitable refractory binder as described above or coated with a suitable refractory binder as described above, the powder or sprayed material forms a slurry with, for example, water, which is deposited on a suitable refractory carrier do. The slurry may also contain other compounds such as stabilizers, defoamers, accelerators, and the like. Typically, the carrier comprises a member, commonly referred to as a "honeycomb" carrier, comprising at least one refractory body having a plurality of fine, parallel gas flow passages extending therethrough. Such carriers are well known in the art and can be made from any suitable material such as cordierite and the like.

Generally, the zeolite material according to any of the preferred specific embodiments described herein can be used as a molecular sieve, an adsorbent, a catalyst, a catalyst support, or a binder therefor. Particularly preferred is the use as a catalyst. For example, the zeolite material may be a molecular sieve for drying a gas or liquid for selective molecular separation, e. G., Separation of hydrocarbons or amides; As ion exchangers; As a chemical carrier; As adsorbents for separating adsorbents, in particular hydrocarbons or amides; Or as a catalyst. Most preferably, the zeolite material according to the invention is used as a catalyst.

According to a preferred embodiment of the present invention, the zeolite material according to any of the preferred specific embodiments described herein is preferably used as a catalyst and / or catalyst support, more preferably as a catalyst for the contact process. In general, the zeolite material of the present invention may be used as a catalyst and / or catalyst support in any recognizable contacting process and may comprise one or more organic compounds, more preferably one or more carbon-carbon and / or carbon-oxygen and / More preferably one or more carbon-carbon and / or carbon-oxygen bonds, even more preferably one or more carbon-carbon bonds. A related process is preferred. Thus, by way of example, zeolite materials can be used as catalysts and / or catalyst supports in a flow catalytic cracking (FCC) process. According to a further embodiment of the present invention, the zeolite material of the present invention is preferably used in a contacting process involving the conversion of one or more compounds comprising at least one nitrogen-oxygen bond.

Therefore, according to the present invention, zeolite materials with a BEA-type framework structure can be used for the oxidation of NH ₃ , in particular for the oxidation of NH ₃ slips in diesel systems; On the decomposition of N ₂ O; On char oxidation; For emission control in advanced emission systems such as a premixed compression ignition (HCCI) engine; As an additive in a flow catalytic cracking (FCC) process; As a catalyst in an organic conversion reaction; Or "stationary source" processes. Therefore, NH ₃ The invention also in the method, in particular a diesel system to oxidize NH ₃ into contact with the stream containing the invention BEA--like skeleton structure of the zeolite catalyst and the NH ₃ containing a substance having under suitable oxidation conditions in accordance with the A method of oxidizing slip; A method of decomposing N ₂ O by contacting a catalyst containing a zeolite material having a BEA-type framework structure according to the present invention with a stream containing N ₂ O under suitable decomposition conditions; A method for controlling exhaust gas in an advanced exhaust gas suppression device such as a premixed compression ignition (HCCI) engine by contacting an exhaust gas stream with a catalyst containing a zeolite material having a BEA-type framework structure according to the present invention under suitable conditions; A flow catalytic cracking (FCC) process using a zeolite material having a BEA-type framework structure according to the present invention as an additive; A method of converting said compound by contacting an organic compound with a catalyst containing a zeolite material having a BEA-type framework structure according to the present invention under suitable conversion conditions; Quot; fixed source "process using a catalyst containing a zeolite material having a BEA-type framework structure according to the present invention.

However, in accordance with a particularly preferred embodiment of the present invention, the zeolite material according to any of the preferred specific embodiments described herein is used in a selective catalytic reduction (SCR) process for the selective reduction of nitrogen oxides NO _x to a catalyst and / Is used as a support, preferably as a catalyst.

As a result, the present invention also relates to a process for the selective catalytic reduction (SCR), preferably using a zeolite material in the catalytic process, preferably as a catalyst, more preferably for the treatment of industrial or automotive exhaust gases, ) ≪ / RTI > according to any of the preferred specific embodiments described herein.

Thus, the present invention also relates to a process for the production of nitrogen oxides NO _< RTI ID = 0.0 & gt _; NO _{< /} RTI & gt _; by contacting a gas stream containing NOx with a catalyst containing a zeolite material having a BEA- type framework according to any of the preferred & _x is selectively reduced. Within the meaning of the present invention, the terms "nitrogen oxides" and "NO _x " refer to nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ) and / or mixtures thereof and preferably a mixture of NO and NO ₂ .

Therefore, the present invention also provides a catalyst comprising (a) a zeolite material having a BEA-type framework structure according to any of the preferred specific embodiments described herein; (b) treating the NO _x by selective catalytic reduction (SCR), comprising contacting the gas stream comprising NO _x with the catalyst provided in step (a).

If the catalyst of the present invention and / or the method of the present invention for treating NO _x are to be used as catalysts, and more particularly if they are suitable for the treatment of NO _x by SCR in the process of the present invention, There is no particular limitation as to the manner or form in which the catalyst of the present invention is used or is provided in step (a) of the process of the present invention. Thus, by way of example, when preparing a specific catalyst composition or composition for a different purpose, the zeolite material according to the invention having a BEA-type framework structure can be blended with one or more other catalytically active materials or materials active with respect to the intended purpose Can be recognized. The presence or absence of additional metals such as YO ₂ : X ₂ O ₃ ratios, preferably SiO ₂ : Al ₂ O ₃ ratios, and / or transition metals, and / or the iron and copper Two or more different inventive materials that may be different in certain aspects of the additional metal, such as transition metal, in addition to the metal. In addition, two or more different inventive materials may be blended with one or more other catalytically active materials or materials that are active in connection with the intended purpose.

The catalysts of the present invention may also be provided in the form of extrudates, pellets, tablets or any other suitable shaped particles for use as packed phases of particulate catalysts or as molded parts such as plates, saddles, .

In addition, the catalyst may be disposed on the substrate. The substrate can be any material typically used in the manufacture of catalysts, and typically includes a ceramic or metal honeycomb structure. Such as a monolithic substrate of the type having fine and parallel gas flow passages extending therethrough from the inlet or outlet face of the substrate (referred to as honeycomb flow through the substrate) such that the passageway is open for fluid flow therethrough Any suitable substrate can be used. The passageway, which is an intrinsic linear path from the fluid inlet to the fluid outlet, is defined by a wall in which the catalytic material is disposed as a washcoat so that the gas flowing through the passageway contacts the catalytic material. The flow path of the monolithic substrate is a thin walled channel and may have any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, Such a structure may contain from about 60 to about 400 gas inlet openings (i.e., cells) per square inch (2.54 cm x 2.54 cm).

The substrate may also be a wall-flow filter substrate, where the channels are alternately interrupted so that the gaseous stream entering the channel in one direction (inlet direction) flows through the channel wall and out of the channel in the other direction do. The catalyst composition may be coated on a through or wall-flow filter. When a wall flow substrate is used, the resulting system can remove particulate matter with gaseous contaminants. The wall-flow filter substrate can be made from materials conventionally known in the art, such as cordierite, aluminum titanate, or silicon carbide. It will be appreciated that the loading of the catalyst composition on the wall flow substrate will depend on substrate properties such as porosity and wall thickness, and typically lower than loading on the through substrate.

The ceramic substrate may comprise any suitable refractory material, such as cordierite, cordierite-alumina, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, silymanite, magnesium silicate, zircon, Alpha-alumina, aluminosilicate, and the like.

Substrates useful in the catalyst of embodiments of the present invention may also be metallic in nature and may consist of one or more metals or metal alloys. The metal substrate may be used in various shapes such as a wavy sheet or monolithic form. Suitable metal supports include heat resistant metals and metal alloys such as titanium and stainless steel, as well as other alloys where iron is a substantial component or a major component. Such alloys may contain one or more of nickel, chromium, and / or aluminum, and the total amount of these metals advantageously is at least 15 wt% (e.g., 10-25 wt% chromium, %, Nickel 20 wt% or less). The alloy may also contain minor or minor amounts of one or more other metals such as manganese, copper, vanadium, titanium, and the like. The corrosion resistance of the alloy can be improved by oxidizing the surface of the metal substrate at a high temperature, for example, 1000 占 폚 or higher, and forming an oxide layer on the surface of the substrate. This high temperature-induced oxidation can improve the adhesion of the metal component promoted by the refractory metal oxide support and the catalyst to the substrate.

In another embodiment, a zeolite material according to the present invention having a BEA-type framework structure may be deposited on an open-celled foam substrate. Such substrates are well known in the art and are typically made of refractory ceramic or metallic materials.

Most preferably, the zeolite material according to any particular preferred embodiment described herein is a catalyst that is shaped to selectively reduce nitrogen oxide NO _x according to the preferred use of the material of the present invention, more preferably a zeolite material The zeolite material according to step (a) of the process of the present invention for treating NO _x by selective catalytic reduction or as a shaped catalyst deposited on a suitable fire resistant carrier, more preferably a "honeycomb &≪ / RTI >

With reference to contacting the gas stream with a catalyst comprising a zeolite material having a BEA-type framework structure according to certain preferred embodiments described herein, the gas stream containing NO _x in step (b) of the process of the present invention and There is no particular limitation as to the manner or condition in which the contact is made, as long as it is suitable for use in the SCR reaction between the catalysts. According to a preferred embodiment of the present invention, the contact is made at an elevated temperature relative to ambient temperature, more preferably at 150 to 700 占 폚, and the contact temperature is more preferably 200 to 650 占 폚, more preferably 250 to 600 占 폚 More preferably 300 to 550 占 폚, still more preferably 350 to 525 占 폚, still more preferably 400 to 500 占 폚. According to a particularly preferred embodiment of the method of the present invention, the contact temperature in step (b) is 425 to 475 占 폚.

However, according to another embodiment of the method of the invention which is particularly preferred, the contact is made at least partly under so-called "cold-start" conditions, which are typically encountered, for example, in the treatment of automotive exhaust gases. Specifically, within the meaning of the present invention, the contacting of a gaseous stream comprising NO _x under "low temperature-initiated" conditions may be used in the process of the present invention, in accordance with any of the preferred specific embodiments described herein for use in SCR Quot; means that the contact is made at a temperature lower than that required for optimal activity of the catalyst. However, in accordance with the present invention, the "cold-start" condition is such that the temperature of the exhaust gas and / or the temperature of the catalyst itself during contact with the catalyst used in the method of the present invention during the first period immediately after ignition of the combustion engine When the combustion engine is not operated for a certain period of time so as to be below the temperature required for optimum activity of the catalyst, it is desirable to indicate the conditions, especially the temperature, which are usually encountered in automotive applications. Within the meaning of the present invention, the "temperature of the optimum activity of the catalyst" refers in particular to the specific composition and temperature of the gas stream in contact with the catalyst in the process of the invention, as well as the contact pressure and time of the gas stream containing the NO _x with the catalyst Refers to the lowest temperature at which the catalyst exhibits maximum activity with respect to the treatment of NO _x in the SCR process, depending on additional parameters,

Therefore, in general, according to this particularly preferred embodiment of the process of the present invention, the temperature of the "cold-start" condition is any temperature below the temperature of the optimum activity of the catalyst used in the process of the present invention, This temperature is in the range of 50 to 500 DEG C, which is less than the optimum catalytic activity temperature, more preferably 100 to 400 DEG C, more preferably 150 to 350 DEG C, which is less than the optimum activation temperature of the catalyst used in the method of the present invention, Is 200 to 300 占 폚, and still more preferably 225 to 275 占 폚. Therefore, according to another embodiment of the method of the present invention, which is particularly preferred, the particular composition of the gas stream comprising the specific catalyst and NO _x according to certain preferred embodiments of the present invention used in the process of the present invention and the contact conditions , The contact temperature in step (b) is 50 to 500 ° C, preferably the contact temperature is 90 to 400 ° C, more preferably 120 to 300 ° C, more preferably 150 to 250 ° C, Lt; / RTI >

With regard to the gas stream comprising NO _x in contact with the catalyst in step (b) of the process of the present invention, if treatment of NO _x by SCR in step (b) is possible, And is not particularly limited. According to a preferred embodiment of the present invention, the gas stream further comprises at least one reducing agent, more preferably at least one reducing agent active in the SCR process when simultaneously contacting both NO _x and catalyst contained in the gas stream. In general, any suitable reducing agent may be used and it is preferred that the reducing agent comprises urea and / or ammonia. In particular, the selective reduction of nitrogen oxides using the zeolite material according to the invention as the catalytically active substance is preferably carried out preferably 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, SCR systems are incorporated into engine and vehicle designs and typically also contain the following key components: a SCR catalyst containing the zeolite material according to the invention; Urea storage tank; Urea pump; Urea injection system; Urea injector / nozzle; And an individual control unit device.

Therefore, according to a preferred embodiment of the process of the present invention, the gas stream further comprises at least one reducing agent, wherein the at least one reducing agent preferably comprises urea and / or ammonia, preferably ammonia.

The invention therefore also relates to a process for the production of a gaseous stream comprising nitrogen oxides NO _x and preferably further comprising at least one reducing agent, preferably in the form of a shaped catalyst, more preferably a refractory carrier suitable for zeolite material, preferably a "honeycomb" as a molded catalyst deposited on a carrier, in a selective catalytic reduction (SCR) process in which contact with a zeolite material in accordance with any particular embodiment preferred according to the present selective reduction in the nitrogen oxides NO _x . With respect to the at least one reducing agent preferably used in the SCR process of the present invention, the compounds that can be used are not particularly limited according to the present invention, and preferably at least one reducing agent includes ammonia and / or urea, Preferably, the reducing agent further preferably included in the gaseous stream is ammonia and / or urea.

Nitrogen oxides that are reduced using a catalyst containing a zeolite material according to any of the preferred specific embodiments described herein can be obtained from any process, particularly as a waste gas stream. In particular, mention is made of a waste gas stream obtained in the process of producing adipic acid, nitric acid, hydroxylamine derivatives, caprolactam, glyoxal, methyl-glyoxalic acid, glyoxylic acid or in burning nitrogen material .

Thus, according to a preferred embodiment of the process of the invention, the gas stream comprises at least one NO _x -containing waste gas, preferably at least one NO _x -containing waste gas from at least one industrial process, more preferably NO _x Containing waste gas stream may comprise one or more of the lungs obtained from the process of producing adipic acid, nitric acid, hydroxylamine derivatives, caprolactam, glyoxal, methyl-glyoxal, glyoxylic acid, Gas stream (including a mixture of waste gas streams from two or more of the above processes).

However, it is also particularly preferred that nitrogen oxides NO < RTI ID = 0.0 > NO < / RTI > from the exhaust of an internal combustion engine, in particular a diesel engine or a lean-burn gasoline engine, operated under combustion conditions using air exceeding the amount required for stoichiometric combustion, _x < / RTI > of the zeolite material according to any of the preferred characteristic embodiments described herein. Specifically, within the meaning of the present invention, "lean condition" means that the ratio of air to fuel in the combustion mixture supplied to such an engine is kept substantially higher than the stoichiometric ratio so that the resulting exhaust gas is & And is relatively high in terms of oxygen content. More particularly, the lean-burn engine is operated at air-to-fuel ratios exceeding lambda = 1.0, preferably above lambda = 1.2, even more preferably above lambda = 1.5.

Therefore, in accordance with another preferred embodiment of the inventive method, the gas stream is supplied from an internal combustion engine, preferably from an internal combustion engine operating under lean-burn conditions, more preferably from a lean-burn gasoline engine or from a diesel engine NO _x containing waste gas.

The present invention includes the following embodiments and these embodiments include certain combinations of embodiments represented by separate mutual dependence as defined herein:

1. YO _2, and a method for manufacturing a zeolite material having a BEA--like skeleton structure containing X ₂ O _3, (1) preparing a mixture comprising at least one source and at least one source of the YO ₂ X ₂ O ₃ ; (2) crystallizing the mixture obtained in step (1); (3) performing an ion-exchange procedure with copper for the zeolite material having the BEA-type framework structure obtained in step (2); And (4) performing an ion exchange procedure with Fe for the Cu ion-exchanged zeolite material obtained in step (3), wherein Y is a tetravalent element and X is a trivalent element , And wherein the mixture provided in step (1) and comprising the at least one zeolite material having a BEA-type framework structure, wherein the mixture crystallized in step (2) comprises at least one zeolite material provided in step (1) 2) does not contain an organic template as a structure-directing agent.

2. The process of embodiment 1, wherein the seeds are zeolite beta.

3. The zeolite material obtained in step (2) comprises at least one alkali metal M, wherein M is preferably selected from the group consisting of Li, Na, K, Cs and combinations of two or more thereof, Li, Na, K, and combinations of two or more thereof, more preferably the alkali metal M is Na and / or K, preferably Na.

Wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more thereof, preferably Si, Ti, Zr and combinations of two or more thereof, The method of any one of the embodiments 1 to 3, wherein Y represents Si and / or Sn, and Y is preferably Si.

5. In the above step (1) a silicate and at least one source of the YO ₂ or more provided by the / or silica, preferably comprising at least one silicate and at least one silica, and the at least one silicate and preferably one or more alkali Wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs, more preferably the alkali metal is Na and / or K, Wherein the metal is Na, more preferably at least one silicate comprises water glass, more preferably sodium silicate and / or potassium silicate, more preferably sodium silicate, and the at least one silica is preferably at least one silica hydrosol And / or one or more colloidal silicas, more preferably one The process of any one of embodiments 1-4 wherein the colloidal silica comprises at least one colloidal silica.

Wherein X is selected from the group consisting of Al, B, In, Ga and combinations of two or more thereof, preferably selected from the group consisting of Al, B, In and combinations of two or more thereof, Lt; RTI ID = 0.0 > Al < / RTI > and / or B and wherein X is preferably Al.

7. The composition of claim 1 wherein said at least one source of X ₂ O ₃ comprises at least one aluminate salt, preferably an alkali metal aluminate, said alkali metal preferably being selected from the group consisting of Li, Na, K, Rb and CS , And more preferably the alkali metal is Na and / or K, and even more preferably the alkali metal is Na.

8. In the above step (1) a mixture of YO ₂ in accordance with: the X ₂ O ₃ molar ratio of 1 to 200, preferably 5 to 100, more preferably from 10 to 50, more preferably from 15 to 40, more preferably Is from 20 to 30, more preferably from 23 to 25. The method of any one of embodiments < RTI ID = 0.0 > 1 to < / RTI >

9. The amount of the seed crystal contained in the mixture according to step (1) YO to one or more of the source of YO _{2 2} on the basis of 100% by weight 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably Is from 1 to 10% by weight, more preferably from 1.5 to 5% by weight, more preferably from 2 to 4% by weight, and still more preferably from 2.5 to 3.5% by weight. Gt;

10. The process according to any one of the preceding claims, wherein the mixture according to step (1) further comprises at least one solvent, wherein the at least one solvent is selected from the group consisting of water, organic solvents and mixtures thereof, more preferably deionized water, And mixtures thereof, more preferably at least one member selected from the group consisting of deionized water, methanol, ethanol, propanol and mixtures thereof, more preferably the solvent is deionized water. RTI ID = 0.0 > 9 < / RTI >

11. The process according to claim 1, wherein the H ₂ O: YO ₂ molar ratio of the mixture according to step (1) is 5 to 100, preferably 10 to 50, more preferably 13 to 30, more preferably 15 to 20, Lt; RTI ID = 0.0 > 17-18. ≪ / RTI >

12. The composition according to the above step (1), wherein the molar ratio of M: YO ₂ is 0.05 to 5, preferably 0.1 to 2, more preferably 0.3 to 1, still more preferably 0.4 to 0.8, 0.7, more preferably 0.5 to 0.65, still more preferably 0.55 to 0.6. ≪ RTI ID = 0.0 > 11. < / RTI >

13. The process according to claim 1, wherein the molar ratio of YO ₂ : X ₂ O ₃ : M of the mixture according to step (1) is (1 to 200): 1: (0.5 to 100), preferably (5 to 100) (10 to 50): 1: (8 to 50), more preferably (15 to 40): 1: (10 to 30), still more preferably (20 to 30): 1 (1) to (14), wherein the ratio of (1 to 12), more preferably (23 to 25): 1: (12 to 15), still more preferably (23.5 to 24) Lt; RTI ID = 0.0 > 12. ≪ / RTI >

14. The method according to claim 1, wherein the crystallization in step (2) is carried out at a temperature of preferably 80 to 200 占 폚, more preferably 90 to 180 占 폚, more preferably 100 to 160 占 폚, further preferably 110 to 140 占 폚, Lt; RTI ID = 0.0 > 130 C, < / RTI >

15. The method of embodiment 14, wherein the crystallization of step (2) is carried out under solvent thermal conditions, preferably under hydrothermal conditions.

16. The method according to claim 1, wherein the crystallization in step (2) is carried out for 5 to 160 hours, more preferably 10 to 140 hours, more preferably 20 to 120 hours, further preferably 40 to 100 hours, Lt; RTI ID = 0.0 > 15, < / RTI >

17. The method according to any of the preceding claims, wherein after step (2) after step (3), the method comprises: (i) isolating the zeolite material having the BEA-type framework structure obtained in step (2) And (ii) optionally, washing the zeolite material having the BEA-type framework structure obtained in step (2); And / or (iii) optionally, drying the zeolite material having the BEA-type framework structure obtained in step (2), wherein step (i) and / or And / or (iii) may be performed in any order, and wherein one or more of the steps are preferably repeated one or more times.

18. The process according to claim 1, wherein the ion-exchange of the zeolite material having a BEA-type framework structure in step (3) comprises: (3a) ionic non-skeleton contained in the zeolite material having a BEA-type framework structure obtained in step Exchanging at least one of the elements with H ^& lt ^{; +} & gt ^; and / or NH ₄ ⁺ , preferably NH ₄ ⁺ ; (3b) The method of any one of embodiments 1-7, comprising performing an ion-exchange procedure with Gu for a zeolite material having a BEA-type framework structure obtained in step (3a).

19. The method of any one of embodiments 1 to 18, wherein after step (3), before step (4), the ion-exchanged zeolite material obtained in step (3) is calcined.

20. The method of any one of embodiments 1 to 19, which calcines the zeolite material obtained in step (4) above.

21. The method according to claim 1, wherein the calcination is carried out at 300 to 850 캜, preferably 350 to 750 캜, more preferably 400 to 650 캜, more preferably 425 to 600 캜, still more preferably 450 to 550 캜, To 525 < 0 > C. The method of any one of embodiments 19, 20,

22. The method of any one of embodiments 1 to 21, wherein the zeolite material having the BEA-type framework structure prepared in step (2) comprises zeolite beta.

23. The process of any of embodiments 2 to 22, wherein said seeds comprise a zeolite material, preferably a zeolite beta, having a BEA-type framework structure synthesized according to the method of any of embodiments < RTI ID = The method of any one embodiment.

24. The method according to any one of the preceding claims, wherein the ion-exchange procedure with Cu in step (3) above is carried out using one or more copper containing compounds and wherein the one or more copper containing compounds are preferably copper (I) and / Is preferably selected from the group consisting of copper (II) compounds and more preferably copper (II) salts, wherein said at least one copper (II) salt is preferably copper (II) halide, preferably copper (II), copper sulfite (II), hydrogen sulfide (II), copper sulfate (II), copper nitrite (II) (II), copper (II) acetate, copper (II) acetate, copper (II) citrate, copper (II) , Copper malonate (II), copper oxalate (II), copper (II) tartrate, and mixtures of two or more thereof. Preferably copper chloride (II), copper (II) chloride, copper (II) sulfate, copper (II) nitrate, copper (II) acetate and mixtures of two or more thereof , More preferably at least one copper-containing compound used in ion-exchange in step (3) comprises copper (II) acetate, more preferably copper (II) acetate is selected from copper Lt; RTI ID = 0.0 > 23 < / RTI >

25. The process of claim 1 wherein the ion exchange procedure with Fe in step (4) is carried out using at least one iron-containing compound and wherein the at least one iron-containing compound is selected from the group consisting of iron (II) and / Wherein the at least one iron-containing compound is selected from the group consisting of iron sulfate, iron sulfite, hydrogen sulfide, iron chloride, iron bromide, iron iodide, iron fluoride, iron perchlorate, iron nitrate, Wherein the iron phosphate is at least one selected from the group consisting of iron phosphate, iron phosphate, iron phosphate, iron carbonate, ferrous carbonate, ferric acetate, ferric citrate, iron malonic acid, iron oxalate, iron tartrate, hexacyano iron salt, ferrocene, More preferably from the group consisting of iron sulfate, iron chloride, iron nitrate, ferrocene and combinations of two or more thereof, more preferably from the group consisting of iron sulfate and / or ferrocene It is chosen, more preferably from embodiment 1 to embodiment 24 of the method of any one of the embodiments of the ferrocene iron-containing compound.

26. The method of claim 1, wherein the ion exchange procedure with Fe in step (4) comprises: (4a) impregnating the Cu ion-exchanged zeolite material obtained in step (3) with one or more iron- The method of any one of embodiments < RTI ID = 0.0 > 1 < / RTI > to 25, comprising calcining the zeolite material obtained in 4a).

27. The method according to any one of the preceding claims, wherein the amount of Cu in the zeolite material obtained in step (4) is from 0.1 to 25% by weight, preferably from 0.2 to 20% by weight, more preferably from 0.5 to 0.5% by weight, calculated as CuO based on the total weight of the zeolite material. To 15% by weight, more preferably 0.8 to 10% by weight, further preferably 1 to 8.0% by weight, still more preferably 1.2 to 7.0% by weight, still more preferably 1.5 to 6.0% by weight, still more preferably 2.5 To 5.5% by weight, more preferably from 3.0% to 4.0% by weight, and the amount of Fe in the zeolite material obtained in step (4) is calculated as Fe ₂ O ₃ based on the total weight of the zeolite material, By weight, preferably 0.2 to 15% by weight, more preferably 0.3 to 10% by weight, further preferably 0.5 to 7.5% by weight, more preferably 0.7 to 5.0% by weight and even more preferably 0.8 to 4.0% by weight %, More preferably 1.0 to 3.5% by weight, more preferably 2.0 to 3.1% by weight, Embodiments 1 to 26, embodiments of the method of any one of embodiments.

28. A zeolite material having a BEA-type framework structure obtainable and / or obtainable according to the method of any one of embodiments < RTI ID = 0.0 > 1 < / RTI &

29. A zeolite having a BEA-type framework structure, having an X-ray diffraction pattern comprising at least the following reflectivities and optionally obtainable / obtained according to the method of any of embodiments < RTI ID = as the material, and 100% of the X- ray powder it relates to the intensity of the maximum peak in the diffraction pattern, wherein Y is a tetravalent element BEA- the skeleton structure comprises a YO ₂ and X ₂ O _3,, wherein X Wherein the zeolite material comprises Cu and Fe in an ion-exchange form and ion-exchange with Cu before ion-exchange with Fe,

30. The composition according to any one of the above items, wherein the YO ₂ : X ₂ O ₃ molar ratio is 2 to 100, preferably 4 to 70, more preferably 5 to 50, more preferably 6 to 30, further preferably 7 to 20, Is from 8 to 15, more preferably from 9 to 13, even more preferably from 10 to 11. The zeolite material of embodiment 29,

31. The composition of claim 1, wherein the loading of Cu is from 0.1 to 25 wt%, preferably from 0.2 to 20 wt%, more preferably from 0.5 to 15 wt%, more preferably from 0.8 to 0.8 wt%, calculated as CuO based on the total weight of the zeolite material. To 10% by weight, more preferably 1.0 to 8.0% by weight, still more preferably 1.2 to 7.0% by weight, still more preferably 1.5 to 6.0% by weight, still more preferably 2.5 to 5.5% To 4.0% by weight, and when the Fe loading is calculated as Fe ₂ O ₃ based on the total weight of the zeolite material, it is 0.1 to 25% by weight, preferably 0.2 to 15% by weight, more preferably 0.3 to 10% By weight, more preferably 0.5 to 7.5% by weight, still more preferably 0.7 to 5.0% by weight, still more preferably 0.8 to 4.0% by weight, still more preferably 1.0 to 3.5% %, Embodiment 29 < RTI ID = 0.0 > The zeolite material of the embodiment 30.

32. The method according to claim 1, wherein the molar ratio of Cu: X ₂ O ₃ is 0.01 to 2.4, preferably 0.02 to 1.9, more preferably 0.05 to 1.45, further preferably 0.08 to 0.8, further preferably 0.1 to 0.7, Is from 0.14 to 0.6, more preferably from 0.2 to 0.5, and still more preferably from 0.3 to 0.4. ≪ Desc / Clms Page number 19 >

33. The method according to claim 1, wherein the molar ratio of Fe: X ₂ O ₃ is 0.01 to 2.4, preferably 0.02 to 1.4, more preferably 0.03 to 1.0, still more preferably 0.05 to 0.7, still more preferably 0.07 to 0.5, Is from 0.08 to 0.4, more preferably from 0.1 to 0.35, and still more preferably from 0.25 to 0.30. The zeolite material of any one of embodiments 29 to 32.

Wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more thereof, preferably Si, Ti, Zr and combinations of two or more thereof, The zeolite material of any one of embodiments 29 to 33, wherein Y represents Si and / or Sn, wherein Y is preferably Si.

Wherein X is selected from the group consisting of Al, B, In, Ga and combinations of two or more thereof, preferably selected from the group consisting of Al, B, In and combinations of two or more thereof, Is Al and / or B, and wherein X is preferably Al. ≪ RTI ID = 0.0 > 34. < / RTI >

36. A method, comprising: (a) providing a catalyst comprising a zeolite material according to any one of embodiments 28 to 35; (b) how to handle the NO _x by the step (a) selective catalytic reduction (SCR), which comprises contacting the gas stream containing the catalyst and NO _x that is provided in the.

37. The method of embodiment 36, wherein said gaseous stream further comprises at least one reducing agent, and wherein said at least one reducing agent preferably comprises urea and / or ammonia, preferably ammonia.

38. The method of claim 38, wherein the gas stream comprises at least one NO _x containing waste gas, preferably at least one NO _x containing waste gas from at least one industrial process, more preferably the NO _x containing waste gas comprises adipic acid, At least one waste gas stream obtained from a process for producing a hydroxylamine derivative, a hydroxylamine derivative, caprolactam, glyoxal, methyl-glyoxal, glyoxylic acid, or a process for burning nitrogen material Lt; RTI ID = 0.0 > 36, < / RTI >

39. The process of any one of embodiments 36 to 44 wherein the gas stream comprises an NO _x -containing waste gas stream from an internal combustion engine, preferably a lean-burn gasoline engine or a diesel engine, operated under an internal combustion engine, preferably under lean- The method of any one of embodiment < RTI ID = 0.0 >

40. As a catalyst preferably in the contacting step, more preferably in the selective catalytic reduction (SCR) of NO _x, preferably, the embodiment 28 to embodiment 35 in the processing of the NO _x containing exhaust gas according to the SCR , More preferably the zeolite material is used for industrial or automobile exhaust gas treatment, preferably for the treatment of automobile exhaust gas.

Example

Example 1 Synthesis Without Organic Templates in Sodium Form of Zeolite Beta

NaAlO ₂ with stirring 335.1g dissolved in H ₂ O and then 7,314g, zeolite beta seed crystal (by calcination at 500 ℃ for 5 hours, a conversion to H- form zeolite product, product number list International CP814C, when the calcination temperature is reached Gt; C / min. ≪ / RTI > was used). 7,340 g of a sodium water glass solution [26.5 to 28.5% by weight of SiO ₂ and 8.0 to 8.6% by weight of Na ₂ O, Wollner GmbH & Co. KG) and 1,436 g of Ludox AS 40 the mixture with 20L are moved into the _{autoclave, 1.00 SiO 2: 0.042 Al 2} O 3: 0.57 Na 2 O: provided the aluminosilicate gel having a molar ratio of H ₂ O 17.5. The reaction mixture was heated to < RTI ID = 0.0 > 120 C < / RTI > The reaction mixture was cooled to room temperature and then the solid was removed by filtration, washed repeatedly with deionized water and dried at 120 ° C for 16 hours to give 1,337 g of white crystalline product.

Chemical analysis shows that the obtained zeolite has a SiO ₂ : Al ₂ O ₃ molar ratio of 10.89 and a sodium content (calculated as Na ₂ O) of 6.69 wt% based on the calcined material. XRD measurements show that the crystalline product obtained is zeolite beta.

Example 2 : NH ₄ -exchange of zeolite beta from Example 1

1,000 g of the sodium form of the zeolite beta obtained from Example 1 was added to 10,000 g of an aqueous solution of ammonium nitrate (10% by weight). The suspension was heated to < RTI ID = 0.0 > 80 C < / RTI > and held at this temperature for 2 hours with continuous stirring. The solids were filtered at high temperature (no further cooling) on the filter press. The filter cake was washed with distilled water at room temperature until the conductivity of the wash water was less than 200 mu S cm <" ^{1 &} gt ;. The filter cake was then dried at 120 DEG C for 16 hours.

Repeat the above procedure once, NH ₄ - provided the exchanged zeolite beta.

Example 3 : Preparation of the H-form of Example 2

Examples of NH 2 from ₄ - to exchange the zeolite material calcined at 500 ℃ for 5 hours to obtain his H- form.

Chemical analysis shows that the H-form zeolite has a SiO ₂ : Al ₂ O ₃ ratio of 10.51 and a sodium content (calculated as Na ₂ O) of 0.08 wt% based on the calcined material.

The specific surface area (BET method) of the H-form product is 458 m ² / g. Temperature-programmed ammonia desorption represents a total absorption of 1.86 mmol of ammonia per gram of zeolite.

Results of ammonium desorption measurements Peak number Maximum temperature (℃) Amount (millimoles / g) One 214.1 1.25 2 340.9 0.61

Example 4 : Preparation of Cu-exchanged zeolite beta (4.1 wt%)

1.0 g of NH ₄ -exchanged zeolite beta from Example 2 was further Cu-exchanged with 100 ml of 0.006 M Cu (CH ₃ COO) ₂ aqueous solution at 40 ° C for 4 hours. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 DEG C for 6 hours. The resulting zeolite product was then calcined at 500 DEG C for 4 hours.

The Cu content of the obtained Cu-exchanged zeolite is 4.1% by weight when determined by ICP measurement.

Example 5 : Preparation of Fe-exchanged zeolite beta (2.7 wt%)

Example 2 NH ₄ from the toluene solution of the exchanged zeolite beta 1.0g ferrocene was impregnated for 48 hours at room temperature with (0.1g ferrocene in toluene 1.04g) (using incipient wetness method). The zeolite product was then calcined at 500 ° C. for 4 hours to allow the Fe species to enter the ion-exchangeable sites of the zeolite beta.

The Fe content of the obtained Fe-exchanged zeolite is 2.7% by weight when determined by ICP measurement.

Example 6 : Preparation of Cu (4.0 wt%) / Fe (0.6 wt%) zeolite beta by ion-exchange

1.0 g of NH ₄ -exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of 0.006 M Cu (CH ₃ COO) ₂ solution at 50 ° C for 2 hours. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 DEG C for 6 hours. The Cu-exchanged zeolite was then calcined at 500 DEG C for 4 hours.

0.82 g of Cu-exchanged zeolite was then impregnated with a toluene solution of ferrocene (0.028 g of ferrocene in 0.86 g of toluene) at room temperature for 48 hours (using an initial wetting method). After the Fe-impregnation process, the zeolite was finally calcined at 500 占 폚 for 2 hours to obtain a Cu / Fe-conjugated zeta.

The Cu and Fe contents of the obtained bimetallic-exchanged zeolite beta are respectively 4.0 wt% and 0.6 wt% when determined by ICP measurement.

Example 7 : Preparation of Cu (3.0 wt%) / Fe (1.3 wt%) zeolite beta by ion-exchange

1.0 g of NH ₄ -exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of 0.0042 M Cu (CH ₃ COO) ₂ aqueous solution at 50 ° C for 2 hours. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 DEG C for 6 hours. The Cu-exchanged zeolite was then calcined at 500 DEG C for 4 hours.

0.82 g of Cu-exchanged zeolite was then impregnated with a toluene solution of ferrocene (0.058 g of ferrocene in 0.9 g of toluene) at room temperature for 48 hours (using an initial wetting method). After the Fe-impregnation process, the zeolite was finally calcined at 500 DEG C for 2 hours to obtain a Cu / Fe-exchanged zeolite beta.

The Cu and Fe contents of the obtained bimetallic-exchanged zeolite beta were 3.0 wt% and 1.3 wt%, respectively, when determined by ICP measurement.

Example 8 : Preparation of Cu (4.7% by weight) / Fe (2.0% by weight) zeolite beta by ion-exchange

1.0 g of the NH ₄ -exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of 0.01 M Cu (CH ₃ COO) ₂ aqueous solution at 50 ° C for 2 hours. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and dried at 110 ° C for 6 hours. The Cu-exchanged zeolite was then calcined at 500 DEG C for 4 hours.

Then 0.81 g of Cu-exchanged zeolite was impregnated with a toluene solution of ferrocene (0.055 g of ferrocene in 0.85 g of toluene) at room temperature (using an initial wetting method) for 48 hours. After the Fe-impregnation process, the zeolite was finally calcined at 500 DEG C for 2 hours to obtain a Cu / Fe-exchanged zeolite beta.

The Cu and Fe contents of the obtained bimetallic-exchanged zeolite beta were determined to be 4.7 wt% and 2.0 wt%, respectively, as determined by ICP measurement.

Example 9 : Preparation of Cu (2.8% by weight) / Fe (2.2% by weight) zeolite beta by ion-exchange

1.0 g of the NH ₄ -exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of 0.004 M Cu (CH ₃ COO) ₂ aqueous solution at 50 ° C for 2 hours. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 DEG C for 6 hours. The Cu-exchanged zeolite was then calcined at 500 DEG C for 4 hours.

0.85 g of Cu-exchanged zeolite was then impregnated with a toluene solution of ferrocene (0.058 g of ferrocene in 0.89 g of toluene) at room temperature for 48 hours (using an initial wetting method). After the Fe-impregnation process, the zeolite was finally calcined at 500 ° C for 2 hours to obtain Cu / Fe-exchanged zeolite beta.

The Cu and Fe contents of the obtained bimetallic-exchanged zeolite beta are 2.8% by weight and 2.2% by weight, respectively, when determined by ICP measurement.

Example 10 : Preparation of Cu (1.9 wt%) / Fe (2.1 wt%) zeolite beta by ion-exchange

0.5 g of NH ₄ -exchanged zeolite beta from Example 2 was Cu-exchanged with 50 ml of 0.01 M Cu (CH ₃ COO) ₂ aqueous solution at 40 ° C for 4 hours. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 DEG C for 6 hours. The Cu-exchanged zeolite was then calcined at 500 DEG C for 4 hours.

Following, Cu- for 24 hours at room temperature 0.41g exchanged zeolite 0.05M FeSO ₄ aqueous solution was exchanged with 50ml Fe-. After the Fe-impregnation process, the zeolite slurry was dried at 110 ° C for 6 hours and finally calcined at 500 ° C for 2 hours to obtain a Cu / Fe-exchanged zeolite beta.

The Cu and Fe contents of the obtained bimetallic-exchanged zeolite beta were 1.9 wt% and 2.1 wt%, respectively, when determined by ICP measurement.

Example 11 : Preparation of Fe (1.2 wt%) / Cu (2.7 wt%) zeolite beta by ion-exchange

1.0 g of the NH ₄ -type zeolite beta from Example 2 was Fe-exchanged with 100 ml of 0.003 M FeSO ₄ aqueous solution for 24 hours at room temperature. After the ion-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 DEG C for 6 hours. The Fe-exchanged zeolite was then calcined at 500 DEG C for 4 hours.

Then, for 12 hours at room temperature Fe- exchanged zeolite 0.8g Cu (NO _{3) 2} was impregnated with an aqueous solution of (in water _{0.64g Cu (NO 3) 2 0.094g} ). After the Cu impregnation process, the zeolite was finally calcined at 500 ° C for 2 hours to obtain Fe / Cu-exchanged zeolite beta.

The Cu and Fe contents of the obtained bimetallic-exchanged zeolite beta were 1.2 wt.% And 2.7 wt.%, Respectively, as determined by ICP measurement.

Example 12 : Preparation of a mixture of Cu-exchanged zeolite beta and Fe-exchanged zeolite beta

A control sample is prepared by mechanically mixing Cu-exchanged zeolite beta (3.0 wt%) and Fe-exchanged zeolite beta (1.3 wt%) at the same mass ratio.

Example 13 : Contact test

The metal (s) -changed zeolite material selected from Examples 4 to 12 was tested in an SCR reaction to reduce NO to NH ₃ . The SCR reaction was carried out in a stationary phase quartz reactor (inner diameter 6 mm) using about 0.18 g of catalyst (40-60 mesh). The catalyst was pretreated in an N ₂ stream (flow rate = 40 ml / min) at 500 ° C for 1 hour and then cooled to room temperature to obtain a reaction gas containing 500 ppm of NO, 500 ppm of NH ₃ , 10% of O ₂ and the remaining amount of N ₂ The mixture was introduced. The total flow rate was 400 ml / min corresponding to a gas hourly space velocity (GHSV) of about 80,000 hr ^-1 . NO, NO ₂ and NO _x (= NO + NO ₂ ) concentrations were continuously measured by a chemical luminescence analyzer (ML9841AS, Monitor, USA). In order to avoid the error caused by the conversion of ammonia in the analyzer, an ammonia trap containing a phosphoric acid solution was installed upstream. All data were obtained when the SCR reaction reached steady state at each temperature. Thus, the contact result of the measured embodiment is provided in Figs. 1 and 2.

Figure 1 shows the contact results of two single-metal-exchanged zeolite beta samples (i.e., Examples 4 and 5) and three bimetallic-exchanged zeolite beta samples (i.e., Examples 8 to 10) / RTI > All three Cu / Fe-exchanged zeolites exhibit a wide temperature window of 125 [deg.] C to 550 [deg.] C with an NO conversion efficiency of 70% to 99%. In particular, bimetallic-exchanged zeolites exhibit higher SCR activity than single-metal-exchanged zeolites at low temperatures. Alternatively, the bimetallic-exchanged zeolite reaches a higher contact reactivity much faster than the single-metal-exchanged zeolite as a function of the elevated temperature. More specifically, in FIG. 1, Cu / Fe-exchanged zeolites have already reached maximum contact reactivity at about 150 ° C, whereas Cu-exchanged zeolites and Fe- 175 < 0 > C and 350 < 0 > C. In addition, the bimetallic-exchanged zeolites of the present invention maintain higher contact reactivity than Cu-exchanged zeolites at high temperatures of 300 ° C to 550 ° C. Therefore, surprisingly, the Cu / Fe-exchanged zeolites of the present invention were found to be superior to two single-metal-exchanged zeolites in terms of contact reactivity as well as operating temperature range.

Fig. 2 shows the results of a comparison of the Cu / Fe-exchanged zeolite beta (Example 7), Fe / Cu-exchanged zeolite beta (Example 11) and a mixture of Cu- exchanged zeolite and Fe- exchanged zeolite 12). Cu / Fe-exchanged zeolite (Example 7) exhibits higher contact reactivity than the mechanical mixture (Example 12), not only in the low temperature range (i.e. below 150 ° C) but also in the high temperature range . Moreover, surprisingly, Cu / Fe-exchanged zeolites have been found to exhibit superior contact reactivity over Fe / Cu-exchanged zeolites, especially at temperatures above 350 ° C. Therefore, the order of ion-exchange with Cu and Fe during the manufacturing process is essential to achieve the high contact performance of the zeolite of the present invention.

Example 14 : Sulfur resistance

Examples 4, 5 and 7 were further tested for sulfur resistance during the contact reaction. For this effect, the procedure of Example 13, in which the gas mixture additionally contained 2% H ₂ O and 100 ppm of SO ₂ , was repeated. Figure 3 shows the time-dependent contact reactivity of Examples 4, 5 and 7 in the presence of 2% H ₂ O and 100 ppm SO ₂ at 250 ° C in the SCR process.

During the measured reaction time, the Cu / Fe-exchanged zeolite beta (Example 7) maintains a high and stable NO conversion efficiency. In contrast, the Fe-exchanged zeolite beta (Example 5) showed about a 15% reduction in NO conversion efficiency within the first 0.5 hour of the SCR reaction and the reactivity of the Cu-exchanged zeolite beta (Example 4) It seems to decrease continuously after time. Therefore, Cu / Fe-exchanged zeolites exhibit much better sulfur resistance than single-metal-exchanged zeolites in the SCR process.

The three zeolite catalysts reacted after sulfidation were analyzed by TG / DTG measurements, the results of which are shown in FIGS. The Cu / Fe-exchanged zeolite beta (Example 7) exhibits a relatively small desorption peak of the sulfur species at about 430 ° C as compared to the single-metal-exchanged zeolite (Examples 4 and 5). The above results of TG / DTG measurements indicate that the bimetallic-exchanged zeolite has low sulfur adsorption during the contact reaction, which is additional evidence of its high sulfur resistance.

In addition, the post-sulfided bimetallic-edited zeolite appears to be able to be regenerated effectively. More specifically, the regeneration of the sulfided catalyst was carried out in an N ₂ stream (flow rate = 40 ml / min) at 450 ° C for 1 hour to decompose the sulfurous salt / sulfate on the surface. Figure 7 shows that the regenerated catalyst of Example 7 maintained almost as high a SCR reactivity as the corresponding new catalyst.

The prior art references cited

- US 3,308,069 A

US 4,554,145 A

US 4,642,226 A

US 5,139,759 A

- Siao et al., Chemistry of Materials, 2008, 20 , pp. 4533-4535

- WO 2010/146156 A1

- Mazano et al., Chemistry of Materials, 2009, 21 , pp. 4184-4191

- Metka et al., Applied catalysis B: Environmental, 2012, 111-112 , pp. 67-80

- Yang et al., Journal of Physical Chemistry, 2012, 116 , pp. 23322-23331

- WO 2013/118063 A1

Claims (40)

A method for producing a zeolite material having a BEA-type framework structure comprising YO ₂ and X ₂ O ₃ ,
(1) preparing a mixture comprising at least one source and at least one source of the YO ₂ X ₂ O _3;
(2) crystallizing the mixture obtained in step (1);
(3) performing an ion-exchange procedure with copper for the zeolite material having the BEA-type framework structure obtained in step (2); And
(4) performing an ion-exchange procedure with Fe for the Cu ion-exchanged zeolite material obtained in step (3)
In this case,
Wherein Y is a tetravalent element, X is a trivalent element,
Wherein the mixture provided in step (1) and crystallized in step (2) further comprises a seed crystal comprising at least one zeolite material having a BEA-type framework structure,
Wherein the mixture provided in step (1) and crystallized in step (2) does not contain an organic template as a structure-directing agent. The method according to claim 1,
Wherein said seeds are zeolite beta. 3. The method according to claim 1 or 2,
Wherein the zeolite material obtained in step (2) comprises at least one alkali metal M. 4. The method according to any one of claims 1 to 3,
Wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof. 5. The method according to any one of claims 1 to 4,
The method of one or more source of YO ₂ provided in the above step (1), comprising at least one silicate and / or silica, preferably at least one silicate and at least one silica. 6. The method according to any one of claims 1 to 5,
Wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof. 7. The method according to any one of claims 1 to 6,
Wherein the at least one source of X ₂ O ₃ comprises at least one aluminate salt. 8. The method according to any one of claims 1 to 7,
The method of X ₂ O ₃ molar ratio of 1 to 200 ranges: YO ₂ in the mixtures according to the above step (1). 9. The method according to any one of claims 1 to 8,
0.1 to 30% by weight of, wherein the amount of the seed crystal on the basis of the YO ₂ 100% by weight of at least one source of the YO ₂ contained in the mixtures according to the above step (1). 10. The method according to any one of claims 1 to 9,
Wherein the mixture according to step (1) further comprises at least one solvent. 11. The method of claim 10,
Wherein the H ₂ O: YO ₂ molar ratio of the mixture according to step (1) ranges from 5 to 100. 12. The method according to any one of claims 1 to 11,
Wherein the M: YO ₂ molar ratio of the mixture according to step (1) ranges from 0.05 to 5. 13. The method according to any one of claims 1 to 12,
Wherein the molar ratio of YO ₂ : X ₂ O ₃ : M of the mixture according to step (1) ranges from (1 to 200): 1: (0.5 to 100). 14. The method according to any one of claims 1 to 13,
Wherein the crystallization of step (2) comprises heating the mixture. 15. The method of claim 14,
Wherein the crystallization of step (2) is carried out under solvothermal conditions. 16. The method according to claim 14 or 15,
Wherein the crystallization of step (2) comprises heating the mixture for 5 to 160 hours. 17. The method according to any one of claims 1 to 16,
After step (2) and before step (3), the method
(i) isolating the zeolite material having the BEA-type framework structure obtained in step (2); And
(ii) optionally, washing the zeolite material having the BEA-type framework structure obtained in step (2); And / or
(iii) optionally, drying the zeolite material having the BEA-type framework structure obtained in step (2)
, ≪ / RTI >
Wherein step (i) and / or (ii) and / or (iii) can be performed in any order. 18. The method according to any one of claims 1 to 17,
The ion-exchange of the zeolite material having a BEA-type framework structure in the step (3)
(3a) exchanging at least one of the ionic non-skeletal elements contained in the zeolite material having the BEA-type framework structure obtained in step (2) with H ⁺ and / or NH ₄ ⁺ ;
(3b) Performing an ion-exchange procedure with Cu for the zeolite material having the BEA-type framework structure obtained in step (3a)
/ RTI > 19. The method according to any one of claims 1 to 18,
Wherein the ion-exchanged zeolite material obtained in step (3) is calcined before step (4) after step (3). 20. The method according to any one of claims 1 to 19,
And calcining the zeolite material obtained in step (4). 26. The method according to any one of claims 19, 20 and 26,
Wherein the calcination is performed at 300 to 850 캜. 22. The method according to any one of claims 1 to 21,
Wherein the zeolite material having the BEA-type framework structure prepared in step (2) comprises zeolite beta. 23. The method according to any one of claims 2 to 22,
Wherein said seeds comprise a zeolite material having a BEA-type framework structure synthesized according to the process according to any one of claims 1 to 22. 24. The method according to any one of claims 1 to 23,
The ion exchange procedure with Cu in step (3) above is carried out using one or more copper containing compounds,
Wherein said at least one copper containing compound is selected from the group consisting of copper (II) salts. 25. The method according to any one of claims 1 to 24,
The ion exchange procedure with Fe in step (4) above is carried out using one or more iron containing compounds,
Wherein said at least one iron-containing compound is selected from the group consisting of iron (II) and / or iron (III) salts and iron complexes. 26. The method according to any one of claims 1 to 25,
The ion exchange procedure with Fe in step (4)
(4a) impregnating the Cu ion-exchanged zeolite material obtained in step (3) with at least one iron-containing compound, and
(4b) calcining the zeolite material obtained in step (4a)
/ RTI > 27. The method according to any one of claims 1 to 26,
Wherein the amount of Cu in the zeolite material obtained in step (4) is from 0.1 to 25% by weight, calculated as CuO based on the total weight of the zeolite material, and the amount of Fe in the zeolite material obtained in step (4) By weight, calculated as Fe ₂ O ₃ based on the total weight of the zeolite material. 27. A zeolite material having a BEA-type framework structure, which can be obtained and / or obtained according to the process according to any one of claims 1 to 27. A zeolite material having a BEA-type framework structure, which has an X-ray diffraction pattern comprising at least the following reflectivities and which can optionally be obtained and / or obtained according to the process according to any one of claims 1 to 27 , At this time
100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern,
The BEA-type framework structure comprises YO ₂ and X ₂ O ₃ ,
Y is a tetravalent element, X is a trivalent element,
Wherein the zeolite material comprises Cu and Fe in ion-exchanged form, wherein ion exchange with Cu prior to ion-exchange with Fe is carried out, wherein the zeolite material:

30. The method of claim 29,
YO ₂ : The zeolite material wherein the X ₂ O ₃ molar ratio ranges from 2 to 100. 32. The method according to claim 29 or 30,
And the loading of Cu of 0.1 to 25 wt% when calculated as CuO, based on the total weight of the zeolite material, 0.1 to 25% by weight when the loading of Fe being calculated as Fe ₂ O _3, based on the total weight of the zeolite material Zeolite material. 32. The method according to any one of claims 29 to 31,
Wherein the molar ratio of Cu: X ₂ O ₃ is in the range of 0.01 to 2.4. 32. The method according to any one of claims 29 to 32,
Fe: 0.01 to 2.4 the molar ratio of the range of X ₂ O _3, the zeolite material. 34. The method according to any one of claims 29 to 33,
Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more of these. 35. The method according to any one of claims 29 to 34,
X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof. (a) providing a catalyst comprising a zeolite material according to any one of claims 28 to 35;
(b) contacting the gas stream comprising NO _x with the catalyst provided in step (a)
Wherein the NO _x is treated by selective catalytic reduction (SCR). 37. The method of claim 36,
Wherein the gas stream further comprises at least one reducing agent. 37. The method of claim 36 or 37,
Wherein said gas stream comprises at least one NO _x containing waste gas. 39. The method according to any one of claims 36 to 38,
Wherein the gas stream comprises a NO _x containing waste gas stream from an internal combustion engine. Use of a zeolite material according to any one of claims 28 to 35 in a catalytic process.

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