process for the preparation of a zeolitic material

专利摘要:
PROCESS FOR THE PREPARATION OF A ZEOLITIC MATERIAL, ZEOLITICAL MATERIAL, AND, USE OF A ZEOLITICAL MATERIAL. The present invention relates to a process for the process for the preparation of a zeolitic material and which process comprises (i) providing a boron-containing zeolitic material and (ii) deboronation of the boron-containing zeolitic material by treating the boron-containing zeolitic material with a liquid solvent system thus obtaining a debonded zeolitic material, wherein the liquid solvent system does not contain an organic or inorganic acid, or a salt thereof.
公开号:BR112014019483B1
申请号:R112014019483-1
申请日:2013-02-05
公开日:2021-04-20
发明作者:Ulrich Müller；Andrei-Nicolae PARVULESCU；Jeff Yang；Hans-Jürgen Lützel；Georg Uhl；Stefan Dumser
申请人:Basf Se；
IPC主号:

专利说明:

[0001] The present invention relates to a process for the preparation of a zeolitic material in which a zeolitic material containing boron, preferably of a structure of the type MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, MEL, RTH, more preferably of MWW type structure, referred to herein as B-zeolite, in particular B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB , B-LEV, B-FER, B-MEL, B-RHT and B-MWW, is subjected to deboronation, thus obtaining a debonded B-zeolite, preferably a B-MWW, B-BEA, B-MFI , B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, crumbled B-RHT, preferably a crumbled B-MWW, referred to herein as MWW, BEA, MFI , CHA, MOR, MTW, RUB, LEV, FER, HONEY, RTH by treatment with a liquid solvent system that is selected from the group consisting of water, monohydric alcohols, polyhydric alcohols, and mixtures of two or more of them, preferably water, and which does not contain specific acids, and which, in particular, does not contain an inorganic acid at all. nico or an organic acid, or a salt of an inorganic acid or an organic acid. Furthermore, the present invention relates to a process which further comprises introducing at least one heteroatom, in particular one or two heteroatoms into MWW. Still further, the present invention relates to the zeolitic material obtainable or obtained by this process, and the use of this zeolitic material, in particular as a catalytically active agent. Still further, the present invention relates to specific zeolitic materials comprising at least two heteroatoms.
[0002] Crystalline silicates, in particular those that have a zeolitic structure, are used in numerous technical applications. Among others, zeolites are used as catalytically active agents for the preparation of chemical compounds and as molecular sieves, for example, for the separation of chemical compounds from a respective mixture. Such technical processes are carried out on a laboratory scale, on a pilot plant scale, and on an industrial scale. In particular, as far as pilot plant and industrial scale processes are concerned where relatively high amounts of zeolitic materials are employed, it is generally desired to prepare the zeolitic materials in an ecologically and economically advantageous manner.
[0003] A known method for the preparation of zeolitic materials comprises the preparation of a borosilicate-containing zeolitic structure, and a subsequent deboronation step where at least a portion of boron is removed from the zeolitic structure. Such debonded zeolitic materials can be used as such, or optionally subjected to other steps where heteroatoms are introduced into the interior of the material. Furthermore, it is well known that for such severe deboronation conditions it has to be applied, where, for example, the borosilicate is subjected to a steam treatment, an acid treatment, and/or a time consuming process involving various individual treatment steps that are necessary to achieve the desired reduction in the boron content of the zeolitic material.
[0004] For zeolitic materials with MWW zeolite structure and containing titanium as heteroatom, herein referred to as TiMWW, such a process is described in EP 1 485 321 A1. According to this process, a boron-containing aluminum-free silicate is prepared and subjected to a deboronation step whereby boron is removed from the silicate by treatment with an acid. In particular, it is described that the boron-containing silicate is contacted with an aqueous solution of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid, or of organic acids such as formic acid, acetic acid, acid propionic or tartaric acid. According to the specific examples of EP 1 485 321 A1, the use of strong inorganic acid nitric acid is preferred.
[0005] According to the scientific literature, the deboronation of B-MWW is more or less exclusively carried out by treatment of B-MWW with highly concentrated and highly corrosive nitric acid. Reference is made, for example, to P. Wu et al., Studies in Surface Science and Catalysis, vol. 154 (2004), p. 2581-2588.
[0006] Thus, according to the established process for deboronation of a B-MWW zeolite, high amounts of an acid are employed which require a high standard of safety measures.
[0007] This is also confirmed in WO 02/057181 A2 where, for the deboronation of a silicate, an acid is employed. According to specific examples, glacial acetic acid is employed, and according to possible embodiments that are not yet realized, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, acid oxalic, and tartaric acid are described.
[0008] The fact that the prior art teaches acid treatment as the method of choice for deboronation of boron-containing silicates is further exemplified in EP 1 490 300 A1 and USA 2006105903 A1, in which, in particular, in examples, the use of highly concentrated nitric acid is described. In addition, reference is made to P. Wu et al., Chemical Communications (2002), p. 1026-1027, where the use of highly concentrated nitric acid is also taught for the deboronation of boron-containing silicate. The same is taught in L. Liu et al., Microporous and Mesoporous Materials vol. 94 (2006) pp. 304-312 where deboronation by a combination of calcination and treatment with a concentrated nitric acid is described.
[0009] Furthermore, the examples of EP 1 324 948 A1 show that for the removal of boron from a silicate containing boron, drastic reaction conditions have to be applied in which highly concentrated nitric acid or sulfuric acid is used , in which the teachings are in accordance with the description of the above referenced documents. According to a general description of EP 1 324 948 A1, and for the specific case of a titanium silicate, steam can be useful for removing at least a portion of boron or aluminum from a respective boron-containing silicate or containing aluminum. According to this teaching, the drastic process conditions of the acid treatment can be replaced by another drastic process condition, i.e., the use of steam. In particular, as far as the industrial scale processes are concerned, the use of steam necessarily requires the production of steam, before a possible treatment of the silicate containing boron or containing aluminum, in which the production of steam, by its time, it also requires a higher standard of security measures.
[00010] Therefore, it was an object of the present invention to provide a process for the preparation of a zeolitic material from a boron-containing zeolitic material, referred to hereinafter as "B-zeolite", preferably of a MWW-type structure ( B-MWW), BEA (B-BEA), MFI (B-MFI), CHA (B-CHA), MOR (B-MOR), MTW (B-MTW), RUB (B-RUB), LEV (B -LEV), FER (B-FER), HONEY (B-MEL), RTH (B-RHT), more preferably of MWW type structure (B-MWW), in which for the deboronation of B-zeolite, preferably , B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, B-RHT, preferably B - MWW, in which none of the adverse reaction conditions as taught in the prior art are employed, in particular without acid treatment and/or without steam treatment.
[00011] It was also an object of the present invention to provide a process for the preparation of a zeolitic material from a boron-containing zeolitic material, referred to hereinafter as "B-zeolite", preferably of a MWW-type structure (B -MWW), BEA (B-BEA), MFI (B-MFI), CHA (B-CHA), MOR (B-MOR), MTW (B-MTW), RUB (B-RUB), LEV (B- LEV), FER (B-FER), HONEY (B-MEL), RTH (B-RHT), more preferably of MWW type structure (B-MWW), in which for deboronation the B-zeolite is preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, B-RHT, preferably B- MWW, where the treatment conditions are ecologically and economically advantageous and thus, in particular, suitable for large-scale industrial production.
[00012] Surprisingly, it has been found that such deboration can be performed by treating a B-zeolite, preferably a B-MWW, B-BEA, B-IMF, B-CHA, B-MOR, B-MTW, B -BRL, B-LEV, B-FER, B-MEL B-RTH, more preferably a B-MWW to a solvent system which is a liquid, ie not in vapor form, and which is not contain the acids, as taught in the prior art, which process is highly ecologically and economically advantageous.
[00013] Therefore, the present invention relates to a process for the preparation of a zeolitic material, and a zeolitic material obtainable and/or obtained by this process, said process comprising (i) providing a material containing zeolitic boron ( B- zeolite), preferably, or a boron-containing zeolitic material of the MWW type structure (B-MWW) or a boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW type structure (B-MWW), most preferably structure of type MWW (B-MWW), BEA (B-BEA), MFI (B-MFI), CHA (B-CHA), MOR (B-MOR), MTW (B-MTW), RUB (B-RUB), LEV (B-LEV), FER (B-FER), HONEY (B-MEL), or RTH (B-RHT); (ii) debombing the B-zeolite, preferably, or the boron-containing zeolitic material of the MWW type structure (B-MWW) or the zeolitic material containing boron, which is not a boron-containing zeolitic material of the MWW type structure (B -MWW), more preferably the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, B - RHT treating the B-zeolite, preferably, or the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW type structure (B- MWW), more preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, B-RTH with a liquid solvent system, thus obtaining a debonded B-zeolite, preferably, or a debonded B-MWW (MWW) or the debonded B-zeolite (zeolite) that is not MWW, more preferably a B-MWW ( MWW), B-BEA (BEA), B- MFI (MFI), B-CHA (CHA), B-MOR (MOR), B- MTW (MTW), B-RUB (RUB), B-LEV (LEV ), B-FER (FER), B-HONEY (HONEY) , B-RTH (RHT) decayed; wherein the liquid solvent system is chosen from the group consisting of water, monohydric alcohols, polyhydric alcohols, and mixtures of two or more thereof, and wherein said system of liquid solvent does not contain an organic or inorganic acid or a salt thereof, the acid being selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid , and tartaric acid.
[00014] Therefore, the present invention more preferably relates to a process for the preparation of a zeolitic material, and a zeolitic material obtainable and/or obtained by this process, said process comprising (i) providing a zeolitic material containing boron of structure of type MWW (B-MWW); (ii) B-MWW debonding by treating the B-MWW with a liquid solvent system, thus obtaining a debonded B-MWW (MWW); wherein the liquid solvent system is chosen from the group consisting of water, monohydric alcohols, polyhydric alcohols, and mixtures of two or more thereof, and wherein said liquid solvent system does not contain an organic acid or inorganic acid or a salt thereof, the acid being selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, and tartaric acid.
[00015] Generally, it is conceivable that the process according to the present invention may be carried out using a boron-containing zeolitic material or a mixture of two or more boron-containing zeolitic materials with a frame-like structure in accordance with the following codes of three letters: ABW, ACO, a AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, ETR, EUO, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFR, ISV, ITE, ITH, ITW, IWR, IWW, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, SEA, MAZ, MEI, HONEY, MEP, MER, MMFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NEES, NON, NPO, OBW, OFF, OSI, OSO, PAIR, PAU, PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG, SFH, SFN SFO, SGT, SOD, S SY, STF, STI, STT, TER, THO, TON, TSC, UEI, UFI, UOZ, USI, UTL, VET, VFI, VNI, VSV, WEI, WEN, YUG and ZON. In relation to the three-letter codes and their definitions, reference is made to the "Atlas of the types of Zeolite Pictures", 5th edition, Elsevier, London, England (2001). "MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL and RTH are preferred, and MWW, BEA and CHA are most preferred. MWW is most preferred. Step (i)
[00016] According to step (i), a boron-containing zeolitic material, preferably, or a boron-containing zeolitic material of the MWW type structure (B-MWW) or a boron-containing zeolitic material that is not a zeolitic material containing boron from the MWW structure type (B-MWW), preferably from the MWW structure type (B-MWW), BEA (B-BEA), MFI (B-MFI), CHA (B-CHA), MOR (B- MOR), MTW (B-MTW), RUB (B-RUB), LEV (B-LEV), FER (B-FER), HONEY (B-MEL), RTH (B-RHT), more preferably of structure of the type MWW (B-MWW) is provided. According to an embodiment of the present invention, the boron-containing zeolitic material provided in (i) is not B-MFI, and preferably, according to this embodiment, a boron-containing zeolitic material of the MWW-type structure ( B-MWW), BEA (B-BEA), CHA (B-CHA), MOR (B-MOR), MTW (B-MTW), RUB (B-RUB), LEV (B-LEV), FER (B -FER), MEL (B-MEL), RTH (B-RHT), more preferably of structure of type MWW (B-MWW) is given in (i).
[00017] The MWW structure zeolites, such as MCM-22 zeolites, have two independent pore systems. One system consists of 10-membered ring (MR) channels of two sinusoidal dimensions with an elliptical ring cross section of 4.1 Angstrom x 5.1 Angstrom. The other system is composed of large 12-MR super cages connected by 10 RM windows. Regarding this type of MWW structure, reference is made, for example, to M.K. Rubin, P. Chu, US 4,954,325, M.E. Leonowicz, J.A. Lawton, S.L. Lawton, M.K. Rubin, Science, vol. 264 (1994) p. 1910, or S.L. Lawton, M.E. Leonowicz, R.D. Partidge, P. Chu, M.K. Rubin, Micropor. Mesopor. Mater., Vol. 23 (1998) p. 109. More details regarding the MWW type structure can be found in W.M. Meier, D.H. Olson and Ch. Baerlocher "Atlas of zeolite structure types", Elsevier, fifth edition, pages 202 and 203, Amsterdam, 2001.
[00018] The term "boron-containing zeolitic material", in particular the term "boron-containing zeolitic material of the MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, RTH type structure", especially the The term "MWW type structure boron-containing zeolitic material" as used in the context of the present invention describes a silicate which preferably has MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER type zeolitic structure , MEL, or RTH, most preferably MWW, and which has a zeolitic structure in which a portion of the silicon atoms is replaced by boron atoms. In addition to silicon, oxygen and boron, B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B- FER, B-MEL, B-RTH, more preferably the B-MWW may contain additional elements such as other tetravalent or trivalent elements such as aluminum, zirconium, vanadium, tin, iron, cobalt, nickel, gallium, germanium, and /or chrome. According to an especially preferred embodiment of the present invention, B-zeolite is preferably B-MWW, B-BEA, B-IMF, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, B-RTH, most preferably, the B-MWW provided in (i) consists essentially of silicon, boron, and oxygen, and thus represents an aluminum-free zeolite material . The term "aluminium-free zeolite material" as used in the context of the present invention refers to a B-zeolite, which contains at most 100 ppm by weight, preferably at most 50 ppm by weight of aluminum, calculated as element and based on the weight of the B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL , or B -RTH, more preferably B-MWW. The term "consists essentially of silicon, boron, and oxygen" as used in this context of the present invention refers to B-zeolite materials, preferably B-MWW, B-BEA, B-MFI, B-CHA materials , B-MOR B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RHT, more preferably B-MWW material which may contain, in addition to silicon, boron, and oxygen, certain impurities resulting from the respective preparation process, such as alkali metals, alkaline earth metals, or organic carbon. These impurities are contained in B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B- MEL, or B-RTH, more preferably B-MWW in amounts preferably up to 1% by weight in total, more preferably up to 0.5% by weight in total, most preferably up to 0.2% by weight in total , more preferably up to 0.1% by weight in total, in each case based on B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW , B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW provided in (i).
[00019] According to the present invention, the B-zeolite, preferably, the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV , B-FER, B-MEL, or B-RTH, more preferably the B-MWW provided in (i) has a B content, preferably in the range of 0.5 to 5.0% by weight, most preferably 0 .75 to 4.0% by weight, more preferably 1.0 to 3.0% by weight, calculated as the element and based on the total weight of B-zeolite, preferably B-MWW, B-BEA , B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW provided in (i ). Especially preferred boron contents are in the range of 1.4 to 2.4% by weight, more preferably 1.6 to 2.4% by weight, most preferably 1.8 to 2.0% by weight. Furthermore, B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL , or B-RTH, more preferably the B-MWW provided in (i) has an Si content, preferably in the range 38 to 44% by weight, more preferably 39 to 43% by weight, most preferably 40 to 42 weight %, calculated as elemental Si and based on the total weight of B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL , B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW provided in (i). Furthermore, B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL , or B-RTH, more preferably the B-MWW provided in (i) has a C (total organic carbon, TOC) content, preferably in the range of 0.14 to 0.25% by weight, most preferably 0.15 to 0.22% by weight, more preferably 0.16 to 0.20% by weight, calculated as elemental C and based on the total weight of B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the supplied B-MWW in (i).
[00020] Therefore, the present invention relates to a process for the preparation of a zeolitic material, and the zeolitic material obtainable and/or obtained by this process, as defined above, wherein the B-zeolite, preferably, or the boron-containing zeolitic material of the MWW structure type (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW structure type (B-MWW), more preferably the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW provided in ( i) consisting essentially of B, Si, and O, and has a B content in the range of 0.5 to 5.0% by weight calculated as elemental B, a Si content in the range of 38 to 44% by weight, calculated as elemental Si, and a TOC content in the range of 0.14 to 0.25% by weight, in each case based on the total weight of B-zeolite, preferably B-MWW, B-BEA, B -MFI, B-CHA, B-MOR, B-MTW, B-CHF, B-LEV, B-FER, B-MEL, or B-RTH, more preferably the B-MWW forn given in (i).
[00021] There are no specific restrictions, as far as the methods to supply the B-zeolite, preferably the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW is concerned. Among others, possible methods are described in P. Wu et al., Hydrothermal Synthesis of a New Titanosilicate with MWW Topology, Chemistry Letters (2000), p. 774775 or in examples 1 to 5 of WO 02/28774 A2.
[00022] According to a preferred process of the present invention, the B-zeolite, preferably, or the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a zeolitic material containing boron of MWW type structure (B-MWW), more preferably the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, more preferably the B-MWW provided in (i) by a process comprising the hydrothermal synthesis of the B-zeolite, preferably, or the boron-containing zeolitic material of structure of the MWW type (B-MWW) or the boron-containing zeolitic material that is not a boron-containing zeolitic material of the MWW type (B-MWW) structure, more preferably the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-CHF, B-LEV, B-FER, B-MEL, or B-RTH, more preferably B-MWW from a synthesis mixture, containing at least at least one suitable source of silicon, at least one suitable boron source, and at least one mineral compound. suitable for the preparation of a boron-containing zeolite, preferably, or a boron-containing zeolitic material of structure MWW type (B-MWW) or a zeolitic material containing boron, which is not a boron-containing non-zeolitic material of structure type MWW (B-MWW), preferably of structure of the MWW type, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, more preferably of structure of the MWW type, to obtain the B-MWW in its mother liquor, with a subsequent separation of the B-zeolite, preferably either the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of structure of the MWW type (B-MWW), more preferably, the B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, most preferably B-MWW from its mother liquor. Suitable boron sources include, for example, boric acid, borate salts, boron halides, B2 O3, with boric acid being especially preferred. Suitable silicon sources include, for example, fumed silica or colloidal silica, such as ammonia-stabilized colloidal silica, with ammonia-stabilized colloidal silica being especially preferred. Suitable model compounds (structure targeting agents) for the preparation of B-MWW include cyclic amines, for example, piperidine or hexamethylene-imine, or N,N,N-trimethyl-1-adamantylammonium hydroxide, with piperidine, hexamethylene imine and a mixture thereof being especially preferred.
[00023] In particular, as far as the B-MWW is concerned, during hydrothermal synthesis, a precursor of B-MWW is prepared from which, after calcination, the B-MWW is obtained.
[00024] Therefore, the present invention relates to a process for the preparation of a zeolitic material, and the zeolitic material obtainable and/or obtained by this process, as defined above, wherein (a) the hydrothermal synthesis of B -zeolite, preferably, or the boron-containing zeolitic material of the MWW-type structure precursor (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW-type structure precursor (B-MWW) ), preferably the precursor B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH , from a synthesis mixture containing at least one silicon source, at least one boron source, and at least one model compound, to obtain the B-zeolite, preferably, or the boron-containing zeolitic material of type MWW structure precursor (B-MWW) or boron containing zeolitic material, which is not a boron containing zeolitic material of type MWW structure precursor (B-MWW), more preferably tion, B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH in your liquor mom; (b) separate the B-zeolite, preferably, or the boron-containing zeolitic material from the MWW-type structure precursor (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material, from the structure precursor of the type MWW (B-MWW), preferably the precursor B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B- HONEY, or B -RTH from its mother liquor; (c) optionally drying the B-zeolite, preferably either the boron-containing zeolitic material of the MWW-type structure precursor (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the boron precursor. MWW type structure (B -MWW), preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B -MEL, or B-RTH separated according to (b); (d) calcination of zeolite-B, preferably, or the boron-containing zeolitic material of the MWW-type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW-type structure ( B-MWW), more preferably, B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RHT obtained from (b) or (c), preferably at a temperature in the range of 500 to 700°C.
[00025] Therefore, the present invention preferably relates to a process for the preparation of a zeolitic material, and the zeolitic material obtainable and/or obtained by this process, as defined above, wherein (a) hydrothermal synthesis of precursor B-MWW from a synthesis mixture containing at least one silicon source, preferably ammonia-stabilized colloidal silica, at least one boron source, preferably boric acid, and at least one model compound, of preferably, selected from the group consisting of piperidine, hexamethylene imine, and a mixture thereof, to obtain the B-MWW in its mother liquor; (b) separate the precursor of B-MWW from its mother liquor; (c) optionally drying the B-MWW precursor separated according to (b); (d) calcination of the B-MWW obtained from (b) or (c), preferably at a temperature in the range of 500 to 700°C, obtaining the B-MWW.
[00026] According to (a), a suitable starting mixture, preferably an aqueous mixture, which contains the B-zeolite precursors, preferably the precursors of or the boron-containing zeolitic material of the MWW-type structure precursor ( B-MWW) or the boron-containing zeolitic material that is not a boron-containing zeolitic material of the MWW-type structure precursor (B-MWW), more preferably the B-MWW precursor, B-BEA precursors, B- MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RHT, more preferably the precursors B-MWW precursors, preferably the precursor containing B, the Si-containing precursor, and at least one suitable model compound (structure-directing agent), is subjected to hydrothermal crystallization under autogenous pressure. For crystallization purposes, it may be possible to use the at least one suitable seed material. Preferably, the crystallization time is in the range of 3 to 8 days, more preferably 4 to 6 days. During hydrothermal synthesis, the crystallization mixture can be stirred. Temperatures applied during crystallization are preferably in the range 160 to 200°C, more preferably 160 to 180°C. The amounts of precursor compounds are conveniently chosen so that B-zeolite described above is preferably the precursor of B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB , B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW precursor can be obtained with the preferred compositions described.
[00027] After hydrothermal synthesis, the B-zeolite obtained is preferably either the zeolitic material containing boron precursor of a structure of the MWW type (B-MWW) or the zeolitic material containing boron, which is not a zeolitic material containing boron precursor of MWW type structure (B-MWW), preferably the precursor B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER , B-MEL, or B-RTH, most preferably, the B-MWW precursor is suitably separated from its mother liquor. All B-zeolite separation methods, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER precursor , B-MEL, or B-RTH, most preferably the precursor of B-MWW from its mother liquor are conceivable. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. According to the present invention, the B-zeolite is preferably the precursor of B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, more preferably, the B-MWW precursor is preferably separated from its mother liquor by filtration to obtain a filter cake, which is preferably subjected to a washing, preferably with water. Then, the filter cake, optionally further processed to obtain a suitable suspension, is subjected to spray drying or ultrafiltration. Before separating the B-zeolite, preferably the precursor of B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B -MEL, or B-RTH, more preferably the precursor of B-MWW from its mother liquor, it is possible to increase the B-zeolite, preferably the precursor of B-MWW, B-BEA, B-MFI , B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW precursor content of the mother liquor through the concentration of the suspension. If washing as applied, it is preferred to continue the washing process until the washing water has a conductivity of less than 1000 microSiemens/cm, more preferably less than 900 microSiemens/cm, more preferably less than 800 microSiemens/cm, more preferably less than 700 microSiemens/cm.
[00028] After the separation of the B-zeolite, preferably, either the zeolitic material containing boron structure precursor of the MWW type (B-MWW) or the zeolitic material containing boron, which is not a zeolitic material containing boron structure precursor type MWW (B-MWW), preferably the precursor B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B- MEL, or B-RTH, more preferably the B-MWW precursor from the suspension, preferably achieved by filtration, and then washing, the washed filter cake preferably containing the B-zeolite or material boron-containing zeolitic precursor of MWW-type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of MWW-type structure precursor (B-MWW), more preferably, the B-precursor MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the precursor of B-MWW is optionally subjected to pre-drying, for example, subjecting the filter cake to a suitable gas stream, preferably a nitrogen stream, for a time, preferably in the range of 4 to 10 hours, more preferably 5 to 8 hours.
[00029] Then, the pre-dried filter cake is optionally dried at temperatures in the range of 100 to 300°C, more preferably 150 to 275°C, more preferably 200 to 250°C in a suitable atmosphere, such as from technical nitrogen, air or lean air, preferably in air or lean air. This drying can be carried out, for example, by spray drying. In addition, it is possible to separate the B-zeolite, preferably, or the boron-containing zeolitic material of the MWW-type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW-type structure (precursor B-MWW), most preferably the precursor of B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, most preferably the precursor of B-MWW from its mother liquor via a suitable method of filtration, followed by washing and spray drying.
[00030] Therefore, the present invention also relates to the process defined above, in which the B-zeolite, preferably, or the boron-containing zeolitic material MWW-type structure precursor (B-MWW) or the boron-containing zeolitic material which it is not a boron containing zeolitic material with a MWW type structure precursor (B-MWW), preferably the precursor B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB , B-LEV, B-FER, B-MEL, or B-RTH, most preferably the B-MWW precursor provided in (i) is provided in the form of a powder spray or a granular spray.
[00031] After drying, the B-zeolite is preferably either the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the type structure MWW (B-MWW), preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RHT, more preferably the B-MWW is subjected to calcination at temperatures in the range 500 to 700°C, more preferably 550 to 675°C, more preferably 600 to 675°C, in a suitable atmosphere such as of technical nitrogen, air, or lean air, preferably in air or lean air.
[00032] According to an especially preferred embodiment of the present invention, the B-zeolite is preferably either the zeolitic material containing boron of structure of the MWW type (B-MWW) or the zeolitic material containing boron, which is not a zeolitic material containing boron type structure MWW (B-MWW), preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, most preferably, the B-MWW is separated from its mother liquor by filtration, subjected to spray drying, with the obtained spray powder being calcined.
[00033] Preferably, if in phase (I) B-MWW is prepared, the B-MWW is prepared by a process whose preferred steps and conditions are defined by the following embodiments 1 to 28 and their dependencies, as indicated : 1. A process for the preparation of an aluminum-free boron-containing zeolitic material comprising the MWW frame structure (B-MWW), which comprises (a) hydrothermal synthesis of a B-MWW precursor from a synthesis mixture containing water, a silicon source, a boron source, and a model compound MWW obtaining the precursor of B-MWW in its mother liquor, the mother liquor having a pH greater than 9; (b) adjust the pH of the mother liquor, obtained in (a) and containing the precursor of B-MWW, to a value in the range of 6 to 9; (c) separating the B-MWW precursor from the pH-adjusted mother liquor obtained in (b) by filtration in a filtration device. 2. The process of embodiment 1, wherein in (a), at least 95% by weight, preferably at least 99% by weight, more preferably at least 99.9% by weight of the synthesis mixture consists of water , the silicon source, the boron source, and the model compound. 3. The process of embodiment 1 or 2, wherein in (a), the silicon source is selected from the group consisting of fumed silica, colloidal silica, and a mixture thereof, the silicon source being from preferably colloidal silica, more preferably ammonia-stabilized silica, the boron source is selected from the group consisting of boric acid, borates, boron oxide, and a mixture of two or more of them, the boron source, preferably being the acid boric, and the MWW model compound selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N', N', N'-hexamethyl-1,5-pentanediammonium ion, 1,4- bis(N-methylpyrrolidinium)butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium hydroxide, and a mixture of two or more of these compounds, the model compound MWW being preferentially piperidine. 4. The process of any one of Embodiments 1 to 3, wherein in (a), the synthesis mixture contains the boron source, calculated as elemental boron, relative to the silicon source, calculated as elemental silicon, in a molar ratio in the range from 0.4:1 to 2.0:1, preferably from 0.6:1 to 1.9:1, more preferably from 0.9:1 to 1.4:1, the water in in relation to the silicon source, calculated as elemental silicon, in a molar ratio in the range from 1:1 to 30:1, preferably between 3:1 to 25:1, more preferably 6:01 to 20:01; and the model compound to the silicon source, calculated as elemental silicon, in a molar ratio in the range from 0.4:1 to 2.0:1, preferably from 0.6:1 to 1.9:1, more preferably from 0.9:1 to 1.4:1. 5. The process of any one of embodiments 1 to 4, wherein in (a), the hydrothermal synthesis is carried out at a temperature in the range of 160 to less than 180°C, preferably 170 to 175°C, for a time period in the range of 1 to 72 hours, preferably 6 to 60 hours, more preferably 12 to 50 hours. 6. The process of any one of embodiments 1 to 5, wherein in (a), the hydrothermal synthesis is carried out, at least partially, under stirring. 7. The process of any one of embodiments 1 to 6, wherein in (a), the synthesis mixture additionally contains a seed material, preferably a zeolitic material comprising the MWW frame structure, more preferably a material boron containing zeolitic comprising the MWW frame structure. 8. The process of embodiment 7, wherein the synthesis mixture contains the seed material, relative to the silicon source, in a weight ratio in the range of 0.01:1 to 1:1, preferably of 0. 02:1 to 0.5:1, more preferably 0.03:1 to 0.1:1, calculated as the amount of seed material in kg relative to the silicon contained in the silicon source calculated as silicon dioxide in kg. 9. The process of any one of embodiments 1 to 8, wherein the pH of the mother liquor obtained from (a) is greater than 10, preferably in the range of 10.5 to 12, more preferably 11 to 11.5. 10. The process of any one of embodiments 1 to 9, wherein in (b), the pH of the mother liquor obtained in (a), is adjusted to a value in the range between 6.5 and 8.5, of preferably between 7 and 8. 11. The process of any one of embodiments 1 to 10, wherein in (b), the pH is adjusted by a method comprising 1) adding an acid to the mother liquor obtained from (a) which contains the B-MWW precursor, wherein the addition is preferably carried out at least partially under stirring. 12. The process of embodiment 11, wherein in (i), the addition is carried out at a temperature in the range from 20 to 70°C, preferably from 30 to 65°C, more preferably from 40 to 60°C. 13. The process of embodiment 11 or 12, wherein in (i), the acid is an inorganic acid, preferably an aqueous solution containing the inorganic acid. 14. The process of embodiment 13, wherein the inorganic acid is selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, and a mixture of two or more of them, the inorganic acid, of preferably being nitric acid. 15. The process of any one of embodiments 11 and 14, the method further comprising (11) stirring the mother liquor to which the acid has been added according to (i), wherein during (ii), no acid is added to the mother liquor. 16. The process of embodiment 15, wherein in (ii), stirring is carried out at a temperature in the range of 20 to 70°C, preferably 25 to 65°C, more preferably 30 to 60°C. 17. The process of any one of embodiments 1 to 16, wherein in (b), the particle size contained in the mother liquor, expressed by the respective Dv10, Dv50, and Dv90 values, is increased to at least 2 %, preferably at least 3%, more preferably at least 4.5% relative to Dv10, for at least 2%, preferably at least 3%, more preferably at least 4.5% relative to Dv50, and for, at least 5%, preferably at least 6%, more preferably at least 7% relative to Dv90. 18. The process of any one of embodiments 1 to 17, wherein the pH-adjusted mother liquor obtained from (b) has a solids content in the range of between 1 and 10% by weight, preferably 4 to 9% by weight, more preferably 7 to 8% by weight, based on the total weight of the pH adjusted mother liquor obtained from (b). 19. The process of any one of embodiments 1 to 18, wherein the pH-adjusted mother liquor obtained from (b) has a filtration strength in the range of 10 to 50 mPa*s/m2, preferably of 15 to 45 mPa*s/m2, more preferably 20 to 40 mPa*s/m2. 20. The process of any one of embodiments 1 to 19, further comprising (d) washing the B-MWW precursor obtained from (c), preferably the filter cake obtained from (c) , wherein the washing is preferably carried out using water in the washing agent. 21. The process of embodiment 20, wherein in (d), the filter cake obtained from (c) is has a washout strength in the range of 10 to 50 mPa*s/m2, preferably of 15 at 45 mPa*s/m2, more preferably from 20 to 40 mPa*s/m2. 22. The process of embodiment 20 or 21, wherein washing is carried out until the filtrate conductivity is at most 300 microSiemens/cm, preferably at most 250 microSiemens/cm, more preferably at most 200 microSiemens/cm /cm. 23. The process of any one of embodiments 1 to 22, further comprising (e) drying the B-MWW precursor obtained from (c), preferably from (d), at a temperature in the range from 20 to 50°C, preferably from 20 to 40°C, more preferably from 20 to 30°C, wherein drying is preferably carried out by subjecting the B-MWW to a stream of gas, preferably a stream of nitrogen. 24. The process of any one of embodiments 1 to 23, wherein the residual moisture of the B-MWW precursor obtained from (c), preferably from (d), more preferably from of (e), is in the range of 80 to 90% by weight, preferably 80 to 85% by weight. 25. The process of any one of embodiments 1 to 24, further comprising (f) preparing a suspension, preferably an aqueous suspension, containing the B-MWW precursor obtained from (c), preferably, from (d), more preferably from (e), and having a solids content in the range of 10 to 20% by weight, preferably from 12 to 18% by weight, more preferably from 14 to 16 % by weight; (g) spray drying the suspension obtained from (f) containing the B-MWW precursor to a spray powder; (h) calcining the spray powder obtained from (g) containing the B-MWW precursor, preferably at a temperature in the range of 500 to 700°C, more preferably 550 to 650°C, more preferably 575 to 625°C for a period of time in the range of 1 to 24 hours, preferably from 2 to 18 hours, more preferably from 6 to 12 hours, obtaining a spray powder, of which at least 99% by weight, more than preferably at least 99.5 by weight consists of B-MWW. 26. The process of embodiment 25, wherein in (h), the calcination is carried out in a continuous mode, preferably in a rotary calciner, preferably at a yield in the range of 0.5 to 20 kg of spray. powder per h. 27. The process of embodiment 25 or 26, wherein the degree of crystallinity of the B-MWW contained in the spray powder obtained from (h) is at least (75 ± 5)%, preferably at least (80 ± 5)% as determined by XRD. 28. The process of any one of embodiments 25 to 27, wherein the BET specific surface area of B-MWW contained in the spray powder obtained from (h) is at least 300 m 2 /g, preferably in the range of 300 to 500 m2/g as determined in accordance with DIN 66131.
[00034] According to the present invention, the B-MWW obtained has a content of B, preferably in the range of 1.2 to 2.4% by weight or 1.4 to 2.4% by weight, calculated as Elementary B. Furthermore, the B-MWW obtained has an Si content, preferably in the range from 38 to 45% by weight or from 38 to 44% by weight, calculated as elemental Si. Furthermore, the B-MWW obtained has a content of C (total organic carbon, TOC), preferably in the range of 0.14 to 0.25% by weight, more preferably 0.15 to 0.22% by weight more preferably 0.16 to 0.20% by weight, calculated as elemental C. More preferably, the B-MWW obtained has a C content (total organic carbon, TOC) of less than 0.3% by weight, more preferably less than 0.2% by weight, more preferably less than 0 .1% by weight. Step (ii)
[00035] The B-zeolite is preferably either the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW type structure (B- MWW), more preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RHT preferably the B-MWW provided in (i), especially preferably the separated, calcined and spray dried B-zeolite, preferably the B-MWW, B-BEA, B-MFI, B-CHA, B -MOR, B-MTW, B-BRL, B-LEV, B-FER, B-MEL, or B-RTH, most preferably B-MWW, is debugged in (ii) with a liquid solvent system. Contrary to the teaching of the prior art, neither steam nor acids described as obligatory de-boring agents are employed. Surprisingly, it was found that for deboronation the supplied B-zeolite is preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, more preferably B-MWW, neither steam nor said acids are needed. Even more surprising, it was found that the deboronation of B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B -FER, B-MEL, or B-RTH, most preferably the B-MWW does not require an acid at all. Therefore, the present invention relates to the above-defined process and zeolitic material obtainable or obtained therefrom, wherein the liquid solvent system does not contain an organic or inorganic acid, or a salt thereof.
[00036] The term "decaying a B-zeolite", in particular the term "decaying a B-MWW" as used in the context of the present invention refers to a process according to which at least a portion of the atoms of boron contained in the zeolitic framework is removed by the inventive treatment. Preferably, the term "crumbling a B-zeolite", especially the term "crumbling a B-MWW" as used in the context of the present invention refers to a process wherein the obtained zeolite, preferably the obtained MWW, BEA , MFI, CHA, MOR, MTW, CHF, LEV, FER, HONEY, RTH, more preferably the MWW obtained contains at most 0.2, more preferably at most 0.1% by weight of boron, calculated as an element and with based on the total weight of the zeolite, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, HONEY, RTH, most preferably MWW.
[00037] The liquid solvent system used in (ii) is selected from the group consisting of water, monohydric alcohols, polyhydric alcohols, and mixtures of two or more thereof. With regard to monohydric and polyhydric alcohols, there are no specific restrictions. Preferably, these alcohols contain 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. Polyhydric alcohols preferably comprise from 2 to 5 hydroxyl groups, more preferably from 2 to 4 hydroxyl groups, preferably from 2 or 3 hydroxyl groups. Especially preferred monoalcohols are methanol, ethanol, and propanol such as 1-propanol and 2-propanol. Especially preferred polyhydric alcohols are ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol. If mixtures of two or more of the compounds described above are used, it is preferred that these mixtures comprise water and at least one monohydric alcohol and/or at least one polyhydric alcohol. Most preferably, the liquid solvent system is water. Therefore, the present invention relates to the above-defined process and zeolitic material obtainable or obtained therefrom, wherein the liquid solvent system is chosen from the group consisting of water, methanol, ethanol, propanol, ethane-1,2 -diol, propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and mixtures of two or more thereof, preferably water.
[00038] As the amount of B-zeolite, preferably either of the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the type MWW structure (B-MWW), preferably from B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL , or B-RTH, more preferably, of B-MWW which is employed in relation to the amount of liquid solvent system, there are no specific restrictions. Surprisingly, it has been found that it is not necessary to use a large excess of liquid solvent system, which makes the inventive process very advantageous. Preferably, the proportion by weight of B-zeolite, preferably of B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B- FER, B-MEL, or B-RTH, more preferably, of B-MWW relative to the liquid solvent system is in the range of 1:5 to 1:40, more preferably 1:10 to 1:30, most preferably from 1:10 to 1:20, such as 1:10 to 1:15, 1:11 to 1:16, 1:12 to 1:17, 1:13 to 1:18, 1:14 to 1:19 , 1:15 to 1:20.
[00039] The reaction conditions according to (ii) are not specifically restricted since the above-described solvent system is in its liquid state. In particular, in relation to the preferred temperatures described below, the person skilled in the art will select the respective pressure under which the deboronation is carried out, in order to keep the solvent system in a liquid state.
[00040] Preferably, the treatment according to (ii) is carried out at a temperature in the range from 50 to 125 °C, more preferably from 70 to 120 °C, more preferably 90 to 115 °C, more preferably from 90 to 110 °C, more preferably 90 to 105°C, more preferably 95 to 105°C, more preferably 95 to 100°C. More preferably, deboronation according to (ii) is carried out at the boiling point of the solvent system. If the solvent system consists of two or more components, the deboronation according to (ii) is preferably carried out at the boiling point of the component with the lowest boiling point. According to another preferred embodiment of the present invention, the deboronation according to (ii) is carried out under reflux. Thus, the preferred vessel used for deboronation according to (ii) is equipped with a reflux condenser. During (ii), the temperature of the liquid solvent system is kept essentially constant, or changed, the deboration thus being carried out at two or more different temperatures. More preferably, the temperature is kept essentially constant.
[00041] Surprisingly, it has been found that it is not necessary to pre-treat the boron-containing zeolitic material with a liquid system at elevated temperatures before the deboronation step in order to remove a part of the boron during these steps. Also, this finding makes the inventive process very advantageous, for example, from an economic point of view, since according to the present invention, only one deboronation step (ii) is needed to achieve the desired boron removal . Therefore, according to the present invention, step (ii) is carried out, preferably only once. According to a preferred embodiment of the present invention, the zeolitic material provided in (i), after its synthesis, is not subjected to a treatment with a liquid system, such as a treatment with a washing agent or the like, at a temperature of 50°C or more before debonding according to (ii).
[00042] During deboronation according to (ii), it is further preferred to properly agitate the liquid solvent system. During (ii), the agitation speed is kept essentially constant or changed, the deburring thus being carried out at two or more different agitation speeds. More preferably, the B-zeolite is preferably either the boron-containing zeolitic material of the MWW-type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of the MWW-type structure (B -MWW), preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B- RHT, more preferably, the B-MWW is suspended in the liquid solvent system at a first stirring rate, and during deboronation at temperatures described above, the stirring rate is changed, preferably increased. Stirring speeds as may be suitably chosen depend, for example, on the volume of the liquid solvent system, the amount of B-zeolite, preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RTH, more preferably, the B-MWW employed, the desired temperature, and the like. Preferably, the agitation speed at which the B-zeolite is preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV , B-FER, B-MEL, or B-RTH, more preferably, the B-MWW is suspended in the liquid solvent system is in the range of 0 to 200 rpm (revolutions per minute), more preferably 10 to 200 rpm , more preferably from 20 to 55 rpm, more preferably from 30 to 50 rpm. The stirring speed at which the deboronation at the above-described temperatures is carried out is preferably in the range of 50 to 100 rpm, more preferably 55 to 90 rpm , more preferably from 60 to 80 rpm.
[00043] Preferably, the B-zeolite, preferably, or the boron-containing zeolitic material of the MWW-type structure (B-MWW) or the zeolitic material containing boron, which is not a boron-containing zeolitic material of the MWW-type structure (B-MWW), more preferably B-MWW, B-BEA, B-MFI, B-CHA, B-MOR, B-MTW, B-RUB, B-LEV, B-FER, B-MEL, or B-RHT, more preferably the B-MWW is suspended in the liquid solvent system at ambient temperature and pressure, where the temperature of the liquid solvent system is then raised to the desired deboronation temperature. Preferably, the temperature is increased at a rate of 5 to 10°C per hour, more preferably 6 to 9°C per hour.
[00044] With regard to the duration of the de-borrowing of (ii), there are no specific restrictions. Surprisingly, it was found that it is not necessary to carry out the treatment according to step (ii) for a long period of time, which makes the inventive process very advantageous, for example, from an economic point of view and in particular , for an industrial scale process. Preferably, the treatment according to (ii) is carried out for a time in the range of 6 to 20 hours, more preferably 7 to 17 hours, more preferably 8 to 15 hours, more preferably 9 to 12 hours. This time is to be understood as the time that the liquid solvent system is kept below the above-described deboronation temperature. Step (iii)
[00045] According to a preferred embodiment of the present invention, the debonded zeolite, preferably, or the boron-containing zeolitic material of type MWW structure (B-MWW) or the boron-containing zeolitic material, which is not a material boron-containing zeolitic of structure type MWW (B-MWW), preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW obtained from (ii) is subjected to a post-treatment comprising separation, preferred drying and an optional calcination of the zeolite, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW .
[00046] Therefore, the present invention relates to the above-defined process and zeolite material obtainable or obtained therefrom, said process further comprising (111) post-treatment of the zeolite, preferably the MWW or the zeolite which is not MWW, more preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW, obtained from (ii) by a process comprising (iii.( 1) separate the zeolite, preferably MWW or non-MWW zeolite, more preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW a from the liquid solvent system; (iii.(2) preferably drying the separated zeolite, preferably the separated MWW or the separated zeolite which is not MWW, preferably the separated MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, more preferably the MWW is separated, preferably by spray drying; (iii.(3) optionally calcining the zeolite, preferably the MWW or zeolite other than MWW, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW, obtained from (iii.1) or (iii .2), preferably at temperatures in the range of 500 to 700°C.
[00047] Therefore, the present invention preferably relates to the above-defined process and zeolitic material obtainable or obtained therefrom, said process further comprising (111) post-treatment of the MWW obtained from (ii) by a process which comprises (iii.(1) separating the MWW from the liquid solvent system; (iii.(2) preferably drying the separated MWW, preferably by spray drying; (iii.(3) optionally, calcining the MWW obtained from (iii.(1) or (iii.2), preferably at temperatures in the range of 500 to 700°C.
[00048] According to (iii.1), the zeolite is preferably either the boron-containing zeolitic material of the MWW type structure (B-MWW) or the boron-containing zeolitic material, which is not a boron-containing zeolitic material of MWW type structure (B-MWW), more preferably the MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, MEL, or RTH, more preferably the MWW is suitably separated from the obtained suspension (ii ), wherein the suspension is preferably cooled before (iii). All methods of separating the zeolite, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW from the suspension are conceivable. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. In accordance with the present invention, the zeolite, preferably MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, MEL, or RTH, more preferably MWW is preferably separated from the suspension by filtration, to a filter cake is obtained which is preferably subjected to washing, preferably with water. Then, the filter cake, optionally further processed to obtain a suitable suspension, is subjected to spray drying or ultrafiltration, preferably spray drying. Before the separation of the zeolite, preferably the MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, MEL, or RTH, more preferably the MWW from the suspension, it is possible to increase the zeolite content of preferably the MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH content, more preferably the MWW content of the suspension concentrating the suspension. If washing, if applied, it may be preferred to continue the washing process until the washing water has a conductivity of less than 1000 microSiemens/cm, more preferably less than 900 microSiemens/cm, more preferably less than 800 microSiemens/cm, more preferably less than 700 microSiemens/cm.
[00049] After separating the zeolite from the suspension, preferably achieved by filtration, and then washing, the washed filter cake containing the zeolite, preferably the MWW or the zeolite, which is not MWW, more preferably the MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, MEL, or RTH, more preferably the MWW is preferably subjected to pre-drying, for example by subjecting the filter cake with a stream of gas suitable, preferably a stream of nitrogen, over a period of time, preferably in the range of 4 to 10 hours, more preferably 5 to 8 hours.
[00050] Thereafter, the pre-dried filter cake is preferably dried at temperatures in the range of 100 to 300°C, more preferably 150 to 275°C, more preferably 200 to 250°C in a suitable atmosphere such as technical nitrogen, air or lean air, preferably in air or lean air. This drying can be carried out, for example, by spray drying. Furthermore, it is possible to separate the zeolite, preferably MWW or zeolite, which is not MWW, more preferably MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, HONEY, or RTH, plus preferably, the MWW from the suspension through a suitable method of filtration, followed by washing and spray drying.
[00051] After drying, the zeolite, preferably MWW or zeolite other than MWW, more preferably MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, HONEY, or RTH, most preferably the MWW is optionally subjected to calcination at temperatures in the range 400 to 700°C, more preferably 550 to 675°C, more preferably 600675°C, in a suitable atmosphere such as technical nitrogen, air, or lean air, preferably in air or poor air. Preferably, no calcination is carried out according to (iii), especially in the case of step (iv) it is carried out as described hereinafter.
[00052] According to the present invention, the zeolite is preferably MWW or a zeolite that is not MWW, more preferably MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, HONEY, or RTH, more preferably the MWW obtained from (iii), preferably after (iii.(2) has a B content, preferably at most 0.1% by weight, most preferably at most 0.09 % by weight, more preferably at most 0.08% by weight, calculated as elemental B. Furthermore, the zeolite, preferably MWW or Zeolite other than MWW, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably the MWW obtained has an Si content preferably in the range of 39 to 45% by weight, more preferably 40 to 44% by weight, most preferably 41 at 43% by weight, calculated as elemental Si. Furthermore, the zeolite, preferably MWW or zeolite other than MWW, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably the MWW obtained has a C content (c total organic arbon, TOC) preferably in the range of 0.15 to 0.30% by weight, more preferably 0.18 to 0.27% by weight, more preferably 0.20 to 0.25% by weight, calculated as Elementary C.
[00053] The optionally post-treated debonded zeolitic material can be subjected, for example, to a subsequent step according to which a mold is prepared based on the zeolitic material, for example, by properly mixing the zeolitic material with at least one binder and/or with at least one binder precursor, and optionally at least one pore-forming agent and/or at least one plasticizing agent. Step (iv)
[00054] According to a preferred embodiment of the present invention with respect to de-bombed MWW, the de-bombed MWW is preferably post-treated obtained from (ii) or (iii), preferably (iii), more preferably (iii .2), is subjected to incorporation of at least one heteroatom Het1 to obtain a zeolitic material having a structure of the MWW type and containing, preferably, in addition to Si and S and optionally any remainder B, the at least one heteroatom Het1. Generally, there are no specific restrictions, as such a heteroatom is introduced in MWW. According to a preferred process, the at least one heteroatom is introduced via hydrothermal synthesis, that is, in aqueous solution, under autogenous pressure at elevated temperatures.
[00055] According to a preferred process of the present invention, a suitable synthesis mixture, preferably an aqueous synthesis mixture is prepared in a step (iv.1), wherein the synthesis mixture contains the MWW, at least one compound suitable model and at least one source of the at least one heteroatom (Het1). Suitable model compounds of structure (structure targeting agents) include the cyclic amines, for example, piperidine or hexamethylene-imine, or N,N,N-trimethyl-1-adamantylammonium hydroxide, with piperidine, hexamethylene-imine and a mixture of the same, being especially preferred. Most preferred is piperidine. With respect to at least one heteroatom Het1 in question, there are no specific restrictions. Preferred heteroatoms are chosen from the group consisting of Ti, Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Pb, and a mixture of two or more of them. Titanium is particularly preferred as Het1.
[00056] With regard to preferred sources of titanium, titanium oxide, titanium halide and tetraalkylorthotitanates can be mentioned. However, the present invention is not limited to them. Among these, titanium halides and tetraalkylorthotitanates are more preferred. More preferred are titanium tetrafluoride, tetraethylorthotitanate, tetrapropylorthotitanate, and tetrabutylorthotitanate, with tetrabutylorthotitanate being especially preferred.
[00057] With regard to preferred sources of aluminum, alumina, aluminum nitrate, can be mentioned, with aluminum nitrate being especially preferred.
[00058] With regard to preferred sources of zirconium, zirconium oxide, zirconium halides and zirconium tetraalkoxides can be mentioned. Among these, zirconium halides and zirconium tetraalkoxides are more preferred. Most preferred are zirconium tetrafluoride, zirconium tetraethoxide, and zirconium tetrabutoxide.
[00059] With regard to preferred sources of vanadium, vanadium oxide, vanadium halides and vanadium trialkoxide oxides can be mentioned. Among these, vanadium halides and vanadium trialkoxides are most preferred. Most preferred are vanadium trichloride and vanadium oxytriisopropoxide.
[00060] With regard to preferred sources of niobium, niobium oxide, niobium halides and niobium tetraalkanoates can be mentioned. More preferred are niobium tetraalkanoates, with niobium tetrakis (2-ethylhexanoate) being especially preferred.
[00061] With regard to preferred sources of tantalum, tantalum oxide, tantalum halides and tantalum disulfide can be mentioned, with tantalum disulfide being especially preferred.
[00062] With regard to preferred sources of chromium, chromium acetate, chromium nitrate and chromium halides can be mentioned, with chromium nitrate being especially preferred.
[00063] With regard to preferred sources of molybdenum, molybdenum oxide, molybdenum halides and molybdenum sulfide can be mentioned, with molybdenum trichloride being especially preferred.
[00064] With regard to preferred sources of tungsten, tungsten oxide and tungsten halides can be mentioned, with tungsten tetrachloride being especially preferred.
[00065] With regard to preferred sources of manganese, manganese oxide, manganese halides, manganese acetate and manganese acetylacetonate can be mentioned, with manganese trisacetylacetonate being especially preferred.
[00066] With regard to preferred sources of iron, iron oxide, iron halides, iron acetate and iron nitrate can be mentioned, with iron nitrate being especially preferred.
[00067] With regard to preferred sources of cobalt, cobalt oxide, cobalt halides and cobalt trisacetylacetonate can be mentioned, with cobalt trisacetylacetonate being especially preferred.
[00068] With regard to preferred sources of nickel, nickel oxide, nickel halides, nickel nitrate and nickel acetate can be mentioned, with nickel nitrate and nickel acetate being especially preferred.
[00069] With regard to preferred sources of zinc, zinc oxide, zinc halides, zinc acetate and zinc nitrate can be mentioned, with zinc acetate and zinc nitrate are especially preferred.
[00070] With regard to preferred sources of gallium, gallium oxide, gallium halides and gallium nitrate can be mentioned, with gallium nitrate, gallium trichloride, and gallium trifluoride being especially preferred.
[00071] With regard to preferred sources of indium, indium oxide, indium halides and indium trialkoxy can be mentioned, with indium trichloride, indium trifluoride and indium triisoprooxide being especially preferred.
[00072] With regard to preferred sources of lead, lead halides and lead tetraalkoxy may be mentioned, with lead acetate, lead chloride, lead nitrate, lead acetylacetonate, and lead being especially preferred.
[00073] In the synthesis mixture (iv.1), the atomic ratio of Het1 to Si in MWW is preferably in the range from 0.001:1 to 0.3:1, such as from 0.005:1 to 0 .2:1, or from 0.01:1 to 0.2:1.
[00074] The synthesis mixture obtained in (iv.1) is subjected to a hydrothermal crystallization under autogenous pressure. It may be possible to use at least one suitable seed material in step (iv.2) to obtain the zeolitic material of type MWW structure, containing at least one heteroatom (Het1MWW) contained in its mother liquor. Preferably, the crystallization time is in the range from 4 to 8 days, more preferably from 4 to 6 days. During hydrothermal synthesis, the crystallization mixture can be stirred. Temperatures applied during crystallization are preferably in the range 160 to 200°C, more preferably 160 to 180°C.
[00075] After hydrothermal synthesis, the obtained crystalline zeolitic material Het1MWW is properly separated from the mother liquor in step (iv.3). All methods of separating Het1MWW from its mother liquor are conceivable. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. According to the present invention, Het1MWW is preferably separated from its mother liquor by filtration to obtain a filter cake, which is preferably subjected to washing, preferably with water.
[00076] Then, the filter cake, optionally further processed to obtain a suitable suspension, is preferably subjected to spray drying or ultrafiltration in step (IV.4). Before separating Het1MWW from its mother liquor, it is possible to increase the Het1MWW content of the mother liquor by concentrating the suspension. If washing as applied, it is preferred to continue the washing process until the washing water has a conductivity of less than 1000 microSiemens/cm, more preferably less than 900 microSiemens/cm, more preferably less than 800 microSiemens/cm, more preferably less than 700 microSiemens/cm.
[00077] After the separation of Het1MWW from its mother liquor, preferably achieved by means of filtration, and after washing, the washed filter cake containing the Het1MWW is preferably subjected to pre-drying, for example, subjecting the filter cake to a suitable gas stream, preferably a nitrogen stream, for a time preferably in the range of 4 to 10 hours, more preferably 5 to 8 hours.
[00078] Thereafter, the pre-dried filter cake is preferably dried at temperatures in the range of 100 to 300°C, more preferably 150 to 275°C, more preferably 200 to 250°C in a suitable atmosphere such as technical nitrogen, air or lean air, preferably in air or lean air. This drying can be carried out, for example, by spray drying.
[00079] After drying, Het1MWW can be subjected to calcination in step (iv.5) at temperatures in the range of 500 to 700°C, more preferably 550 to 675°C, more preferably 600 to 675°C in an atmosphere suitable such as technical nitrogen, air or lean air, preferably in air or lean air. Preferably, no calcination is carried out, in particular in case the Het1MWW is subjected to a step (v) as described hereinafter.
[00080] Therefore, the present invention relates to the above-defined process and zeolitic material obtainable or obtained therefrom, said process further comprising (iv) incorporating at least a first heteroatom (Het1) in the MWW, thus obtaining a zeolitic material with a structure of the MWW type, containing at least one heteroatom (Het1MWW) by a process comprising (iv.1) preparing a synthesis mixture containing the MWW obtained according to (ii) or (iii), preferably, (iii), a model compound, preferably selected from the group consisting of piperidine, hexamethylene-imine, and a mixture thereof, and at least one source of at least one heteroatom (Het1), wherein the heteroatom ( Het1) is preferably selected from the group consisting of Ti, Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Pb, and a mixing two or more of these, more preferably Ti; (iv.2) hydrothermally synthesize Het1MWW from the synthesis mixture obtained from (iv.1), thus obtaining Het1MWW in its mother liquor; (iv.3) separate Het1MWW from its mother liquor; (iv.4) preferably drying the separated Het1MWW according to (iv.3), preferably by spray drying; (iv.5) preferably calcining the Het1MWW obtained from (iv.3) or (iv.4), preferably at temperatures in the range of 500 to 700°C.
[00081] As mentioned above, Ti is preferably incorporated as Het1 in the MWW. According to this embodiment, the TiMWW obtained from (iv) has a Ti content, preferably in the range of 2.0 to 3.0% by weight, more preferably in the range of 2.1 to 2. 7% by weight, more preferably 2.2 to 2.6% by weight, more preferably 2.3 to 2.5% by weight, calculated as elemental Ti. Furthermore, the obtained TiMWW has a Si content, preferably in the range of 34 to 40% by weight, more preferably 35 to 39% by weight, more preferably 36 to 38% by weight, calculated as elemental Si. Furthermore, the obtained TiMWW has a C content (total organic carbon, TOC) preferably in the range of 7.0 to 8.0% by weight, more preferably 7.2 to 7.8% by weight, most preferably 7 .4 to 7.6% by weight, calculated as elemental C.
[00082] Therefore, the present invention also relates to a process for the preparation of a zeolitic material of zeolitic structure MWW containing Ti (TiMWW) and the TiMWW obtainable or obtained according to this process, said process being defined as above and which further comprises (iv) incorporating Ti into the MWW thereby obtaining a zeolitic material of type MWW structure containing Ti (TiMWW) by a process comprising (iv.1) preparing a synthetic mixture containing the MWW obtained in accordance with with (ii) or (iii), preferably (iii), a model compound, preferably selected from the group consisting of piperidine, hexamethylene-imine, and a mixture thereof, and at least one source of Ti ; (iv.2) hydrothermally synthesize TiMWW from the synthesis mixture obtained from (iv.1), thus obtaining TiMWW in its mother liquor; (iv.3) separate TiMWW from its mother liquor; (iv.4) preferably drying the separated TiMWW according to (iv.3), preferably by spray drying; (iv.5) optionally calcining the TiMWW obtained from (iv.3) or (iv.4), preferably at temperatures in the range of 500 to 700°C.
[00083] Still further, the present invention relates to a zeolitic material of zeolitic structure MWW containing Ti (TiMWW), having a Ti content in the range of 2.1 to 2.7% by weight, more preferably 2, 2 to 2.6% by weight, more preferably 2.3 to 2.5% by weight, calculated as elemental Ti, an Si content in the range of 34 to 40% by weight, more preferably 35 to 39% by weight , more preferably 36 to 38% by weight, calculated as elemental Si, and a C (total organic carbon, TOC) content in the range of 7.0 to 8.0% by weight, more preferably 7.2 to 7.8 % by weight, more preferably 7.4 to 7.6% by weight, calculated as elemental C.
[00084] The Het1MWW obtained from (iv) can be prepared, for example, for a subsequent step according to which a mold is prepared based on the zeolitic material, for example, by properly mixing the zeolitic material with fur at least one binder and/or with at least one binder precursor and optionally at least one pore-forming agent and/or at least one plasticizing agent. Step (v)
[00085] According to a preferred embodiment of the present invention, the Het1MWW obtained from (iv) is subjected to an acid treatment in an additional step (v).
[00086] According to step (v), it is preferred to suspend the Het1MWW in one step (v.1) in a liquid solvent system, which preferably comprises water, more preferably consists of water, and which contains hair minus one acid. Appropriate acids contained in the liquid solvent system are, for example, inorganic and/or organic acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, or tartaric acid . More preferably, the liquid solvent system contains at least one inorganic acid, more preferably nitric acid.
[00087] In a subsequent step (v.2), the suspension obtained from (v.2) is heated to a temperature preferably in the range of 75 to 125 °C, more preferably 85 to 115 °C, more preferably from 95 to 105°C, for a time in the range of preferably 17 to 25 h, more preferably 18 to 22 h.
[00088] After treatment with acid in step (v.2), the obtained Het1MWW is preferably properly separated from the suspension which further comprises acid. All methods of separating Het1MWW from suspension are conceivable. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. According to the present invention, the Het1MWW is preferably separated from the suspension by filtration to obtain a filter cake, which is preferably subjected to washing, preferably with water.
[00089] Then, the filter cake, optionally further processed to obtain a suitable suspension, is subjected to spray drying or ultrafiltration. Before separating Het1MWW from the suspension, it is possible to increase the Het1MWW content of the suspension by concentrating the suspension. If washing as applied, it may be preferred to continue the washing process until the washing water has a conductivity of less than 1000 microSiemens/cm, more preferably less than 900 microSiemens/cm, more preferably less than 800 microSiemens/cm, more preferably less than 700 microSiemens/cm.
[00090] After separating the Het1MWW from the suspension, preferably achieved by filtration, and then washing, the washed filter cake containing the Het1MWW is preferably subjected to pre-drying, for example, subjecting the filter cake with a suitable gas stream, preferably in a nitrogen stream, for a time preferably in the range of 4 to 10 hours, more preferably 5 to 8 hours.
[00091] Then, the pre-dried filter cake is preferably dried, in one step (v.4) at temperatures in the range from 100 to 300°C, more preferably 150 to 275°C, more preferably from 200 to 250 °C in a suitable atmosphere such as technical nitrogen, air, or lean air, preferably air or lean air. This drying can be carried out, for example, by spray drying. Furthermore, it is possible to separate the Het1MWW from the suspension through a suitable method of filtration, followed by washing and spray drying.
[00092] After drying, the Het1MWW is preferably subjected to calcination in step (v.5) at temperatures in the range of 500 to 700°C, more preferably 550 to 675°C, more preferably 600 to 675°C in a suitable environment, such as technical nitrogen, air, or lean air, preferably in air or lean air.
[00093] Therefore, the present invention relates to the above-defined process and zeolitic material obtainable or obtained therefrom, said process further comprising (v) acid treatment of Het1MWW obtained from (iv) by a process comprising (v.1) suspending Het1MWW in a liquid solvent system, preferably water, said liquid solvent system containing at least one acid, preferably containing nitric acid; (v.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of 17 to 25 h; (v.3) separate the acid-treated Het1MWW from the suspension; (v.4) preferably drying the separated Het1MWW according to (v.3), preferably by spray drying; (v.5) preferably the calcination of the Het1MWW obtained from (v.3) or (v.4), preferably at temperatures in the range of 500 to 700°C.
[00094] As mentioned above, Ti is preferably incorporated as Het1 in the MWW. According to this embodiment, the TiMWW obtained from (v) preferably has a Ti content in the range of 1.3 to 1.9% by weight, more preferably 1.4 to 1.8% by weight , more preferably 1.5 to 1.7% by weight, calculated as elemental Ti, a Si content, preferably in the range of 39.5 to 45.5% by weight, more preferably 40.5 to 44.5% by weight, more preferably 41.5 to 43.5% by weight, calculated as elemental Si, and a content of C (total organic carbon, TOC), preferably in the range of 0.10 to 0.25% by weight, more preferably 0.11 to 0.20% by weight, more preferably 0.13 to 0.18% by weight, calculated as elemental C.
[00095] Therefore, the present invention also relates to a process for the preparation of a zeolitic material of zeolitic structure MWW containing Ti (TiMWW) and the TiMWW obtainable or obtained according to this process, said process being defined as above and further comprising (v) acid treating the TiMWW obtained from (iv) by a process comprising (v.1) suspending the TiMWW in a liquid solvent system, preferably water, said liquid solvent system containing hair one less acid, preferably containing nitric acid; (v.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of 17 to 25 h; (v.3) separate the acid-treated TiMWW from the suspension; (v.4) preferably drying the separated TiMWW according to (v.3), preferably by spray drying; (v.5) preferably calcin the TiMWW obtained from (v.3) or (v.4), preferably at temperatures in the range of 500 to 700°C.
[00096] Still further, the present invention relates to a zeolitic material of zeolitic structure MWW containing Ti (TiMWW), having a Ti content in the range of 1.3 to 1.9% by weight, more preferably 1, 4 to 1.8% by weight, more preferably from 1.5 to 1.7% by weight, calculated as elemental Ti, a Si content, preferably in the range of 39.5 to 45.5% by weight, plus preferably 40.5 to 44.5% by weight, more preferably 41.5 to 43.5% by weight, calculated as elemental Si, and a C (total organic carbon, TOC) content preferably in the range of 0.10 to 0.25% by weight, more preferably 0.11 to 0.20% by weight, more preferably 0.13 to 0.18% by weight, calculated as elemental C.
[00097] The Het1MWW obtained from (v) can be prepared, for example, to a subsequent step according to which a mold is prepared based on the zeolitic material, for example, by properly mixing the zeolitic material with fur at least one binder and/or with at least one binder precursor and optionally at least one pore-forming agent and/or at least one plasticizing agent. Step (vi)
[00098] According to an embodiment of the present invention, the Het1MWW obtained from (v), is subjected to a step (vi), in which at least one second heteroatom Het2 is incorporated into Het1MWW.
[00099] According to this embodiment, the Het1MWW, obtained from (iv) or (v), is preferably suspended in a step (vi.1) in a liquid solvent system, which preferably comprises water , most preferably, is made up of water. In addition, the liquid solvent system contains at least one suitable source of Het2, also called a Het2-containing precursor. As second heteroatom Het2, Ti, Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, and a mixture of two or more of these are preferred. Generally, Het2 can be the same as Het1. Preferably, Het2 is different from Het1. According to the present invention, Zn is most preferred.
[000100] With regard to preferred sources of zinc, zinc oxide, zinc halides, zinc acetate and zinc nitrate can be mentioned, with zinc acetate and zinc nitrate being especially preferred.
[000101] With regard to preferred sources of titanium, titanium oxide, titanium halide and tetraalkylorthotitanates can be mentioned. However, the present invention is not limited to them. Among these, titanium halides and tetraalkylorthotitanates are more preferred. More preferred are titanium tetrafluoride, tetraethylorthotitanate, tetrapropylorthotitanate, and tetrabutylorthotitanate, with tetrabutylorthotitanate being especially preferred.
[000102] With regard to preferred sources of aluminum, alumina, aluminum nitrate, can be mentioned, with aluminum nitrate being especially preferred.
[000103] With regard to preferred sources of zirconium, zirconium oxide, zirconium halides and zirconium tetraalkoxides can be mentioned. Among these, zirconium halides and zirconium tetraalkoxides are more preferred. Most preferred are zirconium tetrafluoride, zirconium tetraethoxide, zirconium tetrabutoxide.
[000104] With regard to preferred sources of vanadium, vanadium oxide, vanadium halides and vanadium trialkoxide oxides can be mentioned. Among these, vanadium halides and vanadium trialkoxide oxides are most preferred. Most preferred are vanadium trichloride and vanadium oxytriisopropoxide.
[000105] With regard to preferred sources of niobium, niobium oxide, niobium halides and niobium tetraalkanoates can be mentioned. More preferred are niobium tetraalkanoates, with niobium tetrakis (2-ethylhexanoate) being especially preferred.
[000106] With regard to preferred sources of tantalum, tantalum oxide, tantalum halides and tantalum disulfide can be mentioned, with tantalum disulfide being especially preferred.
[000107] With regard to preferred sources of chromium, chromium acetate, chromium nitrate and chromium halides can be mentioned, with chromium nitrate being especially preferred.
[000108] With regard to preferred sources of molybdenum, molybdenum oxide, molybdenum halides and molybdenum sulfide can be mentioned, with molybdenum trichloride being especially preferred.
[000109] With regard to preferred sources of tungsten, tungsten oxide and tungsten halides can be mentioned, with tungsten tetrachloride being especially preferred.
[000110] With regard to preferred sources of manganese, manganese oxide, manganese halides, manganese acetate and manganese acetylacetonate can be mentioned, with manganese trisacetylacetonate being especially preferred.
[000111] With regard to preferred sources of iron, iron oxide, iron halides, iron acetate and iron nitrate can be mentioned, with iron nitrate being especially preferred.
[000112] With regard to preferred sources of cobalt, cobalt oxide, cobalt halides and cobalt trisacetylacetonate can be mentioned, with cobalt trisacetylacetonate being especially preferred.
[000113] With regard to preferred sources of nickel, nickel oxide, nickel halides, nickel nitrate and nickel acetate can be mentioned, with nickel nitrate and nickel acetate being especially preferred.
[000114] With regard to preferred sources of gallium, gallium oxide, gallium halides and gallium nitrate can be mentioned, with gallium nitrate, gallium trichloride, and gallium trifluoride being especially preferred.
[000115] With regard to preferred sources of indium, indium oxide, indium halides and indium trialkoxy can be mentioned, with indium trichloride, indium trifluoride and indium triisoprooxide being especially preferred.
[000116] With regard to preferred sources of tin, tin oxide, tin halides and tin tetraalkoxy can be mentioned, with tin tetrachloride, tin tetrafluoride, tin tetraethoxy, and tin tetra-tert-butoxy being especially preferred.
[000117] With regard to preferred sources of lead, lead halides and lead tetraalkoxy may be mentioned, with lead acetate, lead chloride, lead nitrate, lead acetylacetonate, and lead being especially preferred.
[000118] In the suspension of (vi.1), the ratio of Het2 to Si in Het1MWW is preferably in the range of 0.001:1 to 0.3:1. In particular, as far as the subject Zn-containing precursor is concerned, it is preferable to use it in an amount which allows obtaining the preferred ZnTiMWW described hereinafter.
[000119] In a subsequent step (vi.2), the suspension obtained from (vi.1) is heated to a temperature preferably in the range of 75 to 125°C, more preferably 85 to 115°C, more preferably from 95 to 105°C, for a time in the range of preferably 3 to 6 hours, more preferably 3.5 to 5 hours. Thus, Het2 is wet impregnated into Het1MWW.
[000120] Alternatively, it is conceivable to prepare a liquid solvent system that contains at least Het2 containing precursor, and incorporate the at least one Het2 into Het1MWW by spraying the liquid solvent system onto the Het1MWW. Proper combination of spraying and wet impregnation is also possible.
[000121] After impregnation, the Het2Het1MWW obtained is preferably properly separated from the suspension. All methods of separating Het2Het1MWW from suspension are conceivable. Especially preferably, the separation is carried out by means of filtration, ultrafiltration, diafiltration or centrifugation methods. A combination of two or more of these methods can be applied. According to the present invention, the Het2Het1MWW is preferably separated from the suspension by filtration to obtain a filter cake, which is preferably subjected to washing, preferably with water. If washing as applied, it may be preferred to continue the washing process until the washing water has a conductivity of less than 1000 microSiemens/cm, more preferably less than 900 microSiemens/cm, more preferably less than 800 microSiemens/cm, more preferably less than 700 microSiemens/cm.
[000122] Then, the washed filter cake is preferably subjected to pre-drying, for example, by subjecting the filter cake to a stream of suitable gas, preferably a stream of nitrogen, for a time preferably in the range of 5 to 15 hours, more preferably from 8 to 12.
[000123] Therefore, the present invention relates to the above-defined process and zeolitic material obtainable or obtained therefrom, said process further comprising (vi) the incorporation of at least one second heteroatom (Het2) within the Het1MWW obtaining- if so a zeolitic material of MWW type structure, containing at least two heteroatoms (Het2Het1MWW) by a process comprising (vi.1) suspending Het1MWW in a liquid solvent system, preferably water, said liquid solvent system containing at least one precursor containing Het2, preferably at least one salt of Het2, wherein the second heteroatom (Het2) is preferably selected from the group consisting of Ti, Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, and a mixture of two or more of these, most preferably Zn; (vi.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of 3 to 6 hours; (vi.3) optionally separate the Het2Het1MWW from the suspension.
[000124] As mentioned above, Ti is preferably incorporated as Het1 and Zn is preferably incorporated as Het2. According to the present invention, the ZnTiMWW obtained from impregnation in (vi.2), preferably after washing, and preferably pre-drying, has a zinc content preferably in the range of 1.0 to 2.0% by weight, calculated as elemental Zn, a Ti content, preferably in the range of 1.0 to 2.0% by weight, calculated as elemental Ti, a Si content, preferably in the range of 39 to 45% by weight, calculated as elemental Si, and a C content (total organic carbon, TOC) preferably in the range of 1.1 to 1.7% by weight, more preferably 1.2 to 1.6% by weight , more preferably 1.3 to 1.5% by weight, calculated as elemental C.
[000125] Therefore, the present invention relates to a process for the preparation of a zeolitic material of zeolitic structure MWW containing Zn and Ti (ZnTiMWW) and the ZnTiMWW obtainable or obtained by this process, said process further comprising (vi) the incorporation of Zn in TiMWW, thus obtaining a zeolitic material of MWW type structure containing Zn and Ti (ZnTiMWW) by a process that comprises (vi.1) suspending the TiMWW in a liquid solvent system, preferably water, said liquid solvent system which contains at least one Zn-containing precursor; (vi.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of between 3 and 6 h, and optionally washing and pre-drying the ZnTiMWW obtained; (vi.3) optionally separate ZnTiMWW from suspension.
[000126] Still further, the present invention relates to a zeolitic material of zeolitic structure MWW containing Zn and Ti (ZnTiMWW), with a zinc content preferably in the range of 1.0 to 2.0% in weight, calculated as elemental Zn, a Ti content, preferably in the range of 1.0 to 2.0% by weight, calculated as elemental Ti, a Si content, preferably in the range of 39 to 45% by weight, calculated as elemental Si, and a C content (total organic carbon, TOC) preferably in the range 1.1 to 1.7% by weight, more preferably 1.2 to 1.6% by weight, most preferably 1, 3 to 1.5% by weight, calculated as elemental C.
[000127] The Het2Het1MWW, preferably the ZnTiMWW obtained from separation in (vi.3), optionally followed by washing and pre-drying, can be passed to a drying stage according to which the filter cake preferably pre-dried is preferably dried at temperatures in the range from 100 to 300°C, more preferably from 150 to 275°C, more preferably from 200 to 250°C in a suitable atmosphere such as technical nitrogen, air, or lean air, preferably in air or lean air. It is to be understood that in this context of the present invention, drying is not carried out by a quick drying method, such as spray drying, but by means of conventional drying, such as suitable oven drying or the like. After drying, Het2Het1MWW, preferably ZnTiMWW can be calcined at temperatures in the range 500 to 700°C, more preferably 550 to 675°C, more preferably 600 to 675°C, in a suitable atmosphere such as technical nitrogen, air, or lean air, preferably in air or lean air. This calcination is preferably carried out in a muffle furnace, rotary kiln and/or a belt calcination furnace, wherein the calcination is carried out generally for 0.5 hours or more, for example for a time in the range of 0.25 to 12 hours, preferably from or from 0.5 to 6 hours. During calcination, it is possible to keep the temperature constant, or to change temperatures continuously or discontinuously. If calcination is carried out twice or more, the calcination temperatures in the individual steps may be different or the same. Calcining temperatures are preferably in the range of up to 700°C, preferably 400 to 700°C, more preferably from 500 to 700°C, more preferably 600 to 700°C, more preferably 625 to 675°C.
[000128] The Het2Het1MWW thus obtained can be subjected, for example, to a subsequent step according to which a mold is prepared based on the zeolitic material, for example, by properly mixing the zeolitic material with at least one binder and/ or with at least one binder precursor and optionally at least one pore-forming agent and/or at least one plasticizing agent.
[000129] According to a preferred embodiment of the present invention, the separated Het2Het1MWW and optionally washed and pre-dried, preferably the ZnTiMWW, is subjected to rapid drying, preferably spray drying in one step (vi.4), preferably followed by a step (vi.5) of calcining the powder obtained from spraying (vi.4). Insofar as step (vi.4) is concerned, it is preferred that, based on the separated and optionally washed and pre-dried Het2Het1MWW, an aqueous suspension is prepared, which is subjected to said spray drying in ( vi.4). From spray drying, a spray powder is obtained.
[000130] In general, it is conceivable that this powdered powder contains Het2Het1MWW, preferably ZnTiMWW in arbitrary amounts. For example, it may be possible that the spray powder, in addition to Het2Het1MWW, preferably ZnTiMWW, also contains at least one chemical compound as a binding material. Examples of such binders are metal oxides such as, for example, SiO2, Al2O3, TiO2, ZrO2 or MgO or clays or mixtures of two or more of these oxides or mixed oxides of at least two of Si, Al, Ti, Zr , in G. Naturally occurring or synthetically produced clay and alumina minerals such as, for example, alpha-, beta-, gamma-, delta-, eta-, kappa-, chi- or theta-alumina and their inorganic or precursor compounds or organometallics, such as, for example, gibbsite, bayerite, boehmite or pseudoboehmite, or trialkoxyaluminates, such as, for example, aluminum triisopropylate, are particularly preferred as Al2O3 binders. Other possible binders can be amphiphilic compounds with a polar portion and a non-polar portion and graphite. Other binders can be, for example, clays, such as, for example, montmorillonites, kaolins, metakaolin, hectorite, bentonites, dickite halloysites, nacrites or anaxites. According to this possible embodiment, the spray powder may contain, based on the weight of the spray powder, up to 95% by weight or up to 90% by weight or up to 85% by weight or up to 80% by weight or even 75% by weight or up to 70% by weight or up to 65% by weight or up to 60% by weight or up to 55% by weight or up to 50% by weight or up to 45% by weight or up to 40% by weight or up to 35% by weight or up to 30% by weight or up to 25% by weight or up to 20% by weight or up to 15% by weight or up to 10% by weight or up to 5% by weight of one or more binding materials.
[000131] These binders can be used as such or in the form of suitable precursor compounds, which, during spray drying and/or subsequent calcination form the desired binder. Examples of such ligand precursors are tetraalkoxysilanes, tetraalkoxytitanates, tetraalkoxyzirconates, or a mixture of two or more different tetraalkoxysilanes or a mixture of two or more different tetraalkoxytitanates or one a mixture of two or more different tetraalkoxy zirconates or a mixture of at least one tetraalkoxysilane and at least one tetraalkoxytitanate or of at least one tetraalkoxysilane and at least one tetraalkoxyzirconate or of at least one tetraalkoxytitanate and at least one tetraalkoxyzirconate or a mixture of at least one tetraalkoxysilane and at least one tetraalkoxytitanate and at least one tetraalkoxy -zirconate. Within the scope of the present invention which comprise binders or completely or partially comprise SiO2 or which are a precursor of SiO2 from which SiO2 is formed may be preferred. In this context, both colloidal silica and so-called "wet process" silica and so-called "dry process" silica can be used. Particularly preferably this silica is amorphous silica, the size of the silica particles being, for example, in the range of 5 to 100 nm and a surface area of the silica particles in the range of 50 to 500 m 2 /g. Colloidal silica, preferably as an alkali metal and/or ammonia solution, more preferably as an ammonia solution, is commercially available, inter alia, for example, as Ludox®, Syton®, Nalco® or Snowtex®. "Wet process" silica is commercially available, inter alia, for example, as Hi-Sil®, Ultrasil®, Vulcasil®, Santocel®, Valron-Estersil®, Tokusil® or Nipsil®. "Dry process" silica is commercially available, inter alia, for example as Aerosil®, Reolosil®, Cab-O-Sil®, Fransil® or ArcSilica®. Inter alia, an ammoniacal solution of colloidal silica is preferred in the present invention.
[000132] According to a preferred embodiment of the present invention, no binder and no binder precursor is added to the suspension containing the Het2Het1MWW, preferably the ZnTiMWW, when the suspension is prepared according to (vi.4). Thus, according to a preferred embodiment of the present invention, the suspension which is subjected to spray drying according to (ii) does not contain a binder or a precursor of a binder.
[000133] If desired, at least a pore-forming agent can be added when the suspension according to (vi.4) is prepared. Pore forming agents that can be used are preferably polymers that are dispersible, suspendible or emulsifiable in water or aqueous solvent mixtures. Such polymers can be polymeric vinyl compounds, such as, for example, polyalkylene oxides, such as polyethylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides and polyesters, carbohydrates, such as, for example, cellulose or cellulose derivatives, such as, for example, methyl cellulose, or natural sugars or fibres. Even more suitable pore-forming agents can be, for example, cellulose or graphite. If this is the case with regard to the pore characteristics to be achieved, a mixture of two or more pore-forming agents can be used. In a particularly preferred embodiment of the process according to the invention, the pore-forming agents are removed by calcination according to (vi.5) to obtain the spray powder.
[000134] According to a preferred embodiment of the present invention, no pore-forming agent is added when the suspension is prepared according to (vi.4). Thus, according to a preferred embodiment of the present invention, the suspension which is subjected to spray drying according to (vi.4) does not contain a pore-forming agent.
[000135] As far as the content of the suspension provided in (vi.4) with regard to Het2Het1MWW, preferably the ZnTiMWW in question, there are no specific restrictions. Preferably, such concentrations are chosen that serve for the preparation of the spray powder, as discussed above. Preferably, the suspension introduced in (vi.4) has a solids content in the range of from 5 to 25% by weight, preferably from 10 to 20% by weight. Preferred ranges are 10 to 15% by weight or 11 to 16% by weight or 12 to 17% by weight or 13 to 18% by weight or 14 to 19% by weight or 15 to 20% by weight.
[000136] When providing the suspension, the Het2Het1MWW, preferably the ZnTiMWW can be suspended in any suitable liquid or a mixture of two or more liquids. Preferably the Het2Het1MWW, preferably the ZnTiMWW is suspended in water or a mixture of water and at least one other suitable liquid. More preferably the Het2Het1MWW, preferably the ZnTiMWW is suspended in water as the only liquid. Therefore, the suspension provided in (vi.4) is preferably an aqueous suspension.
[000137] Therefore, according to a preferred embodiment, the suspension supplied and subjected to spray drying in (vi.4) consists essentially of the Het2Het1MWW, preferably the ZnTiMWW supplied as discussed hereinbefore, and water. Preferably, the content of the suspension, provided it is spray dried in (vi.4), with respect to Het2Het1MWW, preferably ZnTiMWW, and water is at least 95% by weight, more preferably at least 99 % by weight, more preferably at least 99.9% by weight, based on the total weight of the suspension.
[000138] According to (vi.4), the suspension provided is preferably subjected to spray drying.
[000139] In general, spray drying is a direct method of drying, eg slurries or suspensions, feeding a well-dispersed solid-liquid suspension or suspension to a suitable atomizer and subsequently flash drying in a stream of hot gas. Thereby, the slurry or suspension is continuously passed along nozzles, atomizing discs or other suitable atomizing means (reference is made, for example, in Arthur Lefebvre, "Atomization and sprays", Hemisphere Publishing Corporation, 1989, ISBN 0- 89116-603-3) and sprayed into a drying chamber that is suitably heated with at least one hot gas. Spray drying is generally carried out continuously, without or with (agglomeration mode) the return of the solid to the spray compartment. Spray drying is described, for example, in K. Masters "Manual on spray drying", Longman Scientific & Technical, 1991, ISBN 0-582-06266-7. The atomizer mentioned above can be of several different types. The most common is wheel atomization which uses high-speed rotation of a wheel or disk to break the suspension into droplets that spin off the wheel in a chamber and are flash dried before hitting the chamber walls. Atomization can also be achieved by single-component nozzles, which rely on hydrostatic pressure to force the suspension through a small nozzle. Multi-component nozzles such as two-component nozzles are also used, where gas pressure is used to force the suspension through the nozzle. The use of a rotary sprayer is also conceivable.
[000140] According to the present invention, it is especially preferred to use a drying gas having a temperature in the range of 100 to 500°C, preferably in the range of 150 to 450°C, more preferably in the range of 200 to 400° C, more preferably in the range 250 to 350°C, more preferably in the range 275 to 325°C. As drying gas, air, lean air or nitrogen-oxygen mixtures with an oxygen content of up to 10% by volume, preferably up to 5% by volume, more preferably less than 5% by volume, e.g. up to 2% by volume can be used. It is preferred to use inert gases as the drying gas. Technical nitrogen is especially preferred as the drying gas. The speed of the drying gas is preferably in the range 400 to 700 kg/h, more preferably 500 to 600 kg/h, more preferably 525 to 575 kg/h, such as 525, 530, 535, 540, 545, 550, 555, 560, 565, 570, or 575 kg/h.
[000141] According to the present invention, it is especially preferred to use a nozzle gas having a temperature in the range of 10 to 100°C, preferably in the range of 15 to 75°C, more preferably in the range of 20 to 50° C, more preferably in the range of 20 to 30°C. Such as nozzle gas, air, lean air or nitrogen-oxygen mixtures with an oxygen content of up to 10% by volume, preferably up to 5% by volume, more preferably less than 5% by volume, e.g. , up to 2% by volume, can be used. It is preferable to use inert gases such as nozzle gas. Technical nitrogen is especially preferred as the nozzle gas. The gas velocity of the nozzle is preferably in the range from 10 to 50 kg/h, more preferably from 15 to 35 kg/h, more preferably from 20 to 25 kg/h.
[000142] As a nozzle, a two-component nozzle is especially preferred. In particular, such a two-component nozzle has a diameter in the range of 2 to 6 mm, preferably from 3 to 5 mm, more preferably 3.5 to 4.5 mm, more preferably 3.9 to 4.1 mm, more preferably 4 millimeters.
[000143] Furthermore, it is preferred to use a spray tower configured with a dehumidifier, a filter, and a scrubber, preferably in this order, through which the configuration of the drying gas together with the suspension to be sprayed is passed. According to this embodiment, the temperature of the drying gas as described above is to be understood as the initial drying temperature that is passed to the dehumidifier.
[000144] Therefore, the present invention relates to the process defined above, wherein in (vi.4), a spray apparatus, preferably a spray tower is used for spray drying the suspension, having said apparatus at least one spray nozzle, preferably at least one two-substance nozzle, more preferably a two-substance nozzle, said nozzle having a diameter in the range 3.5 to 4.5 mm, preferably 3.9 to 4.1 mm.
[000145] Furthermore, the present invention relates to a process, wherein in (vi.4), a spray apparatus, preferably a spray tower is used for spray drying the suspension, said apparatus being used with a nozzle gas having a temperature in the range from 20 to 50°C, preferably from 20 to 30°C, and a drying gas having a temperature in the range from 250 to 350°C, preferably from 275 to 325 °C, said nozzle gas preferably being an inert gas, more preferably technical nitrogen, and said drying gas preferably being an inert gas, most preferably technical nitrogen.
[000146] The spray powder, which is obtained from (vi.4) has a preferred residual moisture content of preferably at least 5% by weight, more preferably at least 4% by weight, most preferably from at least 3% by weight, more preferably at least 2% by weight.
[000147] Furthermore, the present invention also relates to powder spraying, obtainable or obtained by the process as discussed above.
[000148] According to (vi.5), the spray powder obtained from (vi.4) is optionally calcined. According to the present invention, it is preferred to subject the spray powder obtained from (vi.4) to calcination.
[000149] Calcination of the spray powder can be carried out under any suitable gas atmosphere, where air and/or lean air is/are preferred. Furthermore, the calcination is preferably carried out in a muffle furnace, rotary kiln and/or a belt calcination furnace, wherein the calcination is carried out generally for 0.5 hours or more, for example for a time in the interval between 0.25 and 12 hours, preferably from or from 0.5 to 6 hours, more preferably from 1 to 3 hours. During calcination, it is possible to keep the temperature constant, or to change temperatures continuously or discontinuously. If calcination is carried out two or more times, the calcination temperatures in the individual steps may be different or the same. Calcining temperatures are preferably in the range of up to 700°C, preferably 400 to 700°C, more preferably from 500 to 700°C, more preferably from 600 to 700°C, more preferably from 625 to 675°C such as from 625 to 645°C or 635 to 655°C or 645 to 665°C or 655 to 675°C.
[000150] Therefore, the present invention relates to a process for the preparation of a zeolitic material of zeolitic structure MWW containing at least one heteroatom Het1 and at least one heteroatom Het2 (Het2Het1MWW), preferably ZnTiMWW, and Het2Het1MWW, of preferably ZnTiMWW, obtainable or obtained by this process, said process further comprising (vi) incorporating at least one second heteroatom (Het2), preferably Zn, into Het1MWW, preferably TiMWW, thus obtaining a zeolytic material of MWW-type structure, containing at least two heteroatoms (Het2Het1MWW), preferably ZnTiMWW, by a process comprising (vi.1) suspending Het1MWW in a liquid solvent system, preferably water, said liquid solvent system containing, at least one precursor containing Het2, preferably at least one salt of Het2, wherein the second heteroatom (Het2) is preferably selected from the group consisting of Ti, Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, and a mixture of two or more of these, most preferably Zn; (vi.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of 3 to 6 hours; (vi.3) separate Het2Het1MWW from suspension; (vi.4) preferably drying the separated Het2Het1MWW according to (vi.3), preferably by spray drying; (vi.5) optionally calcine the Het2Het1MWW obtained from (vi.3) or (vi.4), preferably at temperatures in the range of 500 to 700°C.
[000151] From said spray drying according to step (vi.4), and preferably the subsequent calcination in step (vi.5), a spray powder is preferably obtained, the particles of which having a Dv10 value of at least 2 micrometers, said spray powder comprising mesopores with an average pore diameter (4V/A) in the range of 2 to 50 nm as determined by Hg porosimetry according to DIN 66133, and which comprises, based on the weight of the spray powder, at least 95% by weight of a zeolitic material Het2Het1MWW, preferably ZnTiMWW. The term "Dv10 value" as referred to in the context of the present invention describes the average particle size where 10% by volume of the spray powder particles have a smaller size. Preferably, the Dv10 value is at least 2.5, more preferably at least 3. According to the present invention, the values are determined by Dv10 by preparing a suspension of 1.0 g of the spray powder in 100 g of deionized water, shake the suspension for 1 minute and measure the Dv10 value in a long-bed Mastersizer S version 2.15, ser. No. 33544325; supplier: Malvern Instruments GmbH, Herrenberg, Germany, with the following instrument parameters: - focal width: 300RF mm - bar length: 10.00 mm - module: MS17 - shading: 16.9% - dispersion model: 3$ $D - analysis model: polydisperse - correction: none.
[000152] The term "4V/A" as used in this context of the present invention refers to four times the accumulated volume V of the pores between 2 and 50 nm, divided by A, which relates to the accumulated surface of pores between 2 and 50 nm.
[000153] According to an especially preferred embodiment of the present invention, the Het2Het1MWW, preferably the ZnTiMWW containing spray powder contains essentially no other chemical compound besides the Het2Het1MWW, preferably the zeolitic material ZnTiMWW as such. Preferably, the spray powder of the present invention comprises, based on the weight of the spray powder, at least 95, more preferably at least 96% by weight, more preferably at least 97% by weight, most preferably at least 98% by weight. weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, more preferably at least 99.7% by weight of the Het2Het1MWW, preferably the ZnTiMWW.
[000154] According to the present invention, the crystallinity of Het2Het1MWW, preferably the ZnTiMWW which is contained in the spray powder of the invention, as determined by X-ray diffraction analysis (XRD), can vary over wide ranges. For example, the crystallinity of Het2Het1MWW, preferably ZnTiMWW may be at least 20%, preferably at least 30%, more preferably at least 40%, more preferably at least 50%, more preferably at least 60%, most preferably at least 70%. According to a preferred embodiment of the present invention, the crystallinity of the Het2Het1MWW, preferably the ZnTiMWW which is contained in the spray powder of the invention is at least 80%, preferably at least 81%, more preferably at least 82%, more preferably at least 83%, more preferably at least 84%, most preferably at least 85%. Each value is to be understood as having a measurement inaccuracy of plus/minus 10%.
[000155] Preferably, the zeolitic material of type MWW 1 2 21 structure which contains at least two heteroatoms Het and Het (Het Het MWW) according to the present invention has a Het2 content in the range of 1.0 at 2.0% by weight, calculated as elemental Het2 and based on the weight of Het2Het1MWW, and having a Het1 content in the range of 1.0 to 2.0% by weight, calculated as elemental Het1 and based on the weight of the Het2Het1MWW.
[000156] In particular, insofar as the preferred ZnTiMWW in question, which is contained in the spray powder of the present invention, no specific restrictions exist as far as the Zn content of the ZnTiMWW in question exists. Generally, Zn contents, calculated as elemental Zn, in the range, for example, up to 5% by weight, are conceivable, with conceivable ranges of 0.01 to 5% by weight, or 0.02 to 4% by weight, or from 0.05 to 3% by weight, or from 0.1 to 2% by weight. Surprisingly, especially if it is used as a catalytically active material, more particularly if it is used as a catalytically active material in epoxidation processes as described in detail below. It has been found to be particularly advantageous if the Zn content of the ZnTiMWW is in a narrow range of 1.0 to 2.0% by weight, calculated as Zn and based on the weight of the ZnTiMWW. There are no specific restrictions regarding the Ti content of the ZnTiMWW in question. Generally, Ti contents, calculated as elemental Ti, in the range, for example, up to 5% by weight, are conceivable, with conceivable ranges of 0.01 to 5% by weight, or 0.02 to 4% by weight , or from 0.05 to 3% by weight, or from 0.1 to 2% by weight. Especially if used as catalytically active material, more particularly if used as catalytically active material in epoxidation processes as described in detail below, it has been found to be particularly advantageous if the Ti content of ZnTiMWW is in a narrow range of 1 .0 to 2.0% by weight, calculated as Ti and based on the weight of ZnTiMWW.
[000157] The Het2Het1MWW thus obtained, in particular the Het2Het1MWW spray powder, can be subjected, for example, to a subsequent step according to which a mold is prepared based on the zeolitic material, for example, by properly mixing the zeolitic material with at least one binder and/or with at least one binder precursor, and optionally at least one pore-forming agent and/or at least one plasticizing agent.
[000158] The zeolitic materials according to the invention, preferably obtained by the process according to the invention, can be used as such for all purposes, such as catalytically active agents, molecular sieves, adsorbents, fillers, material for the preparation of molds, and the like. According to a preferred embodiment, zeolitic materials are used as a catalytically active agent. In particular for the preferred ZnTiMWW, the zeolitic material is used as a catalytically active agent, preferably for the preparation of propylene oxide from propene, preferably in acetonitrile as a solvent and/or preferably using hydrogen peroxide as an oxidizing agent . Furthermore, the present invention relates to an epoxidation process, preferably a process for preparing propylene oxide from propene, more preferably a process for preparing propylene oxide from propene with hydrogen peroxide as oxidizing agent, preferably with a process for the preparation of propylene oxide from propene with hydrogen peroxide as oxidizing agent in acetonitrile as solvent, process in which the zeolitic material, in particular ZnTiMWW as described above, preferably obtained from the process as described above is used as a catalyst.
[000159] With regard to the preferred embodiment of the present invention according to which the zeolitic material has MWW type work structure frame, the present invention is preferably characterized by the following embodiments and the combination of these forms of embodiment, as indicated by its dependencies: 1. A process for preparing a zeolitic material, comprising (i) providing a boron-containing zeolitic material of structure of the MWW type (B-MWW); (ii) decaying the B-MWW by treating the B-MWW with a liquid solvent system, thus obtaining a decayed B-MWW (MWW); wherein the liquid solvent system is chosen from the group consisting of water, monohydric alcohols, polyhydric alcohols, and mixtures of two or more thereof, and wherein said liquid solvent system does not contain an organic acid or inorganic acid or a salt thereof, the acid being selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, and tartaric acid. 2. The process of Embodiment 1, wherein in (i), the boron-containing zeolitic material of the MWW type structure (B-MWW) is provided by a process comprising (a) hydrothermal synthesis of a B-MWW precursor from a synthesis mixture, containing at least one silicon source, preferably ammonia-stabilized colloidal silica, at least one boron source, preferably boric acid, and at least one model compound, preferably selected from the group consisting of piperidine, hexamethylene-imine, and a mixture thereof, to obtain the precursor of B-MWW in its mother liquor; (b) separate the precursor of B-MWW from its mother liquor; (c) optionally drying the B-MWW precursor separated according to (b); (d) calcining the B-MWW precursor obtained from (b) or (c), preferably at a temperature in the range of 500 to 700°C, obtaining the B-MWW. 3. The process of embodiment 1 or 2, wherein the liquid solvent system does not contain an organic or inorganic acid, or a salt. 4. The process of any one of embodiments 1 to 3, wherein the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2 -diol, propane-1,3-diol, propane-1,2,3-triol, and mixtures of two or more thereof, the liquid solvent system preferably being water. 5. The process of any one of embodiments 1 to 4, wherein the treatment according to (ii) is carried out at a temperature in the range of 50 to 125 °C. 6. The process of any one of embodiments 1 to 5, wherein the treatment according to (ii) is carried out for a time in the range of 6 to 20 h. 7. The process of any one of embodiments 1 to 6, wherein the treatment according to (ii) is carried out in at least two separate steps, wherein between at least two treatment steps, the MWW is dried , preferably at a temperature in the range of 100 to 150°C. 8. The process of any one of embodiments 1 to 7, further comprising (111) post-treatment of the MWW obtained from (ii) by a process comprising (iii.(1) separating the MWW from the system of liquid solvent; (iii.(2) preferably drying the separated MWW, preferably by spray drying; (iii.(3) optionally, calcining the MWW obtained from (iii.1) or (iii.2 ), preferably at temperatures in the range of 500 to 700°C. 9. The process of any one of Embodiments 1 to 8, preferably of Embodiment 8, further comprising (iv) incorporating at least one first heteroatom ( Het1) in MWW, thus obtaining a zeolitic material with a MWW-type structure, containing at least one heteroatom (Het1MWW) by a process comprising (iv.1) preparation of a synthesis mixture containing the MWW obtained according to (ii) ) or (iii), preferably (iii), a model compound, preferably selected from the group containing piperidine system, hexamethylene-imine, and a mixture thereof, and at least one source of at least one heteroatom (Het1), wherein the heteroatom (Het1) is preferably selected from the group consisting of Ti, Al, Zr , V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Pb, and a mixture of two or more of these, more preferably Ti; (iv.2) hydrothermally synthesize Het1MWW from the synthesis mixture obtained from (iv.1), thus obtaining Het1MWW in its mother liquor; (iv.3) separate Het1MWW from its mother liquor; (iv.4) preferably drying the separated Het1MWW according to (iv.3), preferably by spray drying; (iv.5) optionally calcining the Het1MWW obtained from (iv.3) or (iv.4), preferably at temperatures in the range of 500 to 700°C. 10. The process of embodiment 9, which further comprises (v) acid treating the Het1MWW obtained from (iv) by a process comprising (v.1) suspending the Het1MWW in a liquid solvent system, preferably water, said liquid solvent system containing at least one acid, preferably containing nitric acid; (v.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of 17 to 25 h; (v.3) separate the acid-treated Het1MWW from the suspension; (v.4) preferably drying the separated Het1MWW according to (v.3), preferably by spray drying; (v.5) preferably the calcination of the Het1MWW obtained from (v.3) or (v.4), preferably at temperatures in the range of 500 to 700°C. 11. The process of embodiment 9 or 10, further comprising (vi) incorporating at least one second heteroatom (Het2) within Het1MWW thereby obtaining a zeolitic material of MWW-type structure, containing at least two heteroatoms (Het2Het1MWW) by a process comprising (vi.1) suspending Het1MWW in a liquid solvent system, preferably water, said liquid solvent system containing at least one precursor containing Het2, preferably at least one salt of Het2, wherein the second heteroatom (Het2) is preferably selected from the group consisting of Ti, Al, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, and a mixture of two or more of these, most preferably Zn; (vi.2) heating the suspension obtained from (v.1) at a temperature in the range of 75 to 125°C for a time in the range of 3 to 6 hours; (vi.3) separate Het2Het1MWW from suspension; (vi.4) preferably drying the separated Het2Het1MWW according to (vi.3), preferably by spray drying; (vi.5) optionally calcining the Het2Het1MWW obtained from (vi.3) or (vi.4), preferably at temperatures in the range of 500 to 700°C. 12. A zeolitic material, obtainable or obtained by a process according to any of embodiments 1 to 11. 13. The zeolitic material of embodiment 12, obtainable or obtained by a process according to embodiment 11, the zeolitic material being Het2Het1MWW, preferably ZnTiMWW. 14. A zeolitic material of type MWW structure, 1 2 21 containing at least two heteroatoms Het and Het (Het Het MWW), having a Het2 content in the range of 1.0 to 2.0% by weight, calculated as Het2 elemental and based on the weight of Het2Het1MWW, and having a Het1 content in the range of 1.0 to 2.0% by weight, calculated as elemental Het1 and based on the weight of Het2Het1MWW. 15. The zeolitic material of Embodiment 14, wherein Het1 is Ti and Het2 is Zn. 16. The zeolitic material of any of embodiments 12 and 15, being contained in the form of a spray powder. 17. The zeolitic material of embodiment 16, wherein the spray powder particles have a Dv10 value of at least 2 micrometers, said spray powder comprising mesopores with an average pore diameter (4V/A) in the range from 2 to 50 nm as determined by Hg porosimetry according to DIN 66133, and comprising, based on the weight of the spray powder, at least 95% by weight of Het2Het1MWW. 18. Use of a zeolitic material according to any one of embodiments 12 and 17 as a catalytically active agent or a precursor thereof. 19. The use of embodiment 18, wherein the zeolitic material is Het2Het1MWW, preferably ZnTiMWW, as active catalytic agent, preferably for the preparation of propylene oxide from propene, preferably in acetonitrile as solvent and/or preferably using hydrogen peroxide as the oxidizing agent. 20. A process for the preparation of propylene oxide, preferably in acetonitrile as a solvent and/or preferably using hydrogen peroxide as an oxidizing agent, wherein a zeolitic material according to any one of embodiments 12 and 17, preferably ZnTiMWW, is employed as a catalytically active agent.
[000160] According to another aspect, the present invention is preferably characterized by the following embodiments and the combination of these embodiments, as indicated by their dependencies: I. A process for the preparation of a zeolitic material, comprising (i) providing a boron-containing zeolitic material (B-zeolite); (ii) decaying the B-zeolite with a liquid solvent system thus obtaining a decayed B-zeolite (zeolite); wherein the liquid solvent system is chosen from the group consisting of water, monohydric alcohols, polyhydric alcohols, and mixtures of two or more thereof, and wherein said liquid solvent system does not contain an organic or inorganic acid or a salt thereof, the acid being selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, and tartaric acid. II. The process of Embodiment I, wherein the boron-containing zeolitic material B-zeolite provided in (i) is either a boron-containing zeolitic material of the MWW type structure (B-MWW) or a boron-containing zeolitic material which is not a Boron-containing zeolitic material of the MWW type structure (B-MWW), preferably a boron-containing zeolitic material of the MWW type structure (B-MWW), BEA (B-BEA), MFI (B-MFI), ACS (B -CHA), MOR (B-MOR), MTW (B-MTW), RUB (B-RUB), LEV (B-LEV), FER (B-FER), HONEY (B-MEL), or RTH (B -RTH), more preferably of a structure of the MWW type (B-MWW), and wherein the debonded B-zeolite (zeolite) obtained in (ii) is either a debonded B-MWW (MWW) or a debonded B-zeolite ( zeolite) that is not MWW, preferably a B-MWW (MWW), B-BEA (BEA), B-IFM (MFI), B-CHA (CHA), B-MOR (MOR), B-MTW (MTW ), B-RUB (RUB), B-LEV (LEV), B-FER (FER), B-HONEY (HONEY), B-RTH (RHT) ground, preferably a B-MWW (MWW) ground. III. The process of Embodiment I or II, wherein in (i), the boron containing B-zeolite zeolitic material is provided by a process comprising (a) hydrothermal synthesis of B-zeolite from a synthesis mixture containing at least one silicon source, at least one boron source, and at least one model compound to obtain the B-zeolite in the mother liquor; (b) separate the B-zeolite from its mother liquor; (c) preferably drying the separated B-zeolite according to (b), preferably spray drying the separated B-zeolite according to (b); (d) optionally calcining the zeolite-B obtained from (b) or (c), preferably at a temperature in the range of 500 to 700°C. IV. The process of Embodiment III, wherein in (i), the boron-containing zeolitic material is B-MWW, provided by a process comprising (a) hydrothermal synthesis of a B-MWW precursor from a synthesis mixture of colloidal silica containing ammonia stabilized as at least one silicon source, boric acid as at least one boron source, and at least one model compound selected from the group consisting of piperidine, hexamethylene imine, and a mixture from them, to obtain the precursor of B-MWW in its mother liquor; (b) separate the precursor of B-MWW from its mother liquor; (c) preferably drying the separated B-MWW precursor according to (b), preferably spray drying the separated B-MWW according to (b); (d) calcining the B-MWW precursor obtained from (b) or (c), preferably at a temperature in the range of 500 to 700°C, obtaining the B-MWW. V. The process of any one of Embodiments I to IV, wherein B-O zeolite provided in (i) is an aluminum-free zeolitic material. SAW. The process of any one of embodiments I to V, wherein the B-zeolite provided in (i) has a B content in the range of 0.5 to 5.0% by weight, more preferably 0.75 to 4.0% by weight, more preferably 1.0 to 3.0% by weight, calculated as the element and based on the total weight of B-zeolite. VII. The process of any one of embodiments I to VI, wherein the B-zeolite provided in (i) is provided in the form of a powder spray or a granular spray. VIII. The process of any one of embodiments I to VII, wherein the liquid solvent system does not contain an organic or inorganic acid, or a salt thereof. IX. The process of any one of Embodiments I to VIII, wherein the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and mixtures of two or more thereof. X. The process of any one of Embodiments I to IX, wherein the liquid solvent system is water. XI. The process of any one of embodiments I to X, wherein the deboronation according to (ii) is carried out at a temperature in the range of 50 to 125 °C. XII. The process of any one of embodiments I to XI, wherein the deburring according to (ii) is carried out for a time in the range of 6 to 20 h. XIII. The process of any one of embodiments I to XII, wherein in deboronation according to (ii), the weight ratio of B-zeolite to liquid solvent system is in the range of 1:5 to 1:40 , preferably from 1:10 to 1:30, more preferably 1:10 to 1:20. XIV. The process of any one of embodiments I to XIII, wherein the deboronation according to (ii) is carried out in at least two separate steps, wherein between at least two treatment steps, the zeolite, preferably the MWW or the zeolite, which is not MWW, more preferably MWW, BEA, MFI, CHA, MOR, MTW, CHF, LEV, FER, MEL, or RTH, most preferably the MWW is dry, preferably at a temperature in the range from 100 to 150 °C. XV. The process of any one of Embodiments I to XIV, wherein the liquid solvent system is water and the deboration according to (ii) is carried out at a temperature in the range from 95 to 105°C, preferably from 95 to 100°C, for a time in the range of 8 to 15 hours, preferably 9 to 12 hours, wherein preferably the deboronation according to (ii) is carried out under reflux. XVI. The process of any one of Embodiments I to XV, wherein during deboronation according to (ii), the liquid solvent system is stirred. XVII. The process of any one of embodiments I to XVI, and wherein the zeolite obtained in (ii) has a B content of at most 0.2% by weight, more preferably at most 0.1% by weight weight, calculated as the element and based on the total weight of the zeolite.
[000161] XVIII. The process of any one of Embodiments I to XVII, further comprising (111) post-treatment of the zeolite, preferably MWW or zeolite other than MWW, preferably MWW, BEA, MFI, CHA, MOR , MTW, RUB, LEV, FER, MEL, or RTH, preferably the MWW, obtained from (ii) by a process comprising (iii.(1) separating the zeolite, preferably the MWW or the non-zeolite is MWW, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, or RTH, preferably MWW from the liquid solvent system; (iii.(2) preferably a drying the separated zeolite, preferably the separated MWW or the separated zeolite which is not MWW, more preferably the separated MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, HONEY, or RTH, most preferably the MWW separated, preferably by spray drying; (iii.(3) optionally calcining the zeolite, preferably MWW or zeolite other than MWW, preferably MWW, BEA, MFI, CHA, MOR, MTW, RUB , LEV, FER, HONEY, or RTH, preferably MWW, obtained from (iii.1) or (iii.2), preferably at temperatures in the range of 500 to 700°C. XIX. A zeolitic material obtainable or obtained by a process according to any of the embodiments I to XVIII. XX. A debonded zeolitic material (zeolite), preferably the zeolitic material of Embodiment XVI, containing at most 0.2% by weight, more preferably at most 0.1% by weight of boron, calculated as element and based on total weight of the zeolite. XXI. The zeolitic material of embodiment XIX or XX, that the zeolitic material is in the form of a powder spray or a granular spray. XXII. Use of a zeolitic material according to any one of embodiments XIX to XXI as a catalytically active agent, as a precursor for the preparation of a catalytically active agent, as a catalyst component, such as a support for a catalytically active agent or as a a component of a washable coating applied over a vehicle.
[000162] The present invention is illustrated by the following examples. Examples Example 1: Preparation of a crumbling MWW 1.1 Preparation of MWW containing boron
[000163] 470.4 kg of deionized water were provided in a container. Under agitation at 70 rpm (revolutions per minute), 162.5 kg of boric acid were suspended in the water. The suspension was stirred for another 3 h. Subsequently, 272.5 kg of piperidine were added, and the mixture was stirred for another hour. To the resulting solution, 392.0 kg of Ludox® AS-40 was added, and the resulting mixture was stirred at 70 rpm for one hour.
[000164] The obtained mixture was finally transferred to a crystallization vessel and heated to 170°C within 5 hours, under an autogenous pressure and under stirring (50 rpm). The temperature of 170°C was kept essentially constant for 120 hours; during these 120 h, the mixture was stirred at 50 rpm. Subsequently, the mixture was cooled to a temperature of 50 to 60°C over a period of 5 h. The aqueous suspension containing B-MWW had a pH of 11.3 as determined by measuring with a pH electrode.
[000165] From said suspension, the precursor of B-MWW was separated by filtration. The filter cake was then washed with deionized water until the wash water had a conductivity of less than 700 microSiemens/cm.
[000166] From the filter cake thus obtained, an aqueous suspension was prepared with a solids content of 15% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen drying gas temperature: - spray tower temperature (inside): 288 a 29°C - Temperature spray tower (outside): 157 to 167°C - Temperature filter (inside): 150 to 160°C - Temperature purifier (inside): 40 to 48°C - Temperature purifier (outside ): 34 to 36°C pressure difference filter: 0.83 to 1.03 kPa (8.3 to 10.3 mbar) nozzle: - nozzle of the top source component Gerig; size 0
[000167] The spray tower consisted of a vertically arranged cylinder, having a length of 2650 mm, a diameter of 1,200 mm, in which the cylinder was conically narrowed at the bottom. The length of the cone was 600 mm. At the cylinder head, the atomizing means (a two-component nozzle) were arranged. The spray dried material was separated from the drying gas in a filter downstream of the spray tower, and the drying gas was then passed through a scrubber. The suspension was passed through the interior opening of the nozzle, and the gas nozzle was passed through the ring-shaped slit surrounding the opening.
[000168] The spray dried material was then subjected to calcination at 650°C for 2 h. The calcined material had a boron (B) content of 1.9% by weight, a silicon (Si) content of 41% by weight, and a total organic carbon (TOC) content of 0.18% by weight. 1.2 Preparation of decayed MWW
[000169] a) Deburring
[000170] Based on the spray-dried material obtained according to Example 1.1 above, four batches of debonded MWW zeolite were prepared. In each of the first three batches, 35 kg of spray dried material obtained according to Example 1.1 and 525 kg of water were used. In the fourth batch, 32 kg of spray dried material obtained according to Example 1.1 and 480 kg of water were used. In total, 137 kg of spray dried material obtained according to Example 1.1 and 2025 kg of water were used.
[000171] For each batch, the respective amount of water was passed to a container equipped with a reflux condenser. Under stirring at 40 rpm, the given amount of spray dried material was suspended in water. Subsequently, the container was closed and the reflux condenser put into operation. Stir speed was increased to 70 rpm. Under stirring at 70 rpm, the contents of the vessel were heated to 100°C within 10 hours and held at this temperature for 10 h. Then, the contents of the container were cooled to a temperature below 50°C.
[000172] The resulting debonded zeolitic material of MWW-type structure was separated from the suspension by filtration under a nitrogen pressure of 250 kPa (2.5 bar) and washed four times with deionized water. After filtration, the filter cake was dried in a stream of nitrogen for 6 h.
[000173] The debonded zeolitic material obtained in four batches (625.1 kg of filter cake was dried with nitrogen in total) had a residual moisture content of 79%, as determined using an IR (infrared) scale at 160 °C.
[000174] b) Spray drying the dry filter cake with nitrogen
[000175] From the filter cake dried with nitrogen having a residual moisture content of 79% obtained according to section a) above, an aqueous suspension was prepared with deionized water, the suspension has a solids content of 15% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: Gas drying temperature: - Temperature spray tower (inside): 304°C - Temperature spray tower (outside) : 147 to 150°C - Temperature filter (inside): 133 to 141°C - Temperature purifier (inside): 106 to 114°C - Temperature purifier (outside): 13 to 20°C pressure difference filter : 0.13 to 0.23 kPa (1.3 to 2.3 mbar) nozzle: - Niro top supplier component nozzle, 4 mm diameter - nozzle gas capacity: 23 kg / h - nozzle gas pressure nozzle: 250 kPa (2.5 bar) operating mode: direct nitrogen Apparatus used: spray tower with one nozzle configuration: spray tower- filter purifier Gas flow: 550 kg/h filter material: Nomex® needle felt 10 m2 dosing via hose pump: VF 10 (supplier: Verder).
[000176] The spray tower consisted of a vertically arranged cylinder having a length of 2650 mm, a diameter of 1200 mm, which cylinder was conically tapered at the bottom. The length of the cone was 600 mm. At the cylinder head, the atomizing means (a two-component nozzle) were arranged.
[000177] The spray dried material was separated from the drying gas in a filter downstream of the spray tower, and the drying gas was then passed through a scrubber. The suspension was passed through the interior opening of the nozzle, and the gas from the nozzle was passed through the ring-shaped slit surrounding the opening.
[000178] The spray dried MWW material obtained had a B content of 0.08% by weight, an Si content of 42% by weight, and a TOC of 0.23% by weight. Example 2: Preparation of Het1MWW, with Het1 = Ti
[000179] Based on the decayed MWW material as obtained according to Example 1, a zeolitic material of the MWW type structure containing titanium (Ti) was prepared, referred to hereinafter as TiMWW. The synthesis was carried out in two experiments, described below as a) and b): a) First experiment Raw materials: deionized water: 244.00 kg piperidine: 118.00 kg tetrabutylorthotitanate: 10.90 kg deboronized zeolitic material: 54, 16 kg 54.16 kg of the decayed zeolitic material from the MWW-type structure were transferred to a first container A.
[000180] In a second container B, 200.00 kg of deionized water were transferred and stirred at 80 rpm. 118.00 kg of piperidine were added, with stirring, and during the addition, the temperature of the mixture was raised to about 15°C. Subsequently, 10.90 kg of tetrabutylorthotitanate and 20.00 kg of deionized water were added. Stirring was then continued for 60 min.
[000181] The mixture from vessel B was then transferred to vessel A, and stirring in vessel A was started (70 rpm). 24.00 kg of deionized water were introduced into container A and transferred to container B.
[000182] The mixture in vessel B was then stirred for 60 min at 70 rpm. At the start of stirring, the pH of the mixture in vessel B was 12.6, as determined with a pH electrode.
[000183] After said stirring at 70 rpm, the frequency was reduced to 50 rpm, and the mixture in container B was heated to a temperature of 170°C, within a period of 5 h. At a constant agitation rate of 50 rpm, the temperature of the mixture in vessel B was maintained at an essentially constant temperature of 170°C for 120 hours under autogenous pressure. During this crystallization of TiMWW, a pressure increase of up to 10.6 bar was observed. Subsequently, the obtained suspension containing TiMWW having a pH of 12.6 was cooled for 5 h.
[000184] The cooled suspension was subjected to filtration, and the separated mother liquor was transferred to the water discharge trash. The filter cake was washed four times with deionized water under a nitrogen pressure of 250 kPa (2.5 bar). After the last washing step, the filter cake was dried in a stream of nitrogen for 6 h.
[000185] From 246 kg of said filter cake, an aqueous suspension was prepared with deionized water, the suspension has a solids content of 15% by weight. This suspension was subjected to spray drying in a spray tower under the following spray drying conditions: drying gas, nozzle gas: technical nitrogen Apparatus used: spray tower with one nozzle configuration: spray tower - filter purifier flow gas: 550 kg/h filter material: Nomex ® needle felt 10 m2 dosing via hose pump: VF 10 (supplier: Verder).
[000186] The spray tower consisted of a vertically arranged cylinder, having a length of 2650 mm, a diameter of 1,200 mm, in which the cylinder was conically tapered at the bottom. The length of the cone was 600 mm. At the cylinder head, the atomizing means (a two-component nozzle) were arranged. The spray dried material was separated from the drying gas in a filter downstream of the spray tower, and the drying gas was then passed through a scrubber. The suspension was passed through the interior opening of the mouthpiece, and the gas from the mouthpiece was passed through the ring-shaped slit surrounding the opening.
[000187] The TiMWW spray dried material obtained from the first experiment had a Si content of 37% by weight, a Ti content of 2.4% by weight, and a TOC of 7.5% by weight. b) Second experiment
[000188] The second experiment was carried out in the same manner as the first experiment described in section a) above. The TiMWW spray dried material obtained from the second experiment had an Si content of 36% by weight, a Ti content of 2.4% by weight, a TOC of 8.0% by weight. TiMWW acid treatment
[000189] Each of the two spray dried TiMWW materials as obtained in the first and second experiment described in Example 2, sections a) and b) above, was subjected to acid treatment as described in the following sections a) and b). In section c) hereafter, it is described how a mixture of the materials obtained from a) and b) are spray dried. In section d) hereafter, the manner in which spray dried material is calcined is described. a) Acid treatment of spray dried material obtained according to Example 2, section a) Starting materials: deionized water: 690.0 kg nitric acid (53%): 900.0 kg spray dried Ti-MWW a ): 53.0 kg
[000190] 670.0 kg of deionized water were placed in a container. 900 kg of nitric acid was added, and 53.0 kg of the spray dried TiMWW was added under stirring at 50 rpm. The resulting mixture was stirred for a further 15 min. Subsequently, the agitation speed was increased to 70 rpm.
[000191] Within one hour, the mixture in the vessel was heated to 100°C and maintained at this temperature and under autogenous pressure for 20 hours under agitation. The mixture thus obtained was then cooled within 2 h to a temperature below 50°C.
[000192] The cooled mixture was subjected to filtration, and the filter cake was washed six times with deionized water under a nitrogen pressure of 250 kPa (2.5 bar). After the last washing step, the filter cake was dried in a stream of nitrogen for 10 h. The wash water after the sixth wash step had a pH of about 2.7. 225.8 kg of dry filter cake were obtained. b) Acid treatment of spray dried material obtained according to Example 2, section b) Starting materials: deionized water: 690.0 kg nitric acid (53%): 900.0 kg spray dried Ti-MWW b ): 55.0 kg
[000193] The acid treatment of the spray dried material obtained according to Example 2, section b) was carried out in the same manner as the acid treatment of the spray dried material obtained according to Example 2, section a), as described above. The wash water after the sixth wash step had a pH of about 2.7. 206.3 kg of dry filter cake were obtained. c) spray drying the mixture of acid-treated materials obtained from a) and b)
[000194] From 462.1 kg of the mixture of filter cakes obtained from a) and b), an aqueous suspension was prepared with deionized water, the suspension having a solids content of 15% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen gas drying temperature: - Spray tower temperature (inside): 304 to 305°C - Temperature spray tower (outside): 151°C - Temperature filter (inside): 141 to 143°C - Temperature purifier (inside): 109 to 118°C - Temperature purifier (outside): 14 to 15°C pressure difference filter: 0.17 to 0.38 kPa (1.7 to 3.8 mbar) nozzle: - top component nozzle: Niro supplier, 4 mm diameter - gas capacity nozzle pressure: 23 kg/h - nozzle gas pressure: 250 kPa (2.5 bar) operating mode: direct nitrogen device used: spray tower with one nozzle configuration: spray tower - filter - purifier 550 kg/h Nomex ® needle felt 10 m2 dosing via hose pump: VF 10 (supplier: Verder).
[000195] The spray tower consisted of a vertically arranged cylinder, having a length of 2650 mm, a diameter of 1200 mm, in which the cylinder was conically tapered at the bottom. The length of the cone was 600 mm. In the cylinder head, the atomizing means (a two-component nozzle) has been arranged. The spray dried material was separated from the drying gas in a filter downstream of the spray tower, and the drying gas was then passed through a scrubber. The suspension was passed through the interior opening of the nozzle, and the gas nozzle was passed through the ring-shaped slit surrounding the opening.
[000196] The spray-dried TiMWW acid-treated material had an Si content of 42% by weight, a Ti content of 1.6% by weight, and a TOC of 1.7% by weight. d) calcination of the spray dried material obtained according to c)
[000197] The spray dried material was then subjected to calcination at 650°C in a rotary kiln for 2 h. The calcined material had an Si content of 42.5% by weight, a Ti content of 1.6% by weight and a TOC content of 0.15% by weight. The Langmuir surface was determined by adsorption of nitrogen at 77 K according to DIN 66134, it was 612 m2/g, the specific surface area BET multipoint determined by adsorption of nitrogen at 77 K according to DIN 66131 standard, was 442 m2/g. The total intrusion volume as determined by Hg porosimetry according to DIN 66133 was 4.9 ml/g (milliliters/gram), the respective total pore area of 104.6 m2/g. The degree of crystallization determined by means of XRD was 80%, the average crystallite size 31 nm. The XRD of the material is shown in Figure 1. Example 3: Preparation of zeolitic materials from B-MWW
[000198] 3.1 22,050 kg of deionized water and 8,515 kg of piperidine were mixed in a stirred tank. 5.076 kg of boric acid was added under stirring, and stirring was continued for 30 min. Then 4900 kg of fumed silica (Aerosil® 200) was added, and stirring was continued for 2 h. The stirring speed was 150 rpm. Subsequently, the resulting suspension was heated within 2 h to a temperature of 170°C and held at this temperature for 120 hours. The pressure increase was 890 kPa (8.9 bar).
[000199] After synthesis, the suspension was subjected to filtration using a suction filter. The filter cake was washed with deionized water, and the pH of the filtrate was 8.5. The filter cake thus washed was dried at 100°C, subjecting it to nitrogen, which was applied at a rate of 6 m3/h for 24 h. Thereafter, the obtained filter cake was subjected to further drying for 2 hours and calcined at 600°C for 10 h.
[000200] The B-MWW obtained had a B content of 2.2% by weight, an Si content of 41% by weight, and a C content (TOC total organic carbon) of less than 0.2% in weight, in each case, calculated as an element and based on the total weight of B-MWW. The XRD of the B-MWW obtained is shown in Figure 2, an SEM (secondary electrons) image is shown in Figure 3.
[000201] 3.2 In a beaker, 203.1 g of boric acid was dissolved in 340.6 g of piperidine and 588.0 g of water. The mixture was stirred for 20 min. Then, under stirring, 490.0 g of ammonia-stabilized colloidal silica (Ludox® AS 40) were added. The resulting mixture was stirred for 1h. The liquid gel was then autoclaved. In the autoclave, the gel was heated to a temperature of 170°C within 1 hour and held at this temperature for 120 hours. A white suspension was obtained.
[000202] The suspension was subjected to filtration and washed with deionized water. The washed filter cake was dried at 100°C for 16 h. The temperature was then raised to 600°C with a temperature rate of 2°C/min, and calcination was carried out at this temperature of 600°C for 10 h in air.
[000203] The B-MWW obtained had a B content of 1.3% by weight, and an Si content of 42% by weight.
[000204] 3.3 In a beaker, 181.3.1 g of boric acid was dissolved in 304.1 g of piperidine and 525.0 g of water. The mixture was stirred for 20 min. Then, under stirring, 437.5 g of ammonia-stabilized colloidal silica (Ludox® AS 40) were added. The resulting mixture was stirred for 1 h. The liquid gel was then autoclaved. In the autoclave, the gel was heated to a temperature of 170°C within 1 hour and held at this temperature for 120 hours. A white suspension was obtained.
[000205] The suspension was subjected to filtration and washed with deionized water. The washed filter cake was dried at 100°C for 16 h. The temperature was then raised to 600°C with a temperature rate of 2°C/min, and calcination was carried out at this temperature of 600°C for 10 h in air.
[000206] The B-MWW obtained had a B content of 1.3% by weight, and an Si content of 42% by weight. The XRD of the B-MWW obtained is shown in Figure 4, an SEM (secondary electrons) photograph is shown in Figure 5. Example 4: Deboronation of B-MWW Zeolitic Materials
[000207] 4.1 A suspension of 100 g of the material obtained according to Example 3.1 in 1000 g of deionized water was heated to reflux for 2 hours under stirring. Thereafter, stirring was stopped, and the suspension subjected to filtration. From the solid obtained, a sample was taken and subjected to drying at 120°C. For the sample, the B content was determined. The remaining solid was suspended in 1000 g of deionized water and heated to 100°C for 1h. The process was repeated 4 times in total. The solid finally obtained was subjected to drying at 100°C for 24h. In the table below, the content of the samples and, finally, the solid obtained is shown:

[000208] 4.2 A suspension of 166 g of the B-MWW obtained from Example 3.2 in 4980.0 g of deionized water was heated to reflux at 100°C, under stirring at 160 rpm for 20 h. The white suspension was filtered and washed with deionized water. The solid obtained was subjected to drying at 100°C for 16 h. The B content of the obtained solid, calculated as element, was less than 0.05% by weight, the Si content, calculated as element, was 44% by weight.
[000209] 4.3 A suspension of 30.0 g of the B-MWW obtained from Example 3.2 in 900.0 g of methanol was refluxed at 64°C under stirring at 200 rpm for 20 h. The white suspension was filtered and washed with deionized water. The solid obtained was subjected to drying at 100°C for 16 h. The B content of the solid obtained, calculated as element, was 0.39% by weight, the Si content, calculated as element, was 42% by weight.
[000210] Compared to the water debonding according to 4.2, a higher B content of debored material B was obtained. However, it can be shown that a liquid solvent system consisting of a monohydric alcohol, i.e. methanol, can be used to considerably decrease the B content of a B-MWW zeolitic material, and thus to decay a B-MWW zeolitic material. Comparative Example
[000211] The zeolitic material B-MWW as obtained in Example 3.3 was subjected to deboration using the teachings of the prior art, that is, a liquid solvent system containing nitric acid was used as the deboration agent. This B-MWW zeolitic material is essentially identical to the B-MWW zeolitic material as obtained from Example 3.2; therefore, the results according to this comparative example can be easily compared with the results of the deboronation according to Example 4.2.
[000212] A suspension of 150 g of B-MWW obtained from Example 3.3 in 4500 ml of 6 moles/l of nitric acid (aqueous solution) was refluxed at 100°C under stirring at 200 rpm for 20 h. The white suspension was filtered and washed with deionized water. The solid obtained was subjected to drying at 100°C for 16 h. The B content of the obtained solid, calculated as element, was 0.09% by weight, the Si content, calculated as element, was 40% by weight.
[000213] Thus, under otherwise identical conditions (deboronation time: 20 h; deboron temperature: 100°C; deboron agitation speed: 200 rpm, drying time: 16 h, drying temperature: 100 °C ), it has been found that the debomination of the invention with water as a liquid solvent system leads to a decayed material having a lower B content (less than 0.05% by weight) than the decayed material according to the prior art ( 0.09% by weight). Example 5: Deboronation of B-MWW zeolitic materials 5.1 Preparation of a B-MWW material (MWW Structure Frame Zeolitic Material)
[000214] 480 kg of deionized water were supplied in a container. Under agitation at 70 rpm (revolutions per minute), 166 kg of boric acid were suspended in the water at room temperature. The suspension was stirred for a further 3 h at room temperature. Subsequently, 278 kg of piperidine were added, and the mixture was stirred for another hour. To the resulting solution, 400 kg of Ludox® AS-40 was added, and the resulting mixture was stirred at 70 rpm for an additional hour at room temperature. The mixture finally obtained was transferred to a crystallization vessel and heated to 170°C within 5 hours, under an autogenous pressure and under stirring (50 rpm). The temperature of 170°C was kept essentially constant for 120 hours. During these 120 h, the mixture was stirred at 50 rpm. Subsequently, the mixture was cooled to a temperature of 50 to 60°C. The aqueous suspension containing B-MWW precursor had a pH of 11.3 as determined by measurement with a pH sensitive electrode. From said suspension, the precursor of B-MWW was separated by filtration. The filter cake was then washed with deionized water at room temperature until the wash water had a conductivity of less than 700 microSiemens/cm.
[000215] The filter cake was then mixed with water to obtain a suspension with a solids content of 15% by weight. This suspension was subjected to spray drying from a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen gas drying temperature: - Spray tower temperature (inside): 235° C - Temperature spray tower (outside): 140°C nozzle: filter material: Nomex ® needle felt 10 m2 dosing via flexible tube pump: VF 10 (supplier: Verder).
[000216] The spray tower consisted of a vertically arranged cylinder having a length of 2650 mm, a diameter of 1200 mm, in which the conical cylinder narrowed at the bottom. The length of the cone was 600 mm. In the cylinder head, the atomizing means (a two-component nozzle) has been arranged. The spray dried material was separated from the drying gas in a filter downstream of the spray tower, and the drying gas was then passed through a scrubber. The suspension was passed through the opening inside the mouthpiece, and the gas from the mouthpiece was passed through the ring-shaped slit surrounding the opening.
The spray dried material was then subjected to calcination at 600°C for 10 h. The B-MWW obtained had a B content, calculated as element, of 1.9% by weight, and an Si content, calculated as element, of 41% by weight. 5.2 Deburring
[000218] 9 kg of deionized water and 600 g of the spray dried material obtained according to Example 5.1 were refluxed at 100°C under stirring at 250 rpm for 10 h. The resulting debonded zeolitic material was separated from the suspension by filtration and washed with 8 liters of deionized water at room temperature. After filtration, the filter cake was dried at a temperature of 120°C for 16 h. The B-MWW obtained had a B content, calculated as element, of 0.07% by weight, and an Si content, calculated as element, of 42% by weight. Example 6: Deboronation of B-BEA zeolitic materials 6.1 Preparation of a B-BEA material (BEA structure frame zeolitic material)
[000219] 209 kg of deionized water were provided in a container. Under stirring at 120 rpm (revolutions per minute), 355 kg of tetraethylammonium hydroxide was added and the suspension was stirred for 10 minutes at room temperature. Subsequently, 61 kg of boric acid were suspended in water and the suspension was stirred for another 30 minutes at room temperature. Subsequently, 555 kg of Ludox® AS-40 was added, and the resulting mixture was stirred at 70 rpm for one hour at room temperature. The liquid gel had a pH of 11.8, as determined by measuring with a pH electrode. The mixture finally obtained was transferred to a crystallization vessel and heated to 160°C within 6 hours under a pressure of 720 kPa (7.2 bar) and under stirring (140 rpm). Subsequently, the mixture was cooled to room temperature. The mixture was again heated to 160°C over a period of 6 h and stirred at 140 rpm for an additional 55 h. The mixture was cooled to room temperature and subsequently the mixture was heated for a further 45 h at a temperature of 160°C under stirring at 140 rpm. 7,800 kg of ionized water were added to 380 kg of this suspension. The suspension was stirred at 70 rpm and 100 kg of a 10% by weight aqueous solution of HNO3 was added. From this suspension the boron-containing zeolitic material having a BEA frame structure was separated by filtration. The filter cake was then washed with deionized water at room temperature until the wash water had a conductivity of less than 150 microSiemens/cm.
[000220] 640 kg of the filter cake thus obtained was suspended in water to obtain a suspension having a solids content of 35% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen gas drying temperature: - Spray tower temperature (inside): 235° C - Temperature spray tower (outside): 140°C Nozzle: - top component nozzle: - nozzle gas temperature: - nozzle gas pressure: operating mode: apparatus used: configuration: gas flow: 1500 kg/h filter material: dosing via flexible tube pump:
[000221] A vertically arranged spray tower, having a length of 2650 mm, a diameter of 1200 mm, in which the cylinder conically narrowed at the bottom. The length of the cone was 600 mm. At the cylinder head, the atomizing means (a two-component nozzle) were arranged. The spray dried material was separated from the drying gas in a filter downstream of the spray tower, and the drying gas was then passed through a scrubber. The suspension was passed through the interior opening of the mouthpiece, and the gas from the mouthpiece was passed through the ring-shaped slit surrounding the opening.
[000222] The spray dried material was then subjected to calcination at 500°C for 5 h. The B content of the solid obtained, calculated as element, was 1.5% by weight, the Si content, calculated as element, was 43% by weight. 6.2 Disbursement
[000223] 840 kg of deionized water were supplied in a vessel equipped with a reflux condenser. Under agitation at 40 rpm, 28 kg of spray dried material obtained according to 6.1 were employed. Subsequently, the container was closed and the reflux condenser put into operation. Stir speed was increased to 70 rpm. Under stirring at 70 rpm, the contents of the vessel were heated to 100°C within 1 hour and held at this temperature for 20 h. Then, the contents of the container were cooled to a temperature below 50°C.
[000224] The debonded zeolitic material resulting from a BEA frame structure was separated from the suspension by filtration under a nitrogen pressure of 250 kPa (2.5 bar) and washed four times with deionized water at room temperature. After filtration, the filter cake was dried in a stream of nitrogen for 6 h. Then, the filter cake was mixed with water to obtain a suspension having a solids content of 40% by weight. Thus, the suspension was subjected to spray drying under the conditions as described in 6.1.
[000225] The spray dried material was then subjected to calcination at 550°C for 5 h (2K/min heating ramp). The B content of the solid obtained, calculated as element, was less than 0.03% by weight, the Si content, calculated as element, was 45% by weight. Example 7: Deboronation of B-CHA zeolitic materials 7.1 Preparation of a B-CHA material (CHA structure frame zeolitic material)
[000226] Based on a synthesis mixture of 1414 g of deionized water, 203.8 g of an aqueous solution of 25% by weight of tetramethylammonium hydroxide, 765.7 g of an aqueous solution of 13. 26% by weight of trimethyl-1-adamantylammonium hydroxide, 31.0 g of boric acid, 999.6 g of Ludox® AS40, and 20 g of seed material, a B-SM zeolite was synthesized under hydrothermal conditions at a temperature of 160°C for 72 h under stirring at 200 rpm. In the autoclave used, the pressure was 500 kPa (5 bar). At the end of the synthesis process, the pH of the synthesis mixture was 11.8.
[000227] 3340 g of the suspension obtained from the crystallization were subjected to filtration and washed with deionized water until the conductivity of the wash water was less than 50 microSiemens/cm. 853 g of the wet filter cake was dried for 5 h at 120°C. The B content of the solid obtained, calculated as element, was 1.1% by weight, the Si content, calculated as element, was 42% by weight. 7.2 Deburring
[000228] 750 g of deionized water were supplied in a vessel equipped with a reflux condenser. Under agitation at 40 rpm, 50 kg of dry material obtained according to 7.1 were used. Subsequently, the container was closed and the reflux condenser put into operation. Under agitation, the contents of the vessel were heated to 100°C within 1 hour and held at this temperature for 10h. Then, the contents of the container were cooled to a temperature below 50°C.
[000229] The decayed zeolitic material resulting from the CHA-type frame structure was separated from the suspension by filtration and washed with deionized water until the wash water had a conductivity of less than 10 microSiemens/cm. After filtration, the filter cake was dried at 120°C overnight. The B content of the obtained solid, calculated as element, was 0.09% by weight, the Si content, calculated as element, was 44% by weight.
[000230] The XRD pattern of the calcined sample (calcining of dry material at 600°C under air) is shown in figure 6. Brief description of the figures
[000231] Figure 1 shows the X-ray diffraction pattern (copper K alpha radiation) of the acid-treated, spray-dried and calcined TiMWW material obtained according to Example 2. On the x-axis, the grade (2 values) theta) are displayed, on the y-axis, the intensity ((Count) Linear).
[000232] Figure 2 shows the X-ray diffraction pattern (copper K alpha radiation) of the zeolitic material B-MWW obtained according to Example 3.1. On the x-axis, the values of degree (2 theta) are shown, on the y-axis, the intensity ((Count) Linear).
[000233] Figure 3 shows an SEM (Scanning Electron Microscopy) image (secondary electron (SE) image at 5 kV (kilovolts)) of a representative sample of the zeolitic material B-MWW obtained according to Example 3.1. The scale is indicated in the lower right corner by the rule which has a length of 2 micrometers.
[000234] Figure 4 shows the X-ray diffraction pattern (copper K alpha radiation) of the zeolitic material B-MWW obtained according to Example 3.3. On the x-axis, the values of degree (2 theta) are shown, on the y-axis, the intensity ((Count) Linear).
[000235] Figure 5 shows an SEM (Scanning Electron Microscopy) image (secondary electron (SE) image at 5 kV (kilovolts)) of a representative sample of the B-MWW zeolite material obtained according to Example 3.3. The scale is indicated in the lower right corner by the rule which has a length of 2 micrometers.
[000236] Figure 6 shows the X-ray diffraction pattern (copper K alpha radiation) of the zeolitic material B-CHA obtained according to Example 7.2. On the x-axis, the values of degree (2 theta) are shown, on the y-axis, the intensity ((Count) Linear). Prior art cited - EP 1 485 321 A1 - . P. Wu et al, Studies in Surface Science and Catalysis, vol. 154 (2004), p. 2581-2588 - WO 02/057181 A2 - EP 1 490 300 A1 - P. Wu et al., Chemical Communications (2002), pp 1026-1027 - L. Liu et al., Microporous and Mesoporous Materials vol. 94 (2006) pp. 304-312. - EP 1 324 948 A1 - US 4,954,325 - M.E. Leonowicz, J.A. Lawton, S.L. Lawton, M.K. Rubin, Science, vol. 264 (1994) p. 1910 - S.L. Lawton et al., Micropor. Mesopor. Mater., Vol. 23 (1998) p. 109. - P. Wu et al., Hydrothermal Synthesis of a Novel Titanosilicate with MWW Topology, Chemistry Letters (2000), p. 774-775 - WO 02/28774 A2

权利要求:
Claims (11)
[0001]
1. Process for the preparation of a zeolitic material, characterized in that it comprises (i) providing a zeolitic material containing boron (B-zeolite); (ii) decaying the B-zeolite with a liquid solvent system at a temperature in the range of 95 to 100°C, thus obtaining a decayed B-zeolite (zeolite); wherein the B-zeolite provided in (i) is a boron-containing zeolitic material of structure type MWW (B-MWW)), and wherein the liquid solvent system is water, and wherein said liquid solvent system is free of an organic or inorganic acid or a salt thereof, wherein the deboronation according to (ii) is carried out for a time in the range of 6 to 20 h.
[0002]
2. Process according to claim 1, characterized in that, in (i), the B-zeolite is B-MWW, provided by a process comprising (a) hydrothermal synthesis of B-zeolite from a synthesis mixture containing at least one silicon source, at least one boron source and at least one model compound, to obtain the B-zeolite in its mother liquor; (b) separate the B-zeolite from its mother liquor; (c) preferably drying the B-zeolite separated according to (b), more preferably spraying the B-zeolite separated according to (b); (d) optionally calcining the B-zeolite obtained in (b) or (c), preferably at a temperature in the range of 500 to 700°C.
[0003]
3. Process according to claim 2, characterized in that, in (i), the B-zeolite is B-MWW, provided by a process comprising (a) hydrothermal synthesis of a precursor of B-MWW to from a synthesis mixture containing colloidal silica stabilized with ammonia as at least one silicon source, boric acid as at least one boron source and at least one model compound selected from the group consisting of piperidine, hexamethylene imine and a mixture from them, to obtain the precursor of B-MWW in its mother liquor; (b) separate the B-MWW from its mother liquor; (c) preferably drying the separated B-MWW precursor according to (b), more preferably spraying the separated B-MWW according to (b); (d) calcination of the B-MWW precursor obtained in (b) or (c), preferably at a temperature in the range of 500 to 700°C, obtaining the B-MWW.
[0004]
4. Process according to any one of claims 1 to 3, characterized in that the B-zeolite provided in (i) is an aluminum-free zeolitic material.
[0005]
5. Process according to any one of claims 1 to 4, characterized in that the B-zeolite provided in (i) has a B content in the range of 0.5 to 5.0% by weight, calculated as element and based on the total weight of the B-zeolite.
[0006]
6. Process according to any one of claims 1 to 5, characterized in that the B-zeolite provided in (i) is provided in the form of a powdered powder or a powdered granules.
[0007]
7. Process according to any one of claims 1 to 6, characterized in that the deburring according to (ii) is carried out for a time in the range from 7 to 17 h.
[0008]
8. Process according to any one of claims 1 to 7, characterized in that in the deboronation according to (ii), the weight ratio of B-zeolite in relation to the liquid solvent system is in the range of 1: 5 to 1:40.
[0009]
9. Process according to any one of claims 1 to 8, characterized in that during the deboronation according to (ii), the liquid solvent system is agitated.
[0010]
10. Process according to any one of claims 1 to 9, characterized in that the liquid solvent system is water and the deboronation according to (ii) is carried out for a time in the range of 8 to 15 hours, in that the deboronation according to (ii) is carried out under reflux.
[0011]
11. Process according to any one of claims 1 to 10, characterized in that it further comprises (111) post-treatment of the zeolite obtained in (ii) by a process comprising (iii.(1) separating the zeolite from the liquid solvent system; (iii.(2) preferably drying the separated zeolite, preferably by spray drying; and (iii.(3) optionally calcining the zeolite obtained in (iii.1) or (iii.2), preferably at temperatures in the range of 500 to 700°C.

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

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-29| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-04-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP12154169|2012-02-07|

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EP12154169.2|2012-02-07|

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EP12189035|2012-10-18|

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EP12189035.4|2012-10-18|

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PCT/EP2013/052224|WO2013117537A1|2012-02-07|2013-02-05|Process for the preparation of a zeolitic material|

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