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WO2015001095A1 - Procédé de préparation de couches de zéolithe soutenues sans matrice organique - Google Patents

Procédé de préparation de couches de zéolithe soutenues sans matrice organique Download PDF

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Publication number
WO2015001095A1
WO2015001095A1 PCT/EP2014/064351 EP2014064351W WO2015001095A1 WO 2015001095 A1 WO2015001095 A1 WO 2015001095A1 EP 2014064351 W EP2014064351 W EP 2014064351W WO 2015001095 A1 WO2015001095 A1 WO 2015001095A1
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Prior art keywords
support
seed crystals
template
organo
zeolite
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English (en)
Inventor
Stephanie REUSS
Wilhelm Schwieger
Marion SCHÜLEIN
Benjamin REIF
Sulaiman BASAHEL
Abdulrahman AL-YOUBI
Shaeel AL-THABAITI
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Friedrich Alexander Universitaet Erlangen Nuernberg
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Friedrich Alexander Universitaet Erlangen Nuernberg
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Definitions

  • Zeolites or zeolite-like materials (“zeo-types” [R.M. Barrer; Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic Press Inc, 1978]) are the workhorses in today's chemical industry and in many other applications, for instance as phosphate substitutes in detergents [C. Gloxhuber, M. Potokar, W. Pittermann; S. Wall at, F. Bartnik; H. Reuter; S. Braig, Zeolite A. A phosphate substitute for detergents: toxicological investigation, Food and Chemical Toxicology, 21 (1983), 209-220]. They are used as catalysts, adsorbents and ion exchangers [S.
  • Structures on which zeolites are deposited in the form of thin layers are advantageous because transport influences can be optimized, or minimized. This leads to shortened and streamlined transport paths both for educts and for the products compared to a solid bed filling of spherical particles. At the same time, pressure loss and heat transfer in a reactor can be optimized. Before this background, the efforts to deposit zeolites or zeolite-like materials in the form of layers on support materials are understandable.
  • zeolites are mostly produced in the form of fine-particle powders.
  • the synthesis usually takes place under hydrothermal conditions at temperatures of 40 °C to
  • a so-called template typically an organic compound, is often required as a structure-directing agent (also referred to as organic structure directing agent, OSDA).
  • OSDA organic structure directing agent
  • the template remains in the structure and has to be removed before the zeolites can be used. The removal is generally effected by thermal treatment at elevated temperatures of 300 °C to 800 °C under an oxidizing and/or reducing atmosphere. During this treatment, the template is evaporated or decomposed so that it, or its fragments, respectively, can leave the pore system of the zeolite. Thus, the pore system is prepared for a desired application.
  • the thermal treatment causes stress on the zeolite crystal itself, or on the layer consisting of zeolites. Moreover, different thermal properties of the support and the zeolitic material can give rise to thermal stresses.
  • seed crystals are prepared with the help of organic template according to a common, known synthesis. After calcination, they serve as seed crystals for the synthesis of the zeolite BEA without adding further organic template molecules at this point. This synthesis is carried out at a temperature of 140 °C for 17 to 19 hours under hydrothermal conditions. Further research teams also refer to the above-mentioned research and, by means of different synthesis conditions, alter for example the Si/Al ratio.
  • BEA-zeolites richer in aluminum, with a Si/Al ratio of 3.9 or lower have been prepared [G. Majano et al.; Chemistry of Materials, 21 (2009) 4184-4191 ; Y. Kamimura et al.; The Journal of Physical Chemistry C, 115 (2011) 744-750].
  • Said BEA-zeolite prepared by seed induction is processed by the team around Li, Hong-xin et al. 2011, [WO 201 1/146615] by means of ion exchange (e.g. with iron ions) and used for catalytic purposes.
  • Template-free MFI zeolite membranes have been produced via a process wherein, in a first step, seeds are deposited on a support and are induced to grow in subsequent steps in order to generate a continuous layer [G. Li et al.; Journal of Membrane Science, 218 (2003) 185-194].
  • MFI-zeolites can be prepared without the use of organic templates the problem of removing a template does not arise.
  • BEA-type zeolite membranes The prior art for the production of BEA-type zeolite membranes is represented by publications by Shao [Shao, G., Materials Letters, 61 (2007) 1443-1445] and Avhale [A. Avhale, Development of Stainless-Steel Supported MFI and BEA-Type Zeolite Membrane, thesis, University of Er Weg-Nuremberg, 2010]. Both describe the synthesis of BEA zeolite membranes relying on a two step procedure involving the use of organic templates in both preparation steps. First, seed crystals are deposited and then the seed crystals are induced to grow (secondary growth) in the presence of at least one organic template in accordance with these two publications. For the membranes resulting from these processes, the problems described above arising from the need to remove the organic template remain.
  • the problem underlying the present invention was the development of a process for the preparation of an organo-template free, supported zeolite layer, preferably a BEA-type zeolite layer, which does not require a removal of an organo-template from the zeolite after the formation of the layer, and thus avoids the negative effects of this removal on the structural integrity of the zeolite layer.
  • the process for the preparation of organo-template free, supported zeolite layers, preferably BEA-type zeolite layers, in accordance with the present invention is characterized that in an at least two-step process, seed crystals, preferably BEA-type zeolite seed crystals, are coated onto a support in the first process step. In a second process step, crystal growth of the desired phase on the support is achieved, either by hydrothermal crystallization or by a steam-assisted conversion (SAC) process. Thus, a uniform zeolite layer which is as continuous as possible is formed.
  • SAC steam-assisted conversion
  • the present invention provides a process for the preparation of an organo- template-free supported zeolite layer, preferably a BEA-type zeolite layer, said process comprising at least two steps, with a first step (i) wherein zeolite seed crystals, preferably BEA-type zeolite seed crystals, are coated onto a support, and a second step (ii) wherein the zeolite layer is prepared on the support in the absence of an organo-template via (iia) a hydrothermal treatment of the support having seed crystals coated thereon, or via (iib) a steam assisted conversion process on the support having seed crystals coated thereon.
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • supported zeolite crystals preferably of the BEA-type, are suitable as a seed material for a continuation of the crystallization process, although their surface is not entirely available for the crystallization and although no structure-directing substances (organo-templates) are present in the reaction system during the second process step.
  • zeolites including BEA-type zeolites have a framework structure formed by tetrahedra which share their corners, and thus can be referred to as T0 2 , or TO4/2.
  • T are atoms which may exist in a tetrahedral coordination, such as Si, Al, P, B, Be, Ti, or Ga. If trivalent atoms are present in the form of tetrahedral, such as Al or B, the tetrahedra, and thus also the overall framework, will carry a negative charge. This charge is balanced by the presence of cations, which are typically present in the pore system formed by the tetrahedral, and are mobile therein.
  • the zeolites of the supported zeolite layers produced in accordance with the invention are preferably BEA-type zeolites, also referred to as BEA-zeolites, zeolites of the BEA-type or zeolites having a BEA framework structure in the art.
  • the zeolite framework of the zeolite layers preferably BEA-type zeolite layers, provided by the process in accordance with the invention is formed by silica and alumina, i.e. by the terahedra Si0 2 and A10 2 . While a certain amount of the Si atoms may be replaced by other four-valent atoms, and/or a certain amount of Al atoms may be replaced by other trivalent atoms, it is more preferred that the framework consists of the terahedra Si0 2 and A10 2 .
  • the structure of a zeolite having such a framework may be represented by the formula M x /n[(A10 2 ) x (Si0 2 )y] ⁇ z H 2 0.
  • M represent one type or different types of cations with the valency (or charge) n, e.g. Na ⁇ or K + , z 3 ⁇ 40 represent the amount of water that may be adsorbed into the pores of the zeolite framework
  • x and y represent the amount of the negatively charged A10 2 tetrahedra and the neutral Si0 2 tetrahedra, respectively.
  • Zeolites can be classified into high silica zeolites and alumina-rich zeolites.
  • the process in accordance with the invention is particularly advantageous and preferably used for the preparation of a supported layer of a high silica zeolite, particularly a high silica zeolite with a zeolite framework that is not formed in the absence of a template, such as an organo-template.
  • the molar ratio of Si/Al (and in particular their ratio y/x in the above formula) in the high silica zeolites is typically not lower than 3.5, more preferably not lower than 10, and even more preferably not lower than 15.
  • the upper limit of the molar ratio of Si/Al (and in particular their ratio y/x in the above formula) is not particularly restricted, but is preferably not higher than 800.
  • the process in accordance with the invention is used for the preparation of a supported BEA-type zeolite layer.
  • their molar ratio of Si/Al (and in particular their ratio y/x in the above formula) is preferably not lower than 3.5, more preferably not lower than 10, and even more preferably not lower than 15.
  • the upper limit of the molar ratio of Si/Al (and in particular their ratio y/x in the above formula) is not particularly restricted, but is preferably not higher than 800.
  • zeolite framework preferably a BEA-type zeolite framework
  • the zeolite seed crystals and the supported zeolite layer referred to herein e.g. as indicated as M in the above structure
  • various types of cations can be used.
  • alkali cations such as Na " or K +
  • the zeolite layer can be subjected to an ion exchange after its formation, if desired, e.g. in order to introduce catalytically-active centers into the layer.
  • the seed crystals coated onto the support in step (i) of the process in accordance with the invention should also be BEA-type zeolite seed crystals.
  • the composition of the seed crystals e.g. in terms of the molar ratio of Si/Al
  • the composition of the seed crystals does not need to be identical to the composition of the final zeolite layer.
  • the support carrying the zeolite layer may consist of porous or dense materials. It may be formed from a single material, or of mixtures (e.g. alloys) or composites of different materials. Examples of suitable materials are metals, such as stainless steel, ceramics (such as alumina) or porous glass. Thus, the support may e.g. consist of stainless steel, ceramics or porous glass.
  • the support may exhibit various geometries, including a plate, a tube, or a foam structure.
  • the supported zeolite layer preferably a BEA-type zeolite layer, may be formed on the total surface of the support, or on a part of the surface of the support.
  • various approaches may be applied to limit the surface area on the support to be coated by the supported zeolite layer. For example, parts of the surface area of the support may be masked, e.g. using PTFE tape, in step (i) and/or (ii).
  • Another suitable approach is the deposition of seed crystals in step (i) using a vapour phase transport or a steam-assisted conversion process, or the continuation of the crystallization in step (ii) using a steam-assisted conversion process, wherein a gel containing the reactants forming the zeolite can be locally applied to the desired surface area.
  • the thickness of the supported zeolite layer preferably a BEA-type zeolite layer, prepared in accordance with the invention, as determined e.g. via SEM microscopy of a cross-section of the support carrying the zeolite layer is not particularly limited. Typically it ranges e.g. from 0.1 to 100 ⁇ , preferably from 0.2 ⁇ - 40 ⁇ . As will be understood by the skilled reader, the procedure of step (ii) can be repeated multiple times, if desired. Thus, thick layers can be conveniently produced.
  • step (i) of the process in accordance with the invention Various methods are available to coat the seed crystals, preferably a BEA-type zeolite seed crystals, onto the support in step (i) of the process in accordance with the invention.
  • the seed crystals In order to arrive at an organo-template free supported zeolite layer without the need to remove an organic template from the layer, the seed crystals should not contain an organo-template when the supported zeolite layer is prepared on the basis of the seed crystals in step (ii) of the process.
  • step (i) may involve the removal of an organo- template from the seed crystals prior to step (ii), in particular if the seed crystals are formed in-situ via reaction on the support.
  • step (i) The deposition of seed crystals, preferably BEA-type zeolite seed crystals, in step (i) can take place both via reaction - in-situ - and by coating of seeds which are prepared ex-situ onto the support.
  • seed crystals preferably BEA-type zeolite seed crystals
  • a first approach for the in-situ formation of a coating of seed crystals, preferably BEA-type zeolite seed crystals, on the support is the crystallization of zeolite seed crystals under hydrothermal conditions (also referred to as hydrothermal crystallization) in the presence of an organo-template.
  • hydrothermal crystallization also referred to as hydrothermal crystallization
  • the hydrothermal crystallization for the preparation of seed crystals is carried out by immersing the support in a suspension or solution containing at least one source of Si0 2 , at least one source of ⁇ 1 2 0 3; water as a solvent, and the organic template.
  • a tetraalkylammonium salt preferably tetraalkylammonium hydroxide is generally used.
  • tetraethylammonium salts in particular tetraethylammonium hydroxide (TEA-OH) are typically used.
  • zeolite seed crystals can be prepared and coated onto the support in-situ according to known processes with organic templates.
  • the hydrothermal crystallization can be carried out e.g. at 90 °C to 250 °C, preferably in the range of 130 °C to 185 °C.
  • a calcination of the composite consisting of at least one zeolite and a support is carried out in order to remove the organic template at a temperature e.g. between 300 °C and 600 °C, preferably between 350 °C and 550 °C and more preferably of 400 °C to 500 °C.
  • a further approach for the in-situ formation of a coating of seed crystals, preferably BEA-type zeolite seed crystals, on the support is the crystallization of the seed crystals under hydrothermal conditions in the presence of ex-situ prepared organo-template free zeolite seed crystals, preferably BEA-type zeolite seed crystals, in the hydrothermal reaction system.
  • no organo-template is needed during the crystallization of zeolite seed crystals under hydrothermal conditions in the presence of ex-situ prepared organo-template free zeolite seed crystals.
  • the hydrothermal crystallization is carried out by immersing the support in a suspension or solution containing at least one source of Si0 2 , at least one source of ⁇ 1 2 0 3> a cation, water as a solvent, and the organo-template free zeolite seed crystals.
  • Organo-template free zeolite seed crystals are commercially available, or can be prepared ex-situ by known methods which may involve the removal of an organo-template.
  • the hydrothermal crystallization can be carried out e.g. at 90 °C to 250 °C, preferably in the range of 130 °C to 1 85 °C,
  • Still a further approach for the in-situ formation of a coating of seed crystals, preferably BEA- type zeolite seed crystals, on the support is the crystallization of zeolite seed crystals using a vapour phase transport or a steam-assisted conversion process in the presence of an organo- template.
  • vapour phase transport or a steam-assisted conversion which may also be generically referred to as dry gel conversion, for the formation of zeolites are known in the art and described, e.g. by Dong et al., J. Chem. Soc, Chem. Comm. (1992), 1056-1058, or Weitkamp et al., Studies in Surface Science and Catalysis, 155, 2005.
  • the vapour- phase transport process or the steam-assisted conversion process is carried out by applying a gel containing at least one source of Si0 2 , and at least one source of ⁇ 1 2 (3 ⁇ 4 onto the support.
  • the gel may be dry or may contain a liquid, provided that the gel is sufficiently viscous to remain on the support as applied during the process.
  • the liquid can be a single solvent, or a mixture of solvents. If a liquid is contained, preferably water, or a mixture of water with an organic solvent is used.
  • the support with the gel applied thereon is placed into an autoclave containing water, without direct contact between the applied gel and the water.
  • the autoclave contains a PTFE lining.
  • the organo-template can be contained in the gel (in which case the process is carried out as "steam assisted conversion” process, SAC), or in the water (in which case the process is carried out as "vapour phase transport", VPT, process including the transport of the organo-template via the vapour phase to the support).
  • a tetraalkylammonium salt preferably tetraalkylammonium hydroxide is generally used.
  • tetraethylammonium salts in particular tetraethyl ammonium hydroxide (TEA-OH) are typically used.
  • the vapour phase transport or steam assisted conversion can be carried out e.g. at 90 °C to 250 °C, preferably in the range of 130 °C to 185 °C.
  • a calcination of the composite consisting of at least one zeolite and a support is carried out in order to remove the organic template at a temperature e.g. between 300 °C and 600 °C, preferably between 350 °C and 550 °C and more preferably of 400 °C to 500 °C.
  • Still a further related approach for the in-situ formation of a coating of seed crystals, preferably BEA-type zeolite seed crystals, on the support is the crystallization of zeolite seed crystals using a steam-assisted conversion process in the presence of ex-situ prepared organo- template free zeolite seed crystals, preferably BEA-type zeolite seed crystals.
  • the steam-assisted conversion process is typically carried out by applying a gel containing at least one source of Si0 2 , and at least one source of AI2O3, a cation (e.g.
  • the gel may be dry or may contain a liquid, provided that the gel is sufficiently viscous to remain on the support as applied during the process.
  • the liquid can be a single solvent, or a mixture of solvents. If a liquid is contained, preferably water, or a mixture of water with an organic solvent is used.
  • the support with the gel applied thereon is placed into an autoclave containing water, without direct contact between the applied gel and the water.
  • the autoclave contains a PTFE lining.
  • the steam-assisted conversion process can be carried out e.g. at 90 °C to 250 C C, preferably in the range of 130 °C to 185 °C.
  • step (i) zeolite seed crystals, preferably BEA-type zeolite seed crystals, produced separately -ex-situ- can also be coated on the support.
  • the process of the present invention also encompasses the variant that the seed crystals are deposited in step (i) via coating the support with ex-situ prepared organo-template free zeolite seed crystals, preferably BEA-type zeolite seed crystals.
  • Such crystals are commercially available or may be prepared according to methods known in the art.
  • such zeolite seed crystals are calcined during their preparation in order to remove the organic template.
  • ex-situ prepared organo-template free zeolite seed crystals preferably BEA-type zeolite seed crystals
  • common methods such as spin-coating, dipping as well as spraying processes can be used.
  • the calcinations, if still necessary, can be carried out either before or after the support is coated.
  • the seed crystals preferably BEA-type zeolite seed crystals, used in the process if the invention can still contain a residue of carbon-containing material, e.g. up to about 4 wt% (Figure 3), which can be decomposition products of the organic template.
  • a residue of carbon-containing material e.g. up to about 4 wt% ( Figure 3)
  • Figure 3 can be decomposition products of the organic template.
  • Such a residue does not have an impact on further synthesis steps of the supported zeolite layer. This can be a relevant factor for systems where e.g. a support is used which has a limited temperature resistance.
  • the crystallization process is continued on the support provided in the absence of an organo-template to form the supported zeolite layer, preferably a supported BEA-type zeolite layer.
  • this may be accomplished via (iia) a hydrothemial treatment of the support having seed crystals, preferably BEA-type zeolite seed crystals, deposited thereon, or via (iib) a steam-assisted conversion process on the support having the seed crystals, preferably BEA-type zeolite seed crystals, coated thereon.
  • the support carrying the seed crystals is subjected in step (ii) to a hydrothermal treatment.
  • the seed crystals present on the support can grow to yield a layer which is homogenous and as continuous as possible.
  • an aqueous reaction mixture which contains a source of Si0 2 , A1 2 0 3 and a cation (e.g. Na + or K + ) can be employed.
  • the reaction mixture is free from an organic template.
  • the reaction mixture may be stirred, typically prior to the hydrothermal treatment.
  • the stirring time of the reaction mixture can be between 15 min and 5 h, preferably it is between 2 h and 3 h.
  • the reaction mixture may be allowed to age, typically prior to the hydrothermal treatment.
  • the subsequent ageing time (in the presence of the seed crystals or without them) can be between 2 h and 10 d, preferably, however, between 3 d and 4 d.
  • the support is immersed in the reaction mixture in an autoclave, preferably an autoclave having a PTFE lining.
  • the position of the support in the autoclave can be varied. If only one side of the support is to be coated, the back side can optionally be covered and the side to be coated can be directed to the top or to the bottom, preferably, however, to the top of the autoclave.
  • the temperature for the hydrothermal treatment can be e.g.
  • the time for synthesis can be between 12 h and 10 d, preferably, however, between 1 d and 5 d and more preferably between 2 d and 3 d.
  • the support carrying the seed crystals is subjected in step (ii) to a steam-assisted conversion process .
  • the seed crystals present on the support can grow to yield a layer which is homogenous and as continuous as possible.
  • the steam-assisted conversion is typically carried out by applying a gel containing at least one source of Si0 2 , at least one source of AI2O3, and a cation (e.g. Na ⁇ or + ) on the support.
  • the gel may be dry or may contain a liquid, provided that the gel is sufficiently viscous to remain on the support as applied during the process.
  • the liquid can be a single solvent, or a mixture of solvents. If a liquid is contained, preferably water, or a mixture of water with an organic solvent is used. As noted above, the gel is free from an organic template. Such a gel may be prepared by combining its constituents in an aqueous reaction mixture, which may be stirred, may be allowed to age (e.g. between 2 h and 10 d, preferably between 3 d and 4 d), and may be subjected to drying. The support with the gel applied thereon is placed into an autoclave containing water, without direct contact between the applied gel and the water. Preferably, the autoclave contains a PTFE lining. No organo-template is contained in the water.
  • the temperature for the steam assisted conversion process can be e.g. between 90 °C and 250 °C, preferably, however, between 130 °C and 185 °C and more preferably between 140 °C and 160 °C.
  • the time for synthesis can be between 12 h and 10 d, preferably, however, between 1 d and 5 d and more preferably between 2 d and 3 d.
  • Sources of Si0 2 for the hydrothermal treatment or the vapour-phase transport process or the steam-assisted conversion process in step (i) or the hydrothermal treatment or the steam- assisted conversion process in step (ii) may be selected, e.g., from silica and silicates.
  • a suitable form of silica is e.g. fumed silica or colloidal silica.
  • Suitable silicates are e.g. alkali metal silicates, such as sodium silicate.
  • Sources of AI 2 O 3 for the hydrothermal treatment or the vapour-phase transport process or the steam-assisted conversion process in step (i) or the hydrothermal treatment or the steam-assisted conversion process in step (ii) may be selected, e.g., from alumina, aluminates, alumina salts, hydrated alumina and aluminium alcoholates. Suitable examples are aluminium triisopropylate, aluminium trihydrate, aluminium nitrate, or sodium aluminate.
  • the zeolite layer preferably a BEA-type zeolite layer
  • the zeolite layer can be subjected to different processing steps, if necessary e.g. after a drying step.
  • an ion exchange can be carried out in order to introduce catalytically-active centers into the layers.
  • zeolite seed crystals preferably BEA-type zeolite seed crystals, coated on a support are suitable as a seed material for a continuation of the crystallization process although their surface is not entirely available for the crystallization and although no structure-directing substances (organo-templates) are present in the reaction system during the second process step.
  • Figure 2 obtained for the products of Example 1.
  • the figure shows a series of X-ray diffraction patterns representing the individual steps of the process according to the invention.
  • Figure 2a the diffraction pattern of the support prior to the deposition of seed crystals (support 0) is shown as Figure 2a;
  • Figure 2 b shows the diffraction pattern of the support after deposition of zeolite seed crystals in step (i) (support 1) and
  • Figure 2c shows a diffraction pattern of the support carrying the zeolite layer after step (ii) (support 2).
  • Figures 2d and 2e show the diffraction patterns of the excess powders which may be formed in the reaction system during a hydrothermal treatment as it may be carried out in the process in accordance with the invention.
  • the starting support (support 0, Fig. 2a) exhibits the typical reflections for supports (Ti0 2 coated stainless steel).
  • the diffraction pattern of the support (support 1 , Fig. 2b) and the diffraction pattern of the excess powder formed in the reaction system but not deposited on the support (Fig. 2d) exhibit typical BEA peaks.
  • such BEA peaks can only be observed for the support (support 2, Fig. 2c). Due to the absence of a template in the reaction system, no excess powder having BEA crystal structure is formed. However, the support 2 exhibits a higher intensity of the BEA peaks when compared to support 1.
  • the increase of BEA -zeolite on the support is induced by the deposition of seed-BEA-crystals in the first process step. This confirms the success of the process according to the invention.
  • step (i) and step (ii) of the process of the present invention are different variants. These variants may be freely combined.
  • certain preferred embodiments of the process in accordance with the present invention are summarized in the following. It will be understood that the general information and the information on preferred materials and procedures provided above applies also with respect to the following embodiments.
  • Embodiment (A) (illustrated in Fig. 1 A):
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a support via a hydrofhermal synthesis in the presence of an organo-template, followed by the removal of the organo-template by a heat treatment of the seed crystals deposited on the support.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a supported BEA zeolite layer, via a hydro thermal treatment of the support having seed crystals coated thereon.
  • BEA zeolite seeds can be coated in the first process step in-situ according to known processes with organic templates (e.g. tetraethylammonium hydroxide).
  • organic templates e.g. tetraethylammonium hydroxide.
  • the hydrothermal crystallization can be carried out at 90 °C to 250 °C, preferably in the range of 130 °C to 185 °C.
  • a calcination of the composite consisting of at least one zeolite and a support is carried out in order to remove the organic template at a temperature between 300 °C and 600 °C, preferably between 350 °C and 550 °C and more preferably of 400 °C to 500 °C.
  • the structure is then subjected to hydrothermal treatment in order to make the seeds which are present grow and to yield a coating which is as homogenous and continuous as possible.
  • an aqueous reaction mixture which contains a source of Si0 2 , AEO3 and cations (e.g. Na + or K + ) is typically employed; however, no organic template is used.
  • the stirring time of the synthesis mixture can be between 15 min and 5 h, preferably, however, between 2 h and 3 h.
  • the subsequent ageing time in the presence of the seed crystals or without them) can be between 2 h and 10 d, preferably, however, between 3 d and 4 d.
  • the position of the support in the autoclave can be varied. If only one side of the support is to be coated, the back side can optionally be covered and the side to be coated can be directed to the top or to the bottom, preferably, however, to the top.
  • the synthesis temperature can be between 50 °C and 250 °C, preferably, however, between 130 °C and 185 °C and more preferably between 140 °C and 160 °C.
  • the time for synthesis is between 12 h and 10 d, preferably, however, between 1 d and 5 d and more preferably between 2 d and 3 d.
  • the zeolite layer can be subjected to different processing steps after a drying step, for example to an ion exchange in order to introduce catalyticaliy-active centers into the layers.
  • Embodiment (B) (illustrated in Fig. 1 B)
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a hydrothermal synthesis in the presence of an organo-template, followed by the removal of the organo-template by a heat treatment of the seed crystals coated onto the support.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeoli te layer, preferably a BEA-type zeolite layer, via a steam assisted conversion process on the support having seed crystals deposited thereon.
  • Embodiment (C) (illustrated in Fig. 1C):
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a hydrothermal synthesis in the presence of ex-situ prepared organo-template free zeolite seed crystals, preferably BEA-type zeolite seed crystals, in the hydrothermal reaction system.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via a hydrothermal treatment of the support having seed crystals coated thereon.
  • Embodiment (D) (illustrated in Fig. ID):
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a steam-assisted conversion process in the presence of ex-situ prepared organo-template free zeolite seed crystals, preferably BEA-type zeolite seed crystals, in the gel applied to the support for the steam assisted conversion.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via a steam-assisted conversion process on the support having seed crystals deposited thereon.
  • Embodiment (E) (illustrated in Fig. IE):
  • a first step (i) of the process of embodiment (E) ex-situ prepared organo-template free zeolite seed crystals, preferably BEA-type zeolite seed crystals, are coated onto the support.
  • a second step (ii) the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via a steam-assisted conversion process on the support having seed crystals coated thereon.
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a vapour phase transport process or steam assisted conversion process in the presence of an organo-template, followed by the removal of the organo-template by a heat treatment of the seed crystals coated onto the support.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via a hydrothermal treatment of the support having seed crystals coated thereon.
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a vapour phase transport process or a steam-assisted conversion process in the presence of an organo-template, followed by the removal of the organo-template by a heat treatment of the seed crystals coated onto the support.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via steam-assisted conversion on the support having seed crystals coated thereon.
  • ex-situ prepared organo-template free zeolite seed crystals preferably BEA-type zeolite seed crystals
  • ex-situ prepared organo-template free zeolite seed crystals preferably BEA-type zeolite seed crystals
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via hydrothermal treatment of the support having seed crystals coated thereon.
  • BEA-type zeolite seeds produced separately - ex-situ - which were calcined in order to remove the organic template or which were prepared via an organo-template free process can be coated onto the support.
  • deposition common methods such as spin-coating, dipping as well as spraying processes can be used.
  • the calcination can be carried out both before and after the support is coated.
  • the structure is then subjected to hydrothermal treatment in order to make the seeds which are present grow and to yield a coating which is as homogenous and continuous as possible.
  • an aqueous reaction mixture which contains a source of S1O2, of AI 2 O3 and cations (e.g.
  • the stirring time of the synthesis mixture can be between 15 min and 5 h, preferably, however, between 2 h and 3 h.
  • the subsequent ageing time in the presence of the seed crystals or without them) can be between 2 h and 10 d, preferably, however, between 3 d and 4 d.
  • the position of the support in the autoclave typically having a PTFE lining
  • the back side can optionally be covered and the side to be coated can be directed to the top or to the bottom, preferably, however, to the top.
  • the synthesis temperature can be between 50 °C and 250 °C, preferably, however, between 130 °C and 185 °C and more preferably between 140 °C and 160 °C.
  • the time for synthesis is between 12 h and l O d, preferably, however, between 1 d and 5 d and more preferably between 2 d and 3 d.
  • the zeolite layer can be subjected to different processing steps after a drying step, for example to an ion exchange in order to introduce catalytically- active centers into the layers.
  • zeolite seed crystals preferably BEA-type zeolite seed crystals
  • a steam-assisted conversion process in the presence of ex-situ prepared organo-template free zeolite seed crystals, preferably BEA-type zeolite seed crystals, in the gel applied to the support for the steam-assisted conversion.
  • the crystallization process is continued on the support in the absence of an organo-template to form the supported zeolite layer, preferably a BEA-type zeolite layer, via hy drothermal treatment of the support having seed crystals coated thereon.
  • a two-step process which provides (i) in a first step the coating of the support with seed crystals and in a second step (ii) a hydrothermal treatment of said support having seeds coated thereon.
  • the hydrothermal synthesis takes place statically (without stirring) under autogenous pressure at a temperature of 150 °C for 48 h. After crystallization, the excess powder was separated from the support, centrifuged, and dried at 70 °C for 24 h. The support was washed with distilled water and dried under air contact at 100 °C for 24 h. After the crystallization process, 0.037 g of BEA-zeolite crystals were located on the support. In the solution above the support, 3.7 g of zeolite powder were formed, which can also be used as seed crystals.
  • the support was heated to a temperature of 400 °C in synthetic air at a heating rate of 0.2 °C min . Said temperature was held for 16 h and was cooled at a rate of 0.3 °C min "1 . In this manner, support I with organo-template free BEA-zeolite seed crystals deposited on its surface was formed.
  • the TEAOH-free (organo-template-free) BEA-zeolite crystals which were suspended on the support were treated hydrothermally with a solution D (reaction mixture 2).
  • a solution D hydrothermally with a solution D (reaction mixture 2).
  • 0.48 g of sodium aluminate (A1 2 0 3 , 50-56 %; Na 2 0, 40-45 %; Riedel-de-Haen) were mixed with 67.6 g of distilled water and 2.43 g of sodium hydroxide (NaOH, 97-100 %, puriss., Appli Chem) and stirred for 60 min (solution E).
  • reaction mixture 2 5.6 g of fumed silica (99.8 wt% silica) were slowly added to solution E and stirred well for 3 h.
  • the molar composition of the resulting solution D was Si0 2 : 0.360 Na 2 0 : 0.025 A1 2 0 3 : 40 H 2 0.
  • 30 ml of said reaction mixture 2 were transferred into a stainless steel autoclave having a PTFE insert.
  • Support 1 provided with BEA-zeolite crystals was covered with PTFE at its back side analogously to the first treatment and positioned in the reaction mixture with the side to be coated facing upwards. Hydrothermal crystallization takes place under autogenous pressure at 140 °C for 72 h.
  • FIG. 2 shows the diffraction patterns of the uncoated (support 0) (Fig. 2a), the coated supports 1 (Fig. 2b) and 2 (Fig. 2c) as well as the corresponding excess powder for the 1 st (Fig. 2d) and 2 nd process steps (Fig. 2e), respectively.
  • Figure 3 shows three TG curves: (i) BEA-seeds after complete calcination at 550 °C, (ii) amorphous excess powder formed after the 2 nd process step (without added template) and (iii) BEA-seeds having TEAOH as templates obtained with an isothermal hold point at 400 °C (16 h).
  • reaction mixture 2 was prepared in accordance with example 1 and 30 ml were transferred to the stainless steel autoclave having a PTFE insert.
  • Support 1 provided with BEA-zeolite crystals was wrapped in PTFE and positioned in the reaction mixture.
  • the filled stainless steel autoclave was then subjected to ageing in static conditions at 5 °C for 72 h.
  • the subsequent hydrothermal treatment, processing of the excess powder formed and of support 2 were carried out as described in example 1.
  • the increase in zeolite on support 2 was 0.03 g.
  • the excess powder formed was amorphous.
  • the mass was 0.66 g.
  • Figure 4 shows the diffraction patterns of the uncoated (Fig. 4a) and the coated supports 1 (Fig. 4b) and 2 (Fig. 4c) as well as of the corresponding excess powders for the respective 1 st (Fig. 4d) and 2 nd process steps (Fig. 4d) according to example 2.
  • the deposition of the template-containing BEA-zeolite seed crystals under hydrothermal conditions on the support and the subsequent calcination process for the removal of the template from the seed crystals were carried out in analogy to example 1 (first process step). Due to the crystallization process, 0.04 g of BEA-zeolite crystals were present on the support.
  • the synthesis mixture was prepared by the method according to example 3 and with a molar composition according to example 1 and was subjected to ageing in a static state at 5 C C for 72 h. Subsequently, 30 ml of said reaction mixture were transferred into a stainless steel autoclave having a PTFE insert.
  • the support provided with BEA-zeolite crystals was wrapped in PTFE and positioned in the PTFE insert analogously to the first treatment.
  • the subsequent crystallization and processing of the excess powder formed and of the support was carried out in accordance with example 1.
  • the increase of BEA-zeolites on the membrane was 0.02 g, which corresponds to 50 % of the increase in the first process step. No zeolite was formed in the excess powder.
  • the diffraction patterns in Figure 5 ( Figure 5 - diffraction patterns "Example 4") illustrates the success of said process.
  • the processes for depositing the template-containing BEA-zeolite seed crystals under hydrothermal conditions on the support and for calcining the support in order to remove the template were carried out.
  • the second process step for the preparation of the BEA-zeolite layer under hydrothermal conditions was also carried out in analogy to example 1, wherein the stirring time of the synthesis mixture after the addition of fumed silica was reduced from 3 h to 30 min.
  • the back side of the support covered with PTFE was slightly tilted towards the top during the crystallization phases.
  • 0.76 g of amorphous excess powder was obtained and the increase of the BEA-zeolite on the support was 0.02 g.
  • the diffracttion pattern of the support carrying a BEA-zeolite layer was shown in Figure 5 ( Figure 5 - diffraction pattern "Example 5").
  • the deposition of the template-containing BEA-zeolite seed crystals on the support under hydrothermal conditions and the calcination process of the support in order to remove the template were carried out as in example 1.
  • the synthesis mixture was stirred for 30 min as in example 5.
  • the subsequent ageing of the synthesis solution in the PTFE insert in the presence of the previously-seeded support was carried out according to the method described in example 2.
  • An increase in zeolite of 0.05 g on the support and 0.57 g of amorphous excess powder were obtained.
  • the XRD pattern depicts a foreign phase, however, which was not determined more specifically.
  • the diffraction pattern of the support carrying a BEA-zeolite layer is shown in Figure 5 ( Figure 5 - diffraction pattern "Example 6").
  • the support was heated to a temperature of 400 °C in synthetic air at a heating rate of 0.2 °C min "1 . This temperature was held for 16 h and was subsequently cooled at a rate of 0.3 °C min "1 . Support 1 was formed ( Figure 6 b).
  • the TEAOH-free (organo-template-free) BEA-zeolite crystals which were fixed on the support were treated with a solution D (reaction mixture 2) and subjected to steam assisted conversion process.
  • a solution D reaction mixture 2
  • 0.47 g of sodium aluminate (A1 2 0 3 , 50- 56 %; Na 2 0, 40-45 %; Riedel-de-Haen) were mixed with 66.7 g of distilled water and 2.39 g of sodium hydroxide (NaOH, 97-100 %, puriss., Merck) and stirred for 60 min (solution E).
  • 5.6 g of fumed silica (99.8 wt% silica) were slowly added to . .
  • reaction mixture 2 The molar composition of the resulting solution D (reaction mixture 2) was Si0 2 : 0.360 Na 2 0 : 0.025 A1 2 0 3 : 40 H 2 0 and was subjected to ageing for 3 d. 1 g of reaction mixture D was then positioned on the active side of the support and the support was placed horizontally into a crucible. The reaction vessel was filled with 26.45 g of distilled water and the crucible was positioned such that neither the crucible nor the support which was located in the crucible was in contact with the water. The steam assisted conversion took place under autogenous pressure at 140 °C for 72 h.
  • Figure 6 shows the diffraction pattern of the uncoated support 0 (6a) and the coated support 1 (6b) and support 2 (6c) for the 1 st and 2 nd process steps.
  • Example 8 (cf. schematic illustration in Fig. 1C)
  • the organo-template-free BEA-zeolite crystals which were fixed on the support were treated hydrothermally with solution B (cf. first process step).
  • solution B for this purpose, 30 g of said solution B, which was stirred for 3 h, were transferred into a stainless steel autoclave with a PTFE insert.
  • Support 1 on which BEA-zeolite crystals were deposited was, in analogy to the first treatment, covered with PTFE at its back side and positioned in the PTFE insert with the side to be coated facing upwards.
  • the crystallization takes place under autogenous pressure at 140 °C for 72 h. After the time for synthesis, the excess powder was separated from the support, centrifugated and stored at 70 °C for 24 h.
  • FIG. 7 shows the diffraction patterns of the uncoated support 0 (7a) and the coated support 1 (7b) and support 2 (7c).
  • Depositing the BEA-zeolite seed crystals was carried out analogously to the first process step of example 8.
  • the support was positioned such that the active side was directed downwards and the side covered with PTFE was directed upwards.
  • the increase of zeolite on the membrane was 0.01 g ( Figure 8b) and 0.86 g of excess powder were formed.
  • the second process step was also carried out analogously to example 2, wherein the support exhibits the same position as in the first process step of said example.
  • the increase of zeolite on the membrane was 0.02 g ( Figure 8c) and 0.69 g of excess powder were formed.
  • Figure 1 Schematic illustration of exemplary variants of the process in accordance with the invention.
  • Figure 2 X-ray diffraction patterns of the products according to Example 1 after the 1 st process step (b and d) and the 2 nd process step (c and e), wherein at the respective left hand side the diffraction patterns of the composite materials and at the right hand side those of the excess powders are depicted. For comparison, the diffraction pattern of the untreated support is also shown (2a).
  • Figure 3 Three TG curves: (i) BEA-seeds after complete calcination at 550 °C, (ii) amorphous excess powder formed after the 2 nd process step (without added template) and (iii) BEA-seeds having TEA-OH as templates obtained with an isothermal hold point at 400 °C (16 h).
  • Figure 4 X-ray diffraction patterns of the products from example 2 after the 1 st process step (b and d) and the 2 nd process step (c and e).
  • the diffraction patterns for the composite materials are depicted on the left hand side and for the respectively obtained excess powders on the right hand side.
  • the diffraction pattern of the untreated support is also shown (4a).
  • Figure 5 X-ray diffraction patterns of the support (support 2) obtained after the second process step in examples 3 to 6.
  • Figure 6 X-ray diffraction patterns for the products of Example 7 after the first process step (b) and (e), wherein (b) shows the composite material obtained and (e) shows the excess powder obtained, (c) depicts the X-ray diffraction pattern of the composite material after the second process step.
  • (a) shows the cleaned, non-treated, porous stainless steel support and (d) a commercially-available H-BEA-zeolite from the Clariant company, having a molar Si/Al-ratio of 25.
  • Figure 7 X-ray diffraction patterns of the composite materials obtained after the first (b) and second (c) process step in Example 8, as well as for comparison the X-ray diffraction patterns of the cleaned support (a) and of a H-BEA-zeolite (d) from Clariant, having a molar Si/Al- ratio of 25.
  • Figure 8 Four X-ray diffraction patterns of the composite materials obtained after the first (b) and the second process step (c) in Example 9, as well as for comparison the X-ray diffraction patterns of the cleaned support (a) and of a H-BEA-zeolites (d) from Clariant, having a molar Si/Al-ratio of 25.

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Abstract

L'invention concerne un procédé de préparation d'une couche de zéolithe soutenue sans matrice organique, de préférence une couche de zéolithe de type BEA, ledit procédé comportant au moins deux étapes, (i) dans une première étape, des germes cristallins sont déposés sur un support, et (ii) dans une seconde étape, la couche de zéolithe est préparée sur le support en l'absence de matrice organique par l'intermédiaire (iia) d'un traitement hydrothermique du support ayant des germes cristallins déposés sur celui-ci, ou par l'intermédiaire (iib) d'un procédé de conversion au moyen de vapeur sur le support ayant des germes cristallins déposés sur celui-ci.
PCT/EP2014/064351 2013-07-05 2014-07-04 Procédé de préparation de couches de zéolithe soutenues sans matrice organique Ceased WO2015001095A1 (fr)

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CN109133082A (zh) * 2018-09-21 2019-01-04 中国科学院上海高等研究院 一种合成纳米sapo-34的方法
CN110143602A (zh) * 2018-02-13 2019-08-20 中国石油天然气股份有限公司 一种β分子筛的制备方法
CN113880103A (zh) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 一种Beta分子筛及其合成方法和应用

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105347359A (zh) * 2015-11-27 2016-02-24 中国石油大学(北京) 一种孔道内含固体酸的沸石分子筛的合成及其应用
CN110143602A (zh) * 2018-02-13 2019-08-20 中国石油天然气股份有限公司 一种β分子筛的制备方法
CN110143602B (zh) * 2018-02-13 2021-01-29 中国石油天然气股份有限公司 一种β分子筛的制备方法
CN109133082A (zh) * 2018-09-21 2019-01-04 中国科学院上海高等研究院 一种合成纳米sapo-34的方法
CN113880103A (zh) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 一种Beta分子筛及其合成方法和应用
CN113880103B (zh) * 2020-07-01 2023-06-06 中国石油化工股份有限公司 一种Beta分子筛及其合成方法和应用

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