DE10309009A1 - Zeolite coating of polymer-derived ceramics where e.g. aluminum is added to the coating solution and/or ceramic which acts as a carrier and also provides network-formers - Google Patents

Abstract

Simplified production of partially or wholly zeolite-coated ceramics derived from polymers is such that the coating is strongly bonded regardless of the filler content of the ceramic, the coating solution being obtained by addition of an aluminum source to a water/template solution, followed by stirring under specified conditions. Production of partially or wholly zeolite-coated ceramics derived from polymers is such that the coating is strongly bonded regardless of the filler content of the ceramic, the coating solution being obtained by (1) addition of an aluminum source at a water : Al ratio 0.1 or above to a solution of water : template ratio 1-5000 (especially 150-700), the template being tetrapropylammonium-hydroxide or -bromide or other suitable material; and (2) stirring for 1 hour with synthesis time being 30 minutes - 1 year (especially 12-200 hours) at 25-350 (especially 120-200)[deg]C with ratio solution : carrier 1-1000 (especially 20- 40). Independent claims are also included for: (i) using various zeolitic network- formers (not only Si) in forming zeolitic films on polymer-derived ceramic carriers, the network-formers being obtained by partial solution from the carrier; and (ii) accelerating the partial transformation of ceramic carriers into zeolite-ceramic composites by addition of metallic Si powder at 0-100% (and optionally also another network-former such as aluminum) into the starting material for the polymer production.

Description

Territory of invention

The present invention relates to an innovative manufacturing technique (chemically and mechanically supported crystallization) of zeolite layers on ceramic supports that require partial dissolution and transformation the surface of the carrier material in a layer with a zeolitic (porous, crystalline) structure. The ceramic carrier materials both the mechanical support as well as the material source required for zeolite formation Networking. The conversion takes place in a hydrothermal Reaction.

background the invention

Zeolites are microporous crystalline materials with a 3-dimensional network structure, which (preferably) are made up of [SiO ₄ ] and [AlO ₄ ] tetrahedra by linking via the oxygen atoms. These materials are of great importance for catalysis, material separation and adsorption.

Zeolites are used in technical syntheses received as a powder. For Most technical application is a shaping under Use of binders (clay, silica sol, aluminum oxide, etc.) is necessary. So the required particle size with sufficient mechanical stability be achieved. This molding process has several disadvantages: In addition to the need for an additional technology step, reduce the binder used the proportion of catalytically active material, can block pores and possibly even unwanted ones show catalytic effects.

In the literature, the Manufacture of self-supporting zeolite membranes reported (Advanced Materials 14, Issue 13-14 (2002) 994-997), but this represents another Solution variant. For the Utilization of zeolitic properties for new applications is that possibility the production of mechanically stable zeolite moldings of different geometries of essential importance.

For this reason, is one of the current research directions in zeolite research, supported crystallization of zeolites for the production of membranes (both inert and catalytically active) for Separation processes and catalysis, adsorption modules, heat pumps, chemical sensors, Microelectronic components and catalytically active coatings (microporous and Mesoporous Materials 21 (1990 213-226).

The interest in zeolitic composite materials increases due to the achievable mechanical strength, the new one possibility the shaping of catalysts and the synergy effect through the Combination of two materials with different properties. In addition, by varying the carrier material and zeolite Realize a whole range of different combinations with new ones Properties and possible uses. The growing interest in these materials is also due to the growing number of publications documented on this topic.

The "carrier-based crystallization" method is described by two Main factors determine - the type of carrier and the preparation technique.

A whole bunch of different ones Materials (structured and shaped) were used for coating with zeolites tested (stainless steel, aluminum alloys, ceramics, glass, plates, moldings, microstructures, etc.). A comprehensive overview is shown in Tab. 1.

In many cases, however, the incompatibility of the film and the carrier leads to problems. In the case of the membranes in particular, a number of problems relating to adhesion, tightness and preferred orientation of the crystals were investigated and partially solved. A large part of the publications and patents therefore also relates to the manufacture of membranes by the crystallization of zeolites on porous steel or ceramic supports (patent US5744035 . US6472016 B1 , Patent Application EP01309932.0 ).

Only a few publications relate on the production of catalytically active layers on porous ceramics (see Tab. 1). However, these are always on creating a layer on inert carrier materials limited.

Ceramic materials stand out thanks to their high thermal and good chemical resistance, mechanical strength and machinability. That makes them for many Applications very attractive.

Another requirement for zeolite carrier composites is that possible good adhesion between carrier material and zeolite layer. According to the invention, this liability is special well realized in that the carrier material is partially in zeolite is converted, creating a bond at the molecular level.

In addition, we use special ceramic materials (polymer-derived ceramics), the advantage of which is, on the one hand, the good and shape-rich processability, but, on the other hand, a wide variety of preceramic polymers (generally Si-containing polymers such as poly (carbosilanes), - (silazanes ), - (siloxane) or - (borosilazane)) and the filler that may be used (metallic, ceramic, inert or reactive) (Peter Greil, Polymer Derived Engineering Ceramics, Advanced Engineering Materials 2 (2000) 339-348).

The carrier materials can be used as dense or porous SiOC (filler) ceramics be preserved. These ceramics alone have no noteworthy catalytic or adsorptive properties, while it attaches to the mechanical zeolites Characteristics lack.

The ceramic composite material and overcomes the zeolite layer the individual disadvantages.

• 1. Die Verwendung von Bindern kann Diffusionsprobleme durch teilweise Blockierung von Poren hervorrufen, verringert die Kristallinität der Schicht und führt oft nicht zu einer ausreichend kompatiblen Bindung zwischen Träger und Zeolith.
• 2. Die sogenannte Seed-Methode erlaubt zwar die Kristallisation von zeolithischem Material in relativ weitem Bereich ist aber als Mehrschritttechnik teuer und deshalb nur für die Präparation spezieller Membranen einsetzbar.
• 3. Eine weitere Methode ist die direkte hydrothermale Synthese auf inerten Substraten (einstufige Technik, reproduzierbar und kostengünstig). Beide Methoden (2, 3) führen zwar zu einer besseren Haftung zwischen Zeolithschicht und Substrat als die Verwendung von Binder, sind aber nicht mit den Ergebnissen der von uns vorgeschlagenen Methode vergleichbar.

In addition, the currently available techniques for the production of zeolite carrier materials will be discussed. An overview with advantages and disadvantages is given in Table 2.

• 1. The use of binders can cause diffusion problems by partially blocking pores, reduces the crystallinity of the layer and often does not lead to a sufficiently compatible bond between the support and the zeolite.
• 2. The so-called seed method allows the crystallization of zeolitic material in a relatively wide range, but is expensive as a multi-step technique and can therefore only be used for the preparation of special membranes.
• 3. Another method is the direct hydrothermal synthesis on inert substrates (single-stage technology, reproducible and inexpensive). Both methods (2, 3) lead to better adhesion between the zeolite layer and the substrate than the use of binder, but are not comparable with the results of the method proposed by us.

The one described in the invention An alternative is a hydrothermal direct synthesis. To do this, the backing material in a reaction mixture of water, template and an alkali source (under increased Temperature) implemented. The peculiarity of this type of zeolite synthesis is that there is no crystallization from the reaction mixture on the surface of the carrier forms the zeolite layer. Rather, the wearer changes partially or completely in zeolite.

This method has already been described by our group for a selected substrate class (porous glasses) (F. Scheffler, W. Schwieger, D. Joy, H. Liu, W. Heyer, F. Janowski, Transformation of porous glass beads into MFI-type containing beads, Microporous and Mesoporous Materials 55 (2002) 181-191; W. Schwieger, M. Rauscher, F. Scheffler, D. Joy, U. Pingel, Biphasic silicate materials based on porous glasses - preparation and properties, 12 ^th International Zeolite Conference, 1999 Materials Research Society).

The materials so produced show a very good adhesion between the carrier (remaining glass structure) and Zeolite layer and are relatively easy to manufacture.

All available literature patents ( US 2001/0048971 A1 . DE 19962374A1 ) and publications (Advanced Materials l2 (2000) 1332-1335; Microporous and Mesoporous Materials 55 (2002) 181-191 refers exclusively to the use of glass substrates or mullite ceramics to which cristobalite, tridymite or glass was added as an SiO ₂ source ,

The challenge now is that a class of substrates should be found alongside the possibility of converting to this method about other interesting properties (mechanical stability, shape and workability, variability the chemical composition, further functionality e.g. electrical Conductivity) features.

The class of Materials -Ceramics by pyrolysis of preceramic polymer or polymer / filler mixtures manufactured, meet these requirements in wide and variable areas.

Description of the invention

The invention provides a new manufacturing method for zeolite layers on ceramic materials. Thereby are used as carrier materials polymer-derived (SiOC + filler) Ceramics used. The zeolite / ceramic composites produced in this way can be used in catalysis, adsorption, separation and sensor technology.

The ceramic materials (containing filler or filler-free) can can be manufactured in a wide range of compositions (combination made of different polymers and fillers, variation of pyrolysis temperature and atmosphere). In addition, there are different geometric shapes (tapes, tubes, balls etc.) and dense as well as porous Structures (e.g. foams) accessible.

The ceramic material fulfills two Functions: (1) it is mechanical support for the zeolite layer and (2) it provides the (or) for the zeolite synthesis necessary network formers silicon (B, Al, Ti, etc.). As a variation of this method, you can also add in the solution Network formers may be included.

A key role for the possibility of using the ceramics described as a support material is their reactivity under the chosen reaction conditions. Ie the ceramic or a component (filler) of the ceramic must be under synthetic conditions (preferably strongly alkaline, increased temp rature) to be able to crystallize into a zeolite structure.

The method is hydrothermal in-situ crystallization, in which the carrier is in a reaction mixture (see below for their manufacture) at elevated temperature (if necessary under autogenous pressure) is reacted.

• – Mischung von dest. Wasser und Templat in verschiedenen Verhältnissen (Template können sein: Tetrapropylammoniumhydroxid (TPAOH), Tetrapropylammoniumbromid (TPABr) oder verschiedene andere Ammoniumsalze und Amine, wie sie für die Zeolithsynthese gebräuchlich sind.
• – Gegebenenfalls Zusatz und Vermischung eines weiteren Netzwerkbildners (Al, Ti etc.).
• – Eventuell muss eine bestimmte Alterungszeit eingehalten werden.

Preparation of the reaction mixture:

• - Mix of dist. Water and template in various ratios (templates can be: tetrapropylammonium hydroxide (TPAOH), tetrapropylammonium bromide (TPABr) or various other ammonium salts and amines, as are used for zeolite synthesis.
• - If necessary, add and mix another network former (Al, Ti, etc.).
• - A certain aging period may have to be observed.

• – Der polymerabgeleitete Keramikträger wird in einem Edelstahlautoklaven (vorzugsweise Teflonausgekleidet) platziert. Es wird Reaktionsmischung zugegeben, so dass der gesamte Träger bedeckt ist.
• – Bei porösen Trägern kann das kurzzeitige Anlegen eines Vakuums erforderlich sein, um auch die inneren Zell- oder Porenwände mit Reaktionsmischung zu benetzen.
• – Für die Reaktion wird der geschlossene Autoklav im Trockenschrank auf Reaktionstemperatur gebracht und für eine entsprechende Zeit (einige Stunden-mehrer Tage oder Wochen) bei dieser Temperatur gehalten. Der Autoklav kann für eine bessere Durchmischung während der Reaktionszeit bewegt werden (Rotation, Schütteln etc.)
• – Nach Ablauf der Reaktionszeit wird der Autoklav aus dem Trockenschrank entnommen und abgekühlt.
• – Kompositmaterial und Lösung werden getrennt und das Kompositmaterial wird mit dest. Wasser abgespült.
• – Das Kompositmaterial wird bei Raumtemperatur über Nacht getrocknet und anschliessend bei 400°C für 16-24 h calciniert. Dabei ist eine langsame Heizrampe zu wählen, das Calcinierungsgas kann Luft, Sauerstoff oder Argon sein.

In certain cases, cleaning of the carrier material (eg with hot water) is necessary to remove surface contaminants.

• - The polymer-derived ceramic carrier is placed in a stainless steel autoclave (preferably lined with Teflon). Reaction mixture is added so that the entire support is covered.
• - In the case of porous supports, it may be necessary to briefly apply a vacuum in order to wet the inner cell or pore walls with the reaction mixture.
• - For the reaction, the closed autoclave is brought to the reaction temperature in the drying cabinet and kept at this temperature for a corresponding time (a few hours or several days or weeks). The autoclave can be moved during the reaction time (rotation, shaking etc.) for better mixing.
• - After the reaction time has elapsed, the autoclave is removed from the drying cabinet and cooled.
• - Composite material and solution are separated and the composite material is distilled. Rinsed off water.
• - The composite material is dried at room temperature overnight and then calcined at 400 ° C for 16-24 h. A slow heating ramp must be selected, the calcining gas can be air, oxygen or argon.

• – Eine einfache und schnelle Präparation;
• – Gute technische Reproduzierbarkeit;
• – Das Verfahren erzeugt eine vollständige und gleichmässige Beschichtung des Trägermaterials auch bei komplizierten oder unregelmässigen Geometrien (z.B. Schäume)
• Die Eigenschaften der Zeolithschicht lassen sich durch Variation der Syntheseparameter (Zusammensetzung, Temperatur, Zeit) beeinflussen.
• – Die Beeinflussung der Eigenschaften ist ebenfalls durch die Variation der Herstellungsparameter der Keramikmaterialien (Art des Polymers, Typ und Gehalt des Füllers, Pyrolysebedingungen etc.)
• – Die Schichtdicke ist durch die Reaktionsparameter einstellbar. Es sind auch sehr dünne Schichten (Filme) erzeugbar.

The main advantages of the described method are:

• - A simple and quick preparation;
• - Good technical reproducibility;
• - The process creates a complete and uniform coating of the carrier material even with complicated or irregular geometries (e.g. foams)
• The properties of the zeolite layer can be influenced by varying the synthesis parameters (composition, temperature, time).
• - The influencing of the properties is also due to the variation of the manufacturing parameters of the ceramic materials (type of polymer, type and content of the filler, pyrolysis conditions etc.)
• - The layer thickness can be adjusted using the reaction parameters. Very thin layers (films) can also be produced.

Ceramic foams or cellular ceramics are porous Materials with closed or open pore structure and one free volume of up to 90%. Such foam materials can also by the pyrolysis of preceramic Polymers are made. These foams can be made by adding different ink pen be functionalized. There was no patent literature on the manufacture such foams found. The production of such foams is described in (M. Scheffler, T. Gambaryan-Roisman, J. Zeschky, F. Scheffler, P. Greif, Self-foamed cellular ceramics from silicone resins with a zeolite surface, Ceramic Engineering and Science Proceedings 23 (2002) 203-210), thereby also the possibility mentioned that the surface can be covered with zeolite.

It is also using this technique possible, magnetic polymer-derived ceramics with a zeolitic To provide layer, the magnetic properties by the choice of filler can be generated. these can then e.g. be heated by induction.

Examples Example 1:

Product class: Manufacture of zeolite coated H 44 / fountain pen derived ceramics with the CMSC (chemical mechanical supported crystallization).

Specific product group: Silicalite and ZSM-5 coating of electrically conductive polymer-derived ceramic Materials.

Individual experiments shown in Ex. 1:

support material:

The supports are ceramic materials with an open pore structure, with an average pore diameter of 1 mm. It is produced by pyrolysis of a mixture of preceramic polymer and various fillers. Here, the polymer H44 silicone resin (Wacker AG, Burghausen, Germany) with the empirical formula [(C ₆ H ₅ ) _0.62 (CH ₃ ) _0.31 (OR) _0.07 SiO] with n≈20 and R = - OC ₂ H ₅ and -OH used. The molar mass is 2100 g / mol and the density is 1.1 g / cm ³ .

In the examples listed here the reaction mixtures of 50 mass% polymer resin and 50 mass% ink pen or filler mix manufactured. The polymer content can vary from 5-100% without the Change manufacturing process. A higher one Polymer content changed however the properties of the carrier (greater shrinkage or higher Porosity) examples for the carriers produced (Foams):

• - H44 (50% wt) -Si (45% wt) -SiC (5% wt) polymer-derived ceramic foam pyrolyzes at 1200 ° C in argon;
• - H44 (∼50% wt) -Si (45% wt) -SiC (5% wt) -Cu ₂ O (0.15%) polymer-derived ceramic foam pyrolyzed at 1200 ° C in argon;
• - H44 (∼50% wt) -Si (45% wt) -SiC (5% wt) -Cu ₂ O (, 15%) polymer-derived ceramic foam pyrolyzed at 1000 ° C in argon;
• - H44 (∼50% wt) -Al ₂ O ₃ (50% wt) -Cu ₂ O (1.5%) polymer-derived ceramic foam pyrolyzed at 1000 ° C in argon;

METHOD AND PROCESS:

The zeolite ceramic composites were made manufactured according to the procedure described above (same Steps, same order).

The synthesis parameters (composition, Reaction conditions of the hydrothermal reaction) are described below described.

• A) Dest.Wasser:TPAOH = 675:1 für Silicalite coating, pH = 13,0
• B) Dest.Wasser:TPAOH = 450:1, pH = 13,2, Zusatz von 3·10^–4 mol Al für ZSM-5 coating
• C) Dest.Wasser:TPAOH = 450:1 für ZSM-5 coating Zusatz von Al (0,03 g Al₂(SO₄)₃· 18H₂O entspricht der Konzentration 9· 10^–5mol Al)

Gewichtsverhältnis Lösung/Träger = 20:1
Synthesezeit:72 h
Heizbedingungen: A)150°C, Rotation 5 rpm
B)175°C, Rotation 0 rpm
C)175°C, Rotation 0 rpmThe following conditions were chosen for the examples described: Composition of the reaction mixture:

• A) Dest. Water: TPAOH = 675: 1 for silicalite coating, pH = 13.0
• B) Dest. Water: TPAOH = 450: 1, pH = 13.2, addition of 3 · 10 ^-4 mol Al for ZSM-5 coating
• C) Dest. Water: TPAOH = 450: 1 for ZSM-5 coating addition of Al (0.03 g Al ₂ (SO ₄ ) ₃ · 18H ₂ O corresponds to the concentration 9 · 10 ^-5 mol Al)

Weight ratio solution / carrier = 20: 1
Synthesis time: 72 h
Heating conditions: A) 150 ° C, rotation 5 rpm
B) 175 ° C, rotation 0 rpm
C) 175 ° C, rotation 0 rpm

After the water and TPAOH have been mixed together, the mixture is stirred for 15 minutes using a magnetic stirrer. If necessary, an additional Al source (eg Catapal B or Al ₂ (SO ₄ ) ₃ .18H ₂ O) is added and the mixture is stirred for a further 15 min. The solution is placed with the ceramic foam in a Teflon lined autoclave. For a complete wetting of the pores and removal of gas from the pores, the foam / reaction mixture can be evacuated for a few minutes.

The sealed autoclaves will placed in an oven on a rotating shaft and for a sufficient Time (e.g. 72 h) at reaction temperature. After that the autoclaves are cooled in air or water. The foam is removed rinsed with water and for 24 h at 100 ° C dried. To remove the template from the micropores of the Zeolite layer is at 400 - 600 ° C for 12-16 h calcined in air or argon.

pictures:

1 SEM representation of silicalite coating on polymer-derived ceramic foam H44 (50% wt) -Si (45% wt) -SiC (5% wt) pyrolyzed at 1200 ° C in argon, synthesis time 72 h, 150 ° C.

2 X-ray diffractogram (XRD) of silicalite coating on polymer-derived ceramic foam H44 (50% wt) -Si (45% wt) -SiC (5% wt) pyrolyzed at 1200 ° C in argon, synthesis time 72 h, 150 ° C.

3 XRD of zeolite foam composite (composition B see above) ZSM-5 coating on H44 (50% wt) -Si (43.5% wt) -SiC (5% wt) -Cu ₂ O (1.5%) pyrolyzed at 1000 ° C in argon, synthesis time 72 h, 175 ° C.

4 XRD of zeolite foam composite (composition C see above) ZSM-5 coating on H44 (50% wt) -Si (43.5% wt) -SiC (5% wt) -Cu ₂ O (1.5%) pyrolyzed at 1000 ° C in argon, synthesis time 72 h, 175 ° C.

5 Micro-computed tomography of a polymer-derived ceramic foam with electrical conductivity

6 SEM image of a silicalite layer on an H44 (∼50% wt) -Al ₂ O ₃ (∼50%) - Cu ₂ O (2%) - substrate, pyrolyzed at 1000 ° C in argon, synthesis conditions for 48 h at 150 ° C

Example 2:

Product class: Manufacture of zeolite coated polymer-derived ceramics with the CMSC (chemical mechanical supported crystallization).

Specific product group: Silicalite coating of H44-derived ceramic materials. Here the crystallization of filler-free materials is described, or the crystallization of materials to which 2% Cu ₂ O has been added.

Individual experiments, which are shown in Ex. 2:

METHOD AND PROCESS:

The zeolite ceramic composites were made manufactured according to the procedure described above (same Steps, same order).

The synthesis parameters (composition, Reaction conditions of the hydrothermal reaction) are described below described.

The following conditions were selected for the examples described:
Composition of the reaction mixture:
Dest. Water: TPAOH = 675: 1 for silicalite coating
Mass ratio solution / carrier = 20: 1
pH = 13.00
Synthesis time: 6-144 h
Crystallization conditions: 150 ° C, rotation 5 rpm

pictures:

7 X-ray diffractograms of silicalite ceramic composites of H44-Cu ₂ O (2%) polymer-derived ceramics (pyrolysis at 1200 ° C in argon) are obtained after various synthesis times

8th X-ray diffractogram of silicalite-ceramic composite of H44 polymer-derived ceramic (pyrolysis at 1000 ° C in argon) obtained after a short synthesis time

Example 3:

Product class: Manufacture of zeolite coated polymer-derived ceramic foams with the CMSC (chemical mechanical supported crystallization).

Specific product group: Silicalite coating of SR350-derived microcellular ceramic foams.

Individual experiments, which are shown in Ex. 3:

Carrier:

Microcellular polymer-derived Ceramic foam made from SR350 (preceramic polymer, hydroxymethyl-silsesquioxane, General Electric Co).

METHOD AND PROCESS:

The zeolite ceramic composites were made manufactured according to the procedure described above (same Steps, same order).

The synthesis parameters (composition, reaction conditions of the hydrothermal reaction) are described below. The individual preparation steps are described in Example 1
The following conditions were selected for the examples described:
Composition of the reaction mixture: Dest. Water: TPAOH = 450: 1 for silicalite coating
Mass ratio solution / carrier = 40: 1
pH = 13.2
Synthesis time: 48 and 72 h
Crystallization conditions: 150 ° C, rotation 5 rpm and 0 rpm

Illustration:

9 X-ray diffractogram of Silicalite-SR350 ceramic foam composite after 72 h synthesis at 150 ° C.

Example 4:

Product class: Manufacture of zeolite coated metallic silicon powder or complete transformation of the same with the CMSC (chemical mechanical supported crystallization). The Application of the described method to Si powder represents a special one Borderline case. On the one hand, the method corresponds to the conversion of polymer-derived ceramics. On the other hand, this opens up Method the possibility of Si waste materials (e.g. wafer sawing sludge) to recycle. The SEM images show that the zeolite crystals are also here directly on the surface of the Si particles grow and maintain their geometric shape becomes.

Specific product group: Silicalite and ZSM-5 coating on metallic Si powder by partial or full Conversion.

Träger (Si-Quelle):
metallisches Si -PulverIndividual experiments, which are shown in Ex. 4:

Carrier (Si source):
metallic Si powder

METHOD AND PROCESS:

The zeolite-Si metal composites were manufactured according to the procedure described above (same Steps, same order).

The synthesis parameters (composition, Reaction conditions of the hydrothermal reaction) are described below described. The individual preparation steps are described in Ex. 1. In this particular (borderline) case not powdered products but powder.

• A)Dest.Wasser:TPAOH = 600:1 für Silicalite coating
• B)Dest.Water:TPAOH = 600:1 für ZSM-5 coating mit Zusatz von Al in der Reaktionsmischung (0,2g of CATAPAL B:A1-source) Masseverhältnis Lösung / Festoff = 20:1 A,B) pH = 13-13,05; Synthese Zeit: A)24-48-96 h; B)96 h; Reaktionsbedingungen: A)150°C, Rotation 5 rpm und 0 rpm; B)175°C, ohne Rotation;

The following conditions were chosen for the examples described: Composition of the reaction mixture:

• A) Dest. Water: TPAOH = 600: 1 for silicalite coating
• B) Dest.Water: TPAOH = 600: 1 for ZSM-5 coating with the addition of Al in the reaction mixture (0.2g of CATAPAL B: A1-source) mass ratio solution / solids = 20: 1 A, B) pH = 13 -13.05; Synthesis time: A) 24-48-96 h; B) 96 h; Reaction conditions: A) 150 ° C, rotation 5 rpm and 0 rpm; B) 175 ° C, without rotation;

pictures:

10 X-ray diffractogram of an almost completely converted Si powder after 48 h crystallization time at 150 ° C (rotation).

11 X-ray diffractograms of Si powders partially converted to silicalite after 24, 48, 96 h at 150 ° C (without rotation).

12 SEM absorption of silicalite on Si powder obtained by the technique described (48 h synthesis at 150 ° C, without rotation).

13 X-ray diffractogram of ZSM-5 crystallized on metallic Si powder obtained by the technique described (96 h, 175 ° C, without rotation).

invention claims

• - New Method for producing partially or completely coated with zeolite polymer-derived ceramic composites with a simple process, characterized in that the materials have a strong bond between carriers and have a zeolite layer. The polymer-derived carrier can be different ink pen contained in any proportion. According to the explanations the following conditions apply: - for the preparation of the solution: - Water: template ratio = 1-5000, preferably 150-700 - Type of template: TPAOH, TPABr, all for the zeolite synthesis in use SDA - encore any aluminum source in a water: Al = 0.1-∞ ratio - Additional stir preferably 1 h - for the synthesis: - Ratio solution: carrier (mass) = 1-1000, preferably 20-40 - synthesis time: 30min-1 year, preferably 12-200 h - Temperature: 25-350 ° C preferably 120-200 ° C
• - method according to claim 1, characterized in that in addition to Si of the carrier material one alternative Si source is added to the synthesis solution;
• - Method according to claim 1, characterized in that different polymer-derived Ke ceramic materials (with and without filler) with any geometric shape can be used to produce zeolite-ceramic composites.
• - method according to claim 1, characterized in that the carrier material both as a mechanical support serves as well as the chemical source for the necessary for the zeolite synthesis Networking agent represents silicon.
• - method for the use of various zeolitic network builders (not only Si) for the production of zeolitic films on polymer-derived Ceramic substrates, by partial solution this network builder from the carrier.
• - method to accelerate the partial transformation of ceramic carriers in zeolite ceramic composites by adding metallic Si powder with a share of 0-100% of the starting material for polymer production.
• - Application the method on 100% metallic Si powder. In this case leads not converting to a ceramic.
• - Application this method on metallic Si powder as exclusive Si source with the addition of another network former (e.g. aluminum).
• - Application this method on substrates any shape and size, that contain 1 to 100% metallic silicon.
• - Zeolite ceramic composite materials any shape and size, which were produced with the described method.
• - zeolite ceramic composite materials, the electrically conductive are and were produced with the method described.
• - zeolite ceramic composite materials, in which cellular structures (foams) were used as carrier material and which were produced with the method described.
• - zeolite ceramic composite materials, show the magnetic properties and with the method described were manufactured.

Tabelle 2

Table 1

Table 2

Claims (13)

New method for producing partially or completely zeolite-coated polymer-derived ceramic composites using a simple process, characterized in that the materials have a strong bond between the support and the zeolite layer. The polymer-derived carrier can contain various fillers in any proportion. According to the explanations above, the following conditions apply: - for the preparation of the solution: - ratio water: template = 1-5000, preferably 150-700 - type of template: TPAOH, TPABr, all SDA commonly used for zeolite synthesis - addition of any aluminum source in a ratio of water: A1 = 0.1-∞ - further stirring preferably 1 h - for carrying out the synthesis: - ratio of solution: carrier (mass) = 1-1000, preferably 20-40 - synthesis time: 30min-1 year, preferably 12- 200 h - temperature: 25-350 ° C, preferably 120-200 ° C Method according to claim 1, characterized in that that in addition to Si of the carrier material an alternative Si source is added to the synthesis solution; Method according to claim 1, characterized in that that different polymer-derived ceramic materials (with and without filler) with any geometric shape for the production of zeolite-ceramic composites be used. Method according to claim 1, characterized in that the carrier material serves both as a mechanical carrier and the chemical source for the network required for zeolite synthesis is silicon. Method for using various zeolitic network formers (not just Si) for the production of zeolitic films on polymer-derived Ceramic substrates, by partial solution this network builder from the carrier. Method for accelerating the partial transformation of ceramic supports in zeolite ceramic composites by adding metallic Si powder with a share of 0-100% of the starting material for polymer production. Application of the method on 100% metallic Si powder. In this case leads not converting to a ceramic. Application of this method to metallic Si powder as the exclusive Si source with the addition of another network former (e.g. aluminum). Application of this method on substrates of any shape and size, that contain 1 to 100% metallic silicon. Zeolite ceramic composite materials of any shape and size, which were produced with the described method. Zeolite ceramic composite materials that are electrical conductive are and were produced with the method described. Zeolite-ceramic composite materials where cellular Structures (foams) used as carrier material were and which were produced with the method described. Zeolite ceramic composite materials, the magnetic Show properties and manufactured with the described method were.