DE102009049767A1 - Process for the catalytic conversion of solid-like hydrocarbons - Google Patents

Abstract

The invention relates to a process for the catalytic conversion of solid-like hydrocarbons, in which the solid-like hydrocarbons undergo a grinding, drying, primary and secondary reaction process. In this case, shaped bodies having a body core forming a carrier material are provided as a grinding body, is applied to the catalyst material. The solid hydrocarbons to be reacted and the catalytically active material which is in the form of the shaped bodies are brought into contact with each other. According to the invention, the milling, drying, primary and secondary reaction processes are carried out simultaneously by simultaneously drying and milling the solid, solid-solid reaction of solid organic solids and solid catalyst, and leaving gaseous or liquid products in secondary reactions on the catalyst surface split and / or converted. The invention is used in particular for the recycling of lignite and / or biomass and / or plastics, such as thermosets and thermoplastics, and / or Petrokoks and / or oil sands and / or oil shale in processing plants.

Description

The The invention relates to a process for the catalytic conversion of solid-like hydrocarbons, in particular for the material Utilization of lignite and / or biomass and / or plastics, such as for example, thermosets and thermoplastics, and / or Petrokoks and / or oil sands and / or oil shale in refineries.

Around Recycling lignite has been four in the past shown significant ways. The first way is coke making, which produces coking gas, tar and coke under inert conditions. main problems However, here are the quality of the resulting coke and the relatively small amounts of liquid and gaseous Value products, since the process is a subsequent charring represents, in which only side chains of carbon molecules be separated and incurred as a product. In coal liquefaction Coal is dried, mashed with oils and in one Hydrogenated reaction process. The coal is thermally split and the resulting radicals are saturated with hydrogen. The product yield is significantly larger here, but the economy is due to needed hydrogen and complex coal preparation compared to oil clearly at a disadvantage. The oils resulting from this process can be used as a liquid product to fuel the residual products to be processed into coke. The coal gasification and recovery of the Synthetic gas according to Fischer-Tropsch is currently one of the most interesting This is how South Africa operates modern plants (SASOL) to be independent of the raw material of petroleum. Similar Efforts are currently taking place in China. At the coal gasification becomes coal with water and oxygen to carbon monoxide, hydrogen, Methane and carbon dioxide (synthesis gas equilibrium) implemented. The resulting gases can then for example for the production of hydrocarbons (synthetic gasoline). In this Process is a process whereby the coal disassembled to smallest possible components and reassembled again becomes. Especially in the exploitation of Eocene lignites, which have a high bitumen content, is the extraction of Grow an interesting process, since here from the brown coal Direct products with high added value can be obtained can. Disassembly into the smallest components remains here. Instead, one uses targeted the composition of the coal. adversely is that most of the coal (not extractable Share) must be thermally utilized (ROMONTA). If you look at the individual procedures, it is found that no procedure is available, which specifically the ingredients the Eocene lignite with a higher yield than 30 percent uses material. With the extraction will be less gained as 30 percent waxes; with coal gasification, coal liquefaction and coke production is not limited to the special bitumen-rich composition received as value product.

Not only in the field of lignite there are efforts to recover valuable materials from hydrocarbon-containing components. So will in the DE 100 49 377 A1 described a catalytic production of diesel oil and gasoline from waste hydrocarbons and oils, which due to the choice of catalysts and the process technology with a reactor temperature of 350 ° C manages and thereby a diesel yield of over 80 percent or a combined diesel and gasoline production from plastics, waste oils and fats of 65 percent diesel and 15 percent gasoline. The plant can be easily decentralized and combines in the catalyst the catalytic cracking, stabilization and dechlorination of the chlorine content of the PVC.

at The method is a catalyst of sodium aluminosilicates in a circulation evaporator in the circulation in a high-boiling hydrocarbon, like thermal oil, base oil or bunker C oil, stirred and it is in the reactor part under the distillation plant the plastics, fats, oils and other hydrocarbon Waste added. The catalyst is doing with the solid Residues discharged as waste from the reactor and must be disposed of become. However, this method is included with the application organic solids, such as lignite and biomass, only conditionally suitable and ultimately both in terms of cost and the Number of necessary process steps too expensive.

Of the The invention is therefore based on the object, a method for recycling of solids, in particular lignite and / or biomass and / or plastics, such as thermosets and thermoplastics, and / or petro-cokes and / or oil sands and / or oil shale that has the special properties these substances for a high material yield of value products uses. This method is intended to combine several process steps into one, wherein the catalyst is separated from the solid residues, regenerated and can be reused.

According to the invention, this object is achieved by a process for the catalytic conversion of solid-like hydrocarbons, in which the solid-like hydrocarbons a Mahl-, Tro undergo cken-, primary reaction and secondary reaction process, wherein as a grinding body moldings are provided with a mold body core forming carrier material, is applied to the catalyst material. In addition to the application of the catalyst to support bodies made of a carrier material, this also includes the possibility that the carrier material and catalyst material are identical and the grinding body is completely formed from catalyst material and thus the catalyst material is present, for example, in the form of grinding balls. The solid hydrocarbons to be reacted as solid carbon-containing reactants and the catalytically active material, which is in the form of preferably spherical shaped bodies, each consisting of a shaped core and attached to the phase boundary, catalytically active material are brought into contact with each other in the process. In accordance with the present invention, the milling, drying, primary and secondary reaction processes proceed simultaneously by simultaneously drying and milling the solid, solid-solid reaction of solid organic solids and solid catalyst, and exiting gaseous or liquid products in secondary reactions further split and / or converted at the catalyst surface. The advantageous simultaneous sequence of grinding, drying, primary and secondary reaction process is possible because the grinding media act with the catalyst material in all process steps. As secondary reactions, for example, reforming reactions, hydrogen transfer reactions or desulfurization components hydrotreating reactions to form hydrogen sulfide can be listed.

Advantageous be in the solid-solid reaction of organic solid, containing solids-like hydrocarbons, with the solid catalyst parts of the organic solid mechanically ground and split off.

When Support materials for the catalyst are all Materials in question, such as glass, steel and ceramics. When Catalyst material can be both solid acids as well as solid bases or both can be used together. Especially The preferred media is a catalytically active composite material used, which consists of a shaped body, respectively a shaped body core of a carrier material and at least one catalytically active layer which Zeolite materials or zeolite-based materials contains. In this case, the catalytically active layer on the one hand exist as a closed layer, on the other hand, but also exists the possibility that only parts of the mold core be provided with the catalytically active layer.

Of the Shaped core preferably consists of a metallic or ceramic carrier material or a mixture of in which. The molded core may also be made of glass, for example in the form of glass balls. The at least one catalytic active layer is preferably an acidic zeolite or acidic zeolite-based materials. In a variant contains the catalytically active layer next to the zeolite-based Materials include other catalyst components used to control the Secondary reactions are applied, in particular hydrotreating catalysts or reforming catalysts.

In An embodiment of the invention is the carrier material tightly formed. In a particularly advantageous embodiment However, according to the invention, the carrier material is porous, preferably macroporous, formed. The advantage of the porous Forming the carrier material is that the Carrier body or the shaped body core Having depressions, whereby the abrasion of the in the wells sitting catalyst is reduced because the catalyst in the Wells remain untouched at Mahlkörperkontakten.

• a) eine Reaktionsmischung angefertigt wird, die eine molare Zusammensetzung von a₁Na₂O:a₂K₂O:bAl₂O₃:10SiO₂:1500H₂O, wobei a₁ + a₂ = 90, a₁ = 9 oder 20 und b = 0,125 bis 3 aufweist,
• b) das unbeschichtete Trägermaterial des Formkörperkerns in die Reaktionsmischung gelegt wird,
• c) das Trägermaterial in der Reaktionsmischung evakuiert wird, so dass das Trägermaterial vollständig von Reaktionsmischung umgeben ist,
• d) in einem Kristallisationsschritt der Zeolith auf der Oberfläche des Trägermaterials synthetisiert wird und
• e) eine Produktentnahme erfolgt.

The application of the catalytically active zeolitic or zeolite-based layer consisting of zeolite types such as FAU, LTA, MFI in detail or mixtures thereof, by various methods, such as the so-called coating (dipping, slurry or spin coating), or by recrystallization on the external support surface. In a preferred embodiment, the application of the catalytically active layer by

• a) a reaction mixture is prepared which has a molar composition of a ₁ Na ₂ O: a ₂ K ₂ O: bAl ₂ O ₃ : 10SiO ₂ : 1500H ₂ O, where a ₁ + a ₂ = 90, a ₁ = 9 or 20 and b = 0.125 to 3,
• b) the uncoated carrier material of the shaped body core is placed in the reaction mixture,
• c) the carrier material is evacuated in the reaction mixture, so that the carrier material is completely surrounded by reaction mixture,
• d) in a crystallization step, the zeolite is synthesized on the surface of the support material, and
• e) a product removal takes place.

For a _1, a value in the range between 60 to 85 and for b a range from 1 to 2.5 is preferred see. Particular preference is given to a value of 70 for a ₁ and a value of 1.6 for b.

The Grinding media can be varied, for example spherical, cylindrical or oval be. Due to the formation of the catalyst as a unit of grinding media and catalyst material is possible, the catalyst advantageous to lead in the circulation. The separation of the reaction products takes place in an advantageous embodiment of the method in one Separator without additional use of substances. For controlling the primary and secondary reactions can advantageous inert or reactive gases, in particular water vapor and / or methanol and / or hydrogen.

Further Details, features and advantages of the invention will become apparent the following description of exemplary embodiments with reference to the accompanying drawings. Show it:

1 FIG. 2: a schematic representation of a rotary tube reactor with internal screw, FIG.

2 : a schematic representation of a combined reactor with drying and screening on a drive,

3 : a scheme for material separation by condensation after the reactor,

4 : a principal route to the catalytically active materials,

5 : An X-ray diffraction pattern for the crystallization of a FAU zeolite structure on ceramic moldings and

6 X-ray diffractograms for the crystallization of a templated MFI zeolite structure on glass moldings as a function of the synthesis time.

The inventive method will be described in more detail below the example of the recycling of Eocene lignite be explained without limiting the invention thereto.

Around the basic idea of the method according to the invention to clarify, should be a parallel to crude oil processing to be pulled. In the oil refurbishment was achieved that with the help of catalysts, the heavy boiling components be split (cracked) into low-boiling constituents, so that a higher yield of raw materials for the chemical industry and for fuels could. Catalytic cracking (FCC) or hydrocracking dissolved the hitherto customary method of thermal cleavage from. On the coal sector is the development of thermal cracking (Coal liquefaction) have stopped. However, it is obvious that the use of cracking catalysts to a similar Development as in petroleum cracking can lead. Although various studies have a catalytic effect at the coal gasification, but in terms of a split under Inert conditions or mild reactive conditions (under hydrogen, Methanol, but no or a small proportion of oxygen) with the aim of a material recycling are none industrially suitable results. This is due to the problem that the catalytic active substance carbon components splits, but then inactive the residual material remains, so that the contact to further fissile material is prevented. At a Process for the catalytic cracking of lignite should therefore on renewal of the carbon / catalyst interface become. The recycling of lignite and / or biomass and / or plastics, such as thermosets and thermoplastics, and / or Petrokoks and / or oil sands and / or oil shale based on catalytic cleavage and using suitable reaction or inert gases as the atmosphere is the subject of the proceedings. As just brown coal a low level of coalification and thus only one to two times condensed aromatics with has many aliphatic radicals, is a high product yield expected. Hard coal, on the other hand, which has a higher degree of coalification, is more difficult to split. The process can start from the lignite Renewable raw materials and the recycling of plastics, Petrokoksbestandteilen and / or oil sand constituents and / or oil shale constituents Here, too, material with a relatively low level of coalification (For example, HC ratio> 0.8) is present.

• a) Betrieb unter Inert- beziehungsweise Reaktionsgasbedingungen (Stickstoff, Methanol, Wasserstoff),
• b) Förderung von Feststoffen im Reaktor (kontinuierlicher Betrieb),
• c) stetige Erneuerung der Kontaktfläche Kohle/Katalysator (simultaner Mahlprozess),
• d) Zerkleinerung des Feststoffs,
• e) Abtrennung des Wassers aus dem Koks,
• f) Abtrennung der Produkte,
• g) mögliche Abtrennung Restkoks/Katalysator über ein Sieb (zum Beispiel Rollensieb am Reaktorende, gekoppelt mit dem Drehrohr) und
• h) mögliche Vortrocknung der Kohle in einem vorgelagerten Drehrohrofen ohne Katalysator, der gegebenenfalls ebenfalls an den Antrieb des Reaktors gekoppelt ist.

The operating principle is analogous to that of the catalytic cracking of petroleum. Since coal, in contrast to crude oil represents a solid, but a different, novel reactor concept must be selected. The following tasks have to be solved during the process: Pyrolysis process

• a) operation under inert or reaction gas conditions (nitrogen, methanol, hydrogen),
• b) conveying of solids in the reactor (continuous operation),
• c) continuous renewal of the contact surface coal / catalyst (simultaneous grinding process),
• d) comminution of the solid,
• e) separation of the water from the coke,
• f) separation of the products,
• g) possible separation of residual coke / catalyst via a screen (for example, roller screen at the reactor end, coupled with the rotary tube) and
• h) possible pre-drying of the coal in an upstream rotary kiln without catalyst, which is optionally also coupled to the drive of the reactor.

As a reactor that meets these conditions, on the one hand offers a fluidized bed reactor, a ball-mill reactor, a rotary kiln (with grinding balls) or a ball-and-cage reactor. The variants are characterized in terms of their additional mechanical contact and by mixing of catalyst (is applied to the balls) and coal and the easy separation of both solids. A schematic diagram of a rotary tube reactor with internal screw is in 1 sketched, with such a constructed laboratory reactor was originally developed for the recycling of electronic waste, but without a catalyst. The 2 and 3 show the process flow schematically. Via a lock, solids and spheres which are to be coated with the catalyst are continuously introduced into the reactor. Inside the reactor there may be a screw conveyor, which conveys the material in the direction of the reactor outlet. It forms a segregated system, in which the gas phase can be regarded as a flow tube and the solid phase as a stirred tank. The actual cracking process takes place on the surface of the catalyst, which is applied to the spherical surface, for example on glass beads. The advantage here is the additionally introduced mechanical energy, which leads to a renewable, intensive formation of an interface between coal / catalyst. At the reactor outlet, the solid residual product (ash, coke fractions), the catalyst spheres and reaction gases are also discharged via a lock. Favorable conditions for the separation of coke and catalyst are present in particular when the carbonaceous materials to be reacted, on the one hand, and the moldings containing the zeolite-based materials (for example catalyst spheres), on the other hand, are characterized by different size and / or density. The separation of coke / catalyst can take place with the aid of a roller screen coupled to the reactor, so that no separate drive is necessary. The catalyst balls can then be regenerated and fed back to the reactor. The system resembles a rotary kiln, as is common in the building materials industry. For coal metering and coke / ash discharge locks are used. Inert gases (possibly also reaction gases) are introduced into the lock system (flushing), so that no gases formed can escape.

Influence of the reaction gas on the pyrolysis

It is known from the literature that the reaction gas has a decisive influence on the conversion of coal. This means that - analogous to the pure pyrolysis process under an inert gas atmosphere - the influence of the reaction atmosphere on the yield of desired product has a significant influence. As possible gases, for example, steam, hydrogen, carbon monoxide and methanol can serve. Secondary reactions (such as cracking processes of the exiting volatiles, isomerizations and alkylations and so on) can contribute to a more olefinic and branched chain product spectrum (higher octane number). The lignite coal tar is thus simultaneously converted to the primary cleavage to low molecular weight higher value products. Process water reduces the deactivation (coke formation) in the reaction and, after condensation, leads to a separation of the water-soluble, the water-insoluble and the gas products. The raw material used does not have to be dried completely, which saves energy. The separation effort is reduced by the three-phase separation. The use of an external additional release agent can be omitted. The reactor can use the regeneration of the catalyst balls as energy supply (the cleavage proceeds endothermically). In this case, the coke, which is either present on and in the catalyst milling bodies, or the coke formed, which is discharged as a solid with the Katalysatormahlkörpern as a fine solid from the reactor, burned in a regenerator. Ideally, the reactor is thereby operated autothermally. A regulation in which a lot of coke is fed into the reactor according to the autothermal mode of operation is to be provided (regenerator is not shown above). Alternatively, heating can also take place via combustion of the pyrolysis gases, but also externally via natural gas and oil. Hydrocarbons in the range of C1 to C8 and coke fall as products when using bitumen-rich lignite in particular, as shown in Tables 1 and 2, wherein in Table 1, the proportions of the products used with lignite without catalyst and Table 2 in the products used lignite with catalyst are each shown under inert conditions. Table 1: Substance content of the products with lignite used without catalyst under inert conditions Fabric raw lignite Share 1 water 0.55 BTX aromatics 0.011 Phenols / Cresole <0.001 naphtha 0,003 olefins <0.001 coke 0.25 rest 0.185 Table 2: Substance share of products / brown coal used with catalyst under inert conditions Fabric raw lignite Share 1 water 0.55 BTX aromatics 0.096 Phenols / Cresole 0.0046 naphtha 0.0162 olefins 0,004 coke 0,254 rest 0.0752

The Products are produced either by the primary and secondary reactions. Furthermore, oxygen-containing compounds, such as phenols, are formed and cresols, as can be seen from Table 2. That lie water-soluble oxygenated compounds and pure Hydrocarbons and coke by-product side by side. This corresponds to a disproportionation of the coal. Will the coke used for further steps, this points through the Cracking a low residual moisture and due to the combined milling process a fine-grained structure on, so he among other things directly at the flue gas cloud gasification to syngas or to energetic use can continue to be used. A special one Workup can be omitted.

The described method thus indicates in addition to a high yield Reaction products in the catalytic conversion of solid-like Hydrocarbons have many more benefits. The process steps (Grinding, primary cracking, secondary reactions, Drying) run combined in a reactor. The reaction products can be easily separated into coarse fractions. Of the Use of expensive hydrogen (as in the coal hydrogenation after Bergius Pier) can be omitted. Separate process steps for coal processing, for gasification or Combustion can be replaced by this method, since processable pyrolysis coke is obtained. This can be an economic success through the generation of value-added products, but also by the simultaneous, incidental processing of the Coal can be generated to higher energy coke.

catalyst development

Our own investigations have shown that with the help of an acidic catalyst (analogous to the cracking of petroleum) a lower decomposition temperature can be achieved. The cracking catalysts must be matched in terms of their catalyst properties to the corresponding lignite and / or biomass and / or the corresponding plastics (such as thermosets and thermoplastics) and / or Petrokoks and / or oil sands and / or oil shale. As already explained in connection with the pyrolysis process, the catalyst must be separated from the residual coal or the solid residues. For this purpose, it is recommended that the catalyst is applied to balls or grinding media, which can then be regenerated at the end of the reactor and fed back into the reactor (ball circulation). In addition to the acidic and / or basic groups, the catalyst may also be catalyzing metals and / or metal oxides or other catalytically active substances. The pore geometry, morphology and element distribution in the catalyst layer and the crystallites can be adjusted according to needs. Suitable catalyst support materials are all materials (for example glass, steel, ceramics). The boundary condition is that they are resistant to a temperature greater than 350 ° C under water during regeneration. A multilayer application of different layers with different properties on the carrier material can take place (primary layer, catalyst layer 1, catalyst layer 2 and so on). In addition to spherical supports, other shapes may also be used, for example cylinders, ovals and so on. The ball size should be adapted to the reactor type (rotary kiln with grinding media about 0.1 to 15 centimeters, ball mill reactor about 0.1 to 10 millimeters, fluidized bed reactor 0.05 to 0.15 millimeters). The carrier bodies may have depressions (0-50%, preferably 1-20% of the carrier body diameter), so that the abrasion is reduced since the catalyst in the depressions remains untouched by ball contacts (golf ball).

Particularly suitable as grinding media are the catalytically active spherical bodies described below, which are also suitable, inter alia, for the reaction of solid materials. Usually, in heterogeneous catalysis, materials are used in which catalysts and reacting media are in different phases, for example when the catalyst is solid and the reactants are in a fluid phase, usually as a gas. Thus, zeolites are also used as solid materials both as acidic or basic catalysts in many reactions. These zeolites have active sites attached to the aluminum of the zeolite network. Zeolites consist of a microporous framework structure composed of AlO ₄ and SiO ₄ tetrahedra. The aluminum and silicon atoms are connected to one another via oxygen atoms. Depending on the type of structure, this results in a structure of uniform pores and / or channels in which substances can be adsorbed / catalyzed. These centers are mostly occupied by a sodium ion after the hydrothermal synthesis of the zeolite. The sodium is later exchanged, for example, with ammonium, which is subsequently removed by calcining to form Lewis and Brönsted acids, which in turn can be exchanged with other cations, especially those having catalytic effects. The zeolites usually form in the synthesis as finely crystalline powders, which can be used neither in gas / solid nor in solid / solid reactions, since high pressure losses or separation of the catalyst from the reactants is difficult. In order to avoid high pressure loss in a catalyst layer during adsorption / catalysis steps, the zeolites are transformed by shaping processes into larger geometric body pellets, strands and monoliths. However, in order to be used in solid / solid reactions, the zeolites must have sufficient strength. Desirable with respect to the present invention would also be other properties, such as a milling or mixing action, that could promote a solid / solid reaction. As an embodiment of the present invention, a material is provided, which can take over both the catalytic function by the special arrangement and the combination of the catalyst with a suitable carrier, is easily separable and still has a supporting function for the grinding and mixing effect of the reactants , The products can also be produced as gas or liquid. Examples of such shaped bodies would be acidic zeolites or acidic zeolitic materials on ceramic or metallic moldings or mixtures thereof, which may be dense or porous, preferably macroporous. The application can be carried out by various methods, such as the so-called coating (dipping, slurry or spin-coating), or by recrystallization on the external surface.

The scheme in 4 indicates the principal route to the catalytically active materials. This will be explained in more detail below with reference to an example:
The composite materials consisting of ceramic support bodies with FAU zeolite (type X and / or type Y) and / or zeolite type A and / or type P layer are prepared by reacting a reaction mixture having the molar composition generally of aMe ₂ O: bAl ₂ O ₃ : cSiO ₂ : dH ₂ O where "Me" represents alkali metal cations, preferably sodium and / or potassium, and wherein
a is a number in the range of 0.8 to 150,
b is a number in the range of 0.125 to 3,
c is a number in the range of 1.3 to 20 and
d is a number in the range of 0 to 3000.

The preferred ranges of the molar composition are for a general notation: a ₁ Na ₂ O: a ₂ K ₂ O: bAl ₂ O ₃ : cSiO ₂ : dH ₂ O listed.

From the raw materials, a reaction mixture is prepared and the uncoated ceramic carrier body are then immersed in the solution. The chemicals for the reaction mixture are sodium silicate, sodium hydroxide and potassium hydroxide, as well as water. Table 3 shows the ranges of the reaction mixture composition for a general notation:
a ₁ Na ₂ O: a ₂ K ₂ O: bAl ₂ O ₃ : cSiO ₂ : dH ₂ O: Table 3: Areas of the Reaction Mixture Composition Area far closely prefers example a ₁ plus a ₂ 0.8 to 150 10-150 50-120 90 a ₁ 0.4-100 5-100 40-80 70 a ₂ 0.4-50 5-50 10-40 20 b 0.125 to 3 0.5-2.5 1-2 1.6 c 1.3-20 3-18 5-12 10 d 0-3000 10-2000 100-1800 1500

With a weight of one gram of support material to 26.8 grams of reaction mixture, the composites are placed in the solution and evacuated for 15 minutes so that the material is completely surrounded by solution. Subsequently, in a sealed Teflon vessel at 80 ° C for 80 hours, a zeolite FAU structure (faujasite) is synthesized directly on the surface of the foamed body. In 5 An X-ray diffractogram showing the successful coating of aluminum-containing ceramics with a faujasitic layer can be seen. Here, an Al-SiC-containing mixture was used. With this method, substrates of almost any geometry can be coated. It has been achieved a mass increase of approximately 30 percent zeolite on the foams. In the special case, the zeolites were crystallized on spherical supports. In this case, zeolite layers were prepared on Si-containing support materials and the crystallized FAU structures on aluminum-containing support materials.

• a) eine Reaktionsmischung angefertigt wird, die eine molare Zusammensetzung von a₁Na₂O:a₂K₂O:bAl₂O₃:cSiO₂:dH₂O hat, wobei a₁ = 70; a₂ = 20; b = 1,6; c = 10 und d = 1500 ist,
• b) das unbeschichtete Trägermaterial des Formkörperkerns in die Reaktionsmischung gelegt wird,
• c) das Trägermaterial in der Reaktionsmischung evakuiert wird, so dass das Trägermaterial vollständig von Reaktionsmischung umgeben ist,
• d) in einem Kristallisationsschritt der Zeolith auf der Oberfläche des Trägermaterials synthetisiert wird und
• e) eine Produktentnahme erfolgt.

In a preferred embodiment, the application of the catalytically active layer by

• a) a reaction mixture is prepared which has a molar composition of a ₁ Na ₂ O: a ₂ K ₂ O: bAl ₂ O ₃ : cSiO ₂ : dH ₂ O, where a ₁ = 70; a ₂ = 20; b = 1.6; c = 10 and d = 1500,
• b) the uncoated carrier material of the shaped body core is placed in the reaction mixture,
• c) the carrier material is evacuated in the reaction mixture, so that the carrier material is completely surrounded by reaction mixture,
• d) in a crystallization step, the zeolite is synthesized on the surface of the support material, and
• e) a product removal takes place.

For a _1, a value in the range between 60 to 85 and for b a range from 1 to 2.5 is preferably provided. Particular preference is given to a value of 70 for a ₁ and a value of 1.6 for b. X-ray diffractograms in 5 show an example of the crystallization of a FAU zeolite structure on ceramic moldings. The three graphs show a) the FAU coating with crystallized material on ceramic after 80 hours of synthesis time; b) a comparative diffractogram of the uncoated ceramic (Al / SiC material) and c) a standard zeolite 13X comparative diffractogram.

Another embodiment relates to a catalytically active, templathaltige zeolite layer. This further preferred embodiment is carried out by applying a catalytic layer in the presence of a structure director, Structure Directing Agent (SDA), which is largely responsible for the formation of the pores. The synthesis mixture used has the following composition:
uNa ₂ O: vB ₂ O ₃ : wAl ₂ O ₃ : xSiO ₂ : ySDA: zH ₂ O, where
u is a number in the range 0-100,
v is a number in the range 0-10,
w is a number in the range 0-100,
x a number in the range 0-100,
y is a number in the range 0-10 ⁶ and
z is a number in the range 0.1-10 ⁸ ,
wherein the molar regions of the starting materials are given in Table 4 and a structure director (SDA) represents the type of template, preferably tetrapropylammonium hydroxide (TPAOH) and / or tetrapropylammonium bromide (TPABr) and / or tetraethylammonium hydroxide (TEAOH) or another SDA according to the desired structure types.

Table 4 shows the preferred ranges of reaction mixture composition: TABLE 4 Regions of reaction mixture composition Area far closely prefers example u 0-100 5-80 7-50 9 v 0-10 1-9 2-7 4 w 0-100 0.2 to 70 0.7 to 30 1 x 0-100 20-90 40-80 72 y 0-10 ⁵ 20-10 ³ 80-500 117 z 0.1-10 ⁶ 100-10 ⁵ 1000-10 ⁴ 2726

• a) eine Reaktionsmischung angefertigt wird, die eine molare Zusammensetzung von uNa₂O:vB₂O₃:wAl₂O₃:xSiO₂:ySDA:zH₂O mit u = 9; v = 4; w = 1; x = 72; y = 117; z = 2726 ist,
• b) die Synthesemischung mit 0–100 Umdrehungen pro Minunte gerührt wird, die Alterungszeit beträgt 0–48 Stunden, vorzugsweise 24 Stunden,
• c) das Trägermaterial des Formkörperkerns in die Reaktionsmischung gelegt wird,
• d) das Trägermaterial in der Reaktionsmischung evakuiert wird, so dass das Trägermaterial vollständig von Reaktionsmischung umgeben ist,
• e) in einem Kristallisationsschritt der Zeolith auf der Oberfläche des Trägermaterials synthetisiert wird und
• f) eine Produktentnahme erfolgt.

In a preferred embodiment, the application of the catalytically active layer by

• a) is made a reaction mixture containing a molar composition of uNa ₂ O: vB ₂ O _3: WAl ₂ O _3: xSiO _2: ySDA: zH ₂ O with u = 9; v = 4; w = 1; x = 72; y = 117; z = 2726,
• b) the synthesis mixture is stirred at 0-100 revolutions per minute, the aging time is 0-48 hours, preferably 24 hours,
• c) the carrier material of the shaped body core is placed in the reaction mixture,
• d) the carrier material is evacuated in the reaction mixture, so that the carrier material is completely surrounded by the reaction mixture,
• e) in a crystallization step, the zeolite is synthesized on the surface of the support material and
• f) a product removal takes place.

Crystallization procedure:

The Synthesis time is 30 minutes to one month (744 hours), preferably 12 to 200 hours, the temperature is: 25-250 ° C, preferably 100-200 ° C. During the crystallization takes a rotation or stirring of the autoclave instead (continuously or stepwise) at 0-1000 Revolutions per minute, preferably 0-20 revolutions per minute Minute.

The diffractograms in 6 show an example of the crystallization of a templated MFI zeolite structure on glass moldings as a function of the synthesis time. The three graphs show crystallinity after 24 hours, 36 hours and 61 hours of synthesis time.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• DE 10049377 A1 [0003]

Claims (12)

Process for the catalytic conversion of solid-like hydrocarbons, in which the solid-like hydrocarbons undergo a grinding, drying, primary and / or secondary reaction process, characterized in that as a grinding body there are provided shaped bodies with a carrier material forming a shaped body core, on which catalyst material is applied, and the solid-state hydrocarbons to be reacted and the catalytically active material which is in the form of the shaped bodies are brought into contact with each other, and that the milling, drying, primary and secondary reaction processes are carried out simultaneously by simultaneously drying and milling the solid , a solid-solid reaction of organic solid and solid catalyst takes place and leaving gaseous or liquid products are further split and / or converted in secondary reactions on the catalyst surface. Method according to claim 1, characterized in that that in the solid-solid reaction of organic solid solid-state hydrocarbons with solid catalyst parts of the organic solid are split off. Method according to claim 1 or 2, characterized that as the catalyst material, a solid acid and / or Solid Base is used. Method according to one of claims 1 to 3, characterized in that as a grinding body catalytically active Composite material is used, which consists of a molding each consists of a shaped body core of a carrier material and at least one catalytically active layer which Contains zeolite-based materials, whereby solid-like Hydrocarbons can be split. Method according to claim 4, characterized in that that the shaped body core of glass or a metallic or ceramic carrier material or a mixture of consists of both. Method according to claim 4 or 5, characterized that the at least one catalytically active layer of an acidic Zeolite or acidic zeolite-based materials. Method according to claim 4 or 5, characterized that additional catalyst components for controlling the secondary reactions are applied, in particular hydrotreating catalysts or reforming catalysts. Method according to one of claims 1 to 7, characterized in that the carrier material recesses having. Method according to one of claims 1 to 8, characterized in that the grinding bodies spherical, cylindrical or are formed as ovals. Method according to one of claims 1 to 9, characterized in that the catalyst is recycled becomes. Method according to one of claims 1 to 10, characterized in that the separation of the reaction products in a separator without additional use of substances he follows. Method according to one of claims 1 to 11, characterized in that for controlling the primary and secondary reactions inert or reactive gases, in particular Water vapor and / or methanol and / or hydrogen can be used.

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