Catalyst system in form of supported catalyst

Abstract

To provide a catalyst system or a supported catalyst with at least one catalytically active component, and a corresponding production method.SOLUTION: A catalyst system comprises at least one catalytically active component fixed to a catalyst support. The catalytically active component comprises at least one specific metal. Spherical activated carbon forming a catalyst support has a total pore volume and a specific BET surface area in specific ranges. The catalyst system has activity in a specific range, and comprises at least one catalytically active component with an average crystallite size in a specific range.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the technical field of catalytically active systems, or catalysts or catalytically active components applied to a support material, and therefore in particular to the technical field of supported catalysts, such as can be used in particular for heterogeneous system catalysis.

[0002] In particular, the present invention relates to a method for preparing a catalyst system comprising at least one catalytically active component, especially a supported catalyst.

[0003] Furthermore, the present invention relates to a catalyst system obtainable on the basis of the method according to the invention, and further to such a catalyst system comprising at least one catalytically active component applied to a catalyst support, in particular at least one catalytically active component fixed to a catalyst support.

[0004] The present invention also relates to the use of the catalyst system according to the invention as a catalyst or as a catalyst support. Furthermore, the present invention also relates to the use of the catalyst system according to the invention for chemical catalysis. Furthermore, the present invention also relates to the use of the catalyst system according to the invention for catalysis of chemical processes and reactions, such as hydrogenation reactions.

[0005] The present invention also relates to the use of the catalyst system according to the invention for the manufacture of filters and filter materials, as adsorption storage for gases or liquids, and in or as a gas sensor or in a fuel cell. The present invention also relates to the use of the catalyst system according to the invention for gas purification or gas treatment, as well as for the removal of pollutants or of substances or gases that are harmful to the environment, health or toxicity. The present invention also relates to the use of the catalyst system according to the invention for the preparation or provision of a clean room atmosphere or the like.

[0006] The present invention also relates to protective materials produced with or comprising the catalyst system according to the invention.The present invention further relates to filters and filter materials produced with or comprising the catalyst system according to the invention. [Background technology]

[0007] A catalyst is generally understood to be a material or substance that can increase the rate of a chemical reaction by lowering the activation energy without being consumed itself.

[0008] In the prior art, catalysts are of great technological and commercial importance in important catalytic processes, such as the catalytic process for the production of sulfuric acid, the catalytic process for the production of methanol, the Haber-Bosch process for the industrial production of ammonia, and the Ostwald process for the large-scale production of nitric acid by oxidation of ammonia. Catalysts are also used in the synthesis of natural products and specialty chemicals, in the synthesis of active pharmaceutical ingredients, and in catalytic hydrogenation. In particular, catalysts are used in catalytic hydrogenation processes.

[0009] Against this background, there is also a high technological demand for specific and efficient catalysts for use in chemical catalysis, particularly since the targeted use of catalysts allows chemical reactions to be carried out quickly or with less energy. In this regard, the use of catalysts in chemical reactions has great commercial importance; for example, about 80% of all chemical products have a catalytic step in their potential production or value chain. Furthermore, catalysts also play an important role in the field of environmental protection, in particular for the treatment of exhaust gases from the (passenger) motor transport sector as well as for the after-treatment of exhaust gases in industries such as industrial power production.

[0010] In principle, the catalysts can be used in the form of homogeneous or heterogeneous catalysts, whereby in the case of homogeneous catalysts or catalysts used in homogeneous catalysts, the reactants or reactants on which the reaction to be catalyzed is based, on the one hand, and the catalyst, on the other hand, are present in the same phase, whereas in the case of heterogeneous catalysts or catalysts used in heterogeneous catalysts, the reactants to be reacted, on the other hand, are present in different phases, for example as a solid relative to the catalyst and as a liquid or gas relative to the reactants.

[0011] In principle, the advantages associated with the use of heterogeneous catalysts lie in the fact that they allow for improved separation or isolation of the catalyst from the reaction mixture, as well as the fundamental possibility of recycling the used catalyst and treating deactivated or inactive catalysts. In particular in industrial processes, heterogeneous catalysts are present as solids or as so-called contacts (catalysts), while the reaction partners or reactants are used in gaseous or liquid form. For example, the above-mentioned industrially established processes are processes in which the catalysts are used as solids.

[0012] For heterogeneous or solid catalysts, metals or metal-containing compounds, such as metal salts or metal oxides, are often used as catalysts. Such catalysts are used, for example, in bulk or in a form in which the catalyst or the underlying catalytically active component is present on, or bound or fixed to, a support system. Such catalyst systems in which the catalytically active component is on a carrier are commonly referred to as supported catalysts.

[0013] The use of supported catalysts is associated with the fundamental advantage of being able to react over a larger surface or larger contact area, which generally translates into increased efficiency or reduced catalyst usage, with associated cost advantages.

[0014] Furthermore, the use of supported systems or supported catalysts is generally associated with the advantage that the underlying catalyst can be better removed or separated from the reaction medium and is generally easier to reuse, especially in the case of catalysts used in large quantities or in the same phase as the reactants, where separation after the reaction or conversion of the reactants is difficult or involves high losses of catalyst mass, which generally leads to poor economic efficiency and makes the recycling of the used catalyst fundamentally difficult.

[0015] For supported catalyst systems or supported catalysts, the state of the art generally considers the use of compact or porous support structures. The use of so-called compact catalysts is associated with the drawback, in particular, that efficient surface enlargement cannot be achieved, resulting in catalytic activity only on a relatively small geometric surface. In contrast, porous solids used as catalyst supports have a large surface (interior), which, as mentioned above, increases efficiency and allows for high catalytic activity even with a small amount of active component (catalytically active metal, such as a noble metal).

[0016] For example, crystalline porous solids of the zeolite system have been used as catalyst supports, particularly in the fields of petrochemicals and refining for processing or upgrading crude oil and petroleum. Zeolites generally have uniform pore sizes, allowing for some degree of selective reaction control by size matching with the reactants. Furthermore, the use of silica, molecular sieves, metal oxides such as aluminum oxide, ceramics, activated carbon, and the like as catalyst supports is generally known in the prior art.

[0017] In principle, such support systems are also used in order to reduce the associated losses during application, particularly in the context of allowing a permanent or elution-stable fixation of costly catalysts, or, as mentioned above, to allow corresponding recyclability or recovery of the catalyst system as a whole.

[0018] In the prior art, activated carbon is typically used as a catalyst support material, particularly to obtain so-called activated carbon-supported catalysts, especially activated carbon-supported precious metal catalysts. The corresponding activated carbon is typically used in finely divided form (powdered carbon) or in the form of a finely ground powder, with particle sizes in the low μm range. The use of finely divided activated carbon as a support system generally aims to reduce the fundamental mass transfer limitations for the catalyzed target reaction by shortening the diffusion or permeation distance, particularly into the pore structure of activated carbon-based support materials. However, the use of small-particle-sized, finely divided activated carbon as a catalyst support has the central drawback of not achieving optimal overall application properties. For example, the use of finely divided activated carbon, especially in discontinuous applications, can lead to performance degradation, e.g., during separation of the catalyst or catalyst system after use, due to low porosity of the filter cake or high density of the substrate. In this regard, it is also emphasized that separation or filtration of the catalyst or catalyst system is an essential or essential process step for discontinuous catalytic processes.

[0019] Additionally, such activated carbons often have pore systems that are not optimally designed for catalyst binding and reactant and product transport, which can compromise overall catalytic performance.

[0020] Under certain operating conditions, particularly in continuous catalytic processes (i.e., catalytic reaction processes) using powdered activated carbon or pulverized coal in the reaction chamber, high pressure losses can occur due to excessive compression of the catalytic system. This is often accompanied by a reduction in the flow rate of the reaction mixture containing the corresponding reactants fed to the catalytic system. Excessive compression can also occur if the abrasion hardness of the catalyst or corresponding support material used is too low.

[0021] Furthermore, the application characteristics of activated carbon supported catalyst systems are often suboptimal in that finely divided catalyst systems, especially in the liquid medium containing the reactants, tend to form sludge and excessive compaction, with the risk of clogging the reactor and excessive reduction in flow rate or filtration rate, to the detriment of the overall catalytic conversion. Excessive compaction of the catalyst system can also create "dead zones" in the underlying equipment and can significantly reduce the conversion of the reactants.

[0022] In this regard, the formation of sludge-like regions is particularly relevant in discontinuous applications. In continuous catalyst applications, for example, a catalyst system is loaded into a corresponding reaction chamber, such as one based on a cartridge system, followed by a particularly continuous flow of reactants or reactant-containing media, but the correspondingly low flow rates of the catalyst system also result in high pressure losses. Furthermore, complex filtration and retention devices that are prone to clogging are often required to prevent the catalyst from being expelled or washed out of continuously flowing reaction systems.

[0023] As a result, catalyst systems using powdered or finely divided activated carbon as a support material do not necessarily have sufficient or satisfactory overall properties for their intended use.

[0024] To reduce the drawbacks associated with small particle sizes, the prior art has attempted to use catalyst supports based on granular activated carbon, whereby activated carbon starting materials based on coconut shells, charcoal, and wood (e.g., sawdust, peat, hard coal, etc.) are considered fundamental. These activated carbons used as catalyst supports can generally be in the form of splinters or grains, which, in principle, offer certain improvements in application characteristics, especially in terms of separation time in discontinuous applications. However, these activated carbons used as catalyst supports often have too low mechanical stability, which is accompanied by high attrition of the support under application conditions, such as sometimes violent agitation methods during catalytic conversion. The low attrition resistance of such activated carbons leads to finely divided particles through the corresponding crushing or grinding methods, resulting in high losses of catalytically active material and the aforementioned disadvantages regarding sedimentation or compaction of the system. Furthermore, such activated carbons often do not have an optimally formed pore system.

[0025] Furthermore, the known concepts of the prior art for providing catalyst systems based on activated carbon as a support material also often have the disadvantage that the catalyst cannot be optimally supported or fixed on the support material, which, on the one hand, results in a low amount of catalyst being applied to the support, and, on the other hand, often leads to release or leaching of the catalyst from the support material under the application conditions, which, on the other hand, often results in release or leaching of the catalyst from the support material under the application conditions, and which can lead to losses of washed-out catalyst amounts, which is disadvantageous from the point of view of process engineering and at least for cost reasons.

[0026] In particular, the activated carbons used in the prior art, such as coconut shell-based activated carbons, often have a low affinity for the applied or immobilized catalysts, due to the fact that - without wishing to be limited to this theory - the underlying activated carbon is often hydrophobic at its pore surface or often does not have a sufficient amount of, especially polar, functional groups to bind the catalyst (this is particularly the case with polymer-based activated carbons, especially PBSAC). However, this is disadvantageous for the overall loading and installation of the catalyst, as well as for the permanent immobilization of the catalyst on the support system. High catalyst losses in the underlying catalytic system are also accompanied by a decrease in the conversion of the reactants in the underlying catalytic reaction, which reduces the economic viability of the used catalytic system.

[0027] Conventional activated carbon has a nonpolar or hydrophobic surface, which does not provide a significant affinity for coating or immobilizing catalysts or catalytically active components used in activated carbon reactors or catalytic devices. Therefore, to ensure a consistent loading on the activated carbon, a large excess of catalyst material must be used during the production or installation of the activated carbon. To ensure a consistent loading on the activated carbon, a large excess of catalyst material must be used during the activated carbon production process or catalyst installation process, or surface centers (centers for attachment of catalytically active components) must be created in advance. In particular, because catalysts are generally attached purely through physical interactions, they can be at least partially removed or washed again (e.g., by leaching, etc.), especially when they come into contact with liquids.

[0028] In principle, with regard to heterogeneous catalyst systems using activated carbon as a support material according to the concepts known in the prior art, there are also disadvantages, particularly as a result of an inoptimal formation of the pore system of the support material, in particular with regard to the underlying pore size and their distribution, or rather their proportion in the total pore volume, that the transport or diffusion processes of the reactants or products are not optimal, which can result, for example, in an inoptimal transport of the reactants to the underlying catalyst centers or an inoptimal removal of the resulting products from the catalyst system, which is associated with a lower conversion rate and an inoptimal space / time yield.

[0029] In this regard, a heterogeneous catalytic reaction using a porous structure such as activated carbon as a catalyst support can be essentially divided into seven sub-stages, each of which can determine the rate, including the corresponding transfer stage of reactants or products. In this regard, reference can also be made to Figure 4 and the related discussion below.

[0030] If the pore system of the support material is not optimally formed, the transport avenues within the system will be insufficient, limiting overall catalytic activity and resulting in poor long-term conversion and space / time yield.

[0031] Furthermore, the conversion rate or space / time yield may also be reduced if such catalytically active centers are not optimally formed or if the support material is insufficiently provided with catalytically active components, which in this respect may also be caused by a pore system of the catalyst support that is not optimally formed.

[0032] Furthermore, catalyst systems known from the prior art can have the drawback of producing high pressure losses during application, especially in fixed beds, and can often result in high levels of dust formation with associated material losses, especially as a result of the underlying catalyst system not always being sufficiently hard or wear-resistant.

[0033] DE 29 36 362 C2 relates to a method for producing a palladium-carbon catalyst, in which palladium is reductively deposited on carbon suspended in an organic solvent as a catalyst support. In this context, it is assumed that palladium is deposited as metal on a floating support. Powdered activated carbon, carbon black, or graphite is used as the carbon support. However, the described catalyst may have the above-mentioned disadvantages in terms of its application characteristics in continuous catalytic processes, particularly in terms of pressure loss or flow rate, especially with regard to catalyst separation or recovery in discontinuous catalytic processes.

[0034] In summary, it can be said that the catalyst systems known in the prior art based on conventional activated carbon or powdered activated carbon as the support material used have production- and application-specific disadvantages, in particular with regard to the loading with catalytically active components and their fixation on the material, on the one hand, and with regard to the use of the basic system in continuous and discontinuous catalysis, on the other hand. [Prior art documents] [Patent documents]

[0035] [Patent Document 1] DE 29 36 362 C2 Summary of the Invention [Problem to be solved by the invention]

[0036] Against this background, it is an object of the present invention to provide a catalyst system or supported catalyst having at least one catalytically active component, and a corresponding method for preparing the same, which at least largely avoids or reduces the above-mentioned disadvantages of the prior art.

[0037] In particular, the present invention aims to provide a catalyst system having at least one catalytically active component or a supported catalyst having at least one catalytically active component, which catalyst system or catalyst has production-specific and application-specific advantages. In this respect, a corresponding method for producing the catalyst system is also provided.

[0038] The objective underlying the present invention can be found in particular in the fact that within the scope of the present invention, an overall high performance catalyst system is provided, which, due to its high durability or stability, allows for high conversions and associated high space / time yields, while at the same time giving high recyclability and stability of the system provided.

[0039] In particular, the present invention provides a catalyst system that allows high or efficient loading with catalytic or catalytically active components while ensuring permanent and consistent loading or loading with the catalytic components.

[0040] Furthermore, according to the present invention, within its scope of application, in particular in chemical catalysis, preferably on an industrial scale, in both discontinuous and continuous catalytic applications, such catalyst systems should also be provided that have improved properties, particularly with regard to their catalytic performance and the separation, recovery or recycling system (particularly in discontinuous processes), and also with regard to ensuring low or adjustable pressure loss and high or adjustable flow rates (particularly in discontinuous processes). It should also be provided that chemical catalysts, preferably on an industrial scale, have improved properties, particularly with regard to their catalytic performance and the separation, recovery or recycling system (particularly in discontinuous processes), and also with regard to ensuring low or adjustable pressure loss and high or adjustable flow rates (particularly in continuous catalytic processes), thereby optimizing the overall process time or increasing the catalytic activity.

[0041] In particular, the present invention also seeks to provide such a catalyst system which, in addition to a high catalytic activity, also has good mechanical properties, in particular with regard to the attrition resistance or burst pressure of the underlying particulate structure.

[0042] Likewise, it may be desirable for the system according to the invention to be custom-made or individually designed or equipped for each application or use.

[0043] Furthermore, the present invention aims to provide an efficient method by which the catalyst system according to the invention having at least one catalytically active component can be obtained. [Means for solving the problem]

[0044] The applicant has discovered in a completely unexpected way that the stated problem underlying the present invention can be solved in an unexpected way by providing within the scope of the present invention a special process for the preparation of a special catalyst system and, as such, the corresponding catalyst system.

[0045] In this regard, according to the present invention, activated carbons having a specially designed pore system, i.e., a high proportion of mesopores and macropores in the total pore volume of the activated carbon, in addition to a granular or spherical design or shape, are used as catalyst supports, so that according to the present invention, activated carbons having a high proportion of mesopores and macropores (and at the same time having a defined proportion of micropores) are used. Furthermore, the activated carbons used according to the present invention have a specific BET surface area and, at the same time, a special ratio of the total pore volume to the specific BET surface area.

[0046] Furthermore, in the method according to the invention, the targeted oxidation, in particular the surface oxidation (i.e. also in particular the oxidation of the inner surface of the catalyst support), of the activated carbon subsequently used as a catalyst support is intended or aimed at adjusting a specific oxygen content, in particular the surface oxygen content, and with the formation of a specific hydrophilicity, such specific activated carbon then being provided with catalytically active components or precursors thereof, which are then reduced to obtain the catalyst system according to the invention.

[0047] In other words, the present invention provides a special catalytic system or supported catalyst having at least one catalytically active component applied to a catalyst support, the catalyst support being in the form of a very specially formed granular or spherical activated carbon with a special porosity, particularly with respect to the formation of high mesopores and macropores (i.e., a high proportion of mesopores and macropores in the total pore volume, with a simultaneously defined proportion of micropores), and the application of the catalytically active component to the activated carbon is carried out in the oxidized form of the activated carbon (i.e., oxidized activated carbon), and then, in this embodiment, by further reduction of the base system (i.e., active centers or active components), the catalytic system according to the present invention is obtained. In addition to high mesoporosity and macroporosity, the activated carbon used as the catalyst support generally exhibits a limited microporosity (i.e., a limited proportion of micropores in the total pore volume), sufficient for the catalytic reaction, although to a degree subordinate to the mesoporosity and macroporosity.

[0048] Surprisingly, the catalyst system or supported catalyst according to the present invention exhibits excellent catalytic properties due to the improved transport or diffusion properties of reactants or products and the improved loading with catalytically active components resulting from the special pore system, providing catalysts based thereon with high catalytic conversion rates and high space / time yields when used in catalytic processes. In this respect, the catalyst system according to the present invention also exhibits a high degree of dispersion of the catalytically active components and an optimized crystallite size, which can be used as a parameter or measure of catalytic performance.

[0049] The catalyst system provided according to the present invention is also particularly suitable for use in the field of chemical catalysis, in particular on a (large) industrial scale. Furthermore, the catalyst system according to the present invention is particularly suitable for corresponding filter applications, for example, for removing pollutants or harmful substances from media containing these substances. In particular, the catalyst system according to the present invention is particularly suitable for use in protective materials, in particular for civil or military applications, in particular for NBCs.

[0050] In particular, due to the spherical design or shape, the excellent mechanical properties of the catalyst support and the controllably or specifically designed meso- and macroporosity (with simultaneously defined microporosity), the catalyst system according to the invention is also of great importance, in particular for continuous catalysts, whereby the drawbacks of the prior art are overcome also with respect to discontinuous catalysts, such as those associated with conventional powder catalysts, as explained above.

[0051] In order to achieve the above-mentioned object, the present invention proposes, according to a first aspect thereof, a method according to the invention for producing a catalyst system having at least one catalytically active component according to the invention as defined in claim 1. Furthermore, particularly advantageous embodiments of the method according to the invention are the subject matter of the associated dependent method claims.

[0052] A further object of the present invention, according to a second aspect thereof, is a catalyst system according to the invention or a supported catalyst according to the invention, which comprises at least one catalytically active component, and in which special granular activated carbon is used as a catalyst support in accordance with the independent claims related thereto and in relation to the catalyst system of the invention.Further, particularly advantageous embodiments of the catalyst system according to the invention are the subject of the dependent claims related thereto and in relation thereto.

[0053] Furthermore, a further subject of the invention, according to a third aspect thereof, is the use according to the invention, which is described in the respective independent use claims.

[0054] Furthermore, a further subject of the present invention is, according to a fourth aspect thereof, a protective material according to the invention, in particular for the civil or military sector, in particular for protective clothing, in accordance with the associated independent claim.

[0055] Furthermore, further subject matter of the present invention, according to a fifth aspect thereof, are filters and filter materials, in particular for removing all kinds of pollutants, odors and harmful substances, according to the related independent claims. Furthermore, particularly advantageous embodiments of the filters and filter materials according to the invention are the subject matter of the related dependent claims.

[0056] It goes without saying that in the following description of the present invention, in order to avoid unnecessary repetition, such embodiments, advantages, examples, etc. described only with respect to one aspect of the present invention naturally apply mutatis mutandis to the remaining aspects of the present invention without the need to explicitly mention them.

[0057] Furthermore, in the following description, the relevant descriptions of values, numbers and ranges are not to be understood as limiting, and it goes without saying that those skilled in the art can deviate from the described ranges or descriptions depending on the particular case or application without departing from the scope of the present invention.

[0058] Furthermore, it is applicable that all values, parameters, etc. described below can basically be determined by standardized or clearly defined determination methods, or determination or measurement methods well known to experts in this field.

[0059] Furthermore, it should be noted that in the case of all relative or proportionate, in particular weight-related, quantitative data listed below, these data must be selected or combined by the skilled artisan within the scope of the present invention in such a way that, as a whole, if necessary, in particular including further components or ingredients as defined below, a result of 100% or 100% by weight is always obtained, although this will be obvious to the skilled artisan.

[0060] The present invention will now be described in more detail.

[0061] Thus, according to a first aspect, the present invention relates to a method for preparing a catalyst system having at least one catalytically active component, in particular a supported catalyst, preferably for use in heterogeneous systems catalysis, at least one catalytically active component is applied and / or fixed to a catalyst support, said catalytically active component comprising and / or consisting of at least one metal, The method comprises the following steps, in sequence (a) to (d) identified below: (a) in the provision and / or production of granular, preferably spherical, activated carbon (=initial activated carbon) to be used as a catalyst support, The activated carbon (so-called initial activated carbon) (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Gurvich, in particular at least 50% of the total pore volume of the activated carbon, in particular the total pore volume according to Gurvich, is formed by pores with a pore diameter of at least 2 nm, in particular by pores with a pore diameter in the range of 2 nm to 500 nm, preferably by meso- and macropores, and (ii) 1,000 m 2 / g~3,000m 2 / g BET ), where the total pore volume (V total ), especially the specific BET surface area of ​​the total pore volume according to Goulwich (S BET ) ratio (quotient; Q), especially Q=V total / S BET but at least 0.5 × 10 -9 Provided that m; after that, (b) oxidation, in particular surface oxidation, of the activated carbon prepared and / or produced in process step (a), provided that the oxidized, in particular surface-oxidized activated carbon has an oxygen content of at least 4% (atomic %) based on the total elemental composition of the oxidized activated carbon, in particular a surface oxygen content measured by X-ray photoelectron spectroscopy (XPS or ESCA), and / or that the oxidized, in particular surface-oxidized activated carbon has hydrophilicity measured as water vapor adsorption behavior, whereby at least 30% of the maximum water vapor saturation load of the activated carbon reaches a partial pressure p / p of 0.60; after that, (c) fitting, in particular loading and / or coating and / or impregnation, of the activated carbon oxidized in process step (b), in particular surface-oxidized, with a catalytically active component, in particular with at least one precursor of a catalytically active component; after that, (d) Reduction of the activated carbon obtained in process step (c) with a catalytically active component, in particular a surface-oxidized activated carbon, in order to transfer a precursor of the catalytically active component to the catalytically active component (i.e., on the one hand, surface reduction of the activated carbon, in particular previously oxidized, and / or, on the other hand, reduction of the catalytically active component or a precursor thereof, preferably of a metal or metal compound containing the catalytically active component), in particular to obtain a catalytic system with at least one catalytically active component, in particular a supported catalyst.

[0062] The basic idea of ​​the present invention is thus to be found in the fact that, as described above, a very specific activated carbon is used as a catalyst support for housing or equipping catalytically active components. The invention relates to an activated carbon that is, on the one hand, in granular or spherical form and, on the other hand, has a defined porosity in terms of particularly high mesoporosity and macroporosity, and at the same time has a defined proportion of micropores (i.e., subordinate to the mesoporosity and macroporosity, but sufficient for catalytic action), and, moreover, is subjected to an oxidative treatment or surface oxidation of the activated carbon in a specific manner before being fitted with the catalytically active components. In this regard, the applicant has surprisingly discovered that the use of an activated carbon with a defined porosity as described above provides an overall improved catalytic property of the resulting catalyst system, in particular in terms of a high conversion with simultaneously high catalytic activity and a correspondingly high space / time yield in the underlying catalytic conversion or reaction.

[0063] Without wishing to be limited to this theory, the use of special activated carbons with a high proportion of mesopores and macropores, and at the same time a defined proportion of macropores, provides high accessibility and optimal formation of the catalytically active components incorporated into the catalyst support, while at the same time improving the transport and diffusion methods of the reactants and products on which the catalytic reaction is based.

[0064] In this connection, the kinetics of the underlying catalytic reaction are generally improved, particularly with regard to improved transport and diffusion methods within the pore system and in the region of the boundary layer of the catalyst support, while the reactants to be reacted have a high degree of accessibility to the catalytically active components or catalytic centers.

[0065] The present invention also provides an overall improved catalyst system, which, due to the special adjustment and formation of the pore system of the activated carbon used as the catalyst support, exhibits a significantly greater efficiency in terms of catalytic activity. In this respect, the targeted (surface) oxidation of the activated carbon used as the catalyst support, prior to being equipped with the catalytically active components, is of great importance, as this improves the binding or loading of the catalytically active components or related precursors, as well as the formation of catalytic centers with a defined (metal) dispersion and crystallite size, as will be explained in more detail below.

[0066] A further central advantage of the present invention is to be found in the fact that the activated carbon used according to the invention has high mechanical stability or resistance with low wear during use in catalytic processes, thus giving a correspondingly high durability of the catalytic system according to the invention with a simultaneous high recyclability.

[0067] The specific use of granular or spherical activated carbon, i.e., activated carbon with a special shape, further improves the application properties of the catalyst system according to the invention, i.e., for the use of the catalyst system provided according to the invention not only in continuous catalytic applications but also in discontinuous catalytic applications. This is because, on the one hand, the special shaping, especially based on discontinuous spheres, achieves improved bulk porosity for discontinuous applications, preventing sludge formation in the reaction system and, at the same time, significantly improving the separation or recovery of the catalyst from the reaction system. On the other hand, the improved bulk properties of the catalyst system according to the invention result in low pressure losses with simultaneous high accessibility of the catalyst system to the reactants or reactants to be reacted, so that even high flow rates for the reactants or the medium containing the reactants to be reacted can be achieved using the catalyst system according to the invention.

[0068] The granular, and in particular spherical, activated carbon used according to the invention (spherical carbon) also offers many advantages, especially compared to other forms of activated carbon such as powdered carbon, crushed carbon, carbon from coal, etc., in terms of improved flowability, resistance to abrasion, freedom from dust, which also translates into at least high mechanical resistance and durability, with a long service life for the base system, which results in less clogging during use and a longer service life.

[0069] As will be shown below, by specifically adjusting the particle size or diameter of the underlying spherical activated carbon, it is possible to provide a totally customized catalyst system with optimized application characteristics in each case, in particular with regard to the recovery rate or flow behavior or pressure drop of the catalyst system, while at the same time further improving the catalytic activity of the catalyst system according to the invention. In particular, by specifying the particle size, it is possible to adjust or change the pressure drop or flow rate, so that it is also possible to provide a system optimized for each use or application context.

[0070] In the present invention, particularly highly attrition-resistant or mechanically stable spherical activated carbon is used for the catalyst support employed, as provided, for example, by special activated carbon based on organic polymers, particularly sulfonated organic polymers, as also defined below. In this regard, it is quite surprising in the present invention that the sulfur content that may be present in activated carbon, which may be, for example, up to 0.1% by weight based on the activated carbon, is not harmful to the catalytic function of the catalyst system according to the present invention, does not cause a harmful impairment of the catalytic activity, and in particular does not lead to so-called catalyst poisoning.

[0071] Furthermore, as a result of the (surface) oxidation of the activated carbon used before loading of the catalytically active components, the present invention has surprisingly succeeded in achieving a high and at the same time permanent or stable loading of the catalytically active components on the activated carbon used as a support, which significantly improves the catalytic activity of the catalyst system according to the present invention and at the same time improves its durability, in particular by reducing or avoiding washing or peeling off of the catalytically active components from the support material during application, thereby improving the durability of the catalyst system according to the present invention.

[0072] Without wishing to be bound by this theory, it is believed that the targeted oxidation or surface oxidation of activated carbon leads to the formation of special oxygen-containing functional groups on the activated carbon used according to the invention or in its pore system, both in the micropore, mesopore and macropore regions, thereby increasing the affinity of the activated carbon for the catalytically active components used according to the invention. As a result of the oxidation or surface oxidation treatment of activated carbon carried out according to the invention before loading with catalytically active components, a less hydrophobic or hydrophilic surface of the activated carbon, or special functional groups, are created or provided on the surface of the activated carbon or in the pore system of the activated carbon, which significantly improves the loading of catalytically active components in a completely surprising way.

[0073] In this regard, it is also completely surprising that the catalyst system according to the invention, based on spherical activated carbon with a defined particle shape or particle size, which is subjected to oxidation before loading catalytically active components, exhibits significantly improved catalytic activity compared to powdered activated carbon. In this regard, it is completely surprising that, for the catalyst system according to the invention, there are no significant limitations or restrictions on mass transport in the pore system of the activated carbon, in particular with respect to the basic reactant or reactants, and this is also particularly due to the defined pore structure, as shown below, of the activated carbon used according to the invention. In this regard, it has been found to be particularly advantageous according to the invention when a specifically defined proportion of subordinate macropores is used as a catalyst support for the catalyst system according to the invention.

[0074] In particular, it is quite surprising that the catalyst systems provided according to the invention exhibit high catalytic activity even at relatively large particle or fine particle sizes, especially compared to powdered carbon. In this regard, the degree of interaction according to the invention - without wishing to be limited to this theory - makes it possible, on the one hand, to achieve a particularly uniform and high loading of the activated carbon with catalytically active components, and, on the other hand, to reduce mass transfer or diffusion limitations in the catalyst system that are detrimental to catalytic activity.

[0075] With regard to the idea according to the invention, in particular due to the special matching of the support system on the one hand and the catalytically active component on the other hand, clogging of the pore system below the activated carbon by the catalytically active component - for example due to excessive crystallite size in the case of crystallization of metal salts - is also at least substantially prevented, which further improves the performance of the catalytic system provided according to the invention.

[0076] According to the present invention, it is now possible for the first time to provide, based on the method according to the invention, a very specific catalytic system having a very specific activated carbon as support material, which is equipped in a targeted manner with at least one catalytically active component, which has significant advantages and improved properties compared to prior art systems and is suitable for both discontinuous and continuous catalytic applications.

[0077] The catalyst systems according to the invention provided by the process according to the invention exhibit both improved mechanical and catalytic properties, with reduced process times and high recovery rates, allowing for good recycling of the underlying catalyst or catalytically active components. Furthermore, as mentioned above, the catalyst systems according to the invention exhibit improved flow properties with low pressure loss, especially when used or applied in (loose) bulk form.

[0078] Furthermore, the catalyst system according to the invention provided by the method according to the invention is also suitable for use in filters or filter materials, in particular for detoxifying harmful or toxic substances, etc.

[0079] Thus, the catalyst system provided by the method according to the invention combines, on the one hand, good mechanical properties and, on the other hand, good catalytic properties.

[0080] Based on the method according to the invention, the result is an effective arrangement of activated carbon used as support material and at least one catalytically active component to obtain a catalyst system according to the invention.

[0081] The term "catalyst system", synonymously referred to as "supported catalyst" as used in accordance with the present invention, is understood very broadly in accordance with the present invention and in particular refers to a functional unit based on at least one catalytically active component, on the one hand, and on the other hand, a support material, the catalytic properties of which are essentially attributable to the catalytically active component, which for this purpose consists of at least one metal. In this regard, the activated carbon used, in particular in the form of a catalyst support, is particularly equipped or filled or coated or impregnated, with the catalytically active component, in particular based on the fixation of the catalytically active component, so that the catalyst system according to the present invention can be obtained.

[0082] Furthermore, the terms "equipped" or "loaded" or "coated" or "impregnated" as used in the present invention refer to the "impregnation" as used in the present invention, and thus to the equipping of the activated carbon used in the present invention as a support material with catalytically active components, whereby the outer and / or inner surface structure of the used activated carbon with suitable pores, especially micropores and / or macropores, is at least partially and / or cross-sectionally in contact with, or is provided or filled with, the catalytically active components. In this regard, without wishing to be limited to this theory, the catalytically active components form, so to speak, catalytic structures or chemisorption properties on the activated carbon surface that functionally complement the physisorption properties of the activated carbon, so that the catalyst system provided by the method according to the present invention essentially combines both chemisorption and physisorption properties in one and the same material. In particular, the catalytically active components can be bound to the activated carbon surface by physical and / or chemical methods, and in particular the properties of the catalytically active centers or catalytically active components may depend in particular on the surface properties of the activated carbon, the catalytically active components themselves, and / or the reduction conditions.

[0083] Furthermore, with regard to the term "spherical", also synonymously called "spherical", as used for activated carbons used as support materials according to the present invention, this term is understood very broadly and, according to preferred embodiments of the present invention, particularly relates to an at least substantially ideal spherical or spherical shape of the activated carbon, but also to forms or physical designs of the activated carbon used that deviate from a spherical shape, such as (spheroidal) shaped activated carbons. Furthermore, the term "spherical" also includes spherical or ellipsoidal forms of activated carbon in which the activated carbon has protrusions or depressions, indentations, dents, cracks, etc. According to the present invention, the use of spherical activated carbon or spherical carbon or spherical activated carbon is therefore crucial.

[0084] As far as the term "surface oxidation" as used in accordance with the present invention is concerned, this particularly means oxidation of the surface of the activated carbon used as starting material, in particular that surface which is in contact with the environment containing the oxidizing agent or that is, so to speak, accessible from the outside to the oxidizing agent used in accordance with the present invention. In particular, this refers to the pore system of the activated carbon in the form of macropores, mesopores and micropores.

[0085] Furthermore, the specific BET surface area (S BET ) to the total pore volume (V total ), in particular the ratio of total pore volumes (quotient; Q) according to Goulwich, in particular the equation Q = V total ×S BETThe value based on this Q can further characterize the pore system of the activated carbon used as the catalyst support according to the present invention, and in particular, the effect that the porosity or pore system of the activated carbon can be characterized and defined based on the Q quotient, i.e., that there is a high proportion of mesopores and macropores in the total pore volume, as well as a defined proportion of micropores, particularly for the activated carbon used according to the present invention as a catalyst support. In particular, the Q quotient describes the high mesoporosity and macroporosity of the activated carbon used according to the present invention. In this context, the Q quotient can also be used as a measure of improved kinetics or improved catalytic activity during heterogeneous catalytic reactions when using the catalyst system according to the present invention, as a result of the specially formed activated carbon. Thus, as a result of the specially formed pore system of the activated carbon further characterized by the Q quotient, there is an overall improvement in the rate-determining steps of the kinetics underlying heterogeneous catalytic reactions, for example, in terms of improved diffusion behavior of reactants or products and accessibility of catalytically active components. Thus, the Q quotient further reflects the properties of the catalyst system according to the present invention provided in the process according to the present invention, in particular, in terms of its improved catalytic performance.

[0086] As far as activated carbons or such related activated carbon particles used as catalyst supports are concerned, the parameter data listed in this respect are determined using standardized or specified determination methods or using determination methods known per se to those skilled in the art. In particular, parameter data relating to the characterization of porosity or pore size distribution and other adsorption properties are generally obtained from the corresponding nitrogen adsorption isotherm of the respective activated carbon or of the product being measured, unless otherwise stated.

[0087] In the context of the present invention, the term "micropores" refers to pores having a pore diameter of less than 2 nm, while the term "mesopores" refers to pores having a pore diameter in the range of 2 nm (i.e., inclusive) to 50 nm inclusive, and the term "macropores" refers to pores having a pore diameter of more than 50 nm (i.e., >50 nm) and more particularly pores up to and including 500 nm.

[0088] The preparation of activated carbon to be used as a catalyst support as described in step (a) is described in more detail below:

[0089] Thus, according to the present invention, the activated carbon prepared or produced in process step (a) (the so-called initial activated carbon) has a surface area of ​​0.9 cm 3 / g~3.4cm 3 / g range, especially 1 cm 3 / g~2.9cm 3 / g, preferably 1.1 cm 3 / g~2.4cm 3 / g, more preferably in the range of 1.2 cm 3 / g~1.9cm 3 / g, particularly preferably 1.5 cm 3 / g~1.9cm 3 Total pore volume (V) in the range of / g total ), and in particular those having a total pore volume according to Goulwich.

[0090] As also indicated above, the activated carbon used as catalyst support according to the present invention is in particular such an activated carbon having a high overall mesoporosity and macroporosity. The present invention provides that the total pore volume, in particular the total pore volume according to Goulwich, of the activated carbon prepared and / or produced in process step (a) is in the range of 50% to 90%, in particular in the range of 52.5% to 87.5%, preferably in the range of 55% to 85%, more preferably in the range of 57.5% to 82.5%, even more preferably in the range of 60% to 80%, passing through the catalyst support (the so-called initial activated carbon) and is formed by pores with a pore diameter of at least 2 nm, in particular by pores with a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores.

[0091] Furthermore, the activated carbon provided or produced in process step (a) can likewise have a limited, subordinate, but sufficient microporosity for catalytic action, whereby generally a relatively small proportion of the total pore volume is associated with micropores (and in particular to an extent sufficient for catalytic action): therefore, according to the invention, it is particularly provided that the total pore volume, in particular the total pore volume according to Goulwich, of the activated carbon provided and / or produced in process step (a) (i.e. the starting activated carbon) is formed by pores with a pore diameter of less than 2 nm, preferably by micropores, of 2.5% to 50%, in particular 5% to 50%, preferably 10% to 50%, particularly preferably 12.5% ​​to 47.5%, more preferably 15% to 45%, very particularly preferably 17.5% to 423.5%, and even more preferably 20% to 40%.

[0092] Furthermore, the activated carbon prepared or produced in process step (a) (the so-called initial activated carbon) has a surface area of ​​0.8 cm 3 / g~3.9cm 3 / g, especially in the 0.9 cm 3 / g~3.4cm 3 / g, preferably in the range of 1 cm 3 / g~2.9cm 3 / g, more preferably in the range of 1.1 cm 3 / g~2.4cm 3 / g, particularly preferably 1.2 cm 3 / g~1.9cm 3 / g, particularly preferably 1.5 cm 3 / g~1.9cm 3 / g, the total pore volume (V total ), in particular a total pore volume according to Goulwich, and the present invention provides that the total pore volume of the activated carbon, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least less than 2 nm, in particular pores having a pore diameter in the range of 2 nm to 500 nm, preferably mesopores or macropores, of which 50% to 90%, in particular 52.5% to 87.5%, preferably 55% to 85%, more preferably 57.5% to 82.5%, and particularly preferably 60% to 80%.

[0093] Furthermore, the activated carbon prepared or produced in process step (a) (the so-called initial activated carbon) has a surface area of ​​0.8 cm 3 / g~3.9cm 3 / g, especially in the 0.9 cm 3 / g~3.4cm 3 / g, preferably in the range of 1 cm 3 / g~2.9cm 3 / g, more preferably in the range of 1.1 cm 3 / g~2.4cm 3 / g, particularly preferably 1.2 cm 3 / g~1.9cm 3 / g, particularly preferably 1.5 cm 3 / g~1.9cm 3 / g, the total pore volume (V total), in particular a total pore volume according to Goulwich, wherein the activated carbon prepared or produced in process step (a) (initial activated carbon) has a total pore volume, in particular a total pore volume according to Goulwich, of which 2.5% to 50%, in particular 5% to 50%, preferably 10% to 50%, more preferably 15% to 45%, particularly preferably 12.5% ​​to 47.5%, especially more preferably 17.5% to 42.5%, and even more preferably 20% to 40% is formed by pores having a pore diameter of less than 2 nm, in particular micropores.

[0094] As far as the determination of the total pore volume according to Golovich is concerned, this is a measurement / determination method well known to experts in this field. For further details on the determination of the total pore volume according to Golovich, see, for example, L. Golovich (1915), Russian Journal of the Physical and Chemical Society. 47 , 805 and Lowell et al., Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density, Kluwer Academic Press, Articles Technical Series, pp. 111ff. In particular, the pore volume of activated carbon can be calculated using the formula V P =W a / ρ l It is determined based on the Goulditch rule according to a represents the adsorption amount of the underlying adsorbate, and ρ l represents the density of the adsorbate used (see also equation (8.20) on page 111 of S. Rowell et al.).

[0095] Further, the activated carbon prepared or produced in process step (a) (i.e., the initial activated carbon) is 1,100 m 2 / g~2,600m 2 / g range, especially 1,200m 2 / g~2,400m 2 / g, preferably 1,300m 2 / g~2,200m 2 / g, more preferably 1,350m 2 / g~1,950m 2 / g, with 1,375m being particularly preferred2 / g~1,900m 2 / g BET )

[0096] Since the determination of specific surface area by BET is basically known to those skilled in the art, no further details need to be elaborated on in this regard. All BET surface area data refer to determinations according to ASTM D6556-04. Within the scope of the present invention, the so-called multipoint BET determination method (MP-BET) is generally, and unless expressly stated otherwise below, used for determining BET surface area in the partial pressure range of 0.05 to 0.1 p / p0.

[0097] For further details regarding the determination of BET surface area or the BET method, reference is made to the above-mentioned ASTM D6556-04 and to Romp Chemielexikon, 10th Edition, Georg Thesis Publishers, Stuttgart / New York, including the keywords: "BET method" and the references cited therein, Winnacker-Küchler (3rd Edition), Vol. 7, p. 93ff, and Z. Anal. Chemistry, 238, pp. 187-193 (1968).

[0098] As mentioned above, the formation of a defined pore system with a high mesopore and macropore volume or proportion leads to improved transport and diffusion properties of the reactants or products underlying the catalytic reaction, as a result of the particularly high mesopore and macropore proportions, as mentioned above. At the same time, improved catalytic properties for the provided catalytic systems also result from the fact that the catalytic active centers or centers are formed in smaller pores, in particular in the micropores.

[0099] As a result of the balanced and tailored pore distribution with an underlying defined hierarchical pore system having high mesopore and macropore volumes and micropore volumes sufficient for catalysis or catalytic activity, respectively, overall improved properties are thus provided in terms of the reaction kinetics of the heterogeneous system catalyst. In this regard, the aforementioned properties of the activated carbon used in process step (a) (i.e., the starting activated carbon) are directly reflected in the catalyst system according to the invention obtained in process step (d).

[0100] In this regard, in particular according to the present invention, the total pore volume (V total ) and, in particular, the specific BET surface area (S BET ) is the ratio (quotient; Q) of total / S BET According to 9 m~1.9×10 9 m, especially in the range of 0.55 × 10 9 m~1.9×10 9 m, preferably in the range of 0.6 × 10 9 m~1.8×10 9 m, preferably 0.65 × 10 9 m~1.7×10 9 m, with 0.65 × 10 9 m~1.6×10 9 m, most preferably in the range of 0.7 × 10 9 m~1.5×10 9 m, more preferably in the range of 0.75 × 10 9 m~1.4×10 9 m, more preferably in the range of 0.8 × 10 9 m~1.3×10 9 It is in the range of m.

[0101] The aforementioned lower limit ensures a good occupancy of the activated carbon with the catalytically active component, and at the same time a good mass transfer rate and thus a high conversion rate in the basic catalytic reaction, while the aforementioned upper limit still ensures a sufficient micropore volume, which is particularly relevant for the formation of a corresponding number of active sites or centers for the catalytic activity involving the catalytically active component.

[0102] According to the present invention, the activated carbon prepared or produced in process step (a) (i.e., the initial activated carbon) is 2 / g~3,000m 2 / g range, especially 1,100m 2 / g~2,600m 2 / g, preferably 1,200m 2 / g~2,400m 2 / g, more preferably 1,300m 2 / g~2,200m 2 / g, particularly preferably 1,350 m 2 / g~1,950m 2 / g, most preferably 1,375m 2 / g~1,900m 2 / g BET ) by which Total pore volume (V total ), especially the total pore volume and specific BET surface area (S BET ) is the ratio (quotient; Q) of total / S BET According to 9 m~1.9×10 9 m, especially in the range of 0.55 × 10 9 m~1.9×10 9 m, preferably in the range of 0.6 × 10 9 m~1.8×10 9 m, preferably 0.65 × 10 9 m~1.7×10 9 m, particularly preferably 0.65 × 10 9 m~1.6×10 9 m, most preferably in the range of 0.7 × 10 9m~1.5×10 9 m, more preferably in the range of 0.75 × 10 9 m~1.4×10 9 m, and particularly preferably in the range of 0.8×10 9 m~1.3×10 9 It is in the range of m.

[0103] Furthermore, it has been found to be advantageous in the context of the present invention if the activated carbon prepared and / or produced in process step (a) (i.e. the starting activated carbon) has an average pore size of at least 15 nm, or if the activated carbon has an average pore size of at most 100 nm.

[0104] In particular, it is preferred that the activated carbon prepared and / or produced in process step (a) (the so-called initial activated carbon) has an average pore size in the range of 15 nm to 100 nm, in particular in the range of 16 nm to 90 nm, preferably in the range of 17 nm to 85 nm, more preferably in the range of 18 nm to 80 nm, even more preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, and even more preferably in the range of 25 nm to 50 nm.

[0105] The determination of the textural properties of the meso- and macroporous activated carbons used according to the invention, or in the mesopore or macropore region, can be carried out in particular with respect to the average pore size by mercury intrusion. According to this method, an evaluation range is recorded for the pore size in the range of 0.01 μm to 20 μm.

[0106] Generally, the average pore size is four times the volume of the liquid (adsorbate) absorbed or adsorbed on the activated carbon when the pores are completely filled (V total ) and, on the other hand, the quotient of the BET surface area (BET) (pore diameter d = 4 × V total / BET). In this respect, reference may be made to the corresponding explanation by R.W. McGee (loc.cit.), in particular the mathematical expression (15) on page 71 of that publication.

[0107] Furthermore, it is advantageous according to the present invention if the activated carbon prepared and / or produced in process step (a) (i.e. the initial activated carbon) is spherical or if the activated carbon prepared and / or produced in process step (a) is used in the form of spherical activated carbon.

[0108] With regard to its catalytic applications based on the catalyst system according to the invention, the special shape of the activated carbon also results in better inflow properties, further improving the transport of reactants and products.

[0109] The spherical activated carbon is particularly relevant for improving properties when the catalyst system according to the present invention is used in a fixed bed reactor, for example.

[0110] According to the present invention, the activated carbon prepared and / or produced in process step (a) (i.e., the initial activated carbon) may have a particle size, in particular a particle diameter, in the range of 60 μm to 1000 μm, in particular in the range of 70 μm to 800 μm, preferably in the range of 80 μm to 600 μm, more preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, and most preferably in the range of 175 μm to 250 μm. In this regard, at least 80% by weight, in particular at least 90% by weight, preferably at least 95% by weight, in particular of the activated carbon particles, may have a particle size, in particular a particle size, in the aforementioned range.

[0111] In general, it is preferred that the activated carbon prepared or produced in process step (a) (i.e., the initial activated carbon) has an average particle size (D50), in particular an average particle diameter (D50), in the range of 60 μm to 900 μm, in particular in the range of 75 μm to 750 μm, preferably in the range of 85 μm to 550 μm, more preferably in the range of 110 μm to 375 μm, even more preferably in the range of 175 μm to 350 μm, and most preferably in the range of 185 μm to 225 μm.

[0112] The corresponding particle size or diameter can be determined in particular based on the method according to ASTM D2862-97 / 04. Furthermore, the size can also be determined using measurement methods such as sieve analysis, X-ray diffraction, laser diffraction, etc. The respective determination methods are so well known to those skilled in the art that no further explanation is necessary in this regard.

[0113] Furthermore, the activated carbon prepared and / or produced in process step (a) (i.e., the starting activated carbon) has a ball pan hardness and / or abrasion hardness of at least 90%, particularly at least 95%, preferably at least 97%, more preferably at least 98%, most preferably at least 99%, and even more preferably at least 99.5%. Abrasion resistance can generally be measured according to ASTM D3802-05. Thus, the activated carbon used according to the present invention is further characterized by excellent mechanical properties, which can also be expressed as high abrasion resistance. The high mechanical strength of the activated carbon used according to the present invention results in low abrasion during application of the catalyst system obtained according to the present invention, which is particularly advantageous in terms of application or service life. Furthermore, the excellent mechanical properties with low abrasion provide further advantages for the production of the catalyst system according to the present method, particularly in terms of avoiding abrasion and the like during the respective process steps. The high mechanical strength of the activated carbon, and therefore of the catalyst system according to the present invention, results in low abrasion during use in catalytic reactions, which is particularly advantageous in terms of service life and avoiding sludge formation due to abrasion and the like.

[0114] The high mechanical stability of the activated carbon used according to the present invention is also reflected in its high compressive strength and / or bursting strength (weight load capacity per activated carbon particle). In this regard, it is preferred that the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) has a compressive and / or bursting strength (weight load capacity) per activated carbon particle, in particular per activated carbon bead, of at least 5 Newtons, in particular at least 10 Newtons, preferably at least 15 Newtons, preferably at least 20 Newtons, and particularly preferably at least 22.5 Newtons. In particular, it is preferred that the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) has a compressive and / or bursting strength (weight load capacity) per activated carbon particle, in particular per activated carbon pellet, in the range of 5 to 50 Newtons, in particular 10 to 45 Newtons, preferably 15 to 40 Newtons, and preferably 17.5 to 35 Newtons. The determination of the compressive strength or bursting strength can be carried out in a manner known to those skilled in the art, in particular based on determining the compressive strength or bursting strength on individual particles or particles by applying a force with a punch until each particle or particle bursts.

[0115] The activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) preferably has a vibration or tamp density in the range of 100 g / L to 1,500 g / L, particularly in the range of 125 g / L to 1,000 g / L, preferably in the range of 150 g / L to 800 g / L, more preferably in the range of 200 g / L to 600 g / L, particularly preferably in the range of 225 g / L to 500 g / L, most preferably in the range of 250 g / L to 400 g / L, and even more preferably in the range of 255 g / L to 395 g / L. In particular, the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) preferably has a bulk density in the range of 150 g / L to 1,000 g / L, particularly in the range of 250 g / L to 700 g / L, preferably in the range of 300 g / L to 600 g / L, and more preferably in the range of 300 g / L to 550 g / L. The bulk density is measured in particular in accordance with ASTM B527-93 / 00.

[0116] Furthermore, it is preferred that the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) has a butane adsorption of at least 35%, in particular at least 40%, preferably at least 45%, preferably at least 47.5%, and / or that the activated carbon has a butane adsorption in the range of 35% to 90%, in particular in the range of 40% to 85%, preferably in the range of 45% to 80%, more preferably in the range of 47.5% to 75%, the butane adsorption being measured in particular according to ASTM D5742-95 / 00.

[0117] Furthermore, the activated carbon prepared and / or produced in process step (a) (i.e., the starting activated carbon) preferably has an iodine value of at least 1,250 mg / g, in particular at least 1,300 mg / g, preferably at least 1,400 mg / g, more preferably at least 1,425 mg / g, and / or the activated carbon prepared and / or produced in process step (a) preferably has an iodine value in the range of 1,250 mg / g to 2,100 mg / g, in particular in the range of 1,300 mg / g to 2,000 mg / g, preferably in the range of 1,400 mg / g to 1,900 mg / g, preferably in the range of 1,425 mg / g to 1,850 mg / g. In particular, the iodine value can be determined according to ASTM D4607-94 / 99. The iodine number can be evaluated as a measure of the available surface area provided primarily by small mesopores, and the above values ​​of the iodine number indicate that the activated carbon used according to the invention can have a particularly high mesoporosity.

[0118] It is further preferred that the activated carbon prepared and / or produced in process step (a) (i.e. the starting activated carbon) has a methylene blue value of at least 17 mL, in particular at least 18 mL, preferably at least 19 mL, more preferably at least 19.5 mL, and / or that the activated carbon prepared and / or produced in process step (a) has a methylene blue value in the range of 17 mL to 65 mL, in particular in the range of 18 mL to 55 mL, preferably in the range of 19 mL to 50 mL, more preferably in the range of 19.5 mL to 47.5 mL.

[0119] In particular, it is preferred that the activated carbon prepared and / or produced in process step (a) (i.e. the starting activated carbon) has a molasses number of at least 255, in particular at least 310, preferably at least 375, more preferably at least 510, and / or that the activated carbon prepared and / or produced in process step (a) has a molasses number in the range of 255 to 1,500, in particular in the range of 310 to 1,400, preferably in the range of 375 to 1,300, more preferably in the range of 510 to 1,250.

[0120] Due to the high mesoporosity and macroporosity, the activated carbon of the present invention thereby exhibits similarly high methylene blue values ​​and molasses adsorption numbers, which together can be evaluated as a measure of the available surface area provided primarily by mesopores and macropores. Therefore, the methylene blue number or methylene blue adsorption, which refers to the amount of methylene blue adsorbed per defined amount of adsorbent under defined conditions (i.e., the volume or milliliters (mL) of a standard methylene blue solution decolorized with a defined amount of dry powdered adsorbent), can be an indicator of the adsorption capacity of the activated carbon of the present invention for molecules having a size comparable to that of methylene blue, since mesopores tend to be small. Furthermore, since the molasses number is considered a measure of mesoporosity and macroporosity and indicates the amount of adsorbent required to decolorize a standard molasses solution, the molasses number is an indicator of the adsorption capacity of the activated carbon of the present invention for molecules having a size comparable to that of molasses (generally sugar beet molasses). Therefore, the values ​​for methylene blue and molasses together can be taken as a measure of the mesoporosity and macroporosity, especially the mesoporosity, of the activated carbon according to the invention.

[0121] The dimensionless molasses number can essentially be determined by the Norit method (Norit NV, Amersfoort, The Netherlands, Norit Standard Method NSTM2.19 "Equivalent Density (Europe)") or PACS = Professional Analytical and Consulting Services Inc, Corapolis, Pennsylvania, USA). In the context of the present invention, the molasses number value is determined according to the PACS method. For determining the molasses number by the Norit or PACS method, the amount of powdered activated carbon required to decolorize a standard molasses solution is determined. The determination is carried out photometrically by adjusting the standard molasses solution against standard activated carbon with molasses number 245 and / or 350. For more information in this regard, reference can be made to the two aforementioned rules.

[0122] The methylene blue value can be determined according to the method according to CEFIC (European Chemical Industry Council, Rue Louis 250, Bte 71, B-1050 Brussels, November 1986, European Chemical Industry, Test Methods for Activated Carbon, Section 2.4 "Methylene Blue Value", pages 27 / 28).

[0123] Therefore, the methylene blue value according to the CEFIC method is defined as the number of milliliters of methylene blue standard solution decolorized with 0.1 g of dry powdered activated carbon. This method requires a glass stoppered container, a filter, and a methylene blue standard solution, which is prepared as follows: 1200 mg of pure methylene blue dye (equivalent to approximately 1.5 g of methylene blue according to DAB VI [German Pharmacopoeia 6th Edition] or equivalent) is dissolved in water in a 1000 mL volumetric flask and the solution is left to stand for several hours or overnight. To confirm, add 5.0 mL to a volumetric flask, make up to 1.0 L with 0.25% (volume fraction) acetic acid, and measure the absorbance at 620 nm with a 1 cm path length to obtain a value of (0.840 ± 0.010). If the absorbance is high, dilute with the calculated amount of water; if low, discard the solution and prepare again. To prepare the sample, crush the activated carbon (<0.1 mm) and dry it at 150 °C to a constant weight. Exactly 0.1 g of spherical carbon is combined with 25 mL (5 mL) of methylene blue standard solution in a ground-glass flask (preliminary tests are performed to determine whether initial additions of 25 mL of methylene blue standard solution with 5 mL of methylene blue standard solution and 5 mL of methylene blue standard solution with 1 mL of methylene blue standard solution can be used). The mixture is shaken until decolorization occurs. An additional 5 mL (1 mL) of methylene blue standard solution is then added and shaken until decolorization occurs. The methylene blue standard solution is repeatedly added in 5 mL (1 mL) volumes as long as decolorization occurs within 5 minutes. The total volume of test solution decolorized by the sample is recorded. The test is repeated to confirm the results. The volume (mL) of methylene blue standard solution decolorized is the methylene blue value of the activated carbon. Note that methylene blue, a dye, is sensitive to heat, so it should not be dried; the moisture content must be corrected purely by calculation.

[0124] According to the present invention, the activated carbon prepared and / or produced in process step (a) (i.e., the starting activated carbon) has a gravimetric N adsorption capacity V determined at a partial pressure p / p of 0.25. ads(wt) But at least 250cm 3 / g, especially at least 300 cm 3 / g, preferably at least 350 cm 3 / g, more preferably at least 375 cm 3 In this regard, it is further contemplated that the activated carbon prepared and / or produced in process step (a) has a solubility of 250 cm 3 / g~850cm 3 / g, especially in the 300 cm 3 / g~700cm 3 / g, preferably 350 cm 3 / g~650cm 3 / g, more preferably 375 cm 3 / g~625cm 3 Gravimetrically adsorbed N2 V determined at a partial pressure p / p0 of 0.25 in the range of / g ads(wt) It is preferred that the compound has the following structure:

[0125] Generally, the activated carbon purified and / or produced in process step (a) (i.e., the initial activated carbon) has a thickness of at least 50 cm 3 / cm 3 , especially at least 100 cm 3 / cm 3 , preferably at least 110 cm 3 / cm 3 The volumetrically adsorbed amount of N2, V, is determined at a partial pressure p / p of 0.25. ads(vol.) In this respect, the activated carbon purified or produced in the process step (a) may have a 50 cm 3 / cm 3 ~300cm 3 / cm 3 Within the range of 80cm 3 / cm 3 ~275cm 3 / cm 3 Within the range of 90cm 3 / cm3 ~250cm 3 / cm 3 within the range of 95cm 3 / cm 3 ~225cm 3 / cm 3 The volumetric adsorption amount of N2 in the range of V ads(vol.) It can be specifically stipulated that the

[0126] Similarly, the activated carbon purified or produced in process step (a) (i.e., the starting activated carbon) has a viscosity of at least 300 cm 3 / g, especially at least 450 cm 3 / g, preferably at least 475 cm 3 The weight-based amount of adsorbed N2 V is determined by the partial pressure p / p0 of 0.995 / g. ads(wt.) In particular, the activated carbon purified or produced in step (a) of the process has a viscosity of 300 cm 3 / g~2,300cm 3 / g, especially in the 400 cm 3 / g~2,200cm 3 / g, preferably within 450 cm 3 / g~2,100cm 3 / g, more preferably in the range of 475 cm 3 / g~2,100cm 3 Gravimetric adsorption capacity V of N2 determined at partial pressure p / p0 in the range of 0.995 / g ads(wt.) It is preferred that the compound has the following structure:

[0127] Further, the activated carbon purified or produced in process step (a) (i.e., the initial activated carbon) has a viscosity of at least 200 cm 3 / cm 3 , especially at least 250 cm 3 / cm 3 , preferably at least 275 cm 3 / cm 3 , more preferably at least 295 cm 3 / cm 3 The volume-related amount of adsorbed N2, V, is determined by the partial pressure p / p0 of 0.995.ads(vol.) According to the present invention, the activated carbon purified or produced in the process step (a) (i.e., the initial activated carbon) preferably has a 200 cm 3 / cm 3 ~500cm 3 / cm 3 Within the range of 250cm 3 / cm 3 ~400cm 3 / cm 3 Within the range of 275 cm 3 / cm 3 ~380cm 3 / cm 3 in the range of, more preferably, at least 295 cm 3 / cm 3 ~375cm 3 / cm 3 The volume-related amount of adsorbed N2 V determined at partial pressures p / p0 in the range of 0.995 ads(vol.) It is preferred that the compound has the following structure:

[0128] As a result, the quantity V related to the weight and volume of the activated carbon according to the invention ads (N2) is very large at different partial pressures p / p0, which can be taken as evidence of the excellent adsorption properties of the activated carbon used according to the present invention and its excellent suitability as a catalyst support.

[0129] According to the present invention, the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) preferably has a fractal dimension of open porosity in the range of 2.6 to 2.99, in particular in the range of 2.7 to 2.95, preferably in the range of 2.8 to 2.95, and / or the activated carbon preferably has a fractal dimension of open porosity of at least 2.7, in particular at least 2.8, preferably at least 2.85, more preferably at least 2.9. The fractal dimension of open pores is an indicator of the micro-irregularities of the inner surface of the activated carbon. For further details in this regard, in particular for determining the fractal dimension of the activated carbon used according to the present invention, reference can be made to the publications DE 102 54 241 A1, WO 2004 / 046033 A1, EP 1 562 855 B1 and US 2006 / 148645 A1, which belong to the same patent family, in particular to Example 4 cited therein. The content of each of the cited publications is hereby incorporated in its entirety by reference.The aforementioned fractal dimensions lead to further improved catalytic properties of the catalyst systems produced by the method according to the invention.

[0130] According to the present invention, the activated carbon purified and / or produced in process step (a) (i.e. the starting activated carbon) is preferably an activated carbon obtained by carbonization and subsequent activation of an organic polymer-based starting material, in particular in the form of a polymer-based, preferably spherical, activated carbon (PBSAC or polymer-based spherical activated carbon).

[0131] Activated carbon in the form of PBSAC is particularly associated with defined pore characteristics, defined shape and high mechanical stability.

[0132] In particular, the starting material for the activated carbon purified and / or produced in process step (a) (i.e., the starting activated carbon) can be used in the form of a granular and / or spherical, preferably spherical, starting material, and / or the starting material for the activated carbon purified and / or produced in process step (a) is used in the form of a granular and / or spherical, preferably spherical, starting material.

[0133] Furthermore, the starting material for the activated carbon purified or produced in process step (a) (i.e., starting activated carbon) preferably has a particle size, especially particle diameter, in the range of 60 μm to 1,000 μm, in particular 70 μm to 800 μm, preferably 80 μm to 600 μm, more preferably 100 μm to 400 μm, particularly more preferably 150 μm to 375 μm, and most preferably 175 μm to 250 μm. In this regard, at least 80 wt. %, in particular at least 90 wt. %, preferably at least 95 wt. % of the particles of the starting material may have a particle size, especially particle diameter, in the above-mentioned range.

[0134] Furthermore, it is preferred that the starting material for the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) has an average particle size (D50), in particular an average particle diameter (D50), in the range of 60 μm to 900 μm, in particular in the range of 75 μm to 750 μm, preferably in the range of 85 μm to 550 μm, more preferably in the range of 110 μm to 375 μm, even more preferably in the range of 175 μm to 350 μm, and most preferably in the range of 185 μm to 225 μm.

[0135] In particular, it is preferred that the starting material for the activated carbon prepared and / or produced in said process step (a) (ie the starting activated carbon) is a starting material based on an ion exchange resin precursor.

[0136] Furthermore, the starting material for the activated carbon prepared and / or produced in process step (a) (i.e., the starting activated carbon) is preferably based on an organic polymer, in particular on divinylbenzene-crosslinked polystyrene, and preferably on a styrene / divinylbenzene copolymer. In this regard, the content of divinylbenzene in the starting material is preferably in the range of 0.1% to 25% by weight, in particular in the range of 0.5% to 20% by weight, preferably in the range of 1% to 15% by weight, and more preferably in the range of 2% to 10% by weight, based on the starting material. For specific starting materials to be used, please refer to the detailed description of the exemplary embodiments.

[0137] According to the present invention, the activated carbon prepared and / or produced in process step (a) (i.e., the initial activated carbon) comprises: (i) carbonization of a polymeric organic sulfonated starting material (containing sulfonic acid groups), in particular a particulate, preferably spherical, polymeric organic sulfonated starting material; then (ii) It is particularly preferably provided that the activated carbon is obtainable by activation of the carbonized material obtained in step (i) (carbonized starting material), in particular to obtain an activated carbon as defined in any of the preceding claims.

[0138] Furthermore, it is provided in this regard that the process step of sulfonating the polymerizable organic starting material is carried out before the process step (i) of carbonization, in particular by contacting the starting material with at least one sulfonating agent, the sulfonating agent being used in liquid form.

[0139] In particular, sulfur trioxide (SO), especially in the form of oleum and / or preferably concentrated sulfuric acid, is used as the sulfonating agent, although it is equally possible according to the invention to start from already sulfonated materials.

[0140] Generally, in the context of the present invention, in said method step (i), the carbonization is carried out at a temperature in the range of 100°C to 1,200°C, in particular in the range of 120°C to 1,100°C, preferably in the range of 140°C to 1,000°C, more preferably in the range of 150°C to 950°C.

[0141] According to the invention, in this respect, it is provided that in process step (i) the carbonization is carried out in multiple stages, in particular in two stages, preferably using a temperature gradient and / or temperature profile. In this respect, in a first stage the process is carried out at a temperature in the range of 100°C to 600°C, in particular in the range of 120°C to 590°C, preferably in the range of 140°C to 570°C, more preferably in the range of 150°C to 550°C. Furthermore, in a second stage the process can be carried out at a temperature in the range of 500°C to 1200°C, in particular in the range of 510°C to 1100°C, preferably in the range of 530°C to 1000°C, more preferably in the range of 550°C to 950°C.

[0142] According to the present invention, in the method step (i), the carbonization is carried out for a time in the range of 0.1 hours to 20 hours, in particular in the range of 0.5 hours to 15 hours, preferably in the range of 1 hour to 10 hours, more preferably in the range of 1.5 hours to 8 hours, and particularly preferably in the range of 2 hours to 6 hours.

[0143] Within the scope of the process according to the invention, in said process step (i), the carbonization is carried out in such a way that chemical groups, in particular strongly acidic chemical groups, preferably sulfonic acid groups, are thermally decomposed or split off, in particular from the sulfonated starting material, in particular with the formation of free radicals or crosslinks, preferably with the initiation of carbonization or pyrolysis of the starting material occurring with crosslinking of the polymer of the starting material and / or with the formation of carbon.

[0144] Furthermore, in said process step (i), the carbonization is carried out in such a way that, in particular after pyrolysis or removal of chemical groups, in particular strongly acidic chemical groups, preferably sulfonic acid groups, a more extensive or in particular complete carbonization of the starting material occurs.

[0145] For example, said method step (i) may be carried out such that the pyrolysis or removal of chemical groups, in particular strongly acidic chemical groups, preferably sulfonic acid groups, is carried out in a first stage of carbonization, and furthermore, method step (i) may be carried out such that further and / or complete carbonization of the starting material is carried out in a second stage.

[0146] Generally, it is preferred that process step (i) is carried out in an inert atmosphere, in particular a nitrogen atmosphere, or at most a slightly oxidizing atmosphere. Optionally, it is preferred according to the invention that process step (i) provides that during carbonization water, in particular in the form of steam, and / or an inert gas / steam mixture, preferably a nitrogen / steam mixture, is added to the carbonization atmosphere, in particular an inert atmosphere.

[0147] Furthermore, with regard to said process step (ii), activation is carried out at a temperature in the range of 500° C. to 1,200° C., in particular in the range of 800° C. to 1,100° C., preferably in the range of 850° C. to 1,000° C., more preferably in the range of 900° C. to 975° C. Furthermore, in said process step (ii), activation is carried out for a period in the range of 0.5 hours to 20 hours, in particular in the range of 1 hour to 15 hours, preferably in the range of 2 hours to 10 hours.

[0148] Generally, in said process step (ii), activation is carried out in the form of at least one activation gas, in particular oxygen, preferably air, water vapor and / or carbon dioxide or a mixture of these activation gases, and / or in the presence of an inert gas / water vapor mixture, preferably a nitrogen / water vapor mixture, and / or in particular pure carbon dioxide or an inert gas / carbon dioxide mixture, in particular nitrogen / carbon dioxide.

[0149] The basic principle of the activation provided in step (ii) of the method according to the invention is in particular the selective and specific decomposition or combustion under suitable conditions of part of the carbon generated during carbonization, which further develops or specifically conditions and so to speak finalizes the pore system.

[0150] The activated carbon provided or produced in process step (a) is generally available commercially, in principle, in the specific form indicated herein, especially from Blücher GmbH. For further details regarding the activated carbon provided or produced according to the present invention in process step (a), particularly with regard to the carbonization and activation process steps, reference may be made to International Patent Application WO 98 / 07655 A1 and patent applications DE 196 53 238 A1, DE 196 50 414 A1, EP 0 952 960 A1, and US Pat. No. 6,300,276 B1, which belong to the same patent family, the disclosures of each of which are hereby incorporated by reference in their entirety. Reference may also be made to DE 4304 026 A1 and US Pat. No. 6,184,177 B1, which belong to the same patent family, the disclosures of each of which are hereby incorporated by reference in their entirety. Further, reference may be made to International Patent Application WO2017 / 097447A1 and parallel patent applications DE 10 2016 101 215 A1, EP3362407A1 and US2019 / 177170A1, the disclosures of each of which are hereby incorporated by reference in their entirety.

[0151] In the following, the process step (b) involving the oxidation of activated carbon is explained in more detail:

[0152] In general, it is provided in accordance with the present invention that the activated carbon oxidized in process step (b), in particular the surface oxidized, has an oxygen content, in particular a surface oxidation content, in the range of 4% (atomic %) to 20%, in particular in the range of 5% to 20%, preferably in the range of 5.5% to 18%, more preferably in the range of 6% to 15%, even more preferably in the range of 7% to 12.5%, based on the total elemental composition of the oxidized activated carbon, determined in particular by X-ray photoelectron spectroscopy [XPS (=X-Ray Photoelectron Spectroscopy), ESCA (=Electron Spectroscopy for Chemical Analysis)].

[0153] According to the invention it is provided that the activated carbon oxidized in process step (b), in particular the surface oxidized, has an oxygen content, in particular a surface oxygen content, of at least 5% (atomic %), preferably at least 5.5%, preferably at least 6%, particularly preferably at least 7%, based on the total elemental composition of the oxidized activated carbon, determined in particular by means of XPS or ESCA.

[0154] According to the invention, it is possible to provide that the activated carbon oxidized in process step (b), in particular the surface oxidized, has an oxygen content, in particular determined by means of X-ray photoelectron spectroscopy (XPS or ESCA), in particular a surface oxygen content, of at most 20% (atomic %), preferably at most 18%, preferably at most 15%, particularly preferably at most 12.5%, based on the total elemental composition of the oxidized activated carbon.

[0155] In this regard, it is preferred according to the invention if the activated carbon oxidized in process step (b), in particular the oxidized surface, is at least essentially formed by carbon. In this regard, it is preferred that the activated carbon oxidized in process step (b), in particular the oxidized surface, has traces of elements other than oxygen and carbon, in particular nitrogen, sulfur and / or chlorine, in an amount of at most 2% (atomic %), in particular at most 1.5%, preferably at most 1%, calculated as the sum of elements other than oxygen and carbon, based on the total elemental composition of the oxidized activated carbon.

[0156] Without wishing to be limited to this theory, the method according to the invention produces an oxide layer, in particular on the (pore) surface of the activated carbon, which oxide layer generally has oxygen-containing functional groups as described below. A surface oxidation finish with catalytically active components is then carried out, in particular in the region of the oxide layer (boundary layer), again without being limited or clarifying this theory, so that the oxygen-containing functional groups increase the affinity and in particular also the interaction with the catalytically active components, or in a sense act as binding or anchoring points for the catalytically active components used according to the invention.

[0157] The process according to the invention therefore provides a catalytic system according to the invention which has a catalytic or reactive surface by equipping the activated carbon with catalytically active components following oxidation.

[0158] With regard to the ranges stated above for the oxygen content of the activated carbon oxidized in process step (b), the stated lower limit ensures that there are still sufficient binding sites for the catalytically active component or precursor thereof, while the stated upper limit ensures that the carbon content in the oxidized activated carbon is high enough to form a stable framework with corresponding mechanical stability and the presence of a pore system that continues to be defined, in particular in terms of a corresponding total pore volume and specific BET surface area according to Goulwich.

[0159] As indicated above, the targeted and purpose-directed oxidation treatment in process step (b) results in a relatively hydrophilic activated carbon, which, on the basis of this, improves the finishing with catalytically active components or their precursors.

[0160] With this background in mind, the hydrophilicity of activated carbon can be stated as follows: In particular, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity, determined as a water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6, at least 35%, in particular at least 40%, preferably at least 50%, more preferably at least 60% of the maximum water vapor saturation load of the activated carbon is achieved. Furthermore, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined as a water vapor absorption behavior such that at a partial pressure p / p0 of 0.6, up to 100%, in particular up to 99%, preferably up to 98%, more preferably up to 95%, particularly preferably up to 90% of the maximum water vapor saturation load of the activated carbon is achieved. Furthermore, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined by its water vapor adsorption behavior such that at a partial pressure p / p0 of 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, more preferably 50% to 95%, particularly preferably 60% to 90% of the maximum water vapor saturation load of the activated carbon is achieved. In particular, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity, determined as a water vapor absorption behavior, such that in the partial pressure range p / p0 of 0.1 to 0.6, at least 30%, in particular at least 35%, preferably at least 40%, more preferably at least 50%, particularly preferably at least 60% of the maximum water vapor saturation load of the activated carbon is achieved. In particular, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined as a water vapor absorption behavior such that in the partial pressure range p / p0 of 0.1 to 0.6, up to 100%, in particular up to 99%, preferably up to 98%, more preferably up to 95%, particularly preferably up to 90% of the maximum water vapor saturation load of the activated carbon is achieved. Furthermore, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined by its water vapor adsorption behavior such that at a partial pressure p / p0 of 0.1 to 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, more preferably 50% to 95%, particularly preferably 60% to 90% of the maximum water vapor saturation load of the activated carbon is achieved.

[0161] In addition to the hydrophilicity of the activated carbon oxidized in process step (b), the following can be mentioned: Therefore, with regard to the activated carbon oxidized in process step (b), it is within the scope of the present invention to carry out the oxidation, in particular the surface oxidation, of the activated carbon prepared or produced in process step (a) in such a way that the oxidized, in particular the surface-oxidized activated carbon has a hydrophilicity determined as a water vapor adsorption behavior, at a partial pressure p / p0 of 0.6, whereby 30% of the maximum water vapor adsorption capacity of the activated carbon is consumed or utilized. In particular, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined as a water vapor adsorption behavior such that at a partial pressure p / p of 0.6, at least 30%, in particular at least 35%, preferably at least 40%, more preferably at least 50%, particularly preferably at least 60% of the maximum water vapor adsorption capacity of the activated carbon is depleted and / or utilized. Furthermore, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined by a water vapor adsorption behavior such that at a partial pressure p / p of 0.6, at most 100%, in particular at most 99%, preferably at most 98%, more preferably at most 95%, particularly preferably at most 90% of the maximum water vapor adsorption capacity of the activated carbon is consumed and / or utilized. Similarly, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined by a water vapor adsorption behavior such that at a partial pressure p / p of 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, more preferably 50% to 95%, particularly preferably 60% to 90% of the maximum water vapor adsorption capacity of the activated carbon is consumed and / or utilized. Furthermore, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined as a water vapor adsorption behavior such that at a partial pressure p / p0 of 0.1 to 0.6, at least 30%, in particular at least 35%, preferably at least 40%, more preferably at least 50%, particularly preferably at least 60% of the maximum water vapor adsorption capacity of the activated carbon is consumed and / or utilized. In particular, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined by a water vapor adsorption behavior such that at a partial pressure p / p0 of 0.1 to 0.6, up to 100%, in particular up to 99%, preferably up to 98%, more preferably up to 95%, particularly preferably up to 90% of the maximum water vapor adsorption capacity of the activated carbon is consumed and / or utilized. According to the invention, the activated carbon oxidized in process step (b), in particular the oxidized surface, has a hydrophilicity determined by a water vapor adsorption behavior such that at a partial pressure p / p0 of 0.1 to 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, more preferably 50% to 95%, particularly preferably 60% to 90% of the maximum water vapor adsorption capacity of the activated carbon is consumed and / or utilized.

[0162] The activated carbon oxidized in process step (b) may also have the following properties with respect to hydrophilicity: Furthermore, the activated carbon oxidized in the process step (b), in particular the oxidized surface, has a water vapor (H2O) adsorbed by the activated carbon at a partial pressure p / p0 of 0.6, based on the weight of the activated carbon. (H2O) But at least 200cm 3 / g, especially at least 250 cm 3 / g, preferably at least 300 cm 3 / g, more preferably at least 325 cm 3 / g, particularly preferably at least 350 cm 3 / g, and has hydrophilicity determined as water vapor adsorption behavior. Furthermore, the activated carbon oxidized in the process step (b), in particular the oxidized surface, has a water vapor (H2O) adsorbed by the activated carbon at a partial pressure p / p0 of 0.6, based on the weight of the activated carbon. (H2O) However, the maximum is 1,000 cm 3 / g, especially up to 900 cm 3 / g, preferably up to 800 cm 3 / g, more preferably up to 700 cm 3 / g, particularly preferably up to 600 cm 3 / g, and has hydrophilicity determined as water vapor adsorption behavior. According to the invention, the activated carbon oxidized in step (b), in particular the oxidized surface, has a water vapor (H2O) adsorbed by the activated carbon at a partial pressure p / p0 of 0.6, based on the weight of the activated carbon. (H2O) But 200cm 3 / g~1,000cm 3 / g, especially in the 250 cm 3 / g~900cm 3 / g, preferably in the range of 300 cm 3 / g~800cm 3 / g, more preferably 325 cm 3 / g~700cm 3 / g, particularly preferably 350 cm 3 / g~600cm 3 The hydrophilicity determined as water vapor adsorption behavior is in the range of 1 / g.

[0163] The above values ​​of the water vapor adsorption behavior refer in particular to the water vapor adsorption isotherm underlying the activated carbon obtained according to the invention in said process step (b).

[0164] As far as the determination of the water vapor adsorption behavior is concerned, it is carried out within the scope of the present invention in accordance with DIN 66135-1, using water or water vapor as the basic adsorbent or adsorbent body. In this connection, the determination of the water vapor adsorption behavior is carried out statically and volumetrically at a temperature of 25°C (298 Kelvin). The pressure-dependent volume of adsorbed water or adsorbed water vapor that is the basis for the water vapor adsorption behavior is determined as follows: (STP) The measurements are carried out at different or variable ambient pressures p / p0 in the range of 0.0 to 1.0, where p0 represents the pressure at standard conditions (1,013.25 hPa). The water vapor adsorption behavior used in accordance with the present invention relates to the adsorption isotherm of the underlying activated carbon.

[0165] For further information and explanations on water vapor adsorption, reference can be made to the doctoral dissertation "Adsorption of Water Vapor and n-Butane on Activated Carbons: Mechanisms, Equilibria and Dynamics of Single-Component and Co-Adsorption" by M. Neutsch, Faculty of Mechanical, Method and Energy Engineering, Freiberg University of Mining and Technology, the entire contents of which, in particular the explanation of water vapor or water adsorption on activated carbon, are hereby incorporated by reference in their entirety.

[0166] The water vapor adsorption behavior defined above serves as a measure of the hydrophilicity or hydrophobicity of the activated carbon used according to the invention, and based on the values ​​defined above, the activated carbon obtained in process step (b) and used in subsequent process steps has an overall polar or hydrophilic nature (i.e. compared to the starting activated carbon used) and therefore an overall effect that can be described as hydrophilic in accordance with normal usage.

[0167] According to the present invention, the oxidation, particularly surface oxidation, of the activated carbon in process step (b) is further provided so that the resulting oxidized, particularly surface-oxidized, activated carbon has an oxygen-containing group content, calculated and / or expressed as a volatile fraction content ("fB") of at least 1 wt. %, in particular at least 2 wt. %, preferably at least 3 wt. %, preferably at least 4 wt. %, and / or in the range of 1 wt. % to 30 wt. %, in particular in the range of 1.5 wt. % to 25 wt. %, preferably in the range of 2 wt. % to 20 wt. %, more preferably in the range of 3 wt. % to 15 wt. %, based on the dry weight of the oxidized activated carbon. The oxygen-containing group content can be adjusted by the temperature and / or time and / or the type and / or concentration of the oxidizing agent.

[0168] In this regard, the method according to the invention can thereby be used to adjust the oxidation of the activated carbon also with a view to optimizing its subsequent work-up with catalytically active components.

[0169] Within the scope of the method according to the invention, it is possible to proceed so that the oxygen content of the activated carbon oxidized on its surface is significantly increased compared to the starting activated carbon used, which is expressed as the volatile content ("fB") and generally has an oxygen content of less than 1% by weight, based on the dry weight of the starting activated carbon. The stated oxygen content particularly refers to the activated carbon oxidized in process step (b) before the subsequent reduction provided by process step (d). The volatile content ("fB") generally serves as a measure of oxidation, and therefore particularly refers to the surface oxides formed by oxidation. In particular, the volatile content can be measured according to ISO 562:1981. In particular, the volatile content (fB) can be measured by heating previously dried activated carbon to 900°C for 7 minutes under inert conditions, where appropriate, to oxidize the surface.

[0170] By targeting and adjusting the content of oxygen-containing functional groups, it is possible to predetermine or influence the loading of the catalytically active component or related precursor used subsequently, in particular in process step (c). In this regard, the skilled person is always able to select the relevant properties and match them to one another so that the desired loading with the catalytically active component occurs within the meaning of the present invention.

[0171] In general, oxidation can be carried out in a gas atmosphere or wet chemically, especially when using acids.

[0172] According to the invention, in process step (b), the oxidation, in particular the surface oxidation, of the activated carbon can be carried out using at least one oxidizing agent, which can be selected from the group consisting of oxygen, ozone, inorganic or organic oxides and peroxides, in particular hydrogen peroxide, inorganic or organic acids and peracids, in particular mineral acids, and combinations thereof.

[0173] In particular, the oxidizing agent may be selected from the group consisting of oxygen, hydrogen peroxide (H2O2), nitrogen oxides (preferably NO and / or NO2), hydrochloric acid (HCl), nitric acid (HNO3), sulfuric acid (H2SO4), perchloric acid (HClO4), phosphoric acid (H3PO4), and combinations thereof.

[0174] More preferably, the oxidizing agent is selected from the group consisting of oxygen (O), hydrochloric acid (HCl), nitric acid (HNO), sulfuric acid (HSO), perchloric acid (HClO), phosphoric acid (HPO), hydrogen peroxide (HO) and combinations thereof, particularly preferably from the group consisting of oxygen (O), hydrochloric acid (HCl) and nitric acid (HNO) and combinations thereof, more preferably from the group consisting of oxygen (O) and nitric acid (HNO) and combinations thereof.

[0175] With regard to the use of oxygen, it is possible to use, in particular, atmospheric oxygen or synthetic air.

[0176] Generally, in the present invention, in process step (b), the oxidation, particularly the surface oxidation, of the activated carbon can be carried out by heating, in particular at a temperature that allows a reaction of the activated carbon with an oxidizing agent, which results in the formation of oxygen-containing functional groups on the surface of the activated carbon. The oxidation, particularly the surface oxidation, of the activated carbon can be carried out at temperatures ranging from -20°C to 1000°C, in particular from 0°C to 800°C, preferably from 5°C to 700°C, more preferably from 10°C to 600°C, and particularly preferably from 20°C to 550°C. In this regard, the oxidation, particularly the surface oxidation, of the activated carbon is carried out for a period of up to 48 hours, in particular up to 24 hours, and preferably up to 12 hours. According to the present invention, the oxidation, particularly the surface oxidation, of the activated carbon is carried out for a period of, for example, 1 minute to 1000 minutes, in particular from 5 minutes to 800 minutes, and preferably from 10 minutes to 600 minutes.

[0177] According to the present invention, oxidation of activated carbon, particularly surface oxidation, is carried out in conjunction with the formation of a hydrophilic surface of the activated carbon. In this regard, oxidation of activated carbon, particularly surface oxidation, is carried out by forming oxygen-containing functional groups on the surface of the activated carbon. Furthermore, oxidation of activated carbon, particularly surface oxidation, results in the formation of oxygen-containing functional groups, particularly on the surface of the activated carbon. In this regard, the oxygen-containing functional groups are preferably selected from acidic and basic oxygen-containing functional groups and combinations thereof, particularly acidic and basic surface oxides. In particular, the oxygen-containing functional groups are preferably selected from the group consisting of hydroxyl groups, carboxyl groups, carbonyl groups, anhydrides, lactones, quinones, pyrones, chromenes, and ether groups and combinations thereof, particularly the group consisting of hydroxyl groups, carboxyl groups, and ether groups and combinations thereof.

[0178] According to a first embodiment of the present invention, in process step (b), the oxidation, in particular the surface oxidation, of the activated carbon is carried out using an oxidizing agent in the form of oxygen (O2). Therefore, in process step (b), the oxidation, in particular the surface oxidation, is carried out using oxygen (O2) as the oxidizing agent. In this regard, the oxidation, in particular the surface oxidation, of the activated carbon is carried out at temperatures in the range of 100°C to 1000°C, in particular in the range of 200°C to 800°C, preferably in the range of 300°C to 700°C, more preferably in the range of 350°C to 600°C, and particularly preferably in the range of 400°C to 550°C. In particular, the oxidation, in particular the surface oxidation, of the activated carbon is carried out for a period of up to 10 hours, in particular up to 8 hours, preferably up to 6 hours. The oxidation, in particular the surface oxidation, of the activated carbon is carried out for a period of 30 minutes to 1000 minutes, in particular in the range of 60 minutes to 800 minutes, preferably in the range of 100 minutes to 600 minutes. In this respect, it is possible to proceed in particular with air oxidation or oxidation in a gas atmosphere.

[0179] In contrast, according to a further embodiment of the present invention, oxidation, in particular surface oxidation, of the activated carbon can also be carried out in process step (b) using an oxidizing agent, for example a mineral acid such as nitric acid (HNO). In this regard, wet chemical methods can be used in particular. In this regard, the present invention therefore preferably provides that oxidation, in particular surface oxidation, is carried out in process step (b) using a mineral acid, in particular nitric acid (HNO), as the oxidizing agent. In this regard, oxidation, in particular surface oxidation, of the activated carbon is preferably carried out at a temperature in the range of -20°C to 250°C, in particular in the range of 0°C to 200°C, preferably in the range of 5°C to 175°C, more preferably in the range of 10°C to 150°C, and particularly preferably in the range of 15°C to 125°C. Furthermore, oxidation, in particular surface oxidation, of the activated carbon is preferably carried out for a period of up to 6 hours, in particular up to 5 hours, preferably up to 4 hours. Similarly, the oxidation of activated carbon, particularly the surface oxidation, is preferably carried out for a period of time within the range of 5 to 500 minutes, particularly within the range of 10 to 400 minutes, and preferably within the range of 20 to 300 minutes.

[0180] According to this embodiment of the present invention, the mineral acid, particularly nitric acid (HNO3), is 10% (volume %) to 75%, particularly 15% to 60%, preferably 20% to 55%, more preferably about 25%, more preferably about 50%.

[0181] The present invention further provides that in process step (b), the oxidation, in particular surface oxidation, is followed by purification and / or drying of the oxidized activated carbon, in particular prior to process step (c). In this case, purification is carried out by at least one washing method in a liquid, in particular water. Furthermore, drying is carried out by heating the oxidized, in particular surface-oxidized, activated carbon, in particular to a temperature in the range of 40°C to 200°C, in particular 50°C to 150°C, preferably 60°C to 120°C. In particular, drying is preferably carried out under reduced pressure and / or in vacuum, and / or in particular at an (air) pressure in the range of 0.01 Pa to 100 Pa, in particular 0.1 Pa to 10 Pa.

[0182] In the following, the method step (c) of the process of the previously oxidized activated carbon with catalytically active components or related precursors is explained in more detail: Generally, in process step (c), the application of the activated carbon oxidized in process step (b), in particular the oxidized surface or the catalyst support, is carried out by applying and / or contacting, preferably fixing, the catalytically active component on the catalyst support.

[0183] In general, it is preferred that the catalytically active component comprises or consists of at least one metal, especially in the form of a metal compound, preferably in the form of an ionic metal compound and / or especially in elemental form.

[0184] In general, the catalytically active component may comprise at least one metal, in particular at least one metal cation, in a positive oxidation state, in particular the oxidation state of the metal is in the range +I to +VII, in particular in the range +I to +IV, preferably in the range +I to +III, particularly preferably in the range +1 or +II, and / or the catalytically active component comprises at least one metal in the oxidation state zero. For simple ions, the oxidation number corresponds to the charge number, whereas in the case of polynuclear ions, in particular so-called clusters, the oxidation number may deviate from the charge number, as is well known to those skilled in the art.

[0185] In particular, the catalytically active component may comprise at least one metal or at least one lanthanide selected from the main group or subgroups of the Periodic Table of the Elements, and in particular preferably at least one metal selected from the elements of main group IV or subgroups I, II, III, IV, V, VI, VII and VIII of the Periodic Table of the Elements, in particular from the elements of main group IV or subgroups I and II of the Periodic Table of the Elements. According to the present invention, it is possible to provide that the catalytically active component comprises at least one metal selected from the group consisting of Cu, Ag, Au, Zn, Hg, Sn, Ce, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Bi, Ru, Os, Co, Rh, Re, Ir, Ni, Pd and Pt, in particular the group consisting of Fe, Bi, V, Cu, Pb, Zn, Ag, Sn, Pd, Pt, Ru and Ni, preferably the group consisting of Fe, Bi, V, Cu, Pt, Ru and Pb, more preferably the group consisting of Pd, Pt and Ru, and particularly preferably the group consisting of Pd and Pt. The catalytically active component is used in step (c) of the method, in particular in the form of a precursor.

[0186] In particular, it is provided by the present invention that a precursor of the catalytically active component is formed or configured such that said precursor is converted into the catalytically active component by the reduction carried out in method step (d). In particular, the precursor of the catalytically active component may be an oxidized form of the catalytically active component or may be formed therefrom.

[0187] In general, the precursor of the catalytically active component may comprise at least one metal compound, preferably based on at least one metal as defined above, which is soluble and / or dissociable in an aqueous and / or especially aqueous-based solvent and / or dispersion medium.

[0188] Furthermore, the precursor of the catalytically active component may comprise at least one inorganic or organometallic compound, preferably at least one of the previously defined metals, in particular a metal salt or metal oxide, preferably based on a metal salt.

[0189] In particular, the precursor of the catalytically active component may comprise at least one organic or inorganic metal salt, preferably based on at least one metal as defined above, the salt being preferably selected from the group consisting of halide salts, hydroxides, amines, sulfates, sulfites, nitrates, nitrates, phosphates, phosphides, carbamates, alkoxides and carboxylate salts, in particular halide salts, nitrates, hydroxides and carboxylate salts.

[0190] Furthermore, the precursor of the catalytically active component preferably comprises at least one metal halide, in particular a fluoride, chloride, bromide or iodide, preferably based on at least one of the above-defined metals, preferably a chloride, and / or at least one carboxylate, in particular an acetate, of a metal, preferably based on at least one of the previously defined metals.

[0191] In general, the precursor of the catalytically active component preferably comprises at least one metal compound selected from the group consisting of palladium chloride, palladium nitrate, hexachloroplatinic acid, platinum nitrate, tetraaminoplatinum dihydroxide, ruthenium chloride, copper chloride, iron chloride, vanadium chloride and lead chloride, in particular from the group consisting of palladium chloride, palladium nitrate, hexachloroplatinic acid, platinum nitrate and tetraaminoplatinum dihydroxide.

[0192] In particular, the precursor preferably comprises or consists of palladium chloride, palladium nitrate, hexachloroplatinic acid, platinum nitrate and / or tetraammine platinum dihydroxide.

[0193] According to the invention, H2PdCl4 and / or Pd(NO3)2 are preferably used as precursors (palladium precursors). According to the invention, H2(PtCl6), (NH3)4Pt(OH)2 and / or Pt(NO3)2 are likewise preferably used as precursors (platinum precursors).

[0194] In particular, the precursors of the catalytically active components are intended to be used for finishing and / or loading and / or coating and / or impregnating oxidized, in particular surface-oxidized, activated carbons, in particular in the form of aqueous and / or especially aqueous-based solutions and / or dispersions (dispersions).

[0195] In this regard, the solution or dispersion may comprise water as a solvent or dispersion medium, and may further comprise at least one organic or inorganic acid or base, preferably hydrochloric acid.

[0196] Furthermore, the precursors of the catalytically active components can be present in the form of a solution or dispersion (dispersion) at least substantially free of crystals and / or crystallites. In particular, the precursors of the catalytically active components in the form of a solution or dispersion (dispersion) can be at least substantially dissolved, in particular at least substantially dissociated.

[0197] Generally, the solution and / or dispersion form (dispersion) can contain precursors of the catalytically active component in an amount ranging from 0.01% to 80% by weight, in particular from 0.1% to 60% by weight, preferably from 1% to 50% by weight, more preferably from 2% to 40% by weight, calculated as metal, based on the solution and / or dispersion form (dispersion).

[0198] The terms "solution" or "dispersion" used in this context in the present invention are understood to mean, in particular, that the precursors of the catalytically active components are present in the basic solvent or dispersion medium at least substantially completely dissolved, dissociated or dispersed in the basic amount or concentration. For example, within the scope of the present invention, it is provided that, in order to equip or load the activated carbon with the catalytically active components, the activated carbon used according to the present invention is immersed or impregnated in the corresponding solution or dispersion of the (precursor of) the catalytically active component. In this way, it is ensured, in particular, that the basic solution or dispersion fills at least substantially the entire pore system of the activated carbon, which results in a homogeneous loading of the activated carbon with the catalytically active component.

[0199] Generally, according to the present invention, in process step (c), the preparation of the oxidized, in particular surface-oxidized activated carbon with the catalytically active component, in particular a precursor of the catalytically active component, comprises applying and / or contacting, preferably fixing, the oxidized, in particular surface-oxidized activated carbon with the catalytically active component, in particular a precursor of the catalytically active component. In particular, the applying and / or contacting, preferably fixing, is carried out by immersing and / or impregnating, wetting, covering, coating and / or spraying the oxidized, in particular surface-oxidized activated carbon with the catalytically active component, in particular a precursor of the catalytically active component. The applying and / or contacting is thereby carried out by energy input, in particular vibration and / or ultrasonic input. In this regard, the catalytically active component, in particular a precursor of the catalytically active component, is used in the form of a solution and / or dispersion (dispersion), as indicated above.

[0200] In order to equip the activated carbon, oxidized, in particular surface-oxidized, with a catalytically active component, in particular with a precursor of the catalytically active component, in particular after application and / or contacting, it is provided that an excess of the catalytically active component, in particular an excess of a precursor of the catalytically active component, in the form of a solution and / or dispersion (dispersion) of the catalytically active component, preferably in the form of a solution and / or dispersion (dispersion) of a precursor of the catalytically active component, is removed and / or separated from the activated carbon or the catalyst system, in particular from the catalyst system.

[0201] In this regard, after application or contact, in particular purification and / or drying of the obtained activated carbon is carried out, in order to finish the oxidized, in particular surface-oxidized, activated carbon with the catalytically active component, in particular a precursor of the catalytically active component. In this respect, purification and / or drying is carried out by at least one washing step in a liquid, in particular water. Furthermore, purification and / or drying can be carried out by heating the activated carbon provided with the catalytic component, in particular to a temperature in the range of 40°C to 200°C, in particular 50°C to 150°C, preferably 60°C to 120°C. Furthermore, purification and / or drying can be carried out under reduced pressure and / or in a vacuum (air). Furthermore, purification and / or drying is carried out at an (air) pressure in the range of 100 Pa to 0.01 Pa, in particular 10 Pa to 0.1 Pa. Removal of the solvent or dispersant and drying of the activated carbon leads in particular to the drying or particulate formation of a precursor of the catalytically active component, which is present in crystalline form on or at the surface of the activated carbon used in particular as a catalyst support.

[0202] In general, the process according to the invention provides that in process step (c) both the outer and inner surfaces of the oxidized, in particular microporous, mesoporous and / or macroporous surface-oxidized activated carbon are provided, in particular supported and / or coated and / or impregnated, with catalytically active components, in particular in the form of corresponding precursors, so that high loadings of catalytically active components can be achieved.

[0203] In the following, process step (d) describes in more detail the reduction of the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) with a catalytically active component, in particular a precursor of a catalytically active component:

[0204] As for the reduction of the oxidized, especially surface-oxidized, activated carbon provided with catalytically active components, especially precursors of catalytically active components, obtained in process step (c) in process step (d) according to the present invention, without wishing to be limited by this theory, it leads in particular to the reduction of at least a portion of the catalytically active components incorporated or applied to the activated carbon or their associated precursors. In particular, catalytically active components or associated precursors or underlying metal compounds or underlying metals can be reduced in this manner, especially if the catalytically active components or associated precursors are present in oxidized form or in the form of salts, ions, etc. Thus, the reduction treatment can generally be carried out in the context of the activation of the catalyst and / or the conversion of the catalyst or catalytically active components or their associated precursors into an active form, in particular the change and / or reduction of the oxidation number of the metals of the catalytically active components. Thus, the reduction treatment can in particular be carried out in the context of the activation of the catalytically active components or their associated precursors.

[0205] The reduction treatment according to process step (d) is carried out, for example, with respect to metals, in particular noble metals, of the catalytically active component or of the relevant precursors that are not used in the zero oxidation state or that are not present in the form of compounds, in particular in the form of salts, in such a way that when the activated carbon is loaded with the catalytically active component or the relevant precursor in process step (c), a corresponding conversion of the metal or noble metal into the elemental form or into the zero oxidation state is carried out in the form of compounds, in particular in the form of salts, whereby activation of the catalyst or conversion into the catalytically active form is achieved or carried out.

[0206] Furthermore, without wishing to be limited to this theory, the reduction treatment according to method step (d) leads to the removal or reduction (surface reduction) of at least a portion of the functional groups, in particular oxygen-containing functional groups, on the surface of the activated carbon or in the pore system associated therewith. In method step (d), a surface reduction of the oxidized activated carbon provided with catalytically active components or associated precursors can thus be carried out. In this way, a neutral surface or neutralization of the catalyst support or the corresponding activated carbon, and thus of the catalyst system, can be achieved.

[0207] The catalytic system according to the invention thus treated, or activated carbon for that matter, consequently also exhibits a reduced self-reaction, in particular as a result of the reduced content of functional groups on its surface that accompanies the reduction treatment, which is beneficial to the catalytic properties as a whole.

[0208] Similarly, without wishing to be limited to this theory, based on the reduction treatment carried out, the activated carbon and therefore the entire catalytic system becomes less hydrophilic or has a lower content of polar groups, which in turn improves the overall penetration or diffusion behavior, especially of hydrophobic or non-polar reactants or products resulting from the catalytic reaction.

[0209] Generally, in process step (d), the reduction can be carried out as a gas phase reduction or as a liquid phase reduction.

[0210] In particular, it is preferably provided according to the invention that in process step (d) the reduction is carried out at a temperature in the range of 20° C. to 400° C., in particular in the range of 50° C. to 300° C., preferably in the range of 100° C. to 250° C., more preferably in the range of 110° C. to 200° C., particularly preferably in the range of 115° C. to 160° C., most preferably in the range of 120° C. to 150° C., and even more preferably in the range of 130° C. to 145° C. Furthermore, in process step (d), the reduction will generally be carried out at a temperature in the range of 0° C. to 750° C., in particular in the range of 10° C. to 600° C.

[0211] According to the invention, in process step (d), the reduction is carried out for a time in the range of 0.05 h to 48 h, in particular in the range of 0.1 h to 36 h, preferably in the range of 0.5 h to 24 h, more preferably in the range of 1 h to 12 h.

[0212] Next, the reduction process using a gaseous reducing agent will be described in detail below, and this embodiment is preferred according to the present invention. In this regard, it can be provided according to the invention that in process step (d) the reduction of the catalyst system is carried out using at least one gaseous reducing agent, in particular a gaseous reducing agent, preferably hydrogen. In this respect, in method step (d), the reduction is carried out in an atmosphere comprising a reducing agent, in particular hydrogen, in particular an inert atmosphere, preferably a nitrogen atmosphere, wherein the atmosphere comprises the reducing agent, in particular hydrogen, in an amount in the range of 0.1% to 20% by volume, in particular in the range of 0.5% to 10% by volume, preferably in the range of 2% to 8% by volume, based on the volume of the atmosphere. Furthermore, in process step (d), the reduction is carried out at a temperature in the range of 50°C to 300°C, in particular in the range of 100°C to 250°C, preferably in the range of 110°C to 200°C, more preferably in the range of 115°C to 160°C, even more preferably in the range of 120°C to 150°C, and most preferably in the range of 130°C to 145°C. Furthermore, in process step (d), the reduction is carried out at a volumetric flow rate of the atmosphere containing the reducing agent in the range of 5 L / h to 1,000 L / h, in particular in the range of 10 L / h to 500 L / h, preferably in the range of 50 L / h to 300 L / h. It is preferred in this respect that, according to the invention, in process step (d) the reduction is carried out using a gaseous reducing agent for a time in the range from 0.1 h to 36 h, in particular in the range from 0.2 h to 24 h, preferably in the range from 0.5 h to 12 h.

[0213] According to another embodiment of the present invention, the reduction treatment using a liquid reducing agent is further described below: Therefore, according to the invention, it is provided that in process step (d) the reduction of the catalyst system is carried out using at least one liquid reducing agent, in particular a liquid alkaline reducing agent, preferably based on at least one alkali metal hydroxide, preferably potassium hydroxide, in particular based in combination with at least one alkali metal formate, preferably potassium formate. In this regard, in process step (d), the reduction is carried out using a liquid reducing agent at a temperature in the range from 10°C to 250°C, in particular in the range from 20°C to 200°C, preferably in the range from 30°C to 150°C, preferably in the range from 40°C to 125°C, particularly preferably in the range from 50°C to 120°C. In this respect, in process step (d), the reduction is carried out for a time in the range of from 0.05 hours to 24 hours, in particular in the range of from 0.1 hours to 12 hours, preferably in the range of from 0.5 hours to 8 hours.

[0214] In the context of the present invention, the reduction carried out in process step (d) can therefore be carried out using at least one gaseous and / or liquid reducing agent. In addition to the above-mentioned reducing agents, formalin, hydrazine, and complex hydrides such as LiAlH4 and / or NaBH4 and / or formic acid can in principle also be considered as reducing agents.

[0215] In general, in carrying out or after carrying out method step (d), and in particular also in the second aspect of the invention, such a catalyst system according to the invention is obtained as described or defined below, so that the descriptions therein apply accordingly to this aspect.

[0216] Overall, in process step (d), a catalyst system according to the invention can be obtained, which comprises at least one catalytically active component applied to and / or fixed on a catalyst support, the catalytically active component comprising and / or consisting of at least one metal, and the catalyst support is in the form of activated carbon and / or formed on the basis of activated carbon, the catalyst support being in the form of granular, preferably spherical, activated carbon, and the activated carbon (i.e. the activated carbon forming the catalyst support) is (i) 0.8 cm 3 / g~3.9cm 3 / g, in particular a Goulwich total pore volume, in which at least 50% of the total pore volume, in particular the Goulwich total pore volume, is formed by pores with a pore diameter of at least 2 nm, in particular by pores with a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores, and (ii) is 1,000m 2 / g~3,000m 2 / g BET ), but the total pore volume (V total ), especially the specific BET surface area of ​​the total pore volume according to Goulwich (S BET ) ratio (quotient: Q), especially the formula Q=V total / S BET The ratio (quotient; Q) is at least 0.5 × 10 -9 The condition is that m.

[0217] In the context of the present invention, in process step (d), in particular a catalyst system can be obtained, the catalyst system comprising at least one catalytically active component applied or fixed to a catalyst support, the catalytically active component comprising and / or consisting of at least one metal, the catalyst support being in the form of activated carbon or formed on the basis of activated carbon, the catalyst support being in the form of granules, preferably spherical activated carbon.

[0218] According to the present invention, the catalyst system may have an activity, measured as the percentage dispersion of the catalytically active components, in particular of the metals of the catalytically active components (dispersity D, metal dispersion), on the catalyst support, preferably measured by chemisorption using the (dynamic) flow method according to DIN 66136-3:2007-01, of at least 15%, in particular at least 20%, preferably at least 25%, more preferably at least 28%, and / or in the range of 15% to 90%, in particular in the range of 20% to 80%, preferably in the range of 25% to 70%, most preferably in the range of 28% to 60%.

[0219] In particular, the catalyst system preferably has a thickness of at most 80 Angstroms (8 nm), in particular at most 70 Angstroms (7 nm), preferably at most 60 Angstroms (6 nm), more preferably at most 58 Angstroms (5.8 nm), even more preferably at most 45 Angstroms (4.5 nm), even more preferably at most 40 Angstroms (4 nm), most preferably at most 38 Angstroms (3.8 nm) and / or in the range of 5 Angstroms (0.5 nm) to 80 Angstroms (8 nm), in particular in the range of 7 Angstroms (0.7 nm) to 70 Angstroms (7 nm). The average crystallite size (average crystallite size d m), preferably measured according to DIN 66136, is in the range of 10 angstroms (1 nm) to 60 angstroms (6 nm), more preferably in the range of 15 angstroms (1.5 nm) to 58 angstroms (5.8 nm), particularly preferably in the range of 17 angstroms (1.7 nm) to 45 angstroms (4.5 nm), especially more preferably in the range of 18 angstroms (1.8 nm) to 40 angstroms (4 nm), and most preferably in the range of 20 angstroms (2 nm) to 38 angstroms (3.8 nm). Me ) and in particular those having a metal of the catalytically active component.

[0220] In this regard, it is therefore generally provided by the present invention that the catalyst system obtained in process step (d) has an activity, measured as a dispersion percentage of the catalytically active components, in particular of the metals of the catalytically active components, on the catalyst support, preferably measured by chemisorption by the (dynamic) flow method according to DIN 66136:2007-01, of at least 15%, in particular at least 20%, preferably at least 25%, preferably at least 28% and / or in the range of 15% to 90%, in particular in the range of 20% to 80%, preferably in the range of 25% to 70%, more preferably in the range of 28% to 60%.

[0221] Furthermore, in this regard, it is preferred that the catalyst system obtained in process step (d) has a maximum diameter of at most 80 Angstroms (8 nm), in particular at most 70 Angstroms (7 nm), preferably at most 60 Angstroms (6 nm), more preferably at most 58 Angstroms (5.8 nm), most preferably 38 Angstroms (3.8 nm), and / or a diameter in the range of 5 Angstroms (0.5 nm) to 80 Angstroms (8 nm), in the range of 7 Angstroms (0.7 nm) to 70 Angstroms (7 nm), preferably in the range of 10 Angstroms (1 nm) to 60 Angstroms (6 nm), more preferably It is also preferably provided within the scope of the present invention to have catalytically active components, in particular the metal of the catalytically active component, having an average crystallite size, preferably determined in accordance with DIN 66136, in the range of 15 angstroms (1.5 nm) to 58 angstroms (5.8 nm), particularly preferably in the range of 17 angstroms (1.7 nm) to 45 angstroms (4.5 nm), even more preferably in the range of 18 angstroms (1.8 nm) to 40 angstroms (4 nm), and most preferably in the range of 20 angstroms (2 nm) to 38 angstroms (3.8 nm).

[0222] Thus, according to the present invention, it is possible to obtain catalyst systems according to the present invention having the above-mentioned characteristics of a particular percentage dispersion of the catalytically active component or metal in question, as well as a particular crystallite size, which characterize the excellent catalytic properties of the catalyst systems according to the present invention, in particular with regard to a large catalytically active surface due to an optimal provision or occupation of the pore system of the activated carbon with the catalytically active component or metals.

[0223] The dispersion of the catalytically active component or metal dispersion also describes the catalytic activity of the catalyst system or supported catalyst according to the invention. Thus, catalytic activity is characterized by the dispersion of the catalytically active component or the metal of the catalytically active component on the catalyst support material, against the background that sufficient surface atoms of the catalytically active component are able to participate in or enable the catalytic conversion. According to the present invention, the term "dispersion" (also referred to as "dispersion D") is used synonymously with the term "metal dispersion" or "metal dispersion D". The percentage dispersion is based in particular on the ratio of the atoms or molecules of the catalytically active component actually present on the surface to the theoretically possible size of the atoms or molecules of the catalytically active component present on the surface. In other words, the percentage dispersion describes, in particular, the ratio of the number of atoms or molecules on the surface of the catalytically active component (as can be determined, for example, by chemisorption of a sample gas with atoms or molecules of the catalytically active component accessible to the sample gas) to the total number of atoms or molecules of the catalytically active component (i.e., relative to the total theoretically available or used atoms or molecules of the catalytically active component or the total atoms or molecules of the catalytically active component present on the catalyst support). In particular, the measurement can be carried out by chemisorption. In particular, carbon monoxide (CO) can be used as the measurement gas. Therefore, the dispersion or metal dispersion can be measured, in particular, by chemisorption of carbon monoxide.

[0224] The percentage dispersion (D) of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support or activated carbon can be calculated in particular on the basis of the following formula (I):

number

[0225] In particular, the average crystallite size (synonymously the average crystallite size d Me ) can be calculated based on the following formula (II):

number

[0226] With respect to formulas (I) and (II) above, the following formula symbols apply: [Table 1]

[0227] As far as the average crystallite size according to the invention is concerned, it also characterizes the catalytic activity, in particular due to the improved accessibility of the catalytically active components to the reactants to be reacted. In particular, the average crystallite size according to the invention optimizes the ratio between the surface area and the corresponding volume of the catalytically active components forming the crystallites, which also leads to an improvement in the catalytic activity.

[0228] In particular, according to the present invention, the average dispersity on the one hand and the average crystallite size on the other hand work together in terms of the overall improved catalytic activity provided and reinforce each other beyond the sum of their respective individual effects, so that in this respect there is a synergistic effect in terms of the improved catalytic activity of the catalyst system according to the present invention, and in particular also in terms of higher conversion rates or improved space / time yields.

[0229] Based on the method according to the invention, the amount or content of catalytically active components can be specifically adjusted or regulated for the catalyst system according to the invention, so that the catalytic activity of the catalyst system obtained according to the invention can also be specifically predetermined from this point of view.

[0230] The present invention therefore provides that the catalyst system obtained in process step (d) comprises catalytically active components in an amount, calculated as metals, of at least 0.05% by weight, in particular at least 0.1% by weight, preferably at least 0.2% by weight, more preferably at least 0.5% by weight, particularly preferably at least 0.6% by weight, most preferably at least 1% by weight, and even more preferably at least 1.5% by weight, based on the total weight of the catalyst system. By setting a lower limit, the desired catalytic activity can be ensured.

[0231] It is furthermore particularly provided according to the invention that the catalyst system obtained in process step (d) comprises catalytically active components in an amount of at most 25% by weight, in particular at most 20% by weight, preferably at most 15% by weight, more preferably at most 10% by weight, particularly preferably at most 8% by weight, and very particularly preferably at most 7% by weight, calculated as metals and based on the total weight of the catalyst system. The upper limit ensures in particular good accessibility to the catalytically active components and in particular avoids clogging of the pores.

[0232] In this regard, it is particularly possible in the context of the present invention for the catalyst system obtained in process step (d) to comprise an amount of catalytically active components, calculated as metals and based on the total weight of the catalyst system, in the range of 0.05% to 25% by weight, in particular in the range of 0.1% to 25% by weight, preferably in the range of 0.2% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, particularly preferably in the range of 0.6% to 10% by weight, even more preferably in the range of 1% to 8% by weight and most preferably in the range of 1.5% to 7% by weight.

[0233] Furthermore, it is preferred that the catalytically active components of the catalyst system obtained in step (d) of the process according to the invention:

[0234] In particular, the catalytically active component of the catalyst system obtained in process step (d) comprises or consists of at least one metal, in particular in the form of a metal compound, preferably in the form of an ionic metal compound and / or in particular in elemental form.

[0235] In particular, the catalytically active component of the catalyst system obtained in process step (d) preferably comprises at least one metal, in particular at least one metal cation, in a positive oxidation state. In this respect, it is preferred that the oxidation state of the metal is in the range +I to +VII, in particular in the range +I to +IV, preferably in the range +I to +III, or particularly preferably +I or +II. It is also preferred according to the invention that the catalytically active component comprises at least one metal in the oxidation state zero.

[0236] In particular, in the course of the reduction carried out in process step (d), the catalytically active component used according to process step (c) or the metal associated therewith can be reduced accordingly, in particular so that in process step (d) the metal is present in the zero oxidation state. In the context of the present invention, it is particularly preferred that the catalytically active component of the catalyst system obtained in process step 8d) (and therefore the end product obtained from this process) comprises at least one metal in the zero oxidation state.

[0237] In particular, the catalytically active component of the catalyst system obtained in process step (d) may comprise at least one metal from a main or subgroup of the periodic table of the elements, or at least one lanthanide.

[0238] In general, it is preferred that the catalytically active component of the catalyst system obtained in process step (d) comprises at least one metal selected from the elements of main group IV or subgroups I, II, III, IV, V, VI, VII and VIII of the Periodic Table of the Elements, in particular from the elements of main group IV or subgroups I and II of the Periodic Table of the Elements.

[0239] In particular, it is preferred that the catalytically active component of the catalyst system obtained in process step (d) comprises at least one metal selected from the group consisting of Cu, Ag, Au, Zn, Hg, Sn, Ce, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Bi, Ru, Os, Rh, Re, Ir, Ni, Pd and Pt, in particular from the group consisting of Fe, Bi, V, Cu, Pb, Zn, Ag, Sn, Pd, Pt, Ru and Ni, preferably from the group consisting of Fe, Bi, V, Cu, Pt, Ru and Pb, more preferably from the group consisting of Pd, Pt and Ru, even more preferably from the group consisting of Pd and Pt, since particularly high catalytic activities are obtained with said metals for catalytic processes such as hydrogenation reactions on which such reactions are based.

[0240] As regards the activated carbon present in the catalytic system, this may be based on or derived from the following types of activated carbon, the properties of which equally lead to an improvement in the performance of the catalytic system according to the invention (for example by improving or forming an arrangement with the catalytically active components): The ((surface-)reduced) activated carbon of the catalyst system obtained in process step (d) (i.e. the activated carbon forming the catalyst support) may therefore be oxidized, in particular at its surface, prior to the application and / or fixation of the catalytically active component, in particular if oxidation, in particular surface oxidation, of the activated carbon has been carried out using and / or in the presence of at least one oxidizing agent. In this respect, reference may also be made to the explanations given above, in particular to process step (c). Likewise, within the scope of the present invention, it is preferred that after being provided with catalytically active components, the activated carbon behaves in such a way that it is reduced, especially on its surface, and in particular that the reduction of the activated carbon is carried out using and / or in the presence of at least one reducing agent. In particular, after being provided with catalytically active components and / or after the reduction has taken place, the activated carbon behaves in such a way that it is reduced, especially as a surface-reduced activated carbon. In particular, according to the present invention, during the reduction process, precursors of the catalytically active components are converted into their active form or into the catalytically active components, in particular the underlying metal components are converted into elemental form. Furthermore, the activated carbon (i.e., the activated carbon forming the catalyst support) is preferably obtained by carbonization and subsequent activation of a starting material based on an organic polymer, followed by an oxidation treatment (wherein the oxidation treatment is carried out before providing the catalytically active component) and a reduction treatment (wherein the reduction treatment is carried out after providing the catalytically active component). In this regard, the above explanations can also be referred to. Likewise, the activated carbon (i.e. the activated carbon forming the catalyst support) may be based on activated carbon obtained by carbonization and subsequent activation of an organic polymer-based starting material and / or based on activated carbon based on a polymer, preferably in the form of spherical activated carbon (PBSAC or polymer-based spherical activated carbon). Furthermore, the activated carbon of the catalyst system obtained in process step (d) (i.e. the activated carbon forming the catalyst support) may be an activated carbon based on or derived from the starting materials described herein (see also claim 21). In particular, the activated carbon of the catalyst system obtained in process step (d) can be based on or revert to an activated carbon obtained according to the method for producing activated carbon described herein (see claims 22 to 25) or according to the oxidation method described herein (see also claims 30 to 34) according to process step (b).

[0241] Furthermore, the catalytically active component of the catalyst system obtained according to the invention can be based on a precursor of the catalytically active component which is reduced, in particular in process step (d).

[0242] In particular, it is preferred in the context of the present invention if the catalyst system obtained in process step (d) is a catalyst system that has been reduced, in particular on its surface (including in particular the catalyst support, and thus the activated carbon associated therewith, and the corresponding oxidation of the catalytically active components or precursors associated therewith).

[0243] Furthermore, for a further description of the catalyst system according to the invention obtained in process step (d), reference may be made to the following description according to the second aspect of the invention comprising a catalyst system, the description therein applying mutatis mutandis.

[0244] Turning further to the first aspect of the invention, the present invention also relates to a method for producing a catalyst system comprising at least one catalytically active component, in particular a supported catalyst, preferably for use in a heterogeneous system catalyst, in particular as defined herein, At least one catalytically active component is applied to and / or fixed on a catalyst support, said catalytically active component comprising and / or consisting of at least one metal; wherein the method comprises the following steps in the order (a) to (d) defined below: (a) Providing and / or producing granular, preferably spherical, activated carbon (=initial activated carbon) to be used as a catalyst support, Activated carbon (so-called early activated carbon) (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Goulwich, wherein at least 50% of the total pore volume of the activated carbon, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter in the range of 2 nm to 500 nm, preferably by mesopores and macropores, (ii) a specific BET surface area (S) in the range of 1,000 m / g to 3,000 m / g BET ), but in particular the equation Q=V total / S BET Total pore volume (V total ) of the total pore volume, especially the specific BET surface area (S BET ) is at least 0.5 × 10 -9 m, and (iii) an average pore size in the range of 15 nm to 100 nm, particularly in the range of 16 nm to 90 nm, preferably in the range of 17 nm to 85 nm, more preferably in the range of 18 nm to 80 nm, particularly preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, and even more preferably in the range of 25 nm to 50 nm; after that, (b) oxidation, in particular surface oxidation, of the activated carbon prepared and / or produced in process step (a), provided that the oxidized, in particular surface-oxidized, activated carbon has an oxygen content of at least 4% (atomic %) based on the total elemental composition of the oxidized activated carbon, in particular a surface oxygen content measured by X-ray photoelectron spectroscopy (XPS or ESCA), and / or provided that the oxidized, in particular surface-oxidized, activated carbon has hydrophilicity determined as a water vapor adsorption behavior such that at least 30% of the maximum water vapor saturation load of the activated carbon reaches a partial pressure p / p0 of 0.6; after that, (c) equipping, in particular loading and / or coating and / or impregnating, the activated carbon oxidized in process step (b), in particular surface-oxidized, with a catalytically active component, in particular at least one precursor of a catalytically active component; after that, (d) reduction of the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) with a catalytically active component, in particular a precursor of a catalytically active component, in order to convert the precursor of the catalytically active component into the catalytically active component, in particular to obtain a catalyst system having at least one catalytically active component, in particular a supported catalyst.

[0245] In this context, the present invention also relates, according to a first aspect of the invention, to a method for preparing a catalyst system comprising at least one catalytically active component, in particular a supported catalyst, preferably for use in a heterogeneous catalyst system, in particular as defined above, at least one catalytically active component is applied and / or fixed to a catalyst support, said catalytically active component comprising and / or consisting of at least one metal; wherein the method comprises the following steps in the order (a) to (d) defined below: (a) Providing and / or producing granular, preferably spherical, activated carbon (=initial activated carbon) to be used as a catalyst support, Activated carbon (so-called early activated carbon) (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Goulwich, wherein at least 50% of the total pore volume of the activated carbon, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter in the range of 2 nm to 500 nm, preferably by mesopores and macropores, (ii) a specific BET surface area (S) in the range of 1,000 m / g to 3,000 m / g BET ), but in particular the equation Q=V total / SBET Total pore volume (V total ) of the total pore volume, especially the specific BET surface area (S BET ) is at least 0.5 × 10 -9 m, and (iii) having an average pore size in the range of 15 nm to 100 nm, particularly in the range of 16 nm to 90 nm, preferably in the range of 17 nm to 85 nm, more preferably in the range of 18 nm to 80 nm, particularly preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, and even more preferably in the range of 25 nm to 50 nm; and (iv) a particle size, in particular a particle diameter, in the range of 60 μm to 1,000 μm, in particular in the range of 70 μm to 800 μm, preferably in the range of 80 μm to 600 μm, with at least 80% by weight, in particular at least 90% by weight, preferably at least 95%, in particular of the activated carbon particles having a particle size, in particular a diameter, in the above-mentioned range; and / or an average particle size (D50), in particular an average particle diameter (D50), in the range of 60 μm to 900 μm, in particular in the range of 75 μm to 750 μm, preferably in the range of 85 μm to 550 μm, more preferably in the range of 110 μm to 375 μm, particularly preferably in the range of 175 μm to 350 μm, very particularly preferably in the range of 185 μm to 225 μm; after that, (b) oxidation, in particular surface oxidation, of the activated carbon prepared and / or produced in process step (a), with the proviso that the oxidized, in particular surface-oxidized activated carbon has an oxygen content of at least 4% (atomic %) based on the total elemental composition of the oxidized activated carbon, in particular a surface oxygen content measured by X-ray photoelectron spectroscopy (XPS or ESCA), and / or with the proviso that the oxidized, in particular surface-oxidized activated carbon has a hydrophilicity determined as a water vapor adsorption behavior, in which at least 30% of the maximum water vapor saturation load of the activated carbon reaches a partial pressure p / p of 0.60; after that, (c) equipping, in particular loading and / or coating and / or impregnating, the activated carbon oxidized in process step (b), in particular surface-oxidized, with a catalytically active component, in particular at least one precursor of a catalytically active component; after that, (d) reduction of the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) with a catalytically active component, in particular a precursor of a catalytically active component, in order to convert the precursor of the catalytically active component into the catalytically active component, in particular to obtain a catalyst system having at least one catalytically active component, in particular a supported catalyst.

[0246] More particularly, according to a first aspect of the invention, the present invention also relates to a method, in particular as defined herein, for preparing a catalyst system comprising at least one catalytically active component, in particular a supported catalyst, preferably for use in heterogeneous systems, at least one catalytically active component is applied to and / or fixed on a catalyst support, said catalytically active component comprising and / or consisting of at least one metal, The method comprises the following steps in the order (a) to (d) specified below: (a) The activated carbon (so-called initial activated carbon) (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Goulwich, wherein at least 50% of the total pore volume of the activated carbon, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter in the range of 2 nm to 500 nm, preferably by mesopores and macropores, (ii) a specific BET surface area (S) in the range of 1,000 m / g to 3,000 m / g BET ), but in particular the equation Q=V total / S BET Total pore volume (V total) of the total pore volume, especially the specific BET surface area (S BET ) is at least 0.5 × 10 -9 m, and (iii) an average pore size in the range of 15 nm to 100 nm, particularly in the range of 16 nm to 90 nm, preferably in the range of 17 nm to 85 nm, more preferably in the range of 18 nm to 80 nm, particularly preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, and even more preferably in the range of 25 nm to 50 nm; (iv) a particle size, in particular a particle diameter, in the range of 60 μm to 1,000 μm, in particular in the range of 70 μm to 800 μm, preferably in the range of 80 μm to 600 μm, with at least 80% by weight, in particular at least 90% by weight, preferably at least 95%, in particular of the activated carbon particles having a particle size, in particular a diameter, in the above-mentioned range; and / or an average particle size (D50), in particular an average particle diameter (D50), in the range of 60 μm to 900 μm, in particular in the range of 75 μm to 750 μm, preferably in the range of 85 μm to 550 μm, more preferably in the range of 110 μm to 375 μm, particularly preferably in the range of 175 μm to 350 μm, very particularly preferably in the range of 185 μm to 225 μm; (v) optionally having a ball pan hardness of at least 90%, in particular at least 95%, preferably at least 97%, preferably at least 98%, particularly preferably at least 99%, very particularly preferably at least 99.5%, and even more preferably at least 99.8%, (vi) optionally having a vibration density or tamping density in the range of 100 g / L to 1,500 g / L, in particular in the range of 125 g / L to 1,000 g / L, preferably in the range of 150 g / L to 800 g / L, more preferably in the range of 200 g / L to 600 g / L, particularly preferably in the range of 225 g / L to 500 g / L, most preferably in the range of 250 g / L to 400 g / L, and even more preferably in the range of 255 g / L to 395 g / L; and / or having a bulk density in the range of 150 g / L to 1,000 g / L, in particular in the range of 250 g / L to 700 g / L, preferably in the range of 300 g / L to 600 g / L, and more preferably in the range of 300 g / L to 550 g / L; (vii) optionally having a butane adsorption capacity in the range of 35% to 90%, particularly in the range of 40% to 85%, preferably in the range of 45% to 80%, more preferably in the range of 47.5% to 75%; (viii) optionally having an iodine value in the range of 1,250 mg / g to 2,100 mg / g, in particular in the range of 1,300 mg / g to 2,000 mg / g, in the range of 1,400 mg / g to 1,900 mg / g, in the range of 1,425 mg / g to 1,850 mg / g, (ix) optionally having a methylene blue value in the range of 17 mL to 65 mL, particularly in the range of 18 mL to 55 mL, preferably in the range of 19 mL to 50 mL, more preferably in the range of 19.5 mL to 47.5 mL; (x) optionally having a molasses number in the range of 255 to 1,500, in particular in the range of 310 to 1,400, preferably in the range of 375 to 1,300, more preferably in the range of 510 to 1,250; (xi) optionally, 250 cm 3 / g~850cm 3 / g, especially in the 300 cm 3 / g~700cm 3 / g, preferably in the range of 350 cm 3 / g~650cm 3 / g, more preferably 375 cm 3 / g~625cm 3 Weight-based absorbed N2 V measured at a partial pressure p / p0 of 0.25 in the range of / g ads(wt.)having (xii) optionally, 50 cm 3 / cm 3 ~300cm 3 / cm 3 Within the range of 80cm 3 / cm 3 ~275cm 3 / cm 3 Within the range of 90cm 3 / cm 3 ~250cm 3 / cm 3 within the range of 95cm 3 / cm 3 ~225cm 3 / cm 3 The volumetrically converted adsorbed amount of N2 measured at a partial pressure p / p0 of 0.25 within the range of ads(vol.) having (xiii) optionally, 300 cm 3 / g~2,300cm 3 / g, especially in the 400 cm 3 / g~2,200cm 3 / g, preferably in the range of 450 cm 3 / g~2,100cm 3 / g, more preferably in the range of 475 cm 3 / g~2,100cm 3 Weight-based absorbed N2 V measured at a partial pressure p / p0 in the range of 0.995 / g ads(wt.) having (xiv) optionally, 200 cm 3 / cm 3 ~500cm 3 / cm 3 Within the range of 250cm 3 / cm 3 ~400cm 3 / cm 3 Within the range of 275 cm 3 / cm 3 ~380cm 3 / cm 3 more preferably in the range of 295 cm 3 / cm 3 ~375cm 3 / cm 3The volumetrically converted adsorbed amount of N2 measured at a partial pressure p / p0 of 0.995 within the range of ads(vol.) and (xv) optionally having a fractal dimension of porosity in the range of 2.6 to 2.99, in particular in the range of 2.7 to 2.95, preferably in the range of 2.8 to 2.95, and / or the activated carbon has a fractal dimension of porosity of at least 2.7, in particular at least 2.8, preferably 2.85, more preferably at least 2.9, after that, (b) oxidation, in particular surface oxidation, of the activated carbon prepared and / or produced in process step (a), with the proviso that the oxidized, in particular surface-oxidized activated carbon has an oxygen content of at least 4% (atomic %) based on the total elemental composition of the oxidized activated carbon, in particular a surface oxygen content measured by X-ray photoelectron spectroscopy (XPS or ESCA), and / or with the proviso that the oxidized, in particular surface-oxidized activated carbon has a hydrophilicity determined as a water vapor adsorption behavior, in which at least 30% of the maximum water vapor saturation load of the activated carbon reaches a partial pressure p / p of 0.60; after that, (c) equipping, in particular loading and / or coating and / or impregnating, the activated carbon oxidized in process step (b), in particular surface-oxidized, with a catalytically active component, in particular at least one precursor of a catalytically active component; after that, (d) reduction of the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) with a catalytically active component, in particular a precursor of a catalytically active component, in order to convert the precursor of the catalytically active component into the catalytically active component, in particular to obtain a catalyst system having at least one catalytically active component, in particular a supported catalyst.

[0247] Furthermore, according to a first aspect of the invention, the invention also relates to a method, in particular as defined herein, for preparing a catalyst system comprising at least one catalytically active component, in particular a supported catalyst, preferably for use in heterogeneous system catalysts, at least one catalytically active component is applied to and / or fixed on a catalyst support, said catalytically active component comprising and / or consisting of at least one metal, The method comprises the following steps in the order (a) to (d) specified below: (a) The activated carbon (so-called initial activated carbon) (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Goulwich, wherein at least 50% of the total pore volume of the activated carbon, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter in the range of 2 nm to 500 nm, preferably by mesopores and macropores, (ii) a specific BET surface area (S) in the range of 1,000 m / g to 3,000 m / g BET ), but in particular the equation Q=V total / S BET Total pore volume (V total ) of the total pore volume, especially the specific BET surface area (S BET ) is at least 0.5 × 10 -9 m, and (iii) having an average pore size in the range of 15 nm to 100 nm, particularly in the range of 16 nm to 90 nm, preferably in the range of 17 nm to 85 nm, more preferably in the range of 18 nm to 80 nm, particularly preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, and even more preferably in the range of 25 nm to 50 nm; (iv) having a particle size, in particular a particle diameter, in the range of 60 μm to 1,000 μm, in particular in the range of 70 μm to 800 μm, preferably in the range of 80 μm to 600 μm, wherein at least 80% by weight, in particular at least 90% by weight, preferably at least 95%, in particular of the activated carbon particles, have a particle size, in particular a particle diameter, in the range mentioned above; and / or in the range of 60 μm to 900 μm, in particular in the range of 75 μm to an average particle size (D50), in particular an average particle diameter (D50), in the range of 750 μm, preferably in the range of 85 μm to 550 μm, more preferably in the range of 110 μm to 375 μm, particularly preferably in the range of 175 μm to 350 μm, very particularly preferably in the range of 185 μm to 225 μm; (v) a ball pan hardness of at least 90%, in particular at least 95%, preferably at least 97%, preferably at least 98%, particularly preferably at least 99%, very particularly preferably at least 99.5%, and even more preferably at least 99.8%; (vi) a vibration density or tamping density within the range of 100 g / L to 1,500 g / L, particularly within the range of 125 g / L to 1,000 g / L, preferably within the range of 150 g / L to 800 g / L, more preferably within the range of 200 g / L to 600 g / L, particularly preferably within the range of 225 g / L to 500 g / L, most preferably within the range of 250 g / L to 400 g / L, and even more preferably within the range of 255 g / L to 395 g / L; and / or a bulk density within the range of 150 g / L to 1,000 g / L, particularly within the range of 250 g / L to 700 g / L, preferably within the range of 300 g / L to 600 g / L, and more preferably within the range of 300 g / L to 550 g / L; (vii) having a butane adsorption capacity in the range of 35% to 90%, particularly in the range of 40% to 85%, preferably in the range of 45% to 80%, and more preferably in the range of 47.5% to 75%; (viii) an iodine value in the range of 1,250 mg / g to 2,100 mg / g, in particular in the range of 1,300 mg / g to 2,000 mg / g, in the range of 1,400 mg / g to 1,900 mg / g, in the range of 1,425 mg / g to 1,850 mg / g; (ix) a methylene blue value in the range of 17 mL to 65 mL, particularly in the range of 18 mL to 55 mL, preferably in the range of 19 mL to 50 mL, and more preferably in the range of 19.5 mL to 47.5 mL; (x) having a molasses number in the range of 255 to 1,500, particularly in the range of 310 to 1,400, preferably in the range of 375 to 1,300, more preferably in the range of 510 to 1,250; (xi) 250cm 3 / g~850cm 3 / g, especially in the 300 cm 3 / g~700cm 3 / g, preferably in the range of 350 cm 3 / g~650cm 3 / g, more preferably 375 cm 3 / g~625cm 3 Weight-based absorbed N2 V measured at a partial pressure p / p0 of 0.25 in the range of / g ads(wt.) having (xii) 50cm 3 / cm 3 ~300cm 3 / cm 3 Within the range of 80cm 3 / cm 3 ~275cm 3 / cm 3 Within the range of 90cm 3 / cm 3 ~250cm 3 / cm 3 within the range of 95cm 3 / cm 3 ~225cm 3 / cm 3 The volumetrically converted adsorbed amount of N2 measured at a partial pressure p / p0 of 0.25 within the range of ads(vol.) having (xiii) 300cm 3 / g~2,300cm 3 / g, especially in the 400 cm 3 / g~2,200cm 3 / g, preferably in the range of 450 cm 3 / g~2,100cm 3 / g, more preferably in the range of 475 cm 3 / g~2,100cm 3 Weight-based absorbed N2 V measured at a partial pressure p / p0 in the range of 0.995 / g ads(wt.) having (xiv) 200cm 3 / cm 3 ~500cm 3 / cm 3 Within the range of 250cm 3 / cm 3 ~400cm 3 / cm 3 Within the range of 275 cm 3 / cm 3 ~380cm 3 / cm 3 more preferably in the range of 295 cm 3 / cm 3 ~375cm 3 / cm 3 The volumetrically converted adsorbed amount of N2 measured at a partial pressure p / p0 of 0.995 within the range of ads(vol.) and (xv) a fractal dimension of porosity in the range of 2.6 to 2.99, in particular in the range of 2.7 to 2.95, preferably in the range of 2.8 to 2.95, and / or the activated carbon has a fractal dimension of porosity of at least 2.7, in particular at least 2.8, preferably 2.85, more preferably at least 2.9, after that, (b) oxidation, in particular surface oxidation, of the activated carbon prepared and / or produced in process step (a), with the proviso that the oxidized, in particular surface-oxidized activated carbon has an oxygen content of at least 4% (atomic %) based on the total elemental composition of the oxidized activated carbon, in particular a surface oxygen content measured by X-ray photoelectron spectroscopy (XPS or ESCA), and / or with the proviso that the oxidized, in particular surface-oxidized activated carbon has a hydrophilicity determined as a water vapor adsorption behavior, in which at least 30% of the maximum water vapor saturation load of the activated carbon reaches a partial pressure p / p of 0.60; after that, (c) equipping, in particular loading and / or coating and / or impregnating, the activated carbon oxidized in process step (b), in particular surface-oxidized, with a catalytically active component, in particular at least one precursor of a catalytically active component; after that, (d) reduction of the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) with a catalytically active component, in particular a precursor of a catalytically active component, in order to convert the precursor of the catalytically active component into the catalytically active component, in particular to obtain a catalyst system having at least one catalytically active component, in particular a supported catalyst.

[0248] Overall, the present invention provides an efficient method for the preparation of a catalyst system according to the invention with high catalytic performance, thereby providing a catalyst system that is specifically tailored or adjusted in particular with respect to its catalytic activity, while at the same time simplifying the method, and the catalyst system has high overall catalytic activity, as evidenced in particular by the average dispersion and average crystallite size of the catalytically active components.

[0249] The provision of a high-performance catalyst system according to the invention is thereby ensured by the specific sequence and coordination of the respective process steps as defined above. In this regard, the use of special activated carbons as catalyst supports with a defined pore system or special oxidation practices are also of great importance, in particular with regard to providing a high loading with catalytically active components and better accessibility for reactants and products.

[0250] Therefore, the method according to the invention and the catalyst system according to the invention obtained thereby have many advantages and special properties, as already indicated above.Due to the excellent catalytic properties of the catalyst system according to the invention obtained by the method according to the invention, a wide range of applications or uses are possible, thereby ensuring correspondingly high catalytic conversion and high space / time yield within the scope of use for catalytic applications.

[0251] With regard to the method according to the invention, in addition to the description of further aspects of the invention, reference is also made to the applicable aspects in the present case where appropriate.

[0252] A further object of the present invention, according to a second aspect thereof, is also a catalyst system according to the invention, in particular a supported catalyst according to the invention, preferably a catalyst system for use in heterogeneous system catalysis, wherein the catalyst system according to the invention or the supported catalyst associated therewith is obtainable or obtainable according to the method according to the invention as described above.

[0253] Likewise, according to this aspect of the invention, the invention relates to a catalyst system according to the invention, in particular a supported catalyst according to the invention, preferably for use in a heterogeneous catalyst system, in particular a catalyst system as defined above, The catalyst system comprises at least one catalytically active component applied and / or fixed to a catalyst support, the catalytically active component comprising and / or consisting of at least one metal, the catalyst support being in the form of activated carbon and / or based on activated carbon, the catalyst support being in the form of granular, preferably spherical, activated carbon, The activated carbon (i.e., activated carbon forming a catalyst carrier) is (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Goulwich, wherein at least 50% of the total pore volume, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular pores having a pore diameter in the range of 2 nm to 500 nm, preferably mesopores and macropores; and (ii) 1,000 m 2 / g~3,000m 2 / g BET ), where the total pore volume (V total ), especially the specific BET surface area of ​​the total pore volume according to Goulwich (S BET ) to the ratio (quotient: Q), specifically the formula Q=V total / S BET The ratio is at least 0.5 × 10 -9 It is conditional on the fact that it is m.

[0254] In this regard, the invention according to a second aspect relates to a catalyst system, in particular a supported catalyst, especially a catalyst system as defined above, preferably for use in heterogeneous systems catalysis, The catalyst system comprises at least one catalytically active component applied to and / or fixed on a catalyst support, wherein the catalytically active component comprises and / or consists of at least one metal, and the catalyst support is in the form of activated carbon and / or is based on activated carbon, wherein the catalyst support is in the form of granular, preferably spherical, activated carbon, The activated carbon (i.e., the activated carbon forming the catalyst support) is (i) 0.8 cm 3 / g~3.9cm 3 Total pore volume (V) in the range of / g total ), in particular a total pore volume according to Goulwich, wherein at least 50% of the total pore volume, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular a pore diameter in the range of 2 nm to 500 nm, preferably mesopores and macropores, (ii) 1,000 m 2 / g~3,000m 2 / g BET ), but in particular the formula Q=V total / S BET According to the specific BET surface area (S BET ) to the total pore volume (V total ), in particular, the ratio of the total pore volume (quotient; Q) according to Goulwich is at least 0.5 × 10 -9 m; and the catalyst system has an activity, measured as a percentage of dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, measured by chemisorption, preferably by the (dynamic) flow method according to DIN 66136-3:2007-01, of at least 15%, in particular at least 20%, preferably at least 25%, more preferably at least 28%, and / or in the range of 15% to 90%, in particular in the range of 20% to 80%, preferably in the range of 25% to 70%, more preferably in the range of 28% to 60%; and / or the catalyst system has a surface roughness of at most 80 Angstroms (8 nm), in particular at most 70 Angstroms (7 nm), preferably at most 60 Angstroms (6 nm), more preferably at most 80 Angstroms (8 nm), more preferably at most 58 Angstroms (5.8 nm), even more preferably at least 45 Angstroms (4.5 nm), particularly preferably at most 40 Angstroms (4 nm). and / or a catalytically active component having an average crystallite size, preferably measured according to DIN 66136, of 10 angstroms (1.5 nm) to 58 angstroms (5.8 nm), most preferably 38 angstroms (3.8 nm), and / or in the range of 5 angstroms (0.5 nm) to 80 angstroms (80 nm), particularly 7 angstroms (0.7 nm) to 70 angstroms (7 nm), preferably 10 angstroms (1 nm) to 60 angstroms (6 nm), more preferably 15 angstroms (1.5 nm) to 58 angstroms (5.8 nm), particularly preferably 17 angstroms (1.7 nm) to 45 angstroms (4.5 nm), even more preferably 18 angstroms (1.8 nm) to 40 angstroms (4 nm), and most preferably 20 angstroms (2 nm) to 38 angstroms (3.8 nm).

[0255] Likewise, according to this aspect, the present invention also relates to a catalyst system, in particular a catalyst system for use in a supported catalyst, preferably a heterogeneous catalyst system, in particular a catalyst system as defined above, the catalyst system comprises at least one catalytically active component applied and / or fixed to a catalyst support, the catalytically active component comprising and / or consisting of at least one metal, the catalyst support being in the form of activated carbon and / or based on activated carbon, the catalyst support being in the form of granular, preferably spherical, activated carbon; and the catalyst system has an activity, measured as a percentage of dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, preferably measured by chemisorption by the (dynamic) flow method according to DIN 66136-3:2007-01, of at least 15%, in particular at least 20%, preferably at least 28%, and / or in the range of 15% to 90%, in particular in the range of 20% to 80%, preferably in the range of 25% to 70%, more preferably in the range of 28% to 60%; and / or the catalyst system has a thickness of at most 80 Angstroms (8 nm), in particular at most 70 Angstroms (7 nm), preferably at most 60 Angstroms (6 nm), more preferably at most 80 Angstroms (8 nm), more preferably at most 58 Angstroms (5.8 nm), even more preferably at most 45 Angstroms (4.5 nm), particularly preferably at most 40 Angstroms (4 nm), most preferably at most has a catalytically active component having an average crystallite size, preferably measured according to DIN 66136, of 38 angstroms (3.8 nm) and / or in the range of 5 angstroms (0.5 nm) to 80 angstroms (80 nm), particularly in the range of 7 angstroms (0.7 nm) to 70 angstroms (7 nm), preferably in the range of 10 angstroms (1 nm) to 60 angstroms (6 nm), more preferably in the range of 15 angstroms (1.5 nm) to 58 angstroms (5.8 nm), particularly preferably in the range of 17 angstroms (1.7 nm) to 45 angstroms (4.5 nm), even more preferably in the range of 18 angstroms (1.8 nm) to 40 angstroms (4 nm), and most preferably in the range of 20 angstroms (2 nm) to 38 angstroms (3.8 nm).

[0256] Therefore, the catalyst system according to the present invention is characterized by a defined percentage dispersion and a defined average crystallite size of the basic catalytically active component, so as to obtain excellent overall catalytic properties. Furthermore, the use of a special activated carbon with a defined pore system as the catalyst support improves the transport properties of the reactants and products of the catalytic reaction, resulting in an overall highly efficient catalyst system that achieves high conversion efficiency as a heterogeneous catalyst and simultaneously high space / time yield.

[0257] It is in particular provided according to the invention that the catalyst system according to the invention has an activity of at least 15%, in particular at least 20%, preferably at least 25%, more preferably at least 28%, and / or an activity in the range of 15% to 90%, in particular in the range of 20% to 80%, preferably in the range of 25% to 70%, preferably in the range of 28% to 60%, preferably determined as the percentage dispersion on the catalyst support of the catalytically active component, in particular the metal of the catalytically active component, measured in accordance with DIN 66136-3:2007-01, in particular by chemisorption by the (dynamic) flow method.

[0258] Furthermore, according to the invention, the catalyst system has a thickness of at most 80 Angstroms (8 nm), in particular at most 70 Angstroms (7 nm), preferably at most 60 Angstroms (6 nm), more preferably at most 58 Angstroms (5.8 nm), particularly preferably at most 45 Angstroms (4.5 nm), especially more preferably at most 40 Angstroms (4 nm), even more preferably at most 38 Angstroms (3.8 nm), and / or a thickness in the range of 5 Angstroms (0.5 nm) to 80 Angstroms (8 nm), in particular in the range of 7 Angstroms (0.7 nm) to 70 Angstroms (7 nm), preferably at most 10 Angstroms ( It is particularly provided that the catalytically active component, in particular the metal of the catalytically active component, has an average crystallite size, preferably determined in accordance with DIN 66136, in the range of from 1 angstrom (1 nm) to 60 angstroms (6 nm), more preferably in the range of from 15 angstroms (1.5 nm) to 58 angstroms (5.8 nm), especially more preferably in the range of from 17 angstroms (1.7 nm) to 45 angstroms (4.5 nm), especially more preferably in the range of from 18 angstroms (1.8 nm) to 40 angstroms (4 nm), and even more preferably in the range of from 20 angstroms (2 nm) to 38 angstroms (3.8 nm).

[0259] Furthermore, since the catalyst system according to the present invention has a defined amount of catalytically active components, the catalytic activity is also specifically specified in this respect, and in particular, it is possible to ensure good accessibility of the catalytically active components and at the same time high overall catalytic activity.

[0260] Therefore, according to the present invention, it is preferably provided that the catalyst system comprises catalytically active components in an amount of at least 0.05% by weight, in particular at least 0.1% by weight, preferably at least 0.2% by weight, more preferably at least 0.5% by weight, especially more preferably at least 0.6% by weight, most preferably at least 1% by weight and even more preferably at least 1.5% by weight, calculated as metal and based on the total weight of the catalyst system.

[0261] In particular, it is preferred that the catalyst system comprises catalytically active components in an amount of not more than 25% by weight, in particular not more than 20% by weight, preferably not more than 15% by weight, more preferably not more than 10% by weight, even more preferably not more than 8% by weight, and most preferably not more than 7% by weight, calculated as metals and based on the total weight of the catalyst system.

[0262] Thus, overall, the present invention preferably provides that the catalyst system comprises catalytically active components in the range of 0.05% to 25% by weight, in particular in the range of 0.1% to 25% by weight, preferably in the range of 0.2% to 20% by weight, more preferably in the range of 0.5% to 15% by weight, especially more preferably in the range of 0.6% to 10% by weight, most preferably in the range of 1% to 8% by weight, and even more preferably in the range of 1.5% to 7% by weight, calculated as metals and based on the total weight of the catalyst system.

[0263] Furthermore, with regard to the catalyst system according to the invention, it is preferred that the catalytically active component consists of or consists of at least one metal, in particular in the form of a metal compound, preferably in the form of an ionic metal compound, and / or in particular in elemental form.

[0264] In particular, the catalytically active component preferably comprises at least one metal, in particular at least one metal cation, in a positive oxidation state, in particular in the range +I to +VII, in particular in the range +I to +IV, preferably in the range +I to +III, particularly preferably +I or +II. According to the invention, it is particularly preferred if the catalytically active component consists of at least one metal in the oxidation state zero.

[0265] In particular, the catalytically active component preferably comprises at least one metal from the main group or subgroup of the periodic table of the elements, or at least one lanthanide.

[0266] Furthermore, it is preferably provided according to the invention that the catalytically active component comprises at least one metal selected from the elements of main group IV or subgroups I, II, III, IV, V, VI, VII and VIII of the periodic table of the elements, in particular from the elements of main group IV or subgroups I and II of the periodic table of the elements.

[0267] In this respect, it is preferred according to the invention if the catalytically active component comprises at least one metal selected from the group consisting of Cu, Ag, Au, Zn, Hg, Sn, Ce, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Bi, Ru, Os, Co, Rh, Re, Ir, Ni, Pd and Pt, in particular Fe, Bi, V, Cu, Pb, Zn, Ag, Sn, Pd, Pt, Ru and Ni, preferably Fe, Bi, V, Cu, Pt, Ru and Pb, more preferably Pd, Pt and Ru, particularly preferably Pd and Pt. Particularly high catalytic activity is obtained with said metals.

[0268] Also with regard to the catalytic system according to the invention, in particular both the outer and inner surfaces of the activated carbon, in particular the micropores, mesopores and / or macropores, behave in such a way as to provide catalytically active components.

[0269] As indicated above, it is particularly preferably envisaged in the context of the present invention that the catalyst system has an activity, measured as the percentage dispersion of the catalytically active components, in particular the metals of the catalytically active components, on the catalyst support, of at least 15%, in particular at least 20%, preferably at least 25%, more preferably at least 28%, and / or in the range of 15% to 90%, in particular in the range of 20% to 80%, preferably in the range of 25% to 70%, more preferably in the range of 28% to 60%, preferably in accordance with DIN 66136-3:2007-01, in particular measured by chemisorption by the (dynamic) flow method.

[0270] According to the invention, the catalyst system has a maximum diameter of at most 80 Angstroms (8 nm), in particular at most 70 Angstroms (7 nm), preferably at most 60 Angstroms (6 nm), more preferably at most 58 Angstroms (5.8 nm), even more preferably at most 45 Angstroms (4.5 nm), even more preferably at most 40 Angstroms (4 nm), and / or a diameter in the range of 5 Angstroms (0.5 nm) to 80 Angstroms (8 nm), in particular in the range of 7 Angstroms (0.7 nm) to 70 Angstroms (7 nm), preferably in the range of 10 Angstroms (1 nm) to 60 Angstroms (1 nm). It is particularly provided that the catalytically active component has an average crystallite size, preferably measured according to DIN 66136, in the range of 15 angstroms (6 nm) to 58 angstroms (5.8 nm), more preferably in the range of 17 angstroms (1.7 nm) to 45 angstroms (4.5 nm), even more preferably in the range of 18 angstroms (1.8 nm) to 40 angstroms (4 nm), and most preferably in the range of 20 angstroms (2 nm) to 38 angstroms (3.8 nm).

[0271] The present invention provides, in particular, that the activated carbon (i.e., the activated carbon forming the catalyst support) is based on activated carbon that has been oxidized, in particular surface-oxidized, before application and / or fixation of the catalytically active components, and reduced, in particular on its surface, after application and / or fixation of the catalytically active components. This, as previously indicated for the catalyst system according to the invention, achieves particularly good compatibility with the catalytically active components. In particular, a correspondingly good degree of dispersion is achieved, as well as the crystallite size, which is reflected in improved properties of the products obtained in the form of the catalyst system according to the invention. As also indicated above, the reduction carried out can also reduce the content of oxygen-containing functional groups and the hydrophilicity of the activated carbon, which is particularly advantageous for the transport properties of reactants or products in activated carbon systems as catalyst supports.

[0272] In general, the present invention further provides that the activated carbon (i.e. the activated carbon forming the catalyst support) is based on activated carbon obtained by carbonization and subsequent activation of a starting material based on an organic polymer, followed by an oxidation (treatment), which is carried out before application and / or fixation of the catalytically active component, followed by a reduction (treatment), which is carried out after application and / or fixation of the catalytically active component.

[0273] In particular, the activated carbon (i.e. the activated carbon forming the catalyst support) can be based on activated carbon obtained by carbonization and subsequent activation of an organic polymer-based starting material, or it is in the form of a polymer-based, preferably spherical, activated carbon (PBSAC or polymer-based spherical activated carbon).

[0274] Such activated carbons have particularly defined properties with regard to their pore system, and they are activated carbons with high mechanical stability, for example high abrasion resistance.

[0275] In general, the activated carbon is based on the starting materials described above (see claim 21). In particular, the activated carbon is based on or traces back to activated carbon obtained according to the manufacturing methods described above (see claims 22 to 25 as well as 30 to 34).

[0276] Furthermore, the catalyst system is preferably a surface-reduced catalyst system.

[0277] Further properties of the activated carbon forming the catalyst support of the catalyst system according to the invention are given below:

[0278] In particular, the activated carbon can have a defined total pore volume: Therefore, the activated carbon (i.e., the activated carbon that forms the catalyst support) is 0.9 cm 3 / g~3.4cm 3 / g range, especially 1 cm 3 / g~2.9cm 3 / g, preferably 1.1 cm3 / g~2.4cm 3 / g, preferably 1.2 cm 3 / g~1.9cm 3 / g, more preferably 1.5 cm 3 / g~1.9cm 3 Total pore volume (V) in the range of / g total ), especially those with a total pore volume according to Goulwich. Furthermore, in this regard, the activated carbon (i.e. the activated carbon forming the catalyst support) behaves in such a way that the total pore volume, in particular the total pore volume according to Goulwich, is formed by pores with a pore diameter of at least 2 nm, in particular by pores with a pore diameter in the range from 2 nm to 500 nm, preferably by pores with a pore diameter of at least 2 nm, in particular by pores with a pore diameter in the range from 2 nm to 500 nm, in other words the activated carbon forming the catalyst support is formed by pores with a pore diameter of at least 2 nm, in particular by pores with a pore diameter in the range from 2 nm to 500 nm, preferably by mesopores and macropores. Furthermore, the activated carbon (i.e., the activated carbon forming the catalyst support) is 0.8 cm 3 / g~3.9cm 3 / g, especially in the 0.9 cm 3 / g~3.4cm 3 / g, preferably in the range of 1 cm 3 / g~2.9cm 3 / g, more preferably in the range of 1.1 cm 3 / g~2.4cm 3 / g, particularly preferably 1.2 cm 3 / g~1.9cm 3 / g, most preferably in the range of 1.5 cm 3 / g~1.9cm 3 Total pore volume (V) in the range of / g total), in particular a total pore volume according to Goulwich, wherein 50% to 90%, in particular 52.5% to 87.5%, preferably 55% to 85%, more preferably 57.5% to 82.5%, and particularly preferably 60% to 80% of the total pore volume of the activated carbon, in particular the total pore volume according to Goulwich, is formed by pores having a pore diameter of at least 2 nm, in particular pores having a pore diameter in the range of 2 nm to 500 nm, preferably mesopores and macropores.

[0279] The activated carbon forming the catalyst support may also have the following properties: In particular, activated carbon (i.e., the activated carbon that forms the catalyst support) is 1,100m 2 / g~2,600m 2 / g, especially in the 1.200m 2 / g~2,400m 2 / g, preferably 1,300m 2 / g~2,200m 2 / g, more preferably 1,350m 2 / g~1,950m 2 / g, more preferably 1,375m 2 / g~1,900m 2 / g BET ) Furthermore, for activated carbon (i.e., the activated carbon forming the catalyst support), the total pore volume (V total ), in particular the pore volume according to Goulwich, total / S BET Specific BET surface area (S BET ) is 0.5×10 -9 m~1.9×10 -9 m, especially in the range of 0.55 × 10 -9 m~1.9×10 -9 m, preferably in the range of 0.6 × 10 -9 m~1.8×10 -9 m, more preferably in the range of 0.65 × 10 -9 m~1.7×10 -9 m, more preferably in the range of 0.65 × 10 -9m~1.6×10 -9 m, particularly preferably 0.7 × 10 -9 m~1.5×10 -9 m, and particularly preferably 0.75×10 -9 m~1.4×10 -9 m, most preferably in the range of 0.8 × 10 -9 m~1.3×10 -9 m. Furthermore, activated carbon (i.e., the activated carbon that forms the catalyst support) is 2 / g~3,000m 2 / g range, especially 1,100m 2 / g~2,600m 2 / g, preferably 1,200m 2 / g~2,400m 2 / g, more preferably 1,300m 2 / g~2,200m 2 / g, more preferably 1,350m 2 / g~1,950m 2 / g, particularly preferably 1,375 m 2 / g~1,900m 2 / g BET ) and the total pore volume (V total ), in particular the pore volume according to Goulwich, total / S BET Specific BET surface area (S BET ) is 0.5×10 -9 m~1.9×10 -9 m, especially in the range of 0.55 × 10 -9 m~1.9×10 -9 m, preferably in the range of 0.6 × 10 -9 m~1.8×10 -9 m, more preferably in the range of 0.65 × 10 -9 m~1.7×10 -9 m, more preferably in the range of 0.65 × 10 -9 m~1.6×10 -9 m, particularly preferably 0.7 × 10 -9 m~1.5×10 -9m, and particularly preferably 0.75×10 -9 m~1.4×10 -9 m, most preferably in the range of 0.8 × 10 -9 m~1.3×10 -9 m.

[0280] Furthermore, the activated carbon used as the catalyst support may also have the following properties: Therefore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has an average pore size of at least 15 nm and / or an average pore size of at most 100 nm. In this regard, it is preferred that the activated carbon (i.e., the activated carbon forming the catalyst support) has an average pore size in the range of 15 nm to 100 nm, particularly in the range of 16 nm to 90 nm, preferably in the range of 17 nm to 85 nm, more preferably in the range of 18 nm to 80 nm, particularly preferably in the range of 20 nm to 70 nm, even more preferably in the range of 22 nm to 60 nm, and most preferably in the range of 25 nm to 50 nm. In the context of the present invention, the activated carbon (i.e., the activated carbon forming the catalyst support) is preferably spherical. In particular, the activated carbon is preferably in the form of spherical activated carbon. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a particle size, in particular a particle diameter, in the range of 60 μm to 1,000 μm, in particular in the range of 70 μm to 800 μm, preferably in the range of 80 μm to 600 μm, more preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, and most preferably in the range of 175 μm to 250 μm. In particular, it is provided in this respect that at least 80% by weight, in particular at least 90% by weight, preferably at least 95% by weight of the activated carbon particles have a particle size, in particular a particle diameter, in the aforementioned range. In particular, the activated carbon (i.e., the activated carbon forming the catalyst support) preferably has an average particle size (D50), in particular an average particle diameter (D50), in the range of 60 μm to 900 μm, in particular in the range of 75 μm to 750 μm, preferably in the range of 85 μm to 550 μm, more preferably in the range of 110 μm to 375 μm, particularly preferably in the range of 175 μm to 350 μm, and most preferably in the range of 185 μm to 225 μm. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a ball pan hardness and / or abrasion hardness of at least 90%, in particular at least 95%, preferably at least 97%, more preferably at least 98%, particularly preferably at least 99%, most preferably at least 99.5%, and even more preferably at least 99.8%. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a compressive strength and / or bursting strength (weight bearing capacity) per activated carbon particle, in particular per activated carbon sphere, of at least 5 Newtons, in particular at least 10 Newtons, preferably at least 15 Newtons, preferably at least 20 Newtons, particularly preferably at least 22.5 Newtons. In particular, the activated carbon (i.e. the activated carbon forming the catalyst support) may have a compression and / or bursting strength (weight bearing capacity) per activated carbon particle, in particular per activated carbon sphere, in the range of 5 to 50 Newtons, in particular 10 to 50 Newtons, preferably 15 to 40 Newtons, more preferably 17.5 to 35 Newtons. Similarly, the activated carbon (i.e., the activated carbon forming the catalyst support) preferably has a bulk density or compacted density within the range of 100 g / L to 1,500 g / L, particularly 125 g / L to 1,000 g / L, preferably 150 g / L to 800 g / L, more preferably 200 g / L to 600 g / L, even more preferably 225 g / L to 500 g / L, particularly preferably 250 g / L to 400 g / L, and even more preferably 255 g / L to 395 g / L. Furthermore, the activated carbon (i.e., the activated carbon forming the catalyst support) preferably has a bulk density in the range of 150 g / L to 1,000 g / L, particularly 250 g / L to 700 g / L, preferably 300 g / L to 600 g / L, and more preferably 300 g / L to 550 g / L.

[0281] Furthermore, the activated carbon forming the catalyst support may have the following properties: Thus, the activated carbon (i.e. the activated carbon forming the catalyst support) may have a butane adsorption of at least 35%, in particular at least 40%, preferably at least 45%, preferably at least 47.5% and / or it is preferred that said activated carbon has a butane adsorption in the range of 35% to 90%, in particular in the range of 40% to 85%, preferably in the range of 45% to 80%, more preferably in the range of 47.5% to 75%. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has an iodine value of at least 1,350 mg / g, in particular at least 1,300 mg / g, preferably at least 1,400 mg / g, preferably at least 1,425 mg / g, and / or that the activated carbon has an iodine value in the range of 1,250 mg / g to 2,100 mg / g, in particular in the range of 1,300 mg / g to 2,000 mg / g, preferably in the range of 1,400 mg / g to 1,900 mg / g, more preferably in the range of 1,425 mg / g to 1,850 mg / g. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a methylene blue value of at least 17 mL, in particular at least 18 mL, preferably at least 19 mL, preferably at least 19.5 mL, and / or that the activated carbon has a methylene blue value in the range from 17 mL to 65 mL, in particular in the range from 18 mL to 55 mL, preferably in the range from 19 mL to 50 mL, more preferably in the range from 19.5 mL to 47.5 mL. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a molasses number of at least 255, in particular at least 310, preferably at least 375, preferably at least 510, and / or that the activated carbon has a molasses number in the range from 255 to 1,500, in particular in the range from 310 to 1,400, preferably in the range from 375 to 1,300, more preferably in the range from 510 to 1,250. Furthermore, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a methylene blue value of at least 17 mL, in particular at least 18 mL, preferably at least 19 mL, more preferably at least 20 mL. Furthermore, the activated carbon preferably has a methylene blue value in the range of 17 mL to 65 mL, particularly in the range of 18 mL to 55 mL, preferably in the range of 19 mL to 50 mL, and more preferably in the range of 20 mL to 47.5 mL. Furthermore, the activated carbon (i.e., the activated carbon forming the catalyst support) has a surface area of ​​at least 250 cm 3 / g, especially at least 300 cm 3 / g, preferably at least 350 cm 3 / g, preferably at least 375 cm 3 / g 0.25 partial pressure p / p0 calculated by weight-based adsorbed N2 amount Vads(wt) In this regard, it is preferable that the activated carbon has a 3 / g~850cm 3 / g, especially 300cm 3 / g~700cm 3 / g, preferably 350 cm 3 / g~650cm 3 / g, more preferably 375 cm 3 / g~625cm 3 Gravimetrically adsorbed N2 V measured at a partial pressure of 0.25 p / p0 / g ads(wt) It is preferred that the compound has the following structure: Similarly, activated carbon (i.e., the activated carbon forming the catalyst support) must be at least 50 cm 3 / cm 3 , especially at least 100 cm 3 / cm 3, preferably at least 110 cm 3 / cm 3 The volumetrically adsorbed amount of N2 measured at a partial pressure p / p of 0.25 is V. ads(vol.) In this regard, the activated carbon preferably has a 3 / cm 3 ~300cm 3 / cm 3 , especially 80cm 3 / cm 3 ~275cm 3 / cm 3 , preferably 90cm 3 / cm 3 ~250cm 3 / cm 3 , more preferably 95 cm 3 / cm 3 ~225cm 3 / cm 3 The volumetrically adsorbed amount of N2 measured at a partial pressure p / p of 0.25 is V. ads(vol.) It is preferred that the compound has the following structure: Furthermore, the activated carbon (i.e., the activated carbon forming the catalyst support) has a surface area of ​​at least 300 cm 3 / g, especially at least 450 cm 3 / g, preferably at least 475 cm 3 The weight-based amount of adsorbed N2, V, measured at a partial pressure of 0.995 p / p0 / g ads(wt.) In this regard, the activated carbon preferably has a surface area of ​​300 cm 3 / g~2,300cm 3 / g, especially 400cm 3 / g~2,200cm 3 / g, preferably 450 cm 3 / g~2,100cm 3 / g, more preferably 475 cm 3 / g~2,100cm 3 Gravimetrically adsorbed N2 V measured at a partial pressure p / p0 of 0.995 / g ads(wt) It is preferred that the compound has the following structure: Similarly, the activated carbon (i.e., the activated carbon forming the catalyst support) must have a surface area of ​​at least 200 cm 3 / cm 3 , especially at least 250 cm 3 / cm 3 , preferably at least 275 cm 3 / cm 3 , more preferably 295 cm 3 / cm 3 The volumetrically adsorbed amount of N2 measured at a partial pressure p / p of 0.995 is V. ads(vol.) In this regard, the activated carbon preferably has a 3 / cm 3 ~500cm 3 / cm 3 , especially 250cm 3 / cm 3 ~400cm 3 / cm 3 , preferably 275cm 3 / cm 3 ~380cm 3 / cm 3 , more preferably 295 cm 3 / cm 3 ~375cm 3 / cm 3 The volumetrically adsorbed amount of N2 measured at a partial pressure p / p of 0.995 is V. ads(vol.) It is preferred that the compound has the following structure: With regard to the activated carbon further used according to the invention, it is preferred that the activated carbon (i.e. the activated carbon forming the catalyst support) has a fractal dimension of open porosity in the range of 2.6 to 2.99, in particular 2.7 to 2.95, preferably 2.8 to 2.95, and / or that the activated carbon has a fractal dimension of open porosity of at least 2.7, in particular at least 2.8, preferably at least 2.85, more preferably at least 2.9.

[0282] Within the scope of the present invention, efficient catalyst systems are thus provided that have the overall improved catalytic properties indicated above. From this perspective, the catalyst systems of the present invention, for example, also lead to a significant reduction in the process time underlying the catalytic reaction, particularly in discontinuous catalytic processes, with correspondingly high rest or operating times, which is also due to the excellent mechanical stability of the catalyst systems of the present invention. Furthermore, the use of the catalyst systems of the present invention is closely related to simplified dosing and significantly lower cleaning efforts of the underlying equipment, minimized material losses, and generally simplified handling. Furthermore, the catalyst systems of the present invention can be reused or recycled in a simple manner after appropriate reactivation of the catalyst. In particular, the defined pore system of the activated carbon used as a support of the present invention leads to a significant improvement in activity, both in terms of improved transport methods for reactants or products and in terms of equipment containing catalytically active components. Overall, the properties of the catalyst systems of the present invention are of great importance, even against the background of the cost-intensive nature of catalysts, since the catalyst systems of the present invention can entail significant cost savings due to their properties.

[0283] In addition to use in discontinuous processes, the catalyst system according to the invention is also highly suitable for use in continuous catalytic applications, whereby the catalyst system according to the invention can, for example, be filled into a corresponding reaction vessel or reactor and the reactant or the medium containing the reactant can be continuously flowed through, whereby only low pressure losses can be achieved at correspondingly high flow rates within the range of use.

[0284] The catalyst system according to the invention has a wide range of applications: in addition to being used in catalytic reactions, especially on a (large) industrial scale, the catalyst system according to the invention is also suitable for adsorptive applications, in particular for removing harmful substances such as pollutants and toxins, due to its combined properties of chemisorption on the one hand and physisorption on the other hand.

[0285] In particular with regard to the spherical shape, the excellent mechanical properties of the underlying activated carbon material in the form of PBSAC, and the now adjustable setting of the porosity, in particular the provision of high meso- and macroporosity, the catalyst system according to the invention is also of high importance, in particular for continuous catalytic reactions (i.e. continuous reaction control in catalytic reactions).

[0286] The catalyst system according to the present invention is, in particular, a supported noble metal catalyst or a metal catalyst supported on activated carbon. In particular, it is based on a polymer-based spherical high-performance adsorbent containing more than 99% by weight of carbon, with activated carbon serving as the catalyst support, as previously mentioned. As previously explained with respect to the method according to the present invention, the catalyst support is pretreated by an oxidative method (before being provided with the catalytically active component). In this method, the proportion of volatile components can vary between 0.1% and 15% by weight. In a further process step, the catalyst support can be loaded with a noble metal, preferably as the catalytically active component, by various impregnation techniques, whereby the impregnation level can vary, for example, between 0.05% and 20% by weight. After the catalytically active component or the associated noble metal ions are immobilized on the catalyst support surface, the metal ions can be converted in a reductive step. This reduction, which also leads to the surface reduction of the activated carbon, can be carried out in particular in the liquid or gas phase. Based on this, the catalyst system according to the present invention described above can be obtained in this way.

[0287] With regard to the embodiment of the catalyst system according to this aspect, reference may also be made to the descriptions of further aspects according to the invention, which may be applied as appropriate.

[0288] A further object of the present invention, according to a third aspect thereof, is to provide further uses of the catalyst system according to the present invention:

[0289] Therefore, the catalyst system according to the invention can be used in particular as a catalyst or catalyst support.Furthermore, the catalyst system according to the invention can be used in particular for chemical catalysis, in particular heterogeneous catalysis and / or discontinuous catalysis or continuous catalysis (i.e. continuous reaction control in catalysis).

[0290] Similarly, the catalyst system according to the present invention can be used as a catalyst for chemical processes and reactions, in particular hydrogenation reactions or oligomerization and polymerization reactions, preferably olefins. Preferably, the catalyst system according to the present invention can be used to catalyze hydrogenation reactions. In particular, the catalyst system according to the present invention can be used for the hydrogenation of various functional groups. For example, the catalyst system according to the present invention can be used for the catalytic conversion or transformation of a nitro group into an amine group. Furthermore, the catalyst system according to the present invention can be used for deprotection.

[0291] Furthermore, the catalyst system according to this embodiment can also be used in the manufacture of filters and filter materials, particularly for the removal of pollutants, odors and toxins from air and / or gas streams, such as NBC protective mask filters, odor filters, surface filters, air filters, particularly filters for indoor air purification, adsorptive support structures and filters for the medical field.

[0292] Additionally, the catalyst system according to the present invention can be used as an adsorption reservoir for gases or liquids.

[0293] Similarly, the catalyst system can be used in gas sensors and fuel cells.

[0294] Furthermore, the catalyst system according to the invention can be used in adsorptive applications, in particular adsorptive or chemisorption applications, preferably chemisorption applications, particularly preferably as a reactive and / or catalytic adsorbent.

[0295] Furthermore, the catalyst system according to the present invention can be used in gas purification and / or gas processing.

[0296] Furthermore, the catalyst system according to the invention can be used for the removal of pollutants, especially gaseous pollutants, or substances or gases that are harmful to the environment, health, or toxicity.

[0297] Furthermore, the catalyst system according to the invention can be used for producing and / or providing a clean room atmosphere, especially in the electrical industry, especially in semiconductor or chip manufacturing.

[0298] Furthermore, according to a fourth aspect of the invention, the present invention relates to protective materials, in particular for civilian or military use, in particular protective clothing, such as protective suits, protective gloves, protective socks, protective hoods as well as protective covers, preferably all of the aforementioned protective materials for NBC use, which are produced using or have a catalyst system according to the invention.

[0299] Furthermore, a further object of the present invention, according to a fifth aspect thereof, are filters and filter materials, in particular for removing all kinds of pollutants, odors and toxic substances from air or gas streams, such as NBC protective mask filters, odor filters, surface filters, air filters, in particular filters for room air purification, adsorbent and / or chemisorbent support structures and filters for the medical field, which are manufactured using or contain the above-defined catalyst system according to the present invention.

[0300] As far as the filters and filter materials according to the invention are concerned, the catalyst systems used in this respect are preferably self-supporting and in the form of bulk materials, in particular loose bulk materials. Furthermore, the catalyst systems can also be applied to a support material.

[0301] With regard to the explanations relating to the third to fifth aspects of the present invention, reference may be made in this respect to the further explanations according to the first and second aspects of the present invention, and the explanations therein also apply where appropriate.

[0302] The present invention will now be described with reference to further figures and / or diagrammatic representations, whereby the description in this respect applies to all aspects according to the invention and whereby the description in this respect is in no way limiting. With regard to the figures or diagrammatic representations, reference may also be made to the following description in the example embodiments. [Brief explanation of the drawings]

[0303] [Figure 1] FIG. 1 is a graph of nitrogen isotherms for various catalyst supports or activated carbons used to determine porosity. [Figure 2] FIG. 2 is a diagram of mercury intrusion curves for various catalyst supports or activated carbons used to determine porosity. [Figure 3] Figure 3 shows a graphical representation of the crystallite size and dispersity of the catalytically active component or metal determined for different catalyst systems (5 wt. % palladium catalyst). [Figure 4] FIG. 4 is a schematic diagram of the kinetics underlying heterogeneous catalytic reactions based on substeps, including a first step (1) of diffusion of reactant (E) to the surface of the catalyst (K) through a fixed boundary layer (G); a second step (2) of dispersion of reactant (E) into the pores of the catalyst (K) relative to catalytically active centers or catalytically active components; a third step (3) of adsorption of reactant (E) onto said active centers; a fourth step (4) of reaction of reactant (E) on the active centers to obtain its product (P); a fifth step (5) of desorption of product (P) from the active centers; a sixth step (6) of diffusion of product (P) through the pore system of the catalyst (K); and a seventh step (7) of diffusion of product (P) to the external region through the boundary layer (G) and removal of product (P). [Figure 5] FIG. 5 is a schematic diagram of a method sequence according to one embodiment of the present invention [EP = precious metal precursor, TR = PBSAC carrier, TV = carrier pretreatment (e.g., mineral acid oxidation or air oxidation), I = impregnation (e.g., immersion impregnation or spray impregnation), W = washing, T = drying, R = reduction (e.g., gas-phase or liquid-phase reduction), Cat = catalyst, CatR = catalyst reactivation, MR = metal recovery]. [Figure 6]FIG. 6 is a schematic diagram of a fixed-bed reactor-based apparatus used for heterogeneous catalytic reactions, particularly hydrogenation reactions. [Figure 7] FIG. 7A is an explanatory diagram showing the reaction underlying the hydrogenation reaction of cinnamic acid using the catalyst system of the present invention. FIG. 7B is a diagram showing the time course of catalytic conversion (hydrogenation) of cinnamic acid as a reactant by various catalyst systems of the present invention using activated carbon as a catalyst support having a high proportion of mesopores and macropores in the total pore volume of the activated carbon (mesoporous and macroporous activated carbon). FIG. 7C is a diagram showing the time course of catalytic conversion (hydrogenation) of cinnamic acid by a catalyst system using activated carbon as a catalyst support and having a high proportion of micropores in the total pore volume of the activated carbon (microporous activated carbon). DETAILED DESCRIPTION OF THE INVENTION

[0304] Further embodiments, modifications and variations as well as advantages of the present invention will be readily apparent to those skilled in the art upon reading this specification and can be realized without departing from the scope of the present invention.

[0305] The following embodiments are merely illustrative of the present invention and are not intended to limit the present invention thereto. [Example]

[0306] 1. Introduction: The use of special polymer-based spherical activated carbons (spherical or spherical PBSAC) with defined porosity, especially high mesoporosity or macroporosity and simultaneously defined microporosity, as catalyst support materials offers the advantages of the inventive concept: on the one hand, optimal transport of reactants / products and, on the other hand, optimal loading of the activated carbon with catalytically active components. This allows the inventive catalyst system to achieve high overall catalytic activity, especially with high conversion and space / time yield. Furthermore, the preferred spherical shape allows for the lowest pressure drop compared to adsorbents of the same size but different shapes. Furthermore, the low dust content and high mechanical load capacity of PBSAC minimize the risk of metal-containing dust and debris being released into the product flow during fixed-bed bulk applications.

[0307] 2. Catalyst support manufacturing a) Highly microporous catalyst support (not according to the present invention) Polymer-based spherical activated carbon (PBSAC) is produced in a three-stage batch process. The process includes a sulfonation stage for thermal stabilization of the polymeric raw material used, a carbonization stage for removing volatile components, and an activation stage for creating an internal pore system using water as an oxidant. A rotary tube reactor is used for the required process steps. The reactor is indirectly electrically heated within a rotary kiln.

[0308] Cross-linked styrene-divinylbenzene polymer (H) manufactured by Lancel + The polymeric raw material (a gel-type polymer) is used as the raw material or starting material for the production of highly microporous PBSAC (Lewapol D60). It is a polystyrene with 4% by weight of divinylbenzene as a crosslinker. The polymer raw material already has a spherical morphology, which is transferred to the resulting PBSAC. The raw material exhibits a particle size distribution in the range of 0.08 mm to 0.7 mm.

[0309] Sulfonation represents a step that stabilizes the polymer for subsequent carbonization. For this, a mixture of oleum (sulfuric acid fumes, 25% free SO3) and sulfuric acid (96% by volume) is added to polystyrene in a 2:1 mass ratio at room temperature and heated to the sulfonation temperature of 423 K. This mixture is then reacted with sulfuric acid.

[0310] In the second stage of activated carbon production, known as carbonization, volatile components are removed at temperatures between 423 and 1223 K. The carbonization process is divided into two stages. In the temperature range up to 823 K, water and sulfur compounds are removed in addition to other volatile components. In the temperature range up to 1223 K, mainly hydrocarbons and hydrogen are removed (activation time 390 minutes). The particle shape and size after carbonization remain unchanged and are consistent with those of the resulting PBSAC.

[0311] In the third stage of activated carbon production, the so-called activation, the carbon is activated at approximately 1223 K in a steam atmosphere (120 kg of liquid water and 2 standard cubic meters of nitrogen per hour).

[0312] b) Mesoporous and macroporous catalyst supports (according to the present invention) For the preparation of mesoporous and macroporous PBSAC, the process steps described in section 2.a) above are followed. Similarly, Lewapol D60 from Lances is used as the raw material or starting material for the preparation of mesoporous / macroporous PBSAC. However, the sulfonation of the crosslinked styrene-divinylbenzene polymer is carried out exclusively with sulfuric acid (96% by volume). The polymer to sulfonating agent ratio is kept constant. The catalyst support is activated for 450 minutes. The resulting PBSAC exhibits an increased mesopore content of more than 25%. Texture data are taken from Table 2.

[0313] c) Mesoporous and macroporous catalyst supports based on sulfonated ion exchange resins with high macroporosity (according to the invention) For the preparation of PBSAC based on macroporous ion exchange resins, the process steps described in section 2.a) above are followed. As raw material or starting material for the preparation of PBSAC based on macroporous ion exchanger (Finex CS16GC), sulfonated crosslinked styrene-divinylbenzene polymer (H + The acidic macroporous ion exchanger is already protected, so the sulfonation step can be omitted (activation time of 150 min). The resulting PBSAC exhibits a high mesopore content and a defined proportion of macropores. Texture data can be taken from Table 2. Alternatively, the corresponding non-sulfonated raw material or starting material can be considered. In this case, for example, a crosslinked styrene-divinylbenzene polymer from Finex Oy can be used (Finex PS08G). Sulfonation can be carried out analogously to point 2.a).

[0314] 3. Characterization of catalyst supports or catalyst systems a) Nitrogen isotherms for determining textural data in the micropore region To determine the textural data of the catalyst supports, nitrogen isotherms are recorded on various catalyst supports. This is performed with Quantachrome's Quantrosolve. The specific internal surface area is measured using the Brunauer-Emmett-Teller (BET) mathematical model. The total pore volume is calculated using the Gouldwig rule, and the micropore volume is measured by the carbon black method.

[0315] For the measurement preparation, the catalyst support is pretreated in a vacuum at 200° C., with the aim in particular of eliminating adsorbed molecules.

[0316] b) Mercury intrusion to measure textural data in the mesopore and macropore region The sample is dried in a drying oven at 150°C for 2 hours and measured using a Quantachrome Poremaster 60GT. To convert the pressure to pore size, the literature value of the contact angle of mercury on carbon (155°) is calculated.

[0317] c) Determination of the elemental composition of catalyst supports by photoelectron spectroscopy (XPS) The samples are analyzed by photoelectron spectroscopy (ESCA / XPS) without any pretreatment. For XPS analysis, measurements are carried out using a Thermo VG Scientific K-α instrument. Monochromatic AlKα X-rays are used for excitation (typically up to 75 W, 400 μm spot size). For copper, silver, and gold standard samples, the transmission function and energy position are measured according to ISO 15472:2001 and ISO 21270:2004. The following settings are used for measuring the spectra: survey spectrum with a pass energy of 80 eV, high-resolution spectrum with a pass energy of 30 eV. Quantitative information on the surface composition is calculated using the Schofield coefficients for the survey measurement, assuming the analysis object is homogeneous. The error can be estimated to be around 10%.

[0318] d) Determination of the dispersion and size of active sites by CO chemisorption (determination of the specific metal surface or dispersion and crystallite size of catalytically active components) Determination of monolayer capacity, dispersity and active surface according to DIN 66136-1, DIN 66136-3: flow method (dynamic), measuring gases e.g. H2, CO, CO2; planned experimental program: H2 treatment, 10 K / min up to 80 °C, isothermal for 4 hours; CO2 titration at 50 °C; then TPR 5 K / min with 5% H2 / Ar up to 250 °C; finally, CO2 titration at 50 °C.

[0319] Specifically, proceed as follows: Normative basis: DIN 66136-1 (basic) and DIN 66136-2 (volumetric method)

[0320] The following steps are recommended or performed for sample preparation and reduction of the sample surface: (i) Evaporate at 100°C for 30 minutes; (ii) 100°C with oxygen flow for 5 min; (iii) Flow oxygen and increase the temperature to 350°C at 10°C / min; (iv) flowing oxygen at 350°C for 30 min; (v) evaporation at 350°C for 15 minutes; (vi) Evaporate at 100°C for 15 minutes; (vii) flowing hydrogen at 100°C for 5 minutes; (viii) Flow hydrogen and increase the temperature to 350°C at 10°C / min; (ix) flowing hydrogen at 350°C for 120 minutes; (x) Evaporate at 350°C for 30 minutes; (xi) Evaporate at 100°C for 15 minutes.

[0321] This is followed by measuring the CO isotherm at 40° C. using the static volume method to determine the active metal surface or metal dispersion.

[0322] The first isotherm measured after step (xi) may represent a superposition of a strongly chemisorbed and a weakly chemisorbed gas fraction (complex chemisorption). If it is necessary to distinguish between the two fractions, the following procedure is recommended or performed: after measuring the last isotherm, the measuring cell is evacuated for 60 minutes at the analysis temperature (40 °C). This removes the weakly bound fraction, leaving the strongly chemisorbed fraction on the sample surface. The isotherm measurement is then repeated to determine the weakly chemisorbed fraction (weak chemisorption). The difference between the two isotherms gives the amount of strongly chemisorbed CO.

[0323] Assuming that a CO molecule chemisorbs onto one metal atom (palladium atom) exposed on the surface of the catalytically active component (stoichiometry = 1), the number of palladium atoms or metal atoms exposed on the surface can be estimated from the amount of chemisorbed CO.

[0324] This is the area per gram (m 2 / g (sample mass) provides an indication of the amount of active metal surface area.

[0325] Using the metal loading of the sample, known as the mass of palladium in g / g sample, further properties and characteristics are calculated: m 2 / g(metal) active metal surface; Metal dispersion (%); and · Average crystallite size of metal clusters. A similar procedure is followed for other metals.

[0326] 4. Catalyst support characteristics The properties of each catalyst support are as different as possible in terms of their textural properties. To measure the textural data, nitrogen isotherms are recorded for each PBSAC. The results obtained at this point are shown in Figure 1. Note that the "200 μm" in the legend indicates the average particle size of the activated carbon investigated in each case. Figure 1 shows the nitrogen adsorption capacity (Vads) as a function of the relative pressure (p / p0) of the investigated activated carbons.

[0327] A characteristic of highly microporous materials is a sharp rise in the isotherm at low relative pressures, which accompanies a large amount of nitrogen uptake. As shown in Figure 1, the isotherm runs almost flat in the higher relative pressure range and does not show a significant hysteresis loop. Since the isotherm of "200 μm_micro I" (a catalyst support or activated carbon A1 not according to the present invention) shows such a course, this material is described as being highly microporous. Furthermore, the ratio of the microporous volume to the total volume is very high, at 89%.

[0328] The isotherm of "200 μm_meso / macro I" (catalyst support or activated carbon B1 according to the present invention) shows a strong increase at a relative pressure of 0.75, as shown in FIG. 1. Furthermore, the isotherm shows a significant hysteresis loop. These two characteristics, together with the micropore content of 61%, attest to a high content of mesopores or macropores.

[0329] When using macroporous ion exchange resins for the production of PBSAC, part of the macroporosity of the polymer is transferred to the resulting activated carbon. This can be seen from the nitrogen isotherm of "200 μm_meso / macro II" (catalyst support or activated carbon B2 according to the invention). Only at a relative pressure of 0.85 does the isotherm and thus the nitrogen uptake increase sharply (FIG. 1). The pronounced hysteresis loop and only 25% micropore volume attest to the presence of pores larger than 2 nm, as well as mesopores and macropores.

[0330] Pore ​​sizes of 2 nm or larger can be achieved by mercury intrusion. Figure 2 shows the mercury intrusion curves of the catalyst support. The diagrammatic representation in Figure 2 shows the mercury intrusion dVp / dlog(dp) versus the underlying pore diameter dp of the investigated activated carbon.

[0331] Here, it is clear that the microporous catalyst support or activated carbon A1 ("200 μm_micro I") does not have a pore volume greater than 2 nm. The meso / macroporous catalyst support or activated carbon B1 ("200 μm_meso / macro I") exhibits a significant pore volume in the range of 10 nm to 20 nm. The further meso / macroporous catalyst support or activated carbon B2 ("200 μm_meso / macro II") also exhibits a very large proportion of mesopores and a significant proportion of macropores. The texture data can be taken from Table 3.

[0332] The chemical composition and high purity of the activated carbon in the PBSAC form are maintained and are comparable in all cases. Likewise, the high mechanical stability of the activated carbon in the PBSAC form is maintained, even with a high porosity and a high proportion of pores larger than 2 nm (see "200 μm_meso / macro I" (B1) and "200 μm_meso / macro II" (B2)). The high mechanical stability is evidenced by a high abrasion resistance of more than 98% (see Table 2).

[0333] Table 2 below shows the corresponding properties of the activated carbons or catalyst supports investigated.

[0334] [Table 2] * A1: Not according to the present invention ** C1, C2: Commercially available coconut shell-based activated carbon (not according to the present invention)

[0335] [Table 3]

[0336] In a corresponding manner, further catalyst supports or activated carbons are provided, namely catalyst supports or activated carbons A2 (200 μm micro II; average particle size 200 μm) and A3 (370 μm micro III; average particle size 370 μm) not according to the invention, which are essentially equivalent to catalyst support A1 in terms of their respective properties in the form of the parameters set out in Tables 2 and 2. Furthermore, further catalyst supports or activated carbons are provided, namely catalyst supports B3 ("370 μm meso / macro III"; average particle penetration 370 μm) and B4 ("470 μm meso / macro III"; average particle penetration 470 μm) used according to the invention, which are essentially comparable to catalyst supports B1 and B2 in terms of their other properties in the form of the parameters set out in Tables 2 and 2.

[0337] 5. Oxidative pretreatment of catalyst supports Oxidative pretreatment of materials in the form of catalyst supports or activated carbon helps create oxygen centers on the surface of each PBSAC. These then interact with metal ions from the salt solution. Electrostatic interactions between the surface oxide and the metal ions immobilize them on the surface, allowing them to preferentially migrate into the pores of the PBSAC rather than remaining in the supernatant.

[0338] a) For oxidation of PBSAC, synthetic air is passed through a heatable, gas-tight fused silica reactor. For surface modification, typically 250 g of PBSAC is placed in a fused silica tube, which is then placed in a furnace with all gas connections attached. Typically, the furnace is operated at 10 Kmin -1 The reaction temperature is in the range of 350°C to 550°C. The reaction time varies from 120 minutes to 600 minutes.

[0339] b) Oxidation treatment with mineral acids or hydrogen peroxide Oxidation with mineral acids is carried out by wet chemical means. Mineral acids are primarily hydrochloric acid (HCl), nitric acid (HNO3), and sulfuric acid (H2SO4). Perchloric acid (HClO4), phosphoric acid (H3PO4), and hydrogen peroxide (H2O2) are also used. These acids are used in a full range of concentrations at temperatures between 20°C and 100°C.

[0340] Typically, 500 g of polymer-based spherical adsorbent is stirred with 1000 g of mineral acid for 30 to 240 minutes, after which the excess mineral acid is decanted and the oxidized base adsorbent is washed with distilled water and dried.

[0341] c) Properties of oxidized catalyst supports As a result of the surface modification, the structural properties do not change, or at most only to a very small extent. The properties of the oxidation catalyst supports used or analyzed according to the invention can be taken from Table 4. The mechanical stability of the oxidation catalyst supports is maintained by a very high abrasion hardness. Measurement of the volatile components is used to characterize the surface oxides. In this case, the material is left at 900°C for 7 minutes according to ISO 562-1981, after which the weight loss is determined gravimetrically.

[0342] However, this method still does not tell us anything about the nature of the oxygen species present on the surface of the PBSAC. To determine this, a photoelectron spectrum is recorded for each catalyst support. From these spectra, the elemental composition can be determined. These can be read from Table 5. The measured volatile components show a correlation with the atomic composition determined by photoelectron spectroscopy. The sample oxidized with hydrochloric acid (90 min) showed the lowest oxygen content of 4.0 atomic %. Oxidizing the catalyst support with 50% by volume of nitric acid showed the highest surface oxygen content of 11.8 atomic %.

[0343] [Table 4]

[0344] [Table 5]

[0345] To characterize the oxygen species, the bound fractions are measured from high-resolution oxygen spectra. These are available in Table 6. It can be seen that more than half of the oxygen species are in the form of surface alcohol oxygens. Approximately 35% to 40% of the oxygen atoms are bound on the surface in the form of carbonyl oxygens. Different oxidized catalyst supports only slightly differ in the proportion of oxygen species.

[0346] [Table 6] O1: Carbonyl oxygen (RC=0 / R-CO=O) * ) O2: Alcohol oxygen (R-OH / R-OR / R-CO-O * O3:pi-pi *

[0347] 6. Catalyst support impregnation treatment The oxidized catalyst support or activated carbon contains catalytically active components or related precursors, thereby obtaining the corresponding impregnated catalyst system, as described below.

[0348] a) Palladium loading in PBSAC A round-bottom flask is charged with water and an acid solution (HCl, HNO). Then, a palladium precursor (usually HPdCl, Pd(NO) 32 ) is added. The cloudy suspension is vigorously stirred with a magnetic stirrer for at least 30 minutes until a clear, brownish solution is obtained. While vigorously stirring, the oxidized catalyst support is rapidly added as described above. The system is stirred at low speed (50 rpm) for 24 hours. The solution is then removed. The solid is then separated using a Büchner funnel and a suction flask. The catalyst is then washed extensively with ultrapure water. For drying, the material is transferred to a drying oven and dried at 80°C for 12 hours. The material is then dried in an oven.

[0349] b) Platinum loading on spherical adsorbent Water and an acid solution (HCl, HNO3) are placed in a round-bottom flask. The platinum precursor (usually H2[PtCl6], (NH3)4Pt(OH)2, or Pt[NO3)2) is then added. The cloudy suspension is vigorously stirred with a magnetic stirrer for at least 30 minutes until a clear, brownish solution is obtained. While vigorously stirring, the oxidized catalyst support is rapidly added. The system is stirred at low speed (50 rpm) for 24 hours. The solid is then isolated using a Büchner funnel and a suction flask. The catalyst is then extensively washed with ultrapure water. For drying, the material is transferred to a drying oven and dried at 80°C for 12 hours. The material is then dried in an oven.

[0350] 7. Reduction of the catalyst or reduction to obtain the catalytic system The above impregnated catalyst system can be subjected to reduction treatment to obtain the corresponding catalyst system as follows: a) Gas-phase reduction Gas phase reduction of the catalytic material is carried out in a horizontal, heatable flow tube containing 5% by volume hydrogen in nitrogen at temperatures between 50°C and 300°C for times between 1 hour and 10 hours. The catalytic material is then heated to a temperature of 1°C. b) Liquid Phase Reduction Liquid-phase reduction is preceded by fixation of the active ingredient with potassium hydroxide (KOH). The base is added stoichiometrically to the impregnation solution at room temperature. Potassium formate (COO) is then added in a 10-fold stoichiometric excess, and the solution is left at 50-120°C for 1-5 hours. The solution is then fixed with potassium hydroxide (KOH).

[0351] 8. Palladium catalyst characteristics Depending on the reduction method and reaction parameters selected, the appearance of metal active centers can be controlled in terms of size and distribution. The dispersion can be set in the range of 15% to 35%. The cluster size of the metal centers varies in the range of 33 Å (3.3 nm) to 76 Å (7.6 nm). In this regard, reference can also be made to Figure 3, which shows the measured values ​​of metal dispersion (MD) and metal crystallite size (KG) for 5 wt. % palladium catalysts (based on catalyst supports B1 and B4, respectively). Figure 3 also shows the reduction temperature T optimized according to the invention. red2 (here 140° C.), the reduction temperature T , designated in FIG. 3 as the so-called standard temperature according to the present invention, red1 (here 80°C) (and therefore explicitly belonging to the present invention), further improved properties in terms of metal dispersion and average crystallite size are obtained, which accordingly also leads to further improvements in the catalytic performance of the catalyst systems according to the present invention, as well as platinum and ruthenium catalysts.

[0352] 9. General aspects of hydrotreating in fixed-bed reactors. The catalytic system according to the invention can be used, particularly on a large scale, for example, as a catalyst for hydrogenation reactions. Hydrogenation is one of the standard reactions in technical chemistry and is used in large-scale processes such as petrochemicals, for example in the desulfurization of petroleum fractions, and in the synthesis of fine chemicals. In addition to unsaturated compounds, other groups of substances are also hydrogenated, such as aldehydes and ketones to alcohols, and nitro compounds and nitriles to amines. In most hydrogenation reactions, the reactants are in the liquid phase; only low-boiling substances, such as butyraldehyde from hydroformylation, are hydrogenated in the gas phase.

[0353] For example, precious metals such as nickel, platinum, ruthenium, and palladium function as hydrogenation catalysts, mostly in the form of supported catalysts. They are either suspended as particulate material in the reaction liquid or used as a fixed bed. In the latter case, trickle-bed reactors are used for three-phase reactions (reaction liquid, gaseous hydrogen, solid catalyst). That is, fixed-bed reactors are used in which the catalyst packing is dispersed in the reaction liquid. The size of the catalyst packing (spheres, cylinders, extrudates, etc.) is, for example, between 1 and 7 mm.

[0354] A corresponding hydrotreating unit is shown in Figure 6, which will be used as an example to explain the process control: reactant A is fed from above into a tubular reactor (a) and flows through the reactor with the catalyst bed in cocurrent or countercurrent with hydrogen H2. In terms of volume, the gas phase is the predominant phase compared to the liquid phase and flows around the catalyst bed, which is wetted by the liquid phase. However, only reactors operating in cocurrent flow are widely used in the technical field. The flow is driven by gravity or external pressure. For temperature control, the reactor is equipped with a double jacket. At its lower end, the hydrogenation product B is removed and finally degassed in a separator (b). The residual gas RG is discharged via a device (c).

[0355] In trickle-bed reactors, conversion and selectivity depend not only on reaction kinetics, pressure, and temperature, but also on the reactor fluid dynamics. Fluid dynamics have a significant impact on the liquid distribution within the reactor, which directly affects catalyst utilization. Uneven fluid distribution results in incomplete wetting of the catalyst bed, which can have a negative impact on catalyst utilization.

[0356] Furthermore, wetting of the catalyst bed can be disrupted by non-optimized technological sizing, such as the ratio of reactor height to diameter and the ratio of reactor inner diameter to catalyst particle size. To prevent these effects of non-wetted reactor interiors and / or catalyst regions, the design of the liquid distributor and the maintenance of corresponding size ratios are important.

[0357] Therefore, trickle-bed reactor design is based on parameters such as liquid holdup (the amount of liquid present throughout the catalyst bed), pressure drop across the bed, gas and liquid phase distribution, and mass and heat transfer coefficients. Industrially used reactors are 5 to 30 m high, and in these, the catalyst bed exists in multiple or single bed configurations. The reactor diameter is limited by the uniform distribution of liquid across the reactor cross section and usually does not exceed 4 to 5 m. Therefore, the reactor height-to-diameter ratio (Hr / Di) is generally between 5 and 25. Laboratory-scale trickle-bed reactors have diameters of 0.03 to 0.2 m and lengths of several meters. At these scales, the ratio of reactor inner diameter to catalyst diameter (Di / dk) cannot be neglected and must be greater than Di / dk = 10 (usually Di / dk > 15). Otherwise, differences in the structure of the packing near the reactor wall and the structure of the packing core may limit the fluid flow, which may result in a decrease in conversion.In industrial reactors, the ratio of the reactor inner diameter to the catalyst diameter is usually between 100 and 1000, to ensure that the influence of liquid moving at the edges can be eliminated.

[0358] Conventional trickle-bed reactors with diameters of 0.2 m or more are generally not well suited to the production of fine chemicals due to the minimal throughput required. However, advances in mini-plant technology have made continuous systems possible, even at very low throughputs (less than 1 kg / h). Mini-plants have primarily been used in process development. However, mini-plants are also suitable for production, particularly for the production of small quantities of consistent quality products, such as fine chemicals and active ingredients for pharmaceuticals and agrochemicals.

[0359] For more detailed explanations, see in particular the following publications: Industrial Chemistry, Manfred Berns et al., 2nd edition, Virey-VCH Publishing Co., Ltd., 2013; the chapter "Three-phase trickle-bed reactors", Ullmann's Encyclopedia of Industrial Chemistry, Vol. 7, Online Education 2008; and the chapter "Types of reactors and their industrial applications", Ullmann's Encyclopedia of Industrial Chemistry, Vol. 7, Online Education 2008.

[0360] 10. Catalyst test (hydrogenation of cinnamic acid) The catalytic performance of the catalyst system according to the invention, in comparison with a system not according to the invention, can also be investigated by carrying out a hydrogenation reaction or a catalytically controlled hydrogenation reaction, for example the hydrogenation of cinnamic acid as a reactant to hydrocinnamic acid as a product. For this purpose, reference can also be made to Figure 7A.

[0361] A 100 mL three-neck flask equipped with a stir bar, N2 inlet, and H2 outlet was charged with cinnamic acid (1) (2 g, 13.5 mmol) and 144 mg of catalyst. The three-neck flask was sealed with a rubber septum and evacuated and refilled with nitrogen (three times). Ethyl acetate (14 mL) was added, and the mixture was stirred (700 rpm) until the reactants were completely dissolved. The flask was evacuated and refilled with hydrogen (three times). Samples were taken periodically at 1, 2, 3, 5, 7, 10, and 16 hours and analyzed by gas chromatography coupled with a mass spectrometer. Catalytic systems based on catalyst supports A1, A2, and A3 (not according to the invention) and catalyst supports B1, B2, and B3 (according to the invention) were investigated.

[0362] The results are shown in Figures 7B and 7C, which show the catalytic conversion (hydrogenation) of cinnamic acid as reactant and starting material, respectively, in terms of the amount of cinnamic acid over time (measured by GC-MS; area %) when 100% of the unreacted cinnamic acid is present as starting material at time t = 0.

[0363] Figure 7B shows the results for catalyst systems according to the invention based on catalyst supports B1, B2 and B3 (where, for t=4 h, the upper line represents catalyst system B3, the middle line represents catalyst system B1, and the lower line represents catalyst system B2), and Figure 7C shows the results for catalyst systems not according to the invention based on catalyst supports A1, A2 and A3 (where, for t=7 h, the upper line represents catalyst system A3, and the lower lines represent catalyst systems A1 and A2, respectively).

[0364] A comparison of the linear curves shown in Figures 7B and 7C shows that the catalytic performance of the catalyst systems according to the invention based on catalyst supports B1, B2 and B3 is significantly higher than that of the non-inventive systems based on catalyst supports A1, A2 and A3. The conversion or hydrogenation of the starting material in the form of cinnamic acid is therefore completed significantly faster in the systems according to the invention than in the non-inventive systems, allowing the systems according to the invention to take advantage of higher conversion rates.

[0365] Thus, the catalyst systems based on the catalyst supports B1, B2 and B3 according to the invention exhibit high overall catalytic performance with particularly high conversion rates and improved space / time yields, the same being true for the corresponding platinum and ruthenium catalyst systems.

[0366] As mentioned above, the special pore system with high meso- and macroporosity of the activated carbon used as catalyst support is of great importance in this context, especially with regard to improving the transport methods of reactants and products.

[0367] The catalyst system according to the present invention also provides an overall improvement in the device using the catalytically active component, due to the special process management in the preparation of the catalyst system according to the present invention, in which the activated carbon is oxidized according to a specific purpose before being loaded with the catalytically active component or a related precursor, and then reduced to obtain the catalyst system. In particular, the special pore structure of the activated carbon, as described in the form of a specific ratio of the total pore volume to the specific BET surface area (quotient Q), results in improved properties in terms of the catalytic activity of the catalyst system according to the present invention.

[0368] In this regard, in particular, as indicated above, the totality, target and purpose-oriented combination of the measures according to the invention in their particular combination leads to the advantages and properties of the catalytic system according to the invention.

[0369] As a result, the fundamental investigations show overall that the catalyst systems according to the invention obtained by the process of the invention have significantly improved properties compared to prior art systems.

Claims

1. A catalyst system in the form of a supported catalyst, comprising: the catalyst system comprises at least one catalytically active component fixed to a catalyst support, the catalytically active component comprising at least one metal, the metal being selected from the group consisting of Cu, Ag, Au, Zn, Hg, Sn, Ce, Ti, Zr, V, Nb, Cr, Mo, W, Mn, Fe, Bi, Ru, Os, Co, Rh, Re, Ir, Ni, Pd and Pt; and The catalyst support is in the form of spherical activated carbon; The spherical activated carbon forming the catalyst support is (i) 1.1 cm ３ / g ~ 2.4 cm ３ / g of the total pore volume V according to Goulwich ｔｏｔａｌ 50% to 90% of the total Gouldich pore volume of the initial activated carbon is formed by pores having a pore diameter in the range of 2 nm to 500 nm; and (ii) 1,300m ２ / g~2,200m ２ Specific BET surface area S in the range of / g ＢＥＴ having; However, the formula Q = V ｔｏｔａｌ / S ＢＥＴ Total pore volume V according to Goulwich ｔｏｔａｌ Specific BET surface area S ＢＥＴ The ratio Q to －９ m ~ 1.8 × 10 －９ be within the range of m; and, the catalyst system has an activity, measured as the percentage dispersion of the catalytically active components on the catalyst support, in the range of 15% to 90%, as determined by chemisorption using the dynamic flow method according to DIN 66136-3:2007-01; and, Catalyst system in the form of a supported catalyst, characterized in that the catalyst system comprises at least one catalytically active component having an average crystallite size, measured according to DIN 66136, in the range of 0.5 nm to 8 nm.

2. 10. The catalyst system of claim 1, wherein the catalyst system has an activity, measured as the percentage dispersion of catalytically active components on the catalyst support, in the range of 20% to 80% as measured by chemisorption using the dynamic flow method according to DIN 66136-3:2007-01.

3. 10. The catalyst system of claim 1, wherein the catalyst system has an activity, measured as the percentage dispersion of catalytically active components on the catalyst support, in the range of 25% to 70% as measured by chemisorption using the dynamic flow method according to DIN 66136-3:2007-01.

4. 10. The catalyst system of claim 1, wherein the catalyst system comprises at least one catalytically active component having an average crystallite size, measured according to DIN 66136, in the range of 0.7 nm to 7 nm.

5. 2. The catalyst system according to claim 1, characterized in that the catalyst system comprises at least one catalytically active component having an average crystallite size, measured according to DIN 66136, in the range of 1 nm to 6 nm.

6. 10. The catalyst system of claim 1, wherein the catalyst system comprises at least one catalytically active component having an average crystallite size, measured according to DIN 66136, in the range of 1.5 nm to 5.8 nm.

7. 2. The catalyst system of claim 1, wherein the catalytically active component comprises at least one metal selected from the group consisting of Fe, Bi, V, Cu, Pb, Zn, Ag, Sn, Pd, Pt, Ru, and Ni.

8. 10. A method for catalyzing a chemical reaction via a heterogeneous catalyst, the method comprising using the catalyst system of claim 1.

9. 9. The method of claim 8, wherein the chemical reaction is selected from the group consisting of a hydrogenation reaction, an oligomerization reaction, and a polymerization reaction.

10. 10. Protective clothing comprising the catalytic system of claim 1.

11. 11. The protective garment of claim 10, wherein the protective garment is selected from the group consisting of civilian protective garments, military protective garments, protective suits, protective gloves, protective shoes, protective socks, protective hoods, and protective covers.

12. A filter for removing pollutants, odors and harmful substances, said filter comprising the catalyst system of claim 1.

13. 13. The filter of claim 12, wherein the filter is selected from the group consisting of NBC respirator filters, odor filters, surface filters, air filters, indoor air purification filters, adsorbable support structures, chemisorbable support structures, and medical field filters.

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