Method for producing supported metal catalyst using granular activated carbon as catalyst carrier

Abstract

The present invention relates to a method for producing a catalyst system comprising a catalytically active component and a supported catalyst, and also to the catalyst system itself. Granular activated carbon is used as a support. The catalytically active component is a metal, such as palladium. The activated carbon has a total pore volume of 0.8 to 3.9 ml / g, and at least 50% of the total pore volume of the activated carbon is formed by pores having a pore diameter of at least 2 nm. The BET specific surface area is 1000 to 3000 m<supgt;2< / supgt> / g. Before impregnating the metal precursor, the starting activated carbon is subjected to surface oxidation. The present invention also relates to the use of the catalyst system according to the present invention, and also to protective materials, filters and filter materials produced using the catalyst system according to the present invention or comprising such a catalyst system.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytically active systems or catalysts or catalytically active components applied to support materials, and therefore in particular to the technical field of supported catalysts (eg particularly useful for heterogeneous catalysis).

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

[0003] Furthermore, the present invention relates to a catalyst system obtainable on the basis of the process according to the invention and also 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. In addition, the present invention relates to the use of the catalyst system according to the invention for chemical catalysis. In addition, the present invention also relates to the use of the catalyst system according to the invention for the catalysis of chemical processes and reactions (such as hydrogenation reactions, etc.).

[0005] The invention furthermore relates to the use of the catalyst system according to the invention for the production of filters and filter materials and as an adsorptive storage of gases or liquids, and in gas sensors or as a gas sensor or in fuel cells. The invention furthermore relates to the use of the catalyst system according to the invention for adsorption applications, gas purification or gas treatment and further for the removal of pollutants or substances or gases that are harmful to the environment, health or toxic. The invention further relates to the use of the catalyst system according to the invention for the preparation or provision of clean indoor air, etc.

[0006] The invention also relates to a protective material produced using the catalyst system according to the invention or comprising the catalyst system according to the invention. The invention also relates to filters and filter materials produced using the catalyst system according to the invention or comprising the catalyst system according to the invention. Background Art

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

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

[0009] Also in this context, there is a high demand in the prior art for specific and efficient catalysts for chemical catalysis, especially since the targeted application of catalysts enables chemical reactions to be carried out more quickly or with lower energy input. In this context, the use of catalysts in chemical reactions is also of great commercial importance: for example, it is assumed that around 80% of all chemical products have a catalytic stage in the basic manufacturing or value chain. Furthermore, catalysts also play a prominent role in the field of environmental protection, in particular in the aftertreatment of industrial exhaust gases, for example in the context of industrial electricity production, and in the treatment of exhaust gases in the (passenger) motor transport sector.

[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 for homogeneous catalysis, the 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, while in the case of heterogeneous catalysts or catalysts for heterogeneous catalysis, the reactants to be reacted on the one hand and the catalyst 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 are, in particular, the fact that the separation or isolation of the catalyst from the reaction mixture can sometimes be improved, as well as the basic possibility of recovering the used catalyst or of treating deactivated or inactive catalysts. In industrial processes in particular, heterogeneous catalysts are often present as solids or so-called contact (-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] As regards heterogeneous catalysts or catalysts in solid form, metals or metal-containing compounds (e.g. metal salts or metal oxides) are usually used as catalysts. Such catalysts can be used, for example, in bulk or in a form in which the catalyst or the essential catalytically active components are present on a support system or are bound or fixed to a support system. Such catalyst systems in which the catalytically active components are on a support are generally referred to as supported catalysts.

[0013] The use of supported catalysts has the fundamental advantage that a larger surface or a larger contact area with the reactants to be reacted can be achieved, which generally leads to an increase in efficiency or a reduction in the amount of catalyst used with associated cost advantages.

[0014] Furthermore, the use of supported systems or supported catalysts generally has the advantage that the basic catalyst can be better removed or separated from the reaction medium and is generally easier to recycle. In particular in the case of catalysts used in bulk or in phase with the reactants, the post-reaction or post-conversion separation of the reactants is difficult or involves high losses in catalyst mass, which generally worsens the economic efficiency and makes the recycling of the used catalyst fundamentally more difficult.

[0015] For supported catalyst systems or supported catalysts, the prior art generally considers the use of compact or porous support structures. The disadvantage of using so-called compact catalysts is that effective surface enlargement cannot be achieved, and therefore catalytic activity can only be provided on relatively small geometric surfaces. In contrast, porous solids used as catalyst supports have enlarged (inner) surfaces, which, as mentioned above, are associated with increased efficiency and higher catalytic activity, even if the loading of active components (i.e. catalytically active metals, such as precious metals) is low.

[0016] For example, crystalline porous solids of the zeolite family are used as catalyst supports, particularly in the field of petrochemicals or for processing or upgrading crude oil or petroleum refining technology. Zeolites generally have uniform pore sizes or diameters, which allow some selective reaction control by matching the size of the substance to be reacted. In addition, the use of silica, molecular sieves, metal oxides (such as aluminum oxide), or ceramics and activated carbon as support systems for catalysts is generally known in the prior art.

[0017] In principle, such support systems are also used in the context of enabling permanent or elution-stable fixation of particularly cost-intensive catalysts, in order to reduce associated losses during use or to enable corresponding recyclability or recycling of the entire catalyst system as described above.

[0018] With regard to the use of activated carbon as a support material for catalysts, in particular for obtaining so-called activated carbon-supported catalysts, in particular activated carbon-supported noble metal catalysts, in the prior art, the corresponding activated carbons are usually used in finely divided or powdered form (powdered carbon) or in the form of finely ground powders, with corresponding particle sizes in the lower μm range. The use of finely divided activated carbon as a support system is generally intended to reduce the limitations of potential mass transport with respect to the catalyzed target reaction, in particular by shortening the diffusion or permeation distance into the pore structure of the activated carbon-based support material. However, the main disadvantage of using finely divided or powdered activated carbon with small particle sizes as catalyst supports is that the overall optimal application properties cannot be achieved. For example, due to the low volume porosity of the filter cake, or due to the high volume density of the base material, the use of finely divided activated carbon, in particular in discontinuous applications, leads to a deterioration in the performance, for example, in the separation of the catalyst or catalyst system after use. In this context, it should also be emphasized that in the case of discontinuous catalytic processes, the separation or filtration of the catalyst or catalyst system is an indispensable or absolutely necessary process step.

[0019] Furthermore, such activated carbons often have a pore system that is not optimally formed with respect to the binding of the catalyst and the transport methods of reactants and products, which can impair the overall catalytic performance.

[0020] Under operating conditions, in particular in continuous catalytic processes (i.e. catalytic reaction processes) using powdered or finely separated activated carbon or powdered carbon in the reaction chamber, there are high pressure losses due to occasional overcompression of the catalyst system. This is usually accompanied by a reduction in the flow rate of the reaction mixture with the corresponding reactants to be fed through the catalyst system. Overcompression can also result if the abrasive hardness of the catalyst used or the corresponding support material is too low.

[0021] In addition, the application performance of activated carbon-supported catalyst systems is often not optimal, because finely divided catalyst systems, especially in liquid media containing reactants, tend to form sludge or over-compact, with the risk of clogging of the reaction unit or excessive reduction of flow rate or filtration rate, which is detrimental to the overall catalytic conversion. Excessive compression of the catalyst system can also lead to "dead zones" in the basic unit or equipment, where the conversion rate of the reactants is significantly reduced.

[0022] In this case, the formation of sludge areas is particularly relevant in discontinuous use. In continuous catalytic applications, in which the catalyst system is, for example, filled into a corresponding reaction chamber, such as those based on a cartridge system, followed by a particularly continuous flow of the medium containing the reactants or the reactants, the same high pressure losses lead to correspondingly low flow rates of the catalyst system. In addition, complex filtering or retaining devices with a tendency to clog are often required to prevent the catalyst from being discharged or flushed out of the continuously flowing reaction system.

[0023] It can therefore be said that catalyst systems based on powdered or finely divided activated carbon as support material generally do not always have adequate or satisfactory performance in their application.

[0024] In order to reduce the disadvantages associated with the small particle size, attempts have been made in the prior art to use catalyst supports based on granular activated carbon, whereby starting materials based on activated carbons on the basis of coconut shells, charcoal, wood (e.g. wood waste, peat, hard coal, etc.) are basically considered in this regard. These activated carbons used as catalyst supports can usually be in the form of fragments or granules, which in principle lead to a certain improvement in the application properties, especially with regard to the separation time for discontinuous applications, but the mechanical stability of such activated carbons used as catalyst supports is usually too low, which is accompanied by high wear of the support material under the application conditions (e.g. due to the sometimes vigorous stirring methods during the catalytic conversion process). Subsequently, the low wear resistance of such activated carbons in turn leads to finely divided particles by corresponding comminution or grinding methods, accompanied by high losses of catalytically active substances, and with the above-mentioned disadvantages with regard to clogging or compaction of the system, etc. In addition, such activated carbons usually 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 support material are also disadvantageous, since it is often not possible to optimally load or fix the catalyst on the support material, which leads on the one hand to small amounts of catalyst applied to the support and on the other hand to frequent release or elution of the catalyst from the support material under the conditions of application. On the other hand, under the conditions of application, a release or elution of the catalyst from the support material can often be observed, with a loss of the amount of catalyst washed out, which is disadvantageous from a process engineering point of view, in particular for cost reasons.

[0026] In particular, the activated carbons used in the prior art, for example based on coconut shells, generally have only a low affinity for the catalyst to be applied or immobilized, which (without wishing to be bound to this theory) is due to the fact that the basic activated carbon is generally hydrophobic in terms of its pore surface or, in particular, does not have a sufficient number of polar functional groups to bind to the catalyst (this is also the case with polymer-based activated carbons, in particular PBSAC). However, this is detrimental to the overall loading or equipment of the catalyst and to the permanent fixation of the catalyst on the support system. The high loss of catalyst of the basic catalyst system is likewise accompanied by a reduction in the conversion of the reactants in the basic catalytic reaction, which also worsens the economic efficiency of the catalyst system used.

[0027] Since conventional activated carbons are non-polar or hydrophobic on their surface and therefore have no significant affinity for the catalyst or catalytically active component to be applied or fixed for the reaction or catalytic device for the activated carbon, in order to ensure a certain loading amount of the activated carbon, it is necessary to use a large excess of catalyst substances during the production of the activated carbon or the process of equipping the activated carbon with the catalyst. In order to fundamentally ensure a certain loading amount of the activated carbon, it is necessary to use a large excess of catalyst substances during the production of the activated carbon or the process of equipping the activated carbon with the catalyst, or it is necessary to generate surface centers (i.e. centers for attaching catalytically active components) in advance. In particular, the catalysts usually adhere only by purely physical interactions and can therefore also be at least partially removed or washed off again (for example by elution methods, etc.), especially when they come into contact with liquids.

[0028] In principle, for heterogeneous catalysts using activated carbon as support material according to the known concepts of the prior art, there are also disadvantages, namely that the transport or diffusion process of the reactants or products is not optimal, in particular due to the non-optimally formed pore system of the support material, in particular with regard to the basic pore diameter and its distribution, or more precisely their proportion in the total pore volume. The transport or diffusion process of the reactants or products is not optimal, which is associated with a reduction in the conversion rate and a non-optimal space / time yield, for example because the reactants are not optimally transported to the underlying catalytic centers or the resulting products are not optimally removed from the catalyst system.

[0029] In this context, heterogeneous catalysis in porous structures (e.g. activated carbon) as catalyst supports can be divided essentially into seven substeps, including the corresponding transport steps of reactants or products, each of which can be rate-determining. In this regard, reference can also be made to Figure 4 and the following explanations associated therewith.

[0030] Therefore, a non-optimal formation of the pore system of the support material can lead to a long-term deterioration in the conversion or the space / time yield, since the transport methods within the system are insufficient and are overall limited in terms of catalytic activity.

[0031] Furthermore, the conversion or the space / time yield can also be reduced by the fact that the catalytically active centers themselves are not formed optimally or the support material is simply not adequately equipped with catalytically active components, which can also be caused by the pore system of the catalyst support which is not formed optimally in this respect.

[0032] Furthermore, the catalyst systems known from the prior art sometimes have the disadvantage during use, in particular in fixed beds or the like, that high pressure losses occur and there is often also a high level of dust formation and associated material losses, in particular since the hardness or abrasion resistance of the basic catalyst system is not always sufficient.

[0033] DE 29 36 362 C2 relates to a method for preparing a palladium-carbon catalyst, wherein palladium is deposited by reduction on carbon suspended in an organic solvent as a catalyst support. In this case, the palladium will be deposited as metal on the suspended support. Powdered activated carbon, carbon black or graphite are used as carbon supports. However, the catalyst is sometimes associated with the above-mentioned disadvantages, especially in discontinuous catalytic processes, especially with regard to the separation or recovery of the catalyst, and its application properties in continuous catalytic processes, especially with regard to pressure loss or flow rate.

[0034] In summary, it can be pointed out that the catalyst systems known from the prior art which are based on conventional activated carbon or powdered activated carbon as support material used have production-specific and application-specific disadvantages, on the one hand, in particular with regard to the support of the catalytically active components and their fixation on the material and on the other hand with regard to the use of the base system in continuous and discontinuous catalytic applications. Summary of the invention

[0035] Against this background, it was therefore an object of the present invention to provide catalyst systems or supported catalysts having at least one catalytically active component, and corresponding methods for their production, which at least largely avoid or at least alleviate the above-mentioned disadvantages of the prior art.

[0036] In particular, the present invention aims to provide a catalyst system with at least one catalytically active component or a supported catalyst with at least one catalytically active component, which catalyst system or catalyst has production-specific and application-specific advantages. In this regard, a corresponding method for producing the catalyst system will also be provided.

[0037] The object of the present invention is also particularly the fact that, within the scope of the present invention, an overall high-performance catalyst system is provided, which has a high durability or stability, is able to achieve high conversion rates and associated high space / time yields, while providing high recyclability and stability of the system provided.

[0038] In particular, according to the present invention, a catalyst system is provided which enables high or efficient loading of catalyst components or catalytically active components while ensuring permanent and consistent loading or equipment of the catalyst components.

[0039] Furthermore, according to the invention, a catalyst system will also be provided which, within its application range, in particular in chemical catalysis, preferably on an industrial scale, has improved performance in both discontinuous and continuous catalytic applications, in particular with regard to its catalytic performance and the separation, recovery or recycling of the system (in particular in discontinuous processes), and in addition, has improved performance in relation to ensuring low or adjustable pressure losses and high or adjustable flow rates (in particular in discontinuous processes). A chemical catalyst, preferably on an industrial scale, has improved performance, in particular with regard to its catalytic performance and the separation, recovery or recycling of the system (in particular in discontinuous processes), and in addition, has improved performance in relation to ensuring low or adjustable pressure losses and high or adjustable flow rates (in particular in continuous catalytic processes), thereby also providing an overall optimized process time or an increased catalytic activity.

[0040] In particular, the present invention also seeks to provide such a catalyst system which, in addition to its high catalytic activity, also has excellent mechanical properties, in particular with regard to the abrasion resistance or bursting pressure of the basic particle structure.

[0041] Similarly, the system according to the invention should also be customized or individually designed or equipped for the respective application or use case.

[0042] Furthermore, the present invention aims at providing an efficient process, on the basis of which the catalyst system according to the invention having at least one catalytically active component can be obtained.

[0043] As the applicant has now discovered in a completely surprising manner, the aforementioned object of the invention can be achieved in an unexpected manner by providing within the scope of the invention a special process for producing a special catalyst system and a corresponding catalyst system.

[0044] In this case, according to the invention, a special activated carbon is used as catalyst support, which, in addition to its granular or spherical design or shape, has a specially designed pore system, i.e. a high proportion of mesopores and macropores in the total pore volume of the activated carbon, so that according to the invention, an activated carbon with mesopores and macropores (with a defined proportion of micropores) is used. In addition, the activated carbon used according to the invention has a special BET surface area and at the same time a special ratio of total pore volume to BET specific surface area.

[0045] Furthermore, in the method according to the invention, targeted oxidation, in particular surface oxidation (i.e. also in particular oxidation of the inner surface of the catalyst support) of the activated carbon subsequently used as catalyst support is directed to or aimed at adjusting the specific oxygen content, in particular the surface oxygen content, and, with the formation of a specific hydrophilicity, this specific activated carbon is equipped with catalytically active components or their precursors and then reduced to obtain the catalyst system of the invention.

[0046] In other words, according to the invention, a special catalyst system or a supported catalyst with at least one catalytically active component applied to a catalyst support is therefore provided, wherein the catalyst support is in the form of a very specially formed granular or spherical activated carbon with a special porosity, in particular with regard to the formation of a high meso- and macroporosity (i.e. a high proportion of mesopores and macropores in the total pore volume, while having a defined proportion of micropores), and wherein the application of the catalytically active component to the activated carbon is carried out in an oxidized form of the activated carbon (i.e. on an oxidized activated carbon), followed by a further reduction of the base system (i.e. the active centers or active components) in this respect to obtain the catalyst system according to the invention. In addition to the high meso- and macroporosity, the activated carbon used as catalyst support also exhibits a defined microporosity (i.e. a specific proportion of micropores in the total pore volume), which, although generally to a lesser extent than the mesopore and macropore volume, is sufficient for catalysis.

[0047] Surprisingly, the catalyst system or supported catalyst according to the invention provides on this basis an improved transport or diffusion behavior for reactants or products due to a special pore system, as well as an improved loading of the catalytically active components, which exhibits excellent catalytic performance, accompanied by high catalytic conversions and high space / time yields when used in a catalytic process. In this regard, the catalyst system according to the invention also exhibits a high dispersion of the catalytically active components and an optimized crystallite size, which can be used as a parameter or measure of the catalytic performance.

[0048] The catalyst system provided according to the invention is also particularly suitable for use in the field of chemical catalysis, in particular on a (large) industrial scale. In addition, the catalyst system according to the invention is also particularly suitable for corresponding filter applications for removing, for example, pollutants and toxic substances from media containing these substances. In particular, the catalyst system according to the invention is also suitable in or for use in protective materials, in particular for use in the civil or military sectors, in particular for NBC applications.

[0049] In particular, due to the spherical design or spherical shape, the outstanding mechanical properties of the catalyst support and the controllable or specifically designed meso- and macroporosity (with a simultaneously defined microporosity), the catalyst system of the present invention is also very important, in particular for continuous catalysis, thereby also overcoming the disadvantages of the prior art with regard to discontinuous catalysis, as explained above, which is associated, for example, with conventional powder catalysts and the like.

[0050] In order to solve the above-mentioned objects, the present invention therefore proposes, according to a first aspect of the invention, a method according to the invention for producing a catalyst system having at least one catalytically active component according to the invention according to patent claim 1. Furthermore, particularly advantageous embodiments of the method according to the invention are the subject matter of the associated method subclaims and the associated method sub-claims.

[0051] According to a second aspect of the invention, a further object of the invention is the catalyst system according to the invention or the supported catalyst according to the invention, wherein the catalyst system or the supported catalyst comprises at least one catalytically active component according to the independent patent claim associated therewith and the catalyst system according to the invention, and wherein a special granular activated carbon is used as catalyst support. Furthermore, particularly advantageous embodiments of the catalyst system according to the invention are the subject matter of the dependent claims associated therewith and of the subclaims associated therewith.

[0052] Again, according to a third aspect of the invention, a further subject matter of the invention is the use according to the invention as stated in the respective independent use claim.

[0053] Furthermore, according to a fourth aspect of the invention, a further subject matter of the invention is a protective material according to the invention, in particular a protective garment, in particular for use in the civilian or military sector, according to the associated independent claim.

[0054] In addition, according to a fifth aspect of the invention, another subject of the invention is also a filter and a filter material, in particular for removing various pollutants, odors and toxic substances, according to the relevant independent claims. In addition, particularly advantageous embodiments of the filter and the filter material according to the invention are the subject of the relevant subclaims.

[0055] It goes without saying that in the following description of the present invention, in order to avoid unnecessary repetition, the implementation methods, advantages, examples, etc. described below are only for a single aspect of the present invention. Without explicit mention, they can naturally be applied to the remaining aspects of the present invention with necessary modifications.

[0056] Furthermore, it goes without saying that in the following statements about values, numbers and ranges, the relevant statements about values, numbers and ranges should not be understood as limiting; it goes without saying for those skilled in the art that, depending on the specific circumstances or applications, the ranges or statements may be deviated from without departing from the scope of the present invention.

[0057] Furthermore, it applies that all values ​​or parameters etc. mentioned below can be determined essentially by standardized or well-defined determination methods or other determination or measurement methods with which experts in the field are familiar.

[0058] Furthermore, it should be noted that in the case of all relative or percentage, in particular weight-based, quantitative data listed below, these data will be selected or combined by a person skilled in the art within the scope of the invention in such a way that overall (including, if necessary, other components or ingredients, in particular as defined below), there is always a result of 100% or 100% by weight. However, this is self-evident for a person skilled in the art.

[0059] That being said, the present invention will be described in more detail below.

[0060] According to a first aspect of the invention, the present invention therefore relates to a process for preparing a catalyst system, in particular a supported catalyst, preferably for heterogeneous catalysis, comprising at least one catalytically active component.

[0061] wherein at least one catalytically active component is applied and / or fixed to the catalyst support, said catalytically active component comprising and / or consisting of at least one metal,

[0062] The method comprises the following steps (a) to (d) in the order specified below:

[0063] (a) providing and / or producing granular, preferably spherical activated carbon (= starting activated carbon) for use as catalyst support,

[0064] The activated carbon (i.e. the starting activated carbon)

[0065] (i) has a total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3 / g, at least 50% of the total pore volume of the activated carbon, in particular the total pore volume according to Gurvich, is formed in particular by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores, and

[0066] (ii) With 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m;

[0067] Then

[0068] (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, in particular surface oxygen content, of at least 4% (atomic %), based on the total elemental composition of the oxidized activated carbon, determined in particular by X-ray photoelectron spectroscopy (XPS or ESCA), and / or provided that the oxidized, in particular surface oxidized activated carbon has a hydrophilicity, determined as water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6 at least 30% of the maximum water vapor saturation loading of the activated carbon is reached;

[0069] Then

[0070] (c) equipping, in particular loading and / or coating and / or impregnating the oxidized, in particular surface-oxidized, activated carbon of process step (b) with a catalytically active component, in particular a precursor of at least one catalytically active component;

[0071] Then

[0072] (d) reduction (i.e. on the one hand, in particular surface reduction of previously oxidized activated carbon, and / or on the other hand, in particular reduction of the catalytically active component or its precursor, preferably the metal or metal compound constituting the catalytically active component) of oxidized, in particular surface-oxidized activated carbon obtained in process step (c) which is equipped with a catalytically active component, in particular a precursor of the catalytically active component, in particular for transferring the precursor of the catalytically active component to the catalytically active component, in particular in order to obtain a catalyst system, in particular a supported catalyst, having at least one catalytically active component.

[0073] Thus, as described above, it can be seen that the basic idea of ​​the present invention consists in particular in the fact that very specific activated carbons are used as catalyst supports for receiving or equipping the catalytically active components, wherein the activated carbon used according to the invention is on the one hand granular or spherical and on the other hand has a defined porosity, in particular with respect to high meso- and macro-porosity, and at the same time has a defined proportion of micropores (i.e. to a degree lower than meso- and macro-pores but sufficient for catalysis), wherein the activated carbon is also subjected to an oxidation treatment or surface oxidation in a specific manner before being equipped with the catalytically active components. In this context, the applicant has also found, quite surprisingly, that with the use of activated carbons having a defined porosity as described above, the overall catalytic performance of the resulting catalyst system is improved, in particular with respect to high conversions with simultaneous high catalytic activity and correspondingly high space / time yields in the underlying catalytic conversion or reaction.

[0074] Without wishing to be bound by this theory, the use of special activated carbons having a high proportion of mesopores and macropores and at the same time a defined proportion of micropores in particular improves the transport and diffusion processes of reactants and products on which the catalytic reactions are based, while at the same time providing for high accessibility and optimized formation of the catalytically active components incorporated into the catalyst support.

[0075] In this case, the kinetics of the basic catalysis are improved overall, in particular with regard to improved transport and diffusion processes within the pore system and in the boundary layer region of the catalyst support, while the reactants to be reacted have high accessibility to the catalytically active components or catalytic centers.

[0076] According to the invention, due to the special adjustment and formation of the pore system of the activated carbon used as catalyst support, an overall improved catalyst system is also provided, which exhibits very good efficiency in terms of catalytic activity. In this regard, the targeted and purpose-oriented (surface) oxidation of the activated carbon used as catalyst support before being equipped with catalytically active components is also very important, since this improves the binding or loading with the catalytically active components or associated precursors, also with regard to the formation of catalytic centers with defined (metal) dispersion and crystallite size, as will be explained in detail below.

[0077] Another central advantage of the present invention is also reflected in the fact that the activated carbon used according to the invention has a high mechanical stability or resistance and low wear during its use in the catalytic process, so that the catalytic system according to the invention has a correspondingly high durability and at the same time a high recyclability.

[0078] The application properties of the catalyst system according to the invention are further improved by the specific use of granular or spherical activated carbon (i.e. activated carbon with a special shape), i.e. also with the use of the catalyst system provided according to the invention in discontinuous and continuous catalytic applications. This is because, on the one hand, an improved bulk porosity is achieved relative to discontinuous applications, especially based on the special shaping of discrete spheres, which both prevents sludge formation in the reaction system and significantly improves the separation or recovery of the catalyst from the reaction system. On the other hand, the overall properties of the catalyst system improved according to the invention lead to lower pressure losses, while the catalyst system has high accessibility to the reactants or reactants to be reacted, so that using the catalyst system according to the invention, high flow rates can also be achieved for the medium containing the reactants or reactants to be reacted.

[0079] The granular, in particular spherical activated carbon (spherical carbon) used according to the invention also has many advantages in terms of improved flowability, wear resistance and dust-freeness, especially compared with other forms of activated carbon (such as powdered carbon, crushed carbon and coal-based carbon, etc.), which also leads to high mechanical resistance and durability and a long service life of the basic system. Therefore, occlusion during use is also reduced, thereby extending the service life.

[0080] As will be shown below, it is also possible to provide an overall tailor-made catalytic system with optimized application properties in each case, in particular with regard to the recovery or flow behavior or pressure loss of the catalyst system, by specifically adjusting the particle size or diameter of the basic spherical activated carbon, while the catalytic activity of the catalyst system according to the invention is further increased. In particular, the pressure loss or the flow rate can be adjusted or varied by specifying the particle size, so that an optimized system can also be provided for the respective use or application context.

[0081] In the context of the present invention, in particular extremely abrasion-resistant or mechanically stable spherical activated carbons are used in a targeted manner for the catalyst support used, for example in particular provided by special activated carbons based on organic polymers, in particular based on sulfonated organic polymers as defined further below. In this case, it was completely surprising in the context of the present invention that the sulfur content that can be present in the activated carbon (which can be, for example, up to 0.1% by weight, based on the activated carbon) does not impair the catalytic function of the catalyst system according to the invention or does not lead to any detrimental impairment of the catalytic activity, in particular does not lead to so-called catalyst poisoning.

[0082] Furthermore, the invention succeeds in a surprising manner in ensuring a high and at the same time permanent or stable loading of the activated carbon used as support material with the catalytically active components due to the (surface) oxidation of the activated carbon used before being equipped with the catalytically active components. This leads to a significant increase in the catalytic activity of the catalyst system according to the invention and at the same time to an increased durability, in particular because in the case of use, washing off or separation of the catalytically active components from the support material is also reduced or avoided.

[0083] Without wishing to be bound by this theory, the targeted oxidation or surface oxidation of the 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 (in the region of micropores, mesopores and macropores), which increases the affinity of the activated carbon for the catalytically active components used according to the invention. Due to the oxidation or surface oxidation treatment of the activated carbon according to the invention before it is equipped with the catalytically active components, less hydrophobic or hydrophilic surfaces or special functional groups of the activated carbon are generated or provided on the surface of the activated carbon or in its pore system, which significantly improve the incorporation of the catalytically active components in a completely unexpected manner.

[0084] In this case, it was 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 was oxidized before being loaded with the catalytically active components, also showed a significantly increased catalytic activity compared to powdered activated carbon. In this case, it was completely surprising that for the catalyst system according to the invention, there were no significant restrictions or limitations in the pore system of the activated carbon for the mass transport, in particular for the basic reactants, which was also due in particular to the defined pore structure of the activated carbon used according to the invention as shown below. In this case, it has proven to be particularly advantageous according to the invention to use, in particular, mesoporous and macroporous activated carbons with a defined but minor proportion of micropores as catalyst supports for the catalyst system according to the invention.

[0085] In particular, it was completely surprising that the catalyst system provided according to the invention, even with relatively large particles or particle sizes, exhibits a high catalytic activity, in particular compared to powdered carbon. In this case, the interaction of the measures according to the invention - without wishing to be bound by this theory - on the one hand enables a particularly uniform and high loading of the activated carbon with catalytically active components and, on the other hand, can reduce mass transport or diffusion limitations in the catalyst system that are detrimental to the catalytic activity.

[0086] In the case of the concept according to the invention, in particular due to the special matching of the support system on the one hand and the catalytically active components on the other hand, clogging of the pore system of the activated carbon by the catalytically active components (for example in the case of metal salt crystallization due to excessively large crystal sizes) is at least substantially prevented, which further improves the performance of the catalyst system provided by the invention.

[0087] Thus, according to the invention, on the basis of the method according to the invention, for the first time a very special catalyst system with a very special activated carbon as support material can be provided, which catalyst system is equipped in a targeted manner with at least one catalytically active component and which has significant advantages and improved properties compared to the systems of the prior art and is suitable for both discontinuous and continuous catalytic applications.

[0088] The catalyst system according to the invention provided by the process according to the invention exhibits improved mechanical properties and improved catalytic properties, with a shortened process time and high recovery rates, while shortening the time and recycling the base catalyst or the catalytically active components very well. In addition, as mentioned above, the catalyst system according to the invention exhibits improved flow properties and low pressure drops, in particular when used or applied in (loose) bulk form.

[0089] Furthermore, the catalyst system of the invention provided on the basis of the method of the invention is also suitable for use in or as a filter or filter material, in particular for rendering harmful or toxic substances etc. harmless.

[0090] The catalyst system provided on the basis of the method according to the invention thus combines excellent mechanical properties on the one hand with excellent catalytic properties on the other hand.

[0091] Based on the process according to the invention, it turns out that the activated carbon used as support material is effectively equipped with at least one catalytically active component to obtain the catalyst system according to the invention.

[0092] The term "catalyst system" used according to the invention, also synonymously referred to as "supported catalyst", is to be understood very broadly according to the invention and refers in particular to a functional unit based on at least one catalytically active component on the one hand and on a support material on the other hand, wherein the catalytic properties are essentially attributable to the catalytically active component, which for this purpose comprises or consists of at least one metal. In this context, it is provided in particular according to the invention that the activated carbon used has the catalytically active component, in particular in the form of an equipment or support or coating or impregnation, in particular based on the fixation of the catalytically active component on a basic catalyst support, in order to obtain the catalyst system according to the invention.

[0093] Furthermore, the term "equipped" or "loaded" or "coated" or "impregnated" as used according to the present invention refers in particular to such "impregnation" as used according to the present invention, in particular to such an arrangement of the activated carbon used according to the present invention with a support material for a catalytically active component, according to which the outer surface and / or inner surface structure and the associated pores (in particular micropores, mesopores and / or macropores) of the activated carbon used are at least partially and / or partially in contact with the catalytically active component, or are provided with or equipped with the catalytically active component. In this case, the catalytically active component, without wishing to be bound to this theory, can be said to form a catalytic structure or chemisorption properties on the surface of the activated carbon, which 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 chemisorption and physisorption properties in the same material. In particular, the catalytically active component can be bound to the surface of the activated carbon in a physisorption and / or chemisorption manner, in particular wherein the properties of the catalytically active centers or the catalytically active component can depend in particular on the surface properties of the activated carbon, the catalytically active component itself and / or the reduction conditions. The catalytically active component is present in or on the activated carbon, in particular in particulate or crystalline form.

[0094] Furthermore, with regard to the term "spherical" (synonymically also referred to as "spheroidal") for the activated carbon used as support material according to the invention, this term is to be understood very broadly and, according to a preferred embodiment of the invention, relates in particular to the at least essentially ideal spherical or spheroidal shape of the activated carbon, but also includes such formations or physical designs of the used activated carbon that deviate from a spherical shape, such as formations of activated carbon in the form of (rotated) ellipsoids, etc. Furthermore, the term "spherical" also includes such spherical or ellipsoidal forms of activated carbon, wherein the activated carbon may have protrusions or indentations, indentations, depressions, cracks, etc. According to the invention, the use of spherical activated carbon or spherical carbon or spherical activated carbon is therefore decisive.

[0095] By the term "surface oxidation", as used according to the invention, this refers in particular to the oxidation of those surfaces of the activated carbon used as starting material which are in contact with the environment, in particular containing the oxidizing agent, or which are accessible from the outside for the oxidizing agent used according to the invention. In particular, this also refers to the pore system of the activated carbon in the form of macropores, mesopores and micropores.

[0096] In addition, the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , the values ​​below serve to further characterize the pore system of the activated carbon used as catalyst support according to the invention, in particular to the effect that the porosity or pore system of the activated carbon is further characterized and defined on the basis of the quotient Q, i.e. in particular to the effect that for the activated carbon used as catalyst support according to the invention, there is generally a high proportion of mesopores and macropores in the total pore volume, with a defined proportion of micropores. In particular, the basic quotient describes the high meso- and macroporosity of the activated carbon used according to the invention. In this case, the quotient Q can also further serve as a measure of the improved kinetics in heterogeneous catalysis when the catalyst system according to the invention is used, or as a measure of the improved catalytic activity due to the specially formed activated carbon. Thus, due to the specially formed pore system of the activated carbon (which is further characterized by the quotient), there is an overall improvement in the rate-determining steps of the kinetics of the heterogeneous catalysis, for example with regard to the improved diffusion behavior of the reactants or products and the accessibility of the catalytically active components. The quotient Q therefore further reflects the performance of the catalyst system according to the invention provided in the process according to the invention, in particular with regard to its improved catalytic performance.

[0097] In the case of activated carbons or corresponding activated carbon granules used as catalyst supports, the parameter data listed in this respect were determined using standardized or clearly defined measurement methods or using measurement methods familiar to the skilled person himself. Unless otherwise stated, parameter data, in particular concerning porosity or pore size distribution and other adsorption property characterizations, are usually derived from the corresponding nitrogen adsorption isotherms of the corresponding activated carbon or the product measured.

[0098] In the context of the present invention, the term "micropore" refers to such pores having a pore size of less than 2 nm, while the term "mesopore" refers to such pores having a pore size in the range of 2 nm (i.e., including 2 nm) to 50 nm (including 50 nm), and the term "macroporous" refers to such pores having a pore size greater than 50 nm (i.e. >50 nm) and more specifically up to 500 nm (including 500 nm).

[0099] In the following, the production of activated carbon used as catalyst support as described in step (a) is described in more detail:

[0100] Therefore, according to the present invention, it can be provided in particular that the total pore volume (V total ), especially according to Gurvich's total pore volume of 0.9 cm 3 / g to 3.4cm 3 / g range, especially in the range of 1cm 3 / g to 2.9cm 3 / g, preferably within the range of 1.1 cm 3 / g to 2.4cm 3 / g, preferably within the range of 1.2 cm 3 / g to 1.9cm 3 / g, particularly preferably within the range of 1.5 cm 3 / g to 1.9cm 3 / g range.

[0101] As also mentioned above, according to the invention, in particular an activated carbon used as a catalyst support has a high overall meso- and macro-porosity. In this case, it can be provided according to the invention that 50% to 90%, in particular 52.5% to 87.5%, preferably 55% to 85%, preferably 57.5% to 82.5%, particularly preferably 60% to 80% of the total pore volume, in particular the total pore volume according to Gurvich, of the activated carbon prepared and / or produced in process step (a), in particular pores with a pore diameter of at least 2 nm, in particular pores with a pore diameter in the range of 2 nm to 500 nm, preferably meso- and macro-pores.

[0102] Furthermore, the activated carbon provided or produced in method step (a) can also have defined, secondary but sufficient micropores for catalysis, whereby a relatively small proportion of the total pore volume is usually present relative to the micropores (in particular to an extent sufficient for catalysis). Thus, according to the invention, it can be provided in particular that 2.5% to 50%, in particular 5% to 50%, preferably 10% to 50%, particularly preferably 12.5% ​​to 47.5%, particularly preferably 15% to 45%, very particularly preferably 17.5% to 42.5%, further preferably 20% to 40% of the total pore volume, in particular pore volume according to Gurvich, of the activated carbon provided and / or produced in method step (a), in particular pores with a pore diameter of less than 2 nm, preferably micropores.

[0103] Furthermore, it can be provided according to the invention that the total pore volume (V total ), especially according to Gurvich's total pore volume of 0.8 cm 3 / g to 3.9cm 3 / g range, especially at 0.9cm 3 / g to 3.4cm 3 / g range, preferably within 1cm 3 / g to 2.9cm 3 / g, preferably within the range of 1.1 cm 3 / g to 2.4cm 3 / g, particularly preferably within the range of 1.2 cm 3 / g to 1.9cm 3 In the range of 1.5 cm / g, very particularly preferably in the range of 1.5 cm / g 3 / g to 1.9cm 3 / g range, wherein 50% to 90%, in particular 52.5% to 87.5%, preferably 55% to 85%, preferably 57.5% to 82.5%, particularly preferably 60% to 80% 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 mesopores and macropores.

[0104] Furthermore, it can be provided according to the invention that the total pore volume (V total ), especially according to Gurvich's total pore area of ​​0.8 cm 3 / g to 3.9cm 3 / g, especially at 0.9cm 3 / g to 3.4cm 3 / g, preferably within 1 cm 3 / g to 2.9cm 3 / g, preferably within the range of 1.1 cm 3 / g to 2.4cm 3 / g, particularly preferably within the range of 1.2 cm 3 / g to 1.9cm 3 In the range of 1.5 cm / g, very particularly preferably in the range of 1.5 cm / g 3 / g to 1.9cm 3 In the range of 50% to 20% of the total pore volume of the activated carbon prepared and / or produced in process step (a) (i.e. the starting activated carbon), in particular 2.5% to 50% of the total pore volume according to Gurvich, in particular 5% to 50%, preferably 10% to 50%, particularly preferably 12.5% ​​to 47.5%, particularly preferably 15% to 45%, very particularly preferably 17.5% to 42.5%, further preferably 20% to 40%, is formed by pores, in particular micropores, having a pore diameter of less than 2 nm.

[0105] As far as the determination of the total pore volume according to Gurvich is concerned, this is a measurement / determination method well known to experts in the field. For further details on the determination of the total pore volume according to Gurvich, reference can be made, for example, to "L. Gurvich (1915), J. Phys. Chem. Soc. Russ. 47 , 805" and "S. Lowell et al., Characterization of Porous Solids and Powders: Surface Area Pore Size and Density, Kluwer Academic Publishers, Article Technology Series, p. 111 et seq.". In particular, the pore volume of activated carbon can be calculated based on the Gurvich rule according to the formula V p =W a / ρ l Determination, where W a represents the adsorption amount of the basic adsorbate, ρ l represents the density of the adsorbate used (see also formula (8.20) in Chapter 8.4 on page 111 of S. Lowell et al.).

[0106] Furthermore, the specific BET surface area (S BET ) can be at 1.100m 2 / g-2.600m 2 / g range, especially at 1.200m 2 / g-2.400m2 / g, preferably 1.300 m 2 / g-2.200m 2 / g, preferably within the range of 1.350 m 2 / g-1.950m 2 / g, particularly preferably 1.375 m 2 / g to 1.900m 2 / g range.

[0107] The determination of the specific surface area according to BET is known in principle to the person skilled in the art, so that no further details need to be specified in this respect. All BET surface area data relate to the determination according to ASTM D6556-04. Within the scope of the present invention, the so-called multipoint BET determination method (MP-BET) is used to determine the BET surface area in the partial pressure range p / p0 from 0.05 to 0.1 (this is usually the case, unless otherwise expressly stated below).

[0108] For more details on the determination of BET surface area or the BET method, refer to the above-mentioned ASTM D6556-04 and " Chemielexikon, 10th edition, Georg Thieme Verlag, Stuttgart / New York, keywords: "BET method" (including references cited therein) and "Winnacker-Küchler (3rd edition), Vol. 7, p. 93 ff." and "Z. Anal. Chem. 238, pp. 187 to 193 (1968)".

[0109] As described above, the formation of a defined pore system with a high volume or ratio of mesopores and macropores also improves the transport and diffusion properties of reactants or products of the catalytic reaction, in particular due to the high ratio of mesopores and macropores. At the same time, with respect to the provided catalyst system, the catalytic performance is also improved, since the catalytically active centers or active centers can also be formed, in particular, in smaller pores, such as micropores.

[0110] Due to the balanced and coordinated pore distribution with the hierarchical pore system defined below, which has high mesopore and macropore volumes and a micropore volume sufficient for catalysis or catalytic activity, an overall improved performance is provided in terms of the kinetics of heterogeneous catalysis. In this case, the above-mentioned 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).

[0111] In this case, it can be provided in particular according to the invention that, for the activated carbon prepared or produced in process step (a) (ie the starting activated carbon), the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) of the ratio (quotient; Q), in particular according to the equation Q = V total / S BET , in 0.5*10 -9 m to 1.9*10 -9 m, especially in the range of 0.55*10 -9 m to 1.9*10 -9 m, preferably in the range of 0.6*10 -9 m to 1.8*10 -9 m, preferably within the range of 0.65*10 -9 m to 1.7*10 -9 m, particularly preferably within the range of 0.65*10 -9 m to 1.6*10 -9 m, most preferably 0.7*10 -9 m to 1.5*10 -9 m, more preferably 0.75*10 -9 m to 1.4*10 -9 m, and more preferably in the range of 0.8*10 -9 m to 1.3*10 -9 m.

[0112] The above lower limit still ensures good occupation of the activated carbon by the catalytically active components with good mass transfer and thus high conversion in the basic catalysis. In addition, the above upper limit still ensures sufficient micropore volume, which is particularly relevant for the formation of a correspondingly high number of active sites or centers for the catalytic activity involving the catalytically active components.

[0113] According to the invention, it can be provided in particular that the activated carbon prepared or produced in process step (a) (ie the starting activated carbon) has a specific BET surface area (SBET) of between 1.000 m 2 / g-3.000m 2 / g range, especially at 1.100m 2 / g-2.600m 2 / g, preferably 1.200 m 2 / g-2.400m 2 / g, preferably 1.300 m 2 / g to 2.200m 2 / g, particularly preferably 1.350 m2 / g to 1.950m 2 / g, most preferably 1.375 m 2 / g to 1.900m 2 / g, where the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , at 0.5×10 -9 m to 1.9×10 -9 m, especially in the range of 0.55×10 -9 m to 1.9×10 -9 m, preferably within the range of 0.6×10 -9 m to 1.8×10 -9 m, preferably within the range of 0.65×10 -9 m to 1.7×10 -9 m, particularly preferably in the range of 0.65×10 -9 m to 1.6×10 -9 m, most preferably 0.7×10 -9 m to 1.5×10 -9 m, more preferably 0.75×10 -9 m to 1.4×10 -9 m, and more preferably 0.8×10 -9 m to 1.3×10 -9 m.

[0114] Furthermore, it has proven advantageous in the context of the present invention if the activated carbon provided and / or produced in process step (a) (ie the starting activated carbon) has an average pore diameter of at least 15 nm or if the activated carbon has an average pore diameter of at most 100 nm.

[0115] In particular, the activated carbon provided and / or produced in process step (a) (i.e. the starting activated carbon) may have 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, more preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, more preferably in the range of 25 nm to 50 nm.

[0116] The determination of the structural properties of the mesoporous and macroporous activated carbon used according to the invention, or the determination of the structural properties of the mesoporous or macroporous region, can be carried out in particular by mercury intrusion porosimetry based on the average pore size. According to this method, an evaluation range of 0.01 μm to 20 μm is recorded with respect to the pore size.

[0117] In general, the average pore size can also be expressed as four times the volume of the liquid (adsorbate) absorbed or adsorbed by the activated carbon having completely filled pores (V total ) and the quotient of the BET surface area (BET) on the other hand (pore size d = 4*V total / BET). In this respect, reference may be made to the corresponding explanation according to RW Magee (loc. cit.), in particular to the formula (15) on page 71 of the reference discussed.

[0118] Furthermore, it is advantageous according to the invention if the activated carbon prepared and / or produced in process step (a) (ie the starting 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.

[0119] In the context of catalytic applications based on the catalyst system according to the invention, the special shape of the activated carbon is also accompanied by better inflow properties, which further improves the transport of reactants and products.

[0120] In the case of spherical activated carbons, this relates in particular to improved properties, for example when the catalyst system according to the invention is used in fixed bed reactors or the like.

[0121] According to the present invention, the activated carbon provided and / or produced in process step (a) (i.e., the starting 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, preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, most preferably in the range of 175 μm to 250 μm. In this case, at least 80 wt%, in particular at least 90 wt%, preferably at least 95 wt% of the activated carbon particles may have a particle size, in particular a particle diameter, in the above range.

[0122] Typically, the activated carbon provided 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, preferably in the range of 110 μm to 375 μm, more preferably in the range of 175 μm to 350 μm, most preferably in the range of 185 μm to 225 μm.

[0123] The corresponding particle sizes or diameters can be determined in particular based on the method according to ASTM D2862-97 / 04. In addition, determination methods based on sieve analysis, X-ray diffraction, laser diffraction methods, etc. can be used to determine the above-mentioned sizes. The corresponding determination methods are known per se to the skilled person, so that no further explanation is required in this respect.

[0124] In addition, the activated carbon provided and / or produced in method step (a) (i.e., the starting activated carbon) can have a ball-on-disk hardness and / or abrasion hardness of at least 90%, in particular at least 95%, preferably at least 97%, more preferably at least 98%, most preferably at least 99%, most preferably at least 99.5%, and further preferably at least 99.8%. Wear resistance can generally be determined according to ASTM D3802-05. Therefore, the activated carbon used according to the present invention is further characterized by excellent mechanical properties, which is also manifested as high wear resistance. The high mechanical strength of the activated carbon used according to the present invention leads to low wear when the obtained catalyst system according to the present invention is applied, which is particularly advantageous in terms of application or service life. Excellent mechanical properties with low wear also lead to further advantages of producing the catalyst system according to the method of the present invention, especially avoiding wear and the like when implementing the respective method steps. The high mechanical strength of the activated carbon and therefore the catalyst system according to the present invention only leads to low wear when used for catalysis, which is particularly advantageous in terms of use time and avoiding sludge formation due to wear and the like.

[0125] The high mechanical stability of the activated carbon used according to the invention is also reflected in a high compression and / or burst strength (weight load capacity per activated carbon particle). In this case, the activated carbon provided or produced in method step (a) (i.e., the starting activated carbon) can have a compression and / or burst strength (weight load capacity) 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 per activated carbon particle, in particular per activated carbon bead. In particular, the activated carbon provided or produced in method step (a) (i.e., the starting activated carbon) can have a compression and / or burst strength (weight load capacity) in the range of 5 to 50 Newtons, in particular 10 to 45 Newtons, preferably 15 to 40 Newtons, preferably 17.5 to 35 Newtons per activated carbon particle, in particular per activated carbon bead. The determination of the compression or burst strength can be carried out in a manner known to the skilled person, in particular based on the determination of the compression or burst strength of a single particle or a plurality of particles by applying a force with the aid of a punch until the corresponding particles burst.

[0126] The activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) may further have a vibration or packing density in the range of 100 g / L to 1500 g / L, in particular 125 g / L to 1000 g / L, preferably 150 g / L to 800 g / L, preferably 200 g / L to 600 g / L, particularly preferably 225 g / L to 500 g / L, most preferably 250 g / L to 400 g / L, further preferably 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) may also have a bulk density of 150 g / L to 1000 g / L, in particular 250 g / L to 700 g / L, preferably 300 g / L to 600 g / L, more preferably 300 g / L to 550 g / L. The vibration or packing density may be determined in particular according to DIN 53194. The bulk density can be determined in particular according to ASTM B527-93 / 00.

[0127] Furthermore, the activated carbon provided or produced in process step (a) (i.e. the starting activated carbon) 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 wherein the activated carbon has a butane adsorption in the range of 35% to 90%, in particular 40% to 85%, preferably in the range of 45% to 80%, preferably 47.5% to 75%. The butane adsorption can be determined in particular according to ASTM D5742-95 / 00.

[0128] Furthermore, the activated carbon prepared and / or produced in process step (a) (i.e. the starting activated carbon) may have an iodine value of at least 1250 mg / g, in particular at least 1300 mg / g, preferably at least 1400 mg / g, more preferably at least 1425 mg / g, and / or wherein the activated carbon prepared and / or produced in process step (a) has an iodine value in the range of 1250 mg / g to 2100 mg / g, in particular in the range of 1300 mg / g to 2000 mg / g, preferably in the range of 1400 mg / g to 1900 mg / g, preferably in the range of 1425 mg / g to 1850 mg / g. In particular, the iodine value can be determined according to ASTM D4607-94 / 99. The iodine value can be evaluated as a measure of the available surface area, which is also mainly provided by small mesopores; the above iodine value indicates that the activated carbon used according to the invention can have a particularly high mesoporosity.

[0129] Furthermore, 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, preferably at least 19.5 mL, and / or wherein 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, preferably in the range of 19.5 mL to 47.5 mL.

[0130] In particular, the activated carbon prepared and / or produced in process step (a) (i.e. the starting activated carbon) may have a molasses number of at least 255, in particular at least 310, preferably at least 375, preferably at least 510, and / or wherein the activated carbon prepared and / or produced in process step (a) has a molasses number in the range of 255 to 1500, in particular in the range of 310 to 1400, preferably in the range of 375 to 1300, preferably in the range of 510 to 1250.

[0131] Due to the high meso- and macro-porosity, the activated carbon according to the invention therefore exhibits equally high methylene blue and molasses adsorption numbers, which together can be evaluated as a measure of the available surface area provided primarily by meso- and macro-pores. Thus, the methylene blue number or methylene blue adsorption refers to the amount of methylene blue adsorbed per a specified amount of adsorbent under specified conditions (i.e., the volume or milliliters (mL) of a methylene blue standard solution decolorized with a specified amount of dry and powdered adsorbent), which is biased towards smaller mesopores and gives an indication of the adsorption capacity of the activated carbon according to the invention relative to molecules of comparable size to methylene blue. In addition, the molasses number is considered a measure of the meso- and macro-porosity and represents the amount of adsorbent required to decolorize the standard molasses solution, so that the molasses number gives an indication of the adsorption capacity of the activated carbon according to the invention relative to molecules of comparable size to molasses (usually beet molasses). Thus, the methylene blue and molasses numbers can be used as a measure of the meso- and macro-porosity, in particular the meso-porosity, of the activated carbon according to the invention.

[0132] The dimensionless molasses value can be determined essentially according to the Norit method (Norit NV, Amersfoort, The Netherlands, Norit standard method NSTM 2.19 "Molasses Number (Europe)") or according to the PACS method (PACS=Professional Analytical and Consulting Services Inc., Coraopolis, Pennsylvania, USA). In the context of the present invention, the value of the molasses value is determined according to the PACS method. In the determination of the molasses value 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, the standard molasses solution being adjusted to a standard activated carbon having a molasses value of 245 and / or 350. For further details in this regard, reference is made to the two aforementioned specifications.

[0133] The methylene blue value can be measured according to the method of CEFIC (Conseil Européen des Federations desl'Industrie Chimique, Avenue Louise 250, Bte 71, B-1050 Brussels, November 1986, European Council of Chemical Manufactures' Federations, Test methods for Activated Carbon, Section 2.4 "Methylene Blue Value", pp. 27 / 28).

[0134] The methylene blue value according to the above CEFIC method is therefore defined as the number of milliliters of a methylene blue standard solution decolorized by 0.1 g of dry powdered activated carbon. To carry out the method, a glass container with a ground glass stopper, a filter and a methylene blue standard solution are required, which is prepared as follows: 1200 mg of pure dye methylene blue (equivalent to about 1.5 g of methylene blue or equivalent according to DAB VI [German Pharmacopoeia, 6th edition]) are dissolved in water in a 1000 mL volumetric flask and the solution is allowed to stand for several hours or overnight; for checking, 5.0 mL of the solution are made up to 1.0 liter with 0.25% (volume fraction) acetic acid in a volumetric flask and the absorbance is measured at 620 nm and a path length of 1 cm, which must be (0.840 ± 0.010). If the absorbance is higher, dilute with the calculated amount of water; if lower, discard the solution and reconstitute it. For sample production, the activated carbon is crushed (<0.1 mm) and then dried at 150°C to constant weight. In a frosted glass flask, combine exactly 0.1 g of spherical carbon with 25 mL (5 mL) of methylene blue standard solution (a preliminary test is performed to determine whether an initial addition of 25 mL of methylene blue standard solution and 5 mL addition or an initial addition of 5 mL of methylene blue standard solution and 1 mL addition can be used). Shake until decolorization occurs. Then add another 5 mL (1 mL) of methylene blue standard solution and shake until decolorization occurs. As long as decolorization still occurs within 5 minutes, repeat the addition of a volume of 5 mL (1 mL) of methylene blue standard solution. Record the total volume of the test solution decolorized by the sample. Repeat the test to confirm the results obtained. The volume (mL) of the methylene blue standard solution that has just been decolorized is the methylene blue value of the activated carbon. It should be noted in this case that the dye methylene blue cannot be dried because it is sensitive to heat; instead, the water content must be corrected purely by calculation.

[0135] According to the present invention, the activated carbon prepared and / or produced in process step (a) (ie the starting activated carbon) may further have a weight-dependent adsorption N measured at a partial pressure p / p0 of 0.25. 2 -Volumetric Vads (wt) , which is at least 250cm 3 / g, especially at least 300cm 3 / g, preferably at least 350cm 3 / g, preferably at least 375cm 3 / g. In this case, the activated carbon provided and / or prepared in process step (a) may have a weight adsorption N measured at a partial pressure p / p0 of 0.25. 2 VolumeVads (wt) , which is at 250cm 3 / g to 850cm 3 / g range, especially at 300cm3 / g to 700cm 3 / g, preferably within the range of 350cm 3 / g to 650cm 3 / g, preferably at 375cm 3 / g to 625cm 3 / g range.

[0136] Typically, the activated carbon provided and / or produced in process step (a) (ie, the starting activated carbon) may have an adsorption capacity based on volume of N determined at a partial pressure p / p0 of 0.25. 2 VolumeVads (vol.) , which is at least 50cm 3 / cm 3 , especially at least 100cm 3 / cm 3 , preferably at least 110cm 3 / cm 3 In this context, it can be provided in particular that the activated carbon provided or produced in process step (a) has a volume-dependent adsorption N measured at a partial pressure p / p0 of 0.25. 2 Volume Vads (vol.), which is 50cm 3 / cm 3 Up to 300cm 3 / cm 3 within the range, especially within 80cm 3 / cm 3 Up to 275cm 3 / cm 3 within the range, preferably within 90cm 3 / cm 3 Up to 250cm 3 / cm 3 within the range, preferably within 95cm 3 / cm 3 Up to 225cm 3 / cm 3 within the range.

[0137] Similarly, it can be provided according to the invention that the activated carbon provided or produced in process step (a) (ie the starting activated carbon) has a weight-based adsorption N determined at a partial pressure p / p0 of 0.995. 2 VolumeVads (wt.) , which is at least 300cm 3 / g, especially at least 450cm 3 / g, preferably at least 475cm 3In particular, the activated carbon provided or produced in process step (a) may have a weight-based adsorption N measured at a partial pressure p / p0 of 0.995. 2 VolumeVads (wt.) , which is at 300cm 3 / g to 2300cm 3 / g range, especially at 400cm 3 / g to 2200cm 3 / g, preferably within the range of 450cm 3 / g to 2100cm 3 / g, preferably at 475cm 3 / g to 2100cm 3 / g range.

[0138] Furthermore, the activated carbon provided or produced in process step (a) (ie the starting activated carbon) may have a volume-dependent adsorption N 20 determined at a partial pressure p / p0 of 0.995. 2 Volume V ads(vol.) , which is at least 200cm 3 / cm 3 , especially at least 250cm 3 / cm 3 , preferably at least 275 cm 3 / cm 3 , preferably at least 295cm 3 / cm 3 According to the invention, it can also be provided that the activated carbon provided or produced in process step (a) has a volume-dependent adsorption N measured at a partial pressure p / p0 of 0.995. 2 Volume Vads (vol.), which is at 200cm 3 / cm 3 Up to 500cm 3 / cm 3 In the range of 250cm, especially 3 / cm 3 Up to 400cm 3 / cm 3 within the range, preferably within 275cm 3 / cm 3 Up to 380cm 3 / cm 3 within the range of 295 cm 3 / cm 3 Up to 375cm 3 / cm 3 within the range.

[0139] Therefore, the weight and volume of the activated carbon according to the present invention are related to the volume V ads (N 2 ) is very large at different partial pressures p / p0, which can also be regarded as evidence of the excellent adsorption properties of the activated carbon used according to the invention (accompanied by outstanding suitability as a catalyst support).

[0140] According to the present invention, the activated carbon prepared or produced in process step (a) (i.e., the starting activated carbon) may have an open porosity fractal dimension 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 wherein the activated carbon has an open porosity fractal dimension of at least 2.7, in particular at least 2.8, preferably at least 2.85, preferably at least 2.9. The open porosity fractal dimension represents a measure of the microscopic roughness of the inner surface of the activated carbon. For further details in this regard, in particular for the determination of the fractal dimension of the activated carbon used according to the present invention, reference may be made to the publications DE 102 54 241 A1, WO 2004 / 046033 A1, EP 1 562 855 B1 and US 2006 / 148645 A1 belonging to the same patent family, in particular to Example 4 cited in the corresponding publications. The corresponding contents of the cited publications are fully incorporated herein by reference. The above-mentioned fractal dimensions lead to a further improvement in the catalytic properties of the catalyst system produced by the process according to the invention.

[0141] According to the present invention, the activated carbon provided and / or produced in process step (a) (i.e., the starting activated carbon) can be an activated carbon obtainable by carbonization and subsequent activation of an organic polymer-based starting material, in particular an organic polymer-based, preferably spherical (pellet-shaped) activated carbon (PBSAC or polymer-based spherical activated carbon).

[0142] Activated carbon in the form of PBSAC is associated with specific pore properties, a particular shape and high mechanical stability.

[0143] In particular, the starting material for the activated carbon provided 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 wherein the starting material for the activated carbon provided and / or produced in process step (a) is used in the form of a granular and / or spherical, preferably spherical, starting material.

[0144] Furthermore, the particle size, in particular the particle diameter, of the starting material of the activated carbon provided or produced in process step (a), i.e. the starting activated carbon, can be 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, preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, most preferably in the range of 175 μm to 250 μm. In this case, it can be provided in particular according to the invention that at least 80 wt %, in particular at least 90 wt %, preferably at least 95 wt % of the starting material particles have a particle size, in particular a particle diameter, in the above range.

[0145] Furthermore, the starting material of the activated carbon provided 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, preferably in the range of 110 μm to 375 μm, more preferably in the range of 175 μm to 350 μm, most preferably in the range of 185 μm to 225 μm.

[0146] In particular, the starting material for the activated carbon provided and / or produced in process step (a) (ie the starting activated carbon) may be a starting material based on an ion exchange resin precursor.

[0147] Furthermore, the starting material of the activated carbon provided and / or produced in process step (a) (i.e. the starting activated carbon) can be a starting material based on an organic polymer, in particular based on a polystyrene crosslinked with divinylbenzene, preferably based on a styrene / divinylbenzene copolymer. In this respect, the content of divinylbenzene in the starting material can be in the range of 0.1 wt % to 25 wt %, in particular in the range of 0.5 wt % to 20 wt %, preferably in the range of 1 wt % to 15 wt %, preferably in the range of 2 wt % to 10 wt %. With regard to the specific starting materials used, reference can be made to the further explanation of the embodiments.

[0148] According to the present invention, it can be provided in particular that the activated carbon provided and / or produced in process step (a) (i.e. the starting activated carbon) can be obtained by the following steps:

[0149] (i) carbonization of a polymeric organic sulfonated starting material (containing sulfonic acid groups), in particular a particulate, preferably spherical, polymeric organic sulfonated starting material; and then

[0150] (ii) activating the carbide obtained in step (i) (carbonized starting material), in particular thereby obtaining activated carbon, in particular as defined in any of the preceding claims.

[0151] Furthermore, it can be provided in this context that a process step of sulfonating the polymerized organic starting materials is carried out before the carbonization process step (i), in particular by contacting the starting materials with at least one sulfonating agent. In this case, the sulfonating agent can be used in liquid form.

[0152] In particular, sulfur trioxide (SO 3 ) can be used as sulfonating agent, in particular in the form of oleum and / or preferably concentrated sulfuric acid. However, according to the invention, it is also possible to start from already sulfonated materials.

[0153] Typically, in the context of the present invention, in the above-mentioned method step (i), the temperature at which carbonization is carried out can be in the range of 100°C to 1200°C, in particular in the range of 120°C to 1100°C, preferably in the range of 140°C to 1000°C, and more preferably in the range of 150°C to 950°C.

[0154] According to the invention, it can be provided herein that in method step (i), the carbonization is carried out in a plurality of stages, in particular in two stages, preferably using a temperature gradient and / or a temperature profile. In this respect, in the first stage, the method can be 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., preferably in the range of 150° C. to 550° C. In addition, in the second stage, the method 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., preferably in the range of 550° C. to 950° C.

[0155] According to the invention, in process step (i), carbonization can be carried out for a period of 0.1 to 20 hours, in particular 0.5 to 15 hours, preferably 1 to 10 hours, preferably 1.5 to 8 hours, particularly preferably 2 to 6 hours.

[0156] Within the scope of the process according to the invention, in process step (i), the carbonization can be carried out in particular in such a way that chemical groups, in particular strongly acidic chemical groups, preferably sulfonic acid groups, are thermally decomposed or separated from the especially sulfonated starting material, in particular with the formation of free radicals or crosslinks, preferably in such a way that in particular the start of the carbonization or thermal decomposition of the starting material is preferably accompanied by crosslinking of the polymers of the starting material and / or the formation of carbon.

[0157] Furthermore, in process step (i), the carbonization can be carried out in such a way that, in particular after the thermal decomposition or elimination of chemical groups, in particular strongly acidic chemical groups, preferably sulfonic acid groups, a more extensive or in particular complete carbonization of the starting materials is carried out.

[0158] For example, process step (i) can be carried out in such a way that the thermal decomposition or elimination of chemical groups, in particular strongly acidic chemical groups, preferably sulfonic acid groups, takes place in a first stage of carbonization. In addition, process step (i) can be carried out in such a way that further and / or complete carbonization of the starting material is carried out in a second stage.

[0159] Typically, process step (i) can be carried out in an inert atmosphere, in particular in a nitrogen atmosphere, or at most in a slightly oxidizing atmosphere. According to the invention, it can optionally be provided that, in process step (i), during the carbonization, water is added to the carbonization atmosphere, in particular to an inert atmosphere, in particular in the form of water vapor and / or an inert gas / water vapor mixture, preferably a nitrogen / water vapor mixture.

[0160] Furthermore, with regard to method step (ii), the temperature at which activation is carried out may be in the range of 500 to 1200° C., in particular in the range of 800 to 1100° C., preferably in the range of 850 to 1000° C., preferably in the range of 900 to 975° C. Furthermore, in method step (ii), activation may be carried out for a period of 0.5 to 20 hours, in particular 1 to 15 hours, preferably 2 to 10 hours.

[0161] Typically, in process step (ii), the activation can be carried out in the presence of at least one activation gas, in particular oxygen, preferably in the form of air, water vapor and / or carbon dioxide or a mixture of these activation gases, and / or the activation can be carried out in the presence of an inert gas / water vapor mixture, preferably a nitrogen / water vapor mixture, and / or the activation can be carried out in the presence of in particular pure carbon dioxide or an inert gas / carbon dioxide mixture, in particular a nitrogen / carbon dioxide mixture.

[0162] The basic principle of the activation provided in step (ii) of the method according to the invention is in particular that under suitable conditions, part of the carbon produced during the carbonization is selectively and specifically decomposed or burned, whereby the pore system can be further formed or specifically regulated and, as it were, finally formed.

[0163] As far as the activated carbon provided or produced in process step (a) is concerned, in general, in the cases indicated here, it is also commercially available in principle, in particular also from Blücher GmbH. In addition, for further details on the activated carbon provided or produced according to the invention in process step (a) and in particular on the process steps of carbonization and activation, reference can be made to the international patent application WO 98 / 07655A1 and the patent applications DE 196 53 238A1, DE 19650 414A1, EP 0 952 960A1 and US 6 300 276B1 belonging to the same patent family, the disclosure contents of each of which are fully incorporated herein by reference. In addition, reference can be made to DE 43 04026A1 and US 6 184 177B1 belonging to the same patent family, the disclosure contents of each of which are also fully incorporated herein by reference. Furthermore, reference may also be made to the international patent application WO 2017 / 097447 A1 and the family patent applications DE 10 2016 101 215 A1, EP 3 362 407 A1 and US 2019 / 177170 A1, the corresponding disclosure content of each of which is equally fully incorporated herein by reference.

[0164] In the following, process step (b) with activated carbon oxidation is described in more detail:

[0165] Generally, it can be provided in the context of the present invention that the activated carbon oxidized, in particular surface-oxidized in method step (b) has an oxygen content, in particular a surface oxygen content, determined in particular by X-ray photoelectron spectroscopy [XPS (= X-ray photoelectron spectroscopy), ESCA (= electron spectroscopy for chemical analysis)] 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%, preferably in the range of 6% to 15%, particularly preferably in the range of 7% to 12.5%, based on the total elemental composition of the oxidized activated carbon.

[0166] According to the invention, it can be provided in particular that the activated carbon oxidized, in particular surface-oxidized, in method step (b) has an oxygen content, in particular a surface oxygen content, determined in particular by X-ray photoelectron spectroscopy (XPS or ESCA), 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.

[0167] According to the invention, it can be provided in particular that the activated carbon oxidized, in particular surface-oxidized, in method step (b) has an oxygen content, in particular a surface oxygen content, determined in particular by X-ray photoelectron spectroscopy (XPS or ESCA), 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.

[0168] In this case, it is preferred according to the invention that the elements other than oxygen of the activated carbon oxidized, in particular surface-oxidized, in process step (b) are formed at least essentially from carbon. In this case, the activated carbon oxidized, in particular surface-oxidized, in process step (b) may have at most traces of elements other than oxygen and carbon, in particular nitrogen, sulfur and / or chlorine, preferably in an amount of at most 2% (atomic %), in particular at most 1.5%, preferably at most 1%, based on the total elemental composition of the oxidized activated carbon and calculated as the sum of elements other than oxygen and carbon.

[0169] Without wishing to be bound by this theory, the process according to the invention produces, in particular, an oxide layer on the (pore) surface of the activated carbon, which generally has oxygen-containing functional groups as described below. The surface is subsequently oxidized with the catalytically active component, in particular in the region of the oxide (boundary) layer (again without wishing to be bound by or committed to this theory), whereby the oxygen-containing functional groups increase the affinity and in particular also the interaction with the catalytically active component or, so to speak, serve as binding or anchoring points for the catalytically active component used according to the invention.

[0170] The process according to the invention thus provides a catalyst system according to the invention having a catalytic or reactive surface by equipping the activated carbon with catalytically active components after oxidation.

[0171] With regard to the aforementioned ranges for the oxygen content of the activated carbon oxidized in process step (b), the lower limit ensures that there are still sufficient binding sites for the catalytically active components or their precursors. The upper limit also ensures that the carbon content in the oxidized activated carbon is still 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 with regard to the corresponding total pore volume and specific BET surface area according to Gurvich.

[0172] As already mentioned, as a result of the targeted and purpose-oriented oxidation treatment in process step (b), a relatively hydrophilic activated carbon is obtained, on the basis of which the finishing with catalytically active components or precursors thereof is improved.

[0173] In this context, the following statements can be made about the hydrophilicity of activated carbon:

[0174] - In particular, the activated carbon oxidized in method step (b), in particular surface-oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6 at least 35%, in particular at least 40%, preferably at least 50%, preferably at least 60% of the maximum water vapor saturation loading of the activated carbon is achieved.

[0175] - Furthermore, the activated carbon oxidized in method step (b), in particular surface-oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6, at most 100%, in particular at most 99%, preferably at most 98%, preferably at most 95%, particularly preferably at most 90% of the maximum water vapor saturation loading of the activated carbon is achieved.

[0176] - Furthermore, the activated carbon oxidized in method step (b), in particular surface-oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, preferably 50% to 95%, particularly preferably 60% to 90% of the maximum water vapor saturation loading of the activated carbon is achieved.

[0177] - In particular, the activated carbon oxidized in method step (b), in particular surface-oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure range p / p0 from 0.1 to 0.6, at least 30%, in particular at least 35%, preferably at least 40%, preferably at least 50%, particularly preferably at least 60% of the maximum water vapor saturation loading of the activated carbon is achieved.

[0178] According to the invention, the activated carbon oxidized, in particular surface-oxidized, in process step (b) can have a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at a partial pressure range p / p0 from 0.1 to 0.6, at most 100%, in particular at most 99%, preferably at most 98%, preferably at most 95%, particularly preferably at most 90% of the maximum water vapor saturation loading of the activated carbon is achieved.

[0179] - Furthermore, the activated carbon oxidized in method step (b), in particular surface-oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that in a partial pressure range p / p0 from 0.1 to 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, preferably 50% to 95%, particularly preferably 60% to 90% of the maximum water vapor saturation loading of the activated carbon is achieved.

[0180] In addition to the hydrophilicity of the activated carbon oxidized in process step (b), the following may also be mentioned:

[0181] -Thus, for the activated carbon oxidized in method step (b), it can be characterized within the scope of the present invention in such a way that in method step (b), oxidation, in particular surface oxidation, of the activated carbon prepared or produced in method step (a) takes place, with the proviso that the oxidized activated carbon has a hydrophilicity determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6, at least 30% of the maximum water vapor adsorption capacity of the activated carbon is consumed or utilized.

[0182] - In particular, the activated carbon oxidized, in particular surface-oxidized, in method step (b) can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6, at least 30%, in particular at least 35%, preferably at least 40%, 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.

[0183] - In addition, the activated carbon oxidized, in particular surface-oxidized, in method step (b) can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6, at most 100%, in particular at most 99%, preferably at most 98%, 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.

[0184] - Similarly, the activated carbon oxidized, in particular surface-oxidized, in method step (b) can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that at a partial pressure p / p0 of 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, 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.

[0185] - In addition, the activated carbon oxidized, in particular surface-oxidized, in method step (b) can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that in a partial pressure range p / p0 from 0.1 to 0.6, at least 30%, in particular at least 35%, preferably at least 40%, 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.

[0186] - In particular, according to the invention it can be provided that the activated carbon which is oxidized, in particular surface-oxidized, in method step (b) has a hydrophilicity which is determined as a water vapor adsorption behavior such that in a partial pressure range p / p0 from 0.1 to 0.6, at most 100%, in particular at most 99%, preferably at most 98%, 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.

[0187] - According to the invention, the activated carbon oxidized, in particular surface-oxidized, in method step (b) can have a hydrophilicity, which is determined as a water vapor adsorption behavior, so that in a partial pressure range p / p0 from 0.1 to 0.6, 30% to 100%, in particular 35% to 99%, preferably 40% to 98%, 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.

[0188] Furthermore, the activated carbon oxidized in process step (b) may also have the following properties with regard to hydrophilicity:

[0189] Furthermore, the activated carbon oxidized in process step (b), in particular surface oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6, the amount of water vapor adsorbed by the activated carbon (H 2 O volume)Vads(H 2 O) is at least 200 cm 3 / g, especially at least 250cm 3 / g, preferably at least 300cm 3 / g, preferably at least 325cm 3 / g, particularly preferably at least 350cm 3 / g.

[0190] Furthermore, the activated carbon oxidized in process step (b), in particular surface oxidized, can have a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6, the amount of water vapor adsorbed by the activated carbon (H 2 O volume)Vads(H 2 O) is at most 1000 cm 3 / g, especially up to 900cm 3 / g, preferably up to 800cm 3 / g, preferably up to 700cm 3 / g, particularly preferably up to 600cm 3 / g.

[0191] According to the invention, it can be provided in particular that the activated carbon oxidized, in particular surface oxidized, in process step (b) has a hydrophilicity, which is determined as a water vapor adsorption behavior such that at a partial pressure p / p0 of 0.6, the amount of water vapor adsorbed by the activated carbon (H 2 O volume)Vads(H 2 O) at 200 cm 3 / g to 1000cm 3 / g range, especially 250cm3 / g to 900cm 3 / g, preferably 300cm 3 / g to 800cm 3 / g, preferably 325cm 3 / g to 700cm 3 / g, particularly preferably 350cm 3 / g to 600cm 3 / g.

[0192] The abovementioned values ​​for the water vapor sorption behavior relate in particular to the basic water vapor sorption isotherm of the activated carbon obtained according to the invention in process step (b).

[0193] As far as the determination of the water vapor sorption behavior is concerned, this is carried out within the scope of the present invention on the basis of DIN 66135-1, wherein water or water vapor is used as the basic adsorbate or adsorbate. In this case, the determination of the water vapor sorption behavior is carried out at a temperature of 25° C. (298 degrees Kelvin) by the static volume method. The pressure-dependent volume V of the adsorbed water or adsorbed water vapor in the water vapor sorption behavior is determined at different or variable ambient pressures p / p0 in the range from 0.0 to 1.0. ads (STP), where p0 denotes the pressure under standard conditions (1013.25 hPa). The water vapor adsorption behavior used according to the invention relates to the following adsorption isotherm of the activated carbon.

[0194] For more information and explanations about water vapor adsorption, reference can also be made to M. Neitsch's doctoral thesis "Water Vapor and n-Butane Adsorption on Activated Carbon-Mechanism, Equilibrium and Dynamics of 1-Component and Coadsorption" (Faculty of Mechanical, Method and Energy Engineering, Freiberg University of Mining and Technology), the entire content of which in this regard, in particular with regard to the explanations about the adsorption of water vapor or water on activated carbon, is hereby incorporated by reference in its entirety.

[0195] As described above, the water vapor adsorption behavior serves as a measure of the hydrophilicity or hydrophobicity of the activated carbon used according to the invention, so that, based on the above values, the activated carbon obtained in process step (b) and used in the subsequent process steps is generally polar or hydrophilic (i.e. in comparison with the starting activated carbon used) and can therefore be described as generally hydrophilic according to typical use.

[0196] Furthermore, according to the invention, the oxidation, in particular the surface oxidation, of the activated carbon in process step (b) can be carried out in such a way that the oxidized, in particular the surface-oxidized activated carbon obtained thereby has a content of oxygen-containing groups (calculated and / or expressed as the content of volatile components ("fB") and based on the dry weight of the oxidized activated carbon) of at least 1 wt%, in particular at least 2 wt%, preferably at least 3 wt%, and most preferably at least 4 wt%, and / or in the range of 1 wt% to 30 wt%, in particular 1.5 wt% to 25 wt%, preferably 2 wt% to 20 wt%, and most preferably 3 wt% to 15 wt%. In this case, the content of oxygen-containing functional groups can be adjusted by temperature and / or duration and / or type and / or concentration of the oxidizing agent.

[0197] In this case, the method according to the invention can therefore also be used to regulate the oxidation of the activated carbon, also in order to optimize the subsequent finishing with catalytically active components.

[0198] Within the scope of the method according to the invention, it can be carried out in such a way that the oxygen content of the activated carbon oxidized on its surface is significantly increased compared to the starting activated carbon used, expressed as the content of volatile components ("fB") and based on the dry weight of the starting activated carbon, which usually has an oxygen content of less than 1 wt.-%. The oxygen content refers in particular to the activated carbon oxidized in method step (b) before carrying out the subsequent reduction provided according to method step (d). Therefore, the volatile content ("fB") is generally used as a measure of oxidation and therefore refers in particular to the surface oxides formed by oxidation. In particular, the volatile content can be determined according to ISO 562:1981. In particular, the content of volatile components ("fB") can be determined on previously dried activated carbon, the surface of which has been oxidized when appropriately heated to 900° C. under inert conditions for 7 minutes.

[0199] By purposefully forming and adjusting the content of oxygen-containing functional groups, the uptake of the catalytically active components or the corresponding precursors subsequently used, in particular in process step (c), can be predetermined or influenced. In this case, a person skilled in the art is able to select the relevant properties at any time and match them to one another in such a way that the desired loading with the catalytically active components leads to the meaning of the present invention.

[0200] In general, oxidation can be performed in an atmosphere or wet chemically (particularly when using acids).

[0201] According to the invention, in process step (b), the oxidation of the activated carbon, in particular the surface oxidation, can be carried out using at least one oxidizing agent. The oxidizing agent 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.

[0202] In particular, the oxidant is selected from oxygen, hydrogen peroxide (H 2 O 2 ), nitrogen oxides (preferably NO and / or NO 2 ), hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), perchloric acid (HClO 4 ), phosphoric acid (H 3 PO 4 ) and their combinations.

[0203] Further preferably, the oxidant is selected from oxygen (O 2 ), hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), perchloric acid (HClO 4 ), phosphoric acid (H 3 PO 4 ), hydrogen peroxide (H 2 O 2 ) and combinations thereof, particularly preferably selected from the group consisting of oxygen (O 2 ), hydrochloric acid (HCl) and nitric acid (HNO 3 ) and combinations thereof, very particularly preferably selected from oxygen (O 2 ) and nitric acid (HNO 3 ) and their combinations.

[0204] As regards the use of oxygen, use may in particular be made of atmospheric oxygen or synthetic air.

[0205] Typically, in the context of the present invention, in process step (b), the oxidation of activated carbon, in particular the surface oxidation, can be carried out under heating, in particular wherein the surface oxidation can be carried out at such a temperature that the reaction of the oxidant with the activated carbon is accompanied by the formation of oxygen-containing functional groups on the surface of the activated carbon. Thus, the oxidation of activated carbon, in particular the surface oxidation, can be carried out at a temperature in the range of -20°C to 1000°C, in particular 0°C to 800°C, preferably 5°C to 700°C, more preferably 10°C to 600°C, particularly preferably 20°C to 550°C. In this case, the oxidation of activated carbon, in particular the surface oxidation, can also be carried out for a period of up to 48 hours, in particular up to 24 hours, preferably up to 12 hours. According to the present invention, the oxidation of activated carbon, in particular the surface oxidation, can be carried out for a period of, for example, 1 minute to 1000 minutes, in particular 5 minutes to 800 minutes, preferably 10 minutes to 600 minutes.

[0206] According to the present invention, the oxidation of activated carbon, in particular surface oxidation, can be carried out by forming a hydrophilic surface of the activated carbon. In this regard, the oxidation of activated carbon, in particular surface oxidation, can be carried out by forming oxygen-containing functional groups on the surface of the activated carbon. In addition, the oxidation of activated carbon, in particular surface oxidation, can lead to the formation of oxygen-containing functional groups, in particular on the surface of the activated carbon. In this regard, the oxygen-containing functional groups can be selected from acidic and basic oxygen-containing functional groups and combinations thereof, in particular acidic and basic surface oxides. In particular, the oxygen-containing functional groups can be selected from hydroxyl, carboxyl, carbonyl, anhydride, lactone, quinone, pyrone, chromene and ether groups and combinations thereof, in particular selected from the group of hydroxyl, carboxylic acid, carbonyl and ether groups and combinations thereof.

[0207] According to a first embodiment of the present invention, in method step (b), the oxidation of activated carbon, in particular the surface oxidation, can be carried out using oxygen (O 2 ) in the form of an oxidant. Thus, in method step (b), oxygen (O 2 ) as an oxidant for oxidation, in particular surface oxidation. In this case, the temperature at which the oxidation, in particular surface oxidation, of the activated carbon is carried out can be 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., preferably in the range of 350° C. to 600° C., particularly preferably in the range of 400° C. to 550° C. In particular, the oxidation, in particular surface oxidation, of the activated carbon can be carried out for a period of up to 10 hours, in particular up to 8 hours, preferably up to 6 hours, wherein the period of oxidation, in particular surface oxidation of the activated carbon is carried out in the range 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 regard, it can be carried out within the framework of oxidation, in particular air oxidation or oxidation in a gas atmosphere.

[0208] On the contrary, according to another embodiment of the present invention, the oxidation of the activated carbon, in particular the surface oxidation, can also be carried out in process step (b) using an oxidizing agent, which is a mineral acid, for example nitric acid (HNO 3 In this respect, in particular, wet chemical methods can be used. In this case, it can be provided according to the invention that in method step (b), an inorganic acid, in particular nitric acid (HNO 3) as an oxidant for oxidation, in particular surface oxidation. In this regard, the oxidation of activated carbon, in particular surface oxidation, can be 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, preferably in the range of 10°C to 150°C, and particularly preferably in the range of 15°C to 125°C. In addition, the oxidation of activated carbon, in particular surface oxidation, can be carried out for a period of up to 6 hours, in particular up to 5 hours, and preferably up to 4 hours. Similarly, the oxidation of activated carbon, in particular surface oxidation, can be carried out for a period of time in the range of 5 minutes to 500 minutes, in particular in the range of 10 minutes to 400 minutes, and preferably in the range of 20 minutes to 300 minutes.

[0209] According to this embodiment of the invention, a mineral acid, in particular nitric acid (HNO 3 ), can be 10% (volume %) to 75%, especially 15% to 60%, preferably 20% to 55%, preferably about 25%, more preferably about 50%.

[0210] Furthermore, it can be provided according to the invention that in method step (b), after oxidation, in particular surface oxidation, and in particular before method step (c), the oxidized activated carbon is purified and / or dried. In this case, the purification can be carried out by at least one washing method in a liquid, in particular water. Furthermore, the drying can be 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 in the range of 50° C. to 150° C., preferably in the range of 60° C. to 120° C. In particular, the drying can be carried out under reduced (air) pressure and / or in a vacuum, and / or in particular, wherein the drying is carried out at an (air) pressure in the range of 0.01 Pa to 100 Pa, in particular 0.1 Pa to 10 Pa.

[0211] In the following, method step (c) of equipping previously oxidized activated carbon with catalytically active components or related precursors is described in more detail:

[0212] Typically, in process step (c), the provision of the oxidized, in particular surface-oxidized, activated carbon or catalyst support in process step (b) can be carried out by applying the catalytically active components to the catalyst support and / or bringing them into contact with the catalyst support, preferably fixing them on the catalyst support.

[0213] In general, the catalytically active component can comprise or consist of at least one metal, in particular in the form of a metal compound, preferably an ionic metal compound and / or in particular in elemental form.

[0214] Typically, the catalytically active component may comprise at least one metal in a positive oxidation state, in particular at least one metal cation, in particular wherein the oxidation state of the metal is in the range from +I to +VII, in particular in the range from +I to +IV, preferably in the range from +I to +III and particularly preferably +I or +II, and / or wherein the catalytically active component comprises at least one metal in an oxidation state of 0. For simple ions, the oxidation number corresponds to the charge number, while 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 the skilled person.

[0215] In particular, the catalytically active component may comprise at least one metal selected from the main group or subgroup of the periodic table or at least one lanthanide. In particular, the catalytically active component may comprise 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, in particular from the elements of main group IV or subgroups I and II of the periodic table. According to the invention, it can be provided 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 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, preferably from the group consisting of Pd, Pt and Ru, particularly preferably from the group consisting of Pd and Pt. The catalytically active component can be used in process step (c), in particular in the form of a precursor.

[0216] In particular, it can be provided according to the invention that the precursor of the catalytically active component is formed or constituted in such a way that the precursor is converted into the catalytically active component by the reduction carried out in process step (d). In particular, the precursor of the catalytically active component can be an oxidized form of the catalytically active component or can be formed therefrom.

[0217] In general, the precursor of the catalytically active component can comprise at least one metal compound, which is preferably based on at least one previously defined metal, which is soluble and / or dissociable, in particular in aqueous and / or particularly water-based solvents and / or dispersants.

[0218] Furthermore, the precursor of the catalytically active component may comprise at least one inorganic or organometallic compound, preferably based on at least one metal defined previously, in particular a metal salt or a metal oxide, preferably a metal salt.

[0219] 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 previously, which salt is selected from the group consisting of halide salts, hydroxides, amines, sulfates, sulfides, sulfites, nitrates, nitrites, phosphates, phosphides, phosphites, carbamates, alkoxides and carboxylates, in particular from the group consisting of halide salts, nitrates, hydroxides and carboxylates.

[0220] Furthermore, the precursor of the catalytically active component may comprise at least one metal halide, preferably based on at least one previously defined metal, in particular a fluoride, chloride, bromide or iodide, preferably a chloride, and / or may comprise at least one metal carboxylate, preferably based on at least one previously defined metal, in particular an acetate.

[0221] Typically, the precursor of the catalytically active component may contain 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.

[0222] In particular, the precursor may comprise or consist of palladium chloride, palladium nitrate, hexachloroplatinic acid, platinum nitrate and / or tetraaminoplatinum dihydroxide.

[0223] According to the present invention, H 2 PdCl 4 and / or Pd(NO 3 ) 2 According to the present invention, H 2 (PtCl 6 ), (NH 3 ) 4 Pt(OH) 2 and / or Pt(NO 3 ) 2 It can also be preferably used as a precursor (platinum precursor).

[0224] In particular, the precursors of the catalytically active components can be used in the form of particularly aqueous and / or particularly water-based solutions and / or in the form of dispersions (dispersions), in particular for the purpose of modifying and / or loading and / or coating and / or impregnating oxidized, in particular surface-oxidized activated carbon.

[0225] In this case, the solution or dispersion form (dispersion) may comprise water as solvent or dispersant. Furthermore, the solution or dispersion form (dispersion) may comprise at least one organic or inorganic acid or base, preferably hydrochloric acid.

[0226] Furthermore, the precursor of the catalytically active component may be present in the form of a solution or dispersion (dispersion) which is at least substantially free of crystals and / or crystallites. In particular, the precursor of the catalytically active component in the form of a solution or dispersion (dispersion) may be at least substantially dissolved, in particular at least substantially dissociated.

[0227] Typically, the solution and / or dispersion form (dispersion) may contain the precursor of the catalytically active component in an amount of 0.01 wt % to 80 wt %, in particular 0.1 wt % to 60 wt %, preferably 1 wt % to 50 wt %, preferably 2 wt % to 40 wt %, based on the solution and / or dispersion form and calculated as metal.

[0228] The term "solution" or "dispersion form (dispersion)" used in the context of the present invention is to be understood in particular in such a way that in a basic amount or concentration, the precursor of the catalytically active component is at least substantially completely dissolved or dissociated or dispersed in the basic solvent or dispersant. For example, within the scope of the present invention, in order to equip or load the activated carbon with the catalytically active component, the activated carbon used according to the invention can be immersed or soaked in a corresponding solution or dispersion of (the precursor of) the catalytically active component. In this way, according to the invention, it is ensured in particular that the basic solution or dispersion form (dispersion) at least substantially fills the entire pore system of the activated carbon, which leads to a uniform loading of the activated carbon with the catalytically active component.

[0229] Generally, according to the present invention, in method step (c), equipping the oxidized, in particular surface-oxidized activated carbon with a catalytically active component, in particular a precursor of a catalytically active component, may include applying the catalytically active component, in particular a precursor of the catalytically active component, to the oxidized, in particular surface-oxidized activated carbon, and / or contacting, preferably fixing it. In particular, the oxidized, in particular surface-oxidized activated carbon may be applied and / or contacted, preferably fixed, by immersing and / or impregnating and / or wetting and / or covering and / or coating and / or spraying the oxidized, in particular surface-oxidized activated carbon in and / or with the catalytically active component, preferably a precursor of the catalytically active component. Thus, the application and / or contacting may be carried out by energy input, in particular by vibration and / or by ultrasonic input. In this case, the catalytically active component, in particular the precursor of the catalytically active component, may be used in the form of a solution and / or in the form of a dispersion (dispersion), as described above.

[0230] Furthermore, in particular after application and / or contacting and / or in particular in order to equip oxidized, in particular surface-oxidized activated carbon with catalytically active components, in particular precursors of catalytically active components, it can be provided that excess catalytically active components, in particular excess precursors of catalytically active components, preferably excess catalytically active components in the form of a solution and / or dispersion (dispersion), preferably excess precursors of catalytically active components in the form of a solution and / or dispersion (dispersion), are removed and / or separated from the activated carbon or the catalyst system.

[0231] In this case, in particular after application or contacting, and / or in particular for the final processing of the oxidized, in particular surface-oxidized activated carbon with the catalytically active component, in particular with a precursor of the catalytically active component, the activated carbon obtained can be purified and / or dried. In this respect, the purification and / or drying can be carried out by at least one washing step in a liquid, in particular water. Furthermore, the purification and / or drying can be carried out by heating the activated carbon equipped with the catalytic component, in particular to a temperature of 40° C. to 200° C., in particular 50° C. to 150° C., preferably 60° C. to 120° C. Furthermore, the purification and / or drying can be carried out under reduced (air) pressure and / or in a vacuum. Furthermore, the purification and / or drying can be carried out under an (air) pressure of 100 Pa to 0.01 Pa, in particular 10 Pa to 0.1 Pa. The removal of the solvent or dispersant or the drying of the activated carbon leads in particular to the formation of a precursor of the catalytically active component in dry or granular form, which is then present in particular in crystalline form on the activated carbon or on the surface used as a catalyst support.

[0232] In general, it is provided in the process according to the invention that in process step (c), both the outer and inner surfaces of the oxidized, in particular surface-oxidized activated carbon, in particular the micropores, mesopores and / or macropores, are provided with catalytically active components, in particular loaded and / or coated and / or impregnated, in particular in the form of corresponding precursors. In this way, a high loading of catalytically active components can be achieved.

[0233] In the following, process step (d) is described in more detail, in which the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) and equipped with a catalytically active component, in particular a precursor of a catalytically active component, is reduced:

[0234] With regard to the reduction of the oxidized, in particular surface-oxidized, activated carbon obtained in method step (c) and equipped with the catalytically active component, in particular a precursor of the catalytically active component, which is carried out according to the invention in method step (d), this leads, without wishing to be bound by this theory, to on the one hand at least partial reduction of the catalytically active component or a precursor associated therewith, in particular introduced into or applied to the activated carbon. In particular, the catalytically active component or the precursor associated therewith or the base metal compound or the base metal can be reduced in this way, in particular if the catalytically active component or the precursor associated therewith is present in oxidized form or in the form of a salt, ion or the like. Thus, the reduction treatment can generally also be carried out against the background of the activation of the catalyst and / or the conversion of the catalyst or the catalytically active component or the precursor associated therewith into an active form, in particular by changing and / or reducing the oxidation number of the metal of the catalytically active component. Thus, the reduction treatment can be carried out in particular against the background of the activation of the catalytically active component or the precursor associated therewith.

[0235] The reduction treatment according to method step (d) can be carried out in particular on the metal, in particular the noble metal, of the catalytically active component or the relevant precursor, which metal is not used in the zero oxidation state or is not present in the form of a compound, in particular a salt, in which case the activated carbon is provided with the catalytically active component or the relevant precursor in method step (c) so that the metal or noble metal is converted into elemental form or into the zero oxidation state accordingly. In the form of a compound, in particular in the form of a salt, it can be carried out in such a way that the metal or noble metal is converted into elemental form or into the zero oxidation state accordingly, in particular so that in this way the activation of the catalyst or the conversion into the catalytically active form is achieved or carried out.

[0236] Furthermore, the reduction treatment according to method step (d) (without wishing to be bound by this theory) can lead to at least partial removal or reduction of functional groups, in particular oxygen-containing functional groups, on the surface of the activated carbon or in the pore system of the activated carbon associated therewith (surface reduction). In method step (d), the oxidized activated carbon equipped with the catalytically active components or the associated precursors can thus be subjected to surface reduction. In this way, a neutralization or neutralization of the catalyst support or the associated activated carbon and thus of the catalyst system can be carried out.

[0237] Therefore, the catalyst system according to the invention or in this respect the activated carbon treated in this way also exhibits, due to the reduction in the content of functional groups on the surface associated with the reduction treatment, in particular reduced self-reactivity, which is beneficial to the overall catalytic performance.

[0238] Similarly, without wishing to be bound by this theory, the hydrophilicity of the activated carbon and therefore of the entire catalyst system is reduced upon the reduction treatment performed, or the content of polar groups is reduced, which in particular improves the overall permeation or diffusion behavior of particularly hydrophobic or non-polar reactants or products originating from the catalytic reaction.

[0239] In general, in process step (d), the reduction can be carried out as a gas phase reduction or as a liquid phase reduction.

[0240] In particular, it can be 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., 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., further preferably in the range of 130° C. to 145° C. Furthermore, in process step (d), the reduction can 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.

[0241] According to the present invention, in process step (d), the reduction may be carried out for a period of time in the range of 0.05 hours to 48 hours, in particular in the range of 0.1 hours to 36 hours, preferably in the range of 0.5 hours to 24 hours, more preferably in the range of 1 hour to 12 hours.

[0242] The reduction treatment using a gaseous reducing agent, which embodiment is preferred according to the present invention, is now described in more detail below.

[0243] In this case, 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, preferably hydrogen.

[0244] - In this regard, in process step (d), the reduction can be carried out in an atmosphere containing a reducing agent, in particular hydrogen, in particular an inert atmosphere, preferably a nitrogen atmosphere. In this case, the atmosphere can contain the reducing agent, in particular hydrogen, in an amount of 0.1% to 20% by volume, in particular 0.5% to 10% by volume, preferably 2% to 8% by volume, based on the volume of the atmosphere.

[0245] - Furthermore, in process step (d), the reduction can be 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, preferably in the range of 115°C to 160°C, more preferably in the range of 120°C to 150°C, most preferably in the range of 130°C to 145°C.

[0246] - Furthermore, in process step (d), when reduction can be carried out, the volume flow rate of the atmosphere containing the reducing agent is in the range of 5 L / h to 1000 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.

[0247] According to the invention, it can also be provided herein that in method step (d), the reduction is carried out using a gaseous reducing agent, the reduction being carried out for a period in the range of 0.1 h to 36 h, in particular in the range of 0.2 h to 24 h, preferably in the range of 0.5 h to 12 h.

[0248] According to another embodiment of the present invention, the reduction process using a liquid reducing agent is further described as follows:

[0249] -According to the invention, it can therefore be 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 on potassium hydroxide, in particular in combination with at least one alkali metal formate, preferably potassium formate.

[0250] - In this case, in process step (d), the reduction can be carried out using a liquid reducing agent at a temperature in the range of 10°C to 250°C, in particular in the range of 20°C to 200°C, preferably in the range of 30°C to 150°C, preferably in the range of 40°C to 125°C, particularly preferably in the range of 50°C to 120°C.

[0251] In this respect, in process step (d), the reduction can be carried out for a period in the range from 0.05 hours to 24 hours, in particular in the range from 0.1 hours to 12 hours, preferably in the range from 0.5 hours to 8 hours.

[0252] 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 (e.g. LiAlH 4 and / or NaBH 4 ) and / or formic acid can in principle also be considered as reducing agents.

[0253] In general, during or after carrying out process step (d), in particular a catalyst system according to the invention is also obtained which is described or defined below in the second aspect of the invention, so that the explanations therein apply correspondingly to the present aspect.

[0254] In general, in process step (d), a catalyst system according to the invention can be obtained, wherein the catalyst system has at least one catalytically active component applied and / or fixed to a catalyst support, wherein the catalytically active component comprises and / or consists of at least one metal, and wherein the catalyst support is in the form of activated carbon and / or is formed on the basis of activated carbon, wherein the catalyst support is present in the form of granular, preferably spherical activated carbon, wherein the activated carbon (i.e. the activated carbon forming the catalyst support) has:

[0255] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3 / g, at least 50% of the total pore volume, in particular the total pore volume according to Gurvich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores, and

[0256] (ii) At 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m.

[0257] In the context of the present invention, in method step (d), in particular a catalyst system can be obtained, wherein the catalyst system has at least one catalytically active component applied or fixed to a catalyst support, wherein the catalytically active component contains and / or consists of at least one metal, and wherein the catalyst support is in the form of activated carbon or is formed on the basis of activated carbon, wherein the catalyst support is in the form of granular, preferably spherical, activated carbon.

[0258] According to the invention, the catalyst system can have an activity, determined as the percentage dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support (dispersion D, metal dispersion), in particular measured by chemical adsorption using a (dynamic) flow method, preferably according to DIN 66136-3:2007-01, 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%, preferably in the range of 28 to 60%.

[0259] In particular, the catalyst system may comprise a catalytically active component, in particular a metal of a catalytically active component, which preferably has an average crystallite size (average crystallite size d Me ) is at most (Angstroms), especially up to Preferred at most Preferred at most Particularly preferably at most Very particularly preferably at most Still more preferably at most and / or (Angstrom) to within the scope, especially in to in the range of to in the range of to In the range of to In the range of to in the range of to within the range.

[0260] In this case, it can thus generally be provided according to the invention that the catalyst system obtained in process step (d) has an activity, determined as the percentage dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, in particular measured by chemical adsorption using a (dynamic) flow method, preferably in accordance with DIN 66136-3:2007-01, of at least 15%, in particular at least 20%, preferably at least 25%, preferably at least 28%, and / or in a range from 15 to 90%, in particular in a range from 20 to 80%, preferably in a range from 25 to 70%, preferably in a range from 28 to 60%.

[0261] Furthermore, within the scope of the present invention, it can likewise be provided in this context that the catalyst system obtained in process step (d) comprises catalytically active components, in particular metals of catalytically active components, which preferably have an average crystallite size, determined in accordance with DIN 66136, of at most (Angstroms), especially up to Preferred at most Preferred at most Particularly preferably at most Very particularly preferably at most It is further preferred that at most and / or (Angstrom) to within the scope, especially in to in the range of to in the range of to In the range of to In the range of to In the range of to within the range.

[0262] Thus, according to the present invention, in particular a catalyst system according to the invention can be obtained which, in addition to a determined percentage dispersion of the catalytically active component or metal in question, also has a determined grain size relative to the catalytically active component or metal in question, wherein the above-mentioned properties of the specific percentage dispersion and the specific grain size characterize the outstanding catalytic properties of the catalyst system according to the invention, in particular with regard to the provision of a large catalytically active surface, in which the pore system of the activated carbon is optimally equipped or occupied by the catalytically active component.

[0263] The dispersity of the catalytically active component or metal dispersion therefore also describes the catalytic activity of the catalyst system or supported catalyst according to the invention. In particular, the catalytic activity is also 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 the surface atoms of the catalytically active component significantly participate in or realize the catalytic conversion. According to the present invention, the term "dispersity" (also referred to as "dispersity D") is used synonymously with the term "metal dispersity" or "metal dispersity D". The percentage dispersity is particularly based on the ratio of the possible size of the atoms or molecules of the catalytically active component actually present on the surface to the atoms or molecules of the catalytically active component theoretically present on the surface. In other words, the percentage dispersity particularly describes the number of surface atoms or molecules of the catalytically active component (for example, the atoms or molecules of the catalytically active component accessible to the sample gas can be determined by chemical adsorption of the sample gas) to the total number of atoms or molecules of the catalytically active component (i.e. the total number of atoms or molecules of the catalytically active component theoretically available or used, or the total number of atoms or molecules of the catalytically active component present in the catalyst support). In particular, the determination can be carried out by chemical adsorption. In particular, carbon monoxide (CO) can be used as a measuring gas. The dispersion or metal dispersion can thus be measured in particular by carbon monoxide chemisorption.

[0264] The percentage dispersion (D) of the catalytically active components, in particular the metals of the catalytically active components, on the catalyst support or activated carbon can be calculated in particular based on the following formula (I):

[0265]

[0266] In particular, the average grain size (synonymically referred to as the average grain size d Me ) can be calculated based on the following formula (II):

[0267]

[0268] With respect to the above given formulae (I) and (II), the following formula notations apply:

[0269]

[0270] With regard to the average crystallite size according to the invention, this also characterizes the catalytic activity, in particular against the background of an increased accessibility of the catalytically active components to the reactants to be reacted. In particular, the average crystallite size according to the invention also has an optimal ratio of the surface area of ​​the catalytically active components forming the crystallites to the corresponding volume, which also leads to an increase in the catalytic activity.

[0271] In particular, according to the invention, the average dispersion on the one hand and the average grain size on the other hand are linked with respect to the overall improved catalytic activity provided and reinforce each other to a degree that exceeds the sum of the respective individual effects, so that in this regard there is also a synergistic effect with respect to the improved catalytic activity of the catalyst system according to the invention, in particular with respect to higher conversions or improved space / time yields.

[0272] On the basis of the process according to the invention, the amount or content of catalytically active components can be specifically adjusted or adjusted relative to the catalyst system according to the invention, so that from this point of view the catalytic activity of the catalyst system obtained according to the invention can also be specifically predetermined.

[0273] Thus, it can be provided according to the invention that the catalyst system obtained in process step (d) comprises the catalytically active component in an amount of at least 0.05 wt. %, in particular at least 0.1 wt. %, preferably at least 0.2 wt. %, optimally at least 0.5 wt. %, particularly preferably at least 0.6 wt. %, most preferably at least 1 wt. %, further preferably at least 1.5 wt. %, calculated as metal and based on the total weight of the catalyst system. Thus, the lower limit ensures that the specified catalytic activity is provided.

[0274] Furthermore, according to the invention, it can be provided in particular that the catalyst system obtained in process step (d) comprises the 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, preferably at most 10% by weight, particularly preferably at most 8% by weight and very particularly preferably at most 7% by weight, calculated as metal and based on the total weight of the catalyst system. This upper limit ensures in particular good accessibility of the catalytically active components and in particular avoids clogging of the pores.

[0275] In this case, it is particularly possible in the case of the present invention that the catalyst system obtained in process step (d) contains the catalytically active components in an amount in the range of 0.05 wt% to 25 wt%, in particular in the range of 0.1 wt% to 25 wt%, preferably in the range of 0.2 wt% to 20 wt%, preferably in the range of 0.5 wt% to 15 wt%, particularly preferably in the range of 0.6 wt% to 10 wt%, very particularly preferably in the range of 1 wt% to 8 wt%, further preferably in the range of 1.5 wt% to 7 wt%, calculated as metal and based on the total weight of the catalyst system.

[0276] Furthermore, for the catalytically active components of the catalyst system obtained in step (d) of the process according to the invention, it may be as follows:

[0277] In particular, the catalytically active component of the catalyst system obtained in process step (d) can comprise or consist of at least one metal, in particular in the form of a metal compound, preferably an ionic metal compound and / or in particular in elemental form.

[0278] In particular, the catalytically active component of the catalyst system obtained in process step (d) may comprise at least one metal in a positive oxidation state, in particular at least one metal cation. In this case, the oxidation state of the metal may be in the range of +I to +VII, in particular in the range of +I to +IV, preferably in the range of +I to +III, or particularly preferably +I or +II. According to the invention, it can also be provided that the catalytically active component comprises at least one metal in an oxidation state of zero.

[0279] In particular, during the reduction process 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 components of the catalyst system obtained in process step (d) (and the end product obtained from this process) comprise at least one metal in the zero oxidation state.

[0280] In particular, the catalytically active components of the catalyst system obtained in process step (d) may comprise at least one metal from a main group or a subgroup of the Periodic Table of the Elements or at least one lanthanide.

[0281] Typically, the catalytically active components of the catalyst system obtained in process step (d) may comprise at least one metal selected from 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 elements of main group IV or subgroups I and II of the Periodic Table of the Elements.

[0282] In particular, the catalytically active components of the catalyst system obtained in process step (d) may comprise 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, preferably Pd, Pt and Ru, particularly preferably Pd and Pt.

[0283] This is because the above-mentioned metals achieve particularly high catalytic activity in basic catalytic processes (eg, hydrogenation reactions, etc.).

[0284] As regards the activated carbon present in the catalyst system, it may be based on or derived from the following types of activated carbon, the properties associated therewith likewise leading to improved properties of the catalyst system according to the invention (e.g. by improving the arrangement or formation of the catalytically active components):

[0285] Thus, the ((surface) reduced) activated carbon of the catalyst system obtained in process step (d), i.e. the activated carbon forming the catalyst support, can be oxidized before the application and / or fixing of the catalytically active components, in particular on its surface, in particular wherein an oxidation, in particular a 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 is also made to the above explanations, in particular process step (c).

[0286] - Similarly, within the scope of the present invention, it can be particularly manifested in such a way that, after being provided with the catalytically active components, the activated carbon has been reduced, in particular on its surface, in particular wherein the reduction of the activated carbon has been carried out using and / or in the presence of at least one reducing agent. In particular, it can be manifested in such a way that, in particular after being provided with the catalytically active components and / or after having been reduced, the activated carbon is reduced, in particular surface-reduced. In particular, according to the invention, it can be manifested in such a way that a precursor of the catalytically active component is converted into an active form or a catalytically active component during the reduction treatment, in particular wherein the basic metal component is converted into elemental form.

[0287] - In addition, activated carbon (i.e. activated carbon forming a catalyst support) can be obtained by carbonizing and subsequently activating a starting material based on an organic polymer, followed by an oxidation treatment, wherein the oxidation treatment is carried out before the provision of the catalytically active components, and then a reduction treatment, wherein the reduction treatment is carried out after the provision of the catalytically active components. In this respect, reference can also be made to the above explanations.

[0288] - Likewise, the activated carbon, i.e. the activated carbon forming the catalyst support, may be an activated carbon based on activated carbon obtainable by carbonization and subsequent activation of an organic polymer-based starting material and / or an activated carbon based on a polymer-based, preferably spherical (pellet-like) activated carbon (PBSAC or polymer-based spherical activated carbon).

[0289] - 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 claim 21). In particular, the activated carbon of the catalyst system obtained in process step (d) may be an activated carbon which is obtained according to or based on the process for producing activated carbon described herein (see claims 22 to 25) or according to the oxidation process described herein according to process step (b) (see also claims 30 to 34).

[0290] Furthermore, the catalytically active components of the catalyst system obtained according to the invention may be based on precursors of the catalytically active components which are reduced, in particular, in process step (d).

[0291] In particular, it is possible in the context of the present invention that the catalyst system obtained in process step (d) is a catalyst system which is reduced in particular at its surface (which in particular includes a corresponding oxidation of the catalyst support and thereby of the activated carbon associated therewith and of the catalytically active components or precursors associated therewith).

[0292] Furthermore, for a further explanation of the catalyst system according to the present invention obtained in process step (d), reference may be made to the following explanation of the catalyst system according to the second aspect of the present invention, to which the relevant explanations apply mutatis mutandis.

[0293] Turning further to the present first aspect of the invention, the present invention also relates to a process for preparing a catalyst system, in particular a process as defined herein, comprising at least one catalytically active component, in particular a supported catalyst, preferably for heterogeneous catalysis,

[0294] wherein at least one catalytically active component is applied and / or fixed to the catalyst support, said catalytically active component comprising and / or consisting of at least one metal,

[0295] The method comprises the following steps (a) to (d) in the order specified below:

[0296] (a) providing and / or producing granular, preferably spherical activated carbon (= starting activated carbon) for use as catalyst support,

[0297] The activated carbon (i.e., the starting activated carbon) has:

[0298] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3In the range of 100 to 200 g / m2, 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 having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores,

[0299] (ii) At 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m, and

[0300] (iii) an average pore diameter 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, 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, further preferably in the range of 25 nm to 50 nm;

[0301] Then

[0302] (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, in particular a surface oxygen content, of at least 4% (atomic %), determined in particular by X-ray photoelectron spectroscopy (XPS or ESCA), based on the total elemental composition of the oxidized activated carbon, and / or provided that the oxidized, in particular surface oxidized activated carbon has a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6 at least 30% of the maximum water vapor saturation loading of the activated carbon is reached;

[0303] Then

[0304] (c) equipping, in particular loading and / or coating and / or impregnating the activated carbon oxidized, in particular surface-oxidized, in process step (b) with a catalytically active component, in particular at least one catalytically active component precursor;

[0305] Then

[0306] (d) reducing the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) and equipped with a catalytically active component, in particular a catalytically active component precursor, thereby in particular converting the catalytically active component precursor into the catalytically active component, in particular thereby obtaining a catalyst system, in particular a supported catalyst, having at least one catalytically active component.

[0307] In this context, according to a first aspect of the invention, the invention likewise relates to a process for preparing a catalyst system, in particular as described above, comprising at least one catalytically active component, in particular a supported catalyst, preferably for heterogeneous catalysis,

[0308] wherein at least one catalytically active component is applied and / or fixed to the catalyst support, said catalytically active component comprising and / or consisting of at least one metal,

[0309] The method comprises the following steps (a) to (d) in the order specified below:

[0310] (a) providing and / or producing granular, preferably spherical activated carbon (= starting activated carbon) for use as catalyst support,

[0311] The activated carbon (i.e., the starting activated carbon) has:

[0312] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3 In the range of 100 to 200 g / g, 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 having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores,

[0313] (ii) 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m,

[0314] (iii) an average pore diameter 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, 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, further preferably in the range of 25 nm to 50 nm, and

[0315] (iv) 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, preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, very particularly preferably in the range of 175 μm to 250 μm, in particular at least 80 wt %, in particular at least 90 wt %, preferably at least 95 wt % of the activated carbon particles The particles have a particle size, in particular a particle diameter, within the above 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;

[0316] Then

[0317] (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, in particular a surface oxygen content, of at least 4% (atomic %), determined in particular by X-ray photoelectron spectroscopy (XPS or ESCA), based on the total elemental composition of the oxidized activated carbon, and / or provided that the oxidized, in particular surface oxidized activated carbon has a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6 at least 30% of the maximum water vapor saturation loading of the activated carbon is reached;

[0318] Then

[0319] (c) equipping, in particular loading and / or coating and / or impregnating the activated carbon oxidized, in particular surface-oxidized, in process step (b) with a catalytically active component, in particular at least one catalytically active component precursor;

[0320] Then

[0321] (d) reducing the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) and equipped with a catalytically active component, in particular a catalytically active component precursor, thereby in particular converting the catalytically active component precursor into the catalytically active component, in particular thereby obtaining a catalyst system, in particular a supported catalyst, having at least one catalytically active component.

[0322] More specifically, according to a first aspect of the invention, the invention likewise relates to a process for preparing a catalyst system, in particular a process as defined herein, comprising at least one catalytically active component, in particular a supported catalyst, preferably for heterogeneous catalysis,

[0323] In this case, at least one catalytically active component is applied and / or fixed to the catalyst support, which comprises and / or consists of at least one metal.

[0324] The method comprises the following steps (a) to (d) in the order specified below:

[0325] (a) providing and / or producing granular, preferably spherical activated carbon (= starting activated carbon) for use as catalyst support,

[0326] The activated carbon (i.e., the starting activated carbon) has:

[0327] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3 In the range of 100 to 200 g / m2, 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 having a pore diameter of at least 2 nm, in particular pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores,

[0328] (ii) At 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m, and

[0329] (iii) an average pore diameter 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, 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, further preferably in the range of 25 nm to 50 nm,

[0330] (iv) 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, preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, very particularly preferably in the range of 175 μm to 250 μm, in particular at least 80 wt %, in particular at least 90 wt %, preferably at least 95 wt % of the activated carbon particles The particles have a particle size, in particular a particle diameter, within the above 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,

[0331] (v) optionally a globe 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%, further preferably at least 99.8%,

[0332] (vi) optionally a vibration or packing density in the range of 100 g / L to 1500 g / L, in particular 125 g / L to 1000 g / L, preferably 150 g / L to 800 g / L, preferably 200 g / L to 600 g / L, particularly preferably 225 g / L to 500 g / L, most preferably 250 g / L to 400 g / L, further preferably 255 g / L to 395 g / L, and / or a bulk density in the range of 150 g / L to 1000 g / L, in particular 250 g / L to 700 g / L, preferably 300 g / L to 600 g / L, preferably 300 g / L to 550 g / L,

[0333] (vii) optionally 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%,

[0334] (viii) optionally an iodine value in the range of 1250 mg / g to 2100 mg / g, in particular in the range of 1300 mg / g to 2000 mg / g, preferably in the range of 1400 mg / g to 1900 mg / g, preferably in the range of 1425 mg / g to 1850 mg / g,

[0335] (ix) optionally 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, preferably in the range of 19.5 mL to 47.5 mL,

[0336] (x) optionally a molasses value in the range of 255 to 1500, in particular in the range of 310 to 1400, preferably in the range of 375 to 1300, more preferably in the range of 510 to 1250,

[0337] (xi) Optional weight-based adsorption of N 2 Volume V ads(wt.) , which is measured at a partial pressure p / p0 of 0.25, at 250 cm 3 / g to 850cm 3 / g range, especially at 300cm 3 / g to 700cm 3 / g, preferably within the range of 350cm 3 / g to 650cm 3 / g, preferably at 375cm 3 / g to 625cm 3 / g within the range

[0338] (xii) Optional volume-dependent adsorption N 2 Volume V ads(vol.) , which is measured at a partial pressure p / p0 of 0.25, at 50cm 3 / cm 3 Up to 300cm 3 / cm 3 range, especially within 80cm 3 / cm 3 Up to 275cm 3 / cm 3 within the range, preferably within 90cm 3 / cm 3 Up to 250cm 3 / cm 3 within the range, preferably within 95cm 3 / cm 3 Up to 225cm 3 / cm 3 within the range of

[0339] (xiii) optionally, a gravimetric adsorption N measured at a partial pressure p / p0 of 0.995 2 Volume V ads(wt.) , which is at 300cm 3 / g to 2300cm 3 / g range, especially at 400cm 3 / g to 2200cm 3 / g, preferably within the range of 450cm 3 / g to 2100cm 3 / g, preferably at 475cm 3 / g to 2100cm 3 / g range,

[0340] (xiv) optionally the volume-dependent adsorption N measured at a partial pressure p / p0 of 0.995 2 VolumeVads (vol.) , whose range is 200cm 3 / cm 3 Up to 500cm 3 / cm 3 , especially 250cm 3 / cm 3 Up to 400cm 3 / cm 3 , preferably 275cm 3 / cm 3 Up to 380cm 3 / cm 3 And preferably 295cm 3 / cm 3 Up to 375cm 3 / cm 3 ;as well as

[0341] (xv) optionally an open porosity fractal dimension in the range of 2.6 to 2.99, in particular 2.7 to 2.95, preferably 2.8 to 2.95, and / or wherein the activated carbon has an open porosity fractal dimension of at least 2.7, in particular at least 2.8, preferably at least 2.85, preferably at least 2.9;

[0342] Then

[0343] (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, in particular a surface oxygen content, of at least 4% (atomic %), determined in particular by X-ray photoelectron spectroscopy (XPS or ESCA), based on the total elemental composition of the oxidized activated carbon, and / or provided that the oxidized, in particular surface oxidized activated carbon has a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at a partial pressure p / p0 of 0.6 at least 30% of the maximum water vapor saturation loading of the activated carbon is reached;

[0344] Then

[0345] (c) equipping, in particular loading and / or coating and / or impregnating the activated carbon oxidized, in particular surface-oxidized, in process step (b) with a catalytically active component, in particular at least one catalytically active component precursor;

[0346] Then

[0347] (d) reducing the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) and equipped with a catalytically active component, in particular a catalytically active component precursor, thereby in particular converting the catalytically active component precursor into the catalytically active component, in particular thereby obtaining a catalyst system, in particular a supported catalyst, having at least one catalytically active component.

[0348] Furthermore, according to a first aspect of the invention, the present invention also relates to a process for preparing a catalyst system, in particular the process defined above, comprising at least one catalytically active component, in particular a supported catalyst, preferably for heterogeneous catalysis,

[0349] wherein at least one catalytically active component is applied and / or fixed to the catalyst support, said catalytically active component comprising and / or consisting of at least one metal,

[0350] The method comprises the following steps (a) to (d) in the order specified below:

[0351] (a) providing and / or producing granular, preferably spherical activated carbon (= starting activated carbon) for use as catalyst support,

[0352] The activated carbon (i.e., the starting activated carbon) has:

[0353] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3In the range of 100 to 200 g / m2, 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 having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores,

[0354] (ii) At 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m, and

[0355] (iii) an average pore diameter 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, 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, further preferably in the range of 25 nm to 50 nm,

[0356] (iv) 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, preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, very particularly preferably in the range of 175 μm to 250 μm, in particular at least 80 wt %, in particular at least 90 wt %, preferably at least 95 wt % of the activated carbon particles The particles have a particle size, in particular a particle diameter, within the above 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,

[0357] (v) a wear resistance (ball-on-disk hardness) and / or abrasion 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%, further preferably at least 99.8%,

[0358] (vi) a vibration or packing density in the range of 100 g / L to 1500 g / L, in particular 125 g / L to 1000 g / L, preferably 150 g / L to 800 g / L, preferably 200 g / L to 600 g / L, particularly preferably 225 g / L to 500 g / L, most preferably 250 g / L to 400 g / L, further preferably 255 g / L to 395 g / L, and / or a tapped density in the range of 150 g / L to 1000 g / L, in particular 250 g / L to 700 g / L, preferably 300 g / L to 600 g / L, preferably 300 g / L to 550 g / L,

[0359] (vii) 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%, preferably in the range of 47.5% to 75%,

[0360] (viii) an iodine value in the range of 1250 mg / g to 2100 mg / g, in particular in the range of 1300 mg / g to 2000 mg / g, preferably in the range of 1400 mg / g to 1900 mg / g, preferably in the range of 1425 mg / g to 1850 mg / g,

[0361] (ix) 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, preferably in the range of 19.5 mL to 47.5 mL,

[0362] (x) a molasses value in the range of 255 to 1500, in particular in the range of 310 to 1400, preferably in the range of 375 to 1300, preferably in the range of 510 to 1250,

[0363] (xi) Weight-based adsorption of N 2 Volume V ads(wt.) , which is measured at a partial pressure p / p0 of 0.25, at 250 cm 3 / g to 850cm 3 / g range, especially at 300cm 3 / g to 700cm 3 / g, preferably within the range of 350cm 3 / g to 650cm 3 / g, preferably at 375cm 3 / g to 625cm 3 / g range,

[0364] (xii) Volume-dependent adsorption N measured at a partial pressure p / p0 of 0.25 2 Volume Vads(vol.) , which is 50cm 3 / cm 3 Up to 300cm 3 / cm 3 range, especially within 80cm 3 / cm 3 Up to 275cm 3 / cm 3 within the range, preferably within 90cm 3 / cm 3 Up to 250cm 3 / cm 3 within the range, preferably within 95cm 3 / cm 3 Up to 225cm 3 / cm 3 within the range of

[0365] (xiii) Gravimetric adsorption of N measured at a partial pressure p / p0 of 0.995 2 Volume V ads(wt.) , which is at 300cm 3 / g to 2300cm 3 / g range, especially at 400cm 3 / g to 2200cm 3 / g, preferably within the range of 450cm 3 / g to 2100cm 3 / g, preferably at 475cm 3 / g to 2100cm 3 / g range,

[0366] (xiv) Volume-dependent adsorption N measured at a partial pressure p / p0 of 0.995 2 Volume V ads(vol.) , whose range is 200cm 3 / cm 3 Up to 500cm 3 / cm 3 , especially 250cm 3 / cm 3 Up to 400cm 3 / cm 3 , preferably 275cm 3 / cm 3 Up to 380cm 3 / cm 3 , preferably 295cm 3 / cm 3 Up to 375cm 3 / cm 3 ;as well as

[0367] (xv) an open porosity fractal dimension in the range of 2.6 to 2.99, in particular 2.7 to 2.95, preferably 2.8 to 2.95, and / or wherein the activated carbon has an open porosity fractal dimension of at least 2.7, in particular at least 2.8, preferably at least 2.85, preferably at least 2.9;

[0368] Then

[0369] (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, in particular a surface oxygen content, of at least 4% (atomic %), determined by X-ray photoelectron spectroscopy (XPS or ESCA), based on the total elemental composition of the oxidized activated carbon, and / or provided that the oxidized, in particular surface oxidized activated carbon has a hydrophilicity, which is determined as a water vapor adsorption behavior, such that at least 30% of the maximum water vapor saturation loading of the activated carbon is reached at a partial pressure p / p0 of 0.6;

[0370] Then

[0371] (c) equipping, in particular loading and / or coating and / or impregnating the oxidized, in particular surface-oxidized, activated carbon of process step (b) with a catalytically active component, in particular at least one catalytically active component precursor;

[0372] Then

[0373] (d) reducing the oxidized, in particular surface-oxidized, activated carbon obtained in process step (c) and equipped with a catalytically active component, in particular a catalytically active component precursor, thereby in particular converting the catalytically active component precursor into the catalytically active component, in particular thereby obtaining a catalyst system, in particular a supported catalyst, having at least one catalytically active component.

[0374] In general, the present invention provides an efficient method for producing a catalyst system according to the invention having high catalytic performance, thereby providing a catalyst system which can be specifically adjusted or tailored to its catalytic activity, while simplifying the method, and the catalyst system has a high catalytic activity overall, which is also known, in particular based on the average dispersion and the average grain size of the catalytically active components.

[0375] The provision of a high-performance catalyst system according to the invention is thus ensured by a specific sequence and coordination of the corresponding method steps as defined above. In this case, the use of special activated carbons with a defined pore system as catalyst supports or the performance of special oxidations is also very important, in particular in providing a higher loading of the catalytically active components and a better access to reactants or products.

[0376] As described above, the process according to the invention and the catalyst system according to the invention obtained therefrom have a large number of advantages and special properties. Due to the outstanding catalytic properties of the catalyst system according to the invention obtained by the process according to the invention, a wide range of applications or uses can be carried out, so that correspondingly high catalytic conversions and high space / time yields can also be ensured within the scope of use of catalytic applications.

[0377] With regard to the method according to the invention, reference may also be made to the explanations of the other aspects of the invention, which explanations apply correspondingly to the present case.

[0378] According to the second aspect of the present invention, another object of the present invention is also the catalyst system of the present invention, in particular the supported catalyst of the present invention which is preferably used for heterogeneous catalysis, wherein the catalyst system of the present invention or the supported catalyst associated therewith is obtainable according to the above-mentioned method according to the present invention or is obtained according to the above-mentioned method according to the present invention.

[0379] Analogously, according to this aspect of the invention, the invention also relates to the catalyst system of the invention, in particular the supported catalyst of the invention preferably for heterogeneous catalysis, in particular the catalyst system defined previously,

[0380] wherein the catalyst system has at least one catalytically active component applied and / or fixed to a catalyst support, wherein the catalytically active component comprises and / or consists of at least one metal, and wherein 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, in particular spherical activated carbon,

[0381] The activated carbon (i.e. the activated carbon forming the catalyst carrier) has:

[0382] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3 / g, at least 50% of the total pore volume, in particular the total pore volume according to Gurvich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores, and

[0383] (ii) At 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = Vtotal / S BET , is at least 0.5*10 -9 m.

[0384] In this context, the present invention according to the second aspect also relates to a catalyst system, in particular a supported catalyst preferably for heterogeneous catalysis, in particular the catalyst system defined previously,

[0385] wherein the catalyst system has at least one catalytically active component applied and / or fixed to a catalyst support, wherein the catalytically active component comprises and / or consists of at least one metal, and wherein 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, in particular spherical, activated carbon,

[0386] The activated carbon (i.e. the activated carbon forming the catalyst carrier) has:

[0387] (i) Total pore volume (V total ), especially according to the total pore volume of Gurvich, which is 0.8 cm 3 / g to 3.9cm 3 / g, at least 50% of the total pore volume, in particular the total pore volume according to Gurvich, is formed by pores having a pore diameter of at least 2 nm, in particular by pores having a pore diameter of 2 nm to 500 nm, preferably by mesopores and macropores, and

[0388] (ii) At 1000m 2 / g to 3000m 2 The specific BET surface area (S BET ), but the condition is that the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (quotient; Q), in particular according to the equation Q = V total / S BET , is at least 0.5*10 -9 m; and

[0389] The catalyst system has an activity, determined as the percentage dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, in particular measured by chemical adsorption by means of the (dynamic) flow method, preferably according to DIN 66136-3:2007-01, 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%, preferably in the range of 28 to 60%; and / or wherein the catalyst system comprises catalytically active components having an average grain size, preferably determined according to DIN 66136, of at most (Angstroms), especially up to Preferred at most More preferably at most Particularly preferably at most Very particularly preferably at most Even more preferably at most and / or (Angstrom) to within the scope, especially in to within the range of to in the range of to In the range of to In the range of to in the range of to within the range.

[0390] Similarly, according to the current aspect, the invention also relates to a catalyst system, in particular a supported catalyst preferably for heterogeneous catalysis, in particular the catalyst system defined previously,

[0391] wherein the catalyst system comprises at least one catalytically active component which is applied and / or fixed to a catalyst support, wherein the catalytically active component comprises and / or consists of at least one metal, and wherein 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, and

[0392] The catalyst system has an activity, determined as the percentage dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, in particular measured by chemical adsorption via the (dynamic) flow method, preferably according to DIN 66136-3:2007-01, 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%, preferably in the range of 28 to 60%; and / or wherein the catalyst system comprises catalytically active components having an average grain size, preferably determined according to DIN 66136, of at most (Angstroms), especially up to Preferred at most More preferably at most Particularly preferably at most Very particularly preferably at most Even more preferably at most and / or (Angstrom) to within the scope, especially in to in the range of to in the range of to In the range of to In the range of to in the range of to within the range.

[0393] The catalyst system according to the invention is therefore characterized by a defined percentage dispersion and a defined average crystallite size of the essential catalytically active components, resulting in overall excellent catalytic performance. In addition, the use of a special activated carbon as catalyst support and the use of a defined pore system improve the transport properties of the reactants and the products of the catalytic reaction, resulting in an overall very efficient catalyst system, also involving the simultaneous provision of high conversions and high space / time yields when used in heterogeneous catalysis.

[0394] According to the invention, it is provided in particular that the catalyst system according to the invention has an activity, determined as the percentage dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, in particular measured by chemical adsorption via a (dynamic) flow method, preferably according to DIN 66136-3:2007-01, which is at least 15%, in particular at least 20%, preferably at least 25%, preferably at least 28%, and / or in a range from 15 to 90%, in particular in a range from 20 to 80%, preferably in a range from 25 to 70%, preferably in a range from 28 to 60%.

[0395] Furthermore, according to the invention, it is provided in particular that the catalyst system comprises a catalytically active component, in particular a metal of the catalytically active component, having an average grain size, preferably determined in accordance with DIN 66136, of at most (Angstroms), especially up to Preferred at most Preferred at most Particularly preferably at most Very particularly preferably at most Still more preferably at most and / or (Angstrom) to within the scope, especially in to In the range of to In the range of to In the range of to In the range of to in the range of to within the range.

[0396] Furthermore, the catalyst system according to the invention has a defined amount of catalytically active components, so that the catalytic activity can also be specified from this point of view. In particular, a high overall catalytic activity and at the same time good accessibility of the catalytically active components can also be ensured on this basis.

[0397] Thus, according to the invention, it can be provided that the catalyst system comprises the catalytically active component in an amount of at least 0.05 wt.-%, calculated as metal and based on the total weight of the catalyst system, in particular at least 0.1 wt.-%, preferably at least 0.2 wt.-%, more preferably at least 0.5 wt.-%, particularly preferably at least 0.6 wt.-%, most preferably at least 1 wt.-%, further preferably at least 1.5 wt.-%.

[0398] In particular, the catalyst system may comprise not more than 25 wt.-%, in particular not more than 20 wt.-%, preferably not more than 15 wt.-%, preferably not more than 10 wt.-%, more preferably not more than 8 wt.-%, most preferably not more than 7 wt.-% of catalytically active components, calculated as metal and based on the total weight of the catalyst system.

[0399] Therefore, according to the present invention as a whole, it can be provided that the catalyst system contains a catalytically active component in an amount in the range of 0.05 wt% to 25 wt%, in particular in the range of 0.1 wt% to 25 wt%, preferably in the range of 0.2 wt% to 20 wt%, more preferably in the range of 0.5 wt% to 15 wt%, particularly preferably in the range of 0.6 wt% to 10 wt%, most preferably in the range of 1 wt% to 8 wt%, further preferably in the range of 1.5 wt% to 7 wt%, calculated as metal and based on the total weight of the catalyst system.

[0400] Furthermore, with regard to the catalyst system according to the invention, the catalytically active component may comprise or consist of at least one metal, in particular as a metal compound, preferably in the form of an ionic metal compound, and / or in particular in elemental form.

[0401] In particular, the catalytically active component may have at least one metal in a positive oxidation state, in particular at least one metal cation, in particular the oxidation state of the metal is in the range of +I to +VII, in particular in the range of +I to +IV, preferably in the range of +I to +III, and particularly preferably +I or +II. According to the invention, it is particularly preferred that the catalytically active component comprises at least one metal in an oxidation state of zero.

[0402] In particular, the catalytically active component can comprise at least one metal from a main group or a subgroup of the periodic table or at least one lanthanide.

[0403] Furthermore, according to the invention, it can be provided that the catalytically active component comprises at least one metal selected from the group consisting of elements of main group IV or subgroups I, II, III, IV, V, VI, VII and VIII of the periodic table, in particular from the group consisting of elements of main group IV or subgroups I and II of the periodic table.

[0404] In this case, it is preferred according to the invention 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 Fe, Bi, V, Cu, Pb, Zn, Ag, Sn, Pd, Pt, Ru and Ni, preferably Fe, Bi, V, Cu, Pt, Ru and Pb, preferably Pd, Pt and Ru, particularly preferably Pd and Pt. The abovementioned metals can provide particularly high catalytic activity.

[0405] With regard to the catalyst system according to the invention, it is also characterized in particular in such a way that both the outer surface and the inner surface, in particular the micropores, mesopores and / or macropores, of the activated carbon are equipped with catalytically active components.

[0406] As mentioned above, it is particularly conceivable in the context of the present invention that the catalyst system has an activity, which is determined as the percentage dispersion of the catalytically active component, in particular the metal of the catalytically active component, on the catalyst support, in particular measured by chemical adsorption via a (dynamic) flow method, preferably according to DIN 66136-3:2007-01, which is 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%, preferably in the range of 28 to 60%.

[0407] According to the invention, it can be provided in particular that the catalyst system comprises a catalytically active component having an average crystallite size, preferably determined in accordance with DIN 66136, of at most (Angstroms), especially up to Preferred at most Preferred at most Particularly preferably at most Very preferred up to Even more preferably at most and / or (Angstrom) to within the scope, especially in to In the range of to in the range of to In the range of to In the range of to in the range of to within the range.

[0408] According to the invention, it can be provided in particular that the activated carbon (i.e. the activated carbon forming the catalyst support) is based on activated carbon which has been oxidized, in particular surface-oxidized, before the application and / or fixation of the catalytically active components and which has been reduced, in particular reduced on its surface, after the application and / or fixation of the catalytically active components. As a result, a particularly good provision of the catalytically active components is achieved for the catalyst system according to the invention, as described above. In particular, a correspondingly good dispersion and grain size are achieved here, so that such activated carbon is reflected in the improved properties of the resulting product in the form of the catalyst system according to the invention. As also described above, the reduction carried out can also reduce the content of oxygen-containing functional groups and the hydrophilicity of the activated carbon, which is also particularly advantageous for the transport properties of reactants or products in the activated carbon system as catalyst support.

[0409] Generally, according to the present invention, it can further be provided that the activated carbon (i.e. the activated carbon forming the catalyst support) is based on activated carbon, which can be obtained as follows: carbonization and subsequent activation of a starting material based on an organic polymer, followed by oxidation (treatment), which occurs before the application and / or immobilization of the catalytically active components, and subsequent reduction (treatment), which occurs after the application or immobilization of the catalytically active components.

[0410] In particular, the activated carbon, i.e. the activated carbon forming the catalyst support, can be based on activated carbon which is obtainable by carbonization of an organic polymer-based starting material and subsequent activation, or it is in the form of a polymer-based, preferably spherical (pellet-shaped) activated carbon (PBSAC or polymer-based spherical activated carbon).

[0411] Such activated carbons have particularly defined properties in relation to the pore system. In addition, these are activated carbons with high mechanical stability, which is associated, for example, with high abrasion resistance and the like.

[0412] Generally, the activated carbon may be an activated carbon based on the aforementioned starting material (see also patent claim 21). In particular, the activated carbon may be an activated carbon that is returned to or based on the activated carbon obtained according to the aforementioned manufacturing method (see patent claims 22-25 and 30-34).

[0413] Furthermore, the catalyst system may in particular be a surface-reduced catalyst system.

[0414] Further properties of the activated carbon constituting the catalyst support of the catalyst system according to the present invention are as follows:

[0415] In particular, activated carbon can have a defined total pore volume:

[0416] - Thus, the activated carbon (ie the activated carbon forming the catalyst support) can have a total pore volume (V total ), especially according to Gurvich's total pore volume of 0.9 cm 3 / g to 3.4cm 3 / g range, especially in the range of 1cm 3 / g to 2.9cm 3 / g, preferably within the range of 1.1 cm 3 / g to 2.4cm 3 / g, preferably within 1.2 cm 3 / g to 1.9cm 3 / g, particularly preferably within the range of 1.5 cm 3 / g to 1.9cm 3 / g range.

[0417] - In addition, in this case it can be expressed in that 50% to 90%, in particular 52.5% to 87.5%, preferably 55% to 85%, preferably 57.5% to 82.5%, particularly preferably 60% to 80% of the total pore volume of the activated carbon (i.e. the activated carbon forming the catalyst support), in particular 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, i.e. the activated carbon forming the catalytic 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 of 2 nm to 500 nm, preferably by mesopores and macropores.

[0418] - In addition, the activated carbon (ie the activated carbon forming the catalyst support) can have a total pore volume (V total ), especially according to Gurvich's total pore volume of 0.8 cm 3 / g to 3.9cm 3 / g, especially at 0.9cm 3 / g to 3.4cm 3 / g, preferably within 1 cm 3 / g to 2.9cm 3 / g, preferably within 1.1 cm 3 / g to 2.4cm 3 / g, particularly preferably within the range of 1.2 cm 3 / g to 1.9cm 3 / g, most preferably within 1.5 cm 3 / g to 1.9cm 3 / g range, wherein 50% to 90%, in particular 52.5% to 87.5%, preferably 55% to 85%, preferably 57.5% to 82.5%, particularly preferably 60% to 80% 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 mesopores and macropores.

[0419] In addition, the activated carbon constituting the catalyst support may also have the following properties:

[0420] - In particular, the activated carbon (ie, the activated carbon forming the catalyst support) may have a specific BET surface area (S BET ) at 1100m 2 / g to 2600m 2 / g range, especially at 1200m 2 / g to 2400m 2 / g, preferably within the range of 1300 m 2 / g to 2200m 2 / g, preferably within the range of 1350 m 2 / g to 1950m 2 / g, particularly preferably within the range of 1375 m 2 / g to 1900m 2 / g within the range

[0421] - In addition, for activated carbon (i.e. activated carbon forming a catalyst support), the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (Q), especially according to the equation Q = V total / S BET , can be 0.5*10 -9 m to 1.9*10 -9 m, especially in the range of 0.55*10 -9 m to 1.9*10 -9 m, preferably in the range of 0.6*10 -9 m to 1.8*10 -9 m, preferably within the range of 0.65*10 -9 m to 1.7*10 -9 m, particularly preferably within the range of 0.65*10 -9 m to 1.6*10 -9 m, most preferably 0.7*10 -9 m to 1.5*10 -9 m, more preferably 0.75*10 -9m to 1.4*10 -9 m, and more preferably in the range of 0.8*10 -9 m to 1.3*10 -9 within the range of m.

[0422] - In addition, the activated carbon (ie, the activated carbon forming the catalyst support) may have a specific BET surface area (S BET ) at 1000m 2 / g to 3000m 2 / g range, especially at 1100m 2 / g to 2600m 2 / g, preferably within the range of 1200 m 2 / g to 2400m 2 / g, preferably within the range of 1300 m 2 / g to 2200m 2 / g, particularly preferably 1350 m 2 / g to 1950m 2 / g, most preferably 1375m 2 / g to 1900m 2 / g, where the total pore volume (V total ), especially according to the total pore volume and specific BET surface area (S BET ) ratio (Q), in particular according to the equation Q = V total / S BET , in 0.5*10 -9 m to 1.9*10 -9 m, especially in the range of 0.55*10 -9 m to 1.9*10 -9 m, preferably in the range of 0.6*10 -9 m to 1.8*10 -9 m, preferably within the range of 0.65*10 -9 m to 1.7*10 -9 m, particularly preferably within the range of 0.65*10 -9 m to 1.6*10 -9 m, most preferably 0.7*10 -9 m to 1.5*10 -9 m, more preferably 0.75*10 -9 m to 1.4*10 -9 m, more preferably 0.8*10 -9 m to 1.3*10 -9 within the range of m.

[0423] In addition, activated carbon used as a catalyst support may also have the following properties:

[0424] - Thus, the activated carbon (ie the activated carbon forming the catalyst support) may have an average pore size of at least 15 nm and / or an average pore size of at most 100 nm.

[0425] - In this regard, the activated carbon (i.e., the activated carbon forming the catalyst support) may have 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, preferably in the range of 18 nm to 80 nm, more preferably in the range of 20 nm to 70 nm, most preferably in the range of 22 nm to 60 nm, further preferably in the range of 25 nm to 50 nm.

[0426] - In the context of the present invention, the activated carbon (ie the activated carbon forming the catalyst support) may be spherical. In particular, the activated carbon may be in the form of spherical activated carbon.

[0427] Furthermore, the activated carbon (i.e. the activated carbon forming the catalyst support) 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, preferably in the range of 100 μm to 400 μm, particularly preferably in the range of 150 μm to 375 μm, most preferably in the range of 175 μm to 250 μm. In particular, it can be provided herein that at least 80 wt.-%, in particular at least 90 wt.-%, preferably at least 95 wt.-% of the activated carbon particles have a particle size, in particular a particle diameter, in the abovementioned range.

[0428] - In particular, the activated carbon (i.e. the activated carbon forming the catalyst support) may have 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, preferably in the range of 110 μm to 375 μm, more preferably in the range of 175 μm to 350 μm, most preferably in the range of 185 μm to 225 μm.

[0429] - In addition, the activated carbon (i.e. the activated carbon forming the catalyst support) can have a ball-on-disc 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%, further preferably at least 99.8%.

[0430] - In addition, the activated carbon (i.e. the activated carbon forming the catalyst support) can have a compression and / or burst strength (weight load capacity) 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 per activated carbon particle, in particular per activated carbon ball.

[0431] - In particular, the activated carbon (i.e. the activated carbon forming the catalyst support) can have a compression and / or burst strength (weight load capacity) in the range of 5 to 50 Newtons per activated carbon particle, in particular per activated carbon ball, in particular 10 to 45 Newtons, preferably 15 to 40 Newtons, preferably 17.5 to 35 Newtons.

[0432] - Similarly, the activated carbon (i.e., the activated carbon forming the catalyst support) may have a shake or packing density in the range of 100 g / L to 1500 g / L, in particular in the range of 125 g / L to 1000 g / L, preferably in the range of 150 g / L to 800 g / L, preferably in the range of 200 g / L to 600 g / L, more 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, further preferably in the range of 255 g / L to 395 g / L.

[0433] - In addition, the activated carbon (i.e., the activated carbon forming the catalyst support) may have a bulk density in the range of 150 g / L to 1000 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, preferably in the range of 300 mg / L to 550 g / L.

[0434] In addition, the activated carbon constituting the catalyst carrier may have the following properties:

[0435] -Thus, the activated carbon (i.e. the activated carbon forming the catalyst support) can have a butane adsorption of at least 35%, in particular at least 40%, preferably at least 45%, preferably at least 47.5%, and / or wherein 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%, preferably in the range of 47.5% to 75%.

[0436] - Furthermore, the activated carbon (i.e. the activated carbon forming the catalyst support) may have an iodine value of at least 1250 mg / g, in particular at least 1300 mg / g, preferably at least 1400 mg / g, more preferably at least 1425 mg / g, and / or wherein the activated carbon has an iodine value in the range of 1250 mg / g to 2100 mg / g, in particular in the range of 1300 mg / g to 2000 mg / g, preferably in the range of 1400 mg / g to 1900 mg / g, preferably in the range of 1425 mg / g to 1850 mg / g.

[0437] - In addition, the activated carbon (i.e. the activated carbon forming the catalyst support) can have 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 wherein the activated carbon 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, preferably in the range of 19.5 mL to 47.5 mL.

[0438] - Furthermore, the activated carbon (i.e. the activated carbon forming the catalyst support) may have a molasses value of at least 255, in particular at least 310, preferably at least 375, preferably at least 510, and / or wherein the activated carbon has a molasses value in the range of 255 to 1500, in particular in the range of 310 to 1400, preferably in the range of 375 to 1300, preferably in the range of 510 to 1250.

[0439] Furthermore, the activated carbon (ie the activated carbon forming the catalyst support) may have 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.

[0440] - Furthermore, the activated carbon may have 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 20 mL to 47.5 mL.

[0441] - In addition, the activated carbon (ie, the activated carbon forming the catalyst support) may have a weight-based adsorption N measured at a partial pressure p / p0 of 0.25. 2 Volume V ads(wt) , which is at least 250cm 3 / g, especially at least 300cm 3 / g, preferably at least 350cm 3 / g, preferably at least 375cm 3 / g. In this regard, the activated carbon may have a weight adsorbed N measured at a partial pressure p / p0 of 0.25. 2 Volume Vads(wt) , which is at 250cm 3 / g to 850cm 3 / g range, especially at 300cm 3 / g to 700cm 3 / g, preferably within the range of 350cm 3 / g to 650cm 3 / g range, preferably at 375cm 3 / g to 625cm 3 / g.

[0442] Similarly, activated carbon (ie, activated carbon forming a catalyst support) may have an adsorption capacity based on volume measured at a partial pressure p / p0 of 0.25. 2 Volume V ads(vol.) , which is at least 50cm 3 / cm 3 , especially at least 100cm 3 / cm 3 , preferably at least 110cm 3 / cm 3 In this case, the activated carbon may have a volume-based adsorption N measured at a partial pressure p / p0 of 0.25. 2 Volume V ads(vol.) , which is 50cm 3 / cm 3 Up to 300cm 3 / cm 3 range, especially within 80cm 3 / cm 3 Up to 275cm 3 / cm 3 within the range, preferably within 90cm 3 / cm 3 Up to 250cm 3 / cm 3 within the range, preferably within 95cm 3 / cm 3 Up to 225cm 3 / cm 3 within the range.

[0443] - In addition, the activated carbon (ie, the activated carbon forming the catalyst support) may have a weight-based adsorption N measured at a partial pressure p / p0 of 0.995. 2 Volume V ads(wt.) , which is at least 300cm 3 / g, especially at least 450cm 3 / g, preferably at least 475cm 3 / g. In this case, the activated carbon may have a weight adsorption N measured at a partial pressure p / p0 of 0.995. 2 Volume V ads(wt.) , which is at 300cm 3 / g to 2300cm 3 / g range, especially at 400cm 3 / g to 2200cm 3 / g, preferably within the range of 450cm 3 / g to 2100cm 3 / g, preferably at 475cm 3 / g to 2100cm 3 / g range.

[0444] In particular, the activated carbon (ie the activated carbon forming the catalyst support) may have a volume-dependent adsorption N measured at a partial pressure p / p0 of 0.995. 2 Volume V ads(vol.) , which is at least 200cm 3 / cm 3 , especially at least 250cm 3 / cm 3 , preferably at least 275cm 3 / cm 3 , preferably at least 295cm 3 / cm 3 In this case, the activated carbon may have a volume-based adsorption N measured at a partial pressure p / p0 of 0.995. 2 Volume Vads. (vol.), which is at 200cm 3 / cm 3 Up to 500cm 3 / cm 3 In the range of 250cm, especially 3 / cm 3 Up to 400cm 3 / cm 3 within the range of 275 cm 3 / cm 3 Up to 380cm 3 / cm 3 within the range of 295 cm 3 / cm 3 Up to 375cm 3 / cm 3 within the range.

[0445] - With regard to the activated carbon further used according to the present invention, the activated carbon (i.e. the activated carbon forming the catalyst support) may have an open porosity fractal dimension 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 wherein the activated carbon has an open porosity fractal dimension of at least 2.7, in particular at least 2.8, preferably at least 2.85, preferably at least 2.9.

[0446] Within the scope of the present invention, as mentioned above, an effective catalyst system is generally provided, which has an overall improved catalytic performance. From this point of view, too, the catalyst system according to the invention leads to a significant reduction in the method time as the basis for catalysis, in particular for discontinuous catalytic methods, with correspondingly high downtimes or operating times, which is also due to the excellent mechanical stability of the catalyst system according to the invention. In addition, the use of the catalyst system according to the invention is closely linked to simplified batching and significantly reduced cleaning workload of the basic equipment, minimized material losses and generally simplified handling. In addition, the catalyst system of the present invention can be reused or recycled in a simple manner after the catalyst is appropriately reactivated. In particular, the defined pore system of the activated carbon used as a support material according to the invention leads to a significant increase in activity, which involves both an improvement in the transport method of the reactants or products and the equipment of the catalytically active components. In general, the performance of the catalyst system according to the invention is also very important against the background of intensive catalyst costs, because the catalyst system according to the invention can be accompanied by considerable cost savings due to its performance.

[0447] In addition to use in discontinuous processes, the catalyst system according to the invention is also very suitable for continuous catalytic applications, whereby the catalyst system according to the invention can, for example, be filled into a corresponding reaction vessel or reactor and a medium containing the reactants or the reactants can flow continuously through it, so that low pressure losses at correspondingly high flow rates can be achieved within the scope of use.

[0448] The catalyst system of the present invention has a wide range of applications: besides its use in catalysis, in particular on a (large) industrial scale, the catalyst system of the present invention is also suitable for adsorption applications, for example for the removal of toxic substances such as pollutants or toxins, in particular due to its combined properties of chemical adsorption on the one hand and physical adsorption on the other hand.

[0449] Due to the special spherical shape, the outstanding mechanical properties of the base activated carbon material in the form of PBSAC and the currently adjustable setting of the porosity (especially with regard to providing high meso- and macroporosity), the catalyst system according to the invention is also of high importance, in particular for continuous catalysis (i.e. for continuous reaction control in catalysis).

[0450] The catalyst system according to the invention is in particular a supported noble metal catalyst or metal catalyst supported by activated carbon. As mentioned above, a spherical high-performance adsorbent, in particular a polymer-based spherical adsorbent, which can usually be composed of more than 99 wt% of carbon, is used as its basis, so that activated carbon is used as a catalyst support. As described above in relation to the method of the invention, the catalyst support is pretreated by an oxidation method (before being equipped with the catalytically active component). In this method, the proportion of volatile components can vary in the range of 0.1 wt% to 15 wt%. With regard to the above-mentioned method according to the invention, in another method step, the catalyst support can be loaded, in particular by various impregnation techniques, preferably with a noble metal as the catalytically active component. Therefore, the impregnation level can vary, for example, in the range of 0.05 wt% to 20 wt%. After the catalytically active component or the noble metal ions associated therewith are fixed on the surface of the catalyst support, the metal ions can be converted in a reduction step. The reduction can also lead to the surface reduction of the activated carbon, in particular in the liquid phase or the gas phase. On this basis, the above-mentioned catalyst system according to the invention can be obtained.

[0451] With regard to the embodiments of the catalyst system according to the present aspect, reference may also be made to the explanations regarding the other aspects of the present invention, which explanations apply accordingly.

[0452] According to the third aspect of the present invention, another object of the present invention is to further provide the use of the catalyst system of the present invention:

[0453] Thus, the catalyst system according to the invention can be used in particular as catalyst or catalyst support. In addition, the catalyst system according to the invention can be used in particular for chemical catalysis, in particular for heterogeneous catalysis, and / or for discontinuous catalysis or for continuous catalysis (i.e. continuous reaction control in catalysis).

[0454] Similarly, the catalyst system according to the invention can be used for catalytic chemical processes and reactions, in particular preferably hydrogenation reactions or oligomerization and polymerization reactions of olefins. Preferably, the catalyst system according to the invention can be used for catalytic hydrogenation reactions. In particular, the catalyst system according to the invention can be used for the hydrogenation of various functional groups. For example, the catalyst system according to the invention can be used for the catalytic conversion or conversion of a nitro group to an amine group. In addition, the catalyst system according to the invention can be used for deprotection.

[0455] In addition, the catalyst system according to the present invention can also be used to produce filters and filter materials, in particular for removing pollutants, odors and toxins from air and / or air flows, such as NBC protective mask filters, odor filters, surface filters, air filters, in particular room air purification filters, adsorbable carrier structures and filters for the medical field.

[0456] Furthermore, the catalyst system according to the invention can be used as an adsorption store for gases or liquids.

[0457] Similarly, the catalyst system may be used in a gas sensor, as a gas sensor, or in a fuel cell.

[0458] Furthermore, the catalyst system according to the invention can be used in adsorption applications, in particular adsorption or chemisorption applications, preferably chemisorption applications, in particular as preferably reactive and / or catalytic adsorbent.

[0459] Furthermore, the catalyst system according to the invention can be used for gas purification and / or gas treatment.

[0460] Furthermore, the catalyst system according to the invention can be used for removing pollutants, in particular gaseous pollutants, or substances or gases which are harmful to the environment, health or toxic.

[0461] Furthermore, the catalyst system according to the invention can be used for producing and / or providing clean room atmospheres, in particular for the electrical industry, in particular for semiconductor or chip production.

[0462] In addition, according to the fourth aspect of the present invention, the present invention relates to protective materials, in particular protective materials for civilian or military use, in particular protective clothing, such as protective suits, protective gloves, protective shoes, protective socks, protective hats and protective covers, preferably all the above-mentioned protective materials for NBC produced using the catalyst system of the present invention or having the catalyst system of the present invention.

[0463] Furthermore, according to a fifth aspect of the present invention, another object of the present invention is filters and filter materials, in particular for removing various pollutants, odors and toxic substances from air or air flows, such as NBC protective mask filters, odor filters, surface filters, air filters, in particular room air purification filters, carrier structures and filters with adsorptive and / or chemical adsorption capacities for use in the medical field, which are produced using a catalyst system as previously defined according to the present invention or include a catalyst system as previously defined according to the present invention.

[0464] With regard to the filters and filter materials according to the invention, the catalyst system used in this context may be self-supported or may be in the form of bulk material, in particular loose bulk material. Furthermore, the catalyst system may be applied to a support material.

[0465] With regard to the explanations relating to the third to fifth aspects of the present invention, reference may also be made in this respect to the further explanations according to the first and second aspects of the present invention, and the explanations relating thereto apply accordingly.

[0466] The invention is also described with reference to further figures and / or diagrams, whereby the explanations in this respect apply to all aspects according to the invention and whereby the explanations in this respect are in no way limiting. With respect to the figures or diagrams, reference is also made to the following explanations in an embodiment example. BRIEF DESCRIPTION OF THE DRAWINGS

[0467] The diagram shows:

[0468] Figure 1 It is the nitrogen isotherm diagram of various catalyst supports or activated carbons used in this context to determine the porosity;

[0469] Figure 2 Mercury intrusion curves for various catalyst supports or activated carbons used in this context for further determination of porosity;

[0470] Figure 3 Graphical representation of the values ​​of dispersion and crystallite size of the catalytically active component or the metal (5 wt. % palladium catalyst) determined for different catalyst systems;

[0471] Figure 4 Schematically illustrated is the kinetics of heterogeneous catalysis, which is based on the following sub-steps: a first step (1) of the diffusion of the reactant (E) to the surface of the catalyst (K) through a fixed boundary layer (G); a second step (2) of the diffusion of the reactant (E) into the pores of the catalyst (K) to the catalytically active centers or to the catalytically active components; a third step (3) of the adsorption of the reactant (E) on the active centers; a fourth step (4) of the reaction with the reactant (E) on the active centers to obtain its product (P); a fifth step (5) of desorbing the product (P) from the active centers; a sixth step (6) of the diffusion of the product (P) through the pore system of the catalyst (K) and a seventh step (7) of the diffusion of the product (P) through the boundary layer (G) to the external area and the removal of the product (P);

[0472] Figure 5 Schematically showing a process sequence according to one embodiment of the present invention [wherein EP=precious metal precursor, TR=PBSAC support, TV=support pretreatment (e.g., oxidation with mineral acid 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];

[0473] Figure 6 A device based on a fixed bed reactor for heterogeneous catalysis, in particular hydrogenation, is schematically shown;

[0474] Fig. 7A is the reaction of hydrogenating cinnamic acid using the catalyst system of the present invention;

[0475] Figure 7B The time course of the 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) is shown;

[0476] Figure 7C The time course of the catalytic conversion (hydrogenation) of cinnamic acid by various catalyst systems using activated carbon as catalyst support, wherein the relevant activated carbon has a high proportion of micropores in the total pore volume (microporous activated carbon).

[0477] Further embodiments, modifications and variations of the present invention, as well as advantages, will be apparent and attainable to those skilled in the art from a reading of the specification without departing from the scope of the present invention. DETAILED DESCRIPTION

[0478] The following embodiments are merely illustrative of the present invention, but the present invention is not limited thereto.

[0479] Example:

[0480] 1. Introduction:

[0481] The use of special polymer-based spherical activated carbons (spherical or spherical PBSAC) with a defined porosity, in particular with respect to high meso- or macro-porosity, and at the same time with a defined micropore content as catalyst support material offers the advantage in the context of the concept according to the invention that an optimal transport method for the reactants / products on the one hand and an optimal equipment of the activated carbon with catalytically active components on the other hand are possible, so that the catalyst system according to the invention has an overall high catalytic activity, in particular accompanied by high conversions and high space / time yields. In addition, due to the preferred spherical shape, the lowest pressure losses can be achieved compared to adsorbents of the same size but different shapes. In addition, due to the low dust content and high mechanical load capacity of the PBSAC, the possibility of emitting metal-laden dust or fragments in the product flow during fixed bed application is minimized.

[0482] 2. Production of catalyst carrier

[0483] a) Highly microporous catalyst supports (not according to the invention)

[0484] Polymer-based spherical activated carbon (PBSAC) is produced in a three-step batch process. The process comprises a sulfonation step for thermal stabilization of the polymer raw material used, a carbonization step for removal of volatile components and an activation step for forming an internal pore system using water as an oxidant. A rotary tube reactor is used for the necessary process steps. The reactor is indirectly electrically heated in a rotary kiln.

[0485] A cross-linked styrene-divinylbenzene polymer (H + The raw material (in the form of a gel type) was used as the raw material or starting material for the production of highly microporous PBSAC (Lewapol D60). It is polystyrene containing 4 wt% of divinylbenzene as a crosslinker. The polymer raw material already has a spherical morphology, which is transferred to the resulting PBSAC. The raw material shows a particle diameter distribution in the range of 0.08 mm to 0.7 mm.

[0486] Sulfonation represents a step to stabilize the polymer for subsequent carbonization. To this end, oleum (sulfuric acid fuming, 25% free SO 3 A mixture of 2:1 mol % sulfonate and sulfuric acid (96 vol %) was added to polystyrene at room temperature and heated to a sulfonation temperature of 423 K. The mixture was then reacted with sulfuric acid.

[0487] In the second step of activated carbon production, i.e., carbonization, volatile components are driven off in the temperature range of 423 K to 1223 K. The carbonization can be divided into two steps. In the temperature range up to 823 K, in addition to other volatile components, in particular water and sulfur compounds are driven off. In the temperature range up to 1223 K, mainly hydrocarbons and hydrogen are driven off (390 min activation time). The particle shape and particle diameter do not change after carbonization and correspond to those of the resulting PBSAC.

[0488] In the third step of activated carbon production, namely activation, the carbide is activated at about 1223 K in a water vapor atmosphere (120 kg of liquid water and two normal cubic meters of nitrogen per hour).

[0489] b) Neutralization of the macroporous catalyst support (according to the invention)

[0490] To produce medium and macroporous PBSAC, the method steps described in Section 2.a) are followed. Similarly, Lewapol D60 from Lanxess is used as a raw material or starting material for the production of medium / macroporous PBSAC. However, the sulfonation of the crosslinked styrene-divinylbenzene polymer is carried out only with sulfuric acid (96% by volume). The ratio of polymer to sulfonating agent remains constant. The catalyst support is activated for 450 minutes. The resulting PBSAC exhibits an increased mesoporous content of greater than 25%. Structural data can be obtained from Table 1.

[0491] c) Neutralized macroporous catalyst supports based on macroporous sulfonated ion exchange resins with high macroporosity (according to the invention)

[0492] For the production of PBSAC based on macroporous ion exchange resins, the process steps described in section 2.a) were followed. Sulfonated cross-linked styrene-divinylbenzene polymer (HSB) from Finex Oy + Form) is used as a raw material or starting material for the production of PBSAC based on a macroporous ion exchanger (Finex CS16GC). Since the acidic macroporous ion exchanger is already protected, the sulfonation step (150 minutes activation time) can be omitted. The resulting PBSAC exhibits a high mesopore content and a determined proportion of macropores. The structural data can be obtained from Table 1. Alternatively, the corresponding unsulfonated raw material or starting material can be assumed. In this case, for example, a crosslinked styrene-divinylbenzene polymer (Finex PS08G) from Finex Oy can be used. The sulfonation can be carried out as described in Section 2.a).

[0493] 3. Characterization of catalyst supports or catalyst systems

[0494] a) Nitrogen isotherm used to determine structural data in the micropore region.

[0495] In order to determine the structural data of the catalyst support, nitrogen isotherms were recorded on various catalyst supports. This was done with Quantachrome's Quadrasorb. The Brunauer-Emmett-Teller (BET) mathematical model was used to determine the specific internal surface area. The total pore volume was calculated using the Gurvich rule, and the micropore volume was determined using the carbon black method.

[0496] For the measured production, the catalyst support was pretreated at 200° C. under vacuum, in particular in order to remove any adsorbed molecules.

[0497] b) Structural data of mercury intrusion to determine the mesoporous and macroporous regions.

[0498] The samples were dried in an oven at 150°C for 2 hours and then measured on a Quantachrome Poremaster-60GT. To convert the pressure to pore size, the literature value of the contact angle of mercury on carbon was calculated (155°).

[0499] c) The elemental composition of the catalyst support was determined by XPS.

[0500] The samples were analyzed by photoelectron spectroscopy (ESCA / XPS) without pretreatment. For XPS analysis, a Thermo VG Scientific model K-Alpha instrument was used for measurement. Monochromatic AlKα X-rays were used for excitation (typically ~75W, 400μm spot size). Transmission functions and energy positions were determined for copper, silver and gold reference samples according to ISO 15472:2001 and ISO 21270:2004. The following settings were used for spectral measurements: measured spectrum with an energy of 80eV, high-resolution spectrum at 30eV. Assuming that the analyzed volume is uniform, the quantitative information of the surface composition is calculated using the Scofield factor in the survey measurement. The error can be estimated to be about 10%.

[0501] d) Determination of the dispersion and size of active sites by CO chemisorption (determination of the dispersion and grain size of specific metal surfaces or catalytically active components)

[0502] Determination of monolayer capacity, dispersion, active surface according to DIN 66136-1, DIN 66136-3: Flow method (dynamic), measuring gas, e.g. H 2 ,CO,CO 2 ; Planned experimental procedure: H 2 Treat at 10K / min to 80℃, isotherm for 4 hours; perform CO titration at 50℃, then use 5% H 2 / Ar, the TPR was raised to 250°C at 5K / min; finally, CO titration was performed at 50°C.

[0503] In particular, you can follow these steps:

[0504] Standards based on: DIN 66136-1 (basic) and DIN 66136-2 (volume method)

[0505] The following steps are recommended or performed to produce the sample and restore the sample surface:

[0506] (i) evacuate at 100°C for 30 minutes;

[0507] (ii) oxygen gas was flowed at 100°C for 5 minutes;

[0508] (iii) oxygen flow, the temperature increased to 350°C at a rate of 10°C / min;

[0509] (iv) oxygen flowing at 350°C for 30 minutes;

[0510] (v) evacuation at 350°C for 15 minutes;

[0511] (vi) evacuation at 100°C for 15 minutes;

[0512] (vii) hydrogen gas was flowed at 100° C. for 5 minutes;

[0513] (viii) hydrogen gas was flowed and the temperature was increased to 350° C. at a rate of 10° C. / min;

[0514] (ix) hydrogen gas was flowed at 350° C. for 120 minutes;

[0515] (x) evacuation at 350°C for 30 minutes;

[0516] (xi) Evacuate at 100°C for 15 minutes.

[0517] Subsequently, the CO isotherm at 40 °C was measured using a static volumetric method to determine the active metal surface or metal dispersion.

[0518] The first isotherm measured after step (xi) may represent a superposition of strongly and weakly chemisorbed gas components (combined chemisorption). If it is necessary to distinguish between these two components, the following procedure is recommended or followed: After the last isotherm point has been measured, the measuring cell can be emptied for 60 minutes at the analysis temperature (40°C). This removes the weakly bound part, while the strongly chemisorbed part remains on the sample surface. The isotherm measurement is then repeated and the weakly chemisorbed part (weak chemisorption) can be determined. The difference between the two isotherms gives the amount of strongly chemisorbed CO.

[0519] Assuming that one CO molecule is chemisorbed onto exactly one surface-exposed metal atom (palladium atom) of the catalytically active component (stoichiometry = 1), the number of surface-exposed palladium atoms or metal atoms can be inferred from the amount of chemisorbed CO.

[0520] This provides an indication of the size of the active metal surface area in m 2 Each g(m 2 / g)(sample mass).

[0521] Using the metal loading of the sample, i.e. the mass of palladium in g / g sample, further characteristics or properties can be calculated:

[0522] - Active metal surface, in m 2 / g(metal);

[0523] - the dispersion of the metal in %; and

[0524] - Average grain diameter of metal clusters.

[0525] The same procedure can be used for other metals.

[0526] 4. Performance of catalyst carrier

[0527] The properties of the individual catalyst supports differ to the greatest extent in their structural features. In order to determine the structural data, the nitrogen isotherms of the individual PBSACs were recorded. The results obtained in this regard are shown in Table 1. Figure 1 , wherein in the legend the corresponding number "200 μm" refers to the average particle diameter of the activated carbon investigated in each case. Figure 1 The diagram shows the nitrogen adsorption V of the investigated activated carbons as a function of the relative pressure p / p0 ads .

[0528] Highly microporous materials are characterized by a sharp rise in isotherms at low relative pressures, which is associated with a high volumetric nitrogen uptake. Figure 1 As shown, the isotherms are almost flat in the further relative pressure range and do not show a clear hysteresis loop. The isotherms of the material "200 μm_microporous I" (not a catalyst support or activated carbon A1 according to the invention) show such a process, so that the material can be described as strongly microporous. In addition, the proportion of micropore volume to total volume is very high, at 89%.

[0529] like Figure 1 As shown, the isotherm of the material "200 μm_Medium / Large I" (catalyst support or activated carbon B1 according to the invention) shows a strong increase at a relative pressure of 0.75. In addition, the isotherm exhibits a clear hysteresis loop. These two properties and a micropore content of only 61% demonstrate a high content of meso or macropores.

[0530] When using macroporous ion exchange resins to produce PBSAC, part of the macroporosity of the polymer is transferred to the resulting activated carbon. This can be seen from the nitrogen isotherm of the material "200 μm_Medium / Large II" (according to the invention, catalyst support or activated carbon B2); only at a relative pressure of 0.85 does the isotherm increase sharply, and therefore the nitrogen uptake also increases sharply ( Figure 1 ). The pronounced hysteresis loop and the micropore volume fraction of only 25% demonstrate the presence of pores larger than 2 nm, and thus the presence of mesopores and macropores.

[0531] The characterization of pores larger than 2 nm can be achieved by the intrusion of mercury. Figure 2 The mercury intrusion curve of the catalyst support is shown. Figure 2 The diagram shows the mercury intrusion dVp / dlog(dp) for the basic pore size dp of the activated carbon studied.

[0532] It is evident here that the microporous catalyst support or activated carbon A1 ("200 μm_micro I") has no pore volume above 2 nm. The meso / macroporous catalyst support or activated carbon B1 ("200 μm_medium / large I") shows 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_medium / large II") also shows a very large proportion of mesopores and a significant proportion of macropores. The structural data can be taken from Table 2.

[0533] The chemical composition and high purity of the activated carbon in the form of PBSAC were retained and were comparable in all cases. Likewise, the activated carbon in the form of PBSAC maintained a high mechanical stability, even with a high porosity and a high proportion of pores larger than 2 nm (see "200 μm_Medium / Large I" (B1) and "200 μm_Medium / Large II" (B2)). The high wear hardness of the material, which exceeded 98%, illustrates the high mechanical stability (see Table 1).

[0534] Table 1 below illustrates the corresponding properties of the investigated activated carbons or catalyst supports.

[0535] Table 1: Properties of catalyst supports.

[0536]

[0537] *A1: Not according to the present invention

[0538] **C1, C2: Commercially available coconut shell based activated carbon; (not according to the present invention).

[0539] Table 2: Structural properties (mercury intrusion, evaluation range 0.01μm to 20μm)

[0540]

[0541] 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 diameter 200 μm) and A3 (370 μm micro-III; average particle diameter 370 μm) not according to the invention, which are essentially comparable to catalyst support A1 with respect to the properties in the form of parameters listed in Tables 1 and 2. In addition, further catalyst supports or activated carbons are provided, namely catalyst supports B3 ("370 μm medium / large-III"; average particle permeability 370 μm) and B4 ("470 μm medium / large-IIII"; average particle permeability 470 μm) used according to the invention, which are essentially comparable to catalyst supports B1 and B2 with respect to the other properties in the form of parameters listed in Tables 1 and 2.

[0542] 5. Oxidation pretreatment of catalyst carrier

[0543] Oxidative pretreatment of the material in the form of a catalyst support or activated carbon is used to generate oxygen centers on the surface of the corresponding PBSAC. These subsequently interact with the metal ions of the salt solution. Due to the electrostatic interaction of the surface oxide with the metal ions, these are fixed on the surface and prefer to migrate into the pores of the PBSAC rather than remaining in the supernatant.

[0544] a) Oxygen oxidation

[0545] For the oxidation of PBSAC, synthetic air is passed through a heatable, gas-tight fused silica reactor. For surface modification, typically 250 grams of PBSAC are placed in a fused silica tube, which is installed in a furnace and connected to all gas connections. Typically, the furnace is heated to the reaction temperature with a ramp of 10 K / min. The reaction temperature is in the range of 350°C to 550°C. The reaction time varies in the range of 120 minutes to 600 minutes.

[0546] b) Oxidation using mineral acids and hydrogen peroxide

[0547] The oxidation of mineral acids is carried out by wet chemical methods. Mineral acids are mainly hydrochloric acid (HCl), nitric acid (HNO 3 ) and sulfuric acid (H 2 SO 4 ). Perchloric acid (HClO 4 ), phosphoric acid (H 3 PO 4 ) and hydrogen peroxide (H 2 O 2 ). These acids are used over the entire concentration range at temperatures between 20°C and 100°C.

[0548] Typically, 500 g of a polymer-based spherical adsorbent is stirred with 1000 g of a mineral acid for 30 to 240 minutes. Subsequently, the excess mineral acid is decanted and the oxidized alkaline adsorbent is washed with distilled water and dried.

[0549] c) Performance of the oxidized catalyst support

[0550] The surface modification does not change the structural properties, or at most only to a small extent. The properties of the oxidized catalyst supports used or analyzed according to the invention can be taken from Table 3. The mechanical stability of the oxidized catalyst supports is maintained at a very high wear hardness. The determination of the volatile components can be used to characterize the surface oxides. In this case, the material was left at 900° C. for 7 minutes and the weight loss was then determined gravimetrically according to ISO 562-1981.

[0551] However, this method still does not explain the nature of the oxygen species on the PBSAC surface. In order to determine these, the photoelectron spectra of the respective catalyst supports were recorded. From these spectra, the elemental composition can be determined. These can be obtained from Table 4. It can be seen that the measured values ​​of the volatile components are correlated with the atomic composition determined by photoelectron spectroscopy. The lowest oxygen content of 4.0 atomic % was found in the sample oxidized with hydrochloric acid (90 minutes). Oxidation of the catalyst support with 50% by volume of nitric acid resulted in the highest oxygen content on the surface, 11.8 atomic %.

[0552] Table 3: Properties of oxidized catalyst supports or activated carbons

[0553]

[0554]

[0555] Table 4: Elemental composition from summary spectra (data in atomic %)

[0556]

[0557] To characterize the oxygen species, the bound components were also determined from the high-resolution oxygen spectra. These can be obtained from Table 5. It can be seen that more than half of the oxygen species are present on the surface in the form of alcohol oxygens. About 35% to 40% of the oxygen atoms are bound on the surface in the form of carbonyl oxygens. The differently oxidized catalyst supports differ only slightly from one another in the proportions of the oxygen species.

[0558] Table 5: Binding components from high resolution oxygen spectroscopy

[0559]

[0560] O1: carbonyl oxygen (RC=O / R-CO=O*); O2: alcohol oxygen (R-OH / ROR / R-CO-O*);

[0561] O3:π-π*

[0562] 6. Impregnation of catalyst carrier

[0563] The oxidized catalyst support or activated carbon is provided with the catalytically active components or related precursors to obtain the corresponding impregnated catalyst system, as described below.

[0564] a) Pd loading of PBSAC

[0565] Water and acid solution (HCl, HNO 3 ) is placed in a round-bottom flask. Then a palladium precursor (usually H 2 PdCl 4 、Pd(NO) 32). The turbid suspension was stirred vigorously with a magnetic stirrer for at least 30 minutes until a clear brown solution was obtained. Under vigorous stirring, the oxidized catalyst support was quickly added as described above. The system was stirred at low speed (50 rpm) for 24 hours. The solution was then removed. The solids were then separated using a Büchner funnel and a suction flask. The catalyst was then rinsed extensively with ultrapure water. For drying, the material was transferred to a drying cabinet and dried at 80°C for 12 hours. The material was then dried in an oven.

[0566] b) Platinum loading on spherical adsorbents

[0567] Water and acid solution (HCl, HNO 3 ) is placed in a round-bottom flask. Then a platinum precursor (usually H 2 [PtCl 6 ]、(NH 3 ) 4 Pt(OH) 2 、Pt(NO 3 ) 2 ). The turbid suspension was stirred vigorously with a magnetic stirrer for at least 30 minutes until a clear brown solution was obtained. Under vigorous stirring, the oxidized catalyst support was quickly added. The system was stirred at a low speed (50 rpm) for 24 hours. The solution was then removed. The solids were then separated using a Büchner funnel and a suction flask. The catalyst was then rinsed extensively with ultrapure water. For drying, the material was transferred to a drying cabinet and dried at 80°C for 12 hours. The material was then dried in an oven.

[0568] 7. Reduce the catalyst to obtain the catalyst system.

[0569] The above impregnated catalyst system was treated by reduction to obtain the corresponding catalyst system as follows.

[0570] a) Gas Phase Reduction

[0571] The gas phase reduction of the catalyst material is carried out in a horizontal, heatable flow tube at a temperature of 50° C. to 300° C. for 1 hour to 10 hours, the flow tube containing 5% by volume of hydrogen in nitrogen.

[0572] b) Liquid Phase Reduction

[0573] The active components are fixed with potassium hydroxide (KOH) before liquid phase reduction. The base is added to the impregnation solution in stoichiometric amounts at room temperature. Subsequently, potassium formate (KHCOO) is added in 10-fold stoichiometric excess, and the solution is placed at 50°C to 120°C for 1 to 5 hours. The solution is then fixed with potassium hydroxide (KOH).

[0574] 8. Performance of palladium catalyst

[0575] Depending on the selected reduction method and reaction parameters, the expression 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 is arrive In this regard, you can also refer to Figure 3 , Figure 3 Measured values ​​of metal dispersion (MD) and metal grain size (KG) of 5 wt.% palladium catalysts (based on catalyst supports B1 and B4, respectively) are shown. Figure 3 It is also shown that at the reduction temperature T optimized according to the present invention red2 (here 140℃), Figure 3 The reduction temperature T is designated according to the invention as the so-called standard temperature (and therefore explicitly belongs to the invention). red1 Compared with 80° C. (here 80° C.), the properties of metal dispersion and average crystallite size are further improved, which correspondingly also leads to further improved catalytic properties of the catalyst system according to the invention. This also applies to platinum and ruthenium catalysts.

[0576] 9. Overview of hydrogenation in fixed bed reactor

[0577] The catalyst system according to the invention can be used in particular on a large scale, for example for the catalysis of hydrogenation reactions. Hydrogenation is one of the standard reactions in technical chemistry and is used both in large-scale processes, such as in petrochemicals, for example for the desulfurization of petroleum fractions, and as a synthesis step in fine chemicals. In addition to unsaturated compounds, other types of substances are also hydrogenated, such as aldehydes and ketones to alcohols, nitro compounds and nitriles to amines. In most hydrogenations, the reactants are in the liquid phase; only low-boiling substances (such as butyraldehyde from hydroformylation) are hydrogenated in the gas phase.

[0578] Nickel and some noble metals (such as platinum, ruthenium and palladium) are used as hydrogenation catalysts, for example, mainly in the form of supported catalysts. They are either suspended in the reaction solution as fine particles, or used as fixed beds. In the latter case, trickle bed reactors are used for three-phase reactions (reaction liquid, gaseous hydrogen, solid catalyst), i.e. fixed bed reactors, whose catalyst packing is sprayed with reaction liquid. The size of the catalyst packing (spheres, cylinders, extrudates, etc.) can be, for example, between 1 and 7 mm.

[0579] The corresponding hydrogenation unit is Figure 6 As shown, it can also be used as an example to describe the process control: reactant A is added to the tubular reactor (a) from above and mixed with hydrogen H 2The flow through the reactor with the catalyst bed is cocurrent or countercurrent. In terms of volume, the gas phase represents the dominant 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 have widespread technical application. 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 can be discharged via device (c).

[0580] In a trickle bed reactor, conversion and selectivity depend not only on the reaction kinetics, pressure and temperature, but also on the fluid dynamics of the reactor. The fluid dynamics have a strong influence on the liquid distribution within the reactor and directly affect the catalyst utilization. Uneven fluid distribution may lead to incomplete wetting of the catalyst bed. This may have a negative impact on the catalyst utilization.

[0581] Furthermore, the wetting of the catalyst bed may be disturbed by non-optimized technical dimensions, such as the ratio of the reactor height to the diameter and the ratio of the reactor interior to the catalyst particle diameter. To prevent these effects of non-wetting of the reactor interior and / or catalyst areas, the design of the liquid distributor and the maintenance of the corresponding dimensional ratios are of corresponding importance.

[0582] The design of trickle bed reactors is therefore based on parameters such as liquid holdup (a measure of the liquid present throughout the catalyst bed), pressure drop across the bed, distribution or mass of the gas and liquid phases and heat transfer coefficients. The height of the industrial reactors used is between 5 and 30 m; in these cases, the catalyst bed is a multiple bed or a single bed. The diameter of the reactor is limited by the uniform distribution of the liquid over the reactor cross section and does not usually exceed values ​​of 4 to 5 m. Therefore, the ratio of the height to the diameter of the reactor (Hr / Di) is usually between 5 and 25. The trickle bed reactors used on a laboratory scale have a diameter of 0.03 to 0.2 m and can be up to several meters in length. At these scales, the ratio of the reactor inner diameter to the catalyst diameter (Di / dk) cannot be neglected and should be above a value of Di / dk=10 (usually Di / dk>15). If this is not the case, differences in the structure of the packing near the reactor wall compared to the core of the packing may lead to marginal fluid flow, which is reflected in lower conversions. In industrially used reactors, the ratio of the reactor inner diameter to the catalyst diameter is usually between 100 and 1000, in order to be able to reliably exclude the influence of liquids moving at the edge.

[0583] Conventional trickle bed reactors with a diameter of 0.2 m or more are generally not very suitable for the production of fine chemicals because of the required minimum throughput. However, with the development of mini-plant technology, it is now possible to run continuous processes even at very low throughputs (1 kg / h and below). So far, mini-plants have been used mainly for process development. However, they are also suitable for production, especially for the production of small quantities of products with consistent quality, such as fine chemicals, pharmaceuticals and crop protection active ingredients.

[0584] For further explanation, reference may in particular be made to the following literature: Technical Chemistry, Manfred Baerns et al., 2nd edition, Wiley VCH Verlag & Co. KGaA, 2013; the chapter “Three-Phase Trickle-Bed Reactors”, Ullmann's Encyclopedia of Industrial Chemistry, Volume 7 Online Edition, 2008; and the chapter “Reactor Types and Their Industrial Application”, Ullmann's Encyclopedia of Industrial Chemistry, Volume 7 Online Edition, 2008.

[0585] 10. Catalytic test (hydrogenation of cinnamic acid)

[0586] The catalytic performance of the catalyst system of the invention can also be studied by hydrogenation or catalytically controlled hydrogenation reactions, for example, by hydrogenating cinnamic acid as a reactant to give a hydrocinnamic acid product. Fig. 7A .

[0587] A stirring rod, N 2 Entrance and H 2 Cinnamic acid (1) (2g, 13.5mmol) and 144mg catalyst are added in the 100mL three-necked flask of entrance.Three-necked flask is sealed with rubber septum, emptied, and refilled with nitrogen (three times).Add ethyl acetate (14mL), stir the mixture (700rpm), until reactant dissolves completely.The flask is emptied, and refilled with hydrogen (three times).Sampling is performed regularly at 1 hour, 2 hours, 3 hours, 5 hours, 7 hours, 10 hours and 16 hours, and analyzed by gas chromatography in conjunction with mass spectrometry.Studied the catalyst system (not according to the present invention) based on catalyst carrier A1, A2 and A3 and the catalyst system (according to the present invention) based on catalyst carrier B1, B2 and B3.

[0588] The results are as follows Figure 7B and7C These figures show the catalytic conversion (hydrogenation) of cinnamic acid as reactant and starting material, respectively, and the amount of cinnamic acid as a function of time (determined by GC-MS; % area), wherein at time t=0, 100% of unreacted cinnamic acid is present as starting material.

[0589] Figure 7B Results are shown for catalyst systems according to the invention based on catalyst supports B1, B2 and B3 (wherein for t=4 h the upper line shows catalyst system B3, the middle line shows catalyst system B1 and the lower line shows catalyst system B2). Figure 7C The results are shown for catalyst systems not according to the invention based on catalyst supports A1, A2 and A3 (wherein for t=7 hours the upper line shows catalyst system A3 and the lower line shows catalyst systems A1 and A2, respectively).

[0590] Figure 7B and 7C A comparison of the lines shown in 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 systems not according to the invention based on catalyst supports A1, A2 and A3. Thus, the conversion or hydrogenation of the starting material in the form of cinnamic acid is completed significantly faster in the systems according to the invention than in the systems not according to the invention, so that higher conversions can be achieved in the systems according to the invention.

[0591] Therefore, the catalyst systems based on the catalyst supports B1, B2 and B3 of the invention exhibit higher overall catalytic performance, in particular with higher conversions and improved space / time yields. The same applies to the corresponding platinum and ruthenium catalyst systems.

[0592] As mentioned above, in this context, the specific pore system of the activated carbon used as catalyst support with high meso- and macroporosity is of great importance, especially with regard to improving the transport process of reactants and products.

[0593] Furthermore, in the catalyst system according to the invention, the provision of the catalytically active components is improved overall, also due to the special process management for producing the catalyst system according to the invention, in which the activated carbon is subjected to a targeted and purpose-oriented oxidation before loading with the catalytically active components or relevant precursors and then reduced to obtain the catalyst system. In particular, the special pore structure of the activated carbon, described in particular in the form of a special ratio of total pore volume to specific BET surface area (quotient Q), leads to improved performance in terms of the catalytic activity of the catalyst system according to the invention.

[0594] In this case, in particular, the totality of the measures according to the invention, with their particular combination as described above, with their targeted and purpose-oriented combination, leads to the advantages and properties of the catalyst system according to the invention.

[0595] Thus, basic studies generally show that the catalyst system according to the invention, which is obtainable by the process according to the invention, has significantly improved properties compared to systems according to the prior art.

Claims

1. A method for preparing a catalyst comprising at least one catalytically active component in the form of a supported catalyst, wherein at least one catalytically active component is fixed to a catalyst support, the catalytically active component comprising 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, The method comprises the following steps (a) to (d) in the order specified below: (a) providing a starting spherical activated carbon for use as a catalyst support, The starting activated carbon has: (i) at 0.9 cm 3 / g to 3.4cm 3 The total pore volume V according to Gurvich is in the range of total , wherein 50% to 90% of the total pore volume according to Gurvich of the starting activated carbon is formed by pores having a pore diameter in the range of 2 nm to 500 nm, and (ii) 1100m 2 / g to 2600m 2 BET specific surface area S in the range of / g BET , but the condition is based on the total pore volume V of Gurvich total BET specific surface area S BET The ratio Q, according to the equation Q = V total / S BET , at 0.55*10 -9 m to 1.9*10 -9 m; Then (b) oxidation of the starting activated carbon provided in process step (a), provided, however, that at least one of the following two conditions (i) and (ii) is satisfied: (i) a first condition according to which the oxidized activated carbon has an oxygen content in the range of 4 atomic % to 20 atomic % based on the total elemental composition of the oxidized activated carbon as determined by X-ray photoelectron spectroscopy, (ii) a second condition, according to which the oxidized activated carbon has a hydrophilicity, which is determined as a water vapor adsorption behavior such that 30% to 100% of the maximum water vapor saturation loading of the activated carbon is reached at a partial pressure p / p0 of 0.6; Then (c) providing the oxidized activated carbon obtained in process step (b) with at least one catalytically active component; Then (d) reducing the oxidized activated carbon obtained in process step (c) with at least one catalytically active component, wherein process step (d) of the reduction is carried out as a gas phase reduction at a temperature in the range of 115° C. to 160° C., thereby obtaining a catalyst with at least one catalytically active component; in, The catalyst has an activity, determined as the percent dispersion of the catalytically active component on the catalyst support, measured by chemical adsorption using a dynamic flow method according to DIN 66136-3:2007-01, in the range of 15% to 90%; and The catalyst comprises at least one catalytically active component, the average crystallite size of which, as determined according to DIN 66136, is in the range of 5Å to 80Å.

2. The method according to claim 1, in, The oxygen content of the oxidized activated carbon obtained in process step (b) is in the range from 5 atom % to 20 atom %, based on the total elemental composition of the oxidized activated carbon.

3. The method according to claim 1, The catalytically active component comprises at least one metal selected from the group consisting of Fe, Bi, V, Cu, Zn, Ag, Sn, Pd, Pt, Ru and Ni.

4. The method according to claim 1, Therein, in process step (c), the oxidized activated carbon obtained in process step (b) is provided with a precursor of at least one catalytically active component, which precursor is subsequently converted into the catalytically active component in process step (d).

5. The method according to claim 1, in, In process step (c), the catalytically active components are applied in solution to the oxidized activated carbon by means of impregnation, thereby providing the oxidized activated carbon with the catalytically active components.

6. The method according to claim 1, in, In process step (c), the catalytically active components are applied in solution to the oxidized activated carbon by means of impregnation, thereby providing the oxidized activated carbon with the catalytically active components.

7. The method according to claim 1, in, In method step (c), the catalytically active component is applied in solution to the oxidized activated carbon by at least one of wetting and covering, thereby providing the oxidized activated carbon with the catalytically active component.

8. The method according to claim 1, in, In process step (c), the catalytically active component is applied in solution to the oxidized activated carbon by means of coating, thereby providing the oxidized activated carbon with the catalytically active component.

9. The method according to claim 1, in, In process step (c), the catalytically active component is applied in solution to the oxidized activated carbon by means of spraying, thereby providing the oxidized activated carbon with the catalytically active component.

10. The method according to claim 1, in, In process step (c), the catalytically active component is applied in the form of a dispersion to the oxidized activated carbon by means of impregnation, thereby providing the oxidized activated carbon with the catalytically active component.

11. The method according to claim 1, in, In process step (c), the catalytically active component is applied in the form of a dispersion to the oxidized activated carbon by means of impregnation, thereby providing the oxidized activated carbon with the catalytically active component.

12. The method according to claim 1, in, In process step (c), the catalytically active component is applied in the form of a dispersion to the oxidized activated carbon by at least one of wetting and covering, thereby providing the oxidized activated carbon with the catalytically active component.

13. The method according to claim 1, in, In process step (c), the catalytically active component is applied in the form of a dispersion to the oxidized activated carbon by means of coating, thereby providing the oxidized activated carbon with the catalytically active component.

14. The method according to claim 1, in, In process step (c), the catalytically active component is applied in the form of a dispersion to the oxidized activated carbon by means of spraying, thereby providing the oxidized activated carbon with the catalytically active component.

15. The method according to claim 1, in, The process step (d) of reducing is carried out at a temperature in the range of 120°C to 150°C for a period of 0.05 hours to 48 hours.

16. The method according to claim 1, in, The catalyst obtained has an activity, determined as the percentage dispersion of the catalytically active components on the catalyst support, measured by chemical adsorption using a dynamic flow method according to DIN 66136-3:2007-01, in the range of 20% to 80%; and The catalyst comprises at least one catalytically active component, the average crystallite size of which, as determined according to DIN 66136, is in the range of 7Å to 70Å.

17. A catalyst in the form of a supported catalyst, wherein the catalyst is obtainable according to the process of claim 1.

18. The catalyst according to claim 17 in the form of a supported catalyst, wherein the catalyst comprises at least one catalytically active component fixed to a catalyst support, wherein the catalytically active component comprises at least one metal, wherein the metal is 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, wherein the catalyst support is in the form of spherical activated carbon, The activated carbon forming the catalyst carrier has: (1) According to Gurvich's total pore volume V total , which is 0.9cm 3 / g to 3.4cm 3 / g, wherein 50% to 90% of the total pore volume according to Gurvich of the starting activated carbon is formed by pores having a pore diameter in the range of 2 nm to 500 nm; and (2) At 1100m 2 / g to 2600m 2 The BET specific surface area S in the range of BET , provided, however, that according to Gurvich's total pore volume V total BET specific surface area S BET The ratio Q, according to the equation Q = V total / S BET , at 0.55*10 -9 m to 1.9*10 -9 m; and wherein the catalyst obtained has an activity, determined as the percentage dispersion of the catalytically active components on the catalyst support, measured by chemical adsorption using a dynamic flow method according to DIN 66136-3:2007-01, in the range of 15% to 90%; and in, The catalyst has at least one catalytically active component whose average crystallite size, determined according to DIN 66136, is in the range of 5 Å to 80 Å.

19. A method of catalyzing a chemical reaction by heterogeneous catalysis, wherein the method comprises using a catalyst according to claim 17 or 18.

20. The method according to claim 19, The chemical reaction is selected from hydrogenation reaction and polymerization reaction.

21. The method according to claim 20, The polymerization reaction is an oligomerization reaction.

22. Protective garment comprising a catalyst according to claim 17 or 18.

23. The protective garment according to claim 22, The protective clothing is selected from the group consisting of protective clothing, protective gloves, protective shoes, protective socks, protective hats and protective covers.

24. The protective garment according to claim 23, The protective clothing is protective clothing for civilian departments or protective clothing for military departments.

25. A filter for removing pollutants, odors and toxic substances, wherein the filter comprises a catalyst according to claim 17 or 18.

26. The filter according to claim 25, The filter is selected from the group consisting of NBC protective mask filters, odor filters, air filters, adsorbable carrier structures and filters used in the medical field.

27. The filter according to claim 26, The support structure capable of adsorption is a support structure capable of chemical adsorption.

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