WO2007131795A2

WO2007131795A2 - Carbon granules, process for producing them and their use

Info

Publication number: WO2007131795A2
Application number: PCT/EP2007/004393
Authority: WO
Inventors: Constant J. Van Lookeren Campagne; Wolfgang Hungerbach
Original assignee: Glatt Systemtechnik Gmbh
Priority date: 2006-05-16
Filing date: 2007-05-16
Publication date: 2007-11-22
Also published as: EP2032251A2; DE102006022866A1; WO2007131795A3

Abstract

The invention relates to carbon granules which are formed by pyrolysis of microcrystalline cellulose. The invention further relates to a process for producing these granules. The granules of the invention are used, in particular, as support structure for solid-state catalysts.

Description

Carbon granules, process for their preparation and their use

The invention relates to a carbon granulate which is formed pyrolytically from microcrystalline cellulose. Furthermore, the invention relates to a method for producing these granules. The granulate according to the invention is used in particular as a carrier structure for solid catalysts.

The performance of solid catalysts is essentially determined by two properties: activity and selectivity. The activity of the catalyst is determined by the catalytically active surface and the accessibility of the active surface. The selectivity of the catalyst defines how strongly the reaction to be catalyzed dominates over competing side reactions. Although the properties of the catalytically active surface are the selectivity of a catalyst In addition, the accessibility of the active surface can be decisive for the selectivity. Thus, the residence time of the educts of the reaction to be catalyzed as well as of the intermediates within the catalyst body can greatly influence the catalytic products and thus the selectivity.

In a solid catalyst, the catalytically active material is generally finely dispersed in order to achieve a sufficiently large active surface area of the catalyst. A high activity of the solid catalyst requires that the catalytically active substance is not sintered into larger particles because this is accompanied by a smaller surface area. The stability of solid catalysts is determined by the resistance of the small catalytically active particles to sintering during use as a catalyst.

It is also important to control the porous structure and mechanical strength of the catalyst bodies. The porous structure determines the transport properties of the catalyst. The mechanical strength is important because fragments of the catalyst body can lead to an increased pressure drop of the gas flow through the fixed bed. With regard to catalyst bodies suspended in a liquid, mechanical strength is important because abrasion leads to the formation of fines which are difficult to separate from the reaction products by filtration or centrifugation.

Since it is generally not possible to accomplish all the desired properties in relation to the catalytically active material at the same time, these different properties of solid state Catalysts usually achieved by using carrier structures together with the catalytically active substances. The support structure determines the shape, size and mechanical strength of the catalyst body as well as the porous structure of the surface of the catalyst. In general, the support structure is not catalytically active, but provides a surface on which the catalytically active substance is finely dispersed.

The most widely used catalyst support structures are based on γ-alumina, which is prepared by dehydrogenation of bayerite or gibbsite (Al (OH) ₃ ) or boehmite (AlOOH). Carrier structures of this type, however, share the common drawback that the recovery of the catalytically active substances from the catalyst is cumbersome. The dissolution of the catalyst body and subsequent separation of the dissolved material is difficult and requires much caustic. Another technique relies on melting the catalyst in a vacuum oven at very high temperatures. However, in view of the expensive equipment required for this purpose and the high energy consumption, this is only economically feasible for noble metal catalysts.

Furthermore, support structures made of activated carbon are known from the prior art. These can be easily removed from the catalytically active substances by simple combustion of the carbon. Since activated carbon does not dissolve in an alkaline or acidic environment, activated carbon is the carrier structure of choice for noble metal catalysts in catalytic reactions in the liquid phase. During combustion of the activated carbon, only the catalytically active substance, eg the noble metal, remains available. back.

Thus, from US 6,906,000 a carbon catalyst with a carbon content in the range of 2 to 25 wt .-% known. Here, the carbonaceous support material is mixed with catalytically active metals or metal oxides, resulting in a lower carbon content. However, this is associated with a reduced compressive strength of these catalysts, which can only be improved by an additional coating with a carbon layer.

US Pat. No. 4,052,336 discloses a carrier structure of activated carbon having a particle size between 1 and 60 μm. This small particle size has the disadvantage that in a fixed bed reactor, a high pressure drop is the result and therefore the use of the catalysts described herein is severely limited.

US 3,576,767 describes a carbon-based catalyst containing a catalytic amount of platinum. Here, carbon is obtained from the residues of organic materials recovered from cellulosic fluid.

WO 03/55599 A1 describes a catalyst composition containing an extruded carbon material. The carbon particles can be obtained from products such as lignite or wood. The shaping takes place here with the carbon particles, which brings considerable disadvantages in terms of mechanical strength with it. In the carbon-containing support structures hitherto known from the prior art, various disadvantages are found. Since activated carbon is extracted from natural materials such as peat, wood or coconut shells, it is difficult to ensure a consistent and consistent quality of the raw material. In addition, the mechanical strength of support structures made of activated carbon is usually problematic. Also, the abrasion of activated carbon is a previously unresolved

Problem, which results in the application as catalysts to the fact that the catalytically active material mixed with the reaction products. Due to the difficulty of separating the noble metals from the reaction products, this is a significant disadvantage in the use of activated carbon as the support structure. Another important disadvantage is that charcoal is difficult to form into bodies that have sufficient mechanical strength. Thus, the use of known from the prior art support structures of activated carbon in fixed bed reactors is only possible.

Based on this, it was an object of the present invention to eliminate the disadvantages of the materials known in the prior art and to provide novel, suitable as a support structure materials which have a high mechanical strength, but at the same time have a porosity, the

Use as support structures for e.g. Enable catalysts.

This object is achieved by the process for the production of a carbon granulate having the features of claim 1, the carbon granules with the Characteristics of claim 12 and the catalyst having the features of claim 31 solved. Claim 21 describes the use of such carbon granulators for producing a catalyst. The other dependent claims show advantageous developments.

According to the invention, a granular carbon is provided which contains 50 to 99.9% by weight of carbon. Furthermore, 0.1 to 50 wt .-% minerals and / or non-charred additives are included. At least 20% by weight of the carbon is formed pyrolytically from granulated microcrystallised cellulose (MCC) and optionally further binders and / or additives. In this case, the individual grains of the carbon granules have a porosity in the core which is greater than the porosity at the surface of the grains.

Since the surface has a lower porosity, the surface of the individual grains is smooth, which results in a high mechanical strength as well as a low abrasion of the granules according to the invention.

The abrasion resistance properties are particularly illustrated by the fact that the granules in the drum abrasion test according to ASTM D4058 preferably have an abrasion in the range from 0.2 to 5% by weight. Particularly preferably, the abrasion is in a range of 0.2 to 1.5 wt .-%.

In principle, the specific surface area of the carbon granules can be adjusted as desired, with the proportion by weight of MCC being greater than that of binders and other additives. the specific one Surface can be controlled. The specific surface is preferably in a range from 60 to 1200 m ² / g.

It is further preferred that the carbon

Granules having a compressive strength according to D 7084-4 in the range of 2 to 20 wt .-%, wherein the compressive strength on the weight fraction of MCC is controllable.

The carbon granules can be present in any geometric form. Particularly preferred here is the spherical shape, since in this case a lower abrasion was found. This brings advantages in particular for the production of catalysts. The spherical granules should preferably be uniform in size when reactions are carried out using catalyst bodies suspended in solutions. However, variations of up to 20% with respect to the diameter of the grains in spherical form are quite acceptable. Another advantage resulting from a uniform size of the grains is the easier loading and unloading of the catalyst bodies. The carbon granulate in spherical form preferably has a length-to-width ratio of not more than 3: 1, preferably not more than 2: 1 and more preferably not more than 1.5: 1. A variant according to the invention further provides that the porosity of the grains of the carbon granules decreases from the core to the surface.

According to the invention, a method is also provided for producing a carbon granulate comprising the following steps: i) mixing a powder consisting of at least 20% by weight of microcrystalline cellulose (MCC) and optionally further binders or additives with water,

ii) agglomeration of the mixture into an MCC

Granules with subsequent drying of the MCC granules and

ii) thermal treatment at temperatures equal to or higher than the decomposition temperature of the MCC granules in an oxygen-poor atmosphere to form the carbon granules.

The binder is preferably selected from the group consisting of carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, glucose or mixtures thereof.

With regard to the further additives, preference is given in particular to those from the group consisting of water glass, carbon powder, colloidal silica, colloidal aluminum oxide, colloidal titanium oxide, colloidal zirconium oxide and mixtures thereof.

With regard to agglomeration, different process variants are possible. A first provides that first the powder is mixed with the water in a weight ratio, so that a dough-like consistency results. This dough is then extruded and processed into a MCC granule of cylindrical shape. Likewise, however, tri-, quadro- or multilobal forms or ring shapes are also possible. Another variant provides that an agglomeration by tabletting of the microcrystalline cellulose he follows. A third preferred variant provides that the agglomeration takes place in a fluidized bed reactor to form a substantially spherical MCC granules. A further variant according to the invention relates to the agglomeration in a raking apparatus, the formation of a substantially spherical MCC granulate.

The thermal treatment is preferably carried out at a temperature of at least 400 ⁰ C. Generally, however, the temperature depends on the composition of the MCC granules, since the decomposition temperature can be determined by this. In a further preferred variant, the temperature is increased in the thermal treatment in stepped steps up to the decomposition temperature of the MCC granules.

The thermal treatment is preferably carried out in an inert gas, nitrogen and / or carbon dioxide being particularly preferably used here.

The invention also provides the use of the previously described carbon granules and at least one catalytically active substance for the preparation of a catalyst. With regard to the catalyst material, there are basically no restrictions. The catalytically active substance is preferably selected from group VIII of the Periodic Table of the Elements or the group of transition metals. These include, for example, platinum,

Ruthenium, palladium, rhodium, rhenium, silver, gold, lead, tin, copper, nickel, cobalt, vanadium, zinc, iron, chromium, molybdenum, tungsten, and mixtures thereof. With regard to the preparation of the catalyst, there are basically two process variants. The first process variant is based on the fact that in the above-described step i) the catalytically active substance or a precursor thereof is added to the mixture of water and microcellulose. Likewise, it is of course also possible to first suspend the catalytically active substance or a precursor thereof in water and then add the microcrystalline cellulose to this suspension. A second variant provides that the carbon granules are brought into contact with a solution or a suspension of the catalytically active substance or a precursor thereof. Particularly preferred here is the contacting with the catalytically active substance by spraying the carbon granules with the solution or suspension.

It is likewise preferred to impregnate the carbon granules with a solution or suspension containing the catalyst. It is particularly preferred that the catalyst is present in oxidized form. The thermal treatment then leads to a reduction of the catalyst.

A further preferred variant provides that the catalyst described above is additionally provided with at least one further final coating, wherein this is preferably formed as an oxygen-protecting layer. This coating preferably consists of a wax and / or a fatty constituent having a melting point of more than 50 ^° C.

With reference to the following figures and examples, the he.findungsgemäße object will be explained in more detail, without this on the special shown here To limit embodiments.

Fig. 1 shows an electron micrograph of the carbon granules according to the invention in spherical form.

Fig. 2 shows an electron micrograph of the surface of the carbon granules according to the invention.

Fig. 3 shows an electron micrograph (SEM) of the core of the carbon granules according to the invention.

4 shows an electron micrograph (TEM) of a catalyst according to the invention with nickel as the catalytically active substance at a magnification of a factor of 135,000.

5 shows an electron micrograph (TEM) of the catalyst according to the invention with nickel as the catalytically active substance at a magnification of a factor of 500,000.

In Fig. 1 is based on an electron micrograph (SEM) with a magnification by a factor of 200, the different porosity in the core and on the surface of the granule grain clarified. It can be seen here that there is a significantly higher porosity in the core than at the surface of the granule grain. A smooth surface of the granule grain can be seen, which explains the good properties in terms of mechanical strength and abrasion. FIG. 2 shows an electron micrograph (SEM) of the surface of the granule grain at a magnification of a factor of 5,000. Here is the small number of pores in the surface.

For comparison, FIG. 3 shows an electron micrograph of the core at a magnification of a factor of 500. Here, a significantly higher porosity relative to the surface becomes apparent.

FIG. 4 shows a catalyst according to the invention on the basis of a transmission electron micrograph at a magnification of a factor of 135,000. Here, the dense coverage of the carbon structure with nickel particles becomes clear. The same result can be seen from Fig. 6, which shows the same picture at a magnification of a factor of 500,000. Here are nickel particles with a size of about 5 nm can be seen. The difference in

Contrast of the individual nickel particles is due to the fact that some nickel particles appear under Bragg reflection conditions.

example 1

Synthesis of a carbon granulate according to the invention

15.1 g of granules of microcrystalline cellulose (MCC granules) of spheres of microcrystalline cellulose were introduced into a fluidized bed reactor. The fluidized bed reactor consisted of a vertical quartz tube with a diameter of 3 cm. The temperature of the fluidized bed reactor could be controlled by a furnace surrounding the quartz tube up to tures of 57 ⁰ C are set. The bulk density of the MCC granules was 15.1 g / ml. The minimum linear velocity of the gas flow of nitrogen to achieve turbulence was 4 cm / sec. at 70 ^° C:

The MCC granules were filled with a gas flow at a linear speed of 5.4 cm / sec. swirled. Previously, the granules were dried at 100 ⁰ C for 1 h and 14 min. The temperature was increased according to the following temperature scheme:

Subsequently, the granules were cooled to room temperature.

This resulted in 3.9 g of carbon granules with a bulk density of 0.6 g / ml, which means a remaining weight of 26%. It is very important that the carbon granules produced according to the invention can be placed in a fluidized bed reactor without friction loss. The mechanical strength and the smooth surface of the balls lead to the high stability in a fluidized bed reactor.

The results obtained were confirmed by a test in the thermobalance. The invention Granules were kept in a nitrogen flow while the temperature was increased by 5 ⁰ C per minute. The weight loss started at about 250 ^° C. and maximum weight loss was observed at 315 ^° C. At 360 ^° C, the weight loss decreased noticeably, but a weight loss up to temperatures of 700 ⁰ C could be observed. The remaining weight was 21% of the original weight.

Example 2

Synthesis of a carbon granulate according to the invention

MCC powder was mixed with water to a dispersion having a solids content of about 30%. This dispersion was agglomerated in a fluidized bed rotor agglomerator and dried. The spherical spherical agglomerates of the MCC powder had a particle size D50 of 300 μm. They were placed in an oven and preheated at 250 ^° C. for 1 h in the absence of oxygen and then thermally treated at 450 ^° C. for 2 h (also under reducing conditions) to initiate decomposition into carbon and gas components and a spherical one To form carbon granules. The carbon granules had a carbon content of more than 98% by weight. The grain size D50 of the carbon granules was reduced by the decomposition process to a value of 150 microns. The coefficient of friction of the carbonaceous spheres was determined by a modified drum abrasion test according to ASTM D4058 with a Heubach tester. The result was an abrasion value of 1.7 wt .-%. Example 3

Synthesis of a carbon granulate according to the invention with a particle size D50> 200 μm

According to another variant of the invention, the MCC powder was mixed with water to form a dough having a moisture content between 30 and 40%. This dough was extruded with a basket extruder Fuj i-Paudall). The extruded particles were placed in a spheronizer (Smooth) to form spherical balls which were dried in a fluid bed dryer (Smooth). The result was spherical granules with a diameter of 800 μm (D50). This granulate was preheated in the same manner as in Example 2 with exclusion of oxygen for 1 h at 250 ⁰ C and then thermally treated at 450 ⁰ C for 2 h. The friction value here was 1.4 wt .-% and the compressive strength was here 11 wt .-%.

Example 4

MCC carrier structure in spherical form

The carbon granules obtained in Example 1 were placed in an oven and preheated in the absence of oxygen. The exclusion of oxygen was achieved by combustion of propane with stoichiometric amounts of oxygen, so that all of the oxygen was converted to CO ₂ . The temperature was 1100 ⁰ C and the duration of the thermal treatment was 3 h.

This resulted in a carbonized support structure with a specific surface area of 694 m ² / g. The grain large D50 of the support structure thus obtained was 300 μm.

Example 5

Synthesis of a catalyst according to the invention with nickel

130.4 g of the MCC granules with a diameter of 1000 to 1400 μm were stored in a solution of 51.7 g of Ni (NO ₃ ) ₂ .6H ₂ O in 118.6 ml of water for 16 hours. Subsequently, the granules were separated from the liquid by decantation. The granules had taken up about 40 ml of the liquid, which corresponds to about 63 g of the solution. The impregnated granules were predried at a low pressure in a Rota Vapor at a pressure of 14 mbar.

5.02 g of the pre-dried granules were maintained in a nitrogen flow, raising the temperature up to 450 ^° C. The granules showed a weight loss of about 65% during the thermal treatment. A sample of the catalyst was ground for testing in a mortar, dispersed in ethanol and sonicated. A small volume of the suspension was placed on a holey carbon film on a copper grid, which is commonly used for studies in a TEM electron microscope. The uptake of the electron microscope, as seen in Figs. 4 and 5, showed that the surface of the catalyst is homogeneously covered with nickel particles about 4 nm in diameter. The BET surface area of the passivated catalyst was measured by the adsorption capacity to nitrogen at 77K. The nickel surface became adsorptive calculated to water, resulting in a surface area of 40 m ₂ / g of nickel. Before the hydrogen adsorption measurement, the catalyst in the adsorption apparatus had been reduced at 400 ^° C.

Example 6

Synthesis of a catalyst according to the invention

The carbon granules produced in Example 2 were placed in a rotor agglomerator. 1 kg of a suspension of 15% by weight of MCC and 20% by weight of iron (III) citrate were sprayed onto the carbon granules per kg of carbon granules. The sprayed carbon granules were heated with the exclusion of oxygen as described in Example 2, and the activated catalyst was placed under a nitrogen atmosphere directly in a cylinder of molten candle wax. The lower part of the cylinder, containing more than 80% of the activated catalyst, was placed in a granulator (Glatt VG) to produce a free-flowing granule of the activated catalyst in the wax-encapsulated catalyst.

Example 7

Synthesis of a catalyst according to the invention

The carbon granules prepared in Example 2 were placed in a rotor agglomerator, with 1 kg of a suspension of 5 wt.% MCC (Avicel PH 102, FMC Corp.) and 15 wt.% NiNO ₃ per kg of carbon granules and 10 wt% ground coconut carbon powder (Pica G202X). This suspension was sprayed in a rotor (smooth) on the carbon granules, whereby a grain size D50 of about 200 microns was obtained. As in Example 2, the carbon granules were thermally treated in the absence of oxygen and the activated catalyst was transferred immediately under a nitrogen atmosphere in a cylinder of molten candle wax and pressed down with a sieve plate. The lower portion of the candle wax cylinder, containing more than 80% of the activated catalyst, was placed in a granulator (Smooth VG) to form a free flowing granule of the activated catalyst encapsulated in the wax. This resulted in a spherical catalyst, wherein at least 50% of the HG porosity value occurs in pores with a diameter of more than 15-00 angstroms.

Claims

claims

1. A method of producing a carbon granule comprising the steps of:

i) mixing a powder consisting of at least 20% by weight of microcrystalline cellulose (MCC) and optionally further binders or additives with water,

ii) agglomeration of the mixture into an MCC granulate with subsequent drying of the MCC granules and

iii) thermal treatment at temperatures greater than or equal to the decomposition temperature of the MCC granules in an oxygen-poor atmosphere to form the carbon granules.

2. The method according to claim 1, characterized in that the binder is selected from the group consisting of carboxymethylcellulose, hydroxyethylcellulose,

Hydroxypropylcellulose, methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, glucose or mixtures thereof.

3. The method according to any one of the preceding claims 1 or 2, characterized in that the further additives are selected from the group consisting of water glass, carbon powder, colloid Silica, colloidal alumina, colloidal titania, colloidal zirconia, and mixtures thereof.

4. The method according to any one of the preceding claims, characterized in that the agglomeration takes place to form a dough, which by subsequent extrusion to an MCC granules with cylindrical tri-, quadro- or multilobal

Form or ring shape is processed.

5. The method according to any one of claims 1 to 3, characterized in that the agglomeration is carried out by tabletting.

6. The method according to any one of claims 1 to 3, characterized in that the agglomeration takes place in a fluidized bed reactor with the formation of a substantially spherical MCC granules.

7. The method according to any one of claims 1 to 3, characterized in that the agglomeration takes place in a Rondierer to form a substantially spherical MCC granules.

8. The method according to any one of the preceding claims, characterized in that the thermal treatment is carried out at a temperature of at least 400 ⁰ C.

9. The method according to any one of the preceding claims, characterized in that in the thermal treatment, the temperature is increased in stepped steps up to the decomposition temperature of the MCC granules.

10. The method according to any one of the preceding claims, characterized in that the thermal treatment is carried out in an inert gas.

11. The method according to the preceding claim, characterized in that nitrogen and / or carbon dioxide is used as the inert gas.

12. carbon granules containing at least 50 wt .-% of granulated microcrystalline cellulose (MCC) and optionally other binders and / or additives pyrolytically formed carbon.

13. carbon granules according to claim 12, characterized in that the carbon granules in the drum abrasion test according to ASTM D4058 has an abrasion in the range of 0.2 wt .-% to 5 wt .-%.

14. Carbon granules according to claim 13, characterized in that the carbon -

Granules in the drum abrasion test according to ASTM D4058 have an abrasion in the range of 0.2% by weight to 1.55 Gew. - % having .

15. Carbon granules according to one of claims 12 to 14, characterized in that the carbon

Granules have a specific surface area in the range of 60 to 1200 m ² / g, wherein the specific surface is controllable on the weight fraction of MCC.

16. carbon granules according to any one of claims 12 to 15, characterized in that the carbon granules having a compressive strength, determined according to ASTM D 7084-4, in the range of 2 to 20 wt .-%, wherein the compressive strength on the weight fraction controllable by MCC.

17. Carbon granules according to one of claims 12 to 16, characterized in that the porosity of the grains of the carbon granules decreases from the core to the surface.

18. carbon granules according to any one of claims 12 to 17, characterized in that the carbon granules are present in spherical form.

19. carbon granules according to any one of claims 12 to 18, characterized in that the carbon granules in spherical form a length-width

r / Ratio of not more than 3: 1, preferably not more than 2: 1 and particularly preferably not more than 1.5: 1.

20. carbon granules according to any one of claims 12 to 19, characterized in that the carbon granules according to one of claims 1 to 11 can be produced.

21. Use of the carbon granulate according to any one of claims 12 to 20 and at least one catalytically active substance for the preparation of a catalyst.

22. Use according to claim 21, characterized in that the catalytically active ^■ tive substance is selected from the group consisting of platinum, ruthenium, palladium, rhodium to, rhenium, silver, gold, lead, tin, copper,

Nickel, cobalt, vanadium, zinc, iron, chromium, molybdenum, tungsten and mixtures thereof.

23. Use according to one of claims 21 or 22, characterized in that in step i) the catalytically active substance is added to the mixture.

24. Use according to one of claims 21 or 22, characterized in that the carbon -

Granules containing a solution or a suspension of the catalytically active substance or a Cursor of this is brought into contact.

25. Use according to claim 24, characterized in that the carbon granules are sprayed with the solution or suspension.

26. Use according to one of claims 21 to 25, characterized in that the carbon granules are finally coated.

27. Use according to claim 26, characterized in that the coating is carried out with a melt, dispersion or emulsion.

28. Use according to claim 26 or 27, characterized in that the carbon granules from oxygen protective coating is used.

29. Use according to one of claims 26 to 28, characterized in that the coating of a wax, a fat and / or a fatty ingredient having a melting point of more than

50 ⁰ C exists.

30. Use according to claim 28, characterized in that the coating is selected from the group consisting of saffron, stearic acid, palmitic acid, whose derivatives and mixtures thereof.

31. A catalyst comprising a carbon granulate according to any one of claims 12 to 20 and at least one catalytically active substance.

32. Catalyst according to claim 31, characterized in that the catalytically active substance is selected from the group consisting of platinum, ruthenium, palladium, rhodium, rhenium, silver, gold, lead, tin, copper, nickel, cobalt, vanadium, Zinc, iron, chromium, molybdenum, tungsten and mixtures thereof.

33. A catalyst according to any one of claims 31 or 32, characterized in that the carbon granules is provided with at least one coating.

34. A catalyst according to claim 33, characterized in that the coating is a coating which protects the catalyst from oxygen.

35. A catalyst according to claim 33 or 34, characterized in that the coating contains a wax, a fat and / or a fat component having a melting point of more than 50 ⁰ C.

36. Catalyst according to the preceding claim, characterized in that the coating is selected from the group consisting of paraffins, stearic acid, palraitic acid, their derivatives and mixtures thereof.

37. A catalyst according to any one of claims 33 to 36, characterized in that the weight fraction of the coating based on the total weight of carbon granules, catalytically active substance and coating in the range of 10 to 60 wt .-%, preferably 10 to 40 wt. -% and particularly preferably 10 to 25 wt .-% is.

38. A catalyst according to any one of claims 33 to 37, characterized in that the content of at least one catalytic active substance in

Catalyst in the range of 20 to 30 wt -.% Is.

39. Use of the catalyst according to any one of claims 33 to 38 in the hydrogenation of

Fats or aromatics as well as the Fischer-Tropsch synthesis.

40. Use of the carbon granules according to any one of claims 12 to 20 as adsorbent, in particular for the adsorption of substances from gaseous media, e.g. in air conditioners, or from liquid media, e.g. Drinking water.

41. Use of the carbon granules according to any one of claims 12 to 20 as a carrier substance for medicaments.