Catalyst system and method for catalytically dehydrating a hydrogen carrier material, reactor arrangement with such a catalyst system and method for producing such a catalyst system

Abstract

The invention relates to a catalyst system (10) which is used for the catalytic dehydrogenation of hydrogen carrier material and comprises reaction materials and carrier material supporting the reaction materials, wherein the reaction materials comprise platinum, rhenium and sulphur.

Description

[0001] Catalyst system and method for catalytic dehydrogenation of a hydrogen carrier material, reactor arrangement with such a catalyst system and method for producing such a catalyst system

[0002] This patent application claims priority from German patent application DE 10 2022 210 825.6, the contents of which are incorporated herein by reference.

[0003] The invention relates to a catalyst system and a method for the catalytic dehydrogenation of a hydrogen carrier material, a reactor arrangement with such a catalyst system and a method for producing such a catalyst system.

[0004] Reversible hydrogenation and dehydrogenation of hydrogen carrier materials, particularly in the form of hydrocarbon compounds, opens up the fundamental possibility of targeted storage and release of hydrogen. Suitable hydrogen carrier materials include pi-conjugated systems known as liquid organic hydrogen carriers (LOHC). These are liquid organic hydrogen carrier materials, particularly perhydrogenated and / or partially hydrogenated cyclic hydrocarbon compounds. Such compounds are known, for example, from EP 1 475 349 A2 and DE 10 2012 221 809 A1.

[0005] Supported precious metal catalysts, in particular supported platinum catalysts from DE 10 2012 221 805 Al, are known for carrying out the dehydrogenation reaction.

[0006] The invention is based on the object of improving the dehydrogenation of hydrogen carrier material.

[0007] This object is achieved according to the invention by a catalyst system having the features of claim 1, by a reactor arrangement having the features of claim 10 and by methods having the features of claims 12 and 14.

[0008] The core of the invention is that a catalyst system comprises platinum, rhenium, and sulfur as reaction materials. The reaction materials platinum and rhenium are catalytically active materials, also referred to as active materials. Sulfur acts as an inhibitor and, in particular, blocks catalytically active sites. Sulfur is, in particular, an additive material. The reaction materials influence the catalytic dehydrogenation reaction. The reaction materials are supported by a support material. In addition, other active materials, inhibitors, and / or additives can be used to specifically adapt the catalyst properties.

[0009] An essential finding of the invention is that the respective advantages for the dehydrogenation reaction of sulfur and rhenium are suitably combined.

[0010] In particular, it has been recognized that sulfur increases catalyst selectivity, meaning that certain hydrocarbon compounds are specifically dehydrogenated. This reduces the risk of undesired by-products being formed, which lead to contamination and / or degradation of the hydrogen carrier material and, in particular, require complex purification or can lead to premature replacement of the hydrogen carrier material. Particularly at comparatively low degrees of hydrogenation, the risk of by-product formation is increased, so sulfur is preferred in the catalyst system, especially at low degrees of hydrogenation. For the purposes of the invention, low degrees of hydrogenation mean that the degree of hydrogenation is at most 50%, in particular at most 40%, in particular at most 30%, in particular at most 25%, in particular at most 20%, in particular at most 15%, in particular at most 10%, and in particular at most 5%.

[0011] A further finding of the invention is based on the fact that rhenium increases catalyst activity, i.e., the reaction rate and thus the hydrogen release rate, particularly compared to pure platinum catalysts. The increase in catalyst activity can be achieved with both small and large degrees of hydrogenation and is particularly pronounced with large degrees of hydrogenation, i.e., when a comparatively low dehydrogenation conversion occurs. A large degree of hydrogenation within the meaning of the invention exists when the degree of hydrogenation is at least 50%, in particular at least 60%, in particular at least 70%, in particular at least 75%, in particular at least 80%, in particular at least 85%, in particular at least 90%, in particular at least 95%, and in particular at least 99%.Because the catalyst system according to the invention comprises both sulfur and rhenium in addition to platinum, dehydrogenation with the catalyst system can be carried out with both high catalyst selectivity and high catalyst activity. In particular, it has been found that the composition of the reaction materials in the catalyst system can be adjusted specifically, in particular depending on the hydrogenation conditions. In particular, it is possible for the catalyst system to have a first catalyst material comprising platinum and rhenium as reaction materials, and a second catalyst material comprising platinum and sulfur as reaction materials. In addition, a third catalyst material can be present, comprising platinum, rhenium, and sulfur as reaction materials.In particular, it is not necessary for each catalyst material to comprise all reaction materials if all reaction materials are present within the catalyst system as a whole.

[0012] It is fundamentally possible to arrange the first catalyst material specifically in a reactor and / or in a region within the reactor where hydrogen carrier material with a high degree of hydrogenation is dehydrogenated. Accordingly, the second catalyst material can preferably be arranged in a reactor vessel and / or in a region of the reactor vessel where hydrogen carrier material with a low degree of hydrogenation is dehydrogenated.

[0013] It is also possible to provide a mixture of the first catalyst material and the second catalyst material.

[0014] Alternatively, it is also possible to use only the third catalyst material. It has been found that the third catalyst material combines the individual advantages of the reaction materials sulfur and rhenium, thus exhibiting improved catalyst activity and selectivity than a pure platinum catalyst.

[0015] In particular, the catalyst selectivity of the third catalyst material is improved compared to the first catalyst material. In particular, the catalyst activity of the third catalyst material is improved compared to the second catalyst material. The hydrogen carrier material is in particular liquid and in particular organic. The hydrogen carrier material comprises cyclic hydrocarbons that are present in perhydrogenated and / or partially hydrogenated form. This means that the hydrocarbon compounds have no or only a small number of carbon-carbon multiple bonds. The cyclic hydrocarbons may contain heteroatoms, in particular nitrogen. In particular, the hydrocarbon compounds are oxygen-free.In particular, the perhydrogenated and / or partially hydrogenated hydrocarbons include methylcyclohexane and / or toluene, perhydrogenated and / or partially hydrogenated diphenylmethane, perhydrogenated and / or partially hydrogenated N-alkylated carbazole, in particular perhydrogenated and / or partially hydrogenated benzyltoluene and / or isomers thereof, and in particular perhydrogenated and / or partially hydrogenated dibenzyltoluene and / or isomers thereof. Benzyltoluene and / or dibenzyltoluene also include, in particular, isomers of the compounds mentioned, as well as substituted benzyltoluenes and / or substituted dibenzyltoluenes in which one or both benzyl groups are substituted by one or more substitution groups, where the substitution groups include alkyl groups such as methyl groups or ethyl groups, aryl groups such as vinyl groups, and / or heteroaryl groups such as pyridinyl groups.

[0016] Partially hydrogenated benzyltoluene includes benzyltoluene compounds in which at least one carbon-carbon double bond of the benzyltoluene is replaced by a carbon-carbon single bond. Perhydrogenated benzyltoluene includes benzyltoluene compounds in which the carbon-carbon double bonds are replaced by carbon-carbon single bonds. Examples of partially hydrogenated benzyltoluenes are l-cyclohexylmethyl-2-methylbenzene, l-cyclohexylmethyl-3-methylbenzene, l-cyclohexylmethyl-4-methylbenzene, 1-benzyl-2-methylcyclohexane, l-benzyl-3-methylcyclohexane, l-benzyl-4-methylcyclohexane, 1- (l-Cyclohexenyl-methyl)-2-methylbenzene, l-(l-cyclohexenyl-methyl)-3-methylbenzene, 1-(1-cyclohexenyl-methyl)-4-methylbenzene, l-(l,3-cyclohexadienylmethyl)-2-methylbenzene, 1-(1,3-cyclohexadienyl-methyl)-3-methylbenzene and l-(l,3-Cyclohexadienylmethyl)-4-methylbenzene.

[0017] Examples of perhydrogenated benzyltoluenes are l-cyclohexylmethyl-2-methylcyclohexane, 1-cyclohexylmethyl-3-methylcyclohexane, and l-cyclohexylmethyl-4-methylcyclohexane. A partially hydrogenated dibenzyltoluene includes any dibenzyltoluene compound in which at least one carbon-carbon double bond of the dibenzyltoluene is replaced by a carbon-carbon single bond. A perhydrogenated dibenzyltoluene includes any dibenzyltoluene compound in which all carbon-carbon double bonds are replaced by carbon-carbon single bonds.Examples of partially hydrogenated dibenzyltoluene are 1-benzyl-3-(cyclohexylmethyl)-5-methylbenzene, ((5-methyl-1,3-phenylene) bis (methylene)dicyclohexane, l-benzyl-4-(cyclohexylmethyl)-2-methylbenzene, ((2-methyl-1,4-phenylene) bis (methylene)dicyclohexane, 2-benzyl-4-(cyclohexylmethyl)-1-methylbenzene, ((4-methyl-1,3-phenylene) bis (methylene)dicyclohexane, l-benzyl-3-(cyclohexylmethyl)-2-methylbenzene, ((2-methyl-1,3-phenylene) bis (methylene)dicyclohexane, l-benzyl-2-(cyclohexylmethyl)-4-methylbenzene ((4-methyl-.

[0018] 1,2-phenylene) bis (methylene)dicyclohexane, l-benzyl-3-(l-cyclohexenylmethyl)-5-methylbenzene, and l-benzyl-3-(l,3-cyclohexadienylmethyl)-5-methylbenzene. Examples of perhydrogenated dibenzyltoluene are ((5-methylcyclohexane-l,3-diyl)bis(methylene)dicyclohexane, ((2-methylcyclohexane-l,4-diyl)bis(methylene)dicyclohexane, ((4-methylcyclohexane-l,3-diyl)bis(methylene)dicyclohexane, ((2-methylcyclohexane-l,3-diyl)bis(methylene)dicyclohexane, and ((4-methylcyclohexane-

[0019] 1.2-diyl)bis(methylene)dicyclohexane.

[0020] A partially hydrogenated N-alkylcarbazole, such as N-ethylcarbazole, includes any N-alkylcarbazole in which at least one carbon-carbon double bond contained therein is replaced by a carbon-carbon single bond. A perhydrogenated N-alkylcarbazole, such as N-ethylcarbazole, includes any N-alkylcarbazole in which all carbon-carbon double bonds contained therein are replaced by carbon-carbon single bonds. Examples of partially hydrogenated N-ethylcarbazole are 9-ethyl-2,3,4,9-tetrahydro-1H-carbazole, 9-ethyl-2,3,4,5,6,9-hexahydro-1H-carbazole, 9-ethyl-2,3,4,5,6,7,8,9-octahydro-1H-carbazole, and 9-ethyl-2,3,4,4a,5,6,7,8,9,9a-decahydro-1H-carbazole. Perhydrogenated N-ethylcarbazole is, for example, 9-ethyldodecahydro-lH-carbazole.

[0021] Dehydrogenation can be partial or complete. Dehydrogenation is preferably complete. Complete dehydrogenation occurs when fully saturated carbocyclyl or heterocyclyl residues (such as cyclohexyl or piperidinyl residues) or partially saturated carbocyclyl or heterocyclyl residues (such as cyclohexenyl or dihydropyridyl residues) are converted into the corresponding aromatic form (such as phenyl or pyridyl residues).

[0022] In a preferred embodiment, the dehydrogenation is carried out continuously in a reactor, in particular a fixed bed reactor, a fluidized bed reactor or a fluidized bed reactor.

[0023] The dehydrogenation is preferably carried out at a temperature in the range from 100 °C to 400 °C, in particular from 200 °C to 330 °C and in particular from 210 °C to 310 °C. The dehydrogenation is preferably carried out at a pressure in the range from 1 to 5 bar, in particular from 2 to 4 bar and in particular about 3 bar.

[0024] The liquid hourly space velocity (LHSV) is preferably in the range between 0.5 and 3 / h, more preferably between 1 and 2 / h. The released hydrogen gas can be expelled from the dehydrogenation reactor by gases, particularly nitrogen or argon.

[0025] The support material comprises, in particular, aluminum oxide (Al2O3), silicon dioxide (SiCh), titanium dioxide (TiO2), zirconium dioxide (ZrCh), silicon carbide (SiC), or mixtures thereof. Aluminum oxide has proven particularly suitable, in particular a shaped body made of aluminum oxide, which comprises, in particular, gamma aluminum oxide, theta aluminum oxide, delta aluminum oxide, alpha aluminum oxide, or mixtures thereof. Additionally or alternatively, the support material can be carbon-based and, in particular, comprise activated carbon.

[0026] A catalyst system having a material composition according to at least one of claims 2 to 4 has proven to be particularly advantageous.

[0027] Platinum is present in a range of 0.01 wt.% to 3.0 wt.% based on the total weight of the catalyst system, in particular in a range of 0.1 wt.% to 2 wt.%, and in particular in a range of 0.2 wt.% to 1.5 wt.%. Rhenium is present in a gravimetric platinum / rhenium ratio in a range of 10:1 to 1:3, in particular in a range of 10:1 to 1:1, and in particular in a range of 10:1 to 2:1.

[0028] Sulphur is present in an atomic ratio of platinum to sulphur in a range of 1:1 to 1:10, in particular in a range of 1:1.5 to 1:5 and in particular in a ratio of 1:2.

[0029] A catalyst system according to claim 5 has proven particularly advantageous for contacting with the hydrogen carrier material. The carrier material comprises at least one shaped body and / or powder particles. The shaped body can be in the form of extrudates, in particular strands or ribbed strands, in the form of tablets, rings, ring tablets, spheres, pellets, honeycomb bodies and / or granules, in particular spherical. The shaped bodies have in particular a particle diameter in the range from 0.05 mm to 50 mm. Spherical shaped bodies have in particular a diameter in the range from 0.1 mm to 20 mm, in particular in the range from 0.5 mm to 10 mm and in particular in the range from 1.0 mm to 6.0 mm. Extruded shaped bodies have a length in the range from 2 mm to 12 mm, in particular in the range from 3 mm to 10 mm and in particular in the range from 4 mm to 7 mm.Tablet-shaped molded bodies are in particular disc-shaped and have a diameter in the range of 1 mm to 10 mm, in particular in the range of 1.5 mm to 8 mm, and in particular in the range of 4 mm to 6 mm. The disc height is in particular between 1 mm and 10 mm, in particular between 1.5 mm and 8 mm, and in particular between 3 mm and 4 mm.

[0030] The powder particles have an average grain size of 40 pm to 500 pm, in particular of 40 pm to 300 pm and in particular of 60 pm to 200 pm.

[0031] The carrier material has in particular a specific surface in the range of 1 m 2 / g up to 300 m 2 / g, especially between 1 m 2 / g up to 250 m 2 / g, especially between 5 m 2 / g up to 150 m 2 / g and especially between 10 m 2 / g up to 150 m 2 / g. The specific surface area is determined by gas adsorption according to the Brunauer, Emmett, and Teller (BET) method, in accordance with DIN 66132. The specific surface area was determined by N2 physisorption using a dedicated measuring device, the QUADRASORB, manufactured by Quadrachrome Instruments. The prepared samples were baked at 250 °C under vacuum for 12 hours.

[0032] The pore volume of the carrier material is in particular between 0.1 cm 3 / g and 1.0 cm 3 / g and especially between 0.1 cm 3 / g and 0.4 cm 3 / g. The pore volume is determined by nitrogen sorption according to DIN 66135. The pore volume was determined by N2 physisorption using a dedicated measuring device, the QUADRASORB, manufactured by Quadrachrome Instruments. The prepared samples were baked at 250 °C under vacuum for 12 h.

[0033] The support material has, in particular, an average BJH pore diameter between 1 nm and 100 nm, in particular between 5 nm and 100 nm, in particular between 10 nm and 60 nm, and in particular between 20 nm and 50 nm. The average BJH pore diameter is determined using nitrogen physisorption hysteresis in accordance with DIN 66134. The average pore diameter was determined using N2 physisorption with a dedicated measuring device, the QUADRASORB, available from Quadrachrome Instruments. The prepared samples were baked at 250 °C under vacuum for 12 h.

[0034] A bed according to claim 6 enables improved contact between the hydrogen carrier material and the catalyst system. The catalyst system can be arranged in a variable manner, in particular advantageously, by arranging and / or mixing catalyst particles with different proportions of reaction materials, i.e., different catalyst materials. In particular, the bed is arranged in a reactor vessel and has a bed height that is oriented, in particular, along the longitudinal axis of the reactor vessel. The bed itself is, in particular, formless and is given a shape predetermined by an inner contour of the reactor vessel. In particular, the inner contour of the reactor vessel and thus the outer contour of the bed can be circular, for example, but also non-circular, in particular elliptical or polygonal. Along the bed height, the contour of the bed is, in particular, constant.A catalyst system according to claim 7 enables flexible adaptation of the properties of the catalyst system. The variable determination of the material proportions of the reaction materials in the catalyst system can be achieved, for example, by arranging the various catalyst materials in layers. For example, the first catalyst material can be arranged in a reactor vessel in the region where hydrogen carrier material enters the catalyst vessel. Hydrogen carrier material with a comparatively high degree of hydrogenation is fed there, for the dehydrogenation of which rhenium-containing catalyst material is particularly suitable. Along the bed height, the second catalyst material, which contains sulfur, can be arranged in particular in an outlet region of the reactor vessel, i.e., where the dehydrogenated hydrogen carrier material is discharged from the reactor vessel.The sulfur-containing catalyst material is particularly suitable for comparatively low degrees of hydrogenation, i.e., in particular, for at least partially dehydrogenated hydrogen carrier material. It is particularly conceivable to insert additional intermediate layers between a first layer containing the first catalyst material and a final layer containing the second catalyst material, which may, for example, comprise corresponding mixtures, in particular of the first and second catalyst materials.

[0035] It is also conceivable to arrange the third catalyst material, which comprises rhenium and sulfur, particularly along the bed height between the first and second catalyst materials. If a mixture of the first catalyst material, the second catalyst material, and / or the third catalyst material is produced, it is possible to establish a continuous progression of the material proportions along the bed height and thus provide for a continuous change in the properties of the reaction materials within the catalyst system. This allows the properties of the catalyst system to be flexibly and individually adjusted to the expected reaction conditions in the reaction vessel. The respective reaction conditions can be utilized in an optimized manner, and improved reaction results can be achieved.

[0036] In particular, it is possible to adjust the material proportions of the reaction materials in the bed even in a plane perpendicular to the bed height, for example, by designing the material properties in the area of ​​the outer wall of the reactor vessel differently than in a central area of ​​the reactor vessel. It is particularly possible to prepare homogeneous reaction properties within the reactor vessel.

[0037] A catalyst system according to claim 8 comprises, in particular, the third catalyst material, i.e., a PtSRe catalyst, in which all three reaction materials are arranged on one and the same support material. Such a material is easier to handle, eliminating the need for mixtures.

[0038] Alternatively, a catalyst system according to claim 9 can be provided in layers and / or containers in a simple and uncomplicated manner, since the production of the respective catalyst materials is simplified.

[0039] A reactor arrangement according to claim 10 essentially has the advantages of the catalyst system, to which reference is hereby made. The catalyst system as a whole can be arranged in a single dehydrogenation reactor.

[0040] A reactor arrangement according to claim 11 enables the targeted utilization of different catalyst materials in different reactor vessels. In particular, it is conceivable to carry out a staged, i.e. serial, dehydrogenation, wherein the catalyst material in the respective dehydrogenation reactor is adjusted depending on the initial degree of hydrogenation of the supplied hydrogen carrier material. In addition, different stratifications and / or continuous property profiles of the catalyst material can be created within the reactor vessel. In particular, the various dehydrogenation reactors are each different and, in particular, are at least partially filled with the catalyst system. The dehydrogenation reactors can be individually adjusted and, in particular, tailored to the expected dehydrogenation properties. In particular, the composition of the catalyst system differs in the various dehydrogenation reactors.In particular, different components of the catalyst system can be arranged in the different dehydrogenation reactors. In particular, it is not necessary for all components of the catalyst system to be stored in one dehydrogenation reactor. Alternatively, it is also possible for the different dehydrogenation reactors to be filled identically by designing the catalyst system identically in the different dehydrogenation reactors. Such a reactor arrangement enables advantageous scaling of the dehydrogenation process.

[0041] A process according to claim 12 essentially has the advantages of the catalyst system, to which reference is hereby made. Because the catalyst material can be specifically and, in particular, individually determined for different reactants, the dehydrogenation process is particularly efficient. The formation of byproducts is reduced and, in particular, avoided. Due to increased catalyst activity, the reaction rate and thus the hydrogen release rate are increased.

[0042] A method according to claim 13 enables an additional increase in efficiency by targeted influencing of the material compositions.

[0043] A process according to claim 14 enables the advantageous production of a catalyst system. In particular, a catalyst system produced thereby can be produced easily and reliably provided. Calcination of the loaded support material takes place for a minimum period of 0.5 h. The calcination can extend over a longer period, in particular several hours, and in particular last up to 6 h, especially up to 12 h or more.

[0044] A process according to claim 15 enables the production of a catalyst system with increased purity and thus with better reaction properties.

[0045] Both the features specified in the patent claims and the features specified in the exemplary embodiments of reactor systems according to the invention are suitable, either individually or in combination with one another, for further developing the subject matter of the invention. The respective combinations of features do not represent any restrictions with regard to further developments of the subject matter of the invention, but essentially have merely exemplary character. Further features, advantages, and details of the invention will become apparent from the following description of exemplary embodiments with reference to the drawings. They show:

[0046] Fig. 1 is a schematic representation of a dehydrogenation reactor with a catalyst system according to the invention arranged therein,

[0047] Fig. 2 is a schematic representation of a reactor arrangement corresponding to Fig. 1 with several dehydrogenation reactors connected in series,

[0048] Fig. 3 shows the functional relationship between the catalytic activity of different catalyst systems with different platinum-rhenium ratios,

[0049] Fig. 4 shows a representation corresponding to Fig. 3 for catalyst materials with and without sulfur,

[0050] Fig. 5 shows a representation of the functional relationship of a methylfluorene content as a function of the degree of dehydrogenation using different catalyst materials in Fig. 4,

[0051] Fig. 6 is a representation corresponding to Fig. 3 of various catalyst materials at different temperatures,

[0052] Fig. 7 is a representation corresponding to Fig. 3 of the reaction rate as a function of temperature for different catalyst materials,

[0053] Fig. 8 shows a representation of various catalyst materials corresponding to Fig. 3,

[0054] Fig. 9 shows a representation of platinum-based catalyst materials corresponding to Fig. 3. A dehydrogenation reactor 1, shown very schematically in Fig. 1, comprises a reactor housing 2 having a longitudinal axis 3. The reactor housing 2 is cylindrical with respect to the longitudinal axis 3. The inner contour of the reactor housing 2 in a plane perpendicular to the longitudinal axis 3 can also be non-circular.

[0055] A supply line 4 is connected to the reactor housing 2. The supply line 4 serves to supply perhydrogenated and / or partially hydrogenated hydrogen carrier material. According to the illustrated embodiment, the supply line 4 is connected to a first, in particular lower, end wall 5 of the reactor housing 2, in particular concentrically to the longitudinal axis 3. The lower end wall 5 is oriented transversely and in particular perpendicularly to the longitudinal axis 3. The supply line 4 can also be connected eccentrically to the longitudinal axis 3 and in particular to an outer wall 6 of the reactor housing 2.

[0056] A discharge line 7 is connected to the reactor housing 2. The discharge line 7 serves to discharge at least partially dehydrogenated hydrogen carrier material. It is conceivable that released hydrogen gas could also be discharged via the discharge line. Additionally or alternatively, a separate hydrogen gas discharge line can be connected to the reactor housing 2.

[0057] The discharge line 7 is connected to the reactor housing 2 at a distance from the supply line 4 along the longitudinal axis 3, in particular at a maximum distance. According to the exemplary embodiment shown, a maximum-distance arrangement of the supply line 4 and the discharge line 7 is achieved in that the discharge line is arranged on an upper end wall 8 arranged opposite the lower end wall 5. The upper end wall 8 is oriented transversely and in particular perpendicularly to the longitudinal axis 3. The discharge line 7 is oriented concentrically to the longitudinal axis 3. The discharge line 7 can also be arranged eccentrically to the longitudinal axis 3 on the upper end wall 8. The discharge line can also be arranged on the outer wall 6.

[0058] It is also conceivable that the arrangement of the lines 4, 7 is reversed, i.e., the supply line 4 is connected to the upper end wall 8 and the discharge line 7 is connected to the lower end wall 5. The arrangement of the supply line 4 and the discharge line 7 determines a flow direction 9 for the hydrogen carrier material within the reactor housing 2. The flow direction 9 is oriented, in particular, parallel to the longitudinal axis 3.

[0059] A catalyst system, designated as a whole by 10, is arranged within the reactor housing 2. The catalyst system 10 has several layers of different catalyst materials. Arranged along the flow direction 9 are a first layer 11 adjacent to the lower end wall 5, a second layer 12 adjoining the first layer 11, a third layer 13 adjoining the second layer 12, and a fourth layer 14 adjoining the third layer 13. The fourth layer 14 borders the upper end wall 8. According to the exemplary embodiment shown, the reactor housing 2 is essentially completely filled with catalyst material of the catalyst system 10.

[0060] According to the embodiment shown, the dehydrogenation reactor 1 has a single reaction chamber which is surrounded by the reactor housing 2.

[0061] Alternatively, the dehydrogenation reactor 1 can also be designed as a tube bundle reactor. Regarding the basic structure and operation of such a tube bundle reactor, explicit reference is made to DE 10 2015 219 305 A1. With the dehydrogenation reactor 1 as a tube bundle reactor, the introduction of heat as reaction energy is simplified, in particular by means of a heat transfer medium. The tube bundle reactor has a plurality of reaction tubes, in particular parallel-oriented, each reaction tube defining a reaction chamber. The heat transfer medium is conducted along the outer shell side of the reaction tubes. Heat transfer oil, in particular thermal oil, serves as the heat transfer medium. The catalyst system 10 is arranged in the reaction tubes. In particular, the catalyst material is immobilized in each of the reaction tubes.The flow direction 9 of the hydrogen carrier material can be oriented in the same direction or opposite to the flow direction of the heat transfer medium.

[0062] For a uniform distribution of the hydrogen carrier material among the reaction tubes, a distribution element can be present in the dehydrogenation reactor 1. The layers 11 to 14 are each made of different catalyst materials. According to the exemplary embodiment shown, each layer has a uniform catalyst material. The layers are each disk-shaped, corresponding to the reactor housing 2, with a circular cross-sectional area perpendicular to the longitudinal axis 3 and a layer height h oriented along the longitudinal axis 3. According to the exemplary embodiment shown, all layers have an identical layer height h. The layer heights can also be set differently.

[0063] Within each layer, a single catalyst material is homogeneously distributed. The material properties within the respective layers, particularly in a plane perpendicular to the longitudinal axis 3 and along the bed height h, are constant.

[0064] It is also conceivable that the material properties are variable within a layer and, in particular, are determined in a variable manner, in particular with a property profile that changes in particular along the longitudinal axis 3, i.e. along the filling height h.

[0065] Each layer 11, 12, 13, 14 comprises a bed of catalyst material comprising a support material and a reaction material supported by the support material. In particular, each layer comprises at least two reaction materials, at least one of which is platinum.

[0066] In particular, the first layer 11 contains exclusively platinum and rhenium as catalytically active materials. In particular, the first layer 11 is free of sulfur. This catalyst material is a first catalyst material and has proven particularly advantageous for the dehydrogenation of hydrogen carrier material with a high degree of hydrogenation. The catalyst material enables high catalyst activity, i.e., a high reaction rate.

[0067] The catalyst material of the fourth layer 14 comprises, in particular, a second catalyst material comprising exclusively platinum and sulfur. The second catalyst material has proven particularly advantageous when the hydrogen carrier material, which is increasingly dehydrogenated as it flows through the reactor housing 2, thus having a comparatively low degree of hydrogenation, results in low by-product formation. In particular, the fourth layer 14 is free of rhenium.

[0068] The second layer 12 and the third layer 13 each comprise a third catalyst material comprising platinum, sulfur, and rhenium. The three reaction materials are each supported on the support material. The catalyst materials of the second layer 12 and the third layer 13 differ from each other in that the rhenium content is greater and / or the sulfur content is lower in the second layer 12 than in the third layer 13.

[0069] In general, the rhenium content in the respective catalyst material for the layers 11, 12, 13, 14 decreases along the flow direction 9 and / or the sulfur content increases.

[0070] A second embodiment is described below with reference to Fig. 2. Structurally identical parts are given the same reference numerals as in the first embodiment, to the description of which reference is hereby made. Structurally different but functionally similar parts are given the same reference numerals with a suffix "a."

[0071] A reactor arrangement, designated as a whole by 15 in Fig. 2, comprises several, in particular three, dehydrogenation reactors 1a. The dehydrogenation reactors 1a are essentially identical and arranged in series. The dehydrogenation reactors 1a have identical sizes. The dehydrogenation reactors 1a can also have different sizes. In particular, the size of the individual dehydrogenation reactors 1a can be specifically selected differently depending on the dehydrogenation reaction to be carried out, in particular depending on the conversion.

[0072] In particular, downstream dehydration stages can be designed larger.

[0073] According to Fig. 2, this particularly applies to the dehydrogenation reactor 1a shown in the middle and on the right, which can have a larger reaction volume than the dehydrogenation reactor 1a shown on the left, which is directly connected to a first storage container 16. It is also conceivable, in particular, that the dehydrogenation reactor 1a shown on the right is larger than the middle dehydrogenation reactor 1a and that the middle dehydrogenation reactor 1a has the same size as the dehydrogenation reactor 1a shown on the left. If the hydrogen carrier material has a comparatively lower degree of hydrogenation, a comparatively lower reaction rate results in the respective dehydrogenation reactor 1a. The lower reaction rate can be compensated for by suitable reaction conditions, in particular temperature and / or pressure in the respective dehydrogenation reactor 1a.

[0074] The series connection is created in particular by the fact that the discharge line 7 of the first dehydrogenation reactor 1a, shown on the left in Fig. 2, is the feed line 4 of the second dehydrogenation reactor 1a, shown in the middle in Fig. 2. Correspondingly, the discharge line 7 of the second dehydrogenation reactor 1a is the feed line 4 of the third dehydrogenation reactor 1a, shown on the right in Fig. 2.

[0075] The first dehydrogenation reactor 1a is connected to the first storage tank 16 via the feed line 4. Perhydrogenated and / or partially hydrogenated hydrogen carrier material LOHC is stored in the first storage tank 16. +stored. A plurality of first storage containers 16 may also be present, in which perhydrogenated and / or partially hydrogenated hydrogen carrier material with varying degrees of hydrogenation is stored. A second storage container 17 is connected to the third dehydrogenation reactor 1a via the discharge line 7 of the third dehydrogenation reactor 1a. At least partially and / or completely discharged hydrogen carrier material LOHC is stored in the second storage container 17.

[0076] It is conceivable that the first and second dehydrogenation reactors 1a are also each connected to the second storage vessel 17 via separate discharge lines. Accordingly, it is possible for the first storage vessel 16 to be directly connected to the second or third dehydrogenation reactor 1a via corresponding supply lines. This provides additional flexibility regarding the supply and discharge of the hydrogen carrier material. The process can be carried out with particular flexibility.

[0077] A hydrogen gas buffer storage 18 and / or a hydrogen gas consumer 19 can additionally be connected to the third dehydrogenation reactor 1a in order to temporarily store and / or consume the released hydrogen gas. An optional separation unit 20 is arranged along the supply line 4 or discharge line 7 to separate released hydrogen gas from at least partially dehydrogenated hydrogen carrier material. The separated hydrogen gas can thus be branched off, in particular upstream of the last dehydrogenation reactor 1a, and fed, in particular, to a hydrogen gas buffer storage 18 and / or a hydrogen gas consumer 19.

[0078] It is advantageous if the released hydrogen gas is conditioned, i.e., purified and / or cooled, in an optional conditioning stage 22. The conditioning stage 22 is, in particular, centrally connected to a hydrogen gas line, which is connected to the hydrogen gas buffer storage 18 and / or to the hydrogen gas consumer 19. The conditioning stage 22 is, in particular, arranged downstream of the separation units 20 and, in particular, fluidically connected thereto. The at least partially discharged hydrogen carrier material can be transferred from the separation unit 20 to the dehydrogenation reactor 1a arranged downstream in each case. An optional purification stage 23 is arranged upstream of the second storage vessel 17 in order to purify impurities from the at least partially dehydrogenated hydrogen carrier material. In addition, purification stages 23 can each be arranged downstream of a dehydrogenation reactor 1a.

[0079] Alternatively, at least a partial flow of the hydrogen carrier material can be fed to the second storage container 17 or separate storage containers by means of a separate bypass line 21 and stored temporarily.

[0080] At least one catalyst material is arranged in each of the dehydrogenation reactors 1a. Due to the series connection of the dehydrogenation reactors 1a, it is possible for the catalyst materials of the various dehydrogenation reactors 1a to differ from one another. It is essential that the various catalyst materials of the reactor arrangement 15 as a whole form the catalyst system 10. In particular, it is not necessary for the catalyst system to be arranged entirely within one dehydrogenation reactor 1a. The various components of the catalyst system 10 can be arranged distributed across different dehydrogenation reactors 1a. According to the exemplary embodiment shown, the first catalyst material, which comprises platinum and rhenium as active materials, is arranged in particular in the first dehydrogenation reactor 1a. The second catalyst material, which comprises, in particular exclusively, platinum and sulfur, is arranged in the third dehydrogenation reactor 1a.The second catalyst material has, in particular, the highest sulfur content and / or, in particular, the lowest rhenium content. The third catalyst material, which comprises platinum, sulfur, and rhenium, is arranged in the second dehydrogenation reactor 1a, which is arranged along the flow direction between the first dehydrogenation reactor and the third dehydrogenation reactor. The effect upon dehydrogenation of the hydrogen carrier material in the series-connected dehydrogenation reactors 1a is functionally essentially equivalent to that of the various layers in the dehydrogenation reactor 1 according to the first embodiment.

[0081] In the first dehydrogenation reactor 1a, the hydrogen carrier material is dehydrogenated with a high degree of hydrogenation and high catalyst activity, i.e., with a high reaction rate. In the third dehydrogenation reactor 1a, the at least partially discharged hydrogen carrier material is dehydrogenated with a comparatively low degree of hydrogenation and high catalyst selectivity. The formation of by-products is essentially prevented. In the second dehydrogenation reactor 1a, dehydrogenation takes place at the intermediate stage.

[0082] It is understood that multiple layers with different material compositions can also be arranged within the individual dehydrogenation reactors 1a. It is particularly advantageous if the individual reactors 1a can be interconnected differently, particularly depending on the degree of hydrogenation of the respective hydrogen carrier material, with the storage vessels 16, 17 and the other dehydrogenation reactors 1a. For this purpose, the supply lines 4 and the discharge lines 7 are designed with corresponding conveying elements and diverters.

[0083] A process for dehydrogenating hydrogen carrier material is explained in more detail below.

[0084] The dehydrogenation takes place continuously in a reactor, in particular a tube-bundle reactor, where the individual reaction tubes each represent, in particular, a fixed bed. The reactor comprises one or more reaction chambers, which can be spatially separated and / or spatially connected and, in particular, are present as a layered catalyst bed. In a particularly preferred embodiment, the dehydrogenation is carried out continuously in one or more fixed-bed reactors, in which the catalyst is selected with different compositions depending on the degree of conversion.

[0085] At the start of the dehydrogenation reaction, perhydrogenated or partially hydrogenated hydrocarbons are brought into contact with a platinum- and rhenium-containing catalyst in a first reactor or in the first region of the fixed bed. This initial dehydrogenation occurs in particular at a conversion level of up to 60%, more preferably at a conversion level of up to 50%, in particular at a conversion level of up to 40%. The conversion level describes the completeness of the dehydrogenation reaction carried out. If, for example, the hydrogen carrier material has an initial hydrogenation level of 50% before the reaction and an initial hydrogenation level of 0% after the reaction, the dehydrogenation stroke is 50%, i.e. the difference between the initial hydrogenation level and the initial hydrogenation level. The conversion level is 100%, since the hydrogen carrier material has been completely dehydrogenated from the initial hydrogenation level to the initial hydrogenation level.

[0086] In the case where the hydrogen carrier material is fully hydrogenated as the starting material, the numerical values ​​for the dehydrogenation rate and the degree of conversion are essentially identical, and in particular, identical. Byproduct formation depends on the concentration of aromatic molecules. The change in the dehydrogenation rate, which directly relates to the degree of hydrogenation and thus to the ratio of aromatic to non-aromatic molecules in the hydrogen carrier material, allows a description of the relationship for byproduct formation.

[0087] Investigations by the applicant have shown that, starting at a hydrogenation level of at least 50%, differences in catalyst selectivity occur between Pt(Re) and Pt(Re) / S catalyst stars. Starting at this hydrogenation level, the use of sulfur-containing catalysts is particularly advantageous.

[0088] The dehydrogenation is preferably carried out at a temperature in the range from 100 °C to 400 °C, in particular from 200 °C to 350 °C and in particular from 210 °C to 330 °C. The dehydrogenation is preferably carried out at a pressure in the range from 1 to 8 bar, in particular in the range from 1 to 5 bar, in particular in the range from 2 to 4 bar and in particular at a pressure of about 3 bar.

[0089] In the reaction chamber, the partially hydrogenated hydrocarbons are contacted with a platinum-containing, rhenium-containing, and sulfur-containing catalyst. This second and optionally further dehydrogenation preferably takes place at a second conversion in the range of 30% to 95%, based on the original, in particular fully hydrogenated, hydrogen carrier material stream, in particular from 40% to 90%, and in particular from 50% to 90%. Based on the degree of hydrogenation, the second and optionally further dehydrogenation stages with sulfur-containing catalysts are advantageous in a hydrogenation degree range from about 60% and in particular from about 50%. The conversion in the respective last dehydrogenation stage is in particular complete. This means that the hydrogen carrier material is completely discharged in the last stage.The degree of hydrogenation after the last dehydrogenation stage is in particular not more than 20%, in particular not more than 10%, in particular not more than 5%, in particular not more than 3%, in particular not more than 1%, in particular not more than 0.1% and in particular not more than 0.01%.

[0090] The dehydrogenation is preferably carried out at a temperature in the range from 180 °C to 400 °C, in particular from 200 °C to 350 °C and in particular from 210 °C to 330 °C. The dehydrogenation is preferably carried out at a pressure in the range from 1 to 5 bar, in particular from 2 to 4 bar and in particular at a pressure of about 3 bar.

[0091] In the following, a method for producing the catalyst system 10 according to the invention, in particular the third catalyst material, in particular a platinum-containing, rhenium-containing and sulfur-containing powder and shaped body catalyst, is explained in more detail.

[0092] In step (a), a solution of platinum sulfite acid and soluble rhenium compounds are mixed in ultrapure water to form a precursor solution. Soluble rhenium compounds include dirhenium heptaoxide (Re2O?) or ammonium perrhenate (NELReC).

[0093] Platinum sulfite acid is often also referred to as platinum sulfurous acid and is usually given by the molecular formula H3Pt(SO3)2OH. Aqueous solutions of platinum sulfite acid (H3Pt(SO3)2OH) are commercially available and often have a precious metal concentration of 5 to 20 weight percent. The solutions may also contain sulfurous acid. The platinum sulfite acid solution used in step (a) can have a concentration in the range of 0.05 to 5 weight percent and is usually prepared by diluting a commercially available, concentrated solution to the desired concentration with water.

[0094] In a step (b), a solution of platinum sulfite acid and soluble rhenium compounds is applied to a carrier as a shaped body or powder.

[0095] The shaped carrier body or powder preferably comprises aluminum oxide (Al2O3), silicon dioxide (SiCl), titanium dioxide (TiCl), zirconium dioxide (ZrCl), silicon carbide (SiC), or mixtures thereof. More preferably, the shaped carrier body comprises aluminum oxide (Al2O3). The aluminum oxide is preferably selected from gamma-aluminum oxide, theta-aluminum oxide, delta-aluminum oxide, alpha-aluminum oxide, or mixtures thereof, and is especially gamma-aluminum oxide.

[0096] In one embodiment, the precursor solution from step (a) is applied to the support in step (b) by impregnation. The so-called "strong electrostatic adsorption" (SEA) method is preferably used here. In ion adsorption processes, electrostatic interactions between the precious metal component and the support surface are used to achieve deposition. Depending on the surface charge of the support, which depends on the pH of the solution from step (a), interactions of opposite charges occur. The precious metal concentration is therefore determined by the desired pH of the precursor solution.

[0097] As an alternative to the “SEA” process, other processes known to the person skilled in the art can also be used to apply the precursor solution to the carrier molding or carrier powder (e.g. spraying, wet impregnation (“incipient wetness impregnation”, “wet impregnation”), diffusion impregnation, chemical vapor deposition (CVD)). The spraying of the precursor solution from step (a) can, for example, be carried out according to the process described in the published application

[0098] DE 10 2007 025 356 A1. For this purpose, carrier moldings are sprayed in a spray chamber with a solution containing platinum sulfite acid and rhenium. The spraying can be carried out, for example, using a device from Innojet such as the “Innojet Aircoater”. The catalyst molding is circulated in the spray chamber in the form of two circular, counter-rotating spiral movements by a suitable propellant (e.g. Innojet Vulcano). The process is described in “Easy Coating: Fundamentals and Trends in Coating Pharmaceutical Products” Editors Mont Kumpugdee-Vollrath, Jens-Peter Krause; Vieweg+Teubner Verlag; 1st edition 2011, pages 120-132. The precursor solution can, for example, be introduced into the spray chamber via vertically arranged spray nozzles.

[0099] After applying the precursor solution to the carrier mold, the loaded carrier molds can be washed and then dried in an optional step (c). Washing of the loaded carrier molds can also be omitted.

[0100] The optional drying of the optionally washed carrier moldings can be carried out, for example, at a temperature in the range from 70°C to 150°C, in particular at about 120°C, over a period of 1 hour to 15 hours, preferably over a period of 5 hours to 10 hours, in particular over a period of 8 hours. In a particularly preferred embodiment, drying takes place over a period of 5 hours to 10 hours at a temperature in the range from 70°C to 150°C.

[0101] The number of impregnations depends, among other things, on the absorption capacity of the carrier molding, i.e., its pore volume, and the desired target loading. Typically, only one impregnation is performed.

[0102] An alternative drying method is the separation of precious metal-containing carrier moldings or carrier powder by rotary evaporation under vacuum. The drying process takes place over a period of 1 to 5 hours, especially 3 hours, at heating bath temperatures of 30 °C to

[0103] 70°C, preferably at 50°C. The loaded and optionally washed and dried carrier moldings or carrier powders are subjected to calcination in a step (d). The calcination is preferably carried out at a temperature in the range of 200°C to 550°C, preferably in the range of

[0104] 300 °C to 450 °C, in particular at about 400 °C over a period of 0.25 h to 6 h, preferably over a period of 0.5 h to 6 h, in particular over a period of about 4 h.

[0105] In a preferred embodiment, the calcination takes place at a temperature in the range of 300 °C to 420 °C over a period of 0.5 h to 6 h, in particular at about 400 °C over a period of about 4 h. The calcined platinum-containing, rhenium-containing, and sulfur-containing carrier moldings or powders obtained in step (d) are subsequently reduced in a step (e).

[0106] The reduction is preferably carried out at a temperature in the range of 200 °C to 500 °C, more preferably in the range of 300 °C to 450 °C, particularly preferably at about 400 °C over a period of 0.25 h to 5 h, preferably over a period of 0.5 h to 4 h, in particular over a period of about 2 h.

[0107] In a preferred embodiment, the reduction takes place at a temperature in the range of 300 °C to 450 °C over a period of 0.5 h to 4 h, in particular at about 400 °C over a period of about 2 h.

[0108] In the following, catalyst systems and / or components thereof and their properties are described in more detail with reference to Figs. 3 to 9.

[0109] Fig. 3 shows the degree of dehydrogenation (DHG) for different catalyst materials as a function of the dehydrogenation time t at ambient pressure and a temperature of 250 °C. The ratio of platinum content to perhydrogenated benzyltoluene as the hydrogen carrier material is 0.01 mol%. The sulfur content is identical for all catalyst materials shown here. It can be seen that the degree of dehydrogenation is lower for a rhenium-free catalyst material than for a rhenium-containing catalyst material. The varying rhenium content has no significant influence on the degree of dehydrogenation.

[0110] Fig. 4 shows the catalytic behavior of a sulfurized platinum-rhenium powder catalyst compared to a platinum-rhenium catalyst that has not been sulfurized. The significantly higher degree of dehydrogenation of the pure platinum-rhenium catalyst is evident, especially at shorter reaction times. At longer reaction times, the degrees of dehydrogenation of the different catalysts become similar, although the sulfurized platinum-rhenium powder catalyst does not reach the level of the pure platinum-rhenium catalyst. The influence of the material on the degree of dehydrogenation is less pronounced at longer reaction times.

[0111] Otherwise, the reaction conditions are the same as for the evaluation in Fig. 3.

[0112] Fig. 5 shows the content of a by-product, using methylfluorene as an example, as a function of the degree of dehydrogenation for the catalyst materials in Fig. 4. Methylfluorene is a selectively formed, dominant by-product that is undesirable and whose formation should be avoided. The undesirable increase in the methylfluorene content of the unsulfurized platinum-rhenium catalyst is clearly visible at high degrees of dehydrogenation, especially above 50%. In contrast, the use of the sulfur-containing catalyst shows that by-product formation, especially methylfluorene formation, can be significantly reduced at high degrees of dehydrogenation, i.e., in low hydrogenation ranges. The risk of catalyst deactivation is thus reduced.

[0113] Fig. 6 shows the catalytic activity of a sulfurized platinum-rhenium powder catalyst compared to a sulfurized platinum powder catalyst, which is rhenium-free. The degree of dehydrogenation of perhydrogenated benzyltoluene is shown over a period of 240 minutes at temperatures of 210 °C, 220 °C, 230 °C, 240 °C, and 250 °C. The pressure is ambient pressure. The ratio of platinum content to perhydrogenated benzyltoluene is 0.01 mol%. The reaction chamber is perfused with 300 ml / min of argon. Fig. 6 clearly shows that the maximum degree of dehydrogenation can be increased with increasing temperature, with the maximum degree of dehydrogenation being greater for the rhenium-containing catalysts than for the rhenium-free catalysts.

[0114] Fig. 7 shows the reaction rate with increasing temperature for the catalyst materials in Fig. 6. The reaction rate was determined at a degree of dehydrogenation of 5% under the reaction conditions already explained for Fig. 6. It can be seen that even at this low degree of dehydrogenation, a significant temperature dependence and a significant dependence on the catalyst material used are evident. The rate increases disproportionately with temperature. The rate is higher for the rhenium-containing catalyst material than for the rhenium-free catalyst material.

[0115] Fig. 8 shows the catalytic activity of a sulfurized platinum-rhenium catalyst compared to a sulfurized platinum catalyst from industrial production, which is therefore rhenium-free. The catalyst material is not powdered, but rather in the form of spherical pellets. The basic observations for the spherical pellets apply analogously to the powder catalyst, although the differences between the different materials are similar depending on temperature and more pronounced depending on rhenium.

[0116] Figure 9 shows the catalytic activity of platinum-rhenium catalysts with varying platinum loading compared to monometallic platinum catalysts with the same loading. The degree of dehydrogenation of perhydrogenated benzyltoluene is shown over a period of 240 minutes under the otherwise known reaction conditions. Improved catalytic activity is evident for rhenium-containing catalysts, with the catalytic activity increasing with decreasing weight percentage of the reaction material.

[0117] The catalyst system according to the invention may comprise one or more catalyst materials, the respective preparation of which is explained below by way of example.

[0118] - Pt: An aqueous solution of hexachloroplatinic acid is applied to a powdered aluminum oxide support using the process described in the patent. The Pt content is constant at 0.3 wt%. The BET surface area is 83 m². 2 / G.

[0119] Pt 0.3 wt%, Pt 1.5 wt%, Pt 3.0 wt%

[0120] An aqueous solution of hexachloroplatinic acid is applied to a powdered aluminum oxide support using the process described in the patent. The Pt content is 0.3 wt%, 1.5 wt%, and 3.0 wt%, respectively. The BET surface area is 83 m². 2 / G.

[0121] Pt-Re

[0122] An aqueous solution of hexachloroplatinic acid and rhenium heptaoxide is applied to a powdered aluminum oxide support using the process described in the patent. The Pt content is 0.3 wt% and the rhenium content is 0.15 wt%. The BET surface area is 83 m². 2 / G.

[0123] Pt-Re 0.3% by weight, Pt-Re 1.5% by weight, Pt-Re 3.0% by weight

[0124] An aqueous solution of hexachloroplatinic acid and rhenium heptaoxide is applied to a powdered alumina support using the process described in the patent. The Pt content is 0.3 wt%, 1.5 wt%, and 3.0 wt%, respectively. The platinum to rhenium ratio is constant at 2:1. The BET surface area is 83 m². 2 / G.

[0125] - PtS-Re 1:2, PtS-Re 10:1, PtS-Re 2:1, PtS-Re 1:1, PtS-Re 1:3

[0126] An aqueous solution of platinum sulfite acid and rhenium heptaoxide is applied to a powdered aluminum oxide support using the process described in the patent. The Pt content is constant at 0.3 wt% and the sulfur content is constant at 0.1 wt%, while the platinum-to-rhenium ratio varies as follows: 1:0, 10:1, 2:1, 1:1, 1:3. The BET surface area is 83 m 2 / G.

[0127] - PtS

[0128] An aqueous solution of platinum sulfide acid is applied to a powdered aluminum oxide support using the process described in the patent. The Pt content is 0.3 wt% and the sulfur content is 0.1 wt%. The BET surface area is 83 m². 2 / g. - PtS-Re

[0129] An aqueous solution of platinum sulfite acid and rhenium heptaoxide is applied to a powdered aluminum oxide support using the process described in the patent. The Pt content is 0.3 wt.%. The BET surface area is 83 m². 2 / G.

[0130] - PtSRe pellet

[0131] An aqueous solution of platinum sulfite acid and rhenium heptaoxide is applied to a pelletized alumina support using the process described in the patent. The Pt content is 0.3 wt%, the rhenium content is 0.15 wt%, and the sulfur content is 0.1 wt%. The BET surface area is 32 m². 2 / G.

[0132] Preparation of the comparison catalyst

[0133] Comparison

[0134] The comparison catalyst is a pellet catalyst produced according to DE 10 2018 109 254 Al, which contains both 0.3 wt% Pt and 0.1 wt% sulfur.

Claims

Patent claims 1. A catalyst system for the catalytic dehydrogenation of hydrogen carrier material, wherein the catalyst system (10) comprises reaction materials and carrier material carrying the reaction materials, wherein the reaction materials comprise platinum, rhenium and sulfur.

2. Catalyst system according to claim 1, characterized in that platinum is present in a range of 0.01 wt.% to 3.0 wt.% based on the total weight of the catalyst system (10).

3. Catalyst system according to one of the preceding claims, characterized in that rhenium is present with a gravimetric platinum / rhenium ratio in a range of 10:1 to 1:

3.

4. A catalyst system according to any one of the preceding claims, characterized in that sulfur is present in an atomic ratio of platinum to sulfur in a range of 1:1 to 1:

10.

5. Catalyst system according to one of the preceding claims, characterized in that the support material comprises at least one shaped body and / or powder particles.

6. Catalyst system according to one of the preceding claims, characterized in that the catalyst system (10) is designed as a bed having a bed height (h).

7. Catalyst system according to claim 6, characterized in that the material proportions of platinum, rhenium and / or sulfur, in particular along the bed height, can be variably determined, in particular continuously or in layers.

8. Catalyst system according to one of the preceding claims, characterized in that platinum, rhenium and sulfur are arranged together on the support material. Catalyst system according to one of the preceding claims, characterized by a first layer with a first catalyst material comprising platinum and rhenium as reaction materials, and a second layer with a second catalyst material comprising platinum and sulfur as reaction materials. Reactor arrangement for the catalytic dehydrogenation of hydrogen carrier material, comprising at least one dehydrogenation reactor (1; 1a) and a catalyst system (10) according to one of the preceding claims. Reactor arrangement according to claim 10, characterized by a plurality of dehydrogenation reactors (1a), which are filled, in particular differently, in particular at least partially, with the catalyst system (10). Method for the catalytic dehydrogenation of hydrogen carrier material, wherein the hydrogen carrier material is contacted with a catalyst system (10) according to one of claims 1 to 10.The method according to claim 12, characterized in that, depending on the degree of hydrogenation, the hydrogen carrier material is contacted with regions of the catalyst system (10) that have different material compositions. A method for producing a catalyst system according to any one of claims 1 to 10, comprising the following method steps. Providing a carrier material, Applying a solution of platinum sulphite acid (H3Pt(SO3)2OH) and at least one soluble rhenium compound in ultrapure water to the carrier material and thereby loading the carrier material, Calcining the loaded support material at a temperature in the range of 200 °C to 550 °C for a minimum period of 0.5 h and thereby producing a calcined platinum-containing, rhenium-containing and sulfur-containing support material, Reducing the calcined platinum-containing, rhenium-containing and sulfur-containing support material in the presence of hydrogen at a temperature in the range from 200 °C to 500 °C over a period of 0.25 h to 5 h.

15. The process according to claim 14, characterized by washing and / or drying the loaded support material, in particular before calcining, wherein in particular the drying takes place at a temperature in the range from 70 °C to 150 °C and in particular over a period of 1 h to 15 h or wherein the drying takes place in particular by rotary evaporation under vacuum over a period of 1 h to 5 h at heating bath temperatures of 30 °C to 70 °C.

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