US20080263954A1 - Use of a Process for Hydrogen Production - Google Patents

Use of a Process for Hydrogen Production Download PDF

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US20080263954A1
US20080263954A1 US12/092,231 US9223106A US2008263954A1 US 20080263954 A1 US20080263954 A1 US 20080263954A1 US 9223106 A US9223106 A US 9223106A US 2008263954 A1 US2008263954 A1 US 2008263954A1
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catalyst
hydrogen
gas
reactor
feed gas
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Ernst Hammel
Klaus-Dieter Mauthner
Walter Briceta
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BESTRONG INTERNATIONAL Ltd
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Electrovac AG
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Definitions

  • the present invention relates to the field of hydrogen production and its distribution infrastructure.
  • Hydrogen a colorless and odorless gas that is almost insoluble in water, was discovered by the English scientist Henry Cavendish in 1766. On a laboratory scale, it is produced by the electrolysis of water or by the exposure of zinc or iron to diluted acids. On an industrial scale, it is produced by a two-step method, with CO and H 2 being produced in a first step by burning hydrocarbons with steam, and CO being converted to CO 2 in a second step by the water gas reaction (CO+H 2 O ⁇ CO 2 +H 2 ) Carbon dioxide is then eliminated by scrubbing.
  • SMR Steam-reforming of natural gas
  • methane in the first place
  • SMR is a very highly developed commercial bulk process, by which 48% of the world's hydrogen production is accomplished.
  • This technology is also feasible with other raw materials such as ethane or naphtha, yet its efficiency will be lower with such higher-molecular substances (C. E. Grégoir Padró and V. Putsche, “Survey of the Economics of Hydrogen Technologies”, September 1999, National Renewable Energy Laboratory).
  • the SMR technology is based on the reaction of methane with steam in the presence of a catalyst. On an industrial scale, this process is run at about 800° C. and a pressure of 2.5 MPa.
  • the first process stage comprises the conversion of methane with steam to CO and hydrogen.
  • CO is further reacted with steam, thus yielding CO 2 and additional hydrogen.
  • the occurring CO 2 is separated from the product gas, which is freed of other impurities in further process steps.
  • the gas occurring in those steps, which, after all, consists of 60% combustible components, is recycled into the reformer.
  • the greatest drawback of the SMR process is its high CO 2 emission. To prevent this is the key issue of the present invention.
  • the process described herein encompasses the economic conversion of hydrocarbon to hydrogen gas and additionally exploitable fiber-shaped hydrocarbon (nanotubes).
  • Non-oxidizing methods include the thermal decomposition, also referred to as temperature-induced dissociation, the pyrolysis or the cracking of hydrocarbons to hydrogen and carbon.
  • U.S. Pat. No. 1,868,921, Schmidt et al. reports on the conversion of unsaturated hydrocarbons, preferably ethylene, to carbon black at temperatures of about 600° C. by the aid of nickel or cobalt catalysts applied on diatomaceous earth or ZnO, yet does not mention any appreciable synthesis of hydrogen.
  • U.S. Pat. No. 2,760,847, Oblad et al. deals with the decomposition of low-molecular hydrocarbons for the production of hydrogen by contact reactions on transition metals of groups VI/b and VIII of the Periodic System, which are dispersed in liquid host metal phases.
  • Pohlenz et al. describes a process for continuously producing hydrogen by catalytically decomposing gaseous hydrocarbons. Methane is cracked in a catalyst fluidized bed at temperatures of between 815 and 1093° C. That process uses Ni, Fe and Co catalysts, preferably Ni/Al 2 O 3 , which are deposited on carriers. The catalyst coated with carbon is continuously removed from the reactor, and the carbon is burned in a regenerator, whereupon the recovered catalyst is recycled into the reactor.
  • Ermakova et al. examined the effect of the SiO 2 content on Ni and Fe catalysts for the synthesis of carbon filaments, also proposing the efficiency of these catalysts for the preparation of hydrogen [Ermakova et al., Catalysis Today, 77, (2202), 225-235].
  • the authors report on Ni and Fe—SiO 2 catalysts having metal contents of between 85 and 90 wt. % and effectively decomposing methane into carbon filaments and hydrogen.
  • the catalyst production comprises a two-stage process, wherein ⁇ -Ni(OH 2 ) with a large specific surface area is dispersed into an SiO 2 -containing alcosol and the resulting mixture is calcined at temperatures of up to 700° C. Although the catalyst reduced at 700° C.
  • JP 2003-146 606 A describes a method for producing hydrogen, in which hydrocarbons on carbon nanohorns are decomposed to hydrogen and carbon. Such carbon nanohorns constitute alternative catalyst surfaces to metals.
  • a water gas shift reaction catalyst can be taken, which is comprised of a titanium nanotube. Such a catalyst can be used for reducing NO x from exhaust gases.
  • That catalyst is comprised of a carrier based on silica titanium carbon fibers or carbon nanofibers, which is impregnated with palladium and nickel compounds.
  • a copper catalyst with a nano-carbon material for the recovery of hydrogen from methanol can be taken from CN 1 586 718 A.
  • EP 1 623 957 A describes a method for producing hydrogen, by which also nano-carbon compounds occur, wherein an Ni catalyst is preferably used.
  • Hydrogen can be stored in large amounts only with energy expenditures, usually either as a gas or as a liquid. Gasometers are used for very large volumes. Medium quantities are stored as a gas in pressure tanks at about 30 bar. Smaller amounts can be filled into high-pressure gas bottles of steel or carbon-fiber-reinforced composite material at, presently, up to 400 bar. Yet, hydrogen can also be stored in liquid form at minus 253° C. All these types of storage involve considerable energy expenditures, both in terms of storage and in terms of maintaining, e.g., a cooled storage tank. The supply of a filling station network may finally be realized by the aid of tank trucks. If hydrogen is stored in high-pressure gas bottles of steel, only very little gas can be transported at a considerable weight.
  • a 40-ton truck will only be able to transport about 530 kilograms of gaseous hydrogen in steel bottles.
  • the transport of deep-frozen liquefied hydrogen in extremely well-insulated, double-walled tank containers is economical even for large volumes.
  • the same 40-ton truck, with the appropriate tank system will be able to load around 3300 kilograms of liquid hydrogen.
  • considerable energy losses will have to be taken into account during transportation.
  • An essential prerequisite for the introduction of hydrogen as a fuel for vehicles is a production and distribution system that must not be more complicated than today's system.
  • U.S. Pat. No. 6,432,283 B1 proposes to produce hydrogen from water directly at filling stations through electrolysis. Due to the high energy consumption in the form of electric power during the electrolysis of water, this method is, however, neither economical nor ecological, considering that current is primarily obtained by the combustion of fossile fuels.
  • Hythane-operated vehicles are regarded as an intermediate stage towards vehicles operated by pure hydrogen.
  • Hythane is a mixture of hydrogen and methane with variable composition portions. From CA 2141065 and EP 0 805 780 B1, a method for producing hythane from methane is known, which has a composition comprising a hydrogen portion of about 5-20%.
  • this is achieved by the use of a method for producing hydrogen, in which at least a portion of a hydrocarbon-containing feed gas is conducted into a reformer, wherein the feed gas is contacted with a catalyst in the reformer, wherein the feed gas is reacted to hydrogen and solid carbon compounds, for the direct (in situ) production of a hydrogen-containing gas at a filling station facility (for consumer supply).
  • the hydrogen-containing gas will constitute pure hydrogen or also mixtures such as, e.g. hythane, still containing a defined portion of unreacted feed gas (e.g. natural gas or methane).
  • a hydrogen-enriched gas is produced in the reformer, which, due to the catalytic decomposition of the feed gas, has a hydrogen content of between 5 and 99.99999 vol. % as well as a CO and CO 2 content of ⁇ 1 vol. %, and which can be intermediately stored at a filling station facility or even directly distributed to a consumer.
  • hydrogen or even hythane can be produced as a function of the production conditions such as, e.g., the catalyst surface area, gas flow and temperature. If the production of pure hydrogen is desired, gas flows having hydrogen contents of about 80 vol. % or more can be directly subjected to further gas cleaning so as to finally obtain pure hydrogen.
  • the advantage of this application resides in that the employed method, in addition to producing hydrogen or hythane, will also produce carbon in the form of carbon black.
  • the carbon thus separated in solid form will, therefore, not be discharged into the environment as the greenhouse gas CO 2 , but can be eliminated by special techniques.
  • Catalysts suitable for the decomposition of the feed gas to hydrogen and solid carbon, e.g. carbon black, are sufficiently known.
  • a nanostructured catalyst on which the feed gas is reacted to hydrogen and nano-carbon in the reformer is, however, used.
  • the production of solid nano-carbons offers a substantial economic advantage apt to accelerate the spreading of hydrogen technology at filling stations.
  • the number of filling stations offering hydrogen is extremely small and, for the time being, only limited to certain company networks. Yet, due to a minimum supply infrastructure, also the demand for hydrogen or hythane-operated motor vehicles is accordingly low. It will only be feasible at considerable financial expenditures to shift this situation in favor of the environmentally friendly hydrogen.
  • Nano-carbons such as, for instance, high-quality technical carbon blacks, nanoonions, nanohorns, nanofibers and/or nanotubes are usable as components in composites, as supercap materials, as storage media in Li ion accumulators, in field emission displays, in PEM fuel cells, in electronics and as active components in actuators.
  • a filling station in general, comprises fuel storage tanks, a line system, a measuring and dosing device and a dispensing device, e.g. a control unit with options for the customer and a line to a dispensing pistol.
  • a compressor may optionally be used to store the produced hydrogen or hythane in a storage tank under pressure.
  • a further pump to the dispensing system may optionally be omitted on account of the elevated pressure in the storage tank.
  • the produced hydrogen can also be stored intermediately in cooled and liquefied form.
  • a cooling unit and, preferably, a thermoinsulated storage tank are provided. Filling station systems for the supply of hydrogen are already known in the prior art and can be readily used for the present invention.
  • DE 101 07 187 A1 describes a filling station for cryogenic media like hydrogen or hythane. There, the fuels are stored in a cooled storage tank and made available through a fuelling device. From DE 102 01 273 A1, a system for filling cars with gaseous fuels and, in particular, hydrogen can be taken. A distribution system for hydrogen fuelling can be taken from DE 102 41 688 A1, and a special embodiment for fuelling hydrogen with oil as an engine-protective additive is known from DE 199 33 791 A1.
  • a system by which, in preferred embodiments, the produced hydrogen or hythane is intermediately stored in cooled form and/or under pressure.
  • the produced hydrogen or hythane can be directly transferred to the end customer.
  • hythane is formed, which is a mixture of hydrogen and unreacted feed gas, preferably methane.
  • feed gas preferably methane.
  • hythane already constitutes the desired end product of the present invention.
  • Pure hydrogen likewise constitutes a requested fuel.
  • the emerging gas flows with hydrogen contents of around 80 vol. % or more can be directly subjected to further gas cleaning, with pure hydrogen being obtained in the end.
  • the hydrocarbon-containing feed gas reacts with water to form H 2 and CO in a first step, and H 2 and CO 2 in a second step.
  • the catalyst e.g. Ni
  • a hot gas mixture enriched with hydrogen and having a composition comprised of 33 vol. % methane and 67 vol. % H 2 will be obtained.
  • This mixture is then fed into the steam reformer, where the remaining 33 vol. % CH 4 are reacted with steam in the presence of a catalyst to form CO and H 2 .
  • a reduction of the CO 2 emission by about 50%, based on the used methane will result in this example.
  • the finally occurring CO 2 is, however, required as a valuable reactant for the oxidation or surface modification of the nano-carbon catalytically produced in the reformer, and hence utilized in a beneficial manner.
  • the oxidizing post-treatment of the nano-carbon is accomplished at temperatures of between 300 and 2000° C. If this oxidation treatment is carried out at a temperature equal to, or higher than, 500° C., CO 2 is substantially converted into CO, which, fed into the shift reactor optionally arranged to follow the steam reformer, will again positively contribute to the quantitative yield, based on hydrogen.
  • the (nanostructured) catalyst used according to the invention may, for instance, also be provided in the form of a pressed pellet, which exhibits sufficient porosity to make the entire active surface of the catalyst available to the incoming feed gas.
  • the invention contemplates that the exhaust gases from the reformer are preheated prior to entering the steam reformer, which, amongst others by the high thermal capacity of the already present hydrogen, is easy to achieve and additionally accomplished by the entrainment of considerable amounts of heat from the reformer, thus providing an energetically more favorable operation of the steam reformer.
  • the exhaust gases from the steam reformer are afterburned to remove carbon monoxide. Since, according to the invention, the exhaust gases of the reformer are combined with the exhaust gases from the steam reformer, this is done in a cost-effective manner at a low energy consumption in a shift reactor usually arranged to follow a conventional steam reformer, anyway.
  • the CO 2 -containing exhaust gas emerging from the shift reactor can, furthermore, be used for the oxidation or surface modification of nano-carbon.
  • the exhausted catalyst covered with nano-carbon can, for instance, be collected in a post-reactor and, there, subjected to an oxidation or surface modification, yet it will also be feasible, if several reformers are provided, to switch between the same and effect such oxidation or surface modification in the reformers respectively loaded with nano-carbon.
  • the exhaust gases from the reformer are combined with the hydrogen-containing gas mixture emerging from the steam reformer and cooled prior to after-burning in order to avoid a back-reaction of the water gas reaction.
  • the elevated concentration of hydrogen which is reached on account of the reformer, also allows for an improved heat dissipation of the heat released from the water gas reaction.
  • the steam required for the steam reformer can also be generated, or heated, by the cooling process preferably taking place in a heat exchanger.
  • the catalyst is arranged on a carrier.
  • the carrier is a flat carrier, thus readily enabling the utilization of the entire catalytically active surface of the catalyst.
  • the carrier comprises particle-shaped ceramic bodies or particle-shaped glass bodies, which, on the one hand, have larger surface areas than flat carriers and, on the other hand, can also be used in fluidized beds. Furthermore, particle-shaped carriers will also exhibit higher mechanical stabilities.
  • the catalyst and the feed gas are preferably conducted in co-current flow within the reformer. Such a guidance will ensure a higher residence time of the feed gas on the catalyst, which will result in an enhanced gas utilization and higher conversion rates.
  • the catalyst and the feed gas are conducted in counter-current flow within the reformer. This will accelerate the reduction of the catalyst so as to reach higher efficiencies.
  • the feed gas is contacted with the catalyst in the reformer at a temperature ranging from 400° C. to 700° C. Within that temperature range, Ni composite catalysts, which are preferably used according to the invention, have extremely high efficiencies.
  • the catalyst is preferably selected from the group consisting of group VIII transition elements. Such catalysts are known per se for the production of nano-carbon.
  • the catalyst is a composite catalyst comprising a member selected from the group consisting of earth alkali metal oxides, silicon, silicon oxide and mixtures thereof.
  • Such catalysts are particularly suitable for the production of filaments, since the inert component in the interior of the catalyst particle will cause a concentration gradient relative to the carbon metastably dissolved in the metal.
  • nickel, cobalt and/or iron is used as a catalyst.
  • an effective range of 300° C. to 1400° C. will be covered by the catalysts mentioned herein, as a function of the respective composition.
  • the highest efficiency will be achieved by the method with methane used as a hydrocarbon; this also with the background that methane comprises the most favorable C/H ratio and can, moreover, be recovered in sufficient quantities from biological processes so as to ensure the independence from hydrocarbons of fossile origin.
  • the catalysts in terms of basic structure, can readily be specifically efficiently configured for other hydrocarbons as well.
  • hydrocarbons of alkanes, alkenes, alkines, cyclic hydrocarbons and their thermal decomposition products are absolutely suitable to run through the catalytic decomposition process, provided they exist in the vapor or gas phase under the indicated reaction temperatures.
  • hydrocarbon gases containing impurities like nitrogen, oxygen and sulfur may also be processed by this method via the reactor.
  • the impurities may be bound both in the air and in the hydro-carbon (e.g. as components of functional groups). Feed gases without such impurities and, in particular, nitrogen impurities amounting to more than 3%, preferably more than 2%, are, however, preferred.
  • Basic reagents used to adjust pH values of 8 or more include both alkali hydroxides, earth alkali hydroxides, earth alkali oxides, ammonia or ammonium hydroxide. If alkali hydroxides are used, it must be taken care that the finished catalyst does no longer contain any alkali metal impurities, since these would affect the activity of the catalyst. The opposite holds for the precipitation with earth alkali hydroxide or earth alkali oxide, since earth alkali oxide as an inert extra component in the composite catalyst will have a positive effect on the catalytic activity of the latter.
  • composite catalysts with MgO, CaO, MgO/CaO are, inter alia, readily accessible as inert components. In a preferred manner, catalysts as described in EP 1 623 957 are used and treated.
  • the catalyst is preferably selected from the group consisting of group VIII transition elements.
  • the catalyst preferably comprises a composite structure and at least one group VIII transition element component, preferably Fe, Ni, Co, Mo and/or mixtures thereof, particularly preferred MoCo.
  • the composite catalyst comprises an inert component preferably selected from oxides and/or hydroxides of earth alkalis, of silicon, aluminum, boron, titanium or mixtures thereof, wherein caustically burnt magnesia and/or freshly precipitated magnesium hydroxide with a specific surface area of >1 m 2 /g are particularly preferred.
  • Such catalysts are particularly suitable for the production of filaments from carbon, since the inert component in the interior of the catalyst particle will cause a concentration gradient relative to the carbon metastably dissolved in the metal.
  • the catalyst is preferably a nanostructured catalyst suitable for the production of nano-carbon.
  • SiO 2 exerts a very positive influence on the activity of group VIII transition metals.
  • the central point also with these catalysts is that, departing from the metal hydroxide precipitates produced in situ, the “Si” or SiO 2 is united with the hydroxide in a likewise nanostructured manner, either by a parallel precipitation or by an immediately following precipitation.
  • nickel, cobalt and/or iron is used as a catalyst.
  • the catalysts preferably used according to the invention are based on Ni, Fe and Co and, in an even more preferred manner, have composite character with a component that is inert relative to the decomposition of hydrocarbon.
  • the catalyst is, in particular, selected from group VIIIB of the Periodic System and, in addition, comprises an f- or d-transition metal preferably selected from vanadium, chromium, manganese, molybdenum, palladium, platinum, or from the group of rare earth metals.
  • SiO 2 -containing Co, Ni and Fe catalysts, or Ni, Fe and Ni/Fe-containing hydroxide or oxide powders are obtained by precipitating SiO 2 “on” the metal hydroxide dispersed in water, alcohol, acetone or any other suitable solvent.
  • SiO 2 is directly deposited on the hydroxide by the decomposition of tetraoxysilane (TEOS) by the addition of a base (e.g. NH 3 /H 2 O).
  • TEOS tetraoxysilane
  • a base e.g. NH 3 /H 2 O
  • substoichiometric SiO 2 —Ni(OH) 2 , SiO 2 —Fe(OH) 3 or SiO 2 —Ni/Fe hydroxides are obtained in one step by the direct, simultaneous precipitation under base addition.
  • the main component of the composite catalyst is the group VIII transition metal, the latter being at least present at a ratio of larger than 50 mol-%, preferably larger than 80 mol-% and, still more preferred, at a ratio of larger than 90 mol-%.
  • organic solvents e.g. alcohol, acetone, THF, acetonitrile, nitromethane etc.
  • inorganic and organic bases e.g. NaOH, NH 3 , NH 4 OH, TMEDA etc.
  • precipitates with composite character containing high-molecular silicone compounds, metal hydroxide and metal-Si metal organyls will be obtained.
  • This mixture which forms the solid deposit, will guarantee very large specific surface areas (>20 m 2 /g) and, hence, the nanostructures of these composite catalysts.
  • the catalyst in the reformer is continuously or discontinuously discharged, optionally as a function of the hydrogen content in the exhaust gas, and separated from adhering carbon compounds. After the separation of the nano-carbon, the discharged catalyst is continuously regenerated and/or recycled, and can be used again. In a particularly preferred manner, this method step can proceed automatically.
  • the catalyst is preferably mechanically separated from adhering carbon compounds, preferably by scraping or in a cyclone. This is of particular advantage when using a flat or solid carrier.
  • the catalyst is chemically separated from adhering carbon compounds, preferably by an etching process.
  • an etching process acid treatment
  • the metallic catalysts can be separated and recycled in a simple manner.
  • the catalyst is physically separated from adhering carbon compounds, preferably by high-temperature treatment, heat removal, inductively, by RF or HF. This separation process is particularly gentle for the nano-carbons formed.
  • natural gas is used as a feed gas. Natural gas is the cheapest and most readily accessible feed gas variant, it is optionally cleaned from sulfur compounds prior to its use.
  • biogas is used as a feed gas. This comes very close to natural gas in its composition and allows for decoupling from fossile energy carriers.
  • a portion of the feed gas is preferably used as a heating gas for heating the reformer and/or steam reformer. This will favorably influence the energy balance, in particular, if an optionally prepurified biogas is used as a feed gas and available in sufficient quantities.
  • waste heat from the steam reformer is used for preheating the feed gas for the reformer and/or for heating the reformer. Due to the temperature differences between the two processes (the hydrogen production in the reformer at the simultaneous production of solid carbon compounds taking place at lower temperatures than the hydrogen production in the steam reformer), the utilization of the waste heat from the steam reformer is quite obvious, and it is readily feasible by suitable measures (e.g. a heat exchanger provided between the two reformers).
  • the composite catalyst preferably used according to the invention can be produced in the following way:
  • SiO 2 has a highly positive effect on the activity of group VIII transition metals.
  • the central point also with these catalysts is that, departing from the metal hydroxide precipitates produced in situ, the “Si” or SiO 2 is united with the hydroxide in a likewise nanostructured manner, either by a parallel precipitation or by an immediately following precipitation.
  • SiO 2 -containing metallic catalysts or metal-containing hydroxide or oxide powders are either obtained by precipitating SiO 2 “on” the metal hydroxide dispersed in water, alcohol, acetone or any other suitable solvent.
  • SiO 2 is directly deposited on the hydroxide by the decomposition of tetraoxysilane (TEOS) by the addition of a base (e.g. NH 3 /H 2 O).
  • TEOS tetraoxysilane
  • a base e.g. NH 3 /H 2 O
  • substoichiometric SiO 2 —Ni(OH) 2 , SiO 2 —Fe(OH) 3 or SiO 2 —Ni/Fe hydroxides are obtained in one step by the direct, simultaneous precipitation under base addition.
  • the main component of the composite catalyst is the group VIII transition metal, the latter being at least present at a ratio of larger than 50 mol-%, preferably larger than 80 mol-% and, still more preferred, at a ratio of larger than 90 mol-%.
  • the catalyst components are directly precipitated from organic solvents (e.g. alcohol, acetone, THF, acetonitrile, nitromethane etc.) with both inorganic and organic bases (e.g.
  • the thus synthesized catalyst powder is dried, while avoiding drying temperatures of above 150° C. in order to keep diffusion procedures between the individual components or particles at a minimum, since this might lead to undesired particle aggregations, which would, in turn, necessitate sintering procedures between the individual catalyst particles under operating conditions at high temperatures. This would inevitably restrict the activities of the catalysts in an undesired manner.
  • Catalysts synthesized by the wet-chemical route described herein additionally contain solvent molecules, which are removed by calcining at higher temperatures.
  • This process step calls for the formation of individual crystallographic phases, both of the inert component and of the catalytically active metal component. If powder calcining is appropriate, an appreciable degradation of hydroxide to oxide will occur at temperatures of above 150° C., and continue with the temperature increasing. At temperatures of above 350° C., this procedure will be largely completed, and further changes in the catalyst will, thus, have to be attributed to sintering effects.
  • Such catalysts freed from foreign components are also directly accessible.
  • Ni, Fe or any transition metal compounds are decomposed in the gas or vapor phase at high temperatures, i.e. temperatures higher than 300° C., along with compounds containing the inert component or its precursor.
  • the decomposition also may take place only on the wall of the heated vessel. The prerequisite here being that compounds be used, which are sufficiently volatile and exist in the gas or vapor phase at least over a short time.
  • the use according to the invention is preferably applied for the production of nano-carbons such as high-quality technical carbon blacks, nanoonions, nanohorns, nanofibers and/or nanotubes, which adhere to the catalyst.
  • nano-carbons constitute a valuable by-product in the production of hydrogen.
  • Consumers preferably comprise motor vehicles to which the hydrogen-containing fuel produced is distributed.
  • a method for fuelling consumers is also provided, wherein the fuel is produced in accordance with the use of the invention.
  • a filling station facility including a device for the production of a hydrogen-containing gas mixture from a hydrocarbon-containing feed gas comprises an inlet for a hydrocarbon-containing feed gas (a), a reformer (c) comprising a catalyst, an exhaust gas line (j) suitable for hydrogen transport, a compressor or a cooling device (f), and a dispensing device (h) suitable for withdrawing either the hydrogen-containing fluid or the hydrogen-containing gas.
  • the expensive transport of hydrogen is also avoided by the CO 2 -poor in-situ production of the same.
  • the catalyst is preferably comprised of a nanostructured catalyst suitable for the production of nano-carbon.
  • the use according to the present invention further enables the production of a gas mixture with a composition to be selected by the consumer.
  • the filling station facility preferably comprises a storage tank (g) for either a cooled liquid hydrogen-containing fluid or a hydrogen-containing gas under pressure, or both.
  • the filling station facility comprises a mixing device (k) for mixing the hydrogen-containing exhaust gas with a hydrocarbon-containing gas.
  • the mixing device in a simple manner enables the preparation and administration of a mixture, e.g. hythane if the hydrocarbon is methane, with a desired hydrogen portion according to the respective demand.
  • the hydrocarbon may, for instance, be present in the form of natural gas or liquefied natural gas or biogas. Mixing may, of course, also be effected elsewhere, for instance directly at the dispensing device (h) during the fill-up of a consumer (i).
  • the filling station facility comprises a compressor.
  • a suitable compressor By a suitable compressor, a hydrogen-containing gas can be compressed for better intermediate storage in a pressure tank.
  • a cooling installation is provided, which is able to convert the exhaust gas from the reformer into a cooled liquid hydrogen-containing fluid.
  • the reformer (c) comprises a supply and discharge device (cl) for the continuous supply and discharge of the catalyst.
  • the filling station facility preferably comprises a steam reformer (d) for the production of pure hydrogen.
  • the filling station facility also comprises a measuring and dosing device for the customized fuelling of a consumer.
  • a reactor device for the production of hydrogen which includes a reactor (or reformer) comprising
  • Catalysts e.g. iron, cobalt or nickel catalysts
  • reach their activities in the presence of hydrogen for this reason, hydrogen is added as a reaction trigger in discontinuous methods.
  • the metal-containing catalyst which is present in its original form as an oxide, will thereby be reduced and only in that state suitable for an oxygen-free cracking process.
  • the produced hydrogen ensures that an active catalyst will already be available to the inflowing feed gas.
  • defined optimized feed gas flow rates and residence times are, therefore, chosen.
  • a further essential characteristic feature resides in the cooling of the produced carbon-catalyst mixture, which is continuously discharged. After discharging from the reactor, no or only marginal cooling measures are required.
  • the discharged catalyst is preferably continuously regenerated and/or recycled, and can be used again. In a particularly preferred manner, this method step can proceed automatically.
  • the catalyst is preferably wet-chemically separated from adhering carbon compounds. It is, moreover, preferred, if the catalyst is chemically separated from adhering carbon compounds, preferably by dissolution in acids.
  • the metallic catalysts can be separated and recycled in a simple manner. In the event of earth alkali oxides as carrier materials, in particular MgO, which will be left as a solid after the acid treatment, this can be dissolved, after the separation of the metallic catalyst components, in the presence of ammonia and subsequently precipitated by bases. The thus obtained MgOH can then be converted into the oxide in a calcining step.
  • the catalyst is physically separated from adhering carbon compounds, preferably by high-temperature treatment (in particular above 2400° C.), heat removal, inductively, by RF or HF. This separation process is particularly gentle for the solid carbon formed as nano-carbon.
  • the reactor comprises a preheating zone.
  • This preheating zone is located upstream of the heating zone—in respect to the catalyst flow.
  • the catalyst is continuously heated in the same, is optionally dehydrated and preferably also already contacted with the feed gas so as to be reduced to its active form.
  • the catalyst is at first introduced into the preheating zone—which may be heated separately or by the waste heat from the heating zone—, then reaches the heating zone, where the catalytic reaction takes place with the formation of solid carbon, and finally the catalyst and the carbon reach the cooling zone, where they are cooled while giving off heat to the feed gas.
  • the preheating zone is preferably configured for operating temperatures of between 100° C. and 900° C. It is particularly preferred if the reactor gas outlet is provided in the preheating zone or in the heating zone, preferably in the preheating zone.
  • the cooling zone is configured for operating temperatures ranging between 100° C. and 600° C., preferably 200° C. and 500° C. This temperature range allows the cracking reaction to already proceed with suitable catalysts, thus enabling cooling of the catalyst and of the solid carbon.
  • the cooling zone may also be cooled by the aid of a water cooler—in addition to the cold feed gas.
  • the heating zone is configured for operating temperatures of between 300° C. and 1400° C., preferably between 500° C. and 1000°.
  • This temperature range offers perfect conditions for the decomposition of the feed gas to hydrogen.
  • the growth and structure of nano-carbons can, furthermore, be influenced or even controlled.
  • Co—, Fe or Ni composite catalysts which are preferably used according to the invention, have extremely highly efficiencies.
  • the region that exhibits suitable temperature conditions in the interior of the reactor is referred to as the reactor zone.
  • the solid-carbon outlet or catalyst outlet is provided in the cooling zone.
  • a gradually decreasing temperature gradient is provided within the reactor—optionally in the preheating zone.
  • the catalyst inlet is preferably provided in the heating zone or in the preheating zone.
  • the optionally preheated catalyst is rapidly heated to operating temperature in the heating zone.
  • the heating zone of the reactor preferably comprises heating rods, heating coils or a gas burner externally.
  • a cooler may optionally be arranged, if it is to be expected that insufficient cooling will be provided in the zone by the inflowing feed gas.
  • the dimension of the heating zone is preferably up to 50%, preferably up to 40%, most preferred up to 30%, of the length of the reactor from the feed gas inlet to the reactor gas outlet.
  • the dimension of the cooling zone is up to 50%, preferably up to 40%, most preferred up to 30%, of the length of the reactor from the feed gas inlet to the reactor gas outlet.
  • the reactor preferably comprises a pressure controller or regulator for an overpressure of 1 to 500 mbar, preferably 50 to 400 mbar, particularly preferred 90 to 250 mbar.
  • the crack reaction can be performed at atmospheric pressure, yet a slight overpressure is applied to avoid the influx of oxygen from the air through untight spots.
  • the catalyst in the reactor is, in particular, provided on or in a mechanical device preferably selected from a conveyor screw, a drum-type conveyor or a tape run.
  • a mechanical device preferably selected from a conveyor screw, a drum-type conveyor or a tape run.
  • Such devices or carriers are also suitable for conveying and continuously transporting the catalyst from the heating zone into the cooling zone, and optionally from the preheating zone into the heating zone.
  • the catalyst is preferably selected from the group consisting of group VIII transition elements, as already pointed out above.
  • the catalyst preferably comprises a composite structure and at least one group VIII transition element component, preferably Fe, Ni, Co, Mo and/or mixtures thereof, particularly preferred MoCo.
  • the composite catalyst comprises an inert component preferably selected from oxides and/or hydroxides of earth alkalis, of silicon, aluminum, boron, titanium or mixtures thereof, wherein caustically burnt magnesia and/or freshly precipitated magnesium hydroxide with a specific surface area of >1 m 2 /g are particularly preferred.
  • Such catalysts are particularly suitable for the production of filaments from carbon, since the inert component in the interior of the catalyst particle will cause a concentration gradient relative to the carbon metastably dissolved in the metal.
  • nickel, cobalt and/or iron are used as a catalyst.
  • the catalysts preferably used according to the invention are based on Ni, Fe and Co and, in an even more preferred manner, have composite character with a component that is inert relative to the decomposition of hydrocarbon.
  • the catalyst is, in particular, selected from group VIIIB of the Periodic System and, in addition, comprises an f- or d-transition metal preferably selected from vanadium, chromium, manganese, molybdenum, palladium, platinum, or from the group of rare earth metals.
  • the device comprises a pressure swing adsorption plant (PSA) downstream of the reactor gas outlet.
  • PSA pressure swing adsorption plant
  • special porous materials are used as molecular sieves to adsorb molecules as a function of their kinetic diameters.
  • hydrogen is separated from unreacted feed gas (e.g. methane).
  • Hydrogen can be stored or supplied to a consumer, and the unreacted gas can optionally be burned, e.g. in a torch, to preferably heat the heating zone of the reactor.
  • reaction-affecting gases e.g. nitrogen
  • the device comprises a filter following the reactor gas outlet and optionally preceding a pressure swing adsorption plant.
  • a filter is arranged downstream of the reactor in the sense of the feedgas/reactor gas flow.
  • a reactor gas compressor may be provided (following the reactor gas outlet and optionally a filter, and preceding the PSA plant) to compress the product gas and optionally store it in a tank or feed it to the PSA plant.
  • a feed gas flow control and optionally a feed gas compressor are provided (each upstream of the feed gas inlet) to enable the control of the inflow into the reactor.
  • the present invention relates to a method for producing a hydrogen-containing gas in a reactor comprising
  • the catalytic cracking of the feed gas in the reactor is preferably carried out at an overpressure of 1 to 500 mbar, preferably 50 to 400 mbar, particularly preferred 90 to 250 mbar, in order to prevent air from flowing in.
  • a further method step for producing pure hydrogen comprises the separation of hydrogen and unreacted feed gas in the reactor gas, e.g. in a PSA plant.
  • the average residence time of the feed gas in the reactor in special embodiments is between 5 and 100 seconds, preferably between 5 and 50 seconds, particularly preferred between 5 and 30 seconds, most preferred between 5 and 20 seconds, in particular between 10 and 15 seconds.
  • the entry pressure of the feed gas and the exit pressure of the reactor gas at the reactor are kept substantially equal.
  • two hydrogen molecules per methane molecule will occur as a gaseous product.
  • the outflowing gas volume as a characterizing method parameter is, therefore, higher than the volume of the inflowing feed gas at an identical pressure.
  • natural gas in particular methane
  • Natural gas is the cheapest and most readily accessible feed gas variant, it is optionally cleaned from sulfur compounds prior to its use.
  • biogas is used as a feed gas. This comes very close to natural gas in its composition and allows for decoupling from fossile energy carriers.
  • the catalyst is preferably a nanostructured catalyst on which the feed gas can be reacted to hydrogen and nano-carbon preferably selected from high-quality technical carbon blacks, nanoonions, nanohorns, nanofibers and/or nanotubes.
  • the present invention relates to the use of a device as described herein for the production of a hydrogen-containing gas, in particular, according to the method described herein.
  • the device is preferably used for the direct production of a hydrogen-containing gas at a filling station facility for distribution to a consumer.
  • the present invention relates to a filling station facility comprising:
  • the filling station or application according to the invention.
  • the filling station, and the use for the production at a filling station using the reactor device as herein, are already generally described above.
  • the filling station or filling station facility suitable for fuelling motor vehicles enables the simple fill-up of hydrogen-operated vehicles or vehicles operated by a hydrogen mixture. According to the invention, the expensive transport of hydrogen will also be avoided by the CO 2 -poor production in situ.
  • the catalyst is preferably a nanostructured catalyst suitable for the production of nano-carbon. It is, moreover, feasible by the use according to the present invention to produce a gas mixture with a composition selectable by the consumer.
  • the filling station facility preferably comprises a storage tank for either a cooled liquid hydrogen-containing fluid or a hydrogen-containing gas under pressure, or both.
  • the filling station facility comprises a mixing device for mixing the hydrogen-containing exhaust gas with a hydrocarbon-containing gas.
  • the mixing device in a simple manner, enables the preparation and administration of a customized mixture of, for instance, hythane if the hydrocarbon is methane, with a desired portion of hydrogen.
  • the hydrocarbon may, for instance, be available in the form of natural gas or liquefied natural gas or biogas. Mixing may, of course, also take place elsewhere, for instance directly at the dispensing device during the fill-up of a consumer.
  • the filling station facility comprises a compressor.
  • a suitable compressor allows for the compression of a hydrogen-containing gas for an enhanced inter-mediate storage in a pressure tank.
  • a cooling installation is provided, which is able to convert the exhaust gas from the reactor into a cooled liquid hydrogen-containing fluid.
  • the reactor comprises a supply and discharge device for the continuous supply and discharge of the catalyst.
  • the filling station facility comprises a steam reformer and/or a PSA plant for the production of pure hydrogen.
  • the filling station facility preferably also comprises a measuring and dosing device for the customized fuelling of a consumer.
  • FIGS. 1-3 Attached FIGS. 1 to 3 graphically illustrate the hydrogen concentrations measured in the exhaust gas of the reformer described in Example 2 over a defined time. From all three Figures, it is apparent that a virtually invariably high and stable hydrogen concentration could be reached in the exhaust gas over the entire test period, which is due to a particularly high activity of the Ni composite catalyst used (Example 1).
  • FIG. 4 illustrates an embodiment of a filling station according to the invention (Example 3).
  • FIG. 5 Course of the hydrogen concentration in the exhaust gas at a discontinuous catalyst supply.
  • FIG. 6 Schematic illustration of the plant comprising an inlet for a hydrocarbon-containing feed gas ( 1 ) and optionally a compressor ( 1 a ) and a flow regulator ( 1 b ) for the feed gas; a reactor ( 2 ) including a CNT cooling zone ( 2 a ); a container for the catalyst ( 3 ) and discharged CNT ( 4 ); a filter ( 5 ), a reactor gas cooler ( 6 ), a reactor gas compressor ( 7 ), a PSA plant ( 8 ) and, optionally, a torch ( 9 ) as well as a hydrogen container ( 10 ).
  • FIG. 7 Schematic illustration of the reactor ( 2 ), which is axially subdivided into a heating zone (b) and a cooling zone (a) and comprises a rotary conveyor screw (c) with catalyst.
  • FIG. 8 Specifications of the components, and design parameters of the components, of a plant.
  • FIG. 9 Nano-carbon fibers wet-chemically separated from MoCo/MgO catalyst (Example 5).
  • Ni(OH) 2 was prepared from an aqueous nickel nitrate solution by ammonia precipitation at pH 9. The precipitate was collected in a Büchner funnel, thoroughly washed with deionized water, followed by acetone, and dried at 100° C. for several hours. 4.5 g of the thus prepared Ni(OH) 2 powder were suspended in 100 ml acetone under vigorous stirring and then supplemented with 2 ml TEOS (tetraethoxysilane), 5 ml water and 2 ml ammonium hydroxide (25%). The suspension was mechanically stirred over night so as to ensure that virtually all of the TEOS was homogenously applied as SiO 2 on the Ni(OH) 2 precipitate. The solid residue was filtered, washed as above, and dried at 120° C. for several hours.
  • TEOS tetraethoxysilane
  • 200 mg of the composite catalyst were loaded into a ceramic boat, which was inserted into a tubular furnace including a hot zone of 30 cm and equipped with a quartz tube of 40 mm diameter and 1000 mm length.
  • the quartz tube was closed on both ends by suitable closures comprising gas supply and gas outlet means.
  • the whole system was flushed with pure methane. After having started heating to the CVD reaction temperature of 620° C., a methane gas flow of 90 ml/min was adjusted. The heating rate was 10° C. per minute, and a constant temperature of 620° C. was maintained for 4 hours. When reaching a temperature of 350° C., an increase in the hydrogen content was observed in the exhaust gas. After 20 minutes, and having reached of the reaction temperature, a hydrogen concentration of 68 vol. % was measured in the exhaust gas. During the four-hour test period, the hydrogen concentration dropped continuously, still amounting to 51 vol. % at the end. After cooling to room temperature, 3.87 g of carbon nanofibers were removed from the reactor.
  • the measurement of the hydrogen concentration in the exhaust gas of a reformer according to the invention was performed using Calomat 6, a device manufactured by Siemens (DE). From the data acquired by the measurements, the activity of the catalyst can be concluded at any time of the reaction. It is, thus, further possible, by providing a hydrogen sensor in the exhaust gas flow of the reformer and an online evaluation of the acquired hydrogen concentration data, to allow the supply of fresh, unused catalyst, as well as the discharge of used catalyst covered with nano-carbon, to proceed automatically with an existing supply and discharge device for the continuous supply and discharge of catalyst.
  • FIG. 4 This schematic illustration depicts an inlet for a hydrocarbon-containing feed gas (a) into a reformer (c).
  • the feed gas is reacted to hydrogen on a catalyst under reaction conditions.
  • the reformer (c) comprises a supply and discharge device (cl) for the continuous supply and discharge of the catalyst.
  • the hydrogen-containing exhaust gas of the reformer is facultatively conducted, via an exhaust gas line (j) that is suitable for the transport of hydrogen, i.e. sufficiently tight, both directly and through a steam reformer (d), via a mixing device (k), into a compressor or a cooling device (f).
  • the feed gas injected into the reformer is preferably preheated via a heat exchanger (b 1 ) by the exhaust gas (j) from the reformer, or from the steam reformer.
  • the steam reformer is equipped with a steam inlet (e).
  • the steam may likewise be preheated via a heat exchanger (b 2 ).
  • a heat exchange (not illustrated) may likewise take place between the reformer (c) and the steam reformer (d) so as to further improve the energy balance.
  • Even the feed gas for the reformer (c) may be additionally or alternatively preheated by direct heat exchange with the steam reformer (d) (not illustrated).
  • the hydrogen-containing fuel in compressed or cooled liquid form is conducted either initially into a storage tank (g) or directly, via line (l), to the dispensing device (h), which is suitable for the withdrawal of either the hydrogen-containing fluid or the hydrogen-containing gas.
  • a motor vehicle (i) is filled up at the dispensing device using an integrated measuring and dosing system.
  • the catalyst (about 200 mg) was loosely poured on ceramic base platelets, inserted in an electrically heated, horizontal tube (4 cm diameter) via its front end, and heated.
  • the surface area covered by the solid was about 5 ⁇ 1 cm.
  • nitrogen was used for inertization, whereupon a gas mixture comprised of 94% methane and 6% hydrogen was introduced.
  • the gas flow was adjusted to 2,500 Nccm and the temperature program was started.
  • the heating rate was 10° C./min and the cracking process temperature was adjusted to 850° C. and maintained for 10 hours.
  • a plant for the production of hydrogen is described with reference to FIGS. 6 and 7 .
  • a hydrocarbon-containing feed gas is precompressed through line ( 1 ) by a compressor ( 1 a ) and conducted into the reactor ( 2 ) via a flow regulator ( 1 b ).
  • the reactor ( 2 ) is axially subdivided into an externally heated heating zone ( 2 b ) and a cooling zone ( 2 a ) and comprises a conveyor screw ( 2 c ), on which the catalyst is conveyed in the direction of the cooling zone.
  • the feed gas introduced. Solid carbon is deposited on the catalyst and discharged into a storage tank ( 4 ) in the cooling zone after conveyance on the conveyor screw.
  • Fresh catalyst is introduced into the reactor from a storage tank ( 3 ) and distributed on the conveyor screw ( 2 c ).
  • Formed hydrogen is discharged from the reactor in the heating zone via a filter ( 5 ), and compressed in a compressor ( 7 ) via a cooler ( 6 ), and introduced into the PSA plant ( 8 ).
  • hydrogen is separated from the residual gas, the latter being burned by a torch ( 9 ) and pure hydrogen being stored in a hydrogen tank ( 10 ).
  • the methane-hydrogen mixture forming is filtered, cooled and compressed.
  • the separation of the hydrogen from the residual gas takes place in a PSA (pressure swing adsorption) plant. Pure hydrogen is formed.
  • PSA pressure swing adsorption
  • the hydrogen is stored in a pressure tank for further use.
  • the residual gas is burned by a torch or other combustion means.
  • Natural gas is taken from the mains and compressed to 2 bar by the aid of a reciprocating compressor.
  • the control of the starting pressure is effected by the aid of a pressure transmitter and bypass adjustment valve to the compressor.
  • the natural gas flow is governed at the desired level by flow measurement and a flow-control valve.
  • the reactor is comprised of a horizontal, electrically heated tube.
  • the latter is axially subdivided into a heating zone and a cooling zone.
  • the natural gas is injected into the cooling zone, flowing to the solid (catalyst+CNT) in counter-current flow.
  • CNT is cooled while the natural gas is preheated. Exit from the reactor occurs at the end side on the hot end of the reactor.
  • the heating zone is comprised of two separately heatable sections. Heating is effected by the aid of heating cables wound or laid around the reactor. They are protected from overheating by a thermostat. The control of the gas temperature is effected via the heating output.
  • the catalyst is charged on the hot end of the reactor and conveyed in counter-current flow to the gas, along with the forming carbon fiber, by a slowly rotating conveyor screw (spirally wound steel belt).
  • the screw is driven via a gas-tight shaft and external drive motor including a frequency converter. The conveying speed is adjusted manually.
  • the reactor comprises inspection glasses with illumination and cleaning means (the dust being blown off by nitrogen) on both ends.
  • the catalyst is dosed from an about 50-liter container (stock for about 200 h) by the aid of a cellular wheel sluice.
  • the dosing rate is manually adjusted.
  • the catalyst from the cellular wheel sluice reaches the reactor by gravity.
  • Discharging of the fiber takes place continuously by gravity on the cold end of the reactor via a pneumatically actuated and a manually actuated slide.
  • the fiber is collected in a collecting container.
  • the container should have a capacity of about 200 liters, corresponding to an 8-hour production.
  • Two containers should be provided; one in operation with the other being conducted to further fiber processing and evacuated.
  • the containers include inspection glasses with illumination and cleaning means (the dust being blown off by nitrogen). To avoid overfilling, a dead man's button is provided. The filling level is to be checked regularly. If no acknowledgment is issued within about 8 hours, the plant will be shut off automatically.
  • the reactor gas is freed from dust in a hot-gas filter.
  • the differential pressure on the hot-gas filter is monitored, and nitrogen backflushing will be effected manually if the maximum value is exceeded.
  • the filter is directly arranged on the reactor, and the dust from backflushing is returned into the reactor.
  • the reactor gas is cooled to a maximum of 30° C. with cooling water in a tubular heat exchanger (gas on the jacket side).
  • the control of the temperature of the gas is effected via a cooling-water flow control valve.
  • the gas is compressed to about 15 bar by a reciprocating compressor.
  • the prepressure of the compressor, and hence the pressure in the reactor, is maintained at an overpressure of about 200 mbar by the aid of a prepressure control valve.
  • the cooled and compressed reactor gas is supplied to the PSA plant for separating and purifying the hydrogen.
  • the reactor gas is alternately conducted, in about 5-minute cycles, through three containers filled with adsorbent.
  • One container is each in adsorption operation, while a second one is in desorption operation (relaxation) and a third one is, at the same time, flushed with hydrogen and repressurized.
  • the produced hydrogen is stored in an about 5-cm 3 container at a maximum overpressure of about 15 bar until further use.
  • Residual gas occurs during the relaxation and flushing of the PSA adsorber and is burned in a torch.

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