WO2022167337A1 - Procédé et système de libération d'un composant chimiquement lié à partir d'un matériau vecteur - Google Patents

Procédé et système de libération d'un composant chimiquement lié à partir d'un matériau vecteur Download PDF

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Publication number
WO2022167337A1
WO2022167337A1 PCT/EP2022/052055 EP2022052055W WO2022167337A1 WO 2022167337 A1 WO2022167337 A1 WO 2022167337A1 EP 2022052055 W EP2022052055 W EP 2022052055W WO 2022167337 A1 WO2022167337 A1 WO 2022167337A1
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WIPO (PCT)
Prior art keywords
lohc
carrier material
reaction area
reaction
partially
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PCT/EP2022/052055
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German (de)
English (en)
Inventor
Federico Westerath
Holger BÜCH
Caspar PAETZ
Alexander SEIDEL
Jonas OBERMEIER
Andreas Kohlhepp
Original Assignee
Hydrogenious Lohc Technologies Gmbh
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Application filed by Hydrogenious Lohc Technologies Gmbh filed Critical Hydrogenious Lohc Technologies Gmbh
Priority to EP22702468.4A priority Critical patent/EP4288381A1/fr
Publication of WO2022167337A1 publication Critical patent/WO2022167337A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0888—Methods of cooling by evaporation of a fluid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream

Definitions

  • the invention relates to a method and a system for releasing a chemically bound component from a carrier material.
  • DE 10 2018 213 689 A1 discloses a device and a method for providing hydrogen gas. According to one embodiment, several dehydrogenation reactors can be connected to one another.
  • the object of the invention is to improve the release of a chemically bound component from a carrier material and in particular to reduce the heat requirement for the release reaction.
  • the core of the invention consists in the fact that the release of a chemically bound component from a carrier material has been recognized as a heat sink on the educt side.
  • the product streams of the release reaction have a greater enthalpy than the educt streams.
  • the enthalpy of the products can be used not only for preheating (c p AT) the starting materials, especially liquid ones, but also for heating the release reaction (Ah r ) and/or for evaporating (Ah va p) the starting materials .
  • the starting materials are understood to mean the compounds that are supplied to release the chemically bound component, in particular the carrier material, in particular at least partially charged and/or at least partially discharged carrier material.
  • Products are the compounds that are formed during the release reaction, in particular the carrier material, in particular at least partially loaded carrier material and/or at least partially discharged carrier material, and the released component, in particular hydrogen gas.
  • this excess enthalpy fraction of the products is used for evaporating the starting materials and/or for the release reaction.
  • a heat sink can be provided on the educt side, which is brought about by endothermic dehydrogenation and/or by evaporation of carrier material.
  • the partial pressure of the carrier material is reduced becomes. This increases the proportion of gas/steam. This means that the heat sink due to evaporation is even more pronounced in the dehydrogenation reaction carried out according to the invention, ie the magnitude of the heat sink is comparatively high.
  • this effect can also be achieved in that hydrogen gas is metered into the first reaction region externally, ie in addition to or instead of the dehydrogenation reaction, in order to reduce the partial pressure on the carrier material to be discharged.
  • An increased phase transition of the carrier material into the gas phase can thus be achieved.
  • Hydrogen gas can be metered in, in particular, from a separate hydrogen gas storage tank and/or via a return flow of hydrogen gas released after the dehydrogenation reactions.
  • the products are cooled more efficiently.
  • the risk of product coolers overheating is reduced. Cooling performance and thus the energy expenditure when releasing the chemically bound components are reduced.
  • the method according to the invention is economical since, in particular, the heating output and thus the operating costs are also reduced.
  • the carrier material is in particular a hydrogen carrier material, in particular an at least partially hydrogenated hydrogen carrier material.
  • the carrier material is a liquid organic hydrocarbon compound (LOHC).
  • the carrier material in the form that is at least partially charged with hydrogen is in particular perhydro-dibenzyltoluene (HisDBT) and/or dibenzyltoluene (HnBT).
  • the chemically bound Component is in particular hydrogen.
  • the starting materials are initially liquid.
  • the products are at least partially gaseous.
  • the release reaction is a dehydration reaction.
  • Carrier material (LOHC+) at least partially loaded with the component is fed to a first reaction area and heated there.
  • the component in particular hydrogen gas, is catalytically released from the at least partially loaded support material (LOHC+), in particular by contacting it with a catalyst material.
  • LOHC+ at least partially loaded support material
  • the catalyst material is arranged in the first reaction area in order to carry out a catalytic release reaction using heat.
  • the first reaction area forms a heat sink.
  • vaporous hydrogen carrier material (LOHC) is at least partially condensed in the first reaction region.
  • the enthalpy of condensation represents the enthalpy of reaction. In the subsequent stages, heat recuperation is favored.
  • a two-stage release reaction is provided, with a release reaction initially taking place in the first reaction region, in which a comparatively small amount of hydrogen gas is released.
  • the loaded carrier material LOHC+ is dehydrogenated from an initial degree of hydrogenation of at least 99.9%, in particular at least 99.5%, in particular 99%, in particular 98%, in particular 97%, to a reduced degree of hydrogenation of at most 95%, in particular at most 90% , in particular at most 91%, in particular at most 93% and in particular at most 94%.
  • the dehydrogenation stroke i.e. the reduction of the initial degree of hydrogenation to the reduced degree of hydrogenation, is at most 10%, in particular at most 9%, in particular at most 8%, in particular at most 7%, in particular at most 6% and in particular at most 5%.
  • platinum, palladium, nickel, rhodium and/or ruthenium is used as the catalyst material for the dehydrogenation reaction.
  • the catalyst material is arranged in particular on a catalyst carrier and in particular attached thereto.
  • Aluminum oxide, silicon oxide, silicon carbide and/or activated carbon are used in particular as the catalyst support.
  • the catalyst support is inert.
  • the proportion by weight of the catalyst material, based on the catalyst support is between 0.1% and 10%.
  • the at least partially charged carrier material (LOHC+) is converted into at least partially discharged carrier material (LOHC-) by the catalytic release reaction in the first reaction region.
  • the released component and the carrier material which can be proportionately at least partially charged and at least partially discharged, form intermediate products in the first reaction region.
  • the intermediate products (H2, LOHC-, LOHC+) are removed from the first reaction area and fed to a second reaction area.
  • the intermediate products (H2, LOHC-, LOHC+) are heated in the second reaction zone.
  • the heating in the second reaction area takes place in particular by means of an external heat source.
  • the at least partially charged carrier material (LOHC+) and/or the at least partially discharged carrier material (LOHC-) evaporate at least partially as a result of the heating in the second reaction area.
  • a catalytic release reaction takes place in the second reaction area, ie a further release of the component, in particular hydrogen gas, from the carrier material (LOHC-, LOHC+).
  • the catalytic release reaction tion in the second reaction zone is essentially analogous to the catalytic release reaction in the first reaction zone.
  • the catalyst material used in the second reaction zone is identical to that in the first reaction zone.
  • the catalyst material used in the first reaction zone can also differ from that of the second reaction zone.
  • the catalyst materials used can be adapted to the reaction temperatures prevailing in the respective reaction region.
  • the reaction temperature in the first reaction area is in particular between 230°C and 300°C.
  • the reaction temperature in the second reaction zone is in particular between 290°C and 320°C.
  • the catalyst material in the first reaction area could be based on the elements ruthenium and/or palladium due to the comparatively lower reaction temperature.
  • the catalyst material for the second reaction region could have platinum as the metal, which is in particular held on an aluminum oxide carrier material.
  • the catalysts in the reaction regions can also be differentiated by the relative proportion of the catalyst material in relation to the support material. It is conceivable to fix the catalyst material with a comparatively higher metal loading in the first reaction region, ie with a higher proportion by weight of the catalyst material based on the catalyst support.
  • the proportion by weight of the catalyst material, based on the catalyst support, for the first reaction zone is greater than the corresponding proportion by weight for the second reaction zone.
  • this weight proportion for the first reaction area at least twice, in particular at least 2.5 times, in particular at least three times, in particular at least four times, in particular at least five times, in particular at least ten times and in particular at least 20 times the weight proportion for the second reaction area.
  • a comparatively lower activity of the catalyst material at lower reaction temperatures could be counteracted with the higher proportion by weight in the first reaction region.
  • the component can be released from at least partially discharged carrier material (LOHC-) and/or from at least partially charged carrier material (LOHC+), whereby a further discharge of the at least partially discharged carrier material (LOHC-) and/or a transfer of the at least partially charged carrier material (LOHC+) into at least partially discharged carrier material (LOHC-).
  • LOHC- at least partially discharged carrier material
  • LOHC+ at least partially charged carrier material
  • the released component, in particular hydrogen gas, and the carrier material (LOHC-, LOHC+) in the second reaction area form end products.
  • the end products are returned from the second reaction area to the first reaction area, in particular to a shell area of the first reaction area.
  • the end products from the second reaction zone are used for heat transfer in the first reaction zone.
  • heat is transferred from the end products to the at least partially loaded carrier material.
  • the heating in the first reaction area takes place exclusively by means of the heat of the end products from the second reaction area.
  • the first reaction area is also referred to as the recuperation area.
  • the end product The heat transferred is used in particular to dehydrate the at least partially loaded carrier material (LOHC+).
  • the transferred heat can also be used to vaporize the at least partially loaded carrier material (LOHC+) and/or to heat the at least partially loaded carrier material (LOHC+).
  • the heat transfer in the first reaction area in particular within the first reactor, which is also referred to as a recuperator, is improved.
  • Heat transfer is the product of the heat transfer coefficient k, the cross-sectional area A and the temperature difference AT.
  • the heat transfer is improved in particular because the temperature difference ⁇ T between the heat-emitting end products from the second reaction area and the at least partially loaded carrier material in the first reaction area is increased.
  • the larger temperature difference is favored and ensured in particular by the heat loss as a result of the dehydrogenation reaction in the first reaction area.
  • the first reaction area that is to say the first reactor and in particular the plant as a whole, can be provided with a reduced installation space requirement.
  • the plant according to the invention can be implemented with small construction and, in particular in comparison to a plant with a dehydrogenation reactor in which there is no heat transfer between the end products from the second reaction area and the at least partially loaded carrier material in the first reaction area, requires less installation space, in particular in comparison to a plant with additional recuperator for heat recovery. Because according to the invention, the reduced installation space particularly because a recuperator and a dehydrogenation reactor are combined in one and the same component as a recuperator.
  • the heat transfer in the first reaction zone is improved.
  • the material flows of the end products and the at least partially loaded carrier material (LOHC+) are separated from one another.
  • the material flows for the heat transfer in the first reaction area are conducted in countercurrent to one another.
  • the heating of the intermediates in the second reaction zone according to claim 3 is efficient.
  • the heat requirement for the second reaction area can be provided flexibly and as required.
  • an external heat exchanger and/or a burner serves as an external heat source.
  • the external heat source can, for example, provide a heated heat exchange medium, in particular a heated thermal oil.
  • the material flows of the heat exchange medium and the intermediate products are separated from one another in the second reaction area.
  • the material flows in the second reaction area are conducted in countercurrent to one another.
  • Preheating according to one of claims 4 or 5 enables an additional increase in efficiency when carrying out the method, in particular an improvement in the release reaction. The efficiency of the subsequent release reaction by the heat recovery preheating is thereby improved.
  • a heat source upstream of the first reaction area in particular an upstream heat exchanger, enables improved phase separation of the end products.
  • the upstream heat source is primarily used for recuperation.
  • the end products discharged from the first reaction area which have been used as heat transfer medium in the first reaction area, serve as the heat exchange medium in the upstream heat exchanger.
  • the at least partially charged hydrogen carrier material (LOHC+) serves as the medium to be heated in the recuperator.
  • the method enables a two-stage and in particular a complete recuperation, ie a complete recovery of the heat.
  • a method according to claim 6 enables an advantageous retrofitting of an existing method.
  • An existing system can be easily upgraded.
  • a method according to claim 7 enables the method to be carried out in a particularly compact and therefore space-saving manner.
  • the investment and/or operating costs for carrying out the method are additionally reduced.
  • a plant according to claim 9 ensures a separation of the material flows in the first reaction area.
  • the at least partially loaded carrier medium LOHC + is in at least one reaction zone and in particular in a plurality of reaction zones, in particular in reaction tubes which are loaded with the catalyst material.
  • the end products are conducted as a heat transfer medium through the first reaction area, around the self-contained reaction zones.
  • the heat transfer medium flows around the reaction zones for heat transfer.
  • An external heat source according to claim 10 enables an uncomplicated and needs-based provision of heat for the second reaction area.
  • a heat source according to one of claims 11 or 12 upstream of the first reaction region enables additional heat recovery, in particular up to complete recuperation, and improved phase separation of the end products.
  • a system according to claim 13 can advantageously be retrofitted.
  • a system according to claim 14 is designed to be compact and, in particular, small in size.
  • a system according to claim 15 enables an advantageous release reaction in the first and in the second reaction area, with the heat transfer being advantageously implemented in both reaction areas.
  • FIG. 1 shows a schematic representation of a plant according to the invention with two reactor vessels
  • FIG. 2 shows a representation corresponding to FIG. 1 of a plant according to a second exemplary embodiment with a common reactor vessel.
  • a plant identified as a whole by 1 in FIG. 1 comprises a first reactor 2 which is designed as a dehydrogenation reactor.
  • the first reactor 2 can be designed as a reactor according to DE 10 2015 219 305 A1, to which reference is expressly made with regard to the details of the structure and the function of the reactor.
  • the first reactor 2 there is at least partially also a heat transfer, which will be explained in more detail below, by means of heat recovery, ie recuperation. Both a dehydrogenation reaction and a recuperation reaction therefore take place in the first reactor 2 .
  • the first reactor 2 is also referred to as a recuperator.
  • the first reactor 2 is a side reactor.
  • the first reactor 2 comprises a first reactor vessel 3 with a first antechamber 4 and a first post-chamber 5. Between the first antechamber 4 and the first post-chamber 5 there are a plurality of reaction zones in the form arranged by first reaction tubes 6. Catalyst material is arranged in each of the first reaction tubes 6 . It is essential that at least one reaction tube 6 is provided, which connects the first antechamber 4 to the first antechamber 5 .
  • a plurality of first reaction tubes 6 are advantageously provided, in particular at least two, in particular at least four, in particular at least ten, in particular at least fifteen, in particular at least twenty, in particular at least fifty, in particular at least one hundred and in particular at most ten thousand.
  • the first reaction tubes 6 are, in particular, each identical in design.
  • the first reaction tubes 6 are closed and only open to the first anteroom 4 and the first afterroom 5 .
  • An area formed between the first anteroom 4 and the first afterroom 5 in the first reaction container 3 is also referred to as the first reaction area 7 .
  • the first reaction area 7 comprises the first reaction tubes 6 and a first surrounding area 38 which surrounds the first reaction tubes 6 and is delimited by the first reactor vessel 3 , the first anteroom 4 , the first afterroom 5 and the first reaction tubes 6 .
  • the first reactor 2 is in fluid communication with a second reactor 9 by means of a first connecting line 8 .
  • the second reactor 9 is designed as a dehydrogenation reactor.
  • the second reactor 9 is a main reactor.
  • the second reactor 9 is essentially identical to the first reactor 2 and has a second reactor vessel 10, a second antechamber 11, a second antechamber 12, second reaction tubes 13 with catalyst material and a second reaction area 14, the second reaction tubes 13 being surrounded by a second surrounding area 39 are surrounded.
  • the first connecting line 8 connects the first post-chamber 5 of the first reactor 2 to the second antechamber 11 of the second reactor 9.
  • the second reactor 9 is in fluid communication with the first reactor 2 by means of a first return line 19 .
  • the first return line 19 connects in particular the second post-chamber 12 of the second reactor 9 to the first reaction area 7, in particular to the first surrounding area 38 of the first reactor 2.
  • the first return line 19 opens into the first reaction area 7, in particular in the first surrounding area 38, in particular adjacent to the first post-chamber 5.
  • the first reactor 2 is oriented vertically and the second reactor 9 is oriented horizontally.
  • the first reactor 2 can also be oriented horizontally and/or the second reactor 9 can be oriented vertically. It is also possible for the first reactor 2 and the second reactor 9 to be arranged in an inclined orientation with respect to the horizontal.
  • the first reactor 2 is preceded by a heat source 15 which is designed as a heat exchanger.
  • the first heat exchanger 15 comprises at least one medium line 16, in particular a plurality of medium lines 16, and a heat exchanger region 18 surrounding the medium lines 16 and delimited by a heat exchanger tank 17.
  • the first heat exchanger 15 is in fluid communication with the first reactor 2 by means of a supply line 20 .
  • the feed line 20 opens into the first anteroom 4 at the first reactor 2.
  • the first reactor 2 is in fluid communication with the first heat exchanger 15 , in particular with the heat exchanger region 18 , via a second return line 21 .
  • the second return line 21 opens into the heat exchanger tank 17 adjacent to the feed line 20 .
  • At the upstream heat exchanger 15 is a first storage tank
  • the second discharge line 25 is arranged on the heat exchanger area 18 on the heat exchanger tank 17 facing away from the feed line 20 .
  • a third storage tank 26 is connected to the upstream heat exchanger 15 by means of a feed line 27 .
  • An external heat source 28 is connected to the second reactor 9 via heat exchanger lines 29 .
  • the external heat source 28 is designed as a heat exchanger.
  • the heat exchanger line 29 for supplying heat exchange medium to the second reactor 9 opens into the second Reaction area 14, in particular in the second surrounding area 39, adjacent to the second afterroom 12.
  • the heat exchanger line 29 for returning heat exchange medium from the second reaction area 14 of the second reactor 9 is connected to the second reaction vessel 10 adjacent to the second antechamber 11.
  • a liquid organic hydrocarbon compound which is also known as a liquid organic hydrogen carrier (LOHC) and to which hydrogen is chemically bound, serves in particular as the carrier material.
  • the carrier material is at least partially charged with hydrogen (LOHC+).
  • the carrier material LOHC+ is stored in the third storage container 26 and is fed via the feed line 27 to the upstream heat exchanger 15 and preheated therein.
  • the preheated carrier material LOHC+ is fed to the first reactor 2 via the feed line 20 and passed from the first antechamber 4 into the first reaction tubes 6 .
  • the carrier material LOHC+ is additionally heated, at least partially vaporized and/or hydrogen gas is released from the carrier material LOHC+.
  • the release of the hydrogen gas converts the carrier material LOHC+ into an at least partially discharged state LOHC-.
  • the carrier material LOHC-, LOHC+ and the released component H2 form intermediates and are discharged from the first reaction tubes 6 into the first post-chamber 5 and from there via the first connecting line 8 from the first reactor 2 and the second reactor 9, in particular into the second antechamber 11, supplied. From there, the intermediate products flow into the second reaction tubes 13.
  • heat transfer takes place by means of the heat exchange medium from the external heat source 28.
  • the heat exchange medium from the external heat source 28 flows countercurrently to the intermediate products through the second surrounding region 39 in the second reactor 9.
  • the intermediate products are heated, as a result of which the carrier material LOHC- and/or LOHC+ at least partially evaporates.
  • An additional catalytic release reaction takes place in the second reaction tubes 13, with the at least partially loaded carrier material LOHC+ being discharged and/or the at least partially already discharged carrier material LOHC- being further discharged.
  • the carrier material LOHC-, LOHC+ and the released component H2 in the second reaction area 14 form end products and are discharged into the second post-chamber 12 .
  • the end products are returned from the second reactor 9 via the first return line 19 to the first reaction area 7 of the first reactor 2 , in particular to the first surrounding area 38 .
  • the end products are used in the first reaction area 7 as a heat transfer medium.
  • the end products flow through the first reaction area 7 and leave the first reactor 2, in particular the first reaction area 7, at least slightly cooled, via the second return line 21.
  • the end products which serve as heat transfer medium, flow through the first surrounding area 38 essentially in countercurrent to the at least partially loaded carrier material LOHC+ and/or the intermediate ducts in the first reaction tubes 6. This favors the heat transfer from the end products to the carrier material LOHC+.
  • the material flows of the end products and the at least partially loaded carrier material LOHC+ are separated from one another in the first reaction area 7 .
  • the heat transfer in the first reaction area 7 takes place without contact.
  • heat is therefore transferred from the product side, i.e. from the end products, to the reactant side, i.e. to the carrier material LOHC+.
  • Gas cooling takes place, i.e. cooling of the released hydrogen gas H2, steam cooling, i.e. cooling of the at least partially vaporized carrier material LOHC+, LOHC-, and condensation of the at least partially vaporized carrier material LOHC+, LOHC- and/or cooling of liquefied carrier material LOHC+ , LOHC- .
  • the supply of heat to the LOHC+ in the reaction tubes 6 causes the liquid LOHC+ to be heated, the reaction, ie the dehydrogenation, the at least partial evaporation of the carrier material LOHC+, the steam heating and the gas heating of the hydrogen gas released.
  • the reaction temperature in the first reactor 2, i.e. in the recuperator, is in particular between 230° C. and 300° C.
  • the reaction temperature in the second reactor 9, i.e. in the main reactor, is between 290° C. and 320° C.
  • the released hydrogen gas can be cooled from about 300° C. to 240° C., cooling and additional at least partial condensation of LOHC vapor from 300°C to 240°C and cooling of liquid LOHC from 300°C to 240°C take place.
  • an energy transfer i.e. the use of thermal energy, with a quantity of at least 0.5 kWh/kg, in particular at least 0.7 kWh/kg, in particular at least 0.8 kWh/kg, kg, in particular at least 0.9 kWh/kg and in particular at least more than 1.0 kWh/kg is possible.
  • the at least partially cooled end products removed from the first reactor 2 are returned to the upstream heat exchanger 15 via the second return line 21 .
  • the end products are used to preheat the carrier material LOHC+.
  • the end products are fed in the heat exchanger 15 in countercurrent to the carrier material LOHC+.
  • the material flows of the end products on the one hand and the carrier material LOHC+ on the other hand are separated from one another in the heat exchanger 15 .
  • the heat transfer is contactless.
  • Carrier material in particular at least partially discharged carrier material LOHC-, is discharged from the heat exchanger 15 via the first discharge line 23 and stored in the first storage tank 22 .
  • the at least partially discharged carrier material LOHC- can be recharged with hydrogen by means of a catalytic hydrogenation process and stored in the third storage tank 26 for renewed dehydrogenation. process are stored.
  • the loading of the at least partially discharged carrier material LOHC- can take place in a hydrogenation reactor which is connected directly to the first storage tank 22 and/or to the third storage tank 23, for example. It is alternatively conceivable that the at least partially discharged carrier material LOHC- is transported away, for example by means of a tanker or a transport line connected to the first storage tank 22 .
  • the third storage container 26 can be filled with carrier material LOHC+ by means of tank vehicles and/or a connected line.
  • the hydrogen gas separated from the carrier material LOHC as a result of the phase separation in the heat exchanger 15 is fed to the second storage tank 24 via the second discharge line 25 .
  • the hydrogen gas can be supplied from the second storage container 24 for a further use, in particular for conversion into electricity in a fuel cell. It is also conceivable to omit the second storage container 24 .
  • the second storage container 24 is connected to the first reactor 2 , in particular to the first antechamber 4 , via an optional hydrogen gas return line 40 .
  • the hydrogen gas return line 40 it is possible for the hydrogen gas return line 40 to be connected to the second discharge line 25 as a branch line. Hydrogen gas can be fed directly from the first heat source 15, in particular the heat exchanger area 18, to the first reactor 2.
  • Hydrogen gas can also be fed into the first reaction area 7 by means of an external hydrogen gas source, i.e. in addition to or as an alternative to the second storage tank 24 and/or the second discharge line 25.
  • the end products fed to the first reactor 2 via the first return line 19 and removed from the first reactor 2 via the second return line 21 match in terms of their composition, i.e. the proportions of released hydrogen gas, at least partially discharged carrier material LOHC- and at least partially charged carrier material LOHC+ . They differ in particular exclusively with regard to the proportions of gaseous, liquid and vaporous phases due to the cooling of the end products taking place in the first reactor 2 . In particular, the proportions of liquid phases in the end products are greater in the second return line 21 than in the first return line 19.
  • a second exemplary embodiment of the invention is described below with reference to FIG.
  • Structurally identical parts are given the same reference numbers as in the first exemplary embodiment, to the description of which reference is hereby made.
  • Structurally different, but functionally similar parts are given the same reference numbers with a suffix a.
  • the reactor vessel 30 has an antechamber 31 which is fluidically connected to reaction tubes 32 .
  • the reaction tubes 32 are formed in a first tube plate 33 facing the antechamber 31 and are held sealed therein.
  • the reaction tubes 32 extend through a second tube sheet 34 into the second reaction region 14 which is closed off at its end remote from the second tube sheet 34 by means of a third tube sheet 35 .
  • the reaction tubes 32 are held sealed in the respective tube sheet 33, 34, 35 and attached thereto.
  • the reaction tubes 32 are continuous and extend from the first reaction area 7 into the second reaction area 14 .
  • the reaction tubes 32 fluidically connect the anteroom 31 with the afterroom 36.
  • the reaction areas 7, 14 are separated from one another by the second tube plate 34.
  • reaction tubes 32 are designed to be continuous through both reaction areas 7, 14 and an additional connecting tube 37 connects the post-chamber 36 to the first reaction area 7, the material flows are separated from one another in the reaction areas, analogously to the first exemplary embodiment. A reliable heat transfer while avoiding the mixing of the material flows is guaranteed.
  • a connecting tube 37 is arranged on the second tube plate 34 and the third tube plate 35 .
  • the connecting pipe 37 connects the post-chamber 36 with the first reaction area 7.
  • the connecting pipe 37 enables the end products to be returned from the second reaction area 14 to the first reaction area 7.
  • the connecting pipe 37 represents a first return line 19 in the sense of the first exemplary embodiment.
  • the catalyst is arranged in the reaction tubes 32 .
  • the filling of the reaction tubes 32 with catalyst can be complete, in particular in the area of the first reaction area 7 .
  • the filling of the reaction tubes 32 can also be catalyst evenly diluted with inert material. It is also conceivable that alternating layers of inert material and catalyst or alternating layers of diluted catalyst and inert material are arranged in the reaction tubes 32 . With an alternating arrangement of the different layers, there is an advantage in that the layers with inert material favor a temperature increase, so that the subsequent layer with catalyst contact enables faster and thus more favored reaction kinetics, the reaction being catalyzed, i.e. reducing the tube-side temperature again. This results in heat integration through heat transfer from the product side to the reaction.
  • reaction tubes 32 on the tube sheets 33, 34, 35 guarantees that the material flows in the first reaction area 7 and in the second reaction area 14 are separated from one another.
  • the external heat source 28 with the heat exchanger lines 29 is connected to the reactor vessel 30 .
  • the first reaction area 7 is preceded by a heat exchanger 15 which is fed with carrier material LOHC+ from the third storage container 26 .
  • the heat exchanger 15 is used for cooling and Phase separation of the end products that can be stored in the storage containers 22, 24.
  • the common reactor vessel 30 allows a particularly compact and small design of a plant according to the invention. A second reactor vessel is not necessary.
  • the common reactor vessel 30 has a robust design.
  • the heat exchanger 15 can also be omitted.
  • Carrier material LOHC+ is fed to the common reactor vessel 30, in particular the antechamber 31, and from there it enters the reaction tubes 32.
  • the intermediate products as explained with reference to the first exemplary embodiment, are formed in the first reaction area 7 and can reach the second reaction area 14 directly.
  • the intermediate products are still in the same reaction tubes 32 as in the first reaction area 7.
  • the dehydrogenation reaction is continued as a result of the additional heating by the external heat source 28 and end products are formed.
  • the end products pass from the reaction tubes 32 into the post-chamber 36 and from there via the connecting tube 37, which is in particular centrally arranged, back into the first reaction area 7, in particular the first surrounding area 38.
  • the end products serve as a heat transfer medium.
  • the savings potential with regard to the amount of energy required for the overall process is identical to that of the first exemplary embodiment for the system 1a according to the second exemplary embodiment. Due to the reduced heat losses due to the savings in connection lines, there is an additional heat advantage in the system la.

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Abstract

L'invention concerne un procédé de libération d'un composant lié chimiquement à partir d'un matériau vecteur, comprenant les étapes de procédé suivantes : l'ajout d'un matériau vecteur, qui est chargé au moins en partie avec le composant, à une première région de réaction (7) ; le chauffage et l'évaporation au moins proportionnelle du matériau vecteur au moins partiellement chargé ; la libération catalytique du composant du matériau vecteur au moins partiellement chargé dans la première région de réaction (7) et ainsi la transition au moins partielle du matériau vecteur au moins partiellement chargé vers un matériau vecteur au moins partiellement vide, le composant libéré et le matériau vecteur étant des produits intermédiaires dans la première région de réaction (7) ; la fourniture des produits intermédiaires de la première région de réaction (7) à une seconde région de réaction (14) ; le chauffage des produits intermédiaires dans la seconde région de réaction (14) et l'évaporation au moins proportionnelle du matériau vecteur ; la libération catalytique du composant du matériau vecteur dans la seconde région de réaction (14), le composant libéré et le matériau vecteur étant des produits finaux dans la seconde région de réaction (14) ; le retour des produits finaux de la seconde région de réaction (14) à la première région de réaction (7), le transfert de chaleur des produits finaux au matériau vecteur au moins partiellement chargé dans la première région de réaction (7), la chaleur transférée agissant pour évaporer le matériau vecteur au moins partiellement chargé et/ou pour déshydrater le matériau vecteur au moins partiellement chargé.
PCT/EP2022/052055 2021-02-03 2022-01-28 Procédé et système de libération d'un composant chimiquement lié à partir d'un matériau vecteur WO2022167337A1 (fr)

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WO2023052216A1 (fr) * 2021-09-28 2023-04-06 Hydrogenious Lohc Technologies Gmbh Procédé et appareil de libération d'hydrogène chimiquement lié d'un matériau vecteur

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DE102022210822A1 (de) 2022-10-13 2024-04-18 Hydrogenious Lohc Technologies Gmbh Verfahren und Anlage zum Freisetzen von Wasserstoffgas von zumindest teilweise beladenem Trägermaterial

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DE102017201454A1 (de) * 2017-01-30 2018-08-02 Friedrich-Alexander-Universität Erlangen-Nürnberg Vorrichtung und Verfahren zum Bereitstellen von Wasserstoffgas
DE102017217748A1 (de) 2017-10-05 2019-04-11 Hydrogenious Technologies Gmbh Anlage und Verfahren zur Bereitstellung und weiteren Nutzung von Wasserstoffgas
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US20160214858A1 (en) * 2013-10-21 2016-07-28 Air Products And Chemicals, Inc. Multi-zone dehydrogenation reactor and ballasting system for storage and delivery of hydrogen
CN109923060A (zh) * 2016-11-16 2019-06-21 海德鲁基尼斯技术有限公司 用于提供氢气的方法、脱氢反应器和运输容器
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WO2023052216A1 (fr) * 2021-09-28 2023-04-06 Hydrogenious Lohc Technologies Gmbh Procédé et appareil de libération d'hydrogène chimiquement lié d'un matériau vecteur

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