• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The invention relates to a plant (1) and a method, which serve the recovery and space-saving storage of carbon in the form of liquid carbon dioxide (17) from a substance (8) of the group hydrocarbons / ethers / alcohols within energy storage systems with carbon cycle and despite the Use of membranes with low hydrogen / carbon dioxide permeation selectivity to achieve complete recovery of the carbon. This is made possible by the construction of a carbon dioxide closed Permeatmassestromkreislaufs between the permeate space of the membrane reformer used for hydrogen separation and the anode space of a solid oxide fuel cell (4), which serves the outfeed of electrical energy from the energy storage system.
    公开号:AT519896A2
    申请号:T413/2017
    申请日:2017-10-23
    公开日:2018-11-15
    发明作者:Mair Christian
    申请人:Mair Christian；
    IPC主号:
    专利说明:

    Plant and process for the recovery and storage of carbon in energy storage systems using low-selectivity membranes
    Description:
    Technical area:
    The invention relates to a system and method for the recovery and storage of carbon in the form of carbon dioxide in energy storage systems based on a carbon cycle by generating carbonaceous compounds (such as hydrocarbons, alcohols or ethers) when feeding energy from carbon dioxide and at outfeed of Energy deposit and store the resulting carbon dioxide in order to use it for further synthesis of carbonaceous compound.
    State of the art:
    The increasing development of intermittent, renewable production facilities for electrical energy (especially photovoltaic and wind power plants) requires an increasing storage of the energy generated in order to be able to use the surplus electricity that can not be fed into the grid and, on the other hand, to adapt the energy production to the energy demand curve. There are a variety of electrical, mechanical and electrochemical storage systems available (capacitors, flywheels, batteries, compressed air storage) for short-term storage (a few hours) of low to medium-capacity electrical energy. For medium- and long-term storage (days to months) of large-capacity electrical energy, only storage systems that save the electrical energy in the form of chemical energy sources ("power-to-chemicals") can be used for pumping power plants for technical and economic reasons. Besides processes which generate and store hydrogen gas, there are also prior art methods which synthesize and store carbonaceous compounds as energy storage media using carbon dioxide. Such carbon-based energy storage systems have, inter alia, the advantage over energy storage systems based on hydrogen gas that they also synthesize chemical compounds for energy storage, which at r ι
    Ambient temperature in liquid form ("power-to-liquid") and thus can be easily and space-saving transported and stored.
    In such carbon-based energy storage systems for storing electrical energy, the supply of electrical energy by the transfer of carbon dioxide in carbon-containing chemical compounds (eg methane, methanol) using water obtained from hydrogen and the storage of these carbonaceous compounds (in tank vessels or underground storage), while the Discharge of energy on the oxidation of the carbon contained in the carbonaceous compound, that is, on the recovery of carbon contained in the carbonaceous compound in the form of carbon dioxide, and based on the storage of this carbon dioxide. Thus, such carbon-based energy storage systems build up a system-internal carbon cycle, for the maintenance of the most complete recovery of carbon contained in the carbonaceous compounds is necessary to maintain. Such carbon-based energy storage systems therefore contain a system for the outfeed of energy which recovers and stores the carbon contained in the carbonaceous compounds as completely as possible in the form of carbon dioxide, thereby releasing mechanical or electrical energy through the oxidation of carbon and hydrogen.
    Such carbon-based energy storage systems are described in the following documents: EP 0539244 describes several methods of energy storage, which synthesize methanol from carbon dioxide to feed energy and recover this carbon dioxide in the outfeed of energy. DE 202010012734 and DE 102012103458 also describe energy storage systems that burn hydrocarbons or alcohols for energy, which deposit resulting carbon dioxide and use this deposited carbon dioxide again for the production of hydrocarbons or alcohols. AT 517934 describes a plant and a process for the gas compression-free recovery and storage of carbon in energy storage systems
    Carbon cycle. In this case, a carbon dioxide-containing retentate gas which is under pressure of at least 5.18 bar is obtained by catalytic steam reforming of a substance of the group hydrocarbons / ether / alcohol in a membrane reactor. For this is under
    Using a Sorptionskälteverfahrens the carbon dioxide condensed out and stored in liquid form, while the hydrogen formed by the steam reforming gas is separated through the membrane and can be used for the outfeed of energy from the energy storage system by this hydrogen gas is oxidized in an internal combustion engine or fuel cell. For this hydrogen separation in a membrane reformer, as described in AT 517934, various types of membranes are prior art. However, these differ, in part, considerably in their permeation selectivity: while certain metal membranes (e.g., palladium membranes) permit pure precipitation of hydrogen from hydrogen-containing gases, e.g. Zeolite or carbon membranes significantly lower permeation selectivity of hydrogen over other gases such as carbon dioxide or gaseous water, When using restricted hydrogen / carbon dioxide permeation-selective membranes in the process described in AT 517934 creates a Permeatmassestrom that not only hydrogen, but also different proportions of Contains carbon dioxide. When this Permeatmassestrom oxidized for the outfeed of energy from the energy storage system by means of atmospheric oxygen and the resulting exhaust gas stream is discharged into the atmosphere, this leads to an incomplete recovery of carbon within the energy storage system, which in non-supply of additional carbon in the energy storage system to a halt this carbon cycle within the energy storage system and thus leads to a malfunction of the energy storage system. Thus, what would be desirable is a process that recovers and stores carbon in carbon storage energy storage systems, thereby permitting the use of membranes that have limited hydrogen / carbon dioxide permeation selectivity without causing the problem of incomplete recovery of carbon.
    Object of the invention:
    The object of the invention is to provide a plant and a method available to deposit within an energy storage system with carbon cycle from a high-energy, carbon-containing compound (hydrocarbon, alcohol, ether) the carbon contained therein in the form of carbon dioxide gas compression-free and high density This plant and method allows the use of separation membranes with low hydrogen / carbon dioxide permeation selectivity without thereby compromising the completeness of carbon recovery within the energy storage system.
    The object is achieved by a system according to the features of the main claim and a method according to the independent method claim. Further advantageous embodiments are specified in the subclaims.
    Presentation of the invention:
    In this patent specification, the term "catalytic steam reforming" is understood to mean that chemical equilibrium reaction in which hydrocarbons, alcohol or ethers are introduced with the addition of water at the appropriate temperature and in the presence of suitable catalysts in a gas mixture, which in addition to hydrogen gas also different proportions of carbon monoxide and carbon dioxide. Corresponding catalysts are well known for a wide variety of hydrocarbons, alcohols and ethers. For steam reforming of methanol, e.g. copper-based catalysts such as Cu / ZnO / AbO3 can be used.
    Carbon monoxide and carbon dioxide are also in a chemical equilibrium relationship with each other in the process of steam reforming (water gas shift reaction). In addition, further equilibrium reactions may occur in the process of steam reforming, depending on the starting materials used. In the case of methanol, the steam reforming and the parallel chemical processes can be summarized by the following reaction equations:
    Water-gas shift reaction
    Methanol decomposition
    Since the steam reforming is usually carried out with a superstoichiometric excess of water, the product gas generated thereby usually also contains water vapor.
    The term "permeate side" of a hydrogen-separating membrane is understood in this patent to be that side of the membrane at which the hydrogen separated from the membrane emerges from the membrane.
    The term "Permeatmasseström" is understood in this specification, the mass flow, which flows around a hydrogen-separating membrane on the permeate side.
    The term "retentate side" of a hydrogen-separating membrane is understood in this patent to be the side of the membrane at which the hydrogen enters the membrane.
    The term "retentate mass flow" is understood in this patent to mean the mass flow which flows around a hydrogen-separating membrane on the retentate side. In the case of a membrane reactor in which a catalytic steam reforming of a substance of the group hydrocarbons / ethers / Aikohole and a deposition of hydrogen gas is carried out, this Retentatmassestrom contains carbon dioxide and may also contain water in superstoichiometric admixture of water to carry out the steam reforming.
    The term "liquefaction and separation of a substance from a gas mixture" is understood in this patent to mean the cooling of the gas mixture below that temperature at which the partial pressure of the substance to be liquefied and separated in the gas mixture is high enough to produce a liquid substance to be separated containing phase, which is then separated from the gas mixture (eg by means of a steam trap).
    An inventive plant (1) for the recovery and storage of carbon in the form of liquid carbon dioxide (17) from substances (8) of the group hydrocarbons / ethers / alcohols has the following devices: - at least one steam generator (2) for the evaporation of water and a Substance of the group hydrocarbons / ethers / alcohols, - at least one membrane reactor (3) for the catalytic steam reforming of a substance of the group hydrocarbons / ethers / alcohols and for the separation of hydrogen gas from the product gas generated by the steam reforming, - at least one device (6) for liquefaction and deposition of carbon dioxide from a gas mixture containing carbon dioxide, - at least one storage tank (7) for carbon dioxide, - at least one solid oxide fuel cell (4), characterized in that - the steam generator (2) is designed to generate steam of over 5.18 bar , and the membrane reactor (3), the device (6) for liquefaction and Ab - the steam generator (2) for the evaporation of water and a substance of the group hydrocarbons / ethers / alcohols, an inlet device for supplying heat (10th carbon dioxide) and the storage tank (7) are operated for carbon dioxide with gas pressures of over 5.18 ) and contains at least one recuperator, and that between said devices consist of the following lines: - at least one conduit for transporting gas at more than 5.18 bar pressure, the steam generator (2), the membrane reactor (3), and the device (6) interconnects for the liquefaction and separation of carbon dioxide, - at least one conduit for transporting a liquid medium above 5,18 bar pressure, which connects the carbon dioxide liquefaction and separation apparatus (6) and the carbon dioxide storage tank (7) , - at least one line which connects the membrane reactor (3) and the solid oxide fuel cell (4) and that for the supply of a water At least one further line which connects the membrane reactor (3) and the solid oxide fuel cell (4) and the anode exhaust gas generated in the solid oxide fuel cell (4) in the membrane reactor (3) is usable.
    The solid oxide fuel cell (4) contained in a plant (1) according to the invention converts about 40-60% of the chemical energy contained in the fuel not into electricity but into heat in the current state of the art. In order that this waste heat can be used to carry out the evaporation, in a plant (1) according to the invention the steam generator (2) has the purpose of evaporating water and a substance of the group
    Hydrocarbons / ethers / alcohols has an inlet device for the supply of heat (10) and contains a recuperator (eg plate heat exchanger, spiral heat exchanger,
    Tube bundle heat exchanger). The steam generator (2) for the evaporation of water and a substance of the group hydrocarbons / ethers / alcohols is also designed in an inventive system (1) that it generates a gas of about 5.18 bar, as this is the smallest thermodynamically possible pressure for the steam generator (2) downstream condensation of carbon dioxide and a system according to the invention does not contain a gas compressor, which could serve to further pressure increase within the system. Of the
    Steam generator (2) is in a system (1) according to the invention also designed so that it generates a superheated gas at a temperature which is not below the operating temperature of the membrane reactor (3). When using methanol as a carbonaceous compound for energy storage, this temperature is about 250-300 ° C. Steam generators containing a recuperator and a gas of more than 5.18 bar (up to more than 200 bar) and up to 500- 600 ° C generate state of the art. They are advantageously built in three stages (with preheater, evaporator and superheater). In particular, steam generators for water and for methanol, which generate gases of 300 ° C, state of the art.
    Membrane reactors for the catalytic steam reforming of a substance of the group
    Hydrocarbons / ethers / alcohols and for the separation of hydrogen gas from the product gas produced by this steam reforming are also prior art. Various embodiments of such membrane reformers for steam reforming are described in the literature (see, eg: Gallucci, F., Basile, A. & Hai, F. Ibney: Introduction - A review of membrane reactors. In: A. Basile & F. Gallucci (ed.): Membranes for membrane reactors; preparation, optimization and selection, 2011. 1-61). At temperatures above 250 °, membrane reactors with metal membranes (eg palladium alloys), ceramic membranes, carbon membranes or zeolite membranes are used. They are heat-stable at temperatures up to 800 ° C and also have sufficient pressure stability up to 60 bar and more when using a suitable support structure on.
    The different types of membrane differ in some cases considerably in their
    permeation; While certain metal membranes (e.g., palladium membranes) allow pure separation of hydrogen from hydrogen-containing gases, e.g. Zeolite or carbon membranes significantly lower permeation selectivity of hydrogen over other gases such as carbon dioxide or gaseous water. When using restricted hydrogen / carbon dioxide permeation-selective membranes, a permeate mass flow is produced which contains not only hydrogen but also different proportions of carbon dioxide from the steam reforming process. When this permeate mass flow is oxidized to expel energy from the energy storage system by means of atmospheric oxygen and the resulting exhaust gas stream is vented to the atmosphere, this leads to incomplete recovery of carbon within the energy storage system, which ceases if further carbon is not added to the energy storage system this carbon cycle within the energy storage system and thus leads to a malfunction of the energy storage system.
    The inventive core of the system described in this patent is to solve the problem that, despite the use of membranes with limited hydrogen / carbon dioxide permeability, a complete separation of the carbon dioxide within the plant (1) for recovery and storage of carbon can be achieved. This is achieved in that between the membrane reactor (3) and the solid oxide fuel cell (4) a carbon dioxide-closed Permeatmassestromkreislauf is constructed: An inventive system (1) contains not only a connecting line between the membrane reactor (3) and the solid oxide fuel cell (4) Transport of the hydrogen-containing Permeatmassestroms (12) from the membrane reactor (3) in the solid oxide fuel cell (4), but at least one further line which serves to oxidize in the anode chamber of the solid oxide fuel cell (4) Permeatmassestrom (13) to the permeate side of the membrane Membrane reactor (3) due. As a result, carbon dioxide which has passed through the membrane of the reactor into the hydrogen-containing permeate mass flow (12) due to the limited hydrogen / carbon dioxide permeation selectivity of the membrane and has passed through the anode space of the solid oxide fuel cell (4) is not released into the atmosphere but into the atmosphere Permeate space of the membrane reactor (3) returned. As a result, the carbon dioxide accumulates in this so-built Permeatmassestromkreislauf until the increased partial pressure of the so-enriched carbon dioxide in Permeatmassestrom causes the exchange of carbon dioxide between the Permeatmassestrom and the Retentatmassestrom through the membrane of the membrane reactor (3) comes to a halt altogether and thus sets a state of equilibrium. Since the partial pressure of carbon dioxide along the membrane changes in the retentate mass flow due to the steam reforming process, there may still be membrane regions in this equilibrium state through which carbon dioxide permeates from the retentate mass flow into the permeate mass flow, but at the same time there will be other membrane regions through which carbon dioxide reverses permeated by the permeate mass flow into the retentate mass flow. The state of equilibrium therefore consists in the fact that the carbon dioxide exchange between the permeate mass flow and the retentate mass flow comes to a standstill over the entire membrane area and not necessarily in the fact that this is the case in every subarea of the membrane. Because in this, self-adjusting. Equilibrium state the amount of carbon dioxide in the
    Permeate mass flow is constant, can be closed by a "carbon dioxide-closed
    Permeatmassestromkreislauf1 be spoken. The gaseous water which accumulates in the carbon dioxide-sealed permeate mass flow circuit produced by the oxidation of hydrogen in the solid oxide fuel cell (4) is also separated from the permeate mass flow into the retentate mass flow through the membrane of the reactor when the required partial pressure is reached in a system according to the invention.
    In the apparatus (6) for liquefying and separating carbon dioxide from a gas mixture containing carbon dioxide, various types of recuperators (eg plate heat exchangers, spiral heat exchangers, tube bundle heat exchangers) can be used to carry out the liquefaction, as known from the prior art and can be easily designed for an operating pressure above 5.18 bar. The deposition of the liquid carbon dioxide may e.g. through a steam trap.
    Solid oxide fuel cells are state of the art. They are distinguished by their
    Insensitivity to carbon dioxide in the fuel gas and typically by high operating temperatures (about 800 ° C) from. These operating temperatures are above the temperatures required for the reforming of substances from the group
    Hydrocarbons / ethers / alcohols in the membrane reactor (3) are necessary, which is why the waste heat generated in the solid oxide fuel cell (4) supplied to the recuperator contained in the steam generator (2) and thus the evaporation process taking place there can be supplied with process heat. In particular, only temperatures of about 250 ° C are required for the steam reforming of methanol. Due to this large temperature difference, sufficient steam for the steam reforming of methanol can be provided in the form of waste heat from the solid oxide fuel cell (4).
    The storage tank (7) for carbon dioxide is to be designed so that it stores the separated in the inventive plant in liquefied form carbon dioxide without pressure loss. The liquid phase which forms during the liquefaction of carbon dioxide may contain not only carbon dioxide but also various amounts of water, as well as residues of the substance (8) of the group hydrocarbons / ethers / alcohols which have not been reacted in the membrane reactor (3). Storage tanks up to pressures of 700 bar are known in the art and are e.g. used for the high-pressure storage of hydrogen.
    All mentioned components of a system for carrying out the method according to the invention must be coordinated with one another in terms of engineering routine work in their design, in particular their capacity, and provided with a common control system.
    A further variant of a system according to the invention comprises a device (5) for the liquefaction and separation of water which is interposed between the membrane reactor (3) and the device (6) for the liquefaction and separation of carbon dioxide from a gas mixture containing carbon dioxide. In addition, this variant of a plant according to the invention comprises a line for transporting water, which connects said device (5) for liquefaction and separation of water and the steam generator (2) for the evaporation of water and a substance of the group hydrocarbons / ethers / alcohols. By this device (5), the amount of water that is in the retentate mass flow of the membrane reactor (3) after the steam reforming of the methanol, reduced, thereby increasing the concentration of carbon dioxide in the retentate mass flow and the space efficiency (defined as the ratio of the by the liquid carbon dioxide in the storage space occupied volume to the volume of the entire storage space) in the storage of the liquid carbon dioxide (17) in the storage tank (7) can be increased.
    A further variant of a system according to the invention comprises a line for gas transport, which connects the device (6) for liquefaction and separation of carbon dioxide from a gas mixture containing carbon dioxide with the steam generator (2) or with the membrane reactor (3). This line allows the resulting in the condensation of carbon dioxide residual gas (16) does not supply the storage tank (7) for carbon dioxide and thus efficiently use the storage space in the storage tank (7) for the storage of liquid carbon dioxide (17).
    The invention described in this patent also includes a process which allows the complete, gas compression-free recovery of carbon in the form of liquid carbon dioxide from high-energy, carbon-containing compounds (hydrocarbon, alcohol, ether) without the completeness of carbon dioxide separation through the use of membranes with limited hydrogen / carbon dioxide permeability is impaired. This method is characterized by the following steps: Step 1: Generation of a superheated gas (11) with more than 5.18 bar pressure by evaporation and heating of water (9) and of a substance (8) of the group
    Hydrocarbons / ethers / alcohols in a steam generator (2) to which heat (10) is supplied; Step 2: Catalytically steam reforming the superheated gas (11) generated in step 1 above 5,18 bar pressure and producing a retentate mass flow (14) by removing hydrogen gas from the product gas produced by the steam reforming by a membrane process; - Step 3: generating a residual gas (16) by liquefying and separating carbon dioxide (17) from the retentate mass flow (14) produced in step 2; Step 4: storing the carbon dioxide (17) liquefied and separated in step 3 in a storage tank (7) for carbon dioxide; - Step 5: Supply of the generated in step 2 by hydrogen separation by means of membrane, hydrogen gas Permeatmassestroms (12) in a solid oxide fuel cell (4), oxidation of the hydrogen contained in this Permeatmassestroms (12) in the solid oxide fuel cell (4) and recycling the resulting oxidized Permeatmassestrom (13) to the permeate side of the membrane of the membrane process used in step 2.
    In order for the gas generated in the steam generator (2) to contain sufficient thermal energy for the steam reforming provided in step 2, a superheated gas (11) is produced in a method according to the invention in step 1.
    In the steam generator (2) gas must be generated with more than 5.18 bar pressure, since this gas in a process according to the invention, after it has passed through the membrane reactor (3), in the device (6) for the liquefaction and separation of carbon dioxide still a pressure must be above 5.18 bar in order to be liquefied by cooling. The gas pressure actually required in the device (6) for the liquefaction and separation of carbon dioxide, however, depends on the composition of the
    Retentate mass flow (14): If the hydrogen separation in step 2 is incomplete and therefore the retentate mass flow (14) contains increased amounts of hydrogen, the pressure required for carbon dioxide condensation increases because the partial pressure of the carbon dioxide in the retentate mass flow (14) is at least 5.18 bar got to. Accordingly, in this case also in the steam generator (2) an overheated gas (11) must be generated at a higher pressure.
    Due to the implementation of steam reforming in a membrane reactor with hydrogen-permeable membrane thermodynamic equilibrium of the steam reforming is shifted in favor of hydrogen and carbon dioxide, so in a membrane reactor almost complete decomposition of the feedstock (8) from the group hydrocarbons / ethers / alcohols to hydrogen gas and Carbon dioxide can be achieved. Depending on the size and nature of the membrane surface, the parital pressure of the hydrogen in the product gas produced by the steam reforming and the mode of operation of the membrane reactor (countercurrent process or DC process) is in step 2, a different large separation efficiency of hydrogen (defined as the ratio of the amount of hydrogen generated in the membrane reactor to the amount of hydrogen deposited by the membrane). It can also be nearly 100% given the corresponding partial pressure of the hydrogen and the corresponding size and nature of the membrane (see Gallucci, F., Basile, A .: Co-current and Counter-current Modes for Methanol Steam Reforming Membrane Reactor Hydrogen Energy 32 (2006) 2243-2249). While, as noted above, certain metal membranes (e.g., palladium membranes) permit pure precipitation of hydrogen from hydrogen-containing gases, other membranes, such as zeolite or carbon membranes, achieve significantly lower permeation selectivities of hydrogen over gases such as e.g. Carbon dioxide or gaseous water. In molecular sieve membranes, such as zeolite or carbon membranes, the hydrogen permeation selectivity to both carbon dioxide and water is relatively low. In order to achieve the most complete recovery of carbon in the form of carbon dioxide, even when using membranes with low hydrogen / carbon permeation selectivity, a method according to the invention therefore provides for the use of a solid oxide fuel cell (4) and the construction of a carbon dioxide-closed permeate mass circulation: by oxidation occurring in the case of low hydrogen / carbon permeation, carbon dioxide and hydrogen-containing Permeatmassestroms (12) in a solid oxide fuel cell (4), the hydrogen contained in this mass flow is oxidized to water without the carbon dioxide can escape from the permeate mass flow. If the oxidized permeate moisture thus generated (13), which from the anode compartment of the
    Solid oxide fuel cell (4) escapes as exhaust gas, led back to the permeate side of the membrane of the membrane reactor (3), so there increases the partial pressure of carbon dioxide. By further operation of this cycle, this partial pressure for carbon dioxide increases so much that it is in equilibrium with the partial pressure of carbon dioxide on the retentate side of the membrane of the membrane reactor (3), so that the further diffusion of carbon dioxide from the retentate side to the permeate side of Completely comes to a standstill membrane and thus builds up a carbon dioxide-closed Permeatmassestromkreislauf consisting of the hydrogen-containing Permeatmassestrom (12) from the membrane reactor (3)
    Solid oxide fuel cell (4) and from the oxidized Permeatmassestrom (13) of the solid oxide fuel cell (4) to the membrane reactor (3).
    The gaseous water which accumulates in this carbon dioxide-closed permeate mass flow circuit produced by the oxidation of the hydrogen in the solid oxide fuel cell (4) is produced when using molecular sieve membranes (such as zeolite or .alpha
    Carbon membranes), which not only have low hydrogen permeation selectivity to carbon dioxide but also to water, are separated from the permeate mass flow circuit by this membrane in the following manner: In the course of operation of this carbon dioxide-closed permeate mass circulation, not only does the partial pressure of the carbon dioxide on the permeate side increase Membrane, but also that of the water, so that, as soon as the partial pressure of water in the Permeatmassestromkreislauf is higher than that in the retentate mass flow, it comes to a diffusion of water from the permeate side to the retentate side of the membrane and thus to a deposition process of water from the Permeatmassestromkreislauf ,
    Since in step 5 of a process according to the invention the hydrogen-containing permeate stream (12) in a solid oxide fuel cell (4) is oxidized and solid oxide fuel cells release heat at a temperature level above the temperature level of the catalytic steam reforming in step 2 (about 800 ° C), heat (10) from the
    Solid oxide fuel cell (4) are supplied to the recuperator of the steam generator (2) in step 1 to operate there taking place evaporation and superheating process. This supply of heat (10) can be done by that from the
    Solid oxide fuel cell (4) exiting, oxidized Permeatmasse ström (13) before it is fed to the membrane reactor (3), partially or completely flows through the recuperator of the steam generator (2). However, the supply of heat (10) from the solid oxide fuel cell (4) to the recuperator of the steam generator may also be effected by means of an intermediate heat transfer medium (e.g., oil) heated by an additional heat exchanger from said oxidized permeate mass flow (13).
    The liquefaction of carbon dioxide (17) in step 3 from the retentate mass flow (14) generated in step 2 can in turn be effected by recuperators. The condensation of carbon dioxide is carried out according to the condensation curve of carbon dioxide at temperatures and partial pressures of about 310 C / 74 bar to about - 56.6 ° C / 5.185 bar. The partial pressure of carbon dioxide in the retentate mass flow (14) must therefore be above 5.18 bar to allow condensation of the carbon dioxide and be built up in step 1 of the process.
    The liquid carbon dioxide (17) separated off in step 3 is stored in liquid form in a process according to the invention in a carbon dioxide storage tank (7). This must therefore also be operated with an internal pressure of at least 5.18 bar. In a variant of the method according to the invention, water (15) is liquefied and separated from the retentate mass flow (14) by cooling, before the resultant water-reduced retentate mass flow (14) is fed to step 3 of the process according to the invention. This separated water (15) is then fed to step 1 of the process according to the invention. Due to the water reduction in the
    Retentatmassestrom (14), the available storage space in the storage tank (7) for
    Carbon dioxide can be used more efficiently for carbon dioxide storage. The cooling of the retentate mass flow (14) necessary for this separation of water can be carried out by means of a recuperator which is operated with ambient air. The separated water (15) also contains those constituents of the retentate mass flow (14) whose partial pressure is also above their respective saturation vapor pressure at the temperature prevailing in the recuperator. Such ingredients may be non-reformed residues of the substance (8) from the group hydrocarbons / ethers / alcohols or by-products of steam reforming. In particular, non-reformed methanol condenses under conditions similar to those of water. As by-products of methanol steam reforming, for example, dimethyl ether and formic acid can occur, which also condense at similar temperatures and partial pressures as water.
    In another variant of the method according to the invention, the residual gas (16) generated in step 3 is fed to step 1 or step 2 of the inventive method. This residual gas (16) can be selected from those residues of the substance (8) from the group
    Hydrocarbons / ethers / alcohols, which were not reacted in the steam reactor and due to their condensation behavior were not already deposited as described in step 3, as well as by-products of steam reforming (eg, carbon monoxide) and hydrogen gas, in the membrane reactor (3) not was separated.
    Brief description of the drawing:
    1 and 2, two variants of the system scheme of the invention are shown schematically:
    1 shows the system diagram according to claim 1 with a solid oxide fuel cell (4) and with two lines between this solid oxide fuel cell (4) and the membrane reactor (3): a first line for supplying the hydrogen-containing permeate mass flow (12) emerging from the membrane reactor (3). in the anode compartment of the
    Solid oxide fuel cell (4) and a second line for supplying the oxidized Permeatmassestroms (13) from the anode space of the solid oxide fuel cell (4) in the membrane reactor (3).
    Fig. 2 shows an embodiment variant as shown in FIG. 1, but with a device (5) for
    Liquefaction and separation of water and a water return line (15) and a return gas line (16) to the steam generator (2). In addition, Fig. 2 lines, which allow the solid oxide fuel cell (4) exiting oxidized Permeatmasse ström (13) for transferring heat from the solid oxide fuel cell (4) partially over the steam generator (2) before the oxidized Permeatmassestrom ( 13) is fed to the membrane reactor.
    LIST OF REFERENCES: 1 plant for the recovery and storage of carbon 2 steam generators for the evaporation of water and a substance of the group
    Hydrocarbons / ethers / alcohols 3 Membrane reactor for the catalytic steam reforming of a substance of the group
    Hydrocarbons / ethers / alcohols and for the separation of hydrogen gas from the product gas produced by the steam reforming 4 Solid oxide fuel cell 5 Apparatus for liquefying and separating water from a water vapor-containing gas mixture 6 Apparatus for liquefying and separating carbon dioxide from a
    Carbon dioxide-containing gas mixture 7 storage tank for carbon dioxide 8 substance from the group hydrocarbons / ethers / alcohols 9 water 10 heat 11 superheated gas 12 hydrogen-containing permeate mass flow 13 oxidized permeate mass flow 14 retentate mass flow 15 water 16 residual gas 17 liquid carbon dioxide
    权利要求:
    Claims (6)
    [1]
    claims:
    1. Plant (1) for the recovery and storage of carbon in the form of liquid carbon dioxide (17) from substances (8) of the group hydrocarbons / ethers / alcohols, comprising - at least one steam generator (2) for the evaporation of water and a substance of the group Hydrocarbons / ethers / alcohols, - at least one membrane reactor (3) for the catalytic steam reforming of a substance of the group hydrocarbons / ethers / alcohols and for the separation of hydrogen gas from the product gas produced by the steam reforming, - at least one device (6) for the liquefaction and separation of Carbon dioxide from a gas mixture containing carbon dioxide, - at least one storage tank (7) for carbon dioxide, - at least one solid oxide fuel cell (4), characterized in that - the steam generator (2) produces steam at a pressure above 5.18 bar, and the membrane reactor (3 ), the device (6) for the liquefaction and separation of carbon dioxide from a carbon dioxide entha The gas generator (2) for the evaporation of water and a substance of the group hydrocarbons / ethers / alcohols, an inlet device for the supply of heat (10) - the steam generator (2) for the evaporation of water and a substance of the group hydrocarbons / ether / alcohols comprising at least one recuperator, and that the following lines exist between said devices: - at least one line for transporting gas at more than 5.18 bar pressure, the steam generator (2), the membrane reactor (3), and the device ( 6) for the liquefaction and separation of carbon dioxide, - at least one line for transporting a liquid medium above 5,18 bar pressure, which connects the carbon dioxide liquefaction and separation device (6) and the carbon dioxide storage tank (7), - At least one line connecting the membrane reactor (3) and the solid oxide fuel cell (4) and for the supply of a Wasserstoffha At least one further line which connects the membrane reactor (3) and the solid oxide fuel cell (4) and the anode exhaust gas generated in the solid oxide fuel cell (4) in the membrane reactor (3) is usable.
    [2]
    2. Plant (1) according to claim 1, characterized in that the plant (1) at least one device (5) for liquefaction and separation of water and a conduit for transporting water containing the device (5) for liquefaction and separation of water and the steam generator (2) for the evaporation of water and a substance of the group hydrocarbons / ether / alcohols connects.
    [3]
    3. Plant (1) according to any one of claims 1 to 2, characterized in that the plant (1) contains at least one conduit for gas transport, the device (6) for liquefying and separating carbon dioxide from a carbon dioxide-containing gas mixture with the steam generator (2) for the evaporation of water and a substance of the group hydrocarbons / ether / alcohols or with the membrane reactor (3) for the catalytic steam reforming of a substance of the group hydrocarbons / ether / alcohols and for the separation of hydrogen gas from the product gas generated by the steam reforming connects.
    [4]
    4. A process for the recovery and storage of carbon in the form of liquid carbon dioxide (17) from substances (8) of the group hydrocarbons / ethers / alcohols, characterized by the following steps: - Step 1: production of a superheated gas (11) with more than 5.18 bar pressure by evaporation and heating of water (9) and of a substance (8) of the group hydrocarbons / ethers / alcohols in a steam generator (2) to which heat (10) is supplied; Step 2: Catalytic steam reforming of the superheated gas (11) produced in step 1 above 5,18 bar pressure and generation of a retentate mass flow (14) by separation of hydrogen gas from the product gas produced by the steam reforming by means of a membrane reactor ( 3) carried out membrane process; - Step 3: generating a residual gas (16) by liquefying and separating carbon dioxide (17) from the retentate mass flow (14) produced in step 2; Step 4: storing the carbon dioxide (17) liquefied and separated in step 3 in a storage tank (7) for carbon dioxide; - Step 5: feeding the generated in step 2 by hydrogen separation by means of membrane, hydrogen gas Permeatmassestroms (12) in a solid oxide fuel cell (4), oxidation of the hydrogen contained in this Permeatmassestroms (12) in the solid oxide fuel cell (4) and recycling the resulting oxidized Permeatmassestroms (13) to the permeate side of the membrane of the membrane process used in step 2.
    [5]
    5. The method according to claim 4, characterized in that between process step 2 and process step 3, water (15) from the retentate mass flow (14) produced in step 2 is liquefied, separated and fed to process step 1.
    [6]
    6. The method according to any one of claims 4 to 5, characterized in that the residual gas (16) generated in step 3 is supplied to the method step 1 or the method step 2.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA221/2016A|AT517934B1|2016-04-28|2016-04-28|Plant and process for the gas compression-free recovery and storage of carbon in energy storage systems|
    PCT/EP2017/000533|WO2017186352A1|2016-04-28|2017-04-28|Installation and method for carbon recovery and storage, without the use of gas compression|
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