WO2014057390A1 - Dispositif de stockage par sorbant pour le stockage de substances gazeuses - Google Patents

Dispositif de stockage par sorbant pour le stockage de substances gazeuses Download PDF

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Publication number
WO2014057390A1
WO2014057390A1 PCT/IB2013/059029 IB2013059029W WO2014057390A1 WO 2014057390 A1 WO2014057390 A1 WO 2014057390A1 IB 2013059029 W IB2013059029 W IB 2013059029W WO 2014057390 A1 WO2014057390 A1 WO 2014057390A1
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WO
WIPO (PCT)
Prior art keywords
tank
channel
gas
sorption store
shaped
Prior art date
Application number
PCT/IB2013/059029
Other languages
English (en)
Inventor
Mathias WEICKERT
Stefan Marx
Ulrich Müller
Peter Renze
Original Assignee
Basf Se
Basf (China) Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf (China) Company Limited filed Critical Basf Se
Priority to CN201380052514.5A priority Critical patent/CN104736223A/zh
Priority to EP13845513.4A priority patent/EP2906329A4/fr
Publication of WO2014057390A1 publication Critical patent/WO2014057390A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0415—Beds in cartridges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4525—Gas separation or purification devices adapted for specific applications for storage and dispensing systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane

Definitions

  • Sorption store for storing gaseous substances relates to a sorption store for storing gaseous substances, comprising a closed tank at least partially filled with an adsorption medium and comprising a feeding device, which comprises a passage through the tank wall, through which a gas can flow into the tank.
  • the invention also relates to a method for filling the sorption store according to the invention and a method for removing gas from the sorption store according to the invention.
  • Sorption stores are increasingly being used nowadays for the storage of gases for stationary and mobile applications.
  • Sorption stores generally comprise an adsorption medium with a large internal surface area, on which the gas is adsorbed and thereby stored. While a sorption store is being filled with gas, the adsorption causes the release of heat, which has to be removed from the store. By analogy, when gas is removed from the store, heat has to be supplied for the process of desorption. Therefore, thermal management is of great importance when designing sorption stores.
  • the patent application US 2008/0168776 A1 describes a sorption store for hydrogen, which comprises an outer tank which is thermally insulated from the surroundings and arranged inside which are a number of pressure vessels, which comprise an adsorption medium. The intermediate spaces between the pressure vessels are filled with a cooling fluid, in order to allow the heat occurring during the adsorption to be removed.
  • the patent application DE 10 2007 058 673 A1 describes an apparatus for storing gaseous hydrocarbons, which comprises an insulated tank filled with an adsorption medium. Provided in the tank is a heating element, which is activated by means of a control system in such a way that, when gas is being removed, a minimum pressure is maintained for as long a time as possible.
  • One disadvantage of known sorption stores is that the filling with gas proceeds only slowly. In particular in the case of mobile applications, for example in motor vehicles, this disadvantage is particularly serious. It is an object of the invention to provide an apparatus for storing gaseous substances that allows quick filling with gas and improved removal of gas. At the same time, the apparatus should be of a simple construction and require little electrical energy during operation. It is also an object of the invention to provide a method for quickly and efficiently filling the store and for removing gas from the store.
  • the sorption store according to the invention for storing gaseous substances comprises a closed tank and a feeding device, which comprises a passage through the tank wall, through which a gas can flow into the tank.
  • the tank has inside it at least one separating element, which is configured in such a way that the interior of the tank is divided into at least one pair of channels comprising two parallel running, channel-shaped compartments, the ends of which are in connection with one another in each case by way of a common space, each channel-shaped compartment being filled at least partially with an adsorption medium.
  • the feeding device is designed in such a way that inflowing gas is diverted almost exclusively into one of the two compartments of each pair of channels.
  • a further improvement of the heat transfer can be achieved if, along with the tank wall, the at least one separating element, or in the case of a number of separating elements one or more of them, is/are cooled or heated.
  • the at least one separating element or a number of separating elements, in particular all the separating elements that are present are of a double-walled configuration, so that they can be flowed through by a heat transfer medium.
  • the channel walls of the channel-shaped compartments are of a double-walled configuration for being flowed through by a heat transfer medium.
  • a portion of the tank wall also forms a channel wall of a channel-shaped compartment or a number of channel-shaped compartments.
  • the tank wall is in this case also preferably of a double-walled configuration.
  • the entire tank wall including the end faces is designed for being flowed through by a heat transfer medium, in particular is of a double-walled configuration.
  • the choice of the wall thickness of the tank and the separating elements is dependent on the maximum pressure to be expected in the tank, the dimensions of the tank, in particular its diameter, and the properties of the material used.
  • the minimum wall thickness has been estimated at 2 mm (according to DIN 17458).
  • the clearance between the double walls is chosen such that it can be flowed through by a sufficiently great volumetric flow of the heat transfer medium. It is preferably from 2 mm to 10 mm, particularly preferably from 3 mm to 6 mm.
  • various transfer media come into consideration, for example water, glycols, alcohols or mixtures thereof. Corresponding heat transfer media are known to a person skilled in the art.
  • the distance between the channel walls in each channel-shaped compartment is from 2 cm to 8 cm.
  • the distance should be understood here as meaning the shortest distance between two points of opposing walls in cross section perpendicularly to the axis of the channel.
  • the distance corresponds to the diameter; in the case of an annular cross section, it corresponds to the width of the ring and, in the case of a rectangular cross section, it corresponds to the shorter distance between the parallel sides.
  • the stated range has proven to be a good compromise between heat transfer and filling volume of the adsorption medium.
  • the distances between the channel walls in the channel-shaped compartments of each pair of channels differ by no more than 40%, particularly preferably by no more than 20%, from one another.
  • the distances between the channel walls in all the channel- shaped compartments preferably differ by no more than 40%, particularly preferably by no more than 20% from one another.
  • the cross-sectional areas of the channel-shaped compartments are chosen such that, during the filling of the tank with gas, the flow rates in the channel- shaped compartments of each pair of channels differ by no more than 20% from one another. Particularly preferably, the flow rates in all the channel-shaped compartments differ by no more than 20% from one another.
  • the requirements mentioned as preferred for distances between walls that are as equal as possible and cross-sectional areas of the channel-shaped compartments that are as equal as possible may conflict with one another, depending on the actual geometrical design of the tank. In such a case, the configuration with distances between the walls that are as equal as possible is preferred, since the effect of the uniform removal of heat has proven to be dominant over the flow effect, in particular when emptying the tank.
  • the contours of the tank inner wall and of the at least one sepa- rating element are substantially conformal. If a number of separating elements are present, the contours of all the separating elements are preferably conformal to the contour of the tank inner wall. Conformal means in this connection that the contours coincide in their form, for example are all circular, all elliptical or all rectangular. The expression “substantially conformal” is understood as meaning that small deviations from the basic form are still regarded as coinciding. Ex- amples are rounded corners in the case of a rectangular basic form or deviations within the limits of production tolerances.
  • the tank of the sorption store is cylindrically designed, and the at least one separating element is arranged substantially coaxially in relation to the cylinder axis.
  • the longitudinal axis of the at least one separating element is inclined by a few degrees to a maximum of 10 degrees with respect to the cylinder axis are still regarded as "substantially" coaxial. This configuration ensures that the channel cross sections vary only little along the cylinder axis, so that a uniform flow over the length of the channel can form.
  • cross-sectional areas are suitable for the cylindrical tank, for example circular, elliptical or rectangular. Irregularly shaped cross-sectional areas also come into consideration, for example if the tank is to be fitted into a hollow space of a vehicle body. For high pressures above about 100 bar, circular and elliptical cross sections are suitable in particular.
  • the at least one separating element in this embodiment is particularly preferred for the at least one separating element in this embodiment to be formed as a tube, so that the space inside the tube forms a first channel-shaped compartment and the space between the tube outer wall and the tank inner wall or possibly between the tube outer wall and a further separating element forms a second, annular-channel-shaped compartment.
  • the cross-sectional areas of the tank and of the tubular separating element preferably have the same form, for example both circular or both elliptical.
  • a number of separating elements are present, all formed as tubes with different diameters and arranged coaxially. Their cross-sectional areas are likewise preferably of the same form.
  • the feeding device comprises at least one passage through the tank wall, through which a gas can flow into the tank, and is designed in such a way that inflowing gas is diverted almost exclusively into one of the two compartments of each pair of channels.
  • the feeding device comprises a tubular supply line, the one end of which is connected to the at least one passage and the other end of which is located in a channel-shaped compartment.
  • the other end may also be located at a distance from the end-face channel inlet of the compartment, the distance being dimensioned in such a way that the gas emerging from the end of the line flows almost exclusively into this compartment.
  • the feeding device comprises components which distribute the gas flowing in through the at least one passage in a directed manner to one compartment of each pair of channels, for example a deflecting element or a distributor device.
  • the feeding device comprises a tubular supply line, the one end of which is connected to the at least one passage.
  • the supply line runs through a first compartment and its other end opens out into the common space, by way of which the compartments are in connection.
  • the tubular supply line is perforated in the region in which it runs through the first compartment, so that the inflowing gas flows partially into this first compartment.
  • the feeding device may also comprise means for influencing the gas flow, for example throttle valves or control valves. These means may be provided inside or outside the tank. It is also possible for a number of passages to be provided in the tank wall, for example in order to feed the gas to the channel-shaped compartments at a number of points or in order to provide different passages for the filling with gas and removal of gas. Preferably the same passage or the same passages is/are used for the removal of gas as for the filling of the tank with gas.
  • the adsorption medium preferably comprises zeolite, activated carbon or metal-organic frameworks.
  • the porosity of the adsorption medium is preferably at least 0.2.
  • the porosity is defined as the ratio of void volume to total volume of any subvolume in the tank. At a lower porosity, the pressure drop on flowing through the adsorption medium increases, which has an adverse effect on the filling time.
  • the adsorption medium is in the form of a bed of pellets, and the ratio of the permeability of the pellets to the smallest pellet diameter is at least 10-14 m 2/ m -
  • the time required for this pressure equalization, and thus also the charging time of the pellets increases. This may have a limiting effect on the overall process of filling and discharging.
  • the common spaces that connect the respective channel-shaped compartments are preferably designed in such a way that the distance between the ends of the separating elements forming the channel-shaped compartments and the respective inner sides of the tank wall is at least double the smallest pellet diameter. Preferably, this distance is also no greater than one tenth of the length of the separating element concerned in the longitudinal direction of the channel.
  • Such a design of the common spaces has an advantageous effect on the formation of a circulating gas flow through the connected compartments.
  • a further subject matter of the invention is a method for filling a sorption store according to the invention with a gas, in a first step gas being supplied in an amount such that a pressure in the store of at least 30% of a predetermined final pressure is reached as quickly as possible, and subsequently in a second step the supplied amount of gas being varied in such a way that the variation of the pressure in the store approximates to the adsorption kinetics of the adsorption medium until the predetermined final pressure in the store is reached after a predetermined time period.
  • sorption stores such as those known from the prior art are usually connected to a pressure line, from which the gas to be stored flows at constant pressure into the store, until the pressure in the store has reached a predetermined final pressure.
  • a pressure line from which the gas to be stored flows at constant pressure into the store, until the pressure in the store has reached a predetermined final pressure.
  • gas is stored both by adsorption on the adsorption medium and in the voids between and in individual particles of the adsorption medium or in regions of the tank that are not filled with adsorption medium.
  • the voids are filled with gas.
  • the pressure in the store follows the pressure of the gas that flows into the tank. In order to minimize the total time required for the filling operation, this first step should be carried out as quickly as possible, for example by introducing the gas at a pressure which corresponds to at least 30% of the predetermined final pressure right at the beginning of the filling operation.
  • the variation of the pressure in the tank approximates to the adsorption kinetics of the adsorption medium.
  • Methods for determining the adsorption kinetics are known to those skilled in the art, for example with the aid of pressure jump experiments or adsorption balances (for example in "Zhao, Li and Lin, Industrial & Engineering Chemistry Research, 48(22), 2009, pages 10015- 10020").
  • Adsorption kinetics is understood as meaning the variation of the adsorption of the gas on the adsorption medium over time under isothermal and isobaric conditions.
  • This variation can often be approximated by an exponentially decaying function which at the beginning displays a sharp rise and then becomes ever flatter as it converges toward a final value.
  • An example of such an approximation is the function a-(1 - e _bt ), where a and b are positive constants.
  • the adsorption kinetics may also be approximated by other functions, for example a concave function, a function which is constant in sections, a function which is linear in sections or a linear function which joins the initial value and the final value.
  • a variation of pressure in the store that approximates to the adsorption kinetics has the effect that the flow rate of the gas in the store is greater than the rate at which the gas is adsorbed. This results in the formation of circulating flows through the channel-shaped compartments, which ensure that the heat produced during the adsorption can be removed more quickly.
  • the thermal conductivity of the adsorption medium in the tank is increased, whereby the time requirement for filling the store is reduced.
  • the supplied amount of gas can be varied, for example, by adapting the inlet pressure appropriately to the approximation function, for example by appropriate valve connections.
  • the variation of pressure in the store is approximated to the adsorption kinetics in the form of pressure oscillations, in particular by appropriate variation of the inlet pressure.
  • the maximum value of the oscillation preferably corresponds to the final pressure
  • the minimum value of the oscil- lation is preferably approximated to the variation of the adsorption kinetics. This corresponds to a reduction in the oscillation amplitude over time.
  • the predetermined final pressure in the store is set.
  • the oscillation may be, for example, sinusoidal, sawtooth-shaped or alternately constant in sections.
  • the form of the oscillation and also its amplitude and period are preferably adapted to the actual adsorption kinetics.
  • p ⁇ + ⁇ ⁇ f(a) ⁇ (sin(2-TT-k-t) - 1 ), where po is the initial pressure, p is the difference between the initial pressure and the final pressure, k is the frequency and f(a) is a damping function.
  • the damping may, for example, decrease linearly or decrease exponentially.
  • the frequency k can be estimated by way of the isothermal and isobaric adsorption kinetics tkin, which are a measure of the minimum filling time.
  • the frequency is preferably cho- sen such that from two to ten oscillation periods lie within tkin.
  • the time required for filling a sorption store is influenced significantly by the material properties of the adsorption medium, in particular its adsorption kinetics.
  • a further influencing factor is the maximum temperature to be expected during filling, which likewise depends on the material properties, in particular the enthalpy of adsorption.
  • the choice of the initial pressure and the type of pressure increase are preferably adapted to the respective adsorption kinetics, the enthalpy of adsorption and the heat conduction to the walls.
  • initial pressures in the range from 30% to 90% of the predetermined final pressure are preferred, with an initial pressure that is as high as possible being chosen.
  • the level of the initial pressure is possibly limited by the temperature increase established during the adsorption.
  • the rate at which the pressure increases is preferably at least 1 bar per minute of filling time, in order to promote the formation of a circulating flow in the channel-shaped compartments.
  • the tempera- ture of the gas stream is measured in at least one channel-shaped compartment and, if required, the amount of gas supplied to the sorption store is adapted in such a way that a predetermined maximum temperature in the channel-shaped compartment is not exceeded.
  • the time period required for the filling can be reduced further if the gas is supplied in a cooled state.
  • a further subject matter of the invention is a method for removing gas from a sorption store according to the invention, the channel walls being flowed through by a heat transfer medium, the temperature of which is greater than the temperature of the gas in the channel-shaped com- partments.
  • the sorption store according to the invention makes it possible for heat to be transported more quickly out of the adsorption medium or into the adsorption medium. This significantly reduces the time required for filling the store with a given amount of gas. Alternatively, the store can be filled with a greater amount of gas in a given time. When removing gas from the store, the invention makes it possible for gas to be provided quickly and constantly.
  • the sorption store according to the invention is of a simple structural design and, as a result of its compact type of construction, is particularly suitable for mobile applications, for example in motor vehicles.
  • the embodiment with double-walled channel walls has the additional advantage that, for changing over from cooling to heating, the heat transfer medium merely has to be changed or its temperature altered appropriately.
  • Fig. 1 shows an embodiment of a sorption store according to the invention with a deflecting element for inflowing gas
  • Fig. 2 shows an embodiment of a sorption store according to the invention with a number of passages
  • Fig. 3 shows an embodiment of a sorption store according to the invention with double- walled channel walls and an elliptical cross-sectional area of the tank
  • Fig. 4 shows an embodiment of a sorption store according to the invention with a feeding tube passing right through
  • Fig. 5 shows an embodiment of a sorption store according to the invention with three channel-shaped compartments
  • Fig. 6 shows an embodiment of a sorption store according to the invention with a rectangular tank cross section
  • Fig. 7 shows an example of a flow diagram for determining the initial pressure for the filling according to the invention of a sorption store
  • Fig. 8 shows a comparison of different tank configurations and filling strategies
  • FIGs. 1 to 6 show diagrammatic sectional drawings of sorption stores according to the invention.
  • the sorption stores shown by way of example have a substantially cylindrical tank 10.
  • the upper illustrations in each case represent longitudinal sections through the cylinder axis, the lower illustrations in each case represent corresponding cross sections perpendicularly to the cylinder axis.
  • Fig. 1 shows a first preferred embodiment of a sorption store according to the invention.
  • the tank 10 has a circular cross section and has at one of its end faces a passage 21 through the tank wall.
  • a separating element 15 which is designed as a tube with a circular cross section and is arranged coaxially in relation to the cylinder axis.
  • the space in- side the tube forms a first channel-shaped compartment 30.
  • the space between the outer wall of the tube and the tank inner wall forms a second, annular-channel-shaped compartment 31.
  • the separating element 15 is at a distance from both end faces of the tank, so that the first and second compartments 30, 31 are in connection with one another at their ends by way of a respective common space 35, 36.
  • the two compartments 30, 31 and the common space 36 opposite from the passage 21 are completely filled with an adsorption medium 40.
  • the common space 35 which is in connection with the passage 21 , is not filled with adsorption material.
  • a deflecting element 22 which is designed in such a way that inflowing gas is diverted almost exclusively into the outer compartment 31.
  • the deflecting element 22 is designed as a baffle plate in the form of a straight cir- cular cone, the vertex of which is located in the cylinder axis.
  • the deflecting element 22 is at a distance in the axial direction both from the end-face tank inner wall and from the separating element 15.
  • the dashed-line arrows symbolize the gas flow within the tank. Inflowing gas is diverted by means of the deflecting element 22 into the outer compartment 31 and flows down. By way of the common space 36, the gas flows up again through the inner compartment 30. In the common space 35, the rising gas is diverted again on the underside of the deflecting element 22 in the direction of the outer compartment 31 , so that there forms a circulating gas flow through the two compartments 30, 31 and the two common spaces 35, 36.
  • FIG. 2 shows a further preferred embodiment of a sorption store according to the invention.
  • the tank 10 has a circular cross section, and a tubular separating element 15 is arranged inside the tank coaxially in relation to the cylinder axis.
  • the pair of channels is formed by the space inside the separating element 15 as the first channel-shaped com- partment 30 and the space between the tube outer wall and the tank inner wall as the second, annular-channel-shaped compartment 31 .
  • the two compartments 30, 31 are connected to one another by way of a respective common space 35, 36. In this ex- ample, the entire interior volume of the tank is filled with adsorption medium 40.
  • the feeding device comprises four passages 21 through the tank wall, through which gas can flow into the space inside the tank.
  • the passages 21 are located on an end face of the tank 10, are formed as tubes and are arranged such that they are uniformly distributed over the circumference in the region of the annular, outer compartment 31. They protrude so far into the common space 35 that inflowing gas is diverted almost exclusively into the outer compartment 31 .
  • the ends of the passage tubes 21 may also be provided in the outer compartment 31.
  • FIG. 3 a variant of the sorption store according to Fig. 2 is represented.
  • the cross sections of the tank and of the separating element 15 are elliptical, the tubular separating element being aligned coaxially in relation to the cylinder axis.
  • the channel walls of the channel- shaped compartments 30 and 31 which are formed by the tank wall 1 1 and the separating element 15, are of a double-walled configuration, in order to make it possible for a heat transfer medium to flow through. Corresponding inflow and outflow connections for a heat transfer medium are provided, but are not represented in the illustration.
  • FIG. 4 shows a further preferred embodiment of a sorption store according to the invention.
  • a separating element 15 is arranged inside the tank coaxially in relation to the cylinder axis, the cross sections are circular.
  • the channel walls, which are formed by the tank wall 1 1 and the separating element 15, are of a double-walled configuration, in order to make it possible for a heat transfer medium to flow through.
  • a passage 21 through the tank wall which is designed in the form of a tube.
  • the tube runs coaxially through the inner channel-shaped compartment 30 and ends in the common space 36 at the end face of the tank opposite from the passage 21.
  • the space inside the tank is completely filled with an adsorption medium.
  • the dashed-line arrows symbolize the path of the gas flow in the tank. Inflowing gas leaves the central tube into the common space 36 and flows laterally into the outer compartment 31 , and there from the bottom up into the common space 35. From there, it flows from the top down through the inner compartment 30, so that there forms a circulating flow through the channel-shaped compartments 30, 31 and the common spaces 35, 36.
  • a further preferred embodiment of a sorption store according to the invention is repre- sented, one in which the space inside the tank is divided by two coaxially arranged, tubular separating elements 15, 16 into three channel-shaped compartments 30, 31 , 32.
  • the cross sections of the tank and of the separating elements 15, 16 are elliptical in this example.
  • the separating elements are at a distance from both end-face tank inner walls.
  • two common spaces 35, 37 at the end face in which the passages 21 for the gas are provided and two common spaces 36, 38 at the opposite end face are obtained.
  • the common spaces 35 and 36 connect the channel-shaped compartments 30 and 31 , the common spaces 37 and 38 connect the channel-shaped compartments 31 and 32.
  • the compartment 30 and the common spaces 35 and 36 are substantially cylindrical, the compartments 31 and 32 and also the common spaces 37 and 38 are substantially hollow- cylindrical.
  • the common spaces 35 and 37 on the one hand and 36 and 38 on the other hand cannot be strictly separated from one another, but are a result of the gas flow, as will be ex- plained in more detail below.
  • the tank wall 1 1 and the separating elements 15, 16 are of a double-walled configuration for being flowed through by a heat transfer medium.
  • four passages 21 are provided, configured as tubes and arranged such that they are uniformly distributed over the circumference. The ends of the tubes protrude so far into the space inside the tank that inflowing gas is diverted almost exclusively into the middle compartment 31 .
  • the space inside the tank is completely filled with an adsorption medium.
  • the dashed-line arrows symbolize the gas flow within the tank. Inflowing gas is diverted almost exclusively into the middle compartment 31 , and flows down there. At the exit from the middle compartment 31 , the gas flow divides into a first component, which flows through the common space 36 into the inner compartment 30 and up there, and a second component, which flows through the common space 38 into the outer compartment 32 and up there. In the upper part of the tank, the first and second components of the gas flow meet one another and flow through the common space 35 or the common space 37 together again into the middle compartment 31 and down there.
  • the common spaces 35 and 37 at the upper end and common spaces 36 and 38 at the lower end of the tank go over into one another. Their limits cannot be exactly localized, since they are influenced by the gas flow. However, the common spaces are in any case present and distinguishable from one another.
  • deflecting elements may be provided for example at the end face on the inlet side, so that, according to Fig. 5, gas flowing up through the compartments 30 and 32 is diverted into the compartment 31 .
  • further components for heat transmission may also be provided, for example a central tube that runs along the cylinder axis in the compartment 30. It goes without saying that such measures may also be advantageously provided in the case of embodiments other than that represented in Fig. 5.
  • Fig. 6 shows a further preferred embodiment of a sorption store according to the invention.
  • the tank is of a cylindrical form with a substantially rectangular cross section.
  • the corners are of a rounded configuration, the tank wall 1 1 double-walled for being flowed through by a heat transfer medium.
  • the interior of the tank is divided by three separating elements 15, 16, 17 into four channel-shaped compartments 30 to 33.
  • the separating elements are arranged such that they are uniformly distributed in the longitudinal direction of the tank, so that rectangular cross sections with substantially identical area contents are likewise obtained for the compartments.
  • the cross sections of the compartments are square with rounded corners.
  • the separating elements are configured as double-walled plates and run coaxially in rela- tion to the cylinder axis.
  • the separating elements in each case reach up to the inner wall of the tank and are connected to it.
  • the middle separating element 16 is also connected at the end faces to the tank inner walls in the axial direction of the tank, so that two completely separate pairs of channels are obtained in the tank.
  • the first pair of channels comprises the channel-shaped compartments 30 and 31 , which run parallel and are in connection with one another at the end faces by way of the common spaces 35 and 36.
  • the second pair of channels comprises the parallel running, channel-shaped compartments 32 and 33, which are connected to one another at the end faces by way of the common spaces 37 and 38.
  • a passage 21 through an end tank wall, through which the gas can flow into the tank, is provided for each pair of channels.
  • the passages 21 are of a tubular configuration and are arranged such that inflowing gas is diverted almost exclusively into one of the two compartments of each pair of channels.
  • these are the compartment 30 for the first pair of channels and the compartment 32 for the second pair of channels. All of the channel-shaped compartments and also the common spaces are filled with an adsorption medium.
  • the dashed-line arrows symbolize the gas flow within the tank. Inflowing gas is diverted almost exclusively into the compartments 30 and 32. Through these compartments it flows through the respective common spaces 36 and 38 into the compartments 31 and 33, respectively. From there, it flows through the inlet-side common spaces 35 and 37 again into the compartments 30 and 32, respectively, so that two circulating gas flows are obtained.
  • the two pairs of channels 30/31 and 32/33 are completely separate.
  • the invention also covers configurational variants in which, for example, the separating element 16 does not extend up to the end faces, so that the common spaces 37 and 37 and also 36 and 38 are respec- tively in connection. Also in such a case, two circulating flows according to the invention would be obtained.
  • the distances between the channel walls in the channel-shaped compartments of each pair of channels do not differ by more than 40%, particularly preferably by more than 20%, in order to be conducive to a uniform removal of heat during filling or supply of heat during the emptying of the tank.
  • the cross-sectional areas of the channel-shaped compartments are chosen such that, during the filling of the tank with gas, the flow rates in the channel-shaped compartments of each pair of channels differ by no more than 20% from one another.
  • Fig. 6 is an example of a sorption store according to the invention in which both criteria can be satisfied simultaneously.
  • both the distances between their walls and their cross-sectional areas are equal. These in turn are proportional to the flow rate of the gas through the sub-channels, so that the flow rates in the sub-channels are also approximately equal.
  • Fig. 7 shows by way of example a flow diagram for determining the initial pressure po for the filling according to the invention of a sorption store.
  • a starting value for the initial pressure po for example 50% of the final pressure to be reached, is first chosen in the initializing phase 52.
  • Step 53 comprises the actual carrying out of the test.
  • An empty sorption store is filled with gas, the pressure of which at the inlet to the store is constantly po, from the starting time to the time to, which is set for example to one minute. Over the time period from to to the end time t e , the pressure at the inlet to the store is increased according to a predetermined function which approximates to the variation of the adsorption kinetics of the adsorption medium used.
  • step 54 The maximum temperature reached during the charging operation is compared in step 54 with the predetermined upper limit T ma x. If the upper limit is exceeded, the initial pressure po is reduced in step 55, for example by a predetermined value, a predetermined percentage or as an interval nesting. However, the pressure should not go below the minimum pressure amounting to 30% of the final pressure. A renewed test (step 53) at the reduced initial pressure is subsequently carried out.
  • the predetermined upper temperature limit T ma x it is checked in the next step 56 whether the complete charging of the store with gas at the end time t e is satisfactory.
  • the criterion may be, for example, a complete charging of at least 95% of the maximum uptake capacity. If the charging is not yet satisfactory, a further iteration is carried out, in which the initial pressure po is increased in step 57.
  • the pressure may be increased, for example, by a predetermined value, a predetermined percentage or as an interval nesting.
  • a renewed test (step 53) at the increased initial pressure is subsequently carried out.
  • step 54 If both the temperature criterion (step 54) is satisfied and the complete charging is satisfactory, the test program is ended (step 58).
  • an optimum value for the initial pressure can be determined in a few, specific tests. The tests are simple to carry out and are required only once for the design of an actual sorption store. In an analogous way, or else in combination with the sequence described above, the feeding strategy from the initial pressure to the final pressure can be established or optimized.
  • pellets have the same properties in respect of size, permeability, density, heat capacity, conductivity, and enthalpy of adsorption and adsorption kinetics.
  • a cylindrical tank with a circular cross section, an inner longitudinal extent of 100 cm and an inside diameter of 17 is considered.
  • a tube with a circular cross section is provided concentrically in relation to the cylinder axis inside the tank as a separating element. It is of a double-walled configuration with an inside diameter of 5 cm. Its wall thickness is altogether 1 cm, the gap width between the walls of the double wall is 3 mm.
  • the interior of the tank is consequently divided into a pair of channels comprising two parallel running, channel-shaped compartments. The distances between the channel walls in both compartments are in each case 5 cm.
  • the distance between the ends of the tube and the respective inner surfaces at the end faces of the tank is 1 cm.
  • the tank wall is likewise of a double-walled configuration, with a wall thickness of altogether 1 cm; the gap width between the walls of the double wall is 3 mm.
  • the tank has a filling volume of 19 liters and is filled with pellets of a metal-organic framework (MOF) of the type 177 as the adsorption medium
  • MOF type 177 consists of zinc clusters, which are bonded by way of 1 ,3,5-tris(4-carboxyphenyl)benzene as an organic linker.
  • the specific surface area (Langmuir) of the MOF lies between 4000 and 5000 m 2 /g. Further details about this type can be found in patent specification US 7,652,132 B2.
  • the pellets are cylindri- cally formed with a length of 3 mm and a diameter of 3 mm. Their permeability is 3-10 "16 m 2 .
  • the same tank configuration as in the comparative scenario is taken as a basis.
  • the gas is supplied at only 80 bar for a time period of one minute, until the internal tank pressure has in- creased to 80 bar.
  • the inlet pressure of the supplied methane is increased to the final pressure of 90 bar over a time period of 20 minutes according to a function that has been adapted to the adsorption kinetics:
  • the variation of pressure over time is represented in the upper diagram in Fig. 8.
  • the simulated MOF type has a relatively quick removal of heat in relation to the adsorption kinetics, and therefore a value of about 90% of the final pressure is chosen as the initial pressure.
  • a large part of the methane to be adsorbed is already adsorbed. The temperature of the adsorption medium thereby increases greatly.
  • the tank configuration is modified to the extent that two tubular separating elements are arranged concentrically and coaxially in relation to the cylinder axis, so that three parallel running compartments are obtained.
  • the configuration corresponds in principle to that represented in Fig. 5, but with circular cross sections.
  • the inside diameter of the tank is 18.1 cm, its inner longitudinal extent 1 m.
  • the double-walled separating elements have a total wall thickness of 1 cm, with an inner gap width of 3 mm. The distances between the walls in all the channel-shaped compartments are 2.8 cm.
  • the feeding strategy corresponded to that described in the first scenario according to the invention; initially filling with an inlet pressure of 80 bar over a time period of half a minute, subsequently a linear increase in the inlet pressure up to the final pressure of 90 bar as an approximation to the adsorption kinetics of the MOF material.
  • the tank In the tank there forms a flow circulating through the channel-shaped compartments, which leads to a better removal of heat and quicker charging of the adsorption medium. In this case, the removal of heat is increased further by more cooling area being available with the further separating element.
  • the time period until 95% of the tank is charged with methane is reduced, to about 16 minutes (time t.3 in the lower diagram of Fig. 8).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

Cette invention concerne un dispositif de stockage par sorbant pour stocker des substances gazeuses, comprenant une cuve fermée (10) et un dispositif d'alimentation (20), qui comporte un passage (21) ménagé dans la paroi de la cuve, par lequel un gaz peut s'écouler dans la cuve (10). La cuve (10) renferme au moins un élément de séparation (15, 16, 17), qui est conçu de façon que l'intérieur de la cuve soit divisé en au moins une paire de canaux comprenant deux compartiments (30, 31, 32, 33) en forme de canaux s'étendant parallèlement, dont les extrémités sont reliées l'une à l'autre dans chaque cas par le biais d'un espace commun (35, 36, 37, 38), chaque compartiment (30, 31, 32, 33) en forme de canal étant au moins partiellement rempli avec un milieu d'adsorption (40), le dispositif d'alimentation (20) étant conçu de façon que le gaz entrant soit dirigé presque exclusivement dans l'un des deux compartiments (30, 31, 32, 33) de chaque paire de canaux.
PCT/IB2013/059029 2012-10-09 2013-10-01 Dispositif de stockage par sorbant pour le stockage de substances gazeuses WO2014057390A1 (fr)

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CN201380052514.5A CN104736223A (zh) 2012-10-09 2013-10-01 用于储存气体物质的吸着储存器
EP13845513.4A EP2906329A4 (fr) 2012-10-09 2013-10-01 Dispositif de stockage par sorbant pour le stockage de substances gazeuses

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JP2016148438A (ja) * 2015-02-13 2016-08-18 株式会社豊田中央研究所 ガス充填タンク
US11079068B2 (en) * 2019-08-08 2021-08-03 Tda Research, Inc. Rapid fill compressed gas storage tank

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CN105570676A (zh) * 2015-12-22 2016-05-11 重庆市高新技术产业开发区潞翔能源技术有限公司 高温吸附装填系统
DE102017220598A1 (de) * 2017-11-17 2019-05-23 Audi Ag Verfahren zum Befüllen eines Gashochdruckspeichers

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US6638348B2 (en) * 2001-01-26 2003-10-28 Honda Giken Kogyo Kabushiki Kaisha Metal hydride tank apparatus
US20100006454A1 (en) * 2006-05-04 2010-01-14 Werner Gruenwald Gas absorption reservoir with optimized cooling
CN101680601A (zh) * 2007-06-06 2010-03-24 株式会社丰田自动织机 氢储藏罐
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US11079068B2 (en) * 2019-08-08 2021-08-03 Tda Research, Inc. Rapid fill compressed gas storage tank

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EP2906329A4 (fr) 2016-06-15
AR092964A1 (es) 2015-05-06
CN104736223A (zh) 2015-06-24

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