CN104838197A - Method of charging sorption store with gas - Google Patents
Method of charging sorption store with gas Download PDFInfo
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- CN104838197A CN104838197A CN201380063745.6A CN201380063745A CN104838197A CN 104838197 A CN104838197 A CN 104838197A CN 201380063745 A CN201380063745 A CN 201380063745A CN 104838197 A CN104838197 A CN 104838197A
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- container
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- channel
- storage
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- 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]
-
- 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
Abstract
The invention relates to a method of charging a sorption store with a gas, wherein the sorption store comprises a closed container (10) and a feed device which has a passage (21) through the container wall, through which the gas can flow into the container, and the container has at least two parallel, channel-shaped subchambers (30,31,32,33) which are located in its interior and are each at least partly filled with an adsorption medium (40) and whose channel walls are coolable, wherein, in a first step, gas is fed in in such an amount that a pressure in the store of at least 30% of a predetermined final pressure is reached as quickly as possible and in a second step, the amount of gas fed in is subsequently varied in such a way that the course of the pressure in the store approximates the adsorption kinetics of the adsorption medium (40) until the predetermined final pressure in the store is reached after a predetermined period of time.
Description
The present invention relates to the sorption storage for stored-gas material, it comprises the seal container being filled with adsorbing medium at least partly and the feeder comprising the path by container wall, and gas flows in container by described path.The present invention further provides the method with gas filling sorption storage, wherein sorption storage comprises seal container and has the feeder of the path by container wall, gas flows in container by described path, and container has at least two parallel channel-style seed cells, described seed cell is positioned at its inside and is filled with adsorbing medium at least in part separately, and its conduit wall is can be lonely.
For fixing and Mobile solution, be stored-gas, except pressurized gas cylinder, day by day use sorption storage at present.Sorption storage comprises the adsorbing medium with large internal surface area usually, and gas absorption thereon and store thus.During the filling of sorption storage, heat discharges due to absorption, and must remove from storage.Similarly, when being taken out from storage by gas, heat must be provided for desorption method.Therefore, heat management is very important in the design of sorption storage.
Patent application US 2008/0168776 A1 describes the sorption storage for hydrogen, and it comprises environment thermal insulation and multiple pressurized container comprising adsorbing medium is placed in the external container of its inside.Intermediate space cooling liquid between pressurized container is filled, can remove the heat developed between adsorption cycle.
Patent application DE 10 2,007 058 673 A1 describes the equipment for gaseous hydrocarbon storage, and it comprises the insulating vessel being filled with adsorbing medium.There is provided heating element in a reservoir, and this heating element being controlled in a certain way by control system, making when taking out gas, pressure minimum keeps desirable long-time.
A shortcoming of known sorption storage fills with gas only to carry out lentamente.Especially, in Mobile solution, such as in the motor vehicle, this shortcoming is especially severe.
The object of this invention is to provide the equipment for stored-gas material, described equipment allows that the rapid reloading of gas and the gas of improvement take out.This equipment should have simple structure and require little electric energy during operation.Another object of the present invention is to provide fast and effectively loads the method for storage.
This object is realized by present subject matter as described in claim 1.Other Favourable implementations of the present invention can find in the dependent claims.Other subject description of the present invention is in claim 9 and in being subordinated to its claim.
The inventive method uses sorption storage to carry out, and described sorption storage comprises seal container and has the feeder of the path by container wall, and gas flows in container by described path.Container has at least two parallel channel-style seed cells, and described seed cell is positioned at its inside and is filled with adsorbing medium at least in part separately, and its conduit wall is coolable.In the first step of the inventive method, by gas with a certain amount of infeed, make to reach as quickly as possible the pressure of at least 30% of predetermined final pressure in storage.In second step subsequently, the amount of the gas of infeed can change in a certain way, makes the press process in storage close to the adsorption dynamics adsorption kinetics of adsorbing medium until reach the predetermined final pressure in storage after the scheduled time.
As by the known sorption storage of prior art in order to load, be usually connected with pressure line, gas to be stored flows into storage, until reach the predetermined final pressure in storage with constant pressure from described pressure line.But, find that the time needed for filling can obviously reduce when filling is carried out according to the inventive method.
In sorption storage, gas is by be adsorbed on adsorbing medium and in space between each adsorbing medium particle and in particle or be adsorbed in the container area of not filled by adsorbing medium and store.During the first step of the inventive method, first space is filled by gas.Pressure in storage substantially without time lag follow the pressure of the gas flowed in container.For making minimizing cumulative time needed for filling operation, this first step should carry out as quickly as possible, such as, pass through from filling operation starts, just introduce pressure and be equivalent to the gas of at least 30% of predetermined final pressure and carry out.
During first step, a part of gas is adsorbed, therefore, sorbing material and therefore flow through it gas temperature improve.In the second step, the press process in storage is close to the adsorption dynamics adsorption kinetics of adsorbing medium.The method measuring adsorption dynamics adsorption kinetics is well known by persons skilled in the art, such as by pressure jump experiment or adsorption equilibrium (in such as " Zhao; Li and Lin; Industrial & Engineering Chemistry Research; 48 (22); 2009,10015-10020 page ").
For the present invention, term adsorption dynamics adsorption kinetics refers to waiting under gentle isobaric condition, the adsorptive process that gas is pass by time on adsorbing medium.This process is counted roughly by decaying exponential function usually, and it demonstrates when starting and is increased sharply, and then constantly becomes more steady when it is concentrated to end value.An example of this method of approximation is function a ● (1-e
-bt), wherein a and b is normal number.Adsorption dynamics adsorption kinetics is also counted roughly by other function, such as concave function, is segmented into the function of constant, is segmented into the linear function of linear function or connection initial value and end value.
Actual flow condition in the channel-style seed cell of storage depends on that the configuration of passage and gas are to the introducing in passage.In a preferred variants of sorption storage of the present invention, channel-style seed cell at one end closes.This is such as the situation that resolution element is at one end connected with the inwall of container.In this variation, advantageously by the opening end of the gas inlet pathways type seed cell in inflow container.In the channel, a part of gas becomes and is adsorbed on adsorbing medium, therefore adsorbing medium and ambient gas heating.The inwall of container and at least one resolution element of optional existence or the cooling of multiple resolution element, make to form radial symmetry gradient between the middle part and its periphery of channel-style seed cell.Continuous flow is introduced in container by the second step of feed strategies of the present invention especially.Circulating air flow is set up in inside in channel-style seed cell by interacting with radial symmetry gradient, and these guarantee that obvious better heat removes and therefore lower in adsorbing medium maximum temperature.
In another preferred variants of energy storage device of the present invention, channel-style seed cell in both ends open, and is in by common space and connects over the ground.In this variation, preferred disposition feeder, in one that makes the gas flowed into substantially only send in the Liang Ge seed cell of often pair of passage.Having in storage causes the flow velocity of gas in channel-style seed cell to be greater than the speed of gas absorption close to the filling strategy of the present invention of the press process of adsorption dynamics adsorption kinetics.This causes forming the circular flow by channel-style seed cell, guarantees that the heat developed between adsorption cycle can remove quickly and in adsorbing medium, set up lower maximum temperature.
Remain compared with high conventional feed strategies with wherein pressure consistently in whole filling time, the inventive method is allowed and during loading, to be introduced more substantial gas within the identical time or realize shorter filling time under the gas of identical amount.
The amount of the gas fed such as by inlet pressure is suitably mated approximate function, such as, can be connected by suitable valve and changes.
In the Favourable implementations of the inventive method, the press process in storage with the form of pressure surge, particularly due to the suitable change of inlet pressure close to adsorption dynamics adsorption kinetics.The maximum value of fluctuation is preferably equivalent to final pressure, and the minimum value of fluctuation is preferably close to the process of adsorption dynamics adsorption kinetics.This fluctuating range being equivalent to pass by time reduces.At the end of the scheduled time, the predetermined final pressure in storage is set.Fluctuation can be such as sinusoidal curve, zigzag fashion or conduct selection piecewise constant.The shape of fluctuation and its amplitude and the concrete adsorption dynamics adsorption kinetics of period Optimum Matching.
An example close to the function of the pressure surge of adsorption dynamics adsorption kinetics is:
P=p0+ Δ pf (a) (sin (2 π kt)-1), wherein:
P
0for initial pressure, p is the difference between initial pressure and final pressure, and k is frequency, and f (a) is damping function.Damping can such as linearly reduce or index reduces.An example is function f (a)=a/ (t+a), and wherein a is positive number.Frequency k can by etc. gentle isobaric adsorption dynamics adsorption kinetics t
kinassessment, it is the tolerance of minimum filling time.Preferred selection frequency, makes 2-10 fluctuating period be positioned at t
kinin.Under comparatively major cycle number, often circulation can remove less heat, makes to provide the energy ezpenditure needed for pressure surge to become uneconomical.
Time needed for filling sorption storage, particularly its adsorption dynamics adsorption kinetics affected substantially by the material property of adsorbing medium.The maximum temperature of expection during another influence factor is filling, it also depends on material property, particularly adsorbs heat content.Initial pressure and pressure is selected to improve type with Optimum Matching adsorption dynamics adsorption kinetics separately, absorption heat content and the heat transfer to wall.When the absorption heat content Rapid Thermal discharged removes, higher initial pressure is favourable, minimizes to make required total loading time.Depend on that adsorption dynamics adsorption kinetics and heat remove, the initial pressure for the 30-90% of predetermined final pressure is favourable, wherein selects desirable high initial pressure.The magnitude of initial pressure may improve restriction by the temperature set up between adsorption cycle.
Tend to advantageously select pressure reduction larger between initial pressure and final pressure, then heat remove slower.Pressure improves speed and is preferably at least 1 ba/min of clock filling time, to promote the formation of circular flow in channel-style seed cell.
In a preferred embodiment of the inventive method, and if measure gas flow temperature at least one channel-style seed cell if required, flux matched in a certain way with the gas fed in sorption storage, makes to be no more than the predetermined maximum temp in channel-style seed cell.
Various material is suitable for and makes adsorbing medium.Adsorbing medium preferably comprises zeolite, active carbon or metallic organic framework.
The porosity ratio of adsorbing medium is preferably at least 0.2.Porosity ratio is defined as the ratio of void volume and the total volume of any sub-volume in container.Under lower porosity ratio, pressure drop when flowing through adsorbing medium improves, and this has adverse effect to filling time.
In a preferred embodiment of the invention, adsorbing medium exists as granule bed, and the permeability of granule is at least 10 with the ratio of minimum granule diameter
-14m
2/ m.During filling, the speed of gas permeation granule depends on the speed of the pressure of granule inside close to the pressure of granule outside.Time needed for this pressure balance and therefore also have granule load time along with permeability reduce and along with granule diameter improve and improve.This can have limited impact to total method of filling and discharge.
When introduce before by gas cooling time, the time needed for filling can reduce further.
At least one resolution element or multiple resolution element, all resolution elements particularly existed preferably have double-walled, make heat transfer medium can flow through them.Also preferably all conduit walls of channel-style seed cell are that double-walled is to allow that heat transfer medium flows through them.Depend on the arrangement of at least one resolution element or resolution element, a part of inwall of container forms the conduit wall of a channel-style seed cell or multiple channel-style seed cell.In this case, container wall is also preferably double-walled.In particularly preferred embodiments, configuration comprises the whole container wall of end face to allow that heat transfer medium flows through it, is particularly configured to double-walled.
Depend on the temperature range being suitable for cooling or heat the gas in sorption storage, various heat transfer medium such as water, glycol, alcohol or its mixture are possible.Suitable heat transfer medium is well known by persons skilled in the art.
Find that advantageously the spacing of conduit wall is 2-8cm in each channel-style seed cell.Herein, term spacing refers to the beeline between cross section two points on opposite walls of the axle perpendicular to passage.When having the passage of circular cross section, such as spacing is equivalent to diameter, and when annular cross section, it is equivalent to the width of ring, and when rectangular cross section, it is equivalent to the comparatively short distance between parallel edges.Especially when by all conduit wall coolings or heating, find that described scope is the good compromise between heat trnasfer and the packing volume of adsorbing medium.Under larger spacing, the heat trnasfer deterioration between adsorbing medium and wall; In more closely spaced situation, under given external container size, the packing volume of adsorbing medium reduces.In addition, weight and its cost of production of sorption storage improve, and this is disadvantageous, particularly when Mobile solution.
In a preferred embodiment, in channel-style seed cell, the spacing of conduit wall is more or less the same in 40%, is particularly preferably more or less the same in 20%.During this configuration helps filling, heat evenly removes or introducing hot during vessel empty.
The container of sorption storage is preferably cylindrical, and at least one resolution element and cylindrical axle essentially coaxially arrange.Wherein relative to the embodiment in cylindrical axle inclination several years to maximum 10 degree, the longitudinal axis of at least one resolution element thinks that " substantially " is coaxial.This configuration guarantees that channel cross-section only slightly changes along cylindrical axle, makes the equal uniform flow that can be based upon on passage length.
Depend on the maximum allowable pressure in the space and container being effective to install, the various cross sectional areas of hydrostatic column are possible, such as circular, oval or rectangle.Such as when container is arranged in the hollow space of car body, also consider erose cross sectional area.For the high pressure in about 100 Palestine and Israels, circular and oval cross section is specially suitable.
The present invention further provides the sorption storage for stored-gas material, its feeder comprising seal container and comprise the path by container wall, gas flows in container by described path.Container has at least one resolution element, and described resolution element is positioned at its inner and configuration and makes the inside of container be divided at least two parallel channel-style seed cells, and described seed cell is filled with adsorbing medium separately at least in part, and its conduit wall is coolable.According to the present invention, with cross-sectional view, the profile of container inner wall and at least one resolution element and optional multiple resolution element is substantially conformal.
In this context, the conformal profile that means is of similar shape, be all such as circular, be all oval or be all rectangle.Statement " substantially conformal " means still to be included in " same shape " with the little deviation of basic shape.Example is the fillet when rectangular basic shape or the deviation in production permissibility.
This configuration is allowed and is used the inner space of container best so that very a large amount of adsorbing mediums and effective heat management combine.
Above-mentioned preferred structure characteristic such as the arranged in co-axial alignment of resolution element in double-walled resolution element, conduit wall spacing and/or hydrostatic column also represents the preferred embodiment of sorption storage of the present invention.
The selection of the wall thickness of container and resolution element depend on expect in container pressure maximum, container size, particularly its diameter, and the performance of material therefor.When having alloy steel container and the 100 bar pressure maximum of 10cm external diameter, minimal wall thickness is such as estimated as 2mm (according to DIN17458).Select the inner pitch of double-walled, make the heat transfer medium of enough large volume stream can flow through them.It is preferably 2-10mm, particularly preferably 3-6mm.
At least one resolution element is particularly preferably configured to pipe, makes the inner space of pipe form first passage type seed cell and space between the outer wall of pipe and the inwall of container or between the outer wall of optional pipe and another resolution element forms the second type seed cell, annular pass.With cross-sectional view, the profile of tubular type resolution element and the profile of container inner wall are conformal; They are all such as circular or are all oval.In another development of this embodiment of the present invention, there is multiple resolution element, and be all configured to have the pipe of various diameter and arranged in co-axial alignment.With cross-sectional view, their profile is also conformal with the profile of container inner wall.
Feeder comprises at least one path by container wall, and gas flows in container by described path.In one particular embodiment, feeder comprises tubular type feeding line, and its one end is connected with at least one path, and it is branched into the multiple ends leading to each channel-style seed cell.In an alternative, feeder comprises multiple path by container wall, and it is all at one end gone up and is connected with tubular type feeding line, and its other end leads to channel-style seed cell.
In another Favourable implementations, feeder comprises the assembly be distributed to specific mode by the gas flowed into by least one path in all seed cells, such as diverter element or dispensing device.
The influx of gas is particularly preferably distributed in channel-style seed cell in a certain way, and the ratio making each gas flow mutual is equivalent to the ratio of the cross sectional area of seed cell.
Feeder also can comprise the device for affecting gas flow, such as throttle valve or modulating valve.These devices can be provided in inside or the outside of container.Multiple path also can be provided in container wall, such as, so that by gas in multiple local introduction passage type seed cell, or to be provided for the different paths filling and take out gas.The one or more path identical with replenishing container of preferred use takes out gas.
Compared with prior art, sorption storage of the present invention makes heat to transport out from adsorbing medium quickly or to be transported in adsorbing medium.This significantly reduced the time needed for the filling of the gas of storage specified rate.As selection, storage is available more substantial gas filling within preset time.When being taken out from storage by gas, the invention enables gas can fast and constantly provide.For this reason, heated by conduit wall, such as, when double-walled configuration, the heat transfer medium of the gas temperature that its temperature is greater than in channel-style seed cell passes through double-walled.Sorption reservoir configuration of the present invention is simple, and due to its compact structure, is particularly suitable for Mobile solution, such as, in motor vehicle.The embodiment with Twin channel wall has another advantage: only must change heat transfer medium or its temperature and suitably change with from cooling or heating change.Therefore, this embodiment is suitable in the mobile purposes during filling and drive pattern.
The present invention is set forth further below by accompanying drawing; Figure should be interpreted as principle and describe.They do not limit the present invention, such as, in the concrete size or structure variable of assembly.In order to clear, their usual nots to scale (NTS), especially in length and width compare.Figure shows:
Fig. 1: the embodiment with the sorption storage of the present invention of the flow equalizer about inflow gas
Fig. 2: the embodiment with Twin channel wall, the oval cross section area of container and the sorption storage of the present invention of multiple path
Fig. 3: the embodiment with the sorption storage of the present invention of the rectangular cross section of container
Fig. 4: for measuring the example of the flow chart loading the initial pressure of sorption storage according to the present invention
Fig. 5: the contrast of filling strategy of the present invention and conventional filling strategy
List of reference numbers used
10 ... container
11 ... container wall
15 ... resolution element
16 ... resolution element
17 ... resolution element
21 ... path
22 ... cover plate
30 ... first seed cell
31 ... second seed cell
32 ... 3rd seed cell
33 ... 4th seed cell
40 ... adsorbing medium
5x ... measure the process step of initial pressure
Fig. 1-3 shows the schematic cross-sectional by sorption storage of the present invention.Illustrative sorption storage has substantially cylindrical container 10.In often kind of situation, upper figure is described through the longitudinal section of cylindrical axle, these separately below figure show respective cross section perpendicular to cylindrical axle.
Fig. 1 shows the first preferred embodiment of sorption storage of the present invention.Container 10 has circular cross section and on its end face, has the path 21 by container wall.Be configured to there is circular cross section and be positioned at the inside of container 10 with the resolution element 15 of the pipe of cylindrical axle arranged in co-axial alignment.The inner space of pipe forms first passage type seed cell 30.Space between the outer wall of pipe and the inwall of container forms the second type seed cell, annular pass 31.Resolution element 15 has the spacing of distance entry end end face; On opposite ends, it extends to the end face of container.In the example shown, Liang Ge seed cell 30,31 is filled by adsorbing medium 40 completely.At the end in the face of path 21, seed cell 30,31 is combined by the cover plate 22 extended on the whole cross section of container.In the example shown, 5 openings that air-flow flows in seed cell by it are present on cover plate 22.Cover plate serves as flow equalizer, and it flows in seed cell 30,31 with guaranteeing gas uniform.Shown opening as an example; They also have another configuration.Such as, annular or interruption annular opening can be provided in the perimeter of connecting path 21 and the second seed cell 31.
Gas flow in broken string arrow symbol container.Flow into gas first between inlet passage 21 and cover plate 22 not by the space that adsorbing medium is filled, and become be uniformly distributed in there.Gas is flowed in Liang Ge seed cell 30,31 by the opening on cover plate, and it is adsorbed on adsorbing medium there.The gas of adsorbing medium and surrounding heats due to absorption.Inwall and the resolution element 15 of container 10 cool, and make to set up radial symmetry gradient between the middle part and its periphery of channel-style seed cell.The second step of feed strategies of the present invention produces the continuous flow entered in container especially.This and radial symmetry gradient interact and produce circulating air flow, and this guarantees that obviously better heat removes and therefore sets up the lower maximum temperature in adsorbing medium in inside, channel-style seed cell 30,31.Therefore, container can be loaded into the gas of identical amount within the time shorter when whole filling time is held constant at high conventional feed strategies than wherein pressure.
Fig. 2 shows another preferred embodiment of sorption storage of the present invention.Container 10 has oval cross section, and the tubular type resolution element 15 equally with oval cross section is coaxially arranged in internal tank with cylindrical axle.As in previous case, the inner space of tubular type resolution element 15 forms first passage type seed cell 30, and the space between the outer wall of pipe and the inwall of container forms the second type seed cell, annular pass 31.The conduit wall of the channel-style seed cell 30 and 31 formed by container wall 11 and resolution element 15 has double-walled, makes heat transfer medium can flow through this wall.The corresponding charging connection about heat transfer medium is provided to be connected with discharge but not show in the drawings.
In this example, the whole internal volume of container is filled by adsorbing medium 40.Feeder comprises 5 paths 21 by container wall, and gas flows into internal tank by described path.Path 21 is positioned on an end face of container 10, be configured to pipe and be arranged in the region of annular, outer seed cell 31 around even circumferential, and Central places is arranged in the middle part of the end face as the entrance of interior sub-chambers 30.In this embodiment, resolution element 15 extends to each end face of container at two ends.
Gas flow in broken string arrow symbol container.In this example, the gas of inflow is directly distributed on adsorbing medium by 5 paths 21.In the formation of temperature gradient and seed cell 30,31, the air-flow of inner loop is similar to and carries out about the example described in Fig. 1 above.
Fig. 3 shows another preferred embodiment of sorption storage of the present invention.Container has cylinder form and basic rectangular cross section.Angle is circular, and container wall 11 is for double-walled is to allow that heat transfer medium flows through it.The inside of container is divided into four channel-style seed cell 30-33 by three resolution elements 15,16,17.Resolution element distributes equably with the longitudinal direction of container, makes seed cell have the rectangular cross section of substantially identical inner area equally.In the example shown, the cross section of seed cell is the square with fillet.Resolution element is configured to Double-wall board, and the container inner wall that be also in the horizontal parallel to adjacent separation element relative or parallel container coaxial with cylindrical axle is advanced in the vertical.With cross-sectional view, therefore the inwall of container and the profile of resolution element are conformal.In the axial direction and in the horizontal, resolution element extends to the inwall of container separately and is connected with it, makes to obtain four distinct seed cells in a reservoir.
For each seed cell 30,31,32,33, the path 21 that gas flows in container by it is provided by the end face of container wall.That path 21 is tubular type and extend in respective seed cell.All channel-style seed cells are filled with adsorbing medium.
In the figure, the arrow that breaks also signifies the gas flow in container.To be similar to the mode of the embodiment of Fig. 2, the gas of inflow is directly distributed on adsorbing medium by path 21.Due to the cooling of conduit wall, be based upon with during cross-sectional view from the middle part of passage to the temperature gradient of conduit wall.As described with regard to FIG. 1, feed strategies of the present invention produces the continuous flow entered in container, and combines with temperature gradient the air-flow producing inner loop in channel-style seed cell 30,31,32,33, obtains above-mentioned advantage.
For improving heat trnasfer, other assembly transmitting heat also can be provided for, the center tube of such as advancing along cylindrical axle in often kind of situation in each seed cell 30,31,32,33.Certainly, this kind of measure also may be favourable in the embodiment shown in Fig. 3 being different from.
Fig. 4 shows as an example for measuring the initial pressure p loading sorption storage according to the present invention
0flow chart.When beginning 51, first in initial phase 52, select initial pressure p
0initial value, 50% of final pressure such as to be achieved.In addition, the temperature T allowed in storage is set
maxthe upper limit and required final filling time t
e, such as 5 minutes.
Step 53 comprises the actual of experiment and carries out.Filled by the sorption storage gas of sky, the pressure of described gas in storage ingress is from start time point to the time point t being set to such as 1 minute
0for constant p
0.Warp is from t
0to final time t
eperiod, improve the pressure of storage ingress according to the predefined function of the adsorption dynamics adsorption kinetics process close to adsorbing medium used.
By the maximum temperature that reaches during load operation in step 54 and predetermined upper limit T
maxcontrast.If exceed the upper limit, then in step 55 by initial pressure p
0reduce such as predetermined value, predetermined percentage or conduct interval nested.But, pressure should be not less than add up to final pressure 30% pressure minimum.The initial pressure of reduction is used again to test (step 53) subsequently.
But, if do not reach predetermined temperature upper limit T
max, then in next step 56, gas total load about storage is carried out at final time t
etime whether gratifying inspection.Standard can be the total load of at least 95% of such as maximum absorbance capacity.If load is still unsatisfactory, then in step 57, carry out raising initial pressure p
0another repeat.Pressure can be improved such as predetermined value, predetermined percentage or as interval nested.The initial pressure of raising is used again to test (step 53) subsequently.
If follow temperature standard (step 54) and total load is also gratifying, then experimental arrangement terminates (step 58).Like this, the optimum value about initial pressure can be measured in several target experiment.Experiment is easily carried out and is only needed once the design of actual sorption storage.In a similar fashion, or combine with said sequence, feed strategies can be set or make from initial pressure to final pressure optimization.Embodiment
The analog computation that service routine OpenFOAM (from ENGYS) carries out the results are shown in hereinafter.Calculate based on following hypothesis:
The homogeneous phase that-granule bed can be thought porous medium and separate with gas phase.Therefore do not need quantitatively to resolve each independent granule.
-all granules have performance identical in granularity, permeability, density, thermal capacitance, conductivity, absorption heat content and adsorption dynamics adsorption kinetics.
-flow effect in the heat transfer of bed is by known relationship description.
Calculate based on having circular cross section, the inner length expansion of 100cm and the hydrostatic column of internal diameter of 17cm.At internal tank, the pipe with circular cross section is installed with one heart as resolution element and cylindrical axle.It has the internal diameter of double-walled and 5cm.Its wall thickness is for amounting to 1cm, and the gap width between the wall of double-walled is 3mm.This configuration is equivalent to the example according to Fig. 2, but has circular cross section.Therefore the inside of container be divided into two the parallel channels type seed cells be mutually separated completely.The spacing of conduit wall is all 5cm in Liang Ge seed cell.Container wall is also double-walled, and it has the total wall thickness of 1cm and the gap width between the wall of double-walled is 3mm.The pipe be connected with path 21 stretches out 8cm in container.
Container there is the packing volume of 19L and the granule being filled with 177 type metallic organic frameworks as adsorbing medium.177 type MOF comprise and divide the zinc bunch of sub-connection by 1,3,5-tri-(4-carboxyl phenyl) benzene as organic bridging agent.The specific surface area (Langmuir (langmuir)) of MOF is 4000-5000m
2/ g.At US 7, can find in 652,132 B2 about this kind of out of Memory.This has the cylinder form of 3mm length and 3mm diameter.Their permeability is 310
-16m
2.Therefore permeability is 10 with the ratio of minimum granule diameter
-13m
2/ m.The porosity ratio of bed is 0.47.
Check and filled by container pure methane, described methane feeds with the temperature of 27 DEG C.Predetermined final pressure is 90 bar absolute pressures.Heat transfer medium flows through container wall and each resolution element in a certain way, makes the constant wall temperature setting up 27 DEG C.Under these conditions, container can be filled with maximum 2kg methane.
The result of figure below display two schemes in Fig. 5.In contrast scheme (full curve), gas feeds in said vesse under the constant pressure of 90 bar from the outset.The final pressure of 90 bar is reached in a reservoir in first minute.After about 32 minutes, 0.9kg methane is adsorbed (the time t in Fig. 5
1).At this time point, the space in granule bed is filled by another kg methane, make container with 95% degree be loaded with methane.
According in the solution of the present invention (broken string curve), the vessel configuration identical with contrast scheme is used as basis.But 1 minutes of gas when starting only feeds until the internal pressure in container rises to 80 bar under 80 bar.Through 30 minutes, the inlet pressure of the methane of infeed is increased to the final pressure of 90 bar subsequently according to the function mated with adsorption dynamics adsorption kinetics:
P (t)=p
0+ Δ p (1 – e
-kt), wherein p
0=80 bar, Δ p=10 clings to and k=0.0025s
-1.
The press process of passing by time is shown in the upper figure in Fig. 8.When considered tank, simulation MOF type demonstrates and removes relative to the Rapid Thermal of adsorption dynamics adsorption kinetics, therefore selects the value of about 90% of final pressure as initial pressure.The methane of major component upon adsorption was adsorbed in first minute.This causes the temperature of adsorbing medium to be increased sharply.
This analog result proves to cause by this operator scheme of the present invention in the flowing of channel-style seed cell inner loop.Due to this flowing, the heat that adsorbing medium develops due to absorption removes quickly on cooling wall.This cause again absorption to occur quickly and container at only about 26 minutes (time t in the figure below in Fig. 5
2) be loaded with methane to 95% degree later.
Claims (13)
1. by the method for gas filling sorption storage, wherein sorption storage comprises seal container (10) and has the feeder of the path (21) by container wall, gas flows in container by described path, and container has at least two parallel channel-style seed cells (30, 31, 32, 33), described seed cell is positioned at its inside and is filled with adsorbing medium (40) at least in part separately, and its conduit wall is coolable, wherein in a first step, gas makes to reach as quickly as possible the pressure at least 30% of predetermined final pressure in storage with a certain amount of infeed, in the second step, change the amount of the gas of infeed subsequently in a certain way, make the press process in storage close to the adsorption dynamics adsorption kinetics of adsorbing medium (40) until reach the predetermined final pressure in storage after the scheduled time.
2. method according to claim 1, wherein the conduit wall of channel-style seed cell (30,31,32,33) is configured to double-walled, and heat transfer medium flows through them.
3., according to the method for claim 1 or 2, wherein in each channel-style seed cell (30,31,32,33), the spacing of conduit wall is 2-8cm.
4. method as claimed in one of claims 1-3, wherein in channel-style seed cell (30,31,32,33), the spacing of conduit wall is more or less the same in 40%, is particularly more or less the same in 20%.
5. method as claimed in one of claims 1-4, wherein the porosity ratio of adsorbing medium (40) is at least 0.2.
6. method as claimed in one of claims 1-5, wherein adsorbing medium (40) exists as granule bed, and the permeability of granule is at least 10 with the ratio of minimum granule diameter
-14m
2/ m.
7. method as claimed in one of claims 1-6, wherein adsorbing medium (40) comprises zeolite, active carbon or metallic organic framework.
8. method as claimed in one of claims 1-7, wherein measure gas flow temperature at least one channel-style seed cell (30,31,32,33) and flux matched in a certain way with the gas fed when needing in sorption storage, make to be no more than the predetermined maximum temp in channel-style seed cell.
9. for the sorption storage of stored-gas material, it comprises seal container (10) and comprises the feeder of the path (21) by container wall, gas flows in container by described path, wherein container has at least one resolution element (15, 16, 17), described resolution element is positioned at its inner and configuration and makes the inside of container be divided at least two parallel channel-style seed cells (30, 31, 32, 33), described seed cell is filled with adsorbing medium (40) separately at least in part, and its conduit wall is coolable, wherein with cross-sectional view, the inwall of container and at least one resolution element (15, 16, 17) and the profile of optional multiple resolution element be substantially conformal.
10. sorption storage according to claim 9, wherein the conduit wall of channel-style seed cell (30,31,32,33) is configured to double-walled to allow that heat transfer medium flows through them.
11. sorption storages according to claim 9 or 10, wherein in each channel-style seed cell (30,31,32,33), the spacing of conduit wall is 2-8cm.
12. sorption storages any one of claim 9-11, wherein container (10) is for cylindrical, and at least one resolution element (15) and cylindrical axle essentially coaxially arrange.
13. sorption storages according to claim 12, wherein at least one resolution element (15) is configured to pipe, make the inside of pipe form first passage type seed cell (30), and the space between the outer wall of pipe and the inwall of container or between the outer wall of optional pipe and another resolution element (16,17) form the second type seed cell, annular pass (31).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12187760 | 2012-10-09 | ||
| EP12187760.9 | 2012-10-09 | ||
| PCT/IB2013/058907 WO2014057382A1 (en) | 2012-10-09 | 2013-09-27 | Method of charging sorption store with a gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104838197A true CN104838197A (en) | 2015-08-12 |
Family
ID=47022515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380063745.6A Pending CN104838197A (en) | 2012-10-09 | 2013-09-27 | Method of charging sorption store with gas |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2906868A4 (en) |
| CN (1) | CN104838197A (en) |
| AR (1) | AR092965A1 (en) |
| WO (1) | WO2014057382A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110337562A (en) * | 2017-11-17 | 2019-10-15 | 奥迪股份公司 | Method for filling gas high pressure accumulator |
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| JP4705251B2 (en) * | 2001-01-26 | 2011-06-22 | 本田技研工業株式会社 | MH tank |
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| EP1633760B1 (en) * | 2003-05-09 | 2010-05-05 | The Regents of The University of Michigan | MOFs with a high surface area and methods for producing them |
| DE102007058673B4 (en) * | 2007-12-06 | 2016-04-14 | Basf Se | Method for storing gaseous hydrocarbons and apparatus therefor |
| CN201363548Y (en) * | 2009-03-05 | 2009-12-16 | 集美大学 | Automobile hydrogen fuel carbon-based material absorbing storage tank body |
| CN102188141A (en) * | 2011-05-25 | 2011-09-21 | 扬州康龙玻璃工艺制品有限公司 | Double-layer drinking cup |
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2013
- 2013-09-27 CN CN201380063745.6A patent/CN104838197A/en active Pending
- 2013-09-27 EP EP13845747.8A patent/EP2906868A4/en not_active Withdrawn
- 2013-09-27 WO PCT/IB2013/058907 patent/WO2014057382A1/en active Application Filing
- 2013-10-09 AR ARP130103672A patent/AR092965A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4187092A (en) * | 1978-05-15 | 1980-02-05 | Billings Energy Corporation | Method and apparatus for providing increased thermal conductivity and heat capacity to a pressure vessel containing a hydride-forming metal material |
| CN1236075A (en) * | 1999-06-08 | 1999-11-24 | 天津大学 | Natural gas storage tank with adsorption matter and injection technology |
| CN101144566A (en) * | 2002-12-10 | 2008-03-19 | 高级技术材料公司 | Gas storage and dispensing system with monolithic carbon adsorbent |
| DE102006020846A1 (en) * | 2006-05-04 | 2007-11-08 | Robert Bosch Gmbh | Gas sorption storage with optimized cooling |
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| CN110337562A (en) * | 2017-11-17 | 2019-10-15 | 奥迪股份公司 | Method for filling gas high pressure accumulator |
| US11473728B2 (en) | 2017-11-17 | 2022-10-18 | Volkswagen Ag | Method for filling a high pressure gas accumulator |
Also Published As
| Publication number | Publication date |
|---|---|
| AR092965A1 (en) | 2015-05-06 |
| EP2906868A4 (en) | 2016-08-24 |
| WO2014057382A1 (en) | 2014-04-17 |
| EP2906868A1 (en) | 2015-08-19 |
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