WO2016075100A1 - Récipient de stockage comprenant des couches de corps formé de solide poreux séparées par un joint d'étanchéité - Google Patents

Récipient de stockage comprenant des couches de corps formé de solide poreux séparées par un joint d'étanchéité Download PDF

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Publication number
WO2016075100A1
WO2016075100A1 PCT/EP2015/076134 EP2015076134W WO2016075100A1 WO 2016075100 A1 WO2016075100 A1 WO 2016075100A1 EP 2015076134 W EP2015076134 W EP 2015076134W WO 2016075100 A1 WO2016075100 A1 WO 2016075100A1
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WIPO (PCT)
Prior art keywords
storage vessel
shaped body
acid
gas
seal
Prior art date
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PCT/EP2015/076134
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English (en)
Inventor
Mathias WEICKERT
Stefan Marx
Ulrich Müller
Lena Arnold
Adam Lack
Joseph Lynch
William Dolan
Michael SANTAMARIA
Original Assignee
Basf Se
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Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2016075100A1 publication Critical patent/WO2016075100A1/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
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • 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]

Definitions

  • the invention relates to a storage vessel comprising a shaped body of a porous solid and a seal.
  • vehicles comprise a storage vessel for keeping a stock of the fuel.
  • the gas is stored in pres- sure vessels, often referred to as compressed natural gas (CNG) technique or in sorption stores, often referred to as adsorbed natural gas (ANG) technique.
  • CNG compressed natural gas
  • ANG adsorbed natural gas
  • Sorption stores are also known as ANG tanks.
  • ANG has the potential to replace compressed natural gas CNG in mobile storage applications such as in vehicles.
  • ANG-applications a porous solid is packed in a storage vessel to increase the storage density, enabling lower pressure operation with the same capacity.
  • Sorption covering adsorption and absorption, is an exothermic process. Any sorption or desorp- tion is accompanied by a temperature change in an ANG-storage system.
  • the heat of sorption has a detrimental effect on performance during both filling cycles and discharge cycles.
  • a tem- perature increase as high as 80°C can occur during the filling cycle.
  • a filling cycle normally will be performed at a fuel station, at least for mobile applications, where the released sorption heat can be removed. Contrary to the filling cycle, the rate of discharge is dictated by the energy demand for desorption.
  • the filling time cannot be widely varied to moderate the impact of cooling during the use of ANG storage vessels.
  • Such storage vessels comprise in particular sorbent media having a large internal surface area on which the gas is adsorbed.
  • the gas is stored by adsorption on the adsorbent medium, in the cavities between an individual particle of the adsorbent medium and in parts of the vessel which are not filled with adsorbent medium.
  • the gas can be absorbed by the sorption medium.
  • the filled storage vessel can be pressurized and non-pressurized. Selection of a suitable vessel depends on the applied maximum pressure. The higher the storage pressure the more gas can be stored per volume.
  • Adsorption describes the attachment of atoms or molecules of a gaseous or liquid fluid onto the surface of a solid material, which is also referred to as adsorbent medium, adsorbent, adsorber, absorber or sorption medium.
  • the sorption capacity of the solid defined by the ratio of the mass of the sorbed gas or liquid to the mass of the solid, strongly depends on temperature and is reduced with increasing temperature. In the aim of a maximal exploitation of the storage space, the temperature profile established in the storage vessel during the filling procedure has to be taken into consideration.
  • An efficient sorption allows a reduced filling time as the same amount of gas can be stored in a shorter time period. Hence, the maximum amount of stored gas can be increased when the available filling time is limited.
  • pulverulent materials are processed to compact shaped bodies. These can be handled more conveniently and especially in a safer manner. Shaped bodies allow better exploitation of volumes available in apparatuses or vessels and reduce pressure drops. Prerequisite for a successful use for shaped bodies are preliminarily a high sorption capacity, adequate thermal and mechanical stability and high abrasion resistance.
  • US 2009/0229555 A1 discloses a storage system for an absorbing gas including a plurality of briquette units in a storage tank. Each briquette can include a liner or open vessel, which are associated with compressed gas-absorbing particulate matter.
  • This storage system provides a mechanism for supplying or removing heat.
  • the heat transfer mechanism comprises channels for transporting gas and/or fluid. These channels can pass through a briquette unit.
  • US 8,100,151 B2 describes gas absorbent media, which are provided in a predetermined length of polygon or curvilinear shape. Additionally, a heat absorbent medium is provided, which allows an improved heat transfer from the absorbent to the outside of the tank during filling.
  • Hexagonal tubes are installed along the radial or the longitudinal axis of a fuel tank. Tubes having a gas sorbent medium therein are installed in a predetermined interrelationship with adjacent spaces, for example also tubes, of similar shape, wherein the adjacent spaces are open or filled with the heat absorbent media.
  • the open spaces are provided to allow gas circulation within the entire interior volume of the tank, which is occupied by a honeycomb assembly.
  • a central heat exchanger is shown in the interior of the tank. Assemblies of sorbent and spacer tubes, which are open or filled with the heat sorbent medium, may be formed into a plurality of disks.
  • Storage vessels and shaped bodies known from the state of the art are not optimized for an efficient heat transfer in the interior of the storage vessel, which is dominated by a flow profile established in the interior of the vessel.
  • a large portion of the inner volume of the storage vessel is occupied by further equipment as for example heat exchangers, which causes additional weight and energy consumption as well as higher construction costs.
  • No particular flow conditions in the storage vessel are disclosed in order to obtain an effective heat transfer.
  • the time required for filling should be shortened.
  • a storage vessel comprising a shaped body of a porous solid, wherein the storage vessel comprises a wall with a section comprising at least one inlet, wherein the storage vessel has a central axis and the central axis is a longitudinal axis of the storage vessel and/or perpendicular to a cross-sectional area of the at least one inlet, wherein the shaped body covers at least 80 % of an inner volume of the storage vessel and the shaped body comprises an opening in the axial direction, axial referring to the central axis of the storage vessel, wherein the opening extends from a first end of the shaped body to an opposing second end of the shaped body, wherein the shaped body, which is comprised in the storage vessel, is partitioned into at least two segments and wherein layers (49), comprising at least one segment (29) of the shaped body (3), are stacked in the axial direction (17) in the storage vessel (1 ), and wherein between two layers (49) a seal (51 ) is provided,
  • the storage vessel according to the invention is provided to store a gas, which is preferably usable as fuel.
  • the gas is fed into the storage vessel through the at least one inlet.
  • the gas inside the storage vessel is compressed and absorbed onto or absorbed into the porous solid during filling. Compression and sorption generate heat and thus the gas, the storage vessel and the at least one shaped body heat up.
  • the temperature distribution in the storage vessel de- pends on the flow conditions and heat transfer conditions in and around the shaped body and tends not to be homogeneous, especially in embodiments according to the state of the art.
  • the gas stream is further conducted in the axial direction into the interior of the storage vessel through the opening in the shaped body.
  • at least 85 %, more preferably 90 % and particularly preferably at least 93 % of the inner volume of the storage vessel is covered by the shaped body and its segments.
  • the storage vessel is filled by the porous solid in a pressed form, which is considered to be a shaped body.
  • the shaped body is partitioned into at least two segments, between which a continuous gas stream can flow.
  • the shaped body is segmented as if a form given by the com- plete shaped body is cut into at least two pieces. Further, a sub-division of the shaped body, named as layer, is defined. Consequently, the shaped body is built up from a stacking of layers in the axial direction.
  • One layer can consist of only one segment or comprise more than one segment.
  • one layer can comprise for example eight segments, which can be arranged for example as circular sectors in the layer when the shaped body has a cylindrical form.
  • one layer consists of one segment of the shaped body and the one layer is not further divided into several segments.
  • Two adjacent layers are isolated from each other by the seal in order to inhibit a direct gas flow over the complete cross-section of the storage vessel from one layer to another.
  • the seal has a permeability of less than 10 -14 m 2 , more preferably less than 10 "16 m 2 .
  • a thickness of the seal is preferably in the range between 0.5 and 5 mm, more preferably between 0.6 and 2 mm and most preferably between 0.8 and 1.2 mm.
  • the seal can be made of any material which provides the above-mentioned permeability; preferably the seal is made of plastics, as for example, polyethylene.
  • the material of the seal is flexible in order to prevent mechanical damage to the porous solid.
  • a soft plastic, more preferably thermoresistant plastics, for example polytetrafluoroethylene (PTFE) is applied for edges of the seal in order to lie flat and fit closely to the porous solid.
  • PTFE polytetrafluoroethylene
  • the shaped body and its segments comprise hollow channels in the axial direction and a cross-sectional area of each hollow channel is smaller than a cross- sectional area of the opening.
  • An inner diameter of the hollow channels is preferably in a range from 0.5 mm to 3 mm.
  • a sum of the cross-sectional areas of all hollow channels is less than 20 %, more preferably less than 10 % and most preferably less than 5 % smaller or greater than the cross-sectional area of the at least one inlet for a reasonable pressure drop during the filling process.
  • a shortest distance between two circumferences of the cross- sectional areas of adjacent hollow channels is less than 2 cm, more preferably in a range from 0.8 to 1 .2 cm and most preferably 1 cm.
  • the hollow channels can be distributed homogeneously in an equal distance to each other over the shaped body. Generally every pattern is possible as for example concentric circles.
  • the hollow channels By means of the hollow channels, a more homogeneous distribution of flow conditions and heat transfer as well as temperature can be achieved in the storage vessel.
  • different cross-sectional areas are suitable for the storage vessel, for example circular, elliptical or rectangular. Irregularly shaped cross-sectional areas are also possible, e.g. when the vessel 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 particularly suitable.
  • the storage vessel size varies according to the application. Diameters of the storage vessel of approximately 50 cm are typical for tanks in trucks and approximately 20 cm for tanks in cars, respectively.
  • a diameter of the at least one inlet is by a factor of 5 to 10 smaller than the diameter of the vessel.
  • the diameter of inlet is smaller than
  • a shortest extension of the shaped body is in a range from 10 cm to 100 cm and a longest extension of the shaped body is in the range from 20 cm to 300 cm.
  • the longest extension of the shaped body is in the range from 20 cm to 120 cm, more preferably from 70 cm to 90 cm, and the shortest extension of the shaped body is in a range from 10 cm to 60 cm, more preferably from 30 cm to 50 cm.
  • the longest extension of the shaped body is in the range from 100 cm to 300 cm, more preferably from 150 cm to 200 cm and the shortest extension of the shaped body is in a range from 30 cm to 100 cm, more preferably from 40 cm to 60 cm.
  • the longest second extension of a segment in the axial direc- tion is less than 50 cm, preferably less than 20 cm and more preferably in a range from 5 cm to 15 cm, most preferably in a range from 8 cm to 12 cm. If the second extension is too large and the thickness of the segments is too large, respectively, no effective heat transfer can be established within the segments.
  • the storage vessel has a cylindrical shape and also the shaped body has the form of a cylinder.
  • the form of a circumference of the storage vessel corresponds to the form of a circumference of the shaped body.
  • the storage vessel is a pressure vessel for the storage of gas at a pressure in the range up to 500 bar, preferably in a range of 1 bar to 400 bar, most preferably in a range of 1 bar to 250 bar. For some applications, a range of 1 bar to 100 bar is most preferred.
  • the storage vessel comprises at least one outlet and the at least one inlet and the at least one outlet are both provided in the same section of the wall of the storage vessel.
  • the at least one inlet and the at least one outlet can be located in the same position and combined in one constructional part or adapter.
  • the close arrangement of the at least one inlet and the at least one outlet is especially advantageous in order to establish a flow-through regime during filling, which is further described in WO 2014/057416.
  • a flow-through regime during filling a flow-through is established in the interior of the storage tank during filling and a gas flow through the gas outlet out of the storage vessel exceeds 0 kg/h prefer- ably 50 kg/h and more preferably 100 kg/h during filling.
  • the storage vessel can be made from any material as for example metal, steel, fabric, fiber, plastic or composite material. Fiber composite material and steel are preferred.
  • the wall of the storage vessel can be configured as a double wall com- prising a heat exchanger medium for heat transfer.
  • a diameter of the opening in the shaped body is in a range from 5 mm to 7 mm, for example 6 mm, for a gas mass flow of 300 kg/h during filling.
  • the preferred diameter varies with the root square of the mass flow.
  • a longest diameter of the opening is in a range from 0.2 % to 20 % of the longest diameter of the radial cross-sectional area of the storage vessel.
  • the opening in the shaped body is arranged centrally with respect to the storage vessel and/or in line with the at least one inlet.
  • the outer dimensions of the shaped body in the radial direction correspond to the dimensions of the wall of the storage vessel and the circumference of the shaped body is in intimate contact with the wall of the storage vessel.
  • a first void space which is free of the shaped body, is provided between the wall of the storage vessel and an end face of the shaped body, which faces in the axial direction and which faces away from the at least one inlet, and wherein the first void space comprises up to 15 % of the inner volume of the storage vessel.
  • incoming gas can be collected after being conducted through the opening.
  • At least one first spacer is arranged between the at least two segments of the shaped body or provided next to or on the end face or the segments of the shaped body.
  • the at least one first spacer is preferably provided on the inner wall of the storage vessel.
  • the wall facing to the interior of the storage vessel is not even, but providing several convexities, which are in contact with and holding the shaped body.
  • the at least one first spacer is provided on the seal or is part of the seal or parts of the seal function as the at least first spacer.
  • At least three first spacers are provided, more preferably four first spacers are provided.
  • the more first spacers are provided, the better a tilting of the shaped body or segments towards the wall of the storage vessel can be avoided.
  • a distance between the end face of the shaped body and the wall of the storage vessel can be adjusted by a height of the at least one first spacer, which is preferably in a range from 0.1 cm to 2 cm, more preferably from 0.3 to 1 cm.
  • a second void space which is free of the shaped body, is provided between the wall of the storage vessel and a peripheral surface of the shaped body, wherein the peripheral surface faces in a radial direction, radial referring to the central axis, and wherein the second void space comprises up to 10 % of the inner volume of the storage vessel.
  • the gas can flow without considerable hindrance.
  • the heat transfer in the storage vessel is improved. This is particularly important for the heat transfer from the center of the storage vessel to the wall of the storage vessel, at which heat can be transferred more easily from or to the environment, for example by means of a double jacket.
  • At least one second spacer is provided next to or on the peripheral surface of the shaped body.
  • the shaped body comprises at least three second spacers, more preferably four second spacers in order to generate a slot with a constant width between the shaped body and the wall of the storage vessel.
  • the at least one second spacer is provided only on several points of the peripheral surface and is not covering the complete circumference of the shaped body in order to ensure the slot being provided between the shaped body and the wall. Through this slot gas can flow without particular flow resistance.
  • the presence of the second spacer is especially advantageous in case of a filling process according to WO 2014/057416.
  • a gas stream can flow through the slot from the at least one inlet to a closed end of the storage vessel and further from the closed end to the at least one outlet.
  • the closed end can be located at the side or at the bottom in relation to the rest of the storage vessel, as the storage vessel can be mounted horizontally or vertically. A horizontal position is preferred.
  • the circumference of the shaped body can have an irregular shape due to which contact areas between the peripheral surface of the shaped body with the wall and slots alternate.
  • the term "spacer" on the one hand covers parts, which are attached additionally to the shaped body or to the wall of the storage vessel and which are made of a material other than the shaped body or the wall of the storage vessel.
  • convexities of the shaped body or the wall of the storage vessel are covered.
  • the spacers are made of the same material as the shaped body or the storage vessel wall, re- spectively, and they are formed continuously in one piece with the shaped body or the wall of the storage vessel, respectively.
  • the spacers can be formed in one process step simultaneously with the pressing of the shaped body or pressing of segments of the shaped body.
  • the at least one first spacers and/or and the at least one second spacers are formed in one piece with segments of the shaped body.
  • the porous solid is selected from the group consisting of ac- tivated charcoal, zeolites, activated aluminia, silica gels, open-pore polymer foams, metal hydrides, metal-organic frameworks (MOF) and combinations thereof.
  • Metal-organic frameworks usually comprise an at least bidentate organic compound, which is coordinated to a metal component and together with the metal component forms the skeleton of the metal-organic framework.
  • the metal-organic framework materials as such are described, for example, in US 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000), pages 3-20, H. Li et al., Nature 402 (1999), pages 276 seq., M. Eddaoudi et al. Topics in Catalysis 9 (1999), pages 105-1 1 1 , B. Chen et al., Science 291 (2001 ), pages 1021 -1023.
  • the metal component in the framework according to the present invention is preferably selected from groups la, lla, Ilia, IVa to Villa and lb to Vlb of the periodic table. Particular preference is given to Mg, Ca, Sr, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb and Bi, where Ln represents lanthanides.
  • Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Yb.
  • Mg, Zr, Ni, Al, Mo, Y, Sc, Mg, Fe, Cu and Zn are preferred.
  • Mg, Fe, Zr, Sc, Al, Cu and Zn are preferred.
  • Mg, Zr, Al, Cu and Zn are preferred.
  • At least bidentate organic compound refers to an organic compound which compris- es at least one functional group which is able to form at least two coordinate bonds to a given metal ion and/or to form one coordinate bond to each of two or more, preferably two, metal atoms.
  • the functional groups can also be heteroatoms of a heterocycle. Particularly nitrogen atoms may here be mentioned.
  • the at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound bearing these functional groups is capable of forming the coordinate bond and of producing the framework.
  • the organic compounds comprising the at least two functional groups are preferably derived from a saturated or unsaturated aliphatic compound or an aromatic compound or a both aliphat- ic and aromatic compound.
  • the aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound can be linear and/or branched and/or cyclic, with a plurality of rings per compound also being possible.
  • the aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound more preferably comprises from 1 to 15, more preferably from 1 to 14, more preferably from 1 to 13, more preferably from 1 to 12, more preferably from 1 to 1 1 and particularly preferably from 1 to 10, carbon atoms, for example 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • Particular preference is here given to, inter alia, methane, adamantane, acetylene, ethylene or butadiene.
  • the aromatic compound or the aromatic part of the both aromatic and aliphatic compound can have one or more rings, for example two, three, four or five rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in fused form.
  • the aromatic compound or the aromatic part of the both aliphatic and aromatic compound particularly preferably has one, two or three rings, with one or two rings being particularly pre- ferred.
  • each ring of said compound can independently comprise at least one heteroatom, for example N, O, S, B, P, Si, Al, preferably N, O and/or S.
  • the aromatic compound or the aromatic part of the both aromatic and aliphatic compound more preferably comprises one or two C6 rings, with the two being present either separately from one another or in fused form.
  • the at least bidentate organic compound is more preferably an aliphatic or aromatic, acyclic or cyclic hydrocarbon which has from 1 to 18, preferably from 1 to 10 and in particular 6, carbon atoms and additionally has exclusively 2, 3 or 4 carboxyl groups as functional groups.
  • the at least one at least bidentate organic compound is preferably derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid.
  • the at least bidentate organic compound is derived from a dicarboxylic acid such as oxalic acid, succinic acid, tartaric acid, 1 ,4-butanedicarboxylic acid, 1 ,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1 ,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1 ,8-heptadecanedicarboxylic acid, 1 ,9-heptadecanedicarboxlic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1 ,2-benzenedicarboxylic acid, 1 ,3-benzenedicarboxylic acid,
  • a dicarboxylic acid such as oxalic acid, succinic acid, tartaric acid, 1 ,4-butanedicarboxylic acid, 1 ,4-butenedicarboxy
  • the at least bidentate organic compound can, for example, be derived from a tricarboxylic acid such as 2-hydroxy-1 ,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1 ,2,3-, 1 ,2,4-benzenetricarboxylic acid, 1 ,2,4-butanetricarboxylic acid, 2-phosphono-1 ,2,4- butanetricarboxylic acid, 1 ,3,5-benzenetricarboxylic acid, 1 -hydroxy-1 ,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1 H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino- 6-methylbenzene-1 ,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1 ,2,4-
  • the at least bidentate organic compound is more preferably one of the tricarboxylic acids mentioned by way of example above as such.
  • Examples of an at least bidentate organic compound derived from a tetracarboxylic acid are 1 ,1 -dioxidoperylo[1 ,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or (perylene-1 ,12-sulfone)-3,4,9,10- tetracarboxylic acid, butanetetracarboxylic acids such as 1 ,2,3,4-butanetetracarboxylic acid or meso-1 ,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1 ,4,7,10,13,16- hexaoxacyclooctadecane-2,3,1 1 ,12-tetracarboxylic acid, 1 ,2,4,5-benzenet
  • the at least bidentate organic compound is more preferably one of the tetracarboxylic acids mentioned by way of example above as such.
  • Preferred heterocycles as at least bidentate organic compound in which a coordinate bond is formed via the ring heteroatoms are the following substituted or unsubstituted ring systems:
  • aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids which can have one, two, three, four or more rings, with each of the rings being able to comprise at least one heteroatom and two or more rings being able to comprise identical or different heteroatoms.
  • Suitable heteroatoms are, for example, N, O, S, B, P, and preferred heteroatoms are N, S and/or O.
  • Suitable substituents here are, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.
  • Particularly preferred at least bidentate organic compounds are imidazolates such as
  • 2-methylimidazolate 2-methylimidazolate, acetylenedicarboxylic acid (ADC), camphordicarboxylic acid, fumaric acid, succinic acid, benzenedicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine (TEDA), methylglycinediacetic acid (MGDA), naphthalenedicarboxylic acids (NDC), biphenyldicarboxylic acids such as 4,4'- biphenyldicarboxylic acid (BPDC), pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid, bipyridinedicarboxylic acids such as 2,2'-bipyridinedicarboxylic acids such as 2,2'- bipyridine-5,5'-dicarboxylic acid, benzenetricarboxylic acids such as 1 ,2,3-, 1 ,2,4-benzen
  • the metal-organic framework can also comprise one or more monodentate ligands and/or one or more at least bidentate ligands which are not derived from a dicarboxylic, tricarboxlic or tetracarboxylic acid.
  • the term “derived” means that the at least one at least bidentate organic compound is present in partially or fully deprotonated form. Furthermore, the term “derived” means that the at least one at least bidentate organic compound can have further substituents. Thus, a dicarboxylic or polycarboxylic acid can have not only the carboxylic acid function but also one or more independent substituents such as amino, hydroxyl, methoxy, halogen or methyl groups. Preference is given to no further substituent being present.
  • the at least one at least bidentate organic compound is selected from the group consisting of fumaric acid (FUM), terephthalic acid (BDC), benzene tricarboxylate (BTC, also known as trimesic acid), 2-methylimidazole and benzene tribenzoate (BTB) and/or the at least one metal ion is an ion selected from the group of metals consisting of Mg, Zr, Zn, Cu and Al (more preferably Zn, Cu and Al).
  • FUM fumaric acid
  • BDC terephthalic acid
  • BTC benzene tricarboxylate
  • BTB also known as trimesic acid
  • the at least one metal ion is an ion selected from the group of metals consisting of Mg, Zr, Zn, Cu and Al (more preferably Zn, Cu and Al).
  • suitable metal-organic framework materials are copper-1 ,3,5-BTC, aluminum fumarate, zinc benzene tribenzoate and zinc 2-methylimidazolate.
  • the pore sizes of the metal-organic framework can be adjusted by selecting suitable organic ligands and/or bidendate compounds, also called linkers. Generally, the larger the linker is, the larger the pore size. Any pore size that is still supported by a metal-organic framework in the absence of a host and at temperatures of at least 200 °C is conceivable. Pore sizes ranging from 0.2 nm to 30 nm are preferred, with pore sizes ranging from 0.3 nm to 3 nm being particularly preferred.
  • Metal organic framework comprises pores, in particular micropores or mesopores.
  • Micropores are defined as pores having a diameter of 2 nm or less and mesopores are defined by a diame- ter in the range from 2 to 50 nm (Pure & Appl. Chem. 57 (1985) 603-619).
  • the presence of micropores and/or mesopores can be checked by means of sorption measurements which determine the uptake capacity of the metal organic frameworks for nitrogen at 77 Kelvin in accordance with DIN 66134:1998-2.
  • WO-A-03/102000 describes in general terms the conversion of metal-organic framework powder into shaped bodies like pellets with a resistance to pressure in the range from 2 to 100 N.
  • pellets which have a resistance to pressure of 10 N are made by means of eccentric press.
  • the term "molding" refers to any process known to the expert in the field by which a porous material, i.e. any powder, powdery substance, array of crystallites etc., can be formed into a shaped body that is stable under the con- ditions of its intended use.
  • the molding may be preceded by a step of mixing.
  • the molding may be preceded by a step of preparing a paste-like mass or a fluid containing the porous material, for example by adding solvents, binders or other additional substances.
  • the molding may be followed by a step of finishing, in particular a step of drying.
  • the step of molding, shaping or forming may be achieved by any method known to a person skilled in the art to achieve agglomeration of a powder, a suspension or a paste-like mass. Such methods are described, for example, in Ullmann's Enzyklopadie der Technischen Chemie, 4th Edition, Vol. 2, p. 313 et seq., 1972, whose respective content is incorporated into the present application by reference.
  • briquetting or tableting i.e. mechani- cal pressing of the powdery material, with or without binders and/or other additives
  • granulating i.e. compacting of moistened powdery materials by subjecting it to rotating movements
  • sintering i.e. subjecting the material to be compacted to a thermal treatment.
  • the latter is limited for the material according to the invention due to the limited temperature stability of the organic materials.
  • the molding step according to the invention is preferably performed by using at least one method selected from the following group: briquetting by piston presses, briquetting by roller pressing, binderless briquetting, briquetting with binders, pelletizing, compounding, melting, extruding, co-extruding, spinning, deposition, foaming, spray drying, coating, granulating, in particular spray granulating or granulating according to any process known within the processing of plastics or any combination of at least two of the aforementioned methods. Bri- quetting and/or pelletizing are in particular preferred.
  • a mixture comprising the porous material can be prepared in a mixer such as intensive mixers, rotary plates, marumerizers, and any other equipment known by a person skilled in the art.
  • Preferred mixers are selected from the group consisting of intensive mixers, rotary plates, ball for- mers and marumerizers.
  • the molding can be carried out at elevated temperatures, for example in the range from room temperature to 300°C, and/or at superatmospheric pressure, for example in the range from atmospheric pressure to a few hundred bar, and/or in a protective gas atmosphere, for example in the presence of at least one noble gas, nitrogen, dry air with a relative humidity of preferably less than 45% or a mixture of two or more thereof.
  • the shaped bodies can be formed for example in an excenter press.
  • a compacting force is preferably between 1 kN and 3000 kN, more preferably between 1 kN and 300 kN and most preferably between 10 kN and 150 kN. For higher forces the permeability of the shaped bodies is unnecessarily reduced and for smaller forces no stable shaped bodies are obtained. The smaller the shaped body, the higher the applied force can be chosen.
  • the shaped body is produced with a pressing pressure in a range from 100 bar to 1000 bar, more preferably from 400 bar to 600 bar.
  • the applied press can comprise an upper punch for compaction or it can compact from both sides with an upper punch and a lower punch. Further, the pressing can be performed under vacuum in order to avoid damaging the porous solid.
  • the step of molding can be performed in the presence of binders, lubricants and/or other addi- tional substances that stabilize the materials to be agglomerated.
  • binders lubricants and/or other addi- tional substances that stabilize the materials to be agglomerated.
  • any material known to an expert to promote adhesion between the particles to be molded together can be employed.
  • a binder, an organic viscosity-enhancing compound and/or a liquid for converting the material into a paste can be added to the pulverulent material, with the mixture being subsequently compacted.
  • binders, lubricants or additives are, for example, aluminum oxide or binders comprising aluminum oxide, as described, for example, in WO 94/29408, silicon dioxide, as described, for example, in EP 0 592 050 A1 , mixtures of silicon dioxide and aluminum oxide, as described, for example, in WO 94/13584, clay minerals as described, for example, in JP 03-037156 A, for example montmorillonite, kaolin, bentonite, hallosite, dickite, nacrite and anauxite, alkoxysilanes as described, for example, in EP 0 102 544 B1 , for example tetraalkoxysilanes such as tetra- methoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or, for example, trial- koxysilanes such as trimethoxysilane, triethoxy
  • Suitable binders are for example commercially available under trade names like Pural® SB (aluminum oxide), Ludox® AS 40 (colloidal silica), or Silres® MSE100 (methyl and methoxy groups containing polysiloxane).
  • Preferred binder, lubricants or additives are graphite, stearic acid, magnesium stearate, copper platelets, silicon carbide, expanded natural graphite (ENG), ascorbyl palmitate, polysaccharides, for example commercially available as Zusoplast PS1 , aluminium oxide, for example commercially available as Pural SB or mixtures thereof.
  • the shaped body comprises at least 1 % by weight of a binder and/or lubricant, which are selected from the group consisting of inorganic oxide, clay, concrete and graphite.
  • a binder and/or lubricant which are selected from the group consisting of inorganic oxide, clay, concrete and graphite.
  • the shaped body comprises less than 10% by weight of a binder and/or lubricant and most preferably, the shaped body comprises between 1 .5% and 5% by weight of a binder and/or lubricant and most preferably between 2.5% and 3.5%.
  • no binder or lubricant is used.
  • Further additives which can be used are, inter alia, amines or amine derivatives such as tetraalkylammonium compounds or amino alcohols and carbonate-comprising compounds, e.g. calcium carbonate. Such further additives are described, for instance, in EP 0 389 041 A1 , EP 0 200 260 A1 or WO 95/19222. Further, pore-forming agents such as organic polymers, preferably methylcellulose, polyethylene oxide or mixtures thereof can be added. Preferably, the shaped body comprises from 1 % to 50% by weight of further additives and more preferably from 3% to 20% by weight. Alternatively, no further additives are used.
  • the gas stored in the storage vessel is selected from the group consisting of natural gas, shale gas, town gas, methane, ethane, hydrogen, propane, propene, ethylene, carbon dioxide and combinations thereof.
  • the stored gas comprises ethane and/or hydrogen to an extent of more than 70 vol.-%.
  • gases storable by means of the porous solid are acetylene, nitrogen oxides, oxygen, sulfur oxides, halogens, halogenated hydrocarbons, NF3, SFe, ammonia, hydrogen sulfide, ammonia, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon.
  • gas is used in the interests of simplicity, but gas mixtures are likewise encompassed.
  • the gas can also comprise small amounts of a liquid.
  • the storage vessel is mounted to a vehicle.
  • vehicle includes but shall not be limited to cars, trucks, ships, airplanes, motorcycles, three-wheelers and the like.
  • the invention further relates to a usage of a seal for gas storage and flow control in a storage vessel.
  • the gas storage and/or flow control can be carried out by a process comprising the following steps: Feeding a gas into a storage vessel according to the invention, leading the gas through an opening in a shaped body and leading the gas between layers of the shaped body in in a radial direction, radial referring to the central axis of the storage vessel.
  • Figure 1 shows a longitudinal sectional view of a storage vessel according to the invention
  • Figure 2 shows a cross-sectional view of a shaped body according to the invention
  • Figure 3 shows a close-up of the longitudinal sectional view of the storage vessel according to the invention.
  • Figure 4 shows a seal according to the invention.
  • Figure 1 shows a storage vessel 1 according to the invention with a shaped body 3 of a porous solid.
  • the storage vessel 1 has a cylindrical shape and the shaped body 3 is partitioned into five segments 29, wherein one segment 29 is considered as a layer 49.
  • one layer 49 can also comprise more than one segment 29, wherein two or more segments 29 are arranged next to each other in a radial direction 41 in one layer 49.
  • At least 80 % of an inner volume 13 of the storage vessel 1 is covered by the shaped body 3.
  • an inlet 9 is provided in a section 7 of a wall 5 of the storage vessel 1 .
  • the section 7 is an end face of the cylindrical storage vessel 1 .
  • a gas can enter the storage vessel 1 through the inlet 9 and further flow in parallel to a central axis 1 1 through an opening 19 of the shaped body 3.
  • An axial direction 17 is parallel to the center axis 1 1 and the radial direction 41 is any rectangular direction referring to the central axis 1 1 .
  • the radial direction 41 is further parallel to a surface of a first end 21 of the shaped body 3 and a surface of the second end 23, which opposes the first end 21 .
  • the opening 19 connects the first end 21 with the second end 23. Apart from the opening 19, the shaped body 3 can be traversed by hollow channels 15, which are parallel to the opening 19 and the central axis 1 1.
  • the hollow channels 15 comprise cross-sectional areas 25, which are smaller than a cross-sectional area 27 of the opening 19.
  • a first void space 43 is pro- vided.
  • an outlet 35 is provided in the section 7 of the wall 5 of the storage vessel 1 .
  • a spacer 47 is arranged between two segments 29 or two layers 49 of the shaped body 3 .
  • the layers 49 are stacked in the axial direction 17 and between two layers 49 a seal 51 is provided, which is impermeable for the gas stored in the storage vessel 1 .
  • a peripheral surface 39 which is curved in this embodiment equal to a cylindrical shell of the cylindrical storage vessel 1 , faces towards the curved part of the wall 5.
  • a second void space 37 is provided between the peripheral surface 39 and the wall 5 of the storage vessel 1 . Consequently, the peripheral surface 39 is in large parts not in direct contact to the wall 5.
  • the second void space 37 can be generated by additional spacers on or next to the peripheral surface 39.
  • Figure 2 shows a cross-sectional view of a shaped body 3.
  • the shaped body 3 provides an opening 19 in a central position.
  • several hollow channels 15 can be provided.
  • the hollow channels 15 are distributed homogeneously over a cross-sectional area of the shaped body 3 and the hollow channels 15 are ar- ranged in a distance 33 to each other.
  • Additional spacers 63 may be provided directly on the peripheral surface 39 and formed in one piece with the shaped body 3 in order to generate the second void space 37 between the wall 5 and the peripheral surface 39 of a segment 29 of the shaped body 3.
  • Figure 3 shows a close-up of the longitudinal cross-sectional view of the storage vessel 1 according to the invention.
  • a gas stream 61 enters the storage vessel 1 through the opening 19 traversing the segments 29 and layers 49 of the shaped body 3.
  • the seal 51 separates a first surface 53 of a first layer 55 from a second surface 57 of an adjacent second layer 59 and from the wall 5 of the storage vessel 1.
  • the first surface 53 and the second surface 57 face in the axial direction 17 and the first surface 53 and the second surface 47 face each other.
  • the seal 51 separates the second surface 57 from the opening 19.
  • the gas stream 61 entering the opening 19 is deflected to flow along the first surface 53 between the first surface 53 and the seal 51 .
  • the gas permeates through the solid porous material of the shaped body 3 and thus permeates through the first surface 53.
  • the gas stream 61 traverses the first layer 55 and reaches on a side of the first layer 55, which opposes the first surface 53, a further seal 51.
  • the gas stream 61 is led towards the wall 5 of the storage vessel 1.
  • an outlet 35 is provided next to an inlet 9 and the storage vessel 1 is filled with establishment of flow through, the gas stream 61 is further led along the wall 5 back towards the inlet 9 and the outlet 35.
  • Figure 4 shows a seal 51 according to the invention.
  • the seal 51 corresponds to a round cap-like device, which possesses a first smaller diameter 65, which corresponds to a diameter of the opening 19.
  • the seal 51 can be considered as a continuous sealing layer between two layers 49 of the shaped body 3.
  • a first circumference of the seal 51 with the first diameter 65 is sealingly joined to a circumference of the opening 19.
  • a second circumference of the seal 51 with the second diameter 67 is sealingly joined to an outer circumference of an adjacent layer 49 of the shaped body 3. Due to the seal 51 gas does not flow directly between two adjacent surfaces of adjacent layers 49 of the shaped body 3.
  • a cylindrical storage vessel possesses an inlet and an adjacent outlet.
  • a longest extension of the cylindrical storage vessel also referred to as length, is 1.5 m and an inner diameter is 0.5 m. Consequently, the total inner volume of the storage vessel accounts to 0.29 m 3 .
  • the storage vessel a cylindrical shaped body is arranged.
  • the shaped body is made of the MOF material Z377 and has a density of 500 g/L.
  • a longest extension of the shaped body is 1.495 m, an outer radius of the shaped body is 0.25 m.
  • a distance of 0.5 cm is provided at the side of the storage vessel, which opposes the inlet and the outlet.
  • the storage vessel is filled with natural gas to a maximum storage pressure of 250 bar within 20 minutes.
  • a flow-through regime is established, which is further described in WO 2014/057416.
  • the pressure is raised from ambient pressure to 80 bar within 5 minutes.
  • the pressure of 80 bar is kept constant for 10 minutes and a flow-trough regime is established, leading gas into the storage vessel through the inlet and out of the storage ves- sel through the outlet simultaneously.
  • the pressure is further raised to 250 bar within 5 minutes.
  • the storage vessel as described in the comparative example is applied.
  • a cylindrical shaped body according to the invention is arranged in the storage vessel.
  • This shaped body is divided into 14 segments, which are stacked in the storage vessel as illustrated in figure 1 .
  • An opening along the central axis of the storage vessel is provided in the shaped body with a radius of the opening of 3 cm.
  • the thickness of each segment is 0.1 m and the ra- dius of each segment is 0.245 m.
  • a distance between the segments in axial direction is 2 mm. Between two segments a seal is arranged. Gas can flow between the wall of the storage vessel and the peripheral surface of the shaped body.
  • the storage vessel is filled as described for the comparative example. Now, 270 g gas per liter of the MOF material are storable in the storage vessel.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

L'invention concerne un récipient de stockage (1) comprenant un corps formé (3) d'un solide poreux, le récipient de stockage (1) comprenant une paroi (5) avec une section (7) comprenant au moins une entrée (9), le récipient de stockage (1) ayant un axe central (11) et l'axe central (11) étant un axe longitudinal du récipient de stockage (1) et/ou perpendiculaire à une surface de section transversale de ladite entrée (9), le corps formé (3) recouvrant au moins 80 % d'un volume intérieur (13) du récipient de stockage (1) et le corps formé (3) comprenant une ouverture (19) dans la direction axiale (17), "axial" se référant à l'axe central (11) du récipient de stockage (1), l'ouverture (19) s'étendant d'une première extrémité (21) du corps formé (3) à une seconde extrémité opposée (23) du corps formé (3), le corps formé (3) qui est compris dans le récipient de stockage (1) étant divisé en au moins deux segments (29), et des couches (49) comprenant au moins un segment (29) du corps formé (3) étant empilées dans la direction axiale (17) dans le récipient de stockage (1), et entre deux couches (49) se trouve un joint d'étanchéité (51) qui est imperméable à un gaz contenu dans le récipient de stockage (1).
PCT/EP2015/076134 2014-11-11 2015-11-10 Récipient de stockage comprenant des couches de corps formé de solide poreux séparées par un joint d'étanchéité WO2016075100A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3234443A1 (fr) * 2014-12-19 2017-10-25 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Reservoir de stockage d'hydrogene a hydrures metalliques comprenant plusieurs étages emboités
US10202324B2 (en) 2015-05-04 2019-02-12 Basf Se Process for the preparation of melonal
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure
US10737944B2 (en) 2015-12-08 2020-08-11 Basf Se Tin-containing zeolitic material having a BEA framework structure
US10766781B2 (en) 2015-12-08 2020-09-08 Basf Se Tin-containing zeolitic material having a BEA framework structure
US11377574B2 (en) 2016-08-23 2022-07-05 Basf Se Composite materials

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3234443A1 (fr) * 2014-12-19 2017-10-25 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Reservoir de stockage d'hydrogene a hydrures metalliques comprenant plusieurs étages emboités
EP3234443B1 (fr) * 2014-12-19 2022-04-20 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Reservoir de stockage d'hydrogene a hydrures metalliques comprenant plusieurs étages emboités
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure
US10202324B2 (en) 2015-05-04 2019-02-12 Basf Se Process for the preparation of melonal
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10737944B2 (en) 2015-12-08 2020-08-11 Basf Se Tin-containing zeolitic material having a BEA framework structure
US10766781B2 (en) 2015-12-08 2020-09-08 Basf Se Tin-containing zeolitic material having a BEA framework structure
US11377574B2 (en) 2016-08-23 2022-07-05 Basf Se Composite materials

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