WO2016116406A1 - Réservoir de gaz comprimé contenant un gaz, un matériau accumulateur de chaleur latente et une substance solide poreuse - Google Patents

Réservoir de gaz comprimé contenant un gaz, un matériau accumulateur de chaleur latente et une substance solide poreuse Download PDF

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Publication number
WO2016116406A1
WO2016116406A1 PCT/EP2016/050906 EP2016050906W WO2016116406A1 WO 2016116406 A1 WO2016116406 A1 WO 2016116406A1 EP 2016050906 W EP2016050906 W EP 2016050906W WO 2016116406 A1 WO2016116406 A1 WO 2016116406A1
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WIPO (PCT)
Prior art keywords
heat storage
latent heat
gas pressure
storage material
pressure vessel
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PCT/EP2016/050906
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German (de)
English (en)
Inventor
Mathias WEICKERT
Stefan Marx
Ulrich Müller
Lena Arnold
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BASF SE
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BASF SE
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • Gas pressure vessel containing a gas, a latent heat storage material and a porous solid
  • the present invention relates to a gas pressure vessel containing a gas, a first latent heat storage material A and a porous solid B, the gas pressure vessel having an upper segment and a lower segment and a container wall and the porous solid B is a sorbent material based on the gas.
  • the present invention also relates to a method of storing gas.
  • sorbents For the sorptive uptake of substances, in particular gases, numerous sorbents have been described in the prior art. Frequently used sorbents are activated carbon, silica gel, zeolites and, more recently, porous organometallic frameworks (MOFs).
  • activated carbon silica gel
  • zeolites zeolites
  • MOFs porous organometallic frameworks
  • the sorption of gases is typically exothermic, so that the sorbent is heated during sorption by absorbing the released energy.
  • this heat absorption may be detrimental to the intended sorption.
  • desorption whereby the desorption process can be adversely affected by lowering the temperature.
  • Sorption is used, for example, to store gaseous fuels in vehicles, and in addition to the compressed natural gas (CNG) technology, adsorbed natural gas (ANG) processes for mobile storage applications are also increasingly known are.
  • ANG applications a solid such as activated carbon or MOF is filled into the gas pressure vessel to increase storage density, either achieving a lower pressure level with the same storage capacity or a larger storage capacity at the same pressure.
  • the heat of sorption has a detrimental effect on the efficiency of the filling process of the gas pressure vessel with gas and on the emptying process, especially when the gas pressure vessel contains a sorption material.
  • the way as the gas pressure vessel on A gas station is filled with gas has a strong influence on the amount of gas that can be introduced in total per filling process in the gas pressure vessel.
  • the temperature in the gas pressure vessel increases during filling due to heat of compression and heat of sorption.
  • the temperature in the gas pressure vessel during charging rises to about 50 ° C above ambient temperature due to compression heat.
  • the temperature in the storage tank can rise to temperatures of approximately 90 ° C, due to the additional heat of sorption that is released during the filling process. This increase in temperature is a limitation of ANG technology, especially if carbon steel gas pressure tanks are currently being manufactured for temperatures up to 80 ° C.
  • the temperature in the gas pressure vessel decreases when gas is withdrawn, and the rate of removal is determined by the energy requirement, since heat must be supplied in order to achieve complete desorption.
  • WO 2009/071435 A1 discloses a method for controlling the removal of gas from a sorption storage, the temperature in the sorption storage being increased with decreasing content of gas in the sorption storage until reaching a maximum permissible temperature, so that a predetermined minimum pressure in the sorption storage not fallen below. Furthermore, a device is described which comprises a heating element with which the sorption storage can be heated. The heating is performed by heat exchangers with a heating medium or by an electric heating element. Likewise, specific thermal bridges are mentioned.
  • the DE 102 008 043 927 A1 has a method for removing a gas from a Sorptions Grande the subject in which gas is withdrawn until reaching a predetermined working pressure at a constant discharge temperature.
  • Sorptions Eaton After reaching the working pressure gas is further removed at the same extraction temperature until reaching a minimum extraction pressure. The gas taken after reaching the predetermined working pressure is compressed to the predetermined working pressure.
  • the Sorptions Eaton may also have a suitable coolant through-flow double jacket and heat exchange means in the form of flow-through coils or heat exchanger plates.
  • No. 7,641,715 B2 describes a method for controlling thermal effects in physicochemical methods and a composite material which contains an active solid and a latent heat store.
  • the active solid is in the form of particles or monoliths in front.
  • the latent heat storage device is in the form of micro-nodes, which can be arranged in pores of the active solid or form a mixture with particles of the active solid, the micro-nodes being arranged between the particles of the solid.
  • WO 2008/122543 A1 and WO 2008/122542 A2 a gas pressure vessel with a predetermined maximum filling pressure for receiving, storing and dispensing a gas is described.
  • the gas pressure vessel contains the gas and a mixture containing, based in each case on the total weight of the mixture, 2 to 60 wt .-% of a latent heat storage component A and 40 to 98 wt .-% of a framework component B.
  • the latent heat storage component A is microencapsulated.
  • Object of the present invention is to provide a gas pressure vessel, which allows sorption heat efficiently dissipate and / or supply, so that the maximum filling with gas can be achieved in a very short time and accelerated the gas removal from the gas pressure vessel and / or done in larger quantities can. Furthermore, the measures for heat supply and / or heat dissipation need little space and no large additional electrical power and represent little additional weight.
  • the object is achieved by a gas pressure vessel containing a gas, a first latent heat storage material A, a porous solid B and optionally a second latent heat storage material C, the gas pressure vessel having an interior, comprising at least two segments, an upper segment and a lower segment, and a container wall the upper segment and the lower segment are equal in respect of their respective total volume, the porous solid B is a sorption material relative to the gas and in the upper segment at least a major portion of the first latent heat storage material A, based on the total mass of the first latent heat storage material A, is included as in the lower segment.
  • the first latent heat storage material A and the porous solid B are positioned so that a temperature control, in particular during the filling and emptying of the gas pressure vessel, is improved and maximum temperatures that occur in the gas pressure vessel can be reduced. This allows the selection of less temperature-resistant materials for the container wall.
  • the space requirement of the latent heat storage material in the gas pressure vessel is relatively low. There is no need for additional electrical power.
  • the gas pressure container according to the invention represents a simple and efficient system that allows effective storage when filled with the gas through the porous solid B and can reduce the effect of heating by the first latent heat storage material A.
  • the storage capacity of the gas pressure vessel according to the invention is increased.
  • the temperature increase occurring during filling can be at least partially compensated by the first latent heat storage material A.
  • the gas pressure vessel additionally contains the second latent heat storage material C, wherein the second latent heat storage material C has a phase transition at a temperature Tc which is lower than a temperature TA, at which the first latent heat storage material A has a phase transition, and in the lower segment at least a major part of the second latent heat storage material C, based on the total mass of the second latent heat storage material C, included.
  • the interior of the gas pressure vessel is heated during emptying with the aid of the first latent heat storage material A and in particular with the aid of the second latent heat storage material C, a larger amount of the gas can be taken from the gas pressure vessel and the desorption is accelerated. A smaller amount of gas remains in the sorbed state on or in the sorbent material in the gas pressure vessel.
  • the range of a vehicle with such a gas pressure vessel between two refueling stops is increased. Since warmer gas flows upwards in the gas pressure vessel due to a lower density, higher temperatures occur in the upper segment of the gas pressure vessel than in the lower segment.
  • a temperature profile the temperature increases from bottom to top.
  • the first latent heat storage material A has a phase transition at a temperature TA of 50 ° C to 100 ° C and, when the gas pressure vessel contains the second latent heat storage material C, the second latent heat storage material C has a phase transition at a temperature Tc of -10 ° C up to 40 ° C. More preferably, the temperature TA is in a range of 60 ° C to 80 ° C. More preferably, the temperature Tc is in a range of 0 ° C to 20 ° C.
  • the first latent heat storage material A and, if the gas pressure vessel contains the second latent heat storage material C, the second latent heat storage material C a heat capacity in each case in a range of 1 kJ / (kg x K) to 6 kJ / (kg x K) on.
  • the heat capacity is particularly preferably from 2 kJ / (kg.K) to 4 kJ / (kg.K).
  • the first latent heat storage material A and the second latent heat storage material C are able to release an enthalpy of at least 10 kJ / kg.
  • the first latent-heat storage material A and, when the gas-pressure vessel contains the second latent-heat storage material C, the second latent-heat storage material C have a density in a range of 800 kg / m 3 to 4000 kg / m 3 .
  • the density is in a range from 1000 kg / m 3 to 2000 kg / m 3 , in particular from 1300 kg / m 3 to 2000 kg / m 3 .
  • latent heat storage materials which have this density it is ensured that not too much space is occupied by the latent heat storage materials and not too much additional weight is introduced into the gas pressure vessel, which is particularly relevant for mobile applications of the gas pressure vessel.
  • the first latent heat storage material A is disposed above the porous solid B and between the vessel wall and the porous solid B, and when the gas pressure vessel contains the second latent heat storage material C, the second latent heat storage material C is below the porous solid B and between the vessel wall and the porous solid B arranged.
  • the first latent heat storage material A is preferably arranged above the porous solid B and adjacent to the container wall and, if the gas pressure container contains the second latent heat storage material C, the second latent heat storage material C below the porous solid B and adjacent to the container wall. This is understood to mean that the first latent heat storage material A, the porous solid B and the second latent heat storage material C form layers arranged in this order from top to bottom in the gas pressure vessel.
  • the gas pressure vessel preferably contains two beds, wherein a bed of the first latent heat storage material A is arranged above a bed of the porous solid B. More preferably, the gas pressure vessel contains three beds, wherein the bed of the first latent heat storage material A is disposed above the bed of the porous solid B and the bed of the porous solid B is disposed over a bed of the second latent heat storage material C. At least parts of the first latent heat storage material A and optionally of the second latent heat storage material C are in direct contact with the container wall. This has the advantage that the container wall is protected from too high an increase in temperature, which is particularly relevant for container walls of carbon fiber composite material. However, the presence in layers does not mean that the at least three substances mentioned here must be spatially separated by straight planes.
  • the shape of the layers may also, for example, at least partially correspond to the shape of the container wall.
  • the first latent heat storage material A is arranged completely above the porous solid B and possibly the second latent heat storage material C completely below the porous solid B along any fictitious vertical straight line passing through the gas pressure vessel. More preferably, this is true for any fictitious vertical line.
  • at least one of the latent heat storage media is present in microencapsulated form.
  • the container wall is designed as a double jacket and the first latent heat storage material A and, when the gas pressure vessel contains the second latent heat storage material C, the second latent heat storage material C are each arranged in a cavity in the double jacket.
  • the double jacket may have one or more, preferably at least two cavities. The at least one cavity may be 100% or less of the total internal volume of the double mantle. The arrangement in the double jacket prevents mixing of the first latent heat storage material A or of the second latent heat storage material C with the porous solid B and the protection against excessively high temperature rise is given directly on the container wall, in particular on the outer container wall.
  • first latent heat storage material A and optionally the second latent heat storage material C are locally fixed in the desired position in the upper or lower segment of the gas pressure vessel in the gas pressure vessel, even if they are in the liquid state.
  • the double jacket may be permeable to the gas on the side facing the interior of the gas pressure vessel. This is advantageous for effective heat transfer to or from the latent heat storage material which is arranged in the double jacket.
  • the container wall is constructed of a carbon fiber composite material, as this represents a weight advantage.
  • the use of the gas pressure container according to the invention is particularly advantageous if the material of the container wall is only temperature-resistant up to a given limit value, which is the case with carbon fiber composite material.
  • the gas pressure vessel is arranged horizontally.
  • an elongated shape of the gas pressure vessel is assumed.
  • the gas pressure vessel has a cylindrical shape.
  • the ratio of the length of the cylinder to the diameter of the cylinder is greater than 1.
  • the surface of the container wall is first the container wall, then the first latent heat - Storage material A and then the porous solid B are arranged side by side and, if the gas pressure vessel contains the second latent heat storage material C, for 2% to 30%, more preferably 3% to 20% and particularly preferably 5% to 15%, the surface of the container wall , Regarded with respect to the gas pressure vessel from outside to inside, first the container wall, then the second latent heat storage material C and then the porous solid B next to each other.
  • Contact surfaces between the first latent heat storage material A and the container wall are preferably arranged where maximum temperatures occur in the gas pressure vessel.
  • the contact surfaces between the second latent heat storage material C and the container wall are preferably arranged where minimum temperatures in the gas pressure vessel occur.
  • the percentages refer to the inwardly facing container wall.
  • the gas pressure vessel based on the total volume of the interior, contains 0.5% by volume to 30% by volume of first latent heat storage material A and from 70% by volume to 99.5% by volume of porous solid B more preferably 1 vol.% to 15 vol.% first latent heat storage material A and 85 vol.% to 99 vol.% porous solid B, more preferably 2 vol.% to 5 vol.% first latent heat storage material A and From 95% by volume to 98% by volume of porous solid B.
  • 0.5% by volume to 25% by volume. % more preferably 1 vol .-% to 10 vol .-% and particularly preferably 2 vol .-% to 5 vol .-%, second latent heat storage material C before.
  • the invention provides a method for storing gas in the gas pressure vessel, wherein the porous solid B adsorbs, absorbs or desorbs the gas and when filling the gas pressure vessel with the gas, a first temperature Ti in the upper segment of the gas pressure vessel is greater than a second one Temperature T2 in the lower segment of the gas pressure vessel and the first latent heat storage material A and optionally the second latent heat storage material C are initially in solid form and then in liquid form and wherein the first latent heat storage material A and optionally the second latent heat storage material C first in.
  • the porous solid B adsorbs, absorbs or desorbs the gas and when filling the gas pressure vessel with the gas, a first temperature Ti in the upper segment of the gas pressure vessel is greater than a second one Temperature T2 in the lower segment of the gas pressure vessel and the first latent heat storage material A and optionally the second latent heat storage material C are initially in solid form and then in liquid form and wherein the first latent heat storage material A and optionally the second latent heat
  • the upper segment and the lower segment are each spatial parts of the gas pressure vessel, which can occupy up to 50 vol .-% of the total volume of the interior of the gas pressure vessel.
  • the upper segment and the lower segment may be the upper and lower halves with respect to the volume of the interior of the gas pressure vessel.
  • the upper segment is disposed completely above the lower segment with respect to a direction opposite to gravity.
  • the upper segment and the lower segment each comprise 0.01 to 40% by volume, more preferably 0.1 to 20% by volume, particularly preferably 1 to 10% by volume and particularly preferably 2 to 4% by volume. % of the total volume of the interior of the gas pressure vessel.
  • Total volume of the interior refers to the total volume of the interior of the gas pressure vessel, which is bounded by the outer container wall.
  • the upper segment of the uppermost part of the gas pressure vessel and the lower segment of the lowest part of the gas pressure vessel is a mental delimitation for the description of a subarea.
  • a physical delineation of the upper segment and the lower segment may be present but is not mandatory. Due to buoyancy forces with temperature differences in the gas pressure vessel is formed in the lower segment of the gas pressure vessel, a cold region in which temperatures between -40 ° C and 20 ° C are present during the filling process. In the upper segment of the gas pressure A hot region with temperatures between 40 ° C and 100 ° C is created during the filling process.
  • the first latent heat storage material A and optionally the second latent heat storage material C are each arranged in only one continuous spatial subregion, which preferably has a physical boundary, of the gas pressure vessel, this subregion containing no porous solid B.
  • the first latent heat storage material A and optionally the second latent heat storage material C may each be arranged in a plurality of separate spatial subregions of the gas pressure vessel, the plurality of separate subregions containing no porous solid B.
  • the first latent heat storage material A, the porous solid B and optionally the second latent heat storage material C are preferably spatially separated from each other by a separator.
  • the separator may also be permeable to the gas and not permeable to the first latent heat storage material A, the porous solid B and the second latent heat storage material C.
  • the separator may be made of various materials, wherein the material is preferably inert, so low in reaction to the gas, the first latent heat storage material A, the porous solid B and the second latent heat storage material C.
  • Preferred materials for the separator are metal, steel, plastics or composite materials.
  • the shape of the separator and the manner of its attachment in the gas pressure vessel are not limited.
  • the separator can be present for example in the form of a grid, fabric or in the form of a perforated plate in particular.
  • the separator may form a basket in which the first latent heat storage material A and optionally the second latent heat storage material C are respectively arranged.
  • the separator may be an aluminum cylinder or steel cylinder, in which the first latent heat storage material A and optionally the second latent heat storage material C are respectively arranged.
  • the cylinder shape of the separator preferably has a diameter which deviates at most 10%, more preferably at most 5%, from one tenth of the diameter of the gas pressure vessel.
  • the porous solid B may comprise one or more sorbents.
  • the porous solid B may be in the form of powder, molded articles or as a monolith.
  • the porous solid B is preferably present in shaped bodies, in particular for applications in vehicles such as motorcycles and three-wheelers. Monoliths are preferred for applications in vehicles such as cars and trucks.
  • Preferred embodiments of the shaped bodies are cubes as well as strand-shaped extrudates, the cubes preferably having at least one rounded edge.
  • the shaped bodies preferably extend in at least one dimension of the space in the range from 0.2 mm to 30 mm, more preferably from 0.5 mm to 5 mm, in particular from 1 mm to 3 mm.
  • a monolith of the porous solid B has a shortest and a longest spatial extent, wherein the shortest spatial extent is shorter than the longest spatial extent.
  • the shortest spatial extent of the monolith is from 10 cm to 100 cm and the longest spatial extent is from 20 cm to 300 cm.
  • the longest spatial extent of the monolith is from 20 cm to 120 cm, more preferably from 70 cm to 90 cm, and the shortest spatial extent is from 10 cm to 60 cm, more preferably from 30 cm to 50 cm.
  • the longest spatial extent of the monolith is from 100 cm to 300 cm, more preferably from 150 cm to 200 cm, and the shortest spatial extent is from 30 cm to 100 cm, more preferably from 40 cm to 60 cm.
  • more than one monolith is disposed in the gas pressure vessel, with the longest spatial extent of the monolith being from 10 cm to 100 cm and the shortest spatial extent being from 0.3 cm to 30 cm.
  • the shortest spatial Liehe expansion of the individual monoliths of 0.5 cm to 10 cm, more preferably from 0.8 cm to 2 cm, and the longest spatial extent is from 10 cm to 60 cm, more preferably from 30 cm to 50 cm.
  • the shortest spatial extent of the individual monoliths is from 0.5 cm to 10 cm, more preferably from 0.8 cm to 2 cm, and the longest spatial extent is 30 cm to 100 cm, more preferably from 40 cm to 60 cm.
  • the porous solid B is in the form of a packed bed of molded articles, and the ratio of the permeability of the molded articles to the smallest molded article diameter is from 1 ⁇ 10 -11 m 2 / m to 1 ⁇ 10 -16 m 2 / m, more preferably 1 x 10 "12 m 2 / m to 1 x 10" 14 m 2 / m, and most preferably about 1 x 10 "13 m 2 / m.
  • the rate at which the gas penetrates into the shaped body during the filling process is dependent upon The rate at which the pressure in the interior of the moldings equalizes the ambient pressure around the moldings in the gas pressure vessel With decreasing permeability and increasing diameter of the moldings, the time for this pressure equalization and thus the time for loading the moldings increases Permeability can be a limiting factor for the entire filling process or the emptying of the gas pressure vessel.
  • a mixture containing the first latent heat storage material A and the porous solid B may be contained in the gas pressure vessel, wherein the content of the first latent heat storage material A increases in the mixture from bottom to top in the gas pressure vessel.
  • the increasing concentration of the first latent heat storage material A from the bottom to the top counteracts the increasing temperature from bottom to top according to the prevailing temperature profile in the gas pressure vessel.
  • the concentration of the first latent heat storage material A or of the second latent heat storage material C can change continuously or else suddenly.
  • a mixture containing the second latent heat storage material C and the porous solid B may be contained in the gas pressure vessel, wherein the content of the second latent heat storage material C in the mixture increases from top to bottom in the gas pressure vessel.
  • a mixture containing the first latent heat storage material A, the second latent heat storage material C and the porous solid B may be contained in the gas pressure vessel, the content of the first latent heat storage material A in the mixture increases from bottom to top in the gas pressure vessel and the content of the second latent heat storage material C in the mixture increases from top to bottom in the gas pressure vessel.
  • the porous solid B is a sorbent material with respect to the gas contained in the gas pressure vessel.
  • the porous solid B may also be referred to as an absorbent, adsorbent or sorbent.
  • the porous solid B has a high specific surface area of more than 200 m 2 / g, more preferably more than 1000 m 2 / g. With a larger specific surface more gas can be taken up.
  • the gas is stored in the gas pressure vessel usually on or in the porous solid B and in voids in the porous solid B and between particles of the porous solid and in voids of the gas pressure vessel, the no porous solid B and no first latent heat storage material A and no second Latent heat storage material C included.
  • the porous solid B is selected from the group consisting of activated carbon, zeolites, alumina, silica gel, open-cell polymer foams, metal hydrides, organometallic frameworks (MOF) and mixtures thereof. Particularly preferred are MOFs.
  • Zeolites are crystalline aluminosilicates with a microporous framework structure of Al0 4 and Si0 4 tetrahedra. The aluminum and silicon atoms are linked together by oxygen atoms. Examples of zeolites are zeolite A, zeolite Y, zeolite L, zeolite X, mordenite, ZSM (zeolite socony mobile) 5 or ZSM 11.
  • the activated carbon preferably has a specific surface area of at least 500 m 2 / g, more preferably at least 1500 m 2 / g and particularly preferably more than 3000 m 2 / g.
  • Such activated carbon is available, for example, under the trade name MAXSORB®.
  • MOFs are known in the art and are described, for example, in US 5,648,508, EP-A-0 790 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000), pages 3 to 20, H. Li et al., Nature 402, (1999), page 276, M. Eddaoudi et al., Topics in Catalysis 9, (1999), pages 105 to 1 1 1, B.
  • MOFs can also be produced, for example, by electrochemical means, as described, for example, in US Pat. No. 5,648,508. Relevant in this respect are DE-A 10 355 087 and WO-A 2005/049892. Electrochemically produced MOFs have in particular good sorption and desorption properties.
  • MOFs contain at least one at least one metal ion coordinating bound, at least bidentate organic compound.
  • the metal component in the MOF is preferably selected from the groups Ia, IIa, IIIa, IVa to Villa and Ib to VIb. Particularly preferred are 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 is lanthanide. Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm and Yb.
  • At least bidentate organic compound refers to an organic compound containing at least one functional group capable of having at least two coordinative bonds to a given metal ion, and / or to two or more, preferably two, metal atoms each having a coordinative bond train.
  • Examples of functional groups which can be used to form the abovementioned coordinative bonds are, for example, the following functional groups: -CO 2 H, -CS 2 H, -NO 2, -B (OH) 2 , -SO 3 H, -Si (OH) 3 , -Ge (OH) 3 , -Sn (OH) 3 , -Si (SH) 4 , -Ge (SH) 4 , -Sn (SH) 3 , -P0 3 H, -As0 3 H, -As0 4 H , -P (SH) 3 , -As (SH) 3 , -CH (RSH) 2 , -C (RSH) 3 , -CH (RNH 2 ) 2 , -C (RNH 2 ) 3 , -CH (ROH) 2 , -C (ROH) 3 , -CH (RCN) 2 , -C (RCN) 3 where R is, for example,
  • functional groups are to be mentioned in which the abovementioned radical R is absent.
  • -CH (SH) 2 , -C (SH) 3 -CH (NH 2 ) 2 , -C (NH 2 ) 3 , -CH (OH) 2 , -C (OH) 3 , -CH (CN) 2 or -C (CN) 3 to call.
  • the functional groups can also be heteroatoms of a heterocycle.
  • nitrogen atoms are mentioned here.
  • 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 having these functional groups is capable of forming the coordinative bond and the preparation of the framework.
  • the organic compounds containing the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or an aliphatic as well as aromatic compound.
  • the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound may be linear and / or branched and / or cyclic, wherein also several cycles per compound are possible. More preferably, the aliphatic compound or the aliphatic portion of the both aliphatic and aromatic compound contains 1 to 15, more preferably 1 to 14, further preferably 1 to 13, further preferably 1 to 12, further preferably 1 to 1 1 and especially preferably 1 to 10 C atoms such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms. Methane, adamantane, acetylene, ethylene or butadiene are particularly preferred in this case.
  • the aromatic compound or the aromatic part of both aromatic and aliphatic compound may have one or more cores, such as two, three, four or five cores, wherein the cores may be separated from each other and / or at least two nuclei in condensed form.
  • the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred.
  • each nucleus of the named compound may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S.
  • the aromatic or aromatic moiety of the both aromatic and aliphatic compounds contains one or two C6 nuclei, the two being either separately or in condensed form.
  • benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
  • the at least bidentate organic compound is derived from a dicarboxylic acid, such as oxalic, succinic, tartaric, 1,4-butanedicarboxylic, 1,4-butenedicarboxylic, 4-oxo-pyran-2,6-dicarboxylic acid, 1,6 Hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecandicarboxylic acid acid, acetylenedicarboxylic acid, 1, 2-benzenedicarboxylic acid, 1, 3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p- Benzenedicarboxylic acid, imid
  • the at least bidentate organic compound may 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-butanetri-carboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4, 5-Dihydro-4,5-dioxo-1H-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-tricarboxylic acid, 1, 2,3-propanetricar
  • the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.
  • an at least bidentate organic compound derived from a tetracarboxylic acid are 1, 1-dioxideperyl [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
  • the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.
  • Preferred heterocycles as at least bidentate organic compounds in which a coordinate bond takes place via the ring heteroatoms are the following substituted or unsubstituted ring systems:
  • each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms can contain.
  • monocarboxylic dicarboxylic acids preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicercaric dicarboxylic acids, dicercaric tricarboxylic acids, dicerous tetracarboxylic acids, tricyclic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic tetracarboxylic acids.
  • Suitable heteroatoms are, for example, N, O, S, B, P.
  • Preferred heteroatoms here are N, S and / or O.
  • a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.
  • Particularly preferred as at least bidentate organic compounds are imidazolates, such as 2-methylimidazolate, acetylenedicarboxylic acid (ADC), campherdicarboxylic acid, fumarate acid, succinic acid, benzenedicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine (TEDA), naphthalenedicarboxylic acids (NDC), biphenyldicarboxylic acids such as 4,4'-biphenyldicarboxylic acid (BPDC), pyrazinedicarboxylic acids, such as 2.5 Pyrazine dicarboxylic acid, bipyridine dicarboxylic acids such as 2,2'-bi
  • pyrenedicarboxylic acids 2-methylimidazole, 2-ethylimidazole, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1, 2,3-benzenetricarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1, 2,4,5-benzenetetracarboxylic acid, amino-BDC, TEDA, fumaric acid, biphenyldicarboxylate, 1,5-naphtha-2,6-naphthaeledicarboxylic acid, tert-butylisophthalic acid and dihydroxyterephthalic acid.
  • the organometallic framework material may also comprise one or more monodentate ligands and / or one or more at least bidentate ligands which are not derived from a di-, tri- or tetracarboxylic acid.
  • Suitable solvents for the preparation of the MOF include i.a. Water, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, caustic soda, N-methylpolidone ether, acetonitrile, benzyl chloride, triethylamine, ethyleneglycol and mixtures thereof.
  • Other metal ions, at least bidentate organic compounds and solvents for the production of MOF include i.a. in US-A 5,648,508 or DE-A 101 1 1 230 described.
  • dicarboxylic acid or polycarboxylic acid may have not only dicarboxylic acid groups but also one or more independent substituents such as amino, hydroxyl, methoxy, halogen or methyl groups. Preferably, there are no further substituents.
  • Derivation also means that dicarboxylic acid groups can be present as sulfur analogues Sulfur analogues are -C (0O) SH and its tautomers and -C (S) SH.
  • the at least one at least bidentate organic component is particularly preferred selected from the group consisting of fumaric acid (FUM), terephthalic acid (BDC), benzenetricarboxylate (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, Cr, Zn, Cu and Al. Especially preferred are Zn, Cu and Al.
  • MOF materials are copper-1, 3,5-BTC, aluminum fumarate, zincbenzene tribenzoate and zinc 2-methylimidazolate.
  • the term "and / or” comprising two options includes the first option or the second option, or both, the first and the second option, particularly preferred as the porous solid B are the MOF materials MOF A 520, MOF Z 377, and MOF C 300.
  • MOF A 520 is based on aluminum fumarate.
  • the specific surface area of the MOF A 520 measured by porosimetry or nitrogen adsorption, is usually 800 m 2 / g to 2000 m 2 / g.
  • the adsorption enthalpy of MOF A 520 with respect to natural gas is approximately 17 kJ / mol. Further details of this MOF type are described in "Metal Organic Frameworks, Wiley-VCH-Verlag, David Farrusseng, 201.
  • MOF Z 377 is based on zinc benzene tribenzoate 377, measured by porosimetry or nitrogen adsorption, is typically 2000 m 2 / g to 5000 m 2 / g
  • the MOF Z 377 typically has an adsorption enthalpy with respect to natural gas of 12 kJ / mol to 17 kJ / mol
  • MOF C 300 is based on copper benzene 1,3,5-tricarboxylate and is available, for example, from Sigma Aldrich under the trade name Basolite® C 300.
  • the framework material can then be further processed into a shaped article according to the method described above.
  • Kneading and / or shaping can be carried out according to any suitable method, as described, for example, in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, volume 2, p. 313 et seq. (1972).
  • kneading and / or shaping by means of a piston press, roll press in the presence or absence of at least one binder material, compounding, pelleting, tableting, extrusion, coextrusion, foaming, spinning, layers, granulation, preferably spray granulation, spraying, spray-drying or a combination of two or more of these methods.
  • Kneading and / or shaping can be carried out at elevated temperatures, for example in the range from 20.degree. C. to 300.degree. C. and / or at elevated pressure, for example in the range from atmospheric pressure to several hundred bar and / or in a protective gas atmosphere such as in the presence of at least one noble gas, nitrogen or a mixture of two or more thereof.
  • binders may be both viscosity-increasing and viscosity-reducing compounds.
  • Preferred binders include, for example, binders comprising aluminum oxide or 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, halloysite, dickite, nacrit 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 trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane,
  • an organic compound and / or a hydrophilic polymer such as cellulose or a cellulose derivative such as methylcellulose and / or a polyacrylate and / or a polymethacrylate and / or a polyvinyl alcohol and / or or a polyvinylpyrrolidone and / or a polyisobutene and / or a polytetrahydrofuran.
  • a pasting agent inter alia, preferably water or at least one alcohol such as a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n- Propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol a water-miscible polyhydric alcohol, alone or as a mixture with water and / or at least one of said monohydric alcohols.
  • a monoalcohol having 1 to 4 carbon atoms such as methanol, ethanol, n- Propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol or 2-methyl-2-propanol or a mixture of water and at least one of said alcohols or a polyhydric alcohol such as a glycol a water-misc
  • the order of the additives such as template compound, binder, pasting agent, viscosity-increasing substance in the shaping and / or kneading is generally not critical.
  • the molding obtained according to kneading and / or molding is subjected to at least one drying, which is generally carried out at a temperature in the range of 25 to 300 ° C, preferably in the range of 50 to 300 ° C and more preferably in the range of 100 to 300 ° C is performed. It is also possible to dry in vacuo or under a protective gas atmosphere or by spray drying.
  • At least one of the compounds added as additives is at least partially removed from the shaped body.
  • latent heat storage materials are substances which have a phase transition in the temperature range in which heat transfer is to be carried out.
  • the latent heat storage materials have a solid / liquid phase transition in the temperature range of -120 ° C to 200 ° C. Accordingly, it is preferred that the latent heat storage material has a melting point in the range of -120 ° C to 200 ° C.
  • melting point is also used in a simplified manner if the latent heat storage material has a melting range. if only one of these occurs within the prescribed temperature range, it is sufficient, however, more than one, in particular all, occur in the predetermined temperature range.
  • latent heat storage materials are organic, preferably lipophilic substances.
  • suitable substances for latent heat storage materials aliphatic hydrocarbon compounds such as saturated or unsaturated C 10 -C 40 -hydrocarbons which are branched or preferably linear, for example n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n Octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane and cyclic hydrocarbons, eg cyclohexane, cyclooctane
  • aromatic hydrocarbon compounds such as benzene, naphthalene, biphenyl, o- or n-terphenyl, Ci-C4o-alkyl-substituted aromatic hydrocarbons such as dodecylbenzene, tetra-decylbenzene, hexadecylbenzene, hexylnaphthalene or decylnaphthalene;
  • saturated or unsaturated C6-C30 fatty acids such as lauric, stearic, oleic or behenic acid, preferably eutectic mixtures of decanoic acid with e.g. Myristic, palmitic or lauric acid;
  • Fatty alcohols such as lauryl, stearyl, oleyl, myristyl, cetyl alcohol, mixtures such as coconut fatty alcohol and the so-called oxo alcohols, which are obtained by hydroformylation of alpha-olefins and further reactions;
  • C6-C3o fatty amines such as decylamine, dodecylamine, tetradecylamine or hexadecylamine
  • Esters such as C 1 -C 10 -alkyl esters of fatty acids such as propyl palmitate, methyl stearate or methyl palmitate, and preferably their eutectic mixtures or methyl cinnamate;
  • waxes such as montanic acid waxes, montan ester waxes, carnauba wax, polyethylene wax, oxidized waxes, polyvinyl ether wax, ethylenevinyl acetate wax or Fischer-Tropsch hard waxes;
  • halogenated hydrocarbons such as chlorinated paraffin, bromoctadecane, bromopentadecane, bromononadecane, bromeicosane, bromodocosane.
  • n-alkanes for example, be the use of pure n-alkanes, n-alkanes having a purity of greater than 80% or alkane mixtures, as obtained as a technical distillate and are commercially available as such.
  • soluble compounds may be added to the substances so as to prevent the crystallization delay which sometimes occurs with the non-polar substances. It is advantageous to use, as described in US-A 5,456,852, compounds having a melting point 20 to 120 K higher than the actual core substance. Suitable compounds are the fatty acids mentioned above as lipophilic substances, fatty alcohols, fatty amides and aliphatic hydrocarbon compounds. They are added in amounts of from 0.1% by weight to 10% by weight, based on the latent heat storage material.
  • the latent heat storage materials are selected.
  • latent heat storage materials with melting points at different temperatures and the variation of the melting point of latent heat storage materials by the addition of additives is described in M. Farid et al., Energy Conversion and Management 45, 2004, pages 1597 to 1615, EP 0255928 A1, US 4,637,888 and US 2012/0048768 A1.
  • Possible latent heat storage materials are aliphatic hydrocarbons, preferably those enumerated by way of example above. In particular, aliphatic hydrocarbons having 14 to 20 carbon atoms and mixtures thereof are used.
  • Eutectic solutions, organic solutions and hydrated salts are preferably used as the first latent heat storage material A and optionally as the second latent heat storage material.
  • clathrates can be used.
  • Preferred eutectic solutions have a melting point in the range of -46 ° C to 0 ° C, organic solutions in the range of +1 ° C to 167 ° C, and hydrated salts in the range of 7 ° C to 17 ° C.
  • Preferred latent heat storage materials are, for example, commercially available under the trade name PlusICE® from PCM Phase Change Material Products Limited.
  • Preferred classes of latent heat storage materials are: Organic, Eutectic Solutions, High Temperature, Hydrated Salts, Organic Solutions and Solid Solid PCM.
  • Organic materials have a phase transition in the range of -100 ° C to -20 ° C, Eutectic Solutions of -46 ° C to 0 ° C, high temperature of + 90 ° C to + 885 ° C, hydrated salts of +7 ° C to +1 17 ° C, Organic Solutions from +1 ° C to + 167 ° C and Solid Solid PCM from + 25 ° C to + 180 ° C.
  • Table 1 below gives an overview of examples of PlusICE® latent heat storage materials commercially available from PCM Phase Change Material Products Limited, which are preferably used as the first latent heat storage material A.
  • Table 2 below gives an overview of examples of PlusICE® latent heat storage materials commercially available from PCM Phase Change Material Products Limited, which are preferably used as the second latent heat storage material C.
  • the latent heat storage material S7 contains: calcium bromide, calcium chloride and ammonium nitrate, S8 and S10: sodium sulfate, ammonium chloride and sepiolite and S58, S70 and S72: magnesium nitrate hexahydrate.
  • the first latent heat storage material A and / or the second latent heat storage material C preferably consist of a microencapsulated latent heat storage component.
  • the latent heat storage component and the microencapsulation together form the latent heat storage material.
  • the microencapsulated latent heat storage materials are preferably particles with a capsule core consisting predominantly of more than 50 wt .-% of the latent heat storage component and a polymer as a capsule wall.
  • the capsule core is solid or liquid depending on the temperature.
  • the average particle size of the capsules (Z means by means of light scattering) is typically 0.5 to 100 ⁇ m, preferably 1 to 80 ⁇ m, in particular 1 to 50 ⁇ m.
  • the weight ratio of capsule core to capsule wall is generally from 50:50 to 95: 5. Preferred is a core / wall ratio of 70:30 to 93: 7.
  • the capsule wall-forming polymers are preferably composed of 30 to 100 wt .-%, more preferably 30 to 95 wt .-% of one or more Ci-C24-alkyl esters of acrylic and / or methacrylic acid as monomers I.
  • the polymers may contain up to 80% by weight, preferably 5 to 60% by weight, in particular 10 to 50% by weight, of a bi- or polyfunctional monomer as monomers il which is insoluble or sparingly soluble in water, incorporated in copolymerized form.
  • the polymers can up to 90 wt .-%, preferably up to 50 wt .-%, in particular up to 30 wt .-% of other monomers I II in copolymerized form.
  • Suitable monomers I are C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid. Particularly preferred monomers I are methyl, ethyl, n-propyl and n-butyl acrylate and / or the corresponding methacrylates. Iso-propyl, isobutyl, sec-butyl and tert-butyl acrylate and the corresponding methacrylates are preferred. Further, methacrylic acid is mentioned. Generally, the methacrylates are preferred. Suitable monomers I I are bi- or polyfunctional monomers which are insoluble or sparingly soluble in water but have good to limited solubility in the lipophilic substance.
  • Low solubility is to be understood as meaning a solubility of less than 60 g / l at 20 ° C.
  • bi- or polyfunctional monomers is meant compounds which have at least two non-conjugated ethylenic double bonds.
  • divinyl and Polyvi- nylmonomere come into consideration, which cause crosslinking of the capsule wall during the polymerization.
  • Preferred bifunctional monomers are the diesters of diols with acrylic acid or methacrylic acid, furthermore the diallyl and divinyl ethers of these diols.
  • Preferred divinyl monomers are ethanediol diacrylate, divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, methallyl methacrylamide and allyl methacrylate. Particular preference is given to propanediol, butanediol, pentanediol and hexanediol diacrylate or the corresponding methacrylates.
  • Preferred polyvinyl monomers are trimethylolpropane triacrylate and methacrylate, pentaerythritol triallyl ether and pentaerythritol tetraacrylate.
  • Suitable monomers I I are other monomers, preference is given to monomers I 1a, such as vinyl acetate, vinyl propionate and vinylpyridine.
  • water-soluble monomers IIb e.g. Acrylonitrile, methacrylonitrile, methacrylamide, acrylic acid, itaconic acid, maleic acid, maleic anhydride, N-vinylpyrrolidone, 2-hydroxyethyl acrylate and methacrylate and acrylamido-2-methylpropanesulfonic acid.
  • N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate may be mentioned in particular.
  • These further ethylenically unsaturated monomers may be the monomers I, II or II I hitherto not mentioned for this embodiment.
  • microcapsules of this embodiment their proportion is preferably ⁇ 20 wt .-%, in particular ⁇ 10 wt .-%.
  • the microencapsulation (capsule wall) particularly preferably contains a homopolymer or copolymer based on methyl methacrylate (MMA), for example polymethyl methacrylate (PMMA).
  • MMA methyl methacrylate
  • PMMA polymethyl methacrylate
  • microcapsules can be prepared by a so-called in situ polymerization.
  • microcapsules are prepared by preparing from the monomers, a radical initiator, a protective colloid and the lipophilic substance to be encapsulated a stable oil-in-water emulsion in which they are present as a disperse phase. Subsequently, the polymerization of the monomers is initiated by heating and controlled by further increase in temperature, wherein the resulting polymers form the capsule wall, which encloses the lipophilic substance.
  • microencapsulated latent heat storage materials is also described in WO 2008/122543 A1 and WO 2008/122542 A2.
  • the first latent heat storage material A and / or the second latent heat storage material C may contain latent heat storage as a powder or as a shaped body, for example as granules.
  • latent heat storage as a powder or as a shaped body, for example as granules.
  • all forms known in the prior art such as, for example, spherical, disc, rod, ring or star-shaped bodies are conceivable.
  • the dimensions of the shaped bodies of the latent heat accumulators are preferably in the range of 200 mm to 5 cm, more preferably in the range of 500 mm to 2 cm and in particular in the range of 1 mm to 1 cm. Accordingly, a corresponding shaped body has an extent in at least one dimension of the space, which is in the range of 0.2 mm to 5 cm.
  • These shaped particles of the latent heat storage can have an amorphous, spherical-like up to a rod-shaped shape, depending on the particular production method.
  • the average diameter is preferably 200 mm to 2 cm, more preferably 500 mm to 1 cm.
  • Rod-like shapes have a maximum length of 5 cm in their longest extent, usually in the range of 1 mm to 2 cm.
  • the shortest extent usually has a value of at least 200 mm, usually from 500 ⁇ to 10 mm, preferably 500 mm to 5 mm.
  • the length to diameter ratio will usually not exceed the value of 10: 1, preferably 5: 1.
  • the particles Preference is given to 90% by weight of the particles> 500 ⁇ m, preferably> 700 ⁇ m, in particular> 1 mm, determined by screening technology.
  • the particles are asymmetric aggregates of powder particles having only approximately the shape of a sphere, a rod, a cylinder and the surface of which is often uneven and jagged. Such particles are often referred to as granules or agglomerate.
  • Another form of agglomerates are pellets, so-called pellets or tablets, as known from the manufacture of pharmaceuticals.
  • the particles can, as stated above, assume any geometric shapes.
  • geometric primitives can be spheres, cylinders, cubes, cuboids, prisms, pyramids, cones, truncated cones, and truncated pyramids.
  • Star strands, cross strands, rib strands and trilobes are also suitable.
  • the geometric bodies can be hollow as well as filled. Cavities, such as incorporated tubes, increase the surface area of the geometric body while reducing its volume.
  • additives in the first latent heat storage material A and / or in the second latent heat storage material C may be: binders, in particular polymeric binders, dyes, pigments, antistatic agents, hydrophilizing agents and preferably graphite, in particular expanded graphite.
  • binders in particular polymeric binders, dyes, pigments, antistatic agents, hydrophilizing agents and preferably graphite, in particular expanded graphite.
  • the first latent heat storage material A and / or the second latent heat storage material C each contain 2 to 20% by weight of graphite, based on the total weight of the respective latent heat storage material.
  • the production of expanded graphite and expanded graphite products is known from US-A 3 404 061.
  • the microcapsules preferably have the latent heat storage component sealed so that no emissions to the environment are detectable.
  • the microcapsules can be used as a bed. They generally show good hardness and are abrasion resistant. Due to the favorable ratios of surface to interstices of the particles with each other, a large heat transfer is possible, which can be dissipated by a good flow through. Based on their volume, the microcapsules generally show a high storage capacity and thus have a high efficiency. So they have a small footprint as well as a low memory weight.
  • the gas pressure container preferably comprises a closed container.
  • the gas pressure container is preferably equipped with at least one supply device, which comprises at least one passage through the container wall and through which the gas can flow.
  • the supply device can comprise both an inlet and an outlet, wherein the inlet and the outlet can each preferably be opened and closed independently of one another by a closing device.
  • the delivery device may include throttle valves or check valves. These valves can be inside or outside the gas pressure vessel.
  • the gas pressure vessel preferably has an outlet and / or an inlet.
  • the gas pressure vessel has an inlet and an outlet.
  • the inlet and the outlet can be combined using an adapter in one component, so that only one opening in the container wall is necessary.
  • the spatial proximity between the inlet and the outlet is particularly advantageous in order to use a filling method, whereby a flow through the gas pressure container is present during the filling process and optionally also during the emptying. Such a method is described in WO 2014/057416.
  • a gas stream is passed through the outlet of the gas pressure vessel, which has a mass flow of more than 0 kg / h, preferably more 50 kg / h and more preferably more than 100 kg / h.
  • Methods for gas storage in general are described, for example, in WO-A 2005/003622, WO-A 2003/064030, WO-A 2005/049484, WO-A 2006/089908 and DE-A 10 2005 012 087.
  • the container wall preferably has at least one resealable opening through which the first latent heat storage material A, the porous solid B and optionally the second latent heat storage material C can be introduced into the gas pressure vessel.
  • the gas pressure vessel is suitable for storage of gas at a pressure of 1 bar to 500 bar, more preferably at a pressure of 1 bar to 400 bar, more preferably at a pressure of 1 bar to 250 bar. In other embodiments, a pressure of 1 to 100 bar may also be preferred.
  • the gas pressure container may have different cross-sectional shapes, for example a round, an elliptical or a rectangular shape. Irregular cross-sectional shapes are also possible, for example, when the gas pressure container free spaces in the vehicle is adjusted. Furthermore, it is possible to divide the entire inner volume of the gas pressure vessel to more than one container. For a storage pressure of more than 100 bar round and ellipsoidal cross-sectional areas are preferred.
  • the size of the gas pressure vessel varies depending on the application.
  • the diameter of the gas pressure vessel is typically about 50 cm for use in trucks and about 20 cm for use in cars.
  • the total internal volume of the gas pressure vessel is preferably 20 L to 40 L, for use in trucks preferably 500 L to 3000 L. These volumes are the void volume of the gas pressure vessel. This is reduced by the volume of the first latent heat storage material A and optionally of the second latent heat storage material C and the porous solid B.
  • a hollow cylinder is preferably first prepared in which the porous solid B and the first latent heat storage material A and optionally the second latent heat storage material C are arranged and is then closed with two caps on the opposite sides.
  • the gas is preferably selected from the group consisting of natural gas, shale gas, city gas, methane, ethane, hydrogen, propane, propene, ethylene, plastic dioxide and mixtures thereof.
  • the gas pressure vessel may contain any gas which sorbs on or in the solid B.
  • the gas is usually present in gaseous and / or sorbed state. Due to the increased pressure and small amounts of liquid may be present in the gas pressure vessel.
  • the gas contains at least 70% by volume of methane and / or hydrogen.
  • the gas pressure vessel can be installed in various vehicles.
  • the gas represents a fuel for the vehicle.
  • vehicle includes in particular cars, trucks, ships, aircraft, motorcycles and tricycles.
  • FIG. 1 shows a gas pressure vessel according to the invention
  • FIG. 2 shows a gas pressure container with double jacket according to the invention
  • Figure 3 is a radial cross section of a gas pressure vessel according to the invention.
  • Figure 4 shows a radial cross section of a gas pressure vessel according to the invention with double jacket.
  • FIG. 1 shows a gas pressure vessel 1 according to the invention, which is conceptually subdivided into an upper segment 7 and a lower segment 9. A physical delineation of the upper segment 7 and / or the lower segment 9 is not present here.
  • the upper segment 7 and the lower segment 9 each occupy 50% by volume of the total volume of an inner space 8 of the gas pressure vessel 1.
  • the gas pressure vessel 1 has a cylindrical shape and has a feeding device 10.
  • the gas pressure vessel 1 contains a first latent heat storage material A 3, a porous solid B 5 and a second latent heat storage material C 13.
  • the first latent heat storage material A 3 is arranged exclusively in the upper segment 7 of the gas pressure vessel 1. Furthermore, the first latent heat storage material A 3 is arranged above the porous solid B 5.
  • the second latent heat storage material C 13 is arranged exclusively in the lower segment 9 of the gas pressure vessel 1. Furthermore, the second latent heat storage material C 13 is arranged below the porous solid B 5.
  • the first latent heat storage material A 3, the second latent heat storage material C 13 and the porous solid B 5 are shown as hatched or checkered surfaces.
  • the porous solid B 5 is in the form of moldings.
  • the first latent heat storage material A 3 and the second latent heat storage material C 13 are in microencapsulated form.
  • the interior 8 of the gas pressure vessel 1 is separated by a container wall 1 1 from the environment.
  • the beds of the first latent heat storage material A 3 and the second latent heat storage material C 13 are arranged in direct contact with the container wall 1 1 and along the container wall 1 1.
  • a fictitious vertical straight line 14 which runs through the gas pressure vessel 1 and on which the first latent heat storage material A 3, the porous solid B 5 and the second latent heat storage material C 13 are present, the porous solid B 5 does not touch the container wall 1 1.
  • the latent heat storage components of the first latent heat storage material A 3 and the second latent heat storage material C 13 are physically delimited from the porous solid B 5, the interior 8 of the gas pressure vessel 1 and also with respect to the vessel wall 1 1.
  • the demarcation is achieved here in each case by the microencapsulation.
  • the first latent heat storage material A 3 and the second latent heat storage material C 13 may each be separated from the porous solid B 5 by a partition 12 as a separator.
  • the partitions 12 may be made of metal, fabric or plastic, for example.
  • Figure 2 shows a gas pressure vessel 1 according to the invention with a double jacket 15.
  • the container wall 1 1 is designed as a double jacket 15.
  • the gas pressure vessel 1 has a cylindrical shape and has a feeding device 10. Double jackets are generally frequently filled with heat exchange media.
  • the double jacket has two cavities 17, 19. A first cavity 17 is filled with the first latent heat storage material A 3. A second cavity 19 is filled with the second latent heat storage material C 13. The first cavity 17 is located in the upper segment 7 of the gas pressure vessel 1, and the second cavity 19 is located in the lower segment 9 of the gas pressure vessel 1.
  • Advantage of an arrangement of the first latent heat storage material A 3 and the second latent heat storage material C 13 in the double jacket 15 is that the interior 8 of the gas pressure vessel 1 need not be further subdivided. This embodiment is therefore less complicated in terms of apparatus design.
  • Figure 3 shows a radial cross section of the gas pressure vessel 1, which is shown in Figure 1 in longitudinal cross-section.
  • the interior 8 of the gas pressure vessel 1 is conceptually divided into the upper segment 7 and the lower segment 9.
  • the first latent heat storage material A 3, the second latent heat storage material C 13 and the porous solid B 5 are completely spatially separated from one another and the two surfaces on which the porous solid B 5 contacts the first latent heat storage material A 3 or the second latent heat storage material C 13 are planes, which are aligned horizontally.
  • FIG. 4 shows a radial cross section of the gas pressure vessel 1 with a double jacket 15, which is shown in longitudinal cross-section in FIG.
  • the double jacket 15 has two cavities 17, 19, the first cavity 17 in the upper segment 7 and the second cavity 19 in the lower segment 9 is arranged.
  • the double jacket 15 is thus only partially filled with the first latent heat storage material A 3 and the second latent heat storage material C 13.
  • the first latent heat storage material A 3 is at the highest point of the gas pressure vessel 1 and the second latent heat storage material C 13 is located at the lowest point of the gas pressure vessel 1, which is also true for the other embodiment illustrated in FIGS. 1 and 3.
  • the remaining inner volume of the double jacket 15 can be flowed through, for example, with a heat exchange medium in order to further support heat removal and / or heat supply.
  • a cylindrical gas pressure vessel with a container wall, made of aluminum, has an internal volume of 40 L.
  • the gas pressure vessel is located on a vehicle that uses the gas contained in the gas pressure vessel as fuel for its drive.
  • the ratio of the length of the gas pressure vessel to its diameter is 3.
  • the gas pressure vessel contains a cylindrical monolith, which consists of MOF C 300 and has a mass of 20 kg.
  • the filling of the gas pressure vessel with natural gas takes place within 5 min, whereby the pressure in the gas pressure vessel is increased from 10 bar to 250 bar. Before filling, the temperature in the gas pressure vessel is 20 ° C.
  • the gas pressure vessel After filling, the gas pressure vessel initially cools to an ambient temperature of less than 30 ° C. During the subsequent drive, so when removing the gas from the gas pressure vessel, the temperature in the gas pressure vessel decreases to -20 ° C, which is the average temperature in the lower third, based on the volume of the gas pressure vessel. example
  • the gas pressure vessel described in the comparative example contains, in addition to the monolith consisting of MOF C 300, two latent heat storage materials.
  • the first latent heat storage material A is 8 kg of the PlusICE® material S72, commercially available from PCM Phase Change Material Products Limited, which has a phase transition at 72 ° C. The material is thus able to store heat at 72 ° C without any increase in temperature.
  • the second latent heat storage material C is 8 kg of PlusICE® S7 material, commercially available from PCM Phase Change Material Products Limited, which has a phase transition at 7 ° C.
  • the latent heat storage materials are each arranged in 3 cylindrical containers in the gas pressure vessel.
  • the gas pressure vessel cools after filling initially to ambient temperature, which is less than 30 ° C from.
  • ambient temperature which is less than 30 ° C from.
  • the temperature in the gas pressure vessel decreases by desorption and relaxation.
  • the temperature decrease is compensated and the temperature in the gas pressure vessel decreases less. More natural gas can be extracted and is available with a necessary minimum pressure of 10 bar.
  • the range with one tank can be increased by 10% compared to the comparative example.
  • the increase in range results from the fact that with the use of the first latent heat storage material A can be filled up to a higher maximum pressure of 250 bar without exceeding the allowable temperature and the fact that the remaining gas pressure in the container residual gas, which is required by a minimum pressure of 10 bar, is reduced by the heating with the second latent heat storage material C.

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

Abstract

L'invention concerne un réservoir de gaz comprimé contenant un gaz, un premier matériau accumulateur de chaleur latente A, une substance solide poreuse B et éventuellement un deuxième matériau accumulateur de chaleur latente C. Le réservoir de gaz comprimé présente un espace intérieur comprenant au moins deux segments, un segment supérieur et un segment inférieur, et une paroi de réservoir, le segment supérieur et le segment inférieur sont identiques quant à leur volume total respectif, la substance solide poreuse B est un matériau de sorption du gaz, et le segment supérieur contient au moins une plus grande part du matériau accumulateur de chaleur latente A par rapport à la masse totale de matériau accumulateur de chaleur latente A que n'en contient le segment inférieur. L'invention concerne par ailleurs un procédé d'accumulation de gaz.
PCT/EP2016/050906 2015-01-21 2016-01-18 Réservoir de gaz comprimé contenant un gaz, un matériau accumulateur de chaleur latente et une substance solide poreuse Ceased WO2016116406A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10202324B2 (en) 2015-05-04 2019-02-12 Basf Se Process for the preparation of melonal
US10737239B2 (en) 2015-11-27 2020-08-11 Basf Se Ultrafast high space-time-yield synthesis of metal-organic frameworks
US11104637B2 (en) 2016-11-30 2021-08-31 Basf Se Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure
US11377574B2 (en) 2016-08-23 2022-07-05 Basf Se Composite materials
US11529618B2 (en) 2016-11-28 2022-12-20 Basf Se Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US10737239B2 (en) 2015-11-27 2020-08-11 Basf Se Ultrafast high space-time-yield synthesis of metal-organic frameworks
US11377574B2 (en) 2016-08-23 2022-07-05 Basf Se Composite materials
US11529618B2 (en) 2016-11-28 2022-12-20 Basf Se Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins
US11104637B2 (en) 2016-11-30 2021-08-31 Basf Se Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure

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