WO2004007633A1 - Thermochemical heat storage and heat transport - Google Patents
Thermochemical heat storage and heat transport Download PDFInfo
- Publication number
- WO2004007633A1 WO2004007633A1 PCT/NL2003/000520 NL0300520W WO2004007633A1 WO 2004007633 A1 WO2004007633 A1 WO 2004007633A1 NL 0300520 W NL0300520 W NL 0300520W WO 2004007633 A1 WO2004007633 A1 WO 2004007633A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- suspension
- heat
- adsorbent
- cold medium
- medium
- Prior art date
Links
- 238000005338 heat storage Methods 0.000 title claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 61
- 239000003463 adsorbent Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000518 rheometry Methods 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract 2
- 229910001868 water Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 2
- 239000012528 membrane Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- -1 MnCla Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- VTCHZFWYUPZZKL-UHFFFAOYSA-N 4-azaniumylcyclopent-2-ene-1-carboxylate Chemical compound NC1CC(C(O)=O)C=C1 VTCHZFWYUPZZKL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 241000287826 Gallus Species 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910020939 NaC104 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CZJFCVCXJPLOTR-UHFFFAOYSA-L O.O.C(C(=O)O)(=O)O.[Ni](Cl)Cl Chemical compound O.O.C(C(=O)O)(=O)O.[Ni](Cl)Cl CZJFCVCXJPLOTR-UHFFFAOYSA-L 0.000 description 1
- GQMAHRAZNLNYNT-UHFFFAOYSA-N O.O.O.O.O.O.N1CCNCC1.O.O.O.O.O.S(=S)(=O)(O)O.[Na+].O.O.O.O.O.O.O.O.O.[S-2].[Na+].O.O.O.O.O.O.O.O.O.O Chemical compound O.O.O.O.O.O.N1CCNCC1.O.O.O.O.O.S(=S)(=O)(O)O.[Na+].O.O.O.O.O.O.O.O.O.[S-2].[Na+].O.O.O.O.O.O.O.O.O.O GQMAHRAZNLNYNT-UHFFFAOYSA-N 0.000 description 1
- MHDUGAJWGHTCMH-UHFFFAOYSA-L O.O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[Zn+2].O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].O Chemical compound O.O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[Zn+2].O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].O MHDUGAJWGHTCMH-UHFFFAOYSA-L 0.000 description 1
- FBFRFMBWLDQMGZ-UHFFFAOYSA-H O.O.O.O.O.S(=O)(=O)([O-])[O-].[Cu+2].O.O.O.[N+](=O)([O-])[O-].[Cu+2].O.C(C)(=O)[O-].[Cu+2].O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].O.O.O.O.O.O.[Co](Cl)Cl.O.O.O.O.C(C)(=O)[O-].[Co+2] Chemical compound O.O.O.O.O.S(=O)(=O)([O-])[O-].[Cu+2].O.O.O.[N+](=O)([O-])[O-].[Cu+2].O.C(C)(=O)[O-].[Cu+2].O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].O.O.O.O.O.O.[Co](Cl)Cl.O.O.O.O.C(C)(=O)[O-].[Co+2] FBFRFMBWLDQMGZ-UHFFFAOYSA-H 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 1
- HQWJONIKECOJSP-UHFFFAOYSA-K [Al+3].[Na+].O.S(=O)(=O)([O-])[O-].[Mn+2].[Cl-].[Mn+2] Chemical compound [Al+3].[Na+].O.S(=O)(=O)([O-])[O-].[Mn+2].[Cl-].[Mn+2] HQWJONIKECOJSP-UHFFFAOYSA-K 0.000 description 1
- YPWGNKDGHJSLQZ-UHFFFAOYSA-L [Cl-].[Mn+2].O.O.O.O.C(C)(=O)[O-].[Mn+2].O.O.O.O.O.O Chemical compound [Cl-].[Mn+2].O.O.O.O.C(C)(=O)[O-].[Mn+2].O.O.O.O.O.O YPWGNKDGHJSLQZ-UHFFFAOYSA-L 0.000 description 1
- NIZDDZYTYCZTEP-UHFFFAOYSA-H [Na+].O.O.[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Na+].O.S(=O)(=O)([O-])[O-].[Mn+2].O.O.O.O.O.S(=O)(=O)([O-])[O-].[Cu+2].O.O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[Fe+2] Chemical compound [Na+].O.O.[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Na+].O.S(=O)(=O)([O-])[O-].[Mn+2].O.O.O.O.O.S(=O)(=O)([O-])[O-].[Cu+2].O.O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[Fe+2] NIZDDZYTYCZTEP-UHFFFAOYSA-H 0.000 description 1
- PYCKIMUFPFQXJN-UHFFFAOYSA-M [Na+].O.[OH-].[Na+].O.O.[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Na+].O.O Chemical compound [Na+].O.[OH-].[Na+].O.O.[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Na+].O.O PYCKIMUFPFQXJN-UHFFFAOYSA-M 0.000 description 1
- YDBTZMREHQMITO-UHFFFAOYSA-J [Ni](Cl)Cl.O.O.O.O.O.S(=S)(=O)([O-])[O-].[Na+].O.O.O.O.O.O.O.O.O.[S-2].[Na+].O.O.O.O.O.O.O.O.O.O.S(=O)(=O)(O)O.[Na+].O.O.O.O.O.[Se](=O)(O)O.[Na+].O.O.O.O.O.O.O.O.O.O Chemical compound [Ni](Cl)Cl.O.O.O.O.O.S(=S)(=O)([O-])[O-].[Na+].O.O.O.O.O.O.O.O.O.[S-2].[Na+].O.O.O.O.O.O.O.O.O.O.S(=O)(=O)(O)O.[Na+].O.O.O.O.O.[Se](=O)(O)O.[Na+].O.O.O.O.O.O.O.O.O.O YDBTZMREHQMITO-UHFFFAOYSA-J 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- OJJLEPPNZOMRPF-UHFFFAOYSA-J dimagnesium;tetrachloride Chemical compound Cl[Mg]Cl.Cl[Mg]Cl OJJLEPPNZOMRPF-UHFFFAOYSA-J 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- QBIHEHITTANFEO-UHFFFAOYSA-N sodium;tetrahydrate Chemical compound O.O.O.O.[Na] QBIHEHITTANFEO-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- FGSOQCKQXKBCDC-UHFFFAOYSA-J tetralithium dibromide dichloride hydrate Chemical compound [Cl-].[Li+].O.[Cl-].[Li+].[Br-].[Li+].[Br-].[Li+] FGSOQCKQXKBCDC-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/16—Materials undergoing chemical reactions when used
-
- 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
- the invention relates to a medium for thermochemical heat storage and heat transport and to methods and apparatuses for heat storage and heat transport in which the mentioned medium is used.
- the stored energy can be recovered as heat by sorption of the cold medium. It is also with salts, in particular hydrates, ammoniacates, and alcoholates that such systems can be formed.
- Characteristic of these systems is that one of the reactants is a solid substance. When developing a technology for the storage of heat at a solid substance by means of binding energy, numerous technical problems arise, connected with the solid substance. The most important obstacles are the physical transport of heat and/or cold medium in the solid substance and the great thermal mass of the solid substance, as a result of which the energetic efficiency is unfavorably influenced.
- the invention relates to a heat storage medium comprising a suspension of an "_ adsorbent that can enter into a binding with a cold medium and is present in a suspension Uquid.
- adsorbent is understood to mean a solid material which is capable of binding a liquid or gas (the cold medium), with heat being released.
- Such sorption media are known per se, examples are zeolites, silica, hydrates, ammoniacates, alcoholates, etc. Examples are solid sulfides such as sodium sulfide and specific chlorides such as calcium chloride. It has been found possible, t ⁇ prepare such adsorption media in a stable suspension, with the capacity of storing heat being retained.
- a rheology additive that is to say one or more substances which influence the rheology of the suspension or emulsion such that sagging of the particles, also on longer term, is prevented while the suspension remains pump able.
- the rheology additive is selected such that the suspension according to the invention behaves as a so-called Bingham Uquid because this is easily pumpable. Composing such additives to prevent sagging of suspensions is known per se. Again, per adsorbent, if desired by way of routine experiments, suitable.. combinations of ingredients can be found to obtain a stable suspension according to the invention which does not sag. Suitable rheology additives are known to those skilled in the art.
- the first important advantage is that the loaded adsorbent in the suspension according to the invention can be stored for longer periods without exceptional insulation requir ⁇ .ments".' Moreover, suspensions are transportable with simple technical means, such as pumps and conduits.
- a second important advantage is that according to the invention a separation becomes possible between the storage and the (re) eneration of heat. This separation renders it possible to bring to temperature only the
- a third important advantage is that the diffusion length for heat and the cold medium can be strongly reduced, as a result of which the power per volume unit increases and the technology becomes compact.
- the selection of the cold medium is, in the first place, determined by the evaporation heat and the temperature level of the heat to be stored.
- Water is particularly suitable for storing heat, the required source heat (evaporation heat) being available above ca. 5°C. When unloading, heat of a temperature of from 30 to 200°C can then be obtained.
- Ammonia and alcohol can be used as cold medium in systems in which the source heat is withdrawn from the environment at or below the freezing point of water. When unloading, the heat is released at temperatures of from 30 to 200°C.
- the adsorbent enters into a binding with the cold medium and thus forms a hydrate (if water is the cold medium), an ammoniacate (with ammonia as cold medium), or an alcoholate (with alcohol as cold medium). Combinations of cold media are optionaUy also possible.
- the adsorbent is soluble in the cold medium (as is, for instance, the case with CaC as adsorbent and water as cold medium), problems could be expected in case of overloading: for the adsorbent will be able to dissolve, as a result of which the suspension disappears. It has been found, however, that a stable emulsion can be formed.
- specific surface active substances are added to facilitate the forming of an emulsion.
- the dissolution (just as the sorption) is accompanied by a heat effect, which heat is stored in the emulsion formed in the form of dissolution heat.
- the stored dissolution heat is also released, and the adsorbent is obtained again as suspension.
- the dissolution heat thus contributes to an increase in the energy density.
- this effect holds as regards the stored heat only if the dissolution of the adsorbent in the cold medium proceeds endothermicaUy. This is, for instance, the case with the CaC water combination. But even if the dissolution proceeds exothermicauy, he forming of an emulsion need not constitute a problem if the dissolution heat is small in comparison with the adsorption heat.
- the dissolution of the adsorbent proceeds endothermically.
- the suspension Uquid according to the invention preferably has a mild affinity with the cold medium to promote the physical transport by the suspension Uquid to tUe adsorbent.
- the Uquid preferably has a high boiUng point. This limits the loss of the suspension Uquid in the form of vapor, which, for instance, could disappear through the employed membrane.
- an apolar Uquid is preferably used as suspension liquid.
- the suspension Uquid is further preferably not toxic. Possible suspension Uquids are phthalates, preferably dibutyl phthalate.
- Suitable adsorbents for use in the present invention are listed in Table 1 below, in which the cold medium is also indicated.
- Suitable adsorbents for use according to the invention Cobalt (II) acetate tetrahydrate Cobalt (II) chloride hexahydrate Cobalt (II) nitrate hexahydrate Copper (II) acetate monohydrate Copper (II) nitrate trihydrate Copper (II) sulfate pentahydrate Lithium bromide Lithium bromide Lithium chloride hydrate Lithium chloride ammoniacate Lead (II) acetate trihydrate Magnesium chloride heptahydrate Magnesium chloride ammoniacate Magnesium chloride Magnesium .nitrate hexahydrate Manganese acetate tetrahydrate Manganese chloride ammoniacate Manganese chloride Manganese sulfate monohydrate Sodium aluminum silicate Sodium carbonate decahydrate Sodium dichloroisocyanurate dihydrate Sodium dichromate dihydrate Sodium hydroxide monohydrate Sodium perborate monohydrate
- BClO 4 H 2 0
- LiCl(H 2 O) LiC104(H 2 0), LiBr(H 2 0), LiI(H 2 O), LiN0 2 (H 2 0), NaC10 2 (H 2 0), NaC104(H 2 0), NaBr(H 2 0), NaI(HaO), NaC 2 H 3 ⁇ 2(H2 ⁇ ), NaCN(H 2 0), KOH (H2O), KF (H2O), RbOH (OH), RbF (H2O), CsOH (H 2 0), and CsF (H 2 0).
- the adsorbent is selected from the group consisting of zeolites, silicates, MnCla, ZnCl 2 , gQlg, NaiS, LiCl, SrCl2, ZnBr 2 , and combinations thereof.
- a method according to the invention comprises the loading of the suspension with a suitable cold medium, followed by storage and/or transport, followed by the unloading of the suspension, with heat being released.
- the loading and unloading cycles will now be explained, also with reference to the figure.
- Fig. 1 gives a schematic representation of an apparatus suitable for carrying out the invention.
- the suspension according to the invention (1) is passed through a space which, on the one hand, is formed by a side (2) through which the useful heat from the suspension according to the invention is discharged and the regeneration heat is supplied.
- the source heat evaporation heat
- the condensation heat is supplied to or discharged from the cold medium (4), respectively.
- a wall (5) Positioned between the source side and the useful or regeneration side is a wall (5), which is permeable to cold medium vapor but not or at least very poorly to heat.
- This wall is, for instance, designed as two membranes, between which a vacuum is provided in which the cold medium is contained.
- Fig. 2 gives a schematic representation of the loading.
- the loading of heat in a system according to the invention takes place by supplying regeneration heat (for instance originating from the sun or an industrial process or another heat surplus) of a high temperature (of, for instance, 90°C) via the wall 2 to the suspension according to the invention.
- regeneration heat for instance originating from the sun or an industrial process or another heat surplus
- a high temperature of, for instance, 90°C
- the cold medium is expelled as vapor from the suspension according to the invention and supplied via the wall 4 to the condenser where it is condensed at low temperature, for instance 15°C, and discharged or stored.
- the dried suspension is stored.
- Fig. 3 gives a schematic representation of the unloading.
- the -._ unloading (that is to say the recovery of heat) of the system according to the invention is carried out by reversing the (heat) currents.
- the cold medium is evaporated by means of source heat at a temperature of, for instance, 10°C.
- the cold medium vapor is adsorbed via the separation wall into the adsorbent, with the useful heat being released at high temperature, for instance 70°C.
- Suitable as membranes are both porous and non-porous membranes.
- non-porous membranes are composite.or homogeneous membranes in which the active layer consists of polymers such as polyvinyl alcohol, polyacrylates, polyamides, polyethylene imine, etc.
- porous membranes are: PTFE, PVDF, polypropylene, polyethylene, etc.
- Possible ceramic membranes are, for instance, silica, aluminum oxides, zirconium oxide, etc.
- a suspension according to the invention was prepared on the basis of the adsorption medium calcium chloride, the suspension medium di-n-butyl phthalate to which a dispersing agent available under the tradename of T3isperbykTM 2050' is added.
- the suspension was prepared by dispersing partly dehydrated calcium chloride (CaCl2-2H2 ⁇ ) under vacuum in the suspension liquid in which the dispersing agent was already present.
- Four different suspensions were prepared according to the Table below:
Abstract
The invention relates to a medium for thermochemical heat storage and heat transport and to methods and apparatuses for heat storage and heat transport in which the mentioned medium is used. The invention provides a heat storage medium comprising a suspension of an adsorbent which can enter into a binding with a cold medium and is present in a suspension liquid, to which, if desired, at least one surface active substance and at least one rheology additive are added.
Description
Title: Thermochemical heat storage and heat transport
The invention relates to a medium for thermochemical heat storage and heat transport and to methods and apparatuses for heat storage and heat transport in which the mentioned medium is used.
Storage and transport of (residual) heat can contribute substantially to the saving of (fossile) fuels.
Existing systems for the storage of heat are particularly based on the storage of sensible or latent heat. This heat can be stored in, for instance, rocks, water, paraffin, glauber salts, etc. Characteristic is that the storage media have a higher temperature than the environment. To preserve the heat for later use, substantial insulation is necessary. A second drawback of the above-described storage methods is the limited energy density, as a result of which large storage volumes are necessary.
The efficiency of existing heat storage and heat transport systems is seriously limited by the losses during storage and transport. In the case of storage, the loss is connected with the duration of the storage. Heat storage at some tenths of °C above ambient temperature is not possible for a longer term (some months). In heat transport systems as, for instance, used in district heating, the losses rise to 30-35% of the transported energy. As a result of these losses, the transport length is limited to ca. 10 km. US-A-4 822 391 describes a method for transporting energy and mass, in which a cold medium is transported by dissolving it in a carrier liquid. Transport of (a suspension of) adsorbent is not mentioned or suggested in US-A-4 822 391.
An alternative could be the storage of heat in the form of binding energy, for instance through the desorption of the cold medium water on or in zeolites, or silica. In such systems, the stored energy can be recovered as
heat by sorption of the cold medium. It is also with salts, in particular hydrates, ammoniacates, and alcoholates that such systems can be formed. Characteristic of these systems is that one of the reactants is a solid substance. When developing a technology for the storage of heat at a solid substance by means of binding energy, numerous technical problems arise, connected with the solid substance. The most important obstacles are the physical transport of heat and/or cold medium in the solid substance and the great thermal mass of the solid substance, as a result of which the energetic efficiency is unfavorably influenced.
It is an object of the invention to provide a system which does not have the above-mentioned drawbacks or at least has them to a lesser degree. It is therefore an object of the invention to provide a system with which, without extensive insulation provisions, with little energy loss and a high energy density, heat can be stored for unUmited duration and can be transported over unUmited distance.
It has been found that, with a heat storage medium on the basis of a suspension of an adsorbent, these objectives can be achieved. Therefore, the invention relates to a heat storage medium comprising a suspension of an "_ adsorbent that can enter into a binding with a cold medium and is present in a suspension Uquid. To the suspension are added, if desired, additives, with the purpose of increasing the load of the suspension with adsorbent, improving the physical, chemical and thermal stability of the suspension, and improving the rheological characteristics. According to the present invention, adsorbent is understood to mean a solid material which is capable of binding a liquid or gas (the cold medium), with heat being released. Such sorption media are known per se, examples are zeolites, silica, hydrates, ammoniacates, alcoholates, etc. Examples are solid sulfides such as sodium sulfide and specific chlorides such as calcium chloride.
It has been found possible, tσ prepare such adsorption media in a stable suspension, with the capacity of storing heat being retained.
To obtain a stable suspension, it is desirable in most cases to add one or more surface active substances to the suspension Uquid. The technique of making stable suspensions of soUd particles in the suspension Uquids according to the invention is known per se. Per adsorbent, if desired by way of routine experiments, suitable combinations of ingredients can be found to obtain a physicaUy, chemically and thermally stable suspension according to the invention. If desired, the conventional surface active substances can be added to the suspension according to the invention to improve the stability. To prevent sagging of the soUd or Uquid particles in the suspension or emulsion, it is desirable in many cases to add a rheology additive, that is to say one or more substances which influence the rheology of the suspension or emulsion such that sagging of the particles, also on longer term, is prevented while the suspension remains pump able. Preferably, the rheology additive is selected such that the suspension according to the invention behaves as a so-called Bingham Uquid because this is easily pumpable. Composing such additives to prevent sagging of suspensions is known per se. Again, per adsorbent, if desired by way of routine experiments, suitable.. combinations of ingredients can be found to obtain a stable suspension according to the invention which does not sag. Suitable rheology additives are known to those skilled in the art.
The first important advantage is that the loaded adsorbent in the suspension according to the invention can be stored for longer periods without exceptional insulation requirό.ments".' Moreover, suspensions are transportable with simple technical means, such as pumps and conduits. A second important advantage is that according to the invention a separation becomes possible between the storage and the (re) eneration of heat. This separation renders it possible to bring to temperature only the
# part of the adsorbent which, at that moment, is necessary for (re)generation.
Consequently, the efficiency losses as a result of thermal mass are minimized, and the energy density of the storage is maximized.
A third important advantage is that the diffusion length for heat and the cold medium can be strongly reduced, as a result of which the power per volume unit increases and the technology becomes compact.
The selection of the cold medium is, in the first place, determined by the evaporation heat and the temperature level of the heat to be stored.
Water is particularly suitable for storing heat, the required source heat (evaporation heat) being available above ca. 5°C. When unloading, heat of a temperature of from 30 to 200°C can then be obtained.
Ammonia and alcohol can be used as cold medium in systems in which the source heat is withdrawn from the environment at or below the freezing point of water. When unloading, the heat is released at temperatures of from 30 to 200°C. As stated, according to the invention, the adsorbent enters into a binding with the cold medium and thus forms a hydrate (if water is the cold medium), an ammoniacate (with ammonia as cold medium), or an alcoholate (with alcohol as cold medium). Combinations of cold media are optionaUy also possible. If the adsorbent is soluble in the cold medium (as is, for instance, the case with CaC as adsorbent and water as cold medium), problems could be expected in case of overloading: for the adsorbent will be able to dissolve, as a result of which the suspension disappears. It has been found, however, that a stable emulsion can be formed. Optionally, specific surface active substances are added to facilitate the forming of an emulsion. Moreover, the dissolution (just as the sorption) is accompanied by a heat effect, which heat is stored in the emulsion formed in the form of dissolution heat. When unloading (that is to say when cold medium is withdrawn from the suspension and/or the emulsion), the stored dissolution heat is also released, and the adsorbent is obtained again as suspension. The dissolution heat
thus contributes to an increase in the energy density. Of course, this effect holds as regards the stored heat only if the dissolution of the adsorbent in the cold medium proceeds endothermicaUy. This is, for instance, the case with the CaC water combination. But even if the dissolution proceeds exothermicauy, he forming of an emulsion need not constitute a problem if the dissolution heat is small in comparison with the adsorption heat. Preferably, the dissolution of the adsorbent proceeds endothermically.
The suspension Uquid according to the invention, that is to say the continuous phase in the suspension (or the emulsion if this is formed), preferably has a mild affinity with the cold medium to promote the physical transport by the suspension Uquid to tUe adsorbent. Moreover, the Uquid preferably has a high boiUng point. This limits the loss of the suspension Uquid in the form of vapor, which, for instance, could disappear through the employed membrane. Furthermore, an apolar Uquid is preferably used as suspension liquid. The suspension Uquid is further preferably not toxic. Possible suspension Uquids are phthalates, preferably dibutyl phthalate.
With the suspension according to the invention, a high energy density can be obtained. With the Na2S/water couple, for instance, ca. 1500 MJ/m3
, can be reached, which is about a factor of seven higher than the energy . t density to be obtained with water in which the heat is stored as sensible heat.
Suitable adsorbents for use in the present invention are listed in Table 1 below, in which the cold medium is also indicated.
Table 1. Suitable adsorbents for use according to the invention
Cobalt (II) acetate tetrahydrate Cobalt (II) chloride hexahydrate Cobalt (II) nitrate hexahydrate Copper (II) acetate monohydrate Copper (II) nitrate trihydrate Copper (II) sulfate pentahydrate Lithium bromide Lithium bromide Lithium chloride hydrate Lithium chloride ammoniacate Lead (II) acetate trihydrate Magnesium chloride heptahydrate Magnesium chloride ammoniacate Magnesium chloride Magnesium .nitrate hexahydrate Manganese acetate tetrahydrate Manganese chloride ammoniacate Manganese chloride Manganese sulfate monohydrate Sodium aluminum silicate Sodium carbonate decahydrate Sodium dichloroisocyanurate dihydrate Sodium dichromate dihydrate Sodium hydroxide monohydrate Sodium perborate monohydrate Sodium perborate tetrahydrate Sodium peroxoborate decahydrate Sodium selenite pentahydrate Sodium sulfate decahydrate Sodium sulfide nonahydrate Sodium thiosulfate pentahydrate Nickel chloride ammoniacate Nickel chloride Oxalic acid dihydrate
Further suitable as adsorbent/cold medium couples (cold medium in brackets): BClO4(H20), LiCl(H2O), LiC104(H20), LiBr(H20), LiI(H2O), LiN02(H20), NaC102(H20), NaC104(H20), NaBr(H20), NaI(HaO), NaC2H3θ2(H2θ), NaCN(H20), KOH (H2O), KF (H2O), RbOH (OH), RbF (H2O), CsOH (H20), and CsF (H20).
All these adsorbents and those Usted in Table 3 can be used alone or in combination.
Preferably, the adsorbent is selected from the group consisting of zeolites, silicates, MnCla, ZnCl2, gQlg, NaiS, LiCl, SrCl2, ZnBr2, and combinations thereof.
Of a number of typical adsorbents, the desorption temperature and the energy storage density are listed in respectively Table 2 and Table 3 below.
Table 2. Desorption temperatures of a number of adsorbents
Adsorbent Molecule formula 1 desorption ' C
Borax Gallus acid
Iron (II) sulfate heptahydrate Copper (II) sulfate pentahydrate Manganese sulfate monohydrate Sodium dichromate dihydrate Sodium peroxoborate decahydrate Sodium sulfide nonahydrate Sodium thiosulfate pentahydrate Piperazine hexahydrate p-Sulfanil acid monohydrate Zinc nitrate hexahydrate Zinc sulfate heptahydrate
Table 3. Energy storage density of a number of adsorbents
A method according to the invention comprises the loading of the suspension with a suitable cold medium, followed by storage and/or transport, followed by the unloading of the suspension, with heat being released. The loading and unloading cycles will now be explained, also with reference to the figure.
Fig. 1 gives a schematic representation of an apparatus suitable for carrying out the invention. According to this embodiment, the suspension according to the invention (1) is passed through a space which, on the one
hand, is formed by a side (2) through which the useful heat from the suspension according to the invention is discharged and the regeneration heat is supplied. On the other side (3), the source heat (evaporation heat) or the condensation heat is supplied to or discharged from the cold medium (4), respectively. Positioned between the source side and the useful or regeneration side is a wall (5), which is permeable to cold medium vapor but not or at least very poorly to heat. This wall is, for instance, designed as two membranes, between which a vacuum is provided in which the cold medium is contained. Fig. 2 gives a schematic representation of the loading. The loading of heat in a system according to the invention (with the cold medium being removed from the adsorbent) takes place by supplying regeneration heat (for instance originating from the sun or an industrial process or another heat surplus) of a high temperature (of, for instance, 90°C) via the wall 2 to the suspension according to the invention. The cold medium is expelled as vapor from the suspension according to the invention and supplied via the wall 4 to the condenser where it is condensed at low temperature, for instance 15°C, and discharged or stored. The dried suspension is stored.
Fig. 3 gives a schematic representation of the unloading. The -._ unloading (that is to say the recovery of heat) of the system according to the invention is carried out by reversing the (heat) currents. In the evaporator space, the cold medium is evaporated by means of source heat at a temperature of, for instance, 10°C. The cold medium vapor is adsorbed via the separation wall into the adsorbent, with the useful heat being released at high temperature, for instance 70°C.
When both loading and unloading, the membrane provides an almost unimpeded transport of the gaseous cold medium and, simultaneously, as good a heat insulation as possible. Suitable as membranes are both porous and non-porous membranes. Examples of non-porous membranes are composite.or homogeneous membranes in which the active layer consists of
polymers such as polyvinyl alcohol, polyacrylates, polyamides, polyethylene imine, etc. Examples of porous membranes are: PTFE, PVDF, polypropylene, polyethylene, etc. Possible ceramic membranes are, for instance, silica, aluminum oxides, zirconium oxide, etc.
EXAMPLE
A suspension according to the invention was prepared on the basis of the adsorption medium calcium chloride, the suspension medium di-n-butyl phthalate to which a dispersing agent available under the tradename of T3isperbyk™ 2050' is added.
The suspension was prepared by dispersing partly dehydrated calcium chloride (CaCl2-2H2θ) under vacuum in the suspension liquid in which the dispersing agent was already present. Four different suspensions were prepared according to the Table below:
O carried out with ground CaCl2
To these exemplary suspensions was added, at room temperature and atmospheric pressure, water in liquid form in an amount exactly sufficient to saturate the CaCl2-2H20 present to CaCl2-6H20. By agitating, the water was adsorbed into the calcium chloride, which became visible by the disappearance of the water and discoloration of the calcium chloride. A mild heat effect (the sorption heat) was sensible. Under a reduced pressure of
ca. 10 kPa and at an elevated temperature of ca. 90°C, a part of this water was then evaporated again (from CI26H2O to Cl2-4H2θ).
Legends of Fig. 1: Schematic representation of the method before unloading.
1. Regenerated suspension of storage vessel 2. Side for discharge of heat from suspension and supply of regeneration heat
3. Side for supply or discharge of source or condensation heat
4. Cold medium supply
5. Permeable wall 6. Saturated suspension to storage vessel
7. Heat supply at low temperature
8. (Useful) heat discharge at low temperature
Claims
1. A heat storage medium comprising a suspension or an emulsion of an adsorbent, which adsorbent can enter into a binding with a cold medium and is present in a suspension Uquid, to which, if desired, a surface active substance and a rheology additive are added.
2. A medium according to claim 1, wherein said adsorbent is a solid substance which forms a hydrate, ammoniacate or an alcoholate with said cold medium which comprises water, ammonia or alcohol, respectively.
3. A medium according to any one of the preceding claims, wherein said adsorbent is a silica, zeolite or a combination of hydrate, ammoniacate or an alcoholate with a silica, zeolite.
4. A medium according to any one of the preceding claims, wherein the suspension behaves as a Bingham liquid.
5. A use of a medium according to any one of the preceding claims in heat storage and/or heat transport.
6. A use according to claim 5, wherein said adsorbent at least partly dissolves by the adsorption of said cold medium, with an emulsion being _ formed.
7. A use according to claim 5, wherein source water (aquifer) is used.
8. A method for storing heat, comprising the steps of: - transporting a suspension which comprises an adsorbent loaded with cold medium, as defined in any one of claims 1-3, through a space, such that heat is supplied to the suspension, the cold medium being removed from the adsorbent, and the cold medium being expelled from the suspension as vapor; and - further transporting, if desired followed by storing, the suspension from which cold medium is at least partly removed.
9. A method according to claim 8, which is followed, or is preceded, by a step in which the suspension from which cold medium is at least partly removed is unloaded by bringing the suspension into a space where the suspension is brought into contact with cold medium vapor, with heat being released. r
10. An apparatus suitable and intended for carrying out a method according to claim 8 or 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003281048A AU2003281048A1 (en) | 2002-07-16 | 2003-07-16 | Thermochemical heat storage and heat transport |
| EP03741662A EP1525286A1 (en) | 2002-07-16 | 2003-07-16 | Thermochemical heat storage and heat transport |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1021088 | 2002-07-16 | ||
| NL1021088A NL1021088C2 (en) | 2002-07-16 | 2002-07-16 | Thermochemical heat storage and transport. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004007633A1 true WO2004007633A1 (en) | 2004-01-22 |
Family
ID=30113386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NL2003/000520 WO2004007633A1 (en) | 2002-07-16 | 2003-07-16 | Thermochemical heat storage and heat transport |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1525286A1 (en) |
| AU (1) | AU2003281048A1 (en) |
| NL (1) | NL1021088C2 (en) |
| WO (1) | WO2004007633A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9179641B2 (en) | 2010-06-28 | 2015-11-10 | Lely Patent N.V. | Loose-house barn with floor heating |
| DE102014222596A1 (en) * | 2014-11-05 | 2016-05-12 | Bayerische Motoren Werke Aktiengesellschaft | Device for heat storage |
| DE102015212395A1 (en) * | 2015-07-02 | 2017-01-05 | Bayerische Motoren Werke Aktiengesellschaft | Process for heat storage |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1038071C2 (en) * | 2010-06-28 | 2011-12-29 | Lely Patent Nv | FREE-WALKING STABLE WITH UNDERFLOOR HEATING. |
| EP3299759A1 (en) | 2016-09-21 | 2018-03-28 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | System and method for thermochemical storage of energy |
| EP3382314A1 (en) | 2017-03-30 | 2018-10-03 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Enhanced tcm production and use |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4277357A (en) * | 1980-01-31 | 1981-07-07 | Boardman Energy Systems Incorporated | Heat or cold storage composition containing a hydrated hydraulic cement |
| US4331556A (en) * | 1978-01-03 | 1982-05-25 | Kay Laboratories, Inc. | Heat storage material |
| US4574051A (en) * | 1982-08-12 | 1986-03-04 | Edeco Holdings Limited | Thermochemical energy storage |
| US4822391A (en) * | 1987-11-02 | 1989-04-18 | Uwe Rockenfeller | Method and apparatus for transferring energy and mass |
| GB2233081A (en) * | 1989-04-15 | 1991-01-02 | Richard Cedric Hart Jones | Heating or cooling device |
-
2002
- 2002-07-16 NL NL1021088A patent/NL1021088C2/en not_active IP Right Cessation
-
2003
- 2003-07-16 AU AU2003281048A patent/AU2003281048A1/en not_active Abandoned
- 2003-07-16 WO PCT/NL2003/000520 patent/WO2004007633A1/en not_active Application Discontinuation
- 2003-07-16 EP EP03741662A patent/EP1525286A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4331556A (en) * | 1978-01-03 | 1982-05-25 | Kay Laboratories, Inc. | Heat storage material |
| US4277357A (en) * | 1980-01-31 | 1981-07-07 | Boardman Energy Systems Incorporated | Heat or cold storage composition containing a hydrated hydraulic cement |
| US4574051A (en) * | 1982-08-12 | 1986-03-04 | Edeco Holdings Limited | Thermochemical energy storage |
| US4822391A (en) * | 1987-11-02 | 1989-04-18 | Uwe Rockenfeller | Method and apparatus for transferring energy and mass |
| GB2233081A (en) * | 1989-04-15 | 1991-01-02 | Richard Cedric Hart Jones | Heating or cooling device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9179641B2 (en) | 2010-06-28 | 2015-11-10 | Lely Patent N.V. | Loose-house barn with floor heating |
| DE102014222596A1 (en) * | 2014-11-05 | 2016-05-12 | Bayerische Motoren Werke Aktiengesellschaft | Device for heat storage |
| DE102015212395A1 (en) * | 2015-07-02 | 2017-01-05 | Bayerische Motoren Werke Aktiengesellschaft | Process for heat storage |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003281048A1 (en) | 2004-02-02 |
| EP1525286A1 (en) | 2005-04-27 |
| NL1021088C2 (en) | 2004-01-20 |
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