EP0591430A1 - Improved cooling medium for use in a thermal energy storage system - Google Patents
Improved cooling medium for use in a thermal energy storage systemInfo
- Publication number
- EP0591430A1 EP0591430A1 EP92914815A EP92914815A EP0591430A1 EP 0591430 A1 EP0591430 A1 EP 0591430A1 EP 92914815 A EP92914815 A EP 92914815A EP 92914815 A EP92914815 A EP 92914815A EP 0591430 A1 EP0591430 A1 EP 0591430A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- energy storage
- thermal energy
- cooling medium
- storage system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000004146 energy storage Methods 0.000 title claims abstract description 23
- 239000002826 coolant Substances 0.000 title claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000693 micelle Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkyl dimethyl benzyl ammonium salt Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 2
- 229940051271 1,1-difluoroethane Drugs 0.000 claims description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
Definitions
- halogenated hydrocarbons which are used as the guest molecules are not water iscible. Clathrates will not form unless the guest and host (lattice) compounds are in contact. In an attempt to bring the guest molecule and water into closer contact, various surfactants have been added.
- U.S. Patent No. 4,540,501 discloses using a nonionic fluorosurfactant having the chemical formula F(CF 2 CF 2 ) 3 - ⁇ CH 2 CH 2 ⁇ (CH 2 CH,0) g .
- Zonyl® Fluorosurfactant and Unidyne DS-401 have been added to water-l,l,l-tetrafluoroethane clathrate forming thermal energy storage medium in Formation of Gas Hydrate or Ice by Direct-Contact Evaporation of CFC Alternatives.
- Halohydrocarbons such as HCFC-141(b) which contain hydrogen, and are believed to pose less of a threat to the ozone layer, and are thus proposed as the guest molecule in clathrate formation according to the present invention.
- the present invention provides a cooling medium for use in a thermal energy storage system comprising water, a guest molecule and a surfactant having a critical micelle concentration in an amount less than about twice the critical micelle concentration.
- the critical micelle concentration is less than about lxlO "3 and more preferably between lxlO"*M and 1 10 " ⁇ .
- a thermal energy storage unit which uses the cooling medium and a process for using the thermal energy storage unit are also disclosed.
- the guest molecules of the present invention may be any compound'capable of forming a clathrate with water. Suitable guest molecules generally have an average diameter of less than about 7 A.
- Clathrates of the present invention are formed from the guest molecule, and water. Depending on the size of the guest molecule between 5 to 17 water molecules per guest molecule are needed to form a clathrate. Preferably the amount of each the guest molecule and water is at least equal to the ratio necessary to form clathrate. More preferably, an excess of water is used to maintain a slurry, and ensure continuous and efficient heat transfer. For example, where HCFC- 141(b) is used, 20 moles of water is used for each 1 mole of HCFC-141(b).
- the optimum concentration of surfactant necessary to provide maximum mixing is not greater than about twice the critical micelle concentration, preferably less than about 1.5 times the cmc and most preferably less than about the cmc.
- the cmc it may be desirable to exceed the cmc in order to acheive a particular effect.
- the concentration of surfactant may still be quite low-as compared to conventional surfactant concentration even though it is above the cmc.
- the competition between the surfactant and the guest molecule is proportionately less severe, even at concentrations which are above the cmc.
- surfactants with critical micelle concentrations below about lxlO"*M are preferred.
- Emulsions formed according to the present invention are stable at room perature, and remain emulsified for as long as two days with minimum drainage.
- the clathrate is formed in a storage tank/crystallizer.
- the pressure in the crystallizer is decreased by means of a compressor, as described in more detail in U.S. Patent No. 4,540,501, and heat is removed until the tempera*-nre of formation for the clathrate is reached. Ti sressure and temperature are maintained until all of t ⁇ clathrate is formed.
- the clathrate is circulated through the heat exchanger via the recirculation loop. Clathrate is circulated through the heat exchanger, decomposed, and the water and guest molecule mixture is returned to the crystallizer.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Medicinal Preparation (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/722,428 US5159971A (en) | 1991-06-27 | 1991-06-27 | Cooling medium for use in a thermal energy storage system |
| US722428 | 1991-06-27 | ||
| US89972292A | 1992-06-23 | 1992-06-23 | |
| US899722 | 1992-06-23 | ||
| PCT/US1992/005368 WO1993000412A1 (en) | 1991-06-27 | 1992-06-24 | Improved cooling medium for use in a thermal energy storage system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0591430A1 true EP0591430A1 (en) | 1994-04-13 |
Family
ID=27110592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92914815A Withdrawn EP0591430A1 (en) | 1991-06-27 | 1992-06-24 | Improved cooling medium for use in a thermal energy storage system |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0591430A1 (ja) |
| JP (1) | JPH06508679A (ja) |
| AU (1) | AU659663B2 (ja) |
| CA (1) | CA2111831A1 (ja) |
| WO (1) | WO1993000412A1 (ja) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999029800A1 (en) * | 1997-12-11 | 1999-06-17 | Alliedsignal Inc. | A cold pack comprising an aqueous clathrate composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4332690A (en) * | 1979-04-23 | 1982-06-01 | Mitsubishi Denki Kabushiki Kaisha | Heat storage system comprising a phase change medium and a nucleating agent |
| US4540501A (en) * | 1984-09-12 | 1985-09-10 | The United States Of America As Represented By The United States Department Of Energy | Gas hydrate cool storage system |
| US4821794A (en) * | 1988-04-04 | 1989-04-18 | Thermal Energy Storage, Inc. | Clathrate thermal storage system |
| WO1993004139A1 (en) * | 1991-08-27 | 1993-03-04 | Allied-Signal Inc. | Improved thermal energy storage system and process for thermal energy storage and transfer |
-
1992
- 1992-06-24 WO PCT/US1992/005368 patent/WO1993000412A1/en not_active Application Discontinuation
- 1992-06-24 EP EP92914815A patent/EP0591430A1/en not_active Withdrawn
- 1992-06-24 AU AU22956/92A patent/AU659663B2/en not_active Ceased
- 1992-06-24 CA CA 2111831 patent/CA2111831A1/en not_active Abandoned
- 1992-06-24 JP JP5501658A patent/JPH06508679A/ja active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9300412A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2295692A (en) | 1993-01-25 |
| JPH06508679A (ja) | 1994-09-29 |
| CA2111831A1 (en) | 1993-01-07 |
| WO1993000412A1 (en) | 1993-01-07 |
| AU659663B2 (en) | 1995-05-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19931221 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL |
|
| 17Q | First examination report despatched |
Effective date: 19941004 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ALLIEDSIGNAL INC. |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19951010 |