CN1083206A - The improved heat-eliminating medium that uses in the thermal energy storage system - Google Patents
The improved heat-eliminating medium that uses in the thermal energy storage system Download PDFInfo
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- CN1083206A CN1083206A CN92105950A CN92105950A CN1083206A CN 1083206 A CN1083206 A CN 1083206A CN 92105950 A CN92105950 A CN 92105950A CN 92105950 A CN92105950 A CN 92105950A CN 1083206 A CN1083206 A CN 1083206A
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- tensio
- active agent
- heat
- energy storage
- micelle
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- 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
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D3/00—Devices using other cold materials; Devices using cold-storage bodies
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a kind of heat-eliminating medium that is used in thermal energy storage system, this medium comprises water, guest compound molecule and the tensio-active agent that has definite micelle-forming concentration and its consumption less than 2 times of these concentration, and micelle-forming concentration is to be lower than about 1 * 10
-3M is good, is preferably in 1 * 10
-4M to 1 * 10
-6Between the M.Use the thermal energy storage device of described heat-eliminating medium and use the method for this device also together open.
Description
The application is that the application number of submitting on June 27th, 1992 is No.722, the continuation part of 428 applications.
Thermal energy storage system comprises one at non-peak hours at night agglomerative heat-eliminating medium.On daytime, the heat of surrounding space fuses heat-eliminating medium.The eliminating that causes the heat of decomposition turns cold surrounding space.
U.S. Patent No. 4,540,501 disclose a kind of thermal energy storage system that uses clathrate as heat-eliminating medium.Clathrate is that every guest compound molecule has the hydrate that water molecules is counted in nonstoichiometry.The guest compound molecule riddles among the lattice, makes the clathrate stabilization.This stablizing can form the crystalline network of water under the temperature that is higher than freezing temperature (0 ℃) significantly.The guest compound molecule must be water-fast fully, and its molecular size must be less than 7
Halohydrocarbon as the guest compound molecule does not mix with water, only just forms clathrate at object when compound contacts with matrix (lattice).For making the tight contact of guest compound molecule and water can add different tensio-active agents.U.S. Patent No. 4,540,501 disclose when the guest compound molecule and have comprised CCl for being selected from
2F
2, CCl
3F, CBrF
3, CHCl
2F, CHClF
2, CH
2ClF and CH
3CClF
2When interior brominated hydrocarbon, chlorinated hydrocarbon and fluorinated hydrocarbons refrigerant, use chemical molecular formula to be F(CF
2CF
2)
3-8CH
2CH
2O(CH
2CH
2O)
9-11The nonionic fluoro surfactants of H.U.S. Patent No. 4,821,794 disclose that to use usual amounts be 1 to 5000ppm Zonyl
Fluoro surfactants and use Zonyl
FSN adds trichlorofluoromethane, and consumption is about 200 to 300ppm." directly contact evaporation by the CFC alternation and generate gas hydrate or ice " (F.Isobe and Y.H.Mori, Int.J.Refrig., vol.15, No.3(1992), Pgs137-142.) in Zonyl
Fluoro surfactants and Unidyne DS-401 are added to water-1,1, form thermal storage medium in the 1-Tetrafluoroethane cage type look compound.At " Proc.Inter.Soc.Energy Convers, Eng Conf. " (Akiya et al., 1991,26th(6) 115-119) uses two kinds of unspecified tensio-active agents in, concentration reaches 500ppm to increase from a kind of water-1, and 1-two chloro-1-fluoroethane heat-eliminating mediums form the ratio of clathrate.
Yet, used a large amount of tensio-active agent of known relatively guest compound molecule (up to surpass 1000ppm), some guest compound molecules combine with tensio-active agent and not with water formation clathrate, this has reduced the efficient of storing hot system.
Before the present invention, be not special heat-eliminating medium option table surface-active agent and amount how the to determine tensio-active agent experience aspect guaranteeing to mix with minimum guest compound molecule bonded is best about how.
In addition, the guest compound molecule that uses at present has many CFCS that are, as: trichlorofluoromethane (CFC-11).The use of these compounds is harmful and become and be out of favour to ozonosphere.The objective of the invention is to find a kind of to the less heat-eliminating medium of ozonosphere threat.Halohydrocarbon is as HCFC-141(b), include hydrogen, ozonosphere is threatened less, in the present invention, serve as the guest molecule of clathrate in synthetic.
Fig. 1 uses surfactant D RSC
The time surfactant concentration and water surface tension graph of a relation.
Fig. 2 tensio-active agent (DRSC
) concentration and 1, the graph of a relation of 1-two chloro-1-fluoroethane/aqueous solution interface tension force.
The invention provides the heat-eliminating medium that a kind of heat supply energy storage system is used, this medium comprises water, guest compound molecule and the tensio-active agent with micelle-forming concentration, and its amount is two times of micelle-forming concentration.Micelle-forming concentration is about 1 * 10
-3M is following to be better, is in 1 * 10
-4M to 1 * 10
-6Better between the M.The thermal energy storage device of use heat-eliminating medium and the using method of this device are open in the lump.Guest compound molecule among the present invention is for forming any compound of clathrate with water.The guest compound molecule mean diameter that is suitable for is generally less than 7
The guest compound molecule is good to be selected from one group of refrigerant being made up of hydrochlorinate fluorocarbon, hydrogenated carbon fluorine cpd and miscellany thereof.The most preferred embodiment of hydrochlorinate fluorocarbon guest compound molecule has 1-fluoro-1, the 1-ethylene dichloride and-chlorodifluoromethane.The preferred example of hydrogenated carbon fluorine cpd guest compound molecule has 1,1,1,2-Tetrafluoroethane, 1,1,1-Halothane, methylene fluoride, pentafluoride ethane and 1,1-C2H4F2 C2H4F2.The configuration of thermal energy storage system of the present invention and U.S. Patent No. 4,540,501 is similar.
The guest compound molecule that forms clathrate must be different with water and contact with each other.Contact closely more, the efficient that clathrate forms is just high more.Therefore, be starved of the emulsion of water and guest compound molecule.Clathrate among the present invention is formed by water and guest compound molecule, and according to the size of guest molecule, each guest compound molecule needs in conjunction with 5 to 17 water moleculess to form clathrate.The guest compound molecule equals to generate the necessary ratio of clathrate at least with the ratio of the number of water, it is excessive in to be maintained in pulpous state and to guarantee the lasting and efficient of heat exchange to be preferably water, for example: use HCFC-141(b), per 1 mole of HCFC-141(b) add 20 moles in water.
The free surfactant concentrations affects the performance of water in the water, surface tension especially, and this point is with DRSC
As seeing among Fig. 1 of tensio-active agent.Guest compound molecule/water mixture that thermal energy storage system uses is as heterogeneous system, and the interfacial tension between its guest compound molecule and the water can be surveyed.The DRSC of different concns
To 1, the influence of 1-two chloro-1-fluorinated ethanic/water as shown in Figure 2.The performance of two kinds of solution exceeds this concentration range approximately undergoing mutation between 25ppm and the 125ppm, and it is slow that changes of properties is tending towards.The narrow and small concentration range that performance is undergone mutation is known as micelle-forming concentration or cmc.When surpassing cmc, add the more surfactant water surface tension and only do very micro-reducing.Because reducing the mixing of water-guest compound molecule, water surface tension promotes, so water-guest compound molecule reaches maximum mixing near cmc.In addition, the DRSC of adding
Tensio-active agent reaches two times of cmc of 200ppm() after, surface tension or interfacial tension all do not have substantial variations.Like this, do not consider to use which kind of tensio-active agent, reach the required tensio-active agent optimum concn of maximum mixing and be not more than 2 times micelle-forming concentration, to be good, preferably less than cmc less than 1.5 times of cmc.Because surfactant concentrations is limited in less than in 2 times of cmc, the usage quantity of tensio-active agent just may be less, particularly when micelle-forming concentration is very little (less than about 10
-3M).
Every kind of tensio-active agent has specific separately cmc according to structure.The tensio-active agent micelle-forming concentration of general belt length hydrocarbon chain is lower, and cmc is low more, and the required tensio-active agent of maximum mixing that reaches becomes few more.Therefore, tensio-active agent preferably among the present invention, its micelle-forming concentration is lower than 1 * 10
-3M is with 1 * 10
-4To 1 * 10
-6M is good.The micelle-forming concentration of many tensio-active agents is listed (Nat.Stand.Ref.Data Ser. by Mukerjee and Mysels in " micelle-forming concentration of aqueous surfactant system ", Nat.Bur.Stand.(U.S) 36, Feb.1971.) Mukerjee and other people described the method for many definite tensio-active agent cmc.In addition, the invention provides a large amount of tensio-active agents that are suitable for, we do not recommend to use those only to gradually change at different concns scope internal surface or interfacial tension, have the tensio-active agent of the clumsy cmc value that limits thus, for example: Zony
FSN. be exactly tensio-active agent with clumsy cmc value that limits.
Preferably select for use cmc less than 1 * 10
-4The tensio-active agent of M, its consumption equal or are slightly larger than cmc.Tensio-active agent by selecting low cmc and the amount of tensio-active agent is limited in the cmc, invalid between guest compound molecule and state of aggregation tensio-active agent combined and tensio-active agent and guest compound molecule between competition be reduced to bottom line.When apolar substance contacted with water, water molecules will arrange around non-polarized part or layout becomes cluster.This bunch crystallization has formed clathrate.Similarly, when tensio-active agent existed, water cluster was around tensio-active agent, and formation tensio-active agent granule.Make the amount that generates clathrate add will lacking that the water molecules total amount can generate to the contention of water molecules between possible guest compound molecule and surfactant molecule.Therefore, preferably the add-on of tensio-active agent is reduced to least restrictive.
In some cases, need add-on to surpass cmc to reach a kind of special-effect.The tensio-active agent lower for cmc even concentration surpasses cmc, still is significantly less than conventional surfactants concentration.Like this, though concentration greater than cmc, the intermolecular degree of contention of tensio-active agent and guest compound is not too fierce.So preferably select for use micelle-forming concentration less than 1 * 10
-4The tensio-active agent of M.
Example table surface-active agent DRSC as a class tensio-active agent
At HCFC-141(b) divide the period of the day from 11 p.m. to 1 a.m to be formed with special-effect as guest compound to improving emulsion.(DRSC
) be the alkyl dimethyl benzyl ammonium salt of octaphenyl phosphoric acid, can on market, buy from Allied-Signal limited-liability company) DRSC
Physical properties shown in following table 1:
Table 1
| Tensio-active agent | Boiling point (°F) | Bi Chong @25 ℃ | @25 ℃ of vapour pressure Hao Migongzhu | Solvability in the water in the time of 25 ℃ |
DRSC
 |
180° | 0.95 | ＜1 | Molten |
* under 10 mmhg
By continuous increase DRSC
Amount, measure water surface tension and determined DRSC
Cmc greatly about 50ppm between the 125ppm, thus, add DRSC
Amount be less than about 200ppm greatly to guarantee water and selected guest compound molecule formation emulsion.The DRSC that adds
Most preferably less than 100ppm, reduce the tensio-active agent add-on and also reduced the loss that combines the guest compound molecule that causes because of the guest compound molecule with tensio-active agent, improved the efficient of clathrate formation and thermal energy storage system thus.
Clathrate forms and need not stir in the heat-eliminating medium of the present invention, yet stirring can play a driving role to the formation of clathrate.
Under the normal temperature, the emulsion that the present invention forms can keep two days, had minimum elutriation amount.Clathrate forms in storage container/crystallizer.Reduce pressure in the crystallizer by a compressor,, this has been done in 501 detailed introduction, before reaching the temperature that clathrate forms, remove heat in U.S. Patent No. 4,540.In whole clathrate forming processes, pressure and temperature remain unchanged.Via the circulation of recirculation closed system, the circulation of clathrate is through over-heat-exchanger by the heat exchanger clathrate, and decomposition and water and guest compound molecule miscellany appear in the crystallizer again to be realized.
Example:
In 1 premium on currency, add 0.025 mole of DRSC
Forming concentration is the solution of 25ppm.In the 500ml container, pour 300ml surfactant soln and 30ml141(b into).Container is added a cover the back and is used forced oscillation 1 minute, just forms in the container to keep two days not emulsions of bleed.
The container of sealing was positioned in 40 the refrigerator after 1.0 hours, just can see some amount flakes crystal (clathrate) in container.Container is placed in refrigerator and is spent the night.To morning, crystallization fully in the container shows that clathrate is completed into.
Thus, the DRSC of low cmc
For a kind of suitable auxiliary agent of clathrate in forming, can under low surfactant concentration, form clathrate.Because, only need small amount of surfactant (two times cmc or still less), thus with to hold body compound molecule (being HCFC-141(b) bonded tensio-active agent here just few, like this, clathrate form and the efficient of thermal energy storage system also higher.
Claims (15)
1, a kind of thermal energy storage system comprises the crystallizer that includes the heat-eliminating medium that forms clathrate, makes heat-eliminating medium carry out round-robin device and the device that reduces temperature in the described crystallizer by heat exchanger, it is characterized in that:
Mixture as the heat-eliminating medium that forms clathrate comprises water, and guest compound molecule and its total amount are for being lower than this tensio-active agent micelle-forming concentration duple tensio-active agent.
2, thermal energy storage system as claimed in claim 1 is characterized in that the micelle-forming concentration of the consumption of described tensio-active agent up to described tensio-active agent.
3, thermal energy storage system as claimed in claim 1 is characterized in that described micelle-forming concentration is 1 * 10
-4M to 1 * 10
-6Between the M.
4, thermal energy storage system as claimed in claim 1 is characterized in that described guest compound molecule is selected from the group of being made up of hydrochlorinate fluorocarbon, hydrogenated carbon fluorine cpd.
5, thermal energy storage system as claimed in claim 4 is characterized in that described guest compound molecule is selected from by 1,1-two chloro-1-fluorinated ethanics, 1-fluoro-1, the 1-ethylene dichloride, monochlorodifluoromethane, 1,1,1, the 2-Tetrafluoroethane, 1,1,1-Halothane, methylene fluoride, pentafluoride ethane and 1, the group that the 1-C2H4F2 C2H4F2 is formed.
6, thermal energy storage system as claimed in claim 1 is characterized in that tensio-active agent is the alkyl dimethyl benzyl ammonium salt of octaphenyl phosphoric acid.
7, thermal energy storage system as claimed in claim 6 is characterized in that the consumption of described tensio-active agent is lower than 200ppm.
8, a kind of method of thermal energy storage comprises and induces a kind of heat-eliminating medium to form a kind of clathrate, and the heat of surrounding environment is absorbed and fuses clathrate, it is characterized in that:
The mixture that is used as described heat-eliminating medium comprises water, guest compound molecule and have micelle-forming concentration less than 1 * 10
-3The tensio-active agent of M, its consumption is less than 2 times of described micelle-forming concentrations.
9, method as claimed in claim 8, the micelle-forming concentration that it is characterized in that described tensio-active agent is 1 * 10
-4M to 1 * 10
-6Between the M.
10, as method as described in the claim 9, it is characterized in that described tensio-active agent is the alkyl dimethyl benzyl ammonium salt of octaphenyl phosphoric acid.
11, method as claimed in claim 10 is characterized in that the consumption of described tensio-active agent is less than 200ppm.
12, a kind of heat-eliminating medium that is used for thermal energy storage system comprises water, guest compound molecule and the tensio-active agent that micelle-forming concentration is arranged, and its consumption is less than 2 times of described micelle-forming concentration.
13, heat-eliminating medium as claimed in claim 12 is characterized in that described micelle-forming concentration is less than 1 * 10
-3M.
14, heat-eliminating medium as claimed in claim 13 is characterized in that described micelle-forming concentration is 1 * 10
-4M to 1 * 10
-6Between the M.
15, heat-eliminating medium as claimed in claim 14 is characterized in that tensio-active agent is the alkyl dimethyl benzyl ammonium salt of octaphenyl phosphoric acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89972292A | 1992-06-23 | 1992-06-23 | |
| US899,722 | 1992-06-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1083206A true CN1083206A (en) | 1994-03-02 |
Family
ID=25411463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92105950A Pending CN1083206A (en) | 1992-06-23 | 1992-07-21 | The improved heat-eliminating medium that uses in the thermal energy storage system |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100218060B1 (en) |
| CN (1) | CN1083206A (en) |
| MX (1) | MX9204399A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434833B (en) * | 2008-12-05 | 2011-07-27 | 西安交通大学 | Nano refrigerant hydrate phase change cold-storage working substance and preparation thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160139763A (en) | 2015-05-28 | 2016-12-07 | 김태훈 | A smoking stand |
| KR20160139765A (en) | 2015-05-28 | 2016-12-07 | 김태훈 | A driving device of smoking stand |
-
1992
- 1992-07-21 CN CN92105950A patent/CN1083206A/en active Pending
- 1992-07-28 MX MX9204399A patent/MX9204399A/en not_active IP Right Cessation
- 1992-12-09 KR KR1019920023704A patent/KR100218060B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434833B (en) * | 2008-12-05 | 2011-07-27 | 西安交通大学 | Nano refrigerant hydrate phase change cold-storage working substance and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9204399A (en) | 1994-01-31 |
| KR940005781A (en) | 1994-03-22 |
| KR100218060B1 (en) | 1999-09-01 |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |