CN100416171C - Cold storage device capable of statically and quickly generating refrigerant gas hydrate - Google Patents
Cold storage device capable of statically and quickly generating refrigerant gas hydrate Download PDFInfo
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- CN100416171C CN100416171C CNB2004100773256A CN200410077325A CN100416171C CN 100416171 C CN100416171 C CN 100416171C CN B2004100773256 A CNB2004100773256 A CN B2004100773256A CN 200410077325 A CN200410077325 A CN 200410077325A CN 100416171 C CN100416171 C CN 100416171C
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention belongs to the energy saving field and relates to a cold storage device capable of statically and quickly generating refrigerant gas hydrates. The cold storage device of the present invention comprises a constant temperature bath and an inner container, wherein the upper end and the lower end of the constant temperature bath are respectively provided with a cooling medium inlet and a cooling medium outlet, and the container is soaked in cooling media which flow circularly; the upper end and the lower end of the container are respectively provided with an inlet and an outlet of refrigerant and anionic surfactant water solution, and the anionic surfactant water solution and the refrigerant form an upper phase and a lower phase in the container; a metal filament is arranged in the container, passes through the two-phase interface of the anionic surfactant water solution and the refrigerant, and is connected with the wall surface of the container. The cold storage device of the present invention can be widely used for energy storage (comprising heat storage and cold storage) and provides an effective path which has the advantages of supply and demand of energy regulation, peak moving and valley filling, energy system balance, energy consumption reduction, running cost saving, and high efficiency and reasonable energy utilization. The present invention has large economic and social value.
Description
Technical field
The invention belongs to energy-saving field, relate to a kind of refrigerant gas hydrate regenerator, particularly a kind of cold storage device capable of statically and quickly generating refrigerant gas hydrate.
Background technology is in City Building, and air-conditioning is one of maximum consumer, and peak season (summer) accounts for the over half of building power consumption total amount.It is the important means that realizes urban electricity supply balance and building energy conservation that air conditioner cold accumulation moves the peak power-saving technique.Refrigerant gas hydrate relatively is fit to do the air conditioner cold accumulation medium at present, and the storage density of cold 334kJ/kg that refrigerant gas hydrate decomposes enthalpy and ice is suitable; Generate temperature between 5～12 ℃, close with the operating condition of general air conditioner cold water unit evaporimeter; Refrigerant gas hydrate can directly be contacted generation, decompose with water by cold-producing medium, has exempted heat transfer resistance, improves heat exchange efficiency greatly.
Refrigerant gas hydrate cold accumulation system in the laboratory adopts circulating pump generation disturbance and mechanical agitation to impel refrigerant gas hydrate to generate fast usually at present.Yet.Perturbation scheme has the following disadvantages: (1) consumes energy; (2) need special design system device; (3) need the hydrate that form be separated immediately, increased the initial cost and the maintenance cost of equipment.
Summary of the invention
The present invention is intended to propose a kind of cold storage device capable of statically and quickly generating refrigerant gas hydrate, promotes the practicability of refrigerant gas hydrate energy storage technology.
A kind of cold storage device capable of statically and quickly generating refrigerant gas hydrate of the present invention comprises thermostat and inner container; The upper and lower end of thermostat is respectively equipped with the import and the outlet of cooling medium, and container is soaked in the cooling medium that circulates; The upper and lower end of container is respectively equipped with the outlet and the import of cold-producing medium and aqueous solution of anionic surfactant, and aqueous solution of anionic surfactant and cold-producing medium form two-phase up and down in container; One wire is arranged in the container, and it passes aqueous solution of anionic surfactant and contacts with the container wall with the cold-producing medium two-phase interface.
Described cold-producing medium comprises in the following material two kinds or two or more:
Methane Derivatives series material: CFC11, CFC12, HCFC22, HCFC21, HCFC31;
Ethane derivative series material: HFC-125, HFC-134a, HFC-143a, HFC-152a;
Propane derive series material: HFC-227ca, HFC-227ea, HFC-236ca, HFC-236cb, HFC-236ea, HFC-236fa, HFC-245ca, HFC-245cb, HFC-245ea, HFC-245eb, HFC-245fa, HFC-254cb, HFC-254ea, HFC-254eb, HFC-254fa, HFC-254fb, HFC-254fb;
Hydrocarbon: propane, normal butane, iso-butane, pentamethylene, cyclopentene, isopentane.
Anion surfactant comprises: four analog anion surfactants such as dodecyl analog anion surfactants, Sulfonates anion surfactant, benzene sulfonate analog anion surfactants, Sulfates anion surfactant.
Wire comprises various wires or its alloying metal silk, for example: iron wire, copper wire, aluminium wire, platinum filament, stainless steel wire etc.
Also crystallization-promoter can be added in the described cold-producing medium or/and assist gas; Crystallization-promoter is selected from the mixture of n-butanol, oxolane, carbon molecular sieve, CNT and above-mentioned crystallization-promoter; Assist gas is selected from the mixture of methane, ethane, carbon dioxide, nitrogen, oxygen and above-mentioned assist gas.
With above-mentioned two or more refrigerant mixed, perhaps/and change aqueous surfactant solution concentration, or/and at the aqueous solution or/and add other surfactant in the above-mentioned cold-producing medium or/and crystallization-promoter or/and assist gas, or/and change number wiry or/and change the shape of metal medium or/and adopt the wire of unlike material, shape can realize that all the static of above-mentioned refrigerant gas hydrate generates fast simultaneously.
In the superincumbent combination, adopt the combined effect of following aqueous solution of anionic surfactant and cold-producing medium better: mass percent concentration is 3.8% sodium dodecyl benzene sulfonate aqueous solution and R141b liquid refrigerant, perhaps mass percent concentration is 3.8% lauryl sodium sulfate aqueous solution and R141b liquid refrigerant, and perhaps mass percent concentration is 3.8% sodium dodecyl sulfate aqueous solution and R141b liquid refrigerant.
A kind of cold storage device capable of statically and quickly generating refrigerant gas hydrate proposed by the invention, wire passes aqueous solution of anionic surfactant and contacts with the container wall with the cold-producing medium two-phase interface, outside under the lasting cooling of cooling medium, refrigerant gas hydrate rapid crystallization nucleation is lured in the acting in conjunction of wire and anion surfactant into, refrigerant gas hydrate generates under the effect of surfactant fast, and whole hydration reaction is carried out in static water always.
Externally under the continuous action of low-temperature receiver, because the inhomogeneities and the wire good heat-conducting of Temperature Distribution in the container, to form " maximum undercooling point " at the contact point of wire and container wall, wire is pasting wall and is destroying original poised state, lure the rapid crystallization nucleation of refrigerant gas hydrate into, the emulsification of adding anion surfactant has promoted the phase counterdiffusion of hydrone with refrigerant molecules, impels the static growth fast of refrigerant gas hydrate.
Regenerator with traditional ice cold-storage, water cold-storage and eutectic salts is compared, and the present invention has developed all advantages of refrigerant gas hydrate regenerator; Compare with stirring-type refrigerant gas hydrate regenerator, this regenerator has not only been saved the energy, has saved initial cost and operating cost, and regenerator can make separately, helps the regenerator standardization, and operation will be simpler.In a word, this invention has huge application potential, will play huge impetus to the practicability of refrigerant gas hydrate cold-storage technology.
Regenerator of the present invention can be widely used in energy storage (comprising accumulation of heat and cold-storage), for regulating energy supply and demand, peak load shifting, the equilibrium energy system cuts down the consumption of energy, and saves operating cost, the efficient and rational utilization that realizes energy provides an effective way, has great economy and social value.
Description of drawings
Fig. 1 is a structure chart of the present invention;
Fig. 2 is a system diagram of the present invention.
The specific embodiment
Further specify this preparation method below by embodiment.
Cold storage device capable of statically and quickly generating refrigerant gas hydrate of the present invention as shown in Figure 1, comprises thermostat 1 and inner container 2; The upper and lower end of thermostat 1 is respectively equipped with the import 11 and outlet 12 of cooling medium, and container 2 is soaked in the cooling medium that circulates; The upper and lower end of container 2 is respectively equipped with the outlet 21 and import 22 of cold-producing medium and aqueous solution of anionic surfactant, and aqueous solution of anionic surfactant and cold-producing medium form two-phase up and down in container 2; One wire 3 is arranged in the container 2, and it passes aqueous solution of anionic surfactant and contacts with container 2 walls with the cold-producing medium two-phase interface.
As shown in Figure 2, cold storage device capable of statically and quickly generating refrigerant gas hydrate of the present invention is positioned at the central authorities of cold accumulation system, one side constantly circulates by refrigeration machine 4 and produces cooling medium, be input in the thermostat 1, opposite side water receiving case 6 and refrigerant cylinder 5, container 2 input aqueous solution of anionic surfactant and the cold-producing mediums in thermostat 1.
Use the static generation fast of the refrigerant gas hydrate experiment that regenerator of the present invention carries out:
Experiment condition: filling the 26.17g mass percent concentration is that 3.8% aqueous solution of anionic surfactant and φ 20 * L200 test tube of 10.00gR141b liquid are put into thermostat, result such as table one:
Table one
| The embodiment numbering | Aqueous solution of anionic surfactant | Cold-producing medium | Wire | The thermostat temperature | The hydrate generation time | The hydration reaction deadline | |
| 1 | Mass percent is 0.038 sodium dodecyl benzene sulfonate aqueous solution | R141b liquid | Iron wire | 1 | 10min | 60min | |
| 2 | Mass percent is 0.038 lauryl sodium sulfate aqueous solution | R141b liquid | |
3 | 30min | 100min | |
| 3 | 0.038 sodium dodecyl sulfate aqueous solution | R141b liquid | Copper wire | 5℃ | 50min | 400min |
Among the embodiment one, filling the 26.17g mass percent concentration is that 3.8% sodium dodecyl benzene sulfonate aqueous solution and φ 20 * L200 test tube of 10.00g R141b liquid are put into 1 ℃ thermostat, pass two-phase interface and can induce the R141b gas hydrate at first to generate hydrate with interior at iron wire and side wall surface contact position at 10min with the contacted iron wire of test tube side wall surface, hydration reaction is finished at 60min.
Among the embodiment two, filling the 26.17g mass percent concentration is that 3.8% lauryl sodium sulfate aqueous solution and φ 20 * L200 test tube of 10.00gR141b liquid are put into 3 ℃ thermostat, pass two-phase interface and can induce the R141b gas hydrate at first to generate hydrate with interior at stainless steel wire and side wall surface contact position at 30min with the contacted stainless steel wire of test tube side wall surface, hydration reaction is finished at 100min.
Among the embodiment three, filling the 26.17g mass percent concentration is that 3.8% sodium dodecyl sulfate aqueous solution and φ 20 * L200 test tube of 10.00gR141b liquid are put into 5 ℃ thermostat, pass two-phase interface and can induce the R141b gas hydrate at first to generate hydrate with interior at copper wire and side wall surface contact position at 50min with the contacted copper wire of test tube side wall surface, hydration reaction is finished at 400min.
Based on same principle, the aqueous solution of anionic surfactant in the foregoing description can be selected four analog anion surfactants such as dodecyl analog anion surfactants, Sulfonates anion surfactant, benzene sulfonate analog anion surfactants, Sulfates anion surfactant for use.
Based on same principle, in the following material of the optional usefulness of the cold-producing medium in the foregoing description two kinds or two or more:
Methane Derivatives series material: CFC11 (CCl
3F), CFC12 (CCl
2F
2), HCFC22 (CHClF
2), HCFC21 (CHCl
2F), HCFC31 (CH
2ClF);
Ethane derivative series material: HFC-125 (CF
3CHF
2), HFC-134a (CF
3CH
2F), HFC-143a (CF
3CH
3), HFC-152a (CH
3CHF
2);
The propane series material of deriving: HFC-227ca (CHF
2CF
2CF
3), HFC-227ea (CF
3CHFCF
3), HFC-236ca (CHF
2CF
2CHF
2), HFC-236cb (CF
3CF
2CH
2F), HFC-236ea (CHF
2CHFCF
3), HFC-236fa (CF
3CH
2CF
3), HFC-245ca (CF
3CF
2CH
3), HFC-245cb (CHF
2CF
2CH
2F), HFC-245ea (CHF
2CHFCHF
2), HFC-245eb (CF
3CHFCH
2F), HFC-245fa (CF
3CH
2CH
2F), HFC-254cb (CH
3CF
2CHF
2), HFC-254ea (CH
2FCHFCHF
2), HFC-254eb (CF
3CHFCH
3), HFC-254fa (CHF
2CH
2CHF
2), HFC-254fb (CF
3CH
2CHF
2), HFC-254fb (CF
3CH
2CH
2F);
Hydrocarbon: propane (C
3H
8), normal butane (C
4H
10), iso-butane (C
4H
10), pentamethylene (C
5H
10) cyclopentene (C
5H
10), isopentane (C
5H
12).
Based on same principle, described wire also can be selected the alloy silk of aluminium wire, platinum filament and above-mentioned metal for use except selecting iron wire, copper wire, stainless steel wire for use.
Also crystallization-promoter can be added in the described cold-producing medium or/and assist gas; Crystallization-promoter is selected from the mixture of n-butanol, oxolane, carbon molecular sieve, CNT and above-mentioned crystallization-promoter; Assist gas is selected from the mixture of methane, ethane, carbon dioxide, nitrogen, oxygen and above-mentioned assist gas.
Claims (6)
1. a cold storage device capable of statically and quickly generating refrigerant gas hydrate comprises thermostat (1) and inner container (2); It is characterized in that: the upper and lower end of thermostat (1) is respectively equipped with the import (11) and outlet (12) of cooling medium, and container (2) is soaked in the cooling medium that circulates; The upper and lower end of container (2) is respectively equipped with the outlet (21) and import (22) of cold-producing medium and aqueous solution of anionic surfactant, and aqueous solution of anionic surfactant and cold-producing medium form two-phase up and down in container (2); One wire (3) is arranged in the container (2), and it passes aqueous solution of anionic surfactant and contacts with container (2) wall with the cold-producing medium two-phase interface.
2. regenerator according to claim 1 is characterized in that: described cold-producing medium comprises in the following material two kinds or two or more:
Methane Derivatives series material: CFC11, CFC12, HCFC22, HCFC21, HCFC31;
Ethane derivative series material: HFC-125, HFC-134a, HFC-143a, HFC-152a;
Propane derive series material: HFC-227ca, HFC-227ea, HFC-236ca, HFC-236cb, HFC-236ea, HFC-236fa, HFC-245ca, HFC-245cb, HFC-245ea, HFC-245eb, HFC-245fa, HFC-254cb, HFC-254ea, HFC-254eb, HFC-254fa, HFC-254fb, HFC-254fb;
Hydrocarbon: propane, normal butane, iso-butane, pentamethylene, cyclopentene, isopentane.
3. regenerator according to claim 1 is characterized in that: described anion surfactant is selected from dodecyl analog anion surfactants, Sulfonates anion surfactant, benzene sulfonate analog anion surfactants, Sulfates anion surfactant four analog anion surfactants.
4. regenerator according to claim 1, it is characterized in that: being combined as of described aqueous solution of anionic surfactant and cold-producing medium: mass percent concentration is 3.8% sodium dodecyl benzene sulfonate aqueous solution and R141b liquid refrigerant, perhaps mass percent concentration is 3.8% lauryl sodium sulfate aqueous solution and R141b liquid refrigerant, and perhaps mass percent concentration is 3.8% sodium dodecyl sulfate aqueous solution and R141b liquid refrigerant.
5. regenerator according to claim 1 is characterized in that: described wire is selected from iron wire, copper wire, aluminium wire, platinum filament, stainless steel wire.
6. regenerator according to claim 1 is characterized in that: also add crystallization-promoter or/and assist gas in the described cold-producing medium; Crystallization-promoter is selected from the mixture of n-butanol, oxolane, carbon molecular sieve, CNT and above-mentioned crystallization-promoter; Assist gas is selected from the mixture of methane, ethane, carbon dioxide, nitrogen, oxygen and above-mentioned assist gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100773256A CN100416171C (en) | 2004-12-15 | 2004-12-15 | Cold storage device capable of statically and quickly generating refrigerant gas hydrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100773256A CN100416171C (en) | 2004-12-15 | 2004-12-15 | Cold storage device capable of statically and quickly generating refrigerant gas hydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1789837A CN1789837A (en) | 2006-06-21 |
| CN100416171C true CN100416171C (en) | 2008-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100773256A Expired - Fee Related CN100416171C (en) | 2004-12-15 | 2004-12-15 | Cold storage device capable of statically and quickly generating refrigerant gas hydrate |
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100538221C (en) * | 2007-10-12 | 2009-09-09 | 邹杰 | A kind of dynamic ice cold-storage method and equipment |
| CN115264679A (en) * | 2022-06-29 | 2022-11-01 | 中南大学 | With CO2Seasonal cold accumulation system with hydrate as cold accumulation material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5140824A (en) * | 1991-05-28 | 1992-08-25 | Hunt Steven C | Gas hydrate thermal energy storage system |
| CN2272997Y (en) * | 1996-12-21 | 1998-01-21 | 中国科学院广州能源研究所 | Gas hydrate cold-storage device |
-
2004
- 2004-12-15 CN CNB2004100773256A patent/CN100416171C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5140824A (en) * | 1991-05-28 | 1992-08-25 | Hunt Steven C | Gas hydrate thermal energy storage system |
| CN2272997Y (en) * | 1996-12-21 | 1998-01-21 | 中国科学院广州能源研究所 | Gas hydrate cold-storage device |
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| Publication number | Publication date |
|---|---|
| CN1789837A (en) | 2006-06-21 |
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Granted publication date: 20080903 Termination date: 20211215 |