CN1789837A - 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 PDF

Info

Publication number
CN1789837A
CN1789837A CNA2004100773256A CN200410077325A CN1789837A CN 1789837 A CN1789837 A CN 1789837A CN A2004100773256 A CNA2004100773256 A CN A2004100773256A CN 200410077325 A CN200410077325 A CN 200410077325A CN 1789837 A CN1789837 A CN 1789837A
Authority
CN
China
Prior art keywords
hfc
chf
container
cold
aqueous solution
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.)
Granted
Application number
CNA2004100773256A
Other languages
Chinese (zh)
Other versions
CN100416171C (en
Inventor
梁德青
樊栓狮
李金平
周薇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Institute of Energy Conversion of CAS
Original Assignee
Guangzhou Institute of Energy Conversion of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangzhou Institute of Energy Conversion of CAS filed Critical Guangzhou Institute of Energy Conversion of CAS
Priority to CNB2004100773256A priority Critical patent/CN100416171C/en
Publication of CN1789837A publication Critical patent/CN1789837A/en
Application granted granted Critical
Publication of CN100416171C publication Critical patent/CN100416171C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This invention relates to one cool agent water compound static rapid generation cool storage device, which comprises the following parts: Constant tank and inside container with cool medium entrance and exit located on top and down ends; the container is dipped to the cool medium for recycling; the container top and down ends are located with cool agent and negative ion surface active agent solvent exit hole and entrance hole; the negative ion surface active water solve and cool agent in the container form upper and down phrases; the container is located with one metal wires through the negative ion surface active agent water solvent and cool agent to touch the container sidewall.

Description

Cold storage device capable of statically and quickly generating refrigerant gas hydrate
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
In City Building, 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 (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).
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, mass percent is that the aqueous solution of 0.038 neopelex or lauryl sodium sulfate or dodecyl sodium sulfate and the R141b liquid refrigerant effect when generating refrigerant gas hydrate is better.
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 is that 0.038 sodium dodecyl benzene sulfonate aqueous solution and φ 20 * L200 test tube of 10.00g R141b 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 Stainless steel wire 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 is that 0.038 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 is that 0.038 lauryl sodium sulfate aqueous solution and φ 20 * L200 test tube of 10.00g R141b 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 is that 0.038 sodium dodecyl sulfate aqueous solution and φ 20 * L200 test tube of 10.00g R141b 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 kind of 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 (CCl 3F), CFC12 (CCl 2 F2), 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).
3, regenerator according to claim 1 is characterized in that: described anion surfactant is selected from four analog anion surfactants such as dodecyl analog anion surfactants, Sulfonates anion surfactant, benzene sulfonate analog anion surfactants, Sulfates anion surfactant.
4, regenerator according to claim 1 is characterized in that: the mass percent that is combined as of described aqueous solution of anionic surfactant and cold-producing medium is 0.038 the neopelex or the aqueous solution and the R141b liquid refrigerant of lauryl sodium sulfate or sodium dodecyl sulfate aqueous solution.
5, regenerator according to claim 1 is characterized in that: described wire is selected from the alloy silk of iron wire, copper wire, aluminium wire, platinum filament, stainless steel wire and above-mentioned metal.
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.
CNB2004100773256A 2004-12-15 2004-12-15 Cold storage device capable of statically and quickly generating refrigerant gas hydrate Expired - Fee Related CN100416171C (en)

Priority Applications (1)

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

Applications Claiming Priority (1)

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 true CN1789837A (en) 2006-06-21
CN100416171C CN100416171C (en) 2008-09-03

Family

ID=36787871

Family Applications (1)

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

Country Status (1)

Country Link
CN (1) CN100416171C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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

Cited By (2)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN100416171C (en) 2008-09-03

Similar Documents

Publication Publication Date Title
Cheng et al. Review and prospects of hydrate cold storage technology
Wang et al. Clathrate hydrate technology for cold storage in air conditioning systems
Fang et al. Preparation and thermal performance of polystyrene/n-tetradecane composite nanoencapsulated cold energy storage phase change materials
Rathod et al. Thermal stability of phase change materials used in latent heat energy storage systems: A review
Zhang et al. Performance analysis of hydrate-based refrigeration system
Shi et al. A comparative study of different methods for the generation of tetra-n-butyl ammonium bromide clathrate hydrate slurry in a cold storage air-conditioning system
CN102533224B (en) Low temperature phase change coolant
CN101974312B (en) Cold-accumulating medium for air-conditioning system and preparation method thereof
US5140824A (en) Gas hydrate thermal energy storage system
Liang et al. Preparation and thermal properties of eutectic hydrate salt phase change thermal energy storage material
CN113004870A (en) Refrigerant mixture, mixed working medium and compressor
US20160137897A1 (en) Mixed refrigerant
CN100457850C (en) CFC-12 substituting environmental-protective cryogen
Wang et al. Research on the application of gas hydrate in cool storage air conditioning
Li et al. Enhancement of hydrate formation with amino acids as promoters
Wang et al. Heat transfer, energy conversion, and efficiency during cold discharge of a novel tetrabutylammonium bromide hydrate cold storage system
CN1789837A (en) Cold storage device capable of statically and quickly generating refrigerant gas hydrate
KR100218063B1 (en) Novel clathrate forming medium and its use in thermal energy storage systems and processes for thermal storage and transfer
Bukhalkin et al. Phase change materials in energy: current state of research and potential applications
Liu et al. Effect of additives on the cyclic thermal stability and thermal properties of sodium acetate trihydrate as a phase change material: An experimental study
CN205311285U (en) On -vehicle cold energy utilization air conditioner condenser cooling device of LNG passenger train
Hoseinynezhad et al. The effect of sodium halide salts on the kinetics of tetrahydrofuran hydrate formation by using a differential scanning calorimetry method
CN1240805C (en) Static fast generation process for refrigerant gas hydrate
CN201229082Y (en) Supermarket refrigeration system with natural working substance
CN1944566A (en) Phase change cold storage agent for air conditioner and its producing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080903

Termination date: 20211215