CN1240805C - Static fast generation process for refrigerant gas hydrate - Google Patents

Static fast generation process for refrigerant gas hydrate Download PDF

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Publication number
CN1240805C
CN1240805C CNB2004100162341A CN200410016234A CN1240805C CN 1240805 C CN1240805 C CN 1240805C CN B2004100162341 A CNB2004100162341 A CN B2004100162341A CN 200410016234 A CN200410016234 A CN 200410016234A CN 1240805 C CN1240805 C CN 1240805C
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China
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refrigerant gas
chf
gas hydrate
energy
wire
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CN1557905A (en
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李金平
郭开华
王如竹
梁德青
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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Abstract

The present invention relates to a static fast generation method for refrigerant gas hydrates, which belongs to the field of energy conservation. In the method, metal filaments penetrate through the two-phase interface between the water solution of an anionic surface active agent, and refrigerant, and are in contact with vessel wall surfaces; the metal filament instantly moves by being appressed to the wall surface so that the refrigerant gas hydrate is quickly crystallized for nucleation at the contact point of the metal filament and the wall surface; thereafter, the refrigerant gas hydrate is quickly generated under the action of a surface active agent; and the entire hydration reaction is performed in static water all the time. The method can be widely used for storing energy, regulating energy requirements for peak-trough balance, and balancing energy system; the method can reduce the power consumption, save the operating cost and realize that the energy is effectively and reasonably utilized. The present invention provides an efficient path, and has great economic and social value.

Description

The static generation method fast of refrigerant gas hydrate
Technical field
The present invention is a kind of gas hydrate generation method, the static generation method fast of particularly a kind of refrigerant gas hydrate.Belong to energy-saving field.
Background technology
In City Building, air-conditioning is one of maximum consumer, and peak season (summer) accounts for the over half of buildings 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 operation condition of general air conditioner cold water unit vaporizer; Refrigerant gas hydrate can directly be contacted generation, decompose with water by refrigeration agent, has exempted heat transfer resistance, improves heat exchange efficiency greatly.
Evenly generating fast of refrigerant hydrate is the key of refrigerant hydrate cold-storage technical applicationization, also is the difficult point of this technology.Usually laboratory using disturbance, interpolation crystal seed or methods such as tensio-active agent or additive realize the quick generation of refrigerant gas hydrate.Yet disturbance also needs the hydrate that forms is separated immediately except that consumes energy, the special design system device of needs, has increased the initial cost and the maintenance cost of equipment; Add crystal seed and then gas hydrate is generated improvement seldom.In the domestic and foreign literature, the research of gas hydrate generation aspect mainly concentrates on Sweet natural gas gas hydrate aspect behind tensio-active agent or the additive to adding, and the refrigerant gas hydrate aspect is then less.Find by literature search, people such as Hiroshi are at " Energy Conversionand Management " (1985, Vol.25, No.2, deliver pp.179186) " Feasibilityof Trichlorofluoromethane (CCl3F; R11) Heptadecahydrate as a HeatStorage Material " (" using the feasibility of Trichloromonofluoromethane ten heptahydrates " as heat storage medium, be published in 1987 the 25th and roll up on the 2nd phase 179-186 page or leaf " energy transforms and management "), this article is mentioned: after adding mass percent and be 0.02 polyoxyethylene nonyl ethylbenzene in the aqueous solution, can make R11 gas hydrate production rate improve four times.In addition, point out in " additive is to the experimental study of gas hydrate process of cool influence " literary composition that people such as Bi Yuehong deliver on " application foundation and engineering science journal " the 11st volume 1 phase 39-45 page or leaf in March, 2003, two kinds of additives of Losantin and benzene sulfonic acid sodium salt have remarkably influenced to R141b gas hydrate process of cool, and the hydrate cool-storage time is shortened.Add-on per-cent is behind 0.0008 the Losantin, 2/3rds when the cold-storage required time shortens to not doping; Amount per-cent is that 0.0003 benzene sulfonic acid sodium salt can make condensate depression be reduced to 1.55 ℃ by not additivated 2.33 ℃.The influence that about tensio-active agent or additive refrigerant gas hydrate is generated in these documents all be have stir or recycle pump turbulent system in take place, have the shortcoming of above-mentioned disturbance aspect equally, hindered their application in practice.In further retrieving, find identical with theme of the present invention or similar bibliographical information as yet.
Summary of the invention
The present invention is directed to the deficiency and the defective that exist in the background technology, a kind of quick generation method of refrigerant gas hydrate is provided, make it be widely used in accumulation of heat and cold-storage, for regulating energy supply and demand, peak load shifting, equilibrium energy system, cut down the consumption of energy, save working cost, realized the efficient and rational utilization of energy, promote and promoted the practicability of refrigerant gas hydrate cold-storage technology.
The present invention is achieved through the following technical solutions, the inventive method is as follows: adopt wire to pass aqueous solution of anionic surfactant and refrigeration agent two-phase interface and contact with the container wall, the moment that wire is pasting wall move make refrigerant gas hydrate at wire with the rapid crystallization nucleation in the contact position of wall, shortened the boot time that generates refrigerant gas hydrate greatly, after this refrigerant gas hydrate generates under the effect of tensio-active agent fast, and whole hydration reaction is carried out in immobilized water always.
Described refrigeration agent select in the following material both 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: HFC125 (CF 3CHF 2), HFC134a (CF 3CH 2F), HFC143a (CF 3CH 3), HFC152a (CH 3CHF 2);
The propane series material of deriving: HFC227ca (CHF 2CF 2CF 3), HFC227ea (CF 3CHFCF 3), HFC236ca (CHF 2CF 2CHF 2), HFC236cb (CF 3CF 2CH 2F), HFC236ea (CHF 2CHFCF 3), HFC236fa (CF 3CH 2CF 3), HFC245ca (CF 3CF 2CH 3), HFC245cb (CHF 2CF 2CH 2F), HFC245ea (CHF 2CHFCHF 2), HFC245eb (CF 3CHFCH 2F), HFC245fa (CF 3CH 2CH 2F), HFC254cb (CH 3CF 2CHF 2), HFC254ea (CH 2FCHFCHF 2), HFC254eb (CF 3CHFCH 3), HFC254fa (CHF 2CH 2CHF 2), HFC254fb (CF 3CH 2CHF 2);
Hydrocarbon polymer: propane, normal butane, Trimethylmethane, pentamethylene, cyclopentenes, iso-pentane.
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 alloyed metal silk, for example: iron wire, copper wire, aluminium wire, platinum filament, Stainless Steel Wire etc.
With above-mentioned two or more refrigerant mixed, perhaps/and change water phase surfactant mixture concentration, or/and at the aqueous solution or/and add other tensio-active agent in the above-mentioned refrigeration agent 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 Sodium dodecylbenzene sulfonate or sodium lauryl sulphate and the liquid refrigerant effect when generating refrigerant gas hydrate is better.
Externally under the continuous action of low-temperature receiver, because the ununiformity and the wire good heat-conducting of temperature distribution in the container, to form " maximum undercooling point " at the point of contact of wire and container wall, wire pasting wall instantaneous sliding failure original equilibrium state, lure the rapid crystallization nucleation of refrigerant gas hydrate into, the emulsifying effect of adding anion surfactant has promoted the phase mutual diffusion of water molecules with refrigerant molecules, impels the static growth fast of refrigerant gas hydrate.
The present invention has kept all advantages of refrigerant gas hydrate cold-storage; Compare with modes such as adding tensio-active agent merely with stirring disturbance, interpolation crystal seed, the static generation method fast of this refrigerant gas hydrate, not only saved the energy, initial cost and working cost have been saved, and behind the adopting said method, regenerator can be made separately, helps the regenerator stdn, and operation will more be seen simply.In a word, this invention will promote and promote practicability to the technology of refrigerant gas hydrate cold-storage.The inventive method can be widely used in energy storage (comprising accumulation of heat and cold-storage), is the supply and demand of adjusting energy, peak load shifting, and the equilibrium energy system cuts down the consumption of energy, and saves working cost, has realized the efficient and rational utilization of energy.
Embodiment
Content in conjunction with the inventive method provides following examples:
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 10.00gR141b liquid are put into 1 ℃ thermostatic bath, 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.
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 ℃ thermostatic bath, 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.
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 ℃ thermostatic bath, 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.

Claims (6)

1, a kind of refrigerant gas hydrate generates method fast, it is characterized in that, adopt wire to pass aqueous solution of anionic surfactant and refrigeration agent two-phase interface and contact with the container wall, wire is pasting the moment of wall and is moving, make refrigerant gas hydrate at wire with the rapid crystallization nucleation in the contact position of wall, after this refrigerant gas hydrate generates under the effect of tensio-active agent fast, and whole hydration reaction is carried out in immobilized water always.
2, refrigerant gas hydrate according to claim 1 generates method fast, it is characterized in that, described refrigeration agent is selected in following two kinds or two or more:
Methane Derivatives series material: CCl 3F, CCl 2F 2, CHClF 2, CHCl 2F, CH 2ClF;
Ethane derivative series material: CF 3CHF 2, CF 3CH 2F, CF 3CH 3, CH 3CHF 2
Propane series material: the CHF that derives 2CF 2CF 3, CF 3CHFCF 3, CHF 2CF 2CHF 2, CF 3CF 2CH 2F, CHF 2CHFCF 3, CF 3CH 2CF 3, CF 3CF 2CH 3, CHF 2CF 2CH 2F, CHF 2CHFCHF 2, CF 3CHFCH 2F, CF 3CH 2CH 2F, CH 3CF 2CHF 2, CH 2FCHFCHF 2, CF 3CHFCH 3, CHF 2CH 2CHF 2, CF 3CH 2CHF 2
Hydrocarbon polymer: propane, normal butane, Trimethylmethane, pentamethylene, cyclopentenes, iso-pentane.
3, refrigerant gas hydrate according to claim 2 generates method fast, it is characterized in that: the anion surfactant mass percent is 0.038 the Sodium dodecylbenzene sulfonate or the aqueous solution of sodium lauryl sulphate.
4, refrigerant gas hydrate according to claim 1 generates method fast, it is characterized in that described anion surfactant is selected from following three analog anion surfactants: Sulfonates anion surfactant, benzene sulfonate analog anion surfactants, Sulfates anion surfactant.
5, refrigerant gas hydrate according to claim 1 generates method fast, it is characterized in that, described wire is various wires or its alloyed metal silk.
6, generate method fast according to claim 1 or 2 or 4 described refrigerant gas hydrates, it is characterized in that, change water phase surfactant mixture concentration, or in the aqueous solution or described refrigeration agent, add other tensio-active agent, or change the static generation fast that number wiry, shape all can realize above-mentioned refrigerant gas hydrate.
CNB2004100162341A 2004-02-12 2004-02-12 Static fast generation process for refrigerant gas hydrate Expired - Fee Related CN1240805C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100387897C (en) * 2005-06-24 2008-05-14 中国石油大学(北京) Hydrate storage tank and hydrate synthesis method employing the same
CN100430124C (en) * 2005-11-25 2008-11-05 中国石油大学(北京) Hydrate production process for gas storage and transportation
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
CN103755073B (en) * 2014-01-24 2015-03-11 广东石油化工学院 Method for treating oil refining alkaline residue

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