CN106367034B - Rapid phase change coolant and preparation method and application thereof - Google Patents

Rapid phase change coolant and preparation method and application thereof Download PDF

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CN106367034B
CN106367034B CN201610810050.5A CN201610810050A CN106367034B CN 106367034 B CN106367034 B CN 106367034B CN 201610810050 A CN201610810050 A CN 201610810050A CN 106367034 B CN106367034 B CN 106367034B
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phase change
hydrate
water
additive
coolant
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CN106367034A (en
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孙志高
朱明贵
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Suzhou University of Science and Technology
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    • 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
    • C09K5/066—Cooling mixtures; De-icing compositions
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    • 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
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    • Y02E60/14—Thermal energy storage

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Abstract

The invention discloses a rapid phase change coolant, which comprises a functional agent, an additive and water; the functional agent is fluorohydrocarbon and/or hydrocarbon; the additive is one or more of an organic phase change material, a surfactant and a cosurfactant; the additive contains an organic phase change material; the cosurfactant is one or more of alcohol, amine and ester. The method comprises the steps of firstly adding an additive containing an organic phase change material to form emulsion or microemulsion, then adding a functional agent, increasing the contact area of the functional agent and water, reducing the crystallization induction time of the hydrate, improving the growth speed of the hydrate, and reducing the energy consumption in the phase change cold storage process of the hydrate; the coolant can be used for obtaining the refrigerant hydrate through rapid phase change, and the problems of long phase change guiding time, difficult growth and large supercooling degree of the hydrate in the prior art are solved.

Description

Rapid phase change coolant and preparation method and application thereof
Technical Field
The invention relates to the technical field of air conditioner cold accumulation, in particular to a rapid phase change technology, and particularly relates to a rapid phase change cold accumulation agent and a preparation method and application thereof.
Background
Phase change forms can generally be divided into four categories: solid-solid phase transition, solid-liquid phase transition, gas-liquid phase transition, and gas-solid phase transition. In the technical field of phase change energy storage, gas-liquid phase change and gas-solid phase change generate gas, the volume change of phase change substances is greatly changed, and although the latent heat of phase change of the two phase change processes is large, the two phase change processes are difficult to adopt practically. Solid-liquid and solid-solid phase transitions are the main modes employed for phase change energy storage.
Cold storage is a common method for time and space inconsistency between adjustment of energy supply and user demand in an air conditioning system, and the air conditioning cold storage mode mainly adopts sensible heat cold storage (such as chilled water) and latent heat cold storage (such as ice cold storage). The water cold accumulation is the cold accumulation by utilizing sensible heat, has simple system and is the main mode of the early air conditioner cold accumulation. The density of water cold accumulation is low, the occupied area of the system is large, and the cold loss is also large. The ice cold accumulation is phase change cold accumulation, the ice cold accumulation capacity with the same volume reaches dozens of times of that of water cold accumulation, and the method is the main mode of the air conditioner cold accumulation at present. The ice cold storage requires that the outlet temperature of refrigerating fluid of the refrigerating unit is below 0 ℃, so the evaporation temperature of the refrigerating unit is low, and the energy consumption is high. Eutectic salt cold accumulation belongs to high-temperature phase change cold accumulation, the cold accumulation temperature is in the temperature range of air conditioner chilled water, a conventional refrigerating unit can be used, and the energy efficiency of the unit is high when cold accumulation is carried out; however, the eutectic salt cold accumulation has the problems of aging of the cold accumulation agent and the like in the use process, and needs to be researched and solved. The refrigerant hydrate cold accumulation belongs to phase change cold accumulation, the cold accumulation density of the refrigerant hydrate is equivalent to that of ice, and the refrigerant hydrate is an ideal air conditioner cold accumulation material and a development direction of air conditioner cold accumulation. Most of the existing refrigerants are not soluble with water, the contact surface of the water and the refrigerants is small, the hydrate phase change guiding time is long and the growth is difficult under common conditions; in addition, the hydrate formation has supercooling degree as the water is frozen, so that the actual phase transition temperature of the hydrate is reduced. Therefore, the key point for promoting the application of the hydrate cold storage technology is to solve the problems of long hydrate formation guide time, large supercooling degree and low growth speed.
Disclosure of Invention
The invention aims to provide a rapid phase change coolant and a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a rapid phase change coolant comprises a functional agent, an additive and water; the functional agent is fluorohydrocarbon and/or hydrocarbon; the additive is one or more of an organic phase change material, a surfactant and a cosurfactant; the additive contains an organic phase change material; the cosurfactant is one or more of alcohol, amine and ester.
The additive used in the invention comprises an organic phase change material or an organic phase change material plus a surfactant plus a cosurfactant, and can effectively promote the formation of a hydrate; the functional agent and the additive are mixed by methods of high-speed stirring or ultrasonic emulsification and the like to form emulsion, so as to obtain the rapid phase change cold storage agent.
In the technical scheme, the hydrofluorocarbon comprises HFC-134a, HFC32, HFC125, HFC143a, HFC-152a, HCFC22, HCFC-141b, HCFC123 and the like; the hydrocarbon comprises propane (C)3H8) N-butane (C)4H10) Isobutane (C)4H10) Cyclopentane (C)5H10) Etc.; the surfactant can be cationic, anionic, zwitterionic and nonionic surfactants, such as sodium oleate, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, Tween surfactant, Span surfactant, lecithin, etc., and is a single surfactant or a mixture of several surfactants when in actual use; the cosurfactant comprises one or more of alcohols, amines and esters, such as ethanol, ethylene glycol, n-butanol, propyl trimethyl ammonium chloride, n-hexylamine, tributyl phosphate and the like; the organic phase change material is a single or mixed organic phase change material with the phase change temperature of 4-15 ℃, the organic phase change material can be one or a mixture of more of cyclopentanoic acid, nonanoic acid, n-decanol, tetradecane, pentadecane, n-decanol and dodecanol, and the like, the phase change temperature of the organic phase change material is above 0 ℃, and the temperature is in the range of an air conditioner.
In the technical scheme, the mass concentration of the added organic phase change material is 0.1-6% and the mass concentration of the surfactant is 0-8% on the basis of the mass of water; the mass concentration of the cosurfactant is 0-3%.
The invention also discloses a preparation method of the rapid phase change coolant, and particularly relates to a rapid phase change coolant obtained by mixing the functional agent, the additive and water by a stirring or ultrasonic emulsification method.
In the technical scheme, the stirring speed is 8000-15000 r/min; the ultrasonic power is 90-110W, and the frequency is 40 kHz; in the dispersion mode of the invention, the functional agent, the additive and the water dispersibility are good, and the contact area of the functional agent and water is increased; and the interface effect between two phases is not destroyed, and the stability of the coolant is maintained.
Preferably, the additive is added into water at first, stirred to form emulsion, then the functional agent is added, and stirring is continued to obtain the rapid phase change cold storage agent; the functional agent is uniformly dispersed in the liquid, so that the contact area of the functional agent and water is increased, the phase change guiding time of the hydrate is reduced, and the growth of the hydrate is promoted.
The quick phase change coolant provided by the invention has short hydrate crystallization induction time and high growth speed of the hydrate, so that the invention further discloses application of the quick phase change coolant in preparation of the coolant.
The invention also discloses a cold storage agent, which is obtained by crystallizing the rapid phase change cold storage agent. Preferably, the crystallization time is 20-120 min.
Compared with the existing preparation technology of the refrigerant hydrate, the invention firstly adds the additive containing the organic phase-change material to form emulsion or microemulsion, and then adds the functional agent to increase the contact area of the functional agent and water, reduce the crystallization induction time of the hydrate, improve the growth speed of the hydrate and reduce the energy consumption of the phase-change cold storage process of the hydrate; the refrigerant hydrate can be obtained by utilizing the cold storage agent of the invention through rapid phase change, the problems of long phase change guiding time, difficult growth and large supercooling degree of the hydrate in the prior art are solved, and a foundation is provided for the industrialization of the hydrate cold storage technology.
Drawings
FIG. 1 is a graph showing the effect of n-decanoic acid and dodecanol on HCFC-141b hydrate formation;
FIG. 2 is a graph showing the effect of additives on HCFC-141b hydrate formation.
Detailed Description
Example one
Firstly, adding a mixture of n-decanoic acid and dodecanol into water, wherein the mass ratio of the n-decanoic acid to the dodecanol is 1:1, the concentration of the mixture of the n-decanoic acid and the dodecanol in the water is 3wt%, and stirring for 20min at the rotating speed of 12000r/min to form emulsion; then dripping HCFC-141b into the emulsion, wherein the mass ratio of HCFC-141b to water is 1:2.62, and stirring for 10min to obtain the rapid phase change cold storage agent; and cooling, namely forming a hydrate after 102min when the temperature of the rapid phase change coolant is reduced to 3 ℃, and rapidly growing the hydrate.
FIG. 1 is a diagram showing the influence of n-decanoic acid and dodecanol on the formation process of HCFC-141b hydrate, and it can be seen that after the temperature of the coolant is reduced to 3 ℃, hydrate can be formed after 102min, and the hydrate grows rapidly; whereas the pure water solution of HCFC-141b has no hydrate formation within 24h under the temperature condition.
Example two
Firstly, adding pentadecane, Tween80 and n-butanol into water, wherein the mass concentrations of the pentadecane, the Tween80 and the n-butanol in the water are respectively 2.5%, 2% and 0.1%, and stirring for 30min at the rotating speed of 10000r/min to form emulsion; then dripping HCFC-141b into the emulsion, wherein the mass ratio of HCFC-141b to water is 1:2.62, and stirring for 10min to obtain the rapid phase change cold storage agent; and cooling, namely forming a hydrate after 41min when the temperature of the rapid phase change coolant is reduced to 1 ℃, and rapidly growing the hydrate.
FIG. 2 is a diagram showing the influence of pentadecane, Tween80 and n-butanol additive on HCFC-141b hydrate formation process, and it can be seen that after the temperature of the coolant is reduced to 1 ℃, hydrate can be formed after 41min, and the hydrate grows rapidly; whereas the pure water solution of HCFC-141b has no hydrate formation within 24h under the temperature condition.
EXAMPLE III
Firstly, adding a mixture of n-decanoic acid and dodecanol and sodium dodecyl sulfate into water, wherein the mass ratio of the n-decanoic acid to the dodecanol is 1:1, the concentration of the mixture of the n-decanoic acid and the dodecanol in the water is 1wt%, and the concentration of the sodium dodecyl sulfate is 0.1wt%, and stirring the mixture for 25min at a rotating speed of 12000r/min to form emulsion; then adding HFC-134a into the emulsion, wherein the mass ratio of the HFC-134a to the water is 1:3, and stirring for 15min to obtain the rapid phase change cold storage agent; cooling, and forming hydrate after 45min when the temperature of the rapid phase change coolant is reduced to 1.3 ℃. And the pure water solution of HFC-134a has no hydrate formation within 24h under the temperature condition.
Example four
Firstly, adding pelargonic acid and sodium dodecyl sulfate into water, wherein the concentration of pelargonic acid in water is 1.5wt%, and the concentration of sodium dodecyl sulfate is 2.5 wt%; stirring for 30min at a rotating speed of 9000r/min to form emulsion; then adding n-butane into the emulsion, wherein the mass ratio of cyclopentane to water is 1:4.3, and stirring for 10min to obtain the rapid phase change cold storage agent; cooling, and forming hydrate after 76min when the temperature of the rapid phase change coolant is reduced to 1 ℃. And under the temperature condition, the pure water solution of cyclopentane has no hydrate formed within 24 h.
EXAMPLE five
Firstly, adding pentadecane, tributyl phosphate and lecithin into water, wherein the concentration of the pentadecane in the water is 1.5wt%, the concentration of the tributyl phosphate is 1wt%, and the concentration of the lecithin is 0.5 wt%; stirring for 30min at the rotating speed of 10000r/min to form emulsion; then adding HCFC134a and cyclopentane into the emulsion, wherein the mass ratio of HCFC134a to cyclopentane is 1:1, and the mass ratio of the total mass of HCFC134a to cyclopentane to water is 1:3.6, and stirring for 15min to obtain the rapid phase change cold storage agent; and cooling, namely forming a hydrate after 83min when the temperature of the rapid phase change coolant is reduced to 2 ℃. And under the temperature condition, the pure water solution of HCFC134a and cyclopentane has no hydrate formed within 24 h.

Claims (5)

1. A quick phase change coolant is characterized in that: the rapid phase change coolant comprises a functional agent, an additive and water; the functional agent is fluorohydrocarbon and/or hydrocarbon; the additive is one or more of an organic phase change material, a surfactant and a cosurfactant; the additive contains an organic phase change material; the cosurfactant is one or more of alcohol, amine and ester; the fluorinated hydrocarbon comprises HFC-134a, HFC32, HFC125, HFC143a, HFC-152a, HCFC22, HCFC-141b or HCFC 123; the hydrocarbon comprises propane, n-butane, isobutane or cyclopentane; the surfactant is a cationic surfactant, an anionic surfactant, a zwitterionic surfactant or a nonionic surfactant; the cosurfactant is one or more of ethanol, ethylene glycol, n-butanol, propyl trimethyl ammonium chloride, n-hexylamine and tributyl phosphate; the organic phase change material is one or more of cyclopentanoic acid, nonanoic acid, n-decanol, tetradecane, pentadecane, n-decanoic acid and dodecanol; based on the mass of water, the mass concentration of the organic phase change material is 0.1-6%, and the mass concentration of the surfactant is 0-8%; the mass concentration of the cosurfactant is 0-3%.
2. The rapid phase change coolant as claimed in claim 1, wherein the preparation method of the rapid phase change coolant comprises the steps of mixing the functional agent, the additive and water by stirring or ultrasonic emulsification to obtain the rapid phase change coolant; the stirring speed is 8000-15000 r/min; the ultrasonic power is 90-110W, and the frequency is 40 kHz.
3. Use of a rapid phase change coolant as claimed in claim 1 in the preparation of a refrigerant.
4. A refrigerant crystallized from the rapid phase change coolant of claim 1.
5. The refrigerant according to claim 4, wherein: the crystallization time is 20-120 min.
CN201610810050.5A 2016-09-08 2016-09-08 Rapid phase change coolant and preparation method and application thereof Expired - Fee Related CN106367034B (en)

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CN107189764A (en) * 2017-06-30 2017-09-22 徐州苏牌高温新材料有限公司 A kind of preparation method of phase-changing energy storage material
CN107325793B (en) * 2017-07-31 2019-11-12 河北麦森钛白粉有限公司 A kind of phase change cold-storage composite material and preparation method
CN110003863A (en) * 2019-03-29 2019-07-12 上海海事大学 A kind of micro- jelly chilled food is fresh-keeping to use phase-change material for cold storage and preparation method

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CN101974312A (en) * 2010-10-12 2011-02-16 苏州科技学院 Cold-accumulating medium for air-conditioning system and preparation method thereof

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CN101974312A (en) * 2010-10-12 2011-02-16 苏州科技学院 Cold-accumulating medium for air-conditioning system and preparation method thereof

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