CN105694822B - A kind of air energy heat pump water heater composite phase-change energy storage material and preparation method - Google Patents
A kind of air energy heat pump water heater composite phase-change energy storage material and preparation method Download PDFInfo
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- CN105694822B CN105694822B CN201610188017.3A CN201610188017A CN105694822B CN 105694822 B CN105694822 B CN 105694822B CN 201610188017 A CN201610188017 A CN 201610188017A CN 105694822 B CN105694822 B CN 105694822B
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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
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H4/00—Fluid heaters characterised by the use of heat pumps
- F24H4/02—Water heaters
Abstract
The invention discloses one kind can be applied to air energy heat pump water heater phase-changing energy storage material and preparation method, belongs to field of material technology.The main component of composite phase-change energy storage material mentioned by the present invention are as follows: the mass percent of polyethylene glycol 2000 is 71~83%, the mass percent of glycerol is 16~28%, the mass percent of antioxidant KY-500 is 0.7%, the mass percent of calcium stearate is 0.3%.The composite phase-change energy storage material has phase transition temperature be 46~48 DEG C, 154~157kJ/Kg of latent heat of phase change, thermal cycle 4000 times after latent heat of phase change lose energy-storage units less than 10%, suitable for air energy heat pump water heater.
Description
Technical field
The invention belongs to field of material technology more particularly to a kind of phase-changing energy storage material, especially a kind of air energy heat pump
Water heater composite phase-change energy storage material.
Background technique
Air energy heat pump water heater can turn air low temperature position thermal energy with few electric energy by inverse Carnot cycle principle
It is melted into high temperature heat, then is reached in water, hot water is heated into.Current air energy heat pump water heater is all made of water as energy storage material
Material, since the thermal capacitance of water is lower so that energy-accumulating water tank there are volumes it is big, energy storage efficiency is not high and heat release is slow the disadvantages of, greatly
Air energy heat pump water heater is affected in the popularization of commercial market, also increases social energy consumption burden.And use phase-change accumulation energy material
Material, then can effectively improve energy utilization rate, energy saving.According to the working principle of air energy heat pump it is found that if using phase transformation
Material carries out energy storage, then material phase transformation temperature at 46~48 DEG C, should can make the thermal transition efficiency of air energy heat pump in this way
It maximizes, while phase-change material should have larger latent heat of phase change and very high thermal stability (it is primary to set thermal cycle in one day, the service life ten
Year, then thermal cycling stability at least should be greater than about 4000 times, and latent heat decaying should be lower than 10%), to make it have practical value.
Chinese invention patent CN103992772A discloses a kind of phase-changing energy storage material and preparation method thereof, the phase-change accumulation energy
Material is formed by palmitinic acid and stearic acid through melting mixing, and composite phase-change energy storage material phase transition temperature is 52~55 DEG C, and phase transformation is latent
Heat is 160~170J/g, after times of thermal cycle 720 times, latent heat of phase change decaying 2.5~3.5%.The problem is that the phase transformation is stored up
Energy material phase transformation temperature is excessively high, while times of thermal cycle is insufficient, is unable to satisfy air energy heat pump water heater needs.
Chinese invention patent ZL2011103999771 discloses a kind of polyethylene glycol (PEG) class phase transformation material, the phase transformation material
Material has the characteristics that enthalpy of phase change is higher, heat stagnation aftereffect is low and adjustable molecular weight section, and the polyethylene glycol of different molecular weight is by certain
After ratio compounds melting mixing mixing, Thermal Parameter can be adjusted, therefore phase transition temperature can be prepared and meet 46
~48 DEG C of phase-changing energy storage material.The problem is that since polyethylene glycol (PEG) class phase transformation material is polymeric blends,
In the case where any anti-aging processing, at thermal cycle 500 times, latent heat of phase change decaying reaches nearly 10%, is unable to satisfy
The needs of air energy heat pump water heater, after commercially available common age resister is added thereto, although its heat can be significantly improved
Stability, but thermal cycle 4000 times are still unable to reach, latent heat of phase change decaying is lower than 10%.
Summary of the invention
In order to overcome the above problem, the object of the present invention is to provide a kind of air energy heat pump water heater composite phase change energy-storings
Material and preparation method, the composite phase-change energy storage material have phase transition temperature be suitable for (46~48 DEG C), latent heat of phase change is big and heat is steady
The features such as qualitative high, while preparation method is simple, repeatability is strong, at low cost.
Technical scheme is as follows: a kind of air energy heat pump water heater composite phase-change energy storage material, mainly by
It is mixed after anhydrous polyethylene glycol 2000, anhydrous glycerol, antioxidant KY-500 and calcium stearate melting.
Preferably, wherein the mass percent of anhydrous polyethylene glycol 2000 is the quality percentage of 71~83%, anhydrous glycerol
Than be 0.7% for the mass percent of 16~28%, antioxidant KY-500, the mass percent of calcium stearate is 0.3%.
Preferably, the phase transition temperature of the air energy heat pump water heater composite phase-change energy storage material is 46~48 DEG C,
Latent heat of phase change is 154~157kJ/Kg, and latent heat of phase change loss is less than 10% after thermal cycle 4000 times.
The present invention also provides a kind of preparation methods of air energy heat pump water heater composite phase-change energy storage material, including with
Lower specific steps:
1) excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly-
Ethylene glycol 2000 saves backup in nitrogen atmosphere；
2) glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol, saves backup in nitrogen atmosphere；
3) be 71~83% according to the mass percent of anhydrous polyethylene glycol 2000, the mass percent of anhydrous glycerol is 16
~28%, the ratio that the mass percent of antioxidant KY-500 is 0.7%, the mass percent of calcium stearate is 0.3%, by four
Person's 55 DEG C of melt blendings in nitrogen atmosphere are uniform, are cooled to room temperature, obtain air energy heat pump water heater composite phase change energy-storing
Material.
Compared with prior art, the beneficial effects of the present invention are: composite phase-change energy storage material provided by the invention, has suitable
Preferably it is applied to the phase transition temperature of air energy heat pump water heater, and latent heat of phase change is big, material thermal stability is good；It is provided by the invention multiple
Phase-changing energy storage material is closed, the utilization efficiency of the energy can be significantly improved compared with water by being applied to air energy heat pump water heater, be dropped
Low amount of residual heat ratio reduces energy-storage units volume；The addition of antioxidant KY-500 and calcium stearate is so that anhydrous polyethylene glycol
The thermal stability of 2000- anhydrous glycerol system obtains amazing raising, reaches thermal cycle 4000 times, and latent heat of phase change decaying is low
In 10% basic demand, and the preparation method of this phase-changing energy storage material is simple, repeatability is high, at low cost.
Specific embodiment
Below with reference to embodiment and comparative example, the present invention is further described.
Embodiment 1
Excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly- second
Glycol 2000；Glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol；Then according to anhydrous polyethylene glycol 2000: anhydrous sweet
Oil: antioxidant KY-500: calcium stearate mass ratio 71:28:0.7:0.3 weighs respective substance；By above-mentioned substance in nitrogen atmosphere
It is added in the beaker of 250mL, 55 DEG C of heating stirrings of constant temperature in electric jacket are cooled to solid at room temperature until completely after melting
Change, obtains the composite phase-change energy storage material of stable homogeneous.
Comparative example 1
According to polyethylene glycol 2000: glycerol: antioxidant KY-500: calcium stearate mass ratio 71:28:0.7:0.3 weighs phase
Answer substance；Above-mentioned substance is added in the beaker of 250mL in nitrogen atmosphere, 55 DEG C of heating stirrings of constant temperature in electric jacket are until complete
After full-fusing, it is cooled to solidification at room temperature, obtains the composite phase-change energy storage material of stable homogeneous.
Embodiment 2
Excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly- second
Glycol 2000；Glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol；Then according to anhydrous polyethylene glycol 2000: anhydrous sweet
Oil: antioxidant KY-500: calcium stearate mass ratio 83:16:0.7:0.3 weighs respective substance；By above-mentioned substance in nitrogen atmosphere
It is added in the beaker of 250mL, 55 DEG C of heating stirrings of constant temperature in electric jacket are cooled to solid at room temperature until completely after melting
Change, obtains the composite phase-change energy storage material of stable homogeneous.
Comparative example 2a
Excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly- second
Glycol 2000；Glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol；Then according to anhydrous polyethylene glycol 2000: anhydrous glycerol
Calcium mass ratio 83:17 weighs respective substance；Above-mentioned substance is added in the beaker of 250mL in nitrogen atmosphere, it is permanent in electric jacket
55 DEG C of heating stirrings of temperature are cooled to solidification at room temperature, obtain the composite phase change energy-storing material of stable homogeneous until completely after melting
Material.
Comparative example 2b
Excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly- second
Glycol 2000；Glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol；Then according to anhydrous polyethylene glycol 2000: anhydrous sweet
Oil: antioxidant KY-500 mass ratio 83:16.3:0.7 weighs respective substance；Above-mentioned substance is added 250mL's in nitrogen atmosphere
In beaker, 55 DEG C of heating stirrings of constant temperature in electric jacket are cooled to solidification until completely after melting at room temperature, obtain uniform steady
Fixed composite phase-change energy storage material.
Comparative example 2c
Excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly- second
Glycol 2000；Glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol；Then according to anhydrous polyethylene glycol 2000: anhydrous sweet
Oil: calcium stearate mass ratio 83:16.7:0.3 weighs respective substance；Above-mentioned substance is added to the beaker of 250mL in nitrogen atmosphere
In, 55 DEG C of heating stirrings of constant temperature in electric jacket are cooled to solidification at room temperature, obtain stable homogeneous until completely after melting
Composite phase-change energy storage material.
Differential scanning calorimeter is taken to measure each embodiment and comparative example by the phase before and after 4000 thermal cycles
Temperature and latent heat of phase change, related data are shown in Table 1.
The phase transition temperature and latent heat of phase change data of 1 embodiment of table and comparative example
It, can be to the thermal stability of product it can be seen that containing water in synthetic in comparative example 1 from 1 data of table
It causes to be substantially reduced；Comparative example 2a is in the case where raw material removes water, material when not adding stabilizer KY-500 and calcium stearate
The thermal stability of material is reduced by up to, and reaches 28.40%；Comparative example 2b or comparative example 2c only adds stabilizer respectively
KY-500 or when calcium stearate cannot still reach requirement although can increase the thermal stability of product, and stabilizer
Effect is obvious when both KY-500 and calcium stearate are added simultaneously, simple superposition of the Effect value beyond the two, although mechanism is still not
It is clear, but should can illustrate there is positive synergistic effect on increasing product thermal stability between the two, it can obviously increase
The thermal stability of product.
Claims (4)
1. a kind of air energy heat pump water heater composite phase-change energy storage material, which is characterized in that the material is mainly by anhydrous poly- second
It is mixed after glycol 2000, anhydrous glycerol, antioxidant KY-500 and calcium stearate melting.
2. air energy heat pump water heater composite phase-change energy storage material according to claim 1, which is characterized in that wherein without
The mass percent of water polyethylene glycol 2000 is 71~83%, the mass percent of anhydrous glycerol is 16~28%, antioxidant KY-
500 mass percent is 0.7%, the mass percent of calcium stearate is 0.3%.
3. it is a kind of according to claim 1~2 in any air energy heat pump water heater composite phase-change energy storage material preparation method,
It is characterised in that it includes step in detail below:
1) excessive anhydrous calcium chloride is added into polyethylene glycol 2000, stirs, 250 DEG C of distillations obtain anhydrous poly- second two
Alcohol 2000 saves backup in nitrogen atmosphere；
2) glycerol distills water removal at 180 DEG C, obtains anhydrous glycerol, saves backup in nitrogen atmosphere；
3) be 71~83% according to the mass percent of anhydrous polyethylene glycol 2000, the mass percent of anhydrous glycerol be 16~
28%, the ratio that the mass percent of antioxidant KY-500 is 0.7%, the mass percent of calcium stearate is 0.3%, by four
55 DEG C of melt blendings are uniform in nitrogen atmosphere, are cooled to room temperature, obtain composite phase-change energy storage material.
4. the preparation method of air energy heat pump water heater composite phase-change energy storage material obtains compound according to claim 3
The phase transition temperature of phase-changing energy storage material is 46~48 DEG C, and latent heat of phase change is 154~157kJ/Kg, and phase transformation is latent after thermal cycle 4000 times
Heat loss is less than 10%.
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| US6063312A (en) * | 1993-02-05 | 2000-05-16 | Southwest Research Institute | Method of increasing the relative heat capacity of a pumpable dielectric heat transfer carrier liquid |
| CN101058719A (en) * | 2006-11-22 | 2007-10-24 | 电子科技大学 | Composite phase-change material and preparation method thereof |
| CN101486894A (en) * | 2009-02-06 | 2009-07-22 | 深圳职业技术学院 | Shape-stabilized phase change material and preparation thereof |
| CN101613592A (en) * | 2009-07-21 | 2009-12-30 | 刘磊 | Phase-change thermal-storage material and production method thereof |
| CN102516949A (en) * | 2011-12-06 | 2012-06-27 | 辽宁科隆精细化工股份有限公司 | Compound polyethylene glycol phase change material |
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Inventor after: Wang Jiping Inventor after: Yu Haiyun Inventor after: Ge Fei Inventor after: Zhang Tianchi Inventor after: Zheng Cuihong Inventor after: Mao Aiqin Inventor after: Lin Na Inventor after: Yan Yong Inventor before: Yu Haiyun Inventor before: Wang Jiping Inventor before: Ge Fei Inventor before: Zhang Tianchi Inventor before: Zheng Cuihong Inventor before: Mao Aiqin Inventor before: Lin Na Inventor before: Yan Yong |
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Denomination of invention: A composite phase change energy storage material for air energy heat pump water heater and its preparation method Effective date of registration: 20201029 Granted publication date: 20190122 Pledgee: Anhui Commercial Bank Co.,Ltd. MAANSHAN Taibai Avenue sub branch Pledgor: MAANSHAN NBWAVE HEAT ENERGY SCIENCE Co.,Ltd. Registration number: Y2020980007340 |