CN1570015A - Na2HPO4.12H2O heat storage material and its making method - Google Patents
Na2HPO4.12H2O heat storage material and its making method Download PDFInfo
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- CN1570015A CN1570015A CN 03133734 CN03133734A CN1570015A CN 1570015 A CN1570015 A CN 1570015A CN 03133734 CN03133734 CN 03133734 CN 03133734 A CN03133734 A CN 03133734A CN 1570015 A CN1570015 A CN 1570015A
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- hpo
- heat accumulating
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Abstract
The invention discloses a low-temperature phase-change material, in particular a Na2HPO4*12H2O heat storage material and method for preparing same, wherein the heat storage material is the jelly prepared by mixing polysaccharide macromolecular grafted acroleic acid copolymer with hydrous salt.
Description
Technical field
The present invention relates to low-temperature phase-change material, specifically a kind of Na
2HPO
412H
2O heat accumulating and preparation method thereof.
Background technology
Na
2HPO
412H
2O is a unit mass heat accumulation value maximum in the low-temperature phase-change material (0~120 ℃), but it belongs to discordant and melt, and phenomenon of phase separation is serious, pure Na
2HPO
412H
2O is after through four thermal cycle experiments, and fusion enthalpy promptly decays to 20~30J/g from 279.6J/g, and loses use value.For a change this situation, existing literature report (U.S. Pat 6,152,212) is at Na
2HPO
412H
2Use crosslinked polyacrylic polymer to its modification in the O system, this base polymer comprises sodium polyacrylate, polyacrylamide or their multipolymer; The phosphatic manner of formulation of main raw material was when heat accumulating was synthetic: anhydrous Na
2HPO
4Be dissolved in the water of metering; The hold back agent that is separated adopts original position synthetic method, is applicable to the container containing that can is complex-shaped; For further improving Na
2HPO
412H
2The phenomenon of phase separation of O, add simultaneously when synthetic less water (for crystal water 1/10~1/4).The system of document after for modification is in thermal cycle experiment, and the changing conditions of fusion enthalpy is narration not, and perhaps the fusion enthalpy of only mentioning when repeatedly melting is constant, but does not provide concrete data; Its thermal circulation performance is difficult to determine.Experiment shows that this method reliability is relatively poor, and nature difference was big between the synthetic material was criticized and criticized, and the bad situation of modified effect usually occurred, and the heat storage capacity of material descends very fast in the thermal cycling test.
Summary of the invention
The object of the present invention is to provide the stable Na of a kind of thermal circulation performance
2HPO
412H
2The O heat accumulating.
Another object of the present invention is to provide the Na of a kind of good reproducibility, good reliability
2HPO
412H
2O heat accumulating preparation method.
For achieving the above object, the technical solution used in the present invention is: heat accumulating is by macromolecular grafted acrylic copolymer of polyose and salt hydrate blended gelling material; In melted state is the hydrogel of first valve state, Na when solid-state
2HPO
412H
2There are (size is about below 200 microns) in O with the dispersive molecule.
The weight content of the macromolecular grafted polyacrylic polymer of polyose is generally 3~10% in the gelling material, water and Na
2HPO
4Mol ratio be generally 1: 15~20.
The preparation method of salt hydrate heat accumulating is with Na
2HPO
412H
2O adds in the deionized water water and Na as main raw material
2HPO
4Mol ratio be 15~20: 1; Original position synthetic (be about to reaction monomers and be dissolved in the phosphate solution that has melted, obtain final product by the initiation reaction afterwards) hold back agent that is separated in reaction system, the weight content of the hold back agent that is separated is 3~10%; The original position building-up process is natural or the natural polysaccharide family macromolecule class material of modification and polyacrylic synthon and linking agent are sneaked in the salt hydrate of thawing, free radical polymerization under 47~53 ℃, protection of inert gas; The jel product insulation got product more than 2 hours after solidifying; In the natural polysaccharide family macromolecule class material of wherein natural or modification and monomer, linking agent, the initiator in oxygenant and the initiator part by weight of reductive agent be: 0.4-0.3: 2.7: 0.05-0.09: 0.05-0.11: 0.05-0.11.
The described hold back agent that is separated is crosslinked natural or through the macromolecular grafted polyacrylic polymer of the polyose of modification; Wherein, linking agent is the organism that contains bifunctional, as, N, N '-methylene-bisacrylamide, N, N '-methylene-bis Methacrylamide etc.These polyose polymers natural or modification comprise starch, sodium alginate, carboxymethyl cellulose, chitosan etc.The synthon of polyacrylic polymer is unsaturated carboxylic acid and salt thereof, as sodium acrylate, acrylamide, sodium methacrylate etc.
Described salt hydrate as main raw material also can be Na
2SO
410H
2O, Na
2S
2O
35H
2O, NaAc5H
2O or CaCl
26H
2O.
The present invention has following advantage:
1. thermal circulation performance is stable.The present invention has developed and has effectively prevented salt hydrate Na
2HPO
412H
2The method that the O phase-change heat-storage material is separated, can improve the problem of the reduction of the thawing enthalpy that salt hydrate causes owing to being separated in heating-refrigeration cycle, the new hold back agent that is separated is the polyelectrolyte with thickening power, good salt tolerance, making heat accumulating simultaneously is tiny crystallization when solid-state, prevented fusion enthalpy reduction in use, the hold back agent that promptly is separated has the effect (hold back agent that promptly is separated plays the effect of thickening material and crystal formation change agent simultaneously) that crystal formation changes agent; The synthetic Na of institute
2HPO
412H
2The phenomenon that is separated of O heat accumulating is greatly improved, and through 17 heating-refrigeration cycle examinations, fusion enthalpy is significantly decay (referring to accompanying drawing 1) not.
2. the good reliability of method.The synthetic material, batch with batch between nature difference little, heat storage capacity keeps stablizing in thermal cycling repeatedly; For further improving Na
2HPO
412H
2The phenomenon of phase separation of O, synthetic method also are included in and add a spot of water in the salt hydrate, and the extra water that adds is Na
2HPO
412H
2About 1/3~1/4 of O hydrated salt crystal water.
3. it is convenient to use.Invent the needs that employed synthetic method is adapted to engineering, because reaction mixture is a flow state in for some time of beginning, at this moment be easy to it successfully is filled in the container, reaction process finally can be finished in container containing; This method especially is adapted to the complex-shaped container containing of can, as: hosepipe, irregularly shaped container etc. satisfy the requirement of practicability.
Description of drawings
Fig. 1 is Na
2HPO
412H
2O heat accumulating thermal circulation performance test pattern; Among the figure: times of thermal cycle is 1 o'clock, and fusion enthalpy is 175.0J/g; Times of thermal cycle is 17 o'clock, and fusion enthalpy is 176.3J/g.
Embodiment
The concrete preparation process of salt hydrate heat accumulating is as follows:
135.0 gram Na
2HPO
412H
2Add 15.00 gram deionized waters among the O, 0.85 gram starch melts 50 ℃ of stirring heating, be incubated 1 hour, the sodium acrylate that adds 25.0 grams 20% (w/w) then, 0.17 gram N, N '-methylene-bisacrylamide, feed nitrogen protection, to N, N '-methylene-bisacrylamide all dissolves, and adds 0.10 gram Potassium Persulphate again, 6.7 milliliter contains 0.10 gram sodium sulfite aqueous solution, solution becomes gelling material after 2 minutes; After 3 hours, place it solidified by room temperature in 50 insulation for jel product.Get 3.0~5.0 milligrams of the heat accumulatings that prepare, on DSC, carry out the thermal circulation performance evaluation, the results are shown in accompanying drawing 1.
The usage ratio of the different embodiment building-up process of table 1. raw material:
Experiment numbers
Raw material % (w/w)
1
*???????2
*????????3
*?????4
*?????5
*
Sodium acrylate 2.7 2.7 2.7 2.7 2.7
Starch 0.4 0.3 0.4 0.4 0.4
MBA?????????????????0.09??????0.09???????0.05?????0.09????0.09
Potassium Persulphate 0.05 0.05 0.05 0.11 0.05
Na
2SO
3???????????0.05??????0.05???????0.05?????0.11????0.05
Mol ratio/H
2O:
18????????18?????????18???????18??????18
Na
2HPO
4
Temperature of reaction/℃ 53 53 53 53 47
Wherein: sodium acrylate is the per-cent that pure acrylic acid sodium accounts for the raw material total mass in the raw material; MBA is N, N '-methylene-bisacrylamide; Remove sodium acrylate, starch, MBA, Potassium Persulphate, Na
2SO
3Outside, remaining composition is H
2O and Na
2HPO
4
Table 2. is the consumption preferred proportion of building-up process raw material of the present invention
Polyreaction raw material/% (w/w) | Temperature/℃ | Starch |
Sodium acrylate MBA Potassium Persulphate Na 2SO 3 | ||
2.7????????0.05-0.09??0.05-0.11??0.05-0.11????47-53??????0.4-0.3 |
Comparative example
US 6,152, Na in 212
2HPO
412H
2The synthetic method of O heat accumulating is: the sodium acrylate (pH=7.0) of 7.50 grams 20% (w/w), and 24.00 gram water, 15.84 gram disodium hydrogen phosphate,anhydrous are heated in 50 ℃ of water-baths and obtain clear soln.In this solution, dissolve in 0.025 gram N, N '-methylene-bisacrylamide, 0.03 gram Potassium Persulphate adds the 2.01 gram solution that water was made into that are dissolved with 0.03 gram S-WAT again.Above-mentioned mixed solution is transferred to rapidly in 25mm * 300mm's (end sealing) polyethylene bag, obtains there is not mobile aqueous gel after 2 minutes.The gel insulation is spent the night for 40 ℃, is cooled to 15 ℃ then.
Claims (5)
1. Na
2HPO
412H
2The O heat accumulating is characterized in that: by macromolecular grafted polyacrylic polymer of polyose and salt hydrate blended gelling material; In melted state is the hydrogel of first valve state, Na when solid-state
2HPO
412H
2O exists with the dispersive molecule.
2. according to the described heat accumulating of claim 1, it is characterized in that: the weight content of the macromolecular grafted acrylic copolymer of polyose is 3~10% in the gelling material, water and Na
2HPO
4Mol ratio be 15~20: 1.
3. the preparation method of the described heat accumulating of claim 1 is characterized in that:
With Na
2HPO
412H
2O adds in the deionized water water and Na as main raw material
2HPO
4Mol ratio be 15~20: 1; The synthetic hold back agent that is separated of original position in reaction system, the weight content of the hold back agent that is separated is 3~10%; The original position building-up process is natural or the natural polysaccharide family macromolecule class material of modification and acrylic acid or the like synthon and linking agent are sneaked in the salt hydrate of thawing, free radical polymerization under 47~53 ℃, protection of inert gas; The jel product insulation got product more than 2 hours after solidifying; In the natural polysaccharide family macromolecule class material of wherein natural or modification and monomer, linking agent, the initiator in oxygenant and the initiator part by weight of reductive agent be: 0.4-0.3: 2.7: 0.05-0.09: 0.05-0.11: 0.05-0.11.
4. according to the preparation method of the described heat accumulating of claim 3, it is characterized in that: described linking agent is N, N '-methylene-bisacrylamide or N, N '-methylene-bis Methacrylamide; Polyose polymer natural or modification is starch, sodium alginate, carboxymethyl cellulose or chitosan; The synthon of polyacrylic polymer is unsaturated carboxylic acid vinylformic acid and salt thereof.
5. according to the preparation method of the described heat accumulating of claim 3, it is characterized in that: described salt hydrate Na as main raw material
2SO
410H
2O, Na
2S
2O
35H
2O, NaAc5H
2O or CaCl
26H
2O.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516947A (en) * | 2011-12-02 | 2012-06-27 | 江南大学 | Degradable gel cool storage agent and preparation method thereof |
CN105601819A (en) * | 2016-01-29 | 2016-05-25 | 深圳职业技术学院 | Low-temperature gel-state phase-changing cold storage agent and preparation method thereof |
CN106675527A (en) * | 2017-01-05 | 2017-05-17 | 江南大学 | Nanocellulose composite hydrogel based phase change material as well as preparation method and application thereof |
CN112574716A (en) * | 2019-09-29 | 2021-03-30 | 长沙理工大学 | Composite phase change regulator and preparation method and application of composite phase change heat storage material thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106433568A (en) * | 2016-11-25 | 2017-02-22 | 苏州安特实业有限公司 | Leak-proof gel low-temperature phase change material and preparation method thereof |
-
2003
- 2003-07-16 CN CN 03133734 patent/CN1255501C/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516947A (en) * | 2011-12-02 | 2012-06-27 | 江南大学 | Degradable gel cool storage agent and preparation method thereof |
CN102516947B (en) * | 2011-12-02 | 2014-12-31 | 江南大学 | Degradable gel cool storage agent and preparation method thereof |
CN105601819A (en) * | 2016-01-29 | 2016-05-25 | 深圳职业技术学院 | Low-temperature gel-state phase-changing cold storage agent and preparation method thereof |
CN106675527A (en) * | 2017-01-05 | 2017-05-17 | 江南大学 | Nanocellulose composite hydrogel based phase change material as well as preparation method and application thereof |
CN106675527B (en) * | 2017-01-05 | 2019-08-27 | 江南大学 | A kind of nano-cellulose composite hydrogel based phase-change material and its preparation method and application |
CN112574716A (en) * | 2019-09-29 | 2021-03-30 | 长沙理工大学 | Composite phase change regulator and preparation method and application of composite phase change heat storage material thereof |
CN112574716B (en) * | 2019-09-29 | 2022-02-25 | 长沙理工大学 | Composite phase change regulator and preparation method and application of composite phase change heat storage material thereof |
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Publication number | Publication date |
---|---|
CN1255501C (en) | 2006-05-10 |
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