CN1635028A - Process for preparing organic montmorillonite / mineral wax composite energy-storage material - Google Patents
Process for preparing organic montmorillonite / mineral wax composite energy-storage material Download PDFInfo
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- CN1635028A CN1635028A CN 200410101553 CN200410101553A CN1635028A CN 1635028 A CN1635028 A CN 1635028A CN 200410101553 CN200410101553 CN 200410101553 CN 200410101553 A CN200410101553 A CN 200410101553A CN 1635028 A CN1635028 A CN 1635028A
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Abstract
The invention provides a process for preparing organic montmorillonite / mineral wax composite energy-storage material, which consists of, preparing alcoholic solution with 15-25% of mass concentration from silicane coupling agent 0.04-0.06 mass times of organic montmorillonite, at room temperature, treating organic montmorillonite 20-30 minutes with the solution in sealed container, stirring and dispersing the treated organic montmorillonite in aqueous solution of 20-25% of ethanol, elevating the temperature to 60-80 deg. C, charging molten paraffin wax with a fusion point lower than 60 deg. C 1.5-2 times of the mass of organic montmorillonite, stirring 4-6 hrs and filtering, washing with 30-60 deg. C, 20-40% of ethanol aqueous solution till the emerge of paraffinum liquidum droplets, drying the washed product at 90-120 deg C to constant weight.
Description
Technical field
The present invention relates to a kind of surface and edge, prepare the preparation method of organo montmorillonite/paraffin composite energy-storage material, belong to the preparing technical field and the Application Areas of energy storage material by silane coupling agent modification organo montmorillonite.
Background technology
Phase-changing energy storage material is development in recent years environmental protection and energy saving technology rapidly, is widely used in Heating,Ventilating and Air Conditioning (HVAC) building etc., and is significant.Solid-solid phase transition material remains fixed profile in storing thermal process, and the solid-liquid phase change material is followed the transformation of mushy stage storing thermal process, thereby special sealed in unit must be arranged, but because available solid-solid phase transition material kind is few, price is high, therefore, caused inconvenience for the use of solid-liquid phase change material, use more abundant, the cheap solid-liquid phase change material of originating that is still at present although store the generation of mobile liquid state in the thermal process.Commonly used have mineral-type (hydrated inorganic salt, melting salt etc.) and an organic class (alkane, resin acid, ester, superpolymer etc.); Inorganic materials has high thermal conductivity, but thermal characteristics is unstable and certain corrodibility arranged; Organic materials has good thermostability, but thermal conductivity is low.Therefore, there is the investigator to carry out preparation and has the fixedly test of inorganic/organic composite phase-change material of outward appearance, attempt preparing a kind of novel setting phase change energy storage material inorganic, the organic materials superiority that integrates.There are many investigators to utilize graft process to prepare the matrix material of layered silicate intercalation organic phase-change thing.
99117018.0), Process for preparing organic phase change matter/bentonite nanometer composite phase change heat storage material (number of patent application: 01114801.2) in following two patent applications: the preparation method of organic/inorganic nano composite phase-change energy storage material (number of patent application:, related to a kind of method for preparing inorganic/organic composite energy-storage material with graft process, and applied in the material of construction.Its preparation method is: elder generation carries out organically-modified to inorganic soil with the organic amine positively charged ion, stirs in the water high speed with organic phase change material (as alkane, resin acid etc.) and carries out intercalation.But this method is complex process not only, and only carried out interlayer modified to inorganic soil, its surface and edge then there is not special modification, thereby its surface polarity does not significantly reduce, can not efficiently increase the consistency of inorganic soil and organic materials, the matrix material that makes is not only apparent undesirable, and latent heat of phase change is also because of being subjected to the restriction of intercalation amount big inadequately.In addition, the organic phase change material in the matrix material of above method preparation is pure compound, as n-hexadecane hydrocarbon, Octadecane hydrocarbon, n-butyl stearate, erucic acid, capric acid and their mixture, costs an arm and a leg.Paraffin is the mixture of multiple alkane, chemical property, thermal characteristics are all stable, wide material sources, cheap, but because of the purer alkanes of its heat accumulation value low, in the preparation intercalation composite material because of it with the inorganic soil consistency is poor, the intercalation amount causes the heat accumulation value of the matrix material that can prepare to reduce in a large number for a short time, it is widely-used thereby limited.
Purpose of the present invention be exactly for costing an arm and a leg of solving that above-mentioned matrix material exists, complex process, the heat accumulation value is not high and store the apparent unfavorable problem of material in the thermal process, adopting the paraffin of low price, wide material sources is organic phase change material, with the organo montmorillonite that has formed scale production and sale in the market is intercalation material, research invention a kind of organo montmorillonite/paraffin composite phase change preparation methods, preparation technology simplifies, the matrix material of preparation has the high heat storage value, good heat transfer, and in storing thermal process, have good apparent.
Summary of the invention
The method of organo montmorillonite/paraffin composite energy-storage material that the present invention proposes comprises following each step:
The first step, with quality is that to be mixed with mass concentration be 15～25% ethanolic soln for the silane coupling agent of 0.04～0.06 times of organo montmorillonite, at room temperature, be that the organo montmorillonite of 2.1～3.8nm handle 20～30 minute by spray method to interlamellar spacing with above-mentioned solution;
Wherein used silane coupling agent general formula is:
R:C
nH
2n+1, C
nH
2n-1, n=2～16, promptly R is a carbon number in 2～16 alkyl, mono alkenyl;
Y:OC
nH
2n+2, n=1～2, promptly Y is methoxyl group, oxyethyl group;
Second step in closed container, was dispersed with stirring in 20～25% the aqueous ethanolic solution with the organo montmorillonite after the above-mentioned processing in mass concentration, and the consumption of ethanolic soln is 10～15 times of organo montmorillonite quality; After being warming up to 60～80 ℃, the fusing point that adds quality and be 1.5～2 times of organo montmorillonites is less than 60 ℃ melt paraffin, continue to stir suction filtration after 4～6 hours, being 20～40% aqueous ethanolic solution washing with 30～60 ℃, mass percent concentration does not ooze and shows to there being paraffin oil;
In the 3rd step, the product after the washing is dried to constant weight at 90～120 ℃, promptly obtains the composite energy-storage material of the present invention's preparation.
Mechanism of the present invention is as follows: organo montmorillonite is by to natural nano imvite (interlamellar spacing is about 1 nanometer), the nano grade inorganic material that makes after organically-modified, its interlayer has not only reduced interlayer polarity because of embedding organic modifiers, and enlarged interlamellar spacing, make that molecular volume is big relatively, polar phase can insert therebetween little organism, thereby prepare nano inorganic-organic composite material.All kinds of organo montmorillonites that occurred scale production and sale in the market are mainly used in preparation nanometer superpolymer, as plastics, resin, rubber etc.But interlayer modified its surface of organo montmorillonite and the edge of this only process still shows as high polar inorganic nature, hinders small organic molecule near organo montmorillonite, reduced the consistency of the two, can not reach high intercalation amount, and packaging effect is also undesirable.
Silane coupling agent is the material that contains two kinds of different chemical character functional groups in the molecule simultaneously, a part of functional group in their molecules can with reactive organic molecule, another part functional group can with the active group on inorganics surface-OH reaction, form firm bonding.Therefore silane coupling agent is usually used in the performance of reinforced composite.By experiment, we find under certain condition, some silane coupling agent can with some inorganic group through surface of the inorganic soil after organically-modified and edge, as-formation mortise such as OH, form organo-functional group unimolecular layer membrane outwardly on its surface and edge, thereby greatly reduce its surface polarity.The inorganic soil of this process secondary modification modification and organism can be good at compatible, and can form mortise, are difficult for resolving.
By experiment, we find that organo montmorillonite is after the secondary treatment of process silane coupling agent, its surface polarity greatly reduces, be greatly improved with the consistency of small molecules paraffin, in certain density ethanolic soln, can realize a large amount of intercalations, and in conjunction with firmly, be difficult for resolving, thereby can also keep good powder outward appearance more than the melting temperature being higher than it.
Meaning of the present invention is: (1) is owing to carried out secondary modification with silane coupling agent to the surface and the edge of organo montmorillonite, so greatly improved itself and organic consistency, not only can significantly improve the amount that to insert the organic phase-change thing, and in storing thermal process, the organic phase-change thing is difficult for resolving, thereby can keep good dried powder outward appearance, can directly contact with hot-fluid carriers such as water, air; (2) the organic phase-change thing of selecting in the prepared composite energy-storage material that goes out of the present invention is wide material sources, cheap petroleum industry product---low melt point paraffin (fusing point is less than 60 ℃), adopt the product of pure alkane, resin acid compounds more in the past, greatly reduced cost; (3) adopt the organo montmorillonite commodity that can purchase on the market directly to modify, and do not need again the special organically-modified and check of process, work simplification, cost reduces, and can effectively promote the application in practice of such energy storage material.
Description of drawings
Fig. 1 is the XRD diffraction curve of not spending the paraffin composite energy-storage material through the organo montmorillonite-20 of silane coupling agent modification of surfaces and edge preparation,
Fig. 2 is the organo montmorillonite-20 degree paraffin composite energy-storage material through silane coupling agent modification of surfaces and edge preparation, i.e. the XRD diffraction curve of the embodiment of the invention one.
Embodiment
The intercal type composite energy-storage material that the present invention makes is tested its quantity of heat storage with differential scanning calorimeter, and differential scanning calorimeter is Pyris Diamond (U.S. PE), and the test atmosphere is high purity nitrogen, and the temperature test scope is 0～100 ℃, and scanning speed is 5K/min; Adopt X-ray diffraction (XRD) to analyze its microtexture, XRD is to use D8ADVANCE (U.S. Bruker), and light source is the Cu gamma ray source, and 2 θ scopes are 0.5-30 °, and step-length is 0.02 °; And by placing down and observed it in 72 hours and store the apparent of thermal process being higher than 15～25 ℃ of used paraffin melting points.
Table 1 is the preparation method of 2 Comparative Examples and 3 embodiments.Table 2 is every performances of the matrix material for preparing of each embodiment.By performance data in the table as can be known, not only heat accumulation value, interlamellar spacing increase substantially the matrix material that organo montmorillonite through silane coupling agent modified surface and edge prepares, and material apparent in storing thermal process also has bigger improvement, the consistency that itself and paraffin are described has obtained big improvement, thereby can insert more paraffin, and paraffin is difficult for resolving.
Fig. 1 is the XRD diffraction curve of not spending the paraffin composite energy-storage material through the organo montmorillonite-20 of silane coupling agent modification of surfaces and edge preparation, and Fig. 2 is the XRD diffraction curve through the organo montmorillonite-20 degree paraffin composite energy-storage material of silane coupling agent modification of surfaces and edge preparation.Contrast as seen by two figure, the composite energy-storage material that the organo montmorillonite at process silane coupling agent modification of surfaces and edge prepares not only diffraction peak moves bigger to Small angle, be that interlamellar spacing increases, and the peak also obviously increases by force, explanation after silane coupling agent is modified organo montmorillonite and the consistency of paraffin be improved, it is also more relatively to insert the paraffin amount.
Table 1
| 150J/g) 1.5 parts of mass percent concentrations are 10 parts of 20% aqueous ethanolic solutions; | 4h; Suction filtration also is 30% the reacted product of aqueous ethanolic solution washing previous step with 50 ℃ of following mass percent concentrations, at 100 ℃ of dry back grind into powders. | |
| Embodiment three | 0.6 part of hexadecyl Trimethoxy silane coupling agent; 1 part of organo montmorillonite (interlayer is of a size of 3.8 nanometers); 56 degree paraffin (55.3 ℃ of fusing points, quantity of heat storage 190J/g) 1.5 parts of mass percent concentrations are 15 parts of 25% aqueous ethanolic solutions; | It is 25% ethanolic soln that silane coupling agent is mixed with concentration, at room temperature, with spray method organo montmorillonite was handled 30 minutes; In 80 ℃ of aqueous ethanolic solutions,, react 5h with organo montmorillonite and paraffin dispersed with stirring; Suction filtration also is 40% the reacted product of aqueous ethanolic solution washing previous step with 60 ℃ of following mass percent concentrations, at 120 ℃ of dry back grind into powders. |
Table 2
Claims (3)
1, the preparation method of organo montmorillonite/paraffin composite energy-storage material is characterized in that, comprises following each step:
The first step, with quality be the silane coupling agent of 0.04～0.06 times of organo montmorillonite to be mixed with mass concentration be 15～25% ethanolic soln, at room temperature, handled 20～30 minutes by the spray method organo montmorillonite with above-mentioned solution;
Second step in closed container, was dispersed with stirring in 20～25% the aqueous ethanolic solution with the organo montmorillonite after the above-mentioned processing in mass concentration, and the consumption of ethanolic soln is 10～15 times of organo montmorillonite quality; After being warming up to 60～80 ℃, the fusing point that adds quality and be 1.5～2 times of organo montmorillonites is less than 60 ℃ melt paraffin, continue to stir suction filtration after 4～6 hours, being 20～40% aqueous ethanolic solution washing with 30～60 ℃, mass percent concentration does not ooze and shows to there being paraffin oil;
In the 3rd step, the product after the washing is dried to constant weight at 90～120 ℃, promptly obtains the composite energy-storage material of the present invention's preparation.
2, the preparation method of organo montmorillonite according to claim 1/paraffin composite energy-storage material, wherein the used silane coupling agent general formula of the first step is:
R:C
nH
2n+1, C
nH
2n-1, n=2～16, promptly R is a carbon number in 2～16 alkyl, mono alkenyl;
Y:OC
nH
2n+2, n=1～2, promptly Y is methoxyl group, oxyethyl group.
3, the preparation method of organo montmorillonite according to claim 1/paraffin composite energy-storage material, wherein the used organo montmorillonite layer of the first step sees that distance is 2.1～3.8nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102535255A (en) * | 2011-11-23 | 2012-07-04 | 浙江金昌纸业有限公司 | Energy-saving temperature-adjusting wall paper and preparation method thereof |
| CN104529321A (en) * | 2014-12-08 | 2015-04-22 | 江苏奥莱特新材料有限公司 | Layered composite phase change energy storage building material |
| CN104559938A (en) * | 2015-01-09 | 2015-04-29 | 中科院广州能源所盱眙凹土研发中心 | Paraffin-attapulgite composite phase-change material and preparation method thereof |
| CN105369102A (en) * | 2015-12-04 | 2016-03-02 | 太仓苏晟电气技术科技有限公司 | Single-bar furnace for bar peeling technique |
| CN106010457A (en) * | 2016-06-02 | 2016-10-12 | 上海工程技术大学 | Modified montmorillonite/paraffin composite phase-change energy storage material and preparation method thereof |
| CN107828385A (en) * | 2017-11-13 | 2018-03-23 | 常州凯途纺织品有限公司 | A kind of solar heat-preservation composite and preparation method thereof |
| CN110734598A (en) * | 2019-10-12 | 2020-01-31 | 界首市奥胜达塑业有限公司 | toughening modification material for PE pipeline and preparation method thereof |
-
2004
- 2004-12-23 CN CN 200410101553 patent/CN1274764C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102535255A (en) * | 2011-11-23 | 2012-07-04 | 浙江金昌纸业有限公司 | Energy-saving temperature-adjusting wall paper and preparation method thereof |
| CN104529321A (en) * | 2014-12-08 | 2015-04-22 | 江苏奥莱特新材料有限公司 | Layered composite phase change energy storage building material |
| CN104529321B (en) * | 2014-12-08 | 2017-02-22 | 江苏中铁奥莱特新材料股份有限公司 | Layered composite phase change energy storage building material |
| CN104559938A (en) * | 2015-01-09 | 2015-04-29 | 中科院广州能源所盱眙凹土研发中心 | Paraffin-attapulgite composite phase-change material and preparation method thereof |
| CN105369102A (en) * | 2015-12-04 | 2016-03-02 | 太仓苏晟电气技术科技有限公司 | Single-bar furnace for bar peeling technique |
| CN106010457A (en) * | 2016-06-02 | 2016-10-12 | 上海工程技术大学 | Modified montmorillonite/paraffin composite phase-change energy storage material and preparation method thereof |
| CN106010457B (en) * | 2016-06-02 | 2019-03-19 | 上海工程技术大学 | A kind of modified montmorillonoid/paraffin composite phase change energy storage material and preparation method thereof |
| CN107828385A (en) * | 2017-11-13 | 2018-03-23 | 常州凯途纺织品有限公司 | A kind of solar heat-preservation composite and preparation method thereof |
| CN110734598A (en) * | 2019-10-12 | 2020-01-31 | 界首市奥胜达塑业有限公司 | toughening modification material for PE pipeline and preparation method thereof |
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| CN1274764C (en) | 2006-09-13 |
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