CN114106411A - Preparation method of flame-retardant self-extinguishing type biomass aerogel phase-change composite heat storage material - Google Patents
Preparation method of flame-retardant self-extinguishing type biomass aerogel phase-change composite heat storage material Download PDFInfo
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- 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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- C08J2201/00—Foams characterised by the foaming process
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Abstract
The invention relates to the field of energy-saving and environment-friendly polymer and a composite material thereof. A preparation method of a flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material comprises the steps of forming gel by cellulose, alginate and montmorillonite in water, carrying out liquid nitrogen freeze drying treatment on the gel to prepare an aerogel matrix with an oriented pore structure, soaking the aerogel matrix with the oriented pore structure in polyethylene glycol phase-change material melt, and enabling a polyethylene glycol phase-change material to be directionally impregnated in an oriented pore channel of the aerogel matrix to obtain the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material. The biomass aerogel phase-change composite heat storage material prepared by the invention has good flame-retardant self-extinguishing function, mechanical property and thermal stability.
Description
Technical Field
The invention relates to the field of energy-saving and environment-friendly polymers and composite materials thereof, in particular to the field of aerogel phase-change composite heat storage materials of an electric heating type phase-change heat accumulator for electric heating.
Background
The traditional heating mode is central heating by coal-fired and gas-fired boilers, the heating area is controlled by 100 percent in series, and serious energy waste and environmental pollution are caused. In recent years, with the rapid development of energy-saving and environment-friendly heat storage technology, the demand for low-temperature phase change heat storage materials is increasingly urgent. An environment-friendly low-temperature phase change heat storage material is urgently needed to replace a non-degradable high-molecular heat storage material so as to meet the requirements of a new generation of energy-saving environment-friendly heat storage technology.
The phase-change temperature (37-67 ℃) of the polyethylene glycol is improved along with the increase of the molecular weight (1000-. Polyethylene glycol is used as an important branch of the solid-liquid phase change material, has high phase change latent heat, low thermal hysteresis effect, no toxicity, no irritation, no hydrolyzation and stable performance, can adjust the phase change temperature and the phase change latent heat by adjusting the length of a molecular chain, has strong molecular designability, and has the following defects as the phase change material: the solid-liquid phase change or the processing process is easy to leak, and the heat conduction is mainly realized by chain links, groups and the like in the phase change process, so that the heat conductivity is lower, the heat exchange performance is poor, and the energy storage and release efficiency is influenced. In recent years, microcapsule encapsulation phase change materials and shape-stabilized phase change materials become hot points of research, but the technology for preparing composite phase change materials by microcapsule encapsulation is complex, the cost is high, and the practical application of the phase change composite materials is not facilitated; the shaping phase-change material is generally a porous support material used for adsorbing the phase-change material to keep the shape of the phase-change material stable, and common porous support materials include bentonite, diatomite, high polymers, aerogel, foam metal and the like, wherein the aerogel has higher porosity, lower density and adjustable pore structure, and is suitable for being used as a packaging shaping framework material of the polyethylene glycol phase-change material. The biomass aerogel has high specific surface area, porosity, small density, good mechanical property, heat storage property and degradability, and is an ideal porous framework material of the energy-saving and environment-friendly medium-low temperature phase change heat storage material.
The application environment of the electric heating type phase-change heat accumulator has different requirements on the phase-change temperature and the phase-change enthalpy of the phase-change material, the comprehensive performance requirements of the civil electric heating field, particularly on the mechanical strength, stability, safety, energy conservation, environmental protection and the like of the phase-change material are higher, and the development of a novel phase-change composite heat accumulation material of the electric heating type phase-change heat accumulator suitable for electric heating is urgently needed. The biomass aerogel phase-change composite heat storage material can absorb or release heat by utilizing the phase change (solid-liquid) process of the phase-change component to realize the heat storage function, and becomes the development trend of the research and application of the heat storage material in the current energy-saving and environment-friendly field.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to provide a flame-retardant self-extinguishing type biomass aerogel phase-change composite heat storage material for an electrothermal phase-change heat accumulator, and the purposes of saving energy, protecting environment and reducing the operation cost of a heating system are achieved.
The technical scheme adopted by the invention is as follows: a preparation method of a flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material comprises the steps of forming gel by cellulose, alginate and montmorillonite in water, carrying out liquid nitrogen freeze drying treatment on the gel to prepare an aerogel matrix with an oriented pore structure, soaking the aerogel matrix with the oriented pore structure in polyethylene glycol phase-change material melt, and enabling a polyethylene glycol phase-change material to be directionally impregnated in an oriented pore channel of the aerogel matrix to obtain the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material.
According to the research of the application, cellulose and alginate are used as the raw materials for preparing the aerogel, and meanwhile, montmorillonite is introduced, so that the obtained cellulose/alginate/montmorillonite-based aerogel not only has the characteristic of low density, but also has good mechanical properties (compression resistance, deformation resistance and the like) and a flame-retardant self-extinguishing function, and the characteristics of low density, mechanical strength, flame retardance, self-extinguishing and the like of the aerogel phase change composite heat storage material can be ensured; the aerogel and the polyethylene glycol phase-change material are directionally impregnated and compounded into a whole, holes in the aerogel are directionally impregnated and attached by using a polyethylene glycol melt, and the method is equivalent to designing a plurality of micro-scale directional phase-change holes in a cellulose/alginate/montmorillonite-based aerogel system for heat conduction, so that the heat storage and heat transfer performance of the aerogel phase-change composite heat storage material is remarkably improved, and the use stability and safety of the electrothermal phase-change heat accumulator are ensured.
The mass ratio of the cellulose to the alginate to the montmorillonite is 2-4: 10: 5-10, and the sum of the cellulose to the alginate to the montmorillonite is 1-3 wt% in the gel.
The molecular weight of the polyethylene glycol phase-change material is 1000-10000, the phase-change temperature and the phase-change enthalpy of the aerogel phase-change composite heat storage material change along with the change of the molecular weight of the polyethylene glycol phase-change material, and the proper molecular weight of the polyethylene glycol phase-change material is selected according to the required phase-change temperature and the required phase-change enthalpy. For example, PEG1500, PEG10000, etc. can be used. The polymer phase-change material is utilized to carry out directional phase-change treatment on cellulose/alginate/montmorillonite aerogel, so that the flame-retardant self-extinguishing aerogel phase-change composite heat storage material can show better comprehensive properties such as heat storage performance, mechanical strength and the like.
The phase-change temperature and the phase-change enthalpy determined according to the environmental temperature requirement of electric heating are determined according to the required phase-change temperature and the required phase-change enthalpy, wherein the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material is used for an electric heating type phase-change heat accumulator of the electric heating.
Adding an inorganic salt cross-linking agent into the aerogel matrix before soaking the aerogel matrix.
The inorganic salt cross-linking agent is calcium chloride.
The invention has the beneficial effects that: the flame-retardant self-extinguishing type biomass aerogel phase-change composite heat storage material prepared by the invention has good flame-retardant self-extinguishing function, mechanical property and thermal stability, and is simple in preparation process, mild in condition, low in cost, low in raw material cost, easy to obtain, green and environment-friendly.
The invention adopts natural green, nontoxic, pollution-free, cheap and easily-obtained cellulose, alginate and montmorillonite as the raw materials of the aerogel matrix, and the flame-retardant self-extinguishing type aerogel matrix is directionally impregnated with the composite polyethylene glycol phase-change material, so that the aerogel phase-change composite heat storage material has the advantages of degradability, environmental protection, low cost and the like, and also has good leakage prevention, heat storage performance, mechanical property, thermal stability and low density characteristic of aerogel, and the phase-change composite heat storage material can be widely applied to the electrothermal type phase-change heat accumulator with higher requirements on the comprehensive properties such as heat storage performance, mechanical property, stability, flame-retardant self-extinguishing and the like, for example, the electrothermal type phase-change heat accumulator can be applied to the field of civil electric heating and the like.
The preparation method of the flame-retardant self-extinguishing aerogel phase-change composite heat storage material provided by the invention can obtain the aerogel phase-change composite heat storage material with comprehensive performances of flame-retardant self-extinguishing function, good heat storage performance, mechanical property, thermal stability and the like, and the preparation method is simple in preparation process, mild, pollution-free, green, environment-friendly, low in raw material cost and easy to obtain, remarkably reduces the production cost, and is beneficial to industrial production and application.
According to the invention, the flame-retardant self-extinguishing aerogel phase-change composite heat storage material is used for the electric heating type phase-change heat accumulator, can be directly used in the field of civil electric heating, can ensure or improve the heating effect, can avoid a large amount of energy waste and serious environmental pollution compared with the existing boiler central heating, achieves energy conservation and environmental protection, and realizes 'carbon peak reaching' and 'carbon neutralization' early by adjusting the energy structure of boosting coal to electricity.
Drawings
FIG. 1 is a microscopic morphology image observed by a Scanning Electron Microscope (SEM) of an aerogel with an oriented pore structure (CNAMMTCA) of example 1 of the present invention, wherein (a) is a cross-sectional microscopic morphology image with a magnification of 500, and (b) is a longitudinal-sectional microscopic morphology image with a magnification of 500;
FIG. 2 is a microscopic morphology of the flame retardant self-extinguishing aerogel phase change thermal storage material (CNAMMTCA/PEG 1500) of example 1 of the present invention observed by a scanning electron microscope;
FIG. 3 is a graph of the compression curve (stress on the ordinate and strain on the abscissa) of the oriented pore structured aerogel (CNAMMTCA) of example 1 of the present invention;
FIG. 4 is a thermogravimetric plot of the aerogel phase change thermal storage material (CNAMMTCA/PEG 1500) of example 1 and another example (A5 MMT5Ca/PEG 10000) of the aerogel phase change thermal storage material of the present invention;
fig. 5 is a differential scanning calorimetry analysis curve of the aerogel phase change thermal storage material (CNAMMTCa/PEG 1500) of example 1 and another example of the aerogel phase change thermal storage material (CNAMMTCa/PEG 10000) of the present invention;
fig. 6 is a microscopic morphology image of the aerogel phase change thermal storage material (CNAMMTCa/PEG 10000) according to example 2 of the present invention, which is observed by a scanning electron microscope.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 5g of sodium montmorillonite, adding the sodium montmorillonite into 70ml of 1wt% cellulose water dispersion, mechanically stirring at 14000r/min, slowly adding 5g of ammonium alginate, and continuously mechanically stirring for 2 hours at constant temperature (about 55 ℃) to obtain uniform cellulose/ammonium alginate/montmorillonite-based composite gel; pouring the gel into a mold, placing the mold in liquid nitrogen for quick freezing, then placing a frozen sample in a freeze dryer, carrying out freeze drying for 72 hours at about-35 ℃, and further drying for 5 hours in a vacuum oven at 40 ℃ to obtain the non-crosslinked cellulose/ammonium alginate/montmorillonite hybrid aerogel CNAMMT; soaking CNAMMT in ethanol solution of saturated calcium chloride for crosslinking reaction for about 6 hours at about 55 ℃, and then transferring the crosslinked product into a vacuum oven at 40 ℃ for drying for 24 hours to remove ethanol, thereby obtaining crosslinked cellulose/ammonium alginate/montmorillonite hybrid aerogel CNAMMTCa (the microstructure is shown in figure 1); weighing a proper amount of polyethylene glycol (PEG 1500) in a beaker, heating to 80 ℃ for complete melting, immersing the CNAMMTCA into a PEG1500 melt along the axial direction of an orientation hole, placing the PEG1500 melt in a vacuum oven at 80 ℃, vacuumizing for 24 hours, and assisting the PEG1500 to fully infiltrate into the aerogel orientation hole channel to obtain the aerogel phase change composite heat storage material CNAMMTCA/PEG1500 (the microstructure of which is shown in figure 2).
The combustion experiment shows that the aerogel CNAMMTCA is not easy to ignite and has only slight cloudy phenomenon, and extinguishes within 1 second away from flame, which indicates that the aerogel has good flame-retardant self-extinguishing function. Through determination, the compressive modulus of the CNAMMTCA reaches 11.07 MPa, and the compressive strength (70%) of the CNAMMTCA is 4.89MPa (figure 3), which shows that the aerogel prepared by the embodiment has good deformation and compression resistance, so that the CNAMMTCA/PEG1500 serving as the aerogel phase-change composite heat storage material has good mechanical strength and shape stability; the thermal stability of CNAMMTCA/PEG1500 at room temperature to 200 ℃ is good, and the weight loss peak value (solid line in figure 4) is reached at about 400 ℃, which shows that the aerogel phase change composite heat storage material prepared by the embodiment has good thermal stability; FIG. 5 shows the endothermic peak and exothermic peak (solid line in FIG. 5) of the phase change in the DSC curve of CNAMMTCA/PEG1500, and the latent heat values are 157.80J/g and 147.65J/g, respectively, which indicates that the aerogel phase change composite heat storage material prepared in this example has good heat storage performance.
The aerogel phase transition composite heat storage material that this embodiment provided, not only have the degradable, green, advantages such as with low costs, still have higher anti deformation, compressive capacity, show good mechanical properties and thermal stability, have the low density characteristic of aerogel simultaneously concurrently, but wide application in the place that comprehensive properties such as fire-retardant self-extinguishing function to heat storage material required height, heat storage capacity, mechanical properties, thermal stability, for example can be applied to electrothermal type phase transition heat accumulator, solve civil electric heating's flexibility, safety, energy-concerving and environment-protective and low-cost scheduling problem.
The cellulose, the alginate and the montmorillonite are natural materials which are abundant in natural reserves, and the cellulose and the alginate are characterized by degradability, no toxicity, no pollution, easy modification and the like. The preparation method provided by the invention takes cellulose, alginate and montmorillonite as production raw materials of the aerogel, controls the process through the steps of crosslinking reaction, liquid nitrogen freeze drying treatment and the like, regulates and controls the characteristics of the aerogel such as porosity, pore structure, mechanical strength, density and the like, is matched with the step of directional infiltration of polyethylene glycol melt, carries out phase change treatment on the aerogel, introduces a plurality of material two-phase interfaces, and regulates and controls the heat storage and mechanical properties through a multi-stage structure, thereby preparing the aerogel phase change composite heat storage material with the excellent properties.
The young modulus of the aerogel matrix of the aerogel phase-change composite heat storage material provided by the embodiment reaches 9.48MPa, the compressive strength (70%) of the aerogel matrix is 1.41MPa, and the aerogel phase-change composite heat storage material has good deformation resistance and pressure resistance, so that the aerogel phase-change composite heat storage material has good mechanical properties; the aerogel phase-change composite heat storage material has good thermal stability at room temperature to 200 ℃. Through experiments, the aerogel phase-change composite heat storage material can be used as a heat storage material of an electrothermal phase-change heat accumulator, and has the advantages of good heat storage property, degradability, environmental friendliness, low cost, no corrosion and the like compared with the existing heat storage material.
Example 2
The present embodiment is different from embodiment 1 in that: polyethylene glycol (PEG 10000) is used for replacing polyethylene glycol (PEG 1500) to obtain the aerogel phase change composite heat storage material CNAMMTCA/PEG10000 (the microscopic morphology is shown in figure 6). Tests prove that the CNAMMTCA/PEG10000 has good thermal stability between room temperature and 200 ℃, and the weight loss peak value (a dotted line in figure 4) is reached at about 400 ℃, which indicates that the aerogel phase change composite heat storage material prepared by the embodiment has good thermal stability; FIG. 5 shows the endothermic peak and exothermic peak (dotted line in FIG. 5) of the phase change in the DSC curve of CNAMMTCa/PEG10000, and the latent heat values are 217.04J/g and 196.46J/g, respectively, which indicates that the aerogel phase change composite heat storage material prepared in this example has good heat storage capacity and thermal stability.
The embodiment provides an aerogel phase transition composite heat storage material, not only have the advantages such as degradable, green, with low costs, still have higher anti deformation, compressive capacity, show good mechanical properties and thermal stability, have the low density characteristic of aerogel concurrently simultaneously, but wide application in the place that comprehensive properties such as fire-retardant self-extinguishing function to heat storage material, heat storage capacity, mechanical properties, thermal stability required height, for example can be applied to electrothermal type phase transition heat accumulator, solve the flexibility of civilian electric heating, the security, energy-concerving and environment-protective and low-cost scheduling problem.
Claims (6)
1. A preparation method of a flame-retardant self-extinguishing type biomass aerogel phase-change composite heat storage material is characterized by comprising the following steps of: the preparation method comprises the steps of forming gel by cellulose, alginate and montmorillonite in water, carrying out liquid nitrogen freeze drying treatment on the gel to prepare an aerogel matrix with an oriented pore structure, soaking the aerogel matrix with the oriented pore structure in polyethylene glycol phase change material melt, and directionally impregnating the polyethylene glycol phase change material in oriented pore channels of the aerogel matrix to obtain the flame-retardant self-extinguishing biomass aerogel phase change composite heat storage material.
2. The preparation method of the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material as claimed in claim 1, characterized in that: the mass ratio of the cellulose to the alginate to the montmorillonite is 2-4: 10: 5-10, and the sum of the cellulose to the alginate to the montmorillonite is 1-3 wt% in the gel.
3. The preparation method of the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material as claimed in claim 1, characterized in that: the molecular weight of the polyethylene glycol phase-change material is 1000-10000, the phase-change temperature and the phase-change enthalpy of the aerogel phase-change composite heat storage material change along with the change of the molecular weight of the polyethylene glycol phase-change material, and the proper molecular weight of the polyethylene glycol phase-change material is selected according to the required phase-change temperature and the required phase-change enthalpy.
4. The preparation method of the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material as claimed in claim 3, characterized in that: the phase-change temperature and the phase-change enthalpy determined according to the environmental temperature requirement of electric heating are determined according to the required phase-change temperature and the required phase-change enthalpy, namely the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material is suitable for the electric heating type phase-change heat accumulator of the electric heating.
5. The preparation method of the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material as claimed in claim 1, characterized in that: adding an inorganic salt cross-linking agent into the aerogel matrix before soaking the aerogel matrix.
6. The preparation method of the flame-retardant self-extinguishing biomass aerogel phase-change composite heat storage material as claimed in claim 5, characterized in that: the inorganic salt cross-linking agent is calcium chloride.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228501B1 (en) * | 1994-09-26 | 2001-05-08 | National Institute For Research In Inorganic Materials | Porous body of polysaccharide or polysaccharide-clay composite, and process for its production |
| WO2014008250A1 (en) * | 2012-07-03 | 2014-01-09 | Peterson Chemical Technology, Inc. | Thermal storage gelatinous triblock copolymer elastomer particles in polyurethane flexible foams |
| CN103980624A (en) * | 2014-05-19 | 2014-08-13 | 四川大学 | Halogen-free flame-retardant polystyrene foam composite material and preparation method thereof |
| CN111454694A (en) * | 2020-04-03 | 2020-07-28 | 中国石油大学(北京) | Phase-change thermal insulation material and preparation method and application thereof |
| CN111892799A (en) * | 2020-07-16 | 2020-11-06 | 王宇昕 | Low-density flame-retardant polymer product, preparation method and application thereof |
| CN113174237A (en) * | 2021-03-30 | 2021-07-27 | 中国地质大学（武汉） | Composite phase-change material and preparation method thereof |
| CN113234256A (en) * | 2021-03-22 | 2021-08-10 | 陕西科技大学 | Preparation method of double-crosslinking flame-retardant composite aerogel |
-
2021
- 2021-12-06 CN CN202111476354.XA patent/CN114106411A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228501B1 (en) * | 1994-09-26 | 2001-05-08 | National Institute For Research In Inorganic Materials | Porous body of polysaccharide or polysaccharide-clay composite, and process for its production |
| WO2014008250A1 (en) * | 2012-07-03 | 2014-01-09 | Peterson Chemical Technology, Inc. | Thermal storage gelatinous triblock copolymer elastomer particles in polyurethane flexible foams |
| CN103980624A (en) * | 2014-05-19 | 2014-08-13 | 四川大学 | Halogen-free flame-retardant polystyrene foam composite material and preparation method thereof |
| CN111454694A (en) * | 2020-04-03 | 2020-07-28 | 中国石油大学(北京) | Phase-change thermal insulation material and preparation method and application thereof |
| CN111892799A (en) * | 2020-07-16 | 2020-11-06 | 王宇昕 | Low-density flame-retardant polymer product, preparation method and application thereof |
| CN113234256A (en) * | 2021-03-22 | 2021-08-10 | 陕西科技大学 | Preparation method of double-crosslinking flame-retardant composite aerogel |
| CN113174237A (en) * | 2021-03-30 | 2021-07-27 | 中国地质大学（武汉） | Composite phase-change material and preparation method thereof |
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