CN113636798A - Preparation method of cement-based paraffin phase-change energy storage material - Google Patents
Preparation method of cement-based paraffin phase-change energy storage material Download PDFInfo
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- CN113636798A CN113636798A CN202110930160.6A CN202110930160A CN113636798A CN 113636798 A CN113636798 A CN 113636798A CN 202110930160 A CN202110930160 A CN 202110930160A CN 113636798 A CN113636798 A CN 113636798A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Inorganic Chemistry (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a preparation method of a cement-based paraffin phase-change energy storage material, which is characterized in that paraffin is emulsified and uniformly dispersed in water according to a tiny particle size to prepare an oil-in-water emulsion with stable performance, the emulsion is diluted and then compounded with a cementing material, meanwhile, a water reducing agent is added to improve the fluidity of the phase-change energy storage material, and the phase-change material is packaged through hydration and hardening of the cementing material to prepare the phase-change energy storage material. The phase-change material in the prepared cement-based phase-change energy storage material is uniformly dispersed, and has excellent mechanical and thermal properties, good packaging effect and excellent durability.
Description
Technical Field
The invention belongs to the field of phase change energy storage building materials, and particularly relates to a preparation method of a cement-based paraffin phase change energy storage material.
Background
The phase change energy storage building material is a thermal function material organically compounding a phase change material and a building material, realizes the conversion of energy at different time and spatial positions by storing/releasing energy through the phase change material, and has wide development prospect in the field of ecological buildings. The organic solid-liquid phase change energy storage material represented by paraffin is used for compounding with a cement-based material to obtain the cement-based phase change material due to the advantages of no supercooling and phase separation, small volume change during phase change, no toxicity, no corrosion and the like.
The cement-based phase change material is prepared by compounding the paraffin phase change material and the cement-based material by an impregnation method, an adsorption method, a capsule method and the like. The impregnation method is to immerse the cement-based material into the molten phase-change material, and the phase-change material is filled into capillary pores of the cement-based material, but the phase-change paraffin is easy to leak and has poor stability in the phase-change process; the adsorption method is that under the conditions of vacuum and the like, phase change materials are adsorbed into porous materials, and then the porous materials are mixed into cement-based materials in the form of coarse aggregates, but the uniformity and mechanical property of heat storage of the method can not be ensured; the phase-change material is encapsulated by microencapsulation technology and then is doped into the cement-based material, so that the problems of easy leakage of the phase-change material, poor mechanical property of the energy storage material and the like can be effectively solved.
The traditional microcapsule preparation technology mostly adopts organic wall materials, has certain toxic and side effects and poor heat-resistant stability. In patent CN105219352A, inorganic calcium carbonate is used as a wall material to package liquid paraffin and calcium chloride hydrate to prepare the phase-change energy-storage composite organic-inorganic microcapsule, the reasonable phase-change temperature and phase-change heat storage can perfectly meet the requirements of building heat preservation, heat insulation and energy storage, but the compatibility of phase-change core materials and the selection of emulsifiers are not reasonable. In patent CN109054768A, a calcium chloride solution is added into a paraffin emulsion, and after being mixed uniformly, a sodium carbonate solution is added dropwise to prepare a paraffin @ calcium carbonate phase-change microcapsule with high encapsulation efficiency and good anti-seepage performance, but the calcium chloride is unevenly distributed around the paraffin particles, which can cause uneven thickness distribution of the calcium carbonate wall material, and the appearance of the calcium carbonate has an important influence on the performance of the phase-change microcapsule, so that the system ph needs to be strictly controlled, which is not beneficial to large-scale popularization and application.
Therefore, how to realize the efficient compounding of the phase-change material and the cement-based material through a simple process and ensure the effective exertion of the functions of the phase-change energy storage building material is a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a cement-based paraffin phase-change energy storage material. The method can realize the distribution of the phase-change material in the cement-based material in a small-particle-size, strong-dispersion and excellent-packaging form, thereby preparing the phase-change energy storage material with excellent mechanical, thermal and durability properties.
The preparation method of the cement-based paraffin phase-change energy storage material comprises the steps of compounding the phase-change material with the cementing material in an oil-in-water emulsion mode, enabling the phase-change material to be uniformly distributed in the cement-based material in small particles with the average particle size of 0.5-1.5 mu m, and utilizing hydration reaction between outer water of the oil-in-water emulsion and the cementing material to form hydration products to achieve good encapsulation of the phase-change material.
The method specifically comprises the following steps:
step 1: mixing 20-25 parts of phase change material and 5-10 parts of emulsifier, heating for melting, uniformly stirring, and pouring into a colloid mill;
step 2: heating 65-75 parts of water to 75-85 ℃, adding the water to the molten mixture in the step 1, and continuously stirring for 30-50 min at a stirring speed of 800-1400 r/min to form an oil-in-water phase-change emulsion with stable performance;
and step 3: diluting 15-60 parts of the oil-in-water phase change emulsion prepared in the step 2 with 0-40 parts of water, pouring the diluted solution into a stirrer to be mixed with 100 parts of a cementing material and 0.05-0.2 part of a water reducing agent, and uniformly stirring;
and 4, step 4: and (3) pouring and molding the mixture obtained in the step (3) in a mold, hardening to form the cement-based paraffin phase-change energy storage material, and removing the mold and then performing conventional maintenance.
In the step 1, the phase-change material is paraffin; the emulsifier is a compound system of ionic surfactant (such as fatty acid soap), nonionic surfactant (such as span80, tween80, span20, tween20 and the like), and the like, and auxiliary emulsion of stearic acid and the like can also be added, wherein the hydrophilic-lipophilic balance (HLB) of the auxiliary emulsion is 10-13.
In the step 2, the emulsification rate of the oil-in-water phase-change emulsion is 90-100%, wherein the average particle size of oil phase particles is 0.5-1.5 μm.
In step 3, the cementing material is general portland cement; the water reducing agent is one of polycarboxylic acid, naphthalene series water reducing agents and resin series water reducing agents.
The raw materials in the preparation process of the invention are all in parts by weight except special instructions.
The invention has the beneficial effects that:
1. the paraffin phase-change material is compounded with cementing materials such as cement and the like in an oil-in-water emulsion mode, so that the paraffin phase-change material is dispersed in the cementing materials in the form of tiny particles, and the influence on the strength is small; and the micro-particle phase change material can improve the heat exchange area between the micro-particle phase change material and a cement matrix, and is favorable for ensuring the thermal property of the energy storage material.
2. According to the invention, the water reducing agent is introduced, so that the fluidity of the cement-based paraffin phase-change energy storage material is improved, the pouring forming is facilitated, and the paraffin and the cement are better combined.
3. The outer water of the oil-in-water paraffin emulsion and the cementing material cement are subjected to hydration reaction, so that the phase change material can be well packaged to prevent leakage, a packaging procedure is not required to be additionally added like an impregnation or adsorption method, the process is simple and convenient, and the large-scale popularization and application are facilitated.
Detailed Description
To further describe the technical means and effects of the present invention adopted to achieve the predetermined purpose, the present invention is further described in detail with reference to the following embodiments, but the present invention is not limited to the examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Example 1:
1) mixing Span-80 and Tween-80 to prepare an emulsifier with HLB of 10;
2) heating 45g of paraffin and 22.5g of emulsifier in a water bath for melting, adding 157.5g of water with the temperature of 80 ℃ into the melt in a colloid mill with the stirring speed of 1000r/min for preparing an oil-in-water emulsion, and continuously stirring for 40min to ensure full emulsification, wherein the emulsification rate reaches 100 percent, and the average particle size of paraffin phase particles is about 0.9 mu m;
3) 500g of ordinary portland cement (P.O 52.5.5) cement, 0.75g of polycarboxylic acid water reducing agent, 42.5g of water and 225g of oil-in-water paraffin emulsion are uniformly stirred and cast for molding, and the standard curing is carried out for 28d, so as to prepare the cement-based phase change energy storage material based on the oil-in-water emulsion.
Example 2:
1) mixing Span-20 and Tween-20 to prepare an emulsifier with HLB of 12;
2) heating 55g of paraffin and 22g of emulsifier in a water bath for melting, adding 143g of water with the temperature of 75 ℃ into the melt in a colloid mill with the stirring speed of 800r/min for preparing an oil-in-water emulsion, and continuously stirring for 50min to ensure full emulsification, wherein the emulsification rate reaches 93.2 percent, and the average particle size of paraffin phase particles is about 1.2 mu m;
3) 500g of ordinary portland cement (P.O 52.5.5) cement, 0.5g of naphthalene water reducer, 47g of water and 220g of oil-in-water paraffin emulsion are uniformly stirred and cast for molding, and the standard curing is carried out for 28d, so as to prepare the cement-based phase-change energy storage material based on the oil-in-water emulsion.
Example 3:
1) mixing Span-20 and Tween-20 to prepare an emulsifier with HLB of 10;
2) heating 35g of paraffin and 15g of emulsifier in a water bath for melting, adding 102g of water with the temperature of 75 ℃ into the melt in a colloid mill with the stirring speed of 1100r/min to prepare an oil-in-water emulsion, and continuously stirring for 35min to ensure full emulsification, wherein the emulsification rate reaches 90.2 percent, and the average particle size of paraffin phase particles is about 1.5 mu m;
3) 500g of ordinary portland cement (P.O 52.5.5) cement, 1g of SMF water reducer, 108g of water and 152g of oil-in-water paraffin emulsion are uniformly stirred and cast for molding, and standard curing is carried out for 28d, so as to prepare the cement-based phase change energy storage material based on the oil-in-water emulsion.
Comparative example 1:
the phase change energy storage material comprises a shape-stabilized phase change material prepared from low-temperature phase change paraffin, low-density polyethylene and graphite powder and a cement matrix material; the preparation method comprises the following steps:
1) placing 100g of low-density polyethylene, 10g of graphite powder and 150g of low-temperature phase change paraffin in an oil bath pot of a heat collection type magnetic stirrer, setting the temperature to be 160 ℃, stirring at a low speed for 30min, then stirring at a high speed for 10min, preparing a melt of the composite phase change material, cooling, and crushing into particles with the particle size of less than 2.5mm to obtain a shaped phase change material;
2) 500g of ordinary portland cement (P.O 52.5.5), 0.75g of polycarboxylic acid water reducing agent and 260g of shaping phase change energy storage microcapsule material are dry-mixed and stirred for 1min, 200g of water is added, pouring forming is carried out after 3min of low-speed stirring, and standard maintenance is carried out for 28d, so as to prepare the cement-based phase change energy storage material.
Comparative example 2:
the comparison example prepares an expanded perlite/paraffin wax composite phase-change material based on a vacuum adsorption mode, wherein two porous materials of ceramsite and expanded perlite are used as base materials, and a eutectic paraffin wax mixture is used as a phase-change material; the preparation method comprises the following steps:
1) mixing solid paraffin and liquid paraffin according to the mass ratio of 1:1, stirring for 6 hours on a constant-temperature magnetic stirrer with the temperature of 20 ℃ and the rotating speed of 2000r/min, and preparing a phase-change material with reasonable phase-change temperature;
2) heating and melting the mixed phase-change material in water bath at 80 ℃, adding expanded perlite serving as a porous carrier material, uniformly stirring, placing the mixed material in a vacuum constant-temperature drying oven at 80 ℃ and the vacuum degree of-0.9 MPa for vacuum adsorption, and filtering, suspending and cooling after adsorption to prepare the composite phase-change material;
3) 500g of ordinary portland cement (P.O 52.5.5), 0.75g of polycarboxylic acid water reducing agent, 150g of composite phase change material and 200g of water are uniformly stirred at a low speed, poured and formed, and subjected to standard maintenance for 28 days to obtain the cement-based phase change energy storage material.
Comparative example 3:
1) mixing Span-80 and Tween-80 to prepare an emulsifier with HLB of 10;
2) physically crushing the solid paraffin into tiny particles with the particle size of about 1 mm;
3) 500g of ordinary portland cement (P.O 52.5.5) cement, 0.75g of polycarboxylic acid water reducing agent, 200g of water, 22.5g of emulsifier and 45g of paraffin particles obtained by crushing in the step 2 are uniformly stirred and cast for molding, and standard maintenance is carried out for 28d, so that the cement-based phase-change energy storage material is prepared.
Tests show that the non-emulsified paraffin can float on the surface layer in the stirring process of the mixed material, so that the defects of uneven distribution, poor stability and the like of the phase change energy storage material are caused.
The test results are shown in table 1 below. As can be seen from Table 1, the mechanical, thermal and durability properties of the phase change energy storage material prepared by the invention are mainly related to the paraffin doping amount, the water-cement ratio and the like. Along with the increase of the doping amount of the paraffin, the compressive strength is gradually reduced, and the latent heat of phase change is increased; the compressive strength gradually decreases with increasing water-cement ratio. Compared with the phase change energy storage material prepared by the microcapsule technology, the phase change energy storage material prepared by the invention can perfectly give consideration to mechanical and thermal properties, and can solve the problem of insufficient durability when the phase change energy storage material is prepared by an adsorption method.
TABLE 1
Claims (6)
1. A preparation method of a cement-based paraffin phase-change energy storage material is characterized by comprising the following steps:
the phase-change material is compounded with the cementing material in an oil-in-water emulsion mode, the phase-change material is uniformly distributed in the cement-based material in small particles with the average particle size of 0.5-1.5 mu m, and the phase-change material is well packaged by utilizing hydration reaction between outer layer water of the oil-in-water emulsion and the cementing material to form hydration products.
2. The method of claim 1, comprising the steps of:
step 1: mixing 20-25 parts of phase change material and 5-10 parts of emulsifier, heating for melting, uniformly stirring, and pouring into a colloid mill;
step 2: heating 65-75 parts of water to 75-85 ℃, adding the water to the molten mixture in the step 1, and continuously stirring for 30-50 min at a stirring speed of 800-1400 r/min to form an oil-in-water phase-change emulsion with stable performance;
and step 3: diluting 15-60 parts of the oil-in-water phase change emulsion prepared in the step 2 with 0-40 parts of water, pouring the diluted solution into a stirrer to be mixed with 100 parts of a cementing material and 0.05-0.2 part of a water reducing agent, and uniformly stirring;
and 4, step 4: and (3) pouring and molding the mixture obtained in the step (3) in a mold, hardening to form the cement-based paraffin phase-change energy storage material, and removing the mold and then performing conventional maintenance.
3. The method of claim 2, wherein:
in the step 1, the phase-change material is paraffin; the emulsifier is a compound system of an ionic surfactant and a nonionic surfactant.
4. The production method according to claim 3, characterized in that:
the hydrophilic-lipophilic balance value HLB of the emulsifier is 10-13.
5. The method of claim 2, wherein:
in the step 2, the emulsification rate of the oil-in-water phase-change emulsion is 90-100%, wherein the average particle size of oil phase particles is 0.5-1.5 μm.
6. The method of claim 2, wherein:
in step 3, the cementing material is general portland cement; the water reducing agent is one of polycarboxylic acid, naphthalene series water reducing agents and resin series water reducing agents.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620976A (en) * | 2022-03-14 | 2022-06-14 | 山东建筑大学 | Phase-change temperature-control controllable low-strength material for heat supply pipeline backfilling and preparation method thereof |
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| WO2021153081A1 (en) * | 2020-01-31 | 2021-08-05 | 富士フイルム株式会社 | Cement composition |
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- 2021-08-13 CN CN202110930160.6A patent/CN113636798A/en active Pending
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