WO2022127074A1 - 一种水合物储能控温材料及其制备方法 - Google Patents

一种水合物储能控温材料及其制备方法 Download PDF

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Publication number
WO2022127074A1
WO2022127074A1 PCT/CN2021/103346 CN2021103346W WO2022127074A1 WO 2022127074 A1 WO2022127074 A1 WO 2022127074A1 CN 2021103346 W CN2021103346 W CN 2021103346W WO 2022127074 A1 WO2022127074 A1 WO 2022127074A1
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hydrate
temperature control
temperature
energy storage
particles
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PCT/CN2021/103346
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English (en)
French (fr)
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赵佳飞
宋永臣
杨明昭
董宏生
张伦祥
史全
杨磊
凌铮
孙翔
李洋辉
刘卫国
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大连理工大学
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Priority to US17/628,104 priority Critical patent/US11911786B2/en
Publication of WO2022127074A1 publication Critical patent/WO2022127074A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/08—Plant for applying liquids or other fluent materials to objects
    • B05B5/081—Plant for applying liquids or other fluent materials to objects specially adapted for treating particulate materials
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/03—Discharge apparatus, e.g. electrostatic spray guns characterised by the use of gas, e.g. electrostatically assisted pneumatic spraying
    • B05B5/032—Discharge apparatus, e.g. electrostatic spray guns characterised by the use of gas, e.g. electrostatically assisted pneumatic spraying for spraying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/08—Plant for applying liquids or other fluent materials to objects
    • B05B5/082—Plant for applying liquids or other fluent materials to objects characterised by means for supporting, holding or conveying the objects
    • B05B5/084—Plant for applying liquids or other fluent materials to objects characterised by means for supporting, holding or conveying the objects the objects lying on, or being supported above conveying means, e.g. conveyor belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06—Applying particulate materials
    • 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
    • C09K5/066—Cooling mixtures; De-icing compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the invention belongs to the field of energy utilization, and specifically relates to a hydrate energy storage temperature control material and a preparation method thereof.
  • Heat energy is an important energy source and plays an irreplaceable role in human production and life.
  • thermal energy storage There are generally three methods of thermal energy storage: sensible heat storage, latent heat storage and thermochemical storage.
  • latent heat storage is a low-cost heat storage method, which utilizes the transformation of the solid-liquid phase of the phase change material to absorb or release heat to achieve the purpose of heat storage and energy storage. It is the most efficient thermal energy storage method, and can provide a higher thermal storage density at a smaller thermal storage interval temperature.
  • Materials used for thermal energy storage are called phase change materials, and are now widely used in construction, refrigeration, air conditioning, textiles, and other fields. In order to avoid environmental pollution and safety problems caused by flammability of phase change materials, phase change materials are usually encapsulated. Microcapsule encapsulation of phase change material not only increases the heat exchange area of the phase change material and improves the thermal conductivity, but also can be applied to energy-saving building materials and thermal regulation fibers due to the small encapsulation diameter.
  • Phase change materials can be divided into organic, inorganic and eutectic materials.
  • Organic materials are widely used for latent heat storage, are non-corrosive, have the same composition melting characteristics and self-nucleating ability.
  • Inorganic materials have high latent heat, thermal conductivity, and are non-toxic.
  • traditional microcapsule phase change materials have some inherent disadvantages: low thermal conductivity, easy phase separation, etc.
  • hydrate has been widely used in energy storage technology. As an ice-like substance, it has three structures. Compared with traditional phase change materials, its latent heat of phase change is higher than that of other traditional phase change materials at the phase change temperature of 4-15 °C. It can be generated by two driving forces, and a large amount of heat can be released by increasing the temperature or reducing the pressure. It has been widely studied and used in air conditioning and refrigeration, food preservation, etc. It is a unique phase change material.
  • the present invention provides a preparation method for preparing a hydrate energy storage temperature control material.
  • the method can not only prepare various types of coolant hydrate materials, but also can process production, and the prepared products can be reused.
  • the present invention provides a method for preparing a hydrate energy storage temperature control material, the purpose is to prepare a refrigerant hydrate temperature control energy storage material, and a further purpose is to provide a hydrate energy storage material that can prepare various types of hydrates. temperature control material method.
  • a hydrate temperature-controlling energy storage material wherein the hydrate temperature-controlling energy storage material comprises a core and a shell, wherein the core is a hydrate obtained from a coolant and water, and the shell is a cross-linked polymer.
  • a preparation method of a hydrate temperature-controlling energy storage material comprising the following steps:
  • Step 1 generating refrigerant hydrate
  • Step 2 hydrate crushing: take out the formed hydrate from the reaction kettle, pulverize and grind the hydrate particles with a particle size of 180-250 ⁇ m, and weigh them, and then use a centrifuge at a rate of not less than 2000 r. Centrifugal solid-liquid separation at the speed of /min for 10-20min;
  • Step 3 spray the hydrate particles with PTFE suspended ultrafine powder with an electrostatic spraying device: place the hydrate particles pulverized in step 2 on the conveyor belt, and add a high-voltage electrostatic field between the nozzle and the hydrate particles. Under the action of electricity and gravity, the PTFE suspended powder will be adsorbed and painted on the hydrate particles;
  • step 4 the hydrate particles sprayed with the polytetrafluoroethylene powder are placed in a plasma instrument, and treated with argon plasma to form free radicals on the surface of the polytetrafluoroethylene.
  • Step 5 place the hydrate particles wrapped by the modified polytetrafluoroethylene powder in a vacuum airtight container, heat the monomer solution until the steam evaporates, keep the airflow pressure at 40-50Pa with a throttle valve, and pass it into the airtight container.
  • the airtight container is cooled with a 25-30 °C water bath, and irradiated with a high-pressure mercury lamp of an ultraviolet lighting system for 80-90 minutes to promote the graft polymerization of monomers and free radicals; a hydrate energy storage temperature control material is obtained.
  • a hydrate is generated: 1 first wash and rinse the reactor with deionized water, then pour the water into the reactor, and use a vacuum pump to discharge the air in the reactor; 2 introduce refrigeration into the reactor
  • the temperature of the reactor is cooled to the equilibrium temperature of the hydrate phase and above the freezing point by the refrigeration cycle cooling system placed in the reactor.
  • the temperature in the reactor is stable, Pressurize the pressure of the reaction kettle to the pressure point in the stable hydrate region corresponding to the temperature in the phase diagram, and then turn on the magnetic stirrer to initiate the formation of hydrate; high, indicating that the hydrate formation reaction began to be exothermic.
  • the temperature in the kettle gradually decreased until it stabilized at the original temperature within 1 hour, indicating that a stable state was reached and the formation of hydrate was completed; the temperature sensor in the reaction kettle can measure the temperature in the reaction kettle, and there is a pressure sensor to measure the reaction kettle.
  • Internal pressure, pressure and temperature signals were acquired by a data logging system and collected by a personal computer.
  • the above-mentioned hydrate coolant is one or more mixed liquids of tetrahydrofuran, cyclopentane, and methylcyclohexane.
  • the electrostatic spraying device includes: a storage bin, a paint propelling device, a DC power supply, a nozzle, a conveyor belt and a collection device; the inside of the storage bin is used to store the spraying material polytetrafluoroethylene suspended superfine powder;
  • the paint propelling device They are respectively connected with the storage bin spraying device and the nozzle; the nozzle is made of conductive material and is used to spray PTFE suspended ultrafine powder, and is connected with the negative electrode of the DC power supply, which will generate dense negative charges;
  • the conveyor belt is made of conductive resin-based material for placing hydrate particles.
  • the conveyor belt faces the nozzle, so that the suspended particles sprayed from the nozzle contact the hydrate particles to be sprayed; the conveyor belt is connected to the positive electrode of the DC power supply, so that the hydrate particles have Positive electricity, and then the electric field required for spraying is formed between the nozzle and the conveyor belt.
  • the device of the above-mentioned step 5 includes: a throttle valve, a capacitance pressure gauge, a gas distribution nozzle, an ultraviolet illuminating high-pressure mercury lamp, a water bath heating device, a vacuum pump and a closed container; a throttle valve and a capacitance pressure gauge are connected at the entrance of the closed container to Control the pressure of monomer vapor entering the airtight container; the outlet of the airtight container is connected to a vacuum pump, which contains a gas distribution nozzle, so that the gas is evenly distributed in the airtight container; the airtight container is placed in a water bath heating device to control the temperature in the airtight container; ultraviolet rays Illumination High-pressure mercury lamps are irradiated outside the airtight container to promote the reaction.
  • polytetrafluoroethylene suspended ultrafine powder with a particle size of 2-12 ⁇ m, is suitable for electrostatic spraying.
  • the conveying speed of the above-mentioned conveyor belt is 0.5-2m/s
  • the linear velocity of the spraying gas of the nozzle is 100-200m/s
  • the powder content of the spraying gas is 1-2kg/m 3
  • the pressure of the high-voltage electrostatic field is 60-90kV
  • the distance between the spraying and the conveyor belt is 200-300mm.
  • the above-mentioned monomer is a monomer solution, which can be a dimethylacetamide solution with a solution concentration of 10%, a hydroxyethyl methacrylate solution with a solution concentration of 30% or a glycidyl methacrylate solution with a solution concentration of 30%. ester solution.
  • the evaporation temperature of the dimethylacetamide solution is 109-110°C
  • the evaporation temperature of the hydroxyethyl methacrylate solution is 95°C
  • the temperature of the glycidyl methacrylate solution is 67°C.
  • the coolant hydrate used in the present invention has higher thermal conductivity and can ensure a higher thermal conductivity. And because it has been nucleated before production, it is easier to nucleate during use, with good reversibility, and the work can be reused.
  • the present invention utilizes the graft polymerization of monomer vapor and surface free radicals to make the polymer distribution on the outer surface of the hydrate temperature control energy storage material uniform;
  • the C(CH 3 )-CO- functional group is attached to the surface of PTFE through its universal adhesion. Under the ultraviolet irradiation system, it can be radically grafted with the surface of PTFE to obtain cross-linking polymerization on the surface of the particle. Due to the existence of graft polymerization, the force generated by the valence between the core and the outer surface shell is much greater than the van der Waals force between the typical core and shell, making the hydrate energy storage and temperature control The material has high stability.
  • the preparation method provided by the present invention can utilize any refrigerant hydrate, and the properties of the refrigerant hydrate will not affect the use of the method.
  • Fig. 1 is the electrostatic spraying device system schematic diagram of the present invention
  • Fig. 2 is the device schematic diagram of monomer of the present invention and radical graft polymerization process
  • (1) Generating hydrate first wash and rinse the reactor with deionized water three times, pour the water into the reactor and seal it, and empty the head space, vacuum the reactor with a vacuum pump for 30 minutes, and remove the The air is expelled, then the vacuum pump is turned off.
  • the reaction kettle is equipped with a temperature sensor to measure the temperature in the reaction kettle, and a pressure sensor to measure the pressure in the reaction kettle. The pressure and temperature signals are collected by a data recording system and collected by a personal computer.
  • the cyclopentane refrigerant can be injected into the reaction kettle first, so that the molar ratio of cyclopentane refrigerant and water is 1:17, and then the refrigerating circulating water bath system placed in the reaction kettle is used to
  • the reactor temperature was cooled to the desired temperature, ie 2°C.
  • the pressure of the reactor was pressurized to the required pressure of 0.2 MPa, and then the magnetic stirrer (stirring speed was 550 rpm) was turned on to initiate the formation of hydrate.
  • the formation of hydrate can be judged by observing the temperature rise and pressure drop in the autoclave.
  • the formation of hydrate is judged by the temperature rise in the kettle, and the temperature in the kettle suddenly rises, indicating that the hydrate formation reaction begins to exothermic. After that, the temperature in the kettle gradually decreased until it stabilized at the original temperature of 2 °C within 1 h, indicating that a stable state was reached and the hydrate formation was completed.
  • the pressure reducing valve was opened, and the hydrate was quickly taken out from the kettle.
  • Hydrate crushing Take out the formed hydrate from the reactor, crush and grind hydrate particles with a particle size of 180-250 ⁇ m, and then use a low-speed centrifuge at a rate of not less than 2000 r/min. Centrifuge solid-liquid separation for 10 min. The hydrate solid particles were taken out and weighed with an electronic analytical balance.
  • the hydrate particles 7 are sprayed with polytetrafluoroethylene suspended ultrafine powder with an electrostatic spraying device.
  • the interior of the storage bin 1 is used to store the PTFE suspended ultrafine powder of the spraying material.
  • the paint propelling device 2 is respectively connected with the spraying device of the storage bin 1 and the nozzle 4, and pressurizes the spraying material inside the storage bin 1, so that the suspended ultrafine powder of polytetrafluoroethylene is sprayed from the nozzle.
  • the paint propelling device 2 includes a liquid propeller and a carrier gas.
  • the nozzle 4 is made of conductive material and is used for spraying the suspended ultrafine powder of PTFE. It is connected to the negative pole of the DC power supply 3, and a dense negative charge will be generated on it.
  • the conveyor belt 5 of the spraying device is made of a conductive resin-based material for placing the hydrate particles 7 .
  • the conveyor belt 5 faces the nozzles so that the suspended particles sprayed from the nozzles 4 can contact the hydrate particles 7 to be sprayed.
  • the conveyor belt 5 is connected to the positive electrode of the DC power supply 3, so that the hydrate particles are positively charged, and the electric field required for spraying is formed between the nozzle 4 and the conveyor belt 5.
  • the charged PTFE suspended particles enter the electric field, under the influence of the electric field force, they will automatically fly towards the hydrate particles until the hydrate particles 7 are completely wrapped by the PTFE suspended ultrafine powder and fall into the collection device 6.
  • the ultraviolet ray irradiation high-pressure mercury lamp 11 has a power of 1000W, and the ultraviolet intensity is 6mW/cm until the graft polymerization reaction is completed, to obtain PDMA- PS forms a stable shell layer on the surface of PTFE. Finally, wash with methanol and dry under nitrogen flow to obtain a hydrate energy storage temperature control material.
  • Product measurement use an electronic analytical balance to measure the quality of the hydrate energy storage and temperature control material; use an LA960 particle size analyzer to measure the particle diameter of the hydrate energy storage temperature control material, and the working temperature of the measuring instrument is 25 °C; use differential scanning A calorimeter was used to determine the composition and latent heat of phase transition of the hydrate energy storage and temperature control materials. All measurements were carried out in a nitrogen atmosphere with a heating or cooling rate of 5 °C/min, respectively. About 6 mg of hydrate energy storage and temperature control material particles were sealed in a stainless steel crucible with an O-ring.
  • the coolant is completely converted to hydrate by thermal cycling: the sample is cooled to a low temperature T low typically -30°C; the sample is then heated and scanned from -30 to 40°C, the first heating scan, the sample is held at each temperature for 5 min , to reduce thermal effects before formal measurements.
  • M hydrate is the mass of hydrate particles after hydrate crushing
  • M is the total mass of hydrate capsule products.
  • ⁇ H m, hydrate is the phase change enthalpy of the melting process of hydrate cracking into liquid water and liquid refrigerant
  • ⁇ H c, hydrate is the phase change enthalpy of the solidification process of liquid water and liquid refrigerant synthesizing hydrate
  • ⁇ H m , ⁇ H c are the phase change enthalpies of the melting and solidification process of the hydrate energy storage temperature-controlled product measured by differential scanning calorimeter, respectively.
  • t 1 and t 2 are the temperature of the hydrate in the particle (phase transition temperature) and the ambient temperature, respectively, k is the thermal conductivity of the material shell, and r 1 and r 2 are the inner and outer radii of a single material particle, respectively.
  • r 1 can be calculated by the following formula:
  • M hydrate is the mass of the hydrate particles after the hydrate is broken, and ⁇ is the density of the hydrate.
  • r 2 is the average radius of the material particles measured by the particle size meter.
  • the density ⁇ of cyclopentane hydrate can be calculated from the following formula:
  • V cell is the volume of each unit cell, which is (17.3 ⁇ 10 ⁇ 10 ) 3 m 3 , and N Avo is Avogadro’s constant.
  • the calculated density of cyclopentane hydrate is 964.691 g/cm 3 .
  • the thermal storage heat of hydrate energy storage and temperature control material particles is represented by Q h :
  • t i is the initial temperature
  • t 2 is the final temperature
  • f is the melting fraction
  • L is the latent heat of phase transition
  • cp is the specific heat capacity of the hydrate.
  • the constant pressure heat capacity cp can be calculated by the following formula:
  • the hydrate energy storage temperature control material is used to release cold energy and adjust the temperature in the room.
  • the initial temperature t i of the material is 2 °C
  • the final temperature (room temperature) t 2 is 15 °C
  • the hydrate in the material is completely
  • cyclopentane hydrate can release 349.118kJ/kg of heat, which is higher than that of formic acid, 279.45kJ/kg, and propylene glycol, 218.37kJ/kg, so it has good energy storage properties.
  • phase transition time of a single hydrate energy storage and temperature control granular material is represented by ⁇ :
  • m H is the phase transition rate of the hydrate energy storage and temperature control material particles.
  • the particle phase transition rate m H of the hydrate energy storage temperature control material can be calculated by the following formula:

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Abstract

一种水合物储能控温材料及其制备方法，所述的材料含有冷却剂水合物和交联聚合物。制备过程首先用高压釜制备冷却剂水合物，并碾压粉碎筛取水合物颗粒；然后用静电喷涂装置将聚四氟乙烯悬浮超微粉均匀涂布在水合物颗粒表面，再将其放入到等离子体仪中，对聚四氟乙烯改性，使聚四氟乙烯粉末表面形成自由基；最后将单体在UV照明系统高压水银灯照射下，与聚四氟乙烯表面自由基接枝聚合，稳定材料结构，制成最终产物。制备的水合物储能控温材料稳定性良好，提供了一种可以制备多种类型冷却剂水合物材料的方法，产物可以充分发挥水合物储能控温的优势，且能周期性使用，可应用于建筑、制冷等多种领域。

Description

一种水合物储能控温材料及其制备方法 技术领域
本发明属于能源利用领域，具体涉及到水合物储能控温材料及其制备方法。
背景技术
热能是一种重要的能源，在人类的生产生活中发挥着不可替代的作用。热能储存一般有三种方法：显热储存、潜热储存和热化学储存。其中，潜热储存是一种低成本的蓄热方法，利用相变材料固液相的转变，吸收或释放热量，达到蓄热储能的目的。它是最有效的热能储存方式，在较小的储放热间隔温度下，可以提供较高的储热密度。用于热能储存的材料称为相变材料，现在被广泛地应用于建筑、制冷、空调、纺织等领域。为了避免相变材料污染环境、因易燃等特点造成的安全问题，通常会封装相变材料。微胶囊封装相变材料，不仅增大了相变材料的换热面积，提高了导热系数，而且由于封装直径小，可以应用于节能建筑材料和热调节纤维等。
相变材料可分为有机、无机和共晶体材料。有机材料广泛应用于潜热储存，无腐蚀性，具有同成分熔融特性和自成核能力。无机材料有较高的潜热、热导率，具有无毒等特点。但传统的微胶囊相变材料会有一些固有缺点：热导率低，易相分离等。近年来，水合物被广泛应用于储能技术中，作为一种类冰的物质，它的结构有三种。与传统的相变材料相比，在相变温度4-15℃，它的相变潜热高于其他传统相变材料的潜热。可由两种驱动力驱动生成，通过提高温度或降低压力可释放大量的热，现已被广泛研究使用在空调制冷、食物保存等方面，是一种独一无二的相变材料。
为了充分发挥水合物储能控温的优势，本发明提供了一种制备方法，制备水合物储能控温材料。该方法不仅可以制备多种类型的冷却剂水合物材料，而 且可流程化生产，制得的产品可重复使用。
发明内容
本发明针对现有技术不足，提供了一种水合物储能控温材料制备方法，目的是制备制冷剂水合物控温储能材料，进一步的目的在于提供一种可以制备多种类型水合物储能控温材料方法。
一种水合物控温储能材料，其中所述水合物控温储能材料包括芯和外壳，其中所述芯是冷却剂和水制得的水合物，所述外壳为交联聚合物。
水合物控温储能材料的制备方法，包括如下步骤：
步骤1，生成制冷剂水合物；
步骤2，水合物破碎：将形成的水合物从反应釜中取出，粉碎研磨用筛网筛取颗粒粒径为180～250μm的水合物颗粒，并称重，再用离心机以不低于2000r/min的转速离心固液分离10-20min；
步骤3，用静电喷涂装置对水合物颗粒喷涂聚四氟乙烯悬浮超微粉：将步骤2粉碎后的水合物颗粒置于传送带上，在喷嘴和水合物颗粒之间加一高压静电场，在静电力和重力作用下，聚四氟乙烯悬浮粉末将会在水合物颗粒上吸附涂装；
步骤4，将喷涂好聚四氟乙烯粉末的水合物颗粒置于等离子体仪中，用氩等离子体处理，使聚四氟乙烯表面形成自由基。
步骤5，将改性聚四氟乙烯粉末包裹的水合物颗粒置于真空密闭容器中，将单体溶液加热直至蒸发出蒸汽，将气流压力用节流阀保持在40～50Pa，通入到密闭容器中，密闭容器用25-30℃水浴冷却，并用紫外线照明系统高压水银灯照射80-90min，促进单体与自由基接枝聚合；获得水合物储能控温材料。
进一步地，上述步骤1，生成水合物：①先用去离子水清洗和冲洗反应釜，再将水倒入到反应釜中，用真空泵将反应釜内的空气排出；②向反应釜内引入 制冷剂，根据冷却剂的种类和冷却剂的水合物相图，用放置反应釜的制冷循环冷却系统将反应釜温度冷却至水合物相平衡温度下、冰点以上，待反应釜内的温度稳定后，将反应釜压力加压至相图内温度对应的水合物稳定区域压力点，然后打开磁力搅拌器引发水合物的生成；③水合物开始形成通过釜内温度升高来判断，釜内温度突然升高，表明水合物生成反应开始放热。之后，釜内温度渐渐降低，直至在1h内稳定在原温度，说明达到了稳定状态，水合物生成完成；所述反应釜内有温度传感器可以测量反应釜内的温度，有压力传感器可以测量反应釜内的压力，压力和温度信号由数据记录系统采集并由个人计算机收集。
进一步地，上述水合物冷却剂为四氢呋喃、环戊烷、甲基环己烷中一种或两种以上混合液体。
进一步地，上述反应釜内有磁力搅拌器，磁力搅拌器的转速为500～600rpm，引发水合物生成。
进一步地，上述步骤3中静电喷涂装置包括：储料仓、涂料推进装置、直流电源、喷嘴、传送带和收集装置；储料仓内部用于存放喷涂材料聚四氟乙烯悬浮超微粉；涂料推进装置分别与储料仓喷涂装置以及喷嘴相连；喷嘴由导电材料制成，用于喷出聚四氟乙烯悬浮超微粉，与直流电源的负极相连接，其上会产生密集的负电荷；喷涂装置的传送带由导电树脂基材料制成，用于放置水合物颗粒，传送带朝向喷嘴，使从喷嘴喷出的悬浮颗粒接触到待喷涂水合物颗粒上；传送带与直流电源正极连接，使水合物颗粒带有正电，进而喷嘴与传送带之间形成喷涂所需的电场。
进一步地，上述步骤5的装置包括：节流阀、电容压力计、气体分配喷头、紫外线照明高压水银灯、水浴加热装置、真空泵和密闭容器；密闭容器入口处连接节流阀和电容压力计，以控制单体蒸气进入密闭容器的压力；密闭容器出 口处连接真空泵，内部含有气体分配喷头，使气体均匀分布在密闭容器的中；密闭容器放置在水浴加热装置中，控制密闭容器内的温度；紫外线照明高压水银灯在密闭容器外照射，促进反应的进行。
进一步地，上述聚四氟乙烯悬浮超微粉，粒径为2～12μm，适用于静电喷涂。
进一步地，上述传送带的传送速度为0.5-2m/s，喷嘴的喷涂气体线速度在100-200m/s，喷涂气体的粉末含量为1-2kg/m 3，高压静电场的压力为60-90kV，喷涂距传送带的距离为200-300mm。
进一步地，上述单体是单体溶液，可以为溶液浓度10％的二甲基乙酰胺溶液，溶液浓度为30％的甲基丙烯酸羟乙酯溶液或溶液浓度为30％的甲基丙烯酸缩水甘油酯溶液。其中，二甲基乙酰胺溶液蒸发温度为109～110℃，甲基丙烯酸羟乙酯溶液蒸发温度为95℃，甲基丙烯酸缩水甘油酯溶液温度为67℃。
与现有的技术相比，本发明的有益效果是：
(1)本发明采用的冷却剂水合物作为相变材料的方式，相比于有机相变材料，具有更高的导热性，可以保证较高的导热系数。且由于在生产前已经成核，在使用过程中，更易成核，可逆性好，可重复使用工作。
(2)本发明利用单体蒸汽与表面自由基的接枝聚合作用，使水合物控温储能材料外表面聚合物分布均匀；由于聚四氟乙烯表面没有液体，单体有H 2C＝C(CH 3)-CO-官能团，通过其普遍粘附力附着到聚四氟乙烯表面，在紫外线照射系统下，可以与聚四氟乙烯表面自由基接枝聚合，在粒子表面获得交联聚合物，使微胶囊表面外壳更加致密；由于接枝聚合的存在，芯与外表面壳层之间的化合价产生的力，远大于典型核壳之间的范德华力，使该水合物储能控温材料具有高稳定性。
(3)本发明提供的制备方法，可以利用任何制冷剂水合物，制冷剂水合物性质不会影响到该方法的使用。
附图说明
图1是本发明的静电喷涂装置系统示意图；
图中：1储料仓；2涂料推进装置；3直流电源；4喷嘴；5传送带；6收集装置；7水合物颗粒。
图2是本发明单体与自由基接枝聚合过程的装置示意图；
图中：8节流阀；9电容压力计；10气体分配喷头；11紫外线照明高压水银灯；12水浴加热装置；13真空泵；14密闭容器；15改性聚四氟乙烯粉末包裹的水合物颗粒。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
以环戊烷水合物为例，一种水合物储能控温材料的制备方法，步骤如下：
(1)生成水合物：先用去离子水清洗和冲洗反应釜三次，将水倒入到反应釜中并密封，并排空顶部空间，用真空泵对反应釜抽真空30min，将反应釜内的空气排出，随后关闭真空泵。反应釜装有内有温度传感器可以测量反应釜内的温度，有压力传感器测量反应釜内的压力，压力和温度信号由数据记录系统采集并由个人计算机收集。由于使用液体制冷剂环戊烷，可以先向反应釜内注入的环戊烷制冷剂，使环戊烷制冷剂与水的摩尔比为1：17，再用放置反应釜的制冷循环水浴系统将反应釜温度冷却为所需温度，即2℃。待反应釜内的温度稳定后，将反应釜压力加压至所需压力0.2MPa，然后打开磁力搅拌器(搅拌速度为550rpm)引发水合物的生成。水合物的形成可以通过观察到釜内温度升高、压力降低来判断。在本具体实施方式中，水合物开始形成通过釜内温度升高来 判断，釜内温度突然升高，表明水合物生成反应开始放热。之后，釜内温度渐渐降低，直至在1h内稳定在原温度2℃，说明达到了稳定状态，水合物生成完成。水合物生成结束，打开减压阀，将水合物迅速从釜内取出。
(2)水合物破碎：将形成的水合物从反应釜中取出，粉碎研磨用筛网筛取颗粒粒径为180～250μm的水合物颗粒，再用低速离心机以不低于2000r/min的转速离心固液分离10min。取出水合物固体颗粒，用电子分析天平称重。
(3)用静电喷涂装置对水合物颗粒7喷涂聚四氟乙烯悬浮超微粉。储料仓1内部用于存放喷涂材料聚四氟乙烯悬浮超微粉。涂料推进装置2分别与储料仓1喷涂装置以及喷嘴4相连，对储料仓1内部的喷涂材料加压，使得聚四氟乙烯悬浮超微粉从喷嘴喷出。涂料推进装置2包括液体推进器和载气。喷嘴4由导电材料制成，用于喷出聚四氟乙烯悬浮超微粉。与直流电源3的负极相连接，其上会产生密集的负电荷。喷涂装置的传送带5由导电树脂基材料制成，用于放置水合物颗粒7。传送带5朝向喷嘴，使从喷嘴4喷出的悬浮颗粒可以接触到待喷涂水合物颗粒7上。传送带5与直流电源3正极连接，使水合物颗粒带有正电，进而喷嘴4与传送带5之间形成喷涂所需的电场。当携带有电荷的聚四氟乙烯悬浮颗粒进入到电场后，受电场力的影响，会自动向水合物颗粒飞行，直至水合物颗粒7完全被聚四氟乙烯悬浮超微粉包裹，掉入收集装置6。
(4)将喷涂好聚四氟乙烯粉末的水合物颗粒置于功率200W的PMT100A等离子体仪中，用氩等离子体处理，气体流量为120ppm，压力为45Pa处理6min，使聚四氟乙烯表面形成自由基。并用紫外线灯照射测量聚四氟乙烯表面的自由基浓度。
(5)将改性聚四氟乙烯粉末包裹的水合物颗粒15置于真空密闭容器14中，将溶液浓度10％的单体溶液二甲基乙酰胺溶液加热直至蒸发出蒸汽，将气流压 力用节流阀8保持在46.7Pa，经电容压力计9，通过气体分配喷头10通入到密闭容器14中。密闭容器14连接真空泵13，用30℃水浴12冷却，并用紫外线照明系统高压水银灯11照射80min，紫外线照射高压水银灯11功率为1000W，紫外线强度为6mW/cm 2直至接枝聚合反应完成，得到PDMA-PS在聚四氟乙烯表面，形成稳定的壳层。最后，用甲醇清洗并在氮气流下干燥，即得到水合物储能控温材料。
(6)产品测量：用电子分析天平测量水合物储能控温材料的质量；用LA960粒度分析仪测量水合物储能控温材料颗粒直径，测量仪的工作温度为25℃；用差示扫描量热仪测定水合物储能控温材料的组成和相变潜热，所有测量均在氮气环境下进行，加热或冷却速率分别为5℃/min。将水合物储能控温材料颗粒约6mg密封在带有O形环的不锈钢坩锅中。通过热循环，冷却剂完全转化为水合物：将样品冷却至低温T low通常为-30℃；再从-30到40℃加热扫描样品，第一次加热扫描，样品在每个温度下保持5min，以减少正式测量之前的热影响。
实验数据处理方法：
由于上述水合物储能控温材料制备装置及方法可以直接得到的测量结果为质量、体积、相变潜热等，因此需要对测量结果进行热力计算，通过计算水合物质量百分比M hydragte％、包封率R、包封效率E、单个微胶囊传递给外界的热量Q等，研究该水合物储能控温材料用于相变控温领域的性能。
样品的理论水合物质量百分比用M hydrate％表示：
Figure PCTCN2021103346-appb-000001
其中，M hydrate是水合物破碎后的水合物颗粒质量，M是水合物胶囊产品的总质量。
样品的水合物包封率用R表示
Figure PCTCN2021103346-appb-000002
样品水合物的包封效率用E表示
Figure PCTCN2021103346-appb-000003
其中，ΔH m，hydrate是水合物裂解成液态水和液态制冷剂的融化过程的相变焓，ΔH c，hydrate是液态水和液态制冷剂合成水合物的凝固过程相变焓，ΔH m、ΔH c分别是差示扫描量热仪测得的水合物储能控温产品的融化、凝固过程相变焓。
单个水合物储能控温颗粒相变过程传递给外界的热量用Q表示：
Figure PCTCN2021103346-appb-000004
积分：
Figure PCTCN2021103346-appb-000005
其中，t 1、t 2分别为颗粒中水合物的温度(相变温度)和外界环境温度，k为材料外壳的导热系数，r 1、r 2分别为单个材料颗粒的内外半径。
r 1可由下式计算：
Figure PCTCN2021103346-appb-000006
其中，M hydrate是水合物破碎后的水合物颗粒质量，ρ为水合物的密度。
Figure PCTCN2021103346-appb-000007
可由下式计算：
Figure PCTCN2021103346-appb-000008
其中，
Figure PCTCN2021103346-appb-000009
为水合物占材料颗粒总体积的百分数，r 2为粒度测量仪测量的材料颗粒的平均半径。
环戊烷水合物的密度ρ可由下式计算：
Figure PCTCN2021103346-appb-000010
其中，ρ根据Sloan(1998)的假设，假设客体分子完全占用水合物的大笼子，N w是单位晶胞水分子的数量，N w＝136；MW是分子质量，
Figure PCTCN2021103346-appb-000011
的分子质量 为18，MW g客体分子质量为70；y是每种空腔的部分占用率，α是每个水分子的空腔数量，下标1和2分别代表小空腔和大空腔，环戊烷水合物只占据大空腔，故y 1＝0，y 2＝1，且α 1＝16，α 2＝8。V cell是每个晶胞的体积，为(17.3×10 -10) 3m 3，N Avo是阿伏伽德罗常数。计算可得环戊烷水合物的密度为964.691g/cm 3。
水合物储能控温材料颗粒的热储热量用Q h表示：
Figure PCTCN2021103346-appb-000012
其中，t i是初始温度，t 2是最终温度，f是熔化分数，L是相变潜热，c p为水合物的比热容。相变潜热根据实验数据可得，L＝338.800kJ/kg，高于甲酸247kJ/kg的相变潜热，丙二醇186kJ/kg的相变潜热。
定压热容c p可由下式计算：
c p＝a+bT+cT 2+dT 3      (10)
其中，a、b、c、d是水合物的热容参数，对于环戊烷水合物，a＝-124.33，b＝3.2592，c＝2×10 -6且d＝-4×10 -9。
将该水合物储能控温材料用于释放冷量，调节房间内的温度，当材料的初始温度t i是2℃，最终温度(室温)t 2为15℃，且材料中的水合物完全熔化时，环戊烷水合物可以释放349.118kJ/kg的热量，高于相同情况下的甲酸释放的热量279.45kJ/kg，丙二醇释放的热量218.37kJ/kg，故具有良好的储能特性。
单个水合物储能控温颗粒材料的相变时间用τ表示：
Figure PCTCN2021103346-appb-000013
其中，m H是水合物储能控温材料颗粒的相变速率。
根据Kamath研究的水合物热分解速率模型，水合物储能控温材料颗粒相变速率m H可由下式计算：
Figure PCTCN2021103346-appb-000014

Claims (10)

  1. 一种水合物储能控温材料制备方法，其特征在于，包括如下步骤：
    步骤1，生成冷却剂水合物；
    步骤2，水合物破碎：将形成的水合物从反应釜中取出，粉碎研磨用筛网筛取颗粒粒径为180～250μm的水合物颗粒，并称重，再用离心机以不低于2000r/min的转速离心固液分离10-20min；
    步骤3，用静电喷涂装置对水合物颗粒喷涂聚四氟乙烯悬浮超微粉：将步骤2粉碎后的水合物颗粒置于传送带(5)上，在喷嘴(4)和水合物颗粒(7)之间加一高压静电场，在静电力和重力作用下，聚四氟乙烯悬浮粉末将会在水合物颗粒上吸附涂装；
    步骤4，将喷涂好聚四氟乙烯粉末的水合物颗粒(15)置于等离子体仪中，用氩等离子体处理，使聚四氟乙烯表面形成自由基；
    步骤5，将改性聚四氟乙烯粉末包裹的水合物颗粒置于真空密闭容器中，将单体溶液加热直至蒸发出蒸汽，将气流压力用节流阀(8)保持在40～50Pa，通入到密闭容器(14)中，密闭容器(14)用25-30℃水浴冷却，并用紫外线照明系统高压水银灯(11)照射80-90min，促进单体与自由基接枝聚合；获得水合物储能控温材料。
  2. 根据权利要求1所述的水合物储能控温材料制备方法，其特征在于：步骤1，生成水合物：①先用去离子水清洗和冲洗反应釜，再将水倒入到反应釜中，用真空泵将反应釜内的空气排出；②向反应釜内引入冷却剂，根据冷却剂的种类和冷却剂的水合物相图，用放置反应釜的制冷循环冷却系统将反应釜温度冷却至水合物相平衡温度下、冰点以上，待反应釜内的温度稳定后，将反应釜压力加压至相图内温度对应的水合物稳定区域压力点，然后打开磁力搅拌器引发水合物的生成；③水合物开始形成通过釜内温度升高来判断，釜内温度突然升高， 表明水合物生成反应开始放热；之后，釜内温度渐渐降低，直至在1h内稳定在原温度，说明达到了稳定状态，水合物生成完成；所述反应釜内有温度传感器可以测量反应釜内的温度，有压力传感器可以测量反应釜内的压力，压力和温度信号由数据记录系统采集并由个人计算机收集。
  3. 根据权利要求2所述的水合物储能控温材料制备方法，其特征在于：水合物冷却剂为四氢呋喃、环戊烷、甲基环己烷中一种或两种以上混合液体。
  4. 根据权利要求2所述的水合物储能控温材料制备方法，其特征在于：所述反应釜内有磁力搅拌器，磁力搅拌器的转速为500～600rpm，引发水合物生成。
  5. 根据权利要求1所述的水合物储能控温材料制备方法，其特征在于：步骤3中使用聚四氟乙烯悬浮超微粉，粒径为2～12μm，适用于静电喷涂。
  6. 根据权利要求1所述的水合物储能控温材料制备方法，其特征在于：步骤3中静电喷涂装置包括：储料仓(1)、涂料推进装置(2)、直流电源(3)、喷嘴(4)、传送带(5)和收集装置(6)；储料仓(1)内部用于存放喷涂材料聚四氟乙烯悬浮超微粉；涂料推进装置(2)分别与储料仓(1)喷涂装置以及喷嘴(4)相连；喷嘴(4)由导电材料制成，用于喷出聚四氟乙烯悬浮超微粉，与直流电源(3)的负极相连接，其上会产生密集的负电荷；喷涂装置的传送带(5)由导电树脂基材料制成，用于放置水合物颗粒(7)，传送带(5)朝向喷嘴，使从喷嘴(4)喷出的悬浮颗粒接触到待喷涂水合物颗粒(7)上；传送带(5)与直流电源(3)正极连接，使水合物颗粒带有正电，进而喷嘴(4)与传送带(5)之间形成喷涂所需的电场。
  7. 根据权利要求1所述的水合物储能控温材料制备方法，其特征在于：步骤3中传送带(5)的传送速度为0.5-2m/s，喷嘴(4)的喷涂气体线速度在100-200m/s，喷涂气体的粉末含量为1-2kg/m 3，高压静电场的压力为60-90kV，喷嘴(4)距 传送带的距离为200-300mm。
  8. 根据权利要求1所述的水合物储能控温材料制备方法，其特征在于：步骤(5)的单体是单体溶液，为溶液浓度10％的二甲基乙酰胺溶液、溶液浓度为30％的甲基丙烯酸羟乙酯溶液或溶液浓度为30％的甲基丙烯酸缩水甘油酯溶液中的一种；其中，二甲基乙酰胺溶液蒸发温度为109～110℃，甲基丙烯酸羟乙酯溶液蒸发温度为95℃，甲基丙烯酸缩水甘油酯溶液温度为67℃。
  9. 根据权利要求1所述的水合物储能控温材料制备方法，其特征在于：步骤5的装置包括：节流阀(8)、电容压力计(9)、气体分配喷头(10)、紫外线照明高压水银灯(11)、水浴加热装置(12)、真空泵(13)和密闭容器(14)；密闭容器(14)入口处连接节流阀(8)和电容压力计(9)，以控制单体蒸气进入密闭容器的压力；密闭容器(14)出口处连接真空泵(13)，内部含有气体分配喷头(10)，使气体均匀分布在密闭容器的(14)中；密闭容器放置在水浴加热装置(12)中，控制密闭容器内的温度；紫外线照明高压水银灯(11)在密闭容器外照射，促进反应的进行。
  10. 权利要求1-9任一所述方法制备得到的水合物储能控温材料，其特征在于，该材料芯为冷却剂和水混合物，外壳为交联聚合物。
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