CN107245326A - A kind of high-temperature phase change heat accumulation microcapsules and preparation method thereof - Google Patents
A kind of high-temperature phase change heat accumulation microcapsules and preparation method thereof Download PDFInfo
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000009825 accumulation Methods 0.000 title 1
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 77
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000003860 storage Methods 0.000 claims abstract description 71
- 239000000843 powder Substances 0.000 claims abstract description 54
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims abstract description 47
- 238000005338 heat storage Methods 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- 239000011268 mixed slurry Substances 0.000 claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920005646 polycarboxylate Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 49
- 239000011232 storage material Substances 0.000 description 20
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000012782 phase change material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
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Abstract
本发明涉及一种高温相变蓄热微胶囊及其制备方法。其技术方案是：将铝硅合金粉和所述表面改性剂搅拌均匀，在水浴和搅拌条件下，匀速加入磷酸二氢铝溶液，搅拌，制得混合料浆。再于水浴和搅拌条件下，向混合料浆中加入无水有机醇，继续搅拌，静置，过滤，得沉淀物。将沉淀物洗涤至pH值为中性，干燥至恒重，制得高温相变蓄热微胶囊坯体。将高温相变蓄热微胶囊坯体在氧化气氛和600~1300℃条件下保温2~8h，制得复合壳层的高温相变蓄热微胶囊；或在氧化气氛和1300~1500℃条件下保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。本发明所用原料成本低、制备工艺简单和容易实现工业生产；所制制品的热量利用率和利用效率高，使用温度高。The invention relates to a high-temperature phase change thermal storage microcapsule and a preparation method thereof. The technical scheme is as follows: uniformly stir the aluminum-silicon alloy powder and the surface modifying agent, add aluminum dihydrogen phosphate solution at a uniform speed under the condition of water bath and stirring, and stir to prepare the mixed slurry. Then, under the conditions of water bath and stirring, add anhydrous organic alcohol to the mixed slurry, continue to stir, stand still, and filter to obtain a precipitate. The precipitate is washed until the pH value is neutral, and dried to a constant weight to prepare a high-temperature phase change thermal storage microcapsule green body. Heat the high-temperature phase-change thermal storage microcapsule body in an oxidizing atmosphere at 600-1300°C for 2-8 hours to prepare high-temperature phase-change thermal storage microcapsules with a composite shell; or in an oxidizing atmosphere at 1300-1500°C Heat preservation for 2-8 hours to prepare high-temperature phase-change heat-storage microcapsules with alumina shell. The raw material used in the invention has low cost, simple preparation process and easy realization of industrial production; the heat utilization rate and utilization efficiency of the manufactured product are high, and the service temperature is high.
Description
技术领域technical field
本发明属于高温相变蓄热复合材料技术领域。具体涉及提供一种高温相变蓄热微胶囊及其制备方法。The invention belongs to the technical field of high temperature phase change thermal storage composite materials. Specifically, it relates to providing a high-temperature phase-change thermal storage microcapsule and a preparation method thereof.
背景技术Background technique
蓄热技术是利用蓄热材料将暂时不需要的热量储存，等需要热量时，再将热量释放出来的一种储能技术。蓄热技术解决了热量供给与需求的时间差矛盾，提高了热量的利用，因此可用于电力负荷的削峰填谷、太阳能的储备、工业余热的回收等，以达到发展新能源、节约旧能源的目的。Heat storage technology is a kind of energy storage technology that uses heat storage materials to store temporarily unnecessary heat, and then releases heat when heat is needed. Heat storage technology solves the time difference between heat supply and demand, and improves the utilization of heat. Therefore, it can be used for peak-shaving and valley-filling of power loads, solar energy storage, and recovery of industrial waste heat, etc., to achieve the goal of developing new energy and saving old energy. Purpose.
蓄热技术的核心问题是蓄热材料的制备和应用，其中相变蓄热材料因其储能高，相变温度可调而成为具有很好潜力的蓄热材料。但相变蓄热材料因在相变时易产生相变介质泄露、体积变化等问题，从而限制了相变蓄热材料的实际应用。将相变材料制备成相变蓄热微胶囊是解决上述问题的主要技术之一。相变蓄热微胶囊由相变材料为核、包覆材料为壳构成。由于相变蓄热微胶囊具有无腐蚀性、防介质泄漏、蓄热密度较大、相变时恒温等优点而成为近年来研究的热点。The core issue of thermal storage technology is the preparation and application of thermal storage materials, among which phase change thermal storage materials have become thermal storage materials with good potential because of their high energy storage and adjustable phase transition temperature. However, phase change heat storage materials are prone to problems such as phase change medium leakage and volume change during phase change, which limits the practical application of phase change heat storage materials. The preparation of phase change materials into phase change heat storage microcapsules is one of the main technologies to solve the above problems. The phase change heat storage microcapsule is composed of a phase change material as a core and a coating material as a shell. Due to the advantages of non-corrosion, anti-medium leakage, high heat storage density, and constant temperature during phase change, phase change heat storage microcapsules have become a research hotspot in recent years.
相变材料按相变温度分类，其中相变温度在500℃以上的相变材料称为高温相变材料。铝及铝硅合金属于高温相变蓄热材料中的一种，具有导热性好、热稳定性较好、相变潜热大、导热系数大和蓄热密度高等优点。若将铝或铝硅合金作为相变蓄热微胶囊的核，则对包覆材料有如下要求：耐,腐蚀性好、周期稳定性好，温度应力强度高，抗氧化性好。Phase change materials are classified by phase change temperature, and phase change materials with a phase change temperature above 500°C are called high temperature phase change materials. Aluminum and aluminum-silicon alloys are one of the high-temperature phase change heat storage materials, which have the advantages of good thermal conductivity, good thermal stability, large latent heat of phase change, high thermal conductivity and high heat storage density. If aluminum or aluminum-silicon alloy is used as the core of phase change heat storage microcapsules, the cladding material has the following requirements: resistance, good corrosion resistance, good cycle stability, high temperature stress intensity, and good oxidation resistance.
近年来，一些学者对铝及铝硅合金作为相变蓄热材料开展了一些研究，公开了一些含有铝或铝硅合金的复合相变蓄热材料。如“一种高温复合相变蓄热材料及其制备方法”（201310175016.1）专利技术，该技术采用白泥、高铝矾土和铝粉为原料，直接混合后压制成型，高温焙烧，制得一种高温复合相变蓄热材料；“一种具有相变蓄热功能的金属陶瓷及其制备方法”（201310293700.X）专利技术，以铝硅合金粉、刚玉粉为原料，以氧化镁为烧结助剂，经干法球磨、成型、焙烧，制得一种具有相变蓄热功能的金属陶瓷。上述技术方法皆是将相变材料作为原料直接用于复合相变蓄热材料的制备中，利用相变材料在发生相变时的吸热和放热实现蓄热目的。但是这种直接混合成型的方法在焙烧过程中铝或铝硅合金粉熔化后极易泄露及溢出，而且液相的铝或者铝硅合金也会降低材料的高温物理性能。In recent years, some scholars have conducted some research on aluminum and aluminum-silicon alloys as phase-change heat storage materials, and disclosed some composite phase-change heat storage materials containing aluminum or aluminum-silicon alloys. For example, "a high-temperature composite phase-change heat storage material and its preparation method" (201310175016.1) patented technology, this technology uses white clay, high-alumina bauxite and aluminum powder as raw materials, directly mixed and then pressed into shape, and then roasted at high temperature to obtain a A high-temperature composite phase-change heat storage material; "a cermet with phase-change heat storage function and its preparation method" (201310293700.X) patented technology, using aluminum-silicon alloy powder and corundum powder as raw materials, sintered with magnesium oxide Auxiliary, through dry ball milling, molding, and roasting, a cermet with phase change heat storage function is prepared. The above-mentioned technical methods all use phase change materials as raw materials directly in the preparation of composite phase change heat storage materials, and use the heat absorption and heat release of phase change materials when phase change occurs to achieve the purpose of heat storage. However, this direct mixed molding method is very easy to leak and overflow after the aluminum or aluminum-silicon alloy powder is melted during the firing process, and the liquid-phase aluminum or aluminum-silicon alloy will also reduce the high-temperature physical properties of the material.
也有一些学者对铝或铝硅合金相变蓄热微胶囊的制作进行了研究：“一种Al/Al2O3蓄热材料及其制备方法”（201010127955.5）专利技术，以铝粉为原料，用雾化后氧气气氛冷却法制备了Al2O3包裹Al粉的核壳式复合相变蓄热材料。此种核壳结构的复合相变蓄热材料对设备要求高，制备工艺复杂，难于控制，制备的壳层较薄，难以满足强度要求。文献（Nomura T, Sheng N, Zhu C等．Microencapsulated phase change materials withhigh heat capacity andhigh cyclic durability for high-temperature thermalenergy storage andtransportation．Applied Energy, 2017, 188:9-18.）报道，利用两步法（水热法+煅烧）制备了Al2O3包裹铝硅合金粉的微胶囊相变蓄热材料。但是此种微胶囊制备过程复杂，且第一步制备的壳层结构疏松，因此第一步制备出的胶囊不能直接应用。Some scholars have also conducted research on the production of aluminum or aluminum-silicon alloy phase change heat storage microcapsules: "A kind of Al/Al 2 O 3 heat storage material and its preparation method" (201010127955.5) patented technology, using aluminum powder as raw material, The core-shell composite phase change heat storage material with Al 2 O 3 wrapped Al powder was prepared by cooling in oxygen atmosphere after atomization. This kind of composite phase change heat storage material with core-shell structure has high requirements on equipment, the preparation process is complex and difficult to control, and the prepared shell layer is thin, which is difficult to meet the strength requirements. Literature (Nomura T, Sheng N, Zhu C, etc. Microencapsulated phase change materials with high heat capacity and high cyclic durability for high-temperature thermal energy storage and transportation. Applied Energy, 2017, 188:9-18.) reported that using the two-step method (water Thermal method + calcination) prepared the microcapsule phase change heat storage material of Al 2 O 3 wrapped Al-Si alloy powder. However, the preparation process of this microcapsule is complicated, and the shell structure prepared in the first step is loose, so the capsule prepared in the first step cannot be directly used.
发明内容Contents of the invention
本发明旨在克服现有技术缺陷，目的是提供一种原料成本低、制备工艺简单和容易实现工业生产的高温相变蓄热微胶囊制备方法；所制备的高温相变蓄热微胶囊能提高热量的利用率和利用效率，使用温度高。The present invention aims to overcome the defects of the prior art, and aims to provide a method for preparing high-temperature phase-change thermal storage microcapsules with low raw material cost, simple preparation process and easy industrial production; the prepared high-temperature phase-change thermal storage microcapsules can improve The utilization rate and utilization efficiency of heat are high, and the use temperature is high.
为实现上述任务，本发明所采用的技术方案是：For realizing above-mentioned task, the technical scheme that the present invention adopts is:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（0.01~2.5），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder: polycarboxylate water reducing agent being 100: (0.01-2.5), the aluminum-silicon alloy powder and the surface modifier are evenly stirred to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（3~100）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为0.1~5L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (3~100); adding at a constant speed means that the aluminum-silicon alloy powder content per kilogram of the mixture is added to the aluminum dihydrogen phosphate The solution is 0.1~5L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（5~15），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3. Under the condition of 20~100℃ water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (5~15), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至600~1300℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 600-1300°C at a rate of 3-10°C/min in an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1300~1500℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1300-1500°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为45 ~150μm，铝硅合金粉中的Si含量为0.1~44wt%。The particle size of the aluminum-silicon alloy powder is 45-150 μm, and the Si content in the aluminum-silicon alloy powder is 0.1-44wt%.
所述磷酸二氢铝溶液中主要物质的含量：P2O5为30~35wt%；Al2O3为6~9wt%。The content of main substances in the aluminum dihydrogen phosphate solution: P 2 O 5 is 30-35wt%; Al 2 O 3 is 6-9wt%.
所述氧化气氛中O2含量大于21Vol%The O2 content in the oxidizing atmosphere is greater than 21Vol%
由于采用上述技术方案，本发明与现有技术相比具有如下积极效果：Owing to adopting above-mentioned technical scheme, the present invention has following positive effect compared with prior art:
本发明采用的磷酸二氢铝溶液属于弱酸性物质，易和铝硅合金中的铝发生反应生成磷酸铝。生成的磷酸铝为无定型态，且铝原子、磷原子和氧原子间通过离子键和共价键结合，原子间结合力强，整体呈现环状无机高分子结构，能形成稳定的壳层包覆在铝硅合金表面。磷酸铝壳层具有粘结性强、不溶于水和耐高温（熔点＞1700℃）的优点，所制备的高温相变蓄热微胶囊坯体因此能有效防止铝硅合金在高温下熔化后泄露，能直接应用于600℃以下太阳能蓄热材料。The aluminum dihydrogen phosphate solution used in the present invention is a weakly acidic substance, which can easily react with aluminum in the aluminum-silicon alloy to form aluminum phosphate. The generated aluminum phosphate is in an amorphous state, and the aluminum atoms, phosphorus atoms and oxygen atoms are combined by ionic bonds and covalent bonds. The interatomic bonding force is strong, and the overall structure presents a ring-shaped inorganic polymer structure, which can form a stable shell. Coated on the surface of aluminum-silicon alloy. The aluminum phosphate shell has the advantages of strong adhesion, insolubility in water and high temperature resistance (melting point > 1700°C). The prepared high-temperature phase change heat storage microcapsule body can effectively prevent aluminum-silicon alloy from leaking after melting at high temperature , can be directly applied to solar heat storage materials below 600°C.
本发明将所述高温相变蓄热微胶囊坯体在600~1300℃的氧化气氛中高温焙烧，铝硅合金高温膨胀使磷酸铝壳层产生裂缝，铝硅合金中的铝在高温下熔融析出并于裂缝处外溢，此时熔融铝与烧成气氛中氧气发生反应生成的氧化铝填充此裂缝，高温条件下形成了氧化铝与磷酸铝复合致密壳层，制得具有氧化铝与磷酸铝复合致密壳层的高温相变蓄热微胶囊。此种具有氧化铝与磷酸铝复合致密壳层的高温相变蓄热微胶囊，能作为原料用来制备1300℃以下使用的高温相变蓄热复合材料。In the present invention, the high-temperature phase-change thermal storage microcapsule green body is roasted at a high temperature in an oxidizing atmosphere at 600-1300°C, the high-temperature expansion of the aluminum-silicon alloy causes cracks in the aluminum phosphate shell, and the aluminum in the aluminum-silicon alloy melts and precipitates at a high temperature And it overflows at the crack. At this time, the molten aluminum reacts with the oxygen in the firing atmosphere to fill the crack. Under high temperature conditions, a composite dense shell of alumina and aluminum phosphate is formed. High temperature phase change heat storage microcapsules with dense shell. The high-temperature phase-change thermal storage microcapsules with a composite dense shell of alumina and aluminum phosphate can be used as raw materials to prepare high-temperature phase-change thermal storage composite materials used below 1300°C.
本发明将所述高温相变蓄热微胶囊坯体在1300℃~1500℃和氧化气氛中高温焙烧，磷酸铝分解生成氧化铝，另外熔融铝与烧成气氛中氧气发生反应生成氧化铝，高温下形成了氧化铝致密壳层。氧化铝具有耐腐蚀、耐高温（熔点＞2070℃）和强度大等优点。制得具有氧化铝致密壳层的高温相变蓄热微胶囊，热循环次数更高和耐压强度更大，能作为原料用来制备1300℃以上使用的高温相变蓄热复合材料。In the present invention, the high-temperature phase-change thermal storage microcapsule green body is roasted at 1300°C to 1500°C in an oxidizing atmosphere at high temperature, and aluminum phosphate is decomposed to produce alumina, and molten aluminum reacts with oxygen in the firing atmosphere to form alumina. A dense shell of alumina is formed underneath. Alumina has the advantages of corrosion resistance, high temperature resistance (melting point > 2070°C) and high strength. The high-temperature phase-change thermal storage microcapsules with dense alumina shells have higher thermal cycle times and greater compressive strength, and can be used as raw materials to prepare high-temperature phase-change thermal storage composite materials used at temperatures above 1300°C.
本发明制备的高温相变蓄热微胶囊及其坯体解决了铝硅合金作为相变蓄热材料在应用过程中熔化后易泄露的问题；高温相变蓄热微胶囊的壳层为Al(H3PO4)3-Al2O3或者为Al2O3，无论哪种壳层都具有强度大和耐高温等优点，因此能有效地为熔融状态的铝硅合金提供保护，避免铝硅合金的流失和由此造成的腐蚀，增加铝硅合金的循环使用次数。The high-temperature phase-change thermal storage microcapsules and their bodies prepared by the present invention solve the problem that the aluminum-silicon alloy is easily leaked after melting as a phase-change thermal storage material in the application process; the shell layer of the high-temperature phase-change thermal storage microcapsules is Al( H 3 PO 4 ) 3 -Al 2 O 3 or Al 2 O 3 , no matter which shell layer has the advantages of high strength and high temperature resistance, it can effectively provide protection for the molten aluminum-silicon alloy and avoid the aluminum-silicon alloy The loss and the resulting corrosion increase the cycle times of the aluminum-silicon alloy.
本发明所用原料成本低、制备工艺简单易控制和容易实现工业生产；所制备的高温相变蓄热微胶囊有效利用了铝硅合金的相变潜热，提高了热量的利用率和利用效率，使用温度高；能满足太阳能电厂、工业炉窑高温热交换和高温工业废气的热量回收。The cost of raw materials used in the present invention is low, the preparation process is simple and easy to control, and it is easy to realize industrial production; the prepared high-temperature phase-change thermal storage microcapsules effectively utilize the phase-change latent heat of the aluminum-silicon alloy, which improves the utilization rate and utilization efficiency of heat. High temperature; it can meet the high temperature heat exchange of solar power plants, industrial furnaces and heat recovery of high temperature industrial waste gas.
具体实施方式detailed description
下面结合具体实施方式对本发明作进一步的描述，并非对其保护范围的限制。The present invention will be further described below in combination with specific embodiments, which are not intended to limit the scope of protection thereof.
为避免重复，先将本具体实施方式中的磷酸二氢铝溶液和氧化气氛统一描述如下，实施例中不再赘述：In order to avoid repetition, the aluminum dihydrogen phosphate solution and the oxidizing atmosphere in the present specific embodiment are first described in a unified manner as follows, and will not be repeated in the examples:
所述磷酸二氢铝溶液中主要物质的含量：P2O5为30~35wt%；Al2O3为6~9wt%；The content of main substances in the aluminum dihydrogen phosphate solution: P2O5 is 30 ~35wt%; Al2O3 is 6 ~9wt%;
所述氧化气氛中O2含量大于21Vol%。The O 2 content in the oxidizing atmosphere is greater than 21 Vol%.
实施例1Example 1
一种高温相变蓄热微胶囊及其制备方法。本实施例所述制备方法的具体步骤是：A high temperature phase change thermal storage microcapsule and a preparation method thereof. The specific steps of the preparation method described in this embodiment are:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（0.01~0.5），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder: polycarboxylate water reducing agent being 100: (0.01-0.5), the aluminum-silicon alloy powder and the surface modifier are evenly stirred to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（3~20）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为0.1~1.1L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (3~20); adding at a constant speed refers to the aluminum-silicon alloy powder content per kilogram of the mixture added to the aluminum dihydrogen phosphate The solution is 0.1~1.1L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（5~10），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3. Under the condition of 20~100℃ water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (5~10), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至600~900℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase change thermal storage microcapsule body in a muffle furnace, raise the temperature to 600-900°C at a rate of 3-10°C/min in an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1300~1400℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1300-1400°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为45 ~80μm，铝硅合金粉中的Si含量为0.1~7wt%。The particle size of the aluminum-silicon alloy powder is 45-80 μm, and the Si content in the aluminum-silicon alloy powder is 0.1-7wt%.
实施例2Example 2
一种高温相变蓄热微胶囊及其制备方法。本实施例所述制备方法的具体步骤是：A high temperature phase change thermal storage microcapsule and a preparation method thereof. The specific steps of the preparation method described in this embodiment are:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（0.4~0.9），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder:polycarboxylate water reducer of 100:(0.4-0.9), the aluminum-silicon alloy powder and the surface modifier are evenly stirred to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（19~36）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为0.8~1.8L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (19-36); adding at a constant speed means that the aluminum-silicon alloy powder content per kilogram of the mixture is added to the aluminum dihydrogen phosphate The solution is 0.8~1.8L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（6~11），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3. Under the condition of 20~100℃ water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (6~11), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至600~900℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase change thermal storage microcapsule body in a muffle furnace, raise the temperature to 600-900°C at a rate of 3-10°C/min in an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1300~1400℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1300-1400°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为45 ~80μm，铝硅合金粉中的Si含量为7~14wt%。The particle size of the aluminum-silicon alloy powder is 45-80 μm, and the Si content in the aluminum-silicon alloy powder is 7-14wt%.
实施例3Example 3
一种高温相变蓄热微胶囊及其制备方法。本实施例所述制备方法的具体步骤是：A high temperature phase change thermal storage microcapsule and a preparation method thereof. The specific steps of the preparation method described in this embodiment are:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（0.8~1.3），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder: polycarboxylate water reducing agent being 100: (0.8-1.3), the aluminum-silicon alloy powder and the surface modifier are evenly stirred to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（35~52）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为1.6~2.6L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (35-52); adding at a constant speed means that the aluminum-silicon alloy powder content per kilogram of the mixture is added to the aluminum dihydrogen phosphate The solution is 1.6~2.6L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（7~12），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3. Under the condition of 20~100℃ water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (7~12), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至800~1100℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 800-1100°C at a rate of 3-10°C/min in an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1350~1450℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1350-1450°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为80 ~115μm，铝硅合金粉中的Si含量为14~21wt%。The particle size of the aluminum-silicon alloy powder is 80-115 μm, and the Si content in the aluminum-silicon alloy powder is 14-21wt%.
实施例4Example 4
一种高温相变蓄热微胶囊及其制备方法。本实施例所述制备方法的具体步骤是：A high temperature phase change thermal storage microcapsule and a preparation method thereof. The specific steps of the preparation method described in this embodiment are:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（1.2~1.7），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder: polycarboxylate water reducing agent being 100: (1.2-1.7), the aluminum-silicon alloy powder and the surface modifier are evenly stirred to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（51~68）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为2.4~3.4L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (51-68); adding at a constant speed means that the aluminum-silicon alloy powder content per kilogram of the mixture is added to the aluminum dihydrogen phosphate The solution is 2.4~3.4L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（8~13），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3, under the condition of 20~100℃ water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (8~13), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至800~1100℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 800-1100°C at a rate of 3-10°C/min in an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1350~1450℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1350-1450°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为80 ~115μm，铝硅合金粉中的Si含量为21~28wt%。The particle size of the aluminum-silicon alloy powder is 80-115 μm, and the Si content in the aluminum-silicon alloy powder is 21-28 wt%.
实施例5Example 5
一种高温相变蓄热微胶囊及其制备方法。本实施例所述制备方法的具体步骤是：A high temperature phase change thermal storage microcapsule and a preparation method thereof. The specific steps of the preparation method described in this embodiment are:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（1.6~2.1），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder: polycarboxylate water reducing agent being 100: (1.6-2.1), the aluminum-silicon alloy powder and the surface modifier are stirred evenly to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（67~84）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为3.2~4.2L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (67-84); adding at a constant speed means that the aluminum-silicon alloy powder content per kilogram of the mixture is added to the aluminum dihydrogen phosphate The solution is 3.2~4.2L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（9~14），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3. Under the condition of 20~100℃ water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (9~14), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1000~1300℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1000-1300°C at a rate of 3-10°C/min under the condition of an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1400~1500℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1400-1500°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为115 ~150μm，铝硅合金粉中的Si含量为28~36wt%。The particle size of the aluminum-silicon alloy powder is 115-150 μm, and the Si content in the aluminum-silicon alloy powder is 28-36 wt%.
实施例6Example 6
一种高温相变蓄热微胶囊及其制备方法。本实施例所述制备方法的具体步骤是：A high temperature phase change thermal storage microcapsule and a preparation method thereof. The specific steps of the preparation method described in this embodiment are:
步骤一、按铝硅合金粉∶聚羧酸类减水剂的质量比为100∶（2.0~2.5），将所述铝硅合金粉和所述表面改性剂搅拌均匀，制得混合料。Step 1. According to the mass ratio of aluminum-silicon alloy powder: polycarboxylate water reducing agent being 100: (2.0-2.5), the aluminum-silicon alloy powder and the surface modifier are evenly stirred to prepare a mixture.
步骤二、在20~100℃水浴和搅拌条件下，向所述混合料中匀速加入浓度为30~80wt%的磷酸二氢铝溶液，磷酸二氢铝溶液加入后继续搅拌1~30min，制得混合料浆。Step 2: Add aluminum dihydrogen phosphate solution with a concentration of 30-80wt% to the mixture at a constant speed under the condition of 20-100°C water bath and stirring, and continue stirring for 1-30 minutes after adding the aluminum dihydrogen phosphate solution to obtain Mix slurry.
所述铝硅合金粉∶所述磷酸二氢铝溶液的质量比为100∶（83~100）；匀速加入是指向铝硅合金粉含量为每千克的混合料中加入的所述磷酸二氢铝溶液为4~5L/min。The mass ratio of the aluminum-silicon alloy powder: the aluminum dihydrogen phosphate solution is 100: (83-100); adding at a constant speed means that the aluminum-silicon alloy powder content per kilogram of the mixture is added to the aluminum dihydrogen phosphate The solution is 4~5L/min.
步骤三、在20~100℃水浴和搅拌条件下，按磷酸二氢铝溶液∶无水有机醇的体积比为1∶（10~15），向所述混合料浆中加入无水有机醇，加入无水有机醇后继续搅拌1~30min，静置，得到分层的混合浆液。Step 3. Under the conditions of 20-100°C water bath and stirring, according to the volume ratio of aluminum dihydrogen phosphate solution: anhydrous organic alcohol is 1: (10-15), add anhydrous organic alcohol to the mixed slurry, After adding the anhydrous organic alcohol, continue to stir for 1-30min, and let stand to obtain a layered mixed slurry.
步骤四、将所述分层的混合浆液过滤，得沉淀物；将所述沉淀物用无水有机醇和去离子水交替洗涤至所述沉淀物的pH值为中性，再干燥至恒重，制得高温相变蓄热微胶囊坯体。Step 4, filtering the layered mixed slurry to obtain a precipitate; alternately washing the precipitate with anhydrous organic alcohol and deionized water until the pH of the precipitate is neutral, and then drying to a constant weight, A high temperature phase change thermal storage microcapsule green body is prepared.
步骤五、将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1000~1300℃，保温2~8h，制得复合壳层的高温相变蓄热微胶囊。Step 5. Put the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1000-1300°C at a rate of 3-10°C/min under the condition of an oxidizing atmosphere, keep it warm for 2-8 hours, and prepare High-temperature phase-change thermal storage microcapsules with composite shells were obtained.
或将所述高温相变蓄热微胶囊坯体置于马弗炉中，在氧化气氛条件下，以3~10℃/min的速率升温至1400~1500℃，保温2~8h，制得氧化铝壳层的高温相变蓄热微胶囊。Or place the high-temperature phase-change thermal storage microcapsule body in a muffle furnace, raise the temperature to 1400-1500°C at a rate of 3-10°C/min in an oxidizing atmosphere, and keep it warm for 2-8 hours to obtain oxidized High temperature phase change heat storage microcapsules with aluminum shell.
所述铝硅合金粉的粒径为115 ~150μm，铝硅合金粉中的Si含量为36~44wt%。The particle size of the aluminum-silicon alloy powder is 115-150 μm, and the Si content in the aluminum-silicon alloy powder is 36-44wt%.
本发明与现有技术相比具有如下积极效果：Compared with the prior art, the present invention has the following positive effects:
本发明采用的磷酸二氢铝溶液属于弱酸性物质，易和铝硅合金中的铝发生反应生成磷酸铝。生成的磷酸铝为无定型态，且铝原子、磷原子和氧原子间通过离子键和共价键结合，原子间结合力强，整体呈现环状无机高分子结构，能形成稳定的壳层包覆在铝硅合金表面。磷酸铝壳层具有粘结性强、不溶于水和耐高温（熔点＞1700℃）的优点，所制备的高温相变蓄热微胶囊坯体因此能有效防止铝硅合金在高温下熔化后泄露，能直接应用于600℃以下太阳能蓄热材料。The aluminum dihydrogen phosphate solution used in the present invention is a weakly acidic substance, which can easily react with aluminum in the aluminum-silicon alloy to form aluminum phosphate. The generated aluminum phosphate is in an amorphous state, and the aluminum atoms, phosphorus atoms and oxygen atoms are combined by ionic bonds and covalent bonds. The interatomic bonding force is strong, and the overall structure presents a ring-shaped inorganic polymer structure, which can form a stable shell. Coated on the surface of aluminum-silicon alloy. The aluminum phosphate shell has the advantages of strong adhesion, insolubility in water and high temperature resistance (melting point > 1700°C). The prepared high-temperature phase change heat storage microcapsule body can effectively prevent aluminum-silicon alloy from leaking after melting at high temperature , can be directly applied to solar heat storage materials below 600°C.
本发明将所述高温相变蓄热微胶囊坯体在600~1300℃的氧化气氛中高温焙烧，铝硅合金高温膨胀使磷酸铝壳层产生裂缝，铝硅合金中的铝在高温下熔融析出并于裂缝处外溢，此时熔融铝与烧成气氛中氧气发生反应生成的氧化铝填充此裂缝，高温条件下形成了氧化铝与磷酸铝复合致密壳层，制得具有氧化铝与磷酸铝复合致密壳层的高温相变蓄热微胶囊。此种具有氧化铝与磷酸铝复合致密壳层的高温相变蓄热微胶囊，能作为原料用来制备1300℃以下使用的高温相变蓄热复合材料。In the present invention, the high-temperature phase-change thermal storage microcapsule green body is roasted at a high temperature in an oxidizing atmosphere at 600-1300°C, the high-temperature expansion of the aluminum-silicon alloy causes cracks in the aluminum phosphate shell, and the aluminum in the aluminum-silicon alloy melts and precipitates at a high temperature And it overflows at the crack. At this time, the molten aluminum reacts with the oxygen in the firing atmosphere to fill the crack. Under high temperature conditions, a composite dense shell of alumina and aluminum phosphate is formed. High temperature phase change heat storage microcapsules with dense shell. The high-temperature phase-change thermal storage microcapsules with a composite dense shell of alumina and aluminum phosphate can be used as raw materials to prepare high-temperature phase-change thermal storage composite materials used below 1300°C.
本发明将所述高温相变蓄热微胶囊坯体在1300℃~1500℃和氧化气氛中高温焙烧，磷酸铝分解生成氧化铝，另外熔融铝与烧成气氛中氧气发生反应生成氧化铝，高温下形成了氧化铝致密壳层。氧化铝具有耐腐蚀、耐高温（熔点＞2070℃）和强度大等优点。制得具有氧化铝致密壳层的高温相变蓄热微胶囊，热循环次数更高和耐压强度更大，能作为原料用来制备1300℃以上使用的高温相变蓄热复合材料。In the present invention, the high-temperature phase-change thermal storage microcapsule green body is roasted at 1300°C to 1500°C in an oxidizing atmosphere at high temperature, and aluminum phosphate is decomposed to produce alumina, and molten aluminum reacts with oxygen in the firing atmosphere to form alumina. A dense shell of alumina is formed underneath. Alumina has the advantages of corrosion resistance, high temperature resistance (melting point > 2070°C) and high strength. The high-temperature phase-change thermal storage microcapsules with dense alumina shells have higher thermal cycle times and greater compressive strength, and can be used as raw materials to prepare high-temperature phase-change thermal storage composite materials used at temperatures above 1300°C.
本发明制备的高温相变蓄热微胶囊及其坯体解决了铝硅合金作为相变蓄热材料在应用过程中熔化后易泄露的问题；高温相变蓄热微胶囊的壳层为Al(H3PO4)3-Al2O3或者为Al2O3，无论哪种壳层都具有强度大和耐高温等优点，因此能有效地为熔融状态的铝硅合金提供保护，避免铝硅合金的流失和由此造成的腐蚀，增加铝硅合金的循环使用次数。The high-temperature phase-change thermal storage microcapsules and their bodies prepared by the present invention solve the problem that the aluminum-silicon alloy is easily leaked after melting as a phase-change thermal storage material in the application process; the shell layer of the high-temperature phase-change thermal storage microcapsules is Al( H 3 PO 4 ) 3 -Al 2 O 3 or Al 2 O 3 , no matter which shell layer has the advantages of high strength and high temperature resistance, it can effectively provide protection for the molten aluminum-silicon alloy and avoid the aluminum-silicon alloy The loss and the resulting corrosion increase the cycle times of aluminum-silicon alloys.
本发明所用原料成本低、制备工艺简单易控制和容易实现工业生产；所制备的高温相变蓄热微胶囊有效利用了铝硅合金的相变潜热，提高了热量的利用率和利用效率，使用温度高；能满足太阳能电厂、工业炉窑高温热交换和高温工业废气的热量回收。The cost of raw materials used in the present invention is low, the preparation process is simple and easy to control, and it is easy to realize industrial production; the prepared high-temperature phase-change thermal storage microcapsules effectively utilize the phase-change latent heat of the aluminum-silicon alloy, which improves the utilization rate and utilization efficiency of heat. High temperature; it can meet the high temperature heat exchange of solar power plants, industrial furnaces and heat recovery of high temperature industrial waste gas.
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| CN112480873A (en) * | 2020-11-30 | 2021-03-12 | 武汉科技大学 | Corundum-mullite composite shell phase-change heat storage ball and preparation method thereof |
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