硝酸钠/兰炭灰复合相变储热材料的制备及性能

药晨华; 熊亚选; 任静; 宋超宇; 王辉祥; 丁玉龙

doi:10.13801/j.cnki.fhclxb.20220222.002

硝酸钠/兰炭灰复合相变储热材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20220222.002

1.
北京建筑大学　供热供燃气通风及空调工程北京市重点实验室，北京 100044
2.
北京中建建筑科学研究院有限公司，北京 100076
3.
伯明翰大学　伯明翰储能中心，伯明翰 B15 2TT

基金项目: 北京市教委科研项目(KM201910016011)

详细信息

通讯作者:
熊亚选，博士，教授，硕士生导师，研究方向为高温熔盐储热　E-mail: xiongyaxuan@bucea.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-11-18
- 修回日期: 2022-01-18
- 录用日期: 2022-01-22
- 网络出版日期: 2022-02-23
- 刊出日期: 2023-01-15

Preparation and properties of sodium nitrate/semi-coke ash shape-stable phase change composite

1.
Beijing Key Lab of Heating, Gas Supply, Ventilating and Air Conditioning Engineering, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
2.
Beijing Building Research Institute CO., LTD. of CSCEC, Beijing 100076, China
3.
Birmingham Center for Energy Storage, University of Birmingham, Birmingham B15 2TT, UK

Funds: Scientific Research Program of Beijing Municipal Education Commission (KM201910016011)

摘要

摘要: 工业固废兰炭灰(SCA)大量堆积会造成局部生态环境破坏，为促进工业固废兰炭灰的规模化消纳及复合相变储热材料(SSPCCs)的低成本制备，创新提出兰炭灰作为骨架材料制备复合相变储热材料。为研究兰炭灰骨架复合相变储热材料的可行性，制备了8种不同比例的NaNO₃/兰炭灰复合相变储热材料，采用差示扫描量热法、激光导热分析法、微观形貌分析法、定速加压法和X射线衍射法对NaNO₃/兰炭灰复合相变储热材料的关键性能进行表征。结果表明，未发生明显泄露和形变的样品NaNO₃/SCA-50具有最佳兰炭灰与NaNO₃质量比(5∶5)，其抗压强度达到96.98 MPa，100~380℃范围内储热密度达到338.24 J/g；经4027次加热/冷却循环后，样品NaNO₃/SCA-50保持良好的热稳定性和化学相容性。兰炭灰作为骨架材料制备复合相变储热材料具有较好的可行性，为工业固废兰炭灰的资源化利用提供了新的途径。
- 固废 /
- 骨架材料 /
- 复合材料 /
- 储热性能 /
- 力学性能 /
- 热稳定性
Abstract: The massive accumulation of industrial solid waste semi-coke ash (SCA) will cause damage to local ecological environment. To promote the large-scale consumption of industrial solid waste semi-coke ash and fabricate low-cost shape-stable phase change composites (SSPCCs), semi-coke ash was innovatively proposed as a skeleton material to fabricate the SSPCCs. To evaluate the feasibility of the semi-coke ash as the skeleton material of the SSPCCs, eight NaNO₃/semi-coke ash SSPCC samples with different mass ratio of the semi-coke ash to NaNO₃ were fabricated. The key performance of the NaNO₃/semi-coke ash SSPCCs were investigated by the differential scanning calorimetry, laser flash analysis, scanning electron microscopy, constant speed pressurization method and X-ray diffraction. Results show that the sample NaNO₃/SCA-50 without visual leakage and deformation holds the optimal mass ratio 5:5 of the semi-coke ash to NaNO₃ with the thermal energy storage capacity of 338.24 J/g ranging from 100 to 380℃ and the mechanical strength of 96.98 MPa. After 4027 heating/cooling cycles, the sample NaNO₃/SCA-50 keeps good thermal stability and chemical compatibility, which indicates that the semi-coke ash is feasible for the SSPCCs fabrication, and provides a new way for recycling the resource of the solid waste semi-coke ash.
- solid waste /
- skeleton material /
- composite material /
- thermal energy storage property /
- mechanical property /
- thermal stability

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图 1 NaNO₃/SCA复合相变储热材料(SSPCCs)的制备流程

Figure 1. Schematic of the shaping process of the NaNO₃/SCA shape-stable phase change composites (SSPCCs)

PVA—Polyvinyl alcohol

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图 2 不同配比NaNO₃/兰炭灰复合相变储热材料样品照片

Figure 2. Photographs of the NaNO₃/SCA SSPCCs with different ratios

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图 9 PCM、NaNO₃/SCA-50和兰炭灰的XRD图谱

Figure 9. XRD patterns of the PCM, NaNO₃/SCA-50 and semi-coke ash

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图 3 PCM、NaNO₃/SCA-50和NaNO₃/SCA-47.5的比热

Figure 3. Specific heat of the PCM, NaNO₃/SCA-50 and NaNO₃/SCA-47.5

T_m—Melting point; ΔH_m—Latent heat

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图 4 NaNO₃/SCA-50以100℃为基点的储热密度

Figure 4. Thermal energy storage capacity of NaNO₃/SCA-50 based on 100℃

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图 5 NaNO₃/SCA-50的热扩散率和导热系数

Figure 5. Thermal diffusivity and thermal conductivity of NaNO₃/SCA-50

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图 6 NaNO₃/SCA的力学性能

Figure 6. Mechanical property of NaNO₃/SCA samples

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图 7 SCA、NaNO₃/SCA-60和NaNO₃/SCA-50的SEM图像

Figure 7. SEM images of the SCA, NaNO₃/SCA-60 and NaNO₃/SCA-50

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图 8 NaNO₃/SCA-50的EDS元素映射图像

Figure 8. EDS element mapping images of NaNO₃/SCA-50

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图 10 NaNO₃和SCA组分间反应的吉布斯自由能

Figure 10. Gibbs free energy of reactions between SCA component and NaNO₃

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图 11 4027次加热/冷却循环过程中NaNO₃/SCA-50的质量变化率

Figure 11. Mass change rate of NaNO₃/SCA-50 during 4027 heating/cooling cycles

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图 12 NaNO₃/SCA-50未进行加热/冷却循环、循环500次和4027次后的比热

Figure 12. Specific heat of NaNO₃/SCA-50 before and after 500, 4 027 heating/cooling cycles

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图 13 NaNO₃/SCA-50未进行加热/冷却循环、循环500次和4027次后以100℃为基点的储热密度

Figure 13. Thermal energy storage capacity of NaNO₃/SCA-50 before and after 500, 4027 heating/cooling cycles based on 100℃

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图 14 NaNO₃/SCA-50未进行加热/冷却循环、循环500次和4027次后的XRD图谱

Figure 14. XRD patterns of NaNO₃/SCA-50 before and after 500, 4027 heating/cooling cycles

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图 15 NaNO₃/SCA-50所承受压力与挤压头位移的关系

Figure 15. Relationship between load pressure on NaNO₃/SCA-50 and displacement of squeeze head

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表 1 兰炭灰(SCA)的组成成分

Table 1. Chemical compositions of semi-coke ash (SCA)

Composition	Content/wt%
CaO	39.49
SiO₂	18.22
Fe₂O₃	16.71
Al₂O₃	10.61
MgO	2.05
Others	12.92

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表 2 不同配比NaNO₃/SCA样品的详细情况

Table 2. Details of the NaNO₃/SCA samples with different proportions

Sample	NaNO₃/wt%	SCA/wt%	Degree of PCM leakage
NaNO₃/SCA-60	60.0	40.0	Slight
NaNO₃/SCA-50	50.0	50.0	No
NaNO₃/SCA-47.5	47.5	52.5	No
NaNO₃/SCA-45	45.0	55.0	No
NaNO₃/SCA-42.5	42.5	57.5	No
NaNO₃/SCA-40	40.0	60.0	No
NaNO₃/SCA-35	35.0	65.0	No
NaNO₃/SCA-30	30.0	70.0	No
Note: PCM—Phase change material.

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表 3 4027次加热/冷却循环过程中NaNO₃/SCA-50的形貌记录(直径13 mm)

Table 3. Morphologies recording of NaNO₃/SCA-50 during 4027 heating/cooling cycles (Diameter of 13 mm)

Sample morphology
Number of cycles	0	508	2001	4027

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表 4 NaNO₃/SCA-50加热/冷却循环前后的相变性能

Table 4. Phase change properties of NaNO₃/SCA-50 before and after heating/cooling cycles

Number of cycles	Onset temperature/℃	Latent heat/(J·g⁻¹)	Terminal temperature/℃
Before cycle	297.6	59.14	315.3
500 cycles	298.8	63.31	315.9
4027 cycles	298.9	65.51	314.4

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