TiO2改性的CaCO3热化学储热的反应性能

doi:10.19799/j.cnki.2095-4239.2021.0281

摘要/Abstract

摘要：

CaCO₃/CaO热化学储热体系在清洁能源发电领域具有广阔的应用前景，有助于尽早实现碳达峰、碳中和。本文通过物理混合法制备了掺杂TiO₂的CaCO₃/CaO复合储热材料，系统研究了TiO₂掺杂对CaCO₃/CaO循环稳定性和储/放热过程中反应性能的影响。实验结果表明：在掺杂摩尔比为100∶2.5(Ca∶Ti)时，复合材料展现出了最佳的循环稳定性，15次循环后的转换率为对照组的1.65倍。表征结果显示，最佳掺杂比例的CaCO₃-TiO₂复合储热材料具有更小的粒径和更发达的孔隙，因而在循环过程中具备更好的抗烧结能力。在碳酸化放热过程中，CaCO₃-TiO₂-2.5在高温区(750 ℃和800 ℃)有更高的反应转换率和放热/储热焓值比例，但由于复合材料中CaCO₃的含量下降，其储热、放热的焓值有所下降。此外，在等温储热分解过程中，N₂气氛下TiO₂掺杂可提升反应速率、减少反应时间；CO₂气氛下TiO₂掺杂可降低起始分解温度，促使反应更早开始与结束。而在非等温储热过程中(10 ℃/min)，CO₂气氛下TiO₂掺杂可将纯CaCO₃的起始分解温度从897.16 ℃降至870.92 ℃。综上，TiO₂改性对CaCO₃/CaO储热技术的实际应用具有深远意义。

关键词: CaCO₃热化学储热, TiO₂改性, 循环稳定性, 碳酸化放热, 分解过程

Abstract:

The CaCO₃/CaO thermochemical energy storage system is promising in the field of clean energy power generation because it helps to peak carbon dioxide emissions and achieve carbon neutrality as soon as possible. In this study, CaCO₃/CaO composite heat storage materials doped with TiO₂ were prepared by employing the physical mixing method. The effects of TiO₂ doping on the cyclic stability and the reaction performance in the exothermic and endothermic processes were then systematically investigated. The composite exhibited the best cyclic stability at a molar doping ratio of 100∶2.5 (Ca∶Ti). Its conversion rate was 1.65 times that of the control group after 15 cycles. Characterization showed that the CaCO₃-TiO₂ composite heat storage material with the best doping ratio had a smaller particle size and more developed pores, leading to a better anti-sintering ability in the cycle process. In the exothermic process of carbonation, CaCO₃-TiO₂-2.5 illustrated higher reaction conversion rate and thermal release/storage enthalpy ratio at a high temperature range (i.e., 750 ℃. and 800 ℃). However, its enthalpies in the exothermic and endothermic processes decreased due to the low CaCO₃ content in the composite material. During the isothermal decarbonation process, the TiO₂ doping increases the reaction rate and reduces the reaction time in the N₂ atmosphere, and decreases the initial decarbonation temperature and promotes earlier reaction in the CO₂ atmosphere. In contrast, during the non-isothermal decarbonation process (10 ℃/min), the TiO₂ doping reduces the initial decarbonation temperature of the pure CaCO₃ from 897.16 ℃ to 870.92 ℃ in the CO₂ atmosphere. The TiO₂ modification is generally of far-reaching significance for the practical application of the CaCO₃/CaO thermal storage technology.

Key words: CaCO₃ thermochemical energy storage, TiO₂ modification, cyclic stability, exothermic carbonation, decarbonation process

中图分类号:

TK 02

徐钿昕, 田希坤, 闫君, 叶强, 赵长颖. TiO₂改性的CaCO₃热化学储热的反应性能[J]. 储能科学与技术, 2022, 11(1): 1-8.

Tianxin XU, Xikun TIAN, Jun YAN, Qiang YE, Changying ZHAO. Thermochemical energy storage reaction performance of CaCO₃ with TiO₂ doping[J]. Energy Storage Science and Technology, 2022, 11(1): 1-8.

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仪器名称	型号	仪器厂家或品牌
电子天平	—	赛多利斯科学仪器(北京)有限公司
电子天平	—	上海瑶新电子科技有限公司
超声波清洗器	KQ-50E	昆山市超声仪器有限公司
恒温磁力搅拌器	H97	上海梅颖浦仪器仪表制造有限公司
真空干燥箱	DZF-6020	上海一恒科技有限公司

样品名称	掺杂材料	掺杂摩尔比(Ca∶Ti)
CaCO₃-TiO₂-0	TiO₂	100∶0
CaCO₃-TiO₂-2.5	TiO₂	100∶2.5
CaCO₃-TiO₂-5	TiO₂	100∶5
CaCO₃-TiO₂-7.5	TiO₂	100∶7.5
CaCO₃-TiO₂-10	TiO₂	100∶10

样品名称	比表面积/(m²/g)	孔容/(cm³/g)	孔径/nm
CaCO₃	3.560	0.00298	2.349
CaCO₃-TiO₂-2.5	7.625	0.01384	7.261

温度/℃	样品名称	反应转换率	放热焓值/(kJ/mol)	储热焓值/(kJ/mol)	放热/储热比值	快速反应阶段比例	样品名称	反应转换率	放热焓值/(kJ/mol)	储热焓值/(kJ/mol)	放热/储热比值	快速反应阶段比例
800	CaCO₃	0.80	94.33	143.65^①	0.66	0.97	CaCO₃-TiO₂-2.5	0.83	88.57	123.34^①	0.72	0.79
750		0.79	99.80		0.69	0.95		0.88	90.98		0.74	0.75
700		0.76	98.06		0.68	0.91		0.81	81.27		0.66	0.62
650		0.72	96.69		0.67	0.92		0.71	65.31		0.53	0.52
600		0.71	85.28		0.59	0.82		0.65	57.54		0.47	0.39
550		0.70	73.24		0.51	0.64		0.58	36.17		0.29	0.33
500		0.70	58.21		0.41	0.35		0.52	23.50		0.19	0.24
450		0.72	50.45		0.35	0.23		0.39	21.48		0.17	0.19

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TiO₂改性的CaCO₃热化学储热的反应性能

Thermochemical energy storage reaction performance of CaCO₃ with TiO₂ doping

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