应用于暖通空调系统的低温相变储能材料的研制
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摘要
随着科学技术的发展和人们生活水平的提高,能源供需在时间上的失配现象越来越严重。为解决此能源矛盾,相变储能技术应运而生。相变储能技术是利用物质在相变过程中吸收或释放能量以达到能源供需匹配的技术。可应用于暖通空调系统中的相变储能材料多在低温范围内,因此研究低温范围内相变储能材料对于解决能源问题意义重大。而低温范围内的最佳相变材料为有机脂酸类和结晶水合盐类两种材料。
首先,利用温度曲线法对癸酸—月桂酸二元体系进行了实验研究,得出了该二元混合物的相变温度曲线。基于实验数据和理论数据,得出该二元混合物存在低共熔点,当癸酸占该二元混合物的质量为66%~70%时,低共熔温度约为19℃~20℃。并通过添加石墨粉对其导热性能进行了改善,但是由于石墨粉的密度大于脂肪酸而沉淀,导致导热性能提高较小。
其次,对钾明矾进行了成核剂添加量的实验,从而找出了使钾明矾相变温度在70℃左右且过冷度较小的最优成核剂添加量。并通过温度曲线法和DSC方法对钾明矾多次循环熔冻后的相变温度、过冷度和相变潜热进行了研究,验证了其稳定性能。通过添加石墨粉来改善钾明矾导热性能的实验,发现石墨粉的添加只是物理混合,随着石墨粉添加量的增加,导热性能也在增加。
第三,根据现有的应用成果,提出了本课题相变储能材料在暖通空调系统中的应用思路。基于以上研究成果,可为该低温相变储能材料在暖通空调系统中的应用提供必要的实验数据和技术支撑。
With the development of science and technology and the improvement of people’s life, the mismatch of energy supply and demand is becoming more and more serious. In order to overcome the mismatch, the energy storage technology with phase change emerged. During the process of phase change, the materials can absorb or release energy, which can match the energy supply and demand.
Materials for energy storage used in HVAC systems have the phase transition temperature range in low-temperature range, therefore, it’s significant to study the low-temperature PCMs to solve the energy problem. fatty acids and hydrated salts usually are the ideal candidates for the low-temperature energy storage system.
First, the phase transition temperature curve of the binary mixture was obtained through the experimental investigation to capric acid and lauric acid by T-history method. Based on the experimental data and theoretical data, the eutectic melting point is between 19℃~20℃, when the proportion of capric acid is between 0.66~0.7.We also studied on their thermal conductivity improvement by adding graphite powder.
Second, the optimal amount of nucleating agent for aluminum potassium sulfate was found by the experimental investigation. The research on phase transition temperature, the degree of supercooling and latent heat after thermal cycles was carried on by T-history method and DSC method. At the same time, the thermal conductivity improvement experiment of aluminum potassium sulfate by adding graphite powder was carried on, and the results showed that the addition of graphite powder id mechanically mixed, and with the increase of the amount of graphite powder, the thermal conductivity increases.
Finally, based on the existing applications, some improvements were put forward to. The production resulted from the above experimental researches will provide the necessary experimental data and technical support for the application in HVAC systems.
首先,利用温度曲线法对癸酸—月桂酸二元体系进行了实验研究,得出了该二元混合物的相变温度曲线。基于实验数据和理论数据,得出该二元混合物存在低共熔点,当癸酸占该二元混合物的质量为66%~70%时,低共熔温度约为19℃~20℃。并通过添加石墨粉对其导热性能进行了改善,但是由于石墨粉的密度大于脂肪酸而沉淀,导致导热性能提高较小。
其次,对钾明矾进行了成核剂添加量的实验,从而找出了使钾明矾相变温度在70℃左右且过冷度较小的最优成核剂添加量。并通过温度曲线法和DSC方法对钾明矾多次循环熔冻后的相变温度、过冷度和相变潜热进行了研究,验证了其稳定性能。通过添加石墨粉来改善钾明矾导热性能的实验,发现石墨粉的添加只是物理混合,随着石墨粉添加量的增加,导热性能也在增加。
第三,根据现有的应用成果,提出了本课题相变储能材料在暖通空调系统中的应用思路。基于以上研究成果,可为该低温相变储能材料在暖通空调系统中的应用提供必要的实验数据和技术支撑。
With the development of science and technology and the improvement of people’s life, the mismatch of energy supply and demand is becoming more and more serious. In order to overcome the mismatch, the energy storage technology with phase change emerged. During the process of phase change, the materials can absorb or release energy, which can match the energy supply and demand.
Materials for energy storage used in HVAC systems have the phase transition temperature range in low-temperature range, therefore, it’s significant to study the low-temperature PCMs to solve the energy problem. fatty acids and hydrated salts usually are the ideal candidates for the low-temperature energy storage system.
First, the phase transition temperature curve of the binary mixture was obtained through the experimental investigation to capric acid and lauric acid by T-history method. Based on the experimental data and theoretical data, the eutectic melting point is between 19℃~20℃, when the proportion of capric acid is between 0.66~0.7.We also studied on their thermal conductivity improvement by adding graphite powder.
Second, the optimal amount of nucleating agent for aluminum potassium sulfate was found by the experimental investigation. The research on phase transition temperature, the degree of supercooling and latent heat after thermal cycles was carried on by T-history method and DSC method. At the same time, the thermal conductivity improvement experiment of aluminum potassium sulfate by adding graphite powder was carried on, and the results showed that the addition of graphite powder id mechanically mixed, and with the increase of the amount of graphite powder, the thermal conductivity increases.
Finally, based on the existing applications, some improvements were put forward to. The production resulted from the above experimental researches will provide the necessary experimental data and technical support for the application in HVAC systems.
引文
1周大地,韩文科.中国能源问题研究.中国环境科学出版社. 2002, (25):4~6
2周风起. 21世纪中国能源工业面临的挑战.暖通空调, 2000, (4):32~37
3冯国会,曹广宇,于瑾,等.夏季昼夜温差较大地区相变墙蓄冷可行性分析.沈阳建筑大学学报. 2005, 21(4):350~353
4张太平,阮德水,张道圣,等.固-固相变贮热的研究(Ⅲ)-三羟甲基乙烷三羟甲基丙烷二元系[J].华中师范大学学报(自然科学版). 1996, 30(1): 65～68
5方春香.中低温定形相变储能材料的研究.北京工业大学硕士学位论文. 2006
6艾明星.相变贮能材料的研究.河北工业大学硕士学位论文. 2003
7姜勇,丁恩勇,黎国康.相变储能材料的研究进展.广州化学.1999,(3):48~54
8黄志光,吴广忠,戴绪绮,等.聚光太阳灶用金属相变贮能装置的研究.太阳能学报. 1992, 13(3):271~275
9 Py X, Mauran S. Paraffin/porous-graphite-matrix Composite As a High and Constant Power Thermal Storage Material. International Journal of Heat and Mass Transfer. 2001, 44: 2727~2732
10 Abhat A. Low Temperature Latent Heat Thermal Energy Storage: Heat Storage Materials. Solar Energy. 1983,30(4): 313~318
11 Sari A. Thermal Reliability Test of Some Fatty Acids as PCMs Used for Solar Thermal Latent Heat Storage Applications Energy. Conversion and Management,2003, 44: 2277~2281
12李金辉,刘晓兰,张荣军,等.新型相变储能材料研究进展.化工新型材料. 2006,34(8):18~21
13 Salyer IO. Low temperature latent heat thermal energy storage. U. S. Patent5, 1994: 370~814
14 Inaba H, Tu P. Evalution of thermophaysical characteristics on shape stabilized paraffin as a solid–liquid phase change material. Heat and Mass Transfer. 1997, 32(4):307~312
15 M Hadjievaa, R Stoykova, Tz Filipovab. Composite salt-hydrate concretesystem for building energy storage. Renewable Energy. 2000, 19:111~115
16 Kenisarin MM. Short-term storage of solar energy.1. Low temperature phase-change materials. Apply Solar Energy. 1993, 29(2):48~65
17 Kadir tuncbilek, Ahmet Sari, Sefa Tarhan, et al. Lauric and palmitic acids eutectic mixture as latent heat storage material for low temperature heating applications. Energy. 2005, 33:677~692
18 Maria Natalia R. Dimaano, Takayuki Watanabe. The capric-lauric acid and p entadecane combination as phase chang material for cooling applications. Applied Thermal Engineering. 2002, 22:365~377
19 Sarit A, Kaygusuz K. Thermal energy storage system using stearic acid as a phase change material. Solar Energy. 2001, 71(6):365~376
20 Takeshi Kondo, Tadahiko Ibamoto, Tsubota Yuuji. Research on the storage of PCM wallboard.日本建筑学会论文集. 2001, 540:53~59
21 KakuichiH, YamazakiM, YabeM, et al. A study of erythrol as phase Change material. In: Proceedings of the 2nd workshop IEA annex 10, phase change materials and chemical Reactions for thermal energy storage, 11~13 April 1998, Sofia, Bulgaria
22 Terry Clara D. Composite Salt Ceramic Media for Thermal Energy Storage Application. Poreeedings of 17th IECEC Meeting. 1982, 2043~2046
23 Randy, Petri R. High-temperature salt/ceramic thermal storage phase-change. Porceedings 17th IECEC Meeting. 1983, 1796~1799
24 B.Pause,钟闻.相变材料用于空调建筑的可能性.国际纺织导报. 2001, 2:55~58
25 D.A. NEEPER. Thermal Dynamics Of Wallboard With Latent Heat Storage. Solar Energy. 2000, 68(5):393~403
26 D.Feldmna, D.Banl. Development and apapplication of orgnic phase change Mixture in thermal storagr gypsum wallboard. Solar Energy Materials&Solar Ce-ils. 1995, 36:147~157
27 Shim H, Meculloogh E A, Jones B W. Using Phase Change Maetrials in Clothing Textile. Research journal. 2001, 177(6):49~52
28 Farid MM, Husian RM. An electrical storage heater using phase change method of heat storage. Energy Convers Mgmt. 1990, 30:219~230
29 Bailey JA, Mulligan JC, Liao CK, et al. Research on solar energy storagesubsystem utilizing the latent hear of phase change of paraffin hydrocarbons for the heating and cooling of buildings. Report to the National Science Foundation for Grant GI-4438, North Carolina State University, USA, 1976
30 Eftekhar J, Haji-Sheikh A, Lou DYS. Heat transfer in paraffin wax thermal storage system. J Solar Energy Eng. 1984, 106:299~306
31 Ismail KAR, Alves CLF, Modesto MS. Numerical and experimental study on the solidification of PCM around a vertical axially finned isothermal cylinder. Appl Therm Eng. 2001, 21:53~77
32闫全英,王威.低温定形相变材料在相变墙体中应用的可行性研究.新型建筑材料. 2005, (2):58~59
33吕石磊,冯国会,付英会,等.脂酸类相变材料墙板在北方寒冷地区应用的DSC分析.节能. 2004, (3):36~38
34邱天.相变蓄能器的设计开发.浙江大学硕士学位论文. 2006
35曾翠华.水合盐储能材料性能研究.广东工业大学硕士学位论文. 2005
36赵兰.硫酸铝铵相变储能材料实验研究.上海海事大学硕士学位论文. 2007
37闫全英,王威.用在相变墙体中的定形相变材料的实验研究.节能技术, 2004, 22(6):3~4
38蔡利海,张兴祥.相变材料微胶囊的研究与应用.材料导报. 2002,16(2): 61~63
39张仁元,柯秀芳,李爱菊.无机盐/陶瓷基复合储能材料的制备和性能.材料研究学报. 2000, 14(6):652~656
40宋婧,曾令可,税安泽,等.钾明矾蓄热性能的研究与改善.人工晶体学报. 2007, 36(2):358~362
41湖南大学,一种储热介质及其用途.中国专利.申请号: 200610104583.8
42姜益强,齐琦,姚杨,等.太阳能季节性相变蓄热热泵系统在哈尔滨应用的模拟研究.暖通空调. 2007, 37(3):15~20
43广州能源研究所,家用分时计度储热电炉.中国专利.申请号:90223080.8
44广州能源研究所,用于空调节能建筑的相变材料及特性.中国专利.申请号:90108359.3
45黄志光.聚光太阳灶用金属相变贮能装置的研究.太阳能学报. 1992, 13(3):271~275
46文越华,张公正,王正刚,等. Na2SO4·10H2O复合相变储冷体系的热力学性质.北京理工大学学报. 1999, 19(6):778~781
47邢玉明,袁修干,王长和.空间站高温固液相变蓄热容器的实验研究.航空动力学报. 2001, 16(1):75~79
48王芳,郑茂余,李忠建,等.相变材料在太阳能-地源热泵系统中的应用.太阳能学报. 2006, 26(12):1231~1234
49周国兵,张寅平,林坤平,等.定形相变贮能材料在暖通空调领域的应用研究.暖通空调. 2007, 37(5):27~32
50康艳兵,江亿,张寅平.夜间通风相变贮能堆积床系统降温效果实验研究.暖通空调. 2003, 33(2):24~26
51沈斌.相变蓄热换热强化及蓄热器性能实验.重庆大学硕士学位论文. 2009
52张寅平,胡汉平,孔祥东,等.相变贮能—理论和应用.中国科学技术大学出版社. 1996
53南京大学,太阳能热水器相变储热材料及其制备方法.中国专利.申请号:200610039026.2
54冯国会.相变墙板热特性及相变墙房间.哈尔滨工业大学博士学位论文. 2006
55 George A L. Solar Heat Storage: Latent Heat Material. CRC Press Inc, 1983,4~67
56 Abhat A. Short term thermal energy storage. Revue Phys. Appl. ,15:477~501
57李莉.相变储热装置传热强化实验研究.北京工业大学硕士学位论文. 2006
58 Kim J.S., Darkwa K. Simulation of an integrated PCM-wallboard system. International Journal of Energy Research. 2003, 27:215~223
59张寒琦,宋利珠,张忆华,等.实用化学手册.科学出版社. 2001
2周风起. 21世纪中国能源工业面临的挑战.暖通空调, 2000, (4):32~37
3冯国会,曹广宇,于瑾,等.夏季昼夜温差较大地区相变墙蓄冷可行性分析.沈阳建筑大学学报. 2005, 21(4):350~353
4张太平,阮德水,张道圣,等.固-固相变贮热的研究(Ⅲ)-三羟甲基乙烷三羟甲基丙烷二元系[J].华中师范大学学报(自然科学版). 1996, 30(1): 65～68
5方春香.中低温定形相变储能材料的研究.北京工业大学硕士学位论文. 2006
6艾明星.相变贮能材料的研究.河北工业大学硕士学位论文. 2003
7姜勇,丁恩勇,黎国康.相变储能材料的研究进展.广州化学.1999,(3):48~54
8黄志光,吴广忠,戴绪绮,等.聚光太阳灶用金属相变贮能装置的研究.太阳能学报. 1992, 13(3):271~275
9 Py X, Mauran S. Paraffin/porous-graphite-matrix Composite As a High and Constant Power Thermal Storage Material. International Journal of Heat and Mass Transfer. 2001, 44: 2727~2732
10 Abhat A. Low Temperature Latent Heat Thermal Energy Storage: Heat Storage Materials. Solar Energy. 1983,30(4): 313~318
11 Sari A. Thermal Reliability Test of Some Fatty Acids as PCMs Used for Solar Thermal Latent Heat Storage Applications Energy. Conversion and Management,2003, 44: 2277~2281
12李金辉,刘晓兰,张荣军,等.新型相变储能材料研究进展.化工新型材料. 2006,34(8):18~21
13 Salyer IO. Low temperature latent heat thermal energy storage. U. S. Patent5, 1994: 370~814
14 Inaba H, Tu P. Evalution of thermophaysical characteristics on shape stabilized paraffin as a solid–liquid phase change material. Heat and Mass Transfer. 1997, 32(4):307~312
15 M Hadjievaa, R Stoykova, Tz Filipovab. Composite salt-hydrate concretesystem for building energy storage. Renewable Energy. 2000, 19:111~115
16 Kenisarin MM. Short-term storage of solar energy.1. Low temperature phase-change materials. Apply Solar Energy. 1993, 29(2):48~65
17 Kadir tuncbilek, Ahmet Sari, Sefa Tarhan, et al. Lauric and palmitic acids eutectic mixture as latent heat storage material for low temperature heating applications. Energy. 2005, 33:677~692
18 Maria Natalia R. Dimaano, Takayuki Watanabe. The capric-lauric acid and p entadecane combination as phase chang material for cooling applications. Applied Thermal Engineering. 2002, 22:365~377
19 Sarit A, Kaygusuz K. Thermal energy storage system using stearic acid as a phase change material. Solar Energy. 2001, 71(6):365~376
20 Takeshi Kondo, Tadahiko Ibamoto, Tsubota Yuuji. Research on the storage of PCM wallboard.日本建筑学会论文集. 2001, 540:53~59
21 KakuichiH, YamazakiM, YabeM, et al. A study of erythrol as phase Change material. In: Proceedings of the 2nd workshop IEA annex 10, phase change materials and chemical Reactions for thermal energy storage, 11~13 April 1998, Sofia, Bulgaria
22 Terry Clara D. Composite Salt Ceramic Media for Thermal Energy Storage Application. Poreeedings of 17th IECEC Meeting. 1982, 2043~2046
23 Randy, Petri R. High-temperature salt/ceramic thermal storage phase-change. Porceedings 17th IECEC Meeting. 1983, 1796~1799
24 B.Pause,钟闻.相变材料用于空调建筑的可能性.国际纺织导报. 2001, 2:55~58
25 D.A. NEEPER. Thermal Dynamics Of Wallboard With Latent Heat Storage. Solar Energy. 2000, 68(5):393~403
26 D.Feldmna, D.Banl. Development and apapplication of orgnic phase change Mixture in thermal storagr gypsum wallboard. Solar Energy Materials&Solar Ce-ils. 1995, 36:147~157
27 Shim H, Meculloogh E A, Jones B W. Using Phase Change Maetrials in Clothing Textile. Research journal. 2001, 177(6):49~52
28 Farid MM, Husian RM. An electrical storage heater using phase change method of heat storage. Energy Convers Mgmt. 1990, 30:219~230
29 Bailey JA, Mulligan JC, Liao CK, et al. Research on solar energy storagesubsystem utilizing the latent hear of phase change of paraffin hydrocarbons for the heating and cooling of buildings. Report to the National Science Foundation for Grant GI-4438, North Carolina State University, USA, 1976
30 Eftekhar J, Haji-Sheikh A, Lou DYS. Heat transfer in paraffin wax thermal storage system. J Solar Energy Eng. 1984, 106:299~306
31 Ismail KAR, Alves CLF, Modesto MS. Numerical and experimental study on the solidification of PCM around a vertical axially finned isothermal cylinder. Appl Therm Eng. 2001, 21:53~77
32闫全英,王威.低温定形相变材料在相变墙体中应用的可行性研究.新型建筑材料. 2005, (2):58~59
33吕石磊,冯国会,付英会,等.脂酸类相变材料墙板在北方寒冷地区应用的DSC分析.节能. 2004, (3):36~38
34邱天.相变蓄能器的设计开发.浙江大学硕士学位论文. 2006
35曾翠华.水合盐储能材料性能研究.广东工业大学硕士学位论文. 2005
36赵兰.硫酸铝铵相变储能材料实验研究.上海海事大学硕士学位论文. 2007
37闫全英,王威.用在相变墙体中的定形相变材料的实验研究.节能技术, 2004, 22(6):3~4
38蔡利海,张兴祥.相变材料微胶囊的研究与应用.材料导报. 2002,16(2): 61~63
39张仁元,柯秀芳,李爱菊.无机盐/陶瓷基复合储能材料的制备和性能.材料研究学报. 2000, 14(6):652~656
40宋婧,曾令可,税安泽,等.钾明矾蓄热性能的研究与改善.人工晶体学报. 2007, 36(2):358~362
41湖南大学,一种储热介质及其用途.中国专利.申请号: 200610104583.8
42姜益强,齐琦,姚杨,等.太阳能季节性相变蓄热热泵系统在哈尔滨应用的模拟研究.暖通空调. 2007, 37(3):15~20
43广州能源研究所,家用分时计度储热电炉.中国专利.申请号:90223080.8
44广州能源研究所,用于空调节能建筑的相变材料及特性.中国专利.申请号:90108359.3
45黄志光.聚光太阳灶用金属相变贮能装置的研究.太阳能学报. 1992, 13(3):271~275
46文越华,张公正,王正刚,等. Na2SO4·10H2O复合相变储冷体系的热力学性质.北京理工大学学报. 1999, 19(6):778~781
47邢玉明,袁修干,王长和.空间站高温固液相变蓄热容器的实验研究.航空动力学报. 2001, 16(1):75~79
48王芳,郑茂余,李忠建,等.相变材料在太阳能-地源热泵系统中的应用.太阳能学报. 2006, 26(12):1231~1234
49周国兵,张寅平,林坤平,等.定形相变贮能材料在暖通空调领域的应用研究.暖通空调. 2007, 37(5):27~32
50康艳兵,江亿,张寅平.夜间通风相变贮能堆积床系统降温效果实验研究.暖通空调. 2003, 33(2):24~26
51沈斌.相变蓄热换热强化及蓄热器性能实验.重庆大学硕士学位论文. 2009
52张寅平,胡汉平,孔祥东,等.相变贮能—理论和应用.中国科学技术大学出版社. 1996
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