CN103298904B - 用于太阳能设备的传热介质 - Google Patents
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- ZBZAQLHRNKFLAZ-UHFFFAOYSA-N barium(2+) nitric acid dinitrate Chemical compound [N+](=O)([O-])[O-].[Ba+2].[N+](=O)(O)[O-].[N+](=O)([O-])[O-] ZBZAQLHRNKFLAZ-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910003251 Na K Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 230000005496 eutectics Effects 0.000 description 9
- 239000011833 salt mixture Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000000374 eutectic mixture Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- -1 Biphenyl Ethers Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
- C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Engine Equipment That Uses Special Cycles (AREA)
- Lubricants (AREA)
Abstract
本发明涉及一种用于太阳能设备的新型传热介质,特别是硝酸盐。通过掺杂Ba和/或Sr到Li‑Na‑K‑NO3,可以改善太阳能盐的性质。
Description
本发明涉及一种用于太阳能设备的新型传热介质,特别是硝酸盐。
下一代的太阳能发电厂设备(聚光太阳能发电“CSP”),例如基于抛物面槽式和菲涅尔反射技术的设备,很大可能性是倾向于从目前的有机传热介质,例如Fa.的导热油VP-1TM,一种由73.5重量%联苯醚和23.5重量%联苯形成的熔点为12℃的共晶混合物,发展到无机介质,从发电站设计和力求不断提高效率的立场看,这是绝对必要的。
无机介质,特别是,例如液态盐,作为传热介质(传热流体“HTF”)显示一系列的优点,与以化石燃料为驱动的能源供应相比,可以显著缩短太阳能CSP设备的成本平价时间(平准化能源成本“LCOE”)。特别是,在太阳能循环中循环的HTF需要高的连续工作温度(T>500℃),因为只有这样才能对于在水-蒸汽循环中最大限度地利用蒸汽涡轮机实现足够高的能量密度。已知的方式用流入的气体和/或蒸汽的温度来测量涡轮的效率,因此CSP设备在太阳能循环中理想方式应该用HTF推动,经受温度直至565℃而没有热分解。当然这种介质的熔点应当非常低,因为必须绝对避免在几公里长的管道和接收系统内循环的熔融盐发生凝固。HTF的熔点越高,为了避免冻结,采取的预防措施必须越费力并且越昂贵。在这种情况下,电和/或热性质的附带加热得到应用,这在恶劣天气期间,保养和/或排水系统运转的情况下,应该要确保热安全边际在实际熔点以上。
盐是由阳离子和阴离子形成的多极性化合物,在固态时形成晶格。
这种混合物(Gemenge)能够加热到温度至550℃而不热降解,并且因此在热力学观点下,与使用上述导热油情况相比,可以实现由太阳能到电能更有效的转换,而使用上述导热油时,由于有机结构的原因,最大工作温度不能超过395℃,因为否则发生降解。
由于在夜间运行中,太阳能发电站本身并不能提供能量,因此合理的和/或潜在的基于盐的蓄热器一直得到应用。用于这一目的的最常用的和现有技术的相应混合物是所谓的“太阳盐”,一种由60重量%硝酸钠和40重量%硝酸钾组成的非共晶混合物,其液相线温度约为240℃。这种混合物用作能量储存(热储能,“TES”),例如在夜间用于提供热能。为了这个目的,当前一代CSP设备在白天运行期间,收集的太阳能一部分在熔融“太阳盐”中通过导热油-盐-热交换器得到缓冲,以便由此能够在夜间运行期间维持,并且还为涡轮机连续提供能源。
因此,本发明的目的是找到一种在太阳能设备中作为传热介质的有机导热油的替代品,其熔点尽可能低,并且确保其在高温下以及连续运行下的稳定性。
本发明的一般知识是,无机盐混合物,尤其是硝酸盐混合物对于用作传热介质,证明是特别有用的,因为这种混合物本身相对熔点较低,通过元素周期表中碱金属和碱土金属族内通过形成相应的共晶而进行二值化(Binaerisierung)、三值化、四值化和五值化等,可以进一步降低该熔点。
在本说明书和权利要求中公开该任务的解决方案。
因此,本发明的主题是用于太阳能发电厂设备的一种传热介质,以硝酸盐为基础,包含阳离子钾、钠,其特征在于,在所述盐混合物中包含钡和/或锶作为其它阳离子。
已经有以硝酸盐为基础的包含阳离子钾和钠的共晶盐混合物,其中,特别包含锂和/或钙作为额外的阳离子。
例如,一种共晶混合物,含有约21mol%Ca2+,49mol%K+,和30mol%Na+,具有约为132~135℃的低熔点,由A.G.Bergmann和I.S.Rassonskaya,以及N.E.Schmidt在出版物Izvest Sectora,,Fiz.-Khim Anal″vom Inst Obshkhei Neorg Khim,Akad NaukS.S.S.R.26(1955),156页中所公开。然而问题在于,在高于500℃的温度时强烈极化性的钙阳离子Ca2+趋向于和硝酸盐中存在的氧形成相应的在盐混合物中不能溶解的氧化物,其熔点非常高,并且趋向于与湿气形成高腐蚀性的氢氧化钙。
本文已经证明了,添加硝酸钡和/或硝酸锶使得氧化物和氢氧化物难以形成,因此改善了共晶盐混合物在高温下的耐久性。
在已知的含锂的具有钾/钠的共晶硝酸盐混合物中不利的是,锂是昂贵的而且含锂的共晶盐混合物总是强吸湿性的。通过添加锶和/或钡而不是锂可以在质量不变下大大降低共晶混合物的价格。此外,硝酸锶和/或硝酸钡不会产生由硝酸锂引起的吸湿性。最后,掺入硝酸锶和/或硝酸钡的共晶盐混合物比掺入硝酸锶的相应盐具有更高的密度。
作为实施例,已知的Na-K-Ca-NO3共晶盐混合物包括约21mol%Ca2+,49mol%K+,和30mol%Na+,熔点范围约为133℃,掺入0.6mol%含量的钡(2+)阳离子。可以观察到熔化温度降低8℃。在不含钡的情况下,该盐混合物在143℃时才达到完全液相,而含钡的盐混合物可以在降低10℃,在134℃就已经达到液相。
为了制备共晶混合物,特别是一种至少三元(就是说,包含3种物质)混合物,钡盐和/或锶盐的使用量为0.01至30mol%;优选为0.1至15mol%。
在共晶点,共晶体即混合物,如同纯物质一样凝固,优选没有温度间隔。
在所有的混合物中,钡和锶的含量比例最多可直到30mol%,优选为直到15mol%的钡和/或锶,特别优选为直到10mol%的钡和/或锶。剩下的阳离子,例如Li,Na,K,Ca位于10-60mol%范围内。
通过掺杂Ba和/或Sr到Li-Na-K-NO3(每次33/27/47mol%,熔点116℃)得到Li-Na-K-Ba/Sr-NO3共晶体,其熔点<116℃。然后,同时降低Li-比例,这使得混合物更便宜,吸湿性更小并且得到更高的密度。这同样适用于四值化,就是说4种物质组成的混合物而不是3种物质组成的三元混合物:硝酸钙、硝酸钠、硝酸钾(Ca-Na-K-NO3)变为Ca-Na-K-Ba/Sr-NO3。优选钡/锶的比例为0.1~15mol%范围内。剩下的阳离子Li,Na,K,Ca相应地按比例降低,亦即总是在10~60%范围内,然后合计为100%。
Claims (3)
1.以硝酸钠和硝酸钾为基础的传热介质用于太阳能设备的用途,其特征在于,以硝酸钠和硝酸钾为基础的传热介质中还包含硝酸钡和/或硝酸锶。
2.根据权利要求1所述的用途,其特征在于,所述传热介质中还包含硝酸锂和/或硝酸钙。
3.根据上述权利要求之一所述的用途,其特征在于,其中所述传热介质包含0.01至30mol%含量的硝酸钡。
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DE102011008091A DE102011008091A1 (de) | 2011-01-07 | 2011-01-07 | Wärmeübertragungsmedium für solarthermische Anlagen |
PCT/EP2011/071596 WO2012093012A1 (de) | 2011-01-07 | 2011-12-02 | Wärmeübertragungsmedium für solarthermische anlagen |
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DE102010041460A1 (de) * | 2010-09-27 | 2012-01-19 | Siemens Aktiengesellschaft | Wärmetransfermedium, Verwendung dazu und Verfahren zum Betreiben einer solarthermischen Kraftwerksanlage |
US10011754B2 (en) * | 2013-01-23 | 2018-07-03 | Basf Se | Method of improving nitrate salt compositions by means of nitric acid for use as heat transfer medium or heat storage medium |
DE202013005845U1 (de) * | 2013-07-01 | 2014-08-04 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Latentwärmespeichermaterial |
DE102013219498A1 (de) * | 2013-09-27 | 2015-04-02 | Siemens Aktiengesellschaft | Salzgemisch als Speichermedium für ein ölbasiertes solarthermisches Kraftwerk |
CN103911122B (zh) * | 2013-12-26 | 2017-01-11 | 深圳市爱能森科技有限公司 | 水玻璃复合二元硝酸熔盐传热蓄热介质及其制备方法与应用 |
ES2579763B1 (es) * | 2015-01-15 | 2017-05-29 | Quimica Del Estroncio, S.A.U. | Nuevas formulaciones de sales de nitratos para su empleo como fluido de almacenamiento y transferencia de calor |
ES2925925T3 (es) | 2015-05-25 | 2022-10-20 | Hindustan Petroleum Corp Ltd | Un proceso para la preparación de mezclas homogéneas para aplicaciones de almacenamiento térmico y transferencia de calor |
CN105131911A (zh) * | 2015-09-21 | 2015-12-09 | 上海交通大学 | 相变蓄热介质及其制备及应用 |
CN105651091B (zh) * | 2016-02-19 | 2017-08-15 | 上海交通大学 | 传热增强型化学蓄热装置及应用该蓄热装置的蓄热系统 |
GB201816380D0 (en) * | 2018-10-08 | 2018-11-28 | Sunamp Ltd | Group II metal nitrate based compositions for use as phase change materials |
CN112523981A (zh) * | 2021-01-21 | 2021-03-19 | 中国科学技术大学 | 利用联苯-联苯醚混合物的直接膨胀式太阳能热发电系统 |
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- 2011-01-07 DE DE102011008091A patent/DE102011008091A1/de not_active Ceased
- 2011-12-02 AU AU2011354220A patent/AU2011354220B2/en not_active Ceased
- 2011-12-02 WO PCT/EP2011/071596 patent/WO2012093012A1/de active Application Filing
- 2011-12-02 EP EP11793737.5A patent/EP2614126A1/de not_active Withdrawn
- 2011-12-02 US US13/978,581 patent/US20130284970A1/en not_active Abandoned
- 2011-12-02 CN CN201180064426.8A patent/CN103298904B/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
EP2614126A1 (de) | 2013-07-17 |
AU2011354220B2 (en) | 2016-01-14 |
CN103298904A (zh) | 2013-09-11 |
US20130284970A1 (en) | 2013-10-31 |
WO2012093012A1 (de) | 2012-07-12 |
AU2011354220A1 (en) | 2013-05-30 |
DE102011008091A1 (de) | 2012-07-12 |
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