JP2018526463A - 蓄熱及び伝熱用途の組成物 - Google Patents
蓄熱及び伝熱用途の組成物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 352
- 238000012546 transfer Methods 0.000 title description 5
- 238000005338 heat storage Methods 0.000 title description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 196
- 150000003839 salts Chemical class 0.000 claims abstract description 194
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 131
- -1 alkali metal salt Chemical class 0.000 claims abstract description 122
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 74
- 239000002184 metal Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 72
- 239000013078 crystal Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 256
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 88
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 88
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 84
- 239000002041 carbon nanotube Substances 0.000 claims description 78
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 77
- 238000002844 melting Methods 0.000 claims description 71
- 230000008018 melting Effects 0.000 claims description 71
- 235000010333 potassium nitrate Nutrition 0.000 claims description 44
- 239000004323 potassium nitrate Substances 0.000 claims description 44
- 229960004643 cupric oxide Drugs 0.000 claims description 42
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 39
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 39
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- 239000002048 multi walled nanotube Substances 0.000 claims description 35
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 28
- 229910052723 transition metal Inorganic materials 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 15
- 239000011833 salt mixture Substances 0.000 claims description 13
- 238000004146 energy storage Methods 0.000 claims description 11
- 150000001449 anionic compounds Chemical group 0.000 claims description 10
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- JJIQGEZLLWXYKV-UHFFFAOYSA-N calcium;dinitrate;hydrate Chemical group O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JJIQGEZLLWXYKV-UHFFFAOYSA-N 0.000 claims 2
- 238000002425 crystallisation Methods 0.000 description 35
- 230000008025 crystallization Effects 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 20
- 238000002411 thermogravimetry Methods 0.000 description 19
- 238000000113 differential scanning calorimetry Methods 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- VMLAJPONBZSGBD-UHFFFAOYSA-L calcium;hydrogen carbonate;hydroxide Chemical compound [OH-].[Ca+2].OC([O-])=O VMLAJPONBZSGBD-UHFFFAOYSA-L 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000013529 heat transfer fluid Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000002507 cathodic stripping potentiometry Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000001878 scanning electron micrograph 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
- F24S80/20—Working fluids specially adapted for solar heat collectors
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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
- C09K5/08—Materials not undergoing a change of physical state when used
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- C—CHEMISTRY; METALLURGY
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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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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Abstract
Description
便宜上、本開示の更なる説明の前に、本明細書中で使用するいくつかの用語及び例をここにまとめる。これらの定義は、本開示の他の部分に照らして読まれるべきであり、そのようなものとして当業者に理解されるべきである。本明細書で使用する用語は、当業者に認知され知られた意味を有するが、利便性及び完全性のために特定の用語とその意味を以下に明らかにする。
ナノ粒子の合成
文献(Yumei Tianら、Materials Letters、2006、60、527−529頁)に記載されたようにMoS2ナノ粒子を合成し、R. Etefaghら(Scientia Iranica、Transactions F: Nanotechnology、2013、20、1055−1058頁)により記載されたようにCuOナノ粒子を合成した。活性炭はMERCK社から購入し、球状活性炭も商用的供給源から収集した。カーボンナノチューブは商用的供給源から入手し、酸官能化は以下のように行った。500mLの丸底フラスコに500mgの多層CNTを入れ、濃H2SO4及び濃HNO3(3:1の比率)の混合物150mLを添加し、70℃で6時間超音波処理した。反応後に反応混合物を蒸留水で希釈し、ろ過した。ろ過ケークを120℃で終夜乾燥させ、酸官能化CNTを得る。
KNO3(60から70質量%)、LiNO3(5から20質量%)等の金属塩、水和した塩(10から30質量%)、及びナノ粒子(0.01から2質量%)をTable 1(表1)に示した組成に従い秤量し、圧力チューブ内で磁性ペレットと共に混合して、均一に分散したナノ粒子を含む塩の混合物を形成した。圧力チューブをテフロン(登録商標)ネジで締めて、200℃で加熱し、作り付けのオイルバスに備えられた磁気撹拌器を使用して撹拌した。水和水の放出後、塩は内部的に溶解して、ナノ粒子は混合物中で均一に分散した。溶液を充分に混合し、200℃で2時間保持し、その後チューブを開いて圧力を開放し、ロータリーエバポレーターを使用して水を除去した。チューブ内の圧力は圧力ゲージを使用して測定し、1.2から3バールの範囲にあることが分かった。組成物の融点をTable 1(表1)に示すが、150℃未満である。混合物全体の水分量はTGA分析を使用して計算できる。組成物の含水量は3から13質量%の範囲にあることが分かった。
溶融塩系熱エネルギー貯蔵は、溶融塩の可用性及び低コスト、有機系蓄熱流体に比べて高い熱安定性及び高い熱伝導率、高温での低粘度等のために、大きな注目を集めている。しかしながら、溶融塩はその熱エネルギー貯蔵容量の点で比較的制限がある。ナノ粒子の添加は、融解熱を大幅に犠牲にする事無しに、熱伝導率、熱安定性、比熱容量を改善する。本開示は、簡単で費用効果があるワンポット合成法を提供し、ナノ粒子及び塩の混合物は、塩の1種が水和物であり、圧力チューブを用いて200℃で2時間撹拌される方法である。減圧下で水分を除去した後に、ナノ粒子が組み込まれた塩は直接、蓄熱並びに伝熱の用途に使用できる。ナノ粒子の含有量を最適化した後に得られるナノ溶融塩(nano−molten salts)は、元の溶融塩と比べてより良い熱伝導率及びより良い比熱容量を示した。
Claims (20)
- 組成物を調製するための方法であって、
a)少なくとも1種のナノ粒子を、少なくとも1種のアルカリ金属塩及び結晶水を有する金属塩と接触させて混合物を得る工程と、
b)前記混合物を閉鎖系で100から200℃の範囲の温度に曝露して、塩の混合物中の分散したナノ粒子を得る工程と、
c)前記塩の混合物中の分散したナノ粒子から水を除去して前記組成物を得る工程と、
を含む方法。 - 前記少なくとも1種のナノ粒子が、二硫化モリブデン、酸化第二銅、カーボンナノチューブ、官能化カーボンナノチューブ、多層カーボンナノチューブ、活性炭、球状活性炭、グラフェン及びそれらの組合せからなる群から選択される、請求項1に記載の方法。
- 前記組成物中の前記少なくとも1種のナノ粒子の質量百分率が0.01から2%の範囲である、請求項1に記載の方法。
- 前記少なくとも1種のナノ粒子が、30から500nmの範囲の粒径を有する、請求項1に記載の方法。
- 前記少なくとも1種アルカリ金属塩が、ナトリウム金属塩、リチウム金属塩、カリウム金属塩及びそれらの組合せからなる群から選択され、前記少なくとも1種のアルカリ金属塩が無機アニオンである、請求項1に記載の方法。
- 前記組成物中の前記少なくとも1種のアルカリ金属塩の質量百分率が5から90%の範囲である、請求項1に記載の方法。
- 前記少なくとも1種のアルカリ金属塩が、硝酸リチウムと硝酸カリウムとの組合せであり、前記組成物中の硝酸カリウムの質量百分率が60から70%の範囲であり、前記組成物中の硝酸リチウムの質量百分率が5から20%の範囲である、請求項1に記載の方法。
- 前記結晶水を有する金属塩が、アルカリ金属塩、アルカリ土類金属塩及び遷移金属塩からなる群から選択される、請求項1に記載の方法。
- 前記結晶水を有する金属塩が、40から120℃の範囲の融点を有する、請求項1に記載の方法。
- 前記組成物中の前記金属塩の質量百分率が10から35%の範囲である、請求項1に記載の方法。
- 前記金属塩が硝酸カルシウム水和物である、請求項1に記載の方法。
- 前記組成物が、3から13%の範囲の含水量を有し、100から150℃の範囲の融点を有する、請求項1に記載の方法。
- 前記分散したナノ粒子を含む塩の混合物が、100から200℃の温度に0.5から2時間かけられる、請求項1に記載の方法。
- (a)30から500nmの範囲の粒径を有する少なくとも1種のナノ粒子、(b)少なくとも1種のアルカリ金属塩、及び(c)結晶水を有する金属塩を含み、100から150℃の範囲の融点を有する組成物。
- 前記少なくとも1種のナノ粒子が、二硫化モリブデン、酸化第二銅、カーボンナノチューブ、官能化カーボンナノチューブ、多層カーボンナノチューブ、活性炭、球状活性炭、及びグラフェンからなる群から選択される、請求項14に記載の組成物。
- 前記組成物中の前記少なくとも1種のナノ粒子の質量百分率が0.01から2%の範囲である、請求項14に記載の組成物。
- 前記少なくとも1種のアルカリ金属塩が、硝酸リチウムと硝酸カリウムとの組合せであり、前記組成物中の硝酸カリウムの質量百分率が60から70%の範囲であり、前記組成物中の硝酸リチウムの質量百分率が5から20%の範囲である、請求項14に記載の組成物。
- 前記組成物中の前記金属塩の質量百分率が10から35%の範囲である、請求項14に記載の組成物。
- 前記金属塩が硝酸カルシウム水和物である、請求項14に記載の組成物。
- 太陽熱エネルギー貯蔵に使用するための、請求項14に記載の組成物。
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IN2352/MUM/2015 | 2015-06-19 | ||
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PCT/IN2016/050188 WO2016203498A1 (en) | 2015-06-19 | 2016-06-17 | Composition for thermal storage and heat transfer applications |
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EP (1) | EP3310872A1 (ja) |
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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 |
US10988655B2 (en) | 2015-06-19 | 2021-04-27 | Hindustan Petroleum Corporation Ltd. | Composition for thermal storage and heat transfer applications |
CN108269982B (zh) * | 2018-01-09 | 2020-07-31 | 中国科学院福建物质结构研究所 | 一种复合材料、其制备方法及在锂离子电池中的应用 |
CN108559457A (zh) * | 2018-04-27 | 2018-09-21 | 中国科学院青海盐湖研究所 | 一种太阳能光热发电传热蓄热介质及其制备方法 |
CN108531142A (zh) * | 2018-04-27 | 2018-09-14 | 中国科学院青海盐湖研究所 | 太阳能光热发电传热蓄热介质及其制备方法 |
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US2211047A (en) * | 1938-04-30 | 1940-08-13 | Degussa | Salt melts as heat transfer media |
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US7588694B1 (en) * | 2008-02-14 | 2009-09-15 | Sandia Corporation | Low-melting point inorganic nitrate salt heat transfer fluid |
US7828990B1 (en) | 2008-02-14 | 2010-11-09 | Sandia Corporation | Low-melting point heat transfer fluid |
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US10988655B2 (en) | 2015-06-19 | 2021-04-27 | Hindustan Petroleum Corporation Ltd. | Composition for thermal storage and heat transfer applications |
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