WO2014026892A1 - Verfahren zur verbesserung von nitritsalzzusammensetzungen bei deren verwendung als wärmeträgermedium oder wärmespeichermedium - Google Patents
Verfahren zur verbesserung von nitritsalzzusammensetzungen bei deren verwendung als wärmeträgermedium oder wärmespeichermedium Download PDFInfo
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- WO2014026892A1 WO2014026892A1 PCT/EP2013/066561 EP2013066561W WO2014026892A1 WO 2014026892 A1 WO2014026892 A1 WO 2014026892A1 EP 2013066561 W EP2013066561 W EP 2013066561W WO 2014026892 A1 WO2014026892 A1 WO 2014026892A1
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- WIPO (PCT)
- Prior art keywords
- nitrite
- additive
- heat transfer
- heat
- nitrite salt
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 150000002826 nitrites Chemical class 0.000 title claims abstract description 96
- 238000012546 transfer Methods 0.000 title claims abstract description 77
- 238000005338 heat storage Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 27
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000654 additive Substances 0.000 claims abstract description 75
- 230000000996 additive effect Effects 0.000 claims abstract description 72
- -1 alkali metal nitrite Chemical class 0.000 claims abstract description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims abstract description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 19
- 230000007774 longterm Effects 0.000 claims abstract description 19
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000003860 storage Methods 0.000 claims description 30
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010327 methods by industry Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000002835 noble gases Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 22
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 24
- 239000011833 salt mixture Substances 0.000 description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 22
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 17
- 229910002651 NO3 Inorganic materials 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 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 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 239000004323 potassium nitrate Substances 0.000 description 12
- 235000010333 potassium nitrate Nutrition 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 239000000470 constituent Substances 0.000 description 11
- 239000004317 sodium nitrate Substances 0.000 description 11
- 235000010344 sodium nitrate Nutrition 0.000 description 11
- 235000010288 sodium nitrite Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 10
- 229910052788 barium Inorganic materials 0.000 description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 10
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 150000002823 nitrates Chemical class 0.000 description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- 238000003889 chemical engineering Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 230000005855 radiation Effects 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000004304 potassium nitrite Substances 0.000 description 5
- 235000010289 potassium nitrite Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 3
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- ZLMJMSJWJFRBEC-LZFNBGRKSA-N Potassium-45 Chemical compound [45K] ZLMJMSJWJFRBEC-LZFNBGRKSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GJTDJAPHKDIQIQ-UHFFFAOYSA-L barium(2+);dinitrite Chemical compound [Ba+2].[O-]N=O.[O-]N=O GJTDJAPHKDIQIQ-UHFFFAOYSA-L 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YBVAXJOZZAJCLA-UHFFFAOYSA-N nitric acid nitrous acid Chemical compound ON=O.O[N+]([O-])=O YBVAXJOZZAJCLA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
- F28D20/0034—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using liquid heat storage material
- F28D2020/0047—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using liquid heat storage material using molten salts or liquid metals
-
- 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
Definitions
- the present invention relates to a method for maintaining or expanding the long-term operating temperature range of a heat transfer medium and / or heat storage medium as defined in the claims, a corresponding process engineering system as defined in the claims, the use of an additive for maintaining or expanding the long-term operating temperature range of a heat transfer medium.
- Heat transfer media are media that are heated by a heat source, such as the sun in solar thermal power plants, and transport the amount of heat contained in them over a certain distance. You can then transfer this heat to another medium, such as water or a gas, preferably via heat exchangers (also called heat exchanger), this other medium then, for example, can drive a turbine. Heat transfer media can continue to heat in chemical engineering reactors (for example Salzbadreaktoren) to the desired temperature, or cool.
- a heat source such as the sun in solar thermal power plants
- heat transfer media can also transfer the amount of heat contained in them to another, located in a reservoir medium (for example, molten salt) and thus pass the heat for storage. Heat transfer media can also be fed into a reservoir and remain there. You are then both heat transfer media and heat storage media.
- a reservoir medium for example, molten salt
- Heat accumulators contain heat storage media, usually material compositions, for example the mixtures according to the invention, which can store a heat quantity over a certain period of time.
- Heat storage for fluid, preferably liquid, heat storage media are usually formed by a solid, preferably insulated against heat loss, container.
- a relatively recent application of heat transfer media or heat storage media are solar thermal power plants (herein and in the art also called solar thermal power plants) for generating electrical energy.
- Example of a solar thermal power plant is shown schematically in Figure 1.
- concentrated solar radiation (1) heats up a heat carrier medium, usually in a receiver system (2), which usually consists of a combination of tubular “receivers.”
- the heat transfer medium usually flows into a pump, usually driven by pumps
- Heat storage system (5a) flows via the line (6) from there on to a heat exchanger (8) (colloquially also referred to as “heat exchanger"), where it gives off its heat to water, thus generating steam (9), the turbine (1 1), which eventually, as in a conventional power plant, drives a generator for generating electrical energy.
- the steam loses heat (13) then flows back as a condensate (10) usually in the heat exchanger (8).
- the cooled heat transfer medium flows from the heat exchanger (8) usually over the cold area (5b) of a heat storage system to the receiver system (2) back, in which it is heated again by the solar radiation and creates a cycle.
- the storage system can consist of a hot (5a) and a cold (5b) tank, for example as two separate vessels.
- An alternative construction of a suitable storage system is for example a stratified storage with a hot area (5a) and a cold area (5b), for example in a vessel. More about solar thermal power plants is described for example in Schm dertician, 3, 2009 pages 82 to 99 and in the following.
- the parabolic trough power plant, the Fresnel power plant and the tower power plant are The parabolic trough power plant, the Fresnel power plant and the tower power plant.
- the solar radiation is focused via parabolic shaped troughs into the focal line of the mirrors.
- a pipe usually called a "receiver”
- the heat transfer medium is heated by the solar radiation and flows to the heat exchanger, where it gives off its heat as described above, to generate steam can reach more than 100 kilometers in current solar thermal power plants.
- the solar radiation is focused into a focal line with generally flat mirrors.
- a pipe usually referred to as "receiver”
- the mirror and the tube are not tracked together the sun, but the position of the mirror is adjusted relative to the permanently installed pipe. The mirror position follows the position of the sun so that the fixed pipeline is always in the focal line of the mirrors, and even in Fresnel power plants, molten salt can be used as heat carrier.
- Fresnel power plants are currently still largely in development.
- the steam generation, or the generation of electrical energy takes place in the salt Fresnel power plant analogous to the parabolic trough power plant.
- a tower surrounded by mirrors, in the professional world also referred to as "heliostats”, which radiate the solar radiation to a so-called central receiver in the upper part of the tower bundled in the receiver Pipe bundles is constructed, a heat transfer medium is heated, which produces analogous to the parabolic trough power plant or Fresnel power plant via heat exchanger steam for generating electrical energy.
- Heat transfer media or heat storage media based on inorganic salts have long been known. They are usually used at such high temperatures, in which water is already vaporous, that is usually at 100 ° C and more.
- compositions containing alkali metal and / or alkaline earth metal nitrates, optionally in admixture with alkali metal nitrites and / or alkaline earth metal nitrites are compositions containing alkali metal and / or alkaline earth metal nitrates, optionally in admixture with alkali metal nitrites and / or alkaline earth metal nitrites.
- Examples are the products of Coastal Chemical Company LLC Hitec® Solar Salt (potassium nitrate: sodium nitrate 40% by weight: 60% by weight), Hitec® (eutectic mixture of potassium nitrate, sodium nitrate and sodium nitrite).
- Hitec® eutectic mixture of potassium nitrate, sodium nitrate and sodium nitrite.
- nitrate salts usually those of the alkali metal lithium, sodium, potassium with nitrite salts, usually those of the alkali metals lithium, sodium, potassium or the alkaline earth metal calcium, can be used to prepare corresponding mixtures which have a relatively lower melting point.
- alkali metal lithium, sodium, potassium, rubidium, cesium, preferably lithium, sodium, potassium, particularly preferably sodium, is to be understood as meaning potassium unless expressly stated otherwise.
- alkaline earth metal beryllium, magnesium, calcium, strontium, barium, preferably calcium, strontium, barium, most preferably calcium and barium, unless otherwise specified.
- the aim is still to develop a heat transfer medium or heat storage medium, which solidifies at relatively low temperature (solidifies) ergo a lower melting point but a high maximum long-term operating temperature (analog: high decomposition temperature) has.
- the maximum long-term operating temperature is herein understood to mean the highest operating temperature of the heat carrier or heat storage medium, in which its properties, such as viscosity, melting temperature, corrosion behavior compared to the starting value over a long period of time, usually 10 to 30 years, do not change significantly.
- mixtures of sodium nitrate or potassium nitrate are used at relatively high temperatures.
- a typical long-term operating temperature range is 290 to 565 ° C.
- Such mixtures are characterized by a relatively high melting point.
- alkali metal nitrate and / or alkaline earth metal nitrate and alkali metal nitrite and / or alkaline earth metal nitrite usually have a lower melting point than the nitrate mixtures mentioned above, but also a lower decomposition temperature.
- Such mixtures are usually used in the temperature range from 150 ° C. to 450 ° C. and generally have a relatively high proportion of alkali metal or alkaline earth metal nitrites, for example 30 to 40% by weight.
- nitrate / nitrite salt mixtures can be negatively affected in several ways. For example, by a malfunction in the plant operation, for example, penetration of oxidative substances, nitrite salts can be oxidized to nitrate salts, which is not desirable because then the melting point of the mixtures is increased.
- nitrate / nitrate salt mixtures and thus, for example, their long-term operating temperature range in solar thermal power plants by receiving traces or even relatively large amounts of water or carbon dioxide can change negatively, for example by a leak in the heat transfer medium / steam heat exchanger or by the so-called open operation in which the heat transfer or heat storage media have contact with the humidity of the outside air.
- the properties of the nitrate / Nitritsalzmischungen can thereby worsen to the extent that they are unsuitable as a heat transfer medium or heat storage medium and usually need to be replaced with fresh mixtures, resulting in the huge amounts, for example, in the tube and storage system of a solar thermal power plant thermal Mehrpen arrivedn are included, technically and economically Häturban or practically impossible.
- the object of the present invention was to find a method which avoids or reverses the deterioration of a heat transfer medium or heat storage medium based on a nitrite salt mixture or extends the long-term operating temperature range of such mixtures.
- nitrite salt compositions defined in the description and in the claims, in particular their preferred and particularly preferred embodiments, are also referred to below as "nitrite salt composition according to the invention".
- the nitrite salt composition of the present invention contains as essential constituents an alkali metal nitrate or an alkaline earth metal nitrate or a mixture of alkali metal nitrate and alkaline earth metal nitrate, and each an alkali metal nitrite and / or alkaline earth metal nitrite.
- the alkali metal nitrate is herein a nitrate, preferably practically anhydrous, more preferably anhydrous, nitrate of the metals lithium, sodium, potassium, rubidium or cesium, preferably lithium, sodium, potassium, more preferably sodium, potassium, generally described as MetNC "3, where Met
- the term alkali metal nitrate includes both a single nitrate and mixtures of the nitrates of these metals, for example potassium nitrate plus sodium nitrate.
- the alkaline earth metal nitrate herein is a nitrate, preferably practically anhydrous, more preferably anhydrous, nitrate of metals, magnesium, calcium, strontium, barium, preferably calcium, strontium, barium, more preferably calcium and barium, generally described as Met (NC "3) 2 wherein Met means the above-described alkaline earth metals, the term alkaline earth metal nitrate including both a single nitrate and mixtures of the nitrates of these metals, for example calcium nitrate plus magnesium nitrate.
- the alkali metal nitrite is herein a nitrite, preferably practically anhydrous, more preferably anhydrous, nitrite of the alkali metals lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium, potassium, more preferably sodium, potassium, generally described as MetNC "2, where Met
- the alkali metal nitrite may be present as a single compound but also as a mixture of different alkali metal nitrites, for example sodium nitrite plus potassium nitrite.
- the alkaline earth metal nitrite is herein a nitrite, preferably practically anhydrous, more preferably anhydrous, nitrite of the metals magnesium, calcium, strontium, barium, preferably calcium, strontium, barium, more preferably calcium and barium, generally described as Met (NC "2) 2, wherein Met means the above-described alkaline earth metals, wherein the term alkaline earth metal nitrite includes both a single nitrite and mixtures of the nitrites of these metals, for example calcium nitrite plus magnesium nitrite.
- Nitrite salt composition according to the invention containing as essential constituents an alkali metal nitrate and / or alkaline earth metal nitrate and in each case an alkali metal nitrite and / or alkaline earth metal nitrite;
- Nitrite salt composition containing as essential constituents an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate and in each case an alkali metal nitrite and / or alkaline earth metal nitrite;
- Nitrite salt composition containing as essential constituents an alkali metal nitrate and an alkali metal nitrite;
- Nitrite salt composition comprising as essential constituents an alkali metal nitrate and an alkali metal nitrite selected from sodium nitrite and / or potassium nitrite;
- Nitrite salt composition comprising as essential constituents an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate and in each case an alkali metal nitrite selected from sodium nitrite and / or potassium nitrite and / or alkaline earth metal nitrite selected from calcium nitrite and / or barium nitrite;
- Nitrite salt composition comprising as essential constituents an alkali metal nitrate and / or alkaline earth metal nitrate and an alkali metal nitrite selected from sodium nitrite and / or potassium nitrite;
- nitrite salt compositions according to the invention comprising as essential constituents an alkali metal nitrate and an alkali metal nitrite are, for example, the following:
- Alkali metal nitrate preferably sodium nitrate and / or potassium nitrate, in an amount ranging from 5 to 95% by weight, preferably 20 to 80% by weight, more preferably 50 to 70% by weight
- alkali metal nitrite preferably sodium nitrite and / or potassium nitrite an amount in the range of 95 to 5 wt .-%, preferably 80 to 20 wt .-%, particularly preferably 50 to 30 wt .-%, each based on the mixture.
- nitrite salt compositions comprise, in addition to alkali metal nitrates and / or alkali metal nitrites, alkaline earth metal nitrates and / or alkaline earth metal nitrites as follows: (i) The nitrate salt content is particularly preferred here in a range from 5 to 98% by weight, preferably 50 to 95% by weight 70 to 90 wt .-% and the Nitritsalzgehalt in a range of 2 to 95 wt .-%, preferably 5 to 50 wt .-% particularly preferably 10 to 30 wt .-% in each case based on the mixture.
- the alkali metal salt content herein is in a range of 5 to 99% by weight, preferably 30 to 90% by weight, more preferably 50 to 80% by weight, and the alkaline earth metal salt content is in a range of 1 to 95% by weight. , preferably 10 to 70 wt .-%, particularly preferably 20 to 50 wt .-% in each case based on the mixture.
- Preferred alkali metals in the above mixtures (i) and (ii) are sodium and potassium.
- Preferred alkaline earth metals in the above mixtures (i) and (ii) are calcium and barium.
- a mixture of potassium nitrate, sodium nitrate and sodium nitrite is commercially available, for example as Hitec® product of Coastal Chemical Company LLC.
- the nitrite salt composition according to the invention may also contain traces of further constituents, for example oxides, chlorides, sulfates, carbonates, hydroxides, silicates of the alkali metals and / or alkaline earth metals, silicon dioxide, iron oxide, aluminum oxide or water.
- the sum of these constituents is generally not more than 1% by weight, based on the nitrite salt composition according to the invention.
- the sum of all constituents of the nitrite salt composition according to the invention is in each case 100% by weight.
- the nitrite salt composition according to the invention passes into the molten and usually pumpable form at a temperature above approximately 100 to 220 ° C., inter alia, depending on the nitrite content and the ratio of the cations forming the mixture.
- the nitrite salt composition according to the invention generally has a concentration of nitrites such that the melting point of the nitrite salt composition according to the invention is in the range from 100 to 220 ° C., preferably in the range from 100 to 180 ° C., hereinafter referred to as "intended nitrite operating concentration".
- nitrite salt composition according to the invention preferably in molten form, for example as a pumpable liquid, is used as heat transfer medium and / or heat storage medium, preferably in power plants for the production of heat and / or electrical energy, in chemical engineering, for example in salt bath reactors and in metal hardening plants.
- Examples of power plants for the production of heat and / or electrical energy are solar thermal power plants such as parabolic trough power plants, Fresnel power plants, tower power plants.
- the thermal energy generated in power plants can be used for thermal water treatment, for example in seawater desalination plants or for process heat generation in industrial applications, for example for ore processing.
- the nitrite salt compositions according to the invention are preferably used in the molten state, for example as a pumpable liquid, both as a heat transfer medium and as a heat storage medium in solar thermal power plants, for example parabolic trough power plants, tower power plants or Fresnel power plants.
- the nitrite salt compositions according to the invention are used, preferably in the molten state, for example as a pumpable liquid, either as a heat transfer medium or as a heat storage medium in the solar thermal power plants, for example the parabolic trough power plants, the tower power plants, the Fresnel power plants.
- the nitrite salt compositions according to the invention are preferably used in the molten state, for example as a pumpable liquid, in tower power plants as heat transfer medium and / or as heat storage medium, particularly preferably as heat transfer medium.
- the Nitritsalzzusammen stuen invention preferably in the molten state, for example as a pumpable liquid, as a heat transfer medium in solar thermal power plants, such as parabolic trough power plants, the tower power plants, the Fresnel power plants, the heat transfer media are guided through solar heated pipes. They usually carry the heat produced there to a heat storage or to the heat exchanger of the steam heater of a power plant.
- the heat storage consists in a variant of several, usually two large containers, usually a cold and a hot container (also referred to as "two-tank storage”) .
- the nitrite salt composition according to the invention preferably in the molten state, for example as a pumpable liquid, It is usually taken from the cold tank of the solar system and heated in the solar field of a parabolic trough or tower receiver.
- the hot molten salt mixture thus heated is usually led into the hot tank and kept there until there is a need to generate electrical energy
- the so-called “thermocline storage” consists of a tank in which the heat storage medium is stored layered in different temperatures. This variant is also called “stratified storage.” During storage, material is removed from its cold area, the material is heated and stored back into its hot area, so that the thermocline is used largely analogously to a two-tank storage tank.
- the hot nitrite salt compositions according to the invention in the molten state are usually taken from the hot tank or the hot zone of the stratified storage tank and pumped to the steam generator of a steam power plant.
- the steam generated there which is stretched to over 100 bar, usually drives a turbine and a generator, which supplies electrical energy to the electricity grid.
- the nitrite salt composition according to the invention in the molten state is generally cooled to about 290 ° C. and is usually passed back into the cold tank or the cold part of the stratified storage tank.
- the nitrite salt composition of the present invention operates in molten form as a heat transfer medium. Filled in the heat storage tank, the same nitrite salt composition according to the invention works as a heat storage medium, for example, to enable on-demand generation of electrical energy.
- the nitrite salt composition according to the invention preferably in molten form, is also used as heat transfer medium and / or heat storage medium, preferably heat transfer medium, in chemical engineering, for example for heating reaction apparatuses of chemical production plants, where as a rule a very high heat flow at very high temperatures Temperatures with narrow fluctuation ranges must be transferred.
- heat transfer medium preferably heat transfer medium
- Examples are salt bath reactors.
- Examples of the said production plants are acrylic acid plants or plants for the production of melamine.
- the nitrite salt composition according to the invention is mixed with an additive (hereinafter also referred to as "additive according to the invention") of nitrogen and / or noble gases, each with elemental oxygen, in an amount in the range from 0 to 20% by volume, preferably in the range from 0.1 to 5% by volume, based on the total amount of the additive, in combination with nitrogen oxides and / or nitrogen oxide generating compounds.
- additive here are nitrogen monoxide and / or nitrogen dioxide.
- the nitrite salt composition according to the invention is generally present in liquid, pumpable, generally molten form.
- a preferred noble gas is argon.
- the elemental oxygen is preferably present in the additive according to the invention in an amount in the range from 0.1 to 5% by volume, based on the total amount of the additive.
- the preferred amount of oxygen is preferably determined by the temperature at the additive additive site and the desired nitrate-nitrite ratio in the nitrite salt composition of the present invention.
- 0.1 to 1% by volume of oxygen, based on the additive according to the invention, at temperatures in the range from 400 to 565 ° C. lead to well-suited nitrite salt compositions according to the invention having a molar
- Nitrate nitrite ratio in the range of 1, 3: 1 to 1: 1.
- nitrogen oxides are present depends on the boundary conditions, such as pressure, temperature, presence or absence of oxygen.
- nitrogen oxides are di nitrogen monoxide, nitrogen monoxide, nitrogen dioxide and dinitrogen tetroxide.
- Nitrogen oxides generating compounds are all those which release nitrogen oxides, for example dinitrogen monoxide, nitrogen monoxide, nitrogen dioxide, dinitrogen tetroxide, under the conditions at the site of the additive addition.
- Such compounds are, for example, highly nitrated organic compounds such as dinitrotoluene.
- Preferred components of the additives according to the invention are selected from the group consisting of nitrogen, argon and the nitrogen oxides nitrogen monoxide and nitrogen dioxide.
- contacting the nitrite salt composition of the present invention with the additive of the invention takes place at a temperature in the range of 150 to 600 ° C, preferably in the range of 150 to 400 ° C, more preferably in the range of 250 to 400 ° C instead of.
- contacting the nitrite salt composition according to the invention with the additive according to the invention takes place at an absolute pressure in the range from 0.1 to 30 bar, preferably in the range from 1 to 10 bar.
- Contacting the additive of the present invention with the nitrite salt composition of the present invention is typically accomplished by feeding the additive of the invention below or above the surface of the nitrite salt composition of the invention, which is usually in liquid, pumpable, generally molten form.
- Contacting the nitrite salt composition according to the invention with the additive according to the invention usually takes place such that the nitrite salt compositions according to the invention preferably take place with thorough mixing, for example by bubbling or by introduction into a turbulent liquid flow.
- the contacting of the nitrite salt composition of the invention with the additive of the invention generally takes place in a suitable apparatus.
- a suitable apparatus This may be a container and / or a pipe through which the nitrite composition according to the invention flows or is at rest or a partial volume of a container or pipe.
- the additive according to the invention can be fed into a container, for example a tank containing the nitrite salt composition according to the invention.
- a container for example a tank containing the nitrite salt composition according to the invention.
- the inventive additive in the hotter tank or the colder tank, each preferably below the surface of the nitrite salt composition according to the invention contained therein is fed.
- the additive according to the invention contains oxygen in an amount of from 0.1 to 5% by volume.
- FIG. 2 shows a two-tank storage system in which an inventive additive (3), below the surface of the nitrite salt composition according to the invention in molten form, is introduced into the hotter tank 1, for example at a temperature greater than about 390 ° C. is fed.
- a gaseous additive can be introduced only slightly below the surface of the heat storage medium. There rising gas bubbles would cause convection of the heat storage system and the temperature stratification of the memory would be damaged.
- One solution to this problem is to lead the additive according to the invention onto the surface of the heat storage medium or into an inflow of the heat transfer medium according to the invention to the storage, for example into the hot region of the storage.
- a well-suited embodiment of a single-tank heat accumulator (also called stratified storage tank) with the addition of the additive according to the invention into the hot region of the heat storage system is shown by way of example in FIG. 3 and will be described below.
- numerals have the following meaning.
- Feed of an additive according to the invention From a solar receiver (2) flows (3) heated inventive heat transfer medium in the hot area (5a) of the memory (1).
- a cold area (5b) is below the hot area (5a).
- an additive (6) according to the invention preferably the additive with oxygen in an amount in the range of 0.1 to 5 vol.%, Preferably, preferably distributed by conventional means, fed.
- the heat storage system (1) requires ventilation during operation over the gas space.
- gases can be released into the environment at overpressure via a nitrogen oxide separator and / or remover (6), for example a DeNOx catalyst and / or a condenser.
- a suitable respiratory gas for example air or nitrogen
- a gas buffer system (5) can be used to buffer (buffer) the amounts of gas that are released from the heat accumulator when heated, in order to return them to the storage system when cooled to avoid negative pressure.
- An alternative to a gas buffer system is the pressure maintenance in the storage system by Ausg. Eintankung of liquid heat storage medium according to the invention in a separate expansion tank or from a separate surge tank.
- the emptying and filling takes place here preferably from or into the cold region of the heat storage system.
- Excess amounts of gas, e.g. Nitrogen and / or nitrogen oxides in the heat storage system can also be caused by decomposition of the heat storage medium. These amounts of excess gas can be passed through the heat transfer medium in the relatively cold compensation tank so that the amount of excess nitrogen oxides is reduced.
- the residual gas can then be fed to a nitrogen oxide separator and / or remover, for example DeNOx catalyst and / or condenser.
- the feeds of the additive according to the invention described in heat storage systems usually lead, thanks to the above-outlined pressure holding systems, to no significant printer increase in the gas space above the surface of the heat storage medium in the heat storage system.
- the overpressure is usually in a range of 0 to 0.01 bar.
- the additive according to the invention can be fed into a container, which is in molten form in addition to the main amount of the nitrite salt composition according to the invention and in which, discontinuously or preferably continuously, a partial amount of the nitrite salt composition according to the invention is metered in and out.
- the feed of the additive according to the invention into a shunt to the main stream of the flowing nitrite salt composition according to the invention has the advantage that, independently of the respective operating pressure of the main stream in the container, another - advantageously higher - pressure and / or a different temperature can be selected, which is usually a faster one Reaction and thereby a higher rate of regeneration of the nitrite salt mixture according to the invention has resulted.
- the additive according to the invention it is possible to feed the additive according to the invention at a relatively low temperature, for example 250 to 350 ° C, and then to pass the thus treated nitrite salt mixture according to the invention into the generally colder heat transfer circuit.
- suitable additives for this process variant are nitrogen with oxygen, the latter in an amount in the range from 15 to
- the additive according to the invention in another example, in this embodiment it is possible to carry out the feed of the additive according to the invention at a relatively high temperature, for example 400 to 550 ° C., and then to feed the thus treated nitrite salt mixture according to the invention into the generally hotter heat transfer circuit.
- suitable additives for this process variant are nitrogen with an oxygen scavenger in an amount in the range from 0.1 to 5% by volume, based on the total amount of the additive in combination with nitrogen oxides.
- FIG. 5 three variants are outlined in FIG. 5, such as a contacting of the nitrite salt mixture according to the invention with an additive according to the invention for a solar thermal
- Power plant (see Figure 1) can be designed. Common to all variants is a receiver system (2) which exchanges a heat carrier / storage medium via lines (3) and (4) with a heat storage system (1).
- the heat storage system (1) has a hot (5a) and a cold (5b) area.
- the partial flow reduction takes place from an average temperature range of the heat storage system. Removal from a hot or cold area of the storage system is also possible.
- the partial flow take-off takes place from the heated main flow (3) of the heat transfer medium.
- the removal takes place from the cold main flow (4) of the heat transfer medium.
- the Molstroma notede may be carried out for example by pumping. After removal, contact with the additive according to the invention takes place in a separate reaction vessel.
- the reaction vessel can be adjusted by customary means to another, preferably higher, pressure and / or a temperature which is changed with respect to the take-off temperature, in order, for example, to achieve a higher regeneration rate of the nitrite salt mixture according to the invention.
- the amount of the additive according to the invention which is brought into contact with the nitrite salt composition according to the invention depends on the technical problem to be solved and can be determined by the person skilled in the art by customary methods for determining the composition of the nitrite salt composition which is to be brought into contact with the additive according to the invention to be determined.
- the basicity of the nitrite salt composition according to the invention to be brought into contact with the additive according to the invention is determined, for example, by acid-base titration or potentiometrically. This determination can be made inline, online or offline.
- the amount of the additive according to the invention is determined and metered, which leads to complete neutralization of the nitrite salt composition according to the invention, but preferably obtains a low residual basicity, as defined below, in the nitrite salt composition according to the invention.
- alkalinity herein is meant the specific amount of acid equivalents that an aqueous solution of molten salt can take up to pH neutrality.
- the sensor quantity "alkalinity” can be measured inline, online or offline
- the setpoint "alkalinity” can be 0.001 -5%, preferably 0.005-1% and particularly preferably 0.01-0.5%.
- Substitute sizes can be: density, optical parameters (spectrum), etc.
- the additive according to the invention is used in deficit, it may be possible to dispense with an exhaust gas treatment, for example with a nitrogen oxide separator and / or remover, for example DeNOx catalyst and / or condenser.
- an exhaust gas treatment for example with a nitrogen oxide separator and / or remover, for example DeNOx catalyst and / or condenser.
- the additive according to the invention can deliberately be used in excess.
- Unused additive according to the invention can, for example, be disposed of and / or, preferably after work-up, for example by metering in nitrogen and / or nitrogen oxides, back into the reaction system, for example the process engineering system as defined below.
- the subject matter of the present application is also a process engineering system as defined below and in the claims.
- Heat transfer media or heat storage media ensure, for example, the primary circuit for heat transfer media and / or heat storage media in solar thermal power plants.
- Examples of such pipelines are those which are located in solar thermal power plants in the focal line of parabolic trough or Fresnel mirrors, and / or the receiver tubes or form bundles of receiver tubes in solar thermal tower power plants and / or those which, for example in solar thermal power plants, connect certain devices to one another without having a sunbeam collecting function.
- Another example of a process engineering system defined in claims are salt bath reactors of chemical engineering and their interconnections, each containing the nitrite salt composition of the present invention. Wherein all or a subset thereof is contacted with an additive as defined herein.
- the present application also provides the use of an additive as defined in the claims for maintaining or extending the long-term operating temperature range of a heat transfer and / or heat storage medium containing a nitrite salt composition as defined in the claims.
- Nitritsalzzusammen here is to be understood that which is described in more detail above and herein also described as nitrite salt composition according to the invention, including all preferred embodiments.
- the above-mentioned use preferably relates to a heat transfer medium and / or heat storage medium in a) power plants for generating heat and / or electricity, particularly preferably solar thermal power plants, in particular those of the parabolic trough power plant, Fresnel power plant or tower power plant the chemical process engineering, particularly preferably Salzbadreaktoren, or c) in metal hardening plants.
- the subject of the present application is also a process for generating electrical energy in a solar thermal power plant with a Nitritsalzzusammen ammen amin, as defined in the claims, as heat transfer and / or heat storage medium, wherein the Nitritsalzzusammen ammen ammen ammen ammen ammen amin total or a subset thereof with an additive, as in Claims is brought into contact.
- the above-mentioned method preferably relates to a heat transfer medium and / or heat storage medium in solar thermal power plants of the parabolic trough power plant, Fresnel power plant or tower power plant.
- the present application also relates to a process for the preparation of nitrite salt mixtures according to the invention, as defined above, wherein mixtures of alkali metal salts are used. and / or alkaline earth metal nitrates with an additive according to the invention, as defined above including its preferred embodiments, in the temperature range of 150 to 600 ° C in contact.
- alkali metal nitrates and alkaline earth metal nitrates are as defined above, including their preferred embodiments.
- the mixtures of alkali metal and / or alkaline earth metal nitrates are chosen such that the molar ratio of the respective cations of the nitrate salt mixture corresponds to that in the nitrite salt mixture according to the invention.
- the bringing into contact of the mixtures of alkali metal and / or alkaline earth metal nitrates with the additive according to the invention is generally carried out analogously as described above.
- the process according to the invention for the preparation of nitrite salt mixtures according to the invention generally results in the nitrite concentration in nitrite salt-containing heat carrier and / or heat storage media being increased to the "intended nitrite operating concentration" (as defined herein) and / or too high alkalinity in nitrate salt-containing heat carrier and / or Heat storage media is avoided.
- the present application also relates to the use of an additive according to the invention for reducing or eliminating the corrosivity of a nitrite salt mixture according to the invention.
- additive is to be understood as meaning what has been described in greater detail above and is also described herein as an inventive additive, including all preferred embodiments.
- nitrite salt composition here is to be understood as meaning what has been described in more detail above and is also described herein as the nitrite salt composition according to the invention, including all preferred embodiments.
- Corrosivity usually refers to ferrous materials, preferably steel materials, and usually at temperatures in the range of 290 to 650 ° C, and usually the nitrite salt composition of the present invention is in molten, preferably pumpable form.
- the aforementioned materials are commonly used in pipelines or containers, for example storage vessels such as tanks or other devices, for example devices for conveying fluids (for example molten salts), such as pumps.
- pipelines are those which are located in solar thermal power plants in the focal line of the parabolic trough or fresnel, and / or the receiver tubes or receiver bundles in solar thermal tower power plants and / or those who connect, for example, in solar thermal power plants, certain devices together, without having a sunbeam collection function.
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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AU2013304224A AU2013304224A1 (en) | 2012-08-17 | 2013-08-07 | Method for improving nitrite salt compositions used as heat transfer medium or heat storage medium |
EP13745849.3A EP2885368A1 (de) | 2012-08-17 | 2013-08-07 | Verfahren zur verbesserung von nitritsalzzusammensetzungen bei deren verwendung als wärmeträgermedium oder wärmespeichermedium |
CN201380043423.5A CN104583357A (zh) | 2012-08-17 | 2013-08-07 | 改进用作传热介质或储热介质的亚硝酸盐组合物的方法 |
MA37926A MA20150382A1 (fr) | 2012-08-17 | 2013-08-07 | Procédé d'amélioration de compositions de sels de nitrates lors de leur utilisation comme milieu caloporteur ou accumulateur de chaleur |
IL236976A IL236976A0 (en) | 2012-08-17 | 2015-01-29 | A method for improving nitrite salt compositions used as a heat transfer medium or a heat storage medium |
ZA2015/01765A ZA201501765B (en) | 2012-08-17 | 2015-03-16 | Method for improving nitrite salt compositions used as heat transfer medium or heat storage medium |
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EP12180836.4 | 2012-08-17 | ||
EP12180836 | 2012-08-17 |
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WO2014026892A1 true WO2014026892A1 (de) | 2014-02-20 |
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PCT/EP2013/066561 WO2014026892A1 (de) | 2012-08-17 | 2013-08-07 | Verfahren zur verbesserung von nitritsalzzusammensetzungen bei deren verwendung als wärmeträgermedium oder wärmespeichermedium |
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EP (1) | EP2885368A1 (de) |
CN (1) | CN104583357A (de) |
AU (1) | AU2013304224A1 (de) |
CL (1) | CL2015000378A1 (de) |
IL (1) | IL236976A0 (de) |
MA (1) | MA20150382A1 (de) |
WO (1) | WO2014026892A1 (de) |
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Cited By (2)
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DE102015212057A1 (de) | 2015-06-29 | 2016-12-29 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Verfahren zur Reduktion korrosiver Eigenschaften von Nitratsalzmischungen |
US10850982B2 (en) | 2015-04-29 | 2020-12-01 | Basf Se | Stabilization of sodium dithionite by means of various additives |
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TN2018000353A1 (en) * | 2016-04-28 | 2020-06-15 | Basf Se | Use of a nitrate salt composition as a heat transfer or heat storage medium for first operation of an apparatus containing these media |
CN108003845B (zh) * | 2017-12-08 | 2020-12-04 | 中国科学院青海盐湖研究所 | 一种三元硝酸熔盐及其制备方法 |
DE102021127566A1 (de) * | 2021-10-22 | 2023-04-27 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Stabilisierung von Salzen in Hochtemperatur-Nitratsalzsystemen |
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US2375761A (en) * | 1944-10-18 | 1945-05-15 | Houdry Process Corp | Treatment of alkali metal salts |
US20100038581A1 (en) * | 2006-12-13 | 2010-02-18 | Solar Millennium Ag | Multinary salt system for storing and transferring thermal energy |
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CN101050355B (zh) * | 2007-05-14 | 2010-05-19 | 中山大学 | 一种熔融盐传热蓄热介质及其制备方法 |
CN102585779B (zh) * | 2011-11-18 | 2014-02-05 | 牟邦志 | 一种高纯度导热储能熔盐的制备方法 |
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2013
- 2013-08-07 MA MA37926A patent/MA20150382A1/fr unknown
- 2013-08-07 CN CN201380043423.5A patent/CN104583357A/zh active Pending
- 2013-08-07 EP EP13745849.3A patent/EP2885368A1/de not_active Withdrawn
- 2013-08-07 WO PCT/EP2013/066561 patent/WO2014026892A1/de active Application Filing
- 2013-08-07 AU AU2013304224A patent/AU2013304224A1/en not_active Abandoned
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2015
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US2375761A (en) * | 1944-10-18 | 1945-05-15 | Houdry Process Corp | Treatment of alkali metal salts |
US20100038581A1 (en) * | 2006-12-13 | 2010-02-18 | Solar Millennium Ag | Multinary salt system for storing and transferring thermal energy |
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RENE I. OLIVARES: "The thermal stability of molten nitrite/nitrates salt for solar thermal energy storage in different atmospheres", vol. 86, no. 9, 23 June 2012 (2012-06-23), pages 2576 - 2583, XP055050146, ISSN: 0038-092X, Retrieved from the Internet <URL:http://ac.els-cdn.com/S0038092X12002034/1-s2.0-S0038092X12002034-main.pdf?_tid=76d2c8de-616f-11e2-a0a1-00000aacb362&acdnat=1358514393_b11db88f444fc5387a3985ccae45aa5b> DOI: 10.1016/j.solener.2012.05.025 * |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10850982B2 (en) | 2015-04-29 | 2020-12-01 | Basf Se | Stabilization of sodium dithionite by means of various additives |
DE102015212057A1 (de) | 2015-06-29 | 2016-12-29 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Verfahren zur Reduktion korrosiver Eigenschaften von Nitratsalzmischungen |
Also Published As
Publication number | Publication date |
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CN104583357A (zh) | 2015-04-29 |
AU2013304224A1 (en) | 2015-03-05 |
IL236976A0 (en) | 2015-03-31 |
CL2015000378A1 (es) | 2015-05-04 |
MA20150382A1 (fr) | 2015-10-30 |
ZA201501765B (en) | 2016-12-21 |
EP2885368A1 (de) | 2015-06-24 |
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