WO2014114508A1 - Verfahren zur verbesserung von nitratsalzzusammensetzungen mittels salpetersäure bei deren verwendung als wärmeträgermedium oder wärmespeichermedium - Google Patents
Verfahren zur verbesserung von nitratsalzzusammensetzungen mittels salpetersäure bei deren verwendung als wärmeträgermedium oder wärmespeichermedium Download PDFInfo
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- WO2014114508A1 WO2014114508A1 PCT/EP2014/050424 EP2014050424W WO2014114508A1 WO 2014114508 A1 WO2014114508 A1 WO 2014114508A1 EP 2014050424 W EP2014050424 W EP 2014050424W WO 2014114508 A1 WO2014114508 A1 WO 2014114508A1
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- Prior art keywords
- nitrate salt
- salt composition
- nitrate
- heat transfer
- heat
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- 239000000203 mixture Substances 0.000 title claims abstract description 142
- 150000002823 nitrates Chemical class 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000000996 additive effect Effects 0.000 claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 52
- -1 alkali metal nitrite Chemical class 0.000 claims abstract description 42
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 24
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims abstract description 22
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 230000007774 longterm Effects 0.000 claims abstract description 16
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005338 heat storage Methods 0.000 claims description 55
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000010327 methods by industry Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 18
- 229910002651 NO3 Inorganic materials 0.000 abstract description 17
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 31
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 30
- 150000003839 salts Chemical class 0.000 description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 235000010333 potassium nitrate Nutrition 0.000 description 15
- 239000004323 potassium nitrate Substances 0.000 description 15
- 239000004317 sodium nitrate Substances 0.000 description 15
- 235000010344 sodium nitrate Nutrition 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- 239000000470 constituent 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 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 9
- 229910052788 barium Inorganic materials 0.000 description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 9
- 239000011833 salt mixture Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 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
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 238000003889 chemical engineering Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002826 nitrites Chemical class 0.000 description 5
- 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 4
- 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 4
- 238000000354 decomposition reaction 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
- 239000000463 material Substances 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 239000004304 potassium nitrite Substances 0.000 description 4
- 235000010289 potassium nitrite Nutrition 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali 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
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229960001730 nitrous oxide Drugs 0.000 description 3
- 239000001272 nitrous oxide Substances 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
- 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
- 239000002253 acid Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 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
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 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
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution 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
- 235000019400 benzoyl peroxide Nutrition 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 150000001768 cations Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002918 waste heat Substances 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
-
- 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. and / or heat storage medium as defined in the claims and a method for generating electrical energy in a solar thermal power plant as defined in the claims.
- Heat transfer mediums or heat storage media based on inorganic solids, in particular salts are known both in chemical technology and in power plant technology. They are usually used at high temperatures, for example, beyond 100 ° C, ergo beyond the boiling point of water at atmospheric pressure.
- so-called Salzbadreaktoren be used at temperatures of about 200 to 500 ° C in chemical plants for large-scale production of various chemicals.
- 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 quantity of heat 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.
- An example of a solar thermal power plant is shown schematically in FIG.
- 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.
- Examples are the products of the Coastal Chemical Company LLC Hitec® Solar Salt (potassium nitrate: sodium nitrate 40 wt%: 60 wt%), 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, optionally additionally with nitrite salts, usually those of the alkali metals lithium, sodium, potassium or the alkaline earth metal calcium
- nitrite salts usually those of the alkali metals lithium, sodium, potassium or the alkaline earth metal calcium
- 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, more 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 transfer medium or heat storage medium, in which its properties, for example viscosity, melting temperature, corrosion behavior do not change significantly over a long period of time, generally 10 to 30 years, compared to the initial value.
- 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.
- Mixtures of alkali metal nitrate and alkali metal nitrite usually have a lower melting point than the nitrate mixtures mentioned above, but also a lower decomposition temperature. Mixtures of alkali metal nitrate and alkali metal nitrite are usually used in the temperature range of 150 ° C to 450 ° C.
- nitrate salt mixtures or nitrate / nitrite salt mixtures can change negatively in several ways, for example, if the mixtures mentioned, in particular over a long time, comparatively high temperatures, for example more than 565 ° C for Nitratsalzmischungen, and more than 450 ° C for nitrate / nitrite salt mixtures are exposed. They then generally decompose into various degradation products.
- Nitratsalzmischungen or nitrate / Nitritsalzmischungen and thus, for example, their long-term operating temperature range in solar thermal power plants by recording traces or even relatively large amounts of water or carbon dioxide can change negative, 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 contact the humidity of the outside air.
- Nitratsalzmischungen or nitrate / Nitritsalzmischungen can thereby worsen so far that they are unsuitable as a heat transfer medium or heat storage medium and usually have 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 with 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 nitrate salt mixture or nitrate / nitrite salt mixture or extends the long-term operating temperature range of such mixtures.
- nitrate salt compositions defined in the description and in the claims, in particular their preferred and particularly preferred embodiments, are also referred to below as "nitrate salt composition according to the invention".
- the nitrate salt composition of the present invention is selected from the group consisting of alkali metal nitrate and alkaline earth metal nitrate and optionally alkali metal nitrite and alkaline earth metal nitrite as essential components.
- a highly suitable embodiment of the nitrate salt composition according to the 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 in each case optionally 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 the metals, magnesium, Calcium, strontium, barium, preferably calcium, strontium, barium, more preferably calcium and barium, generally described as Met (NC "3) 2, where Met is the alkaline earth metals described above, the term alkaline earth metal nitrate both a single nitrate and mixtures ofnitrates of these
- 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, where Met means the above-described alkaline earth metals, where 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.
- Nitrate salt composition according to the invention containing as essential constituents an alkali metal nitrate and / or alkaline earth metal nitrate and in each case optionally an alkali metal nitrite and / or alkaline earth metal nitrite; Nitrate salt composition according to the invention containing as essential constituents an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate and in each case optionally an alkali metal nitrite and / or alkaline earth metal nitrite;
- Nitrate salt composition containing as essential constituents an alkali metal nitrate and optionally an alkali metal nitrite;
- Nitrate salt composition containing as essential constituents an alkali metal nitrate and optionally an alkali metal nitrite selected from sodium nitrite and / or potassium nitrite;
- Nitrate salt composition containing as essential constituents an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate and in each case optionally 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;
- Nitrate salt composition containing as essential constituents an alkali metal nitrate and / or alkaline earth metal nitrate;
- Nitrate salt composition comprising as essential constituents an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate and / or alkaline earth metal nitrate selected from calcium nitrate and / or barium nitrate;
- a nitrate salt composition of the present invention containing as an essential ingredient an alkali metal nitrate;
- Nitrate salt composition according to the invention containing as essential constituents an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate.
- nitrate salt compositions according to the invention containing as essential components an alkali metal nitrate selected from sodium nitrate and / or potassium nitrate are, for example, the following: Potassium nitrate in an amount ranging from 20 to 55% by weight, and
- Sodium nitrate in an amount ranging from 45 to 80% by weight, based in each case on the mixture; Potassium nitrate in an amount in the range of 35 to 45 wt .-%, preferably 40 wt .-% and sodium nitrate in an amount ranging from 55 to 65 wt .-%, preferably 60 wt .-%, each based on the mixture.
- nitrate salt compositions according to the invention comprising as essential constituents an alkali metal nitrate and optionally an alkali metal nitrite selected from sodium nitrite and / or potassium nitrite are, for example, the following:
- Potassium nitrate in an amount ranging from 30 to 70% by weight, preferably 50 to 60% by weight and sodium nitrate in an amount ranging from 3 to 30% by weight, preferably 5 to 10% by weight and sodium nitrite an amount in the range of 20 to 60 wt .-%, preferably 35 to 45 wt .-% each based on the mixture.
- a mixture of potassium nitrate, sodium nitrate and sodium nitrite is also commercially available, also as product Hitec® from Coastal Chemical Company LLC.
- the nitrate 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.
- 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 novel nitrate salt composition.
- the nitrate salt composition according to the invention passes into the molten and usually pumpable form at a temperature above about 100 to 300 ° C., inter alia, depending on the nitrite content and the ratio of the cations forming the mixture.
- the nitrate 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 nitrate salt compositions according to the invention preferably in the molten state, for example as a pumpable liquid, both as a heat transfer medium and as a heat storage medium in the solar thermal power plants, such as parabolic trough power plants, tower power plants or Fresnel power plants.
- the nitrate salt compositions according to the invention 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, such as parabolic trough power plants, the tower power plants, the Fresnel power plants.
- the nitrate salt compositions according to the invention are preferably used in the molten state, for example as a pumpable liquid, in tower power plants as the heat transfer medium and / or as a heat storage medium, particularly preferably as a heat transfer medium.
- the Nitratsalzzusammen 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 store comprises a plurality of usually two large containers, generally a cold and a hot container (also referred to as "two-tank store”) .
- the nitrate salt composition according to the invention preferably in the molten state, for example as pumpable Liquid, which is usually taken from the cold tank of the solar system and heated in the solar field of a parabolic trough plant or a tower elevator, is heated in the hot container and kept there until there is a need to generate electrical energy
- a heat accumulator the so-called “thermocline storage” consists of a tank in which the heat storage medium is stored in layers at different temperatures, this variant also being called “stratified storage”. When storing material is removed from its cold area. The material is heated and stored back in its hot area.
- the thermokline memory is thus used largely analogously to a two-tank memory.
- the hot nitrate 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 nitrate salt composition according to the invention in the molten state, for example as a pumpable liquid, usually cooled to about 290 ° C and usually fed back into the cold tank or the cold part of the stratified storage.
- the nitrate salt composition of the present invention operates in molten form as a heat transfer medium. Filled in the heat storage tank, the same nitrate salt composition according to the invention works as a heat storage medium, for example, to enable on-demand generation of electrical energy.
- the nitrate salt composition according to the invention preferably in molten form, is also used as a 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 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.
- GB 545,590 describes on page 7, lines 90 to 1 12 that from 1, 5 million “pounds” of a mixture, the 54 wt .-% potassium nitrate (KNO3) and 46 wt .-% sodium nitrite (NaNO ⁇ ) and 0.8 % "Alkali” contains 40,000 "pound” per week to be withdrawn into a tower, mixed with nitric acid of concentration 91.4% and the salt mixture so treated returned to the "system".
- KNO3 potassium nitrate
- NaNO ⁇ sodium nitrite
- Alkali contains 40,000 "pound” per week to be withdrawn into a tower, mixed with nitric acid of concentration 91.4% and the salt mixture so treated returned to the "system".
- GB 545,590 on page 8, lines 17 to 65 describes that in vessels in which "salt" is stored an atmosphere with less oxygen partial pressure than in air is to be used with an additive containing the components nitric acid and / or nitrous acid and oxygen-containing gas with an oxygen partial pressure equal to or greater than those in air and / or oxygen generating compounds and optionally nitrogen oxides and / or other nitrogen oxide generating compounds disclosed GB 545,590 not.
- the nitrate salt composition according to the invention is used with an additive containing the components nitric acid and / or nitrous acid, and oxygen-containing gas having an oxygen partial pressure equal to or greater than those in air and / or oxygen-generating compounds and optionally nitrogen oxides and / or other nitrogen oxide-generating compounds brought into contact.
- This additive is also referred to below as "inventive additive”.
- oxygen-containing gas herein is meant pure elemental oxygen or oxygen-containing gas mixtures having an oxygen partial pressure equal to or greater than that in air.
- Oxygen-containing gas is (i) air, (ii) mixtures of oxygen with other gases such as nitrogen or noble gases, wherein in each case the oxygen content, based on the gas mixture and measured at 1013.25 hPa and 20 ° C, in the range of 22 to 99.9 vol.% And (iii) pure elemental oxygen (O2).
- oxygen contents in the oxygen-containing gas are preferred:
- the oxygen content in the oxygen-containing gas is preferably in the range of 60 to 99.9 vol.%, Particularly preferably in the range of 80 to 99.9 vol.% Or the oxygen-containing gas is pure elemental oxygen.
- the oxygen content in the oxygen-containing gas is preferably in the range of 22 to 40% by volume.
- the respective acids nitric acid or nitrous acid are usually present as a solution in water of different concentrations.
- the nitrate salt composition according to the invention is generally present in liquid, pumpable, generally molten form.
- the concentration of nitric acid HNO 3 is usually in the range of 1 to 100% by weight, preferably 50 to 100% by weight, particularly preferably 60 to 90% by weight of HNO 3 in water.
- the concentration of nitrous acid HNO2 is usually in the range of 1 to 40
- Nitric acid and nitrous acid can be used both individually and in mixtures, the mixing ratio not being considered critical.
- oxygen-containing gas having an oxygen partial pressure equal to or greater than that used in air and / or oxygen-generating compounds and optionally nitrogen oxides and / or nitrogen oxides generating compounds.
- nitrogen oxides are present depends on the boundary conditions, such as pressure, temperature, presence or absence of oxygen.
- Oxygen generating compounds are all those which release elemental oxygen, for example as atomic oxygen, dioxygen or ozone, under the conditions at the site of additive addition.
- Such compounds are, for example, inorganic or organic peroxides, for example sodium peroxide, potassium superoxide, dibenzoyl peroxide.
- 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
- Preferred further components of the additives according to the invention - in addition to the nitric acid and / or nitrous acid - are oxygen-containing gas having an oxygen partial pressure equal to or greater than that in air and / or oxygen-generating compounds and optionally the nitrogen oxides nitrous oxide, nitrogen monoxide, nitrogen dioxide, dinitrogen tetroxide and these nitrogen oxides generating compounds.
- additives according to the invention in addition to the nitric acid and / or nitrous acid - are oxygen-containing gas having an oxygen partial pressure equal to or greater than that in air and optionally the nitrogen oxides nitrogen monoxide, nitrogen dioxide.
- Particularly preferred further components of the additives according to the invention - in addition to the nitric acid and / or nitrous acid - are combinations of air or virtually pure elemental oxygen and nitrogen oxides, preferably nitrogen monoxide.
- a particularly preferred additive according to the invention contains nitric acid and an oxygen-containing gas having an oxygen partial pressure equal to or greater than that in air, preferably air or virtually pure elemental oxygen and nitrogen oxides, preferably nitrogen dioxide and / or nitrogen monoxide.
- Another particularly preferred additive of the present invention contains nitric acid and an oxygen-containing gas having an oxygen partial pressure equal to or greater than that in air, preferably air or substantially pure elemental oxygen, but substantially no nitrogen oxides.
- Contacting the additive of the present invention with the nitrate salt composition of the present invention is generally accomplished by feeding the additive of the invention above or preferably below the surface of the nitrate salt composition of the present invention, which is usually in liquid, pumpable, generally molten form.
- the additive according to the invention When contacting the additive according to the invention with the nitrate salt composition according to the invention, it is preferred to distribute the nitric acid uniformly, which can be achieved for example by stirring or a longer mixing distance.
- the contacting of the nitrate 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 conduit through which the nitrate composition according to the invention flows or is at rest or a partial volume of a container or a pipeline.
- the container or the pipe are preferably made of a material which is technically resistant to nitric acid or nitrous acid.
- nitrate salt composition of the present invention Contacting the nitrate salt composition of the present invention with the additive of the present invention generally occurs at a temperature just above, for example, 50 ° C above, the melting temperature of the nitrate salt composition of the invention, usually in the range of 150 ° C to 650 ° C, preferably at one temperature in which a possible formation of nitrous oxide (N2O) is reduced or virtually completely suppressed.
- the additive according to the invention can be added as a complete mixture to the nitrate salt composition according to the invention or in the form of the individual components or groups of individual components, for example in the last two cases, successively.
- the following variants of contacting the nitrate salt composition according to the invention with the additive according to the invention are preferred: If the nitrate salt composition according to the invention contains a proportion of total
- the oxygen content in the oxygen-containing gas is preferably in the range of 60 to 99.9 vol.%, Particularly preferably in the range of 80 to 99, 9 vol.%
- the oxygen-containing gas is pure elemental oxygen
- the above-described oxygen-containing gas or the oxygen-containing gas in the form of pure elemental oxygen is added to the above-described nitrate salt composition at a temperature in the range of 450 to 650 ° C and before and / or thereafter, the nitric acid and / or nitrous acid is added at a temperature in the range of 150 to 350 ° C to the above-described nitrate salt composition.
- the oxygen content in the oxygen-containing gas is preferably in the range from 22 to 40% by volume, with the additive according to the invention in the temperature range of 150 to 350 ° C, preferably as a complete mixture, is added to the above-described Nitratsalzzusammen stuct. More preferably, after the additive of the invention has been added to the nitrate salt composition described above, oxygen is removed from the system again, for example by metering in inert gas, such as nitrogen, noble gases in or over the nitrate salt composition described above.
- inert gas such as nitrogen, noble gases in or over the nitrate salt composition described above.
- the contacting of the nitrate salt composition according to the invention with the additive according to the invention is generally carried out at a pressure which is so high that it does not lead to significant outgassing of, for example. Nitrous oxides and / or water vapor and / or other gaseous components comes. Corresponding pressures can be taken from the relevant tables, for example for nitric acid or water.
- the contacting of the nitrate salt composition according to the invention with the additive according to the invention can be carried out continuously or batchwise. Continuous operation not only means that the contact is done without interruption, but also includes intermittent interruption. Batch mode of operation is present, for example, when a portion of the nitrate salt composition according to the invention is introduced into a container where it is brought into contact with the additive, if appropriate degassed and thus, for example, water is substantially completely or partially removed, and then the nitrate salt composition according to the invention is recycled to the system becomes.
- nitrate salt composition according to the invention in contact with the additive according to the invention, inter alia water is introduced into the nitrate salt composition according to the invention and / or water is also formed.
- This incorporated and / or formed water is removed in one embodiment of the invention, optionally in addition to other volatile compounds virtually completely or in part from the additized nitrate salt composition according to the invention.
- at least 99% by weight of the water formed from the additized nitrate salt composition of the present invention is removed at least to the extent that the water content of the nitrated salt additive composition of the present invention is not greater than that of the nitrate salt composition of the present invention immediately prior to Contact with the additive of the invention.
- the removal of the formed and / or introduced water is preferably carried out at a, compared with the bringing into contact with the additive according to the invention, reduced pressure and elevated temperature.
- the pressure usually corresponds to the system pressure of the plant in which the nitrate salt composition according to the invention is in the form of heat transfer medium and / or heat storage medium, for example 1 to 2 bar abs.
- the temperature is usually at the maximum operating temperature of the plant in which the nitrate salt composition according to the invention is as a heat transfer and / or heat storage medium, for example at a temperature in the range of 500 to 650 ° C.
- the removal of the formed and / or introduced water or optionally further volatile compounds in a separate phase separator, for example, a downstream container is performed.
- the nitrate salt composition according to the invention treated by removal of the formed and / or introduced water or optionally further volatile compounds is usually recycled to the system in which the majority of the nitrate salt composition according to the invention is present as heat carrier and / or heat storage medium.
- the water vapor, optionally with nitrogen oxides, is condensed and removed from the system.
- the additive according to the invention is fed into a vessel which is in molten form, in addition to the main amount of the nitrate salt composition according to the invention, in molten form, for example a mixture of sodium nitrate and potassium nitrate in molten form
- a vessel which is in molten form, in addition to the main amount of the nitrate salt composition according to the invention, in molten form, for example a mixture of sodium nitrate and potassium nitrate in molten form
- All of the embodiments described in the preceding passages for contacting the additive according to the invention with the nitrate salt composition according to the invention expressly refer to the "shunt” embodiment described here ".
- the nitrate salt composition according to the invention can be prepared from the deepest possible location of the system in which the main amount of the nitrate salt composition according to the invention is used as heat carrier and / or heat carrier.
- the feed of the additive according to the invention into a bypass to the main stream of the flowing nitrate 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 usually has a faster Reaction and thereby a higher rate of regeneration of the nitrate salt mixture according to the invention has resulted.
- the nitrate salt composition according to the invention thus treated can subsequently be freed of interfering disperse components, for example metal oxides, by filtration and is then returned to the heat transfer circuit.
- FIG. 2 Two variants are outlined, for example, in FIG. 2, how a contacting of the nitrate salt mixture according to the invention with the additive according to the invention for a solar thermal power plant (see FIG. 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 take-off takes place from an average temperature range of the heat storage system. Removal from the cold area of the storage system is also possible.
- FIG. 2b In the second variant (FIG. 2b), removal takes place from the cold main flow (4) of the heat transfer medium.
- the Molstroma notede is carried out for example by pumping. After removal, contact with the additive according to the invention takes place in a separate reaction vessel. In the reaction vessel, turbulence can be achieved by stirring or various internals to improve the mixing of the additive with the nitrate salt composition.
- 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 removal temperature in order, for example, to achieve a higher regeneration rate of the nitrate salt mixture according to the invention.
- the amount of the additive according to the invention which is brought into contact with the nitrate 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 nitrate salt composition which is to be brought into contact with the additive according to the invention become.
- Examples of these methods are analytical methods such as the determination of the basicity, determination of the nitrite and / or nitrate content of the nitrate salt composition which is to be brought into contact with the additive according to the invention.
- the basicity of the inventive nitrate salt composition to be brought into contact with the additive according to the invention for example, determined by acid-base titration or potentiometric. This determination can be made inline, online or offline. Based on the basicity value thus determined, the amount of the additive according to the invention is determined and metered, which leads to complete neutralization of the nitrate salt composition according to the invention.
- the nitrate salt composition according to the invention thereby obtains a low residual basicity, as defined below.
- alkalinity basic or offline
- it may be 0.001 to 5%, preferably 0.005 to 1% and particularly preferably 0.01 to 0.5%
- a replacement sensor size Parameter (spectrum) ua instead of measuring the alkalinity by means of titration, it is also possible, after suitable adjustment, to apply a replacement sensor size Parameter (spectrum) ua.
- the subject of the present application is also a process engineering system as defined in the claims.
- This is understood to be containers connected by pipelines, for example storage vessels such as tanks, in particular heat storage tanks and / or devices, for example devices for conveying fluids (for example molten salts), such as pumps, which transport or / and store thermal energy by means of heat transfer media
- Heat storage media ensure, for example, the primary circuit for heat transfer media and / or heat storage media in solar thermal power plants.
- pipelines are those which are located in solar thermal power plants in the focal line of the parabolic trough or Fresnel mirrors, and / or the Receiverroh- re or Receiverrohrbündel in solar thermal tower power plants and / or those who, for example, in solar thermal power plants, certain devices together connect without having a sunbeam collection function.
- the present application also relates to the use of the additive as defined in the claims for maintaining or expanding the long-term operating temperature range of a heat transfer and / or heat storage medium containing a nitrate salt composition as defined in the claims.
- the nitrate salt composition here is to be understood as meaning what has been described in more detail above and is also described herein as the nitrate salt composition according to the invention, including all preferred embodiments.
- the above-mentioned use preferably relates to a heat transfer and / or heat storage medium in a) power plants for generating heat and / or electricity, more preferably solar thermal power plants, in particular those of the type parabolic turbine power plant, Fresnel power plant or tower power plant, b) in chemical engineering, particularly preferably Salzbadreaktoren, or c) in metal hardening plants.
- the subject matter of the present application is also a process for producing electrical energy in a solar thermal power plant having a nitrate salt composition as defined in the claims as a heat transfer and / or heat storage medium, wherein the nitrate salt composition is in contact with an additive as defined in the claims is brought.
- an additive is here to understand what is described in more detail above and herein also described as inventive additive, including all preferred embodiments.
- the nitrate salt composition here is to be understood as meaning what has been described in more detail above and is also described herein as the nitrate salt composition according to the invention, including all preferred embodiments.
- the above-mentioned method preferably relates to a heat transfer and / or heat storage medium in solar thermal power plants of the parabolic trough power plant, Fresnel power plant or tower power plant.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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MA38312A MA38312B2 (fr) | 2013-01-23 | 2014-01-13 | Procédé destiné à améliorer des compositions de sels de nitrate, au moyen d'acide nitrique, au cours de leur utilisation en tant que milieu caloporteur ou milieu accumulateur de chaleur |
AU2014210130A AU2014210130B2 (en) | 2013-01-23 | 2014-01-13 | Method for improving nitrate salt compositions by means of nitric acid in the use thereof as a thermal transfer medium or as a thermal accumulator medium |
EP14700358.6A EP2948518A1 (de) | 2013-01-23 | 2014-01-13 | Verfahren zur verbesserung von nitratsalzzusammensetzungen mittels salpetersäure bei deren verwendung als wärmeträgermedium oder wärmespeichermedium |
CN201480017351.1A CN105051147A (zh) | 2013-01-23 | 2014-01-13 | 借助硝酸改进硝酸盐组合物用作传热介质或储热介质的方法 |
IL240113A IL240113B (en) | 2013-01-23 | 2015-07-23 | A method for improving the compositions of nitrate salt using nitric acid used as a thermal transfer agent as a thermal accumulation agent |
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EP13152308 | 2013-01-23 | ||
EP13152308.6 | 2013-01-23 |
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EP (1) | EP2948518A1 (de) |
CN (1) | CN105051147A (de) |
AU (1) | AU2014210130B2 (de) |
CL (1) | CL2015002065A1 (de) |
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MA (1) | MA38312B2 (de) |
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WO2016184961A1 (de) | 2015-05-21 | 2016-11-24 | Basf Se | Behälter zur speicherung einer flüssigkeit sowie dessen verwendung |
DE102015212057A1 (de) | 2015-06-29 | 2016-12-29 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Verfahren zur Reduktion korrosiver Eigenschaften von Nitratsalzmischungen |
US11150031B2 (en) * | 2016-04-28 | 2021-10-19 | 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 |
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CN102433104B (zh) * | 2011-09-26 | 2014-06-11 | 上海交通大学 | 一种传热流体及其制备方法和用途 |
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2014
- 2014-01-13 EP EP14700358.6A patent/EP2948518A1/de not_active Withdrawn
- 2014-01-13 MA MA38312A patent/MA38312B2/fr unknown
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GB545590A (en) | 1940-02-17 | 1942-06-03 | Houdry Process Corp | Improvements relating to the use of molten salts in heat exchange circulating systems |
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WO2016184961A1 (de) | 2015-05-21 | 2016-11-24 | Basf Se | Behälter zur speicherung einer flüssigkeit sowie dessen verwendung |
DE102015212057A1 (de) | 2015-06-29 | 2016-12-29 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Verfahren zur Reduktion korrosiver Eigenschaften von Nitratsalzmischungen |
US11150031B2 (en) * | 2016-04-28 | 2021-10-19 | 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 |
Also Published As
Publication number | Publication date |
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EP2948518A1 (de) | 2015-12-02 |
AU2014210130A1 (en) | 2015-08-20 |
IL240113A0 (en) | 2015-09-24 |
IL240113B (en) | 2018-03-29 |
CL2015002065A1 (es) | 2016-01-08 |
MA20150379A1 (fr) | 2015-10-30 |
AU2014210130B2 (en) | 2017-08-31 |
CN105051147A (zh) | 2015-11-11 |
MA38312B2 (fr) | 2017-12-29 |
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