WO2011083054A1 - Mélanges de polysulfures alcalins - Google Patents
Mélanges de polysulfures alcalins Download PDFInfo
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- WO2011083054A1 WO2011083054A1 PCT/EP2010/070617 EP2010070617W WO2011083054A1 WO 2011083054 A1 WO2011083054 A1 WO 2011083054A1 EP 2010070617 W EP2010070617 W EP 2010070617W WO 2011083054 A1 WO2011083054 A1 WO 2011083054A1
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- WIPO (PCT)
- Prior art keywords
- mixtures
- alkali metal
- mixtures according
- mixture
- heat transfer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 239000005077 polysulfide Substances 0.000 title claims abstract description 42
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 42
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 40
- 239000003513 alkali Substances 0.000 title claims abstract description 24
- 238000005338 heat storage Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 41
- 150000001340 alkali metals Chemical class 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- -1 alkali metal thiocyanates Chemical class 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 1
- 150000003567 thiocyanates Chemical class 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002844 melting Methods 0.000 description 39
- 230000008018 melting Effects 0.000 description 36
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 34
- 239000011734 sodium Substances 0.000 description 20
- 239000003708 ampul Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000155 melt Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 9
- 239000013529 heat transfer fluid Substances 0.000 description 8
- 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 6
- 238000006243 chemical reaction Methods 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229940116357 potassium thiocyanate Drugs 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 239000000374 eutectic mixture Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000004639 Schlenk technique Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 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
- 238000002485 combustion reaction Methods 0.000 description 2
- ZLCCLBKPLLUIJC-UHFFFAOYSA-L disodium tetrasulfane-1,4-diide Chemical compound [Na+].[Na+].[S-]SS[S-] ZLCCLBKPLLUIJC-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000004636 glovebox technique Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940016373 potassium polysulfide Drugs 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000078491 Almeria Species 0.000 description 1
- 229910016332 Bi—Pb—Cd—Sn Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- MUEQIIHZTPKZTI-UHFFFAOYSA-N [Na+].[S-2].S.S.[K+] Chemical compound [Na+].[S-2].S.S.[K+] MUEQIIHZTPKZTI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000003181 co-melting 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
- 210000003298 dental enamel Anatomy 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910000634 wood's metal Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/34—Polysulfides of sodium or potassium
-
- 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
Definitions
- the present invention relates to mixtures of alkali metal polysulfides and mixtures of alkali metal polysulfides and alkali thiocyanates, processes for their preparation, their use as heat transfer or heat storage liquids and jackpot trecangeo- or heat storage liquids containing the mixtures of Alkalipolysulfiden or the mixtures of Alkalipolysulfiden and Alkalithiocyanaten include.
- Liquids for transferring heat energy are used in a variety of fields of technology.
- mixtures of water and ethylene glycol carry the waste heat of combustion into the radiator. Similar mixtures transport the heat from solar roof collectors into heat storage.
- thermal solar power plants which generate large scale electrical energy (Butscher, R., Schm dertician 2009, 3, pages 84 to 92). So far, such power plants were built with an installed capacity of a few hundred MW and many more are in Spain, but also in North Africa and the US in planning.
- the solar radiation is focused, for example via parabolic shaped mirror grooves in the focal line of the mirror.
- There is a metal tube which is located in a glass tube to avoid heat losses, the space between the concentric tubes is evacuated. The metal tube is flowed through by a heat transfer fluid.
- a mixture of diphenyl ether and diphenyl is used here.
- Diphenyl is at 68-72 ° C, the diphenyl ether at 26-39 ° C.
- the melting point is lowered to 12 ° C.
- the mixture of both substances can be used up to a maximum of 400 ° C, at higher temperatures decomposition occurs.
- the vapor pressure at this temperature is about 10 bar, a pressure that is still tolerable in the art.
- liquid sodium or sodium-potassium alloy as heat carrier, which is known from nuclear technology.
- the production of these metals is very expensive and they govern with traces of water to hydrogen gas, which is a safety challenge.
- low-melting solders such as Wood's metal (Bi-Pb-Cd-Sn alloy, melting point about 75 ° C) are known.
- the very high specific gravity argues against use as a heat transfer fluid.
- Further possible high-temperature heat carriers have been proposed on the basis of sulfur, which is used, for example, mixed with smaller amounts of selenium and / or tellurium (WO 2005/071037).
- Liquid sulfur is problematic as a heat carrier, since it is highly viscous in the range 150 to 200 ° C and thus not pumpable. Although the viscosity can be reduced by additives such as bromine or iodine
- inorganic salt melts as a heat transfer fluid.
- molten salts are state of the art in processes that operate at high temperatures.
- the eutectic mixture of potassium nitrate, sodium nitrate and sodium nitrite has a melting point of 146 ° C and is commercially available.
- the upper application temperature is limited to 450 ° C, since above this temperature considerable decomposition of the nitrite to nitrous gases, alkali metal oxides and elemental nitrogen takes place.
- the eutectic mixture of sodium nitrate and potassium nitrate can be used up to temperatures of 600 ° C.
- the use of this mixture as a heat transfer fluid in solar power plants is problematic due to the high melting point of about 220 ° C.
- alkali metal polysulfides especially sodium and potassium polysulfides
- the phase diagram for the ternary system sodium sulfide-potassium sulfide-sulfur is calculated to use invariant points with low melting temperatures for the compositions K0.84Na0.26S3.6i (78 ° C),
- alkali metal polysulfides A disadvantage of the alkali metal polysulfides is their relatively high viscosity in the molten state, especially that of sodium polysulfides (Cleaver, B., Davis, A.J., Electrochimica Acta 1973, Vol. 18, pages 727 to 731).
- DE 3824517 describes the use of mixtures of alkali thiocyanates as heat transfer fluids, in particular of potassium thiocyanate and sodium thiocyanate. Potassium thiocyanate melts at 173 ° C, sodium thiocyanate at 310 ° C.
- the eutectic mixture of the two salts with a ratio of 73 mol% of potassium thiocyanate to 27 mol% of sodium thiocyanate has a melting point of about 130 ° C.
- the melt is low viscosity and thus pumpable without increased energy consumption.
- alkali thiocyanates A disadvantage of the alkali thiocyanates is that they begin to decompose at temperatures above 450 ° C already. Excluding sulfur, the higher-melting alkali cyanides are formed (Gmelin's Handbook of Anorganic Chemistry 1938, Vol. 22, page 899).
- the melting point of the alkali thiocyanates can be lowered further by admixing further salts.
- the admixture of nitrites or nitrates lowers the melting point.
- the addition of the oxidizing nitrites or nitrates causes an explosive decomposition at elevated temperatures, which can be additionally accelerated by possibly dissolved heavy metal traces. Thus, the use of such mixtures for technical use is excluded.
- storage Heat can be generated directly by storing the heated heat transfer medium in well-insulated storage tanks, or indirectly by transferring the heat to another storage medium.
- the indirect method is implemented in the 50 MW Andasol I power plant in Almeria, where approximately 28,000 t of a melt of sodium nitrate and potassium nitrate (60:40) are used. The melt is pumped from a colder tank (about 280 ° C) through an oil-salt heat exchanger into a hotter tank during the solar irradiation times while being heated to about 380 ° C.
- the power plant can be run at full load for approximately 7.5 hours under full load
- the object of the invention is to provide a readily available, improved heat transfer and heat storage liquid.
- the liquid should be able to be used at temperatures higher than 400 ° C, preferably above 500 ° C. At the same time, the melting point should be as low as possible, preferably below 200 ° C.
- the liquid should also have a technically controllable, the lowest possible vapor pressure, preferably lower than 10 bar.
- the object is achieved by mixtures of alkali metal polysulfides.
- M 1 K
- M 2 Na, 0.50 ⁇ x ⁇ 0.90
- y 4.0, 5.0 or 6.0.
- Another embodiment relates to alkali metal polysulfides (Na 05 to o, 65K 0 , 5 to 0.35) 282.4 u * 2,%. or those having the composition (Na 0 , 6K 0 , 4 ) 2S 2 , e.
- Melting point of the mixture according to the invention below 200 ° C, in a particularly preferred embodiment below 160 ° C.
- the mixtures according to the invention have a high thermal stability.
- the mixtures according to the invention are stable up to a temperature of 450 ° C., in a particularly preferred embodiment up to a temperature of 500 ° C., in a very particularly preferred embodiment also at temperatures above 500 ° C.
- the mixtures according to the invention have a vapor pressure of less than 5 bar, more preferably less than 2 bar, at 500 ° C.
- alkali metal polysulfides The preparation of alkali metal polysulfides is known and can be carried out, for example, by reacting alkali metal sulfides with sulfur.
- An alternative is the direct reaction of alkali metals with sulfur, as described in US 4,640,832 for sodium.
- the reaction of alkali metals in liquid ammonia with sulfur is also described.
- Another possibility for synthesis is the reaction of alkali hydrogen sulfides or alkali metal sulfides with sulfur in alcoholic solution.
- Another object of the invention is a process for preparing the mixtures of alkali metal polysulfides according to the invention, characterized in that corresponding alkali metal sulfides are heated with sulfur or corresponding alkali metal polysulfides with or without sulfur under inert gas or in vacuo.
- the starting materials are heated to at least 400 ° C. for at least 0.5 hours.
- Suitable inert gases are noble gases, preferably argon, or nitrogen.
- Another object of the invention is a process for preparing the mixtures according to the invention of alkali metal polysulfides, characterized in that a solution of corresponding alkali metals in liquid ammonia is reacted with sulfur under inert gas.
- Another object of the invention is the use of the mixtures according to the invention of alkali metal polysulfides as heat transfer or heat storage liquids.
- the use of the mixtures according to the invention of alkali metal polysulfides with the exclusion of air and moisture preferably in a closed system of, for example, pipelines, pumps, control elements and containers to hydrolytic reactions during operation or the oxidation of the heat transfer or To avoid heat storage fluid.
- Another object of the invention are heat transfer or heat storage liquids, which comprise the inventive mixtures of alkali metal polysulfides sen.
- mixtures of alkali metal polysulfides according to the invention can be further expanded if they are mixed with alkali thiocyanates.
- Another object of the invention are mixtures of alkali metal polysulfides and alkali metal thiocyanates according to the general formula
- 0.20 ⁇ x ⁇ 1. In a particularly preferred embodiment of the invention, 0.50 ⁇ x ⁇ 1. In another preferred embodiment of the invention, 3.0 ⁇ y ⁇ 6.0. In a particularly preferred embodiment of the invention y 4.0, 5.0 or 6.0. In a further preferred embodiment of the invention, 0.20 ⁇ z ⁇ 1. In a particularly preferred embodiment of the invention, 0.50 ⁇ z ⁇ 1.
- 0.20 ⁇ m ⁇ 0.80 In a further preferred embodiment of the invention, 0.20 ⁇ m ⁇ 0.80. In a particularly preferred embodiment of the invention, 0.33 ⁇ m ⁇ 0.80.
- M 1 and M 3 K
- M 2 and M 4 Na, 0.20 ⁇ x ⁇ 1, 0.20 ⁇ z ⁇ 0.95, 3.0 ⁇ y ⁇ 6.0 and 0.20 ⁇ m ⁇ 0.95.
- M 1 and M 3 K
- alkali thiocyanates The preparation of alkali thiocyanates is known and is carried out on an industrial scale.
- Another object of the invention is a process for the preparation of the inventive mixtures of alkali metal polysulfides and alkali thiocyanates by co-melting of alkali metal polysulfides and alkali thiocyanates.
- the process can also be carried out while stirring the melt.
- the mixtures of alkali polysulfides and alkali thiocyanates according to the invention are generally suitable for high-temperature applications which require a heat transfer medium with a wide liquid temperature range.
- Another object of the invention is the use of the mixtures according to the invention of alkali metal polysulfides and alkali thiocyanates as heat transfer or heat storage liquids.
- Another object of the invention are heat transfer or heat storage liquids comprising the novel mixtures of alkali metal polysulfides and alkali metal thiocyanates.
- Method 1 Corresponding amounts of potassium polysulfide (K 2 S X ) or potassium sodium polysulfide ((K x Nai-x) 2Sy) and potassium thiocyanate (KSCN) were heated in a closed, evacuated quartz glass ampoule for 30 minutes at 400 ° C and then the melt to room temperature cooled. The vial was opened in an argon glovebox and the enamel was pulverized by mortars. Orange solids were obtained, the melting ranges of which are shown in Tab.
- K 2 S X potassium polysulfide
- K x Nai-x) 2Sy potassium sodium polysulfide
- KSCN potassium thiocyanate
- K2S X potassium polysulfide
- K x Nai-x 2SY potassium sodium polysulfide
- KSCN potassium thiocyanate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Lubricants (AREA)
- Glass Compositions (AREA)
Abstract
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012547484A JP2013516531A (ja) | 2010-01-05 | 2010-12-23 | アルカリ金属ポリスルフィドの混合物 |
AU2010340924A AU2010340924A1 (en) | 2010-01-05 | 2010-12-23 | Mixtures of alkali polysulfides |
CN2010800606647A CN102712474A (zh) | 2010-01-05 | 2010-12-23 | 碱金属多硫化物的混合物 |
MA35098A MA33949B1 (fr) | 2010-01-05 | 2010-12-23 | Melanges de polysulfures alcalins |
EP10795730A EP2521692A1 (fr) | 2010-01-05 | 2010-12-23 | Mélanges de polysulfures alcalins |
MX2012007392A MX2012007392A (es) | 2010-01-05 | 2010-12-23 | Mezclas de polisulfuros alcalinos. |
CA2785174A CA2785174A1 (fr) | 2010-01-05 | 2010-12-23 | Melanges de polysulfures alcalins |
BR112012016656-5A BR112012016656A2 (pt) | 2010-01-05 | 2010-12-23 | mistura de polissulfetos de metal alcalino, uso das misturas de polissulfetos de metal alcalino, mistura de polissulfetos de metal alcalino e tiocianatos de metal alcalino, e, fluido de transferência de calor ou de armazenamento de calor. |
IL220543A IL220543A0 (en) | 2010-01-05 | 2012-06-21 | Mixtures of alkali polysulfides |
TNP2012000337A TN2012000337A1 (en) | 2010-01-05 | 2012-06-27 | Mixtures of alkali polysulfides |
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DE102010004063 | 2010-01-05 | ||
EP10154392 | 2010-02-23 | ||
EP10154392.4 | 2010-02-23 |
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WO2011083054A1 true WO2011083054A1 (fr) | 2011-07-14 |
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PCT/EP2010/070617 WO2011083054A1 (fr) | 2010-01-05 | 2010-12-23 | Mélanges de polysulfures alcalins |
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EP (1) | EP2521692A1 (fr) |
JP (1) | JP2013516531A (fr) |
KR (1) | KR20120104423A (fr) |
CN (1) | CN102712474A (fr) |
AU (1) | AU2010340924A1 (fr) |
BR (1) | BR112012016656A2 (fr) |
CA (1) | CA2785174A1 (fr) |
CL (1) | CL2012001795A1 (fr) |
IL (1) | IL220543A0 (fr) |
MA (1) | MA33949B1 (fr) |
MX (1) | MX2012007392A (fr) |
TN (1) | TN2012000337A1 (fr) |
WO (1) | WO2011083054A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8679668B2 (en) | 2010-06-22 | 2014-03-25 | Basf Se | Industrial apparatus for the large-scale storage of electric energy |
US8933262B2 (en) | 2011-05-24 | 2015-01-13 | Basf Se | Process for preparing polyisocyanates from biomass |
US9957625B2 (en) | 2012-06-11 | 2018-05-01 | Basf Se | Electrode unit |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102884154B (zh) * | 2010-04-09 | 2016-04-13 | 巴斯夫欧洲公司 | 作为传热介质的具有改进粘度的流体硫 |
US20190127221A1 (en) * | 2016-05-19 | 2019-05-02 | Guillaume Lambotte | Sulfides electrolyte for metal processing and extraction |
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- 2010-12-23 MA MA35098A patent/MA33949B1/fr unknown
- 2010-12-23 JP JP2012547484A patent/JP2013516531A/ja not_active Withdrawn
- 2010-12-23 KR KR1020127020658A patent/KR20120104423A/ko not_active Application Discontinuation
- 2010-12-23 BR BR112012016656-5A patent/BR112012016656A2/pt not_active IP Right Cessation
- 2010-12-23 AU AU2010340924A patent/AU2010340924A1/en not_active Abandoned
- 2010-12-23 EP EP10795730A patent/EP2521692A1/fr not_active Withdrawn
- 2010-12-23 CA CA2785174A patent/CA2785174A1/fr not_active Abandoned
- 2010-12-23 MX MX2012007392A patent/MX2012007392A/es unknown
- 2010-12-23 CN CN2010800606647A patent/CN102712474A/zh active Pending
- 2010-12-23 WO PCT/EP2010/070617 patent/WO2011083054A1/fr active Application Filing
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- 2012-06-21 IL IL220543A patent/IL220543A0/en unknown
- 2012-06-27 TN TNP2012000337A patent/TN2012000337A1/en unknown
- 2012-07-03 CL CL2012001795A patent/CL2012001795A1/es unknown
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8679668B2 (en) | 2010-06-22 | 2014-03-25 | Basf Se | Industrial apparatus for the large-scale storage of electric energy |
US8933262B2 (en) | 2011-05-24 | 2015-01-13 | Basf Se | Process for preparing polyisocyanates from biomass |
US9957625B2 (en) | 2012-06-11 | 2018-05-01 | Basf Se | Electrode unit |
Also Published As
Publication number | Publication date |
---|---|
CN102712474A (zh) | 2012-10-03 |
CL2012001795A1 (es) | 2012-10-12 |
CA2785174A1 (fr) | 2011-07-14 |
BR112012016656A2 (pt) | 2018-05-15 |
JP2013516531A (ja) | 2013-05-13 |
MA33949B1 (fr) | 2013-01-02 |
AU2010340924A1 (en) | 2012-08-30 |
EP2521692A1 (fr) | 2012-11-14 |
TN2012000337A1 (en) | 2013-12-12 |
IL220543A0 (en) | 2012-08-30 |
KR20120104423A (ko) | 2012-09-20 |
MX2012007392A (es) | 2012-08-23 |
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