EP2521692A1 - Mélanges de polysulfures alcalins - Google Patents

Mélanges de polysulfures alcalins

Info

Publication number
EP2521692A1
EP2521692A1 EP10795730A EP10795730A EP2521692A1 EP 2521692 A1 EP2521692 A1 EP 2521692A1 EP 10795730 A EP10795730 A EP 10795730A EP 10795730 A EP10795730 A EP 10795730A EP 2521692 A1 EP2521692 A1 EP 2521692A1
Authority
EP
European Patent Office
Prior art keywords
mixtures
alkali metal
mixtures according
mixture
heat transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10795730A
Other languages
German (de)
English (en)
Inventor
Fabian Seeler
Felix Major
Kerstin Schierle-Arndt
Jürgen WORTMANN
Martin GÄRTNER
Michael Lutz
Stephan Maurer
Otto Machhammer
Günther Huber
Hans-Josef Sterzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10795730A priority Critical patent/EP2521692A1/fr
Publication of EP2521692A1 publication Critical patent/EP2521692A1/fr
Withdrawn legal-status Critical Current

Links

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

Landscapes

  • 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

La présente invention concerne des mélanges de polysulfures alcalins ainsi que des mélanges de polysulfures alcalins et de thiocyanates alcalins, un procédé permettant de les fabriquer, leur utilisation comme liquides caloporteurs ou accumulateurs de chaleur, ainsi que liquides caloporteurs ou accumulateurs de chaleur qui comprennent les mélanges de polysulfures alcalins ou les mélanges de polysulfures alcalins et de thiocyanates alcalins.
EP10795730A 2010-01-05 2010-12-23 Mélanges de polysulfures alcalins Withdrawn EP2521692A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10795730A EP2521692A1 (fr) 2010-01-05 2010-12-23 Mélanges de polysulfures alcalins

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102010004063 2010-01-05
EP10154392 2010-02-23
PCT/EP2010/070617 WO2011083054A1 (fr) 2010-01-05 2010-12-23 Mélanges de polysulfures alcalins
EP10795730A EP2521692A1 (fr) 2010-01-05 2010-12-23 Mélanges de polysulfures alcalins

Publications (1)

Publication Number Publication Date
EP2521692A1 true EP2521692A1 (fr) 2012-11-14

Family

ID=43500011

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10795730A Withdrawn EP2521692A1 (fr) 2010-01-05 2010-12-23 Mélanges de polysulfures alcalins

Country Status (13)

Country Link
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)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
US20190127221A1 (en) * 2016-05-19 2019-05-02 Guillaume Lambotte Sulfides electrolyte for metal processing and extraction

Family Cites Families (11)

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Publication number Priority date Publication date Assignee Title
US2020661A (en) * 1923-06-20 1935-11-12 Phillips Petroleum Co Process for treating hydrocarbon oils
US2077856A (en) * 1935-04-01 1937-04-20 Rohm Otto Method for producing stable alkali polysulphides
GB736750A (en) * 1952-09-17 1955-09-14 Nat Lead Co Improvements in or relating to the treatment of titanium metal surfaces
BE522839A (fr) * 1952-09-17
US3296224A (en) * 1963-03-29 1967-01-03 Koppers Co Inc Polybenzothiazole preparation
US4335578A (en) 1980-05-30 1982-06-22 Ford Aerospace & Communications Corporation Solar power converter with pool boiling receiver and integral heat exchanger
DE3436698C1 (de) 1984-10-06 1986-05-22 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von Natriumpolysulfiden aus den Elementen Natrium und Schwefel
DE3824517A1 (de) 1988-07-20 1990-01-25 Bayer Ag Waermeuebertragungsmittel
AU622177B2 (en) * 1988-07-25 1992-04-02 Jgc Corporation A process for removal of mercury from a liquid hydrocarbon
JP2887694B2 (ja) * 1990-04-16 1999-04-26 日揮株式会社 液状炭化水素中の水銀の除去方法
HU225602B1 (en) 2004-01-26 2007-05-02 Solar Technologia Es Vegyi Any Method for extraction of thermal energy from solar collector and absorber therefore

Non-Patent Citations (1)

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Title
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Also Published As

Publication number Publication date
IL220543A0 (en) 2012-08-30
WO2011083054A1 (fr) 2011-07-14
JP2013516531A (ja) 2013-05-13
KR20120104423A (ko) 2012-09-20
CL2012001795A1 (es) 2012-10-12
MX2012007392A (es) 2012-08-23
BR112012016656A2 (pt) 2018-05-15
TN2012000337A1 (en) 2013-12-12
MA33949B1 (fr) 2013-01-02
AU2010340924A1 (en) 2012-08-30
CN102712474A (zh) 2012-10-03
CA2785174A1 (fr) 2011-07-14

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