US20190178584A1 - Method for thermo-chemical energy storage - Google Patents

Method for thermo-chemical energy storage Download PDF

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Publication number
US20190178584A1
US20190178584A1 US16/309,130 US201716309130A US2019178584A1 US 20190178584 A1 US20190178584 A1 US 20190178584A1 US 201716309130 A US201716309130 A US 201716309130A US 2019178584 A1 US2019178584 A1 US 2019178584A1
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Prior art keywords
transition metal
chemical
reactions
energy
storage
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Danny Mueller
Christian Knoll
Peter Weinberger
Andreas Werner
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Akademie Der Bildenden Kuenste Wien
Technische Universitaet Wien
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Akademie Der Bildenden Kuenste Wien
Technische Universitaet Wien
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to a method for thermo-chemical energy storage by carrying out endothermic chemical reactions for the storage of heat energy in the form of chemical energy in one or more chemical compounds for later re-release in the form of heat energy by carrying out chemical equilibrium reactions of ammine complexes of transition metal salts.
  • Thermo-chemical energy storage i.e. storage of heat energy in the form of chemical energy
  • storage of heat energy in the form of chemical energy is a method of energy storage by cycling at least one chemical compound between the states of at least one reversible equilibrium reaction, said method having been known for decades, but only been subject to more intense research in the last few years.
  • U.S. Pat. No. 4,365,475 discloses the combination of two equilibrium reactions for the purpose of thermo-chemical energy storage, namely the alternating reversible endothermic formation of two ammine complexes, CaCl 2 .8NH 3 and ZnCl 2 .NH 3 .
  • the reactions suitable for thermo-chemical energy storage can be divided into two categories, namely the category of “sorption processes”, where the primary valences of the chemical compounds involved remain unchanged and coordinate bonds are formed only via secondary valences, as is the case with the above cited reactions to form ammine complexes, but also, for example, to form hydrates and other solvates such as hydrates, and the category of “chemical reactions”, where the primary valences are changed.
  • the category of “sorption processes” where the primary valences of the chemical compounds involved remain unchanged and coordinate bonds are formed only via secondary valences, as is the case with the above cited reactions to form ammine complexes, but also, for example, to form hydrates and other solvates such as hydrates
  • the category of “chemical reactions” where the primary valences are changed.
  • mainly metal salts are used due to the relatively high number of coordination sites and oxidation states, respectively.
  • thermo-chemical energy storage decreases as the number of cycles increases, so that it either has to be exchanged or, in some cases, cleaned expensively.
  • a quality decrease can either result from incomplete conversion, e.g. due to formation of a nonreactive layer at the surface of the thermal storage material, or from changes in the mechanical properties of the solid particles, e.g. by abrasion, sintering, etc., both being equatable with a decrease in thermal storage capacity, i.e. energy storage density.
  • Ishitobi et al. J. Chem. Eng. Japan 45(1), 58-63 (2012)
  • the aim of the invention was to at least partly solve the above problems.
  • the present invention achieves said aim by providing a method for thermo-chemical energy storage by carrying out reversible chemical reactions for the storage of heat energy in the form of chemical energy in one or more chemical compounds for later re-release in the form of heat energy using chemical equilibrium reactions, wherein equilibrium reactions of ammine complexes of transition metal salts are carried out for the storage and re-release of the energy, characterized in that
  • Me represents at least one transition metal ion and X represents one or more counterion(s) in a quantity sufficient for charge equalizing the complex, according to the valence thereof and that of the transition metal ion; and b) one or more transition metal salt(s), carried on a carrier material that is inert with regard to the reaction, is/are used.
  • the ammine complex formation reaction of the at least one transition metal salt is carried out, rather than a combination of two parallel reactions complementing each other chemically or thermodynamically. This means that the reaction does not alternate between different coordination numbers of the ammine complexes, but rather the entire enthalpy of formation of the ammine complexes is recovered during the exothermic reaction.
  • the inventors have found out that transition metal ammine complexes have very high enthalpies of formation.
  • the invention solves said issue by applying the metal salts onto a carrier, whereby simultaneously a “dilution” of the salts is achieved, which precludes melting processes and an associated agglutination of the salts. Rather, the transition metal salts applied onto the carrier remain easy to handle even at higher temperatures. For example, when using a particulate carrier, as is preferred according to the invention, the material remains free-flowing and thus easily transportable and storable.
  • the at least one transition metal is preferably selected from Mn, Fe, Co, Ni, Cu, and Cd, because ammine complexes of salts of these metals have particularly high enthalpies of formation during the exothermic reaction, i.e. the “reverse reaction” in the above reaction equation, thus releasing high amounts of heat per mass unit, and they are relatively inexpensive, too.
  • the at least one transition metal is selected from Cu and Cd, most preferably Cd, as these two metals when used in the inventive method have advantageous heat balances relative to the other transition metals.
  • copper salts show very high enthalpies of formation, thus releasing very high amounts of heat even after “dilution” and application onto the carrier.
  • ammine complexes of cadmium salts may be decomposed even by simple purging with air, optionally while heating them to relatively low temperatures in order to increase the already high reaction rate. Therefore, when using cadmium in a cycle of the above forward and reverse reactions hardly any heat needs to be invested. Rather, a considerable amount of heat may be recovered, making cadmium salts, especially CdCl 2 , also suitable in a method for recovering thermal energy from chemical energy, even without applying them onto a carrier.
  • a sulfate ion SO 4 2 ⁇ or two chloride ions Cl ⁇ are used as the counterion(s) X, as these salts are both well researched and available without limitations, and have high enthalpies of formation of their ammine complexes.
  • the sulfates do not undergo irreversible decomposition even when heated to very high temperatures exceeding 600° C., whereas the chlorides tend to have higher enthalpies of formation than the sulfates when complexed with ammonia.
  • both of the above also seem to be due to the fact that the chlorides are capable of coordinating five ammonia molecules, with the sulfates being able to coordinate only four thereof.
  • the sulfate or chloride of copper or cadmium, or a mixture of two or more thereof is used as the transition metal salt, CuSO 4 and CdCl 2 being particularly preferred.
  • the use of mixtures of two or more transition metal salts on the same or on separate carrier(s)/carrier particle(s) may be preferred in order to control, for example, the amount of heat released during the exothermic reaction.
  • embodiments are preferred where each salt is applied on separate carriers/carrier particles. As a rule, embodiments where only a single transition metal salt is used are particularly preferred.
  • the carrier material as such is not particularly limited, as long as it is chemically and thermally inert under the reaction conditions chosen.
  • it is preferably selected from vermiculite, porous aluminium silicates, and zeolites, more preferably from zeolites and expanded vermiculite, zeolites being particularly preferred due to the wide range of usable modifications thereof.
  • a particulate carrier material having a grain size of 0.1 to 5 mm, more preferably 0.5 to 3 mm, most preferably 1 to 2 mm is used because, for one thing, particulate material can be handled more easily than, for example, pellets or even larger pieces of the carrier.
  • bulk material is easily transportable via chutes, and finely divided, e.g. powdery, material having grain sizes below about 2 mm may be conveyed using a blower and may be collected using funnels.
  • powdery material may be reacted in fluidized-bed reactors, which reduces equipment use, increases turnovers and prolongates the durability of the material.
  • regenerated material may be sized using sieves in order to create reproducible reaction conditions.
  • fine grains have a relatively large surface area and thus may be loaded with higher ratios of transition metal salt.
  • the carrier material preferably is loaded with about 10 to 70 wt % of the transition metal salt, expressed as the weight of the transition metal salt based on the carrier weight.
  • the load depends, among other things, on the enthalpies of formation of the respective ammine complexes, on the equipment configuration, such as the intended use of the exothermic reaction, and on the nature and amount of waste heat available for the decomposition of the complexes.
  • loads below 10 wt % may be uneconomical.
  • the latter also applies to the preparation of very high loads, e.g. higher than 80 wt %. So far, loads between about 35 and about 65 wt %, more preferably between about 40 and about 60 wt %, have been shown to be preferred according to the invention.
  • the present invention also discloses the use of ammine complexes of transition metal salts for thermo-chemical energy storage by carrying out chemical equilibrium reactions of the ammine complexes of transition metal salts for the storage and re-release of energy, characterized in that
  • Me represents at least one transition metal ion and X represents one or more counterion(s) in a quantity sufficient for charge equalizing the complex, according to the valence thereof and that of the transition metal ion; and b) one or more transition metal salt(s), carried on a carrier material that is inert with regard to the reaction, is/are used.
  • FIG. 1 shows a photograph of the fluidized-bed reactor used in the examples and reference examples.
  • FIG. 2 shows the temperature profile of the ammine complex formation reaction of Comparative Example 1.
  • FIG. 3 shows the temperature profile of the ammine complex formation reaction of Example 1.
  • FIG. 4 shows the temperature profile of the ammine complex formation reaction of Comparative Example 2.
  • FIG. 5 shows the temperature profile of the ammine complex formation reaction of Example 2.
  • FIG. 6 shows the temperature profile of the ammine complex formation reaction of Example 3.
  • FIG. 7 shows the temperature profile of cycles of the ammine complex formation reaction and ammine complex decomposition reaction of Example 7.
  • the zeolite Y used had a particle size of about 2 mm, and the expanded vermiculite had a particle size of about 2 to 3 mm. Both carriers as well as all transition metal salts were obtained from Sigma Aldrich.
  • XRF x-ray fluorescence
  • STA simultaneous thermal analysis
  • zeolite Y was soaked with a saturated CuCl 2 solution.
  • a CuCl 2 content of 44.3 wt % was determined using XRF analysis.
  • the respective metal salt powder (Comparative Examples 1 to 4) and the loaded carrier material, respectively, of Synthesis Examples 1 to 6 (Examples 1 to 6) were provided at room temperature in a fluidized-bed reactor, and the solid material was then fluidized with a stream of 10 I/min of NH 3 as the reactive carrier gas for 15 min, and was simultaneously converted to the respective ammine complex, with the temperature developing inside the reactor due to the exothermic reaction being measured continuously by means of temperature sensors at different heights of the reactor.
  • FIG. 1 shows a photograph of the fluidized-bed reactor used. Before fluidizing, the bulk particle bed in all cases reached a height just above the lowermost thermal sensor.
  • FIGS. 2 to 6 the temperature profiles of the ammine complex formation reactions measured for Examples 1 to 3 as well as Comparative Examples 1 and 2 are shown, wherein T1 shows the measured curve of the lowermost temperature sensor and T4 shows that of the uppermost temperature sensor, respectively.
  • T1 shows the measured curve of the lowermost temperature sensor
  • T4 shows that of the uppermost temperature sensor, respectively.
  • the highest temperature was measured at the lowermost thermal sensor, because the fluidized particle bed came into contact with the reactive gas NH 3 before reaching a higher height, and the bed material was mixed immediately due to fluidi-zation, which is why such temperatures could not be reached at higher heights.
  • the temperature corresponding to the uppermost of the four temperature curves of the lowermost thermal sensor T1 is to be used throughout.
  • FIG. 2 and FIG. 3 A comparison of FIG. 2 and FIG. 3 , i. e. between pure CuSO 4 powder (without a carrier) of Comparative Example 1 and CuSO 4 on zeolite Y of Example 1, shows that the maximum temperature reached using the salt carried on zeolite, i.e. 215° C., was considerably lower than that reached using the pure CuSO 4 powder (about 330° C.).
  • FIGS. 4 and 5 in which the curves of pure CuCl 2 powder (without a carrier) of Comparative Example 2 and CuCl 2 on zeolite Y of Example 2 are shown.
  • the pure powder When reacted with NH 3 , the pure powder causes a temperature increase inside the reactor to about 365° C., whereas the “dilution” on the zeolite carrier reached a temperature of “only” about 203° C. Nevertheless, the amount of heat thus released is, of course, still usable for various applications, i.e. by separately storing defined amounts of transition metal salt and ammonia and mixing them, if required, in order to release the heat.
  • FIG. 6 the temperature profile for CdCl 2 carried on zeolite when reacted with ammonia is shown, where a temperature of about 74° C. was reached, while the temperature increased to about 174° C. with pure CdCl 2 powder (data not shown).
  • the transition metal salts applied onto carriers release comparable amounts of heat that are only slightly below those becoming available by cycling ammine complexes of transition metal salts between different coordination numbers according to the prior art.
  • the salts applied onto carriers according to the present invention are resistant to agglomeration due to melting processes.
  • ammine complexes obtained in the above reactions with ammonia were subsequently thermally decomposed by heating using an air current having 400° C. in the fluidized-bed reactor and noting the decomposition temperatures measured at the lowermost thermal sensor, which are listed in Table 3 below.
  • FIG. 7 shows the temperature profile of these cycles.
  • Cadmium chloride therefore constitutes a particularly promising material for future use as a thermo-chemical heat storage medium.
  • the invention thus provides a method through which relatively large amounts of energy in the form of chemical energy may be stored in transition metal salts applied onto a solid carrier, and may be spontaneously re-released by being reacted with ammonia without the risk of agglomeration due to partial melting or of irreversible decomposition of the salts.

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US16/309,130 2016-07-11 2017-07-05 Method for thermo-chemical energy storage Abandoned US20190178584A1 (en)

Applications Claiming Priority (3)

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ATA327/2016A AT518826B1 (de) 2016-07-11 2016-07-11 Verfahren zur thermochemischen Energiespeicherung
ATA327/2016 2016-07-11
PCT/EP2017/066753 WO2018011032A1 (de) 2016-07-11 2017-07-05 Verfahren zur thermochemischen energiespeicherung

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EP (1) EP3482147B1 (de)
AT (1) AT518826B1 (de)
ES (1) ES2866901T3 (de)
WO (1) WO2018011032A1 (de)

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US5441716A (en) * 1989-03-08 1995-08-15 Rocky Research Method and apparatus for achieving high reaction rates
JPH04310236A (ja) * 1991-04-09 1992-11-02 Nok Corp 水素ガス吸着用ゼオライト
JP5232510B2 (ja) * 2008-03-14 2013-07-10 株式会社豊田中央研究所 化学蓄熱材成形体の製造方法
RU2012112013A (ru) * 2009-09-30 2013-11-10 Амминекс А/С Соединенные теплопроводящие структуры в системах хранения твердого аммиака
US9120959B2 (en) * 2010-03-25 2015-09-01 Kabushiki Kaisha Toyota Chuo Kenkyusho Chemical thermal energy storage material structure, method of producing the same, and chemical heat accumulator
JP5521967B2 (ja) * 2010-10-08 2014-06-18 株式会社豊田中央研究所 化学蓄熱体およびその製造方法
EP2749624B1 (de) * 2011-08-23 2019-02-20 Kabushiki Kaisha Toyota Chuo Kenkyusho Chemische wärmespeicherstruktur enthaltend ein chemisches wärmespeichermaterial
CN102796999B (zh) * 2012-08-02 2014-04-16 黑龙江大学 一种二维自支持过渡金属超薄片的制备方法
WO2015006666A1 (en) * 2013-07-11 2015-01-15 Eos Energy Storage, Llc Mechanical-chemical energy storage

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AT518826B1 (de) 2018-09-15
AT518826A1 (de) 2018-01-15
ES2866901T3 (es) 2021-10-20
WO2018011032A1 (de) 2018-01-18
EP3482147A1 (de) 2019-05-15

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