DE102007006512B4 - Method and device for energy storage and for controlled, low-loss heat energy conversion - Google Patents

Abstract

An emission-free and cyclic closed-loop method of storing energy, characterized in that the method comprises the steps of: a) supplying a heat energy Q from a first arbitrary heat reservoir to a heat collector; b) separating a storage medium into at least two components by means of the supplied heat energy Q; c) releasing an amount of heat containing the Entropieterm to a second heat reservoir having a lower temperature than the first heat reservoir; d) storing the remaining energy in the form of the at least two separated components or working media; e) establishing a pressure difference between the separated components, wherein by heating above the boiling point of a component, the pressure difference can be increased; f) relaxing the vaporized component in an energy converter, preferably a steam engine or a steam turbine; g) condensing the vaporized component in the second component of the storage medium, thereby liberating the heat of condensation and the heat of solution; h) using the heat of condensation and the heat of solution in the heating of the two separated components in step e); and i) returning the recombined storage medium to the heat collector at step a); j) Use of the energy stored after step d) in the form of heat by recycling the separated components using a suitable dynamic reversible equilibrium system as the storage medium.

Description

SCOPE OF THE INVENTION

The present invention generally relates to methods of energy storage and controlled thermal energy conversion, and to apparatus for performing these methods. In particular, the invention relates to methods and devices for energy storage in the production of renewable energy, such. As solar and wind energy to store excess energy and release it again when needed, as well as for the conversion of heat energy into mechanical energy or electrical work. In this case, heat energy from any heat sources is used, whereby alternative energy or energy sources can be used. The temperature of the heat source can also be below the freezing point of the water, insofar as another, colder heat reservoir is available.

BACKGROUND OF THE INVENTION

Today, energy is "extracted" from fossil fuels (oil, natural gas, coal), from nuclear energy, hydropower or even from the so-called regenerative energies (wind energy, solar energy, biogas, geothermal energy, etc.). Motor vehicles, ships and aircraft are almost exclusively powered by fossil fuels. In the so-called regenerative energy production a continuous energy extraction is not guaranteed, such as in the case of storms and wind surges in wind power plants or in the case of cloudy weather or darkness in solar systems.

In modern thermal power plants, high temperature, high pressure steam is generated which then relaxes in a steam engine or steam turbine. Work is done and the steam cools down.

mit

T_k

Temperatur des unteren (kalten) Wärmereservoirs bzw. Wärmebehälters

T_w

Temperatur des oberen (warmen) Wärmereservoirs bzw. Wärmebehälters.

The efficiency η of a heat engine can be determined as follows:

With

T _k

Temperature of the lower (cold) heat reservoir or heat tank

T _w

Temperature of the upper (warm) heat reservoir or heat tank.

With Θ _k = T _k - 273 = 10 ° C and Θ _w = T _w - 273 = 170 ° C results, for example, a theoretical efficiency of 36%. The remainder (64%) remains unused and accumulates as waste heat. As the temperature difference increases, the efficiency improves; However, an efficiency of 100% is not achievable in principle. The injected energy E thus consists of completely convertible energy, the so-called exergy E _E , and non-convertible energy, the so-called anergy E _A : E = E _E + E _A. (Equation 2)

In thermodynamics, instead of the term anergy E _A, the amount of heat TdS is used, which is sometimes also referred to as entropy term. The entropy S describes the reduction in quality of energy, which is not very descriptive, so that here continues to be spoken of anergy.

As the above example shows, the energy conversion of heat into mechanical work by forcing anergy is associated with poor efficiency. In addition, the environment is polluted or damaged by significant amounts of carbon dioxide, possibly sulfur dioxide, and other environmental toxins or radioactive substances that are generated during production.

Also known is the "chemical storage" of electrical energy, such as the z. B. in accumulators is the case. The lead-acid battery is probably the most widespread electrical storage. The quite complex electrode processes can be simplified as follows:

Technically, the principle is implemented so that a lead electrode and a lead dioxide electrode immersed in sulfuric acid. When closing the circuit, electrical energy is released, which can be harnessed to perform work (ΔH ₀ = -506.2 kJ / mol). It forms insoluble lead (II) sulfate. For recharging, an external voltage of more than 0.3588 + 1.6913 = 2.0501 V must be applied to the electrodes to reverse the chemical processes according to equations 3 and 4, so that in total the lead sulphate returns to lead and according to equation 5 Lead dioxide is transformed.

The lead-acid battery does not generate electrical energy, i. H. the energy taken from the accumulator must first be fed in as electrical energy. Due to the electrical resistance, considerable amounts of energy are inevitably lost when charging and discharging the battery.

With the exception of nuclear energy and geothermal energy, every form of energy used on Earth ultimately comes directly or indirectly from the sun. However, the energy of the sun is not continuously available, because at night and in winter energy storage systems must be used.

The German Patent No. 695 10 821 T2 describes a cooling and / or heating system for an absorption cycle. The cooling and / or heating system contains a flowing working medium consisting essentially of an aqueous solution containing 30 to 80% by weight of sodium hydroxide, potassium hydroxide or mixtures thereof and increasing the rate of water vapor sorption of the flowing working medium from an effective amount of additive between 2 and 5,000 ppm, based on the weight of a primary, secondary or tertiary aliphatic, cycloaliphatic or aromatic amine.

The U.S. Patent No. 4,823,864 describes a system for storing chemical energy. The system comprises a first and a second container. The first container contains a liquid solution of ammonium halide or thiocyanate, alkali or a basic earth metal halide, hydroxide or thiocyanate or mixtures thereof, with an initial concentration of about 30% and about 80%. In the second container is a liquid, preferably water, although ammonia and ammonia-water mixtures are useful for low temperature applications. Above the liquid in the containers is a respective area, and a connecting pipe communicates with these spaces via a valve to selectively allow steam to pass between the areas. The system further includes a heater to heat the liquid solution to a temperature above about 26 ° C, cooling means to cool the liquid solution to a temperature of about 12 ° C, and a heat exchanger to remove heat from the liquid heated liquid solution to transfer the cooled liquid.

The U.S. Patent No. 4,614,605 describes a water vapor absorbing composition containing cesium hydroxide which is useful in processes and apparatus in which heat is pumped in absorption cycles. When the composition is combined with at least one of either KOH or NaOH, the absorbent allows exceptionally high rises in the heat temperature, although the initial temperature is at a low ambient temperature. With standard construction materials and using common corrosion inhibitors, acceptable low corrosion rates are achieved.

The U.S. Patent No. 340,718 describes the generation of steam for driving steam engines. The steam engines are powered by the heat generated by the absorption of water vapor by passing it into a high boiling point liquid, such as a solution of caustic soda.

The U.S. Patent No. 3,147,744 describes a steam power plant that converts thermal energy into mechanical energy. The thermal power plant is integrated with a steam turbine power plant such that water is heated by heat exchange through a circulating medium heated by a combustion device. The heat exchange medium may be circulated through the heater and the heat sink to store heat, or it may be circulated through the heat sink and boiler of the steam power plant to drive off the turbine when no air is available for combustion.

The German Patent No. 24993 describes the use of caustic soda or caustic potash for absorbing engine exhaust steam and utilizing the heat released thereby to generate strained steam.

The German Patent No. 26234 describes the use of caustic, chloro-calcium and other salts whose solutions have a high boiling point to absorb engine steam and use the heat released to develop stressed vapors.

The aim of the invention is to close a significant gap for the continuous release of energy in the production of renewable energy (such as solar and wind energy), by storing excess energy, which will be released when needed, as well as for heat energy conversion into mechanical or Electrical work of relatively cold heat sources that can not be used at present.

SUMMARY OF THE INVENTION

The cyclic and emission-free method according to the invention for storing energy and converting this energy into mechanical or electrical energy consists essentially of storing thermal energy by means of a suitable dynamic equilibrium system and / or converting it into mechanical or electrical work.

According to a first aspect of the invention there is provided an emission-free and cyclic method of storing energy, the method comprising the steps of: a) supplying a heat energy Q from a first arbitrary heat reservoir to a heat collector; b) separating a storage medium into at least two components by means of the supplied heat energy Q; c) delivering a quantity of heat, including the Entropieterm, to a second heat reservoir, which has a lower temperature than the first heat reservoir; and d) storing the remaining energy in the form of the at least two separated components, also called working media in the text.

Optionally, the method may further comprise the following further steps: e) establishing a pressure differential between the separated components whereby heating above the boiling point of a component may increase the pressure differential; f) relaxing the vaporized component in an energy converter, preferably a steam engine or a steam turbine; g) condensing the vaporized component in the second component of the storage medium, thereby liberating the heat of condensation and the heat of solution; h) using the heat of condensation and the heat of solution in the heating of the two separated components in step e); and i) returning the recombined storage medium to the heat collector at step a); and j) using the energy stored after step d) in the form of heat by recycling the separated components.

A first device according to the invention for storing energy and for converting this energy into mechanical or electrical energy (in combination with a generator), with which the method according to the invention can be implemented, comprises an energy collector (consisting of heat collector and condenser), an energy store, a reactor and an energy converter. In the heat transfer from the heat collector to the capacitor of the energy collector, the exergy with an efficiency according to Eq. 1 stored in the energy storage.

A second device according to the invention for converting stored energy into mechanical or electrical energy (in combination with a generator) with which the method according to the invention can be implemented comprises a pressure chamber, an energy converter, a concentration chamber and a dilution chamber connected to the thermal pressure chamber Contact stands. The components are configured, arranged and connected to one another via lines, such that a first working medium heated in the pressure chamber generates mechanical or electrical energy in the energy converter, then the relaxed first working medium dilutes a second working medium, which is supplied from the concentration chamber, in the dilution chamber and the heat energy released thereby in the dilution chamber is taken up by the first working medium in the pressure chamber.

A third device according to the invention for storing energy and converting this energy into mechanical or electrical energy (in combination with a generator) with which the method according to the invention can be implemented comprises a first circuit comprising an evaporation zone, an energy converter Condensation zone and a pump, which are in fluid communication with each other, and a separate second circuit. This second one Circuit consists of a chamber in which an endothermic process takes place, a condenser, a reservoir for the first storage medium, a heat exchanger, a reservoir for the second storage medium, a chamber in which an exothermic process takes place, a dilution reservoir and at least one pump, each in fluid communication with each other via lines. The heat exchanger and the chamber of the second cycle, in which the exothermic process takes place, are in each case in thermal communication with the condensation zone or the evaporation zone of the first cycle. Through the chamber in which the endothermic process takes place, energy is supplied to the system, while the condenser is in thermal communication with the cold heat reservoir.

A fourth device according to the invention for converting thermal energy into mechanical or electrical energy, with which the method according to the invention can be implemented, comprises a circuit connected to a bypass. The circuit comprises a hot zone, a cold zone, a heat exchanger and a pump, which are each in fluid communication with each other via lines. In addition, the hot zone is connected to the cold zone via a bypass. In this bypass is an energy converter, which optionally drives a generator.

BRIEF DESCRIPTION OF THE DRAWINGS

1 schematically shows the main components of a Carnot machine.

2 shows schematically the main components of the devices according to the invention and the energy flow between these components during the energy conversion process.

3 shows an embodiment of a preferred device according to the invention for the conversion of energy.

4 shows a further embodiment of a preferred device according to the invention for the storage and conversion of energy.

5 shows a further embodiment of a preferred device according to the invention for the storage and conversion of energy.

6 shows a further embodiment of a preferred device according to the invention for the conversion of energy.

DETAILED DESCRIPTION OF THE INVENTION

The core of the invention is a reversible working energy storage. For this purpose, for example, reversible dynamic equilibrium systems or equilibrium reactions, in particular with high heat of reaction are suitable. It is well known to the person skilled in the art that in the case of chemical equilibrium reactions, the position of the equilibrium can be influenced by the choice of the "boundary conditions".

In an equilibrium reaction takes place in addition to a metabolic rate and an energy conversion. According to the invention, a reversible process, which proceeds with pronounced heat of reaction, is used as energy store or heat store. The reaction proceeds until equilibrium is established, releasing or absorbing energy. In the case of energy release one speaks of an exothermic and in the other case of an endothermic process.

If the equilibrium is shifted in the endothermal direction, energy must be supplied from the outside. If, on the other hand, no energy is supplied, the temperature of the reaction space drops. At the start of the reaction, the reaction vessel has the temperature of the hot heat reservoir. In a rapid endothermic reaction, the reaction vessel cools below ambient temperature, and the reaction stops when no energy is supplied by the environment. The environment tries to compensate for the resulting asymmetry, thereby cooling itself off, or in other words, the energy of the environment is stored in the equilibrium system. This stored energy is returned by the system when the process is reversed. If the time of this back reaction is freely selectable, then excess energy, eg. B. the summer half-year using this method and then release in the winter months. Thus, the method according to the invention includes a storage system for storing energy in order to then release it again when needed. This closes a significant gap to the continuous supply of energy from solar or wind power plants.

A preferred embodiment of the device according to the invention 10 like these in 2 is composed of the following elements: an energy collector 12 (consisting of heat collector 12a and capacitor 12b ), an energy storage 14 , a reactor 16 and an energy converter 18 , Preferably, it further comprises a pump (not shown) for the working medium, for example water, and a pump (not shown) for the storage medium, for example sodium hydroxide solution. If a water tractor, such as toluene, is to be used, another pump is needed. Optionally, a vacuum pump is used to generate a static vacuum to utilize low temperature heat sources. If the energy is stored only for heating purposes, the energy converter can be dispensed with.

The energy collector 12 is in thermal communication with both a heat source and a heat sink. The heat source or energy source, for example the sun, supplies the heat collector 12a preferably uniform with energy. The heat source can be solar energy, geothermal heat, heat of condensation, heat of crystallization, waste heat (eg from power plants or chemical processes and / or waste water, etc.), heat from the environment (eg from air, water, eg sea, rivers, etc.) , Lakes and / or groundwater when a colder heat reservoir is available) or other energy sources or heat reservoirs. In addition, there is the capacitor 12b with the cold heat reservoir (eg air and water, eg sea, rivers, lakes and / or groundwater, if a warmer heat reservoir is available) in thermal contact. As a heat collector 12a Any commercially available collector or only a large-area chamber, which is preferably filled with a liquid serve. As with the heat collector 12a can as a capacitor 12b a large-area chamber, which is preferably filled with a liquid or any commercial cooler, are used.

The heat collector 12a is in direct energy exchange with the warm heat reservoir. The carrier liquid, as described in more detail below, transports the heat from the heat collector 12a to the energy storage 14 from which the energy is absorbed and leads to the end of an endothermic process. As energy storage 14 serves a suitable reversible process with the highest possible heat of reaction. This may, for example, be a chemical equilibrium, a dilution or solution equilibrium, the number of process participants not being limited. Chemical equilibrium z. B .: A + B → C + D exergonically I C + D → A + B endergonic II

Dilution equilibrium z. B .:

• A _konz + LM → A _verd + n kJ

  A _conc

  concentrated solution of A

  A _verd

  diluted solution of A

  LM

  solvent

At the energy storage 14 It is a dynamic reversible equilibrium system, in which preferably at least one reactant can be easily separated by a distillation, sublimation or crystallization process. Likewise, any other separation method is possible, for. As extraction, precipitation, chromatographic separation, dialysis, diffusion, filtration, osmotic processes and adsorption or even simple operations such as mixing and demixing. AB ⇌ A + B + n kJ dynamic equilibrium system (energy storage) A _fl. ⇌ A _gasf. distillation process

To stay with the example of a distillation: The storage system is supplied with energy, whereby the component A passes into the gas phase, while the component B in the liquid phase (consisting of AB, A and B) remains. Because the reaction AB ⇌ A + B is an equilibrium reaction, the removal of A disturbs the equilibrium and the reaction begins to run in a directed manner until new equilibrium conditions are established. With the condensation of component A on the capacitor 12b the heat of condensation is released to the cold heat reservoir. A is collected in a separate vessel. For the separation of 1 mol A from the equilibrium system in addition to the heat of vaporization and the Energy of n kJ can be applied to shift the balance in the desired direction. The heat of vaporization is delivered as condensation heat to the cold reservoir, but n kJ / mol remain stored as chemical energy in the form of A and B. The theoretical efficiency of the distillation or any other separation of substances can be determined according to the Carnot cycle according to Eq. 1 determine.

The stored chemical energy of the two separated components of the storage system is in a heat converter, consisting of a reactor 16 and an energy converter 18 , converted into mechanical work. As a heat converter or energy converter 18 For example, steam engines or turbines or any other conventional heat engine. In this case, steam is usually used as the working medium. However, it can also function any other vaporous medium or a flowing liquid as the working medium. To minimize heat losses, the reactor is isolated. The insulation also includes the energy converter, because in contrast to conventional energy conversion, the temperature of the working medium does not change. While in the energy collector 12 the endothermic process of the equilibrium reaction of the energy store 14 expires, is in the reactor 16 the reaction shifts in the exothermic direction.

The reactor 16 preferably consists of at least two chambers that allow heat exchange and in which the reactants are located. If the reactants are brought together, that is in the energy collector 12 stored energy released. The stored chemical energy can theoretically be accessed without loss because the entire machine, including the distillation, is a Carnot machine. In combination with a generator, the inventive devices described in more detail below provide electrical energy. If, however, the energy is stored only for heating purposes, can on the energy converter 18 be waived.

Example 1: Sodium hydroxide / water

The process according to the invention is first explained using the example of caustic soda (storage system - sodium hydroxide solution / water, enthalpy of dilution is exothermic): NaOH _conc + H ₂ O → NaOH + _dil 44.51 kJ (ΔH = -44.51 kJ / mol) NaOH _dil + 44.51 kJ → NaOH + H ₂ O _conc (ΔH = + 44.51 kJ / mol) NaOH · H ₂ O + H ₂ O → NaOH + _dil 21.41 kJ (ΔH = -21.41 kJ / mol)

An inventive device for carrying out this method is in 4 shown. A more detailed representation of the reactor shows the 3 , In the concentration chambers 112 . 114 is hot concentrated sodium hydroxide (boiling point above 170 ° C) with a temperature of, for example, 170 ° C and in a pressure chamber 120 there is water. In the dilution chambers 116 . 118 is dilute sodium hydroxide solution. Because of the heat balance between the chambers, the water is heated and pressure builds up in the pressure chamber or water chamber 120 on. The water vapor relaxes in the energy converter 124 , z. As a steam engine or turbine, while doing work.

In the method according to the invention, the relaxed water vapor over the lines 126 . 128 passed into the hot concentrated caustic soda coming out of the concentration chambers 112 . 114 comes, so then in the dilution chambers 116 . 118 to stream. Concentrated caustic soda is diluted in this process. In addition to the condensation heat, the dilution enthalpy of the sodium hydroxide solution is released, which serves to re-water in the pressure chamber 120 to evaporate. During the energy conversion, the temperature in the reactor and in the energy converter remains constant.

The solution process of the water in caustic soda takes place so abruptly that in the lines 126 and 128 would immediately form a vacuum, which would have the consequence that the caustic soda is drawn into the energy converter. This effect is prevented by the wires 126 and 128 be filled with a gas that dissolves neither in the caustic soda nor in the water. Helium, hydrogen, nitrogen, argon and / or air are preferably used because of the low solubility and the inertness of the reaction. Furthermore, oxygen, methane, noble gases and other gases or gas mixtures are used, which are inert and almost insoluble under the given conditions (pressure and temperature). The bubble generated by the gas prevents the caustic soda from being expelled back into the pipes 126 and 128 or even an intrusion into the energy converter. Processes in the reactor: Process in the pressure chamber 120: H ₂ O _fl → H ₂ O _gasf. Δ _vap H = +2260 kJkg ^-1 Process in the dilution chambers 116, 118: H ₂ O _gasf. → H ₂ O _{fl. Δcond} H = -2260 kJkg ^-1 _{NaOH.H 2} + H ₂ O → NaOH _verd. Δ _s H = -369 kJkg ^-1

Energy balance reactor:

• Δ H _vap + Δ + Δ _fus H _s H = -369 kJkg ^-1 With:

  Δ _vap H

  evaporation

  _Δcond H

  condensation enthalpy

  Δ _s H

  Verdünnungsenthalpie

The energy amount of 369 kJkg ^-1 is converted into work. The enthalpy of vaporization and the enthalpy of condensation are identical under the same conditions with the opposite sign.

The dilute caustic soda solution is replaced when its boiling point drops below 170 ° C, because then no more water can condense in this sodium hydroxide, but it begins to boil itself. The hot dilute sodium hydroxide solution flows through a heat exchanger 216 in the energy collector 210 ,

The dilute sodium hydroxide solution is heated by a heat collector 212 Energy, such as sunlight or even heat supplied. The water condensed in the reactor evaporates and condenses on the condenser 226 which is cooled. In this heat transfer, the dilute sodium hydroxide solution is concentrated and the enthalpy of solution of the sodium hydroxide solution is stored in the form of concentrated sodium hydroxide solution and water. The concentrated caustic soda and the water are returned to the circulation.

The temperature difference between the heat collector and the condenser is given by Eq. 1 the efficiency η of the Carnot machine. For example, with Θ _k = 10 ° C and Θ _w = 200 ° C, a theoretical efficiency of about 40% is obtained.

Because the temperature in the reactor 220 is constant (eg 170 ° C), water can only condense in the concentrated sodium hydroxide solution if the boiling point of the caustic soda solution is above 170 ° C, ie to store energy, therefore, the temperature in the heat collector 212 be higher than in the reactor 220 , If it is underneath, the previously stored energy must be used. Caustic soda and water are used in two separate containers 214 respectively. 228 stored.

There are two options for using colder heat sources, namely a reduction in pressure or azeotropic distillation. Of course, the use of colder heat sources leads to a reduction in the efficiency.

Since it is a closed apparatus, the heat conversion does not necessarily have to be carried out at normal pressure (1013 mbar). By changing the pressure, the boiling point of the sodium hydroxide solution can be adapted to the temperature of the heat source. For example, the boiling point of the caustic soda shifts from 240 ° C at atmospheric pressure to about 90 ° C at 10 mbar. Also, the boiling point of the water (to about 20 ° C) and the temperature in the reactor shift 220 (to about 60 ° C). With a temperature of Θ _k = 10 ° C for the cold heat reservoir and Θ _w = 90 ° C for the hot reservoir, despite the dramatic reduction in the temperature difference, there is still a theoretical efficiency of about 20%.

By adding an inert, water-immiscible solvent also cold heat sources can be used. Toluene is one such solvent. Water and toluene form two phases, with only about 0.1% water in the toluene phase and also only about 0.1% toluene are soluble in the water phase. The Toluene-water azeotrope boils at 85 ° C and consists of 79.8% toluene and 20.2% water. This azeotrope condenses on the capacitor, two phases quickly form. As the toluene is returned to the dilute caustic soda in the heat collector, the water is collected in a separate vessel or sent to the vaporization chamber (reactor).

The combination of a vacuum and the azeotropic distillation allows the use of heat sources with a temperature of only 40 ° C. The theoretical efficiency drops to 9% (with Θ _k = 10 ° C), but there are many more heat reservoirs available at this temperature than at 200 ° C and higher. In addition, the energy is stored primarily in the form of caustic soda and water, which means that the distillation or better just the energy storage with the theoretical efficiency of 9% is afflicted. In the subsequent conversion of the stored energy into mechanical or electrical work, the theoretical efficiency is 100% (in practice the efficiency is somewhat reduced by the pumps used and by friction). For the entire performance of the invention is a Carnot machine whose efficiency is in accordance with Eq. 1 determined. Both heat reservoirs are in the energy collector 210 , ie only the separation of substances is associated with a low efficiency. With the method according to the invention, therefore, even such small heat transfer can be used inexpensively.

Energy Balance Energy Collector Azeotropic Distillation:

Energy balance heat collector:

• Q _intake = Δ _s H + (Δ _vap H _Tol + Δ _vap H _H₂O ) _{heat collector}

Energy balance capacitor:

• Q _output = - (Δ _kond H _Tol + Δ _kond H _H₂O ) _capacitor

Energy balance energy collector:

• Q _absorption = Δ _s H + Q _delivery
• Q _storage = Δ _s H With:

  Δ _vap H

  evaporation

  _Δcond H

  condensation enthalpy

  Δ _s H

  Verdünnungsenthalpie

  Q

  warmth

The _{amount of} energy Δ _vap H _Tol + Δ _vap H _H₂O is delivered to the cold heat reservoir. With the separation of the water, the sodium hydroxide solution is concentrated and thus stored the solution enthalpy. The concentrated sodium hydroxide solution is returned to the circulation. To complete the closed cycle, the water is returned.

Total energy balance:

• W = Q _recording - (Δ _vap H _Tol + Δ _vap H _H₂O ) _capacitor = Δ _s H

Δ _s H of solution Tol toluene Δ _vap H evaporation H ₂ O water

In the present description, the water is both working medium and reactant. These two functions can be taken over by different substances. A multi-circuit system in which the water only performs the function of a reaction participant is in 5 shown. The working medium, which may be different from water, remains spatially separate from the other processes.

The water represents the working medium in the upper circuit, which consists of an evaporation zone 326 , an energy converter 328 , a condensation zone 330 and possibly a pump 332 exists, which are in fluid communication with each other via lines. The water is in the evaporation zone 326 evaporated, done in the energy converter 328 Work and cool in the condensation zone 330 continue down. By means of a pump 332 or even by gravity, the condensed water is again fed to the evaporation zone. The lower circuit consists of a chamber 310 in which the endothermic process takes place, a reservoir with concentrated caustic soda 312 , a capacitor 322 , a chamber with water as a reactant 320 , a heat exchanger 318 , a chamber 314 , in which the exothermic process takes place, a reservoir of dilute sodium hydroxide solution 324 and at least one pump 316 (only one shown), these elements, as in 5 represented, in fluid communication with each other. The heat exchanger 318 and the chamber 314 , in which the exothermic process takes place, are each in thermal communication with the condensation zone 330 or the evaporation zone 326 of the first cycle.

The device according to the invention 300 is about the chamber 310 , in which the endothermic process takes place, energy, for example, sunlight supplied. This energy causes the dynamic equilibrium to shift into the endothermic direction. In the in 5 This embodiment means that from the dilute sodium hydroxide solution (reservoir 324 ) the water is withdrawn and the condenser 322 condensed. The efficiency of the separation of substances can be calculated from the temperature of the chamber 310 and the temperature of the capacitor 322 to calculate. The products resulting from the separation of substances, concentrated caustic soda and water, are passed through the reservoirs 312 respectively. 320 and the heat exchangers 313 respectively. 318 the chamber 314 fed, in which the exothermic process takes place, whereby the sodium hydroxide solution is diluted again. This results in an energy release, via the thermal connection of the chamber 314 with the evaporation zone 326 the first circuit to the working medium located there, such as water, communicates, whereby the water is heated and evaporated. The dilute caustic soda is countercurrently through the heat exchanger 313 the reservoir 324 fed, in turn, with the chamber 310 connected, in which the endothermic process takes place.

While the Einkreislaufsystem, ie the inventive device in 4 , only one Carnot engine is set in the multi-cycle system 5 two coupled Carnot machines. The efficiency of the upper-cycle heat-exchanger depends on the temperature difference between the evaporation zone 326 and the condensation zone 330 However, the efficiency has already been diminished in the first cycle of energy storage. With the feedback from the condensation zone 330 to the heat exchanger 318 the unconverted heat is returned to the conversion process. A full use of the stored energy as in the single-circuit system can only be achieved with 100% heat transfer.

In the device according to the invention 400 from 6 serves dissolved in a liquid gas as the working medium, eg. As the system carbon dioxide dissolved in acetone or the system methane dissolved in n-pentane or the equilibrium dinitrogen tetroxide / nitrogen dioxide dissolved in nitroethane. Here, the temperature-dependent solubility of gases in liquids is exploited. In the following, only the upper cycle of 6 described, consisting of the hot zone 410 , a heat exchanger 412 , a pump 414 , the cold zone 416 and an energy converter 418 , These elements are in fluid communication with each other via lines. Because of the temperature difference, the concentration of dissolved gas is in the hot zone 410 and in the cold zone 416 differently. Gases dissolve at the boiling point of a liquid worse than near the fixed point. This is why there is a gas-rich solution in the cold zone and a low-gas solution in the hot zone. With the pump 414 the liquid is transferred through the heat exchanger 412 circulated in countercurrent, causing the gas-rich solution in the hot zone 410 and the low-gas solution in the cold zone 416 arrives. The dissolved gas will be in the hot zone 410 expelled from the solution and performed in the energy converter 418 Work and then dissolves in the cold zone 416 , Analogous to the device 100 is also in the device according to the invention 400 In addition, an inert gas filled to prevent excessive increase of the liquid in the pipe 420 or even to prevent penetration into the energy converter. Preferably, helium and / or hydrogen is used for this purpose. About the second cycle described above, the energy is supplied, in high-energy time via alternative energy sources or any other heat source.

Example 2: sulfuric acid / water

The process according to the invention will now be explained using the example of the system sulfuric acid / water (storage system - sulfuric acid / water, enthalpy of dilution is exothermic): H ₂ SO _{4 conc} + H ₂ O → H ₂ SO _4verd + 95.33 kJ (ΔH = -95.33 kJ / mol) H ₂ SO _{4 conc} + 95.33 kJ → H ₂ SO _4verd + H ₂ O (ΔH = +95.33 kJ / mol) M _G = 98.072 gmol ^-1 → 0.972 kJ / g → 0.972 MJ / kg (M _G = molar mass)

A device according to the invention for carrying out this method is again the one in 4 illustrated device. A more detailed description of a possible reactor again shows the 3 , In the concentration chambers 112 . 114 is hot concentrated sulfuric acid (boiling point above 170 ° C) with a temperature of for example 170 ° C and in a pressure chamber 120 there is water. In the dilution chambers 116 . 118 is dilute sulfuric acid. Because of the heat balance between the chambers, the water is heated and pressure builds up in the pressure chamber or water chamber 120 on. The steam relaxes in the energy converter 124 (eg a steam engine or turbine) and doing work.

According to the method of the invention, the relaxed water vapor over the lines 126 . 128 passed into the hot concentrated sulfuric acid coming out of the concentration chambers 112 . 114 comes to the dilution chambers 116 . 118 to stream. During this process, concentrated sulfuric acid is diluted. In addition to the heat of condensation, the dilution enthalpy of the sulfuric acid is released, which serves to re-water in the pressure chamber 120 to evaporate. During the energy conversion, the temperature in the reactor and in the energy converter remains constant.

Δ_vapH

Verdampfungsenthalpie

Δ_kondH

Kondensationsenthalpie

Δ_sH

Verdünnungsenthalpie

Analogously to the example of caustic soda / water, an inert gas is also filled in here to create a permanent gas bubble in the lines 126 and 128 to maintain. This prevents the penetration of sulfuric acid into the energy converter. Preferably, helium and hydrogen are introduced as the inert gas. Process in the pressure chamber 120: H ₂ O _fl → H ₂ O _gasf. Δ _vap H = +2260 kJkg ^-1 Process in the sulfuric acid chambers 116, 118: H ₂ O _gasf. → H ₂ O _{fl. Δcond} H = -2260 kJkg ^-1 H ₂ SO _{4 conc} + H ₂ O → H ₂ SO _4verd. Δ _s H = -972 kJkg ^-1 Δ H _vap + Δ + Δ _fus H _s H = -972 kJkg ^-1 With:

Δ _vap H

evaporation

_Δcond H

condensation enthalpy

Δ _s H

Verdünnungsenthalpie

The energy amount of 972 kJkg ^-1 is converted into work. The enthalpy of vaporization and the enthalpy of condensation are identical under the same conditions with the opposite sign.

The diluted sulfuric acid is exchanged when its boiling point falls below 170 ° C, because then no more water can condense in this sulfuric acid, but it begins to boil itself. The hot dilute sulfuric acid flows through the heat exchanger 216 in the energy collector 210 , The dilute sulfuric acid is using a heat collector 212 Energy, z. As sunlight, fed. The water condensed in the reactor evaporates and condenses on the condenser 226 which is cooled. In this heat transfer, the dilute sulfuric acid is concentrated, and the solution enthalpy of sulfuric acid is stored in the form of concentrated sulfuric acid and water. The concentrated sulfuric acid and the water are returned to the circulation.

Analogously to Example 1 (caustic soda / water), the use of cold heat sources is possible by means of pressure change and azeotropic distillation.

Example 3: Ammonia / water

The process according to the invention will now be explained using the example of the ammonia-water system (storage system - ammonia / water, solution enthalpy is exothermic): NH _{3 gasf.} + H ₂ O → NH _3aq + 30.50 kJ (ΔH = -30.50 kJ / mol) NH _3aq + 30.50 kJ → NH _{3 gasf.} + H ₂ O (ΔH = +30.50 kJ / mol) M _{G NH3} = 17.031 gmol ^-1 → 1.791 kJ / g → 1.791 MJ / kg (M _{G NH3} = molar mass)

A device according to the invention for carrying out this method is again the one in 4 illustrated device. A more detailed description of a possible reactor again shows the 3 , Under normal conditions, ammonia is a gas that liquefies due to pressure increase and dissolves extremely easily in water with strong heat of reaction (see Table 1). In contrast to the first two examples (caustic soda / water and sulfuric acid / water) in the example of water / ammonia, the ammonia is the working medium and not the water. To condense ammonia on the condenser, the system is under pressure. The overpressure depends on the temperature of the cold reservoir and is usually kept above 5 bar. melting point -78 ° C molar mass 17.03 g / mol Critical temperature 132.4 ° C Critical pressure 113 bar Vapor pressure at 21 ° C 8.9 bar Solubility in 1 kg of water at 0 ° C (1012 mbar) 899 g (52.8 mol) Solubility in 1 kg of water at 20 ° C (1012 mbar) 518 g (30.4 mol) Solubility in 1 kg of water at 100 ° C (1012 mbar) 74 g (4.3 mol) Table 1: Physico-chemical data of ammonia

The concentrated ammonia solution is in the energy collector 210 separated into liquid ammonia and low-ammonia water. This is done by supplying energy to the heat collector 212 , z. As solar energy, and by cooling the capacitor 226 , At the condenser separates liquid ammonia. With the separation of substances, the heat of solution of the ammonia is stored in water. The two separate liquids pass over the reservoirs 214 (for water) and 228 (for ammonia) as well as the heat exchanger 218 in the reactor 220 , The ammonia relaxes in the energy converter 222 (For example, a steam engine or turbine) and then dissolves in low-ammonia water. For this process, on the one hand, the heat of evaporation of the ammonia is needed and on the other hand, the stored solution heat and the heat of condensation is released. The condensation heat and the heat of vaporization are identical in magnitude only with the opposite sign. Thus, the enthalpy of solution is converted into work. The ammonia-rich solution returns via the heat exchanger 218 and the reservoir 224 in the chamber 212 in which the endothermic process takes place.

Δ_vapH₂₅

Verdampfungsenthalpie bei 25°C

Δ_kondH₂₅

Kondensationsenthalpie bei 25°C

Δ_SolH

Lösungsenthalpie

In this example, an inert gas is additionally introduced to a permanent gas bubble in the pipes 126 and 128 maintained, so that a return of the water is prevented in the energy converter. Preferably, helium and hydrogen are used as the inert gas. Process in the pressure chamber 120: NH _3fl → NH _{3 gasf.} Δ _vap H ₂₅ = +19.86 kJmol ^-1 → 1166 kJ / kg Process in the water chamber 116, 118: NH _{3 gasf.} → NH _{3fl. Δcond} H ₂₅ = -19.86 kJmol ^-1 → -1166 kJ / kg NH _{3 gasf.} + H ₂ O → (NH ₃ ) _aq. Δ _Sol H = -30.50 kJ mol ^-1 → -1790 kJ / kg Δ H _vap + Δ + Δ _fus H _s H = -1790 kJkg ^-1 With:

Δ _vap H ₂₅

Evaporation enthalpy at 25 ° C

Δ _cond H ₂₅

Condensation enthalpy at 25 ° C

Δ _Sol H

of solution

The equilibrium system ammonia / water can also be used with in 6 illustrated device according to the invention can be used. It is about the hot zone 410 , in which there is an ammonia-rich solution, the system energy, z. As solar energy supplied. Because it is an equilibrium reaction, the equilibrium shifts towards ammonia (gas) and water. Pressure builds up. In the cold zone 416 , which is in thermal contact with the cold heat reservoir, is a cold ammonia solution. Here, the equilibrium is shifted in exothermic direction (dissolving NH ₃ in water). The hot zone 410 and the cold zone 416 are about the heat engine 418 and the heat exchanger 412 connected. The entire apparatus is closed and does not allow any mass transfer with the environment. Due to the temperature difference between the two heat reservoirs, the working medium (in this case ammonia) performs the heat engine 418 Job. The working fluid (ammonia) dissolves in the water, which is then diverted away to prevent the system from becoming equilibrated. Ammonia-rich solution from a cold zone 416 becomes a hot zone through a heat exchanger 410 returned, while it is brought in countercurrent process of hot ammonia-poor solution to the temperature of the warm heat reservoir. In contrast, the low-ammonia solution in the heat exchanger cools to the temperature of the cold reservoir. To prevent excessive ingress of water into the pipe 420 To avoid helium or hydrogen is preferably introduced as an inert gas.

The efficiency η of this heat engine can be analogous to Eq. 1 determine. With this method can not save energy, but only convert.

In addition to the equilibrium systems given in the preceding examples, Table 2 contains further examples of exothermic equilibrium systems. working medium storage medium Δ _s H o. _Sol Δ H / kJ / mol Δ _s H o. _Sol Δ H / kJ / kg HCl water -74.84 -2050 SO ₂ water -29 -453 HBr water -85.14 -1,052 HF water -61.5 -3,075 HI water -81.87 -640 water LiCl · H ₂ O -19.08 -315 water LiBr · H ₂ O -23.26 -222 water LiI · H ₂ O -29.66 -195 water LiOH -23.56 -982 water KOH · H ₂ O -14.64 -198 water RbOH · H ₂ O -17.99 -149 Table 2: Exothermic equilibrium systems

Example 4: Dissolution of Chemical Compounds in Solvents with Positive Solution Enthalpy

The process according to the invention will now be illustrated by the example of the dissolution of potassium nitrate (KNO ₃ ) in water and a separate working medium (eg dichloromethane) (storage system - potassium nitrate-water / acetonitrile, solution enthalpy is endothermic, the temperature dependence of the solubility of potassium nitrate in water is shown in Table 3): KNO _{3 solid} + H ₂ O + 34.89 kJ → KNO _3aq (ΔH = +34.89 kJ / mol) KNO _3aq → KNO _{3 solid} + H ₂ O + 30.50 kJ (ΔH = -34.89 kJ / mol) M _{G KNO3} = 101.102 gmol ^-1 → 0.345 kJ / g → 0.345 MJ / kg (M _{G KNO3} = molar mass)

Tabelle 3: Temperaturabhängigkeit der Löslichkeit von Kaliumnitrat in Wasser

Table 3: Temperature dependence of the solubility of potassium nitrate in water

To carry out the method, in the 4 and 5 use illustrated devices according to the invention. The method is based on the inventive device of 5 explained.

In the upper circuit is the working medium, an easily evaporable liquid, eg. For example, dichloromethane. The upper circuit is characterized by being from the evaporation zone 326 , the energy converter 328 , the condensation zone 330 and the pump 332 where the elements are in fluid communication with each other via conduits. The dichloromethane is in the evaporation zone 326 evaporated, done in the energy converter 328 Work and cool in the condensation zone 330 continue down. By means of the pump 332 The condensed dichloromethane is in turn the evaporation zone 326 fed.

The lower circuit consists of the chamber 310 in which the endothermic process takes place, the reservoir with concentrated potassium nitrate solution at ambient temperature 312 , the heat exchanger 313 , the chamber 314 in which the exothermic process takes place, the reservoir for a low potassium nitrate concentration acetonitrile-water mixture 324 , the reservoir for acetonitrile 320 , the capacitor 322 , the heat exchanger 318 as well as the at least one pump 316 (only one shown), these elements, as in 5 represented, in fluid communication with each other.

By adding acetonitrile, it is possible to remove the potassium nitrate from the aqueous solution and thus release the stored energy, because the dissolution process of potassium nitrate in water is endothermic, which is why the reaction enthalpy, the precipitation of the dissolved salt, the solution enthalpy is free again.

The chamber 314 , in which the exothermic process takes place, is in thermal communication with the evaporation zone 326 of the first cycle.

The device according to the invention 300 is about the chamber 310 in which the endothermic process takes place, energy, for example, sunlight or even heat supplied. This energy causes the balance to shift to the endothermic direction. In the in 5 As shown, this means that acetonitrile from the acetonitrile-water mixture from the reservoir 324 Will get removed. The acetonitrile (water and acetonitrile boil azeotropically, therefore it is actually a mixture) condenses on the condenser 322 and will be in a separate container 320 collected. That in the chamber 310 Remaining water is now able to dissolve potassium nitrate. The dissolution process is also endothermic.

Upon further heating of the potassium nitrate solution, the solubility of the salt improves and thus energy is stored in the potassium nitrate solution.

In order to release the stored energy, the concentrated potassium nitrate solution is diluted with the acetonitrile produced during the endothermic process. The potassium nitrate precipitates abruptly, and it comes to the energy delivery to the over the chamber 314 in thermal connection evaporation zone 326 of the first cycle. The working medium, z. As dichloromethane, is heated, evaporated and performed work.

The potassium nitrate-lean water-acetonitrile mixture is countercurrent to the feed with concentrated potassium nitrate solution into the chamber 324 led, in turn, with the chamber 310 connected, in which the endothermic process takes place.

In addition to the equilibrium system given in the preceding example, Table 4 contains further examples of endothermic equilibrium systems.

By precipitation of the salt with any organic solvent, such as. As acetone, alcohols, nitroalkanes, tetrahydrofuran, dioxane, etc., the stored energy of the concentrated salt solutions is released, the concentrated salt solution contains as solvent water or another solvent. salt Molecular weight / g / mol Δ _s H o. Δ _sol H kJ / mol Solubility at 0 ° C in g / 100 g water Solubility at 100 ° C in g / 100 g Temp dep. Solubility / g Temp dep. Solubility / mol Storage capacity of saline solution / kJ NH ₄ Cl 53.5 14.78 29.74 76.18 46.45 0.8683 12.83 NH ₄ ClO ₄ 117.5 33.47 12:11 87.27 75.16 0.6397 21:41 NH ₄ Br 97.9 16.78 60.00 134.74 74.74 0.7631 12.80 NH ₄ NO ₃ 80.0 25.69 117.39 930.93 813.54 10.1678 261.21 LiClO ₄ 90.4 32.61 43.06 249.65 206.59 2.2855 74.53 NaClO ₃ 106.4 21.72 79.44 203.95 124.51 1.1698 25.41 NaClO ₄ 122.4 22:51 162.47 329.18 166.72 1.3616 30.65 CaCl ₂ 111.0 14:40 57.98 149.63 91.65 0.8258 11.89 NaBrO ₃ 150.9 26.90 25.00 73.97 48.97 0.3246 8.73 NaBr 102.9 18.64 79.86 121.73 41.87 0.4070 7:59 NaNO ₃ 85.0 20:50 73.01 176.24 103.23 1.2146 24.90 NaNO ₂ 69.0 13.89 72.12 161.78 89.66 1.2996 18.5 NaC ₂ H ₃ O ₂ 82.0 19.66 36.05 169.54 133.49 1.6272 31.99 KClO ₃ 122.5 41.38 3.12 57.85 54.73 0.4466 18:48 KClO ₄ 138.5 51.04 0.70 22.96 22:25 0.1606 8.20 KBr 119.0 19.87 53.85 103.25 49.41 0.4152 8.25 KCl 74.6 17:22 27.78 56.37 28.59 0.3835 6.60 KBrO ₃ 167.0 41.13 3:06 49.88 46.82 0.2804 11:53 KI 166.0 20:33 127.27 206.75 79.48 0.4788 9.73 KIO ₃ 214.0 27.74 4.74 31.63 26.89 0.1256 3:48 KNO ₂ 85.1 13:35 280.23 402.51 122.28 1.4369 19:18 KNO ₃ 101.1 34.89 13.64 242.47 228.83 2.2633 78.97 KMnO ₄ 158.0 43.56 2.82 22:19 19:37 0.1226 5:34 CsNO ₃ 194.9 40.00 9.24 195.86 186.62 0.9575 38.30 CsClO ₄ 232.4 55.44 0.80 29.99 29.19 0.1256 6.96 RbNO ₃ 147.5 36.48 19.62 431.91 412.30 2.7958 101.99 RbClO ₃ 168.9 47.74 2.15 62.87 60.72 0.3595 17:16 RbBrO ₃ 213.5 48.95 0.98 26.20 25.22 0.1181 5.78 CsI 259.8 33.35 44.72 224.68 179.96 0.6927 23:10 RbI 212.4 25.10 126.24 281.68 155.44 0.7319 18:37 CsBrO ₃ 260.8 50.46 1.17 35.10 33.93 0.1301 6:56 Table 4: Temperature dependence of the solubility of salts in water (endothermic systems)

Example 5: Gas dissolved in a liquid as a working medium

To carry out this example can be in the 6 use illustrated device according to the invention.

The lower cycle has been explained in detail with respect to Examples 1 and 4 above. In the upper circuit is the working fluid, dissolved in a liquid gas, eg. As the system carbon dioxide dissolved in acetone or the system methane dissolved in n-pentane or the equilibrium dinitrogen tetroxide / nitrogen dioxide dissolved in nitroethane. At the boiling point of the solvent (acetone, n-pentane, nitroethane), the gases (carbon dioxide, methane, nitrogen dioxide) are poorly soluble. Upon cooling, the solubility of the gases in the liquid improves. Close to the fixed point of the liquid, gases dissolve best.

The upper circuit is characterized by being out of the hot zone 410 , the energy converter 418 , the cold zone 416 , the heat exchanger 412 and the pump 414 where the elements are in fluid communication with each other via conduits. The dissolved gas will be in the hot zone 410 expelled from the liquid at high temperature. The gas performs in the energy converter 418 Job. In the cold zone 416 is located at low temperature, the low-gas solvent, which is why after completion of the work, the gas dissolves again in the solvent. By means of the pump 414 This gas-rich solution is passed through the heat exchanger 412 in the hot zone 410 returned. This happens in countercurrent, ie the hot low-gas liquid (eg acetone, n-pentane, nitroethane) from the hot zone 410 heats cold gas-rich solution from the cold zone 416 , To prevent the liquid from entering the pipe 420 to avoid, there is a bubble of inert gas, preferably helium or hydrogen.

Of the systems described, the equilibrium dinitrogen tetroxide / nitrogen dioxide system is a peculiarity: N ₂ O ₄ ⇌ 2NO ₂

In the liquid and in the solid state of matter practically only dinitrogen tetroxide (mp: -9.3 ° C. bp: 21.15 ° C.) is present, which thermally dissociates into twice the number of moles of nitrogen dioxide (above 21.15 ° C. under normal pressure) and thus a particularly advantageous procedure allows the inventive method. This process is completely reversible, leaving in the hot zone 410 Nitrogen dioxide is produced and in the cold zone 416 reacts to dinitrogen tetroxide, which is then returned to the hot zone by means of the solvent nitroethane as described 410 to be led.

Because the heat of the equilibrium systems methane / pentane, carbon dioxide / acetone and dinitrogen tetroxide / nitrogen dioxide / nitroethane is low compared to the other described equilibrium systems (eg ammonia / water), their application to a continuous energy supply or an external invention Energy storage instructed. The decisive advantage of these equilibrium systems, however, is the low fixed point of the solvents acetone (mp: -94.7 ° C b.p .: 56.05 ° C), pentane (-129.67 ° C b.p .: 36.06 ° C) and nitroethane (mp: -89 , 5 ° C bp: 114.0 ° C). As a result, energy storage systems whose temperature is below the freezing point of the water can be used with good efficiency.

In the cold regions of the earth, frozen oceans, lakes or even groundwater with a temperature around the freezing point of the water are available as "warm" heat reservoirs. The outside temperature is often far below. This heat transfer is in accordance with the device according to the invention 6 very good to use. With temperatures of Θ _W = 0 ° C and Θ _k = -40 ° C, the theoretical efficiency is approx. 15%.

M_G

Molare Masse

Klassische Energieträger: Brennwert Braunkohle: 8,5 MJ/kg Vergaserkraftstoff: 47 MJ/kg The energy storage capacity of the equilibrium systems caustic soda / water (Example 1) and water / ammonia (Example 3) is considered below. In low energy time, z. As in winter, at night or even in windy winds, energy that is stored in the concentrated sodium hydroxide solution or liquid ammonia can be removed by dilution with water. Verdünnungsenthalpie Δ _s H _{NaOH ·} H 2 O = -21.41 kJ / mol M _G = 58.012 g / mol → 0.369 kJ / g → 369 MJ / t Verdünnungsenthalpie ΔH _NH3 = -30.50 kJ / mol M _{G NH3} = 17.031 gmol ^-1 → 1.791 kJ / g → 1791 MJ / t With

M _G

Molar mass

Classic energy sources: condensing Brown coal: 8.5 MJ / kg Gasoline: 47 MJ / kg

Tabelle 5: Verhältnis der Energieinhalte

Table 5: Ratio of energy contents

Of course, the storage capacities of caustic soda and ammonia are lower compared to conventional energy sources (see Table 5). It requires 23 times the amount of sodium hydroxide or 4.7 times the amount of ammonia to store the energy content of lignite. For carburetor fuel, the ratio is 127: 1 (sodium hydroxide solution) or 26: 1 (ammonia). However, the combustion processes of classical energy sources are irreversible. A particular advantage of the method according to the invention is that the processes are reversible. In contrast to a vehicle with an internal combustion engine, which consumes fuel at the traffic light with the engine running, a vehicle with a "soda lye engine" fills the energy storage, eg. B. by solar energy on. It should be mentioned here that statistically speaking, passenger cars are only moved one hour a day on average. During their lifetime, the surface of these vehicles for receiving energy that can be stored by the method according to the invention is available.

It is also advantageous that the energy of the "soda lye engine" is constantly available, it does not have to be extracted extra from mines or on oilfields. In addition, no further treatment processes are required, such as extraction, distillation or conversion of materials; the energy is generated directly as mechanical work or in combination with a generator as electrical energy. Here it should be emphasized that the "sodium hydroxide engine" from the outset is an emission-free engine. It stores accumulating heat in the form of a reversible equilibrium system and then converts this stored energy into mechanical or electrical energy. All sources of energy are available, including low-temperature energy reservoirs. In principle, any reversible dynamic equilibrium with a non-zero heat of reaction can be used as an energy store, ie. H. it is also not bound to the solvent and / or the reactant water.

The present invention relates to a system for generating mechanical or electrical energy, which consists of a combination of the following components: heat collector, condenser, heat exchanger and a storage system for energy, the task of which is met by a suitable reversible dynamic equilibrium process, and an energy converter, a steam engine or steam turbine for converting the stored energy into work, wherein the heat generated in addition to the work (solution and condensation heat) is returned to the storage system.

Claims (30)

An emission-free and cyclic closed-loop method of storing energy, characterized in that the method comprises the steps of: a) supplying a heat energy Q from a first arbitrary heat reservoir to a heat collector; b) separating a storage medium into at least two components by means of the supplied heat energy Q; c) releasing an amount of heat containing the Entropieterm to a second heat reservoir having a lower temperature than the first heat reservoir; d) storing the remaining energy in the form of the at least two separated components or working media; e) establishing a pressure difference between the separated components, wherein by heating above the boiling point of a component, the pressure difference can be increased; f) relaxing the vaporized component in an energy converter, preferably a steam engine or a steam turbine; g) condensing the vaporized component in the second component of the storage medium, thereby liberating the heat of condensation and the heat of solution; h) using the heat of condensation and the heat of solution in the heating of the two separated components in step e); and i) returning the recombined storage medium to the heat collector at step a); j) Use of the energy stored after step d) in the form of heat by recycling the separated components using a suitable dynamic reversible equilibrium system as the storage medium. A method according to claim 1, characterized in that is used as the dynamic equilibrium system, the solubility and the temperature-dependent solubility of gases, salts, acids, bases or other chemical compounds and mixtures thereof with negative or positive heat of reaction in water or another solvent. A method according to claim 1 or 2, characterized in that as a dynamic equilibrium system, a chemical reaction equilibrium is used. A method according to claim 1 or 2, characterized in that the dynamic equilibrium system used is a combination which is selected from the group consisting of: sodium hydroxide solution and water; Sulfuric acid and water; Caustic potash and water; Lithium hydroxide and water; Rubidium hydroxide and water; Cesium hydroxide and water; Hydrogen chloride and water; Hydrogen bromide and water; Hydrogen iodide and water; Hydrogen fluoride and water; Sulfur dioxide and water; Lithium chloride and water or an analogous solvent; Lithium bromide and water or an analogous solvent; Lithium iodide and water or an analogous solvent; Ammonia and water; Sulfur trioxide and sulfuric acid; Potassium nitrate / water and an organic solvent; Ammonium chloride / water or an analogous solvent and an organic solvent; Ammonium perchlorate / water or an analogous solvent and an organic solvent; Ammonium bromide / water or an analogous solvent and an organic solvent; Ammonium nitrate / water or an analogous solvent and an organic solvent; Lithium perchlorate / water or an analogous solvent and an organic solvent; Sodium chlorate / water and an organic solvent; Sodium perchlorate / water and an organic solvent; Calcium chloride hexahydrate / water and an organic solvent; Magnesium chloride / water and an organic solvent; Sodium bromate / water and an organic solvent; Sodium bromide / water and an organic solvent; Sodium nitrate / water and an organic solvent; Sodium nitrite / water and an organic solvent; Sodium acetate / water and an organic solvent; Potassium chlorate / water and an organic solvent; Potassium perchlorate / water and an organic solvent; Potassium bromide / water and an organic solvent; Potassium chloride / water and an organic solvent; Potassium bromate / water and an organic solvent; Potassium iodide / water and an organic solvent; Potassium iodate / water and an organic solvent; Potassium nitrite / water and an organic solvent; Potassium nitrate / water and an organic solvent; Potassium permanganate / water and an organic solvent; Cesium nitrate / water and an organic solvent; Cesium perchlorate / water and an organic solvent; Rubidium nitrate / water and an organic solvent; Rubidium chlorate / water and an organic solvent; Rubidium bromate / water and an organic solvent; Cesium iodide / water and an organic solvent; Rubidium iodide / water and an organic solvent; Cesium bromate / water and an organic solvent. A method according to claim 4, characterized in that the stored energy is released by the fact that the dissolved salt is precipitated with an organic solvent or solvent mixture. Method according to one of the preceding claims, characterized in that an at least partially miscible with water organic solvent or solvent mixture is used for precipitation, comprising acetonitrile, acetone, tetrahydrofuran, dioxane, methanol, ethanol, n-propanol, iso-propanol, n-butanol , 2-butanol, tert-butanol, pentanol, allyl alcohol, benzyl alcohol, polyethylene glycol, glycol, amines, amides, nitroalkanes or the like. A method according to claim 2 or 3, characterized in that the dynamic equilibrium system used is a combination of solubility and temperature-dependent solubility in conjunction with a chemical reaction equilibrium. A method according to claim 2 or 3, characterized in that as a chemical equilibrium, for. For example, ester formation, lactone cleavage, proton-transition reactions, or the like is used. Method according to one of the preceding claims, characterized in that a suitable working medium is used in a heat engine for mechanical Arbeitsverrichtung. A method according to claim 9, characterized in that the working medium is an easily vaporizable substance or an easily evaporable substance mixture which is present separated from the storage medium, such. As alcohols, fluorinated and halogenated hydrocarbons, alkanes and cycloalkanes, ethers, esters, amines and aromatic hydrocarbons or the like is used. A method according to claim 9, characterized in that the working medium is an easily liquefied gas or an easily liquefied gas mixture which is present separated from the storage medium, such as. As sulfur dioxide, sulfur hexafluoride, carbon disulfide, lower alkanes and cycloalkanes, amines, carbon dioxide and carbon monoxide is used. A method according to claim 9, characterized in that as working medium gases which dissolve depending on the temperature in liquids, such as. As methane, ethane, lower alkanes and cycloalkanes, amines, carbon dioxide and carbon monoxide are used. A method according to claim 12, characterized in that the liquid in which the gases dissolve depending on temperature, is an organic solvent with a low fixed point, such. As alkanes (propane, butane, pentane, hexane, heptane), acetone, alcohols (methanol, ethanol, propanol, iso-propanol, butanol) and / or halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, etc.) and / or nitroalkanes (nitromethane , Nitroethane). A method according to claim 9, characterized in that a substance is used as the working medium, which is the same reaction medium, which is selected from the group consisting of: ammonia, hydrogen chloride; bromide; Hydrogen iodide, hydrogen fluoride, sulfur dioxide, sulfur trioxide, water, methanol, ethanol, acetonitrile, isopropanol, n-propanol, amines or the like. Method according to one of the preceding claims, characterized in that a tractor for removing the working medium is used, with which the working medium boils azeotrope. A method according to claim 15, characterized in that a water tractor is added as a tractor. A method according to claim 16, characterized in that a water-immiscible miscible solvent or solvent mixture, such as. As aromatic hydrocarbons, ethers, esters, alcohols, amines and the like is added. A method according to claim 16, characterized in that as water trawler an infinitely miscible with water solvent or solvent mixture, such as. As acetone, acetonitrile, tetrahydrofuran, dioxane, amines, alcohols, nitroalkanes, etc., is added. A method according to claim 1, characterized in that the energy source is selected from the group consisting of: heat and waste heat from chemical reactions; Solar energy; geothermal energy; Wind energy; biogas; Nuclear energy; Fusion energy; fossil resources; renewable resources; Groundwater and surface water; Ambient heat or other energy sources. A method according to claim 1, characterized in that the cold heat reservoir is selected from the group consisting of: ground and surface water or ambient air. Method according to one of the preceding claims, characterized in that a gas bubble of inert gas separates the two working media. A method according to claim 21, characterized in that as inert gas a gas selected from the group: hydrogen, noble gases, oxides, z. As carbon monoxide, carbon dioxide, nitrogen oxides, oxygen, nitrogen, sulfur hexafluoride. Method according to one of the preceding claims, characterized in that the substance separation according to known methods, such as. As distillation, extraction, crystallization, sublimation, precipitation, chromatographic separation, dialysis, diffusion, filtration, osmotic processes, adsorption and segregation, takes place as Carnot process and is used for energy storage. Contraption ( 10 ) for storing energy and converting this energy into mechanical or electrical energy by the method of claim 1, characterized in that the device ( 10 ) an energy collector ( 12 ), consisting of heat collector ( 12a ) and capacitor ( 12b ), an energy store ( 14 ), a reactor ( 16 ) and an energy converter ( 18 ), wherein the released after the energy conversion condensing and solution heat energy storage ( 14 ) is returned. Contraption ( 100 ) for storing energy and converting this energy into mechanical or electrical energy by the method of claim 1, characterized in that the device ( 100 ) a pressure chamber ( 120 ), an energy converter ( 124 ), a concentration chamber ( 112 . 114 ) and a dilution chamber ( 116 . 118 ), which is in thermal contact with the pressure chamber has, wherein these components are configured, arranged and connected to each other via lines that one in the pressure chamber ( 120 ) heated first working medium in the energy converter ( 124 ) performs mechanical or electrical work, the relaxed first working medium then in the dilution chamber ( 116 . 118 ) a second working medium emerging from the concentration chamber ( 112 . 114 ) and diluted in the dilution chamber ( 116 . 118 ) released energy from the first working medium in the pressure chamber ( 120 ) is recorded. Contraption ( 200 ) for storing energy and converting this energy into mechanical or electrical energy by the method of claim 1, characterized in that the device ( 200 ) an energy collector ( 210 ), consisting of heat collector ( 212 ) and capacitor ( 226 ), a reservoir for a first working medium ( 228 ), a reservoir for a second working medium ( 214 ), a reservoir for the reaction medium ( 224 ), a pump ( 216 ), a heat exchanger ( 218 ), a reactor ( 220 ) and an energy converter ( 222 ) and a generator (not shown), which are each in fluid communication with each other and that the heat collector ( 212 ) and the capacitor ( 226 ) are each in thermal contact with a hot and cold heat reservoir, whereby a reaction medium separates into two working media and thereby stores energy, which then via the separate working media via two separate, but in thermal contact lines through a heat exchanger ( 218 ) to the reactor ( 220 ), whereby a working medium in the reactor ( 220 ) evaporates, in the energy converter ( 222 ) Performs work, then condensed in the second working medium and thereby releases the stored energy in the form of heat of reaction, enthalpy of mixing or other amounts of heat in addition to the heat of condensation and returns this energy to the first working medium. Contraption ( 400 ) for converting heat into mechanical or electrical energy by the method of claim 1, characterized in that the device ( 400 ) from a circuit with a hot zone ( 410 ), a heat exchanger ( 412 ), a pump ( 414 ) and a cold zone as well as a bypass, which is the hot zone ( 410 ) and the cold zone ( 416 ) with an energy converter ( 418 ), where in the hot zone ( 410 ) a gas is driven by heat from a liquid and flows into the bypass, in the energy converter ( 418 ) Work, while the hot low-gas liquid through the heat exchanger ( 412 ) into the cold zone ( 416 ) is pumped to there to dissolve the gas flowing out of the heat engine again, and then as a gas-rich liquid through the heat exchanger ( 412 ) into the hot zone ( 410 ) to get. Contraption ( 200 ) for storing energy and releasing this energy as heat by the method of claim 1, characterized in that the device ( 200 ) an energy collector ( 210 ), consisting of heat collector ( 212 ) and capacitor ( 226 ), a reservoir for a first working medium ( 228 ), a reservoir for a second working medium ( 214 ), a reservoir for the reaction medium ( 224 ), a pump ( 216 ) and a reactor ( 220 ), which are each in fluid communication with each other via lines, and that the heat collector ( 212 ) and the capacitor ( 226 ) are each in thermal contact with a hot and cold heat reservoir, whereby a reaction medium separates into two working media and thereby stores energy, which then via the separate working media via two separate, but in thermal contact lines to the reactor ( 220 ), where both working media are recombined and release the stored energy in the form of heat of reaction, enthalpy of mixing or other amounts of heat. Device according to one of claims 24 to 28, characterized in that as energy converter or heat engine, a steam engine, a turbine or Stirling engine is used. Device according to one of claims 24 to 29, characterized in that the device, for example, a generator, a heat pump, land and water vehicles, rail vehicles or special airships (zeppelins, for example) drives.

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