EP2326802B1 - Operational fluid for a vapour circuit processing device and a method for operating same - Google Patents

Abstract

The invention relates to an operating fluid for a steam cycle process apparatus comprising a steam generator, an expander, a condenser and a reservoir for the operating fluid, comprising a working medium that evaporates by supplying heat in the steam generator, performs mechanical work in the vapour phase by expanding in the expander and condenses in the condenser and an ionic liquid which forms a mixture with the working medium, wherein the melting point of the mixture lies below −5° C.

Description

The invention relates to a working fluid for a steam cycle device, a method for the operation thereof, and a steam cycle device suitable for carrying out the method.

Steam cycle processes serve to convert thermal energy into mechanical energy and are used, for example, for energy generation units which generate a heat flow by means of a burner device, which is supplied to a steam generator. In the steam generator, a working medium is vaporized by supplying heat, wherein the resulting vapor phase relaxed by performing mechanical work in an expander and subsequently condensed in the condenser. Typically, the condensate is fed to a reservoir, from which by means of a feed pump for the working medium of the renewed influx to the steam generator takes place.

A steam engine can also be used to utilize the waste heat of an internal combustion engine, for example, by the exhaust gas stream is fed to a heat exchanger device in the steam generator. Alternatively or additionally, it is possible to use the waste heat in the cooling water of an internal combustion engine for the operation of a steam cycle process. The mechanical power generated in the expander can then be at least indirectly supplied to a shaft of the drive system or there is a drive of an electric generator through the expander. In this way, a device for carrying out a steam cycle process can be designed as an auxiliary unit utilizing the waste heat of a main drive machine, which either supports the propulsion of the vehicle by engine or provides electrical energy for secondary consumers.

On the working medium for the operation of the steam cycle process is basically required to achieve a high efficiency, the requirement that a large temperature difference between the vapor phase and the condensate exists. This presupposes that the working medium remains thermally stable up to high temperatures, typically above 400 ° C. In addition, there are other requirements with respect to the corrosion protection of the steam generating device and the transport of lubricants in the vapor phase, in particular for carrying out a self-lubrication of the movable components of the expander. Furthermore, peripheral components of the drive system are to be lubricated, typically for this purpose a separate lubricant circuit is provided with a separate from the working fluid for operating the steam engine lubricant. Furthermore, in a non-continuous operation, in particular for use in a vehicle, a longer stoppage of the steam cycle process at the same time low ambient temperatures, so that as by WO 2007 014942 A2 called antifreeze precautions must be taken.

Accordingly, the operating fluid for a steam cycle process comprises additives to the working fluid. These can form an azeotrope with the working medium. An example of this is the DE 103 28 289 B3 discloses that proposes as a working fluid for a steam cycle a mixture of water and at least one heterocyclic compound and additional, miscible polymers, surfactant and / or other organic lubricants. As a heterocyclic compound, in particular, 2-methylpyridine, 3-methylpyridine, pyridine, pyrrole and pyridazine are proposed. Due to the use of the heterocyclic compound, the freezing point of the working fluid is set below 0 ° C. At the same time, the heterocyclic compound forms an azeotrope with water, so that this goes into the gas phase together with the water content in the steam generator. Here, lubricants are also transported in the vapor phase to perform a self-lubrication to the expander.

WO 2007/014942 A2 discloses a working fluid for a steam cycle process that absorbs thermal energy at different temperatures by vaporizing individual components of the working fluid. For this purpose, mixtures of water and ammonia are mentioned, wherein the component of the operating fluid with the lower boiling point serves as antifreeze.

A disadvantage of the known operating fluids for steam cycle processes is their toxicity, so that expensive precautions must be taken to to prevent leakage of the operating fluid or its gas phase safe. When used in vehicles, especially motor vehicles, however, this can not be completely ruled out with regard to possible accident hazards.

The invention is therefore based on the object of specifying a working fluid for a steam cycle process, which enables a cold start of the steam cycle process at any time, in particular for the discontinuous operation and longer downtimes even at low ambient temperatures, and in particular ensures the antifreeze safety of the system. At the same time, the operating fluid should be environmentally friendly and, in particular, non-toxic to plants and animals and should be distinguished by a high level of accident safety. In addition, a further object of the invention is to provide a method with which the steam cycle can be operated with the operating fluid so that it is designed as energy efficient as possible, and an apparatus for carrying out the method. For a further embodiment of the invention, the operating fluid for the steam cycle process is additionally intended to lubricate the circulating components of the steam engine and, in the case of a vehicle application, preferably to lubricate the moving parts of the drive system including the internal combustion engine.

The operating fluid according to the invention according to independent claim 1 comprises at least two components. The first component represents a working medium used for the actual operation of the steam cycle process. Accordingly, an evaporation of the working medium by heat in the steam generator, a subsequent relaxation by performing mechanical work in the expander and then a condensation with recycling of the condensate, typically via a reservoir and a feed pump, to re-enter the circuit, that is, for re-evaporation in the steam generator.

Another component of the operating fluid according to the invention for the steam cycle process is an antifreeze, which under normal operating conditions substantially no evaporation in the steam generator and only serves to keep the operating liquid in the reservoir liquid at low outdoor temperatures and thus to allow a cold start of the system. Advantageously, the antifreeze also has lubricant properties.

According to the invention, the antifreeze used is an ionic liquid, the mixture of ionic liquid and working medium having a melting point which is below the freezing point of the pure working medium. In the present case, water is used as the preferred working medium, so that a melting point for the mixture of the selected ionic liquid and water is below -5 ° C. Preference is given to a melting point below -10 ° C and particularly preferably below -30 ° C. In the present case, a pressure of 1 bar is assumed for all temperatures. A mixture between an ionic liquid suitable for antifreeze and the working medium is understood here to mean that each of the two components has at least a minimum weight fraction of 0.01% by weight of the mixture. In this case, there should be no complex formation in the mixture between the ionic liquid and the working medium in order not to have to break any significant binding forces to evaporate the working medium.

A mixture according to the invention of ionic liquid and working medium with a proportion of 99.99% by weight to 0.01% by weight of working medium accordingly has a melting point for the mixture of below -5 ° C. and more preferably below -10 ° C. and more preferably below -30 ° C. According to the invention, the ionic liquid used in pure form for the mixture has a melting point which is above the freezing point of the pure working medium. In this case, an ionic liquid is used, which in pure form in the temperature range 0-100 ° C melts. The required antifreeze effect therefore only exists in the mixture of ionic liquid and working medium. In this case, the melting point of the mixture in the present case is understood to be the temperature of the crystallization boundary of the mixture, so that the mixture above the melting point is liquid and can be pumped out of a reservoir.

In general, the melting point of the mixture depends on the mixing ratio between ionic liquid and working medium. In this case, for a working fluid according to the invention, the characteristic of a melting point lying below the freezing point of the pure working medium should at least be in a mixing ratio range which is present in a collecting reservoir of a stopped, cold steam cycle device. Preferably, a weight fraction of the working medium of at least 10 gw .-% and at most 90 gw .-% is assumed, more preferably the interval 20 gw .-% to 80 gw .-% for the proportion of working medium. In the case of a cold system, it is particularly preferred that the weight ratio of the ionic liquid to the working medium is in the range of 60:40 to 40:60.

Furthermore, the case may occur that the above-mentioned reference pressure of 1 bar is exceeded or undershot in certain operating phases or parts of the steam cycle device. As far as there is a deviation from the reference pressure 1 bar even at standstill for a cold, frost-prone reservoir, the above-mentioned temperature condition with respect to the melting point of the mixture of ionic liquid and working fluid for the prevailing system pressure apply. In the following, for simplification, a ventilated reservoir for the operating fluid is assumed.

During operation, the mixing ratio in the operating fluid may shift with increasing temperature. This may result in substantially complete separation of the ionic liquid from the working medium. It is conceivable within the scope of the invention, the mixing ratio in Move operation to temperature so far that the temperature condition for the melting point of the mixture, as lying below the freezing point of the working medium for certain operating phases is no longer met. This is still understood as part of the invention. After the plant has stopped, the mixing ratio is returned to a collection reservoir to ensure frost protection again.

Ionic liquids owe their low melting point to poor ion coordination. The delocalized charges are responsible for this, whereby typically at least one ion is based on an organic molecule and the formation of a stable crystal lattice is prevented even at low temperatures.

Typical of ionic liquids is the choice of their physical / chemical properties by the choice of cations / anion pairing, so that it is possible to tailor an ionic liquid for the operating liquid according to the invention for the steam cycle process so that when mixed with the working medium a low melting point in the sense a frost protection effect arises.

A particular advantage of ionic liquids for use as part of a working fluid for a steam cycle is that the ionic liquid is characterized by a vanishing vapor pressure up to its decomposition temperature. If the decomposition temperature is set by an appropriate choice of the cations / anion pairing for the ionic liquid such that it lies above the temperature of the liquid phase of the operating liquid in the steam generator, it is possible that the ionic liquid does not pass into the gas phase like the actual working medium and Expander is passed. This results in a simple way of separating the ionic liquid from the operating fluid, in the event that the operating temperature of the steam cycle process is achieved, or that a temperature is present in the system in which frost protection is no longer necessary.

After separation of the ionic liquid from the operating fluid can be prevented for operation on temperature of the energetically disadvantageous case that the antifreeze component, that is, the ionic liquid must be heated in the steam generator without making an energetic contribution in the steam cycle. The withdrawn ionic liquid or a branched, enriched with ionic liquid mixture containing a reduced proportion of working medium, can be used for further development of the invention for lubrication. In the steam cycle process device, expander lubrication is particularly suitable for this purpose. In vehicle applications, additional components to be lubricated can be supplied. This also includes the lubrication of rotating parts of an internal combustion engine, which is combined as a hybrid drive with the steam engine, a.

• Ausgangspunkt ist zunächst der Stillstand des Dampfkreisprozesses bei kalten Außentemperaturen. Hierbei wird die Betriebsflüssigkeit in einem Reservoir gesammelt und enthält eine Mischung umfassend das Arbeitsmedium, das zur Verdampfung im Dampferzeuger vorgesehen ist, und die ionische Flüssigkeit, die in der Mischung als Frostschutzmittel wirkt, sodass auch bei tiefen Außentemperaturen die Betriebsflüssigkeit beim Stillstand des Dampfkreisprozesses flüssig in einem Reservoir vorliegt.

According to an advantageous embodiment, the operating method comprises the following steps:

• The starting point is initially the stoppage of the steam cycle in cold outside temperatures. Here, the operating fluid is collected in a reservoir and contains a mixture comprising the working fluid, which is provided for evaporation in the steam generator, and the ionic liquid, which acts as antifreeze in the mixture, so that even at low ambient temperatures, the operating fluid at standstill of the steam cycle in liquid a reservoir is present.

When the steam cycle process is started, thermal energy is supplied to the steam generator, for example via an exhaust gas stream from an internal combustion engine. At the same time, the operating fluid enters the steam generator. The feeder can for example by means of a Feed pump can be realized. In the steam generator evaporation of the working medium takes place while the ionic liquid generates a vapor pressure approaching zero and is returned to the reservoir. According to an alternative embodiment, the recirculation does not take place to a reservoir, but to a separate tank for the ionic liquid.

The vaporous working fluid is fed to the condenser after its expansion and operation in the expander, according to an advantageous embodiment, the resulting condensate of the working medium is not returned to the reservoir, but a separate tank for the working fluid is supplied. This measure creates a progressive separation of the ionic liquid and the working medium. It should be noted that this separation should advantageously be made only above a certain operating temperature. Therefore, the operating temperature can be measured at different points in the apparatus for carrying out the steam cycle process, wherein advantageously the location of the temperature measurement, the operating fluid can be used in the reservoir. If a certain temperature is reached in the reservoir, which is above the freezing point of the working medium, the above-described separation of the working medium and the ionic liquid can be made. In this case, different separation methods can be used.

After a certain period of time and / or when reaching a certain level in the tank for the working fluid, a switch can be made and the reservoir can be separated from the steam generator and instead an exclusive liquid supply from the tank for the working fluid can be made. This switching characterizes the operation of the steam cycle process to temperature, in which essentially the working medium without the ionic liquid comes into contact with the heat flow in the steam generator and passes through the steam cycle. For a further embodiment of the invention, there is the possibility that with the ionic Use liquid-enriched mixture in the reservoir for lubrication purposes.

When the steam cycle process is stopped again, the separated ionic liquid can be combined with the other components of the operating fluid at a correspondingly low ambient temperature. Advantageously, mixing takes place only below a lower limit temperature in the reservoir for the operating fluid. According to a simplified embodiment, the renewed mixing can also take place after a predetermined time interval after switching off the steam cycle process or one of its subcomponents, for example the feed pump for the volume flow to the steam generator.

Alternatively, the separation of the ionic liquid and the working medium during operation of the steam cycle process can be carried out so that the operating fluid is passed through the separator after passing through the steam generator, in which the vaporous working medium is separated. In the liquid phase, the ionic liquid is enriched due to the approaching zero partial pressure and can be withdrawn into a separate reservoir. For this purpose, a lubricating circuit can be supplied from this reservoir for a further development of the invention, wherein, in addition to the antifreeze effect, the lubricating material properties of the ionic liquid or a mixture enriched with it are advantageously utilized.

In addition to the above-mentioned possibility to use the ionic liquid as an antifreeze or as a combined antifreeze and lubricant, which can be removed during operation to temperature from the steam cycle, ionic liquids are characterized by further advantageous properties. Thus, ionic liquids are typically nonflammable, they are electrically conductive and thus suppress the build-up of flow potentials. In addition, by the choice of cations / anion pairing their viscosity and density and their Mixing behavior can be adjusted with other liquids in a wide range.

In particular, ionic liquids come into consideration, which contain as anion a C1 to C4 alkyl sulfonate, preferably methyl sulfonate, a fully or partially fluorinated C1 to C4 alkyl sulfonate, preferably trifluoromethylsulfonate.

Particularly preferred ionic liquids are those which are a cation of the formula IV a (pyridinium) or IV e (imidazolium) or IV x (phosphonium) or IV y (morpholinium) and as anion a C 1 to C 4 alkyl sulfonate, preferably a methylsulfonate or partially fluorinated C1 to C4 alkyl sulfonate, preferably trifluoromethylsulfonate, or in a very particularly preferred embodiment consist exclusively of such a cation and anion.

• Eine ionische Flüssigkeit ist ein Salz mit einem Schmelzpunkt kleiner 100 °C bei 1 bar.

In the present case, the following definition of ionic liquids is used for carrying out the invention, it also being possible for there to be two or generally more than one ionic liquid in the mixture with the working medium according to the following list:

• An ionic liquid is a salt with a melting point of less than 100 ° C at 1 bar.

Preferably, the ionic liquid has a melting point of less than 70 ° C, more preferably less than 30 ° C at 1 bar.

In a particularly preferred embodiment, the ionic liquid under normal conditions (1 bar, 21 ° C), that is, at room temperature, liquid. Preferred ionic liquids contain at least one organic compound as cation, very particularly preferably they contain only organic compounds as cations.

Suitable organic cations are, in particular, organic compounds containing heteroatoms, such as nitrogen, sulfur or phosphorus. Particular preference is given to organic compounds having at least one, preferably exactly one cationic group, selected from an ammonium group, an oxonium group, a sulfonium group or a phosphonium group.

In a particular embodiment, the ionic liquids are salts with ammonium cations, including compounds with tetravalent nitrogen and located positive charge on the nitrogen or aromatic ring systems with at least one, preferably one or two, more preferably two nitrogen atoms in the ring system and a delocalized positive charge.

Particularly preferred ammonium cations are the imidazolium cations, which are understood to mean all compounds having an imidazolium ring system and optionally any desired substituents on the carbon and / or nitrogen atoms of the ring system.

The anion may be an organic or inorganic anion. Particularly preferred ionic liquids consist exclusively of the salt of an organic cation with one of the anions listed below.

The molar weight of the ionic liquids is preferably less than 2000 g / mol, more preferably less than 1500 g / mol, more preferably less than 1000 g / mol, and most preferably less than 750 g / mol; in a particular embodiment, the molecular weight is between 100 and 750 or between 100 and 500 g / mol.

Suitable ionic liquids are, in particular, salts of the general formula I below

[A] _n ⁺ [Y] ^n- (I)

where n is 1, 2, 3 or 4, [A] ^{+ is} an ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation and [Y] ^{n- is} a trivalent or tetravalent anion is;

Or mixed salts of the general formulas (II)

[A ¹ ] ⁺ [A ² ] ⁺ [Y] ^2- (IIa);

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^3- (IIb);

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^4- (IIc)

wherein [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ^{n- has} the meaning given under B1) ; or
or mixed salts of the general formulas (III)

[A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [M ¹ ] ⁺ [Y] ^4- (IIIa);

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] ^4- (IIIb);

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [M ³ ] ⁺ [Y] ^4- (IIIc);

[A ¹ ] ⁺ [A ² ] ⁺ [M ¹ ] ⁺ [Y] ^3- (IIId);

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ² ] ⁺ [Y] ^3- (IIIe);

[A ¹ ] ⁺ [M ¹ ] ⁺ [Y] ^2- (IIIf);

[A ¹ ] ⁺ [A ² ] ⁺ [M ⁴ ] ²⁺ [Y] ^4- (IIIg);

[A ¹ ] ⁺ [M ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] ^4- (IIIh);

[A ¹ ] ⁺ [M ⁵ ] ³⁺ [Y] ^4- (IIIi);

or

[A ¹ ] ⁺ [M ⁴ ] ²⁺ [Y] ^3- (IIIj)

wherein [A ¹ ] ⁺ , [A ² ] ⁺ and [A ³ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ , [Y] ^{n- has} the meaning given under B1) and [M ¹ ] ⁺ , [M ² ] ⁺ , [M ³ ] ⁺ monovalent metal cations, [M ⁴ ] ²⁺ divalent metal cations and [M ⁵ ] ³⁺ trivalent metal cations;
or mixtures thereof.

Preferred are ionic liquids in which the cation [A] ^{+ is} an ammonium cation, which generally contains 1 to 5, preferably 1 to 3 and particularly preferably 1 to 2 nitrogen atoms.

sowie Oligomere, die diese Strukturen enthalten.

Suitable cations are, for example, the cations of the general formulas (IVa) to (IVy)

and oligomers containing these structures.

Furthermore, morpholinium can be chosen.

sowie Oligomere, die diese Struktur enthalten.Another suitable cation is also a phosphonium cation of the general formula (IVy)

and oligomers containing this structure.

In the above formulas (IVa) to (IVy)
R is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical, unsubstituted or substituted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms; and
the radicals R ¹ to R ⁹ independently of one another are hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (IV) are bonded to a carbon atom (and not to a heteroatom), additionally may also stand for halogen or a functional group; or
two adjacent radicals from the series R ¹ to R ⁹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or substituted 1 to 30 carbon atoms.

Suitable hetero atoms in the definition of the radicals R and R ¹ to R ^{9 are in} principle all heteroatoms in question which are capable of formally a -CH ₂ -, a -CH =, a -C≡ or a = C = group to replace. Contains the carbon-containing radical heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred. Preferred groups which may be mentioned are in particular -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, -POR'- and -SiR ' ₂ -, wherein it the radicals R 'are the remainder of the carbon-containing radical. The radicals R ¹ to R ⁹ are, in the cases in which those in the above formulas (IV) to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom. When suitable examples are -OH (hydroxy), = O (especially as carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxy), -CONH ₂ (carboxamide), -SO ₃ H (sulfo) and -CN (cyano). Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), - CONH- (secondary amide) or -CONR'- (tertiary amide) are included, for example, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkyloxycarbonyl or C ₁ -C ₄ alkyloxy.

Halogens are fluorine, chlorine, bromine and iodine.

The radical R preferably stands for
unbranched or branched unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C _{1 to} C ₆ alkoxycarbonyl and / or sulfonic acid substituted C ₁ - to C ₁₈ -alkyl having a total of 1 to 20 carbon atoms, such as methyl, Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl , 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2 Hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl 2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl , 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1 Dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid; Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C ₁ - to C ₈ -alkyl as end group, such as R ^A O- (CHR ^B -CH ₂ -O) _p -CHR ^B -CH ₂ - or
R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _p -CH ₂ CH ₂ CH ₂ CH ₂ O- with R ^A and R ^B preferably hydrogen, methyl or ethyl and p preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12 -Tetraoxatetradecyl; Vinyl; and N, N-di-C ₁ -C ₆ -alkylamino such as N, N-dimethylamino and N, N-diethylamino.

Particularly preferably, the radical R is unbranched and unsubstituted C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1 Decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular methyl, ethyl, 1-butyl and 1-octyl and CH ₃ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - with p equal to 0 to 3.

The radicals R ¹ to R ⁹ are preferably each independently
Hydrogen;
Halogen;
a functional group;
optionally C ₁ -C ₁₈ substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups alkyl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ alkenyl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ aryl; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ -cycloalkyl;
optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ cycloalkenyl; or
an optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms having heterocycle; or
two adjacent radicals together for
an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups broken ring.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C _{1 to} C ₁₈ alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl , 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3 pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2, 3-Dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1- Decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexy methyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p-butylphenyl ) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, methoxy, ethoxy, formyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3- dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3 Aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _q F _{2 (qa) + (1-b)} H _{2a + b} where q is 1 to 30, 0 ≤ a ≤ q and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _(q-2) F _{2 (q-2) +1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C _{1 2} F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2 - (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3 , 6-dioxo-octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8 , 12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl , 11-Methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl , 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3 , 6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5 oxa-no nyl or 14-ethoxy-5,10-oxa-tetradecyl.

In optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C ₂ -C ₁₈ alkenyl it is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _q F _{2 (qa) - (1-b)} H _2a-b with q ≤ 30, 0 ≤ a ≤ q and b = 0 or 1.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₆ -C ₁₂ aryl is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4- Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, t-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6 Dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl , 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5.

C ₅ -C ₁₂ -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _q F _{2 (qa) - (1-b)} H _2a-b with q ≦ 30, 0 ≦ a ≦ q and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

C ₅ -C ₁₂ -cycloalkenyl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2.5- Cyclohexadienyl or C _q F _{2 (qa) -3 (1-b)} H _2a-3b with q ≤ 30, 0 ≤ a ≤ q and b = 0 or 1.

An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, pyrryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.

Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1,3-propylene, 1,4-butylene, 1,5-pentylene, 2-oxa-1,3-propylene, 1-oxa-1,3- propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 3-oxa-1,5-pentylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ - Alkyl 1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-butane 1.3 dienylene.
If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.

If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.

Particularly preferably, the radicals R ¹ to R ⁹ are each independently
Hydrogen;
unbranched or branched unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C ₁ -C ₆ alkoxycarbonyl and / or sulfonic acid substituted C ₁ -C ₁₈ alkyl having a total of 1 to 20 carbon atoms, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3 Pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2 Hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl 2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl , 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1 Dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2 - (n-butoxy-carbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;
Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C ₁ -C ₈ alkyl as an end group, such as R ^A O- (CHR ^B -CH ₂ -O) _p -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _p -CH ₂ CH ₂ CH ₂ CH ₂ O- with R ^A and R ^B preferably hydrogen, methyl or ethyl and p preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12 -Tetraoxatetradecyl;
Vinyl; and
N, N-di-C ₁ -C ₆ -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Most preferably, the radicals R ¹ to R ⁹ independently of one another are hydrogen or C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, for phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N -Diethylamino, for chlorine and CH ₃ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _p CH ₂ CH ₂ - with p being 0 to 3.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyridinium ion (IVa) in which
one of R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining R ¹ to R ^{5 are} hydrogen;
R ^{3 is} dimethylamino and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;
all radicals R ¹ to R ^{5 are} hydrogen;
R ^{2 is} carboxy or carboxamide and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; or
R ¹ and R ² or R ² and R ^{3 is} 1,4-buta-1,3-dienylene and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;
and in particular one in which
R ¹ to R ^{5 are} hydrogen; or
one of the radicals R ¹ to R ^{5 is} methyl or ethyl and the remaining radicals R ¹ to R ^{5 are} hydrogen.

Very particularly preferred pyridinium ions (IVa) which may be mentioned are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1 Hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1,2-dimethyl pyridinium , 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1 dodecyl) -2-methylpyridinium,
1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium,
1- (1-Tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethyl-pyridinium, 1,5-diethyl-2-methyl-pyridinium, 1 (1-Butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl) -2-methyl-3-ethyl- pyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexadecyl) -2-methyl- 3-ethylpyridinium.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyridazinium ion (IVb), in which
R ¹ to R ^{4 are} hydrogen; or
one of the radicals R ¹ to R ^{4 is} methyl or ethyl and the remaining radicals R ¹ to R ^{4 are} hydrogen.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyrimidinium ion (IVc), in which
R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl; or
R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyrazinium ion (IVd), in which
R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl;
R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen;
R ¹ to R ^{4 are} methyl; or
R ¹ to R ^{4 are} methyl hydrogen.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} an imidazolium ion (IVe), in which
R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R ² to R ^{4 are} independently hydrogen, methyl or ethyl.

As very particularly preferred imidazolium ions (IVe) may be mentioned 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium,
1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl ) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl ) -3-butyl-imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3 = butylimidazolium, 1- (1-dodecyl ) -3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) - 3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3- methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3- Trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-O ctyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1.4 , 5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium and 1,4,5-trimethyl-3-octylimidazolium ,

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyrazolium ion (IVf), (IVg) or (IVg '), in which
R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyrazolium ion (IVh), in which
R ¹ to R ^{4 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a 1-pyrazolinium ion (IVi) in which
independently of one another R ¹ to R ^{6 are} hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a 2-pyrazolinium ion (IVj ') in which
R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a 3-pyrazolinium ion (IVk) or (IVk '), in which
R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ³ to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} an imidazolinium ion (Ivl) in which
R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R ³ and R ^{4 are} independently hydrogen, methyl or ethyl, and R ⁵ and R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} an imidazolinium ion (IVm) or (IVm '), in which
R ¹ and R ^{2 are} independently hydrogen, methyl or ethyl and R ³ to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} an imidazolinium ion (IVn) or (IVn '), in which
R ¹ to R ^{3 are} independently hydrogen, methyl or ethyl and R ⁴ to R ^{6 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a thiazolium ion (IVo) or (IVo ') and also oxazolium ion (IVp), in which
R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² and R ^{3 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a 1,2,4-triazolium ion (IVq), (IVq ') or (IVq "), in which
R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ^{3 is} hydrogen, methyl or phenyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a 1,2,3-triazolium ion (IVr), (IVr ') or (IVr "), in which
R ^{1 is} hydrogen, methyl or ethyl, and R ² and R ^{3 are} independently hydrogen or methyl, or R ² and R ³ together are 1,4-buta-1,3-dienylene.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a pyrrolidinium ion (IVs) in which
R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{9 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} an imidazolidinium ion (IVt) in which
R ¹ and R ^{4 are} independently hydrogen, methyl, ethyl or phenyl and R ² and R ³ and R ⁵ to R ^{8 are} independently hydrogen or methyl.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} an ammonium ion (IVu), in which
R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl; or
R ¹ to R ^{3 are} independently hydrogen or C ₁ -C ₁₈ alkyl and R ^{4 is} 2-hydroxyethyl; or
R ¹ and R ² together are 1,5-pentylene or 3-oxa-1,5-pentylene and R ^{3 is} C ₁ -C ₁₈ alkyl, 2-hydroxyethyl or 2-cyanoethyl.

As very particularly preferred ammonium ions (IVu) may be mentioned methyl tri (1-butyl) -ammonium, 2-hydroxyethyl-ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a guanidinium ion (IVv), in which
R ¹ to R ^{5 are} methyl.

An especially preferred guanidinium ion (IVv) is N, N, N ', N', N ", N" -hexamethylguanidinium.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a cholinium ion (IVw) in which
R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ;
R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁴ group and R ³ and R ^{4 are} independently hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ; or
R ^{1 is} a -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁵ group and R ³ to R ^{5 are} independently hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or PO (OH) ₂ are.

Very particular preference is given to ionic liquids in which the cation [A] ^{+ is} a phosphonium ion (IVx) in which
R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

Among the cations mentioned above, the pyridinium ions (IVa), imidazolium ions (IVe) and ammonium ions (IVu) are preferred, in particular 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1 - (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- ( 1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1, 5-diethyl-2-methyl-pyridinium, 1- (1-butyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexyl) -2-methyl-3-ethyl-pyridinium, 1- (1 -Octyl) -2-methyl-3-ethyl-pyridinium, 1- (1-dodecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl ) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-methylimi dazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2, 3-dimethylimidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1, 4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium and 2-hydroxyethylammonium.

The metal cations [M ¹ ] ⁺ , [M ² ] ⁺ , [M ³ ] ⁺ , [M ⁴ ] ²⁺ and [M ⁵ ] ³⁺ mentioned in formulas (IIIa) to (IIIj) are generally to metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th and 13th group of the periodic table. Suitable metal cations are, for example, Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Cr ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Ni ²⁺ , Cu ^{2 +} , Ag ⁺ , Zn ²⁺ and Al ³⁺ .

As anions, in principle, all anions can be used which, in conjunction with the cation, lead to an ionic liquid.

• der Gruppe der Halogenide und halogenhaltigen Verbindungen der Formeln:
  • F^-, Cl^-, Br^-, I^-, BF₄ ^-, PF₆ ^-, AlCl₄ ^-, Al₂Cl₇ ^-, Al₃Cl₁₀ ^-, AlBr₄ ^-, FeCl₄ ^-, BCl₄ ^-, SbF₆ ^-, AsF₆ ^-, ZnCl₃ ^-, SnCl₃ ^-, CuCl₂ ^-, CF₃SO₃ ^-, (CF₃SO₃)₂N^-, CF₃CO₂ ^-, CCl₃CO₂ ^-, CN^-, SCN^-, OCN^-, NO^2-, NO^3-, N(CN)^-;
• der Gruppe der Sulfate, Sulfite und Sulfonate der allgemeinen Formeln:
  • SO₄ ^2-, HSO₄ ^-, SO₃ ^2-, HSO₃ ^-, R^aOSO₃ ^-, R^aSO₃ ^-;
• der Gruppe der Phosphate der allgemeinen Formeln:
  • PO₄ ^3-, HPO₄ ^2-, H₂PO₄ ^-, R^aPO₄ ^2-, HR^aPO₄ ^-, R^aR^bPO₄ ^-;
• der Gruppe der Phosphonate und Phosphinate der allgemeinen Formel:
  • R^aHPO₃ ^-, R^aR^bPO₂ ^-, R^aR^bPO₃ ^-;
• der Gruppe der Phosphite der allgemeinen Formeln:
  • PO₃ ^3-, HPO₃ ^2-, H₂PO₃ ^-, R^aPO₃ ^2-, R^aHPO₃ ^-, R^aR^bPO₃ ^-;
• der Gruppe der Phosphonite und Phosphinite der allgemeinen Formel:
  • R^aR^bPO₂ ^-, R^aHPO₂ ^-, R^aR^bPO^-, R^aHPO^-;
• der Gruppe der Carboxylate der allgemeinen Formeln:
  • R^aCOO^-;
• der Gruppe der Borate der allgemeinen Formeln:
  • BO₃ ^3-, HBO₃ ^2-, H₂BO₃ ^-, R^aR^bBO₃ ^-, R^aHBO₃ ^-, R^aBO₃ ^2-, B(OR^a)(OR^b)(OR^c)(OR^d)^-, B(HSO₄)^-, B(R^aSO4)^-;
• der Gruppe der Boronate der allgemeinen Formeln:
  • R^aBO₂ ^2-, R^aR^bBO^-;
• der Gruppe der Carbonate und Kohlensäureester der allgemeinen Formeln:
  • HCO₃ ^-, CO₃ ^2-, R^aCO₃ ^-;
• der Gruppe der Silikate und Kieselsäuresäureester der allgemeinen Formeln:
  • SiO₄ ^4-, HSiO₄ ^3-, H₂SiO₄ ^2-, H₃SiO₄ ^-, R^aSiO₄ ^3-, R^aR^bSiO₄ ^2-, R^aR^bR^cSiO₄ ^-, HR^aSiO₄ ^2-, H₂R^aSiO₄ ^-, HR^aR^bSiO₄ ^-;
• der Gruppe der Alkyl- bzw. Arylsilan-Salze der allgemeinen Formeln:
  • R^aSiO₃ ^3-, R^aR^bSiO₂ ^2-, R^aR^bR^cSiO^-, R^aR^bR^cSiO₃ ^-, R^aR^bR^cSiO₂ ^-, R^aR^bSiO₃ ^2-;
• der Gruppe der Carbonsäureimide, Bis(sulfonyl)imide und Sulfonylimide der allgemeinen Formeln:
  
• der Gruppe der Methide der allgemeinen Formel:
  
• der Gruppe der Alkoxide und Aryloxide der allgemeinen Formeln:
  • R^aO^-;
• der Gruppe der Halometallate der allgemeinen Formel
  • [M_rHal_t]^s-,
    wobei M für ein Metall und Hal für Fluor, Chlor, Brom oder Iod steht, r und t ganze positive Zahlen sind und die Stöchiometrie des Komplexes angeben und s eine ganze positive Zahl ist und die Ladung des Komplexes angibt;
• der Gruppe der Sulfide, Hydrogensulfide, Polysulfide, Hydrogenpolysulfide und Thiolate der allgemeinen Formeln:
  • S^2-, HS^-, [S_v]^2-, [HS_v]^-, [R^aS]^-,
    wobei v eine ganze positive Zahl von 2 bis 10 ist;
• der Gruppe der komplexen Metallionen wie Fe(CN)₆ ^3-, Fe(CN)₆ ^4-, MnO₄ ^-, Fe(CO)₄ ^-.

The anion [Y] ^{n of} the ionic liquid is for example selected from:

• the group of halides and halogen-containing compounds of the formulas:
  • F ^-, Cl ^-, Br ^-, I ^-, BF ₄ ^-, PF ₆ ^-, AlCl ₄ ^-, Al ₂ Cl ₇ ^-, Al ₃ Cl ₁₀ ^-, AlBr ₄ ^-, FeCl ₄ ^-, BCl ₄ ^-, SbF ₆ ^-, AsF ₆ ^-, ZnCl ₃ ^-, SnCl ₃ ^-, CuCl ₂ ^-, CF ₃ SO ₃ ^-, (CF ₃ SO _{3) 2} N ^-, CF ₃ CO ₂ ^-, CCl ₃ CO ₂ ^-, CN ^-, SCN ^- , OCN ^- , NO ² , NO ³ , N (CN) ^- ;
• the group of sulfates, sulfites and sulfonates of the general formulas:
  • SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^- ;
• the group of phosphates of the general formulas:
  • PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^- ;
• the group of phosphonates and phosphinates of the general formula:
  • R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^- ;
• the group of phosphites of the general formulas:
  • PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^- ;
• the group of phosphonites and phosphinites of the general formula:
  • R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^- ;
• the group of carboxylates of the general formulas:
  • R ^a COO ^- ;
• the group of borates of the general formulas:
  • BO ₃ ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO4) ^- ;
• the group of boronates of the general formulas:
  • R ^a BO ₂ ^2- , R ^a R ^b BO ^- ;
• the group of carbonates and carbonic esters of the general formulas:
  • HCO ₃ ^- , CO ₃ ^2- , R ^a CO ₃ ^- ;
• the group of silicates and silicic acid esters of the general formulas:
  • SiO ₄ ^4- , HSiO ₄ ^3- , H ₂ SiO ₄ ^2- , H ₃ SiO ₄ ^- , R ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^- ;
• the group of the alkyl or aryl silane salts of the general formulas:
  • R ^a SiO ₃ ^3-, R ^a R ^b SiO ₂ ^2-, R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^-, R ^a R ^b SiO ₃ ^2- ;
• the group of carboximides, bis (sulfonyl) imides and sulfonylimides of the general formulas:
  
• the group of methides of the general formula:
  
• the group of alkoxides and aryloxides of the general formulas:
  • R ^a O ^- ;
• the group of halometalates of the general formula
  • [M _r Hal _t ] ^s ,
    where M is a metal and Hal is fluoro, chloro, bromo or iodo, r and t are integer positive numbers and indicate the stoichiometry of the complex and s is an integer positive number indicating the charge of the complex;
• the group of sulfides, hydrogen sulfides, polysulfides, hydrogen polysulfides and thiolates of the general formulas:
  • S ^2-, HS ^-, [S _v] ^2-, [HS _v] ^- [R ^a S] ^-,
    where v is a whole positive number from 2 to 10;
• the group of complex metal ions such as Fe (CN) ₆ ^3- , Fe (CN) ₆ ^4- , MnO ₄ ^- , Fe (CO) ₄ ^- .

In this R ^a , R ^b , R ^c and R ^d are each independently
Hydrogen;
C ₁ -C ₃₀ -alkyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO-, -CO-O- or -CO- N <substituted components such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (Isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl 2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2, 2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3- Dimethyl-2-butyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, Nonacosyl, triacontyl, phenylmethyl (benzyl), diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy, ethoxy, formyl, acetyl or C. _q F _{2 (qa) + (1-b)} H _{2a + b} with q ≤ 30, 0 ≤ a ≤ q and b = 0 or 1 (for example, CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _(q-2) F _{2 (q-2) +1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ); C ₃ -C ₁₂ cycloalkyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components, such as for example cyclopentyl, 2-methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl or C _q F _{2 ( qa) - (1-b)} H _2a-b with q ≤ 30, 0 ≤ a ≤ q and b = 0 or 1;
C ₂ -C ₃₀ alkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components, such as For example, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _q F _{2 (qa) (1-b)} H _2a-b with q ≤ 30, 0 ≤ a ≤ q and b = 0 or 1;
C ₃ -C ₁₂ cycloalkenyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted components, such as For example, 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C _q F _{2 (qa) -3 (1-b)} H _2a-3b with q ≤ 30, 0 ≤ a ≤ q and b = 0 or 1; Aryl or heteroaryl having 2 to 30 carbon atoms and their alkyl, aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O- substituted components such as phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-tolyl), 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Dimethylphenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5; or two radicals an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted ring.

Very particularly preferred anions are chloride; Bromide; iodide; thiocyanate; hexafluorophosphate; trifluoromethylsulfonate; methylsulfonate; formate; Acetate; mandelate; Nitrate; Nitrite; trifluoroacetate; Sulfate; Bisulfate; Methyl sulfate; ethyl sulfate; 1-propyl sulfate; 1-butyl sulfate; 1-hexyl sulfate; 1-octyl sulfate; Phosphate; dihydrogen phosphate; Hydrogen phosphate; C ₁ -C ₄ dialkyl phosphates; propionate; tetrachloroaluminate; Al ₂ Cl ₇ ^- ; chlorozincate; Chloroferrat; imide, bis (trifluoromethylsulfonyl); Bis (pentafluoroethylsulfonyl) imide; Bis (methylsulfonyl) imide; Bis (p-tolylsulfonyl) imide; Tris (trifluoromethylsulfonyl) methide; Bis (pentafluoroethylsulfonyl) methide; p-tolylsulfonate; tetracarbonylcobaltate; Dimethylenglykolmonomethylethersulfat; oleate; stearate; acrylate; methacrylate; maleate; hydrogen citrate; vinylphosphonate; Bis (pentafluoroethyl) phosphinate; Borates such as bis [salicylato (2 -)] borate, bis [oxalato (2 -)] borate, bis [1,2-benzenediolato (2 -) - O, O '] borate, tetracyano borate, tetrafluoroborate; dicyanamide; Tris (pentafluoroethyl) trifluorophosphate; Tris (heptafluoropropyl) trifluorophosphate, cyclic aryl phosphates such as Brenzcatechol-phosphate (C ₆ H ₄ O ₂₎ P (O) O ^- and Chlorocobaltat.

Very particularly preferred anions are
Chloride, bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methylsulfate, ethylsulfate, methylsulfonate, formate, acetate, dimethyl phosphate, diethyl phosphate, p-toluenesulfonate, tetrafluoroborate and hexafluorophosphate.

Particular preference is given to ionic liquids which are used as cation
Methyl tri (1-butyl) ammonium, 2-hydroxyethyl ammonium, 1-methyl imidazolium, 1-ethyl imidazolium, 1- (1-butyl) imidazolium, 1- (1-octyl) imidazolium, 1- (1-dodecyl ) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3- butyl imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3- methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3- methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1 - (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3- octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium or 1,4,5- trimethyl-3-octylimidazolium;
and as an anion
Chloride, bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methylsulfate, ethylsulfate, methylsulfonate, formate, acetate, dimethylphosphate, diethylphosphate, p-tolylsulfonate, tetrafluoroborate and hexafluorophosphate;
contain.

• 1,3-Dimethylimidazolium-methylsulfat, 1,3-Dimethylimidazolium-hydrogensulfat, 1,3-Dimethylimidazolium-dimethylphosphat, 1-Ethyl-3-methylimidazolium-methylsulfat, 1-Ethyl-3-methylimidazolium-trifluormethylsulfonat, 1-Ethyl-3-methylimidazolium-hydrogensulfat, 1-Ethyl-3-methylimidazolium thiocyanat, 1-Ethyl-3-methylimidazolium acetat, 1-Ethyl-3-methylimidazolium methylsulfonat, 1-Ethyl-3-methylimidazolium diethylphosphat, 1-(1-Butyl)-3-methylimidazolium methylsulfat, 1-(1-Butyl)-3-methylimidazolium hydrogensulfat, 1-(1-Butyl)-3-methylimidazolium thiocyanat, 1-(1-Butyl)-3-methylimidazolium acetat, 1-(1-Butyl)-3-methylimidazolium methylsulfonat, 1-(1-Dodecyl)-3-methylimidazolium methylsulfat, 1-(1-Dodecyl)-3-methylimidazolium hydrogensulfat, 1-(1-Tetradecyl)-3-methylimidazolium methylsulfat, 1-(1-Tetradecyl)-3-methylimidazolium hydrogensulfat, 1-(1-Hexadecyl)-3-methylimidazolium methylsulfat oder 1-(1-Hexadecyl)-3-methylimidazolium hydrogensulfat, 1-Hexyl-3-methylimidazolium trifluormethylsulfonat, 1-Hexyl-3-methylimidazolium methylsulfonat 1-Butyl-3-methylimidazolium trifluormethylsulfonat, Tetrabutylphosphonium methylsulfonat, Tetrabutylphosphonium trifluormethylsulfonat, Tetramethylphosphonium methylsulfonat, Tetramethylphosphonium trifluormethylsulfonat, Tributylmethylphosphonium methylsulfonat, Tributylmethylphosphonium trifluormethylsulfonat oder 2-Hydroxyethylammonium formiat.

Also particularly preferred are the following ionic liquids:

• 1,3-dimethylimidazolium methylsulfate, 1,3-dimethylimidazolium hydrogensulfate, 1,3-dimethylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium trifluoromethylsulfonate, 1-ethyl-3-yl methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1- (1-butyl) -3- methylimidazolium methylsulfate, 1- (1-butyl) -3-methylimidazolium hydrogensulfate, 1- (1-butyl) -3-methylimidazolium thiocyanate, 1- (1-butyl) -3-methylimidazolium acetate, 1- (1-butyl) - 3-methylimidazolium methylsulfonate, 1- (1-dodecyl) -3-methylimidazolium methylsulfate, 1- (1-dodecyl) -3-methylimidazolium hydrogensulfate, 1- (1-tetradecyl) -3-methylimidazolium methylsulfate, 1- (1-tetradecyl ) -3-methylimidazolium hydrogensulfate, 1- (1-hexadecyl) -3-methylimidazolium methylsulfate or 1- (1-hexadecyl) -3-methylimidazolium hydrogensulfate, 1-hexyl-3-methylimidazolium trifluoromethyls ulfonate, 1-hexyl-3-methylimidazolium methylsulfonate 1-butyl-3-methylimidazolium trifluoromethylsulfonate, tetrabutylphosphonium methylsulfonate, tetrabutylphosphonium trifluoromethylsulfonate, tetramethylphosphonium methylsulfonate, tetramethylphosphonium trifluoromethylsulfonate, tributylmethylphosphonium methylsulfonate, tributylmethylphosphonium trifluoromethylsulfonate or 2-hydroxyethylammonium formate.

Figur 1

zeigt in einer Prinzipienskizze eine Vorrichtung zur Ausführung eines Dampfkreisprozesses, die zur Umsetzung des erfindungsgemäßen Betriebsverfahrens dient.

Figur 2

zeigt eine alternative Ausgestaltung zur Vorrichtung aus Figur 1.

Figur 3

zeigt eine Weitergestaltung einer Dampfkreisprozessvorrichtung zur Verwendung der für den Frostschutz eingesetzten ionischen Flüssigkeit als Schmierstoff.

The invention will be described in more detail below with reference to figures. These details show:

FIG. 1

shows in a schematic diagram of an apparatus for performing a steam cycle process, which serves to implement the operating method according to the invention.

FIG. 2

shows an alternative embodiment of the device FIG. 1 ,

FIG. 3

shows a further development of a Dampfkreisprozessvorrichtung for use of the used for antifreeze ionic liquid as a lubricant.

FIG. 1 schematically shows simplified the basic components for an apparatus for performing a steam cycle process 1. As possible embodiments, the steam process 1 may be designed as a Rankine Rankine process or as a Kalina-type cycle. In the latter case, the working medium consists of several components, which pass into the vapor phase at different temperature levels.

A reservoir for the operating fluid 2 stores the working fluid as a liquid phase. From there, it is typically conducted by means of a feed pump 8, which is advantageously designed to be variable in speed for adjusting the volume flow, to the steam generator 3. The vapor phase generated there enters the expander 4 and performs mechanical work while relaxing. Subsequently, a condensation takes place in the condenser 5 and the return of the condensate.

According to the invention, the operating liquid comprises, in addition to the working medium provided for evaporation in the steam generator 3, at least under cold start conditions, an ionic liquid as antifreeze. Accordingly, the melting point of the mixture of working medium and ionic liquid is chosen to be lower than the freezing point of the pure working medium. If water is used as the working medium, the ionic liquid used can be, for example, 1-ethyl-3-methylimidazolium methylsulfonate (EMIM MeSO ₃ ). Here, EMIN MeSO ₃ in pure form has a melting point of 35 ° C. In a mixture with water with a water content of 20 gw .-%, the glass transition for the mixture is at a temperature below-100 ° C. As the water content increases, the melting temperature increases and is -10 ° C. for a weight fraction of 80% by weight of water. For the typically present in a stagnant steam cycle device, In approximately balanced weight ratio, that is a 50:50 mixture based on the weight fraction, the melting point of the mixture is advantageously low at -36 ° C. Similar values include a mixture of 1-ethyl-3-methylimidazolium hydrogen sulfate as an ionic liquid and water as a working medium. Further, tetramethylammonium methylsulfonate can be used as an ionic liquid for mixing with water as far as the water content is at least 34 wt%. Thus, for this mixture, the melting point is at least in a mixing ratio with a weight fraction of water of 50-80 gw .-% below -20 ° C. Further mixtures of ionic liquid to water in a weight ratio of 60:40 or 50:50 with a melting point below -20 ° C. may be used as possible ionic liquids 1,2,3-trimethylimidazolium methylsulfonate, ethyltrimethylammonium methylsulfonate, tris (2) hydroxyethyl) methylammonium methylsulfonate, diethyldimethylammonium methylsulfonate, N-dimethylmorpholinium methylsulfonate, methylimidazolium butanesulfonate, N-methyl-pyridinium-methylsulfonate, N-ethyl-pyridinium-methylsulfonate.

During operation of the steam generator 3, the ionic liquid essentially generates a partial pressure approaching zero. Accordingly, the cation / anion pairing of the ionic liquid is selected so that the decomposition temperature is above the operating temperature in the steam generator 3. In this case, it is possible for the steam generator 3 to be designed so that the temperature in the liquid phase of the operating liquid in the steam generator 3 is set below the decomposition temperature of the ionic liquid, at least during a specific operating phase. Accordingly, it is possible in parts of the steam generator 3, in which only the working medium is present as a vapor phase, to allow temperatures above the decomposition temperature or to provide an operating phase, which allows a temperature at least for parts of the steam generator 3 after removal of the ionic liquid from the operating fluid, which is above the decomposition temperature of the ionic liquid. The measure described above ensures that the ionic liquid in the steam generator 3 remains stable and except for a drop of nitrite does not pass into the vapor phase and thus can be led out liquid from the steam generator 3.

According to a first embodiment, the in FIG. 1 is sketched, the ionic liquid is returned after passing through the steam generator 3 by means of a bypass line 10 to the reservoir for the operating fluid 2. In addition, a tank for the working medium 6 is provided, in which the condensate from the condenser 5 collects. The condensate should contain essentially no ionic liquid. Consequently, it is possible, after a certain operating temperature is reached, for example, a certain threshold temperature in the reservoir for the operating fluid 2 to remove the ionic liquid at least partially from the operating fluid, so that no unused heat removal results from the steam generator. For this purpose, it is preferred to take a weight fraction of at least 50% of the ionic liquid originally present in the operating fluid from the steam cycle. Preference is given to the removal of a higher proportion, in particular of 80% and more, particularly preferably of at least 95%.

According to the in FIG. 1 shown drawing, the removal of the ionic liquid from the operating liquid by the evaporation of the working medium in the steam generator 3 and its collection in the tank for the working medium 6. It is preferred after reaching a certain level in the tank for the working medium 6, the for the operation of the Steam circuit process 1 necessary volume of working medium, a valve unit 11, which controls the inflow from the tank for the working fluid 6 and the reservoir for the operating fluid 2 to the steam generator 3, switched so that the reservoir for the operating fluid 2 is disconnected and the feed pump. 8 draws exclusively from the tank for the working medium 6. This switching by means of the valve unit 11 can either time and / or level control and / or temperature controlled and / or dependent on the Concentration of the ionic liquid can be controlled in the operating fluid.

FIG. 2 shows a further possible embodiment variant of an apparatus for carrying out a steam cycle process with the operating fluid according to the invention with a possibility for separating the ionic liquid from the operating fluid for a system to temperature. In contrast to the embodiment according to FIG. 1 is in FIG. 2 a separate tank for the ionic liquid 7 is sketched, which is connected to a drain for the liquid phase at the steam generator 3. Accordingly accumulate in the tank for the ionic liquid 7 preferably the non-evaporated portions of the operating fluid, so there is an enrichment of the ionic liquid here. Below the operating temperature and in particular at temperatures at which there is a risk of frost, the ionic liquid is returned from the tank for the ionic liquid 7 to the reservoir for the operating fluid 2. This can be done, for example, via the in FIG. 2 sketched line connection and a return pump 9 provided therein take place. Once the operating temperature has been reached, this flow can be reduced or reduced to zero, resulting in an enrichment of the ionic liquid in the tank for the ionic liquid 7 during further operation of the steam generator 3 and at the same time the proportion of ionic liquid in the reservoir for the operating fluid 2 is reduced by constantly the condensate of the working medium from the condenser 5 is supplied. After a certain period of time, a major part, and preferably substantially all, of the ionic liquid is removed from the steam cycle process. After this has been achieved, it is possible according to an embodiment to close the connection between the steam generator 3 and the tank for the ionic liquid 7 and to set a suitable high temperature for the exhaust steam according to a possible embodiment of the steam generator.

Based on FIG. 3 a further embodiment of the invention is explained below, for which the ionic liquid fulfills a dual function. On the one hand It serves as an admixture to the working fluid to achieve adequate frost protection, on the other hand, the ionic liquid, possibly with a residual amount of working fluid, as a lubricant. Accordingly, the embodiment of the invention comprises a Dampfkreisprozessvorrichtung with a device for withdrawing the ionic liquid or a mixture enriched with this. The inventive method for this design uses the trigger for lubrication of rotating components of the steam cycle device, in particular the expander. Further, the lubricant may find use for other moving components outside the steam cycle process device. In the event that there is a hybrid drive with a steam engine and an internal combustion engine, in particular there is the possibility to realize the lubrication of the internal combustion engine via a lubricant containing the ionic liquid.

In detail, in the schematically simplified representation of FIG. 3 the basic components for the execution of the steam cycle process 1 shown. Provided is a reservoir for the operating fluid 2, which receives a mixture of the working medium and the ionic liquid for frost protection purposes at least when at rest. This mixture is conveyed via the feed pump 8, which supplies it to the steam generator 3. The steam generator 3 is acted upon by an exhaust duct 21 from the engine 20 with a stream of hot exhaust gases and thus allows the evaporation of the working medium. When leaving the steam generator 3, a mixture of liquid and gas phase is fed to a separator 12, which separates the vaporous working medium and the expander 4 zuleitet. For starting an additional starting valve 15 is provided, which allows bypassing the expander.

The ionic liquid remains liquid in the separator due to the approaching zero partial pressure and can be fed from the sump of a valve device 11. The valve device 11 allows either the leadership of Operating liquid via the condenser 5 and the filter 13 back to the reservoir for the operating fluid 2 or the supply to an ionic liquid tank 7. When stopping the Dampfkreisprozessvorrichtung occurs an inflow from the tank for the ionic liquid 7 to the reservoir for the operating fluid 2 by gravity or by a pump to ensure there the frost-proof mixing ratio of working fluid to ionic liquid.

In operation of the steam cycle device, that is at a sufficient temperature of the steam generator 3, the valve device 11 is supplied to a mixture which is rich in ionic liquid. This can be used as a lubricant or as a lubricant additive in a suitable choice of ionic liquid, which has both the required antifreeze properties and sufficient lubricating properties. The first case is in FIG. 3 shown.

• Die kinematische Viskosität bei einer Temperatur von 90 °C liegt bei 5,3 cst. Die Dichte, das Schaumverhalten und das Luftabscheidevermögen (nach DIN ISO 9120 bei 50 °C) liegen bei schmiermitteltauglichen Werten. Die Schmiermitteleigenschaften wurden mittels eines Shell-Vierkugelapparats gemessen. Eine Messung nach DIN 51350-T2 bei einer Drehzahl von 1420 min^-1 ergab eine Schweißkraft von 2400 N. Eine Messung nach DIN 51350-T3 bei derselben Drehzahl und einer Last von 300 N führte zu einem Kalotten-Durchmesser von 1,04 mm. Ferner wurde die Oxidationsstabilität und das Korrosionsschutzverhalten der Mischung ermittelt, wobei die Ergebnisse den Einsatz als Schmierstoff ermöglichen.

For lubrication, the lubricant pump 16 delivers from the ionic liquid tank 7 and supplies the lubricant to the expander 4. The return of the lubricant via the lubricant return 17. Further, from the volume of air that is trapped in the tank for the ionic liquid 7, via the steam outlet 19, a remaining remainder of evaporating working fluid to the reservoir for operating fluid 2 are supplied. Furthermore, due to the operation of the expander an unavoidable, permanent leakage of the working medium, which flows via the return for escaping working fluid 18 to the tank for the ionic liquid 7, so that an equilibrium state with a tolerable proportion of working fluid in the lubricant circuit will set , The lubricant properties can also be fulfilled at a weight proportion of 10% by weight of working medium. This is explained below with reference to a mixture of EMIM-MeSO ₃ as ionic liquid with water as the working medium with a proportion by weight of 5% by weight:

• The kinematic viscosity at a temperature of 90 ° C is 5.3 cst. The density, the foam behavior and the air separation capacity (according to DIN ISO 9120 at 50 ° C) are suitable for lubricants. The lubricant properties were measured by means of a shell four-ball apparatus. A measurement according to DIN 51350-T2 at a speed of 1420 min ^-1 gave a welding force of 2400 N. A measurement according to DIN 51350-T3 at the same speed and a load of 300 N resulted in a dome diameter of 1.04 mm. Furthermore, the oxidation stability and the anti-corrosive behavior of the mixture were determined, the results allowing the use as a lubricant.

The above-mentioned requirements for the ionic liquid relating to a sufficiently low melting point for an antifreeze in the mixture with working fluid and a sufficiently high decomposition temperature to avoid decomposition of the ionic liquid in the steam generator 3, are determined by a suitable choice for the cations and the anions the ionic liquid is fulfilled. In addition, a good lubricity is present for a suitable ionic liquid. Furthermore, the cation / anion pairing is chosen so that an environmentally friendly, non-toxic and reliable ionic liquid is present. In particular, 1-ethyl-3-methyl-imidazolium (EMIM) is used as a possible choice for the cation and is linked to an anion from the group HSO ₄ ^- , MeSO ₃ and CF ₃ SO ₃ ^- .

Further embodiments of the invention as described in the independent claims are conceivable within the skill of the art. Thus, it is possible to use a combination of different working media to perform a Kalina process and provide heat sources at different temperature levels to form different vapor phases. Accordingly, it is conceivable to form the expander in multiple stages. Moreover, it is advantageous to design the expander so that in the case of an error occurring, in which a liquid component, for example, a portion of the ionic liquid, enters the expander, there is a sufficient water resistance.

LIST OF REFERENCE NUMBERS

1

Steam cycle

2

Reservoir for operating fluid

3

steam generator

4

expander

5

capacitor

6

Tank for working medium

7

Tank for the ionic liquid

8th

feed pump

9

Recirculation pump

10

bypass line

11

valve means

12

separator

13

filter

14

steam line

15

diverter

16

lubricant pump

17

Lubricant return

18

Return for escaping working medium

19

steam vent

20

internal combustion engine

21

exhaust system

Claims (18)

1. An operational fluid for a steam circuit process device, including:

   a vaporisable working medium and an antifreeze agent,

   characterised in that

   the antifreeze agent is an ionic fluid, whereas at a pressure of 1 bar the ionic fluid in pure form exhibits a melting point which lies in the range of 0 - 100 °C and above the freezing point of the pure working medium, and has a decomposition temperature which lies above the evaporating temperature of the working medium; and

   whereas the ionic fluid and the working medium form in the operational fluid a blend without complex bonds and the weight portions of the ionic fluid and of the working medium on the mixture amount at least to 0.01 % in weight and lies below -5 °C for a pressure of 1 bar of the melting point of the mixture.
2. The operational fluid according to claim 1, characterised in that the working medium includes water.
3. The operational fluid according to any of the claims 1 or 2, characterised in that the decomposition temperature of the ionic fluid is greater than 200 °C and preferably greater than 300 °C and in particular greater than 350 °C.
4. The operational fluid according to at least one of the preceding claims, characterised in that the melting temperature of the mixture of working medium and ionic fluid lies below -10 °C and in particular preferably below -30 °C.
5. The operational fluid according to at least one of the preceding claims, characterised in that the weight ratio between ionic fluid and working medium in the mixture is 90:10 - 10-90, preferably 80:20 - 20:80 and in particular preferably 60:40 - 40:60.
6. The operating fluid according to any one of the preceding claims, characterised in that the anion of the ionic fluid is a C1 to C4 alkyl sulphonate, preferably methyl sulphonate or a completely or partially fluorinated C1 to C4 alkyl sulphonate, preferably trifluoromethyl sulphonate.
7. The operating fluid according to any one of claims 1 - 5, characterised in that the cation of the ionic fluid is pyridinium or imidazolium or phosphonium or morpholinium and the anion of the ionic fluid is a C1 to C4 alkyl sulphonate, preferably methyl sulphonate or a completely or partially fluorinated C1 to C4 alkyl sulphonate, preferably trifluoromethyl sulphonate.
8. The operational fluid according to at least any of the claims 1 - 5, characterised in that the ionic fluid includes as cations 1-ethyl-3-methylimidazolium (EMIM) and the anion is selected from the group consisting of HSO₄ ^-, MeSO₃ ^- and CF₃SO₃ ^-.
9. The operational fluid according to one of the preceding claims, characterised in that the operational fluid is additionally a lubricant or a supplement to a lubricant.
10. A method for operating a steam circuit process (1), which is carried in a device comprising a steam generator (3), an expander (4), a condenser (5) and a reservoir for an operational fluid (2), the method comprising the following steps of:

    during cold start of the steam circuit process (1) an operational fluid according to one of the claims 1 - 9 is conveyed to the steam generator (3);

    in the steam generator (3), the working medium is evaporated from the mixture and conveyed in steam form to the expander (4) for expansion by way of a mechanical effect and then condensed in the condenser (5);

    the mixture of antifreeze agent and working medium is separated as of a prescribed operating temperature so that the weight portion of the antifreeze agent to the operational fluid which is conveyed to the steam generator (3) is reduced by at least 50 % and preferably 80 % and most preferably 95 %.
11. The method according to claim 10, characterised in that as of a specific operating temperature, the condensate of the working medium generated in the condenser (5) is guided in a tank for the working medium (6) which is separate from the reservoir for the operational fluid (2).
12. The method according to claim 11, characterised in that as of a specific filling level, the inflow of the operational fluid is interrupted from the reservoir (2) to the steam generator (3) in the separate tank for the working medium (6) and exclusively working medium is conveyed from the separate tank for the working medium (6) to the steam generator (3).
13. The method according to claim 10, characterised in that the operational fluid, which is not evaporated in the steam generator (3) is conveyed to a tank for the ionic fluid (7), which is formed separately to the reservoir for the operational fluid (2).
14. The method according to claim 13, characterised in that a lubrication circuit is supplied by the tank for the ionic fluid (7).
15. The method according to claim 14, characterised in that the lubrication circuit serves for lubricating the expander (4).
16. The method according to claim 14 or 15, characterised in that the steam circuit process is operated in a vehicle with an internal combustion engine and the lubrication circuit serves for lubricating at least of one mobile component of the internal combustion engine.
17. The method according to at least one of the claims 10 - 16, characterised in that the operating temperature is determined by a measurement of the temperature of the operational fluid in the reservoir (2).
18. The method according to at least one of the claims 10 - 17, characterised in that when shutting down the steam circuit process (1) after a preset period of time and/or within a specific ambient temperature the ionic fluid and the working medium are brought together.

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