EP2326802B1 - Liquide de fonctionnement pour un dispositif à cycle vapeur et procédé pour faire fonctionner un tel dispositif - Google Patents

Liquide de fonctionnement pour un dispositif à cycle vapeur et procédé pour faire fonctionner un tel dispositif Download PDF

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Publication number
EP2326802B1
EP2326802B1 EP09777858.3A EP09777858A EP2326802B1 EP 2326802 B1 EP2326802 B1 EP 2326802B1 EP 09777858 A EP09777858 A EP 09777858A EP 2326802 B1 EP2326802 B1 EP 2326802B1
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Prior art keywords
working medium
fluid
methyl
butyl
ionic
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German (de)
English (en)
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EP2326802A2 (fr
Inventor
Jürgen Berger
Markus Dittes
Christian Bausch
Dirk Gerhard
Aurelie Alemany
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Voith Patent GmbH
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Voith Patent GmbH
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/06—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using mixtures of different fluids
    • F01K25/065—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using mixtures of different fluids with an absorption fluid remaining at least partly in the liquid state, e.g. water for ammonia
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K13/00—General layout or general methods of operation of complete plants
    • F01K13/02—Controlling, e.g. stopping or starting

Definitions

  • 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.
  • 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.
  • 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.
  • a heat exchanger device in the steam generator in the steam generator.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the antifreeze also has lubricant properties.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the melting point of the mixture depends on the mixing ratio between ionic liquid and working medium.
  • 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.
  • 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.
  • the weight ratio of the ionic liquid to the working medium is in the range of 60:40 to 40:60.
  • 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.
  • a ventilated reservoir for the operating fluid is assumed.
  • 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.
  • 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.
  • expander lubrication is particularly suitable for this purpose.
  • 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.
  • thermal energy is supplied to the steam generator, for example via an exhaust gas stream from an internal combustion engine.
  • the operating fluid enters the steam generator.
  • the feeder can for example by means of a Feed pump can be realized.
  • evaporation of the working medium takes place while the ionic liquid generates a vapor pressure approaching zero and is returned to the reservoir.
  • 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.
  • 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.
  • the separated ionic liquid can be combined with the other components of the operating fluid at a correspondingly low ambient temperature.
  • mixing takes place only below a lower limit temperature in the reservoir for the operating fluid.
  • 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.
  • 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.
  • the ionic liquid is enriched due to the approaching zero partial pressure and can be withdrawn into a separate reservoir.
  • 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.
  • ionic liquids are characterized by further advantageous properties.
  • ionic liquids are typically nonflammable, they are electrically conductive and thus suppress the build-up of flow potentials.
  • cations / anion pairing their viscosity and density and their Mixing behavior can be adjusted with other liquids in a wide range.
  • 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.
  • the ionic liquid has a melting point of less than 70 ° C, more preferably less than 30 ° C at 1 bar.
  • 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.
  • 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.
  • 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;
  • Suitable cations are, for example, the cations of the general formulas (IVa) to (IVy) and oligomers containing these structures.
  • morpholinium can be chosen.
  • Another suitable cation is also a phosphonium cation of the general formula (IVy) and oligomers containing this structure.
  • 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
  • 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.
  • -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-
  • 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.
  • C 1 -C 18 -alkyl such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octy
  • 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;
  • 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
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C 6 -C 12 aryl is preferably phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 4- Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, t-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl
  • 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
  • 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,
  • 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.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • 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-butyl,
  • 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.
  • C 1 -C 18 -alkyl such as, for example, methyl, ethyl, 1-buty
  • 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.
  • IVa pyridinium ion
  • 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-tetradec
  • 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.
  • IVc pyrimidinium ion
  • 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.
  • IVd pyrazinium ion
  • 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.
  • IVe imidazolium ion
  • imidazolium ions 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-methylimidazolium, 1- (1-hexyl) -3-ethylimid
  • 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.
  • Ivl imidazolinium ion
  • 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.
  • IVs pyrrolidinium ion
  • 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.
  • IVt imidazolidinium ion
  • 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.
  • IVu ammonium ion
  • ammonium ions may be mentioned methyl tri (1-butyl) -ammonium, 2-hydroxyethyl-ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • guanidinium ion (IVv) is N, N, N ', N', N ", N" -hexamethylguanidinium.
  • 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
  • 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.
  • 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
  • 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+ .
  • anions in principle, all anions can be used which, in conjunction with the cation, lead to an ionic liquid.
  • 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,
  • 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) -
  • 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 (pentafluoroethylsulfon
  • Very particularly preferred anions are Chloride, bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methylsulfate, ethylsulfate, methylsulfonate, formate, acetate, dimethyl phosphate, diethyl phosphate, p-toluenesulfonate, tetrafluoroborate and hexafluorophosphate.
  • 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-methyl
  • FIG. 1 schematically shows simplified the basic components for an apparatus for performing a steam cycle process 1.
  • the steam process 1 may be designed as a Rankine Rankine process or as a Kalina-type cycle.
  • 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.
  • 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.
  • 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.
  • the ionic liquid used can be, for example, 1-ethyl-3-methylimidazolium methylsulfonate (EMIM MeSO 3 ).
  • EMIN MeSO 3 in pure form has a melting point of 35 ° C.
  • the glass transition for the mixture is at a temperature below-100 ° C.
  • the melting temperature increases and is -10 ° C. for a weight fraction of 80% by weight of water.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the ionic liquid is returned from the tank for the ionic liquid 7 to the reservoir for the operating fluid 2.
  • the ionic liquid fulfills a dual function.
  • the ionic liquid serves as an admixture to the working fluid to achieve adequate frost protection
  • the ionic liquid possibly with a residual amount of working fluid, as a lubricant.
  • the embodiment of the invention comprises a Dampf Vietnamese mixesvoriques 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.
  • 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.
  • FIG. 3 the basic components for the execution of the steam cycle process 1 shown.
  • 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.
  • a mixture of liquid and gas phase is fed to a separator 12, which separates the vaporous working medium and the expander 4 zu implicit.
  • 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.
  • valve device 11 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.
  • 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.
  • a good lubricity is present for a suitable ionic liquid.
  • the cation / anion pairing is chosen so that an environmentally friendly, non-toxic and reliable ionic liquid is present.
  • 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 - .

Claims (18)

  1. Liquide d'exploitation pour dispositif de procédé de vaporisation, comprenant:
    un fluide de travail vaporisable et un antigel,
    caractérisé en ce que
    que l'antigel est un liquide ionique, le liquide ionique sous forme pure présentant un point de fusion à une pression d'un bar, point de fusion situé dans la fourchette de 0 - 100 °C et supérieur au point de gel du liquide de travail pur, et présentant une température de décomposition supérieure à la température d'évaporation du fluide de travail; et
    le liquide ionique et le fluide de travail dans le liquide d'exploitation constituant un mélange sans liaisons complexes et les rapports en poids du liquide ionique et du fluide de travail dans le mélange sont au moins de 0,01 pourcent en poids et le point de fusion du mélange étant inférieur à -5 °C pour une pression d'un bar.
  2. Liquide d'exploitation selon la revendication 1, caractérisé en ce que le fluide de travail comprend de l'eau.
  3. Liquide d'exploitation selon l'une des revendications 1 ou 2, caractérisé en ce que la température de décomposition du liquide ionique est supérieure à 200 °C et de préférence supérieure à 300 °C et en particulier supérieure à 350 °C.
  4. Liquide d'exploitation selon l'une quelconque au moins des revendications précédentes, caractérisé en ce que la température de fusion du mélange de fluide de travail et de liquide ionique est inférieure à -10 °C et en particulier de préférence inférieure à -30 °C.
  5. Liquide d'exploitation selon l'une quelconque des revendications précédentes, caractérisé en ce
    que le rapport en poids entre le liquide ionique et le fluide de travail dans le mélange est de 90:10 - 10:90, de préférence 80:20 - 20:80 et de préférence particulière 60:40 - 40:60.
  6. Liquide d'exploitation selon l'une quelconque des revendications précédentes, caractérisé en ce que l'anion du liquide ionique est un C1-C4 alkylsulfonate, de préférence un méthylsulfonate ou bien un C1-C4 alkylsulfonate fluoré en tout ou partie, de préférence un trifluorméthylsulfonate.
  7. Liquide d'exploitation selon l'une quelconque des revendications 1 - 5, caractérisé en ce que le cation du liquide ionique est du pyridinium ou de l'imidazolium ou du phosphonium ou du morpholinium et l'anion du liquide ionique est un C1-C4 alkylsulfonate, de préférence un méthylsulfonate ou bien un C1-C4 alkylsulfonate fluoré en tout ou partie, de préférence un trifluorméthylsulfonate.
  8. Liquide d'exploitation selon l'une au moins des revendications 1 - 5, caractérisé en ce que le liquide ionique contient comme cations de 1-éthyl-3-méthyl-imidazolium (EMIM) et que l'anion est sélectionné par le groupe composé de HSO4 -, MeSO3 - et CF3SO3 -.
  9. Liquide d'exploitation selon l'une quelconque des revendications précédentes, caractérisé en ce que le liquide d'exploitation est en outre un lubrifiant ou bien supplément de lubrifiant.
  10. Procédé de fonctionnement d'un procédé de vaporisation (1), constitué
    dans un dispositif comprenant un générateur de vapeur (3), un expanseur (4), un condenseur (5) et un réservoir pour un liquide d'exploitation (2), où le procédé comporte les phases de procédé suivantes: en cas de démarrage à froid du procédé de vaporisation (1), un liquide d'exploitation selon l'une des revendications 1-9 est acheminé au générateur de vapeur (3);
    dans le générateur de vapeur (3), le fluide de travail s'évapore du mélange puis est acheminé sous forme de vapeur à l'expanseur (4) pour se détendre par un effet mécanique pour se condenser dans le condenseur (5);.
    le mélange d'antigel et de liquide de travail se sépare à partir d'une température d'exploitation donnée, de sorte que le rapport en poids de l'antigel au liquide d'exploitation acheminé au générateur de vapeur (3) baisse au moins de 50 % et de préférence de 80% et de préférence particulière de 95 %.
  11. Procédé selon la revendication 10, caractérisé en ce qu'à partir d'une température d'exploitation donnée le condensat du fluide de travail produit dans le condenseur (5) est guidé dans une citerne destinée au liquide de travail (6) et séparé du réservoir destiné au liquide d'exploitation (2).
  12. Procédé selon la revendication 11, caractérisé en ce qu'à partir d'une niveau de remplissage donné dans la citerne séparée et destinée au liquide de travail (6), l'arrivée du liquide d'exploitation allant du réservoir (2) vers le générateur de vapeur (3) est interrompue et exclusivement le fluide de travail est acheminé au générateur de vapeur (3) à partir de la citerne séparée et destinée au liquide de travail (6).
  13. Procédé selon la revendication 10, caractérisé en ce que le liquide d'exploitation non évaporé dans le générateur de vapeur (3) est acheminé vers une citerne destinée au liquide ionique (7), séparé du réservoir destiné au liquide d'exploitation (2).
  14. Procédé selon la revendication 13, caractérisé en ce qu'un circuit de lubrification provient de la citerne destinée au liquide ionique (7).
  15. Procédé selon la revendication 14, caractérisé en ce que le circuit de lubrification sert à la lubrification de l'expanseur (4).
  16. Procédé selon la revendication 14 ou 15 caractérisé en ce que le procédé de vaporisation se déroule dans un véhicule muni d'un moteur à combustion et le circuit de lubrification sert à la lubrification d'au moins un composant mobile du moteur à combustion.
  17. Procédé selon l'une au moins des revendications 10 - 16, caractérisé en ce que la température d'exploitation est définie par une mesure de la température du liquide d'exploitation dans le réservoir (2).
  18. Procédé selon l'une au moins des revendications 10 - 17, caractérisé en ce qu'en cas d'arrêt du procédé de vaporisation (1) le liquide ionique et le fluide de travail se rejoignent au bout d'un laps de temps donné et/ou à une température inférieure à une température ambiante donnée.
EP09777858.3A 2008-08-14 2009-08-13 Liquide de fonctionnement pour un dispositif à cycle vapeur et procédé pour faire fonctionner un tel dispositif Not-in-force EP2326802B1 (fr)

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PCT/EP2009/005875 WO2010017981A2 (fr) 2008-08-14 2009-08-13 Liquide de fonctionnement pour un dispositif à cycle vapeur et procédé pour faire fonctionner un tel dispositif

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WO2010017981A3 (fr) 2010-09-16

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