WO2010017981A2 - 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
WO2010017981A2
WO2010017981A2 PCT/EP2009/005875 EP2009005875W WO2010017981A2 WO 2010017981 A2 WO2010017981 A2 WO 2010017981A2 EP 2009005875 W EP2009005875 W EP 2009005875W WO 2010017981 A2 WO2010017981 A2 WO 2010017981A2
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WO
WIPO (PCT)
Prior art keywords
ionic liquid
methyl
operating fluid
working medium
steam generator
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Application number
PCT/EP2009/005875
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German (de)
English (en)
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WO2010017981A3 (fr
Inventor
Jürgen Berger
Markus Dittes
Christian Bausch
Dirk Gerhard
Aurelie Alemany
Original Assignee
Voith Patent Gmbh
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Application filed by Voith Patent Gmbh filed Critical Voith Patent Gmbh
Priority to US12/737,670 priority Critical patent/US20110265476A1/en
Priority to EP09777858.3A priority patent/EP2326802B1/fr
Publication of WO2010017981A2 publication Critical patent/WO2010017981A2/fr
Publication of WO2010017981A3 publication Critical patent/WO2010017981A3/fr

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Classifications

    • 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 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.
  • BEST ⁇ nGUNGSKOPte 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.
  • 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.
  • 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 disclosed by DE 103 28 289 B3, which proposes a mixture of water and at least one heterocyclic compound as operating liquid for a steam cycle process and additional, miscible polymers, surface-active 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.
  • 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 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 0 ° C.
  • a melting point below -5 0 C, more preferably below -10 0 C and particularly preferably below -30 0 C.
  • a pressure of 1 bar is assumed for all temperature data.
  • 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, preferably no complex formations are present in the mixture between the ionic liquid and the working medium so as not to have to break any substantial binding forces in order to evaporate the working medium.
  • an inventive mixture of ionic liquid and working medium in a proportion of 99.99 gw .-% to 0,01gw .-% working medium has a melting point for the mixture which is below 0 0 C, preferably below -5 0 C, and more preferably below -10 0 C and more preferably below -30 0 C.
  • the pure ionic liquid used for the mixture has a melting point which is above the freezing point of the pure working medium.
  • an ionic liquid can be used which is in pure form in the temperature interval 0 - 100 0 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.
  • the operating method comprises the following steps:
  • the starting point is initially the stoppage of the steam cycle in cold outside temperatures.
  • 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.
  • 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.
  • ionic liquids are 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 0 C at 1 bar.
  • the ionic liquid has a melting point of less than 70 0 C, more preferably less than 30 0 C and most preferably less than 0 ° C at 1 bar.
  • the ionic liquid under normal conditions (1 bar, 21 0 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
  • n 1, 2, 3 or 4
  • [A] + is an ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation and [Y] n ' for a one-, two- or three-membered trivalent or tetravalent anion is;
  • [A 1 ] + , [A 2 ] + , [A 3 ] + and [A 4 ] + are independently selected from the groups mentioned for [A] + and [Y] n ⁇ has the meaning mentioned under B1) ; or
  • Suitable cations are, for example, the cations of the general formulas (IVa) to (IVy)
  • morpholinium can be chosen.
  • Another suitable cation is also a phosphonium cation of the general formula (IVy)
  • the radical R represents a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or aromatic radical aliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms;
  • 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.
  • Contains the carbon-containing radical heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred.
  • the radicals R 1 to R 9 are, in the cases in which those in the above-mentioned 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 1 - (tertiary amide), are included, for example, di- (Ci-C 4 alkyl) amino, dC 4 alkyloxycarbonyl or dC 4 - alkyloxy.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • the radical R particularly preferably represents 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, especially for methyl, ethyl, 1-butyl and 1-octyl and for 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,
  • radicals R 1 to R 9 are preferably each independently
  • Halogen a functional group; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy,
  • C 1 -C 4 -alkyl which is substituted by 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; optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy,
  • Halogen, heteroatoms and / or heterocycles substituted C 5 -C 2 -cycloalkyl; 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
  • aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted Cr to C-i ⁇ -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, 2-methyl-3-p
  • 2- Aryl is preferably phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / so-propylphenyl, tert Butyl-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C 5 - to C-12-cycloalkyl is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C q F 2 ( qa ) - (i- b ) H 2a-b with q ⁇ 30, 0 ⁇ a ⁇
  • 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 a plurality of 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, 3rd -propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-C- ⁇ -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 -
  • 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.
  • radicals R 1 to R 9 are each independently
  • R 1 is - (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 is preferably hydrogen, methyl or ethyl and p is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9, 12-tetraoxatetradecyl; Vinyl; and
  • N, N-di-Ci-C 6 alkyl-amino such as N, N-dimethylamino and N 1 N-diethylamino.
  • the radicals R 1 to R 9 are each independently hydrogen or Ci-Cis-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 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 - where p is O to third
  • R 1 to R 5 is methyl, ethyl or chlorine and the remaining radicals
  • 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
  • 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
  • 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.
  • pyridinium ions (IVa) there may be mentioned 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1 Hexyl) -pyhdinium, 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,
  • 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.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independent of one another
  • R 1 is hydrogen, methyl or ethyl
  • R 2 and R 4 are methyl and R 3 is hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independent of one another
  • 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
  • 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.
  • imidazolium ions IVe
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • R 1 to R 4 are independently hydrogen or methyl.
  • R 1 to R 6 are hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are independently hydrogen or methyl.
  • ionic liquids in which the cation [A] + is an imidazolinium ion (IvI), 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.
  • IvI imidazolinium ion
  • R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R 6 are independently hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently hydrogen or methyl.
  • 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.
  • R 1 to R 3 are independently C 1 -C 6 alkyl
  • R 1 to R 3 are independently hydrogen or C 1 -C 18 -alkyl and R 4
  • R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R 3 is CrCl 8 -
  • Alkyl, 2-hydroxyethyl or 2-cyanoethyl Alkyl, 2-hydroxyethyl or 2-cyanoethyl.
  • ammonium ions may be mentioned methyl tri (i-butyl) -ammonium, 2-hydroxyethyl-ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • guanidinium ion may be mentioned N, N, N 1 , N ⁇ N ", N" hexamethylguanidinium.
  • R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group
  • 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
  • R 3 to
  • R 5 is independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -
  • R 1 to R 3 are independently CiC-i ⁇ -alkyl, especially 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-oct
  • the metal cations [M 1 ] + , [M 2 J + , [M 3 ] + , [M 4 ] 2+ and [M 5 ] 3+ mentioned in formulas (IIIa) to (MIj) 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.
  • the anion [Yf ' ] of the ionic liquid is selected, for example, from: the group of halides and halogen-containing compounds of the formulas:
  • R 3 BO 2 2 -, R 3 R b BO " the group of carbonates and carbonic esters of the general formulas:
  • R b is -O 2 S ' SO 2 -R C
  • M is a metal and Hal is fluorine, chlorine, bromine or iodine, r and t are positive integers indicating the stoichiometry of the complex and s is an integer positive number and the charge of Indicates complex; the group of sulfides, hydrogen sulfides, polysulfides, hydrogen polysulfides and
  • R a , R b , R c and R d are each independently
  • CrC 30 -AlkVl 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-p
  • 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-ToIyI), 3-methyl-phenyl (3
  • 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; chloroferrate; bis (trifluoromethylsulfonyl) imide; bis (pentafluoroethylsulfonyl
  • 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
  • Chloride bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methylsulfate, ethylsulfate, methylsulfonate, formate, acetate, dimethylphosphate, diethylphosphate, p-tolylsulfonate, tetrafluoroborate and hexafluorophosphate;
  • FIG. 1 shows in a principle sketch a device for carrying out a steam cycle process, which serves to implement the operating method according to the invention.
  • FIG. 2 shows an alternative embodiment to the device from FIG. 1.
  • FIG. 3 shows a further development of a steam cycle device for the
  • FIG. 1 schematically shows in simplified form the basic components for a device for carrying out a steam cycle process 1.
  • the steam process 1 can be designed as a Rankine cycle process or as a Kalina-type cyclic process.
  • 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 to the steam generator 3 by means of a feed pump 8, which is advantageously designed to be variable in speed for adjusting the volume flow.
  • 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.
  • water for example 1-ethyl-3-methylimidazolium methylsulfonate (EMIM MeSO.sub.3) can be used as the ionic liquid.
  • EMIN MeSO ß in pure form has a melting point of 35 0 C.
  • the glass transition for the mixture is at a temperature below -100 ° C.
  • the melting temperature increases and is for a weight fraction of 80 gw .-% of water, at -10 0 C.
  • the melting point of the mixture is advantageously low at -36 0 C.
  • 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 proportion of water of 50-80 gw .-% below -20 0 C.
  • Other mixtures of ionic liquid to water in a weight ratio of 60:40 and 50:50 with a melting point below -20 0 C may 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.
  • 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 ionic liquid after passing through the steam generator 3, the ionic liquid is returned to the reservoir for the operating fluid 2 by means of a bypass line 10.
  • 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.
  • 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 is preferred after reaching a certain level in the tank for the working medium 6, the corresponds to the necessary for the operation of the steam cycle process 1 volume of working medium, a valve unit 11 which controls the influx of 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 decoupled is and the feed pump 8 scoops 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 a device for carrying out a steam cycle with the operating fluid according to the invention with a possibility of separating the ionic liquid from the operating fluid for a system to temperature.
  • a separate tank for the ionic liquid 7 is sketched in FIG. 2, 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 liquid 2.
  • 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. 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.
  • 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 zuorg.
  • 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 shown in FIG.
  • the lubricant pump 16 delivers from the ionic liquid tank 7 and supplies the lubricant to the expander 4.
  • a remaining remainder of evaporating working fluid to the reservoir for operating fluid 2 are supplied.
  • the lubricant properties can also be fulfilled at a weight proportion of 10% by weight of working medium.
  • 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 linked to an anion from the group HSO 4 ' , MeSO 3 and CF 3 SO 3 ' .

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)

Abstract

L'invention concerne un liquide de fonctionnement pour un dispositif à cycle vapeur comprenant un générateur de vapeur, un détendeur, un condenseur et un réservoir pour le liquide de fonctionnement. Le liquide de fonctionnement selon l'invention comprend un fluide de travail qui s'évapore par apport de chaleur dans le générateur de vapeur, qui effectue un travail mécanique dans la phase vapeur par détente dans le détendeur et qui condense dans le condenseur, ainsi qu'un liquide ionique formant un mélange avec le fluide de travail, le point de fusion du mélange étant inférieur à -5 °C.
PCT/EP2009/005875 2008-08-14 2009-08-13 Liquide de fonctionnement pour un dispositif à cycle vapeur et procédé pour faire fonctionner un tel dispositif WO2010017981A2 (fr)

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US12/737,670 US20110265476A1 (en) 2008-08-14 2009-08-13 Operational fluid for a vapour circuit processing device and a method for operating same
EP09777858.3A EP2326802B1 (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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DE102008037744A DE102008037744A1 (de) 2008-08-14 2008-08-14 Betriebsflüssigkeit für eine Dampfkreisprozessvorrichtung und ein Verfahren für deren Betrieb

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JP2013538315A (ja) * 2010-08-26 2013-10-10 イゴール・アナトリエヴィッチ・レヴェンコ エネルギーを変換し、エンタルピーを増加させ、圧縮係数を高めるための方法
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US11293309B2 (en) 2014-11-03 2022-04-05 Echogen Power Systems, Llc Active thrust management of a turbopump within a supercritical working fluid circuit in a heat engine system
US11435120B2 (en) 2020-05-05 2022-09-06 Echogen Power Systems (Delaware), Inc. Split expansion heat pump cycle
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WO2011131482A3 (fr) * 2010-04-21 2012-01-05 Robert Bosch Gmbh Dispositif de récupération de chaleur perdue
US9382816B2 (en) * 2010-06-01 2016-07-05 Man Truck & Bus Ag Method and apparatus for operating a steam cycle process with a lubricated expander
US20130263598A1 (en) * 2010-06-01 2013-10-10 Man Truck & Bus Ag Method and Apparatus for Operating a Steam Cycle Process with a Lubricated Expander
AU2011260641B2 (en) * 2010-06-01 2015-12-17 Man Truck & Bus Ag Method and apparatus for operating a steam cycle process with a lubricated expander
JP2013538315A (ja) * 2010-08-26 2013-10-10 イゴール・アナトリエヴィッチ・レヴェンコ エネルギーを変換し、エンタルピーを増加させ、圧縮係数を高めるための方法
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WO2012100897A3 (fr) * 2011-01-24 2014-04-17 Robert Bosch Gmbh Dispositif et procédé pour récupérer la chaleur dégagée par un moteur à combustion interne
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EP2520771A1 (fr) * 2011-05-03 2012-11-07 Technische Universität München Procédé et dispositif de chauffage rapide de lubrifiant pour machines d'expansion lubrifiées
US10934895B2 (en) 2013-03-04 2021-03-02 Echogen Power Systems, Llc Heat engine systems with high net power supercritical carbon dioxide circuits
US11293309B2 (en) 2014-11-03 2022-04-05 Echogen Power Systems, Llc Active thrust management of a turbopump within a supercritical working fluid circuit in a heat engine system
US11187112B2 (en) 2018-06-27 2021-11-30 Echogen Power Systems Llc Systems and methods for generating electricity via a pumped thermal energy storage system
US11435120B2 (en) 2020-05-05 2022-09-06 Echogen Power Systems (Delaware), Inc. Split expansion heat pump cycle
US11629638B2 (en) 2020-12-09 2023-04-18 Supercritical Storage Company, Inc. Three reservoir electric thermal energy storage system

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EP2326802A2 (fr) 2011-06-01
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DE102008037744A1 (de) 2010-02-25
US20110265476A1 (en) 2011-11-03

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