US20110265476A1 - Operational fluid for a vapour circuit processing device and a method for operating same - Google Patents

Operational fluid for a vapour circuit processing device and a method for operating same Download PDF

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Publication number
US20110265476A1
US20110265476A1 US12/737,670 US73767009A US2011265476A1 US 20110265476 A1 US20110265476 A1 US 20110265476A1 US 73767009 A US73767009 A US 73767009A US 2011265476 A1 US2011265476 A1 US 2011265476A1
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Prior art keywords
ionic liquid
working medium
operating fluid
methyl
mixture
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Jurgen 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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Assigned to VOITH PATENT GMBH reassignment VOITH PATENT GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALEMANY, AURELIE, GERHARD, DIRK, DITTES, MARKUS, BAUSCH, CHRISTIAN, BERGER, JURGEN
Publication of US20110265476A1 publication Critical patent/US20110265476A1/en
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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 an operating fluid for a steam cycle process apparatus, a method for the operation thereof and a suitable steam cycle process apparatus for implementing the method.
  • Steam cycle processes are used to convert thermal energy into mechanical energy and are used, for example, for power generating units which generate a heat flow by means of a burner device, which is fed to a steam generator.
  • a working medium is evaporated by supplying heat, wherein the vapour phase thus produced expands whilst performing mechanical work in an expander and then condenses in a condenser.
  • the condensate is supplied to a reservoir from which a renewed inflow to the steam generator is accomplished by means of a feed pump for the working medium.
  • a steam engine can furthermore be used to utilise the waste heat of an internal combustion engine, whereby, for example, its exhaust gas flow is fed to a heat exchanger device in the steam generator.
  • the waste heat in the cooling water of an internal combustion engine can then be supplied at least indirectly to a shaft of the drive system or an electrical generator is driven by the expander.
  • an apparatus for executing a steam cycle process can be configured as an auxiliary unit utilising the waste heat of a main engine which either provides motor assistance to the propulsion of the vehicle or provides electrical energy for secondary consumers.
  • the operating fluid for a steam cycle process comprises additives to the working medium. These can form an azeotrope with the working medium.
  • An example for this is disclosed by DE 103 28 289 B3, which proposes as operating fluid for a steam cycle process, a mixture of water and at least one heterocyclic compound as well as additional, miscible polymers, tenside and/or other organic lubricants.
  • 2-methyl pyridine, 3-methyl pyridine, pyridine, pyrrole and pyridazine are suggested as heterocyclic compound.
  • the freezing point of the operating fluid is set below 0° C.
  • the heterocyclic compound forms an azeotrope with water so that this goes over into the gas phase together with the water fraction in the steam generator.
  • lubricant is also transported to the expander in the vapour phase for executing a self-lubrication.
  • a disadvantage of the known operating fluids for steam cycle processes is their toxicity so that expensive precautions must be taken to reliably prevent any escape of the operating fluid or its gas phase. When used in vehicles, in particular in motor vehicles, this cannot however be completely eliminated in view of possible accident risks.
  • the operating fluid should be environmentally compatible and in particular not toxic for plants and living organisms and should be characterised by a high accident safety.
  • a further object of the invention is to provide a method by which means the steam cycle process can be operated with the operating fluid such that this is configured as energy-efficiently as possible, as well as an apparatus for executing the method.
  • the operating fluid for the steam cycle process should additionally be used for the lubrication of the revolving components of the steam engine and in the case of a vehicle application, preferably for the lubrication of the moving parts of the drive system including the internal combustion engine.
  • the object of the invention is achieved by the operating fluid comprising at least two components.
  • the first component is a working medium which is used for the actual operation of the steam cycle process. Accordingly, evaporation of the working medium is accomplished by supplying heat in the steam generator, a subsequent expansion takes place in the expander whilst performing mechanical work and then condensation takes place whilst returning the condensate, typically via a reservoir and a feed pump, for renewed entry into the cycle, that is, for renewed evaporation in the steam generator.
  • a further component of the operating fluid for the steam cycle process according to the invention is a frost protection agent that under normal operating conditions undergoes substantially no evaporation in the steam generator and merely serves to keep the operating liquid in the reservoir liquid at low external temperature and therefore to allow a cold starting of the system.
  • the frost protection agent simultaneously exhibits lubricant properties.
  • an ionic liquid is used as frost protection agent, wherein the mixture of ionic liquid and working medium has a melting point which lies 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 lies below 0° C.
  • a melting point below ⁇ 5° C. is preferred, particularly preferably below ⁇ 10° C. and especially preferably below ⁇ 30° C.
  • a pressure of 1 bar is assumed for all the temperature information.
  • a mixture between an ionic liquid suitable for frost protection and the working medium is understood in the present case such that each of the two components is present in the mixture at least with a minimum weight fraction of 0.01 gw. % (percent by weight).
  • no complex formations should be present in the mixture between the ionic liquid and the working medium so that no substantial binding forces need to be broken to evaporate the working medium.
  • a mixture of ionic liquid and working medium according to the invention having a fraction of 99.99 gw. % (percent by weight) to 0.01 gw. % (percent by weight) working medium accordingly has a melting point for the mixture that lies below 0° C., preferably below ⁇ 5° C. and particularly preferably below ⁇ 10° C. and further preferably below ⁇ 30° C.
  • the ionic liquid used for the mixture in pure form has a melting point which lies above the freezing point of the pure working medium.
  • an ionic liquid can be used which in pure form melts in the temperature range of 0-100° C.
  • the required frost protection effect accordingly consists in the mixture of ionic liquid and working medium.
  • the melting point of the mixture in the present case is understood as the temperature of the crystallisation boundary of the mixture so that the mixture is liquid above the melting point and can be pumped from the reservoir.
  • the melting point of the mixture is dependent on the mixing ratio between ionic liquid and working medium.
  • the feature of a melting point lying below the freezing point of the pure working medium should apply at least in a mixing ratio range which is present in a collecting reservoir of a cold, stopped steam cycle process apparatus.
  • a weight fraction of the working medium of at least 10 gw. % and at most 90 gw. % is assumed, the range of 20 gw. % (percent by weight) to 80 gw. % (percent by weight) being more strongly preferred for the fraction of working medium.
  • the weight ratio of the ionic liquid to working medium lies in the range of 60:40 to 40:60.
  • the previously specified reference pressure of 1 bar is exceeded or fallen below in certain operating phases or parts of the steam cycle process apparatus.
  • the previously specified temperature condition relating to the melting point of the mixture of ionic liquid and working medium should be valid for the prevailing system pressure.
  • a ventilated reservoir for the operating fluid is assumed.
  • the mixing ratio in the operating fluid can shift with increasing temperature. This can lead to substantially complete separation of the ionic liquid from the working medium.
  • the mixing ratio shifts so far that the temperature condition for the melting point of the mixture as lying below the freezing point of the working medium is no longer satisfied for certain operating phases. This will still be understood as part of the invention.
  • the mixing ratio is restored again in a collecting reservoir in order to ensure the frost safety again.
  • Ionic liquids owe their low melting point to a poor ionic coordination.
  • the delocalised charges are responsible for this, wherein typically at least one ion is based on an organic molecule and the formation of a stable crystal lattice is already prevented at low temperatures.
  • Typical for ionic liquids is the possibility of selecting their physical/chemical properties through the choice of cation/anion pairing so that it is possible to tailor an ionic liquid for the operating fluid according to the invention for the steam cycle process such that when mixed with the working medium, a low melting point is formed in the sense of a frost protection effect.
  • ionic liquids for use as part of an operating fluid for a steam cycle process can be seen in that the ionic liquid is characterised by a vanishing vapour pressure up to its decomposition temperature. If the decomposition temperature is adjusted by means of a corresponding choice of the cation/anion pairing for the ionic liquid such that this lies above the temperature of the liquid phase of the operating fluid in the steam generator, it is possible that the ionic liquid does not go over into the gas phase and is passed to the expander like the actual working medium. As a result, a simple possibility for separating the ionic liquid from the operating fluid is obtained for the case that the operating temperature of the steam cycle process is reached or that a temperature is present in the system at which frost safety is no longer necessary.
  • the energetically disadvantageous case can be prevented that the frost protection agent component, that is the ionic liquid, must be heated in the steam generator without making an energy contribution in the steam cycle.
  • the extracted ionic liquid or a branched-off mixture enriched with ionic liquid containing a reduced fraction of working medium can be used for a further embodiment of the invention for lubrication.
  • the expander lubrication comes into consideration for this.
  • further components to be lubricated can be supplied. This also includes the lubrication of revolving parts of an internal combustion engine which is combined with a steam engine as a hybrid drive.
  • the operating method comprises the following operations:
  • the starting point is initially the steam cycle process being at a standstill at cold external temperatures.
  • the operating fluid is collected in a reservoir and contains a mixture comprising the working medium that is provided for evaporation in the steam generator and the ionic liquid which acts as a frost protection agent in the mixture, so that even at low external temperatures when the steam cycle process is at a standstill, the operating fluid is present in liquid form in a reservoir.
  • thermal energy for example, via an exhaust gas flow stream from an internal combustion engine
  • the operating fluid enters into the steam generator.
  • the supply can be accomplished, for example, by means of a feed pump.
  • evaporation of the working medium takes place whilst the ionic liquid produces a vapour pressure which tends to zero and is returned to the reservoir.
  • said liquid is not returned to a reservoir but to a separate tank for an ionic liquid.
  • the vaporous working medium is fed to the condenser, wherein according to an advantageous embodiment the condensate of the working medium thus formed is not returned to the reservoir but is fed to a separate tank for the working medium.
  • a continuous separation of the ionic liquid and the working medium is produced by this measure.
  • this separation should advantageously only be made above a specific operating temperature.
  • the operating temperature can therefore be measured at various positions in the apparatus for executing the steam cycle process, wherein the operating fluid in the reservoir can advantageously be used at the location of the temperature measurement. If a specific temperature which lies above the freezing point of the working medium is reached in the reservoir, the previously described separation of the working medium and the ionic liquid can be made.
  • Various separation methods can be used here.
  • the separated ionic liquid can be combined with the further components of the operating fluid.
  • a mixing only takes place below a lower limiting 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 partial components, 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 take place such that after running through the steam generator, the operating fluid is passed through a separator in which the vaporous working medium is separated.
  • the ionic liquid is enriched as a result of the partial pressure which tends to zero, and can be extracted into a separate reservoir.
  • a lubrication circuit can be supplied from this reservoir, wherein in addition to the frost protection effect, the lubrication properties of the ionic liquid or a mixture enriched with this can advantageously be utilised.
  • ionic liquids are characterised by further advantageous properties. Ionic liquids are typically not combustible, they are electrically conductive and thus suppress the build-up of flow potentials. Furthermore, their viscosity and density and their mixing behaviour with other liquids can be adjusted in a wide range through the choice of the cation/anion pairing.
  • ionic liquids come into consideration which contain as anion a C1 to C4 alkyl sulphonate, preferably methyl sulphonate or a completely or partially fluorinated C1 to C4 alkyl sulphonate, preferably trifluoromethyl sulphonate.
  • Particularly preferred ionic liquids are those containing a cation of the formula IV a (pyridinium) or IV e (imidazolium) or IV x (phosphonium) or IV y (morpholinium) and as anion a C1 to C4 alkyl sulphonate, preferably methyl sulphonate or a completely or partially fluorinated C1 to C4 alkyl sulphonate, preferably trifluoromethyl sulphonate, or in a quite particularly preferred embodiment consist exclusively of such a cation and anion.
  • An ionic liquid is a salt having a melting point below 100° C. at 1 bar.
  • the ionic liquid preferably has a melting point below 70° C., particularly preferably below 30° C. and quite particularly preferably below 0° C. at 1 bar.
  • the ionic liquid is liquid under normal conditions (1 bar, 21° C.), that is at room temperature.
  • Preferred ionic liquids contain at least one organic compound as a cation, quite particularly preferably they contain exclusively organic compounds as cations.
  • Suitable organic cations are in particular organic compounds with heteroatoms such as nitrogen, sulphur or phosphorus. Particularly preferably these comprise organic compounds with at least one, preferably precisely one cationic group selected from an ammonium group, an oxonium group, a sulphonium group or a phosphonium group.
  • the ionic liquids comprise salts with ammonium cations which are understood to be compounds with quadricovalent nitrogen and positive charge localised at nitrogen or aromatic ring systems with at least one, preferably one or two, particularly preferably two nitrogen atoms in the ring system and a delocalised positive charge.
  • ammonium cations are the imidazolium cations, which are understood to be all compounds having an imidazolium ring system and possibly arbitrary substituents at the carbon and/or nitrogen atoms of the ring system.
  • the anion can comprise an organic or inorganic anion.
  • Particularly preferred ionic liquids consist exclusively of the salt of an organic cation with one of the anions named hereinafter.
  • the molar weight of the ionic liquids is preferably less than 2000 g/mol, particularly preferably less than 1500 g/mol, particularly preferably less than 1000 g/mol and quite particularly preferably less than 750 g/mol; in a particular embodiment the molar weight is between 100 and 750 or between 100 and 500 g/mol.
  • Suitable ionic liquids are in particular salts having the following general formula I
  • n denotes 1, 2, 3 or 4
  • [A] + denotes an ammonium cation, an oxonium cation, a sulphonium cation or a phosphonium cation
  • [Y] n ⁇ denotes a mono-, di-, tri- or tetravalent anion
  • [A 1 ] + , [A 2 ] + , [A 3 ] + and [A 4 ] + are selected independently of one another from the groups specified for [A] + and [Y] n ⁇ have the meaning specified under B1); or
  • [A 1 ] + , [A 2 ] + and [A 3 ] + are selected independently of one another from the groups specified for [A] + , [Y] n ⁇ has the meaning specified under B1) and [M 1 ] + , [M 2 ] + , [M 3 ] + denote monovalent metal cations, [M 4 ] 2+ denote divalent metal cations and [M 5 ] 3+ denote trivalent metal cations;
  • Suitable cations are, for example, the cations of the general formulae (IVa) to (IVy)
  • Morpholinium can furthermore be selected.
  • Another suitable cation is a phosphonium cation having the general formula (IVy)
  • the group R denotes 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, or substituted group having 1 to 20 carbon atoms;
  • the groups R 1 to R 9 independently of one another can denote hydrogen, a sulpho-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, or substituted group having 1 to 20 carbon atoms, wherein the groups R1 to R9, which in the aforesaid formulae (IV) are bound to a carbon atom (and not to a heteroatom), can additionally also denote halogen or a functional group; or
  • two neighbouring groups from the series R 1 to R 9 together can also denote 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, or substituted group having 1 to 30 carbon atoms.
  • Possible heteroatoms in the definition of the groups R and R 1 to R 9 are in principle all heteroatoms which are capable of formally replacing a —CH 2 —, a —CH ⁇ , a —C ⁇ or a ⁇ C ⁇ . If the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulphur, phosphorus and silicon are preferred. As preferred groups, mention is made in particular of —O—, —S—, —SO—, —SO 2 —, —NR′—, —N ⁇ , —PR′—, —POR′— and —SiR′ 2 —, wherein the groups R 1 comprise the remaining part of the carbon-containing group. In cases where the groups R 1 to R 9 are bound to a carbon atom (and not a heteroatom) in the aforesaid formulae (IV), these can also be directly bound via the heteroatom.
  • Possible functional groups are in principle all functional groups which can be bound to a carbon atom or a heteroatom.
  • —OH hydroxy
  • ⁇ O in particular as a carbonyl group
  • —NH 2 amino
  • ⁇ NH amino
  • imino amino
  • —COOH carboxy
  • —CONH 2 carboxy
  • SO 3 H sulpho
  • CN cyano
  • Functional groups and heteroatoms can also be directly adjacent so that combinations of several neighbouring atoms such as —O— (ether), —S— (thioether), —COO— (ester), —CONH— (secondary amide) or —CONR′— (tertiary amide), are also comprised, for example, di-(C 1 -C 4 -alkyl)-amino, C 1 -C 4 -alkyloxy-carbonyl or C 1 -C 4 -alkyloxy.
  • halogens mention is made of fluorine, chlorine, bromine and iodine.
  • the group R preferably denotes
  • the group R denotes 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 as well as 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 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
  • the groups R 1 to R 9 independently of one another preferably denote
  • C 1 -C 18 -alkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds and/or interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted imino groups;
  • C 2 -C 18 -alkenyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds and/or interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted imino groups;
  • C 6 -C 12 -aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds;
  • C 5 -C 12 -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds;
  • C 5 -C 12 -cycloalkenyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds; or
  • heterocyclic compound comprising oxygen, nitrogen and/or sulphur atoms optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds; or
  • two neighbouring groups together denote an unsaturated, saturated or aromatic ring optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds and optionally interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted imino groups;
  • C 1 - to C 18 -alkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds preferably comprises 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-penty
  • C 6 -C 12 -aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds preferably comprises phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert.-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaph
  • a five- to six-membered heterocyclic compound comprising oxygen, nitrogen and/or sulphur atoms optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds preferably comprises furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylchinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluorpyridyl.
  • the aforesaid groups contain oxygen and/or sulphur atoms and/or substituted or unsubstituted imino groups
  • the number of oxygen and/or sulphur atoms and/or imino groups is not restricted. Usually these amount to no more than 5 in the group, preferably no more than 4 and quite particularly preferably no more than 3.
  • the aforesaid groups contain heteroatoms, usually at least one carbon atom, preferably at least two carbon atoms are found between two heteroatoms.
  • C 1 -C 18 -Alkyl having a total of 1 to 20 carbon atoms such as, for example, 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
  • N,N-Di-C 1 -C 6 -alkyl-amino such as, for example, N,N-dimethylamino and N,N-diethyl-amino.
  • the groups R 1 to R 9 independently of one another stand for 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 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 — where p is 0 to 3.
  • C 1 -C 18 -alkyl such as for example methyl, ethyl, 1-butyl, 1-pentyl
  • ionic liquids in which the cation [A] + is a pyridinium ion (IVa) in which
  • R 3 is dimethylamino and the remaining groups R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 2 is carboxy or carboxamide and the remaining groups 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 groups R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 1 to R 5 are hydrogen;
  • one of the groups R 1 to R 5 is methyl or ethyl and the remaining groups R 1 to R 5 are hydrogen.
  • pyridinium ions IVa
  • ionic liquids in which the cation [A] + is a pyridazinium ion (IVb) in which
  • R 1 to R 4 are hydrogen;
  • one of the groups R 1 to R 4 is methyl or ethyl and the remaining groups R 1 to R 4 are hydrogen.
  • 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 independently of one another are hydrogen or methyl; or
  • R 1 is hydrogen, methyl or ethyl
  • R 2 and R 4 are methyl and R 3 is hydrogen.
  • 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 of one another 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
  • R 1 to R 4 are methyl [or] hydrogen.
  • 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 independently of one another are hydrogen, methyl or ethyl.
  • imidazolium ions mention may be made of 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-methyl-imidazolium, 1-(1-hexyl)-3-ethylimidazolium, 1-(1-hexyl)-3-methyl-imidazolium, 1-(1-hexyl)-3-ethy
  • ionic liquids in which the cation [A] + is a pyrazolium ion (IVf), (IVg) or (IVg′), in which
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is a pyrazolium ion (IVh) in which
  • R 1 to R 4 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is a 1-pyrazolinium ion (IVi) in which
  • R 1 to R 6 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is a 2-pyrazolinium ion (IVj′) in which
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is a 3-pyrazolinium ion (IVk) or (IVk′) in which
  • R 1 and R 2 independently of one another are hydrogen, methyl, ethyl or phenyl, and R 3 to R 6 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is an imidazolinium ion (Ivl) in which
  • R 1 and R 2 independently of one another are hydrogen, methyl, ethyl, 1-butyl or phenyl
  • R 3 and R 4 independently of one another are hydrogen, methyl or ethyl
  • R 5 and R 6 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is an imidazolinium ion (IVm) or (IVm′), in which
  • R 1 and R 2 independently of one another are hydrogen, methyl or ethyl and R 3 to R 6 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is an imidazolinium ion (IVn) or (IVn′), in which
  • R 1 to R 3 independently of one another are hydrogen, methyl or ethyl and R 4 to R 6 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is a thiazolium ion (IVo) or (IVo′) and is an oxazolium ion (IVp) in which
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is a 1,2,4-triazolium ion (IVq), (IVq′) or (IVq′′) in which
  • R 1 and R 2 independently of one another are hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • ionic liquids in which the cation [A] + is a 1,2,3-triazolium ion (IVr), (IVr′) or (IVr′′) in which
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 3 independently of one another are hydrogen or methyl, or R 2 and R 3 together is 1,4-buta-1,3-dienylene.
  • 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 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is an imidazolidinium ion (IVt) in which
  • R 1 and R 4 independently of one another are hydrogen, methyl, ethyl or phenyl and R 2 and R 3 as well as R 5 to R 8 independently of one another are hydrogen or methyl.
  • ionic liquids in which the cation [A] + is an ammonium ion (IVu) in which
  • R 1 to R 3 independently of one another are C 1 -C 18 -alkyl; or
  • R 1 to R 3 independently of one another are 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.
  • ammonium ions IVu
  • ionic liquids in which the cation [A] + is a guanidinium ion (IVv) in which
  • R 1 to R 5 are methyl.
  • ionic liquids in which the cation [A] + is a cholinium ion (IVw) in which
  • R 1 and R 2 independently of one another are 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 independently of one another are 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 independently of one another are hydrogen, methyl, ethyl, acetyl, —SO 2 OH or —PO(OH) 2 .
  • ionic liquids in which the cation [A] + is a phosphonium ion (IVx) in which
  • R 1 to R 3 independently of one another are 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-oc
  • the metal cations [M 1 ] + , [M 2 ] + , [M 3 ] + , [M 4 ] 2+ and [M 5 ] 3+ specified in formulae (IIIa) to (IIIj) generally comprise metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th and 13th group of the periodic system.
  • 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+ .
  • the anion [Y] n ⁇ of the ionic liquid is, for example, selected from:
  • M denotes a metal and Hal denotes fluorine, chlorine, bromine or iodine, r and t are positive integers and define the stoichiometry of the complex and s is a positive integer and gives the charge of the complex;
  • the group of sulphides, hydrogen sulphides, polysulphides, hydrogen polysulphides and thiolates having the general formulae:
  • v is a positive integer from 2 to 10;
  • the group of complex metal ions such as Fe(CN) 6 3 ⁇ , Fe(CN) 6 4 ⁇ , MnO 4 ⁇ , Fe(CO) 4 ⁇ .
  • R a , R b , R c and R d independently of one another denote
  • C 3 -C 12 -cycloalkenyl and the aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, —O—, —CO— or —CO—O-substituted components thereof such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C q F 2(q ⁇ a) ⁇ 3(1 ⁇ b) H 2a ⁇ 3b where q ⁇ 30, 0 ⁇ a ⁇ q and b 0 or 1;
  • aryl or heteroaryl having 2 to 30 carbon atoms and the alkyl-, aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, —O—, —CO— or —CO—O-substituted components thereof such as phenyl, 2-methyl-phenyl (2-tolyl), 3-methyl-phenyl (3-tolyl), 4-methyl-phenyl, 2-ethyl-phenyl, 3-ethyl-phenyl, 4-ethyl-phenyl, 2,3-dimethyl-phenyl, 2,4-dimethyl-phenyl, 2,5-dimethyl-phenyl, 2,6-dimethyl-phenyl, 3,4-dimethyl-phenyl, 3,5-dimethyl-phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrroly
  • two groups are an unsaturated, saturated or aromatic ring, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocyclic compounds and optionally interrupted by one or more sulphur atoms and/or one or more substituted or unsubstituted imino groups.
  • anions are chloride; bromide; iodide; thiocyanate; hexafluorophosphate; trifluormethylsulphonate; methylsulphonate; formate; acetate; mandelate; nitrate; nitrite; trifluoracetate; sulphate; hydrogen sulphate; methylsulphate; ethylsulphate; 1-propylsulphate; 1-butylsulphate; 1-hexylsulphate; 1-octylsulphate, phosphate; dihydrogen phosphate; hydrogen phosphate; C 1 -C 4 -dialkylphosphate, propionate; tetrachloroaluminate; Al 2 Cl 7 ⁇ ; chlorozincate; chloroferrate; bis(trifluoromethylsulphonyl)imide; bis(pentafluoroethylsulphonyl)imide; bis(methylsulphonyl)imide; bis(bis(
  • Chloride bromide, hydrogen sulphate, tetrachloroaluminate, thiocyanate, methylsulphate, ethylsulphate, methylsulphonate, formiate, acetate, dimethylphosphate, diethylphosphate, p-tolylsulphonate, tetrafluoroborate and hexafluorophosphate.
  • ionic liquids which contain as cation
  • FIG. 1 shows a schematic diagram of an apparatus for executing a steam cycle process which is used to implement the operating method according to the invention.
  • FIG. 2 shows an alternative embodiment to the apparatus from FIG. 1 .
  • FIG. 3 shows a further configuration of a steam cycle process apparatus for using the ionic liquid used for frost protection as lubricant.
  • FIG. 1 shows in schematic simplified form the basic components for an apparatus for executing a steam cycle process 1 .
  • the steam process 1 can be executed as a Clausius-Rankine process or as a cyclic process of the Kalina type. In the latter case the working medium consists of several components which go over into the vapour phase at different temperature levels.
  • a reservoir for the operating fluid 2 supplies the operating fluid as liquid phase. From there it is typically supplied to the steam generator 3 by means of a feed pump 8 which is advantageously configured as variable-speed for adaptation of the volume flow.
  • the vapour phase generated there enters into the expander 4 and performs mechanical work by expanding. Subsequently, a condensation takes place in the condenser 5 and the condensate is returned.
  • the operating fluid in addition to the working medium provided for the evaporation in the steam generator 3 , the operating fluid comprises an ionic liquid as a frost protection agent. Accordingly, the melting point of the mixture of working medium and ionic liquid is lower than the freezing point of the pure working medium.
  • water for example, 1-ethyl-3-methylimidazolium-methylsulphonate (EMIM MeSO 3 ) can be used as ionic liquid.
  • EMIM MeSO 3 1-ethyl-3-methylimidazolium-methylsulphonate
  • EMIN MeSO 3 In pure form EMIN MeSO 3 has a melting point of 35° C. In a mixture with water having a water fraction of 20 gw. %, the glass transition for the mixture lies at a temperature below ⁇ 100° C.
  • the melting point With increasing water content, the melting point increases and for a weight fraction of 80 gw. % water is ⁇ 10° C.
  • the melting point of the mixture is advantageously low at ⁇ 36° C.
  • a mixture of 1-ethyl-3-methylimidazolium hydrogen sulphate as ionic liquid and water as working medium has similar values.
  • tetramethylammonium-methylsulphonate can be used as ionic liquid for mixing with water if the water content is at least 34 gw. %.
  • the melting point for this mixture at least in a mixing ratio having a weight fraction of water of 50-80 gw. % lies below ⁇ 20° C.
  • ionic liquids 1,2,3-trimethylimidazolium-methylsulphonate, ethyltrimethylammonium-methylsulphonate, tris-(2-hydroxyethyl)methylammonium-methylsulphonate, diethyldimethylammonium-methylsulphonate, N-dimethylmorpholinium-methylsulphonate, methylimidazolium-butansulphonate, N-methyl-pyridinium-methylsulphonate, N-ethyl-pyridinium-methylsulphonate.
  • the ionic liquid produces a partial pressure which substantially tends to zero. Accordingly, the cation/anion pairing of the ionic liquid is selected so that the decomposition temperature lies above the operating temperature in the steam generator 3 .
  • the steam generator 3 is configured such that at least during a certain operating phase the temperature in the liquid phase of the operating fluid in the steam generator 3 is set below the decomposition temperature of the ionic liquid.
  • the ionic liquid is returned to the reservoir for the operating fluid 2 by means of a bypass line 10 .
  • a tank is provided for the operating medium 6 in which the condensate from the condenser 5 collects.
  • the condensate should contain substantially no ionic liquid. Consequently, after a certain operating temperature is reached, for example, a certain threshold temperature in the reservoir for the operating fluid 2 , it is possible to remove the ionic liquid at least partly from the operating fluid so that no unused removal of heat from the steam generator results. For this purpose, it is preferable to take a weight fraction of at least 50% of the ionic liquid originally present in the operating fluid from the steam cycle process. The removal of a higher fraction, in particular of 80% and more, is preferred, particularly preferably at least 95%.
  • the removal of the ionic liquid from the operating fluid is accomplished by the evaporation of the working medium in the steam generator 3 and its collection in the tank for the working medium 6 .
  • a valve unit 11 which controls the inflow from the tank for the working medium 6 or the reservoir for the operating fluid 2 to the steam generator 3 such that the reservoir for the operating fluid 2 is decoupled and the feed pump 8 draws exclusively from the tank for the working medium 6 .
  • This switching by means of the valve unit 11 can either be time- and/or level-controlled and/or temperature-controlled and/or controlled depending on the concentration of the ionic liquid in the operating fluid.
  • FIG. 2 shows a further possible embodiment of an apparatus for implementing a steam cycle process using the operating fluid according to the invention with a possibility for separating the ionic liquid from the operating fluid for a system at temperature.
  • FIG. 2 shows a separate tank for the ionic liquid 7 which is connected to an outlet for the liquid phase at the steam generator 3 . Accordingly, preferably the non-evaporated fractions of the operating fluid collect in the tank for the ionic liquid 7 so that an enrichment of the ionic liquid takes place here. Below the operating temperature and in particular at temperatures at which there is a risk of frost, the ionic liquid is returned from the tank for the ionic liquid 7 to the reservoir for the operating fluid 2 .
  • this conveying stream can be reduced or returned to zero so that an enrichment of the ionic liquid in the tank for the ionic liquid 7 results during further operation of the steam generator 3 and at the same time the fraction of the ionic liquid in the reservoir for the operating fluid 2 is reduced since the condensate of the working medium is continuously supplied from the condenser 5 .
  • a main part and preferably substantially the entire fraction of the ionic liquid is removed from the steam cycle process. After this is achieved, according to one embodiment it is possible to close the connection between the steam generator 3 and the tank for the ionic liquid 7 and according to a possible embodiment at the steam generator, set a suitably high temperature for the exhaust steam.
  • the embodiment of the invention comprises a steam cycle process apparatus having an apparatus for withdrawing the ionic liquid or a mixture enriched with said liquid.
  • the method according to the invention for this embodiment uses the withdrawal for lubricating revolving components of the steam cycle process apparatus, in particular the expander.
  • the lubricant can be used for further moving components outside the steam cycle process apparatus.
  • a hybrid drive comprising a steam engine and an internal combustion engine is provided, it is possible in particular to achieve the lubrication of the internal combustion engine by means of a lubricant containing the ionic liquid.
  • FIG. 3 the basic components for implementing the steam cycle process 1 are shown in the schematically simplified diagram of FIG. 3 .
  • a reservoir is provided for the operating fluid 2 which at least in the rest state holds a mixture of the working medium and the ionic liquid for frost protection purposes. This mixture is conveyed by means of the feed pump 8 which supplies this to the steam generator 3 .
  • the steam generator 3 is exposed to a stream of hot exhaust gases via an exhaust gas duct 21 from the internal combustion engine 20 and thus enables 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 supplies it to the expander 4 .
  • An additional starting valve 15 which makes it possible to bypass the expander is provided for starting up.
  • the ionic liquid remains liquid in the separator and can be fed from its sump to a valve device 11 .
  • the valve device 11 either allows the operating fluid to be passed via the condenser 5 and the filter 13 back to the reservoir for the operating fluid 2 or allows it to be supplied to a tank for ionic liquids 7 .
  • an inflow takes place from the tank for the ionic liquid 7 to the reservoir for the operating fluid 2 by means of gravity or by a pump in order to ensure the frost-safe mixing ratio of working medium to ionic liquid there.
  • a mixture rich in ionic liquid is supplied to the valve device 11 .
  • this can be used as lubricant and as lubricant additive.
  • the first case is shown in FIG. 3 .
  • the lubricant pump 16 conveys from the tank for ionic liquid 7 and supplies the lubricant to the expander 4 .
  • the lubricant is returned via the lubricant return 17 .
  • a remaining residue of working medium to be evaporated can be supplied via the steam outlet 19 to the reservoir for operating fluid 2 .
  • an unavoidable continuous leakage of working medium occurs, which flows via the return for outflowing medium 18 to the tank for the ionic liquid 7 so that an equilibrium state with a still-tolerable fraction of working medium in the lubricant circuit is established.
  • the lubricant properties can even be satisfied with a weight fraction of 10 gw. % (percent by weight) of working medium.
  • a weight fraction of 10 gw. % (percent by weight) of working medium This will be set out hereinafter by reference to a mixture of EMIM-MeSO 3 as ionic liquid with water as working medium having a weight fraction of 5 gw. % (percent by weight).
  • the kinematic viscosity at a temperature of 90° C. is 5.3 cst.
  • the density, the foam behaviour and the air separation capacity are values suitable for lubricants.
  • the lubricant properties were measured by means of a Shell four-ball apparatus. A measurement in accordance with DIN 51350-T2 at a rotational speed of 1420 min ⁇ 1 gave a welding force of 2400 N. A measurement in accordance with DIN 51350-T3 at the same rotational speed and a load of 300 N yielded a ball indentation diameter of 1.04 mm. The oxidation stability and the corrosion protection behaviour were also determined, the results allowing the use as lubricant.
  • a suitable choice for the cations and the anions of the ionic liquid is satisfied by a suitable choice for the cations and the anions of the ionic liquid.
  • a good lubricity is additionally provided for a suitable ionic liquid.
  • the cation/anion pairing is selected 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)
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US20140199200A1 (en) * 2013-01-14 2014-07-17 Magna Powertrain Ag & Co Kg Expander circuit
US9732616B2 (en) 2011-01-17 2017-08-15 Orcan Energy Ag Lubrication of volumetrically operating expansion machines
US20180030857A1 (en) * 2011-05-03 2018-02-01 Orcan Energy Ag Method and Device For Rapid Oil Heating For Oil-Lubricated Expansion Machines
US20180142578A1 (en) * 2016-11-21 2018-05-24 Mahle International Gmbh Heat recovery device and method
US10168080B2 (en) * 2016-05-26 2019-01-01 Yazaki Corporation Eutectic mixtures of ionic liquids in absorption chillers
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US10465950B2 (en) 2016-05-26 2019-11-05 Yazaki Corporation Guanidinium-based ionic liquids in absorption chillers
US10830046B2 (en) * 2015-10-05 2020-11-10 Bitzer Kuehlmaschinenbau Gmbh Expansion system
CN113882921A (zh) * 2021-11-12 2022-01-04 中国石油大学(北京) 一种以二氧化碳气体为工质的低温循环发电系统和方法
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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
US20130263594A1 (en) * 2010-12-01 2013-10-10 Ola Hall Arrangement and method for converting thermal energy to mechanical energy
US9341087B2 (en) * 2010-12-01 2016-05-17 Scania Cv Ab Arrangement and method for converting thermal energy to mechanical energy
US9732616B2 (en) 2011-01-17 2017-08-15 Orcan Energy Ag Lubrication of volumetrically operating expansion machines
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US20180030857A1 (en) * 2011-05-03 2018-02-01 Orcan Energy Ag Method and Device For Rapid Oil Heating For Oil-Lubricated Expansion Machines
US20140159369A1 (en) * 2012-12-12 2014-06-12 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Power generation apparatus and power generation system
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US20140199200A1 (en) * 2013-01-14 2014-07-17 Magna Powertrain Ag & Co Kg Expander circuit
US10385751B2 (en) * 2014-06-26 2019-08-20 Volvo Truck Corporation Exhaust gas waste heat recovery system
US10830046B2 (en) * 2015-10-05 2020-11-10 Bitzer Kuehlmaschinenbau Gmbh Expansion system
US10168080B2 (en) * 2016-05-26 2019-01-01 Yazaki Corporation Eutectic mixtures of ionic liquids in absorption chillers
US10465950B2 (en) 2016-05-26 2019-11-05 Yazaki Corporation Guanidinium-based ionic liquids in absorption chillers
US10774689B2 (en) * 2016-11-21 2020-09-15 Mahle International Gmbh Heat recovery device and method
US20180142578A1 (en) * 2016-11-21 2018-05-24 Mahle International Gmbh Heat recovery device and method
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US20240035397A1 (en) * 2022-08-01 2024-02-01 Solutiatech Llc Accumulating And Storing Energy in Separated Mixed Refrigerants for Conversion to Electrical or Mechanical Power
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DE102008037744A1 (de) 2010-02-25

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