WO2015127331A1 - Apparatus, systems and methods for lubrication of fluid displacement machines - Google Patents
Apparatus, systems and methods for lubrication of fluid displacement machines Download PDFInfo
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- WO2015127331A1 WO2015127331A1 PCT/US2015/016990 US2015016990W WO2015127331A1 WO 2015127331 A1 WO2015127331 A1 WO 2015127331A1 US 2015016990 W US2015016990 W US 2015016990W WO 2015127331 A1 WO2015127331 A1 WO 2015127331A1
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- lubricant
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01C—ROTARY-PISTON OR OSCILLATING-PISTON MACHINES OR ENGINES
- F01C21/00—Component parts, details or accessories not provided for in groups F01C1/00 - F01C20/00
- F01C21/04—Lubrication
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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
- F01K25/04—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for the fluid being in different phases, e.g. foamed
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/06—Well-defined hydrocarbons aromatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01C—ROTARY-PISTON OR OSCILLATING-PISTON MACHINES OR ENGINES
- F01C1/00—Rotary-piston machines or engines
- F01C1/08—Rotary-piston machines or engines of intermeshing engagement type, i.e. with engagement of co- operating members similar to that of toothed gearing
- F01C1/12—Rotary-piston machines or engines of intermeshing engagement type, i.e. with engagement of co- operating members similar to that of toothed gearing of other than internal-axis type
- F01C1/14—Rotary-piston machines or engines of intermeshing engagement type, i.e. with engagement of co- operating members similar to that of toothed gearing of other than internal-axis type with toothed rotary pistons
- F01C1/16—Rotary-piston machines or engines of intermeshing engagement type, i.e. with engagement of co- operating members similar to that of toothed gearing of other than internal-axis type with toothed rotary pistons with helical teeth, e.g. chevron-shaped, screw type
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01C—ROTARY-PISTON OR OSCILLATING-PISTON MACHINES OR ENGINES
- F01C21/00—Component parts, details or accessories not provided for in groups F01C1/00 - F01C20/00
- F01C21/06—Heating; Cooling; Heat insulation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
- F01D25/18—Lubricating arrangements
- F01D25/22—Lubricating arrangements using working-fluid or other gaseous fluid as lubricant
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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
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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
- F01K25/08—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 special vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
- C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to appa ratus, systems, and methods of lubricating fluid displacement machines, including positive displacement machines and, in pa rticu lar, rotary screw expanders via the use of non-soluble, non-miscible, and/or undissolved lubricants mixed with the fluid upon which the machi ne acts or is acted upon by the machine.
- Machines which incorporate the flow of a fluid as a cha racteristic of their ope ration have a myriad of applications.
- Devices that fall within this definition a re those machines which provide compression, expansion, pum ping functionality and therefore encompass all ma nner of compressors, expande rs, a nd pum ps.
- Positive displacement machines are a particularly usefu l subset of such fluid-based machines. Configurations include linea r displacement machines, reciprocating displacement machi nes, and rotating displacement machines.
- a motive force is applied to the machine and a fluid, in liquid or gaseous state, is propelled from the inlet of the machine to the outlet via displacement of the fluid by one or more movable surfaces of the machine.
- the mass flow of the fluid or a physical process experienced by the fluid within the machine, such as expansion imposes a force on one or more mova ble surfaces within the machine thereby causing the fluid to be propelled from the inlet to the outlet of the machine while generating a corresponding force that may be applied to perform work on an interconnected device or system.
- One pa rticular class of positive displacement machine for which proper lubrication is essential is a rotational positive displacement device known as a plural screw positive displacement machine as described in U.S. Patent No. 6,296,461. Also referred to as a "twin screw expander", the device comprises a pair of helical-style intermeshing rotors mounted on parallel axes .
- a working fluid such as a refrigerant
- the refrigerant is caused to expand within the machine, thereby providing a rotational torque at the shaft output of the machine that may be coupled to perform work on another device or system, such as driving an electric generator to produce electric power.
- ORC organic Rankine cycle
- therma l Rankine process A closed- loop flow of liquid working fluid, often but not necessarily a refrigerant, is heated to a gaseous or semi-gaseous state by an available and sufficient source of heat, allowed to expand in a suitable device such as a twin screw expander, cooled back into its liquid state, and then pumped and re-heated for subsequent expansion in a continuous process.
- a suitable device such as a twin screw expander
- heat energy is converted into mecha nical energy which may be used for any other useful purpose such as generating electric power via a generator or when coupled to one or more alternative or additional systems or devices.
- Heat exchanger 101 receives a flow of a heat exchange medium in a closed loop system heated by energy from a large internal combustion engine at port 106.
- this heat energy may be directly supplied from the combustion engine via the jacket water heated when cooling the combustion engine, or it may be coupled to the ORC system via an intermediate heat exchanger system installed proximate to the source of hot exhaust gas of one or more combustion engines.
- matter heated by the combustion engine or heat exchanger is pumped to port 106 or its dedicated equivalent.
- the heated matter flows through heat exchanger 101 and exits at port 107 after transferring a portion of its latent heat energy to the separate but thermally coupled closed loop ORC system which typically employs an organic refrigerant as a working fluid.
- the heated working fluid Under pressure from the system pump 105, the heated working fluid, predominantly in a gaseous state, is applied to the input port of expander 102, which may be a turbomachine , a positive displacement machine of various configurations, including but not limited to a twin screw expander, or the like .
- the heated and pressurized working fluid is allowed to expand within the machine and such expansion produces rotational kinetic energy that is operatively coupled to drive electrical generator 103 and produce electric power which then may be delivered to a local isolated power grid or the commercial power grid.
- the expanded working fluid at the output port of the expander which typically is a mixture of liquid and gaseous working fluid, is then delivered to condenser subsystem 104 where it is cooled until it has returned to its fully liquid state.
- Condenser subsystem 104 may optionally include or be operatively coupled to a receiver tank, reservoir, or equivalent vessel for storing a quantity of cooled working fluid to insure a sufficient supply for system pump 105 at all times.
- ORC systems are not limited to use with combustion engines and electric generators. Any sufficient source of heat may be applied to port 106 to vaporize the ORC working fluid, including but not limited to boilers, geothermally-heated water, fluid used to cool large solar arrays, gas compressors, or other industrial processes, or the like. Likewise, the rotationa l kinetic energy presented by the expander in the form of mechanical power may be applied for any useful purpose in addition to, or in lieu of, driving an electric power generator. Such purposes may include, but are not limited to, driving at least one of any of a pump, a combustion engine, a fan, a turbine, a com pressor, or returning power to the source of input heat.
- the condenser subsystem sometimes includes an array of air-cooled or liquid-cooled radiators or another system of equivalent heat-removal performance through which the working fluid is circulated until it reaches the desired temperature and state, at which point it is applied to the input of system pump 105.
- System pump 105 provides the motive force to pressurize the entire system and supply the liquid working fluid to heat exchanger 101, where it is once again heated by the energy supplied by the input heat and experiences at least a partial phase change to its gaseous state as the organic Rankine cycle process continues.
- the presence of working fluid throughout the closed loop system ensures that the process is continuous as long as sufficient heat energy is present at input port 106 to provide the requisite energy to heat the working fluid to the necessary temperature. See, for example, Langson US 7,637,108 (“Power Compounder”) which is hereby incorporated herein by reference in its entirety and for all useful purposes.
- a separate lubrication subsystem comprising a pump, sump, interconnected tubing or conduits, and/or other associated equipment provides the necessary recovery of lubrication oil from various points in the system and returns a continuous flow of oil to the bearings and surfaces of the machine requiring lubrication.
- lubrication is not intentionally combined with the working fluid, although they may flow simultaneously in certain regions of the system as separate fluids.
- Such lubrication subsystems increase the number of components required to support the machine's proper operation, thereby increasing its cost and decreasing reliability since failure of the lubrication subsystem will render the machine inoperable.
- a lubricant that is soluble or miscible in the liquid phase of the working fluid is directly mixed with said working fluid and flows, as a homogenous, uniform, and stable mixture, throughout the ORC system. It is taught by Smith that when heated, the liquid working fluid vaporizes (evaporates), leaving a higher concentration of lubricant in liquid form which is ostensibly sufficient to provide the necessary lubrication for the machine's operation. In particular, this patent teaches that when the mixture of working fluid and lubricant is injected at a bearing location associated with a rotary element of the expander, the heat generated by said bearing evaporates the liquid phase of the working fluid to leave sufficient concentrated lubricant in the bearing for adequate lubrication.
- This system and method provides the distinct advantage of not requiring a separate lubrication subsystem, thereby providing increased reliability and a lower manufacturing cost. However, this method and does not address situations where the bearing heat may be insufficient to evaporate the working fluid.
- lubrication systems and methods require neither a separate lubrication subsystem nor sufficient bearing heat for vaporization of working fluid mixed with a lubricant that is soluble or miscible in the liquid phase of the working fluid.
- this invention utilizes one or a combination of more than one wholly or substantially non-soluble or immiscible lubricant(s) mixed with the working fluid with special apparatus and methods to provide highly effective and reliable lubrication for a wide range of fluid displacement machines.
- one or more lubricants that are not substantially soluble or miscible in the liquid phase of the working fluid are mixed in certain prescribed proportion with a working fluid for use in a n ORC system.
- a working fluid for use in a n ORC system.
- Such mixture of working fluid (“WF”) and one or more non-soluble, immiscible lubricant(s) (“NSIL”) comprises a non-homogenous colloidal WF/NSIL mixture of inherently unstable com position over time and that tends toward separation.
- the NSIL component of the colloidal WF/NSI L mixture is evenly dispersed at locations of interest in the system, At rest for a sufficient time, such colloidal mixture may achieve partial or nearly complete self-separation of the WF and NSIL components such that the NSI L component is no longer dispersed within the WF/NSIL mixture. Only traces of each component may by present in the separated strata of the other(s).
- the NSI L in the WF/NSIL mixture coats and lubricates the metallic surfaces of the machine and incidentally accumulates in the bearings and at other points requiring lubrication without the need for direct injection.
- the WF/NSIL mixture is directly supplied under positive pressure to one or more points in the system requiring lubrication with such lubrication provided by the NSIL component of the mixture.
- a lubrication line may be run from an extraction point in the system where a supply of the WF/NSIL mixture is available at a preferred temperature to communicate a portion of said mixture to the lubrication points.
- cooled WF/NSIL mixture is extracted at the output of a system pump and operatively comm unicated to the housings of one or more bearings, the bearings directly, or other locations in the machine requiring lubrication.
- the NSIL present in the WF/NSIL mixture coats the bearings to provide exemplary lubrication as a result of the high affinity between the NSIL and metallic surfaces.
- WF/NSI L mixture is extracted from one or more other source points within the system and provided to the desired points of lubrication. If the pressure differential between the source of the WF/NSIL mixture and the lubrication input ports at the bearing housings and/or other points of lubrication is insufficient to provide the necessary flow, a supplemental lubrication pump may be employed to achieve reliable and controllable flow. I n some ORC embodiments, expanded WF/NSIL mixture taken from the outlet of positive displacement machine 102 may be captured and immediately pumped back to the machine as necessary for lubrication.
- This WF/NSIL mixture may provide a source of lubrication closest to the operating temperature of the lubricated machine in circumstances when such temperature matching is optimal for the pa rticular application.
- WF/NSIL mixture may be obtained from any more desirable location within the system.
- the WF/NSI L mixture used for lubrication has a significant liquid component. Extracting wholly or substantially vaporized pre-expansion WF/NSIL mixture from the output of ORC heat exchanger 101, for example, may not be well-suited for lubrication of a twin screw expander in some ORC embodiments due to its high temperature and potential extraction difficulties at the point of greatest system enthalpy.
- different types of machines used in applications other than ORCs may have a myriad of preferable sources from which the lubricating WF/NSI L mixture may be extracted and no single solution will necessarily be optimal for every conceivable application.
- WF/NSI L mixture may be extracted from one or more positions within a fluid reservoir or receiver tank and supplied, via a supplemental lubrication pump, to the desired points of lubrication. Due to the tendency of the colloidal WF/NSIL mixture to separate as described elsewhere herein, the position within the reservoir or receiver tank at which a portion of the mixture is extracted for lubrication purposes will largely determine the relative proportion of working fluid to NSIL. Also as described in greater detail elsewhere herein, the colloidal mixture will tend to separate into layers, or strata, with indefinite boundaries but with varied com positions of the mixture that vary from comprising
- the point of extraction of the WF/NSIL mixture for lubrication purposes may be variable, via a moveable inlet port or similar means, and controlled either manually or via a microprocessor-based control system further comprising sensors capable of determining the composition of the WF/NSIL mixture a nd adjusting the position accordingly.
- multiple extraction locations may be used, with the WF/NSI L mixture extracted from the location most favorable at any particular time for lubrication purposes.
- this embodiment may comprise either manual control or be operated via a microprocessor-based control system further com prising sensors responsive to the composition of the WF/NSIL mixture.
- a combination of multiple extraction locations and movable inlet ports may be utilized in other embodiments.
- WF/NSI L mixture may be extracted by use of one or more skimmer(s) disposed at fluid reservoirs or receiver tanks.
- skimmer(s) disposed at fluid reservoirs or receiver tanks.
- separation via gravitational force provides NSIL-enriched fluid in the upper strata of the tank.
- Use of a skimmer to extract a portion of the WF/NSIL mixture from that uppermost strata would advantageously yield the portion of the mixture richest in lubricant for injection at the desired lubrication points.
- no agents are present within the colloidal WF/NSI L mixture to increase its compositional stability.
- one or more agent(s), such as emulsifying agent(s) are present in the WF/NSI L mixture to increase the stability of the WF/NSI L mixture over time and therefore reduce its tendency to separate due to gravity or other internal or external stimuli.
- the WF/NSIL mixture varies in the relative proportion of non- soluble immiscible lubricant and working fluid as a function of position in the system.
- samples of the WF/NSI L mixture extracted at various points throughout the closed loop within which the WF/NSIL mixture circulates may contain non-identical concentrations of NSIL.
- observed separation of the WF/NSIL mixture will be the greatest and relative proportions of each component are likely to vary greatly with relatively minor variations in sampling position.
- the relative proportions of non-soluble immiscible lubricant and working fluid within the WF/NSIL mixture as measured at a fixed location in the closed-loop path within which the mixture is circulating may vary as a function of time.
- repeated measurements of NSI L concentration taken at a single location over a period of time during operation of the ORC system will vary as a function of time until a state of equilibrium has been achieved. This is particularly true during the initial start-up of an ORC system previously at rest for a ny appreciable period.
- a re-started system may begin operation with a highly non-uniform distribution of working fluid and non-soluble immiscible lubricant.
- a disproportionately large concentration of NSIL may collect at certain strata within the reservoir or receiver tank used to store cooled working fluid or elsewhere within an idle system.
- the initia l draw of WF/NSI L mixture from said receiver tank may be highly enriched with or essentially depleted of non-soluble immiscible lubricant since the NSIL component of the WF/NSIL mixture is not evenly dispersed at points in the system where such dispersion is important to system operation.
- the distribution of NSIL throughout the system will begin to approach the normally-expected distribution of NSIL mixture at each point in the system, eventually reaching the proper concentration of NSIL under essentially steady-state operating conditions, at which point such concentration may still vary with position as described with respect to a previous embodiment.
- the state of operation in which the optimal dispersion of NSIL within the WF/NSI L mixture is achieved for steady-state operation may be referred to as lubrication equilibrium.
- a fluid bypass circuit comprising a valve may be employed around the machine to prevent its operation during period when the WF/NSIL mixture has not yet reached the state of lubrication equilibrium. During such periods, insufficient lubrication for the rotating surfaces and bearings of the machine would likely cause damage to or failure of the machine were it operate, so the initial flow of WF/NSIL is routed around, rather than through, the machine to prevent the machine's operation under conditions of unfavorable lubricity. Once the WF/NSIL mixture has reached proper lubrication equilibrium, the bypass valve may be closed, blocking the bypass flow and allowing the properly reconstituted WF/NSIL mixture to flow through the machine as it begins to operate. Control of the bypass valve may be accomplished either by manual methods or by a microprocessor-based control system used to monitor and control other aspects of the ORC system's operation.
- the localized homogeneity of the WF/NSIL mixture is relatively uniform at all points in the closed-loop circulation path between the outlet of a system pump and the outlet of the machine once the WF/NSI L mixture has attained lubrication equilibrium.
- the circulating WF/NSIL mixture driven by positive pressure from the system pump is subject to an increase in enthalpy from the transfer of heat energy from a external source via one or more heat exchangers and subsequent expansion in the positive displacement machine. All of the WF/NSIL mixture present at the pump output appea rs directly at the output of the machine without any change in overall composition.
- the localized homogeneity of the WF/NSIL mixture is not uniform at all points in the closed-loop circulation path between the outlet of a system pump and the outlet of the machine once the WF/NSI L mixture has attained lubrication equilibrium. Even though there are no inlets or outlets for the mixture between these two points, the fact that the working fluid is at least partially vaporized by the heat supplied to the ORC system in these embodiments while the lubricant is not vaporized will result in a mixture comprised of liquid NSIL, vaporized working fluid, and possibly liquid (non-vaporized) working fluid. Under such conditions, the relative proportion of NSIL in any remaining non-vaporized liquid mixture will understandably higher than if the entire working fluid at that point were still in its liquid state, as it exists at the outlet of the system pump prior to vaporization in the heat exchanger.
- the total non-homogenous WF/NSIL mixture within the entire closed-loop ORC system comprises between 3% and 8% NSI L by mass.
- the NSIL component is between 5% and 6% of the total WF/NSIL mixture by mass.
- the portion of non-homogenous WF/NSIL mixture flowing within the segment of the closed-loop circuit between the system pump output and the outlet of the machine under conditions of lubrication equilibrium is between 1% and 3% NSIL by mass.
- this concentration is approximately 2% NSIL by mass.
- the concentration of NSIL in the extracted portion of the mixture is the same as the concentration of NSIL within the segment of the closed-loop circuit between the system pump output a nd the outlet of the machine because both mixture portions are obtained from a common source.
- the non-homogenous WF/NSIL mixture is subjected to intentional agitation for the purpose of temporarily increasing the homogeneity of said mixture. In some embodiments, no intentional attempt is made to increase the homogeneity of the colloidal WF/NSI L mixture and the only agitation provided is that which is incidental to the normal operation of the ORC system.
- the ORC system includes one or more receivers, reservoirs, or vessels in which a portion of the WF/NSI L mixture is allowed to accumulate. These locations introduce the greatest likelihood that the WF/NSIL mixture will separate as is collects there, temporarily not subjected to incidental kinetic forces experienced during fluid circulation and thermal transfer. As the colloida l WF/NSI L mixture separates, a substantial portion of the total NSIL present in the system begins to collect at the uppermost layer of the non-circulating WF/NSIL mixture where it provides no lubrication to the system. It has been found that reducing the concentration of NSI L within the system does not prevent this accumulation but instead reduces the concentration of NSI L available in the WF/NSIL mixture for lubrication purposes, to the detriment of system operation.
- the ORC system does not include any receiver(s), reservoirs, or other vessels that permit WF/NSI L mixture to accumulate.
- embodiments of the invention may include one or more of the features described in detail below and elsewhere herein.
- the machine requiring lubrication may be any fluid displacement machine suitable for use in the preferred system, whether for expansion, compression, pumping, or other purposes.
- the machine may impose a force on the fluid passing there through or the fluid may impose a force on the machine due to physical phenomena such as, but not limited to, expansion of the fluid, fluid mass flow through the machine under pressure, or in any other manner.
- the machine is a positive displacement machine such as a twin screw expander particularly suitable for use in ORC heat recovery systems.
- the machine may be any manner of rotational, reciprocating, linear, or non-linear machine suitable for use in the desired application which requires lubrication and which is also suitable for use with a working fluid in liquid, gaseous, or mixed liquid/gaseous phases.
- the working fluid may be an organic refrigerant of the hydrofluorocarbon (HFC) class such as R-245fa, commercially known as Genetron ® and manufactured by Honeywell.
- HFC hydrofluorocarbon
- any organic refrigerant including but not limited to R-123, R-134A, R-22, and the like, as well as any other suitable hydrocarbons or other fluids, may be employed in other embodiments.
- the working fluid may also be water or any other substance suitable for the intended purpose of the machine and the system.
- the NSIL may comprise mineral oil or one or more of any other suitable liquid lubricant(s) that are neither soluble nor miscible in the liquid phase of the working fluid.
- Mineral oil is not soluble or miscible in HFC refrigerants such as R-245fa and its use therewith is compatible with this disclosure.
- R-245fa HFC refrigerants
- One such type of mineral oil demonstrated to be sufficiently non-soluble and immiscible with R-245fa is manufactured by Nu-Calgon of St. Louis, MO and available in several viscosities (C-3s, C-4s, and C-5s) for different applications.
- mineral oil is known to be miscible with other refrigerants, including those
- the NSIL may comprise synthetic replacements for mineral oil or other lubricants that are similarly neither soluble nor miscible in the liquid phase of the chosen working fluid.
- One such synthetic alternative for mineral oil is the family of alkylbenzene oil compounds manufactured by N u-Calgon under the product name Zerol ® .
- this product is known to be miscible with CFC and HCFC refrigerants but neither soluble nor miscible with HFC refrigerants such as R-245fa, rendering it suitable for use as an NSIL according to this disclosure with HFC refrigerants but not with CFC or HFC refrigerants.
- the particular formulation of NSI L used in accordance with this disclosure is critica lly dependent upon the type and characteristics of the working fluid as well as the operating temperatures and pressures of the system since the miscibility of lubricants is partially dependent upon its temperature.
- the NSIL may comprise a solid lubricant additive compound held in colloidal suspension in the working fluid in combination with, or in lieu of, one or more non-soluble immiscible or other liquid lubricant(s).
- solid lubricant additives may be of the type manufactured under the Acheson brand name and available from Henkel Corporation in Rocky Hill, CT.
- the system further comprises one or more filters through which the WF/NSIL mixture extracted for injection at desired lubrication points, such as bearings, is passed to remove impurities, including but not limited to moisture and particulate
- Filters suitable for these embodiments may include, but are not limited to, the OF series of filters offered by the Sporlan Division of the Parker Hannifin Corporation of Washington, MO, the HF2P series of filters offered by
- Agitation of the WF/NSI L mixture increases the homogeneity of the WF/NSIL mixture by dispersing the NSIL component within the WF/NSI L mixture,
- Such agitation may be provided incidental to the process of circulating said mixture through the ORC system.
- Kinetic energy imparted to the WF/NSI L mixture in the ORC-related acts of pumping, circulating, heating, expanding, and condensing the WF/NSI L mixture provides a "mixing" action that works to counteract the mixture's natural tendency to separate.
- this incidental agitation is sufficient to meet system requirements for achieving and maintaining lubrication equilibrium.
- this incidental agitation is insufficient to meet system requirements for achieving and maintaining lubrication equilibrium.
- additional agitation is required for proper operation.
- Such agitation may be provided by passive techniques, including but not limited to the placement of flow inlets and outlets in receiver tanks that allow gravity to act on the WF/NSIL mixture flow in a manner that disperses the NSI L within the WF/NSIL mixture, the use of fixed vanes in conduits and/or vessels through which the WF/NSIL mixture flows, rotating devices propelled by the motive force of the system pump acting on the WF/NSIL mixture, and the like.
- Active means of agitation including but not limited to stirrers, circulators and circulation pumps, mixers, injection jets, and other mechanical or electromechanical devices or methods may also be used to maintain a suitable dispersion of NSIL within the colloida l WF/NSI L mixture at system points of interest.
- Figure 1 is a block diagram of a prior art ORC system used to convert heat energy into electric power
- Figure 2 is a block diagram of an ORC system used with this invention depicting a lubrication feed system from the outlet of the system pump to the positive displacement machine;
- Figure 3 is a graph that depicts the concentration of non-soluble immiscible lubricant present at the outlet of a system pump as a function of time after startup;
- Figure 4 is cross sectional side view of a receiver tank in an ORC system depicting the stratification of the mixture of working fluid and non-soluble immiscible lubricant.
- FIG. 2 depicts an ORC system configuration suitable for use with the present invention.
- lubrication line 108 is operatively connected between the output of system pump 105 and one or more points requiring lubrication in positive displacement machine 102.
- these points are bearing housings within which one or more ball, roller, sleeve, or other configuration of bearings are housed.
- the flow of WF/NSIL mixture under positive pressure from the system pump 105 which may be controlled by a microprocessor- directed variable frequency drive (“VFD”) system, provides a stream of lubricating mixture to the bearings and/or other lubrication points.
- VFD microprocessor- directed variable frequency drive
- the WF/NSI L mixture at this point has been fully condensed and will provide the maximum heat dissipation when applied to the bearings or other lubrication points at the machine. While the use of warmer mixture may be acceptable or even desired in some embodiments, the cooler lubrication source is often preferred.
- the flow rate may be controlled by one or more valves or other flow control devices so as to achieve the desired flow rate. This is particularly useful when the WF/NSIL mixture is obtained at the output of system pump 105, as the speed of the VFD-controlled pump is dictated by the larger operational requirements of the ORC system and cannot be varied to accommodate lubrication concerns.
- the flow of WF/NSIL mixture to the bearings or other points of lubrication may be controlled in whole or in part by controlling the operation of said dedicated supplemental pump in place of, or in combination with, suitable valves or other flow control devices.
- the choice of lubricant to be mixed with the chosen working fluid is critical. There are a wide variety of working fluids suitable for use in the many applications to which this disclosure applies.
- the essential cha racteristic of the WF/NSIL mixture of this invention is that the working fluid and the non-soluble immiscible lubricant form a colloidal mixture rather than a homogenous, uniform solution.
- examples will be provided using preferred ORC systems. The same principles apply to other applications when appropriately adjusted for their specific requirements.
- Some ORC systems utilize water, vaporized into steam by the input heat, as a working fluid.
- ORC systems utilize refrigerants, including but not limited to organic refrigerants, in lieu of water as a working fluid.
- refrigerants including but not limited to organic refrigerants, in lieu of water as a working fluid.
- the complex chemical composition of refrigerants is an area of active development driven in large measure by concerns surrounding the potential effect of legacy refrigerants on the environment.
- the refrigerant discussed above is classified as a hydrofluorocarbon (HFC) compound and lacks the chlorine component of the earlier generation of chlorofluorocarbons (CFCs), such as R-12, as well as the later generation of hydrochlorofluorocarbon (HCFC) refrigerants, such as R-22, both now deprecated since being deemed environmentally undesirable. Due to their different compositions, certain lubricants soluble or miscible in chlorinated refrigerants are not similarly soluble or miscible in non-chlorinated refrigerants, including but not limited to HFCs such as R-245fa.
- HFC hydrofluorocarbon
- An essential element of this invention is the non-soluble immiscible character of the WF/NSIL mixture. It is not sufficient to identify a fluid and a lubricant independently of this requirement. Due to the differences in composition of both components, each must be carefully selected in full consideration of the characteristics of the other.
- a bove one such combination experimentally and operationally verified to produce the desired non-soluble immiscible WF/NSI L mixture consistent with this disclosure is the refrigerant R-245fa and mineral oil or its closely-related synthetic alternatives such as alkylbenzene oil.
- the WF/NSI L mixture is colloida l in nature, it is by definition non-uniform at the microscopic level and for a certain sample range above that. Unlike soluble or miscible compositions where the components in a homogenous mixture may be difficult or even impossible to separate without elaborate processing, the colloidal WF/NSIL mixture is self- separating. Even with extreme agitation, visual inspection of the WF/NSI L mixture reveals the presence of NSIL droplets (as the discontinuous phase) distributed throughout the working fluid (as the continuous phase).
- the NSIL droplets constantly seek to combine with each other, forming larger droplets that collect on the upper layers of any accumulation of WF/NSIL mixture at rest as they are displaced in the mixture by the working fluid of greater specific gravity settling to the lower layers due to gravitational force.
- any assessment of the composition of the colloidal WF/NSI L mixture it must be understood that determination of the proportional composition of the colloidal WF/NSIL mixture requires a sample of appropriate size for the purpose at hand.
- a sample size of 5 mL or less may be optimal for the purpose of characterizing a WF/NSIL mixture at rest that has essentially separated into strata when the task at hand is to determine the boundaries of such strata as precisely as possible.
- a 5 mL sample taken at a particular location may be highly misleading due to the lack of uniformity in the WF/NSIL mixture.
- a sample between 100 and 500 mL, or greater may be advisable.
- a sample size of between 10 and 50 mL may suffice to accurately determine its proportional composition. All discussions herein regarding the proportional composition of a WF/NSIL mixture are predicated on the basis that such composition is based a suitable sample size for the state of dispersion of NSIL within the WF/NSIL mixture, as such state will vary greatly throughout the system as discussed below.
- the time-dependent variation in the relative concentration of NSIL in the WF/NSIL mixture should understood to be a function of many characteristics of the materials and the system within which the WF/NSI L mixture circulates in a closed loop.
- Factors which affect the time-dependent concentration of NSIL in the WF/NSIL mixture include, but are not limited to, a) the time-dependent propensity for the WF/NSIL mixture to separate while at rest, b) the amount of time that has lapsed since the ORC system's last shutdown and/or the state of the WF/NSIL mixture at commencement of operation, c) the physical operating constants of the system, such as mass flow rate of the WF/NSIL mixture, the capacity of a ny WF/NSIL mixture receiver or storage tanks, temperature and pressure of the WF/NSIL mixture at any point, and the like, 4) the absence or presence of any mechanical or other agitation that would affect the time required for the WF/NSIL mixture to reach its optimum state of lubrication equilibrium
- the tendency of the unstable colloidal WF/NSIL mixture to naturally separate on its own when the mixture is at rest and not subject to agitation (listed as factor (a) above) is a characteristic of the properties of the working fluid component(s) and non-soluble immiscible lubricant component(s) of the WF/NSIL mixture and is largely independent of the system in which the WF/NSI L mixture is utilized.
- the degree of dispersion of NSI L in the WF/NSI L mixture is of interest only at certain points in the system.
- One such point is the location in the system where a portion of the mixture is extracted for application at desired points of lubrication. It important that the mixture obtained for direct injection lubrication contain the desired quantity of NSIL lubricant. Extracting lubricant-depleted mixture for lubrication purposes, particularly when done unintentionally, would jeopa rdize the operation of the machine. As described above, extracting a portion of the WF/NSIL mixture at the output of the system pump would be preferred in some embodiments.
- the mixture would be relatively homogeneous and well-dispersed, and if the input flow to the system pump contained an appropriate concentration of lubricant, the portion extracted for lubrication purposes would likewise contain an appropriate concentration of NSIL evenly dispersed within the output flow of the system pump.
- the mixture extracted for lubrication injection may be taken from a reservoir or receiver where the mixture has been allowed to rest relatively undisturbed for a period of time. Due to the self-separating nature of the colloida l mixture, the location of the extraction point within the reservoir or receiver tank will largely determine the concentration of lubricant in the extracted mixture.
- extracting fluid from the upper strata of separated mixture will yield a much higher concentration of lubricant than if the sample is extracted near the bottom of the tank.
- the relative concentration of lubricant in the WF/NSIL mixture is not critical to the operation of the system, although due to the closed-loop circulating nature of the system, the relative proportion of working fluid and lubricant(s) will generally be constant on the whole for a similar and appropriate sample size obtained between the source point and the exit point if a similar degree of agitation is maintained for the mixture.
- WF/NSI L mixture was measured at the start, at 10 minute increments for the first 30 minutes of operation, and again after 60 minutes of operation. Following collection of the data, the ORC system was stopped and the WF/NSI L mixture in the closed-loop system was allowed to rest without movement or agitation until it was believed to have reached its naturally quiescent state.
- Curve 302 represents the data associated with the iteration with the maximum observed concentration of NSI L at the start
- curve 304 represents the same data for the iteration with the lowest observed concentration at the start
- curve 303 represents the average (mean) data for all test iterations performed. It can be seen that the starting values va ried widely over a range of almost 3 :1. This variation is attributable to the fact that the WF/NSI L mixture readily sepa rates when the ORC system is stopped and the data provides insight that the separation of the WF/NSI L mixture within the closed-loop circuit has at some degree of random ness and therefore is not a highly repeatable or predictable phenomenon.
- a particula rly valua ble conclusion that may be drawn from the data is that regardless of the sta rting concentration of NSI L in the WF/NSI L mixture, the measured concentration of NSIL in the WF/NSI L mixture was seen to converge on a highly repeatable value of approximately 2%. It is also important to observe the difference between this value and the overall NSI L concentration of 5.8% based on known a nd carefully measured quantities installed at the test commissioning of this pa rticu lar system. It is also important to note that this 2% concentration of lubricant flowing withi n the active portion of the system is substantially less than the 5% ta ught by Smith in that prior art system.
- NSI L has extremely strong affinity to bond with metal surfaces in the ORC system, including but not limited to the surfaces and bearings of the positive displacement machine, the metallic inner surfaces of heat exchanger 101, a nd metallic inner surfaces of condenser subsystem 104, all of which are directly in contact with the WF/NSIL mixture flow. This affinity causes a thin film of NSIL to be deposited on these surfaces, providing lubrication on the case of the surfaces, bearings, and other lubrication points of the positive displacement machine.
- Stratum 402 is a faintly milky colloidal mixture comprising primarily organic refrigerant working fluid with a small quantity of suspended NSIL. This stratum extends upward
- Stratum 403 is a transition zone approximately 1 inch in depth and, although similarly milky in appearance, further comprises droplets of NSIL of increasing size and number toward its upper edge.
- Stratum 404 is a transition zone approximately 1 inch in depth and, although similarly milky in appearance, further comprises droplets of NSIL of increasing size and number toward its upper edge.
- Stratum 405 approximately 1.5 inches thick, is largely comprised of NSIL with random droplets of working fluid refrigerant.
- Stratum 405 approximately 0.5 inches high, is a region comprised of agitated working fluid and NSIL. Due to the agitation, the upper surface is irregular and subject to variation. Partially vaporized working fluid occupies the remaining volume between the upper surface of stratum 405 and the upper inside surface of receiver tank 401.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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KR1020167025667A KR20160125426A (en) | 2014-02-21 | 2015-02-21 | Apparatus, systems and methods for lubrication of fluid displacement machines |
JP2016570921A JP2017511860A (en) | 2014-02-21 | 2015-02-21 | Lubricating apparatus, system and method for positive displacement fluid machinery |
EP15751428.2A EP3108126A4 (en) | 2014-02-21 | 2015-02-21 | Apparatus, systems and methods for lubrication of fluid displacement machines |
AU2015218734A AU2015218734A1 (en) | 2014-02-21 | 2015-02-21 | Apparatus, systems and methods for lubrication of fluid displacement machines |
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US201461943301P | 2014-02-21 | 2014-02-21 | |
US61/943,301 | 2014-02-21 |
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US (2) | US20150240639A1 (en) |
EP (1) | EP3108126A4 (en) |
JP (1) | JP2017511860A (en) |
KR (1) | KR20160125426A (en) |
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CA2971469C (en) * | 2016-06-13 | 2023-05-02 | Geoff Rowe | System, method and apparatus for the regeneration of nitrogen energy within a closed loop cryogenic system |
CN106224019A (en) * | 2016-08-24 | 2016-12-14 | 河北省电力勘测设计研究院 | Solar cogeneration method and device |
CN106285791A (en) * | 2016-08-24 | 2017-01-04 | 河北省电力勘测设计研究院 | Mobile solar energy reverse osmosis high-pressure pump installation |
CN108894829B (en) * | 2018-07-18 | 2019-04-19 | 北京工业大学 | A kind of pneumatic lubricating oil supply system of Organic Rankine Cycle expanding machine based on four-way reversing valve |
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US4916914A (en) * | 1988-05-27 | 1990-04-17 | Cpi Engineering Services, Inc. | Rotary displacement compression heat transfer systems incorporating highly fluorinated refrigerant-synthetic oil lubricant compositions |
US6374629B1 (en) * | 1999-01-25 | 2002-04-23 | The Lubrizol Corporation | Lubricant refrigerant composition for hydrofluorocarbon (HFC) refrigerants |
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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 |
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JPS5848733B2 (en) * | 1976-08-11 | 1983-10-31 | 株式会社日立製作所 | Small power generation plant using waste heat |
JPS5477848A (en) * | 1977-12-02 | 1979-06-21 | Hitachi Ltd | Compact type power plant utilizing waste heat |
US5636520A (en) * | 1995-12-12 | 1997-06-10 | Spauschus Associates, Inc. | Method of removing an immiscible lubricant from an refrigeration system |
GB9610289D0 (en) * | 1996-05-16 | 1996-07-24 | Univ City | Plural screw positive displacement machines |
US6981377B2 (en) * | 2002-02-25 | 2006-01-03 | Outfitter Energy Inc | System and method for generation of electricity and power from waste heat and solar sources |
US7637108B1 (en) * | 2006-01-19 | 2009-12-29 | Electratherm, Inc. | Power compounder |
-
2015
- 2015-02-21 US US14/628,247 patent/US20150240639A1/en not_active Abandoned
- 2015-02-21 JP JP2016570921A patent/JP2017511860A/en active Pending
- 2015-02-21 AU AU2015218734A patent/AU2015218734A1/en not_active Abandoned
- 2015-02-21 KR KR1020167025667A patent/KR20160125426A/en unknown
- 2015-02-21 WO PCT/US2015/016990 patent/WO2015127331A1/en active Application Filing
- 2015-02-21 EP EP15751428.2A patent/EP3108126A4/en not_active Withdrawn
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2018
- 2018-07-18 US US16/038,945 patent/US20180320520A1/en not_active Abandoned
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US4916914A (en) * | 1988-05-27 | 1990-04-17 | Cpi Engineering Services, Inc. | Rotary displacement compression heat transfer systems incorporating highly fluorinated refrigerant-synthetic oil lubricant compositions |
US6374629B1 (en) * | 1999-01-25 | 2002-04-23 | The Lubrizol Corporation | Lubricant refrigerant composition for hydrofluorocarbon (HFC) refrigerants |
US20120312009A1 (en) * | 2005-06-10 | 2012-12-13 | City University | Expander lubrication in vapour power systems |
US20100034684A1 (en) * | 2008-08-07 | 2010-02-11 | General Electric Company | Method for lubricating screw expanders and system for controlling lubrication |
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 |
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AU2015218734A1 (en) | 2016-09-29 |
EP3108126A4 (en) | 2017-09-20 |
US20150240639A1 (en) | 2015-08-27 |
US20180320520A1 (en) | 2018-11-08 |
KR20160125426A (en) | 2016-10-31 |
EP3108126A1 (en) | 2016-12-28 |
JP2017511860A (en) | 2017-04-27 |
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