US20110232305A1 - Systems and methods for generating power and chilling using unutilized heat - Google Patents

Systems and methods for generating power and chilling using unutilized heat Download PDF

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US20110232305A1
US20110232305A1 US13/050,189 US201113050189A US2011232305A1 US 20110232305 A1 US20110232305 A1 US 20110232305A1 US 201113050189 A US201113050189 A US 201113050189A US 2011232305 A1 US2011232305 A1 US 2011232305A1
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Prior art keywords
working fluid
feed
sorbent
fluid
generator
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US13/050,189
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English (en)
Inventor
Bhupender S. Minhas
Tahmid I. Mizan
Sufang ZHAO
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Priority to US13/050,189 priority Critical patent/US20110232305A1/en
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Abandoned legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
    • F25B17/083—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt with two or more boiler-sorbers operating alternately
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
    • F25B15/02—Sorption machines, plants or systems, operating continuously, e.g. absorption type without inert gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2309/00—Gas cycle refrigeration machines
    • F25B2309/06—Compression machines, plants or systems characterised by the refrigerant being carbon dioxide
    • F25B2309/061—Compression machines, plants or systems characterised by the refrigerant being carbon dioxide with cycle highest pressure above the supercritical pressure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y02B30/62—Absorption based systems

Definitions

  • the present application relates to systems and methods employing sorbent materials to generate power and chilling using unutilized heat.
  • the present invention relates to a system and method for the simultaneous generation of power and chilling utilizing waste heat.
  • Petroleum refining and petrochemical processing operations are energy intensive. It is often necessary to conduct these operations at high temperatures using high temperature heat sources including, but not limited to, steam. After the steam or other hot streams have performed the intended functions, there remains unutilized energy.
  • Refineries and petrochemical facilities typically utilize only 70% of the input energy and a large amount of energy loss occurs at lower temperatures, 450° F. or below. There is a strong need to recapture or utilize this energy. Potential uses of this energy include production of electric power, shaft power, or chilling of process streams. However, the cost of equipment to capture this heat can be a disincentive because of the low efficiencies of waste heat capture devices when the source of heat is at or below 450° F. Electric power, shaft power, and chilling can be effectively utilized in refineries and petrochemical processes to increase the overall efficiency of the facility.
  • One embodiment of the present application provides a sorption system for generating power and chilling including a first vessel containing a sorbent material in fluid communication with a working fluid and operatively connected to a heat source to yield a feed of working fluid at a supercritical state, a generator in fluid communication with the feed of working fluid at supercritical state to yield power and a feed of working fluid in an at least partially condensed state, and an evaporator in fluid communication with the feed of working fluid in the at least partially condensed state to yield chilling and a feed of uncondensed working fluid.
  • the heat source is an unutilized heat source.
  • the present application also provides a process for generating power and chilling including adsorbing a working fluid onto a sorbent material, heating the sorbent material to desorb the working fluid from the sorbent material at a supercritical state, directing the desorbed fluid to drive a generator to generate power and to at least partially condense the desorbed working fluid, and evaporating the at least partially condensed desorbed fluid to yield chilling and a feed of uncondensed working fluid.
  • the heating is provided by unutilized heat from one of a refining operation and chemical processing operation.
  • the present application also provides a sorption system for generating both power and chilling that includes an absorber to absorb a working fluid in a liquid sorbent, a pump in fluid communication with the absorber to yield a feed of pressurized liquid sorbent and absorbed working fluid, a heat source to heat the feed of pressurized liquid sorbent and absorbed working fluid to yield a feed of working fluid at a supercritical state, a generator in fluid communication with the feed of working fluid at a supercritical state to yield power and a feed of working fluid in an at least partially condensed state, and an evaporator in fluid communication with the feed of working fluid in the at least partially condensed state to yield chilling and uncondensed working fluid.
  • the heat source may be an unutilized heat source.
  • the present application also provides a process for generating both power and chilling that includes absorbing a working fluid into a liquid sorbent to yield a liquid sorbent and absorbed working fluid, pressurizing the liquid sorbent and absorbed working fluid to increased pressure, heating the pressurized liquid sorbent and absorbed working fluid to desorb the working fluid from the sorbent material in a supercritical state, directing the desorbed working fluid to drive a generator to generate power and to at least partially condense the desorbed working fluid, and evaporating the at least partially condensed desorbed working fluid to yield chilling and uncondensed working fluid.
  • the heating is provided by unutilized heat from one of a refining operation and chemical processing operation.
  • a sorption system for generating power includes a first vessel in fluid communication with a working fluid and a liquid sorbent material such that the working fluid is adsorbed in the liquid sorbent in the first vessel to yield a feed of liquid sorbent with an adsorbed working fluid.
  • the working fluid is selected from carbon dioxide, methane, ethane, propane, butane, ammonia and chlorofluorocarbons.
  • the feed of liquid sorbent with an adsorbed working fluid is fed to a heat source.
  • the heat source may be an unutilized heat source which includes a vapor generator.
  • the heat source disengages the liquid sorbent from the adsorbed working fluid to create a feed of working fluid at a supercritical state and a feed of liquid sorbent.
  • a first generator is in fluid communication with the feed of working fluid at supercritical state to yield power and a feed of working fluid in an at least partially condensed state which is in fluid communication with the first vessel.
  • the first generator may be turbo expander.
  • a second generator is in fluid communication with the feed of liquid sorbent to yield power and a feed of liquid sorbent in fluid communication with the first vessel.
  • the second generator may be a twin screw expander.
  • FIG. 1 is a schematic of a sorption system for the generation of chilling in accordance with an aspect of the present invention.
  • FIG. 2 is a Mollier Diagram annotated to show four points that correspond to four stages of the sorption system described in FIG. 1 .
  • FIG. 3 is a Mollier Diagram annotated to show alternative process points based on the use of waste heat to achieve a temperature of about 450° F. and alternative process points based on the use of higher sorbing pressures for use in connection with the generation of chilling.
  • FIG. 4 is a schematic of an adsorption system for the generation of power and/or chilling in accordance with an embodiment of the present application.
  • FIG. 5 is a schematic of an absorption system for the generation of power and/or chilling in accordance with an embodiment of the present application.
  • FIG. 6 is a schematic of an absorption system for the generation of power in accordance with an embodiment of the present application.
  • sorbent material refers to a material that reversibly binds a working fluid.
  • Sorbent materials include, but are not limited to, absorbents and adsorbents.
  • working fluid refers to a liquid or gas that can reversibly bind to the sorbent material.
  • the term “generator” refers to a turbine, shaft or other mechanism driven by a working fluid (e.g., a working fluid pressurized by an absorption or adsorption system) to generate power or work.
  • a working fluid e.g., a working fluid pressurized by an absorption or adsorption system
  • the term “vessel” refers to a container suitable for containing a sorbent material and a working fluid under suitable conditions to permit sorption (e.g., absorption or adsorption) and/or desorption.
  • unutilized heat refers to the residual or remaining heat source (e.g., steam) following the processing operation after the heat source has been used for its primary purpose in the refining or petrochemical processing operation. Unutilized heat is also referred to as waste heat.
  • the unutilized heat or unutilized heat source refers to a heat source that is no longer of any use in refining and/or petrochemical processing operations and would traditionally be discarded.
  • the unutilized heat can be provided as an unutilized heat stream.
  • unutilized heat can include steam that was employed in a heat exchanger used in petroleum and petrochemical processing, and is of no value to current processes and is being discarded.
  • pump refers to a physical device that assists in transporting fluids and/or pressurizing fluids to an increased pressure.
  • the term “efficiency” in context of the present invention is defined as the power plus chilling generated over the heat input.
  • twin screw expander in the context of the present invention is defined as a device driven by high pressure liquid or mixed phase sorbent liquid to generate power or shaft work.
  • a zeolite 13X/CO 2 adsorption system 100 is provided, as depicted schematically in FIG. 1 .
  • a Mollier Diagram for carbon dioxide at various temperatures and pressures for this embodiment is shown in FIGS. 2 and 3 for reference.
  • two vessels 111 and 112 are maintained in an adsorption mode and a desorption mode, respectively.
  • the sorbent material is zeolite 13X and the working fluid is CO 2 .
  • carbon dioxide is adsorbed by the zeolite 13X at a pressure of about 140 psi and a temperature of about 95° F. These conditions are denoted in FIG. 2 as Stage 1 .
  • the adsorbent bed is isolated (e.g., by operating the relevant valve (e.g., valve 141 for vessel 111 or valve 142 for vessel 112 )) and heated using unutilized heat from a petroleum refining or chemical process.
  • the adsorption mode can last for several seconds (e.g., 10 seconds) to several minutes. The duration of the adsorption mode varies based upon the adsorbent material and fluid selected.
  • Unutilized heat 121 or 122 is applied to the vessel in order to desorb the carbon dioxide, thus initiating the desorption mode. Using the unutilized heat, the vessel is heated to about 212° F. in this particular embodiment.
  • a pressurized stream is generated due to desorption of CO 2 from the 13X sorbent material as the adsorbent bed heats to 212° F.
  • a back pressure regulator valve e.g., valve 113 for vessel 111 or valve 114 for vessel 112
  • high pressure CO 2 is released from the vessel to pressure damper or cooler 115 at a preset pressure (e.g., ⁇ 1400 psig), which is denoted in FIG. 2 as stage 2 .
  • the temperature of the CO 2 is approximately 212° F.
  • the pressurized CO 2 stream is cooled in the pressure damper/cooler 115 to approximately 110° F., which is denoted as stage 3 in FIG. 2 .
  • the pressure of the cooled CO 2 stream in the line 131 is approximately 1380 psi and the temperature is approximately 110° F.
  • the cooled working fluid stream is subsequently expanded adiabatically using an expansion valve 116 to about 140 psi and ⁇ 40° F., which is denoted as stage 4 in FIG. 2 .
  • the expansion valve 116 may be a flow restrictor or a needle valve to restrict but not stop flow.
  • This cooled stream 132 can be used as a high quality refrigeration load for many different applications within refineries or similar facilities where unutilized heat is readily available.
  • the refrigerated CO 2 can be directed to a heat exchanger 118 to chill process streams within refineries and chemical plants.
  • the carbon dioxide of this representative embodiment can have a temperature of about 60° F. to 100° F. and a pressure of about 140 psi.
  • the carbon dioxide working fluid 133 is then recycled back to one of the vessels for use in a subsequent adsorption mode.
  • the CO 2 /zeolite 13X system has a pressure index of greater than 3.5.
  • the pressure index is determined in accordance with the procedure set forth below.
  • stage 2 is now stage 2 A, in which a higher-temperature unutilized heat source is used to heat the bed to 450° F., instead of 212° F.
  • the pressurized stream is to be cooled to 110° F. before expansion. It, therefore, will require a much higher amount of cooling media at stage 2 .
  • the efficiency of this alternative system based on a 450° F. heat source, using the selection of zeolite 13X and carbon dioxide, will be significantly different as it requires higher level of heating and cooling. It is understood, however, that a selection of sorbent material and fluid based on a higher level heat pressure index can produce a sorption system that is better suited for a higher quality of heat.
  • each vessel can be a shell in tube-type configuration with adsorbents in the tube.
  • the vessel can have an inner diameter of about 5 ft and contains tubes having a length of about 20 ft.
  • Other suitable vessels can be used.
  • exchanges other than shell-in-tube heat exchanges can be selected based on ordinary skill in the art.
  • an adsorption system for generating power and chilling.
  • the adsorption system includes a first vessel containing a sorbent material in fluid communication with a working fluid and operatively connected to a heat source to yield a feed of working fluid at a supercritical state, a generator in fluid communication with the feed of working fluid at supercritical state to yield power and a feed of working fluid in an at least partially condensed state, and an evaporator in fluid communication with the feed of working fluid in the at least partially condensed state to yield chilling and a feed of uncondensed working fluid.
  • the heat source is an unutilized heat source or stream.
  • the unutilized heat source is from a chemical processing or petrochemical refining operation.
  • the system can also include a second vessel containing sorbent material in fluid communication with the working fluid and operatively connected to a heat source to yield a second feed of working fluid at a supercritical state.
  • Each of the first vessel and the second vessel has a sorption mode and a desorption mode, wherein in the desorption mode the working fluid is released from the sorbent material in response to the heat source, and wherein in the sorption mode, the working fluid is sorbed by the sorbent material, wherein when the first vessel is operating in the adsorption mode, the second vessel is operating in the desorption mode and, wherein when the first vessel is operating in the desorption mode, the second vessel is operating in the adsorption mode.
  • the adsorption system 400 includes a first vessel 411 , a second vessel 412 , a generator 413 , and an evaporator 414 for which cooling is desired.
  • the first and second vessel 411 and 412 can be a shell-in-tube type configuration with the sorbent material in the tubes.
  • the first and second vessels can have an inner diameter of about 5 feet and contain tubes having a length of about 20 feet. Other vessel sizes are considered to be well within the scope of the present application.
  • the present application is not limited to shell-in-tube heat exchangers, other exchangers and other vessels can be selected based on ordinary skill in the art and are considered to be well within the scope of the present application including but not limited to the use of sorbent beds, structured adsorbents, and hollow fiber adsorbents.
  • An unutilized heat stream 431 passes through the first vessel 411 . Unutilized heat contained in the stream 431 passes through the walls of the line containing the stream into the first vessel 411 .
  • An unutilized heat stream 432 passes through the second vessel 412 . Unutilized heat contained in the stream 432 passes through the walls of the line containing the stream into the second vessel 412 .
  • the unutilized heat streams 431 and 432 can supply from the same unutilized heat source or separate unutilized heat sources.
  • vessels 411 and 412 can also be adapted to receive a feed of cooling media to regenerate the adsorbents housed therein.
  • a valve assembly 441 is interposed between the first vessel 411 and the generator 413 .
  • the valve assembly 441 functions as a back pressure regulator which permits the working fluid to escape from the first vessel 411 at a predetermined or pre-set pressure.
  • the predetermined or pre-set pressure can range, for example, from about 500 psig to about 3000 psig, which is dependent upon the amount of sorbent material contained in the vessel and the temperature of the unutilized heat stream.
  • a second valve assembly 442 is interposed between the second vessel 412 and the generator 413 . Like the first valve assembly 441 , the second valve assembly 442 functions as a back pressure regulator, which permits the working fluid in the second vessel to escape from the second vessel 412 at a pre-set pressure.
  • the first vessel 411 is in fluid communication with a feed of working fluid 421 fed to the first vessel at pressure ⁇ 100 psia and temperature ⁇ 100 F.
  • a control valve 451 controls the flow of working fluid to the first vessel 411 .
  • the second vessel 412 is in fluid communication with a feed of working fluid 421 fed to the second vessel at pressure 100 psia and temperature 100 F.
  • a control valve 452 controls the flow of fluid to the second vessel 412 .
  • the first and second vessels 411 and 412 operate in tandem.
  • the working fluid 421 flows into the first vessel 411 when the valve 451 is open.
  • the valve 451 remains open until equilibrium is established within the first vessel 411 .
  • the adsorption mode can last for several seconds (e.g., ⁇ 10 seconds) to several minutes. The duration of the adsorption mode varies based upon the adsorbent material and fluid selected.
  • the unutilized heat stream 431 passes through the first vessel 411 such that the sorbent material and the working fluid are heated, which results in the desorption of the working fluid from the sorbent material. This increases the pressure of the working fluid contained in the first vessel 411 . Once the pre-set pressure is reached, the working fluid is released from the first vessel 411 via the valve assembly 441 , to yield a feed of working fluid at a super-critical state 422 at pressure ⁇ 1600 psia and temperature ⁇ 255 F.
  • the feed of working fluid at a supercritical state 422 is used to run to the generator 413 to generate power.
  • the generator is run using a turbine, a turboexpander or any other suitable device to create shaft work to be able to run the generator for power. It is also contemplated that the generator may also be used to drive rotating equipment such as pumps or compressors to perform work on a process stream. Additionally, the device yields a feed of working fluid in an at least partially condensed state 423 at a pressure about 100 psia and temperature ⁇ 58 F.
  • the feed of working fluid at supercritical state 422 passes through the generator to either generate electricity or perform work by driving a shaft or other suitable mechanism.
  • the amount of power generated is 0.95 mega watts (MW) based on 60,000 lb/hr CO 2 flow rate. It is contemplated that the amount of power generated may vary based upon the system components.
  • the feed of working fluid in an at least partially condensed state 423 is fed to an evaporator 414 to provide chilling and a feed of uncondensed working fluid.
  • the uncondensed working fluid 421 is then to be reintroduced to the first or second vessel.
  • the working fluid in an at least partially condensed state 423 is processed through an evaporator to generate chilling by using the latent heat of vaporization as well as sensible heat of the working fluid, although other suitable vessels to create chilling can be utilized.
  • the chilling generated can be used in many refinery processes.
  • the chilling can be used in a heat exchanger to cool a process stream for refining or petrochemical processing operations.
  • chilling can be used to cool water to provide cooling water to an overhead condenser in a distillation tower. Chilling can be used to recover gas molecules from a fuel stream. The chilling can also be used in cooling the air intake of a gas turbine generator to improve power output.
  • the heat exchanger can be used in connection with a building cooling system located in one of the buildings located at the facility such that the unutilized heat can be used to cool one or more of the buildings. It is also contemplated that the system can be used in connection with air conditioning using exhaust heat from automobiles.
  • the valve 451 is closed such that after the passing through the evaporator 414 , the working fluid at a pressure close to 100 psia and temperature ⁇ 100 F, is fed to the second vessel through open control valve 452 .
  • the valve 452 remains open until equilibrium is established within the second vessel 412 .
  • the adsorption mode can last for several seconds (e.g., ⁇ 10 seconds) to several minutes. The duration of the adsorption mode varies based upon the adsorbent material and fluid selected.
  • the unutilized heat stream 432 passes through the second vessel 412 such that the sorbent material and the working fluid are heated, which results in the desorption of the working fluid from the sorbent material.
  • the working fluid is released from the second vessel 412 via valve assembly 442 , to yield a feed of working fluid at a supercritical state 422 .
  • the working fluid passes through the system, as described above. After passing through the evaporator 414 , the working fluid is returned to the first vessel 411 .
  • first and second vessels 411 and 412 are operated in tandem such that one is operating in an adsorption mode when the other is operating in a desorption mode and vice versa.
  • the first and second vessels 411 and 412 operate to provide a continuous supply of working fluid to the generator 413 .
  • the working fluid is selected from carbon dioxide, methane, ethane, propane, butane, ammonia and chlorofluorocarbons (e.g., FreonTM), other refrigerants, or other suitable fluids.
  • the sorbent material is selected from zeolites, metal organic frameworks (MOFs), zeolitic imidazolate frameworks (ZIFs), ionic liquids, silicagel, adsorbing polymers, carbon, and activated carbon, and combinations thereof.
  • the working fluid is carbon dioxide and/or the sorbent material is a zeolite.
  • the working fluid is carbon dioxide and the zeolite is a zeolite X, preferably a zeolite 13X.
  • the present application also provides an adsorption process for generating both power and chilling.
  • the process includes adsorbing a working fluid onto a sorbent material, heating the sorbent material to desorb the working fluid from the sorbent material at a supercritical state, directing the desorbed fluid to drive a generator to generate power or do shaft work and to at least partially condense the desorbed working fluid, and evaporating the at least partially condensed desorbed fluid to yield chilling and a feed of uncondensed working fluid.
  • the process can use any of the features described above for the adsorption system.
  • the heating is provided by unutilized heat from one of a refining operation and chemical processing operation.
  • the unutilized heat can be at a temperature of 450 F or lower.
  • adsorption system and process described herein do not require the use of a pump or additional components to facilitate movement of the working fluid through the system.
  • the table below compares generation of power and chilling together with power or chilling alone.
  • the examples are based on the use of a CO 2 -Zeolite 13X combination.
  • the adsorber/desorber bed is a shell and tube design with sorbent material packed inside the tube. This comparison is based on same amount of gas flow 60,000 lb/hr CO2.
  • the equipment size of adsorber/desorber beds is related with thermal swing time of the process.
  • Each adsorber/desorber vessel may have an inner diameter of about 5 ft and contains tubes having a length of about 20 ft.
  • the process scheme illustrated in FIG. 1 can be used for the chilling only case. To generate both power and chilling, the process scheme illustrated in FIG. 4 can be utilized. To generate power only, the process scheme is similar to FIG. 4 without the evaporator.
  • an absorption system for generating power and chilling.
  • the absorption system includes an absorber to absorb a working fluid in a liquid sorbent, a pump in fluid communication with the absorber to yield a feed of pressurized liquid sorbent and absorbed working fluid, a heat source to heat the feed of pressurized liquid sorbent and absorbed working fluid to yield a feed of working fluid at a supercritical state, a generator in fluid communication with the feed of working fluid at a supercritical state to yield power and a feed of working fluid in an at least partially condensed state, and an evaporator in fluid communication with the feed of working fluid in the at least partially condensed state to yield chilling and uncondensed working fluid.
  • the absorption system 500 includes an absorber 511 , a pump 512 , a vapor generator 513 , a generator 514 , an evaporator 515 , a cooler 516 and a cooler 517 .
  • the absorber 511 is in fluid communication with a working fluid 521 fed to the absorber at a first pressure ( ⁇ 560 psia) and a first temperature ( ⁇ 100 F) and a liquid sorbent 522 .
  • the working fluid 521 is absorbed in the liquid sorbent 522 to yield a liquid sorbent with an absorbed working fluid 523 .
  • the absorber 511 can be an absorption column or any other suitable vessel. During absorption there is heat generated in the absorber that can be removed from the absorber using cooling water, or any other suitable means, to maintain the absorber at a temperature favorable for absorbing the working fluid.
  • the pump 512 pumps the liquid sorbent with an absorbed fluid 523 from the absorber to a higher pressure to yield a feed of pressurized liquid sorbent and absorbed working fluid 524 .
  • the pressurized liquid sorbent and absorbed working fluid 524 is at a higher pressure ( ⁇ 1400 psia) and a second temperature ( ⁇ 104 F), generally greater than (100 F).
  • the present invention is not intended to be limited to the specified pressures and temperatures; rather, other temperatures and pressures are considered to be well within the scope of the present invention provided such temperatures and pressures are suitable for the pressurized liquid sorbent and absorbed working fluid.
  • the feed of pressurized liquid sorbent and absorbed working fluid 524 is heated using a heat source which can include a vapor generator 513 , e.g., a rectification column or any other suitable vessel.
  • the heat source 531 can pass through the vapor generator, to disengage the working fluid from the liquid absorbent to yield a feed of working fluid at a supercritical state 525 and the liquid sorbent 527 , which is fed to a cooler 516 before the liquid sorbent 522 is returned to the absorber 511 .
  • the cooler 516 can be in fluid communication with the vapor generator and can include cooling water.
  • the feed of working fluid at a supercritical state 525 from the vapor generator 513 is passed through a cooler 517 to reduce the temperature from ⁇ 275 F to ⁇ 60 F.
  • the pressure remains at ⁇ 1400 psia. Other temperatures and pressures are considered to be well within the scope of the present invention.
  • the unutilized heat stream or source 531 can be operatively connected to the vapor generator 513 such that unutilized heat from the unutilized heat source can be transferred to the liquid sorbent with an absorbed fluid contained within the vapor generator.
  • the feed of working fluid at a supercritical state 525 is used to run to a generator 514 to generate power.
  • the generator can be a turbine, a turboexpander or any other suitable device to generate power or work.
  • a working fluid is selected such that the generator yields a feed of working fluid in an at least partially condensed state 526 at a pressure about ⁇ 560 psia and a temperature ⁇ 43 F less than 100 F.
  • the present invention is not intended to be limited to the pressures and temperatures stated herein; rather, other temperatures and pressures are considered to be well within the scope of the present invention provided such temperatures and pressures yield the partially condensed state 526 .
  • the feed of working fluid at supercritical state 525 passes through the generator to either generate power or perform work by driving a shaft or other suitable mechanism.
  • the power generated can be supplied to the power grid for refinery use or for supplying a third party.
  • the amount of power generated by the system in accordance with the present invention may vary based upon the design of the system and the selected components. For example, the system may generate ⁇ 32 kilo watts (KW) of power based on 45,000 lb/hr mixture of CO 2 and amyl acetate (stream 525 ). The molar concentration of amyl acetate in 525 is 3%. It is contemplated that the system may generate amounts in excess of 32 KW based upon the system design and other constraints.
  • the working fluid in an at least partially condensed state 526 is fed to an evaporator 515 to yield chilling and uncondensed working fluid 521 to be fed to the absorber 511 .
  • the evaporator 515 can be in fluid communication with the absorber 511 .
  • the working fluid in an at least partially condensed state 526 is processed through an evaporator 515 to generate chilling by using the latent heat of vaporization of the working fluid, although other suitable vessels to create chilling can be utilized.
  • the chilling generated can be used in many refinery processes.
  • the chilling can be used in a heat exchanger to cool a process stream for refining or petrochemical processing operations.
  • Chilling can be used to cool water to provide cooling water to an overhead condenser in a distillation tower. Chilling can also be used to recover gas molecules from a fuel stream. The chilling can also be used in cooling the air intake of a gas turbine generator to improve power output.
  • an absorption system for generating power is provided. Power is generated using both gas phase expansion and liquid phase expansion.
  • the absorption system includes an absorber to absorb a working fluid in a liquid sorbent, a pump in fluid communication with the absorber to yield a feed of pressurized liquid sorbent and absorbed working fluid, a heat source to heat the feed of pressurized liquid sorbent and absorbed working fluid to yield a feed of working fluid at a supercritical state, at least one generator.
  • the absorption system 600 includes an absorber 611 , a pump 612 , a vapor generator 613 , generators 614 and 615 , a cooler 616 and a cooler 617 .
  • the absorber 611 is in fluid communication with a working fluid 621 fed to the absorber at a first pressure ( ⁇ 600 psia) and a first temperature ( ⁇ 127 F) and a liquid sorbent 622 .
  • the working fluid 621 is absorbed in the liquid sorbent 622 to yield a liquid sorbent with an absorbed working fluid 623 .
  • the absorber 611 can be an absorption column or any other suitable vessel. During absorption there is heat generated in the absorber that can be removed from the absorber using cooling water, or any other suitable means, to maintain the absorber at a temperature favorable for absorbing the working fluid.
  • the pump 612 pumps the liquid sorbent with an absorbed fluid 623 from the absorber to a higher pressure to yield a feed of pressurized liquid sorbent and absorbed working fluid 624 .
  • the pressurized liquid sorbent and absorbed working fluid 624 is at a higher pressure ( ⁇ 1200 psia) and a second temperature ( ⁇ 102 F).
  • the present invention is not intended to be limited to the specified pressures and temperatures; rather, other temperatures and pressures are considered to be well within the scope of the present invention provided such temperatures and pressures are suitable for the pressurized liquid sorbent and absorbed working fluid.
  • the feed of pressurized liquid sorbent and absorbed working fluid 624 is heated using a heat source which can include a vapor generator 613 , e.g., a rectification column or any other suitable vessel.
  • the heat source 631 can pass through the vapor generator, to disengage the working fluid from the liquid absorbent to yield a feed of working fluid at a supercritical state 625 and the liquid sorbent 627 , which is fed to a cooler 616 and then to a generator 615 before the liquid sorbent 622 is returned to the absorber 611 .
  • the generator 615 is suitable for use in liquid phase expansion to generate.
  • the generator 615 may be a twin screw expander, but other power generating assemblies are considered to be well within the scope of the present invention.
  • the cooler 616 can be in fluid communication with the vapor generator 613 and can include cooling water.
  • the feed of working fluid at a supercritical state 625 is at a pressure ( ⁇ 1200 psia) and a temperature ( ⁇ 450 F). Other temperatures and pressures are considered to be well within the scope of the present invention.
  • the unutilized heat stream or source 631 can be operatively connected to the vapor generator 613 such that unutilized heat from the unutilized heat source can be transferred to the liquid sorbent with an absorbed fluid contained within the vapor generator.
  • the feed of working fluid at a supercritical state 625 is used to run to a generator 614 to generate power.
  • the generator 614 can be a turbine, a turboexpander or any other suitable device to generate power or work.
  • a working fluid is selected such that the generator yields a feed of working fluid 626 at a pressure about ⁇ 600 psia and a temperature ⁇ 398 F.
  • the present invention is not intended to be limited to the pressures and temperatures stated herein; rather, other temperatures and pressures are considered to be well within the scope of the present invention.
  • the working fluid 626 is fed to a cooler 617 .
  • the reduced temperature working fluid 621 from the cooler 617 is then fed back to the absorber 611 .
  • the heat exchanger can be used in connection with a building cooling system located in one of the buildings located at the facility such that the unutilized heat can be used to cool one or more of the buildings.
  • the absorption system generates power and chilling by recovering unutilized heat from an unutilized heat stream or source.
  • the unutilized heat source can be used heat from a heat exchanger, or other process area of a chemical processing plant or petrochemical refining plant.
  • the absorption system includes a liquid sorbent or a mixture of liquid sorbents and a working fluid or a mixture of working fluids.
  • liquid sorbents and working fluids are considered to be within the scope of the present application. It should be noted that a combination that is suitable for application with a higher temperature unutilized heat stream may not be applicable for a lower temperature unutilized heat stream.
  • the liquid sorbent in the absorption system has an average heat of sorption (Q) between about 2 kcal/mole and about 25 kcal/mole, or more preferably between about 3 kcal/mole and about 10 kcal/mole.
  • the working fluid is a gas and is selected from carbon dioxide, methane, ethane, propane, butane, ammonia, chlorofluorocarbons (e.g., FreonTM), other refrigerants, or other suitable fluids.
  • the liquid sorbent is selected from water, ethylene glycols, Triethylene glycol, polyethylene glycol, polyethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, dimethylsulfoxide, potassium carbonate, amyl acetate, acetone, pyridine, ethyl alcohol, methyl alcohol, acetic acid, isobutyl acetate, acetic anhydride, ionic liquids, etc., or other suitable liquids and combinations thereof.
  • the working fluid is carbon dioxide and/or the liquid sorbent is N-methyl-2-pyrrolidone and ionic liquids.
  • a process for generating power and chilling includes absorbing a working fluid into a liquid sorbent to yield a liquid sorbent and absorbed working fluid, pressurizing the liquid sorbent and absorbed working fluid to increased pressure, heating the pressurized liquid sorbent and absorbed working fluid to desorb the working fluid from the sorbent material in a supercritical state, directing the desorbed working fluid to drive a generator to generate power and to at least partially condense the desorbed working fluid, and evaporating the at least partially condensed desorbed working fluid to yield chilling and uncondensed working fluid.
  • the process can use any of the features described above for the absorption system.
  • the heating is provided by unutilized heat from one of a refining operation and chemical processing operation.
  • the unutilized heat is at a temperature of 450° F. or lower.
  • Embodiments of the present application employ a “pressure index” that can be determined at various desorbing temperatures, which is used to determine suitable combinations of a sorbent material and a working fluid. These combinations are especially adaptable to be used in the sorption process disclosed herein, since they collectively maximize pressurization of working fluid ( ⁇ P) from available energy sources, which are often, but not necessarily, low grade heat sources primarily intended to be used for some other specific purpose (e.g., waste heat).
  • ⁇ P working fluid
  • the pressure index is determined by the following method.
  • One hundred (100) grams of sorbent material are placed in a 1 liter vessel designed to be isolated from associated equipment with existing valves on both ends of the vessel.
  • the vessel also has indicators to measure the inside pressure and temperature.
  • the vessel is flushed and filled with a pure fluid (e.g., CO 2 ) at one atmospheric pressure.
  • the sorbent material adsorbs fluid and the sorbent may heat up.
  • the vessel is heated to a pre-selected desorbing temperature (e.g., 348 K i.e. 167° F.).
  • a pre-selected desorbing temperature e.g., 348 K i.e. 167° F.
  • the pressure index is defined as the ratio of P F to P I .
  • embodiments of the present application make use of a lower temperature of unutilized heat.
  • a sorbent material/fluid combination that is preferred for use with low level heat (e.g., sorption systems that utilize low grade unutilized heat)
  • a pressure index of at least 1.5 is generally appropriate for use in low level unutilized heat applications.
  • other embodiments of the present application can use high level heat sources.
  • combinations of sorbent material and working fluid can have a pressure index as low as 1.2.
  • sorbent material refers to a material that reversibly binds the working fluid.
  • Sorbent materials include, but are not limited to, absorbents and adsorbents.
  • Absorbent materials that can be used in embodiments of the present application include, but are not limited to, water, glycols, amyl acetate, acetone, pyridine, ethyl alcohol, methyl alcohol, acetic acid, isobutyl acetate, acetic anhydride, ionic liquids, etc.
  • Adsorbent materials that can be used in embodiments of the present application include, but are not limited to, metal-organic framework-based (MOF-based) sorbents, zeolitic imidazole framework (ZIF) sorbent materials, zeolites and carbon.
  • MOF-based metal-organic framework-based
  • ZIF zeolitic imidazole framework
  • MOF-based sorbents include, but are not limited to, MOF-based sorbents with a plurality of metal, metal oxide, metal cluster or metal oxide cluster building units.
  • the metal can be selected from the transition metals in the periodic table, and beryllium.
  • Exemplary metals include zinc (Zn), cadmium (Cd), mercury (Hg), beryllium (Be) and copper (Cu).
  • the metal building units can be linked by organic compounds to form a porous structure, where the organic compounds for linking the adjacent metal building units can include 1,3,5-benzenetribenzoate (BTB); 1,4-benzenedicarboxylate (BDC); cyclobutyl 1,4-benzenedicarboxylate (CB BDC); 2-amino 1,4 benzenedicarboxylate (H2N BDC); tetrahydropyrene 2,7-dicarboxylate (HPDC); terphenyl dicarboxylate (TPDC); 2,6 naphthalene dicarboxylate (2,6-NDC); pyrene 2,7-dicarboxylate (PDC); biphenyl dicarboxylate (BDC); or any dicarboxylate having phenyl compounds.
  • BTB 1,3,5-benzenetribenzoate
  • BDC 1,4-benzenedicarboxylate
  • CB BDC cyclobutyl 1,4-benzenedicarboxylate
  • MOF-based sorbent materials include: MOF-177, a material having a general formula of Zn 4 O(1,3,5-benzenetribenzoate) 2 ; MOF-5, also known as IRMOF-I, a material having a general formula of Zn 4 O(1,4-benzenedicarboxylate) 3 ; IRMOF-6, a material having a general formula of Zn 4 O(cyclobutyl 1,4-benzenedicarboxylate); IRMOF-3, a material having a general formula of Zn 4 O(2-amino 1,4 benzenedicarboxylate) 3 ; and IRMOF-11, a material having a general formula of Zn 4 O(terphenyl dicarboxylate) 3 , or Zn 4 O(tetrahydropyrene 2,7-dicarboxylate) 3 ; IRMOF-8, a material having a general formula of Zn 4 O(2,6 naphthalene dicarboxylate
  • Exemplary zeolitic imidazole framework (ZIF) sorbent materials include, but are not limited to, ZIF-68, ZIF-60, ZIF-70, ZIF-95, ZIF-100 developed at the University of California at Los Angeles and generally discussed in Nature 453, 207-211 (8 May 2008), hereby incorporated by reference in its entirety.
  • Zeolite adsorbent materials include, but are not limited to, aluminosilicates that are represented by the formula M 2/n O.Al 2 O 3 .ySiO 2 .wH 2 O, where y is 2 or greater, M is the charge balancing cation, such as sodium, potassium, magnesium and calcium, N is the cation valence, and w represents the moles of water contained in the zeolitic voids.
  • Examples of zeolites that can be included in the methods and systems of the present application include natural and synthetic zeolites.
  • Natural zeolites include, but are not limited to, chabazite (CAS Registry No. 12251-32-0; typical formula Ca 2 [(AlO 2 ) 4 (SiO 2 ) 8 ].13H 2 O), mordenite (CAS Registry No. 12173-98-7; typical formula Na 8 [(AlO 2 ) 8 (SiO 2 ) 40 ].24H 2 O), erionite (CAS Registry No. 12150-42-8; typical formula (Ca, Mg, Na 2 , K 2 ) 4.5 [(AlO 2 ) 9 (SiO 2 ) 27 ].27H 2 O), faujasite (CAS Registry No.
  • Synthetic zeolites include, but are not limited to, zeolite A (typical formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ].27H 2 O), zeolite X (CAS Registry No. 68989-23-1; typical formula: Na 86 [AlO 2 ) 86 (SiO 2 ) 106 ].264H 2 O), zeolite Y (typical formula: Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ].250H 2 O), zeolite L (typical formula: K 9 [(AlO 2 ) 9 (SiO 2 ) 27 ].22H 2 O), zeolite omega (typical formula: Na 6.8 TMA 1.6 [AlO 2 ) 8 (SiO 2 ) 28 ].21H 2 O, where TMA is tetramethylammonium) and ZSM-5 (typical formula: (Na, TPA) 3 [(AlO 2 ) 3 (SiO 2 )
  • Zeolites that can be used in the embodiments of the present application also include the zeolites disclosed in the Encyclopedia of Chemical Technology by Kirk-Othmer, Volume 16, Fourth Edition, under the heading “Molecular Sieves,” which is hereby incorporated by reference in its entirety.
  • Synthetic zeolite sorbent materials are commercially available, such as under the Sylosiv® brand from W.R. Grace and Co. (Columbia, Md.) and from Chengdu Beyond Chemical (Sichuan, P.R. China).
  • Sylosiv® A10 is one commercially available zeolite 13X product.
  • fluid refers to a liquid or gas that reversibly binds to the sorbent material.
  • fluids that can be used in accordance with the present application include carbon dioxide, methane, ethane, propane, butane, ammonia, chlorofluorocarbons (e.g., FreonTM), and other suitable fluids and refrigerants.
  • any suitable fluid or refrigerant satisfying the above-described pressure index can be used.
  • a method for selecting a sorbent material and a working fluid for use in combination in an unutilized-heat sorbent system within a chemical processing or petrochemical refining operation.
  • the method generally includes identifying a sorbent that meets the pressure index criterion of at least 1.5.
  • the sorbent material and the working fluid for use in combination are selected if the measured internal pressure within the secured chamber is at least two times, or at least three times, or at least four times, or at least six times, or at least eight times the sorbing pressure.
  • the sorption system can be used to generate power and chilling. The above-described method is not applicable to absorption systems.
  • the sorbent material and fluid couple has an average heat of sorption (Q) from about 2 kcal/mole to about 25 kcal/mole, and more preferably from about 4 kcal/mole to about 10 kcal/mole for heat sources up to 450° F.
  • the heat of sorption should be between 2 kcal/mole to about 40 kcal/mole if a higher temperature heat source (e.g., greater than 450° F. and up to 1700° F.) is available.
  • the sorbent material should also have a high capacity for the working fluid.
  • the adsorbent systems of the present application can be used in various applications provided the setting allows for the presence of a vessel that contains a sorbent material, a supply of working fluid, a heat supply and means to effectively direct the desorbed fluid to a generator to generate power and a evaporator to provide chilling.
  • the desorbed gas can be directed to a turboexpander to provide power.
  • the absorbent systems and methods of the present application can be used in various applications provided the setting allows for the presence of a absorber for absorbing a working fluid in a liquid sorbent and a vapor generator for desorbing the working fluid from the liquid sorbent, a supply of working fluid, a heat supply and a pump, and means to effectively direct the desorbed fluid to a generator to generate power and a evaporator to provide chilling thereto.
  • Possible applications for sorption systems of the present application include residential (for generating air conditioning in the summer and a heat pump in the winter), vehicular (where the on-board air conditioning utilizes exhaust heat) and industrial (refining and chemical plants).
  • the sorbent system or method is used within a chemical or petrochemical plant, and the desorbed fluid is used to generate power and to provide chilling to aid in other process areas, particularly areas that rely on temperature differences to separate components of a mixture.
  • the chilling can be used to recover liquefied petroleum gas (LPG, C 3+ ) from flue gases going up a stack, or the chilling can be used to operate condensers to improve the effectiveness of vacuum distillation columns, particularly in the summer months.
  • LPG liquefied petroleum gas
  • the sorbent system or method can make effective use of lower grade heat than previously provided by sorption systems in the prior art.
  • the heat supply is “unutilized heat” which has a temperature of from about 70° C. (158 F) to about 300° C. (572 F), more preferably from about 90° C. (194 F) to about 180° C. (356 F).

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  • Sorption Type Refrigeration Machines (AREA)
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EP4276388A1 (fr) 2022-05-09 2023-11-15 Vaillant GmbH Dispositif de circuit frigorifique avec échangeur de chaleur à espace intermédiaire
DE102022117111A1 (de) 2022-07-08 2024-01-11 Technische Universität Dresden, Körperschaft des öffentlichen Rechts Kühlgemisch, Kältemittelkreislauf und Verfahren davon

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EP2553357A1 (fr) 2013-02-06
EP2553357B1 (fr) 2017-09-20
SG183864A1 (en) 2012-10-30
CN102834680A (zh) 2012-12-19
JP2013524139A (ja) 2013-06-17
CA2792637A1 (fr) 2011-09-29
WO2011119787A1 (fr) 2011-09-29

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