WO2006115597A2 - Integrated ngl recovery and lng liquefaction - Google Patents
Integrated ngl recovery and lng liquefaction Download PDFInfo
- Publication number
- WO2006115597A2 WO2006115597A2 PCT/US2006/009103 US2006009103W WO2006115597A2 WO 2006115597 A2 WO2006115597 A2 WO 2006115597A2 US 2006009103 W US2006009103 W US 2006009103W WO 2006115597 A2 WO2006115597 A2 WO 2006115597A2
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- WO
- WIPO (PCT)
- Prior art keywords
- absorber
- stream
- distillation column
- bottom product
- plant
- Prior art date
Links
- 238000011084 recovery Methods 0.000 title claims description 97
- 239000006096 absorbing agent Substances 0.000 claims abstract description 123
- 238000004821 distillation Methods 0.000 claims abstract description 85
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 73
- 239000007789 gas Substances 0.000 claims description 65
- 238000010992 reflux Methods 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 49
- 239000003345 natural gas Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 16
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 47
- 238000005057 refrigeration Methods 0.000 description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000003507 refrigerant Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- -1 methane hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005380 natural gas recovery Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
- F25J1/0235—Heat exchange integration
- F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
- F25J1/0239—Purification or treatment step being integrated between two refrigeration cycles of a refrigeration cascade, i.e. first cycle providing feed gas cooling and second cycle providing overhead gas cooling
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0022—Hydrocarbons, e.g. natural gas
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0244—Operation; Control and regulation; Instrumentation
- F25J1/0254—Operation; Control and regulation; Instrumentation controlling particular process parameter, e.g. pressure, temperature
- F25J1/0255—Operation; Control and regulation; Instrumentation controlling particular process parameter, e.g. pressure, temperature controlling the composition of the feed or liquefied gas, e.g. to achieve a particular heating value of natural gas
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0209—Natural gas or substitute natural gas
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0238—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 2 carbon atoms or more
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/78—Refluxing the column with a liquid stream originating from an upstream or downstream fractionator column
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
- F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/08—Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/60—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being hydrocarbons or a mixture of hydrocarbons
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/02—Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/20—Integration in an installation for liquefying or solidifying a fluid stream
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2280/00—Control of the process or apparatus
- F25J2280/02—Control in general, load changes, different modes ("runs"), measurements
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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
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/10—Mathematical formulae, modeling, plot or curves; Design methods
Definitions
- the field of the invention is natural gas liquids (NGL) recovery and LNG liquefaction, and particularly integrated plant configurations for same.
- NNL natural gas liquids
- Natural gas is typically recovered from oil and gas production wells located onshore and offshore. Most typically, natural gas predominantly comprises Cl (methane). Depending on the particular formations and reservoirs, natural gas also contains relatively low quantities of non-methane hydrocarbons, including C2, C3, C4, C5, and heavier components. Still further components of natural gas include water, nitrogen, carbon dioxide, hydrogen sulfide, mercaptans, and other gases.
- Natural gas from wellheads is commonly treated and processed, and transported to gas processing plants in high pressure transmission pipelines.
- natural gas is commonly transported by liquefying the natural gas and moving the liquefied gas (e.g., using LNG cargo carriers).
- direct liquefaction of natural gas is often problematic as natural gas often contains C5, aromatics, and heavier hydrocarbons, which solidify when cooled to cryogenic temperatures. Consequently, such heavier components must be removed to a relatively low level (typically less than 1 ppmv) to avoid solidification and ultimately plugging of the cryogenic heat exchange equipment.
- lighter hydrocarbons such as C2, C3, and C4 must also be removed at least to some degree for the north American market, which typically requires the natural gas to meet a heating value of between 1050 to 1070 Btu/SCF.
- C2 can often be used as a feedstock for petrochemical manufacture
- C3 and C4 can be sold as LPG fuels
- C5+ hydrocarbons can be used for gasoline blending.
- NGL recovery from a natural gas feed is a natural gas feed.
- past efforts have focused on removal of the NGL hydrocarbons from natural gas using standalone NGL recovery plants, which operate independently from LNG liquefaction plants. These processes generally produce a relatively low pressure residue gas at ambient temperature, which would necessitate re-compression and re-cooling of the residue gas in an LNG liquefaction plant.
- Typical examples include various expander processes described in U.S. Pat. Nos.
- NGL processes are designed for either high C2 or C3 recovery, and generally not designed for varying levels of C2 recovery without lowering C3 recovery.
- standalone NGL recovery plants are used to produce a low pressure and ambient temperature residue gas that requires re-compression and re-cooling in the LNG liquefaction plant, thereby duplicating many of the refrigeration and heat exchange equipment in the NGL recovery plant.
- compositions and methods for NGL recovery are known in the art, all or almost all of them, suffer from one or more disadvantages. Therefore, there is still a need for improved NGL recovery, and especially where the NGL plant is integrated with or coupled to a LNG liquefaction unit.
- the present invention is directed to configurations and methods of NGL recovery, preferably coupled to an LNG liquefaction process, in which recovery of C2 components can be adjusted using flow ratios of selected process streams.
- the absorber in such configurations and methods is operated at significantly higher pressure than the distillation column to provide a cryogenic pressurized gas, while the absorber and distillation column temperatures are adjusted to such that desired quantities of C2 and C3+ products are recovered in the NGL.
- Cryogenic absorber overhead product is then compressed to a pressure suitable for liquefaction using energy derived from expansion of a vapor portion of the feed gas.
- a plant in one aspect of the inventive subject matter, includes an absorber configured to receive an absorber feed stream and a first and a second reflux stream, and that is further configured to provide a bottom product stream.
- a distillation column is configured to receive a first portion of the bottom product stream and a second portion of the bottom product stream at different points, wherein the distillation column is further configured to operate at a pressure that is lower than an operating pressure in the absorber.
- Contemplated plants will further include a control unit having one or more control valves that are configured to control flow ratios of (a) the feed stream to the second reflux stream and (b) the first portion of the bottom product stream to the second portion of the bottom product stream, wherein the flow ratios are a function of desired ethane recovery in the distillation column bottom product stream.
- a heat exchanger and/or a reflux condenser are configured to heat the first portion of the bottom product stream, and that an expansion device cools the second portion of the bottom product stream.
- the distillation column is configured to produce a distillation column overhead, and that the plant further comprises a compressor that compresses the distillation column overhead to at least absorber pressure. Where desired, the so compressed overhead is cooled and used as first reflux.
- the absorber produces an absorber overhead product that has a temperature of equal or lower than -90 0 F and a pressure of between 500 psig and 700 psig, which may be further compressed by a compressor to a pressure suitable for liquefaction of the absorber overhead product (e.g., at least 800 psig).
- the compressor is operationally coupled to an expander that expands the absorber feed stream.
- a method of processing a gas includes a step of providing an absorber that receives an absorber feed stream and a first and a second reflux stream, and that produces a bottom product stream.
- the absorber is fluidly coupled to a distillation column such that a first portion of the bottom product stream and a second portion of the bottom product stream are fed to the distillation column at different points, and in another step the distillation column is operated at a pressure that is lower than an operating pressure of the absorber, hi yet another step, flow ratios of (a) the feed stream to the second reflux stream and (b) the first portion of the bottom product stream to the second portion of the bottom product stream is controlled as a function of the desired ethane recovery in the distillation column bottom product stream.
- the distillation column overhead product is fed to the absorber, most preferably as compressed and cooled first reflux stream, hi further preferred methods, the distillation column is operated at a pressure between 300 psig and 500 psig, and the absorber is operated at a pressure of between 500 psig and 800 psig.
- a cooled feed gas is separated into a liquid portion and a vapor portion, and a portion of the liquid portion is after at least partially depressurized and heated and fed into the distillation column.
- the vapor portion in such methods is preferably split into a first and second stream to thereby form the second reflux stream and the absorber feed stream.
- the cryogenic absorber overhead stream is compressed to a pressure suitable for liquefaction using energy from the expansion of the absorber feed stream.
- a method of variably recovering C2 from a feed gas includes a step of feeding an expanded and heated liquid portion of a feed gas to a distillation column and feeding a vapor portion of the feed gas to an absorber.
- a flow ratio of an absorber feed to a second reflux to the absorber is controlled, and a first reflux that is provided by a distillation column overhead product is used to thereby control an absorber overhead temperature, and the degree of C2 recovery.
- the temperature of the absorber bottom product that is fed to the distillation column is adjusted to thereby control distillation column overhead temperature, controlling the desirable NGL recoveiy levels.
- the absorber is typically operated at a higher pressure than the distillation column.
- the step of adjusting the absorber bottom product is performed by heating at least one portion of the absorber bottom product in a heat exchanger, while the step of adjusting the absorber bottom product is performed by cooling at least another portion of the absorber bottom product using a JT valve, hi further preferred aspects, the step of adjusting the flow ratio of the absorber feed to the second reflux to the absorber is a function of desired C2 recovery.
- FIG. 1 is a schematic of an exemplary known plant.
- Figure 2 is a schematic of an exemplary plant configuration according to the inventive subject matter.
- Figure 3 is a graph depicting composite heat curves for heat exchanger 51 and 54 in a plant according to Figure 2 for C3 recovery.
- Figure 4 is a graph depicting composite heat curves for heat exchanger 51 and 54 in a plant according to Figure 2 for C2 recovery.
- Figure 5 is a graph comparing the relative volatilities of the NGL components at 600 psig between the prior art and a plant according to Figure 2 in C2 recovery.
- C2 and C3+ components can be effectively and economically separated from natural gas in a plant (which is preferably coupled to an LNG liquefaction plant) using an absorber that operates at high pressure and produces a cryogenic pressurized lean gas, while a distillation column located downstream of an absorber operates at low pressure and produces the NGL as a bottom product and a reflux stream for the absorber.
- recovery of C2 in the NGL can be adjusted by controlling process streams within the plant.
- the cryogenic absorber overhead product stream is already at relatively high pressure, and energy for recompression to a pressure suitable for liquefaction is typically provided by expansion of a vapor portion of the natural gas feed stream.
- a C2 NGL recovery plant has a single column operating at lower pressure typically 450 psig or lower, which necessitates substantial recompression for delivery of the natural gas to the liquefaction plant.
- contaminants- free and dried feed gas stream typically supplied at about 1200 psig, is cooled in exchanger 51 using column overhead vapor side reboiler stream 22 and external refrigerant 32. Liquid is removed from separator 52 and sent to the NGL column 58 that acts as a demethanizer.
- the flashed vapor from the separator 52 is split into two portions, one portion is cooled in the exchanger 54 to provide reflux to the column, while the other portion is expanded in turbo- expander 64, cooled and sent to the lower section for rectification.
- the above gas subcooled process produces a residue gas at ambient temperature and about 550 psig which must be recompressed using re-compressor 100 prior to the standalone LNG plant.
- re-compressor 100 prior to the standalone LNG plant.
- Such difficulties can be overcome in configurations according to the inventive subject matter in which a high pressure cryogenic vapor stream predominantly comprising methane is produced from a NGL recovery plant that advantageously reduces, or even eliminates the duplication of refrigeration and heat exchange steps and equipment in the LNG liquefaction plant.
- Such configurations and methods greatly reduce the refrigeration requirement in the LNG liquefaction plant, while advantageously allowing recovery of 99% propane and of up to 85% ethane from the feed gas.
- Contemplated NGL recovery plants will typically produce a lean gas predominantly comprising methane with a predetermined heating value (e.g., to meet the North America natural gas pipeline requirement).
- contemplated plants and configurations can be integrated with an LNG liquefaction plant, which will in turn increase the throughput of the LNG liquefaction train for the same energy input. Still further, it is noted that contemplated configurations can be changed from C3 recovery to C2 recovery by adjusting a flow ratio between the top reflux and the expansion flow while diverting at least a portion of the absorber bottoms product flow to a distillation column.
- the gas processing portion of an integrated plant comprises a refluxed absorber producing a bottom stream and receiving a feed gas and an absorber reflux stream that is produced from the overhead vapor from a distillation column (preferably after the overhead vapor is compressed and cooled).
- the distillation column is fluidly coupled to the absorber, receives a column feed stream and operates at a pressure that is at least 50 to 100 psi lower, and more preferably 100 psi to 300 psi lower than the operating pressure of the absorber.
- Seamless changeover of C3 recovery operation to C2 recovery operation (or vice versa) while maintaining 95% or higher C3 recovery for any level of C2 recovery is achieved by increasing the second reflux to the absorber while reducing the flow to the expander, with simultaneously diverting at least a portion of the absorber bottoms product flow to the distillation column.
- FIG. 2 One exemplary configuration for integrated NGL recovery with LNG liquefaction is depicted in Figure 2 in which two columns operate at a pressure differential of about 300 psi, and in which the absorber has an operating pressure about 600-700 psig. It should be pointed out that very high recovery of C2 plus components is possible in such plants and that the high pressure column operation is particularly beneficial in reducing the refrigeration duty in the LNG liquefaction plant. It should be further noted that such configurations and methods can be used for flexible C3 and C2 recovery. Exemplary compositions, temperatures, pressures, and flow rates of feed gas, product gas, and liquid product for typical operation are shown in the tables below. Table 1 is a table depicting the overall mass balance for C2 recovery when the plant is operated on C2 recovery mode, while Table 2 is a table depicting the overall mass balance for C3 recovery when the plant is operated on C3 recovery mode.
- feed gas stream 1 enters the plant at about 1200 psig and 120 °F, and is cooled in heat exchanger 51 to typically -10 °F to -40 °F, forming stream 2 using letdown absorber bottoms stream 15, liquid stream 5 from separator 52, side reboiler stream 22 from the distillation column, and external refrigeration stream 32.
- any type of refrigeration system is suitable, including pure component cascade refrigeration cycles, mixed refrigerant cycles, or a combination of both systems. Further refrigeration is provided to the system with expansion using the turbo-expander 64 and various Joule-Thomson (JT) valves.
- JT Joule-Thomson
- the chilled feed gas stream 2 is separated in separator 52, forming a gaseous portion 3 and a liquid portion 4.
- the liquid portion 4 is letdown in pressure via JT valve 53 forming stream 5 typically at about -40 °F.
- stream 5 is heated in exchanger 51 to about 80 °F forming stream 6, using the heat content in the feed gas stream 1.
- Stream 6 enters the stripping section of the distillation column 61 for removal of the C2 and lighter components.
- the gaseous portion 3 from separator 52 is split into two portions.
- stream 7 One portion (stream 7) is routed to the exchanger 54 to provide reflux 12 to the absorber via stream 9 and JT valve 55, while the other portion (stream 8) is expanded in turbo-expander 64 which generates power to operate compressor 65 to thereby form a chilled vapor stream 10, typically at -80 0 F to -100 °F or lower.
- the chilled vapor is letdown in pressure to the absorber 58, which operates at 500 psig to 700 psig, typically at 600 psig.
- the flow ratio i.e., ratio of stream 8 to stream 3
- Table 3 shows examples of different flow ratios and the results of C3 and C2 recovery. Most notably, high C3 recoveries (typically over 98%) are maintained for all C2 recovery levels.
- Absorber 58 is refluxed with two cold streams, with a first reflux stream 11 (top reflux) supplied by stream 27 from the distillation column 61, and a second reflux stream 12 from exchanger 54.
- first reflux stream 11 top reflux
- second reflux stream 12 from exchanger 54.
- twin reflux streams and suitable flow ratios high C3 recovery can be maintained for the various levels of ethane recovery.
- C3 recovery the C2 content in the NGL product from the distillation column is lowered by increasing the column bottom temperature using heat supplied from the side reboiler and the bottom reboiler 63.
- the absorber produces an overhead vapor stream 28 at about -100 °F to -110 0 F and a bottoms stream 14 at about -90 °F to -100 °F.
- the overhead vapor is compressed by residue gas compressor 65 using power generated by turbo-expander 64 forming a discharge stream 29, typically at about 900 psig and -70 0 F to -80°F.
- turbo-expander 64 forming a discharge stream 29, typically at about 900 psig and -70 0 F to -80°F.
- compression of a cold vapor is energy efficient as the achievable compression ratio across the compressor is significantly higher than that using a warm vapor of heretofore known plants.
- contemplated processes produce a high pressure and cryogenic temperature vapor that can be fed to the LNG liquefaction plant 67 for LNG production forming stream 30 at about - 255°F to -260 °F.
- the absorber bottoms stream 14 is letdown in pressure in JT valve 59 to about 460 psig, and is chilled to about -100 °F forming stream 15. During C3 recovery, this cold stream is used to provide a least a portion of the cooling duty of feed exchanger 51 and the reflux duty in condenser 62 to form streams 17 and 18, respectively.
- the overhead condenser 62 typically includes a heat exchange coil that is integral to the distillation column, generating internal reflux stream 19 to the rectification section of the distillation column.
- the integral condenser 62 system can also be replaced by an external system, which would include an external heat exchanger, a separator and a reflux pump (not shown).
- the NGL product composition is controlled with a side reboiler integral to exchanger 51, and a bottom reboiler 63 using an external heat source 34.
- the distillation column 61 produces an NGL bottoms products 25 (C2 plus and/or C3 plus) and an overhead vapor stream 24 that is compressed in compressor 66 to about 500 psig to 700 psig, or as needed to enter the absorber as a top reflux to form stream 26, further cooled in heat exchanger 54, and then used after pressure reduction in JT valve 56 as the first (top) reflux 11 to the absorber.
- Refrigerant stream 31 is supplied from an external refrigeration unit to the exchanger 54 for cooling and partially or totally condensing this recycle stream. Heated refrigerant stream 33 is later returned to the refrigeration unit.
- contemplated configurations take advantage of the relative volatilities of the NGL components (that is Cl to C2) in the columns using the pressure differential as compared to known configurations.
- both the present configurations and the known configurations are compared for a column operating at 600 psig pressure for C2 recovery.
- the relative volatilities of the NGL components of the known configurations are represented by curve A, which drops to a very low value of 2 in the mid section of the column.
- contemplated configurations and processes can achieve 95% or higher propane recovery when operating in a propane recovery mode, and can also achieve up to 50 to 85% ethane recovery when operating in an ethane recovery mode without substantial reduction (i.e., less than 5% absolute in reduction) in propane recovery.
- Contemplated configurations and processes can also provide a seamless and gradual changeover from a C3 recovery operation to a C2 recovery operation (or vice versa) by only adjusting flow ratios of streams to the absorber and the distillation column.
- high C2 and C3 recovery from a feed gas with relatively high pressure can be realized by operating an absorber in a gas processing plant at a higher pressure than a distillation column (e.g., a demethanizer or deethanizer), and in which a compressor is used to recycle the distillation column overhead to the absorber, hi such configurations, the absorber bottoms product is preferably expanded to provide cooling for the feed gas and the reflux stream.
- the overhead vapor from the absorber is then further compressed with power provided by the turboexpander, forming a feed gas to an LNG liquefaction plant without further recompression.
- feed gas pressures for plant configurations according to Figure 2 will generally be in the range between about 800 psig and about 1600 psig, and that at least a portion of the feed gas is expanded in a turboexpander to provide cooling and/or power for the residue gas recompression.
- the absorber is configured to separately receive a first and a second portion of a feed gas vapor and a distillation column overhead, wherein the first portion of the feed gas vapor and the distillation column overhead provide the reflux to the absorber.
- a flow control adjusts the ratio of at least one of the first and second portions of the feed gas vapor to produce the desired recovery levels of ethane.
- an optimum flow ratio of the first and - second flow of the feed gas is employed for the variable C2 recovery while maintaining a high C3 (95% or above) recovery.
- the flow control will include one or more manual and/or automatic valves, which are most preferably operated using microprocessor- based control equipment well known in the art.
- Such control units may operate entirely automatic without user intervention and may be configured to receive compositional information by sensors. Alternatively, or additionally, an operator may also provide compositional information based on a known or determined feed gas composition, and/or flow control may also be regulated at least in part by product volume flow in one or more products.
- the absorber preferably produces an overhead vapor product that is predominantly methane (e.g., at least 85%, more typically at least 90%, and most typically at least 93%) at cryogenic temperature (-80 0 F or lower), which is further compressed in a compressor using power generated by the turbo-expansion of the feed gas.
- cryogenic temperature e.g., at least 85%, more typically at least 90%, and most typically at least 93%)
- Such configuration produces a high pressure cryogenic vapor at 800 psig to 900 psig or higher that can advantageously be directly fed to the LNG liquefaction plant. It should be recognized that compressing a cryogenic vapor from the high pressure absorber is more energy efficient, and therefore allows operation of an LNG liquefaction plant with relatively low, and more typically no additional compression of the feed gas.
- At least a portion of the absorber bottoms product is used as a lean oil for C2 absorption in the distillation column during C2 recovery, hi such configurations, the flow to the feed cooler is reduced or stopped, thereby directing most or all of the absorber bottom product to the distillation column.
- C2 recovery in such configurations increases when the first portion of the feed gas vapor increases relative to the second portion of the feed gas vapor.
- preferred configurations permit a seamless changeover of the C3 recovery operation to the C2 recovery operation (or vise versa) while maintaining 95% or higher C3 recovery.
- the bottom product of the absorber is preferably expanded in a range of 50 psi to 350 psi, thereby chilled by Joule-Thomson effect to -90 °F to -130 °F. It is also contemplated that the cooled and expanded bottoms product stream is fed as the distillation column feed stream into the distillation column, and it is further contemplated that the expanded bottoms product stream may further provide cooling for the feed gas and reflux to the column, and at least of a portion of the expanded absorber bottoms product may also be routed directly to the distillation column for C2 absorption during the C2 recovery operation.
- the distillation column in preferred configurations typically comprises a demethanizer or deethanizer column and produces an overhead stream, which is compressed, cooled, and fed to the absorber as the first absorber reflux stream.
- the compressor can be located in various locations between the absorber and distillation column, and that this reflux stream can be fed to various locations in the absorber for C3 recovery and/or C2 recovery, hi yet further contemplated aspects, an external refrigeration unit is fluidly coupled to feed gas exchangers and reflux exchangers to supply feed gas chilling and column reflux duties.
- Such external refrigeration unit can be implemented using numerous configurations well known in the art using pure components or mixed refrigerants.
- a cascade refrigeration process may employ heat exchange of the natural gas with several pure component refrigerants having successively lower boiling points.
- a single mixed refrigerant with multiple pure components can be used by evaporating the refrigerant at several different pressure levels.
- natural gas cooling can be achieved by expansion of the natural gas using either Joule-Thomson expansion or expansion turbine.
- an external refrigeration unit can be employed to cool at least one of the first and second reflux streams, and may further cool at least one of the natural gas feed and a vapor portion of the natural gas feed.
- the first lean reflux stream from the feed gas may be fed into the absorber as a subcooled liquid (i. e. , a liquid cooled below its bubble point temperature), and that the distillation column is a demethanizer.
- a method of operating a plant includes a step of providing an absorber and a distillation column, wherein the absorber receives a plurality of absorber feed streams and provides a bottom product to the distillation column, and an overhead absorber vapor that is used as feed to the LNG liquefaction.
- At least one of the feed streams is split into a first and second portion, wherein the first and second portions are introduced into the absorber at different locations, and in still another step, the flow ratio between the first and second portions is used to control the degree of recovery of C2 components in the bottom product of the distillation column, hi yet a further step, the absorber bottoms product is used as a lean oil for absorption of the C2 component in the distillation column.
- contemplated configurations may also be used in a method of increasing throughput and/or energy consumption in an LNG liquefaction plant that is coupled to a natural gas recovery plant having an absorber and a distillation column.
- Such methods will typically include one step in which a first reflux stream is provided to the absorber, wherein the first reflux stream comprises an overhead product from the distillation column, hi another step, a bypass is provided upstream of a turbo expander, wherein the bypass receives a vapor portion of a cooled natural gas and provides the vapor portion to the absorber, and in yet another step, the pressure of the vapor portion is cooled, at least partially condensed and reduced in pressure before the vapor portion enters the absorber as a second reflux stream, hi a still further step, a heat exchanger cools at least one of the first and second reflux streams using an external refrigerant.
- a method of operating a plant may include one step in which an absorber and a distillation column are provided, hi a further step, a cooled lean overhead product from the distillation column is fed to the absorber as a first reflux stream, and in another step, the pressure of a cooled vapor portion of a natural gas feed is reduced via a device other than a turbo expander, wherein the cooled vapor portion that is at least partially condensed or subcooled, reduced in pressure and fed to the absorber as a second reflux stream.
Abstract
Description
Claims
Priority Applications (4)
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EA200800893A EA013357B1 (en) | 2005-04-20 | 2006-03-14 | Integrated ngl recovery and lng liquefaction |
CA2619021A CA2619021C (en) | 2005-04-20 | 2006-03-14 | Integrated ngl recovery and lng liquefaction |
US10/574,671 US20080271480A1 (en) | 2005-04-20 | 2006-03-14 | Intergrated Ngl Recovery and Lng Liquefaction |
AU2006240459A AU2006240459B2 (en) | 2005-04-20 | 2006-03-14 | Integrated NGL recovery and LNG liquefaction |
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US67351805P | 2005-04-20 | 2005-04-20 | |
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- 2006-03-14 WO PCT/US2006/009103 patent/WO2006115597A2/en active Application Filing
- 2006-03-14 CA CA2619021A patent/CA2619021C/en not_active Expired - Fee Related
- 2006-03-14 EA EA200800893A patent/EA013357B1/en not_active IP Right Cessation
- 2006-03-14 US US10/574,671 patent/US20080271480A1/en not_active Abandoned
- 2006-03-14 AU AU2006240459A patent/AU2006240459B2/en not_active Ceased
Patent Citations (3)
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US5685170A (en) * | 1995-11-03 | 1997-11-11 | Mcdermott Engineers & Constructors (Canada) Ltd. | Propane recovery process |
US6742358B2 (en) * | 2001-06-08 | 2004-06-01 | Elkcorp | Natural gas liquefaction |
US6564580B2 (en) * | 2001-06-29 | 2003-05-20 | Exxonmobil Upstream Research Company | Process for recovering ethane and heavier hydrocarbons from methane-rich pressurized liquid mixture |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2119758A1 (en) * | 2007-03-13 | 2009-11-18 | Mitsui Engineering and Shipbuilding Co, Ltd. | Method of producing gas hydrate |
EP2119758A4 (en) * | 2007-03-13 | 2011-08-31 | Mitsui Shipbuilding Eng | Method of producing gas hydrate |
AU2009216745B2 (en) * | 2008-02-20 | 2012-03-22 | Shell Internationale Research Maatschappij B.V. | Method and apparatus for cooling and separating a hydrocarbon stream |
US9151537B2 (en) | 2008-12-19 | 2015-10-06 | Kanfa Aragon As | Method and system for producing liquefied natural gas (LNG) |
FR3056223A1 (en) * | 2016-09-20 | 2018-03-23 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | PROCESS FOR PURIFYING NATURAL GAS TO BE LIQUEFIED |
WO2018055264A1 (en) * | 2016-09-20 | 2018-03-29 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for purifying natural gas to be liquefied |
Also Published As
Publication number | Publication date |
---|---|
WO2006115597A3 (en) | 2008-04-03 |
EA013357B1 (en) | 2010-04-30 |
CA2619021C (en) | 2010-11-23 |
US20080271480A1 (en) | 2008-11-06 |
CA2619021A1 (en) | 2007-11-02 |
EA200800893A1 (en) | 2009-02-27 |
AU2006240459B2 (en) | 2010-07-22 |
WO2006115597B1 (en) | 2008-05-15 |
AU2006240459A1 (en) | 2006-11-02 |
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