WO2011123253A1 - Hydrocarbon gas processing - Google Patents
Hydrocarbon gas processing Download PDFInfo
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- WO2011123253A1 WO2011123253A1 PCT/US2011/028872 US2011028872W WO2011123253A1 WO 2011123253 A1 WO2011123253 A1 WO 2011123253A1 US 2011028872 W US2011028872 W US 2011028872W WO 2011123253 A1 WO2011123253 A1 WO 2011123253A1
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- 238000012545 processing Methods 0.000 title claims abstract description 103
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 54
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 165
- 238000004821 distillation Methods 0.000 claims abstract description 107
- 238000012546 transfer Methods 0.000 claims abstract description 107
- 238000001816 cooling Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000005057 refrigeration Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 13
- 239000013589 supplement Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims 24
- 239000007789 gas Substances 0.000 description 57
- 238000011084 recovery Methods 0.000 description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 11
- 239000003345 natural gas Substances 0.000 description 10
- 239000001294 propane Substances 0.000 description 9
- 238000005194 fractionation Methods 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000153 supplemental effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000013844 butane Nutrition 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 naphtha Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QUJJSTFZCWUUQG-UHFFFAOYSA-N butane ethane methane propane Chemical class C.CC.CCC.CCCC QUJJSTFZCWUUQG-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
- C10G5/06—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas by cooling or compressing
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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
- 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
- F25J3/0242—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 3 carbon atoms or more
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1025—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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/02—Processes or apparatus using separation by rectification in a single 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
- F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
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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
- F25J2200/80—Processes or apparatus using separation by rectification using integrated mass and heat exchange, i.e. non-adiabatic rectification in a reflux exchanger or dephlegmator
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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
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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
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
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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
- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (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
- F25J2270/00—Refrigeration techniques used
- F25J2270/02—Internal refrigeration with liquid vaporising loop
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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
- F25J2270/12—External refrigeration with liquid vaporising loop
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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
- F25J2270/60—Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-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
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/40—Vertical layout or arrangement of cold equipments within in the cold box, e.g. columns, condensers, heat exchangers etc.
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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
- F25J2290/42—Modularity, pre-fabrication of modules, assembling and erection, horizontal layout, i.e. plot plan, and vertical arrangement of parts of the cryogenic unit, e.g. of the cold box
Definitions
- Ethylene, ethane, propylene, propane, and/or heavier hydrocarbons can be recovered from a variety of gases, such as natural gas, refinery gas, and synthetic gas streams obtained from other hydrocarbon materials such as coal, crude oil, naphtha, oil shale, tar sands, and lignite.
- Natural gas usually has a major proportion of methane and ethane, i.e., methane and ethane together comprise at least 50 mole percent of the gas.
- the gas also contains relatively lesser amounts of heavier hydrocarbons such as propane, butanes, pentanes, and the like, as well as hydrogen, nitrogen, carbon dioxide, and other gases.
- the present invention is generally concerned with the recovery of ethylene, ethane, propylene, propane, and heavier hydrocarbons from such gas streams.
- a typical analysis of a gas stream to be processed in accordance with this invention would be, in approximate mole percent, 90.0% methane, 4.0% ethane and other C 2 components, 1.7% propane and other C 3 components, 0.3% iso-butane, 0.5% normal butane, and 0.8% pentanes plus, with the balance made up of nitrogen and carbon dioxide. Sulfur containing gases are also sometimes present.
- Patent No. 33,408; and co-pending application nos. 11/430,412; 11/839,693; 11/971,491; 12/206,230; 12/689,616; 12/717,394; 12/750,862; 12/772,472; 12/781,259; 12/868,993; 12/869,007; 12/869,139; and 12/979,563 describe relevant processes (although the description of the present invention in some cases is based on different processing conditions than those described in the cited U.S. Patents).
- a feed gas stream under pressure is cooled by heat exchange with other streams of the process and/or external sources of refrigeration such as a propane compression-refrigeration system.
- liquids may be condensed and collected in one or more separators as high-pressure liquids containing some of the desired C 2 + components.
- the high-pressure liquids may be expanded to a lower pressure and fractionated. The vaporization occurring during expansion of the liquids results in further cooling of the stream. Under some conditions, pre-cooling the high pressure liquids prior to the expansion may be desirable in order to further lower the temperature resulting from the expansion.
- the expanded stream comprising a mixture of liquid and vapor, is fractionated in a distillation (demethanizer or deethanizer) column.
- the expansion cooled stream(s) is (are) distilled to separate residual methane, nitrogen, and other volatile gases as overhead vapor from the desired C 2 components, C 3 components, and heavier hydrocarbon components as bottom liquid product, or to separate residual methane, C 2 components, nitrogen, and other volatile gases as overhead vapor from the desired C 3 components and heavier hydrocarbon components as bottom liquid product.
- the vapor remaining from the partial condensation can be split into two streams.
- One portion of the vapor is passed through a work expansion machine or engine, or an expansion valve, to a lower pressure at which additional liquids are condensed as a result of further cooling of the stream.
- the pressure after expansion is essentially the same as the pressure at which the distillation column is operated.
- the combined vapor-liquid phases resulting from the expansion are supplied as feed to the column.
- the remaining portion of the vapor is cooled to substantial condensation by heat exchange with other process streams, e.g., the cold fractionation tower overhead.
- Some or all of the high-pressure liquid may be combined with this vapor portion prior to cooling.
- the resulting cooled stream is then expanded through an appropriate expansion device, such as an expansion valve, to the pressure at which the demethanizer is operated. During expansion, a portion of the liquid will vaporize, resulting in cooling of the total stream.
- the flash expanded stream is then supplied as top feed to the demethanizer.
- the vapor portion of the flash expanded stream and the demethanizer overhead vapor combine in an upper separator section in the fractionation tower as residual methane product gas.
- the cooled and expanded stream may be supplied to a separator to provide vapor and liquid streams.
- the vapor is combined with the tower overhead and the liquid is supplied to the column as a top column feed.
- the present invention employs a novel means of performing the various steps described above more efficiently and using fewer pieces of equipment. This is accomplished by combining what heretofore have been individual equipment items into a common housing, thereby reducing the plot space required for the processing plant and reducing the capital cost of the facility. Surprisingly, applicants have found that the more compact arrangement also significantly reduces the power consumption required to achieve a given recovery level, thereby increasing the process efficiency and reducing the operating cost of the facility. In addition, the more compact arrangement also eliminates much of the piping used to interconnect the individual equipment items in traditional plant designs, further reducing capital cost and also eliminating the associated flanged piping connections.
- piping flanges are a potential leak source for hydrocarbons (which are volatile organic compounds, VOCs, that contribute to greenhouse gases and may also be precursors to atmospheric ozone formation), eliminating these flanges reduces the potential for atmospheric emissions that can damage the environment.
- the present invention although applicable at lower pressures and warmer temperatures, is particularly advantageous when processing feed gases in the range of 400 to 1500 psia [2,758 to 10,342 kPa(a)] or higher under conditions requiring NGL recovery column overhead temperatures of -50°F [-46°C] or colder.
- FIG. 1 is a flow diagram of a prior art natural gas processing plant in accordance with United States Patent No. 4,157,904;
- FIG. 2 is a flow diagram of a natural gas processing plant in accordance with the present invention.
- FIGS. 3 through 17 are flow diagrams illustrating alternative means of application of the present invention to a natural gas stream.
- the molar flow rates given in the tables may be interpreted as either pound moles per hour or kilogram moles per hour.
- the energy consumptions reported as horsepower (HP) and/or thousand British Thermal Units per hour (MBTU/Hr) correspond to the stated molar flow rates in pound moles per hour.
- the energy consumptions reported as kilowatts (kW) correspond to the stated molar flow rates in kilogram moles per hour.
- FIG. 1 is a process flow diagram showing the design of a processing plant to recover C 2 + components from natural gas using prior art according to U.S. Pat. No.
- inlet gas enters the plant at 101°F [39°C] and 915 psia [6,307 kPa(a)] as stream 31. If the inlet gas contains a concentration of sulfur compounds which would prevent the product streams from meeting specifications, the sulfur compounds are removed by appropriate pretreatment of the feed gas (not illustrated). In addition, the feed stream is usually dehydrated to prevent hydrate (ice) formation under cryogenic conditions. Solid desiccant has typically been used for this purpose. [0017] The feed stream 31 is divided into two portions, streams 32 and 33.
- Stream 32 is cooled to -31°F [-35°C] in heat exchanger 10 by heat exchange with cool residue gas (stream 41a), while stream 33 is cooled to -37°F [-38°C] in heat exchanger 11 by heat exchange with demethanizer reboiler liquids at 43°F [6°C] (stream 43) and side reboiler liquids at -47 °F [-44°C] (stream 42).
- Streams 32a and 33a recombine to form stream 31a, which enters separator 12 at -33°F [-36°C] and 893 psia [6,155 kPa(a)] where the vapor (stream 34) is separated from the condensed liquid (stream 35).
- Stream 36 containing about 32% of the total vapor, is combined with the separator liquid (stream 35), and the combined stream 38 passes through heat exchanger 13 in heat exchange relation with the cold residue gas (stream 41) where it is cooled to substantial condensation.
- the resulting substantially condensed stream 38a at -131°F [-90°C] is then flash expanded through expansion valve 14 to the operating pressure (approximately 410 psia [2,827 kPa(a)]) of fractionation tower 18. During expansion a portion of the stream is vaporized, resulting in cooling of the total stream.
- the operating pressure approximately 410 psia [2,827 kPa(a)
- the expanded stream 38b leaving expansion valve 14 reaches a temperature of -137°F [-94°C] and is supplied to separator section 18a in the upper region of fractionation tower 18.
- the liquids separated therein become the top feed to demethanizing section 18b.
- the remaining 68% of the vapor from separator 12 enters a work expansion machine 15 in which mechanical energy is extracted from this portion of the high pressure feed.
- the machine 15 expands the vapor substantially isentropically to the tower operating pressure, with the work expansion cooling the expanded stream 39a to a temperature of approximately -97°F [-72°C].
- the typical commercially available expanders are capable of recovering on the order of 80-85% of the work theoretically available in an ideal isentropic expansion.
- the work recovered is often used to drive a centrifugal compressor (such as item 16) that can be used to re-compress the residue gas (stream 41b), for example.
- the partially condensed expanded stream 39a is thereafter supplied as feed to fractionation tower 18 at a mid-column feed point.
- the demethanizer in tower 18 is a conventional distillation column containing a plurality of vertically spaced trays, one or more packed beds, or some combination of trays and packing.
- the fractionation tower may consist of two sections.
- the upper section 18a is a separator wherein the partially vaporized top feed is divided into its respective vapor and liquid portions, and wherein the vapor rising from the lower distillation or demethanizing section 18b is combined with the vapor portion of the top feed to form the cold demethanizer overhead vapor (stream 41) which exits the top of the tower at -136°F [-93°C].
- the lower, demethanizing section 18b contains the trays and/or packing and provides the necessary contact between the liquids falling downward and the vapors rising upward.
- the demethanizing section 18b also includes reboilers (such as the reboiler and the side reboiler described previously) which heat and vaporize a portion of the liquids flowing down the column to provide the stripping vapors which flow up the column to strip the liquid product, stream 44, of methane and lighter components.
- the liquid product stream 44 exits the bottom of the tower at 65°F [19°C], based on a typical specification of a methane to ethane ratio of 0.010: 1 on a mass basis in the bottom product.
- the residue gas (demethanizer overhead vapor stream 41) passes countercurrently to the incoming feed gas in heat exchanger 13 where it is heated to -44°F [-42°C] (stream 41a) and in heat exchanger 10 where it is heated to 96°F [36°C] (stream
- the residue gas is then re-compressed in two stages.
- the first stage is compressor 16 driven by expansion machine 15.
- the second stage is compressor 20 driven by a
- FIG. 2 illustrates a flow diagram of a process in accordance with the present invention.
- the feed gas composition and conditions considered in the process presented in FIG. 2 are the same as those in FIG. 1. Accordingly, the FIG. 2 process can be compared with that of the FIG. 1 process to illustrate the advantages of the present invention.
- inlet gas enters the plant as stream 31 and is divided into two portions, streams 32 and 33.
- the first portion, stream 32 enters a heat exchange means in the upper region of feed cooling section 118a inside processing assembly 118.
- This heat exchange means may be comprised of a fin and tube type heat exchanger, a plate type heat exchanger, a brazed aluminum type heat exchanger, or other type of heat transfer device, including multi-pass and/or multi-service heat exchangers.
- the heat exchange means is configured to provide heat exchange between stream 32 flowing through one pass of the heat exchange means and a distillation vapor stream arising from separator section 118b inside processing assembly 118 that has been heated in a heat exchange means in the lower region of feed cooling section 118a.
- Stream 32 is cooled while further heating the distillation vapor stream, with stream 32a leaving the heat exchange means at -26°F
- the second portion, stream 33 enters a heat and mass transfer means in demethanizing section 118d inside processing assembly 118.
- This heat and mass transfer means may also be comprised of a fin and tube type heat exchanger, a plate type heat exchanger, a brazed aluminum type heat exchanger, or other type of heat transfer device, including multi-pass and/or multi- service heat exchangers.
- the heat and mass transfer means is configured to provide heat exchange between stream 33 flowing through one pass of the heat and mass transfer means and a distillation liquid stream flowing downward from absorbing section 118c inside processing assembly 118, so that stream 33 is cooled while heating the distillation liquid stream, cooling stream 33a to -38°F [-39°C] before it leaves the heat and mass transfer means.
- the heat and mass transfer means provides continuous contact between the stripping vapors and the distillation liquid stream so that it also functions to provide mass transfer between the vapor and liquid phases, stripping the liquid product stream 44 of methane and lighter components.
- Streams 32a and 33a recombine to form stream 31a, which enters separator section 118e inside processing assembly 118 at -30°F [-34°C] and 898 psia [6,189 kPa(a)], whereupon the vapor (stream 34) is separated from the condensed liquid (stream 35).
- Separator section 118e has an internal head or other means to divide it from demethanizing section 118d, so that the two sections inside processing assembly 118 can operate at different pressures.
- Stream 36 containing about 32% of the total vapor, is combined with the separated liquid (stream 35, via stream 37), and the combined stream 38 enters a heat exchange means in the lower region of feed cooling section 118a inside processing assembly 118.
- This heat exchange means may likewise be comprised of a fin and tube type heat exchanger, a plate type heat exchanger, a brazed aluminum type heat exchanger, or other type of heat transfer device, including multi-pass and/or multi-service heat exchangers.
- the heat exchange means is configured to provide heat exchange between stream 38 flowing through one pass of the heat exchange means and the distillation vapor stream arising from separator section 118b, so that stream 38 is cooled to substantial condensation while heating the distillation vapor stream.
- the resulting substantially condensed stream 38a at -130°F [-90°C] is then flash expanded through expansion valve 14 to the operating pressure (approximately 415 psia [2,861 kPa(a)]) of absorbing section 118c (an absorbing means) inside processing assembly 118. During expansion a portion of the stream is vaporized, resulting in cooling of the total stream.
- the expanded stream 38b leaving expansion valve 14 reaches a temperature of -136°F [-94°C] and is supplied to separator section 118b inside processing assembly 118.
- the liquids separated therein are directed to absorbing section 118c, while the remaining vapors combine with the vapors rising from absorbing section 118c to form the distillation vapor stream that is heated in cooling section 118a.
- the trays and/or packing in absorbing section 118c provide the necessary contact between the vapors rising upward and cold liquid falling downward.
- the liquid portion of the expanded stream 39a commingles with liquids falling downward from absorbing section 118c and the combined liquid continues downward into demethanizing section 118d.
- the stripping vapors arising from demethanizing section 118d combine with the vapor portion of the expanded stream 39a and rise upward through absorbing section 118c, to be contacted with the cold liquid falling downward to condense and absorb the C 2 components, C 3 components, and heavier components from these vapors.
- the volatile components are stripped out of the liquid continuously, reducing the concentration of the volatile components in the stripping vapors more quickly and thereby improving the stripping efficiency for the present invention.
- the present invention offers two other advantages over the prior art in addition to the increase in processing efficiency.
- Second, elimination of the interconnecting piping means that a processing plant utilizing the present invention has far fewer flanged connections compared to the prior art, reducing the number of potential leak sources in the plant.
- Hydrocarbons are volatile organic compounds (VOCs), some of which are classified as greenhouse gases and some of which may be precursors to atmospheric ozone formation, which means the present invention reduces the potential for atmospheric releases that can damage the environment.
- VOCs volatile organic compounds
- exchanger 10 is representative of either a multitude of individual heat exchangers or a single multi-pass heat exchanger, or any combination thereof.
- Each such heat exchanger may be comprised of a fin and tube type heat exchanger, a plate type heat exchanger, a brazed aluminum type heat exchanger, or other type of heat transfer device, including multi-pass and/or multi-service heat exchangers.
- Some circumstances may favor supplying liquid stream 35 directly to the lower region of absorbing section 118c via stream 40 as shown in FIGS. 2, 4, 6, 8, 10, 12, 14, and 16.
- an appropriate expansion device such as expansion valve 17
- expansion valve 17 is used to expand the liquid to the operating pressure of absorbing section 118c and the resulting expanded liquid stream 40a is supplied as feed to the lower region of absorbing section 118c (as shown by the dashed lines).
- Some circumstances may favor combining a portion of liquid stream 35 (stream 37) with the vapor in stream 36 (FIGS. 2, 6, 10, and 14) or with cooled second portion 33a (FIGS.
- the heat and mass transfer means in demethanizing section 118d may be configured in upper and lower parts so that expanded liquid stream 40a can be introduced between the two parts. As shown by the dashed lines, some circumstances may favor combining a portion of liquid stream 35 (stream 37) with the vapor in stream 36 (FIGS. 3, 7, 11, and 15) or with cooled second portion 33a (FIGS. 5, 9, 13, and 17) to form combined stream 38, while the remaining portion of liquid stream 35 (stream 40) is expanded to lower pressure and supplied between the upper and lower parts of the heat and mass transfer means in demethanizing section 118d as stream 40a.
- the cooled second portion 33a is combined with the separated liquid (stream 35, via stream 37), and the combined stream 38 is directed to the heat exchange means in the lower region of feed cooling section 118a inside processing assembly 118 and cooled to substantial condensation.
- the substantially condensed stream 38a is flash expanded through expansion valve 14 to the operating pressure of absorbing section 118c, whereupon expanded stream 38b is supplied to separator section 118b inside processing assembly 118.
- separator 12 can be used to separate cooled feed stream 31a into vapor stream 34 and liquid stream 35.
- separator 12 can be used to separate cooled first portion 32a into vapor stream 34 and liquid stream 35.
- the cooled feed stream 31a entering separator section 118e in FIGS. 2, 3, 10, and 11 or separator 12 in FIGS. 6, 7, 14, and 15 may not contain any liquid (because it is above its dewpoint, or because it is above its cricondenbar). In such cases, there is no liquid in streams 35 and 37 (as shown by the dashed lines), so only the vapor from separator section 118e in stream 36 (FIGS. 2, 3, 10, and 11), the vapor from separator 12 in stream 36 (FIGS.
- the use of external refrigeration to supplement the cooling available to the inlet gas from the distillation vapor and liquid streams may be employed, particularly in the case of a rich inlet gas.
- a heat and mass transfer means may be included in separator section 118e (or a gas collecting means in such cases when the cooled feed stream 31a or the cooled first portion 32a contains no liquid) as shown by the dashed lines in FIGS. 2 through 5 and 10 through 13, or a heat and mass transfer means may be included in separator 12 as shown by the dashed lines in FIGS. 6 though 9 and 14 through 17.
- This heat and mass transfer means may be comprised of a fin and tube type heat exchanger, a plate type heat exchanger, a brazed aluminum type heat exchanger, or other type of heat transfer device, including multi-pass and/or multi- service heat exchangers.
- the heat and mass transfer means is configured to provide heat exchange between a refrigerant stream (e.g., propane) flowing through one pass of the heat and mass transfer means and the vapor portion of stream 31a (FIGS. 2, 3, 6, 7, 10, 11, 14, and 15) or stream 32a (FIGS. 4, 5, 8, 9, 12, 13, 16, and 17) flowing upward, so that the refrigerant further cools the vapor and condenses additional liquid, which falls downward to become part of the liquid removed in stream 35.
- a refrigerant stream e.g., propane
- conventional gas chiller(s) could be used to cool stream 32a, stream 33a, and/or stream 31a with refrigerant before stream 31a enters separator section 118e (FIGS. 2, 3, 10, and 11) or separator 12 (FIGS. 6, 7, 14, and 15) or stream 32a enters separator section 118e (FIGS. 4, 5, 12, and 13) or separator 12 (FIGS. 8, 9, 16, and 17).
- the heat and mass transfer means in demethanizing section 118d may include provisions for providing supplemental heating with heating medium as shown by the dashed lines in FIGS. 2 through 17.
- another heat and mass transfer means can be included in the lower region of demethanizing section 118d for providing supplemental heating, or stream 33 can be heated with heating medium before it is supplied to the heat and mass transfer means in demethanizing section 118d.
- the multi-pass and/or multi-service heat transfer device will include appropriate means for distributing, segregating, and collecting stream 32, stream 38, and the distillation vapor stream in order to accomplish the desired cooling and heating.
- a mass transfer means can be located below where expanded stream 39a (FIGS. 2, 3, 6, 7, 10, 11, 14, and 15) or expanded stream 34a (FIGS. 4, 5, 8, 9, 12, 13, 16, and 17) enters the lower region of absorbing section 118c and above where cooled second portion 33a leaves the heat and mass transfer means in demethanizing section 118d.
- FIGS. 2, 3, 6, 7, 10, 11, 14, and 15 A less preferred option for the FIGS. 2, 3, 6, 7, 10, 11, 14, and 15
- embodiments of the present invention is providing a separator vessel for cooled first portion 32a, a separator vessel for cooled second portion 33a, combining the vapor streams separated therein to form vapor stream 34, and combining the liquid streams separated therein to form liquid stream 35.
- Another less preferred option for the present invention is cooling stream 37 in a separate heat exchange means inside feed cooling section 118a (rather than combining stream 37 with stream 36 or stream 33a to form combined stream 38), expanding the cooled stream in a separate expansion device, and supplying the expanded stream to an intermediate region in absorbing section 118c.
- each branch of the split vapor feed will depend on several factors, including gas pressure, feed gas composition, the amount of heat which can economically be extracted from the feed, and the quantity of horsepower available. More feed above absorbing section 118c may increase recovery while decreasing power recovered from the expander and thereby increasing the recompression horsepower requirements. Increasing feed below absorbing section 118c reduces the horsepower consumption but may also reduce product recovery.
- the present invention provides improved recovery of C 2 components, C 3 components, and heavier hydrocarbon components or of C 3 components and heavier hydrocarbon components per amount of utility consumption required to operate the process.
- An improvement in utility consumption required for operating the process may appear in the form of reduced power requirements for compression or re-compression, reduced power requirements for external refrigeration, reduced energy requirements for supplemental heating, or a combination thereof.
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Abstract
Description
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US6361582B1 (en) * | 2000-05-19 | 2002-03-26 | Membrane Technology And Research, Inc. | Gas separation using C3+ hydrocarbon-resistant membranes |
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CA2764737C (en) | 2016-10-11 |
EA023977B1 (en) | 2016-08-31 |
BRPI1105257A2 (en) | 2016-05-03 |
WO2011123253A8 (en) | 2012-03-08 |
CA2764737A1 (en) | 2011-10-06 |
CO6480967A2 (en) | 2012-07-16 |
JP5798180B2 (en) | 2015-10-21 |
AU2011233648A8 (en) | 2012-06-14 |
TN2012000333A1 (en) | 2013-12-12 |
CN102510987A (en) | 2012-06-20 |
BRPI1105257B1 (en) | 2021-01-26 |
AU2011233648A1 (en) | 2012-02-02 |
CN102510987B (en) | 2015-05-13 |
AU2011233648A2 (en) | 2012-03-01 |
EA201200008A1 (en) | 2013-03-29 |
JP2013527414A (en) | 2013-06-27 |
AU2011233648B2 (en) | 2016-01-07 |
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