WO2020198588A2 - Perfectionnements apportés à la récupération de c3+ avec des membranes - Google Patents

Perfectionnements apportés à la récupération de c3+ avec des membranes Download PDF

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Publication number
WO2020198588A2
WO2020198588A2 PCT/US2020/025219 US2020025219W WO2020198588A2 WO 2020198588 A2 WO2020198588 A2 WO 2020198588A2 US 2020025219 W US2020025219 W US 2020025219W WO 2020198588 A2 WO2020198588 A2 WO 2020198588A2
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stream
carbon atoms
hydrocarbons containing
producing
separating
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PCT/US2020/025219
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WO2020198588A3 (fr
Inventor
Vincent Follaca
Paul Terrien
Pascal Marty
Martin Raventos
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L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
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Publication of WO2020198588A2 publication Critical patent/WO2020198588A2/fr
Publication of WO2020198588A3 publication Critical patent/WO2020198588A3/fr

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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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
    • 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
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • 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
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • 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
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/28—Propane and butane
    • 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
    • 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
    • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
    • 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
    • F25J2205/80—Processes or apparatus using other separation and/or other processing means using membrane, i.e. including a permeation step
    • 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
    • F25J2210/12—Refinery or petrochemical off-gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/62—Ethane or ethylene
    • 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
    • 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

Definitions

  • NGLs C3+ components
  • Most traditional plants remove NGLs via cryogenic plants but those technologies usually are very expensive and consume a lot of power required by external refrigeration cycles.
  • a less costly technology that can be used to concentrate NGLs is membrane technology.
  • Feed gas stream 101 is compressed in feed compressor 102, then introduced into first phase separator 103.
  • the compressed feed gas stream may be cooled in a heat exchanger (not shown) prior to admission into first phase separator 103.
  • First phase separator 103 produces first condensate stream 104 and damp gas stream 105. Damp gas stream 105 is then introduced into first dehydration unit 106.
  • the dehydrated gas stream is cooled in heat exchanger 107, wherein it forms at least partially condensed stream 108. At least partially condensed stream is then introduced into second phase separator 109. Second phase separator 109 produces C3+ rich liquid stream 110 and C3+ lean gas stream 111. C3+ rich liquid stream 110 is then warmed in heat exchanger 107, producing warmed C3+ rich liquid stream 123. Warmed C3+ rich liquid stream 123 is then introduced into separator drum 112.
  • Separator drum 112 may be a flash drum or a distillation column.
  • Separator drum 112 produces overhead gas stream 113 which is enriched in methane, and C3+ liquid product stream 114.
  • C3+ lean gas stream 111 then enters membrane separator 115, thereby producing permeate stream 116 and retentate stream 117.
  • Permeate stream 116 may be combined with feed gas stream 101 (not shown).
  • Retentate stream 117 then combined with overhead gas stream 113, thus producing first combined stream 118.
  • First combined stream 118 is heated in heat exchanger 107 then dried in second dehydration unit 119. Dried retentate stream is then introduced into third phase separator 120.
  • Third phase separator 120 produces second condensate stream 121 and fuel gas stream 122.
  • a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream includes separating a light ends stream from a fractionator, thereby producing a stream rich in hydrocarbons containing three or more carbon atoms, and a stream lean in hydrocarbons containing three or more carbon atoms, separating the stream lean in hydrocarbons containing three or more carbon atoms in a membrane unit, thereby producing a permeate stream enriched in hydrocarbons containing three or more carbon atoms and a retentate stream, and separating the stream rich in hydrocarbons containing three or more carbon atoms in one or more separation columns, thereby producing one or more streams selected from the group consisting of a propylene stream, a propane stream, a butane stream, a light cat naptha stream, and a heavy cat naptha stream.
  • a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream including combining a light ends stream from a fractionator including hydrocarbons containing three or more carbon atoms and a permeate stream to form a combined stream, separating the combined stream in main absorption unit, thereby producing a stream rich in hydrocarbons containing three or more carbon atoms, and a stream lean in hydrocarbons containing three or more carbon atoms, separating an at least partially condensed stream lean in hydrocarbons containing three or more carbon atoms in a cold separator, thereby producing a liquid stream, and a vapor stream, warming the vapor stream to ambient temperature, then separating the ambient temperature stream in a membrane unit, thereby producing the permeate stream and a retentate stream, and separating the stream rich in hydrocarbons containing three or more carbon atoms in one or more separation columns, thereby producing one or more streams selected from the group consisting of a propylene stream, a propane stream,
  • Figure 1 is a schematic representation of a method for separating light ends from heavier hydrocarbon streams as known to the prior art.
  • FIG. 2 is a schematic representation of a typical fluidic catalytic cracking (FCC) plant as known to the prior art.
  • FCC fluidic catalytic cracking
  • Figure 3 is a schematic representation illustrating the details of a series of separating columns in accordance with one embodiment of the present invention.
  • FIG. 4 is a schematic representation illustrating the details of a membrane separation system in accordance with one embodiment of the present invention.
  • Figure 5 is a schematic representation of a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream including a secondary absorber and a membrane system, in accordance with one embodiment of the present invention.
  • Figure 6 is a schematic representation of a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream in which a secondary absorber is replaced by a membrane system, in accordance with one embodiment of the present invention.
  • Figure 7 is a schematic representation of a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream which includes a carbon dioxide removal system, in accordance with one embodiment of the present invention.
  • Figure 8 is a schematic representation of a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream which includes introducing a C3+ enriched permeate stream into the separation columns, in accordance with one embodiment of the present invention.
  • Figure 9 is a schematic representation of a method of separating hydrocarbons containing three or more carbon atoms from an off-gas stream including an ambient temperature membrane system, in accordance with one embodiment of the present invention.
  • MCO medium cycle oil
  • main absorber output stream 212 main absorber off-gas stream
  • phase separator liquid stream 904 phase separator vapor stream
  • ambient temperature is defined as the temperature of the surrounding air. Ambient temperature may be defined as between 32 and 150 F. Ambient temperature may be defined as between 32 and 100 F. Ambient temperature may be defined as between 50 and 80 F. Ambient temperature may be defined as between 65 and 75 F.
  • Fluid Catalytic Cracking is a common technology that has been used for many years inside refineries. They are typically used for cracking crude oil into different fractions.
  • Feed gas stream 201 is introduced into FCC reactor unit 202.
  • the output stream from FCC reactor unit 202 is then introduced into fractionator 203, which produces one or more of the following streams: light ends stream 204, light cycle oil stream 205, medium cycle oil stream 206, heavy cycle oil stream 207 and slurry stream 208.
  • Light ends stream 204 may pass through a knock-out drum (not shown), and then is compressed in fractionator overhead stream compressor 209 and sent to main absorber 410.
  • Main absorber 210 produces output stream 211 and off-gas stream 212.
  • Offgas stream 212 and a lean oil stream 213 from the fractionator are introduced into secondary absorber 214.
  • Secondary absorber 214 may be a sponge absorber.
  • Secondary absorber 214 produces a rich oil stream 216 that is returned to fractionator 203, and off-gas stream 215.
  • Output stream 211 is then introduced into separation column 217.
  • separation column 217 is shown on Figures 2 and 5-9 as a single unit. However as shown in Figure 3, separation column 217 may be series of columns.
  • the feed stream in this case main absorber off-gas stream 211, is introduced into debutanizer column 218.
  • Debutanizer column 218 sends a bottom stream to gasoline splitting column 219 and a top stream to depropanizer column 220.
  • Gasoline splitting column 219 produces light cat naptha stream 225 and high cat naptha stream 226.
  • Depropanizer column 220 sends a top stream to propane splitting column 221 and produces butane stream 224.
  • Propane splitting column 221 produces propylene stream 222 and propane stream 223.
  • Downstream of FCC unit 202 is typically the main fractionator 203, which recovers the different fractions of oil (light and heavy, gasoline and gas).
  • the gas portion 204 is mainly composed with the light components and is treated in the gas plant for separation in different sub-components.
  • Polypropylene 222 is one of the lightest components typically recovered from an FCC refinery in the gas plant.
  • the gas plant typically also recovers propane 223, butane 224, light cycle naphtha 225, or high cycle naphtha 226, each of these streams being additionally processed or further purified into sub-components.
  • Propylene recovery ratios are therefore typically in the range of 90- 96%.
  • Propylene is recovered in the gas plant in successive debutanizer, depropanizer and C3 splitter. The propylene recovery ratio can be improved to its higher limit using a larger amount of refrigeration energy in the system, which may be produced, for example, by a propane refrigeration cycle.
  • the unrecovered propylene is present in the secondary absorber off-gas 214.
  • secondary absorber 214 because the absorption is achieved through lean oil, the highest fractions are the most recovered but the propylene recovery is not optimized.
  • a typical composition of the inlet and the off-gas of the secondary absorber off-gas is shown in Table 1 , along with the recovery achieved in the secondary absorber.
  • the secondary absorber off-gas is typically sent to a fuel gas system (or flared).
  • the proposed improvement is using membrane technology, and integration of such membrane technology into the FCC separation system, and in particular membranes selective for C3+ (or C2+) over C2- (or C1 -), to improve the overall recovery of propylene beyond state-of-the art FCC.
  • the membrane technology that is used may be the“rubbery-type”.
  • a membrane system is used to treat the off-gas of the secondary adsorber ( Figure 5) and in another embodiment a membrane system directly replaces the secondary absorber ( Figure 6).
  • the concept is similar for both, with a slightly different stream to manage. The stream at the inlet of the secondary absorber still contains some C6+ while the off-gas doesn’t.
  • membrane separator 502 is shown on Figures 5-8 as a single unit.
  • membrane separator 501 may comprise, at least, a filter 402 and a heat exchanger 408.
  • Membrane 501 may further comprise a phase separator 405 as described below.
  • the feed gas 401 to be treated is first sent to filter 402, which produces particulate stream 403 and phase separator inlet stream 404.
  • Feed gas stream 401 may be the off-gas stream 215 from secondary absorber 214, or it may be the off-gas stream 212 from the main absorber 210.
  • Stream 404 is then introduced into separation drum 405, which separates the liquid phase 406 from the gaseous phase 407. A first portion of the C3+ fraction is recovered in this drum which can be sent back to the fractionator or to the inlet of any system that would ensure its separation into all the sub-components (not shown).
  • Membrane permeate 503 will be a C3+ enriched stream that can be re-injected back to the fractionator or to the inlet of any system that would ensure its separation into all the sub-components (not shown). Membrane retentate 502 is also produced.
  • Such a membrane system can achieve a recovery of up to 70% in propylene. If we assume a typical propylene recovery of 94% in the gas plant, 70% propylene recovery in the membrane system applied to the absorber off-gas will boost the overall refinery propylene recovery to 98.2%. This is not only a significant revenue gain but also it exceeds the typical 96% recovery achievable in a gas plant when adding propane refrigeration.
  • feed gas stream 201 is introduced into FCC unit 202.
  • the output stream from FCC unit 202 is then introduced into fractionator 203, which produces light ends stream 204, light cycle oil stream 205, medium cycle oil stream 206, heavy cycle oil stream 207 and slurry stream 208.
  • Light ends stream 204 is compressed in fractionator overhead stream compressor 209 and sent to main absorber 210.
  • Main absorber 210 produces output stream 211 and off-gas stream 212.
  • Offgas stream 212 and a lean oil stream 213 from the fractionator are introduced into secondary absorber 214.
  • Secondary absorber 214 produces a rich oil stream 216 that is returned to fractionator 203, and off-gas stream 215.
  • Off-gas stream 215 is then introduced into membrane separator 501 , which produces retentate off-gas stream 502 and C3+ enriched permeate stream 503. C3+ enriched permeate stream 503 is then recycled back to fractionator 203.
  • Output stream 211 is then introduced into separation column 217, which produces, at least propylene stream 222, propane stream 223, butane stream 224, light cat naptha stream 225, and high cat naptha stream 226.
  • This embodiment allows the utilization of membranes on FCC secondary absorber off-gas to improve the overall C3+ recovery of the plant without use of external refrigeration.
  • feed gas stream 201 is introduced into FCC unit 202.
  • the output stream from FCC unit 202 is then introduced into fractionator 203, which produces light ends stream 204, light cycle oil stream 205, medium cycle oil stream 206, heavy cycle oil stream 207 and slurry stream 208.
  • Light ends stream 204 is compressed in fractionator overhead stream compressor 209 and sent to main absorber 210.
  • Main absorber 210 produces output stream 211 and off-gas stream 212. Offgas stream 212 is then introduced into membrane separator 501 , which produces retentate off-gas stream 502 and C3+ enriched permeate stream 503. C3+ enriched permeate stream 503 is then recycled back to fractionator 203.
  • Output stream 211 is then introduced into separation column 217, which produces, at least propylene stream 222, propane stream 223, butane stream 224, light cat naptha stream 225, and high cat naptha stream 226.
  • This embodiment also allows the replacement of the full secondary absorber by a membrane unit which improves the overall recovery beyond the state-of-the art values, while reducing the complexity and cost of the gas plant.
  • feed gas stream 201 is introduced into FCC unit 202.
  • the output stream from FCC unit 202 is then introduced into fractionator 203, which produces light ends stream 204, light cycle oil stream 205, medium cycle oil stream 206, heavy cycle oil stream 207 and slurry stream 208.
  • Light ends stream 204 is compressed in fractionator overhead stream compressor 209 and sent to main absorber 210.
  • Main absorber 210 produces output stream 211 and off-gas stream 212.
  • Offgas stream 212 is then introduced into carbon dioxide removal unit 701 , which carbon dioxide rich stream 702 and carbon dioxide poor stream 703.
  • Carbon dioxide poor stream 703 is then introduced into membrane separator 501, which produces retentate off-gas stream 502 and C3+ enriched permeate stream 503.
  • C3+ enriched permeate stream 503 is then recycled back to fractionator 203.
  • Output stream 211 is then introduced into separation column 217, which produces, at least propylene stream 222, propane stream 223, butane stream 224, light cat naptha stream 225, and high cat naptha stream 226.
  • This embodiment addresses the situation where C3+ enriched stream 503 is recycled to fractionater 203 or the inlet of fractionator overhead stream compressor 209 (not shown).
  • This stream contains carbon dioxide, and this carbon dioxide tends to enrich with the C3+. This can produce an undesirable size effect, as it will keep accumulating in the system and increase the recycle flowrate. This artificially large recycle flowrate may directly result in an oversizing of compressor 209. Reducing the recycle flowrate by removal of the accumulating C02 may be important.
  • a second stage of membranes is added that would prevent the carbon dioxide from accumulating. Upstream of the rubbery membrane, a carbon dioxide selective glassy membrane may be installed in order to permeate preferentially carbon dioxide. Permeate flow can be kept to a minimum in order to limit losses of the products without accumulating carbon dioxide in the recycle loop. This carbon dioxide rich permeate may be routed to fuel (not shown).
  • feed gas stream 201 is introduced into FCC unit 202.
  • the output stream from FCC unit 202 is then introduced into fractionator 203, which produces light ends stream 204, light cycle oil stream 205, medium cycle oil stream 206, heavy cycle oil stream 207 and slurry stream 208.
  • Light ends stream 204 is compressed in fractionator overhead stream compressor 209 and sent to main absorber 210.
  • Main absorber 210 produces output stream 211 and off-gas stream 212.
  • Offgas stream 212 is then introduced into carbon dioxide removal unit 701 , which carbon dioxide rich stream 702 and carbon dioxide poor stream 703.
  • Carbon dioxide poor stream 703 is then introduced into membrane separator 501 , which produces retentate off-gas stream 502 and C3+ enriched permeate stream 503.
  • Output stream 211 and C3 enriched permeate stream 503 are then introduced into separation column 217, which produces, at least propylene stream 222, propane stream 223, butane stream 224, light cat naptha stream 225, and high cat naptha stream 226.
  • a “Dead-end glassy-type” membrane is utilized. With this membrane the recovered C3+ is recovered under pressure. It also has the advantage of increasing the recovery with higher pressure without any refrigeration therefore achieving a close to 100% C3+ recovery higher than the“rubbery-type” membrane.
  • This system requires to increase the pressure of the off-gas of the secondary absorber or of the light ends coming from the main absorber. The recovery of such system is directly linked to the compression power, and so the power of this system can be directly adjusted to the required recovery level.
  • the membrane unit can also be a more integrated design with propane refrigeration cycle 914 and deethanizer column 905, in lieu of the secondary absorber.
  • This embodiment has the advantage of reaching higher C3+ recovery than single membrane system, up to 90% and slightly above.
  • C3+ recovery of the FCC gas plant is improved by replacing the secondary absorber with a combination of propane-cooled cold separator 902 and deethanizer 905, complemented by membrane unit 909 recycling the C3+ content 911 from the gaseous phase 904 of cold separator 902 to the inlet of the light end fractionation compressor 209.
  • the primary absorber off-gas 212 is cooled in economizer 901, using propane refrigeration cycle 914, where it is cooled down and sent to a cold separator 902.
  • Gaseous phase 904 from cold separator 902 is sent to the innovative membrane system 909 after being heated up to about ambient temperature in the economizer 901.
  • Membrane residual 910 then cooled in the economizer 901, expanded in JT valve 915, combined with deethanizer top stream 907, and combined stream 916 is heated up again in economizer 901.
  • the cold point of economizer 901 remains provided by the cold expanded residual 916.
  • the residual 913 is exported as fuel gas at ambient temperature.
  • Membrane permeate 911 recovers the C3+ that had been lost in the gaseous phase 904 of the cold separator 902 and is recycled back at the inlet of the light end compressor 209. Liquid phase 903 from cold separator 902 is sent to deethanizer 805. Light end fraction 907 is combined with expanded membrane residual 910, sent back to economizer 901 and exits the system as off-gas 913.
  • C3+ fraction 906 is recovered at the bottom of deethanizer column 905 and sent to de-C4 column 217 of the gas plant, where it will go through the existing separation steps of the gas plant. C3+ fraction 906 will generate significant revenue as it will now able to be processed in the downstream part of the gas plant.
  • Refrigeration unit 914 (preferably propane cycle type) could be used a source of cold for the condenser, while some steam could be used for the reboiler.
  • One advantage of this embodiment is high recovery without a recycling compressor and a lower recycle flowrate. Also, the de-ethanizer column is smaller than secondary absorber because less flowrate to treat.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de séparation d'hydrocarbures contenant trois atomes de carbone ou plus à partir d'un flux de dégagement gazeux. Ce procédé consiste à séparer un flux de fractions légères à partir d'un fractionnateur, produisant ainsi un flux riche en hydrocarbures contenant trois atomes de carbone ou plus, et un flux pauvre en hydrocarbures contenant trois atomes de carbone ou plus, à séparer le flux pauvre en hydrocarbures contenant trois atomes de carbone ou plus dans une unité de membrane, ce qui permet de produire un flux de perméat enrichi en hydrocarbures contenant trois atomes de carbone ou plus et un flux de rétentat et à séparer le flux riche en hydrocarbures contenant trois atomes de carbone ou plus dans une ou plusieurs colonnes de séparation, ce qui permet de produire un ou plusieurs flux choisis dans le groupe constitué par un flux de propylène, un flux de propane, un flux de butane, un flux de naphte catalytique léger et un flux de naphte catalytique lourd.
PCT/US2020/025219 2019-03-27 2020-03-27 Perfectionnements apportés à la récupération de c3+ avec des membranes WO2020198588A2 (fr)

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US7799964B2 (en) * 2006-04-04 2010-09-21 Exxonmobil Research And Engineering Company Membrane process for LPG recovery
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